CN108611793A - A kind of preparation method of high intensity electrostatic spinning polyacrylonitrile base nano carbon fibre felt - Google Patents
A kind of preparation method of high intensity electrostatic spinning polyacrylonitrile base nano carbon fibre felt Download PDFInfo
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
- D06C7/00—Heating or cooling textile fabrics
- D06C7/04—Carbonising or oxidising
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4209—Inorganic fibres
- D04H1/4242—Carbon fibres
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Fibers (AREA)
Abstract
A kind of preparation method of high intensity Static Spinning polyacrylonitrile base nano carbon fibre felt, belongs to technical field of carbon fiber preparation.During Static Spinning polyacrylonitrile fibre felt is pre-oxidized, it is pre-oxidized in short-term by least three stages (multi-temperature zone), avoid the cyclization and oxidation reaction that pre-oxidizing the stage is violent, fault of construction excessive in fiber is caused to cause fiber portion fractures and relaxation occur in carbonisation to reduce so that the tensile strength of carbon fiber felt increases substantially.Further avoided because of long-time pre-oxidation in carbonisation so that oxidation reaction is long, caused by decarburization it is serious and cause carbon fiber structural impaired, improve the tensile strength of carbon nanofiber felt.This method can effectively improve the mechanical property of Static Spinning acrylonitrile carbon nanofiber felt, and improve production efficiency.
Description
Technical field
The present invention relates to a kind of preparation methods of high intensity Static Spinning polyacrylonitrile base nano carbon fibre felt.Specifically to use
Three stages (multi-temperature zone) control the preoxidation time of Static Spinning polyacrylonitrile fibre felt in short-term, reduce fibrous inside knot in carbonization
Structure defect greatly improves carbon nano-fiber felt mechanical property.
Background technology
Static Spinning carbon nanofiber felt has a big surface area (deriving from nanofiber diameter), relatively high conductivity,
Structural integrity, chemical property is good, and absorption property is good etc., is commonly applied to the electrode material of capacitor, electrochemical capacitor desalination
Carbon fibre web, filter medium, adsorption layer in protective garment etc..But at present to the further of the mechanical property of carbon fiber felt
Raising is in bottleneck.Carbon fiber felt has the drawback that：1) brittle, 2) it is frangible, 3) poor mechanical property.It generally surveys at present
The intensity for trying obtained Static Spinning PAN base carbon nanofiber felts is no more than 100MPa, and poor mechanical property, which is it, to answer on a large scale
The reason of using.
Carbon fiber belongs to fragile material, and the mechanical property of property material is determined by two factors, when the mechanical property of itself,
That is tensile strength；Second is that the fault of construction of itself, intensity is determined by structure, its structure includes high order morphosis, is gathered
Collect state structure, chemical constitution etc..Pre-oxidation process plays a decisive role to the mechanical property of carbon fiber.Therefore it is effectively improved pre- oxygen
Chemical industry skill reduces preoxidation time, is the key that further increase carbon fiber mechanical property.
However it is existing research for Static Spinning acrylonitrile non-woven fabrics pre-oxidation the problem of do not cause enough attention,
Most researchers still consider a problem from the pre-oxidation feature of traditional micron order precursor, to non-woven fabrics carry out for a long time (2~
Heat treatment method 8h) can only be come because exothermic reaction and cyclization are violent in preoxidation process using prolonged reaction
Heat preservation, while a slow temperature-rise period is needed again, it is therefore an objective to mitigate the vigorous reaction degree in preoxidation process.And thus
Two kinds of defects can be caused, when high energy consumption, second is that influencing the major reason of carbon fiber mechanical property.Because of the heat of pre-oxidizing the stage
We cannot directly shorten preoxidation time to chemical reaction feature, and no it will cause following two consequences：1. the extent of reaction is inadequate；
2. it is violent to react transition.
In order to solve this problem, we devise the concept of at least three stage gradients heating, are solved by stage reaction
The certainly above problem.The present invention is pre-oxidized using the multi-temperature zone in short-term of 40min (240 DEG C/260 DEG C/274 DEG C), and energy consumption shortens
80%, improve the efficiency of carbon fiber felt preparation process.Since carbon nano-fiber size is small, large specific surface area, with oxygen atom
In conjunction with fast, infiltration rate is accelerated, therefore preoxidation time is long that decarburization can be caused serious, and fibre structure is caused to be destroyed
Existing fiber relaxation, influences the mechanical property of carbon fiber felt.So we should be pre-oxidized using multi-temperature zone in short-term.
However it ought further shorten preoxidation time to 20min (240 DEG C/260 DEG C/274 DEG C), pre-oxidizing the stage fiber
Inner core incomplete oxidation, it is possible to create skin-core structure.In carbonation stage since fibre core is by burn off, lead to skin-core structure
Fibroplastic carbon fiber mechanical property is worse.
Invention content
The main object of the present invention is to provide a kind of pre-oxidation work of science, intuitive Static Spinning acrylonitrile-based fiber felt
Skill pre-oxidizes the carbon fiber felt that excellent in mechanical performance can be obtained by using at least three stages (warm area) in short-term.For Static Spinning
The characteristics of Dralon felt, reasonably optimizing pre-oxidation process：It is pre-oxidized in short-term by multi-temperature zone, avoids pre-oxidizing the stage violent
Cyclization and oxidation reaction make carbon fiber to cause the formation of result defect excessive in fiber in carbonisation
The tensile strength of felt increases substantially.Also, the pre-oxidation process in short-term of Static Spinning acrylonitrile nanofiber mats, really improves
The production efficiency of carbon fiber preparation process.
To achieve the above object, the technical solution adopted by the present invention is as follows.
A kind of preparation method of high intensity Static Spinning polyacrylonitrile base nano carbon fibre felt, which is characterized in that by using
Three stage multi-temperature zones pre-oxidize in short-term, shorten preoxidation time, are then carbonized；It pre-oxidizes while keeping away in short-term using multi-temperature zone
It is violent to exempt from cyclization and oxidation reaction transition in preoxidation process；To reduce in carbonisation due to excessively being tied in fiber
Decarburization caused by structure defect is serious, and then reduces fibrous fracture, relaxation occurs, and the final stretching for increasing carbon fiber felt is strong
Degree；
Further, degree of cyclization can pass through 1590cm in infrared spectrum-1And 2243cm-1The peak intensity at place calculate
It arrives；
It is preferred that multi-temperature zone pre-oxidizes in short-term, including three phases：First stage, 240 DEG C~260 DEG C reaction time are 5
~20min；Second stage, 260 DEG C~274 DEG C reaction time are 5~20min；Phase III, 274 DEG C~280 DEG C reaction when
Between obtain Static Spinning acrylonitrile group oxidized fibre felt for 5~15min；Each stage is arranged 1-3 warm area, each stage it is total when
Between include set warm area heat preservation and the heating-up time；Temperature-rise period of the acrylonitrile-based fiber felt without the first warm area, heating
It is put into the environment of the first warm area temperature to after the temperature of the first warm area, then by acrylonitrile-based fiber felt；Acrylonitrile group is fine later
It ties up under the heating and thermal environment of felt afterwards；Temperature rise period between 240 DEG C~260 DEG C is the time of first stage, 260
DEG C soaking time is the time of second stage；Temperature rise period between 260 DEG C~274 DEG C is the time of second stage, 274 DEG C of guarantors
The warm time is the time of phase III.
Wherein pre-oxidation can be reduced to 15-55min total time by 2 traditional~6h.Further preferably, three phases
Total time is 40-50min.
Further, the tensile strength of Static Spinning acrylonitrile carbon nanofiber felt can be surveyed using universal testing machine
Amount (total length of sample is 4cm, fixes each 1cm, effective length 2cm, width 0.5cm up and down).
The present invention provides a kind of effective methods, for preparing the electrostatic for the pre-oxidation rate for controlling fibrofelt
Spin acrylonitrile group carbon nanofiber felt.It is conventional to pre-oxidize for a long time, the oxidation reaction transition in preoxidation process, in carbonisation
In decarburization can be caused serious in conjunction with more carbon atoms, destroy fibrous inner structure, influence the mechanical strength of carbon fiber felt.Relatively
It is pre-oxidized in long-time, multi-temperature zone pre-oxidizes the oxidation reaction that can effectively control Static Spinning acrylonitrile group oxidized fibre felt in short-term
Rate reaches the oxidation reaction degree of standard, and the size of carbon nano-fiber is small, large specific surface area, contacted with oxygen atom it is more,
Its infiltration rate is accelerated, therefore pre-oxidizing the stage oxidation reaction degree should be reduced.
The carbonization of the present invention can be the carbonization under a nitrogen atmosphere of routine.
In the above method collection device of involved electrostatic spinning be speed governing roller, speed governing turntable, parallel-plate electrode,
Speed governing parallel-plate turns rod, Static Water collects bath or circulating water collects bath.
Involved acrylonitrile is acrylonitrile homopolymer in the above method, or comprising mass fraction 15% below one
Kind or a variety of comonomers acrylonitrile copolymer, one kind in carboxyl, amido, amide groups or ester group is included in comonomer
Or it is several.
Involved acrylonitrile-based fiber felt is produced by solution injection during electrostatic spinning in the above method,
And the drying of the acrylonitrile-based fiber felt formed is that the volatilization of organic solvent directly carries out during electrostatic spinning.
The extent of reaction of pre-oxidizing the stage is characterized using degree of cyclization and oxygen content；Oxygen content can pass through test elements
Analysis obtains, and characterizes pre-oxidizing the stage oxidation reaction degree, and Static Spinning preoxidized fiber felt standard oxygen content is cyclized 8~12%
Degree passes through 1590cm in infrared spectrum-1And 2243cm-1The peak intensity at place is calculated.
The advantage of the invention is that：
(1) it is pre-oxidized in short-term by using three stages (at least three-temperature-zone), avoids the cyclization that pre-oxidizing the stage is violent
And oxidation reaction keeps the stretching of carbon fiber felt strong to cause the formation of result defect excessive in fiber in carbonisation
Degree increases substantially, and detects the tensile strength of corresponding carbon nanofiber felt and can reach 200MPa or more, simultaneously effective
The cost of electrostatic spinning pre-oxidation process is reduced, working efficiency is improved.
(2) it is pre-oxidized in short-term by using three stages (at least three-temperature-zone), it is pre- that Static Spinning acrylonitrile can be efficiently controlled
The oxygen content of oxidized fibre felt.
(3) Static Spinning acrylonitrile group non-woven fabrics is collected using speed governing roller.
Description of the drawings
Fig. 1 is the sample drawing in Dralon felt preoxidation process.
Fig. 2 is the batten figure of carbon fiber felt test tensile strength.
Fig. 3 is for PAN non-woven fabrics and its respectively under following preoxidation time (0min, 20min, 40min, 300min)
Dsc analysis curve.
Wherein 1, which corresponds to 1,2 corresponding embodiment 3,3 of comparative example, corresponds to PAN nonwoven of the correspondence of comparative example 2,4 without pre-oxidation
Cloth.
Specific implementation mode
It is following specific using the electrostatic spinning and the pretreatment that use identical homo-polypropylene nitrile to carry out the same terms in embodiment
Afterwards, electrostatic spinning Dralon felt is prepared, it is comprehensive to first pass around a series of means of testing such as DSC, infrared spectrum, elemental analysis
It closes analysis and makes a series of suitable pre-oxidation processes.
Comparative example 1
Make Static Spinning Dralon felt at the same tension without being carried out in Muffle furnace in drawing-off, normal pressure, air dielectric
Pre-oxidation, total time 300min.280 DEG C are warming up to from room temperature (10 DEG C) with the heating rate of 1.5 DEG C/min, and at 280 DEG C
Keep the temperature 120min.Carbonization treatment is carried out in nitrogen later, first passes through that 5 DEG C/min is warming up to 300 DEG C from 0,4 DEG C/min is from 300
DEG C be warming up to 700 DEG C, 3 DEG C/min be warming up to 1000 DEG C, 1.5 DEG C from 1000 DEG C from 700 DEG C and be warming up to 1200 DEG C, it is anti-at 1200 DEG C
2min is answered, then carries out being cooled to room temperature with identical rate, takes out sample, obtain Static Spinning acrylonitrile group carbon nano-fiber
Felt.The tensile strength of the Static Spinning acrylonitrile group carbon nanofiber felt prepared according to the method described above is 80MPa.
Embodiment 1
Make Static Spinning Dralon felt at the same tension without in drawing-off, normal pressure, air dielectric air dry oven into
4 pre-oxidation warm areas of row, total time 50min.First warm area reaction temperature is 240 DEG C, and the reaction time is set to 5min, then
240 DEG C~260 DEG C heating 15min, the second warm area reaction temperature is 260 DEG C, and the reaction time is set to 5min, then 260 DEG C~274
DEG C heating 11min, third warm area reaction temperature is 274 DEG C, and the reaction time is set to 5min, then is heated up at 274 DEG C~280 DEG C
4min, four-temperature region reaction temperature are 280 DEG C, and it is (directly that Static Spinning Dralon felt is straight first that the reaction time is set to 5min
It connects and is put into 240 DEG C of stove, the temperature-rise period of front, electrospinning Dralon felt is not in stove；Exist always after putting into
Until reaction terminates).Carbonization treatment is carried out in nitrogen later, first pass through 5 DEG C/min from 0 be warming up to 300 DEG C, 4 DEG C/min from
300 DEG C be warming up to 700 DEG C, 3 DEG C/min be warming up to 1000 DEG C, 1.5 DEG C from 1000 DEG C from 700 DEG C and be warming up to 1200 DEG C, 1200
DEG C reaction 2min, be then cooled to room temperature with identical rate, takes out sample, obtain Static Spinning acrylonitrile group carbon Nanowire
Tie up felt.The tensile strength of the Static Spinning acrylonitrile group carbon nanofiber felt prepared according to the method described above is 181.2MPa.
Embodiment 2
Make Static Spinning Dralon felt at the same tension without in drawing-off, normal pressure, air dielectric air dry oven into
4 pre-oxidation warm areas of row, total time 45min.First warm area reaction temperature is 240 DEG C, and the reaction time is set to 5min, then
240 DEG C~260 DEG C heating 14min, the second warm area reaction temperature is 260 DEG C, and the reaction time is set to 5min, then 260 DEG C~274
DEG C heating 10min, third warm area reaction temperature is 274 DEG C, and the reaction time is set to 5min, then is heated up at 274 DEG C~280 DEG C
4min, four-temperature region reaction temperature are 280 DEG C, and it is (directly that Static Spinning Dralon felt is straight first that the reaction time is set to 2min
It connects and is put into 240 DEG C of stove, the temperature-rise period of front, electrospinning Dralon felt is not in stove；Exist always after putting into
Until reaction terminates).Carbonization treatment is carried out in nitrogen later, first pass through 5 DEG C/min from 0 be warming up to 300 DEG C, 4 DEG C/min from
300 DEG C be warming up to 700 DEG C, 3 DEG C/min be warming up to 1000 DEG C, 1.5 DEG C from 1000 DEG C from 700 DEG C and be warming up to 1200 DEG C, 1200
DEG C reaction 2min, be then cooled to room temperature with identical rate, takes out sample, obtain Static Spinning acrylonitrile group carbon Nanowire
Tie up felt.The tensile strength of the Static Spinning acrylonitrile group carbon nanofiber felt prepared according to the method described above is 196.6MPa.
Embodiment 3
Make Static Spinning Dralon felt at the same tension without in drawing-off, normal pressure, air dielectric air dry oven into
3 pre-oxidation warm areas of row, total time 40min.First warm area reaction temperature is 240 DEG C, and the reaction time is set to 5min, then
240 DEG C~260 DEG C heating 15min, the second warm area reaction temperature is 260 DEG C, and the reaction time is set to 5min, then 260 DEG C~274
DEG C heating 10min, third warm area reaction temperature is 274 DEG C, and it is (directly that Static Spinning acrylonitrile is fine first that the reaction time is set to 5min
Dimension felt is placed directly in 240 DEG C of stove, and the temperature-rise period of front, electrospinning Dralon felt is not in stove；After putting into
Always until reaction terminates).Carbonization treatment is carried out in nitrogen later, first pass through 5 DEG C/min from 0 be warming up to 300 DEG C, 4 DEG C/
Min be warming up to from 300 DEG C 700 DEG C, 3 DEG C/min be warming up to 1000 DEG C, 1.5 DEG C from 1000 DEG C from 700 DEG C and be warming up to 1200 DEG C,
Then 1200 DEG C of reaction 2min are carried out being cooled to room temperature with identical rate, are taken out sample, obtain Static Spinning acrylonitrile group carbon and receive
Rice fibrofelt.The tensile strength of the Static Spinning acrylonitrile group carbon nanofiber felt prepared according to the method described above is 230MPa.
Comparative example 2
Make Static Spinning Dralon felt at the same tension without in drawing-off, normal pressure, air dielectric air dry oven into
4 pre-oxidation warm areas of row, total time 20min.First warm area reaction temperature is 240 DEG C, and the reaction time is set to 5min, the second temperature
Area's reaction temperature is 260 DEG C, and the reaction time is set to 5min, and third warm area reaction temperature is 274 DEG C, and the reaction time is set to 5min,
Four-temperature region reaction temperature is 280 DEG C, and the reaction time is set to 5min (only after reaching corresponding warm area temperature, just by Static Spinning
Dralon felt is put stove into and is reacted, and Static Spinning Dralon felt does not react in stove during heating).
Carbonization treatment is carried out in nitrogen later, first pass through 5 DEG C/min from 0 be warming up to 300 DEG C, 4 DEG C/min be warming up to 700 from 300 DEG C
DEG C, 3 DEG C/min be warming up to 1000 DEG C, 1.5 DEG C from 1000 DEG C from 700 DEG C and be warming up to 1200 DEG C, at 1200 DEG C react 2min, then
It carries out being cooled to room temperature with identical rate, takes out sample, obtain Static Spinning acrylonitrile group carbon nanofiber felt.According to above-mentioned side
The tensile strength of Static Spinning acrylonitrile group carbon nanofiber felt prepared by method is 67MPa.
Comparative example 3
Make Static Spinning Dralon felt at the same tension without in drawing-off, normal pressure, air dielectric air dry oven into
4 pre-oxidation warm areas of row, total time 17min.First warm area reaction temperature is 240 DEG C, and the reaction time is set to 5min, the second temperature
Area's reaction temperature is 260 DEG C, and the reaction time is set to 5min, and third warm area reaction temperature is 274 DEG C, and the reaction time is set to 5min,
Four-temperature region reaction temperature is 280 DEG C, and the reaction time is set to 2min (only after reaching corresponding warm area temperature, just by Static Spinning
Dralon felt is put stove into and is reacted, and Static Spinning Dralon felt does not react in stove during heating).
Carbonization treatment is carried out in nitrogen later, first pass through 5 DEG C/min from 0 be warming up to 300 DEG C, 4 DEG C/min be warming up to 700 from 300 DEG C
DEG C, 3 DEG C/min be warming up to 1000 DEG C, 1.5 DEG C from 1000 DEG C from 700 DEG C and be warming up to 1200 DEG C, at 1200 DEG C react 2min, then
It carries out being cooled to room temperature with identical rate, takes out sample, obtain Static Spinning acrylonitrile group carbon nanofiber felt.According to above-mentioned side
The tensile strength of Static Spinning acrylonitrile group carbon nanofiber felt prepared by method is 74MPa.
Comparative example 4
Make Static Spinning Dralon felt at the same tension without in drawing-off, normal pressure, air dielectric air dry oven into
3 pre-oxidation warm areas of row, total time 15min.First warm area reaction temperature is 240 DEG C, and the reaction time is set to 5min, the second temperature
Area's reaction temperature is 260 DEG C, and the reaction time is set to 5min, and third warm area reaction temperature is 274 DEG C, and the reaction time is set to 5min
It (only after reaching corresponding warm area temperature, just puts Static Spinning Dralon felt into stove and reacts, in the process of heating
Middle Static Spinning Dralon felt does not react in stove).Carbonization treatment is carried out in nitrogen later, first passes through 5 DEG C/min from 0
Be warming up to 300 DEG C, 4 DEG C/min be warming up to from 300 DEG C 700 DEG C, 3 DEG C/min 1000 DEG C, 1.5 DEG C from 1000 are warming up to from 700 DEG C
DEG C 1200 DEG C are warming up to, 2min is reacted at 1200 DEG C, then carried out being cooled to room temperature with identical rate, take out sample, obtain
Static Spinning acrylonitrile group carbon nanofiber felt.The stretching of the Static Spinning acrylonitrile group carbon nanofiber felt prepared according to the method described above
Intensity is 87MPa.
Claims (7)
1. a kind of preparation method of high intensity Static Spinning polyacrylonitrile base nano carbon fibre felt, it is characterised in that：By using more
Warm area pre-oxidizes in short-term, shortens preoxidation time, is then carbonized；It is pre-oxidized in short-term using multi-temperature zone while avoiding pre-oxidizing
Cyclization and oxidation reaction transition are violent in the process；It reduces in carbonisation due to caused by excessive fault of construction in fiber
Decarburization is serious, and then reduces carbon nano-fiber fault of construction, the final tensile strength for increasing carbon nanofiber felt.
2. a kind of preparation method of high intensity Static Spinning polyacrylonitrile base nano carbon fibre felt described in accordance with the claim 1,
It is characterized in that, multi-temperature zone pre-oxidizes in short-term, including three phases：First stage, 240 DEG C~260 DEG C reaction time are 5~
20min；Second stage, 260 DEG C~274 DEG C reaction time are 5~20min；Phase III, 274 DEG C~280 DEG C reaction time
Static Spinning acrylonitrile group oxidized fibre felt is obtained for 5~15min；1-3 warm area, the total time in each stage is arranged in each stage
The heating-up time of heat preservation including set warm area and heating-up time, the first warm area do not count；Wherein pre-oxidize total time
15-55min is reduced to by 2 traditional~6h.
3. a kind of preparation method of high intensity Static Spinning polyacrylonitrile base nano carbon fibre felt according to claim 2,
It is characterized in that, temperature-rise period of the acrylonitrile-based fiber felt without the first warm area, after being warming up to the temperature of the first warm area, then by third
Alkene itrile group fibrofelt is put into the environment of the first warm area temperature；Acrylonitrile-based fiber felt heating afterwards later and insulating ring
Under border.
4. a kind of preparation method of high intensity Static Spinning polyacrylonitrile base nano carbon fibre felt according to claim 2,
It is characterized in that, the temperature rise period between 240 DEG C~260 DEG C is the time of first stage, and 260 DEG C of soaking times are second stage
Time；Temperature rise period between 260 DEG C~274 DEG C is the time of second stage, 274 DEG C of soaking times be the phase III when
Between.
5. a kind of preparation method of high intensity Static Spinning polyacrylonitrile base nano carbon fibre felt according to claim 4,
It is characterized in that, the total time of three phases is 40-50min.
6. a kind of preparation method of high intensity Static Spinning polyacrylonitrile base nano carbon fibre felt described in accordance with the claim 1,
It is characterized in that, presoma is acrylonitrile homopolymer, or comprising mass fraction in 15% one or more comonomers below
Acrylonitrile copolymer includes one or more of carboxyl, amido, amide groups or ester group in comonomer.
7. a kind of preparation method of high intensity Static Spinning polyacrylonitrile base nano carbon fibre felt described in accordance with the claim 1,
It is characterized in that, involved acrylonitrile-based fiber felt is to be produced by solution injection during electrostatic spinning, and formed
The drying of acrylonitrile-based fiber felt be that the volatilization of organic solvent directly carries out during electrostatic spinning.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810481889.8A CN108611793B (en) | 2018-05-18 | 2018-05-18 | Preparation method of high-strength electrostatic spinning polyacrylonitrile-based carbon nanofiber felt |
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| CN201810481889.8A CN108611793B (en) | 2018-05-18 | 2018-05-18 | Preparation method of high-strength electrostatic spinning polyacrylonitrile-based carbon nanofiber felt |
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| CN108611793B CN108611793B (en) | 2020-11-20 |
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