CN103937295A - Graphene-titanium diboride oxide compound and preparation method thereof - Google Patents
Graphene-titanium diboride oxide compound and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a graphene-titanium diboride oxide compound and a preparation method thereof. The method comprises the steps of dispersing graphite oxide into N,N-dimethylformamide, adding titanium diboride oxide subjected to amination, then filtering, washing, and drying reactants to obtain a graphene surface-loaded titanium diboride oxide compound, wherein titanium diboride oxide is a core-shell structure of which the surface layer is an insulating layer namely titanium dioxide, and the core is a conductor namely titanium diboride. The compound provided by the invention can be used for forming a micro-capacitor structure which takes titanium diboride and graphene as electrodes, and takes titanium dioxide as a dielectric medium. By adding the compound into a polymer, the conductivity loss caused by conductor contact can be reduced, and the dielectric constant can be greatly increased. Meanwhile, the surface of the compound contains a great number of active functional groups such as amino groups, hydroxyl groups and the like, thus providing guarantees for modifying and preparing compound materials with good dispersibility. The preparation method of the compound has the characteristics of simple process, low cost and wide applicability.
Description
Technical field
The present invention be more particularly directed to a kind of Graphene-oxidation TiB2 mixture and preparation method thereof, belong to technical field of inorganic nanometer material.
Background technology
Graphene is with sp by carbon atom
2hydridization rearranges the two-dimensional slice of polynuclear plane, has huge electronic mobility, high heat conductance, the physical strength of excellence and large specific surface area.In recent years, Graphene is subject to extensive concern with its superior electricity, calorifics, mechanical property, has wide application potential in fields such as electron device, dielectric materials and stored energies.
At present, the main method of preparing high dielectric material is in polymkeric substance, to introduce conductor, and the Graphene Chang Zuowei conductor with excellent electric property is introduced in prepares composite material with high dielectric constant in polymeric matrix.But because the acquisition of high-k is based on seepage flow mechanism, therefore, near percolation phenomenon occurs, it is larger that the electricity of material is led loss, causes the dielectric loss of matrix material higher.
So far, a kind of method that can effectively reduce matrix material dielectric loss is at conductive surface coated insulation layer.But this method is usually brought two side effects, the one, reduced dielectric constant.As the people such as Dang (Dongrui Wang, Yaru Bao, Junwei Zha, Jun Zhao, Zhimin Dang, Guohua Hu. ACS Appl. Mater. Interfaces 2012; 4; 6273 6279) prepared polyvinyl alcohol coating graphite alkene/polyvinylidene fluoride resin matrix material, find in the situation that Graphene conductor content is identical, the dielectric loss of polyvinyl alcohol-Graphene/polyvinylidene fluoride composite material and specific inductivity are all lower than the analog value of Graphene/polyvinylidene fluoride composite material.This is because the polyvinyl alcohol covering on graphene platelet has hindered the motion of electronics on Graphene, and the electric property of Graphene excellence is fully played.Another side effect is that the percolation threshold of matrix material increases.It is to come from seep effect that conductor/polymer composites is obtained high-k, and the existence of insulation layer has hindered the formation of conductive network, usually needs the existence of more conductor.In other words, want to obtain high-k, often need to add the functive of high-content, this is the manufacturability of deteriorated matrix material, even other performances such as mechanical property.Therefore, how to overcome above-mentioned two side effects, researching and developing a kind of functive for the preparation of high-k, low-dielectric loss and low percolation threshold polymer matrix composites is a problem with major application value.
Summary of the invention
Problem to be solved by this invention is to overcome the deficiency that prior art exists, Graphene-oxidation TiB2 mixture that a kind of surface contains a large amount of amino, hydroxyl isoreactivity functional group and preparation method thereof is provided, and the product providing can be used for preparing high-k, low-dielectric loss and low percolation threshold polymer matrix composites.
Realize the preparation method that object technical scheme of the present invention is to provide a kind of Graphene-oxidation TiB2 mixture, comprise the steps:
(1) by mass, 10 parts of oxidation TiB2s are distributed in the superoxol that 50～60 parts of massfractions are 35%～40%, under the temperature condition of 100～106 DEG C, react 5～6h; After reaction finishes, through washing, suction filtration, obtains hydroxylated oxidation TiB2;
(2) by mass, hydroxylated oxidation TiB2 prepared by 10 parts of steps (1) joins in 100～120 parts of dehydrated alcohols, obtains suspension after mixing; In described suspension, add 0.1～0.2 part of γ-aminopropyl triethoxysilane, under the temperature condition of 60～65 DEG C, react 5～6h, after reaction finishes, through suction filtration, washing, dry, obtain amidized oxidation TiB2;
(3) by mass, under agitation condition, 1 part of graphite oxide is scattered in 500～600 parts of DMFs, obtains graphene oxide dispersion liquid; Amidized oxidation TiB2 prepared by 0.005～0.5 part of step (2) joins in described graphene oxide dispersion liquid, under the temperature condition of 60～70 DEG C, reacts 12～24h; Add again 10 parts of L-AAs, under the temperature condition of 80～100 DEG C, react 24～48h, after reaction finishes, through suction filtration, washing, dry, obtain a kind of Graphene-oxidation TiB2 mixture.
Graphite oxide described in technical solution of the present invention, its preparation method comprises the steps:
(1) by mass, the vitriol oil that is 98% by 2 parts of graphite, 1 part of SODIUMNITRATE and 46 parts of mass concentrations joins in reactor and is uniformly mixed, and it is in the ice-water bath of 0～4 DEG C that reactor is positioned over temperature;
(2) under the temperature condition of 10～15 DEG C, in reactor, slowly add 6 parts of potassium permanganate, then insulated and stirred 2～3h;
(3) reactor being moved to temperature is in the water-bath of 30～40 DEG C, insulated and stirred 30～35min;
(4) after reaction finishes, in reactor, slowly drip 92 parts of deionized waters, be warming up to 95～98 DEG C, insulation 15～20min;
(5) in reactor, add the hydrogen peroxide that 15 parts of mass concentrations are 30%, stir after 20～30min, add 140 parts of deionized waters, obtain crude product; By described crude product through salt acid elution centrifugal, that mass concentration is 5%, deionized water wash process to pH be 6～7, obtain graphite oxide after dry.
The preparation method of the oxidation TiB2 described in technical solution of the present invention comprises the steps: under aerobic conditions, by mass, the TiB2 that 1 part of median size is less than to 200 nanometers, under the temperature condition of 600～700 DEG C, oxide treatment 5～10min, obtains crude product; Described crude product is distributed in 20～30 parts of ethanol, again through suction filtration, dry after stirring, obtain being oxidized TiB2.
Technical solution of the present invention also comprises that one obtains Graphene-oxidation TiB2 mixture by above-mentioned preparation method.
Compared with prior art, the invention has the beneficial effects as follows:
1, the present invention is at Graphene area load oxidation TiB2, wherein being oxidized TiB2 forms TiB2 through high temperature oxidation process, its top layer is that insulation layer titanium dioxide, core are conductor TiB2, is therefore a kind of nucleocapsid structure with conductor@insulation layer.This conductor loading that is coated with isolator, on Graphene, is formed to mixture.Because TiB2 and Graphene are all conductor, can be used as electrode; And middle titanium dioxide is insulation layer, can be used as dielectric medium, Graphene-oxidation TiB2 mixture has formed micro-capacitance structure like this.This mixture is added to polymkeric substance, not only reduce the electricity causing because of conductor contact and lead loss, and can increase substantially specific inductivity.
2, Graphene-oxidation TiB2 composite surface contains a large amount of amino, hydroxyl isoreactivity functional group, and the matrix material for its further modification and (or) preparation with good dispersion provides guarantee.
3, the electrical property of mixture can regulate by the content of the oxidization time of control TiB2 and oxidation TiB2, has the controllability of structure and performance and the feature of convenience.
4, the preparation method of Graphene-oxidation TiB2 mixture provided by the invention has the features such as technique is simple, cost is low, suitability is wide.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of the oxidation TiB2 in the embodiment of the present invention 1, amidized oxidation TiB2, Graphene and Graphene-oxidation TiB2 mixture.
Fig. 2 is the X-ray diffractogram of the oxidation TiB2 in the embodiment of the present invention 1, amidized oxidation TiB2, Graphene and Graphene-oxidation TiB2 mixture.
Fig. 3 is that Graphene-oxidation TiB2 mixture of preparation in the embodiment of the present invention 1～4 amplifies the scanning electron microscope (SEM) photograph of 25,000 times.
Fig. 4 is the X-ray diffractogram of Graphene-oxidation TiB2 mixture of preparation in the embodiment of the present invention 2～4.
Fig. 5 is the transmission scanning electron microscope figure of Graphene-oxidation TiB2 mixture in the embodiment of the present invention 4.
Fig. 6 is that the specific inductivity of Graphene-oxidation TiB2 mixture/epoxy resin composite material of providing of Graphene/epoxy resin composite material of providing of comparative example 1 of the present invention and comparative example 2 is with change of frequency figure.
The specific conductivity of Graphene-oxidation TiB2 mixture/epoxy resin composite material that Graphene/epoxy resin composite material that Fig. 7 comparative example 1 of the present invention provides and comparative example 2 provide is with change of frequency figure.
Fig. 8 is that the electric capacity of Graphene-oxidation TiB2 mixture/epoxy resin composite material of providing of Graphene/epoxy resin composite material of providing of comparative example 1 of the present invention and comparative example 2 is with change of frequency figure.
Fig. 9 is that the dielectric loss of Graphene-oxidation TiB2 mixture/epoxy resin composite material of providing of Graphene/epoxy resin composite material of providing of comparative example 1 of the present invention and comparative example 2 is with change of frequency figure.
Figure 10 is that the electric conductivity-mixture of Graphene-oxidation TiB2/epoxy resin composite material of preparing of comparative example 3 under 1Hz is containing discharge curve.
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 oxidation TiB2
Under aerobic conditions, 10g TiB2 particle diameter is less than to 200 nanometers, at 600 DEG C, oxide treatment 10min, obtains crude product, is distributed in 200mL ethanol, again through suction filtration, dry after stirring, obtains being oxidized TiB2.The infrared spectrogram of prepared oxidation TiB2, X-ray diffractogram are respectively referring to attached Fig. 1 and 2.
2, the preparation of amidized oxidation TiB2
10g is oxidized to TiB2 and is distributed in the superoxol that 50mL part massfraction is 35%, at 100 DEG C, react 5h; After reaction finishes, through washing, suction filtration, at the dry 12h of the vacuum drying ovens of 60 DEG C, obtains hydroxylated oxidation TiB2;
Hydroxylated 10g oxidation TiB2 is joined in 100mL dehydrated alcohol, and ultrasonic mixing, under nitrogen protection, adds the γ-aminopropyl triethoxysilane of 0.1g, at 60 DEG C, stirs 5h.Reaction finishes rear with absolute ethanol washing, suction filtration, and at 70 DEG C vacuum-drying 12h, obtain amidized oxidation TiB2.The infrared spectrogram of prepared amidized oxidation TiB2, X-ray diffractogram are respectively referring to attached Fig. 1 and 2.
3, the preparation of graphite oxide
Getting 2g graphite, 1g SODIUMNITRATE and 46mL 98% vitriol oil mixes and is placed in the ice-water bath of 0 DEG C and stirs 30min, getting 6g potassium permanganate slowly adds in above-mentioned mixed solution, temperature is controlled at 10 DEG C and stirring 2h, then flask is transferred in 30 DEG C of water-baths, and insulated and stirred 30min.After reaction finishes, slowly drip 92mL deionized water, and temperature is risen to 95 DEG C, insulation 15min, then add the hydrogen peroxide of 15mL 30%, stir after 20min, add 140mL deionized water, products therefrom is 7 through centrifugal, 5% salt acid elution, deionized water wash to pH, the dry graphite oxide that obtains.
4, the preparation of Graphene
1g graphite oxide is scattered in the deionized water of 2000mL, ultrasonic and stirring obtains yellowish brown settled solution, adding 10g L-AA is that graphene oxide is reduced into Graphene by reductive agent, at 80 DEG C, react 24h, reaction finishes rear with deionized water wash, suction filtration, at the dry 12h of 60 DEG C of vacuum chambers, grinds and obtains Graphene.The infrared spectrogram of prepared Graphene, X-ray diffractogram are respectively referring to attached Fig. 1 and 2.
5, the preparation of Graphene-oxidation TiB2 mixture
Take 1g graphite oxide and be scattered in 500mL N, in dinethylformamide, after stirring and supersound process 1h, obtain graphene oxide dispersion liquid, add the amidized oxidation TiB2 of 0.005g in graphene oxide dispersion liquid, ultrasonic agitation, at 60 DEG C, react 12h, then add 10g L-AA, reacting liquid temperature is risen to after 80 DEG C of reaction 24h, through suction filtration, washing, after being dried, obtain Graphene-oxidation TiB2 mixture, the quality that is wherein oxidized TiB2 is 0.01 times of Graphene quality.The scanning electron microscope (SEM) photograph of 25,000 times of infrared spectrogram, X-ray diffractogram, the amplifications of prepared Graphene-oxidation TiB2 mixture is respectively referring to accompanying drawing 1,2 and 3.
Referring to accompanying drawing 1, it is the infrared spectrogram of the oxidation TiB2 in the present embodiment, amidized oxidation TiB2, Graphene and Graphene-oxidation TiB2 mixture.In the spectrogram of oxidation TiB2,1380cm
-1the absorption peak at place is to be caused by the flexural vibration of the hydroxyl on oxidation TiB2 surface.This peak in the spectrogram of amidized oxidation TiB2 a little less than, illustrate that the oxyethyl group in γ-aminopropyl triethoxysilane, with the hydroxyl on oxidation TiB2 surface, condensation reaction has occurred, γ-aminopropyl triethoxysilane is received oxidation TiB2 surface by chemical bond-linking.Meanwhile, the 2853cm in the spectrogram of amidized oxidation TiB2
1and 2930cm
1the absorption peak at place belongs in γ-aminopropyl triethoxysilane structure stretching vibration symmetrical and asymmetric methylene radical, further proves that γ-aminopropyl triethoxysilane receives the surface of oxidation TiB2 by chemical bond-linking.Can see C=O(1648cm from the spectrogram of Graphene-oxidation TiB2
1), N – H and C – N (1509cm
1) characteristic peak, it is interconnective by chemical bond showing to be oxidized between TiB2 and Graphene.
Referring to accompanying drawing 2, it is the X-ray diffractogram of the oxidation TiB2 in the present embodiment, amidized oxidation TiB2, Graphene and Graphene-oxidation TiB2 mixture.As seen from the figure, the Graphene obtaining after L-AA reduction has shown wider diffraction peak at 24.85 °.Amidized oxidation TiB2 has shown the characteristic diffraction peak of TiB2 and titanium dioxide, but intensity weakens relatively, and this is because load has γ-aminopropyl triethoxysilane on the surface of oxidation TiB2.And the diffraction peak of Graphene-oxidation TiB2 mixture comprises Graphene and the characteristic peak that is oxidized TiB2; Than oxidation TiB2, TiB2 in Graphene-oxidation TiB2 mixture and the characteristic peak of titanium dioxide a little less than, this is because the lip-deep oxidation TiB2 of Graphene content is less in the present embodiment, be only one of percentage of Graphene quality, therefore shown very weak diffraction peak.
Embodiment 2
The preparation of Graphene-oxidation TiB2 mixture
Take 1g graphite oxide and be scattered in 600mL N, in dinethylformamide, after stirring and supersound process 1h, obtain graphene oxide dispersion liquid, add the amidized oxidation TiB2 of 0.025g in graphene oxide dispersion liquid, ultrasonic agitation, at 60 DEG C, react 12h, then add 10g L-AA, reacting liquid temperature is risen to after 90 DEG C of reaction 24h, through suction filtration, washing, after being dried, obtain Graphene-oxidation TiB2 mixture, the content that is wherein oxidized TiB2 is 0.05 times of Graphene quality.Its scanning electron microscope (SEM) photograph, X-ray diffractogram that amplifies 25,000 times is respectively referring to accompanying drawing 3 and 4.
Embodiment 3
The preparation of Graphene-oxidation TiB2 mixture
Take 1g graphite oxide and be scattered in 600mL N, in dinethylformamide, after stirring and supersound process 1h, obtain graphene oxide dispersion liquid, add the amidized oxidation TiB2 of 0.5g in graphene oxide dispersion liquid, ultrasonic agitation, at 60 DEG C, react 12h, then add 10g L-AA, reacting liquid temperature is risen to after 90 DEG C of reaction 24h, through suction filtration, washing, after being dried, obtain Graphene-oxidation TiB2 mixture, be wherein oxidized the identical in quality of the content of TiB2 and Graphene.Its scanning electron microscope (SEM) photograph, X-ray diffractogram that amplifies 25,000 times is respectively referring to accompanying drawing 3 and 4.
Embodiment 4
The preparation of Graphene-oxidation TiB2 mixture
Take 1g graphite oxide and be scattered in 600mL N, in dinethylformamide, after stirring and supersound process 1h, obtain graphene oxide dispersion liquid, add the amidized oxidation TiB2 of 0.05g in graphene oxide dispersion liquid, ultrasonic agitation, at 60 DEG C, react 12h, then add 10g L-AA, reacting liquid temperature is risen to after 90 DEG C of reaction 24h, through suction filtration, washing, after being dried, obtain Graphene-oxidation TiB2 mixture, the content that is wherein oxidized TiB2 is 0.1 times of Graphene quality.Its scanning electron microscope (SEM) photograph, X-ray diffractogram, transmission scanning electron microscope figure that amplifies 25,000 times is respectively referring to accompanying drawing 3,4 and 5.
Comparative example 1: the preparation of Graphene/epoxy resin composite material
Join in flask by 0.75g Graphene and with 100g epoxy resin (trade mark E-51), at 60 DEG C, stirring is also after ultrasonic 1 hour, and vacuum defoamation 30min, adds 4g 2-ethyl-4-methylimidazole, continues stirring 10min, obtains uniform mixture; Mixture is poured in mould, and 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, obtains Graphene/epoxy resin composite material.Its specific inductivity 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, electric capacity with change of frequency figure, specific conductivity.
Comparative example 2: the preparation of Graphene-oxidation TiB2/epoxy resin composite material
0.825g Graphene-oxidation TiB2 mixture prepared by embodiment 4 and 100g epoxy resin (trade mark E-51) join in flask, at 60 DEG C, stir also after ultrasonic 1 hour, vacuum defoamation 30min, add 4g 2-ethyl-4-methylimidazole, continue to stir 10min, obtain uniform mixture; Mixture is poured in mould, and 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, obtains Graphene-oxidation TiB2 mixture/epoxy resin composite material.Its specific inductivity 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, electric capacity with change of frequency figure, specific conductivity.
Referring to accompanying drawing 3, it is that Graphene-oxidation TiB2 mixture prepared by the embodiment of the present invention 1～4 amplifies the scanning electron microscope (SEM) photograph of 25,000 times, can see, along with the increase of the mass ratio of oxidation TiB2 and Graphene, the content that oxidation TiB2 loads on Graphene also presents the trend increasing progressively, until cover completely on graphene platelet.
Referring to accompanying drawing 4, it is the X-ray diffractogram of Graphene-oxidation TiB2 mixture of the embodiment of the present invention 2～4 preparations.From figure, know, along with the increase of oxidation TiB2 and Graphene mass ratio, Graphene in Graphene-oxidation TiB2 mixture 24.85 ° of diffraction peak intensities of locating more and more a little less than, and TiB2 and titanium dioxide diffraction peak in oxidation TiB2 is more and more obvious, the oxidation TiB2 content that shows grafting on Graphene is controlled, can regulate the quality of oxidation TiB2 and Graphene recently to realize.
Comprehensive above performance data analysis, compared with Graphene, Graphene-oxidation TiB2 mixture prepared by the present invention has the controlled feature of charge capacity of oxidation TiB2, and the surface that oxidation TiB2 covers Graphene can hinder its reunion, improve the dispersiveness of Graphene in resin, the preparation that can be applicable to the polymer matrix composites with good dispersion, has broad application prospects.
Referring to accompanying drawing 5, it is the transmission electron microscope picture of Graphene-oxidation TiB2 mixture in the present embodiment, can see that oxidation titanium diboride particle loads on Graphene.
Referring to accompanying drawing 6, it is that the specific inductivity of the matrix material that provides of comparative example 1 and 2 is with the change curve of frequency.As seen from the figure, the specific inductivity of Graphene-oxidation TiB2 mixture/epoxy resin composite material in whole range of frequency be higher than Graphene/epoxy resin composite material, shows that Graphene-oxidation TiB2 mixture has significant application prospect preparing aspect high dielectric constant material.
Referring to accompanying drawing 7, it is that the specific conductivity of the matrix material that provides of comparative example 1 and 2 is with frequency variation curve.As seen from the figure, the specific conductivity of Graphene-oxidation TiB2 mixture/epoxy resin composite material is lower than the specific conductivity of Graphene/epoxy resin composite material, this is because be coated with the oxidation TiB2 with low conductivity on Graphene surface, prove that oxidation TiB2 is carried on Graphene and has reduced and then wear electric current between contiguous Graphene, thereby made Graphene-oxidation TiB2 mixture/epoxy resin to there is lower specific conductivity.
Referring to accompanying drawing 8, it is that the electric capacity of the matrix material that provides of comparative example 1 and 2 is with frequency variation curve.As seen from the figure, the electric capacity of Graphene-oxidation TiB2 mixture/epoxy resin composite material is higher than the electric capacity of Graphene/epoxy resin composite material.7 conductivity data by reference to the accompanying drawings, can think that the reason that Graphene-oxidation TiB2 mixture/epoxy resin composite material that comparative example 2 provides has a high-k is the increase of material electric capacity.
Referring to accompanying drawing 9, it is that the dielectric loss of the matrix material that provides of comparative example 1 and 2 is with the change curve of frequency.The dielectric loss of Graphene/epoxy resin composite material prepared by comparative example 1 has strong dependency to frequency, has very high dielectric loss (for example the dielectric loss of the matrix material under 100Hz is up to 9.3) under low frequency.And the dielectric loss of Graphene-oxidation TiB2 mixture/epoxy resin composite material prepared by comparative example 2 to the dependency of frequency a little less than, simultaneously the dielectric loss under low frequency obviously reduces.This is because oxidation TiB2 covers on Graphene, because titanium dioxide insulation layer has completely cut off being in contact with one another between graphene sheet layer, hinder electronics running through between conductor Graphene, thereby cause the reduction of the dielectric loss of Graphene-oxidation TiB2 mixture/epoxy resin composite material, show that Graphene-oxidation TiB2 mixture has outstanding advantage preparing aspect low-dielectric loss matrix material.
Comparative example 3: the preparation of serial Graphene-oxidation TiB2/epoxy resin composite material
With reference to the preparation process of comparative example 2, prepare Graphene-oxidation TiB2 mixture content and be respectively Graphene-oxidation TiB2/epoxy resin composite material of 0.757%, 0.787%, 0.825%, 0.900%, 1.13%, 1.50% of epoxy resin quality.Electric conductivity-mixture under its 1Hz is shown in accompanying drawing 10 containing discharge curve.Therefrom known, the percolation threshold of Graphene-oxidation TiB2/epoxy resin composite material is only the 0.767wt% of resin quality, while having proved Graphene-oxidation TiB2 as functional stuffing, can in the time of low levels, just can prepare the matrix material of high-k, low-dielectric loss.
The result of comprehensive accompanying drawing 6,7,8,9 and 10 is known, add a small amount of Graphene-oxidation TiB2 mixture just can significantly improve the specific inductivity of matrix material and greatly reduce dielectric loss, have concurrently aspect high-k, low-dielectric loss and low percolation threshold matrix material and have significant advantage in preparation, this comes from the structure of Graphene-oxidation TiB2 mixture uniqueness.
Embodiment 5
The preparation of Graphene-oxidation TiB2 mixture
Take 1g graphite oxide and be scattered in 600mL N, in dinethylformamide, after stirring and supersound process 1h, obtain graphene oxide dispersion liquid, add the amidized oxidation TiB2 of 0.1g in graphene oxide dispersion liquid, ultrasonic agitation, at 60 DEG C, react 12h, then add 10g L-AA, reacting liquid temperature is risen to after 90 DEG C of reaction 24h, through suction filtration, washing, after being dried, obtains Graphene-oxidation TiB2 mixture.
Embodiment 6
The preparation of Graphene-oxidation TiB2 mixture
Take 1g graphite oxide and be scattered in 600mL N, in dinethylformamide, after stirring and supersound process 1h, obtain graphene oxide dispersion liquid, add the amidized oxidation TiB2 of 0.25g in graphene oxide dispersion liquid, ultrasonic agitation, at 60 DEG C, react 12h, then add 10g L-AA, reacting liquid temperature is risen to after 90 DEG C of reaction 24h, through suction filtration, washing, after being dried, obtains Graphene-oxidation TiB2 mixture.
Embodiment 7
1, the preparation of oxidation TiB2
Under aerobic conditions, 10g TiB2 particle diameter is less than to 200 nanometers, at 700 DEG C, oxide treatment 5min, obtains crude product, is distributed in 250mL ethanol, again through suction filtration, dry after stirring, obtains being oxidized TiB2.
2, the preparation of amidized oxidation TiB2
10g is oxidized to TiB2, and to be scattered in 60mL massfraction be in 35% superoxol, at 100 DEG C, reacts 5.5h; Reaction finishes rear with deionized water wash, and suction filtration, at the dry 12h of the vacuum drying ovens of 60 DEG C, obtains hydroxylated oxidation TiB2.
Hydroxylated 10g oxidation TiB2 is joined in 110mL dehydrated alcohol, and ultrasonic mixing, under nitrogen protection, adds the γ-aminopropyl triethoxysilane of 0.15g, at 65 DEG C, stirs 5h.Reaction finishes rear with absolute ethanol washing, suction filtration, and at 70 DEG C vacuum-drying 12h, obtain amidized oxidation TiB2.
3, the preparation of graphite oxide
Getting 2g graphite, 1g SODIUMNITRATE and 46mL 98% vitriol oil mixes and is placed in the ice-water bath of 4 DEG C and stirs 30min, getting 6g potassium permanganate slowly adds in above-mentioned mixed solution, temperature is controlled at 15 DEG C and stirring 2.5h, then flask is transferred in 35 DEG C of water-baths, and insulated and stirred 35min.After reaction finishes, slowly drip 92mL deionized water, and temperature is risen to 98 DEG C, insulation 15min, then add the hydrogen peroxide of 15mL 30%, stir after 25min, add 140mL deionized water, products therefrom is 6 through centrifugal, 5% salt acid elution, deionized water wash to pH, the dry graphite oxide that obtains.
4, the preparation of Graphene-oxidation TiB2 mixture
Take 1g graphite oxide and be scattered in 600mL N, in dinethylformamide, after stirring and supersound process 1.5h, obtain graphene oxide dispersion liquid, add the amidized oxidation TiB2 of 0.15g to be placed in graphene oxide dispersion liquid, ultrasonic agitation, at 70 DEG C, react 15h, then add 10g L-AA, reacting liquid temperature is risen at 80 DEG C and reacted after 24h, through suction filtration, washing, after being dried, obtains Graphene-oxidation TiB2 mixture.
Embodiment 8
1, the preparation of oxidation TiB2
Under aerobic conditions, 10g TiB2 particle diameter is less than to 200 nanometers, at 680 DEG C, oxide treatment 6min, obtains crude product, is distributed in 280mL ethanol, again through suction filtration, dry after stirring, obtains being oxidized TiB2.
2, the preparation of amidized oxidation TiB2
10g is oxidized to TiB2, and to be scattered in 50mL massfraction be in 40% superoxol, at 106 DEG C, reacts 5h; Reaction finishes rear with deionized water wash, and suction filtration, at the dry 12h of the vacuum drying ovens of 60 DEG C, obtains hydroxylated oxidation TiB2.
Hydroxylated 10g oxidation TiB2 is joined in 110mL dehydrated alcohol, and ultrasonic mixing, under nitrogen protection, adds the γ-aminopropyl triethoxysilane of 0.2g, at 65 DEG C, stirs 5h.Reaction finishes rear with absolute ethanol washing, suction filtration, and at 70 DEG C vacuum-drying 12h, obtain amidized oxidation TiB2.
3, the preparation of graphite oxide
Getting 2g graphite, 1g SODIUMNITRATE and 46mL 98% vitriol oil mixes and is placed in the ice-water bath of 2 DEG C and stirs 30min, getting 6g potassium permanganate slowly adds in above-mentioned mixed solution, temperature is controlled at 15 DEG C and stirring 2h, then flask is transferred in 38 DEG C of water-baths, and insulated and stirred 32min.After reaction finishes, slowly drip 92mL deionized water, and temperature is risen to 96 DEG C, insulation 18min, then add the hydrogen peroxide of 15mL 30%, stir after 20min, add 140mL deionized water, products therefrom is 6.5 through centrifugal, 5% salt acid elution, deionized water wash to pH, the dry graphite oxide that obtains.
4, the preparation of Graphene-oxidation TiB2 mixture
Take 1g graphite oxide and be scattered in 600mL N, in dinethylformamide, after stirring and supersound process 1.5h, obtain graphene oxide dispersion liquid, add the amidized oxidation TiB2 of 0.2g to be placed in graphene oxide dispersion liquid, ultrasonic agitation, at 70 DEG C, react 20h, then add 10g L-AA, reacting liquid temperature is risen to after 85 DEG C of reaction 24h, through suction filtration, washing, after being dried, obtains Graphene-oxidation TiB2 mixture.
Embodiment 9
1, the preparation of oxidation TiB2
Under aerobic conditions, 10g TiB2 particle diameter is less than to 200 nanometers, at 700 DEG C, oxide treatment 5min, obtains crude product, is distributed in 290mL ethanol, again through suction filtration, dry after stirring, obtains being oxidized TiB2.
2, the preparation of amidized oxidation TiB2
10g is oxidized to TiB2, and to be scattered in 55mL massfraction be in 40% superoxol, at 106 DEG C, reacts 6h; Reaction finishes rear with deionized water wash, and suction filtration, at the dry 12h of the vacuum drying ovens of 60 DEG C, obtains hydroxylated oxidation TiB2.
Hydroxylated 10g oxidation TiB2 is joined in 120mL dehydrated alcohol, and ultrasonic mixing, under nitrogen protection, adds the γ-aminopropyl triethoxysilane of 0.2g, at 60 DEG C, stirs 6h.Reaction finishes rear with absolute ethanol washing, suction filtration, and at 70 DEG C vacuum-drying 12h, obtain amidized oxidation TiB2.
3, the preparation of graphite oxide
Getting 2g graphite, 1g SODIUMNITRATE and 46mL 98% vitriol oil mixes and is placed in the ice-water bath of 4 DEG C and stirs 30min, getting 6g potassium permanganate slowly adds in above-mentioned mixed solution, temperature is controlled at 12 DEG C and stirring 2h, then flask is transferred in 38 DEG C of water-baths, and insulated and stirred 33min.After reaction finishes, slowly drip 92mL deionized water, and temperature is risen to 96 DEG C, insulation 20min, then add the hydrogen peroxide of 15mL 30%, stir after 30min, add 140mL deionized water, products therefrom is 6.5 through centrifugal, 5% salt acid elution, deionized water wash to pH, the dry graphite oxide that obtains.
4, the preparation of Graphene-oxidation TiB2 mixture
Take 1g graphite oxide and be scattered in 600mL N, in dinethylformamide, after stirring and supersound process 1.5h, obtain graphene oxide dispersion liquid, add the amidized oxidation TiB2 of 0.3g to be placed in graphene oxide dispersion liquid, ultrasonic agitation, at 65 DEG C, react 18h, then add 10g L-AA, reacting liquid temperature is risen to after 90 DEG C of reaction 48h, through suction filtration, washing, after being dried, obtains Graphene-oxidation TiB2 mixture.
Embodiment 10
1, the preparation of oxidation TiB2
Under aerobic conditions, 10g TiB2 particle diameter is less than to 200 nanometers, at 650 DEG C, oxide treatment 8min, obtains crude product, is distributed in 300mL ethanol, again through suction filtration, dry after stirring, obtains being oxidized TiB2.
2, the preparation of amidized oxidation TiB2
10g is oxidized to TiB2, and to be scattered in 60mL massfraction be in 40% superoxol, at 106 DEG C, reacts 5h, after reaction finishes, with deionized water wash, suction filtration, in the dry 12h of 60 DEG C of vacuum drying ovens, obtains hydroxylated oxidation TiB2.
Hydroxylated 10g oxidation TiB2 is joined in 120mL dehydrated alcohol, and ultrasonic mixing, under nitrogen protection, adds the γ-aminopropyl triethoxysilane of 0.2g, at 65 DEG C, stirs 6h.Reaction finishes rear with absolute ethanol washing, suction filtration, and at 70 DEG C vacuum-drying 12h, obtain amidized oxidation TiB2.
3, the preparation of graphite oxide
Getting 2g graphite, 1g SODIUMNITRATE and 46mL 98% vitriol oil mixes and is placed in the ice-water bath of 4 DEG C and stirs 30min, getting 6g potassium permanganate slowly adds in above-mentioned mixed solution, temperature is controlled at 12 DEG C and stirring 3h, then flask is transferred in 35 DEG C of water-baths, and insulated and stirred 35min.After reaction finishes, slowly drip 92mL deionized water, and temperature is risen to 96 DEG C, insulation 18min, then add the hydrogen peroxide of 15mL 30%, stir after 28min, add 140mL deionized water, products therefrom is 7 through centrifugal, 5% salt acid elution, deionized water wash to pH, the dry graphite oxide that obtains.
4, the preparation of Graphene-oxidation TiB2 mixture
Take 1g graphite oxide and be scattered in 600mL N, in dinethylformamide, after stirring and supersound process 1.5h, obtain graphene oxide dispersion liquid, add the amidized oxidation TiB2 of 0.4g to be placed in graphene oxide dispersion liquid, ultrasonic agitation, at 65 DEG C, react 24h, then add 10g L-AA, reacting liquid temperature is risen to after 95 DEG C of reaction 48h, through suction filtration, washing, after being dried, obtains Graphene-oxidation TiB2 mixture.
Claims (4)
1. a preparation method for Graphene-oxidation TiB2 mixture, is characterized in that comprising the steps:
(1) by mass, 10 parts of oxidation TiB2s are distributed in the superoxol that 50～60 parts of massfractions are 35%～40%, under the temperature condition of 100～106 DEG C, react 5～6h; After reaction finishes, through washing, suction filtration, obtains hydroxylated oxidation TiB2;
(2) by mass, hydroxylated oxidation TiB2 prepared by 10 parts of steps (1) joins in 100～120 parts of dehydrated alcohols, obtains suspension after mixing; In described suspension, add 0.1～0.2 part of γ-aminopropyl triethoxysilane, under the temperature condition of 60～65 DEG C, react 5～6h, after reaction finishes, through suction filtration, washing, dry, obtain amidized oxidation TiB2;
(3) by mass, under agitation condition, 1 part of graphite oxide is scattered in 500～600 parts of DMFs, obtains graphene oxide dispersion liquid; Amidized oxidation TiB2 prepared by 0.005～0.5 part of step (2) joins in described graphene oxide dispersion liquid, under the temperature condition of 60～70 DEG C, reacts 12～24h; Add again 10 parts of L-AAs, under the temperature condition of 80～100 DEG C, react 24～48h, after reaction finishes, through suction filtration, washing, dry, obtain a kind of Graphene-oxidation TiB2 mixture.
2. the preparation method of a kind of Graphene-oxidation TiB2 mixture according to claim 1, is characterized in that, the preparation method of described graphite oxide comprises the steps:
(1) by mass, the vitriol oil that is 98% by 2 parts of graphite, 1 part of SODIUMNITRATE and 46 parts of mass concentrations joins in reactor and is uniformly mixed, and it is in the ice-water bath of 0～4 DEG C that reactor is positioned over temperature;
(2) under the temperature condition of 10～15 DEG C, in reactor, slowly add 6 parts of potassium permanganate, then insulated and stirred 2～3h;
(3) reactor being moved to temperature is in the water-bath of 30～40 DEG C, insulated and stirred 30～35min;
(4) after reaction finishes, in reactor, slowly drip 92 parts of deionized waters, be warming up to 95～98 DEG C, insulation 15～20min;
(5) in reactor, add the hydrogen peroxide that 15 parts of mass concentrations are 30%, stir after 20～30min, add 140 parts of deionized waters, obtain crude product; By described crude product through salt acid elution centrifugal, that mass concentration is 5%, deionized water wash process to pH be 6～7, obtain graphite oxide after dry.
3. the preparation method of a kind of Graphene-oxidation TiB2 mixture according to claim 1, it is characterized in that, the preparation method of described oxidation TiB2 comprises the steps: under aerobic conditions, by mass, 1 part of median size is less than to the TiB2 of 200 nanometers, under the temperature condition of 600～700 DEG C, oxide treatment 5～10min, obtains crude product; Described crude product is distributed in 20～30 parts of ethanol, again through suction filtration, dry after stirring, obtain being oxidized TiB2.
4. one kind obtains Graphene-oxidation TiB2 mixture by preparation method claimed in claim 1.
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