CN107746505B - Coating carbon fiber reinforced ABS/PP electromagnetic shielding composite material and preparation method thereof - Google Patents
Coating carbon fiber reinforced ABS/PP electromagnetic shielding composite material and preparation method thereof Download PDFInfo
- Publication number
- CN107746505B CN107746505B CN201711006344.3A CN201711006344A CN107746505B CN 107746505 B CN107746505 B CN 107746505B CN 201711006344 A CN201711006344 A CN 201711006344A CN 107746505 B CN107746505 B CN 107746505B
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- nickel
- composite material
- electromagnetic shielding
- alloy coating
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention discloses a coating carbon fiber reinforced ABS/PP electromagnetic shielding composite material and a preparation method thereof, wherein the electromagnetic shielding composite material is obtained by melting, extruding and molding nickel-based alloy coating carbon fibers, ABS/PP blending resin, a cross-linking agent and a coupling agent; the prepared composite material has good electromagnetic shielding effect in a very wide frequency band range, has the comprehensive properties of high strength, high modulus, corrosion resistance, excellent thermal stability and the like, and the preparation method is simple to operate, low in cost and capable of meeting the requirement of industrial production.
Description
Technical Field
The present invention relates to an electromagnetic shielding material; in particular to a coating carbon fiber reinforced ABS/PP electromagnetic shielding composite material and a preparation method thereof, belonging to the field of electromagnetic shielding materials.
Background
With the rapid development of modern electronic technology, electronic appliances and radio equipment are widely used, and the problem of electromagnetic radiation caused by the electronic appliances and the radio equipment is becoming serious, which becomes another public hazard following noise pollution, atmospheric pollution, water pollution and solid waste pollution. The electromagnetic waves not only interfere the normal operation of various electronic equipment, influence the physical health of human beings, but also cause information leakage and threaten the political, economic and military safety of the country. Therefore, the search for efficient electromagnetic shielding materials has become an urgent problem to be solved.
At present, commonly used reinforcement fibers comprise carbon fibers, glass fibers, silicon carbide fibers and the like, but the glass fibers are not conductive and cannot generate dielectric loss, so the reinforcement fibers are hardly used in electromagnetic shielding materials, and the preparation technology of the silicon carbide fibers is not mature, so the cost is high. The carbon fiber has better conductivity than silicon carbide fiber, mature preparation technology and low cost, and the composite material prepared by using the carbon fiber as a reinforcement has a series of excellent performances such as high strength, high modulus, low density, high temperature resistance and the like, and is expected to replace the traditional metal shielding material and be used for various electronic components. However, carbon fibers have high resistivity and are seriously worn on a die and processing equipment, and an extrusion molding process cannot be adopted. The electrical resistivity and the electromagnetic shielding effectiveness of the fiber can be effectively adjusted by coating the metal coating on the surface of the carbon fiber. The common matrix resins of the thermoplastic resin matrix composite material comprise ABS resin, PP resin, PC resin and the like, which all have better strength and toughness, but the PC resin has poorer hardness and chemical stability, and the surface is easy to corrode and scratch. The PP resin is a crystalline polymer and can form a conductive network in the composite material, so that the composite material prepared by taking the PP resin as a matrix has better electromagnetic shielding performance, but the interaction between the PP resin and metal is weaker, and the PP resin is not tight in fiber wrapping an alloy coating. ABS resin and metal have strong interaction, can wrap up the fiber closely, but the resistivity is relatively high.
Chinese patent (application number: CN201710088664.1) discloses a preparation method of a high-strength and high-conductivity composite fiber reinforced composite material, and specifically discloses that carbon fibers and carbon nanotube fibers are wound together to form composite fibers, and a ceramic or resin matrix is prepared on the composite fibers to prepare a one-dimensional carbon fiber/carbon nanotube fiber/silicon carbide ceramic matrix composite material and a one-dimensional carbon fiber/carbon nanotube fiber/phenolic resin matrix composite material. However, a conductive network is not easily formed between the material fiber and the resin matrix, and the electromagnetic shielding performance of the material fiber is limited to a certain extent.
Chinese patent application No. CN201710028677.X discloses a chopped carbon fiber electromagnetic shielding composite material and a preparation method thereof, and particularly discloses a resin/chopped carbon fiber shielding felt/resin three-layer composite material prepared by a hot pressing method, so as to obtain the chopped carbon fiber electromagnetic shielding composite material with adjustable shielding performance. However, the material cannot well improve the defect of high resistivity of the carbon fiber, and the bonding between the resin and the fiber is not good.
Chinese patent (application number: CN201710014263.1) discloses a preparation process of a carbon fiber and polyamide resin composite material, and particularly discloses that carbon fiber and polyamide resin are sequentially input into a coating die through an output mechanism and then enter a granulating mechanism for granulating to form the carbon fiber and polyamide resin composite material. However, the preparation method has high requirements on equipment and complicated procedures, and is not suitable for mass production.
Extrusion molding is a more common method for preparing thermoplastic resin composite materials, and has the advantages of low production cost, high efficiency and the like, wherein the double-screw extrusion method has the unique advantages of excellent mixing and plasticizing effects, low energy consumption, easy feeding and the like. However, the conventional twin-screw extrusion method is often used for preparing a composite material with a granular or powdery reinforcing body, and the twin-screw extrusion method has some defects in preparing a fiber reinforced composite material, such as abrasion on a fiber material, reduction of the mechanical property of the fiber and the like, so that the application of the fiber reinforced composite material is limited.
Disclosure of Invention
Aiming at the defects of high resistivity, weak combination between carbon fibers and a matrix and the like of the existing carbon fiber composite material, the invention aims to provide a low-density coating carbon fiber reinforced ABS/PP electromagnetic shielding composite material with excellent electromagnetic shielding performance and mechanical performance, and solves the problems of high resistivity, poor compatibility between fibers and resin, non-tight combination and the like of the existing composite material.
The invention also aims to provide a method for preparing the coating carbon fiber reinforced ABS/PP electromagnetic shielding composite material based on the double-screw extrusion method, the carbon fiber reinforced ABS/PP based composite material with uniform material mixing, good bonding strength and good plasticizing effect can be prepared by the double-screw extrusion method, and the method has the advantages of low cost, high efficiency, low energy consumption and the like.
In order to achieve the technical purpose, the invention provides a coating carbon fiber reinforced ABS/PP electromagnetic shielding composite material which is formed by melting and extruding the following components in parts by mass: 10-50 parts of nickel-based alloy coating carbon fiber; 50-88 parts of ABS/PP blended resin; 0.1-0.5 part of a crosslinking agent; 2-5 parts of a coupling agent.
The technical scheme of the invention firstly proposes that the nickel-based alloy coating carbon fiber and ABS/PP resin are prepared into the composite material. The copper-nickel alloy, the aluminum-nickel alloy and the tin-nickel alloy in the nickel-based alloy have good conductivity and higher dielectric loss, the iron-nickel alloy and the cobalt-nickel alloy have two loss mechanisms of dielectric loss and magnetic loss, the coating of the nickel-based alloy coating on the surface of the carbon fiber can improve the conductivity of the coated carbon fiber and increase the loss of electromagnetic waves, thereby playing the roles of absorbing electromagnetic waves and increasing the electromagnetic shielding efficiency, meanwhile, the mechanical property of the fiber is not influenced by the coating of the alloy coating, particularly, the carbon fiber is difficult to be formed by adopting a screw extrusion process, the mechanical property and the chemical stability of the fiber are influenced because the fiber is abraded in the screw extrusion process, and after the nickel alloy coating is coated, the processing property of the fiber is improved, the wear resistance of the fiber is improved, and the fiber can. The PP resin is a crystalline polymer, and is influenced by PP crystallization, so that the coating carbon fiber is more enriched in an amorphous area and is easy to form a conductive network, and the resistivity of the composite material is further reduced. However, the PP resin and the fibers have weak interaction and are not tightly combined with the fibers, so that the mechanical property of the composite material is influenced. The ABS resin has strong interaction with metal, and the addition of a certain amount of ABS resin can enable the resin to wrap the fiber more tightly, thereby maintaining good mechanical properties. Meanwhile, the metal and the resin have poor compatibility, the metal-plated carbon fiber is difficult to uniformly disperse in a composite system, and the fiber is easy to wind and agglomerate, so that a certain amount of silane coupling agent is added, the compatibility between the fiber and a matrix can be improved, the alloy coating on the surface of the fiber is kept complete, a conductive network formed by the alloy coating is relatively perfect, and the electromagnetic shielding performance of the fiber can be further improved.
Preferably, the nickel-based alloy coating in the nickel-based alloy coated carbon fiber comprises a copper-nickel alloy coating, an aluminum-nickel alloy coating, an iron-nickel alloy coating, a tin-nickel alloy coating or a cobalt-nickel alloy coating.
In a preferred scheme, the nickel content in the nickel-based alloy coating is 1-99% by mass.
In a more preferable scheme, the thickness of the nickel-based alloy coating is 50-500 nm. In the preferred scheme, the selection of the thickness of the coating is mainly considered from the aspects of absorption wave band, fiber diameter, fiber density and the like, the diameter of the carbon fiber is 7 mu m, and the carbon fiber has the characteristics of small density and high axial strength, and the excessive total thickness of the coating can cause the excessive change of the fiber diameter and the weight increase, thereby influencing the preparation and the use of the composite material; the total thickness of the coating is too small, and the electromagnetic parameters of the carbon fibers cannot be well adjusted, so that the total thickness of the coating in the preferred scheme is 50-500 nm.
In a preferable scheme, the mass ratio of the ABS to the PP in the ABS/PP blended resin is 10: 90-50: 50.
In a preferable scheme, the carbon fiber in the nickel-based alloy coating carbon fiber is a short carbon fiber with the length of 1-10 mm. The length of the carbon fiber in the preferred scheme is mainly selected from the consideration of the dispersion degree, the bearing condition and the coating combination condition, the continuous long fiber can only bear stronger unidirectional load, and the chopped fiber can be distributed in the composite material along all directions to bear the load in all directions. Too long short fiber length is not easy to disperse in the composite material and easy to bend and break, and too short fiber length is easy to fall off in the processing process. Therefore, the carbon fiber in the preferable scheme is a chopped carbon fiber with the length of 1-10 mm.
In a preferred embodiment, the crosslinking agent is dicumyl peroxide.
Preferably, the coupling agent is a silane coupling agent.
The invention provides a preparation method of a coating carbon fiber reinforced ABS/PP electromagnetic shielding composite material, which comprises the steps of mixing and melting ABS resin, PP resin, a cross-linking agent and a coupling agent, and extruding and compounding the mixture and chopped nickel-based alloy coating carbon fibers together.
The preparation method of the coating carbon fiber reinforced ABS/PP electromagnetic shielding composite material comprises the following specific steps: mixing ABS resin, PP resin, a cross-linking agent and a coupling agent in a high-speed mixer to prepare a premix; and (3) placing the premix into a main feed inlet of a double-screw extruder, adding the chopped nickel-gold alloy coating carbon fiber from a side feed inlet, and carrying out melt extrusion to obtain the nickel-gold alloy carbon fiber composite material.
In a preferred scheme, the nickel-based alloy coating carbon fiber is prepared by the following method: carrying out high-temperature treatment on carbon fibers at 650-750 ℃, and then placing the carbon fibers in acetone for ultrasonic washing; and (3) taking the washed carbon fiber as a matrix, and preparing the nickel-based alloy coating on the surface of the carbon fiber matrix by a radio frequency magnetron sputtering method or a direct current magnetron sputtering method.
In a preferable scheme, the ultrasonic washing time is 10-30 min.
In a preferred scheme, the time of the high-temperature treatment is 5-20 min. Within the preferable high-temperature treatment time range, the organic components on the surface of the carbon fiber can be effectively removed, and the surface of the carbon fiber is properly roughened.
According to the invention, the film forming capability of the magnetron sputtering method on the surface of the carbon fiber can be effectively improved by carrying out high-temperature treatment and acetone washing treatment on the carbon fiber. The carbon fiber can be carbonized and removed with organic components on the surface through high-temperature treatment, simultaneously, the surface of the carbon fiber can be coarsened, and then the carbon fiber is washed by combining acetone to further remove surface impurities, and simultaneously, the surface of the carbon fiber is protected from being damaged.
In a more preferable scheme, when the nickel-based alloy coating is prepared by adopting radio frequency magnetron sputtering, the radio frequency magnetron sputtering condition is controlled to be that the vacuum degree before sputtering is 1.0 × 10-3～1.0×10-4Pa, the radio-frequency sputtering power is 100-3000W, the deposition time is 30-100 min, the distance between the target and the carbon fiber is 50-80 mm, and the argon flow is 30-50 sccm;
in a more preferable scheme, when the nickel-based alloy coating is prepared by adopting direct-current magnetron sputtering, the direct-current magnetron sputtering condition is controlled to be that the vacuum degree before sputtering is 1.0 × 10-3～1.0×10-4Pa, direct current sputtering current of 2-50A, deposition time of 30-100 min, distance between the target and the carbon fiber of 50-80 mm, and argon flow of 30-50 sccm.
In a preferable scheme, the melt extrusion adopts a double-screw extrusion process; the process conditions are as follows: the temperature of each zone of the extrusion section is sequentially T1-165-170 ℃, T2-170 ℃, T3-165 ℃, T4-175 ℃, T hole-155-160 ℃, the rotation speed of the screw is 9-20 r/min, the diameter of the screw is 20mm, and the length-diameter ratio L/D of the equipment is 40 from a feeding end to a discharging end.
In the preferable scheme, in the preparation process of the premix, the rotating speed of a high-speed mixer is 800-1000 r/min, and the mixing time is 5-15 minutes.
The purity of the nickel-based alloy target material in the technical scheme of the invention is not lower than 99.999%.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
according to the technical scheme, the carbon fiber with the nickel-based alloy coating is used as a reinforcing material, and the ABS/PP blended resin is used as a matrix material. The nickel-based alloy has good electrical conductivity and high dielectric loss, the iron-nickel alloy and the cobalt-nickel alloy have two loss mechanisms of dielectric loss and magnetic loss, meanwhile, the nickel-based alloy coating can improve the wear resistance and mechanical property of the fiber, the coating can improve the electrical conductivity of the coated carbon fiber and increase the loss of electromagnetic waves by coating the coating on the surface of the carbon fiber, thereby playing the roles of absorbing electromagnetic waves and increasing the electromagnetic shielding efficiency, simultaneously improving the processing performance of the fiber and improving the wear resistance of the fiber, and the fiber can be formed by extruding through a screw. The PP resin and the ABS resin are blended to improve the binding capacity between the carbon fiber and the resin of the nickel-based alloy coating, so that the coating carbon fiber reinforced ABS/PP electromagnetic shielding composite material with excellent comprehensive performance is obtained.
According to the invention, the coated carbon fiber reinforced ABS/PP electromagnetic shielding composite material is prepared by adopting a double-screw extrusion method for the first time, the coated carbon fiber and the ABS/PP blended resin are perfectly combined, a good wire network is formed in a composite system, and the prepared composite material has lower resistivity, excellent electromagnetic property and lower density, and simultaneously gives play to excellent mechanical properties, corrosion resistance, high temperature resistance, heat conductivity and other excellent comprehensive properties of the carbon fiber to the maximum extent.
The prepared coating carbon fiber reinforced ABS/PP electromagnetic shielding composite material adopts a vector network analyzer to measure electromagnetic parameters, and obtains electromagnetic shielding performance through calculation, wherein the qualified bandwidth of the electromagnetic shielding performance of more than 20dB reaches 14.8GHz within the range of 2-18 GHz, the qualified bandwidth of more than 30dB reaches 8.2GHz, and the maximum shielding performance value is 46.19dB and is positioned at 12.64 GHz. The tensile strength of the composite material is detected, and the maximum tensile strength can reach 1.09 GPa. The density is only 1.12g/cm at the lowest3。
The preparation method of the coating carbon fiber reinforced ABS/PP electromagnetic shielding composite material is simple, rapid and low in cost; the coating fiber reinforced ABS/PP-based composite material with uniform material mixing, good bonding strength and good plasticizing effect can be prepared by a double-screw extrusion method.
Drawings
FIG. 1 is a graph showing electromagnetic shielding of a nickel-aluminum coated carbon fiber reinforced ABS/PP electromagnetic shielding composite material; fig. 2 is a cross-sectional scanning picture of the coating carbon fiber in the ferronickel coating carbon fiber reinforced ABS/PP electromagnetic shielding composite material.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Example 1
The preparation method of the coating carbon fiber reinforced ABS/PP electromagnetic shielding composite material comprises the following steps of firstly, placing carbon fibers in a 720-DEG C temperature tube furnace for heat preservation for 10min, secondly, placing the carbon fibers processed in the first step into acetone for ultrasonic cleaning for 15min, thirdly, preparing a nickel-aluminum coating on the surface of the carbon fibers processed in the second step by adopting a radio frequency magnetron sputtering method, fourthly, cutting the coated carbon fibers processed in the third step into 2mm in length to obtain chopped coated carbon fibers, fifthly, placing ABS resin, PP resin, a cross-linking agent and a coupling agent into a high-speed mixer according to the ratio of 20:57:0.2:3, mixing for 10min at the speed of 900r/min to prepare a premix, sixthly, placing the carbon fibers processed in the fourth step and the premix processed in the fifth step into a side feed inlet and a main feed inlet of a double-screw extruder according to the ratio of 20:80, performing melt extrusion to complete the preparation of the chopped nickel-aluminum coating reinforced ABS/PP electromagnetic shielding composite material, wherein the purity of a nickel-aluminum target in the third step is 99.999%, and the purity of the nickel-aluminum target is 0.×.25.25-4Pa, radio frequency sputtering power of 1500W, deposition time of 120min, distance between the target and the fiber of 60mm, argon flow of 40 sccm; in the sixth step, the temperature of each zone is T1-165 ℃, T2-170 ℃, T3-165 ℃, T4-175 ℃, T hole-155 ℃, the screw speed is 15r/min, the screw diameter is 20mm, and the length-diameter ratio L/D of the equipment is 40.
The mechanical property of the chopped nickel-aluminum coating carbon fiber reinforced ABS/PP electromagnetic shielding composite material prepared by the method is tested, the average tensile strength is 1.05GPa, the error range is 0.04GPa, and the value is far higher than that of metals and compounds. The density of the powder was measured and found to be only 1.12g/cm3。
Electromagnetic parameters of the chopped nickel-aluminum coating carbon fiber reinforced ABS/PP electromagnetic shielding composite material prepared by the method are detected within the frequency range of 2-18 GHz, and data of the electromagnetic shielding effectiveness of the composite material are obtained through calculation, wherein within the frequency range of 2-18 GHz, the qualified bandwidth of the electromagnetic shielding effectiveness of the composite material is up to 14.8GHz when being more than 20dB, the qualified bandwidth of the electromagnetic shielding effectiveness of the composite material is up to 8.2GHz when being more than 30dB, and the maximum shielding effectiveness value is 46.19dB and is located at 12.64 GHz. FIG. 1 is an electromagnetic shielding curve diagram of a nickel-aluminum coating carbon fiber reinforced ABS/PP electromagnetic shielding composite material.
Example 2
The preparation method of the coating carbon fiber reinforced ABS/PP electromagnetic shielding composite material comprises the following steps of firstly, placing carbon fibers in a 720-DEG C temperature tube furnace for heat preservation for 10min, secondly, placing the carbon fibers treated in the first step into acetone for ultrasonic cleaning for 15min, thirdly, preparing a nickel-iron coating on the surface of the carbon fibers treated in the second step by adopting a direct-current magnetron sputtering method, fourthly, cutting the coated carbon fibers treated in the third step into 5mm in length to obtain chopped coated carbon fibers, fifthly, placing ABS resin, PP resin, a cross-linking agent and a coupling agent into a high-speed mixer according to the ratio of 30:33:0.1:2, mixing for 10min at the speed of 900r/min to prepare a premix, sixthly, placing the carbon fibers treated in the fourth step and the premix treated in the fifth step into a side feed inlet and a main feed inlet of a double-screw extruder according to the ratio of 35:65, performing melt extrusion to complete the preparation of the chopped carbon fiber coated carbon fiber reinforced ABS/PP electromagnetic shielding composite material, wherein the purity of nickel-iron targets in the third step is 99.999%, and the purity of 3510.25.8-4Pa, direct current sputtering current of 5A, deposition time of 20min, distance between target and fiber of 60mm, argon flow of 40 sccm; in the sixth step, the temperature of each zone is T1-170 ℃, T2-180 ℃, T3-175 ℃, T4-175 ℃, T hole-160 ℃, the screw speed is 20r/min, the screw diameter is 20mm, and the length-diameter ratio L/D of the equipment is 40.
The chopped ferronickel coating carbon fiber reinforced ABS/PP electromagnetic shielding composite material prepared by the method is tested, the average tensile strength is 1.09GPa, the error range is 0.04GPa, and the value is far higher than that of metals and compounds. The density of the product is only 1.18g/cm3。
Electromagnetic parameters of the chopped ferronickel coating carbon fiber reinforced ABS/PP electromagnetic shielding composite material prepared by the method are detected within the frequency range of 2-18 GHz, and electromagnetic shielding effectiveness data of the chopped ferronickel coating carbon fiber reinforced ABS/PP electromagnetic shielding composite material are obtained through calculation, wherein within the frequency range of 2-18 GHz, the qualified bandwidth of the electromagnetic shielding effectiveness reaches 15.5GHz when being more than 20dB, and the qualified bandwidth reaches 10.2GHz when being more than 30 dB. Fig. 2 is a cross-sectional scanning picture of the nickel-iron coated carbon fiber in the composite material.
Example 3
The preparation method of the coated carbon fiber reinforced ABS/PP electromagnetic shielding composite material comprises the following steps of firstly, placing carbon fibers in a 720-DEG C temperature tube furnace for heat preservation for 10min, secondly, placing the carbon fibers treated in the first step into acetone for ultrasonic cleaning for 15min, thirdly, preparing a nickel-copper coating on the surface of the carbon fibers treated in the second step by adopting a direct-current magnetron sputtering method, fourthly, cutting the coated carbon fibers treated in the third step into 8mm in length to obtain chopped coated carbon fibers, fifthly, placing ABS resin, PP resin, a cross-linking agent and a coupling agent into a high-speed mixer according to the ratio of 30:57:0.2:3, mixing for 10min at the speed of 900r/min to prepare a premix, sixthly, placing the premix treated in the fourth step and the premix treated in the fifth step into a side feed inlet and a main feed inlet of a double-screw extruder respectively according to the ratio of 10:90, performing melt extrusion to complete the preparation of the chopped copper coated carbon fiber reinforced ABS/PP electromagnetic shielding composite material, wherein the purity of nickel-copper targets in the third step is 99.999%, and the purity of 398.10 before vacuum degree is 8.0 × 10-4Pa, direct current sputtering current of 5A, deposition time of 20min, distance between target and fiber of 60mm, argon flow of 40 sccm; in the sixth step, the temperature of each zone is T1-165 ℃, T2-180 ℃, T3-175 ℃, T4-165 ℃, T hole-160 ℃, the screw speed is 20r/min, the screw diameter is 20mm, and the length-diameter ratio L/D of the equipment is 40.
Comparative example 1
Comparative example 1 is a preparation method of a coating carbon fiber reinforced PP electromagnetic shielding composite material, which is implemented according to the following steps: firstly, putting the carbon fiber in a tube furnace with the temperature of 720 ℃ and preserving the heat for 10 min; secondly, putting the carbon fiber treated in the step one into acetone for ultrasonic cleaning for 15 min; thirdly, preparing a nickel-copper coating on the surface of the carbon fiber treated in the step two by adopting a direct-current magnetron sputtering method; fourthly, cutting the coated carbon fiber treated in the third step into short carbon fibers with the length of 1mm to obtain short coated carbon fibers; fifthly, the PP resin, the cross-linking agent and the coupling agent are mixed according to the proportion of 87:0.2:3Putting the carbon fiber treated in the step four and the premix treated in the step five into a side feed inlet and a main feed inlet of a double-screw extruder respectively according to the proportion of 10:90, and performing melt extrusion to finish the preparation of the chopped nickel-copper coating carbon fiber reinforced PP electromagnetic shielding composite material, wherein the purity of the nickel-copper target in the step three is 99.999%, and the vacuum degree before sputtering is 8.0 × 10-4Pa, direct current sputtering current of 5A, deposition time of 20min, distance between target and fiber of 60mm, argon flow of 40 sccm; in the sixth step, the temperature of each zone is T1-165 ℃, T2-180 ℃, T3-175 ℃, T4-165 ℃, T hole-160 ℃, the screw speed is 20r/min, the screw diameter is 20mm, and the length-diameter ratio L/D of the equipment is 40.
The chopped nickel-copper coated carbon fiber reinforced PP electromagnetic shielding composite material prepared by the method has the average tensile strength of only 0.45GPa and the error range of 0.04GPa, and the value of the average tensile strength is far lower than that of the composite material added with ABS resin.
Comparative example 2
Comparative example 2 is a preparation method of a carbon fiber reinforced ABS/PP electromagnetic shielding composite material, which is implemented according to the following steps: firstly, putting the carbon fiber in a tube furnace with the temperature of 720 ℃ and preserving the heat for 10 min; secondly, putting the carbon fiber treated in the step one into acetone for ultrasonic cleaning for 15 min; (ii) a Thirdly, cutting the carbon fiber treated in the second step into pieces with the length of 2mm to obtain short carbon fibers; fourthly, placing the ABS resin, the PP resin, the cross-linking agent and the coupling agent in a high-speed mixer according to the ratio of 30:33:0.1:2, and mixing for 10 minutes at the speed of 900r/min to prepare a premix; fifthly, respectively placing the carbon fibers treated in the third step and the premix treated in the fourth step into a side feed inlet and a main feed inlet of a double-screw extruder according to the ratio of 35:65, and performing melt extrusion to complete the preparation of the chopped carbon fiber reinforced ABS/PP electromagnetic shielding composite material; wherein the temperature of each zone in the fifth step is T1-170 ℃, T2-180 ℃, T3-175 ℃, T4-175 ℃, T hole-160 ℃, the screw speed is 20r/min, the screw diameter is 20mm, and the length-diameter ratio L/D of the equipment is 40.
Electromagnetic parameters of the chopped carbon fiber reinforced ABS/PP electromagnetic shielding composite material prepared by the method are detected within the frequency range of 2-18 GHz, and the electromagnetic shielding effectiveness data is calculated, wherein within the frequency range of 2-18 GHz, the electromagnetic shielding effectiveness does not exceed 30dB, and the qualified bandwidth above 20dB is only 1.5 GHz.
Comparative example 3
The comparative example 3 is a preparation method of a coating carbon fiber reinforced ABS/PP electromagnetic shielding composite material without a coupling agent, and the preparation method is implemented according to the following steps of firstly, placing carbon fibers in a 720 ℃ temperature tube furnace for heat preservation for 10min, secondly, placing the carbon fibers treated in the step one in acetone for ultrasonic cleaning for 15min, thirdly, preparing a nickel-aluminum coating on the surface of the carbon fibers treated in the step two by adopting a radio frequency magnetron sputtering method, fourthly, cutting the coated carbon fibers treated in the step three into 6mm in length to obtain chopped coated carbon fibers, fifthly, placing the ABS resin, the PP resin and a cross-linking agent in a high-speed mixer according to the ratio of 20:60:0.2, mixing for 10min at the speed of 900r/min to prepare a premix, sixthly, placing the carbon fibers treated in the step four and the premix treated in the step five in the ratio of 20:80 into a side feed inlet and a main feed inlet of a double-screw extruder respectively, performing melt extrusion to complete the preparation of the chopped nickel-aluminum coating carbon fiber reinforced ABS/PP electromagnetic shielding composite material without the coupling agent, wherein the purity of the nickel-aluminum target in the step three is 99.999%, and the degree of 358.-4Pa, radio frequency sputtering power of 1500W, deposition time of 120min, distance between the target and the fiber of 60mm, argon flow of 40 sccm; in the sixth step, the temperature of each zone is T1-165 ℃, T2-170 ℃, T3-165 ℃, T4-175 ℃, T hole-155 ℃, the screw speed is 15r/min, the screw diameter is 20mm, and the length-diameter ratio L/D of the equipment is 40.
Electromagnetic parameters of the chopped nickel-aluminum coating carbon fiber reinforced ABS/PP electromagnetic shielding composite material without the coupling agent are detected within the frequency range of 2-18 GHz, electromagnetic shielding effectiveness data are obtained through calculation, within the frequency range of 2-18 GHz, the electromagnetic shielding effectiveness does not exceed 35dB, qualified bandwidth above 30dB is only 1.0GHz, and qualified bandwidth above 20dB is only 4.8 GHz.
Claims (8)
1. The utility model provides a coating carbon fiber reinforcing ABS/PP electromagnetic shield combined material which characterized in that: the composite material is formed by melt extrusion of the following components in parts by mass:
10-50 parts of nickel-based alloy coating carbon fiber;
50-88 parts of ABS/PP blended resin;
0.1-0.5 part of a crosslinking agent;
2-5 parts of a coupling agent;
the nickel-based alloy coating in the nickel-based alloy coating carbon fiber comprises a copper-nickel alloy coating, an aluminum-nickel alloy coating, an iron-nickel alloy coating, a tin-nickel alloy coating or a cobalt-nickel alloy coating; the mass percentage content of nickel in the nickel-based alloy coating is 1-99%;
the mass ratio of the ABS to the PP in the ABS/PP blended resin is 10: 90-50: 50.
2. The coated carbon fiber reinforced ABS/PP electromagnetic shielding composite material as claimed in claim 1, wherein: the thickness of the nickel-based alloy coating is 50-500 nm.
3. The coated carbon fiber reinforced ABS/PP electromagnetic shielding composite material as claimed in claim 1, wherein: the carbon fiber in the nickel-based alloy coating carbon fiber is a short carbon fiber with the length of 1-10 mm.
4. The coated carbon fiber reinforced ABS/PP electromagnetic shielding composite material as claimed in claim 1, wherein:
the cross-linking agent is dicumyl peroxide;
the coupling agent is a silane coupling agent.
5. The preparation method of the coated carbon fiber reinforced ABS/PP electromagnetic shielding composite material as claimed in any one of claims 1 to 4, wherein the preparation method comprises the following steps: mixing and melting ABS resin, PP resin, a cross-linking agent and a coupling agent, and extruding and compounding the mixture and the chopped nickel-based alloy coating carbon fiber together to obtain the composite material.
6. The preparation method of the coated carbon fiber reinforced ABS/PP electromagnetic shielding composite material according to claim 5, wherein the preparation method comprises the following steps: the nickel-based alloy coating carbon fiber is prepared by the following method: carrying out high-temperature treatment on carbon fibers at 650-750 ℃, and then placing the carbon fibers in acetone for ultrasonic washing; and (3) taking the washed carbon fiber as a matrix, and preparing the nickel-based alloy coating on the surface of the carbon fiber matrix by a radio frequency magnetron sputtering method or a direct current magnetron sputtering method.
7. The preparation method of the coated carbon fiber reinforced ABS/PP electromagnetic shielding composite material according to claim 6, wherein the preparation method comprises the following steps:
when the nickel-based alloy coating is prepared by adopting radio frequency magnetron sputtering, the radio frequency magnetron sputtering condition is controlled to be that the vacuum degree before sputtering is 1.0 × 10-3～1.0×10-4Pa, the radio-frequency sputtering power is 100-3000W, the deposition time is 30-100 min, the distance between the target and the carbon fiber is 50-80 mm, and the argon flow is 30-50 sccm;
when the nickel-based alloy coating is prepared by adopting direct current magnetron sputtering, the direct current magnetron sputtering condition is controlled to be that the vacuum degree before sputtering is 1.0 × 10-3～1.0×10-4Pa, direct current sputtering current of 2-50A, deposition time of 30-100 min, distance between the target and the carbon fiber of 50-80 mm, and argon flow of 30-50 sccm.
8. The preparation method of the coated carbon fiber reinforced ABS/PP electromagnetic shielding composite material according to claim 5, wherein the preparation method comprises the following steps: the melt extrusion adopts a double-screw extrusion process; the process conditions are as follows: the temperature of each zone of the extrusion section is sequentially T1-165-170 ℃, T2-170 ℃, T3-165 ℃, T4-175 ℃, T hole-155-160 ℃, the rotation speed of the screw is 9-20 r/min, the diameter of the screw is 20mm, and the length-diameter ratio L/D of the equipment is 40 from a feeding end to a discharging end.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2017109645138 | 2017-10-17 | ||
| CN201710964513 | 2017-10-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107746505A CN107746505A (en) | 2018-03-02 |
| CN107746505B true CN107746505B (en) | 2020-09-08 |
Family
ID=61253063
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711006344.3A Active CN107746505B (en) | 2017-10-17 | 2017-10-25 | Coating carbon fiber reinforced ABS/PP electromagnetic shielding composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107746505B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108638619B (en) * | 2018-03-14 | 2024-01-02 | 华南理工大学 | Impact-resistant electromagnetic shielding laminated board and preparation method and application thereof |
| CN109501327B (en) * | 2018-10-29 | 2021-02-09 | 北京卫星制造厂有限公司 | Transition layer of inner surface of carbon fiber composite pipe fitting and preparation method thereof |
| CN111454546B (en) * | 2020-04-26 | 2022-06-10 | 诺思贝瑞新材料科技（苏州）有限公司 | Electromagnetic shielding composite material and preparation method thereof |
| CN112724699A (en) * | 2021-01-19 | 2021-04-30 | 天津泰吉诺新材料科技有限公司 | Preparation process of multifunctional high-thermal-conductivity composite resin with structural orientation |
| CN114261036A (en) * | 2021-12-22 | 2022-04-01 | 中国科学院宁波材料技术与工程研究所 | Thermoplastic electromagnetic shielding prepreg, preparation method and prepared composite material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103806042A (en) * | 2014-01-20 | 2014-05-21 | 天津大学 | Preparation method for carbon fiber electroplating iron-nickel alloy |
| CN104262890A (en) * | 2014-08-28 | 2015-01-07 | 青岛文晟汽车零部件有限公司 | Impact resistant high strength alloy material |
| CN104480698A (en) * | 2014-11-24 | 2015-04-01 | 天津大学 | Method for preparing permalloy-coated carbon fiber employing two-step electrodeposition method |
| CN105778392A (en) * | 2016-03-21 | 2016-07-20 | 东莞职业技术学院 | Halogen-free flame-retardant electroconductive wear-resistant ABS/PP composite material and preparation method thereof |
| CN106751384A (en) * | 2016-11-29 | 2017-05-31 | 四川锦泰佳环保建材有限公司 | A kind of PP ABSs and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6689835B2 (en) * | 2001-04-27 | 2004-02-10 | General Electric Company | Conductive plastic compositions and method of manufacture thereof |
| CN102746556A (en) * | 2012-07-14 | 2012-10-24 | 深圳市飞荣达科技股份有限公司 | Shielding plastic and preparation method thereof |
| CN106906647B (en) * | 2017-03-28 | 2019-05-10 | 中南大学 | A kind of composite coating fiber and preparation method thereof with electro-magnetic screen function |
-
2017
- 2017-10-25 CN CN201711006344.3A patent/CN107746505B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103806042A (en) * | 2014-01-20 | 2014-05-21 | 天津大学 | Preparation method for carbon fiber electroplating iron-nickel alloy |
| CN104262890A (en) * | 2014-08-28 | 2015-01-07 | 青岛文晟汽车零部件有限公司 | Impact resistant high strength alloy material |
| CN104480698A (en) * | 2014-11-24 | 2015-04-01 | 天津大学 | Method for preparing permalloy-coated carbon fiber employing two-step electrodeposition method |
| CN105778392A (en) * | 2016-03-21 | 2016-07-20 | 东莞职业技术学院 | Halogen-free flame-retardant electroconductive wear-resistant ABS/PP composite material and preparation method thereof |
| CN106751384A (en) * | 2016-11-29 | 2017-05-31 | 四川锦泰佳环保建材有限公司 | A kind of PP ABSs and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| A study on synergetic EMI shielding behaviors of Ni-Co alloy-coated carbon fibers-reinforced composites;Jin Tae Kim 等;《Synthetic Metals》;20161128;第212-217页 * |
| Studies on electroless nickel polyalloy coatings over carbon fibers/CFRP composites;J.N.Balaraju 等;《Surface & Coatings Technology 》;20160616;第389-397页 * |
| Studies on the influence of double-layer electroless metal deposition on the electromagnetic interference shielding effectiveness of carbon fiber/ABS composites;Chi-Yuan Huang 等;《 Surface and Coatings Technology》;20040205;第163-169页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107746505A (en) | 2018-03-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107746505B (en) | Coating carbon fiber reinforced ABS/PP electromagnetic shielding composite material and preparation method thereof | |
| CN100405886C (en) | Polyethylene composite film for shielding wideband electromagnetic wave and its preparing method | |
| KR101469683B1 (en) | Methods for Preparing of Electromagnetic Shielding Composite Using Copper-Nickel Plated Carbon Fiber Prepared by Electroless-Electronic Continuous Process and Electromagnetic Shielding Material Prepared by the Methods | |
| US10400370B2 (en) | Nonwoven fabric or nonwoven composite material for shielding and absorbing electromagnetic wave | |
| CN102140186B (en) | Natural rubber composite with electromagnetic shielding property and preparation method thereof | |
| EP2134783B1 (en) | Electrically conducting polymeric compositions, methods of manufacture thereof and articles comprising the same | |
| KR20120023490A (en) | High modulus composite for emi shielding | |
| JP4160138B2 (en) | Thermoplastic resin molded product, material for molded product, and method for producing molded product | |
| CN103450665A (en) | Long-carbon-fiber-reinforced nylon composite material with electromagnetic shielding function and preparation method thereof | |
| WO2013085246A1 (en) | Composite, and molded product thereof | |
| CN114957855B (en) | Wave-absorbing heat-conducting thermoplastic composite material and preparation method thereof | |
| CN101205640A (en) | Method for producing skin-core structural micro-wave screening functional fibre by melt direct spinning | |
| WO2014008669A1 (en) | Modified resin composition used for depositing a metal film, preparation method and use thereof | |
| CN111393744B (en) | TPE material with antibacterial conductivity and preparation method thereof | |
| CN116083060A (en) | Composite heat and electricity conducting material formed by carbon fiber based on ASPN (advanced manufacturing process) treatment technology | |
| JPS6252771B2 (en) | ||
| CN113829686A (en) | Degradable polymer-based biochar electromagnetic shielding composite material and preparation method thereof | |
| CN108384177B (en) | Four-phase double-percolation electromagnetic shielding material and preparation method thereof | |
| RU2243980C1 (en) | Composite material for shielding electromagnetic emission and a method for manufacture thereof | |
| CN108059765A (en) | A kind of conductive polymeric composite and preparation method thereof | |
| WO2019069134A1 (en) | Carbon fiber reinforced polypropylene and polyethylene composite materials | |
| CN115477813B (en) | PP-based composite material for electromagnetic shielding and preparation method thereof | |
| CN108586942A (en) | Low temperature resistant anlistatig glass fiber reinforced polypropylene material of one kind and preparation method thereof | |
| WO2019069141A9 (en) | Electrically conductive polypropylene and polyethylene composite materials and method of making thereof | |
| KR102080021B1 (en) | Food collection container utilizing carbon composite material having enhanced antimicrobial and mechanical strength and manufacturing 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 |