CN107337804A - A kind of PET/ micro crystal graphites alkene composite heat conducting film and preparation method thereof - Google Patents
A kind of PET/ micro crystal graphites alkene composite heat conducting film and preparation method thereof Download PDFInfo
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- CN107337804A CN107337804A CN201710661706.6A CN201710661706A CN107337804A CN 107337804 A CN107337804 A CN 107337804A CN 201710661706 A CN201710661706 A CN 201710661706A CN 107337804 A CN107337804 A CN 107337804A
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Abstract
The present invention relates to graphene composite material preparation field, discloses a kind of PET/ graphene composite materials heat conducting film and preparation method thereof.Creative uses micro crystal graphite to prepare expanded graphite by secondary intercalation for raw material, then mechanical stripping method, pass through ultrasound, obtain the graphene product of high-quality, the optimization for passing through technique around graphene product, it is possible to achieve be prepared on a large scale to obtain the PET/ graphene composite material heat conducting films of high thermal conductivity.The graphene coating layer thickness for the PET/ graphene composite material heat conducting films being prepared is 3~9 μm, and thermal diffusion coefficient is 8~12 cm2/ S, thermal conductivity factor are 1400~1700 W/（m·k）.
Description
Technical field
It is compound more particularly, to a kind of PET/ micro crystal graphites alkene the invention belongs to graphene composite material preparation field
Material conducts heat film and preparation method thereof.
Background technology
For electronic product, its all parts effectively radiates is used for the longevity to obtain relatively low operating temperature
Life and the speed of service can produce extremely important influence.As the continuous development and progress of science and technology, particularly computer chip are more
Coring has become main flow, and the speed of service is constantly accelerated, and power also increases, and effective radiating rises to its speed of service
Very important effect.At present, the radiating main product of in the market is graphite-like heat conducting film, however, its heat dispersion is much
It can not meet the radiating requirements of electronics and IT products radiating element, become the radiating bottleneck of most electronic product.
Graphene composite material heat conducting film generally use oxidation-reduction method prepares graphene, takes the side for spraying to substrate
Formula, as Chinese patent CN2014103071579 discloses the preparation method and product of graphene composite heat conduction film, preparation method
Comprise the following steps：S1, crystalline flake graphite or graphite powder are placed in the mixed liquor of the concentrated sulfuric acid, potassium peroxydisulfate and phosphorus pentoxide
Diel is soaked, then filters and dries, completes pre-oxidation；S2, it is further to the graphite after pre-oxidation using Hummers methods
Oxidation, i.e., fully oxidized, then addition deionized water dilution is carried out in the concentrated sulfuric acid and potassium permanganate, after washing filters repeatedly,
Obtain graphene oxide water solution；S3, graphene oxide water solution is sprayed on substrate using hot spray process, deposition obtains
Graphene oxide film；S4, graphene oxide film is reduced, obtain graphene film；S5, graphene film is entered
Row aluminum coated steel, obtain graphene composite heat conduction film；Problems be present in the patent：1. if using Hummers methods, in oxygen
The conjugated structure of graphene film can be destroyed during change, causes heat transfer limited, so as to influence heat conductivility.2. use spraying process
It is inefficient, can also cause graphene oxide to waste.
Meanwhile at present the usually used graphene of graphene composite material heat conducting film be all by crystalline flake graphite be prepared into Lai,
Micro crystal graphite compares with Scaly graphite, and crystal habit has prominent otherness, and, in aggregate is inlayed, particle is small for the former,
Visible morphon under electron microscope；The latter disperses flakey in monocrystalline, and chip naked eyes are visible.The two belongs in chemical reaction
Property, crystalline orientation etc. have notable difference.It is few at present to expand microlite on being prepared using micro crystal graphite
Ink, graphene is then prepared again, and the graphene being prepared using micro crystal graphite prepares PET/ micro crystal graphite alkene composite woods
Expect the technical method research report of heat conducting film.
The content of the invention
In view of the shortcomings of the prior art, at the same for rationally, fully exploitation micro crystal graphite resource, break through using micro crystal graphite as
Raw material prepares the technical bottleneck of graphene composite material, and the present invention provides a kind of system of PET/ graphene composite materials heat conducting film
Preparation Method, creative uses micro crystal graphite to prepare expanded graphite by secondary intercalation method for raw material, then mechanical stripping method,
By ultrasound, the graphene product of high-quality is obtained, the optimization around graphene product by technique, while can also realize
It is prepared on a large scale to obtain the PET/ micro crystal graphite alkene composite heat conducting films of high thermal conductivity.
The present invention also provides a kind of PET/ graphene composite material heat conducting films being prepared using the above method.
The purpose of the present invention is achieved by the following technical programs：
A kind of preparation method of PET/ micro crystal graphites alkene composite heat conducting film, comprises the following steps：
S1. graphene is placed in de-airing mixer, adds absolute ethyl alcohol, stirring obtains graphene/ethanol mixing slurry
Material；
S2.PET film coronas：Sided corona treatment is carried out to 30 μ m thick PET using corona machine；
S3. desk-top coating machine is used to be coated on mixed uniformly graphene/ethanol slurry at corona in a manner of hanging painting
In the PET film managed, scraper is highly 20~40mm；
S4. processing is dried in the coated PET films of step S4；
S5. hot rolling processing is carried out to dried PET film using two pairs of rollers roll squeezer, obtains PET base graphene heat conduction
Film；
S6. the PET base graphenes heat conducting film after handling rolling carry out cutting edge handle to obtain the consistent PET/ of size it is micro-
Brilliant graphene composite material heat conducting film；
Wherein：Graphene described in step S1 is prepared by micro crystal graphite, is comprised the following steps that：
S11. micro crystal graphite raw material, crushing and grinding, to the microlite ink powder that granularity is 300~400 mesh, to microlite are taken
Ink powder carries out first time intercalation processing, second of intercalation processing, high temperature puffing processing successively, obtains expansion micro crystal graphite；
S12. expansion micro crystal graphite obtained by step S11 is mixed with stripper, be placed on after dilution in supersonic reaction device
Instead, obtain peeling off material；
S13. material press filtration, separation will be peeled off in step S12, then collects Graphite Cake, stripper, which can then circulate, to be made
With；
S14. clean：Graphite Cake in step S13 is cleaned, obtains graphene；
Wherein, stripper described in step S12 is graphene quantum dot, and extension rate is 5 times, supersonic reaction device
Temperature is 50 DEG C, frequency 25000Hz, flow velocity 5.0m3/ h, circulation stirring speed are 2000r/min, ultrasonic disperse time
For 2h；
Cleaned described in step S14 and refer to use deionized water, wash number is 3~5 times.
Preferably, the mass ratio of graphene and absolute ethyl alcohol is 1 in step S1:60~80.
Preferably, the rotating speed of de-airing mixer is 800~1800r/min in step S1, and stirred tank pressure is -0.1 Mpa,
Mixing time is 6~10h.
Preferably, the discharge power of corona machine is 0.5KVA~1.8KVA, 150~450r/min of rotating speed in step S2.
Preferably, drying process refers in 60 DEG C of vacuum drying chamber described in step S4, dries 12h.
Preferably, the upper mould temperature stabilization of the processing of heat rolling described in step S5 is 90~110 DEG C, lower mould temperature stabilization
For 90~110 DEG C, rotating speed is 30~100r/min.
Preferably, the preparation of step S11 expansions micro crystal graphite comprises the following steps：
S111. micro crystal graphite raw material, phosphorus content 75%, crushing and grinding, to the microlite ink powder that granularity is 300 mesh are taken；
S112. microlite ink powder obtained by step S111 is placed in reaction unit with perchloric acid and potassium permanganate and carries out the
Chemical graft processing, obtains inflatable micro crystal graphite acidic suspension, micro crystal graphite acidic suspension is may expand to gained
Filtering, reservation filtrate is standby, wherein, first time chemical graft concretely comprises the following steps：S1121. by perchloric acid and microlite ink powder
Body is 20 by liquid-solid ratio：1L/Kg is mixed evenly；S1122. it is 6 by the mass ratio of micro crystal graphite powder and strong oxidizer：1
Strong oxidizer is added, after being stirred at room temperature uniformly, 50 DEG C is warming up to and continues stirring reaction 1h；S1123. deionized water is added
The temperature in reaction unit is increased to 90 DEG C, be further continued for stirring reaction 1h；
S113. it may expand toward step S112 gained and concentrated nitric acid added in micro crystal graphite acidic suspension, carry out second and change
Intercalation processing is learned, obtains secondary inflatable micro crystal graphite acidic suspension, inflatable micro crystal graphite secondary to gained is acid to suspend
Liquid filtering, washing, dry, obtain inflatable micro crystal graphite；Wherein, what second of chemical graft was handled concretely comprises the following steps：S1131.
It is 5 that concentrated nitric acid and microlite ink powder are pressed into liquid-solid ratio：1L/Kg is added in inflatable acidic suspension, is mixed evenly；
S1132. adding deionized water makes the temperature in the reaction unit be increased to 100 DEG C, is further continued for stirring reaction 1h.
S114. inflatable micro crystal graphite obtained by step S113 is placed in graphite expansion stove, carries out high-temperature expansion, obtain
Expand micro crystal graphite；Wherein high-temperature expansion concretely comprises the following steps：S1141. feed：Using conserving graphite expanding furnace, by expansible graphite
Put into by charging aperture in burner hearth, the temperature of the charging aperture is 30 DEG C, and dispensing speed is 2Kg/h；S1142. expand：Stove
The expansion temperature of thorax is 900 DEG C, by controlled wind speed come to control Bulking Time be 5s；S1143. discharge：Complete step S1142
Afterwards, discharging opening temperature is 50 DEG C, then collects to obtain expansion micro crystal graphite in discharge outlet.
The present invention also protects a kind of preparation method of PET/ graphene composite materials heat conducting film that PET/ graphenes are prepared
Composite heat conducting film.
Preferably, the graphene coating layer thickness of the PET/ graphene composite materials heat conducting film is 3~9 μm, thermal diffusion system
Number is 8~12cm2/ S, thermal conductivity factor are 1400~1700W/ (mk).
Compared with prior art, the beneficial effects of the invention are as follows：
(1) present invention can destroy the conjugated structure of graphene film for Hummers methods in oxidizing process, cause to conduct heat
The problem of limited, using mechanical stripping method, in order to provide graphene product quality, graphene quantum dot is used as stripper,
Increasing prestripping handling process in prior art basis, coordinate and be ultrasonically treated, the graphene film Rotating fields being prepared are homogeneous,
Permeability is preferable, and the graphene product of oxidation-reduction method preparation, the graphene are superior on electric conductivity and heat conductivility
It can be applied to prepare PET/ graphene composite material heat conducting films by processing further.
(2) graphene product that the present invention obtains around ultrasonic mechanical stripping, has been carried out preferably to technique, specifically right
Rolling pressure, coating thickness, solvent species and slurry viscosity are adjusted, and it is compound to drastically increase PET/ graphenes
The heat conductivility of material conducts heat film, and large-scale production can be realized.
(3) the graphene coating layer thickness for the PET/ graphene composite material heat conducting films that the present invention is prepared is 3~9 μm,
Thermal diffusion coefficient is 8~12cm2/ S, thermal conductivity factor are 1400~1700W/ (mk).
(4) present invention prepares expanded graphite alkene material using micro crystal graphite, there is provided a kind of new application of micro crystal graphite.
Preparing creative use intercalation combination twice high-temperature expansion during grapheme material using micro crystal graphite, to prepare expansion micro-
Spar ink, makes the expansion multiple of expansion micro crystal graphite reach 260 times.The present invention is added without during preparing grapheme material
The material of sulfur-bearing, therefore during high temperature prepares expansion micro crystal graphite, do not produce sulfur dioxide pollution thing, preparation it is swollen
Swollen graphite products and grapheme material also not sulfur-bearing, improve the corrosion resistance of grapheme material, the present invention is at high-temperature expansion
During reason, traditional high-temperature expansion method and graphite expansion stove are combined, using optimal expansion temperature, and around expansion temperature
Degree can effectively improve the stability of product by the control to raw material and technological parameter, using above-mentioned expanded graphite as machine
Tool stripping method prepares the raw material of graphene, and the stripping rate of graphene can be greatly improved.It is more beneficial for subsequent ultrasonic stripping
Process.
(5) present invention uses micro crystal graphite, and the chip of micro crystal graphite is less than crystalline flake graphite, is given birth to by raw material of micro crystal graphite
The cost of graphene will be not only greatly lowered in production graphene, while will also make up market to small size, specific area graphene
Demand, solve in the prior art the features such as graphene preparation method cycle is long, is difficult to meet industrialized production, while also sharp
With the micro crystal graphite resources advantage of China's abundant.
Brief description of the drawings
Fig. 1 is graphite expansion furnace structure figure of the present invention.
Embodiment
The present invention is further illustrated with reference to specific embodiment.Following examples are only illustrative examples, not structure
Into inappropriate limitation of the present invention, the multitude of different ways that the present invention can be limited and covered by the content of the invention is implemented.It is unless special
Do not mentionlet alone bright, the present invention reagent, compound and the equipment that use is the art conventional reagent, compound and equipment.
Embodiment 1
The present embodiment provides a kind of preparation method of expanded graphite, specially following steps：
S111. micro crystal graphite raw material, phosphorus content 75%, crushing and grinding, to the microlite ink powder that granularity is 300 mesh are taken；
S112. microlite ink powder obtained by step S111 is placed in reaction unit with perchloric acid and potassium permanganate and carries out the
Chemical graft processing, obtains inflatable micro crystal graphite acidic suspension, micro crystal graphite acidic suspension is may expand to gained
Filtering, reservation filtrate is standby, wherein, first time chemical graft concretely comprises the following steps：S1121. by perchloric acid and microlite ink powder
Body is 20 by liquid-solid ratio：1L/Kg is mixed evenly；S1122. it is 6 by the mass ratio of micro crystal graphite powder and strong oxidizer：1
Strong oxidizer is added, after being stirred at room temperature uniformly, 50 DEG C is warming up to and continues stirring reaction 1h；S1123. deionized water is added
The temperature in reaction unit is increased to 90 DEG C, be further continued for stirring reaction 1h；
S113. it may expand toward step S112 gained and concentrated nitric acid added in micro crystal graphite acidic suspension, carry out second and change
Intercalation processing is learned, obtains secondary inflatable micro crystal graphite acidic suspension, inflatable micro crystal graphite secondary to gained is acid to suspend
Liquid filtering, washing, dry, obtain inflatable micro crystal graphite；Wherein, what second of chemical graft was handled concretely comprises the following steps：S1131.
It is 5 that concentrated nitric acid and microlite ink powder are pressed into liquid-solid ratio：1L/Kg is added in inflatable acidic suspension, is mixed evenly；
S1132. adding deionized water makes the temperature in the reaction unit be increased to 100 DEG C, is further continued for stirring reaction 1h.
S114. inflatable micro crystal graphite obtained by step S113 is placed in graphite expansion stove, carries out high-temperature expansion, obtain
Expand micro crystal graphite；Wherein high-temperature expansion concretely comprises the following steps：S1141. feed：Using conserving graphite expanding furnace, by expansible graphite
Put into by charging aperture in burner hearth, the temperature of the charging aperture is 30 DEG C, and dispensing speed is 2Kg/h；S1142. expand：Stove
The expansion temperature of thorax is 900 DEG C, by controlled wind speed come to control Bulking Time be 5s；S1143. discharge：Complete step S1142
Afterwards, discharging opening temperature is 50 DEG C, then collects to obtain expansion micro crystal graphite in discharge outlet.
The expansion multiple of expansion micro crystal graphite is 260 obtained by the present embodiment, is wormlike porous material, pore-size distribution model
Enclose for 1~100nm, specific surface area 598m2/ g, resistivity are 8.12 × 10-4Ω·m。
Comparative example 1
Comparative example 1 is with the difference of embodiment 1：High-temperature expansion is without using high-temperature expansion stove, using traditional Muffle
Stove, coordinate high-temperature expansion method, specifically different steps is as follows：
S114. inflatable micro crystal graphite obtained by step S113 is placed in Muffle furnace and heats calcination process, at 900 DEG C
High-temperature expansion is carried out, Bulking Time 30s, obtains expanding micro crystal graphite；
The expansion multiple of expansion micro crystal graphite is 190 obtained by the present embodiment, is wormlike porous material, pore-size distribution model
Enclose for 1~100nm, specific surface area 498m2/ g, resistivity are 8.65 × 10-4Ω·m。
Embodiment 2
The present embodiment provides a kind of method for preparing graphene using expanded graphite in embodiment 1, is specially following walk
Suddenly：
S11. the expansion micro crystal graphite that Example 1 obtains；
S12. expansion micro crystal graphite obtained by step S11 is mixed with graphene quantum dot, ultrasound is placed on after 5 times of dilution
React 2h in reaction unit, the temperature of supersonic reaction device is 50 DEG C, frequency 25000Hz, flow velocity 5.0m3/ h, circulation are stirred
It is 2000r/min to mix speed, after obtain peel off material；
S13. material press filtration, separation will be peeled off in step S12, then collects Graphite Cake, stripper, which can then circulate, to be made
With；
S14. clean：By the Graphite Cake deionized water in step S13, wash number is 4 times, obtains graphene.
Comparative example 2
The difference of this comparative example and embodiment 2 is that this comparative example uses the expansion that embodiment 1 is prepared
Micro crystal graphite.
Comparative example 3
The difference of this comparative example and embodiment 2 is that this comparative example uses the expansion that comparative example 1 is prepared
Micro crystal graphite.
The graphene that embodiment 2 and comparative example 2~3 are prepared carries out AFM test, and atomic force shows
Micro mirror is used to the lateral dimension and longitudinal thickness of analysis test nanometer two-dimensional material.Specifically, the AFM in this experiment is characterized
It is to be completed by Chinese Marine University, the NtegraPrimaSPM type AFMs produced using Russian NT-MDT,
Prepare the two-dimentional thickness phenetic analysis of material, conclusion is as shown in table 1.
Table 1
| Embodiment | Vertical height (nm) | Lateral separation (nm) | Lamella particle diameter (nm) | Lamellar spacing (nm) |
| Embodiment 2 | 3.86 | 467 | 467 | 3.86 |
| Comparative example 2 | 4.84 | 521 | 521 | 4.84 |
| Comparative example 3 | 4.51 | 508 | 508 | 4.51 |
As known from Table 1, can the piece number of plies of the preliminary graphene of projection example 1 (thickness of single-layer graphene is for 1~5 layer
0.334nm).This shows that the graphene film number of plies is mainly distributed on 1~10 layer, but there is also a small amount of piece number of plies in sample to be more than
10 layers of class graphene product.And embodiment 2, the effect of embodiment 3 it is poor once, the effect of comparative example 1 is worst.
Embodiment 3
The present embodiment provides a kind of preparation method of PET/ graphene composite materials heat conducting film, comprises the following steps：
S1. the graphene that selection example 2 is prepared is as raw material；
S2. the graphene in step S1 is placed in de-airing mixer, adds absolute ethyl alcohol, graphene and absolute ethyl alcohol
Mass ratio be 1:60, the rotating speed of de-airing mixer is 1800r/min, and stirred tank pressure is -0.1 Mpa, mixing time 6h,
Stirring obtains graphene/ethanol mixed slurry；
S3.PET film coronas：Sided corona treatment is carried out to 30 μ m thick PET using corona machine, the discharge power of corona machine is
1.8KVA, rotating speed 150r/min；
Use desk-top coating machine that mixed uniformly graphene/ethanol slurry is coated on into sided corona treatment in a manner of hanging painting
In the PET film crossed, scraper is highly 20mm；
S5. processing is dried in the coated PET films of step S4, specifically in 60 DEG C of vacuum drying chamber, dried
12h；
S6. hot rolling processing is carried out to dried PET film using two pairs of rollers roll squeezer, mould temperature is gone up in hot rolling process
90 DEG C are stabilized to, lower mould temperature stabilization is 90 DEG C, rotating speed 100r/min, obtains PET base graphene heat conducting films；
S7. the PET base graphenes heat conducting film after handling rolling carries out cutting edge and handles to obtain the consistent PET/ stones of size
Black alkene composite heat conducting film.
Embodiment 4
The present embodiment provides a kind of preparation method of PET/ graphene composite materials heat conducting film, comprises the following steps：
S1. the graphene that selection example 2 is prepared is as raw material；
S2. the graphene in step S1 is placed in de-airing mixer, adds absolute ethyl alcohol, graphene and absolute ethyl alcohol
Mass ratio be 1:70, the rotating speed of de-airing mixer is 1000r/min, and stirred tank pressure is -0.1 Mpa, mixing time 8h,
Stirring obtains graphene/ethanol mixed slurry；
S3.PET film coronas：Sided corona treatment is carried out to 30 μ m thick PET using corona machine, the discharge power of corona machine is
1.0KVA, rotating speed 300r/min；
S4. desk-top coating machine is used to be coated on mixed uniformly graphene/ethanol slurry at corona in a manner of hanging painting
In the PET film managed, scraper is highly 30mm；
S5. processing is dried in the coated PET films of step S4, specifically in 60 DEG C of vacuum drying chamber, dried
12h；
S6. hot rolling processing is carried out to dried PET film using two pairs of rollers roll squeezer, mould temperature is gone up in hot rolling process
100 DEG C are stabilized to, lower mould temperature stabilization is 100 DEG C, rotating speed 80r/min, obtains PET base graphene heat conducting films；
S7. the PET base graphenes heat conducting film after handling rolling carries out cutting edge and handles to obtain the consistent PET/ stones of size
Black alkene composite heat conducting film.
Embodiment 5
The present embodiment provides a kind of preparation method of PET/ graphene composite materials heat conducting film, comprises the following steps：
S1. the graphene that selection example 2 is prepared is as raw material；
S2. the graphene in step S1 is placed in de-airing mixer, adds absolute ethyl alcohol, graphene and absolute ethyl alcohol
Mass ratio be 1:80, the rotating speed of de-airing mixer is 800r/min, and stirred tank pressure is -0.1 Mpa, mixing time 10h,
Stirring obtains graphene/ethanol mixed slurry；
S3.PET film coronas：Sided corona treatment is carried out to 30 μ m thick PET using corona machine, the discharge power of corona machine is
0.5KVA, rotating speed 450r/min；
S4. desk-top coating machine is used to be coated on mixed uniformly graphene/ethanol slurry at corona in a manner of hanging painting
In the PET film managed, scraper is highly 40mm；
S5. processing is dried in the coated PET films of step S4, specifically in 60 DEG C of vacuum drying chamber, dried
12h；
S6. hot rolling processing is carried out to dried PET film using two pairs of rollers roll squeezer, mould temperature is gone up in hot rolling process
110 DEG C are stabilized to, lower mould temperature stabilization is 110 DEG C, rotating speed 30r/min, obtains PET base graphene heat conducting films；
S7. the PET base graphenes heat conducting film after handling rolling carries out cutting edge and handles to obtain the consistent PET/ stones of size
Black alkene composite heat conducting film.
Comparative example 4
The present embodiment is substantially the same manner as Example 3, and difference is, is prepared in step S1 using comparative example 2
Graphene is raw material.
Comparative example 5
The present embodiment is substantially the same manner as Example 3, and difference is, is prepared in step S1 using comparative example 3
Graphene is raw material.
Comparative example 6
This comparative example provides one kind and prepares graphene oxide using Hummers methods, then obtains PET/ graphenes through reduction
The preparation method of composite heat conducting film, comprises the following steps：
S1. graphene oxide is prepared using Hummers methods；
S2. the graphene oxide in step S1 is placed in de-airing mixer, add absolute ethyl alcohol, graphene oxide with
The mass ratio of absolute ethyl alcohol is 1:70, the rotating speed of de-airing mixer is 1000r/min, and stirred tank pressure is -0.1Mpa, stirring
Time is 8h, and stirring obtains graphene oxide/ethanol mixed slurry；
S3.PET film coronas：Sided corona treatment is carried out to 30 μ m thick PET using corona machine, the discharge power of corona machine is
1KVA, rotating speed 300r/min；
S4. use desk-top coating machine that mixed uniformly graphene oxide/ethanol slurry is coated on into electricity in a manner of hanging painting
Swoon in treated PET film, scraper is highly 30mm；
S5. processing is dried in the coated PET films of step S4, specifically in 60 DEG C of vacuum drying chamber, dried
12h；
S6. dried graphene oxide/PET film is put into high temperature graphitization stove, is passed through argon gas and makees protection gas, flowed
Measure as 100cm3/ min, 30min is calcined under 2900 DEG C of high temperature and carries out high temperature reduction reaction, after reaction terminates, is down to room naturally
Temperature obtains graphene/PET film；
S7. the graphene obtained using two pairs of rollers roll squeezer to step S6 /PET film carries out hot rolling processing, hot rolling process
In upper mould temperature stabilization be 100 DEG C, lower mould temperature stabilization is 100 DEG C, rotating speed 80r/min, obtains PET base graphene heat conduction
Film；
S8. the PET base graphenes heat conducting film after handling rolling carries out cutting edge and handles to obtain the consistent PET/ stones of size
Black alkene composite heat conducting film.
The PET/ graphene composite material heat conducting film thermal properties that embodiment 3~6 and comparative example 5~8 are prepared
Tested, it is specific as shown in table 1:
Table 1
| Embodiment | Graphene coating layer thickness (μm) | Thermal diffusion coefficient (cm2/S) | Thermal conductivity factor (W/ (mk)) |
| Embodiment 3 | 6 | 10 | 1400 |
| Embodiment 4 | 9 | 8 | 1700 |
| Embodiment 5 | 3 | 12 | 1600 |
| Comparative example 4 | 10 | 8 | 1300 |
| Comparative example 5 | 9 | 6 | 1200 |
| Comparative example 6 | 8 | 4 | 1000 |
Embodiment 8
Referring to Fig. 1, the graphite expansion stove that is used for embodiment 1 first time high-temperature expansion and second of high-temperature expansion process,
Graphite expansion stove includes body of heater 1, feeding device 2, drawing mechanism 3 and control device, raw material by feeding device 2 to body of heater 1,
Then collected by drawing mechanism 3；Drawing mechanism 3 is located above body of heater, and feeding device 2 is located at below body of heater；Set in body of heater 1
There is heater 11, using Resistant heating, the inner bottom part of body of heater 1 is additionally provided with air-flow shower nozzle 4, and air-flow shower nozzle 4 also includes source of the gas
41st, airflow line 42 and control damper 43, source of the gas 41 is air, and connects airflow line 42, and airflow line 42 connects air-flow
Shower nozzle 4, control damper 43 are located in airflow line 42, and the top of air-flow shower nozzle 4 is provided with feeding device 2, specifically using spiral
Charger, control device include processor 5 and controller, and processor 5 is provided with control panel and is connected with controller, controller
Including the first controller 53, the controller 51 of second controller 52 and the 3rd, the air-flow control of the first controller 53 and air-flow shower nozzle 4
Valve 43 processed is connected, and second controller 52 is connected with feeding device 2, and the 3rd controller 51 is connected with heater 11；
Wherein, processor 5 uses microprocessor, and the first controller uses air inlet valve-driving circuit, and second controller uses
Feed valve-driving circuit, and the 3rd controller uses heat driven circuit.
Cooling device 7 is additionally provided between drawing mechanism 3 and body of heater 1, cooling device 7 includes heat exchanger tube 71 and water cooling tube 72,
One end connection body of heater 1 of heat exchanger tube 71, other end connection drawing mechanism 3, heat exchanger tube 71 and horizontal angle are 45~90
DEG C, water cooling tube 72 is arranged on heat exchanger tube 71 in the shape of a spiral；
Drawing mechanism 3 includes multiple reserves storehouses 31 and connecting pipe 32, and the one end of connecting pipe 32 is connected with heat exchanger tube 71,
And be provided with cyclone separator 33, the other end is connected with exhaust outlet 34, be additionally provided with connecting pipe 32 multiple subtubes 35 respectively with
Reserves storehouse 31 connects；Connecting pipe and 32 horizontal angles are 45~90 DEG C；
Agitator 8 is additionally provided with body of heater 1, agitator 8 is spiral agitator, coordinates by motor and ball-screw, makes
Obtain agitator 8 and upper and lower linear motion is done in body of heater 1, so as to drive the airflow reflux in body of heater 1.
Wherein：The temperature of discharging opening is controlled by cooling device, and heater 6 also is provided with charging aperture
The temperature of charging aperture is controlled, specific the present embodiment can be heated using resistance wire 61 to the discharge pipe in feeding device.
Time and the temperature of expansion can be controlled by control panel, specifically processor is by controlling the first controller
Air velocity and charging rate are controlled with second controller, so as to control the reaction time that intercalated graphite expands, the 3rd control
Device can control the temperature of heater, realize the intellectuality of graphite expansion, reach and be precisely controlled.
Graphite expansion stove is placed using two floors, and the processing sequence according to raw material is heat exchanger tube and connection from the bottom up
Pipeline and horizontal line have certain angle, by the cooperation of gravity and wind speed, that is, solve expanded graphite and get stuck problem, improve
Reaction yield, while also solve space compared to being disposed vertically.
Graphite expansion stove adds agitator 8 in body of heater 1 so that the air-flow in body of heater 1 forms convection current, ensure that intercalation
Graphite is heated evenly, so as to which the expanded reaction efficiency of intercalated graphite be significantly increased.
Claims (9)
1. a kind of preparation method of PET/ graphene composite materials heat conducting film, it is characterised in that comprise the following steps：
S1. graphene is placed in de-airing mixer, adds absolute ethyl alcohol, stirring obtains graphene/ethanol mixed slurry；
S2.PET film coronas：Sided corona treatment is carried out to 30 μ m thick PET using corona machine；
S3. use desk-top coating machine that mixed uniformly graphene/ethanol slurry is coated on into sided corona treatment mistake in a manner of hanging painting
PET film on, scraper is highly 20 ~ 40 mm；
S4. processing is dried in the coated PET films of step S4；
S5. hot rolling processing is carried out to dried PET film using two pairs of rollers roll squeezer, obtains PET base graphene heat conducting films；
S6. the PET base graphenes heat conducting film after handling rolling carries out cutting edge and handles to obtain the consistent PET/ graphenes of size
Composite heat conducting film；
Wherein：Graphene described in step S1 is prepared by micro crystal graphite, is comprised the following steps that：
S11. take micro crystal graphite raw material, crushing and grinding, to the microlite ink powder that granularity is 300 ~ 400 mesh, to microlite ink powder according to
Secondary progress first time intercalation processing, second of intercalation processing, high temperature puffing processing, obtain expansion micro crystal graphite；
S12. reexpansion micro crystal graphite obtained by step S11 is mixed with stripper, be placed on after dilution in supersonic reaction device
Instead, obtain peeling off material；
S13. material press filtration, separation will be peeled off in step S12, then collects Graphite Cake, stripper can then recycle；
S14. clean：Graphite Cake in step S13 is cleaned, obtains graphene；
Wherein, stripper described in step S12 is graphene quantum dot, and extension rate is 5 times, and the temperature of supersonic reaction device is
50 DEG C, frequency 25000Hz, flow velocity 5.0m3/ h, circulation stirring speed are 2000r/min, the ultrasonic disperse time is 2h；
Cleaned described in step S14 and refer to use deionized water, wash number is 3 ~ 5 times.
2. the preparation method of PET/ graphene composite materials heat conducting film according to claim 1, it is characterised in that in step S1
The mass ratio of graphene and absolute ethyl alcohol is 1:60~80.
3. the preparation method of PET/ graphene composite materials heat conducting film according to claim 1, it is characterised in that in step S1
The rotating speed of de-airing mixer is 800 ~ 1800 r/min, and stirred tank pressure is -0.1 Mpa, and mixing time is 6~10h.
4. the preparation method of PET/ graphene composite materials heat conducting film according to claim 1, it is characterised in that in step S2
The discharge power of corona machine is 0.5 KVA ~ 1.8 KVA, 150 ~ 450r/min of rotating speed.
5. the preparation method of PET/ graphene composite materials heat conducting film according to claim 1, it is characterised in that in step S4
The drying process refers in 60 DEG C of vacuum drying chamber, dries 12h.
6. the preparation method of PET/ graphene composite materials heat conducting film according to claim 1, it is characterised in that in step S5
The upper mould temperature stabilization of the heat rolling processing is 90 ~ 110 DEG C, and lower mould temperature stabilization is 90 ~ 110 DEG C, and rotating speed is 30 ~ 100 r/
min。
7. the preparation method of PET/ graphene composite materials heat conducting film according to claim 1, it is characterised in that step S11
The preparation of reexpansion micro crystal graphite comprises the following steps：
S111. micro crystal graphite raw material, phosphorus content 75%, crushing and grinding, to the microlite ink powder that granularity is 300 mesh are taken；
S112. microlite ink powder obtained by step S111 and perchloric acid and potassium permanganate are placed in progress first time in reaction unit
Intercalation processing is learned, obtains inflatable micro crystal graphite acidic suspension, the filtering of micro crystal graphite acidic suspension is may expand to gained, is protected
Reserved filtrate is standby, wherein, first time chemical graft concretely comprises the following steps：S1121. perchloric acid is consolidated with micro crystal graphite powder by liquid
Than for 20：1L/Kg is mixed evenly；S1122. it is 6 by the mass ratio of micro crystal graphite powder and strong oxidizer：1 adds strong oxygen
Agent, after being stirred at room temperature uniformly, it is warming up to 50 DEG C and continues stirring reaction 1h；S1123. adding deionized water makes reaction unit
Interior temperature is increased to 90 DEG C, is further continued for stirring reaction 1h；
S113. it may expand toward step S112 gained and concentrated nitric acid added in micro crystal graphite acidic suspension, it is slotting to carry out second of chemistry
Layer processing, obtains secondary inflatable micro crystal graphite acidic suspension, inflatable micro crystal graphite acidic suspension mistake secondary to gained
Filter, washing, dry, obtain inflatable micro crystal graphite；Wherein, what second of chemical graft was handled concretely comprises the following steps：S1131. will be dense
Nitric acid is 5 by liquid-solid ratio with microlite ink powder：1L/Kg is added in inflatable acidic suspension, is mixed evenly；S1132.
Adding deionized water makes the temperature in the reaction unit be increased to 100 DEG C, is further continued for stirring reaction 1h;
S114. inflatable micro crystal graphite obtained by step S113 is placed in graphite expansion stove, carries out high-temperature expansion, obtain expanding micro-
Spar ink；Wherein high-temperature expansion concretely comprises the following steps：S1141. feed：Using conserving graphite expanding furnace, by expansible graphite by entering
Material mouth is put into burner hearth, and the temperature of the charging aperture is 30 DEG C, and dispensing speed is 2Kg/h；S1142. expand：The expansion of burner hearth
Temperature is 900 DEG C, by controlled wind speed come to control Bulking Time be 5s；S1143. discharge：After completing step S1142, discharging opening
Temperature is 50 DEG C, then collects to obtain expansion micro crystal graphite in discharge outlet.
8. a kind of PET/ graphene composite materials heat conducting film, it is characterised in that by claim 1~7 any one PET/ graphite
The preparation method of alkene composite heat conducting film is prepared.
9. PET/ graphene composite materials heat conducting film according to claim 8, it is characterised in that the PET/ graphenes are compound
The graphene coating layer thickness of material conducts heat film is 3~9 μm, and thermal diffusion coefficient is 8~12 cm2/ S, thermal conductivity factor be 1400~
1700 W/（m·k）.
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| CN108285547A (en) * | 2018-01-16 | 2018-07-17 | 湖南国盛石墨科技有限公司 | One kind is based on heat cure PET/ graphene heat conducting films and preparation method thereof |
| CN109019582A (en) * | 2018-09-05 | 2018-12-18 | 七台河宝泰隆石墨烯新材料有限公司 | A kind of device of continuous two-way penetration formula cleaning separation graphene oxide |
| CN112520731A (en) * | 2020-12-24 | 2021-03-19 | 广东工业大学 | Preparation method and production line of graphene heat-conducting film |
| CN117019154A (en) * | 2023-09-07 | 2023-11-10 | 深圳市贝特瑞新能源技术研究院有限公司 | Photocatalyst based on microcrystalline graphite and preparation method and application thereof |
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Application publication date: 20171110 |