CN1789338A - Electricity conductive polyaniline carbon nanotube combined electromagnetic shielding composite material and its production method - Google Patents
Electricity conductive polyaniline carbon nanotube combined electromagnetic shielding composite material and its production method Download PDFInfo
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Abstract
The invention relates electromagnetic screen complex film made by electric polyaniline and carbon nano pipe and preparing method. The method comprises the following steps: dispersing the carbon nano pipe into chloroform tobacco extract mixed with 4-dodecylbenzene sulfonic acid, then mixing it with polyaniline m-cresol solution doped with camphor sulfonic acid to form filming solution, pouring the filming solution on the slide glass, getting the complex film of polyaniline and carbon nano pipe whose concentration is 5wt%-50wt% in form filming solution. The optimum electric conductivity of complex film is 212 S/cm and mechanics intensity is 14.53Mpa. When the frequency of complex film is between 106Hz and 109Hz and thickness of complex film is 20mum, the electromagnetic screen efficiency is between 35dB and 40dB. The more the electric conductivity and thickness of complex film, the higher the electromagnetic screen efficiency.
Description
Technical field
The present invention relates to be used for electromagnetic shielding and anlistatig matrix material and preparation method thereof.Be particularly related to a kind of electrically conductive polyaniline and carbon nanotube compound electromagnetic shielding composite material and preparation method thereof.
Background technology
Metal, conductive plastics (comprising coating), graphite carbon material and conduction high polymer are currently used four big class electromagnetic shielding and antistatic materials.Wire netting or bulk, as: Cu, the known material of those of ordinary skills such as Al is traditional electromagnetic shielding material, it has advantages such as high electromagnetic shielding coefficient (SE) and good mechanical property.But it is than great, perishable, poor processability (special shape) and consumption of natural resource.Graphite material is the electro-conductive material of being made through high temperature pyrolysis (800～1200 ℃) greying by resistant to elevated temperatures polymkeric substance.It has high specific conductivity, good air stability and little characteristics of proportion.But the preparation of this material needs shortcomings such as high temperature, oxygen free operation, material mechanical performance difference, and it can only be used as the conductive filler material of conductive plastics.Conductive plastics is a kind of conductive polymer composite evenly compound by organic and macromolecular material of insulating and various conductive material (Cu, graphite, carbon dust etc.) or that formation surface conduction film modes such as (metallization) makes.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 in it, improves the limitation of limited and difficult compatible electricity of specific conductivity and mechanical property.
Conduction high polymer is the type material that grows up the latter stage seventies.It has following excellent specific property: (1) specific conductivity can change (10 in isolator-semi-conductor-metallic state broad range
-7～10
5S/cm), this is that present any material is incomparable; (2) structure and physical and chemical performance are controlled; (3) can realize the multifunction of conduction high polymer by methods such as structural modification (replacement, grafting, copolymerization), blend (wet method and dry method) or doped in situ polymerizations; (4) the soluble conductive superpolymer can prepare big area and gentle bent coating or film and electro-conductive fiber or composite conducting fiber; (5) conduction high polymer is many is made of light elements such as C, H, N, O, so light specific gravity (1.0～1.2g/cm
3).Therefore, it has a tempting widely application prospect in that the energy, information, opto-electronic device, stealthy and electromagnetic shielding etc. are technical.Conduction high polymer, the especially development of soluble conductive superpolymer have promoted it in the technical research of stealthy and overall plastic absorbing material.But conduction high polymer exists processability poor, and the shortcoming that mechanical strength is not high is restricted in actual applications.(Handbook of Conducting Polymers，second edition，1997)
Summary of the invention
An object of the present invention is in order to overcome the deficiencies in the prior art, a kind of electrically conductive polyaniline and carbon nanotube compound electromagnetic shielding composite material that can improve conduction high polymer specific conductivity, mechanical property and thermostability is provided.
Another object of the present invention provides the preparation method of a kind of electrically conductive polyaniline and carbon nanotube compound electromagnetic shielding composite material.
The present invention effectively disperses and the blend film forming with electrically conductive polyaniline and inorganic carbon nanotube, by the evaluation to specific conductivity, mechanical property and thermostability, confirms that the more simple polyaniline film of acquired composite membrane all increases on every performance.
Electrically conductive polyaniline of the present invention and carbon nanotube compound electromagnetic shielding composite material are made up of carbon nanotube and electrically conductive polyaniline, and wherein the mass percent of carbon nanotube and electrically conductive polyaniline is 5%～50%.The specific conductivity of composite membrane the best is 212S/cm, and mechanical strength is 14.53Mpa, and thermostability obviously improves.This composite membrane is 10
6～10
9Between the Hz frequency, when the thickness of film was 20 μ m, its electromagnetic shielding efficiency was in 35～40dB scope, and electromagnetic shielding efficiency increases with the increase of composite membrane specific conductivity and thickness.
The preparation method of electrically conductive polyaniline of the present invention and carbon nanotube compound electromagnetic shielding composite material may further comprise the steps:
(1) adopt the method for blend even carbon nanotube to be dispersed in the chloroform extraction liquid of the adulterated polyaniline of 4-Witco 1298 Soft Acid uniform mixing; Wherein, the concentration of the adulterated polyaniline chloroform extraction of 4-Witco 1298 Soft Acid liquid is 15wt%～55wt%.
(2) solution and the adulterated polyaniline m-cresol solution of the camphorsulfonic acid uniform mixing that step (1) is doped with carbon nanotube is film-forming soln, at last film-forming soln is cast on the carrier substrate, makes the composite membrane (typical composite membrane sample as shown in Figure 1) of polyaniline and carbon nanotube by solvent evaporates; Wherein, the concentration of the adulterated polyaniline m-cresol solution of camphorsulfonic acid is 45wt%～85wt%.
The concentration of carbon nanotube in film-forming soln is 5wt%～50wt%.Mass ratio between adulterated polyaniline of 4-Witco 1298 Soft Acid and the adulterated polyaniline of camphorsulfonic acid is 3～150: 100.
Described blend method comprises ultrasonic wave, ball milling, improves the dispersiveness of carbon nanotube in solution with this.
Described film-forming soln is made of according to weight percent concentration 4-Witco 1298 Soft Acid adulterated polyaniline chloroform extraction liquid that is dispersed with carbon nanotube and the adulterated polyaniline m-cresol solution of camphorsulfonic acid.
Described carrier comprises sheet glass, conductive glass, metal sheet, plastics film or fabric etc.
Preparation method's advantage of the present invention is that it can operate at normal temperatures, and method is simple, good film-forming property, easily big area system film.The specific conductivity of composite membrane the best is 212S/cm, and mechanical strength is 14.53Mpa, and thermostability obviously improves.Theoretical Calculation shows that the composite membrane of the inventive method preparation is 10
6～10
9Between the Hz frequency, when the thickness of film was 20 μ m, its electromagnetic shielding efficiency was in 35～40dB scope, and electromagnetic shielding efficiency further increases with the increase of composite membrane specific conductivity and thickness.These data show that conduction high polymer of the present invention and carbon nanotube compound electromagnetic shielding composite material have the potential application prospect as lightweight, the bent organic electromagnetic shielding material that can soften.
Adopt the composite membrane specific conductivity under the four point probe method measurement room temperature, for example, find of the increase earlier increase of the specific conductivity of polyaniline/carbon nano-tube compound film along with content of carbon nanotubes, specific conductivity reaches maximum value 212S/cm when the content of carbon nanotube reaches 25%, and specific conductivity begins descend (seeing accompanying drawing 2) subsequently.Data in the summary accompanying drawing 3 can draw the phase transition temperature of the composite membrane specific conductivity shown in the table 1, as seen, the specific conductivity of composite membrane-temperature variation relation exists a phase transition temperature from isolator-metallic state, promptly be lower than phase transition temperature, composite membrane presents semi-conductive characteristic ( σ/ T＞0), is higher than the characteristic ( σ/ T＜0) that phase transition temperature has then shown metal.Simultaneously, the phase transition temperature of the specific conductivity of composite membrane increases (as table 1) with the increase of content of carbon nanotubes.Performance and thermostability corresponding to the polyaniline/carbon nano-tube compound film mechanics of high conductivity are tested, and compare with polyaniline film, and the mechanical property of its composite membrane is listed in the table 2.Polyaniline/carbon nano-tube compound film intensity and modulus all increase to some extent than polyaniline film as can be seen from Table 2, and elongation descends to some extent.In addition from accompanying drawing 4 as can be known the decomposition temperature of polyaniline/carbon nano-tube compound film also raise to some extent, but amplitude is little.The Theoretical Calculation of the electromagnet shield effect near field and far field shows, 10
6～10
9In the Hz range of frequency, electromagnet shield effect has surpassed 90dB during the low frequency of near field, still can remain on 40dB above (accompanying drawing 5) during high frequency.The calculation result in far field shows that the electromagnet shield effect of composite membrane has surpassed 32dB (accompanying drawing 6).No matter be near field or far field, the electromagnet shield effect of composite membrane increases along with the increase of composite membrane specific conductivity.
Conductive polymers that the application is related and carbon nano-tube compound film, improved the defective of material aspect mechanical property and workability, simultaneously, this combination is that the carbon nanotube that will conduct electricity is compounded in the conducting polymer materials, compare with traditional filling mode, be about to electro-conductive material such as carbon nanotube or conducting polymer composite and be filled in the non electrically conductive material, the prepared composite membrane of present method has novelty and using value aspect electric property and the electromagnetic shielding character more.
Description of drawings
Fig. 1. the photo of embodiment of the invention 1518cm * 18cm polyaniline/carbon nano-tube compound film.
Fig. 2. the room-temperature conductivity of polyaniline/carbon nano-tube compound film and the relation of content of carbon nanotubes.
Fig. 3. the specific conductivity-temperature dependence of polyaniline/carbon nano-tube compound film, a wherein, b, c, d, e, f are respectively the weight percent of carbon nanotube.
Fig. 4 (a). polyaniline film DSC curve.
Fig. 4 (b). the DSC curve of the carbon nano-tube compound film of embodiment 3.
Fig. 5. under the Theoretical Calculation room temperature of near field, content of carbon nanotubes not simultaneously, the electromagnetic shielding coefficient of polyaniline/carbon nano-tube compound film and the relation of frequency.Figure (b) is the enlarged view of figure (a).
Embodiment
Embodiment 1
At first adopt ultransonic method that carbon nanotube 0.0022g is dispersed among the chloroform extraction liquid 0.9g of the adulterated polyaniline of 4-Witco 1298 Soft Acid that concentration is 15wt%, the adulterated polyaniline m-cresol solution of the camphorsulfonic acid 5.1g uniform mixing that with above-mentioned solution and concentration is 85wt% then is a film-forming soln, at last film-forming soln is cast on the slide glass, by trichloromethane volatilization film forming.
Wherein, carbon nanotube mass percent concentration (CNT wt%) is 5wt%, and specific conductivity～170S/cm, phase transition temperature are 196K.
Embodiment 2
At first adopt ultransonic method that carbon nanotube 0.0072g is dispersed among the chloroform extraction liquid 0.9g of the adulterated polyaniline of 4-Witco 1298 Soft Acid that concentration is 15wt%, the adulterated polyaniline m-cresol solution of the camphorsulfonic acid 5.1g uniform mixing that with above-mentioned solution and concentration is 85wt% then is a film-forming soln, at last film-forming soln is cast on the slide glass, by trichloromethane volatilization film forming.
Wherein, carbon nanotube mass percent concentration (CNT wt%) is 15wt%, and specific conductivity～180S/cm, phase transition temperature are 215K.
Embodiment 3
At first adopt ultransonic method that carbon nanotube 0.0137g is dispersed among the chloroform extraction liquid 0.9g of the adulterated polyaniline of 4-Witco 1298 Soft Acid that concentration is 15wt%, the adulterated polyaniline m-cresol solution of the camphorsulfonic acid 5.1g uniform mixing that with above-mentioned solution and concentration is 85wt% then is a film-forming soln, at last film-forming soln is cast on the slide glass, by trichloromethane volatilization film forming.
Wherein, carbon nanotube mass percent concentration (CNT wt%) is 25wt%, and specific conductivity～210S/cm, phase transition temperature are 219K, and mechanical strength is 14.53MPa, and elongation is 6.0243%, and Young's modulus is 286.39MPa.(seeing Table 2)
Embodiment 4
At first adopt ultransonic method that carbon nanotube 0.0221g is dispersed among the chloroform extraction liquid 0.9g of the adulterated polyaniline of 4-Witco 1298 Soft Acid that concentration is 15wt%, the adulterated polyaniline m-cresol solution of the camphorsulfonic acid 5.1g uniform mixing that with above-mentioned solution and concentration is 85wt% then is a film-forming soln, at last film-forming soln is cast on the slide glass, by trichloromethane volatilization film forming.
Wherein, carbon nanotube mass percent concentration (CNT wt%) is 35wt%, and specific conductivity～150S/cm, phase transition temperature are 245K.
Embodiment 5
At first adopt ultransonic method that carbon nanotube 0.0335g is dispersed among the chloroform extraction liquid 0.9g of the adulterated polyaniline of 4-Witco 1298 Soft Acid that concentration is 15wt%, the adulterated polyaniline m-cresol solution of the camphorsulfonic acid 5.1g uniform mixing that with above-mentioned solution and concentration is 85wt% then is a film-forming soln, at last film-forming soln is cast on the slide glass, by trichloromethane volatilization film forming.
Wherein, carbon nanotube mass percent concentration (CNT wt%) is 45wt%, and specific conductivity～110S/cm, phase transition temperature are 264K.
Embodiment 6
At first adopt ultransonic method that carbon nanotube 0.0031g is dispersed among the chloroform extraction liquid 1.5g of the adulterated polyaniline of 4-Witco 1298 Soft Acid that concentration is 25wt%, the adulterated polyaniline m-cresol solution of the camphorsulfonic acid 4.5g uniform mixing that with above-mentioned solution and concentration is 75wt% then is a film-forming soln, at last film-forming soln is cast on the slide glass, by trichloromethane volatilization film forming.
Wherein, carbon nanotube mass percent concentration (CNT wt%) is 5wt%, and specific conductivity～170S/cm, phase transition temperature are 196K.
Embodiment 7
At first adopt ultransonic method that carbon nanotube 0.0105g is dispersed among the chloroform extraction liquid 1.5g of the adulterated polyaniline of 4-Witco 1298 Soft Acid that concentration is 25wt%, the adulterated polyaniline m-cresol solution of the camphorsulfonic acid 4.5g uniform mixing that with above-mentioned solution and concentration is 75wt% then is a film-forming soln, at last film-forming soln is cast on the slide glass, by trichloromethane volatilization film forming.
Wherein, carbon nanotube mass percent concentration (CNT wt%) is 15wt%, and specific conductivity～180S/cm, phase transition temperature are 215K.
Embodiment 8
At first adopt ultransonic method that carbon nanotube 0.0198g is dispersed among the chloroform extraction liquid 1.5g of the adulterated polyaniline of 4-Witco 1298 Soft Acid that concentration is 25wt%, the adulterated polyaniline m-cresol solution of the camphorsulfonic acid 4.5g uniform mixing that with above-mentioned solution and concentration is 75wt% then is a film-forming soln, at last film-forming soln is cast on the slide glass, by trichloromethane volatilization film forming.
Wherein, carbon nanotube mass percent concentration (CNT wt%) is 25wt%, and specific conductivity～210S/cm, phase transition temperature are 219K.
Embodiment 9
At first adopt ultransonic method that carbon nanotube 0.0041g is dispersed among the chloroform extraction liquid 2.1g of the adulterated polyaniline of 4-Witco 1298 Soft Acid that concentration is 35wt%, the adulterated polyaniline m-cresol solution of the camphorsulfonic acid 3.9g uniform mixing that with above-mentioned solution and concentration is 65wt% then is a film-forming soln, at last film-forming soln is cast on the slide glass, by trichloromethane volatilization film forming.
Wherein, carbon nanotube mass percent concentration (CNT wt%) is 5wt%, and specific conductivity～170S/cm, phase transition temperature are 196K.
At first adopt ultransonic method that carbon nanotube 0.0137g is dispersed among the chloroform extraction liquid 2.1g of the adulterated polyaniline of 4-Witco 1298 Soft Acid that concentration is 35wt%, the adulterated polyaniline m-cresol solution of the camphorsulfonic acid 3.9g uniform mixing that with above-mentioned solution and concentration is 65wt% then is a film-forming soln, at last film-forming soln is cast on the slide glass, by trichloromethane volatilization film forming.
Wherein, carbon nanotube mass percent concentration (CNT wt%) is 15wt%, and specific conductivity～180S/cm, phase transition temperature are 215K.
Embodiment 11
At first adopt ultransonic method that carbon nanotube 0.0051g is dispersed among the chloroform extraction liquid 2.7g of the adulterated polyaniline of 4-Witco 1298 Soft Acid that concentration is 45wt%, the adulterated polyaniline m-cresol solution of the camphorsulfonic acid 3.3g uniform mixing that with above-mentioned solution and concentration is 55wt% then is a film-forming soln, at last film-forming soln is cast on the slide glass, by trichloromethane volatilization film forming.
Wherein, carbon nanotube mass percent concentration (CNT wt%) is 5wt%, and specific conductivity～170S/cm, phase transition temperature are 196K.
Embodiment 12
At first adopt ultransonic method that carbon nanotube 0.017g is dispersed among the chloroform extraction liquid 2.7g of the adulterated polyaniline of 4-Witco 1298 Soft Acid that concentration is 45wt%, the adulterated polyaniline m-cresol solution of the camphorsulfonic acid 3.3g uniform mixing that with above-mentioned solution and concentration is 55wt% then is a film-forming soln, at last film-forming soln is cast on the slide glass, by trichloromethane volatilization film forming.
Wherein, carbon nanotube mass percent concentration (CNT wt%) is 15wt%, and specific conductivity～180S/cm, phase transition temperature are 215K.
Embodiment 13
At first adopt ultransonic method that carbon nanotube 0.0012g is dispersed among the chloroform extraction liquid 3.3g of the adulterated polyaniline of 4-Witco 1298 Soft Acid that concentration is 55wt%, the adulterated polyaniline m-cresol solution of the camphorsulfonic acid 2.7g uniform mixing that with above-mentioned solution and concentration is 45wt% then is a film-forming soln, at last film-forming soln is cast on the slide glass, by trichloromethane volatilization film forming.
Wherein, carbon nanotube mass percent concentration (CNT wt%) is 5wt%, and specific conductivity～170S/cm, phase transition temperature are 196K.
Embodiment 14
At first with carbon nanotube 0.0198g ball milling 3 hours, it is dispersed among the chloroform extraction liquid 1.5g of the adulterated polyaniline of 4-Witco 1298 Soft Acid that concentration is 25wt%, be the adulterated polyaniline m-cresol solution of the camphorsulfonic acid 4.5g ball milling 20 minutes of 75wt% then with above-mentioned solution and concentration, uniform mixing is a film-forming soln, pours into film again on sheet glass.Wherein, carbon nanotube mass percent concentration (CNT wt%) is 25wt%, and specific conductivity～210S/cm, phase transition temperature are 219K.
Embodiment 15
At first with carbon nanotube 0.0198g ball milling 3 hours, it is dispersed among the chloroform extraction liquid 1.5g of the adulterated polyaniline of 4-Witco 1298 Soft Acid that concentration is 25wt%, be the adulterated polyaniline m-cresol solution of the camphorsulfonic acid 4.5g ball milling 20 minutes of 75wt% then with above-mentioned solution and concentration, uniform mixing is a film-forming soln, pours into film again on aluminium sheet.Wherein, carbon nanotube mass percent concentration (CNT wt%) is 25wt%, and specific conductivity～210S/cm, phase transition temperature are 219K.At present, adopt this method on aluminium sheet, to prepare polyaniline/carbon nano-tube compound film of the finely dispersed 18cm of being of a size of of carbon nanotube * 18cm, see accompanying drawing 1.
Embodiment 16
At first with carbon nanotube 0.0198g ball milling 3 hours, it is dispersed among the chloroform extraction liquid 1.5g of the adulterated polyaniline of 4-Witco 1298 Soft Acid that concentration is 25wt%, be the adulterated polyaniline m-cresol solution of the camphorsulfonic acid 4.5g ball milling 20 minutes of 75wt% then with above-mentioned solution and concentration, uniform mixing is a film-forming soln, pours into film again on canvas.Wherein, carbon nanotube mass percent concentration (CNT wt%) is 25wt%, and specific conductivity～210S/cm, phase transition temperature are 219K.
Table 1
| CNTs content (Wt%) | 0％ | 5％ | 15％ | 25％ | 35％ | 45％ |
| Phase transition temperature (K) | 188 | 196 | 215 | 219 | 245 | 264 |
Table 2
| Numbering | Intensity σ (MPa) | Elongation ε (%) | Modulus (MPa) |
| PANi | 13.877 | 8.9488 | 275.34 |
| PANi-CNTs | 14.530 | 6.0243 | 286.39 |
Claims (8)
1. electrically conductive polyaniline and carbon nanotube compound electromagnetic shielding composite material, it is characterized in that: this composite membrane is made up of carbon nanotube and electrically conductive polyaniline, and wherein the mass percent of carbon nanotube and electrically conductive polyaniline is 5%～50%.
2. composite membrane according to claim 1 is characterized in that: the specific conductivity of described composite membrane is 212S/cm, and mechanical strength is 14.53Mpa.
3. composite membrane according to claim 1 and 2 is characterized in that: when the thickness of described composite membrane is 20 μ m, 10
6～10
9Between the Hz frequency, its electromagnetic shielding efficiency is in 35～40dB scope.
4. composite membrane according to claim 3 is characterized in that: described electromagnetic shielding efficiency further increases with the increase of composite membrane specific conductivity and thickness.
5. preparation method according to each described electrically conductive polyaniline of claim 1～4 and carbon nanotube compound electromagnetic shielding composite material is characterized in that described method may further comprise the steps:
(1) adopt the method for blend even carbon nanotube to be dispersed in the chloroform extraction liquid of the adulterated polyaniline of 4-Witco 1298 Soft Acid uniform mixing; Wherein, the concentration of the adulterated polyaniline chloroform extraction of 4-Witco 1298 Soft Acid liquid is 15wt%～55wt%.
(2) solution and the adulterated polyaniline m-cresol solution of the camphorsulfonic acid uniform mixing that step (1) is doped with carbon nanotube is film-forming soln, and film-forming soln is cast on the carrier substrate, makes the composite membrane of polyaniline and carbon nanotube by solvent evaporates; Wherein, the concentration of the adulterated polyaniline m-cresol solution of camphorsulfonic acid is 45wt%～85wt%.
The concentration of carbon nanotube in film-forming soln is 5wt%～50wt%, and the mass ratio between adulterated polyaniline of 4-Witco 1298 Soft Acid and the adulterated polyaniline of camphorsulfonic acid is 3～150: 100.
6. method according to claim 5 is characterized in that: described carrier comprises sheet glass, conductive glass, metal sheet, plastics film or fabric.
7. method according to claim 5 is characterized in that: described composite membrane is made up of carbon nanotube and electrically conductive polyaniline, and wherein the mass percent of carbon nanotube and electrically conductive polyaniline is 5%～50%.
8. method according to claim 5 is characterized in that: the specific conductivity of described composite membrane is 212S/cm, and mechanical strength is 14.53Mpa.
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| CN115433511B (en) * | 2022-10-21 | 2023-06-23 | 吉林大学 | Blended aqueous polyurethane-based electromagnetic shielding coating and preparation method thereof |
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