CN114456588B - High-strength high-heat-conductivity electromagnetic shielding nylon composite material and preparation method thereof - Google Patents
High-strength high-heat-conductivity electromagnetic shielding nylon composite material and preparation method thereof Download PDFInfo
- Publication number
- CN114456588B CN114456588B CN202210121527.4A CN202210121527A CN114456588B CN 114456588 B CN114456588 B CN 114456588B CN 202210121527 A CN202210121527 A CN 202210121527A CN 114456588 B CN114456588 B CN 114456588B
- Authority
- CN
- China
- Prior art keywords
- composite material
- electromagnetic shielding
- parts
- carbon
- nylon
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
Abstract
The invention discloses a high-strength high-heat-conductivity electromagnetic shielding nylon composite material and a preparation method thereof, wherein the composite material comprises the following raw materials in parts by weight: 40-60 parts of nylon resin, 20-40 parts of carbon fiber, 20-40 parts of mesophase carbon microsphere, 0.1-5 parts of dispersing agent and 0.1-1 part of antioxidant; the invention utilizes the bridging effect of the micron-sized spherical mesophase carbon microspheres and the chopped carbon fibers to form a perfect heat conduction network, greatly improves the heat conduction performance and the electromagnetic shielding performance, and greatly improves the strength of the composite material under the reinforcing effect of the carbon fibers.
Description
Technical Field
The invention belongs to the technical field of electromagnetic shielding heat conduction materials, and particularly relates to a high-strength high-heat conduction electromagnetic shielding nylon composite material and a preparation method thereof.
Background
With the progress of technology, electronic devices are rapidly developed to be miniaturized and integrated, the heat productivity of equipment is gradually increased, and the requirements on heat conducting materials are also higher and higher. In addition, electromagnetic waves can be generated when the electronic element works, electromagnetic interference can be generated on the electronic element, and normal work of other elements can be influenced by the fact that the electromagnetic interference is too strong, so that development of novel electromagnetic shielding materials is urgently needed to ensure normal operation of the elements.
Carbon materials such as graphene and carbon nanotubes have excellent heat conduction performance and electric conduction performance, but the particle sizes of the graphene and the carbon nanotubes are small, the graphene and the carbon nanotubes are extremely easy to agglomerate, and good dispersion is difficult to achieve by simple melt blending. As CN104844795a discloses a nylon 6 with high heat conductivity and a preparation method thereof, authors add modified graphene dispersion liquid into a caprolactam polymerization system, and successfully improve the dispersion degree of graphene in a nylon 6 matrix by matching with a magnetic field and ultrasonic treatment.
And the materials such as graphene and carbon nano tubes are high in price, are not fully industrialized, and the cost problem is difficult to solve. As CN111040428A discloses an electromagnetic shielding high thermal conductivity nylon composite material, the authors extrusion injection-molded the fillers such as graphene, carbon nanotubes, silicon dioxide, modified red mud and nylon resin to prepare the composite material. Although the material has excellent performance, the content of graphene and carbon nano tubes is not low, and the cost of the composite material is high.
In order to solve the problems, the performance of the nylon matrix is improved by taking the one-dimensional mesophase carbon microspheres and the two-dimensional carbon fibers as mixed fillers, and after melt blending, the fillers are well dispersed, and more heat conduction paths are constructed due to size difference, so that the heat conduction performance of the composite material is remarkably improved. The mesocarbon microbeads have good chemical stability, thermal stability and excellent electrical and thermal conductivity, and are isotropic materials. Carbon fibers are two-dimensional materials, and have excellent electrical conductivity and thermal conductivity along the fiber axis direction, but the thermal conductivity in the radial direction is not ideal, and orientation easily occurs during melt blending injection molding, so that the composite material has higher heat conductivity and the axial heat conductivity is not ideal. The two fillers are combined, so that the facing and axial heat conducting capacity of the composite material can be improved simultaneously. And the addition of the carbon fiber improves the overall mechanical property of the material, improves the dimensional stability and reduces the water absorption rate of nylon.
Disclosure of Invention
The invention provides a high-strength high-heat-conductivity electromagnetic shielding nylon composite material and a preparation method thereof.
The high-strength high-heat-conductivity electromagnetic shielding nylon composite material prepared by the invention can simultaneously meet the performance requirements of injection molding, good mechanical property, high thermal deformation temperature, effective shielding of electromagnetic interference, heat generated by conducting electronic device operation and the like, and the electromagnetic shielding performance is mainly absorption loss, so that secondary pollution is greatly reduced. The preparation process of the composite material does not need a solvent, is environment-friendly, can be realized only by simple melt blending, has low manufacturing cost and wide application range, and is suitable for industrial production.
The invention utilizes the bridging effect of the micron-sized spherical mesophase carbon microspheres and the chopped carbon fibers to form a perfect heat conduction network, greatly improves the heat conduction performance and the electromagnetic shielding performance, and greatly improves the strength of the composite material under the reinforcing effect of the carbon fibers.
The technical scheme of the invention is as follows:
the high-strength high-heat-conductivity electromagnetic shielding nylon composite material comprises the following raw materials in parts by weight:
40-60 parts of nylon resin, 20-40 parts of carbon fiber, 20-40 parts of mesophase carbon microsphere, 0.1-5 parts of dispersing agent and 0.1-1 part of antioxidant.
Further:
the nylon resin is one or a combination of PA6 and PA66, and the viscosity is 2.7; preferably, the weight ratio of PA6 to PA66 is 5:1, compounding;
the diameter of the carbon fiber is 10-20 mu m, the length is 2-5 mm, and the carbon content is higher than 95%; preferably, the carbon fibers are chopped filaments coated by a polar polymer bundling agent;
the particle size of the mesophase carbon microsphere is 10-20 mu m, and the graphitization degree is more than 99%;
the dispersing agent is one or more selected from silicone powder, TAF-A, EBS and zinc stearate;
the antioxidant is selected from 1098[ N, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine ] or 626[ bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite ], or a mixture of the two, preferably in a weight ratio of 1: 1-2.
The preparation method of the high-strength high-heat-conductivity electromagnetic shielding nylon composite material comprises the following steps:
(1) Vacuum drying the raw materials at 85 ℃ for 12 hours, and mixing nylon resin, mesophase carbon microspheres, an antioxidant and a dispersing agent according to a formula to obtain a premix;
(2) Adding premix from a main feed inlet of a double-screw extruder, adding carbon fiber through a side feed device, and obtaining a nylon composite material through melt extrusion, cooling, granulating and drying;
preferably, the length-diameter ratio of the screw of the double-screw extruder is 36-46, and the temperature range in the extrusion process is 260-290 ℃; the filler is uniformly distributed in the matrix, and the multi-size filler is easier to form a good heat conduction path.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention utilizes the combination of the three-dimensional filler and the two-dimensional filler to construct a denser interpenetrating electric conduction and heat conduction network (see the schematic diagram of figure 1 and a scanning electron microscope), and obviously improves the heat conduction and electromagnetic shielding performance of the composite material;
2. according to the invention, the mesophase carbon microsphere is used as a filler, has excellent electrical conductivity and thermal conductivity, has a microstructure with spherical size, can play a role in improving electromagnetic wave absorption in a polymer matrix, and avoids secondary pollution of electromagnetic waves;
3. according to the invention, carbon fibers are used as fillers, the carbon fibers have good electrical conductivity and thermal conductivity along the fiber axis direction, and the carbon fibers are compounded with the mesocarbon microbeads, so that the axial thermal conductivity of the material can be greatly improved while the surface thermal conductivity of the composite material is not influenced, and the carbon fibers have high strength and modulus along the fiber axis direction, so that the mechanical property of the composite material can be greatly improved;
4. the invention uses nylon 6 and nylon 66 to compound as the matrix material, which has good compatibility, reduces crystallinity, and improves toughness while maintaining the strength of the composite material.
Drawings
FIG. 1 is a schematic view of the structure of the composite material of the present invention and a sectional scanning electron microscope image.
FIG. 2 is a sectional scanning electron microscope image of the composite material of example 3.
Detailed Description
The present invention is further described below by way of specific examples, but the scope of the present invention is not limited thereto.
The mesophase carbon microspheres used in the following examples were 10 to 20 μm in size and had a graphitization degree of 99% or more, which was provided by Tianjin Aimin corporation; the carbon fiber has the diameter of 10-20 mu m, the length of 2-5 mm and the carbon content of more than 95 percent, is chopped and cut by the polar polymer bundling agent coated carbon fiber, and is provided by Shanghai Yu Tongcheng chemical industry Co-Ltd, and is preferably marked as CBZ-HT2; the silicone powder is provided by a Kedgy plastic, preferably with the brand of polyamide lubricant PA-B.
Example 1
1kg of nylon 6, 200g of nylon 66, 800g of carbon fiber, 10g of silicone powder, 4g of antioxidant 1098 and 4g of antioxidant 626 are dried in vacuum at 85 ℃ for 12 hours, and are extruded and granulated by double screws, and then mechanical test bars, heat conduction test discs and electromagnetic shielding test bars are injection molded.
Extruder zone temperatures: a region: 260 ℃, two regions: 265 ℃, three regions: 270 ℃, four regions: 275 ℃, five regions: 280 ℃, six regions: 280 ℃, seven regions: 275 ℃, eight regions: 270 ℃, nine regions: 270 ℃, ten areas: 275 ℃. The specific properties are shown in Table II.
Example 2
1kg of nylon 6, 200g of nylon 66, 200g of mesophase carbon microspheres, 600g of carbon fibers, 10g of silicone powder, 4g of antioxidant 1098 and 4g of antioxidant 626 are dried in vacuum at 85 ℃ for 12 hours, and are extruded and granulated by double screws, and then mechanical test bars, heat conduction test discs and electromagnetic shielding test bars are injection molded.
Extruder zone temperatures: a region: 260 ℃, two regions: 265 ℃, three regions: 270 ℃, four regions: 275 ℃, five regions: 280 ℃, six regions: 280 ℃, seven regions: 275 ℃, eight regions: 270 ℃, nine regions: 270 ℃, ten areas: 275 ℃. The specific properties are shown in Table II.
Example 3
1kg of nylon 6, 200g of nylon 66, 400g of mesophase carbon microspheres, 400g of carbon fibers, 10g of silicone powder, 4g of antioxidant 1098 and 4g of antioxidant 626 are dried in vacuum at 85 ℃ for 12 hours, and are extruded and granulated by double screws, and then mechanical test bars, heat conduction test discs and electromagnetic shielding test bars are injection molded.
Extruder zone temperatures: a region: 260 ℃, two regions: 265 ℃, three regions: 270 ℃, four regions: 275 ℃, five regions: 280 ℃, six regions: 280 ℃, seven regions: 275 ℃, eight regions: 270 ℃, nine regions: 270 ℃, ten areas: 275 ℃. The specific properties are shown in Table II.
Example 4
1kg of nylon 6, 200g of nylon 66, 600g of mesophase carbon microspheres, 200g of carbon fibers, 10g of silicone powder, 4g of antioxidant 1098 and 4g of antioxidant 626 are dried in vacuum at 85 ℃ for 12 hours, and are extruded and granulated by double screws, and then mechanical test bars, heat conduction test discs and electromagnetic shielding test bars are injection molded.
Extruder zone temperatures: a region: 260 ℃, two regions: 265 ℃, three regions: 270 ℃, four regions: 275 ℃, five regions: 280 ℃, six regions: 280 ℃, seven regions: 275 ℃, eight regions: 270 ℃, nine regions: 270 ℃, ten areas: 275 ℃. The specific properties are shown in Table II.
Example 5
1kg of nylon 6, 200g of nylon 66, 800g of mesophase carbon microspheres, 10g of silicone powder, 4g of antioxidant 1098 and 4g of antioxidant 626 are dried in vacuum at 85 ℃ for 12 hours, and are subjected to extrusion granulation by double screws, and then mechanical test bars, heat conduction test discs and electromagnetic shielding test bars are injection molded.
Extruder zone temperatures: a region: 260 ℃, two regions: 265 ℃, three regions: 270 ℃, four regions: 275 ℃, five regions: 280 ℃, six regions: 280 ℃, seven regions: 275 ℃, eight regions: 270 ℃, nine regions: 270 ℃, ten areas: 275 ℃. The specific properties are shown in Table II.
The formula raw materials of the different heat conduction electromagnetic shielding nylon materials in the embodiment of the invention are shown in the following table 1:
TABLE 1
The mechanical, thermal conductivity and electromagnetic shielding properties of the heat-conducting electromagnetic shielding nylon composite material prepared by the embodiment of the invention are shown in the following table 2:
the mechanical properties of the composites were tested using a universal tester ((Instron-5966, USA). For flexural testing, samples were prepared according to ISO 178 and tested at a span of 64mm and a speed of 2mm/min, respectively, using type A samples at 23℃and 50% relative humidity according to ISO 527-2.
Based on the Hot plate transient plane source method, a thermal constant analyzer (Hot Disk TPS2500S, sweden) was used to quantitatively analyze the thermal conductivity of the composite material. The thermal conductivity was measured at room temperature and in an air atmosphere using a disc having a radius of 25 mm and a thickness of 2 mm.
The electromagnetic shielding performance of the composite material was tested using a vector network analyzer. Rectangular bars with a length of 22.86 mm, a width of 10.16 mm and a thickness of 2mm were used for testing under electromagnetic waves in the 8-12GHz band.
Table 2 shows the mechanical, thermal and electromagnetic shielding properties of different thermally conductive and electromagnetic shielding nylon embodiments of the present invention.
TABLE 2
After the heat conducting filler is added, compared with pure nylon (the heat conducting coefficient is about 0.3W/mK), the heat conducting performance of the composite material is greatly improved. However, in example 5, only the mesocarbon microbeads were used as fillers, which did not greatly improve the mechanical properties of the composite material, and the electromagnetic shielding effect was general. In example 1, only carbon fiber was used as the filler, but the improvement of the thermal conductivity and the electromagnetic shielding performance was not significant although the mechanical properties were significantly improved.
In the embodiment 3, a perfect heat conduction path is constructed through the compounding of the carbon fiber and the mesocarbon microbead, so that the material has the heat conduction coefficient of about 2W/m.K in the face and the axial direction, has good electromagnetic shielding effect, and has excellent overall mechanical property. A cross-sectional scanning electron microscope of example 3 is shown in FIG. 2.
Claims (5)
1. The high-strength high-heat-conductivity electromagnetic shielding nylon composite material is characterized by comprising the following raw materials in parts by weight:
40-60 parts of nylon resin, 20-40 parts of carbon fiber, 20-40 parts of mesophase carbon microsphere, 0.1-5 parts of dispersing agent and 0.1-1 part of antioxidant;
the nylon resin is prepared from PA6 and PA66 in a weight ratio of 5:1, compounding;
the diameter of the carbon fiber is 10-20 mu m, the length is 2-5 mm, and the carbon content is higher than 95%; the carbon fibers are chopped filaments coated by a polar polymer bundling agent;
the particle size of the mesophase carbon microsphere is 10-20 mu m, and the graphitization degree is more than 99%.
2. The high-strength high-heat-conductivity electromagnetic shielding nylon composite material according to claim 1, wherein the dispersing agent is one or more selected from silicone powder, TAF-A, EBS and zinc stearate.
3. The high strength, high thermal conductivity electromagnetic shielding nylon composite of claim 1, wherein said antioxidant is selected from 1098[ n, n' -bis- (3, 5-di-t-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine ] or 626[ bis (2, 4-di-t-butylphenol) pentaerythritol diphosphite ], or a mixture of both.
4. The method for preparing the high-strength high-heat-conductivity electromagnetic shielding nylon composite material according to claim 1, which is characterized by comprising the following steps:
(1) Vacuum drying the raw materials at 85 ℃ for 12 hours, and mixing nylon resin, mesophase carbon microspheres, an antioxidant and a dispersing agent according to a formula to obtain a premix;
(2) Adding premix from a main feed inlet of a double-screw extruder, adding carbon fiber through a side feed device, and obtaining the nylon composite material through melt extrusion, cooling, granulating and drying.
5. The process according to claim 4, wherein the twin-screw extruder has a screw aspect ratio of 36 to 46 and a temperature during extrusion of 260 to 290 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210121527.4A CN114456588B (en) | 2022-02-09 | 2022-02-09 | High-strength high-heat-conductivity electromagnetic shielding nylon composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210121527.4A CN114456588B (en) | 2022-02-09 | 2022-02-09 | High-strength high-heat-conductivity electromagnetic shielding nylon composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114456588A CN114456588A (en) | 2022-05-10 |
| CN114456588B true CN114456588B (en) | 2023-09-05 |
Family
ID=81414162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210121527.4A Active CN114456588B (en) | 2022-02-09 | 2022-02-09 | High-strength high-heat-conductivity electromagnetic shielding nylon composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114456588B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787645A (en) * | 2010-03-02 | 2010-07-28 | 东华大学 | Carbon fiber surface electropolymerization treatment method |
| CN102931560A (en) * | 2012-11-21 | 2013-02-13 | 天津市贝特瑞新能源科技有限公司 | Brush material with excellent performance, and preparation method and application thereof |
| CN107118556A (en) * | 2017-06-21 | 2017-09-01 | 安徽江淮汽车集团股份有限公司 | A kind of PPS composites and preparation method thereof |
| CN110655413A (en) * | 2019-09-18 | 2020-01-07 | 济宁碳素集团有限公司 | Preparation method of isotropic graphite material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4759122B2 (en) * | 2000-09-12 | 2011-08-31 | ポリマテック株式会社 | Thermally conductive sheet and thermally conductive grease |
| US11772975B2 (en) * | 2015-12-03 | 2023-10-03 | Global Graphene Group, Inc. | Chemical-free production of graphene materials |
-
2022
- 2022-02-09 CN CN202210121527.4A patent/CN114456588B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787645A (en) * | 2010-03-02 | 2010-07-28 | 东华大学 | Carbon fiber surface electropolymerization treatment method |
| CN102931560A (en) * | 2012-11-21 | 2013-02-13 | 天津市贝特瑞新能源科技有限公司 | Brush material with excellent performance, and preparation method and application thereof |
| CN107118556A (en) * | 2017-06-21 | 2017-09-01 | 安徽江淮汽车集团股份有限公司 | A kind of PPS composites and preparation method thereof |
| CN110655413A (en) * | 2019-09-18 | 2020-01-07 | 济宁碳素集团有限公司 | Preparation method of isotropic graphite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114456588A (en) | 2022-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113150541B (en) | High-strength high-thermal-conductivity nylon composite material and preparation method thereof | |
| CN113025039A (en) | Polyphenylene sulfide composite material and preparation method thereof | |
| CN105462246B (en) | Powder compound modified super-high heat-conductive nylon of a kind of graphene/metal and preparation method thereof | |
| CN103897241A (en) | Heat conductive plastics and manufacturing method thereof | |
| CN106675008B (en) | High-thermal-conductivity nylon 6 composite material and preparation method thereof | |
| CN115785671B (en) | Aerogel/polyphenylene sulfide self-lubricating friction material and preparation method thereof | |
| CN110903597A (en) | Polyether-ether-ketone composite material and preparation method and application thereof | |
| CN102533228A (en) | Coated heat conducting material, heat conducting composite material and preparing methods thereof | |
| CN114456588B (en) | High-strength high-heat-conductivity electromagnetic shielding nylon composite material and preparation method thereof | |
| CN111423723A (en) | Reinforced polyphenylene sulfide composition for 5G and preparation method thereof | |
| CN114957855A (en) | Wave-absorbing heat-conducting thermoplastic composite material and preparation method thereof | |
| CN112662077B (en) | Antistatic graphene-coated aluminum microsphere modified PP composite material and preparation method thereof | |
| CN111534075B (en) | Thermoplastic heat-conducting composite material and preparation method thereof | |
| CN102532883B (en) | High-performance semi-transparent enhanced PA66 material and preparation method thereof | |
| CN115785864A (en) | PI-Al 2 O 3 Preparation method of PI-BN codoped high-thermal-conductivity epoxy resin composite material | |
| CN111909511B (en) | High-wear-resistance heat-conducting nylon composite material and preparation method thereof | |
| CN109233197A (en) | A kind of thin-walled electric appliance graphene/polyether-ether-ketone engineering plastics and preparation method | |
| CN102020826B (en) | Chopped fiber reinforced ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof | |
| CN113512256A (en) | Antistatic polyolefin master batch and preparation method thereof | |
| CN107541011A (en) | A kind of high-performance polyether-ether-ketone composite material formula and preparation method thereof | |
| CN111334042A (en) | Low-dielectric-constant polyphenylene sulfide composition and preparation method thereof | |
| CN116478496B (en) | Heat-conducting master batch and preparation method thereof | |
| CN114891350B (en) | High-performance antistatic filler, polyether sulfone composite material containing antistatic material and preparation method of composite material | |
| CN114507379B (en) | Heat-conducting composite filler, preparation method thereof, heat-conducting thermoplastic resin composite material and application thereof | |
| CN114989608B (en) | Heat-conducting polysulfone 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 |