CN104403275A - Modified grapheme/thermosetting resin composite material and preparation method thereof - Google Patents
Modified grapheme/thermosetting resin composite material and preparation method thereof Download PDFInfo
- Publication number
- CN104403275A CN104403275A CN201410732443.XA CN201410732443A CN104403275A CN 104403275 A CN104403275 A CN 104403275A CN 201410732443 A CN201410732443 A CN 201410732443A CN 104403275 A CN104403275 A CN 104403275A
- Authority
- CN
- China
- Prior art keywords
- modified
- graphene
- carbon nanotube
- preparation
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a modified grapheme/thermosetting resin composite material and a preparation method thereof. The preparation method comprises the following steps: adding a hydrochloric acid doped polyaniline modified carbon nano tube to oxidized grapheme aqueous dispersion, filtering, washing and drying the reactant to obtain the modified grapheme, uniformly mixing the modified grapheme with molten resin capable of thermosetting, and solidifying the mixture, so as to obtain the modified grapheme/thermosetting resin composite material. The modified grapheme provided has a micro capacitance structure; the hydrochloric acid doped polyaniline modified carbon nano tube is loaded on the surface of the grapheme through Pi to Pi conjugation; the excellent electrical property of the grapheme is maintained; the lamellas of the grapheme are prevented from mutually contacting; the obtained modified grapheme/thermosetting resin composite material has the advantages of high dielectric constant, low dielectric loss, and low percolation threshold, and can realize control on the dielectric property of the composite material by adjusting the variation of the content of the hydrochloric acid doped polyaniline modified carbon nano tube coated on the surface of the grapheme.
Description
Technical field
The present invention relates to a kind of matrix material and preparation method thereof, particularly a kind of modified graphene/thermoset ting resin composite and preparation method thereof.
Background technology
High-k, low-dielectric loss matrix material are functional materialss important at present, have huge using value in fields such as electronics, aerospace, biomedicines.Graphene as two-dirnentional structure has huge electronic mobility, larger specific surface area, and the reinforcement of Chang Zuowei high performance polymer base composite material.Graphene/polymer matrix composite is the important kind preparing high dielectric constant material, Chinese scholars launched large quantity research to Graphene/polymer matrix composite in recent years, result shows, the agglomeration traits of Graphene is the key factor affecting the raising of matrix material specific inductivity, modification is carried out to Graphene and can effectively solve its agglomeration traits, improve the dielectric properties of matrix material.
Before the present invention makes, document (Jiwu Shang, Yihe Zhang, Li Yu, Xinglong Luan, Bo Shen, Zhilei Zhang, Fengzhu Lva and Paul K. Chu. J. Mater. Chem. A 2013; 1; 884 – 890.) report and prepare polyvinylidene fluoride-based composite with polyaniline-coated Graphene, research shows that polyaniline-coated is on the surface of Graphene, improves the dispersiveness of Graphene, and the existence of coating layer reduces the dielectric loss of material.But the specific inductivity of this material not high (specific inductivity is 11), this is because polyaniline is coated on the surface of Graphene completely, can hinder the delocalization of electronics on graphene planes, Graphene electric property is made to can not get playing.Document (Dongrui Wang, Yaru Bao, Junwei Zha, Jun Zhao, Zhimin Dang, Guohua Hu. ACS Appl. Mater. Interfaces 2012; 4; 6273 6279.) by chemical graft process polyvinyl alcohol is coated on Graphene and prepared polyvinylidene fluoride resin matrix material, polyvinyl alcohol covers and Graphene makes the percolation threshold of matrix material increase, want to obtain high-k, often need the functive of interpolation high-content (by volume, the percolation threshold of Graphene/polyvinylidene difluoride (PVDF) is 0.61%, and the percolation threshold of the coated Graphene/polyvinylidene difluoride (PVDF) of polyvinyl alcohol is 2.24%, the latter is the former 3.67 times), this is by the manufacturability of deteriorated matrix material, even other performances such as mechanical property.Similar example also occurs on polyaniline-coated Carbon Nanotube/Polymer Composite (see document: Tao Zhou; Jun-Wei Zha; Yi Hou, Dongrui Wang, Jun Zhao and ZhiMin Dang. ACS Appl. Mater. Interfaces 2011; 3 (12); 4557 – 4560.).Although polyaniline covers on the surface of carbon nanotubes, improve the specific inductivity of material and reduce dielectric loss, but when the volume fraction of the carbon nanotube of polyaniline-coated is 8%, could obtain high-k and low-dielectric loss, the carbon nanotube of the polyaniline-coated of high-content can make the processing characteristics of matrix material decline.
Therefore, research and development have the Graphene/polymer matrix composite of high-k, low-dielectric loss and low percolation threshold is a problem having major application and be worth.
Summary of the invention
The present invention is directed to the deficiency that in prior art, polymer matrix composite exists, provide a kind of and there is modified graphene/thermoset ting resin composite of high-k, low-dielectric loss and low percolation threshold and preparation method thereof.
The technical scheme realizing the object of the invention is to provide a kind of preparation method of modified graphene/thermoset ting resin composite, and step is as follows:
1, by mass, the carbon nanotube of 0.005 ~ 1 part of doped hydrochloride Polyaniline-modified is joined in 1 part of graphene oxide aqueous dispersions, being after reacting 12 ~ 24h under the condition of 60 ~ 70 DEG C in temperature, then adding 10 parts of L-AAs, is react 24 ~ 48h under the condition of 80 ~ 100 DEG C in temperature;
2, after reaction terminates, be soak 1 ~ 2h in the ammoniacal liquor of 1mol/L 500 ~ 700 parts of concentration, through suction filtration, washing, drying, obtain a kind of mixture be made up of the carbon nanotube of Graphene and doped hydrochloride Polyaniline-modified, be modified graphene;
3, by the thermal curable resin of 100 parts of molten states and 0.757 ~ 2.25 part of modified graphene Homogeneous phase mixing, after solidification treatment, a kind of modified graphene/thermoset ting resin composite is obtained.
In technical solution of the present invention, in the carbon nanotube of described doped hydrochloride Polyaniline-modified, the mass ratio of doped hydrochloride polyaniline and carbon nanotube is 0.4:1; Carbon nanotube is Single Walled Carbon Nanotube, multi-walled carbon nano-tubes or its combination.Described heat-setting resin is self heat-setting resin, comprises the one in bismaleimides and modified resin, cyanate ester resin and modified resin thereof; Or can not the resin system that forms of the resin of thermofixation and solidifying agent by self, comprise epoxy resin etc.
Technical solution of the present invention also comprises the modified graphene/thermoset ting resin composite obtained by above-mentioned preparation method.
Compared with prior art, the invention has the beneficial effects as follows:
1. the modified graphene that prepared by the present invention be by the carbon nanotube of doped hydrochloride Polyaniline-modified by π-πconjugation load on the surface of Graphene, do not destroy the conjugate planes structure of Graphene, maintain the electric property of Graphene excellence, be conducive to obtaining high-k and low percolation threshold.With this simultaneously, the carbon nanotube of doped hydrochloride Polyaniline-modified interts the sheet interlayer at Graphene, hinders contacting with each other of graphene sheet layer, decreases to be interconnected because of conductor the conductance loss caused, thus ensure that matrix material has low-dielectric loss.On the other hand, the carbon nanotube of doped hydrochloride Polyaniline-modified is carbon nanotube is core, doped hydrochloride polyaniline is the nucleocapsid structure of shell, wherein carbon nanotube and Graphene can be used as electrode, and the doped hydrochloride polyaniline insulation layer of centre is dielectric medium, therefore, modified graphene constitutes micro-capacitance structure.By modified graphene and thermosetting resin compound tense, the specific inductivity of material can be increased substantially.
2., by the adjustment to the charge capacity of carbon nanotube on graphenic surface of doped hydrochloride Polyaniline-modified, realize the control to the control of graphene dispersion and the dielectric properties of matrix material thereof.
3. the feature that the preparation method of modified graphene/thermoset ting resin composite provided by the invention has that technique is simple, environmental protection, cycle are short.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of the carbon nanotube of doped hydrochloride Polyaniline-modified in the embodiment of the present invention 1, Graphene, modified graphene.
Fig. 2 is the Raman spectrogram of the carbon nanotube of doped hydrochloride Polyaniline-modified in the embodiment of the present invention 1, Graphene, modified graphene.
Fig. 3 is the X-ray diffractogram of modified graphene prepared by the carbon nanotube of the doped hydrochloride Polyaniline-modified that embodiment 1 provides, Graphene and embodiment 1 ~ 3.
Fig. 4 is the scanning electron microscope (SEM) photograph of modified graphene prepared by the carbon nanotube of the doped hydrochloride Polyaniline-modified that embodiment 1 provides, Graphene and embodiment 1 ~ 3.
Fig. 5 is the specific conductivity histogram of modified graphene under frequency is 1Hz prepared by the carbon nanotube of the doped hydrochloride Polyaniline-modified that the embodiment of the present invention 1 provides, Graphene and embodiment 1 ~ 3.
Fig. 6 is that the specific conductivity of modified graphene/epoxy resin composite material prepared by Graphene/epoxy resin composite material of providing of comparative example 1 of the present invention and embodiment 1 ~ 3 is with change of frequency figure.
Fig. 7 is that the electric capacity of modified graphene/epoxy resin composite material prepared by Graphene/epoxy resin composite material of providing of comparative example 1 of the present invention and embodiment 1 ~ 3 is with change of frequency figure.
Fig. 8 is that the specific inductivity of modified graphene/epoxy resin composite material prepared by Graphene/epoxy resin composite material of providing of comparative example 1 of the present invention and embodiment 1 ~ 3 is with change of frequency figure.
Fig. 9 is that the dielectric loss of modified graphene/epoxy resin composite material prepared by Graphene/epoxy resin composite material of providing of comparative example 1 of the present invention and embodiment 1 ~ 3 is with change of frequency figure.
Figure 10 is that the specific conductivity of modified graphene/epoxy resin composite material under frequency 1Hz prepared of the embodiment of the present invention 1 ~ 8 is with modified graphene content figure.
Embodiment
Below in conjunction with accompanying drawing, embodiment and comparative example, technical solution of the present invention will be further described.
Embodiment 1
1, the preparation of the carbon nanotube of doped hydrochloride Polyaniline-modified
At N
2under protection, under 0 ~ 5 DEG C of condition, 1g multi-walled carbon nano-tubes is distributed in the deionized water of 500mL, adds 0.99g sodium lauryl sulphate, under agitation condition, mix 0.5h; Then add 0.4g aniline, and add 100mL hydrochloric acid soln (0.043mol/L), under agitation condition, fully mix 1h; Slow dropping 100mL ammonium persulfate solution (0.043mol/L), after dropwising, reaction 6h, after reaction terminates, through suction filtration, washing, the dry carbon nanotube obtaining Polyaniline-modified.Specific conductivity under the infrared spectrum of the carbon nanotube of prepared doped hydrochloride Polyaniline-modified, Raman spectrogram, X-ray diffractogram, scanning electron microscope (SEM) photograph, 1Hz is shown in accompanying drawing 1,2,3,4 and 5 respectively.
2, the preparation of graphite oxide
Get the ice-water bath that the mixing of 2g graphite, 1g SODIUMNITRATE and 46mL 98% vitriol oil is placed in 0 ~ 4 DEG C and stir 30min, getting 6g potassium permanganate slowly adds in above-mentioned mixed solution, temperature controls at 10 ~ 15 DEG C and stirs 2h, is then transferred to by flask in 35 DEG C of water-baths, and insulated and stirred 30min.After reaction terminates, slow dropping 92mL deionized water, and temperature is risen to 95 DEG C, insulation 15min, then add the hydrogen peroxide of 15mL 30%, after stirring 20min, add 140mL deionized water, products therefrom is 7 through centrifugal, 5% salt acid elution, deionized water wash to pH, and drying obtains graphite oxide.
3, the preparation of Graphene
Above-mentioned for 1g graphite oxide is scattered in the deionized water of 500mL, ultrasonic and stir obtain yellowish brown settled solution, adding 10g L-AA is that graphene oxide is reduced into Graphene by reductive agent, 24h is reacted at 80 DEG C, reaction terminates rear deionized water wash, suction filtration, at the dry 12h of 60 DEG C of vacuum chambers, grinding obtains Graphene.Specific conductivity under the infrared spectrum of prepared Graphene, Raman spectrogram, X-ray diffractogram, 1Hz is shown in accompanying drawing 1,2,3 and 5 respectively.
4, the preparation of modified graphene
Taking the above-mentioned graphite oxide of 1g is scattered in 500mL deionized water, stir and obtain graphene oxide dispersion after supersound process 1h, add the carbon nanotube of 0.25g doped hydrochloride Polyaniline-modified in graphene oxide dispersion, ultrasonic agitation, 12h is reacted at 60 DEG C, then 10g L-AA is added, after reacting liquid temperature being risen to 80 DEG C of reaction 24h, 1h is soaked in the ammoniacal liquor of the 1mol/L of 500mL, through suction filtration, washing, after drying, obtain modified graphene, wherein the quality of doped hydrochloride Polyaniline-modified carbon nanotube is 0.5 times of Graphene quality.Specific conductivity under the infrared spectrum of prepared modified graphene, Raman spectrogram, X-ray diffractogram, scanning electron microscope (SEM) photograph, 1Hz is shown in accompanying drawing 1,2,3,4 and 5 respectively.
5, the preparation of modified graphene/epoxy resin composite material
1.125g modified graphene and 100g bisphenol A type epoxy resin (trade mark E-51) are joined in flask, at 60 DEG C stir and after ultrasonic 1h, vacuum defoamation 30min, adds 4g 2-ethyl-4-methylimidazole, continue stir 10min, obtain uniform mixture; Mixture is poured in mould, vacuum defoamation 30min, is cured and thermal treatment according to 80 DEG C/2h+100 DEG C/2h+120 DEG C/2h and 140 DEG C/4h technique, namely obtains modified graphene/epoxy resin composite material.Its specific conductivity is respectively shown in accompanying drawing 6,7,8 and 9 with change of frequency figure, dielectric loss with change of frequency figure with change of frequency figure, specific inductivity with change of frequency figure, electric capacity.
See accompanying drawing 1, it is the infrared spectrum of the carbon nanotube of the doped hydrochloride Polyaniline-modified that the present embodiment provides, Graphene, modified graphene, for the spectral line of the carbon nanotube of doped hydrochloride Polyaniline-modified, is 1290cm in wave number
-1the characteristic peak at place belongs to the C-N key in polyaniline, indicates the success of doped hydrochloride polyaniline on the surface of carbon nanotubes coated.In the spectrogram of modified graphene, quinone ring C=C stretching vibration (1569 cm of polyaniline are there are
-1), the C=C of phenyl ring vibrates (1492 cm
-1) and secondary amine N-H vibrate (1124 cm
-1) characteristic peak, show that the carbon nanotube of doped hydrochloride Polyaniline-modified has been coated on Graphene.
See accompanying drawing 2, it is the Raman spectrogram of the carbon nanotube of the doped hydrochloride Polyaniline-modified that the present embodiment provides, Graphene, modified graphene, has occurred that G is with peak (1576cm in the spectral line of Graphene
-1) and D band peak (1315 cm-
-1).G band represents the SP of graphenic surface
2the carbon atom of hybrid structure, and D band represents in Graphene due to sp
3unordered and the defect structure that hydridization causes, the strength ratio of G band and D band, represents the change of graphenic surface chemical environment.Compared with the spectrogram of Graphene, the G of the Raman spectrogram of modified graphene is with the Raman shift at peak to be increased to 1586 cm
-1, absorption peak there occurs blue shift, and its reason is that the electronic cloud between the carbon nanotube of doped hydrochloride Polyaniline-modified and Graphene interacts and causes, and has strong π-π reactive force between the carbon nanotube showing Graphene and doped hydrochloride Polyaniline-modified.Being with the G of Graphene is with the strength ratio at peak (0.84) to compare with D, and the G of modified graphene is with and the strength ratio of D band brings up to 0.98, shows the sp of the Graphene in modified graphene
2hybrid structure increases.Its reason is that the carbon nanotube of doped hydrochloride Polyaniline-modified covers on Graphene, and the conjugated structure on polyaniline and the conjugated structure on graphenic surface define π-π reactive force.Owing to there is not chemical reaction with Graphene, fail to increase the sp on graphenic surface
3structure, so the increase not causing the disordered structure (D band) of modified graphene.
Embodiment 2
1, the preparation of modified graphene
Taking 1g graphite oxide (embodiment 1 provides) is scattered in 500mL deionized water, stir and obtain graphene oxide dispersion after supersound process 1h, add the carbon nanotube (embodiment 1 provides) of 0.50g doped hydrochloride Polyaniline-modified in graphene oxide dispersion, ultrasonic agitation, 12h is reacted at 60 DEG C, then 10g L-AA is added, after reacting liquid temperature being risen to 80 DEG C of reaction 24h, 1h is soaked in the ammoniacal liquor of the 1mol/L of 500mL, through suction filtration, washing, after drying, obtain the carbon mano-tube composite of Graphene-doped hydrochloride Polyaniline-modified, wherein the quality of the carbon nanotube of doped hydrochloride Polyaniline-modified is 1 times of Graphene quality.Specific conductivity under the X-ray diffractogram of prepared Graphene modified graphene, scanning electron microscope (SEM) photograph, 1Hz is shown in accompanying drawing 3,4 and 5 respectively.
2, the preparation of modified graphene/epoxy resin composite material
1.5g modified graphene and 100g epoxy resin (trade mark E-51) are joined in flask, at 60 DEG C stir and after ultrasonic 1h, vacuum defoamation 30min, adds 4g 2-ethyl-4-methylimidazole, continue stir 10min, obtain uniform mixture; Mixture is poured in mould, vacuum defoamation 20min, carries out thermofixation according to 80 DEG C/2h+100 DEG C/2h+120 DEG C/2h and 140 DEG C/4h technique, namely obtain modified graphene/epoxy resin composite material.Its specific conductivity is respectively shown in accompanying drawing 6,7,8 and 9 with change of frequency figure, dielectric loss with change of frequency figure with change of frequency figure, specific inductivity with change of frequency figure, electric capacity.
Embodiment 3
1, the preparation of modified graphene
Taking 1g graphite oxide (embodiment 1 provides) is scattered in 500mL deionized water, stir and obtain graphene oxide dispersion after supersound process 1h, add the carbon nanotube (embodiment 1) of 1.0g doped hydrochloride Polyaniline-modified in graphene oxide dispersion, ultrasonic agitation, 12h is reacted at 60 DEG C, then 10g L-AA is added, after reacting liquid temperature being risen to 80 DEG C of reaction 24h, 1h is soaked in the ammoniacal liquor of the 1mol/L of 500mL, through suction filtration, washing, after drying, obtain modified graphene, wherein the quality of the carbon nanotube of doped hydrochloride Polyaniline-modified is 2 times of Graphene quality.Specific conductivity under the X-ray diffractogram of prepared modified graphene, scanning electron microscope (SEM) photograph, 1Hz is shown in accompanying drawing 3,4 and 5 respectively.
2, the preparation of modified graphene/epoxy resin composite material
2.25g modified graphene and 100g epoxy resin (trade mark E-51) are joined in flask, at 60 DEG C stir and after ultrasonic 1h, vacuum defoamation 30min, adds 4g 2-ethyl-4-methylimidazole, continue stir 10min, obtain uniform mixture; Mixture is poured in mould, vacuum defoamation 20min, carries out thermofixation according to 80 DEG C/2h+100 DEG C/2h+120 DEG C/2h and 140 DEG C/4h technique, namely obtain modified graphene/epoxy resin composite material.Its specific conductivity is respectively shown in accompanying drawing 6,7,8,9 and 10 with change of frequency figure, dielectric loss with the specific conductivity under change of frequency figure, frequency 1Hz with change of frequency figure, specific inductivity with change of frequency figure, electric capacity.
See accompanying drawing 3, it is the X-ray diffractogram of modified graphene prepared by the carbon nanotube of the Polyaniline-modified that the embodiment of the present invention 1 provides, Graphene and embodiment 1 ~ 3.For the carbon nanotube spectrogram of doped hydrochloride Polyaniline-modified, correspond to the complete graphite-structure of carbon nanotube at the peak that diffraction angle is 25.8 ° of places, and the peak at 19.5 ° of places is the diffraction peak of polyaniline.Graphene shows wider diffraction peak at 24.5 ° of places, this is because Graphene is obtained by chemistry redox method, reduces the conjugated structure on its surface.And modified graphene shows narrower diffraction peak at 24.5 ° of places in embodiment 1 ~ 3, the conjugated degree indicating Graphene increases, this is because the carbon nanotube of doped hydrochloride Polyaniline-modified and Graphene are acted on by π-π be coated on its surface.
See accompanying drawing 4, it is the scanning electron microscope (SEM) photograph of modification prepared by the carbon nanotube of the doped hydrochloride Polyaniline-modified that the embodiment of the present invention 1 provides, Graphene and embodiment 1 ~ 3.Can find out, for the carbon nanotube of doped hydrochloride Polyaniline-modified, doped hydrochloride polyaniline particles is coated on the surface of carbon nanotube.The lamella of Graphene by the carbon nanotube of doped hydrochloride Polyaniline-modified separately, hinders contacting with each other of sheet interlayer, reaches the agglomeration traits solving Graphene.
See accompanying drawing 5, it is the specific conductivity histogram of modified graphene under frequency is 1Hz prepared by the carbon nanotube of the doped hydrochloride Polyaniline-modified that the embodiment of the present invention 1 provides, Graphene and embodiment 1 ~ 3.Can see, the specific conductivity of the carbon nanotube of doped hydrochloride Polyaniline-modified is suitable with the specific conductivity of Graphene, and when the carbon nanotube covering amount along with doped hydrochloride Polyaniline-modified increases on Graphene, the specific conductivity of its modified graphene increases.Indicate the carbon nanotube loaded on graphenic surface of doped hydrochloride Polyaniline-modified, do not reduce the electric property of Graphene.
The performance analysis of comprehensive accompanying drawing 1,2,3,4 and 5, modified graphene prepared by the present invention has the controlled feature of the covering amount of the carbon nanotube of doped hydrochloride Polyaniline-modified, by the content of the carbon nanotube controlling doped hydrochloride Polyaniline-modified, the surface of Graphene is not completely covered, reaches the uncrossed object of π-electron delocalization of graphenic surface; And the sheet interlayer that the carbon nanotube of doped hydrochloride Polyaniline-modified interts at Graphene, solve the agglomeration traits of Graphene.In addition, the carbon nanotube of doped hydrochloride Polyaniline-modified has excellent electric property, by π-πconjugation load on Graphene, maintains the electric property of Graphene self excellence.
The preparation of comparative example 1 Graphene/epoxy resin composite material
0.75g Graphene (embodiment 1) and 100g epoxy resin (trade mark E-51) are joined in flask, at 60 DEG C stir and after ultrasonic 1h, vacuum defoamation 30min, adds 4g 2-ethyl-4-methylimidazole, continue stir 10min, obtain uniform mixture; Mixture is poured in mould, vacuum defoamation 30min, is cured and thermal treatment according to 80 DEG C/2h+100 DEG C/2h+120 DEG C/2h and 140 DEG C/4h technique, namely obtains Graphene/epoxy resin composite material.Its specific conductivity is respectively shown in accompanying drawing 6,7,8 and 9 with change of frequency figure, dielectric loss with change of frequency figure with change of frequency figure, specific inductivity with change of frequency figure, electric capacity.
See accompanying drawing 6, it is that the specific conductivity of the modified graphene/epoxy resin composite material that Graphene/epoxy resin composite material of providing of comparative example 1 of the present invention and embodiment 1 ~ 3 provide is with frequency variation curve.As seen from the figure, the specific conductivity of modified graphene/epoxy resin composite material is lower than the specific conductivity of Graphene/epoxy resin composite material, this is because Graphene is separated by the polyaniline insulated, carbon nanotube loaded the reducing on Graphene demonstrating doped hydrochloride Polyaniline-modified wears electric current between contiguous Graphene then, thus makes modified graphene/epoxy resin have lower specific conductivity.On the other hand, along with the increase of the content of carbon nanotubes of doped hydrochloride Polyaniline-modified, in embodiment 1 ~ 3, modified graphene/epoxy resin composite material specific conductivity presents the trend increased progressively.Learnt that by accompanying drawing 5 specific conductivity of the conductance of the carbon nanotube of doped hydrochloride Polyaniline-modified and graphene powder is suitable, so, along with the increase of the content of carbon nanotubes of doped hydrochloride Polyaniline-modified, the specific conductivity of modified graphene/epoxy resin composite material also can increase thereupon, demonstrates the performance that can be controlled modified graphene/epoxy resin composite material by the content changing the carbon nanotube of doped hydrochloride Polyaniline-modified on Graphene.
See accompanying drawing 7, it is that the electric capacity of the modified graphene/epoxy resin composite material that Graphene/epoxy resin composite material of providing of comparative example 1 of the present invention and embodiment 1 ~ 3 provide is with frequency variation curve.As seen from the figure, the electric capacity of modified graphene/epoxy resin composite material is higher than the electric capacity of Graphene/epoxy resin composite material.This is because the carbon nanotube of graphenic surface load doped hydrochloride Polyaniline-modified, wherein the carbon nanotube of doped hydrochloride Polyaniline-modified to take carbon nanotube as core, forming nucleocapsid structure at its Surface coating doped hydrochloride polyaniline, is therefore a kind of nucleocapsid structure with conductor@insulation layer.The modified graphene that this conductor loading being coated with isolator obtains on Graphene is constituted micro-capacitance structure, and wherein carbon nanotube and Graphene are electrode, and middle doped hydrochloride polyaniline insulation layer is dielectric medium.Micro-electric capacity number in modified graphene/epoxy resin composite material is more, also more favourable for acquisition high-k.
See accompanying drawing 8, it is the change curve of specific inductivity with frequency of the modified graphene/epoxy resin composite material that Graphene/epoxy resin composite material of providing of comparative example 1 of the present invention and embodiment 1 ~ 3 provide.As seen from the figure, the specific inductivity of modified graphene mixture/epoxy resin composite material in whole range of frequency is higher than Graphene/epoxy resin composite material, if embodiment 2 is under 100Hz, its specific inductivity can reach 210, its value is 3 times of Graphene/epoxy resin (68), this is because have a large amount of micro-capacitance structures in modified graphene/epoxy resin composite material, impel the increase of its specific inductivity, shown to there is significant application prospect with the Graphene of the carbon nano-tube modification of doped hydrochloride Polyaniline-modified preparing in high dielectric constant material.
See accompanying drawing 9, it is that the dielectric loss of the modified graphene/epoxy resin composite material that Graphene/epoxy resin composite material of providing of comparative example 1 of the present invention and embodiment 1 ~ 3 provide is with frequency variation curve.Graphene/epoxy resin composite material prepared by comparative example 1 has very high dielectric loss, if the dielectric loss of the Graphene/matrix material under 100Hz is up to 9.2.And the dielectric loss of modified graphene/epoxy resin composite material prepared by embodiment 1 ~ 3 obviously reduces.This is because the carbon nanotube of doped hydrochloride Polyaniline-modified interts between graphene sheet layer, because doped hydrochloride polyaniline insulation layer has completely cut off contacting with each other between graphene sheet layer, hinder electronics running through between conductor graphite alkene, thus cause the reduction of the dielectric loss of modified graphene/epoxy resin composite material, show that the Graphene of the carbon nano-tube modification of doped hydrochloride Polyaniline-modified has outstanding advantage preparing in low-dielectric loss matrix material.
The data analysis of comprehensive accompanying drawing 6,7,8 and 9, the Graphene of the carbon nano-tube modification of doped hydrochloride Polyaniline-modified is joined the specific inductivity that can improve matrix material in resin, and reduce its dielectric loss, there is significant advantage preparing in high-k and low-dielectric loss matrix material.
Embodiment 4
1, the preparation of modified graphene
Taking 1g graphite oxide (embodiment 1 provides) is scattered in 500mL deionized water, stir and obtain graphene oxide dispersion after supersound process 1h, add the carbon nanotube (embodiment 1 provides) of 0.005g doped hydrochloride Polyaniline-modified in graphene oxide dispersion, ultrasonic agitation, reacts 12h at 60 DEG C, then 10g L-AA is added, after reacting liquid temperature being risen to 80 DEG C of reaction 24h, through suction filtration, washing, after drying, obtain modified graphene.
2, the preparation of modified graphene/epoxy resin composite material
0.757g modified graphene and 100g epoxy resin (trade mark E-51) are joined in flask, at 60 DEG C stir and after ultrasonic 1h, vacuum defoamation 30min, adds 4g 2-ethyl-4-methylimidazole, continue stir 10min, obtain uniform mixture; Mixture is poured in mould, vacuum defoamation 20min, carries out thermofixation according to 80 DEG C/2h+100 DEG C/2h+120 DEG C/2h and 140 DEG C/4h technique, namely obtain modified graphene/epoxy resin composite material.Specific conductivity under its frequency 1Hz is shown in accompanying drawing 10.
Embodiment 5
1, the preparation of modified graphene
Taking 1g graphite oxide (embodiment 1 provides) is scattered in 500mL deionized water, stir and obtain graphene oxide dispersion after supersound process 1h, add the carbon nanotube (embodiment 1 provides) of 0.025g doped hydrochloride Polyaniline-modified in graphene oxide dispersion, ultrasonic agitation, 12h is reacted at 60 DEG C, then 10g L-AA is added, after reacting liquid temperature being risen to 80 DEG C of reaction 24h, 1h is soaked in the ammoniacal liquor of the 1mol/L of 500mL, through suction filtration, washing, after drying, obtains modified graphene.
2, the preparation of modified graphene/epoxy resin composite material
0.787g modified graphene and 100g epoxy resin (trade mark E-51) are joined in flask, at 60 DEG C stir and after ultrasonic 1h, vacuum defoamation 30min, adds 4g 2-ethyl-4-methylimidazole, continue stir 10min, obtain uniform mixture; Mixture is poured in mould, vacuum defoamation 20min, carries out thermofixation according to 80 DEG C/2h+100 DEG C/2h+120 DEG C/2h and 140 DEG C/4h technique, namely obtain modified graphene/epoxy resin composite material.Specific conductivity under its frequency 1Hz is shown in accompanying drawing 10.
Embodiment 6
1, the preparation of modified graphene
Taking 1g graphite oxide (embodiment 1 provides) is scattered in 500mL deionized water, stir and obtain graphene oxide dispersion after supersound process 1h, add the carbon nanotube (embodiment 1 provides) of 0.05g doped hydrochloride Polyaniline-modified in graphene oxide dispersion, ultrasonic agitation, 12h is reacted at 60 DEG C, then 10g L-AA is added, after reacting liquid temperature being risen to 80 DEG C of reaction 24h, 1h is soaked in the ammoniacal liquor of the 1mol/L of 500mL, through suction filtration, washing, after drying, obtains modified graphene.
2, the preparation of modified graphene/epoxy resin composite material
0.825g modified graphene and 100g epoxy resin (trade mark E-51) are joined in flask, at 60 DEG C stir and after ultrasonic 1h, vacuum defoamation 30min, adds 4g 2-ethyl-4-methylimidazole, continue stir 10min, obtain uniform mixture; Mixture is poured in mould, vacuum defoamation 20min, carries out thermofixation according to 80 DEG C/2h+100 DEG C/2h+120 DEG C/2h and 140 DEG C/4h technique, namely obtain modified graphene/epoxy resin composite material.Specific conductivity under its frequency 1Hz is shown in accompanying drawing 10.
Embodiment 7
1, the preparation of modified graphene
Taking 1g graphite oxide (embodiment 1 provides) is scattered in 500mL deionized water, stir and obtain graphene oxide dispersion after supersound process 1h, add the carbon nanotube (embodiment 1 provides) of 0.10g doped hydrochloride Polyaniline-modified in graphene oxide dispersion, ultrasonic agitation, 12h is reacted at 60 DEG C, then 10g L-AA is added, after reacting liquid temperature being risen to 80 DEG C of reaction 24h, 1h is soaked in the ammoniacal liquor of the 1mol/L of 500mL, through suction filtration, washing, after drying, obtains modified graphene.
2, the preparation of modified graphene/epoxy resin composite material
1.30g modified graphene and 100g epoxy resin (trade mark E-51) are joined in flask, at 60 DEG C stir and after ultrasonic 1h, vacuum defoamation 30min, adds 4g 2-ethyl-4-methylimidazole, continue stir 10min, obtain uniform mixture; Mixture is poured in mould, vacuum defoamation 20min, carries out thermofixation according to 80 DEG C/2h+100 DEG C/2h+120 DEG C/2h and 140 DEG C/4h technique, namely obtain modified graphene/epoxy resin composite material.Specific conductivity under its frequency 1Hz is shown in accompanying drawing 10.
Embodiment 8
1, the preparation of modified graphene
Taking 1g graphite oxide (embodiment 1 provides) is scattered in 500mL deionized water, stir and obtain graphene oxide dispersion after supersound process 1h, add the carbon nanotube (embodiment 1 provides) of 0.20g doped hydrochloride Polyaniline-modified in graphene oxide dispersion, ultrasonic agitation, 12h is reacted at 60 DEG C, then 10g L-AA is added, after reacting liquid temperature being risen to 80 DEG C of reaction 24h, 1h is soaked in the ammoniacal liquor of the 1mol/L of 500mL, through suction filtration, washing, after drying, obtains modified graphene.
2, the preparation of modified graphene/epoxy resin composite material
1.05g modified graphene and 100g epoxy resin (trade mark E-51) are joined in flask, at 60 DEG C stir and after ultrasonic 1h, vacuum defoamation 30min, adds 4g 2-ethyl-4-methylimidazole, continue stir 10min, obtain uniform mixture; Mixture is poured in mould, vacuum defoamation 20min, carries out thermofixation according to 80 DEG C/2h+100 DEG C/2h+120 DEG C/2h and 140 DEG C/4h technique, namely obtain modified graphene/epoxy resin composite material.Specific conductivity under its frequency 1Hz is shown in accompanying drawing 10.
See accompanying drawing 10, it be in the present embodiment 1-8 the specific conductivity of modified graphene/epoxy resin composite material under frequency 1Hz with modified graphene content graphic representation, ask calculate percolation threshold (
f c) be plotted in illustration.Therefrom known, the percolation threshold of modified graphene/epoxy resin composite material
f cbe only 1.10% of resin quality, when demonstrating modified graphene as functional stuffing, just can prepare the matrix material of high-k, low-dielectric loss when low levels.
Embodiment 9
1, the preparation of doped hydrochloride Polyaniline-modified carbon nanotube
At N
2under protection, at 0 ~ 5 DEG C, 1g Single Walled Carbon Nanotube is distributed in the deionized water of 600mL, adds 0.99g sodium lauryl sulphate, under agitation condition, mix 40min; Then add 0.4g aniline, and add 50mL hydrochloric acid soln (0.086 mol/L), under agitation condition, fully mix 1h; Slow dropping 50mL ammonium persulfate solution (0.086mol/L), after dropwising, reaction 6h, after reaction terminates, through suction filtration, washing, the dry carbon nanotube obtaining doped hydrochloride Polyaniline-modified.
2, the preparation of modified graphene
Taking 1g graphite oxide (embodiment 1 provides) is scattered in 550mL deionized water, stirs and obtains graphene oxide dispersion after supersound process 1h; The carbon nanotube of 0.15g doped hydrochloride Polyaniline-modified the present embodiment step 1 prepared joins in graphene oxide dispersion, ultrasonic agitation, 15h is reacted at 65 DEG C, then add 10g L-AA, after reacting liquid temperature being risen to 80 DEG C of reaction 48h, in the ammoniacal liquor of the 1mol/L of 500mL, soak 1h, through suction filtration, washing, after drying, obtains modified graphene.
3, the preparation of modified graphene/cyanate composite material
0.975g modified graphene and 100g bisphenol A cyanate ester are joined in flask, stir 2h at 150 DEG C after, obtains uniform mixture; Mixture is poured into mould and vacuumizes 0.5h at 140 DEG C, carry out thermofixation according to 160 DEG C/2h+180 DEG C/2h+200 DEG C/2h and 240 DEG C/6h technique, namely obtain modified graphene/cyanate ester resin composite material.
Embodiment 10
1, the preparation of doped hydrochloride Polyaniline-modified carbon nanotube
At N
2under protection, at 0 ~ 5 DEG C, the composition of 1g Single Walled Carbon Nanotube and multi-walled carbon nano-tubes is distributed in the deionized water of 700mL, adds 0.99g sodium lauryl sulphate, under agitation condition, mix 50min; Then add 0.4g aniline, and add 50mL hydrochloric acid soln (0.086 mol/L), under agitation condition, fully mix 1h; Slow dropping 50mL ammonium persulfate solution (0.086mol/L), after dropwising, reaction 8h, after reaction terminates, through suction filtration, washing, the dry carbon nanotube obtaining doped hydrochloride Polyaniline-modified.
2, the preparation of modified graphene
Taking 1g graphite oxide (embodiment 1 provides) is scattered in 600mL deionized water, stir and obtain graphene oxide dispersion after supersound process 1h, add the carbon nanotube of the 0.40g doped hydrochloride Polyaniline-modified of the present embodiment step 1 preparation in graphene oxide dispersion, ultrasonic agitation, 20h is reacted at 70 DEG C, then 10g L-AA is added, after reacting liquid temperature being risen to 90 DEG C of reaction 30h, 2h is soaked in the ammoniacal liquor of the 1mol/L of 600mL, through suction filtration, washing, after drying, obtains modified graphene.
The preparation of 3, modified graphene/ethylene rhodanate/epoxide resin matrix material
1.35g modified graphene, 90g bisphenol A cyanate ester, 10g epoxy resin are joined in flask, stir 2h at 150 DEG C after, obtains uniform mixture; Mixture is poured into mould and vacuumizes 0.5h at 140 DEG C, carry out thermofixation according to 160 DEG C/2h+180 DEG C/2h+200 DEG C/2h and 240 DEG C/4h technique, namely obtain modified graphene/ethylene rhodanate/epoxide resin matrix material.
Embodiment 11
1, the preparation of doped hydrochloride Polyaniline-modified carbon nanotube
At N
2under protection, under the temperature condition of 0 ~ 5 DEG C, 1g Single Walled Carbon Nanotube is distributed in the deionized water of 800mL, adds 0.99g sodium lauryl sulphate, under agitation condition, mix 1h; Then add 0.4g aniline, and add 50mL hydrochloric acid soln (0.086 mol/L), under agitation condition, fully mix 2h; Slow dropping 50mL ammonium persulfate solution (0.086mol/L), after dropwising, reaction 10h, after reaction terminates, through suction filtration, washing, the dry carbon nanotube obtaining doped hydrochloride Polyaniline-modified.
2, the preparation of modified graphene
Taking 1g graphite oxide (embodiment 1 provides) is scattered in 600mL deionized water, stir and obtain graphene oxide dispersion after supersound process 1h, add the carbon nanotube of the 0.70g doped hydrochloride Polyaniline-modified of the present embodiment step 1 preparation in graphene oxide dispersion, ultrasonic agitation, 24h is reacted at 70 DEG C, then 10g L-AA is added, after reacting liquid temperature being risen to 95 DEG C of reaction 24h, 2h is soaked in the ammoniacal liquor of the 1mol/L of 650mL, through suction filtration, washing, after drying, obtains modified graphene.
The preparation of 3, modified graphene/Bismaleimide-Cyanate Ester Resin matrix material
By 1.80g modified graphene, 54g N, N-4,4 '-diphenyl methane dimaleimide, 10g bisphenol A cyanate ester and 36g 0,0 '-diallyl bisphenol joins in flask, stir and ultrasonic 40min at 140 DEG C, namely obtain modified graphene/Bismaleimide-Cyanate Ester Resin mixture.Mixture is poured into mould and vacuumizes 0.5h at 140 DEG C, carry out thermofixation according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h and 220 DEG C/8h technique, namely obtain modified graphene/Bismaleimide-Cyanate Ester Resin matrix material.
Embodiment 12
1, the preparation of doped hydrochloride Polyaniline-modified carbon nanotube
At N
2under protection, under the temperature condition of 0 ~ 5 DEG C, 1g multi-walled carbon nano-tubes is distributed in the deionized water of 800mL, adds 0.99g sodium lauryl sulphate, under agitation condition, mix 0.5h; Then add 0.4g aniline, and add 50mL hydrochloric acid soln (0.086 mol/L), under agitation condition, fully mix 2h; Slow dropping 100mL ammonium persulfate solution (0.043mol/L), after dropwising, reaction 12h, after reaction terminates, through suction filtration, washing, the dry carbon nanotube obtaining doped hydrochloride Polyaniline-modified.
2, the preparation of modified graphene
Taking 1g graphite oxide is scattered in 600mL deionized water, stir and obtain graphene oxide dispersion after supersound process 1h, adding the carbon nanotube of the 0.90g doped hydrochloride Polyaniline-modified of the present embodiment step 1 preparation in graphene oxide dispersion, ultrasonic agitation, 24h is reacted at 70 DEG C, then add 10g L-AA, after reacting liquid temperature being risen to 100 DEG C of reaction 24h, in the ammoniacal liquor of the 1mol/L of 700mL, soak 2h, through suction filtration, washing, after drying, obtains modified graphene.
3, the preparation of modified graphene/bismaleimide resin composite material
By 2.1g modified graphene, 70g N, N-4,4 '-diphenyl methane dimaleimide, 30g 0,0 '-diallyl bisphenol joins in flask, at 130 DEG C, stir 45min, namely obtains modified graphene/bimaleimide resin mixture.Mixture is poured into mould and vacuumizes 0.5h at 130 DEG C, carry out thermofixation according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h and 220 DEG C/8h technique, namely obtain modified graphene/bismaleimide resin composite material.
Claims (7)
1. a preparation method for modified graphene/thermoset ting resin composite, is characterized in that comprising the steps:
(1) by mass, the carbon nanotube of 0.005 ~ 1 part of doped hydrochloride Polyaniline-modified is joined in 1 part of graphene oxide aqueous dispersions, being react 12 ~ 24h under the condition of 60 ~ 70 DEG C in temperature, then adding 10 parts of L-AAs, is react 24 ~ 48h under the condition of 80 ~ 100 DEG C in temperature;
(2), after reaction terminates, be soak 1 ~ 2h in the ammoniacal liquor of 1mol/L 500 ~ 700 parts of concentration, through suction filtration, washing, drying, obtain a kind of mixture be made up of the carbon nanotube of Graphene and doped hydrochloride Polyaniline-modified, be modified graphene;
(3) by the thermal curable resin of 100 parts of molten states and 0.757 ~ 2.25 part of modified graphene Homogeneous phase mixing, after solidification treatment, a kind of modified graphene/thermoset ting resin composite is obtained.
2. the preparation method of a kind of modified graphene/thermosetting resin according to claim 1, is characterized in that: in the carbon nanotube of described doped hydrochloride Polyaniline-modified, the mass ratio of doped hydrochloride polyaniline and carbon nanotube is 0.4:1.
3. the preparation method of a kind of modified graphene/thermosetting resin according to claim 1 and 2, is characterized in that: described carbon nanotube is Single Walled Carbon Nanotube, multi-walled carbon nano-tubes or its combination.
4. the preparation method of a kind of modified graphene/thermosetting resin according to claim 1, is characterized in that: described heat-setting resin is self heat-setting resin; Or can not the resin system that forms of the resin of thermofixation and solidifying agent by self.
5. the preparation method of a kind of modified graphene/thermoset ting resin composite according to claim 4, it is characterized in that: self described heat-setting resin comprises the one in bismaleimides and modified resin, cyanate ester resin and modified resin thereof, or their arbitrary combination.
6. the preparation method of a kind of modified graphene/thermoset ting resin composite according to claim 4, is characterized in that: described can not comprise epoxy resin by the resin system that forms of the resin of thermofixation and solidifying agent by self.
7. modified graphene/the thermoset ting resin composite obtained by preparation method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410732443.XA CN104403275B (en) | 2014-12-06 | 2014-12-06 | A kind of modified graphene/thermoset ting resin composite and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410732443.XA CN104403275B (en) | 2014-12-06 | 2014-12-06 | A kind of modified graphene/thermoset ting resin composite and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104403275A true CN104403275A (en) | 2015-03-11 |
| CN104403275B CN104403275B (en) | 2017-08-11 |
Family
ID=52640949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410732443.XA Active CN104403275B (en) | 2014-12-06 | 2014-12-06 | A kind of modified graphene/thermoset ting resin composite and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104403275B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104804159A (en) * | 2015-05-04 | 2015-07-29 | 芜湖市宝艺游乐科技设备有限公司 | Graphene oxide melamine resin and preparation method thereof |
| CN104845009A (en) * | 2015-05-19 | 2015-08-19 | 中国科学院化学研究所 | Fluorine resin/graphene composite material with isolation structure and preparation method and application thereof |
| CN105062070A (en) * | 2015-09-07 | 2015-11-18 | 苏州大学 | Polyion liquid modified graphene/thermosetting resin composite and preparation method thereof |
| CN105330857A (en) * | 2015-11-19 | 2016-02-17 | 浙江大学 | Preparation method of PANI (polyaniline)-GO (graphene oxide)-CNTs (carbon nanotubes) composited electromagnetic shielding material |
| CN105912759A (en) * | 2016-04-06 | 2016-08-31 | 清华大学 | Calculating method for determining percolation threshold of voltage-sensitive micro-balloons in nonlinear insulating material |
| CN106098400A (en) * | 2016-06-30 | 2016-11-09 | 合肥工业大学 | A kind of aminooimidazole Ionic Liquid Modified graphene nanometer sheet/composite polyethylene material and preparation method thereof |
| CN106810818A (en) * | 2015-11-30 | 2017-06-09 | 航天特种材料及工艺技术研究所 | A kind of Graphene modified epoxy and preparation method thereof |
| CN107057006A (en) * | 2017-05-25 | 2017-08-18 | 成都新柯力化工科技有限公司 | A kind of thermosetting phenolic resin special graphite alkene mother liquor and preparation method |
| CN107573645A (en) * | 2017-09-06 | 2018-01-12 | 深圳市峰泳科技有限公司 | A kind of built-in high-k flexible resin composite and its preparation method and application |
| CN108219368A (en) * | 2016-12-21 | 2018-06-29 | 南京中赢纳米新材料有限公司 | It is a kind of to modify nano-carbon material to strengthen the method for epoxy resin-base composite material |
| CN110079087A (en) * | 2019-05-07 | 2019-08-02 | 中国电子科技集团公司第三十八研究所 | A kind of modified nano graphite/cyanate composite material, preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103680973A (en) * | 2012-09-14 | 2014-03-26 | 海洋王照明科技股份有限公司 | Polyaniline/graphene/carbon nanotube composite and preparation method thereof, as well as electrode plate and capacitor |
| CN103772975A (en) * | 2012-10-25 | 2014-05-07 | 黑龙江鑫达企业集团有限公司 | Graphene/polymer conductive composite material |
| CN103937240A (en) * | 2014-04-21 | 2014-07-23 | 苏州大学 | Modified graphene/thermosetting resin composite material and preparation method thereof |
-
2014
- 2014-12-06 CN CN201410732443.XA patent/CN104403275B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103680973A (en) * | 2012-09-14 | 2014-03-26 | 海洋王照明科技股份有限公司 | Polyaniline/graphene/carbon nanotube composite and preparation method thereof, as well as electrode plate and capacitor |
| CN103772975A (en) * | 2012-10-25 | 2014-05-07 | 黑龙江鑫达企业集团有限公司 | Graphene/polymer conductive composite material |
| CN103937240A (en) * | 2014-04-21 | 2014-07-23 | 苏州大学 | Modified graphene/thermosetting resin composite material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| XIANGJUN LU ET AL.: "Fabrication and electrochemical capacitance of hierarchical graphene/polyaniline/carbon nanotube ternary composite film", 《ELECTROCHIMICA ACTA》 * |
| 魏从杰: "聚苯胺基复合物的制备及其电化学性能研究", 《中国优秀硕士学位论文全文数据库 工程科技II辑》 * |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104804159A (en) * | 2015-05-04 | 2015-07-29 | 芜湖市宝艺游乐科技设备有限公司 | Graphene oxide melamine resin and preparation method thereof |
| CN104845009B (en) * | 2015-05-19 | 2018-03-23 | 中国科学院化学研究所 | Fluororesin/graphene composite material with isolation structure and preparation method and application |
| CN104845009A (en) * | 2015-05-19 | 2015-08-19 | 中国科学院化学研究所 | Fluorine resin/graphene composite material with isolation structure and preparation method and application thereof |
| CN105062070A (en) * | 2015-09-07 | 2015-11-18 | 苏州大学 | Polyion liquid modified graphene/thermosetting resin composite and preparation method thereof |
| CN105330857A (en) * | 2015-11-19 | 2016-02-17 | 浙江大学 | Preparation method of PANI (polyaniline)-GO (graphene oxide)-CNTs (carbon nanotubes) composited electromagnetic shielding material |
| CN106810818B (en) * | 2015-11-30 | 2019-09-13 | 航天特种材料及工艺技术研究所 | A kind of graphene modified epoxy and preparation method thereof |
| CN106810818A (en) * | 2015-11-30 | 2017-06-09 | 航天特种材料及工艺技术研究所 | A kind of Graphene modified epoxy and preparation method thereof |
| CN105912759B (en) * | 2016-04-06 | 2019-07-23 | 清华大学 | Determine the calculation method of the percolation threshold of pressure-sensitive microballoon in non-linear dielectric materials |
| CN105912759A (en) * | 2016-04-06 | 2016-08-31 | 清华大学 | Calculating method for determining percolation threshold of voltage-sensitive micro-balloons in nonlinear insulating material |
| CN106098400B (en) * | 2016-06-30 | 2018-05-18 | 合肥工业大学 | A kind of aminooimidazole Ionic Liquid Modified graphene nanometer sheet/composite polyethylene material and preparation method thereof |
| CN106098400A (en) * | 2016-06-30 | 2016-11-09 | 合肥工业大学 | A kind of aminooimidazole Ionic Liquid Modified graphene nanometer sheet/composite polyethylene material and preparation method thereof |
| CN108219368A (en) * | 2016-12-21 | 2018-06-29 | 南京中赢纳米新材料有限公司 | It is a kind of to modify nano-carbon material to strengthen the method for epoxy resin-base composite material |
| CN108219368B (en) * | 2016-12-21 | 2019-11-12 | 南京中赢纳米新材料有限公司 | A method of modification nano-carbon material is to strengthen epoxy resin-base composite material |
| CN107057006A (en) * | 2017-05-25 | 2017-08-18 | 成都新柯力化工科技有限公司 | A kind of thermosetting phenolic resin special graphite alkene mother liquor and preparation method |
| CN107057006B (en) * | 2017-05-25 | 2019-10-08 | 成都新柯力化工科技有限公司 | A kind of thermosetting phenolic resin special graphite alkene mother liquor and preparation method |
| CN107573645A (en) * | 2017-09-06 | 2018-01-12 | 深圳市峰泳科技有限公司 | A kind of built-in high-k flexible resin composite and its preparation method and application |
| CN110079087A (en) * | 2019-05-07 | 2019-08-02 | 中国电子科技集团公司第三十八研究所 | A kind of modified nano graphite/cyanate composite material, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104403275B (en) | 2017-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104403275A (en) | Modified grapheme/thermosetting resin composite material and preparation method thereof | |
| CN101781459B (en) | Graphene/polyaniline conductive composite material and preparation method thereof | |
| CN102533216B (en) | Ferroferric oxide/reduced graphene oxide composite wave-absorbing material with hollow hemisphere structure and preparation method | |
| CN105253871B (en) | Ultracapacitor nitrogenous carbon material and preparation method thereof, electrode material for super capacitor | |
| CN105860064A (en) | Preparation method of polyaniline/carboxylated graphene composite material | |
| CN104479424A (en) | Graphene-polyaniline modified carbon nanotube composite and preparation method thereof | |
| CN102875973B (en) | Modified carbon nanotube/thermosetting resin composite and preparation method thereof | |
| Wang et al. | Nitrogen-doped carbon-wrapped porous FeMnO3 nanocages derived from etched prussian blue analogues as high-performance anode for lithium ion batteries | |
| CN103937295B (en) | A kind of Graphene-titanium diboride oxide mixture and preparation method thereof | |
| CN108862366B (en) | Flake Cu2-xApplication of S nanocrystal as microwave absorbent and preparation method thereof | |
| CN102610331A (en) | Preparation method of electrode material of silver/graphene thin film supercapacitor | |
| CN110808175A (en) | Electroactive biomass/polypyrrole hydrogel and preparation method and application thereof | |
| CN103971942A (en) | Graphene/polyaniline/ferric oxide composite material applied to supercapacitor and manufacturing method thereof | |
| CN112430352B (en) | Double-network cross-linked and coated polyaniline/multi-walled carbon nanotube composite conductive filler and preparation method thereof | |
| CN107697905A (en) | A kind of preparation method of three-dimensional nitrogen-doped graphene aeroge | |
| CN109003826A (en) | N and S codope graphene-graphene nanobelt aeroge preparation method | |
| CN109082264B (en) | MoS2Application of/RGO composite material | |
| CN105441029A (en) | Ag@Fe3O4/reduced graphene oxide ternary composite wave absorbing material and preparation method thereof | |
| CN108831757A (en) | A kind of preparation method of N and S codope graphene/carbon nano-tube aeroge | |
| CN105085907A (en) | Method for preparing polyaniline grafted carbon material | |
| Li et al. | Waste-honeycomb-derived in situ N-doped Hierarchical porous carbon as sulfur host in lithium–sulfur battery | |
| CN104064366A (en) | Graphene-hard carbon composite material, preparation method thereof and application thereof | |
| CN103579626A (en) | Graphene/tin composite material, preparation method of grapheme/tin composite material, lithium ion battery and preparation method of lithium ion battery | |
| CN103680973A (en) | Polyaniline/graphene/carbon nanotube composite and preparation method thereof, as well as electrode plate and capacitor | |
| CN106653398A (en) | Preparation method of flexible composite electrode material of supercapacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |