CN107032335B - A kind of method that graphene is prepared based on magnetorheological glue stripping - Google Patents
A kind of method that graphene is prepared based on magnetorheological glue stripping Download PDFInfo
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- CN107032335B CN107032335B CN201710455770.9A CN201710455770A CN107032335B CN 107032335 B CN107032335 B CN 107032335B CN 201710455770 A CN201710455770 A CN 201710455770A CN 107032335 B CN107032335 B CN 107032335B
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- C01B2204/00—Structure or properties of graphene
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Abstract
The invention belongs to graphene to peel off preparing technical field, there is provided a kind of method that graphene is prepared based on magnetorheological glue stripping.This method is dispersed with the magnetorheological glue of crystalline flake graphite by preparing, and applies externally-applied magnetic field to it, and in the presence of magnetic shear force and magnetorheological glue stretching, crystalline flake graphite overcomes Van der Waals force between layers, and relative displacement occurs, realizes that stripping prepares graphene.Shearing force, material flow, material movement direction can effectively control in this method, can ensure that the shearing force that graphite is born is more uniform, and collision and stretching are uniform, and the graphene thickness for peeling off to obtain is uniform, and quality is high.
Description
Technical field
The technical field prepared is peeled off the present invention relates to graphene, is peeled off and prepared based on magnetorheological glue more particularly, to one kind
The method of graphene.
Background technology
Graphene is to construct the sp2 such as zero dimension fullerene, one-dimensional CNT, three-dimensional graphite as a kind of carbonaceous new material
The basic structural unit of hydridization carbon, it has unique carrier properties, electric transmission resistance is small, mechanical property is good, can produce
Quantum Interference and irregular quantum hall effect etc..Graphene has wide application space, in China, for its application
In nano biological sensor, nano anti-biotic material, conductive film, solar cell, energy accumulating device, high-speed chip etc.
Research obtained some progress.Abroad, graphene research starting it is more early, its in aerospace field, photon sensor, receive
Obvious leading China of research of rice electronic device, enhancing composite etc..Therefore, China should strengthen grinding graphene
Study carefully.
In the preparation method of graphene, mechanical stripping method is simple, efficient, environment friendly and pollution-free, turns into preferable selection, but
It is that mechanical energy caused by traditional ball mill is difficult to be accurately controlled, or the graphene that damage has been peeled off, or the stone that will have been peeled off
Black alkene extruding is overlapping again.Existing high mixer is also detrimental to due to shearing force, material flow, the uncontrollable of material movement direction
Peel off graphene.In these methods, with the continuous reduction of graphite size, its energy transfer efficiency it is more and more lower, it is necessary to
Energy is transmitted by medium, and this transmit is uneven, wants to be difficult to by grinding thinned graphite by force,
And particle position is geo-stationary in process of lapping, it is difficult to ensure that the uniform contact between raw material, so as to can not guarantee to produce
The uniformity of product, not only time-consuming, and obtained graphene number of plies distributed pole is uneven, thus quality defect.
The research for magnetic flow liquid is reported more at present.Xu et al. invented using three-procedure method prepare it is magnetorheological
The method of liquid, the carbonyl iron dust magnetic-particle coated with uniform of suspension nickel metal, not only reduce magnetic-particle generation
The possibility of reunion, the sedimentation of particle is effectively prevented, can also prevent the oxidation of magnetic-particle, and make to obtain magnetorheological
The magnetic saturation intensity of liquid greatly improves, and enhances resistance to settling, inoxidizability and anti-agglomeration.He et al. with polytetrafluoroethylene (PTFE),
Carbonyl iron dust is aided with filler and processing aid, and the magnetorheological materials with negative Poisson characteristics have been made.Liao et al. systems of having invented
The preparation method of standby Magneto-rheological viscoelastic fluid, mainly using hydroxy iron powder, methylsiloxane, phenyl siloxane, base catalysis
Agent and other auxiliary agents are raw material, and obtained viscoelastic fluid has compressibility, wear-resistant, service life length, and suspended phase is static
Stability is good, and mounting medium and additive are preferable in -90 ~ 250 DEG C of internal stabilities.
Research report at present to magnetorheological glue is less.Liu etc. is using polymer monomer, FeCl2•4H2O、FeCl3•
6H2O, surfactant, NaOH, initiator and catalyst, magnetorheological high-molecular gel has been prepared, the process forms three-dimensional friendship
Join network structure, loading is bigger, and controllability is more preferable, and the magnetorheological gel mechanical property of gained and rheomagnetic can be simultaneous excellent, stretching
Intensity and elongation at break are also higher.Guo etc. is prepared magneto-rheological combined using magnetic-particle, methyl-silicone oil and sol solution
Glue, shear yield strength add Nano-meter SiO_2 up to more than 92kPa2It can further improve its yield strength and storage modulus.Ye
For magnetorheological glue Deng development under larger magnetic field intensity, shear stress is larger, and to the dependence very little of shearing rate, storage modulus
Up to 7.98MPa, and the change curve of storage modulus is consistent with the variation tendency of magnetic flow liquid.
At present, crystalline flake graphite is scattered in magnetorheological glue, and caused collision stretching is acted on to peel off by magnetic shear
The research for preparing graphene has not been reported.Therefore, the present invention proposes such a method, prepares corresponding magnetorheological glue, leads to
Externally-applied magnetic field is crossed, makes to be scattered in interior graphite and generation graphene is peeled off in disorderly state, to solve the drawbacks of tradition machinery stripping,
With very big researching value.
The content of the invention
It is an object of the invention to provide a kind of method that graphene is prepared based on magnetorheological glue stripping, it has been found that magnetic current
Variant is tied up in the presence of external magnetic field, can produce shear stress, and its viscosity, the motion of magnetic particle and system stressing conditions can lead to
External magnetic field is crossed to be controlled by.Crystalline flake graphite is introduced in magnetorheological system, can be in disorderly shape during external magnetic field is applied
Graphite is collided under state and stretched, stripping turns into graphene.In order to reach stable dispersion of the crystalline flake graphite in magnetorheological system, I
Use magnetorheological glue, rather than magnetic flow liquid as magnetorheological system.And magnetorheological glue has to stone in motion process
The stretching action of ink, so as to peel off graphite；Solve conventional method to be difficult to accurately control, shear transfer is uneven, and damage has been shelled
From graphene or make the defects of it is overlapping again, and graphene product thickness is extremely uneven, it is most important, it is creative to apply magnetic current
Become stress and movement characteristic of the glue under magnetic field, collision stretching is carried out to crystalline flake graphite, it is ensured that graphene thickness is uniform, quality
It is high.
Concrete technical scheme of the present invention is as follows：
A kind of method that graphene is prepared based on magnetorheological glue stripping, using the viscosity of magnetorheological glue, magnetic pellet hardness and
The characteristics of motion of magnetic particle is controlled by external magnetic field, is scattered in magnetorheological glue by crystalline flake graphite, applies externally-applied magnetic field to it, in magnetic
In the presence of shearing force, magnetorheological glue stretching, crystalline flake graphite overcomes Van der Waals force between layers, and relative displacement occurs, real
Now stripping prepares graphene, comprises the following steps that：
（1）Surfactant is added in absolute ethyl alcohol, loads ball grinder, carbonyl iron dust is also then added into ball grinder
In, stir 10 ~ 20min；Then big small ball is put into ball grinder, 30 ~ 40min of ball milling, products obtained therefrom is placed in baking oven very
Sky drying, drying time are not less than 8h, cooled down after removing absolute ethyl alcohol, obtain surface-treated iron powder；
（2）Titanate coupling agent and natural scale graphite are added in high-speed mixer, temperature and rotating speed are set, at a high speed
20 ~ 30min of mixed processing, obtain surface-treated scale graphite；
（3）Rubber powder, glycerine, water are mixed, heating stirring is scattered to being completely dissolved, and then adds methyl-silicone oil, stirring
After uniformly, composite colloid is obtained；
（4）By step（1）The iron powder of gained, step（2）The graphite and step of gained（3）The colloid of gained, add in proportion
Enter ball grinder, initially stir 15 ~ 20min, be then placed in 1 ~ 1.5h of big small ball ball grinding stirring, after being thoroughly mixed and cooling down, obtain
To the equally distributed magnetorheological glue of scale graphite；
（5）Stir while to magnetorheological glue application externally-applied magnetic field, continue 30 ~ 60min, graphite occurs in disorderly state
Collision and stretching, phased separation is into graphene, after postmenstruation separating treatment, obtains that yield is higher, the more complete graphene of structure
Product.
Preferably, step（1）The surfactant is polyethylene glycol, its add quality for carbonyl iron dust quality 2% ~
3%；
Preferably, step（1）The average grain diameter of the carbonyl iron dust is not higher than 3.5 μm, and its iron content is not less than 98%；
Preferably, step（1）The addition quality of the absolute ethyl alcohol is the 20% ~ 30% of carbonyl iron dust；
Preferably, step（1）The speed initially stirred is 250 ~ 280r/min, the speed of ball grinding stirring for 200 ~
220r/min；
Preferably, step（1）The temperature of the vacuum drying is 80 ~ 90 DEG C, and vacuum is -0.09MPa；
Preferably, step（2）The temperature of the mixed at high speed processing is 80 ~ 100 DEG C, and rotating speed is 100 ~ 120r/min；
Preferably, step（2）The addition quality of the titanate coupling agent is the 1% ~ 2% of scale graphite quality；
Preferably, step（3）The rubber powder is the mixed-powder of gelatin and agaropectin, and its mass ratio is 3:1；
Preferably, step（3）The addition quality of the glycerine is the 30% ~ 40% of rubber powder quality, and the quality of water is rubber powder
1 ~ 1.5 times of quality, the quality of methyl-silicone oil are the 20 ~ 40% of rubber powder quality；
Preferably, step（4）In the mixture, iron powder quality proportion be 50% ~ 70%, graphite quality proportion be 10% ~
20%, colloid quality proportion is 20% ~ 30%；
Preferably, step（4）The speed initially stirred is 400 ~ 450r/min, and the speed of secondary ball milling stirring is
200~250r/min；
Preferably, step（5）The magnetic field intensity of the externally-applied magnetic field is 0.5 ~ 0.9T.
Generally, when mechanical lapping prepares graphene, with the reduction of graphite size, energy transfer efficiency reduces, and transmits
Uneven, the thickness discreteness of obtained graphene is larger, and graphene is difficult to keep complete molecular structure, and it is overlapping again to ask
Topic also fails to be resolved.And graphene is prepared using the collision and shearing stripping of high-speed mixer merely, its shearing force, graphite
The direction of motion and speed are difficult to control, and need to be improved.The present invention is by preparing the dispersed magnetorheological glue therein of graphite
Body, shearing force being produced by externally-applied magnetic field so that graphite follows the continuous varying motion of colloidal dispersion, and in collision and shearing force
Under effect, Van der Waals force is overcome between layers, relative displacement occurs, and phased separation obtains graphene.The presence of colloid, a side
Face improves the sedimentation stability of particle, is advantageous to the dispersed of magnetic particle and graphene, on the other hand has during exercise
Draftability, the distance between magnetic particle, between magnetic particle and graphite and between graphite flake layer is added, weaken Van der Waals force, make
It is more easily peelable to obtain graphene, and is not susceptible to again overlapping.
The invention provides a kind of method that graphene is prepared based on magnetorheological glue stripping, and compared with prior art, it is prominent
The characteristics of going out and excellent effect are：
1. the preparation method of the present invention controls viscosity, stressing conditions and the magnetic particle of magnetorheological glue to transport by externally-applied magnetic field
It is dynamic, accurate control can be achieved.
2. the present invention solves tradition machinery and peels off the graphene or make it again that shear transfer is uneven, and damage has been peeled off
The defects of overlapping.
3. the magnetic particle and graphite in the present invention stable dispersion, graphite can be peeled off uniform and stable in composite colloid.
4. graphene single layer content produced by the present invention is higher, thickness is more uniform.
Embodiment
Below by way of embodiment, the present invention is described in further detail, but this should not be interpreted as to the present invention
Scope be only limitted to following example.In the case where not departing from above method thought of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
A kind of method that graphene is prepared based on magnetorheological glue stripping, it is as follows that it prepares the detailed process of graphene：
1kg polyethylene glycol is added in 10kg absolute ethyl alcohols, loads ball grinder, 50kg carbonyl iron dusts is also then added into ball
In grinding jar, 10min is stirred with 280r/min speed.Then big small ball is put into ball grinder, with 210r/min speed
Ball milling 40min, products obtained therefrom are placed in baking oven, at 80 DEG C, are dried, time 8h, removed anhydrous with -0.09MPa vacuum
Cooled down after ethanol, obtain surface-treated iron powder；0.3kg titanate coupling agents and the natural scale graphites of 20kg are added to height
In fast mixer, it is 90 DEG C, rotating speed 120r/min to set temperature, handles 30min, obtains surface-treated scale graphite；
It is 3 by 30kg mass ratios:Rubber powder, 9kg glycerine and the mixing of 30kg water of 1 gelatin and agaropectin composition, heating stirring is extremely
It is completely dissolved, then adds 9kg methyl-silicone oils, after stirring, obtain composite colloid；Above-mentioned iron powder, graphite and colloid are added
Enter ball grinder, 20min is initially stirred with 400r/min speed, be then placed in after big small ball with 240r/min speed ball milling
1h is stirred, after being thoroughly mixed and cooling down, obtains the equally distributed magnetorheological glue of scale graphite；Stir while to magnetorheological glue
Apply the externally-applied magnetic field that intensity is 0.5T, continue 50min, graphite collides and stretched in disorderly state, phased separation Cheng Shi
Black alkene, after postmenstruation separating treatment, obtain that yield is higher, the more complete graphene product of structure.
The magnetorheological colloid obtained to embodiment 1, using its rheological property of rheometer test, obtained 10s-1During shearing rate
Shear stress values it is as shown in table 1；Structured testing and analysis are carried out to final graphene product, obtain individual layer and 2 ~ 5 layers of stone
The content of black alkene is as shown in table 2.
Embodiment 2
A kind of method that graphene is prepared based on magnetorheological glue stripping, it is as follows that it prepares the detailed process of graphene：
1kg polyethylene glycol is added in 10kg absolute ethyl alcohols, loads ball grinder, 50kg carbonyl iron dusts is also then added into ball
In grinding jar, 15min is stirred with 270r/min speed.Then big small ball is put into ball grinder, with 220r/min speed
Ball milling 35min, products obtained therefrom are placed in baking oven, at 85 DEG C, are dried, time 8h, removed anhydrous with -0.09MPa vacuum
Cooled down after ethanol, obtain surface-treated iron powder；0.3kg titanate coupling agents and the natural scale graphites of 20kg are added to height
In fast mixer, it is 80 DEG C, rotating speed 120r/min to set temperature, handles 25min, obtains surface-treated scale graphite；
It is 3 by 30kg mass ratios:Rubber powder, 9kg glycerine and the mixing of 30kg water of 1 gelatin and agaropectin composition, heating stirring is extremely
It is completely dissolved, then adds 9kg methyl-silicone oils, after stirring, obtain composite colloid；Above-mentioned iron powder, graphite and colloid are added
Enter ball grinder, 20min is initially stirred with 440r/min speed, be then placed in after big small ball with 200r/min speed ball milling
1.5h is stirred, after being thoroughly mixed and cooling down, obtains the equally distributed magnetorheological glue of scale graphite；Stir while to magnetorheological
Glue applies the externally-applied magnetic field that intensity is 0.6T, continues 40min, and graphite collides and stretch in disorderly state, phased separation into
Graphene, after postmenstruation separating treatment, obtain that yield is higher, the more complete graphene product of structure.
The magnetorheological colloid obtained to embodiment 2, using its rheological property of rheometer test, obtained 10s-1During shearing rate
Shear stress values it is as shown in table 1；Structured testing and analysis are carried out to final graphene product, obtain individual layer and 2 ~ 5 layers of stone
The content of black alkene is as shown in table 2.
Embodiment 3
A kind of method that graphene is prepared based on magnetorheological glue stripping, it is as follows that it prepares the detailed process of graphene：
1kg polyethylene glycol is added in 10kg absolute ethyl alcohols, loads ball grinder, 50kg carbonyl iron dusts is also then added into ball
In grinding jar, 20min is stirred with 270r/min speed.Then big small ball is put into ball grinder, with 220r/min speed
Ball milling 30min, products obtained therefrom are placed in baking oven, at 90 DEG C, are dried, time 8h, removed anhydrous with -0.09MPa vacuum
Cooled down after ethanol, obtain surface-treated iron powder；0.3kg titanate coupling agents and the natural scale graphites of 20kg are added to height
In fast mixer, it is 85 DEG C, rotating speed 110r/min to set temperature, handles 30min, obtains surface-treated scale graphite；
It is 3 by 30kg mass ratios:Rubber powder, 9kg glycerine and the mixing of 30kg water of 1 gelatin and agaropectin composition, heating stirring is extremely
It is completely dissolved, then adds 9kg methyl-silicone oils, after stirring, obtain composite colloid；Above-mentioned iron powder, graphite and colloid are added
Enter ball grinder, 20min is initially stirred with 400r/min speed, be then placed in after big small ball with 230r/min speed ball milling
1.5h is stirred, after being thoroughly mixed and cooling down, obtains the equally distributed magnetorheological glue of scale graphite；Stir while to magnetorheological
Glue applies the externally-applied magnetic field that intensity is 0.7T, continues 30min, and graphite collides and stretch in disorderly state, phased separation into
Graphene, after postmenstruation separating treatment, obtain that yield is higher, the more complete graphene product of structure.
The magnetorheological colloid obtained to embodiment 3, using its rheological property of rheometer test, obtained 10s-1During shearing rate
Shear stress values it is as shown in table 1；Structured testing and analysis are carried out to final graphene product, obtain individual layer and 2 ~ 5 layers of stone
The content of black alkene is as shown in table 2.
Embodiment 4
A kind of method that graphene is prepared based on magnetorheological glue stripping, it is as follows that it prepares the detailed process of graphene：
1.1kg polyethylene glycol is added in 11kg absolute ethyl alcohols, loads ball grinder, then also adds 55kg carbonyl iron dusts
In ball grinder, 10min is stirred with 250r/min speed.Then big small ball is put into ball grinder, with 200r/min speed
Ball milling 40min is spent, products obtained therefrom is placed in baking oven, at 80 DEG C, is dried with -0.09MPa vacuum, time 8h, is removed nothing
Cooled down after water-ethanol, obtain surface-treated iron powder；0.3kg titanate coupling agents and the natural scale graphites of 20kg are added to
In high-speed mixer, it is 100 DEG C, rotating speed 100r/min to set temperature, handles 30min, obtains surface-treated phosphorus slabstone
Ink；It is 3 by 25kg mass ratios:Rubber powder, 8kg glycerine and the mixing of 25kg water of 1 gelatin and agaropectin composition, heating stirring
To being completely dissolved, 8kg methyl-silicone oils are then added, after stirring, obtain composite colloid；By above-mentioned iron powder, graphite and colloid
Ball grinder is added, 15min is initially stirred with 430r/min speed, is then placed in after big small ball with 250r/min speed ball
Mill stirring 1h, after being thoroughly mixed and cooling down, obtains the equally distributed magnetorheological glue of scale graphite；Stir while to magnetorheological
Glue applies the externally-applied magnetic field that intensity is 0.7T, continues 50min, and graphite collides and stretch in disorderly state, phased separation into
Graphene, after postmenstruation separating treatment, obtain that yield is higher, the more complete graphene product of structure.
The magnetorheological colloid obtained to embodiment 4, using its rheological property of rheometer test, obtained 10s-1During shearing rate
Shear stress values it is as shown in table 1；Structured testing and analysis are carried out to final graphene product, obtain individual layer and 2 ~ 5 layers of stone
The content of black alkene is as shown in table 2.
Embodiment 5
A kind of method that graphene is prepared based on magnetorheological glue stripping, it is as follows that it prepares the detailed process of graphene：
1.2kg polyethylene glycol is added in 12kg absolute ethyl alcohols, loads ball grinder, then also adds 60kg carbonyl iron dusts
In ball grinder, 20min is stirred with 260r/min speed.Then big small ball is put into ball grinder, with 200r/min speed
Ball milling 30min is spent, products obtained therefrom is placed in baking oven, at 90 DEG C, is dried with -0.09MPa vacuum, time 8h, is removed nothing
Cooled down after water-ethanol, obtain surface-treated iron powder；0.3kg titanate coupling agents and the natural scale graphites of 20kg are added to
In high-speed mixer, it is 100 DEG C, rotating speed 110r/min to set temperature, handles 30min, obtains surface-treated phosphorus slabstone
Ink；It is 3 by 20kg mass ratios:Rubber powder, 6kg glycerine and the mixing of 20kg water of 1 gelatin and agaropectin composition, heating stirring
To being completely dissolved, 6kg methyl-silicone oils are then added, after stirring, obtain composite colloid；By above-mentioned iron powder, graphite and colloid
Ball grinder is added, 15min is initially stirred with 450r/min speed, is then placed in after big small ball with 220r/min speed ball
Mill stirring 1.5h, after being thoroughly mixed and cooling down, obtains the equally distributed magnetorheological glue of scale graphite；Stir while to magnetic current
Become glue and apply externally-applied magnetic field of the intensity into 0.7T, continue 60min, graphite collides and stretched in disorderly state, phased separation
Into graphene, after postmenstruation separating treatment, obtain that yield is higher, the more complete graphene product of structure.
The magnetorheological colloid obtained to embodiment 5, using its rheological property of rheometer test, obtained 10s-1During shearing rate
Shear stress values it is as shown in table 1；Structured testing and analysis are carried out to final graphene product, obtain individual layer and 2 ~ 5 layers of stone
The content of black alkene is as shown in table 2.
Embodiment 6
A kind of method that graphene is prepared based on magnetorheological glue stripping, it is as follows that it prepares the detailed process of graphene：
1kg polyethylene glycol is added in 10kg absolute ethyl alcohols, loads ball grinder, 50kg carbonyl iron dusts is also then added into ball
In grinding jar, 15min is stirred with 260r/min speed.Then big small ball is put into ball grinder, with 210r/min speed
Ball milling 35min, products obtained therefrom are placed in baking oven, at 85 DEG C, are dried, time 8h, removed anhydrous with -0.09MPa vacuum
Cooled down after ethanol, obtain surface-treated iron powder；0.3kg titanate coupling agents and the natural scale graphites of 20kg are added to height
In fast mixer, it is 80 DEG C, rotating speed 120r/min to set temperature, handles 25min, obtains surface-treated scale graphite；
It is 3 by 30kg mass ratios:Rubber powder, 9kg glycerine and the mixing of 30kg water of 1 gelatin and agaropectin composition, heating stirring is extremely
It is completely dissolved, then adds 9kg methyl-silicone oils, after stirring, obtain composite colloid；Above-mentioned iron powder, graphite and colloid are added
Enter ball grinder, 20min is initially stirred with 410r/min speed, be then placed in after big small ball with 230r/min speed ball milling
1.5h is stirred, after being thoroughly mixed and cooling down, obtains the equally distributed magnetorheological glue of scale graphite；Stir while to magnetorheological
Glue applies the externally-applied magnetic field that intensity is 0.8T, continues 30min, and graphite collides and stretch in disorderly state, phased separation into
Graphene, after postmenstruation separating treatment, obtain that yield is higher, the more complete graphene product of structure.
The magnetorheological colloid obtained to embodiment 6, using its rheological property of rheometer test, obtained 10s-1During shearing rate
Shear stress values it is as shown in table 1；Structured testing and analysis are carried out to final graphene product, obtain individual layer and 2 ~ 5 layers of stone
The content of black alkene is as shown in table 2.
Embodiment 7
A kind of method that graphene is prepared based on magnetorheological glue stripping, it is as follows that it prepares the detailed process of graphene：
1kg polyethylene glycol is added in 10kg absolute ethyl alcohols, loads ball grinder, 50kg carbonyl iron dusts is also then added into ball
In grinding jar, 20min is stirred with 260r/min speed.Then big small ball is put into ball grinder, with 210r/min speed
Ball milling 30min, products obtained therefrom are placed in baking oven, at 85 DEG C, are dried, time 8h, removed anhydrous with -0.09MPa vacuum
Cooled down after ethanol, obtain surface-treated iron powder；0.3kg titanate coupling agents and the natural scale graphites of 20kg are added to height
In fast mixer, it is 90 DEG C, rotating speed 115r/min to set temperature, handles 30min, obtains surface-treated scale graphite；
It is 3 by 30kg mass ratios:Rubber powder, 9kg glycerine and the mixing of 30kg water of 1 gelatin and agaropectin composition, heating stirring is extremely
It is completely dissolved, then adds 9kg methyl-silicone oils, after stirring, obtain composite colloid；Above-mentioned iron powder, graphite and colloid are added
Enter ball grinder, 15min is initially stirred with 400r/min speed, be then placed in after big small ball with 250r/min speed ball milling
1h is stirred, after being thoroughly mixed and cooling down, obtains the equally distributed magnetorheological glue of scale graphite；Stir while to magnetorheological glue
Apply the externally-applied magnetic field that intensity is 0.9T, continue 50min, graphite collides and stretched in disorderly state, phased separation Cheng Shi
Black alkene, after postmenstruation separating treatment, obtain that yield is higher, the more complete graphene product of structure.
The magnetorheological colloid obtained to embodiment 7, using its rheological property of rheometer test, obtained 10s-1During shearing rate
Shear stress values it is as shown in table 1；Structured testing and analysis are carried out to final graphene product, obtain individual layer and 2 ~ 5 layers of stone
The content of black alkene is as shown in table 2.
Table 1：
, can by the shear stress of obtained magnetorheological colloid and the individual layer of graphene in embodiment and 2 ~ 5 layers of content
See：
（1）The magnetic field intensity of stationary magnetic field is higher, and the shear stress of magnetorheological colloid is bigger, and the stripping rate of graphene is got over
Height, single-layer graphene content is higher, and graphene thickness distribution is more uniform.When magnetic field intensity increases to more than 0.8T, this influence
It is gradually reduced.
（2）In the range of colloid usage amount involved in the present invention, colloidal content increase, it is also beneficial to improve to shear and answers
Power, obtain thickness smaller graphene product evenly.
Claims (10)
- A kind of 1. method that graphene is prepared based on magnetorheological glue stripping, it is characterised in that be scattered in crystalline flake graphite magnetorheological Glue, externally-applied magnetic field is applied to it, in the presence of magnetic shear force and magnetorheological glue stretching, crystalline flake graphite overcomes between layers Van der Waals force, relative displacement occurs, realizes that stripping prepares graphene；What is prepared comprises the following steps that：（1）Surfactant is added in absolute ethyl alcohol, loads ball grinder, then carbonyl iron dust is also added in ball grinder, stirred 10 ~ 20min is mixed, then big small ball is put into ball grinder, 30 ~ 40min of ball milling, products obtained therefrom is placed in vacuum in baking oven and dried Dry, drying time is not less than 8h, is cooled down after removing absolute ethyl alcohol, obtains surface-treated iron powder；（2）Titanate coupling agent and natural scale graphite are added in high-speed mixer, temperature and rotating speed, mixed at high speed are set 20 ~ 30min is handled, obtains surface-treated scale graphite；（3）Rubber powder, glycerine and water are mixed, then heating stirring adds methyl-silicone oil to being completely dissolved, after stirring, Obtain composite colloid；（4）By step（1）The iron powder of gained, step（2）The graphite and step of gained（3）The colloid of gained, is proportionally added into ball Grinding jar, 15 ~ 20min is initially stirred, 1 ~ 1.5h of big small ball ball grinding stirring is then placed in, after being thoroughly mixed and cooling down, obtains phosphorus The equally distributed magnetorheological glue of piece graphite；（5）Stir while to magnetorheological glue application externally-applied magnetic field, continue 30 ~ 60min, graphite collides in disorderly state And stretching, phased separation is into graphene, after postmenstruation separating treatment, obtains that yield is higher, the more complete graphene product of structure.
- A kind of 2. method that graphene is prepared based on magnetorheological glue stripping according to claim 1, it is characterised in that：Step （1）The surfactant is polyethylene glycol, and it adds 2% ~ 3% that quality is carbonyl iron dust quality；The carbonyl iron dust is put down Equal particle diameter is not higher than 3.5 μm, and its iron content is not less than 98%；The addition quality of the absolute ethyl alcohol for carbonyl iron dust 20% ~ 30%。
- A kind of 3. method that graphene is prepared based on magnetorheological glue stripping according to claim 1, it is characterised in that：Step （1）The speed initially stirred is 250 ~ 280r/min, and the speed of ball grinding stirring is 200 ~ 220r/min.
- A kind of 4. method that graphene is prepared based on magnetorheological glue stripping according to claim 1, it is characterised in that：Step （1）The temperature of the vacuum drying is 80 ~ 90 DEG C, and vacuum is -0.09MPa.
- A kind of 5. method that graphene is prepared based on magnetorheological glue stripping according to claim 1, it is characterised in that：Step （2）The temperature of the mixed at high speed processing is 80 ~ 100 DEG C, and rotating speed is 100 ~ 120r/min.
- A kind of 6. method that graphene is prepared based on magnetorheological glue stripping according to claim 1, it is characterised in that：Step （2）The addition quality of the titanate coupling agent is the 1% ~ 2% of scale graphite quality.
- A kind of 7. method that graphene is prepared based on magnetorheological glue stripping according to claim 1, it is characterised in that：Step （3）The rubber powder is the mixed-powder of gelatin and agaropectin, and its mass ratio is 3:1；The addition quality of the glycerine is glue The 30% ~ 40% of silty amount, the quality of water are 1 ~ 1.5 times of rubber powder quality, and the quality of methyl-silicone oil is the 20 ~ 40% of rubber powder quality.
- A kind of 8. method that graphene is prepared based on magnetorheological glue stripping according to claim 1, it is characterised in that：Step （4）In the mixture, iron powder quality proportion is 50% ~ 70%, and graphite quality proportion is 10% ~ 20%, and colloid quality proportion is 20% ~30%。
- A kind of 9. method that graphene is prepared based on magnetorheological glue stripping according to claim 1, it is characterised in that：Step （4）The speed initially stirred is 400 ~ 450r/min, and the speed of secondary ball milling stirring is 200 ~ 250r/min.
- A kind of 10. method that graphene is prepared based on magnetorheological glue stripping according to claim 1, it is characterised in that：Step （5）The magnetic field intensity of the externally-applied magnetic field is 0.5 ~ 0.9T.
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