CN101451057A - Bamboo charcoal base electro-magnetic screen composite material and preparation method thereof - Google Patents
Bamboo charcoal base electro-magnetic screen composite material and preparation method thereof Download PDFInfo
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- CN101451057A CN101451057A CNA2009100712151A CN200910071215A CN101451057A CN 101451057 A CN101451057 A CN 101451057A CN A2009100712151 A CNA2009100712151 A CN A2009100712151A CN 200910071215 A CN200910071215 A CN 200910071215A CN 101451057 A CN101451057 A CN 101451057A
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Abstract
The invention discloses a bamboo charcoal-based electromagnetic shielding composite material and a method for preparing the same, which relate to an electromagnetic shielding composite material and a method for preparing the same. The invention solves the problems that the prior filling-type electromagnetic shielding material has uneven distribution of filler and poor electrical and mechanical performance. The bamboo charcoal-based electromagnetic shielding composite material is prepared from polymer resin, bamboo charcoal powder, a metal particle additive, a magnetic medium and a coupling agent. The preparation method comprises: bamboo is prepared into bamboo charcoal powder; the additive and magnetic powder for producing metal particles and the bamboo charcoal powder are mixed by a solution blending method; and after drying, the bamboo charcoal powder adhered with the metal particles is mixed with the coupling agent and the polymer resin and is dried, cured, pressed, molded and calcined to obtain the bamboo charcoal-based electromagnetic shielding composite material adhered with the metal particles. The bamboo charcoal-based electromagnetic shielding composite material manufactured through the method has shielding efficiency of more than or equal to 40dB in the shielding range between 500MHz and 1.5GHz, and can be applied to aerospace, military, home appliances and other fields.
Description
Technical field
The present invention relates to a kind of electromagnetic shielding composite material and preparation method thereof.
Background technology
Along with the develop rapidly of electronic technology, electromagnetic interference, problems such as electromagnetic environment pollution also become more and more serious.The electromagnetic radiation meeting is to various electronicss, and infosystem causes electromagnetic interference, causes data transmission fault, causes various accidents.The human body long-term exposure can make cytolemma and protein structure change under electromagnetic radiation, destroys the biological structure and the neural system of human body, produces visual deterioration, hypomnesis, consequences such as abalienation, severe patient even can bring out cancer, leukemia etc.Therefore, the problem of electromagnetic interference has been subjected to paying close attention to widely, and adopting electromagnetic shielding material is one of effective technological approaches, and with respect to traditional metal species shielding material, electromagnetic shielding material develops towards direction light, thin, easily processing at present.
Metal, conductive plastics (comprising coating), graphite carbon material and conduction high polymer are present four used big class electromagnetic shielding and antistatic materials.Metallic substance has advantages such as the high and good mechanical property of electromagnetic shielding coefficient (SE) as Ag, Ni, Cu, Al etc., but the cost height, than great, perishable, poor processability and exist electromagnetic than strong reflection.Conduction high polymer is evenly compound or form a kind of conductive polymer composite that surface conduction film modes such as (metallization) makes by insulating organic polymer material and various conductive material (copper, graphite, carbon dust etc.), advantage such as it has that moulding is easy, in light weight, cost is low, the electricity of material and mechanical property are adjustable, but also there is lack of homogeneity, improves the limitation of limited and difficult compatible electricity of specific conductivity and mechanical property.
At present, mainly study and design about the preparation of electromagnetic shielding material from electromagnetic performance and two aspects of absorbing property characteristic of material.In general, the electroconductibility of material is good more, its capability of electromagnetic shielding is also good more, and the raw material of wood-charcoal material is as being that raw material of wood-charcoal material with various forms joins in the macromolecule matrix as " conductive additive " basically aspect the electromagnetic shielding material, to prepare the high matrix material that conducts electricity.But the capability of electromagnetic shielding of these macromolecular materials is still not ideal enough, and the heat radiation because some electronic machine need be breathed freely when work louvre is arranged, and louvre can cause electromagnetic leakage.
Summary of the invention
The present invention is inhomogeneous in order to solve present filled-type electromagnetic shielding material filler distribution, the cost height, electricity and poor mechanical property, louvre can cause the problem of hertzian wave leakage etc., the invention provides a kind ofly have the electroconductibility height, energy is high temperature resistant, corrosion-resistant, filler distribution is even, moulding process is easy, with low cost, bamboo charcoal base electro-magnetic screen composite material that effectiveness is good and preparation method thereof.
Among the present invention, bamboo charcoal base electro-magnetic screen composite material is made by 20～90 parts fluoropolymer resin, 14～50 parts conducting medium, 0～10 part magnetic conductive media and 0.2～0.3 part coupling agent by mass fraction.
The preparation process of bamboo charcoal base electro-magnetic screen composite material is as follows: one, with pulverizer bamboo is pulverized the well-thought-out plan powder, in electric drying oven with forced convection under 75 ℃～85 ℃ conditions dry 18～24 hours, again the bamboo powder is put into tube furnace after being cooled to room temperature, temperature rise rate with 3～5 ℃/min under protection of inert gas begins to heat up, when temperature is raised to 120 ℃～200 ℃, be incubated 0.5～1 hour, continuation is heated to 600 ℃～800 ℃ carbonization temperature with the temperature rise rate of 3～5 ℃/min, be incubated 1～2 hour postcooling to room temperature, make bamboo charcoal powder; Two, it is soluble in water with 4～7 parts of metallics additives to press mass fraction, forming concentration is the metal salt solution of 0.25～1mol/L, the bamboo charcoal powder that in metal salt solution, adds 10～50 parts then, place ultrasonic wave ultra-sonic dispersion 10min～30min, the solution that will contain bamboo charcoal powder and metallics additive then carries out drying treatment, becomes 40 purposes bamboo charcoal powder-metallics additive mixed powder with the ball mill ball milling; Three, bamboo charcoal powder-metallics additive mixed powder and 0.2～0.3 part of coupling agent are put into organic solvent for ultrasonic dispersion and get solution A, with 0～10 part magnetic conductive media powder and 20～90 parts of fluoropolymer resins also be dissolved in the organic solvent solution B; Four, solution A is mixed with B, carry out dispersion treatment with ultrasonic wave again, the dispersion treatment temperature is 20 ℃～50 ℃, and the treatment time is 0.5h～2h, gets bamboo charcoal based composites mixing solutions; Five, the bamboo charcoal based composites mixing solutions that makes is cast in the mould, after putting into 70 ℃ of vacuum chambers and vacuumizing 30min～60min, the moulding of thermocompressor hot-press solidifying is being gone in dry back, and hot pressing temperature is 135 ℃～220 ℃, pressure is 5MPa～15MPa, and hot pressing time is 15～20min; Six, the sample of compression moulding is put in the vacuum oven calcines, calcining temperature is warmed up to 400 ℃～500 ℃ with the temperature rise rate of 3～5 ℃/min earlier, be incubated 0.5～1 hour, temperature rise rate with 1～3 ℃/min is warmed up to 1000～1400 ℃ again, kept temperature 1～2 hour, naturally cool to room temperature then, promptly make bamboo charcoal base electro-magnetic screen composite material.
The bamboo charcoal base electro-magnetic screen composite material of the present invention's preparation has following advantage:
1, density is little, light weight: the bamboo charcoal base electro-magnetic screen composite material of the present invention's preparation, density is 1.83～2.32g/cm
3, thickness is the matrix material of the present invention of 4.5mm, the metallic aluminium effect of its shield effectiveness and 4mm is suitable, and quality (area is identical) only is 64% of an aluminium shielding material;
2, good permeability, mechanical property is good: the bamboo charcoal base electro-magnetic screen composite material of the present invention's preparation is actually a kind of charcoal-carbon composite, form the glass charcoal after the fluoropolymer resin charing, good vesicular structure is arranged, and its void content is 15.6～22.7%, the mechanical property that shows in addition, its bending strength is 5.63～6.89MPa, Young's modulus is 1.33～1.38GPa, and surface hardness is 8.61～10.65MPa, and ultimate compression strength is 8.99～10.40MPa;
3. electromagnet shield effect is good: the bamboo charcoal base electro-magnetic screen composite material of the present invention's preparation is the electroconductibility height of filler than general carbon, this be because with bamboo charcoal powder as a kind of porous medium, by ultrasonic wave effect and metal-salt uniform mixing, made the bamboo charcoal powder-metallics conducting medium of stable in properties, and between the interface of metallics and bamboo charcoal grain, because the katalysis of metallics, generated one deck charcoal nanometer conduction band network, the structure of nanometer charcoal is graphite-structure, increased the electric conductivity of matrix material, and along with the increase of calcining temperature, interfacial layer thickness increases.In general, the structure of making conductive filler material and raw material of wood-charcoal material with the raw material of wood-charcoal material has relation, and the electric conductivity of the raw material of wood-charcoal material of graphite-structure is than the electric conductivity height of unformed carbon structure; And by the magnetic conductive media powder that mixes and the porousness on the composite structure, more help absorption of electromagnetic wave decay and multiple attenuation, bamboo charcoal base electro-magnetic screen composite material to the present invention's preparation carries out shielding properties test, its effectiveness of shielding 〉=40dB by ASTMD4935-99 in 500MHz～1.5GHz hertzian wave band limits.
Preparation technology of the present invention is simple, micro-porous adsorption effect by bamboo charcoal, make the metal additive of introducing can enter deposition, the different carbonization temperature of bamboo wood and the speed of intensification controlled according to bamboo age and bamboo kind obtain the bamboo charcoal powder that electric conductivity is high, that specific surface area is big, particle diameter is little.Make the conducting medium of forming by bamboo charcoal powder and conductive metal particles with ultrasonic wave, by introduce coupling agent (effect of coupling agent is that mineral filler is evenly distributed) in macromolecule resin, under ultrasonic wave, adopt the method for solution blending to make conductive filler material uniform distribution in resin matrix, overcome conductive filler material and be difficult for being evenly distributed to difficulty in the fluoropolymer resin, improved the traditional defective of the material that conductive filler material is filled into gained in the superpolymer aspect mechanical property and workability.By compression moulding, can make required various electromagnetic shielding composite materials.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: bamboo charcoal base electro-magnetic screen composite material is made by 20～90 parts fluoropolymer resin, 10～50 parts of bamboo charcoal powder, 4～7 parts of metallics additives, 0～10 part magnetic conductive media and 0.2～0.3 part coupling agent by mass fraction in this embodiment.
Embodiment two: what this embodiment and embodiment one were different is: bamboo charcoal base electro-magnetic screen composite material is made by 40～70 parts fluoropolymer resin, 20～40 parts of bamboo charcoal powder, 5～6 parts of metallics additives, 2～8 parts magnetic conductive media and 0.2～0.3 part coupling agent by mass fraction.Other is identical with embodiment one.
Embodiment three: what this embodiment and embodiment one were different is: bamboo charcoal base electro-magnetic screen composite material is made by 60 parts fluoropolymer resin, 30 parts of bamboo charcoal powder, 5 parts of metallics additives, 6 parts magnetic conductive media and 0.3 part coupling agent by mass fraction.Other is identical with embodiment one.
Embodiment four: what this embodiment and embodiment one were different is: fluoropolymer resin is one or more in resol, urea-formaldehyde resin, Resins, epoxy, unsaturated polyester, urethane, the polyimide resin.Other is identical with embodiment one.
Embodiment five: what this embodiment and embodiment one were different is: bamboo charcoal powder is by the bamboo one-tenth of mao bamboon, sinocalamus latiflorus, green bamboo or Thorny of life in 3～5 years.Other is identical with embodiment one.
Embodiment six: what this embodiment and embodiment five were different is: the specific conductivity of bamboo charcoal powder is greater than 1.5S/cm, and particle diameter is 500 μ m～600 μ m, and pore size distribution is 10nm～100nm.Other is identical with embodiment five.
Embodiment seven: what this embodiment and embodiment five were different is: the pore size distribution of bamboo charcoal powder is 30nm～70nm.Other is identical with embodiment five.
Embodiment eight: what this embodiment and embodiment five were different is: the pore size distribution of bamboo charcoal powder is 40nm～60nm.Other is identical with embodiment five.
Embodiment nine: what this embodiment and embodiment one were different is: the metallics additive is NiNO
3, CuSO
4, AgNO
3, FeSO
4In one or more.Other is identical with embodiment one.
When the metallics additive is two or more, presses arbitrary proportion and mix.
Embodiment ten: what this embodiment and embodiment one were different is: magnetic is Fe
2O
3, Fe
3O
4In one or both mixture, Effective permeability μ〉2.85, granularity is 1 μ m～3 μ m.Other is identical with embodiment one.
When magnetic is the mixture of two kinds of materials, presses arbitrary proportion and mix.
Embodiment 11: what this embodiment and embodiment one were different is: coupling agent is one or more in polyethylene vinyl acetate between to for plastic, Sodium dodecylbenzene sulfonate, vinyltriethoxysilane and the titanate coupling agent.Other is identical with embodiment one.
When coupling agent is the mixture of two kinds or two kinds materials, presses arbitrary proportion and mix.
Embodiment 12: bamboo charcoal base electro-magnetic screen composite material is made by 20～90 parts fluoropolymer resin, 10～50 parts of bamboo charcoal powder, 4～7 parts of metallics additives, 0～10 part magnetic conductive media and 0.2～0.3 part coupling agent by mass fraction in this embodiment.Wherein, fluoropolymer resin is one or more in resol, urea-formaldehyde resin, Resins, epoxy, unsaturated polyester, urethane, the polyimide resin; Bamboo charcoal powder is by the bamboo one-tenth of mao bamboon, sinocalamus latiflorus, green bamboo or Thorny of life in 3～5 years; The specific conductivity of bamboo charcoal powder is greater than 1.5S/cm, and particle diameter is 500 μ m～600 μ m, and pore size distribution is 10nm～100nm; The metallics additive is NiNO
3, CuSO
4, AgNO
3, FeSO
4In one or more; Magnetic is Fe
2O
3, Fe
3O
4In one or both, Effective permeability μ〉2.85, granularity is 1 μ m～3 μ m; Coupling agent is one or more in polyethylene vinyl acetate between to for plastic, Sodium dodecylbenzene sulfonate, vinyltriethoxysilane and the titanate coupling agent.
Embodiment 13: the preparation process of bamboo charcoal base electro-magnetic screen composite material is as follows in this embodiment: one, with pulverizer bamboo is pulverized the well-thought-out plan powder, in electric drying oven with forced convection under 75 ℃～85 ℃ conditions dry 18～24 hours, again the bamboo powder is put into tube furnace after being cooled to room temperature, temperature rise rate with 3～5 ℃/min under protection of inert gas begins to heat up, when temperature is raised to 120 ℃～200 ℃, be incubated 0.5～1 hour, continuation is heated to 600 ℃～800 ℃ carbonization temperature with the temperature rise rate of 3～5 ℃/min, be incubated 1～2 hour postcooling to room temperature, make bamboo charcoal powder; Two, it is soluble in water with 4～7 parts of metallics additives to press mass fraction, forming concentration is the metal salt solution of 0.25～1mol/L, the bamboo charcoal powder that in metal salt solution, adds 10～50 parts then, place ultrasonic wave ultra-sonic dispersion 10min～30min, the solution that will contain bamboo charcoal powder and metallics additive then carries out drying treatment, becomes 40 purposes bamboo charcoal powder-metallics additive mixed powder with the ball mill ball milling; Three, bamboo charcoal powder-metallics additive mixed powder and 0.2～0.3 part of coupling agent are put into organic solvent for ultrasonic dispersion and get solution A, with 0～10 part magnetic conductive media powder and 20～90 parts of fluoropolymer resins also be dissolved in the organic solvent solution B; Four, solution A is mixed with B, carry out dispersion treatment with ultrasonic wave again, the dispersion treatment temperature is 20 ℃～50 ℃, and the treatment time is 0.5h～2h, gets bamboo charcoal based composites mixing solutions; Five, the bamboo charcoal based composites mixing solutions that makes is cast in the mould, after putting into 70 ℃ of vacuum chambers and vacuumizing 30min～60min, the moulding of thermocompressor hot-press solidifying is being gone in dry back, and hot pressing temperature is 135 ℃～220 ℃, pressure is 5MPa～15MPa, and hot pressing time is 15～20min; Six, the sample of compression moulding is put in the vacuum oven calcines, calcining temperature is warmed up to 400 ℃～500 ℃ with the temperature rise rate of 3～5 ℃/min earlier, be incubated 0.5～1 hour, temperature rise rate with 1～3 ℃/min is warmed up to 1000～1400 ℃ again, kept temperature 1～2 hour, naturally cool to room temperature then, promptly make bamboo charcoal base electro-magnetic screen composite material.
The organic solvent of the solution A of step 3 and solution B volatilizees in the ultrasonic dispersing of step 4 and step 5 and drying process in the present embodiment.
In the present embodiment in the step 2 bamboo charcoal powder of per 12～15g need use the metal salt solution of 100mL, per 40～50g fluoropolymer resin need use the organic solvent of 250～300mL in the step 3, and the coupling agent of per 0.2～0.5g need use the organic solvent of 200mL in the step 3.
Embodiment 14: what this embodiment and embodiment 13 were different is: the used organic solvent of solution A is one or more in acetone, dimethyl formamide, two propyl carbinols, N-BUTYL ACETATE, cyclohexanone, the dimethylbenzene in the step 3.Other is identical with embodiment 13.
When organic solvent is the mixture of two or more material, presses arbitrary proportion and mix.
Embodiment 15: what this embodiment and embodiment 13 were different is: the used organic solvent of solution B is one or more in acetone, dimethyl formamide, two propyl carbinols, N-BUTYL ACETATE, cyclohexanone, the dimethylbenzene in the step 3.Other is identical with embodiment 13.
When organic solvent is the mixture of two or more material, presses arbitrary proportion and mix.
Embodiment 16: bamboo charcoal base electro-magnetic screen composite material is made by 20～90 parts fluoropolymer resin, 10～50 parts of bamboo charcoal powder, 4～7 parts of metallics additives, 0～10 part magnetic conductive media and 0.2～0.3 part coupling agent by mass fraction in this embodiment.Preparation by the following method: one, bamboo is pulverized the well-thought-out plan powder with pulverizer, in electric drying oven with forced convection under 75 ℃～85 ℃ conditions dry 18～24 hours, again the bamboo powder is put into tube furnace after being cooled to room temperature, temperature rise rate with 3～5 ℃/min under protection of inert gas begins to heat up, when temperature is raised to 120 ℃～200 ℃, be incubated 0.5～1 hour, continuation is heated to 600 ℃～800 ℃ carbonization temperature with the temperature rise rate of 3～5 ℃/min, be incubated 1～2 hour postcooling to room temperature, make bamboo charcoal powder; Two, it is soluble in water with 4～7 parts of metallics additives to press mass fraction, forming concentration is the metal salt solution of 0.25～1mol/L, the bamboo charcoal powder that in metal salt solution, adds 10～50 parts then, place ultrasonic wave ultra-sonic dispersion 10min～30min, the solution that will contain bamboo charcoal powder and metallics additive then carries out drying treatment, becomes 40 purposes bamboo charcoal powder-metallics additive mixed powder with the ball mill ball milling; Three, bamboo charcoal powder-metallics additive mixed powder and 0.2～0.3 part of coupling agent are put into organic solvent for ultrasonic dispersion and get solution A, with 0～10 part magnetic conductive media powder and 20～90 parts of fluoropolymer resins also be dissolved in the organic solvent solution B; Four, solution A is mixed with B, carry out dispersion treatment with ultrasonic wave again, the dispersion treatment temperature is 20 ℃～50 ℃, and the treatment time is 0.5h～2h, gets bamboo charcoal based composites mixing solutions; Five, the bamboo charcoal based composites mixing solutions that makes is cast in the mould, after putting into 70 ℃ of vacuum chambers and vacuumizing 30min～60min, the moulding of thermocompressor hot-press solidifying is being gone in dry back, and hot pressing temperature is 135 ℃～220 ℃, pressure is 5MPa～15MPa, and hot pressing time is 15～20min; Six, the sample of compression moulding is put in the vacuum oven calcines, calcining temperature is warmed up to 400 ℃～500 ℃ with the temperature rise rate of 3～5 ℃/min earlier, be incubated 0.5～1 hour, temperature rise rate with 1～3 ℃/min is warmed up to 1000～1400 ℃ again, kept temperature 1～2 hour, naturally cool to room temperature then, promptly make bamboo charcoal base electro-magnetic screen composite material; Wherein, fluoropolymer resin is one or more in resol, urea-formaldehyde resin, Resins, epoxy, unsaturated polyester, urethane, the polyimide resin; Bamboo charcoal powder is by the bamboo one-tenth of mao bamboon, sinocalamus latiflorus, green bamboo or Thorny of life in 3～5 years; The specific conductivity of bamboo charcoal powder is greater than 1.5S/cm, and particle diameter is 500 μ m～600 μ m, and pore size distribution is 10nm～100nm; The metallics additive is NiNO
3, CuSO
4, AgNO
3, FeSO
4In one or more; Magnetic is Fe
2O
3, Fe
3O
4In one or both, Effective permeability μ〉2.85, granularity is 1 μ m～3 μ m; Coupling agent is one or more in polyethylene vinyl acetate between to for plastic, Sodium dodecylbenzene sulfonate, vinyltriethoxysilane and the titanate coupling agent.
Embodiment 17: bamboo charcoal base electro-magnetic screen composite material is pressed mass fraction by 60 parts resol, 30 parts of mao bamboon powdered carbons, 6 parts of NiNO in this embodiment
3Make with 0.25 part dodecylbenzene semi-annular jade pendant acid sodium.Preparation according to the following steps: one, choose the mao bamboon in 4 years bamboo ages and be ground into the bamboo powder that particle diameter is 200 μ m with pulverizer, in electric drying oven with forced convection, kept under 80 ℃ of conditions dry 24 hours, again sample is put into tube furnace after the cooling, temperature rise rate with 4 ℃/min under protection of inert gas begins to heat up, when temperature is raised to 150 ℃, constant temperature 1h, the temperature rise rate with 4 ℃/min is warming up to 700 ℃ of carbonization temperatures again, makes elementary bamboo charcoal powder; Two, an amount of bamboo charcoal powder is infiltrated on the NiNO that concentration is 0.5mol/L
3In the solution, place ultrasonic wave ultra-sonic dispersion 20min, then mixture is carried out drying treatment, ball milling becomes 40 purpose powder; Three, ultra-sonic dispersion in acetone gets mixed liquor A with a certain amount of bamboo charcoal/Ni mixed powder and dodecylbenzene semi-annular jade pendant acid sodium, resol also is dissolved in get solution B in the acetone; Four, with above-mentioned two kinds of solution A with after B mixes, carry out dispersion treatment with ultrasonic wave again, the dispersion treatment temperature is 35 ℃, the treatment time is 1h; Five, the mixing solutions that makes is cast in the mould, vacuumizes 40min, send into thermocompressor under the normal temperature after the drying again and be hot pressed into external diameter 115mm, the sheet sample of thickness 4.5mm, hot pressing temperature is 180 ℃, and hot pressing pressure is 10Mpa, and hot pressing time is 18min; Six, the sample with compression moulding places vacuum oven to calcine, calcining temperature is warmed up to 400～500 ℃ earlier with the temperature rise rate of 3～5 ℃/min, constant temperature 0.5～1h, temperature rise rate with 1～3 ℃/min is warmed up to 1000 ℃ again, constant temperature 1～2h, vacuum oven naturally cools to room temperature, and making thickness is the sheet bamboo charcoal base electro-magnetic screen composite material of 4.5mm.The electromagnet shield effect that records the material of present embodiment preparation in the range of frequency of 500MHz～1.5GHz is more than the 46dB.
The electromagnetic shielding material density of present embodiment preparation is 1.83g/cm
3, void content is 22.7%, and its bending strength is 5.63MPa, and Young's modulus is 1.33GPa, and surface hardness is 8.61MPa, ultimate compression strength is 8.99MPa.
Embodiment 18: what this embodiment and embodiment 17 were different is: in the step 3, with 6 parts Fe
2O
3Powder and resol are dissolved in the acetone; In the step 6, the sample of compression moulding is calcined in vacuum oven, calcining temperature is warmed up to 420～480 ℃ earlier with the temperature rise rate of 3 ℃/min, constant temperature 0.5～1h, temperature rise rate with 1～3 ℃/min is warmed up to 1400 ℃ again, behind constant temperature 1～2h, vacuum oven naturally cools to room temperature, and making thickness is the sheet bamboo charcoal base electro-magnetic screen composite material of 4.5mm.Other is identical with embodiment 17.The electromagnet shield effect that records the material of present embodiment preparation in the range of frequency of 500MHz～1.5GHz is more than the 65dB.
The electromagnetic shielding material density of present embodiment preparation is 2.32g/cm
3, void content is 15.6%, and its bending strength is 6.89MPa, and Young's modulus is 1.38GPa, and surface hardness is 10.65MPa, ultimate compression strength is 10.40MPa.
Embodiment 19: what this embodiment and embodiment 17 were different is: in the step 3, with 6 parts Fe
2O
3Powder and resol are dissolved in the acetone; In the step 6, the sample of compression moulding is calcined in vacuum oven earlier, calcining temperature is warmed up to 450 ℃ earlier with the temperature rise rate of 4 ℃/min, constant temperature 1h, temperature rise rate with 2 ℃/min is warmed up to 1000 ℃ again, behind the constant temperature 1.5h, vacuum oven naturally cools to room temperature, and making thickness is the sheet bamboo charcoal base electro-magnetic screen composite material of 4.5mm.Other is identical with embodiment 17.The electromagnet shield effect that records the material of present embodiment preparation in the range of frequency of 500MHz～1.5GHz is more than the 58dB.
The electromagnetic shielding material density of present embodiment preparation is 2.23g/cm
3, void content is 20.1%, and its bending strength is 6.56MPa, and Young's modulus is 1.36GPa, and surface hardness is 9.95MPa, ultimate compression strength is 10.12MPa.
Embodiment 20: what this embodiment and embodiment 17 were different is: in the step 6, the sample of compression moulding is calcined in vacuum oven, calcining temperature is warmed up to 450 ℃ earlier with the temperature rise rate of 3 ℃/min, constant temperature 1h, temperature rise rate with 2 ℃/min is warmed up to 1400 ℃ again, behind the constant temperature 1h, vacuum oven naturally cools to room temperature, and making thickness is the sheet bamboo charcoal base electro-magnetic screen composite material of 4.5mm.Other is identical with embodiment 17.The electromagnet shield effect that records the material of present embodiment preparation in the range of frequency of 500MHz～1.5GHz is more than the 47dB.
The electromagnetic shielding material density of present embodiment preparation is 1.92g/cm
3, void content is 18.9%, and its bending strength is 6.23MPa, and Young's modulus is 1.35GPa, and surface hardness is 9.60MPa, ultimate compression strength is 9.56MPa; Thickness is the matrix material of the present embodiment preparation of 4.5mm, and the metallic aluminium effect of its shield effectiveness and 4mm is suitable, and quality (area is identical) only is 64% of an aluminium shielding material.
Claims (10)
1. bamboo charcoal base electro-magnetic screen composite material is characterized in that bamboo charcoal base electro-magnetic screen composite material made by 20～90 parts fluoropolymer resin, 10～50 parts of bamboo charcoal powder, 4～7 parts of metallics additives, 0～10 part magnetic conductive media and 0.2～0.3 part coupling agent by mass fraction.
2. a kind of bamboo charcoal base electro-magnetic screen composite material according to claim 1 is characterized in that fluoropolymer resin is one or more the mixture in resol, urea-formaldehyde resin, Resins, epoxy, unsaturated polyester, urethane, the polyimide resin.
3. a kind of bamboo charcoal base electro-magnetic screen composite material according to claim 1 is characterized in that mao bamboon, sinocalamus latiflorus, green bamboo or the Thorny bamboo one-tenth of bamboo charcoal powder by life in 3～5 years.
4. a kind of bamboo charcoal base electro-magnetic screen composite material according to claim 3, the specific conductivity that it is characterized in that bamboo charcoal powder are greater than 1.5S/cm, and particle diameter is 500 μ m～600 μ m, and pore size distribution is 10nm～100nm.
5. a kind of bamboo charcoal base electro-magnetic screen composite material according to claim 1 is characterized in that the metallics additive is NiNO
3, CuSO
4, AgNO
3, FeSO
4In one or more mixture.
6. a kind of bamboo charcoal base electro-magnetic screen composite material according to claim 1 is characterized in that magnetic is Fe
2O
3, Fe
3O
4In one or both, Effective permeability μ〉2.85H/m, granularity is 1 μ m～3 μ m.
7. a kind of bamboo charcoal base electro-magnetic screen composite material according to claim 1 is characterized in that coupling agent is one or more in polyethylene vinyl acetate between to for plastic, Sodium dodecylbenzene sulfonate, vinyltriethoxysilane and the titanate coupling agent.
8. the method for preparing the described a kind of bamboo charcoal base electro-magnetic screen composite material of claim 1, the preparation process that it is characterized in that bamboo charcoal base electro-magnetic screen composite material is as follows: one, with pulverizer bamboo is pulverized the well-thought-out plan powder, in electric drying oven with forced convection under 75 ℃～85 ℃ conditions dry 18～24 hours, again the bamboo powder is put into tube furnace after being cooled to room temperature, temperature rise rate with 3～5 ℃/min under protection of inert gas begins to heat up, when temperature is raised to 120 ℃～200 ℃, be incubated 0.5～1 hour, continuation is heated to 600 ℃～800 ℃ carbonization temperature with the temperature rise rate of 3～5 ℃/min, be incubated 1～2 hour postcooling to room temperature, make bamboo charcoal powder; Two, it is soluble in water with 4～7 parts of metallics additives to press mass fraction, forming concentration is the metal salt solution of 0.25～1mol/L, the bamboo charcoal powder that in metal salt solution, adds 10～50 parts then, place ultrasonic wave ultra-sonic dispersion 10min～30min, the solution that will contain bamboo charcoal powder and metallics additive then carries out drying treatment, becomes 40 purposes bamboo charcoal powder-metallics additive mixed powder with the ball mill ball milling; Three, bamboo charcoal powder-metallics additive mixed powder and 0.2～0.3 part of coupling agent are put into organic solvent for ultrasonic dispersion and get solution A, with 0～10 part magnetic conductive media powder and 20～90 parts of fluoropolymer resins also be dissolved in the organic solvent solution B; Four, solution A is mixed with B, carry out dispersion treatment with ultrasonic wave again, the dispersion treatment temperature is 20 ℃～50 ℃, and the treatment time is 0.5h～2h, gets bamboo charcoal based composites mixing solutions; Five, the bamboo charcoal based composites mixing solutions that makes is cast in the mould, after putting into 70 ℃ of vacuum chambers and vacuumizing 30min～60min, the moulding of thermocompressor hot-press solidifying is being gone in dry back, and hot pressing temperature is 135 ℃～220 ℃, pressure is 5MPa～15MPa, and hot pressing time is 15～20min; Six, the sample of compression moulding is put in the vacuum oven calcines, calcining temperature is warmed up to 400 ℃～500 ℃ with the temperature rise rate of 3～5 ℃/min earlier, be incubated 0.5～1 hour, temperature rise rate with 1～3 ℃/min is warmed up to 1000～1400 ℃ again, kept temperature 1～2 hour, naturally cool to room temperature then, promptly make bamboo charcoal base electro-magnetic screen composite material.
9. the preparation method of a kind of bamboo charcoal base electro-magnetic screen composite material according to claim 8 is characterized in that the used organic solvent of solution A in the step 3 is one or more the combination in acetone, dimethyl formamide, two propyl carbinols, N-BUTYL ACETATE, cyclohexanone and the dimethylbenzene.
10. the preparation method of a kind of bamboo charcoal base electro-magnetic screen composite material according to claim 8 is characterized in that the used organic solvent of solution B in the step 3 is one or more the combination in acetone, dimethyl formamide, two propyl carbinols, N-BUTYL ACETATE, cyclohexanone and the dimethylbenzene.
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