CN107868278A - A kind of preparation method of carbon nanomaterial modifying agent and carbon nanomaterial modified pitch - Google Patents
A kind of preparation method of carbon nanomaterial modifying agent and carbon nanomaterial modified pitch Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of carbon nanomaterial modifying agent and carbon nanomaterial modified pitch, comprise the following steps：1b) matrix pitch is positioned in container, then container is toasted, matrix pitch is in molten condition, is then stirred for evaporating the moisture in matrix pitch；Carbon nanomaterial modifying agent 2b) is taken, then carbon nanomaterial modifying agent is added in container, then is stirred, makes untill carbon nanomaterial modifying agent all submerges by matrix pitch, to obtain mixture；3b) mixture that step 5) obtains is stirred by mechanical agitator, constant temperature shearing is carried out again, obtain carbon nanomaterial modified pitch, the modified pitch that this method is prepared has the characteristics of temperature sensitivity, high-temperature stability, excellent bin stability and ageing resistace, while the requirement to matrix pitch and mixing plant reduces.
Description
Technical field
The invention belongs to field of asphalt modification, is related to a kind of carbon nanomaterial modifying agent and carbon nanomaterial modified pitch
Preparation method.
Background technology
At present, combination property excellent SBS becomes the modified bitumen product of main flow.But SBS modified pitch there is also
Some deficiencies, height, to mixing plant requirement high, in process aging at temperature, bin stability are such as required matrix pitch
Difference and accelerated material aging etc. of being degraded under action of ultraviolet radiation.
The content of the invention
The shortcomings that it is an object of the invention to overcome above-mentioned prior art, there is provided a kind of carbon nanomaterial modifying agent and
The preparation method of carbon nanomaterial modified pitch, the modified pitch that this method is prepared have temperature sensitivity, high-temperature stable
Property, the characteristics of bin stability and ageing resistace are excellent, while the requirement to matrix pitch and mixing plant reduces.
To reach above-mentioned purpose, the preparation method of carbon nanomaterial modifying agent of the present invention comprises the following steps：
It is dilute 1a) to obtain DC5700 grafting graphite, then DC5700 grafting dilute are added to of graphite is filled into methanol and deionized water
In the three-necked flask of mixed solution, RGO-DC5700 dispersion liquids are obtained after ultrasonic disperse；
The NPES-10 aqueous solution 2a) is taken, then the NPES-10 aqueous solution is added to step 1a) obtained RGO-DC5700 points
In dispersion liquid, reaction is then stirred under the conditions of water bath with thermostatic control, after the completion for the treatment of its reaction, obtains reaction product；
3a) by step 2a) obtained reaction product carries out dialysis treatment by dialysis membrane, then it is dried in vacuo again,
Obtain carbon nanomaterial modifying agent.
The NPES-10 aqueous solution, the DC5700 grafting dilute ratio with methanol and the mixed solution of deionized water of graphite are
0.2g：40mL：The concentration of 5ml, the NPES-10 aqueous solution is 10.5%wt./voi.
The volume ratio of methanol and deionized water is 1 in methanol and the mixed solution of deionized water：1.
Step 2a) in water bath with thermostatic control temperature be 70 DEG C；
Step 3a) in vacuum drying carried out under 60 DEG C of environment.
Step 3a) in the molecular cut off of dialysis membrane be 8000-14000.
Also include：Graphene is prepared, then it is dilute based on graphene synthesis DC5700 grafting graphite oxides, it is then based on
The dilute synthesis DC5700 grafting graphite of DC5700 grafting graphite oxides is dilute.
The preparation method of carbon nanomaterial modified pitch of the present invention comprises the following steps：
1b) matrix pitch is positioned in container, then container is toasted, matrix pitch is in molten condition, so
It is stirred for evaporating the moisture in matrix pitch afterwards；
Carbon nanomaterial modifying agent 2b) is taken, then carbon nanomaterial modifying agent is added in container, then is stirred, is made
Untill carbon nanomaterial modifying agent is all submerged by matrix pitch, mixture is obtained；
3b) mixture that step 5) obtains is stirred by mechanical agitator, then carries out constant temperature shearing, carbon is obtained and receives
Rice material modification pitch.
Step 1b) in the concrete operations of moisture in stirring evaporation matrix pitch be：Container is positioned over and is equipped with asbestos
On the electric furnace of net, and the moisture in evaporation matrix pitch is stirred, mixing time 10min, stir evaporation process mesostroma pitch
Temperature be 170 DEG C.
Step 3b) in by step 2b) obtained mixture be stirred by mechanical agitator during mixing speed
For 2000 turns/min, mixing time 20min.
Step 3b) in constant temperature shearing during, shear rate is 5000~6000 turns/min, and shear time is
40min。
The invention has the advantages that：
The preparation method of carbon nanomaterial modifying agent and carbon nanomaterial modified pitch of the present invention is in concrete operations
When, the characteristics of skin effect, bulk effect and quantum size effect, is had based on nano material, it is dilute with DC5700 grafting graphite
For raw material, by DC5700 grafting, graphite is dilute prepares carbon nanomaterial modifying agent, then using carbon nanomaterial modifying agent from point
Matrix pitch is modified in sub- size, to obtain carbon nanomaterial modified pitch, so as to effectively improve carbon nanomaterial
Temperature sensitivity, high-temperature stability, bin stability and the ageing resistace of modifying agent.It should be noted simultaneously that the present invention
In preparation process, the requirement to matrix pitch is relatively low, while only needs in general mechanical agitator to be stirred, and
And it is simple, convenient, while broken the less situation of current modified pitch type, enrich the species of modified pitch.
Brief description of the drawings
Fig. 1 is the schematic diagram that graphene is prepared in the present invention；
Fig. 2 is CNT surface sweeping electron microscope；
Fig. 3 is different addition quantity carbon nanomaterial modified pitch PI result of the test figures；
Fig. 4 a are 15 DEG C of penetration test result figures；
Fig. 4 b are 25 DEG C of penetration test result figures；
Fig. 4 c are 30 DEG C of penetration test result figures；
Fig. 5 a are carbon nanomaterial modified pitch softening point test result figure；
Fig. 5 b are carbon nanomaterial modified pitch equivalent softening point test result figure；
Fig. 6 a are carbon nanomaterial modified pitch ductility test result figure under different addition quantity；
Fig. 6 b are carbon nanomaterial modified pitch equivalent brittle point result of the test figure under different addition quantity；
Fig. 7 is softening point increment result of the test figure before and after carbon nanomaterial modified pitch aging under different addition quantity；
Fig. 8 is the front and rear residual penetration ratio result of the test figure of carbon nanomaterial modified pitch aging under different addition quantity；
Fig. 9 is viscosity ageing index result of the test figure before and after carbon nanomaterial modified pitch aging under different addition quantity；
Figure 10 a are 90 DEG C of viscosity result of the test figures；
Figure 10 b are 105 DEG C of viscosity result of the test figures；
Figure 10 c are 90 DEG C of viscosity result of the test figures；
Figure 10 d are 120 DEG C of viscosity result of the test figures.
Embodiment
The present invention is described in further detail below in conjunction with the accompanying drawings：
With reference to figure 1, the preparation method of carbon nanomaterial modifying agent of the present invention comprises the following steps：
It is dilute 1a) to obtain DC5700 grafting graphite, then DC5700 grafting dilute are added to of graphite is filled into methanol and deionized water
In the three-necked flask of mixed solution, RGO-DC5700 dispersion liquids are obtained after ultrasonic disperse；
The NPES-10 aqueous solution 2a) is taken, then the NPES-10 aqueous solution is added to step 1a) obtained RGO-DC5700 points
In dispersion liquid, reaction is then stirred under the conditions of water bath with thermostatic control, after the completion for the treatment of its reaction, obtains reaction product；
3a) by step 2a) obtained reaction product carries out dialysis treatment by dialysis membrane, then it is dried in vacuo again,
Obtain carbon nanomaterial modifying agent.
The NPES-10 aqueous solution, the DC5700 grafting dilute ratio with methanol and the mixed solution of deionized water of graphite are
0.2g：40mL：The concentration of 5ml, the NPES-10 aqueous solution is 10.5%wt./voi.
The volume ratio of methanol and deionized water is 1 in methanol and the mixed solution of deionized water：1.
Step 2a) in water bath with thermostatic control temperature be 70 DEG C；
Step 3a) in vacuum drying carried out under 60 DEG C of environment.
Step 3a) in the molecular cut off of dialysis membrane be 8000-14000.
Present invention additionally comprises：Prepare graphene, then dilute, the Ran Houji based on graphene synthesis DC5700 grafting graphite oxides
It is dilute in the dilute synthesis DC5700 grafting graphite of DC5700 grafting graphite oxides, wherein, the preparation process of graphene is：
1c) 2.25~2.75g natural flake graphite powder and 0.45~0.55g sodium nitrate are positioned in ice-water bath
In three-necked flask, it is then that 98% concentrated sulfuric acid is poured slowly into three-necked flask by 50ml, concentration, is stirring, whipping process
The temperature of liquid is less than or equal to 1 DEG C in middle guarantee three-necked flask, mixing time 1h；
2c) 5~6g potassium permanganate is put into three-necked flask in 0.5h in three times while stirring, and is kept for three mouthfuls
The temperature of liquid is less than or equal to 10 DEG C in flask；
3c) by step 2c) obtained product is positioned in 35 DEG C of water bath with thermostatic control, is stirred for reacting 2h, then places into
100 DEG C of water bath with thermostatic control carries out deep oxidation reaction, treats that it adds 120~130ml deionization while stirring after the completion of reacting
Water, obtain mixed solution；
4c) to step 3c) add in obtained mixed solution 127.5~132.5ml deionized water and 29.5~
30.5ml hydrogen peroxide, then reaction is stirred, after the completion for the treatment of its reaction, obtain glassy yellow graphite oxide dispersion；
5c) by step 4c) obtained glassy yellow graphite oxide dispersion filtered by 0.22 μm of PTFE polytetrafluoroethylene (PTFE) micropore
Film is filtered by vacuum, then is washed and filtered as solvent using concentration as 10% hydrochloric acid, is then entered again with deionized water
Row washing, then be dried in vacuo under 60 DEG C of environment, obtain graphite oxide；
0.09~0.11g graphite oxide 6c) is weighed, and is pulverized, is then added to 39~41ml deionized waters
In, graphene oxide dispersion is obtained after ultrasonic disperse, 85 μ L hydrazine hydrate is then sequentially added into graphene oxide dispersion
And 1.42ml ammoniacal liquor, and reacted at a temperature of 95 DEG C, after the completion for the treatment of its reaction, obtain graphene dispersing solution；
7c) by step 6c) obtained graphene dispersing solution carried out by 0.22 μm of PTFE polytetrafluoroethylene (PTFE) miillpore filter it is true
Sky filters, then is washed with deionized water, is then dried in vacuo in the environment of 60 DEG C, obtains graphene.
It is based on the graphene synthesis DC5700 grafting dilute process of graphite oxide：
1d) it is placed in 0.09~0.11g graphite oxides are dilute in the three-necked flask for filling 99~101mL deionized waters, ultrasound
Graphene oxide dispersion is obtained after scattered, then three-necked flask is positioned in 95 DEG C of waters bath with thermostatic control；
Two parts of 4mlDC5700 methanol solutions 2d) are taken, while stirring drip first part of 4mlDC5700 methanol solution in three times
Enter in three-necked flask, treat that it instills second part of 4ml DC5700 methanol solutions again after the completion of reacting, after the completion for the treatment of its reaction, obtain
Reaction product, wherein, the concentration of DC5700 methanol solutions is 40wt.%,
3d) by step 2d) obtained reaction product is dissolved in 100mL tetra oxygen furyl, after centrifugal treating, take out supernatant
Liquid, dialysis treatment then is carried out with the dialysis membrane that molecular cut off is 8000-14000, until dialysis film quality quality is no longer reduced
Untill；
5d) product in bag filter is dried in vacuo, obtains the graphene oxide of DC5700 grafting.
It is based on the dilute detailed process of the dilute synthesis DC5700 grafting graphite of DC5700 grafting graphite oxides：
1e) the DC5700 graphene oxides being grafted are positioned over and are contained with 40ml methanol and deionized water mixed solution
In three-necked flask, wherein, the volume ratio of methanol and deionized water is 1：1, ultrasonic disperse is then carried out again, obtains GO-DC5700 points
Dispersion liquid；
2e) to step 1e) 85 μ L hydrazine hydrates and 1.42ml ammoniacal liquor are added in obtained GO-DC5700 dispersion liquids, then 95
Reacted in DEG C water bath with thermostatic control, after the completion for the treatment of its reaction, obtain dispersion liquid；
3e) by step 2e) obtained dispersion liquid carries out vacuum by 0.22 μm of PTFE polytetrafluoroethylene (PTFE) miillpore filter and takes out
Filter, then cleaned with deionized water, then it is dried in vacuo again under conditions of 60 DEG C, it is dilute obtains DC5700 grafting graphite.
The preparation method of carbon nanomaterial modified pitch of the present invention comprises the following steps：
1b) matrix pitch is positioned in container, then container is toasted, matrix pitch is in molten condition, so
It is stirred for evaporating the moisture in matrix pitch afterwards；
Carbon nanomaterial modifying agent 2b) is taken, then carbon nanomaterial modifying agent is added in container, then is stirred, is made
Untill carbon nanomaterial modifying agent is all submerged by matrix pitch, mixture is obtained；
3b) mixture that step 5) obtains is stirred by mechanical agitator, then carries out constant temperature shearing, carbon is obtained and receives
Rice material modification pitch.
Step 1b) in the concrete operations of moisture in stirring evaporation matrix pitch be：Container is positioned over and is equipped with asbestos
On the electric furnace of net, and the moisture in evaporation matrix pitch is stirred, mixing time 10min, stir evaporation process mesostroma pitch
Temperature be 170 DEG C.
Step 3b) in by step 2b) obtained mixture be stirred by mechanical agitator during mixing speed
For 2000 turns/min, mixing time 20min.
Step 3b) in constant temperature shearing during, shear rate is 5000~6000 turns/min, and shear time is
40min。
Contrast test
Using Kelamayi 90# as matrix pitch, wherein, Kelamayi 90# is that the performance of matrix pitch is as shown in table 1：
Table 1
Modified pitch is prepared as modifying agent using carbon nanomaterial, graphene and the present invention, then respectively to its performance
Tested, wherein, carbon nanomaterial is the multi-walled carbon nanotube of Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences's production
(MWCNT), leading indicator is：External diameter is 815nm, and OH contents are 3.70wt%, and length is 50 μm, purity>95wt%, it is swept
Electromicroscopic photograph is retouched as shown in Fig. 2 referred to as MWCNT, test result are as follows：
1st, temperature-sensitive performance
By the use of penetration index PI as Susceptibility Indexes, to study carbon nanomaterial under matrix pitch and different addition quantity
The response to temperature of modified pitch, from the figure 3, it may be seen that after three kinds of carbon nanomaterials are mixed into pitch with different mass fractions, pin enters
Degree indices P I is correspondingly improved, and is illustrated the addition of carbon nanomaterial and matrix pitch is reduced the sensitiveness of temperature.Together
When, three kinds of carbon nanomaterials are not quite similar to the influence degree of temperature susceptibility for asphalt, wherein, the influence degree of CNT is most
Substantially, the influence degree of graphene is most weak, and influence of the invention is placed in the middle.
2nd, high-temperature behavior
From Fig. 4 a, Fig. 4 b and Fig. 4 c, with the increase of several carbon nanomaterial volumes, modified drip at three temperature
Blue or green needle penetration is all reducing, the denseness increase of pitch.Wherein, CNT influences minimum on bitumen consistency, and graphene is to drip
Blue or green denseness influences maximum, and the present invention influences to reduce on bitumen consistency, in addition, the present invention shown in pitch it is preferably compatible
Property, bitumen consistency is influenceed smaller.
As shown in Figure 5, three kinds of carbon nanomaterials and pitch melt blending are prepared into modified pitch, softening point and equivalent are soft
Changing point has corresponding rise, i.e. the addition of modifying agent increases the viscosity of matrix pitch, and high-temperature behavior is all improved.This
Invent prepare modified pitch effect it is preferable, this is closely related with the two-dimensional layered structure that graphene has, flake graphite alkene with
Pitch polymer segment is mutually wound, and hinders the motion of asphaltene molecule chain, have impact on the high-temperature behavior of pitch.
3rd, cryogenic property
Numerous studies data shows that influence of the asphalt binder to Cracks of Bituminous Pavement at Low-temperature is than more sensitive, at present
Evaluation and asphalt binder crack resistance at low-temperature index are a lot, such as low temperature susceptibility ratio, brittle point, equivalent brittle point and low-temperature ductility
Deng of the invention to use equivalent brittle point T1.2And 10 DEG C of ductilities evaluate the cryogenic property of pitch.
From Fig. 6 a and Fig. 6 b, after graphene-doped and CNT, the low-temperature ductility value of pitch declines, low temperature
Cracking resistance weakens, because graphene and CNT are reunited in pitch so that defect increases in pitch, outside
The lower stress concentration of power effect makes pitch more early be broken.Meanwhile after present invention incorporation pitch, fail to improve the low temperature of pitch
Performance, illustrate that the flexible layer of graphenic surface cladding hinders the interaction between graphene sheet layer, influence graphene performance
Play.
4th, carbon nanomaterial modified pitch aging research
In order to preferably reflect the decay degree of performance after ageing of asphalt, the ageing properties of pitch are evaluated, before aging
The amplitude of variation of each performance is analyzed the ageing properties of asphalt sample afterwards, i.e., softening point increment, residual penetration ratio and
Viscosity ageing index VAI.
(1) softening point increment
Sensitivity of the asphalt sample to aging has also been reacted in the change of asphalt softening point, with the softening point after aging with
The difference of softening point before aging represents that test result is as shown in Figure 7.
(2) penetration ratio is remained
Pitch volatilizees in ageing process mainly due to light components, and low molecule converts to macromolecule, so as to show as dripping
Blue or green viscosity increase, needle penetration reduces, therefore the change of penetration number can react the old of asphalt binder to a certain degree before and after aging
Change degree, result of the test are as shown in Figure 8.
(3) viscosity ageing index
The viscosity of hot air aging post-modification pitch all increased, because during thermo-oxidative ageing, free oxygen
Aoxidized into modified pitch, cause pitch relative molecular mass to become big, and the environment heated accelerates in pitch light group
The volatilization divided so that molecular motion is obstructed, and allows it to vibrate or move without enough spaces, and macro manifestations are exactly poor fluidity,
So the viscosity of pitch has a certain degree of increase after aging.
Viscosity be react asphaltic nature window, before and after ageing of asphalt the change of viscosity can react the process of ageing of asphalt,
It is used for characterizing the degree of ageing of asphalt using viscosity ageing index (VAI), test result is as shown in table 1.
As seen from Figure 7, after TFOT agings, with the increase of three kinds of carbon nanomaterial dosages, the softening point of pitch increases
Value is all reducing, and the softening point increment of matrix pitch is 7.2 DEG C, and CNT when volume is 0.5%, graphene and this
Softening point increment corresponding to invention is respectively 5.4,4.9 and 5.4, that is, fills the later modified pitch aging journey of carbon nanomaterial
Degree is both less than matrix pitch.As seen from Figure 8, after aging, with the increase of three kinds of carbon nanomaterial dosages, pitch it is residual
Penetration ratio is stayed all to increase, the residual penetration ratio of matrix pitch is 0.658, and CNT, stone when volume is 0.5%
Black alkene and the corresponding residual penetration ratio of the present invention are respectively 0.689,0.772 and 0.759, i.e., after admixture carbon nanomaterial
Modified pitch degree of aging be both less than matrix pitch.As seen from Figure 9, after TFOT agings, with three kinds of carbon nanomaterials
The increase of dosage, the viscosity ageing index of pitch are all reducing, and the softening point increment of matrix pitch is 0.83, and volume is
Corresponding softening point increment is respectively 0.63,0.58 and 0.61 when CNT, graphene and the present invention when 0.5%, that is, is filled
The later modified pitch degree of aging of carbon nanomaterial is both less than matrix pitch.
In summary analysis it can be found that three kinds it is material modified have different degrees of improvement to pitch ageing-resistant performance,
Graphene and modified pitch resistance to ag(e)ing prepared by the present invention are better than what carbon nano-tube modification pitch showed.
5th, carbon nanomaterial modified pitch viscosity is studied
This experiment is using CNT, graphene and the present invention under Bu Shi viscosity apparatus measure different addition quantity to pitch viscosity
Influence, test temperature is respectively 90 DEG C, 105 DEG C, 120 DEG C and 135 DEG C.Figure 10 a, Figure 10 b, Figure 10 c and Figure 10 d give respectively
Different carbon nanomaterials are gone out at four temperature to the effect tendency figure of pitch viscosity.
With reference to figure 10a, Figure 10 b, Figure 10 c and Figure 10 d it can be found that influence of several carbon nanomaterials to pitch viscosity
It is not quite similar, using 0.3% volume as cut-point, the carbon nanomaterial modified pitch viscosity at four temperature before this volume
Size is arranged as graphene>CNT>The present invention is big in pitch under high speed shear and the effect of churned mechanically external force
Strand enters the piece interlayer of graphene, increases the distance of piece interlayer, forms intercal type and exfoliated composite construction,
Under high temperature, Sheet Graphite alkene hinders the molecular chain movement in pitch, molecule constricted flow, so as to can more lift the viscosity of pitch
Value.Carbon nanomaterial modified pitch viscosity size is arranged as CNT at four temperature after this volume>Graphene>This
Invention, its reason are：Compared with large dosage, CNT with after pitch blending, macromolecular chain and tubular structure in pitch
CNT be cross-linked with each other so that the change of frictional resistance is big between its interior molecules when flowing for pitch, shows as carbon and receives
Mitron can more improve the viscosity of pitch.
Claims (10)
1. a kind of preparation method of carbon nanomaterial modifying agent, it is characterised in that comprise the following steps：
It is dilute 1a) to obtain DC5700 grafting graphite, then DC5700 is grafted dilute be added to of graphite and fills methanol and deionized water mixing
In the three-necked flask of solution, RGO-DC5700 dispersion liquids are obtained after ultrasonic disperse；
The NPES-10 aqueous solution 2a) is taken, then the NPES-10 aqueous solution is added to step 1a) obtained RGO-DC5700 dispersion liquids
In, reaction is then stirred under the conditions of water bath with thermostatic control, after the completion for the treatment of its reaction, obtains reaction product；
3a) by step 2a) obtained reaction product carries out dialysis treatment by dialysis membrane, and then it is dried in vacuo again, obtains carbon
Nano-material modified dose.
2. the preparation method of carbon nanomaterial modifying agent according to claim 1, it is characterised in that the NPES-10 aqueous solution,
The dilute ratio with methanol and the mixed solution of deionized water of DC5700 grafting graphite is 0.2g：40mL：5ml, the NPES-10 aqueous solution
Concentration be 10.5%wt./voi.
3. the preparation method of carbon nanomaterial modifying agent according to claim 1, it is characterised in that methanol and deionized water
Mixed solution in the volume ratio of methanol and deionized water be 1：1.
4. the preparation method of carbon nanomaterial modifying agent according to claim 1, it is characterised in that step 2a) in constant temperature
The temperature of water-bath is 70 DEG C；
Step 3a) in vacuum drying carried out under 60 DEG C of environment.
5. the preparation method of carbon nanomaterial modifying agent according to claim 1, it is characterised in that step 3a) in dialyse
The molecular cut off of film is 8000-14000.
6. the preparation method of carbon nanomaterial modifying agent according to claim 1, it is characterised in that also include：Prepare stone
Black alkene, then it is dilute based on graphene synthesis DC5700 grafting graphite oxides, it is then based on the DC5700 grafting dilute synthesis of graphite oxide
DC5700 grafting graphite is dilute.
7. a kind of preparation method of carbon nanomaterial modified pitch, it is characterised in that comprise the following steps：
1b) matrix pitch is positioned in container, then container is toasted, matrix pitch is in molten condition, Ran Houzai
Moisture in stirring evaporation matrix pitch；
The carbon nanomaterial modifying agent that claim 1 is prepared 2b) is taken, then carbon nanomaterial modifying agent is added to container
In, then it is stirred, makes untill carbon nanomaterial modifying agent all submerges by matrix pitch, to obtain mixture；
3b) by step 2b) obtained mixture is stirred by mechanical agitator, then carries out constant temperature shearing, obtain carbon nanometer material
Expect modified pitch.
8. the preparation method of carbon nanomaterial modified pitch according to claim 7, it is characterised in that step 1b) in stir
The concrete operations of moisture mixed in evaporation matrix pitch are：Container is positioned on the electric furnace for being equipped with asbestos gauge, and stirs steaming
The moisture in matrix pitch is sent out, mixing time 10min, the temperature of stirring evaporation process mesostroma pitch is 170 DEG C.
9. the preparation method of carbon nanomaterial modified pitch according to claim 7, it is characterised in that step 3b) in will
Step 2b) mixing speed is 2000 turns/min during obtained mixture is stirred by mechanical agitator, during stirring
Between be 20min.
10. the preparation method of carbon nanomaterial modified pitch according to claim 1, it is characterised in that step 3b) in it is permanent
During temperature shearing, shear rate is 5000~6000 turns/min, shear time 40min.
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| CN108752850A (en) * | 2018-05-08 | 2018-11-06 | 上海浦兴路桥建设工程有限公司 | A kind of graphene oxide Modified coloured asphalt cementitious matter and preparation method thereof |
| CN109554072A (en) * | 2018-11-22 | 2019-04-02 | 武汉纺织大学 | A kind of water-based anticorrosive paint preparation method |
| CN110951266A (en) * | 2019-10-23 | 2020-04-03 | 长安大学 | High-performance modified asphalt and preparation method thereof |
| CN111983321A (en) * | 2020-08-19 | 2020-11-24 | 南京林业大学 | Preparation and electric heating performance evaluation method of nano graphene oxide modified asphalt mixture |
| CN112179936A (en) * | 2020-10-12 | 2021-01-05 | 南京林业大学 | Method for preparing nano graphene oxide modified asphalt and evaluating anti-aging performance |
| CN113817222A (en) * | 2021-09-15 | 2021-12-21 | 南京林业大学 | Method for improving dispersion degree of graphene powder and preparation of modified asphalt |
| CN115322410A (en) * | 2022-08-16 | 2022-11-11 | 哈尔滨工业大学 | Preparation method of graphene reinforced asphalt composite material with uniform dispersion and directional arrangement |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391299A (en) * | 2011-08-06 | 2012-03-28 | 江苏迅扬环保新材料有限公司 | Preparation method for organosilicon quaternary ammonium salt composite and application thereof |
| CN105372274A (en) * | 2015-10-30 | 2016-03-02 | 长安大学 | Method for evaluating dispersed state of nano ZnO in pitch |
-
2017
- 2017-11-22 CN CN201711176257.2A patent/CN107868278B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391299A (en) * | 2011-08-06 | 2012-03-28 | 江苏迅扬环保新材料有限公司 | Preparation method for organosilicon quaternary ammonium salt composite and application thereof |
| CN105372274A (en) * | 2015-10-30 | 2016-03-02 | 长安大学 | Method for evaluating dispersed state of nano ZnO in pitch |
Non-Patent Citations (2)
| Title |
|---|
| 苏东艳 等: "欧美石墨烯增强型复合材料项目近况眼镜", 《江苏科技信息》 * |
| 蔡秋红 等: "添加氧化石墨烯对煤沥青成焦行为的影响", 《煤炭学报》 * |
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| CN108587196A (en) * | 2018-04-20 | 2018-09-28 | 石梦成 | A kind of building asphalt and preparation method thereof that graphene is modified |
| CN108752850A (en) * | 2018-05-08 | 2018-11-06 | 上海浦兴路桥建设工程有限公司 | A kind of graphene oxide Modified coloured asphalt cementitious matter and preparation method thereof |
| CN109554072A (en) * | 2018-11-22 | 2019-04-02 | 武汉纺织大学 | A kind of water-based anticorrosive paint preparation method |
| CN110951266A (en) * | 2019-10-23 | 2020-04-03 | 长安大学 | High-performance modified asphalt and preparation method thereof |
| CN110951266B (en) * | 2019-10-23 | 2021-12-17 | 长安大学 | High-performance modified asphalt and preparation method thereof |
| CN111983321A (en) * | 2020-08-19 | 2020-11-24 | 南京林业大学 | Preparation and electric heating performance evaluation method of nano graphene oxide modified asphalt mixture |
| CN112179936A (en) * | 2020-10-12 | 2021-01-05 | 南京林业大学 | Method for preparing nano graphene oxide modified asphalt and evaluating anti-aging performance |
| CN113817222A (en) * | 2021-09-15 | 2021-12-21 | 南京林业大学 | Method for improving dispersion degree of graphene powder and preparation of modified asphalt |
| CN115322410A (en) * | 2022-08-16 | 2022-11-11 | 哈尔滨工业大学 | Preparation method of graphene reinforced asphalt composite material with uniform dispersion and directional arrangement |
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