CN111205512B - Conductive filler and preparation method of semiconductive shielding material thereof - Google Patents

Conductive filler and preparation method of semiconductive shielding material thereof Download PDF

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CN111205512B
CN111205512B CN202010018405.3A CN202010018405A CN111205512B CN 111205512 B CN111205512 B CN 111205512B CN 202010018405 A CN202010018405 A CN 202010018405A CN 111205512 B CN111205512 B CN 111205512B
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hollow glass
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glass beads
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CN111205512A (en
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虞家桢
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Jiangsu Kemaite Technology Development Co ltd
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    • 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
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    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K7/00—Use of ingredients characterised by shape
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    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • 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
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    • C08K2201/001—Conductive additives
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    • 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
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    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K2201/002—Physical properties
    • C08K2201/004—Additives being defined by their length
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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Abstract

The invention belongs to the field of conductive shielding materials, and relates to a conductive filler and a preparation method of a semiconductive shielding material thereof. The invention discloses a Ag/Fe-Ni/hollow glass bead conductive filler, which is prepared by firstly adopting a high-temperature metal oxide reduction process to repeatedly coat iron-nickel alloy on hollow glass beads, then adopting a chemical reduction method to repeatedly coat silver on the glass beads coated with the iron-nickel alloy, and setting the coating times in the preparation process of an intermediate coating layer and the Fe in the coating layer2O3The mass ratio of the conductive filler to NiO and the dosage of the prepared conductive filler ensure that the semiconductive shielding material has excellent shielding performance at low frequency or high frequency, the shielding effectiveness at low frequency is 10-19 dB, and the shielding effectiveness at high frequency is 30-44 dB. After the conductive filler replaces part of carbon black, the conductive filler not only cooperates with the carbon black to conduct and shield, but also reduces the total parts of the filler and ensures the light weight of the semiconductive shielding material.

Description

Conductive filler and preparation method of semiconductive shielding material thereof
Technical Field
The invention belongs to the field of conductive shielding materials, and relates to a conductive filler and a preparation method of a semiconductive shielding material thereof.
Background
With the continuous improvement of electric power systems in China, various large hydroelectric power stations, large intensive development coal, hydraulic power, nuclear power, renewable new energy power stations and the like are in accelerated construction, so that the demand of medium-high voltage power cables is increased year by year. IEC 502 stipulates that cables with a rated voltage of above 1.8/3.0kv, which are insulated with polyvinyl chloride and ethylene propylene rubber, and rated voltage of above 3.6/6.0kv must use inner and outer semiconductive shield layers.
The research on the semiconductive shielding material has been carried out since the fifties of the last century in foreign countries, and after the seventies, the semiconductive shielding material having practical application value has been developed and successfully put into use in foreign countries. The research of China on the semiconductive shielding material starts at the end of the last century and starts later than that of developed countries, but China is always dedicated to improving the quality level of the semiconductive shielding material and reducing the gap with the foreign advanced level.
Generally, a semiconductive shielding material is a polymer composite material filled with a certain amount of conductive filler to achieve a certain conductivity. Carbon black is one of the most preferred conductive fillers because of its conductivity and reinforcing properties, but when carbon black is used as a conductive filler, it is necessary to add a large amount of carbon black to form a conductive network. In order to obtain good conductivity of the material, the addition amount of the carbon black is about 30-40%, and the high filling amount is undoubtedly not beneficial to the production and processing of the semiconductive shielding material. At present, the method of reducing the amount of carbon black used while ensuring the conductivity of the material is to replace it with a filler having a higher conductivity. In addition, the semiconductive shielding material filled with carbon black has low shielding effectiveness at low frequency bands.
Therefore, there is a need to develop a conductive filler with excellent conductivity to replace carbon black, reduce the amount of the filler used, and improve the shielding performance of the semiconductive shielding material in low or high frequency bands.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a conductive filler and a preparation method of a semiconductive shielding material thereof, wherein the conductive filler has excellent conductivity and can replace carbon black; the carbon black can play a synergistic role in the semiconductive shielding material, and the shielding performance of the semiconductive shielding material in a low-frequency or high-frequency wave band is obviously improved.
One of the purposes of the invention is to provide a conductive filler, and the preparation method comprises the following steps:
(1) coating Fe on the surface of hollow glass microsphere2O3And NiO to prepare the hollow glass microspheres coated by the metal oxide; then reducing the metal oxide to obtain hollow glass beads coated by the iron-nickel alloy; said Fe2O3The mass ratio of NiO to NiO is (0.65-1.08): (2.14-2.35);
(2) repeating the step (1) for 1-2 times to prepare the hollow glass microspheres coated by the multilayer iron-nickel alloy;
(3) continuously coating silver on the surface of the hollow glass microsphere coated with the iron-nickel alloy obtained in the step (2);
(4) and (4) repeating the step (3) for 1-2 times, and coating multiple layers of silver on the surfaces of the hollow glass beads coated with the iron-nickel alloy to obtain the conductive filler.
Further, in the step (1), the Fe2O3And NiO is ball-milled and then coated, wherein the ball-milling method comprises the following steps: mixing Fe2O3And mixing the NiO and the absolute ethyl alcohol, and ball-milling for 8-12 h at the speed of 200-250 r/min.
Further, in the step (1), the ball milling method specifically comprises the following steps: putting the weighed grinding balls into a grinding tank, and then adding Fe2O3NiO and absolute ethyl alcohol, and finally ball milling for 8-12 h at the speed of 200-250 r/min; fe2O3The mass ratio of the NiO to the NiO is (0.65-1.08): (2.14-2.35), wherein the mass ratio of the total mass of the metal oxides to the absolute ethyl alcohol is (2-3): (1-2), the mass ratio of the grinding balls to the total mass of the metal oxide is (10-15): (1-1.5).
Further, Fe2O3The mass ratio of NiO to NiO is 0.65: 2.14, 0.82: 2.19 or 1.08: 2.35, the mass ratio of the total mass of the metal oxides to the absolute ethyl alcohol is 2: 1. 3: 1 or 3: 2, the mass ratio of the grinding balls to the total mass of the metal oxide is 10: 1. 15: 1 or 15: 1.5; the ball milling speed is 200r/min, 210r/min, 220r/min, 230r/min, 240r/min or 250r/min, and the ball milling time is 8h, 9h, 10h, 11h or 12 h.
Further, drying the metal oxide obtained after ball milling in an oven at 100-120 ℃ for 4-6 h, and sieving with a 200-300 mesh gauze.
Further, the oven temperature is 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃, the drying time is 4h, 5h or 6h, and the mesh number is 200 meshes, 250 meshes or 300 meshes.
Further, the hollow glass beads in the step (1) are pretreated, and the pretreatment method comprises the following steps: soaking the hollow glass beads in 2% of methyltriethoxysilane hydrolysate by mass for 20-30 min, filtering, and drying, wherein the mass ratio of the methyltriethoxysilane hydrolysate to the hollow glass beads is (4-5): (0.8 to 1.2).
Further, in the method for pretreating the hollow glass beads, the soaking temperature is 35-45 ℃, the drying temperature is 60-65 ℃, and the drying time is 12-15 hours.
Further, the mass ratio of the surface treatment liquid to the hollow glass beads is 4: 0.8, 5: 0.8 or 5: 1.2; the hollow glass beads are soaked at the temperature of 35 ℃, 37 ℃, 39 ℃, 41 ℃, 43 ℃ or 45 ℃, the soaking time is 20min, 22min, 24min, 26min, 28min or 30min, the drying temperature is 60 ℃, 61 ℃, 62 ℃, 63 ℃, 64 ℃ or 65 ℃, and the drying time is 12h, 13h, 14h or 15 h.
Further, the coating in the step (1) comprises the following specific steps: mixing Fe2O3Mixing with NiO, hollow glass beads and water, stirring, standing, filtering to obtain lower mixture, and drying to obtain metal oxide coated hollow glass beads, Fe2O3The mass ratio of the NiO to the hollow glass beads to the water is (11-13): (1-1.1): (29 to 32).
Further, in the coating process of the step (1), the stirring and standing steps are as follows: stirring at the speed of 80-100 r/min for 30-40 min, standing for 2-3 h, then adding deionized water, stirring at the speed of 45-60 r/min for 20-30 min, and standing for 25-30 min; and finally, filtering out the mixture at the lower layer, and drying the mixture in an oven at the temperature of 100-120 ℃ for 6-8 hours to obtain the metal oxide coated hollow glass beads.
Further, the mass ratio of the metal oxide to the hollow glass beads to the deionized water is 11: 1: 29. 12: 1: 31 or 13: 1.1: 32, a first step of removing the first layer; stirring at 80r/min, 85r/min, 90r/min, 95r/min or 100r/min for 30min, 32min, 34min, 36min, 38min or 40min, and standing for 2h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h, 2.9h or 3 h; adding deionized water, stirring at 45r/min, 48r/min, 51r/min, 54r/min, 57r/min or 60r/min for 20min, 22min, 24min, 26min, 28min or 30min, and standing for 25min, 26min, 27min, 28min, 29min or 30 min; the drying temperature is 100 deg.C, 105 deg.C, 110 deg.C, 115 deg.C or 120 deg.C, and the drying time is 6h, 6.5h, 7h, 7.5h or 8 h.
Further, the reduction in the step (1) comprises the following specific steps: reducing the hollow glass beads coated with the metal oxide at 650-700 ℃ for 3-4 h in an ammonia atmosphere to obtain the iron-nickel alloy coated hollow glass beads.
Further, the reduction temperature is 650 ℃, 660 ℃, 670 ℃, 680 ℃, 690 ℃ or 700 ℃, and the reduction time is 3h, 3.1h, 3.2h, 3.3h, 3.4h, 3.5h, 3.6h, 3.7h, 3.8h, 3.9h or 4 h.
Further, the step (3) is specifically as follows: adding hollow glass beads coated with iron-nickel alloy into a mixed solution of ethanol and water, adding hydrazine hydrate, dropwise adding a 0.2mol/L silver-ammonia solution, adjusting the pH value of the system to 10-11, and filtering, washing and drying after reaction to obtain silver-coated iron-nickel alloy coated hollow glass beads; the dosage of the silver-ammonia solution relative to the hollow glass microspheres coated by the iron-nickel alloy is 5-15 mL/g.
Further, the step (3) is specifically as follows: weighing 20g of Fe-Ni/hollow glass microspheres obtained in the step 6), adding 100mL of a solution with a volume ratio of ethanol to water of 3:7, carrying out ultrasonic treatment for 25-30 min, then adding 200mL of 0.25mol/L hydrazine hydrate, stirring at a speed of 500-600 r/min, dropwise adding 200mL of 0.2mol/L silver ammonia solution, finally adding 0.4mol/L sodium hydroxide solution until the pH value of the system is 10-11, carrying out ultrasonic reaction for 45-60 min at 50-60 ℃, filtering, washing a solid mixture with 400-500 mL of deionized water, then washing with 250-350 mL of an ethanol solution containing 3-5% by mass of fatty acid, and drying in an oven at 60-65 ℃ for 20-24 h to obtain the silver-coated iron-nickel alloy coated hollow glass microspheres (Ag/Fe-Ni/hollow glass microspheres).
Further, the ultrasonic treatment time after adding ethanol and water is 25min, 26min, 27min, 28min, 29min or 30 min; adding hydrazine hydrate, stirring at 500r/min, 520r/min, 540r/min, 560r/min, 580r/min or 600r/min, adjusting pH to 10, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9 or 11, and performing ultrasonic treatment at 50 deg.C, 52 deg.C, 54 deg.C, 56 deg.C, 58 deg.C or 60 deg.C for 45min, 48min, 51min, 54min, 57min or 60 min; the dosage of the rinsed deionized water is 400mL, 420mL, 440mL, 460mL, 480mL or 500mL, the dosage of the ethanol solution containing the fatty acid is 250mL, 270mL, 290mL, 310mL, 330mL or 350mL, the oven temperature is 60 ℃, 61 ℃, 62 ℃, 63 ℃, 64 ℃ or 65 ℃, and the drying time is 20h, 21h, 22h, 23h or 24 h.
The invention also aims to provide a semiconductive shielding material which has excellent conductivity, light weight and wide shielding wave band, and the semiconductive shielding material comprises the following components in parts by weight:
65-75 parts of EVA; 15-20 parts of modified PP; 10-15 parts of SBS; 10-15 parts of conductive filler; 10 parts of carbon black; 3-5 parts of a lubricant; 0.5-1 part of antioxidant.
Further, the addition amount of EVA is 65 parts, 67 parts, 69 parts, 71 parts, 73 parts or 75 parts, the addition amount of modified PP is 15 parts, 16 parts, 17 parts, 18 parts, 19 parts or 20 parts, the addition amount of SBS is 10 parts, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts, the addition amount of conductive filler is 10 parts, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts, the addition amount of lubricant is 3 parts, 4 parts or 5 parts, and the addition amount of antioxidant is 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part or 1 part.
Furthermore, the EVA has a VA content of 18-28% and an MFR (melt flow rate) of 2.3-2.6 g/10 min.
Further, the EVA has a VA content of 18%, 20%, 22%, 24%, 26% or 28%, and an MFR of 2.3g/10min, 2.4g/10min, 2.5g/10min or 2.6g/10 min.
Further, the modified PP is glass fiber reinforced PP, the content of the glass fiber is 20%, the length of the glass fiber is 0.3-0.5 mm, for example, the length of the glass fiber is 0.3mm, 0.35mm, 0.4mm, 0.45mm or 0.5 mm.
Further, the ratio of styrene to butadiene in SBS is 40/60.
Further, the carbon black has an average particle diameter of 55nm, an iodine absorption value of 100 to 150g/kg and a DBP absorption value of 100 x 105～130×105m3Per kg, e.g. a carbon black iodine value of 100g/kg, 110g/kg, 120g/kg, 130g/kg, 140g/kg or 150g/kg, a DBP absorption value of 100X 105m3/kg、110×105m3/kg、120×105m3/kg or 130X 105m3/kg。
Further, the lubricant is one or a mixture of more than two of polyethylene wax, microcrystalline paraffin and liquid paraffin.
Further, the antioxidant is one or a mixture of more than two of an antioxidant 1010, an antioxidant 1076, an antioxidant 168, an antioxidant 626 and an antioxidant 300;
further, the preparation method of the semiconductive shielding material comprises the following steps:
(1) preparing a conductive master batch: putting 15-20 parts of modified PP, 10-15 parts of SBS, 10-15 parts of conductive filler, 2-3 parts of lubricant and 0.5-0.7 part of antioxidant into a mixer for uniform mixing, and then carrying out melt blending, extrusion and granulation on an extruder;
(2) preparing a semiconductive shielding material: putting 65-75 parts of EVA (ethylene vinyl acetate), 10 parts of carbon black, all parts of the conductive master batch obtained in the step (1), 1-2 parts of lubricant and 0.2-0.3 part of antioxidant into a mixer, uniformly mixing, and then carrying out melt blending, extrusion and granulation on an extruder.
Further, in the step (1), the temperature of each section of the extruder is respectively 160-170 ℃, 170-180 ℃, 180-190 ℃, 190-200 ℃, 180-190 ℃ and the screw rotation speed is 300-350 r/min.
Further, in the step (1), the temperature of each section of the extruder is respectively 160 ℃/170 ℃/180 ℃/180 ℃/190 ℃/190 ℃/190 ℃/180 ℃/180 ℃, 160 ℃/180 ℃/180 ℃/190 ℃/190 ℃/180 ℃, 170 ℃/180 ℃/190 ℃/200 ℃/190 ℃/190 ℃/180 ℃, 170 ℃/190 ℃/200 ℃/200 ℃/190 ℃/190 ℃/180 ℃, 170 ℃/170 ℃/180 ℃/190 ℃/190 ℃/200 ℃/200 ℃/190 ℃/180 ℃, and the screw rotation speed is 300r/min, 310r/min, 320r/min, 330r/min, 340r/min or 350 r/min.
Further, in the step (2), the temperatures of all sections of the extruder are respectively 140-150 ℃, 150-160 ℃, 160-170 ℃, 175-185 ℃, 190-200 ℃, 180-190 ℃ and the screw rotation speed is 480-500 r/min.
Further, in the step (2), the temperature of each section of the extruder is respectively 140 ℃/150 ℃/160 ℃/170 ℃/180 ℃/190 ℃/190 ℃/180 ℃, 140 ℃/150 ℃/160 ℃/170 ℃/185 ℃/200 ℃/200 ℃/180 ℃, 150 ℃/150 ℃/160 ℃/170 ℃/190 ℃/190 ℃/190 ℃/180 ℃, 150 ℃/160 ℃/170 ℃/190 ℃/190 ℃/190 ℃/180 ℃, 150 ℃/160 ℃/160 ℃/170 ℃/185 ℃/190 ℃/190 ℃/180 ℃, and the screw rotation speed is 480r/min, 484r/min, 488r/min, 492r/min, 496r/min or 500 r/min.
Compared with the prior art, the invention has the beneficial effects that:
(1) the conductive filler of the invention takes the hollow glass beads as the matrix, and compared with metal fillers, the density of the filler is greatly reduced, and the weight of the filler is reduced; the surface of the hollow glass bead is coated with the iron-nickel alloy, so that the filler can obtain good shielding performance by absorbing electromagnetic waves in a low-frequency band; and finally, the surface of the iron-nickel alloy is coated with the metallic silver, so that the conductive filler obtains excellent conductivity, and the shielding performance of the conductive filler in a high-frequency band is further improved.
(2) The volume resistivity of the semiconductive shielding material is reduced from 654 omega from 30 parts of carbon black used singly to 10-15 parts of conductive filler and 10 parts of carbon black by replacing part of carbon black with the conductive filler.The cm is reduced to 234-383 omega.cm, the shielding effectiveness of the low frequency band is increased from 1dB to 10-19 dB, and the shielding effectiveness of the high frequency band is increased from 20dB to 30-44 dB. The added modified PP and SBS effectively improve the tensile property of the semiconductive shielding material, so that the tensile strength and the elongation at break of the material are respectively improved to 15-19 MPa and 320-351%.
Therefore, the prepared Ag/Fe-Ni/hollow glass bead conductive filler not only ensures the conductivity and light weight of the semiconductive shielding material, but also enables the semiconductive shielding material to have more excellent electromagnetic shielding performance in low-frequency or high-frequency wave bands.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
A preparation method of a conductive filler comprises the following steps:
1) wet ball milling of metal oxide: mixing Fe2O3And NiO according to the mass ratio of 1.08: 2.35, mixing the total mass of the metal oxides with the absolute ethyl alcohol according to a mass ratio of 2: 1. the total mass of the grinding balls and the metal oxide is 13: 1.1, then putting the weighed grinding balls into a grinding tank, and then adding Fe2O3NiO and absolute ethyl alcohol, and finally ball milling for 10 hours at the speed of 200 r/min.
2) Sieving the metal oxide: drying the metal oxide obtained in the step 1) in an oven at 110 ℃ for 4 hours, and sieving the dried metal oxide by using a 250-mesh gauze.
3) Surface treatment of hollow glass beads: mixing the surface treatment liquid and the hollow glass beads according to a mass ratio of 4: weighing 1, wherein the surface treatment liquid is 2% of methyltriethoxysilane hydrolysate by mass fraction, soaking the hollow glass beads in the methyltriethoxysilane hydrolysate at 45 ℃ for 25min, filtering, and drying in a 65 ℃ oven for 12 h.
4) Coating the hollow glass beads with the metal oxide: mixing the metal oxide obtained in the step 2), the hollow glass beads obtained in the step 3) and deionized water according to a mass ratio of 11: 1: 30, then putting the metal oxide and the hollow glass beads into a stirring tank, stirring for 30min at the speed of 100r/min, standing for 2.5h, then adding deionized water into the stirring tank, stirring for 30min at the speed of 50r/min, standing for 25min, finally filtering out the mixture at the lower layer, and drying the mixture in an oven at the temperature of 100 ℃ for 6h to obtain the metal oxide coated hollow glass beads.
5) Reducing the metal oxide: putting the metal oxide coated hollow glass beads obtained in the step 4) into a high-temperature furnace at 660 ℃, introducing ammonia gas for reduction for 3 hours, and cooling to room temperature to obtain the iron-nickel alloy coated hollow glass beads (Fe-Ni/hollow glass beads).
6) And (3) sequentially operating the hollow glass microspheres coated with the iron-nickel alloy obtained in the step 5) according to the steps 3) to 5), and repeating the coating for 1 time.
7) Coating with metal silver: weighing 20g of Fe-Ni/hollow glass microspheres obtained in the step 6), adding 100mL of solution with the volume ratio of ethanol to water being 3:7, carrying out ultrasonic treatment for 25min, then adding 200mL of 0.25mol/L hydrazine hydrate, stirring at the speed of 600r/min, dropwise adding 200mL of 0.2mol/L silver ammonia solution, finally adding 0.4mol/L sodium hydroxide solution until the pH value of the system is 10.2, carrying out ultrasonic reaction for 60min at 50 ℃, filtering, washing a solid mixture with 500mL of deionized water, then washing with 350mL of ethanol solution containing fatty acid with the mass fraction of 3%, and drying in a 65 ℃ oven for 20h to obtain the silver-coated iron-nickel alloy coated hollow glass microspheres (Ag/Fe-Ni/hollow glass microspheres).
8) Repeating the step 7) to coat the Ag/Fe-Ni/hollow glass microspheres obtained in the step 7) for 1 time to obtain the conductive filler.
A preparation method of a semiconductive shielding material comprises the following steps:
1) preparing a conductive master batch: 15 parts of 20 mass percent glass fiber modified PP (glass fiber length of 0.4mm), 10 parts of SBS, 10 parts of the conductive filler prepared in the embodiment, 2.5 parts of polyethylene wax and 0.5 part of antioxidant 1010 are put into a mixer to be uniformly mixed, and then are melted, blended and extruded on an extruder for granulation, wherein the temperature of each section of the extruder is 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 190 ℃, 180 ℃, and the screw rotation speed is 320 r/min.
2) Preparing a semiconductive shielding material: putting 75 parts of EVA, 10 parts of carbon black, all parts of the conductive master batch obtained in the step 1), 1.5 parts of polyethylene wax and 0.3 part of antioxidant 1010 into a mixer, uniformly mixing, then carrying out melt blending and extrusion granulation on an extruder, wherein the temperatures of all sections of the extruder are respectively 140 ℃, 150 ℃, 160 ℃, 170 ℃, 185 ℃, 200 ℃, 190 ℃, 180 ℃ and the screw rotation speed is 500 r/min.
Example 2
A preparation method of a conductive filler comprises the following steps:
1) wet ball milling of metal oxide: mixing Fe2O3And NiO according to the mass ratio of 1.08: 2.35, mixing the total mass of the metal oxides with the absolute ethyl alcohol according to a mass ratio of 2: 1. the total mass of the grinding balls and the metal oxide is 13: 1.1, then putting the weighed grinding balls into a grinding tank, and then adding Fe2O3NiO and absolute ethyl alcohol, and finally ball milling for 10 hours at the speed of 200 r/min.
2) Sieving the metal oxide: drying the metal oxide obtained in the step 1) in an oven at 110 ℃ for 4 hours, and sieving the dried metal oxide by using a 250-mesh gauze.
3) Surface treatment of hollow glass beads: mixing the surface treatment liquid and the hollow glass beads according to a mass ratio of 4: weighing 1, wherein the surface treatment liquid is 2% of methyltriethoxysilane hydrolysate by mass fraction, soaking the hollow glass beads in the methyltriethoxysilane hydrolysate at 45 ℃ for 25min, filtering, and drying in a 65 ℃ oven for 12 h.
4) Coating the hollow glass beads with the metal oxide: mixing the metal oxide obtained in the step 2), the hollow glass beads obtained in the step 3) and deionized water according to a mass ratio of 11: 1: 30, then putting the metal oxide and the hollow glass beads into a stirring tank, stirring for 30min at the speed of 100r/min, standing for 2.5h, then adding deionized water into the stirring tank, stirring for 30min at the speed of 50r/min, standing for 25min, finally filtering out the mixture at the lower layer, and drying the mixture in an oven at the temperature of 100 ℃ for 6h to obtain the metal oxide coated hollow glass beads.
5) Reducing the metal oxide: putting the metal oxide coated hollow glass beads obtained in the step 4) into a high-temperature furnace at 660 ℃, introducing ammonia gas for reduction for 3 hours, and cooling to room temperature to obtain the iron-nickel alloy coated hollow glass beads (Fe-Ni/hollow glass beads).
6) And (3) sequentially operating the hollow glass microspheres coated with the iron-nickel alloy obtained in the step 5) according to the steps 3) to 5), and repeating the coating for 2 times.
7) Coating with metal silver: weighing 20g of Fe-Ni/hollow glass microspheres obtained in the step 6), adding 100mL of solution with the volume ratio of ethanol to water being 3:7, carrying out ultrasonic treatment for 25min, then adding 200mL of 0.25mol/L hydrazine hydrate, stirring at the speed of 600r/min, dropwise adding 200mL of 0.2mol/L silver ammonia solution, finally adding 0.4mol/L sodium hydroxide solution until the pH value of the system is 10.2, carrying out ultrasonic reaction for 60min at 50 ℃, filtering, washing a solid mixture with 500mL of deionized water, then washing with 350mL of ethanol solution containing fatty acid with the mass fraction of 3%, and drying in a 65 ℃ oven for 20h to obtain the silver-coated iron-nickel alloy coated hollow glass microspheres (Ag/Fe-Ni/hollow glass microspheres).
8) Repeating the step 7) to coat the Ag/Fe-Ni/hollow glass microspheres obtained in the step 7) for 2 times to obtain the conductive filler.
A preparation method of a semiconductive shielding material comprises the following steps:
1) preparing a conductive master batch: 15 parts of 20 mass percent glass fiber modified PP (glass fiber length of 0.4mm), 10 parts of SBS, 10 parts of the conductive filler prepared in the embodiment, 2.5 parts of polyethylene wax and 0.5 part of antioxidant 1010 are put into a mixer to be uniformly mixed, and then are melted, blended and extruded on an extruder for granulation, wherein the temperature of each section of the extruder is 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 190 ℃, 180 ℃, and the screw rotation speed is 320 r/min.
2) Preparing a semiconductive shielding material: putting 75 parts of EVA, 10 parts of carbon black, all parts of the conductive master batch obtained in the step 1), 1.5 parts of polyethylene wax and 0.3 part of antioxidant 1010 into a mixer, uniformly mixing, then carrying out melt blending and extrusion granulation on an extruder, wherein the temperatures of all sections of the extruder are respectively 140 ℃, 150 ℃, 160 ℃, 170 ℃, 185 ℃, 200 ℃, 190 ℃, 180 ℃ and the screw rotation speed is 500 r/min.
Example 3
A preparation method of a conductive filler comprises the following steps:
1) wet ball milling of metal oxide: mixing Fe2O3And NiO according to the mass ratio of 1.08: 2.35, mixing the total mass of the metal oxides with the absolute ethyl alcohol according to a mass ratio of 2: 1. the total mass of the grinding balls and the metal oxide is 13: 1.1, then putting the weighed grinding balls into a grinding tank, and then adding Fe2O3NiO and absolute ethyl alcohol, and finally ball milling for 10 hours at the speed of 200 r/min.
2) Sieving the metal oxide: drying the metal oxide obtained in the step 1) in an oven at 110 ℃ for 4 hours, and sieving the dried metal oxide by using a 250-mesh gauze.
3) Surface treatment of hollow glass beads: mixing the surface treatment liquid and the hollow glass beads according to a mass ratio of 4: weighing 1, wherein the surface treatment liquid is 2% of methyltriethoxysilane hydrolysate by mass fraction, soaking the hollow glass beads in the methyltriethoxysilane hydrolysate at 45 ℃ for 25min, filtering, and drying in a 65 ℃ oven for 12 h.
4) Coating the hollow glass beads with the metal oxide: mixing the metal oxide obtained in the step 2), the hollow glass beads obtained in the step 3) and deionized water according to a mass ratio of 11: 1: 30, then putting the metal oxide and the hollow glass beads into a stirring tank, stirring for 30min at the speed of 100r/min, standing for 2.5h, then adding deionized water into the stirring tank, stirring for 30min at the speed of 50r/min, standing for 25min, finally filtering out the mixture at the lower layer, and drying the mixture in an oven at the temperature of 100 ℃ for 6h to obtain the metal oxide coated hollow glass beads.
5) Reducing the metal oxide: putting the metal oxide coated hollow glass beads obtained in the step 4) into a high-temperature furnace at 660 ℃, introducing ammonia gas for reduction for 3 hours, and cooling to room temperature to obtain the iron-nickel alloy coated hollow glass beads (Fe-Ni/hollow glass beads).
6) And (3) sequentially operating the hollow glass microspheres coated with the iron-nickel alloy obtained in the step 5) according to the steps 3) to 5), and repeating the coating for 2 times.
7) Coating with metal silver: weighing 20g of Fe-Ni/hollow glass microspheres obtained in the step 6), adding 100mL of solution with the volume ratio of ethanol to water being 3:7, carrying out ultrasonic treatment for 25min, then adding 200mL of 0.25mol/L hydrazine hydrate, stirring at the speed of 600r/min, dropwise adding 200mL of 0.2mol/L silver ammonia solution, finally adding 0.4mol/L sodium hydroxide solution until the pH value of the system is 10.2, carrying out ultrasonic reaction for 60min at 50 ℃, filtering, washing a solid mixture with 500mL of deionized water, then washing with 350mL of ethanol solution containing fatty acid with the mass fraction of 3%, and drying in a 65 ℃ oven for 20h to obtain the silver-coated iron-nickel alloy coated hollow glass microspheres (Ag/Fe-Ni/hollow glass microspheres).
8) Repeating the step 7) to coat the Ag/Fe-Ni/hollow glass microspheres obtained in the step 7) for 2 times to obtain the conductive filler.
A preparation method of a semiconductive shielding material comprises the following steps:
1) preparing a conductive master batch: 20 parts of 20 mass percent glass fiber modified PP (glass fiber length of 0.4mm), 15 parts of SBS, 10 parts of the conductive filler prepared in the embodiment, 2.5 parts of polyethylene wax and 0.5 part of antioxidant 1010 are put into a mixer to be uniformly mixed, and then are melted, blended and extruded on an extruder for granulation, wherein the temperature of each section of the extruder is 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 190 ℃, 180 ℃, and the screw rotation speed is 320 r/min.
2) Preparing a semiconductive shielding material: putting 65 parts of EVA, 10 parts of carbon black, all parts of the conductive master batch obtained in the step 1), 1.5 parts of polyethylene wax and 0.3 part of antioxidant 1010 into a mixer, uniformly mixing, then carrying out melt blending and extrusion granulation on an extruder, wherein the temperatures of all sections of the extruder are respectively 140 ℃, 150 ℃, 160 ℃, 170 ℃, 185 ℃, 200 ℃, 190 ℃, 180 ℃ and the screw rotation speed is 500 r/min.
Example 4
A preparation method of a conductive filler comprises the following steps:
1) wet ball milling of metal oxide: mixing Fe2O3And NiO according to the mass ratio of 1.08: 2.35, mixing the total mass of the metal oxides with the absolute ethyl alcohol according to a mass ratio of 2: 1. the total mass of the grinding balls and the metal oxide is 13: 1.1, then putting the weighed grinding balls into a grinding tank, and then adding Fe2O3NiO and absolute ethyl alcohol, and finally ball milling for 10 hours at the speed of 200 r/min.
2) Sieving the metal oxide: drying the metal oxide obtained in the step 1) in an oven at 110 ℃ for 4 hours, and sieving the dried metal oxide by using a 250-mesh gauze.
3) Surface treatment of hollow glass beads: mixing the surface treatment liquid and the hollow glass beads according to a mass ratio of 4: weighing 1, wherein the surface treatment liquid is 2% of methyltriethoxysilane hydrolysate by mass fraction, soaking the hollow glass beads in the methyltriethoxysilane hydrolysate at 45 ℃ for 25min, filtering, and drying in a 65 ℃ oven for 12 h.
4) Coating the hollow glass beads with the metal oxide: mixing the metal oxide obtained in the step 2), the hollow glass beads obtained in the step 3) and deionized water according to a mass ratio of 11: 1: 30, then putting the metal oxide and the hollow glass beads into a stirring tank, stirring for 30min at the speed of 100r/min, standing for 2.5h, then adding deionized water into the stirring tank, stirring for 30min at the speed of 50r/min, standing for 25min, finally filtering out the mixture at the lower layer, and drying the mixture in an oven at the temperature of 100 ℃ for 6h to obtain the metal oxide coated hollow glass beads.
5) Reducing the metal oxide: putting the metal oxide coated hollow glass beads obtained in the step 4) into a high-temperature furnace at 660 ℃, introducing ammonia gas for reduction for 3 hours, and cooling to room temperature to obtain the iron-nickel alloy coated hollow glass beads (Fe-Ni/hollow glass beads).
6) And (3) sequentially operating the hollow glass microspheres coated with the iron-nickel alloy obtained in the step 5) according to the steps 3) to 5), and repeating the coating for 2 times.
7) Coating with metal silver: weighing 20g of Fe-Ni/hollow glass microspheres obtained in the step 6), adding 100mL of solution with the volume ratio of ethanol to water being 3:7, carrying out ultrasonic treatment for 25min, then adding 200mL of 0.25mol/L hydrazine hydrate, stirring at the speed of 600r/min, dropwise adding 200mL of 0.2mol/L silver ammonia solution, finally adding 0.4mol/L sodium hydroxide solution until the pH value of the system is 10.2, carrying out ultrasonic reaction for 60min at 50 ℃, filtering, washing a solid mixture with 500mL of deionized water, then washing with 350mL of ethanol solution containing fatty acid with the mass fraction of 3%, and drying in a 65 ℃ oven for 20h to obtain the silver-coated iron-nickel alloy coated hollow glass microspheres (Ag/Fe-Ni/hollow glass microspheres).
8) Repeating the step 7) to coat the Ag/Fe-Ni/hollow glass microspheres obtained in the step 7) for 2 times to obtain the conductive filler.
A preparation method of a semiconductive shielding material comprises the following steps:
1) preparing a conductive master batch: 20 parts of 20 mass percent glass fiber modified PP (glass fiber length of 0.4mm), 15 parts of SBS, 15 parts of the conductive filler prepared in the embodiment, 2.5 parts of polyethylene wax and 0.5 part of antioxidant 1010 are put into a mixer to be uniformly mixed, and then are melted, blended and extruded on an extruder for granulation, wherein the temperature of each section of the extruder is 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 190 ℃, 180 ℃, and the screw rotation speed is 320 r/min.
2) Preparing a semiconductive shielding material: putting 65 parts of EVA, 10 parts of carbon black, all parts of the conductive master batch obtained in the step 1), 1.5 parts of polyethylene wax and 0.3 part of antioxidant 1010 into a mixer, uniformly mixing, then carrying out melt blending and extrusion granulation on an extruder, wherein the temperatures of all sections of the extruder are respectively 140 ℃, 150 ℃, 160 ℃, 170 ℃, 185 ℃, 200 ℃, 190 ℃, 180 ℃ and the screw rotation speed is 500 r/min.
Example 5
A preparation method of a conductive filler comprises the following steps:
1) wet ball milling of metal oxide: mixing Fe2O3And NiO according to the mass ratio of 0.82: 2.19, mixing the total mass of the metal oxides with absolute ethyl alcohol according to a mass ratio of 2: 1. the total mass of the grinding balls and the metal oxide is 13: 1.1, then putting the weighed grinding balls into a grinding tank, and then adding Fe2O3NiO and absolute ethyl alcohol, and finally ball milling for 10 hours at the speed of 200 r/min.
2) Sieving the metal oxide: drying the metal oxide obtained in the step 1) in an oven at 110 ℃ for 4 hours, and sieving the dried metal oxide by using a 250-mesh gauze.
3) Surface treatment of hollow glass beads: mixing the surface treatment liquid and the hollow glass beads according to a mass ratio of 4: weighing 1, wherein the surface treatment liquid is 2% of methyltriethoxysilane hydrolysate by mass fraction, soaking the hollow glass beads in the methyltriethoxysilane hydrolysate at 45 ℃ for 25min, filtering, and drying in a 65 ℃ oven for 12 h.
4) Coating the hollow glass beads with the metal oxide: mixing the metal oxide obtained in the step 2), the hollow glass beads obtained in the step 3) and deionized water according to a mass ratio of 11: 1: 30, then putting the metal oxide and the hollow glass beads into a stirring tank, stirring for 30min at the speed of 100r/min, standing for 2.5h, then adding deionized water into the stirring tank, stirring for 30min at the speed of 50r/min, standing for 25min, finally filtering out the mixture at the lower layer, and drying the mixture in an oven at the temperature of 100 ℃ for 6h to obtain the metal oxide coated hollow glass beads.
5) Reducing the metal oxide: putting the metal oxide coated hollow glass beads obtained in the step 4) into a high-temperature furnace at 660 ℃, introducing ammonia gas for reduction for 3 hours, and cooling to room temperature to obtain the iron-nickel alloy coated hollow glass beads (Fe-Ni/hollow glass beads).
6) And (3) sequentially operating the hollow glass microspheres coated with the iron-nickel alloy obtained in the step 5) according to the steps 3) to 5), and repeating the coating for 2 times.
7) Coating with metal silver: weighing 20g of Fe-Ni/hollow glass microspheres obtained in the step 6), adding 100mL of solution with the volume ratio of ethanol to water being 3:7, carrying out ultrasonic treatment for 25min, then adding 200mL of 0.25mol/L hydrazine hydrate, stirring at the speed of 600r/min, dropwise adding 200mL of 0.2mol/L silver ammonia solution, finally adding 0.4mol/L sodium hydroxide solution until the pH value of the system is 10.2, carrying out ultrasonic reaction for 60min at 50 ℃, filtering, washing a solid mixture with 500mL of deionized water, then washing with 350mL of ethanol solution containing fatty acid with the mass fraction of 3%, and drying in a 65 ℃ oven for 20h to obtain the silver-coated iron-nickel alloy coated hollow glass microspheres (Ag/Fe-Ni/hollow glass microspheres).
8) Repeating the step 7) to coat the Ag/Fe-Ni/hollow glass microspheres obtained in the step 7) for 2 times to obtain the conductive filler.
A preparation method of a semiconductive shielding material comprises the following steps:
1) preparing a conductive master batch: 20 parts of 20 mass percent glass fiber modified PP (glass fiber length of 0.4mm), 15 parts of SBS, 15 parts of the conductive filler prepared in the embodiment, 2.5 parts of polyethylene wax and 0.5 part of antioxidant 1010 are put into a mixer to be uniformly mixed, and then are melted, blended and extruded on an extruder for granulation, wherein the temperature of each section of the extruder is 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 190 ℃, 180 ℃, and the screw rotation speed is 320 r/min.
2) Preparing a semiconductive shielding material: putting 65 parts of EVA, 10 parts of carbon black, all parts of the conductive master batch obtained in the step 1), 1.5 parts of polyethylene wax and 0.3 part of antioxidant 1010 into a mixer, uniformly mixing, then carrying out melt blending and extrusion granulation on an extruder, wherein the temperatures of all sections of the extruder are respectively 140 ℃, 150 ℃, 160 ℃, 170 ℃, 185 ℃, 200 ℃, 190 ℃, 180 ℃ and the screw rotation speed is 500 r/min.
Example 6
A preparation method of a conductive filler comprises the following steps:
1) wet ball milling of metal oxide: mixing Fe2O3And NiO according to the mass ratio of 0.65: 2.14, mixing the total mass of the metal oxides with absolute ethyl alcohol according to a mass ratio of 2: 1. the total mass of the grinding balls and the metal oxide is 13: 1.1, then putting the weighed grinding balls into a grinding tank, and then adding Fe2O3NiO and absolute ethyl alcohol, and finally ball milling for 10 hours at the speed of 200 r/min.
2) Sieving the metal oxide: drying the metal oxide obtained in the step 1) in an oven at 110 ℃ for 4 hours, and sieving the dried metal oxide by using a 250-mesh gauze.
3) Surface treatment of hollow glass beads: mixing the surface treatment liquid and the hollow glass beads according to a mass ratio of 4: weighing 1, wherein the surface treatment liquid is 2% of methyltriethoxysilane hydrolysate by mass fraction, soaking the hollow glass beads in the methyltriethoxysilane hydrolysate at 45 ℃ for 25min, filtering, and drying in a 65 ℃ oven for 12 h.
4) Coating the hollow glass beads with the metal oxide: mixing the metal oxide obtained in the step 2), the hollow glass beads obtained in the step 3) and deionized water according to a mass ratio of 11: 1: 30, then putting the metal oxide and the hollow glass beads into a stirring tank, stirring for 30min at the speed of 100r/min, standing for 2.5h, then adding deionized water into the stirring tank, stirring for 30min at the speed of 50r/min, standing for 25min, finally filtering out the mixture at the lower layer, and drying the mixture in an oven at the temperature of 100 ℃ for 6h to obtain the metal oxide coated hollow glass beads.
5) Reducing the metal oxide: putting the metal oxide coated hollow glass beads obtained in the step 4) into a high-temperature furnace at 660 ℃, introducing ammonia gas for reduction for 3 hours, and cooling to room temperature to obtain the iron-nickel alloy coated hollow glass beads (Fe-Ni/hollow glass beads).
6) And (3) sequentially operating the hollow glass microspheres coated with the iron-nickel alloy obtained in the step 5) according to the steps 3) to 5), and repeating the coating for 2 times.
7) Coating with metal silver: weighing 20g of Fe-Ni/hollow glass microspheres obtained in the step 6), adding 100mL of solution with the volume ratio of ethanol to water being 3:7, carrying out ultrasonic treatment for 25min, then adding 200mL of 0.25mol/L hydrazine hydrate, stirring at the speed of 600r/min, dropwise adding 200mL of 0.2mol/L silver ammonia solution, finally adding 0.4mol/L sodium hydroxide solution until the pH value of the system is 10.2, carrying out ultrasonic reaction for 60min at 50 ℃, filtering, washing a solid mixture with 500mL of deionized water, then washing with 350mL of ethanol solution containing fatty acid with the mass fraction of 3%, and drying in a 65 ℃ oven for 20h to obtain the silver-coated iron-nickel alloy coated hollow glass microspheres (Ag/Fe-Ni/hollow glass microspheres).
8) Repeating the step 7) to coat the Ag/Fe-Ni/hollow glass microspheres obtained in the step 7) for 2 times to obtain the conductive filler.
A preparation method of a semiconductive shielding material comprises the following steps:
1) preparing a conductive master batch: 20 parts of 20 mass percent glass fiber modified PP (glass fiber length of 0.4mm), 15 parts of SBS, 15 parts of the conductive filler prepared in the embodiment, 2.5 parts of polyethylene wax and 0.5 part of antioxidant 1010 are put into a mixer to be uniformly mixed, and then are melted, blended and extruded on an extruder for granulation, wherein the temperature of each section of the extruder is 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 190 ℃, 180 ℃, and the screw rotation speed is 320 r/min.
11) Preparing a semiconductive shielding material: putting 65 parts of EVA, 10 parts of carbon black, all parts of the conductive master batch obtained in the step 1), 1.5 parts of polyethylene wax and 0.3 part of antioxidant 1010 into a mixer, uniformly mixing, then carrying out melt blending and extrusion granulation on an extruder, wherein the temperatures of all sections of the extruder are respectively 140 ℃, 150 ℃, 160 ℃, 170 ℃, 185 ℃, 200 ℃, 190 ℃, 180 ℃ and the screw rotation speed is 500 r/min.
Comparative example 1
This comparative example differs from example 1 in that there are no steps 6) and 8), i.e. no multiple coating, and is otherwise the same as example 1.
Comparative example 2
This comparative example is different from example 1 in that the number of times of coating repetition in step 6) and step 8) was 3 times, and the others were the same as example 1.
Comparative example 3
The comparative example is different from example 2 in that 8 parts of glass fiber modified PP having a mass fraction of 20% in step 9) and step 10) and 5 parts of SBS are added, and the rest is the same as example 2.
Comparative example 4
The comparative example is different from example 3 in that the addition amount of Ag/Fe-Ni/hollow glass beads in step 9) and step 10) is 5 parts, and other raw materials and preparation methods are the same as those of example 3.
Comparative example 5
The comparative example is different from example 4 in that no Ag/Fe-Ni/hollow glass bead conductive filler was added in steps 1) to 8), 9) and 10), the mother particle obtained in step 10) was a non-conductive mother particle, and only carbon black was added in step 11), the amount of carbon black added was 30 parts, and others were the same as in example 4.
Comparative example 6
The main difference between the comparative example and the example 4 is that the preparation method of the semiconductive shielding material comprises the following steps:
1) weighing 20g of hollow glass microspheres, adding the hollow glass microspheres into 100mL of solution with the volume ratio of ethanol to water being 3:7, carrying out ultrasonic treatment for 25min, then adding 200mL of 0.25mol/L hydrazine hydrate, stirring at the speed of 600r/min, dropwise adding 200mL of 0.2mol/L silver ammonia solution, finally adding 0.4mol/L sodium hydroxide solution until the pH value of the system is 10.2, carrying out ultrasonic reaction for 60min at 50 ℃, filtering, washing the solid mixture with 500mL of deionized water, washing with 350mL of ethanol solution containing fatty acid with the mass fraction of 3%, and drying in a 65 ℃ oven for 20h to obtain the silver-coated hollow glass microspheres (Ag/hollow glass microspheres).
2) Repeating the step 1) to coat the Ag/hollow glass microspheres obtained in the step 1) for 2 times.
3) Weighing, namely weighing the components of the semiconductive shielding material according to the following weight part ratios: 65 parts of EVA; 20 parts of modified PP; 15 parts of SBS; 15 parts of Ag/hollow glass beads; 10 parts of carbon black; 4 parts of a lubricant; 0.8 part of antioxidant.
4) Preparing conductive master batches, putting 20 parts of glass fiber modified PP (glass fiber with the length of 0.4mm) with the mass fraction of 20%, 15 parts of SBS, 15 parts of Ag/hollow glass microsphere prepared in the step 2), 2.5 parts of polyethylene wax and 0.5 part of antioxidant 1010 into a mixer, uniformly mixing, then carrying out melt blending and extrusion granulation on an extruder, wherein the temperatures of all sections of the extruder are respectively 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 190 ℃, 180 ℃, and the screw rotation speed is 320 r/min.
5) Preparing a semiconductive shielding material, putting 65 parts of EVA (ethylene vinyl acetate), 10 parts of carbon black, all parts of the conductive master batch obtained in the step 4), 1.5 parts of polyethylene wax and 0.3 part of antioxidant 1010 into a mixer, uniformly mixing, then carrying out melt blending and extrusion granulation on an extruder, wherein the temperatures of all sections of the extruder are respectively 140 ℃, 150 ℃, 160 ℃, 170 ℃, 185 ℃, 200 ℃, 190 ℃, 180 ℃, and the screw rotation speed is 500 r/min.
Comparative example 7
This comparative example differs from example 4 in that there is no component Fe in step 1)2O3Namely, only a single component NiO is added, the nickel-coated hollow glass beads are obtained in the step 6), the silver-coated nickel-coated hollow glass beads are obtained in the step 8), and the rest is the same as that of the embodiment 4.
Comparative example 8
This comparative example differs from example 4 in that there are no step 7) and step 8), i.e., no silver coating layer, and the conductive filler prepared was an iron-nickel alloy coated hollow glass microsphere, otherwise the same as in example 4.
Comparative example 9
This comparative example differs from example 4 in that Fe is present in step 1)2O3The mass ratio of NiO to NiO is 2.23: 1.41, the rest being the same as in example 4.
Comparative example 10
This comparative example differs from example 4 in that Fe is present in step 1)2O3Mass ratio to NiO was 0.49: 4.15, otherwise the same as in example 4.
The semiconductive shielding materials prepared in examples 1 to 6 and comparative examples 1 to 10 were tested for conductivity, shielding effectiveness and mechanical properties, and the test results are shown in table 1.
Test sample preparation: the semiconductive shield materials obtained in examples 1 to 6 and comparative examples 1 to 10 were hot-pressed into sheets having a thickness of 1mm and 2mm on a press vulcanizer having a temperature of 175 ℃.
The conductivity is measured by the volume resistivity, and the shielding effectiveness-1 and the shielding effectiveness-2 are respectively measured in the frequency bands of 500Hz and 15 GHz. The volume resistivity is measured by referring to the GB/T15662-1995 method, the shielding effectiveness is measured by referring to the GB/T12190-2006 method, and the tensile property is measured by referring to the GB/T1040-2006 method.
In addition, the density of the conductive filler is measured by referring to GB/T5162-2006, and the measured result is that the density of the metal silver, the density of the metal iron and the density of the metal nickel are respectively 10.49g/cm3、7.85g/cm3、8.90g/cm3The density of the conductive filler is 1.25-1.58 g/cm3。
TABLE 1 test results of the semiconductive shield materials
Figure BDA0002359810040000161
Figure BDA0002359810040000171
As can be seen from Table 1, comparative examples 1-2 and examples 1-2 illustrate the influence of the number of metal coatings on the performance of the semiconductive shielding material in the preparation process of the conductive filler, and the volume resistivity of the semiconductive shielding material is continuously reduced from 513 Ω along with the increase of the number of coatings.The cm is reduced to 327-383 omega.cm, the shielding effectiveness is continuously improved, the shielding effectiveness of the low-frequency band is increased from 7dB to 10-12 dB, the shielding effectiveness of the high-frequency band is increased from 27dB to 30-36 dB, and if the shielding effectiveness exceeds the shielding effectiveness of the low-frequency band, the shielding effectiveness of the high-frequency band is increased from 7dB to 30-36 dBCompared with the example 2, the volume resistivity and the shielding effectiveness of the semiconductive shielding material are not substantially changed by the coating times of the present invention, such as the comparative example 2. This shows that the increase of the metal coating times in the preparation process of the conductive filler can improve the conductivity and the shielding effectiveness of the semiconductive shielding material, but the coating times of the invention are exceeded, and the prepared conductive filler can not obviously improve the performance of the material.
Comparative example 3 and example 2 are to illustrate the effect of the content of modified PP and SBS on the performance of the conductive shielding material,
with the increase of the contents of the modified PP and SBS, the tensile property of the semiconductive shielding material is obviously improved, which is beneficial to enhancing the conductivity and shielding effectiveness of the semiconductive shielding material. The reason is probably that the glass fiber reinforced PP is beneficial to improving the strength of the material, and the SBS has certain toughening effect and is beneficial to improving the fracture elongation of the material; in addition, the modified PP and SBS are used as disperse phases, which is beneficial to the local concentration of the conductive filler and increases the density of the conductive chain, thereby improving the conductive shielding property of the material.
Comparative example 4 and examples 3 to 4 are to show the influence of the content of the prepared conductive filler (Ag/Fe-Ni/hollow glass bead) on the performance of the semiconductive shielding material, and the conductivity and shielding effectiveness of the semiconductive shielding material are obviously improved along with the increase of the content of the Ag/Fe-Ni/hollow glass bead. Compared with the comparative example 5 (the conductive fillers are all carbon black), in the examples 3-4, the prepared Ag/Fe-Ni/hollow glass beads are used for replacing part of the carbon black, the total parts of the conductive fillers (the total amount of the Ag/Fe-Ni/hollow glass beads and the carbon black) are reduced to 20-25 parts from 30 parts, the conductivity and the shielding effectiveness of the semiconductive shielding material are obviously enhanced, and particularly at the low frequency of 500Hz, the shielding effectiveness is increased from 1dB to 13-16 dB. The Ag/Fe-Ni/hollow glass beads prepared can cooperate with carbon black to obviously improve the conductivity of the material and the shielding efficiency of low-frequency or high-frequency wave bands.
In comparison to example 4, the conductive filler prepared in comparative example 6 did not have an iron-nickel alloy intermediate coating layer, comparative example 7 was a conductive filler prepared in comparative example 8 that did not have a silver coating layer, and the intermediate layer contained only nickel metal. If the middle coating layer of the iron-nickel alloy is not used, the shielding effectiveness of the low-frequency band is reduced from 16dB to 2dB, if the middle layer only contains nickel metal, the shielding effectiveness of the low-frequency band is reduced from 16dB to 9dB, if the silver coating layer is not used, the shielding effectiveness of the high-frequency band is reduced from 43dB to 36dB, which shows that the middle coating layer of the iron-nickel alloy is the key for improving the shielding effectiveness of the low-frequency band of the semiconductive shielding material, and compared with the single metal coating layer, the shielding effectiveness of the low-frequency band of the semiconductive shielding material is better, and the silver coating layer at the outermost part can obviously improve the shielding effectiveness of the high-frequency band of the semiconductive shielding material, and on the basis of the iron-nickel alloy of the middle coating layer, the shielding effectiveness of the material is further improved.
Examples 4 to 6 are Fe2O3Influence of mass ratio to NiO on the Performance of the semiconductive Shielding Material, depending on Fe2O3The mass ratio of the NiO is reduced, the low-frequency band shielding effectiveness of the semiconductive shielding material tends to increase firstly and then decrease, and the low-frequency band shielding effectiveness is in the Fe range2O3Mass ratio to NiO was 0.82: at 2.19, the shielding effectiveness of the semiconductive shielding material in the low frequency band reaches the highest value, 19 dB. If the Fe content of the inventive arrangement is increased or decreased2O3Compared with NiO in the mass ratio of the NiO, the semiconductive shielding material has the advantages that the shielding effectiveness of the semiconductive shielding material in the low-frequency band is changed from 16-19 dB to 11-12 dB in comparison examples 9-10. This indicates that Fe2O3The mass ratio of NiO to the low-frequency band shielding effectiveness of the semiconductive shielding material has a large influence, and the low-frequency band shielding effectiveness of the semiconductive shielding material can be exerted to the maximum extent only by controlling the mass ratio of NiO to NiO within the range set by the invention.
Therefore, the number of coating times in the preparation process of the intermediate coating layer, Fe in the coating layer2O3The mass ratio of the NiO and the dosage of the prepared conductive filler are important factors influencing the low-frequency band shielding effectiveness of the semiconductive shielding material. Besides the above influencing factors, the outermost layer of silver is also the main influence affecting the high-frequency band shielding performance of the material.
In summary, the conductive filler of the present invention has a density of the metallic filler from 7.85 to 10.49g/cm3Reducing the temperature to 1.25 to 1.58g/cm3Compared with the single method for preparing the semiconductive shielding material by using the conductive filler prepared by the invention and the carbon blackWith carbon black, not only the amount is reduced, but also the volume resistivity of the semiconductive shielding material is from 654 omega.The cm is reduced to 234-383 omega cm, the shielding effectiveness of the low-frequency band is increased from 1dB to 10-19 dB, and the shielding effectiveness of the high-frequency band is increased from 20dB to 30-44 dB. The added modified PP and SBS effectively improve the tensile property of the semiconductive shielding material, so that the tensile strength and the elongation at break of the material are respectively improved to 15-19 MPa and 320-351%.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (8)

1. The conductive filler is characterized in that the preparation method comprises the following steps:
(1) coating Fe on the surface of hollow glass microsphere2O3And NiO to prepare the hollow glass microspheres coated by the metal oxide; then reducing the metal oxide to obtain hollow glass beads coated by the iron-nickel alloy; said Fe2O3The mass ratio of NiO to NiO is (0.65-1.08): (2.14-2.35);
(2) repeating the step (1) for 1-2 times to prepare the hollow glass microspheres coated by the multilayer iron-nickel alloy;
(3) continuously coating silver on the surface of the hollow glass microsphere coated with the iron-nickel alloy obtained in the step (2);
(4) repeating the step (3) for 1-2 times, and coating multiple layers of silver on the surfaces of the hollow glass beads coated with the iron-nickel alloy to obtain the conductive filler;
the coating in the step (1) comprises the following specific steps: mixing Fe2O3Mixing with NiO, hollow glass beads and water, stirring, standing, filtering out a mixture at the lower layer, and drying to obtain the hollow glass beads coated with the metal oxide; fe2O3The mass ratio of the NiO to the hollow glass beads to the water is (11-13): (1-1.1): (29-32);
the step (3) is specifically as follows: adding hollow glass beads coated with iron-nickel alloy into a mixed solution of ethanol and water, adding hydrazine hydrate, dropwise adding a 0.2mol/L silver-ammonia solution, adjusting the pH value of the system to 10-11, and filtering, washing and drying after reaction to obtain silver-coated iron-nickel alloy coated hollow glass beads; the dosage of the silver-ammonia solution relative to the hollow glass microspheres coated by the iron-nickel alloy is 5-15 mL/g.
2. The electrically conductive filler of claim 1, wherein said Fe in step (1)2O3And NiO is ball-milled and then coated, wherein the ball-milling method comprises the following steps: mixing Fe2O3And mixing the NiO and the absolute ethyl alcohol, and ball-milling for 8-12 h at the speed of 200-250 r/min.
3. The conductive filler according to claim 1, wherein the hollow glass microspheres in step (1) are pretreated by: soaking the hollow glass beads in 2% by mass of methyltriethoxysilane hydrolysate for 20-30 min, filtering and drying; the mass ratio of the methyl triethoxysilane hydrolysate to the hollow glass beads is (4-5): (0.8 to 1.2).
4. The conductive filler according to claim 1, wherein the reduction in step (1) comprises the following steps: reducing the hollow glass beads coated with the metal oxide at 650-700 ℃ for 3-4 h in an ammonia atmosphere to obtain the iron-nickel alloy coated hollow glass beads.
5. A semiconductive shielding material comprising a conductive filler according to any of claims 1 to 4, comprising the following components in parts by weight:
65-75 parts of EVA; 15-20 parts of modified PP; 10-15 parts of SBS; 10-15 parts of conductive filler; 10 parts of carbon black; 3-5 parts of a lubricant; 0.5-1 part of antioxidant.
6. The semiconducting shield material of claim 5, wherein the method of preparing the semiconducting shield material comprises the steps of:
(1) preparing a conductive master batch: putting 15-20 parts of modified PP, 10-15 parts of SBS, 10-15 parts of conductive filler, 2-3 parts of lubricant and 0.5-0.7 part of antioxidant into a mixer for uniform mixing, and then carrying out melt blending, extrusion and granulation on an extruder;
(2) preparing a semiconductive shielding material: putting 65-75 parts of EVA (ethylene vinyl acetate), 10 parts of carbon black, all parts of the conductive master batch obtained in the step (1), 1-2 parts of lubricant and 0.2-0.3 part of antioxidant into a mixer, uniformly mixing, and then carrying out melt blending, extrusion and granulation on an extruder.
7. The semiconductive shielding material according to claim 5, wherein the EVA has a VA content of 18-28% and a melt flow rate of 2.3-2.6 g/10 min.
8. The semiconducting shield material of claim 5, wherein the ratio of styrene to butadiene in SBS is 40/60.
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