CN102733010A - Method for preparing polyacrylonitrile-based carbon fiber - Google Patents
Method for preparing polyacrylonitrile-based carbon fiber Download PDFInfo
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- CN102733010A CN102733010A CN2012102304055A CN201210230405A CN102733010A CN 102733010 A CN102733010 A CN 102733010A CN 2012102304055 A CN2012102304055 A CN 2012102304055A CN 201210230405 A CN201210230405 A CN 201210230405A CN 102733010 A CN102733010 A CN 102733010A
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Abstract
The invention provides a method for preparing a polyacrylonitrile-based carbon fiber which is obtained through the preoxidation, low temperature charring, and high temperature charring of a polyacrylonitrile precursor. The peroxidation and the high temperature charring in the invention have fixed technology conditions. Under the conditions of a fixed low temperature charring temperature and a fixed operating speed, through changing the extending rate of the low temperature charring, different extending rates in each low temperature charring technology are realized. In the low temperature charring stage, about 43.3% of the fiber weight is pyrolyzed. Through controlling the extending rate, increasing the compactness and orientation degree of the carbon fiber, decreasing fiber surface defects, namely the fiber defect number, and decreasing the defect size, excessive tension which causes filament breakage, broken filament, and the like can be avoided, fiber defects further increased by an incomplete reaction caused by excessive tension can also be avoided, thereby improving the mechanical properties of the carbon fiber product, and the tension strength of the carbon fiber can reach 4621 Mpa.
Description
Technical field
The present invention relates to polyacrylonitrile-based carbon fibre charing field, specifically is a kind of preparation method of polyacrylonitrile-based carbon fibre.
Background technology
Polyacrylonitrile (PAN) base carbon fibre, Gao Mo and high temperature resistant high-strength because of having; And have little thermal coefficient of expansion and become a kind of typical dual-use high-tech material, high-performance carbon fibre has become the strategic basic material that most advanced and sophisticated national defense industry such as Aero-Space can not be substituted.In the process of making polyacrylonitrile-based carbon fibre, fibre structure takes place to be converted into phosphorus content at the DIC fiber more than 93% by organic polyacrylonitrile fibril after twice great change.This twice thaumatropy is respectively: the heat-resisting trapezium structure that is converted into pre-oxidized fibers by the linear molecule chain warp pre-oxidation of polyacrylonitrile-based precursor; It is the random graphits structure that is converted into carbon fiber by pre-oxidized fibers through carbonization process that secondary structure transforms.
Pre-oxidation and charing all are complicated physicochemical change and thaumatropy processes.Wherein charing is thermal decomposition, the thermal contraction process that under inert gas shielding, takes place.Carbonization process is divided into low-temperature carbonization and high temperature carbonization again, and both formation temperature gradients are carried out the solid phase charing in proper order, makes that thaumatropy is controlled to be carried out.The low-temperature carbonization temperature generally is controlled at 300 ℃-600 ℃, and in the starting stage of low-temperature carbonization, the hydroxyl in the pre-oxidized fibers begins to carry out crosslinked condensation reaction, and this helps reconfiguring of cyclized structure.The carrying out of cross-linking reaction can be fixed the structure of polymer, and remaining linear segment or become circulus, or fracture takes place discharges the micro-molecular gas product.Get into the low-temperature carbonization stage, it is crosslinked that the circulus of pre-oxidized fibers begins dehydrogenation, and the segment of cyclisation part does not continue cyclisation at this; Carry out intermolecular cross-linking; Polymer generation deep pyrolytic discharges HCN gas, and non-carbons such as N, H, O react in stove and discharge; Wherein also some segment generation fragmentation of cyclisation not produces a large amount of high-molecular weight compounds, and the fibrous inside strand is reset, and length changes; Intermolecular generation dehydrogenation simultaneously, dehydration are cross-linked to form network structure, and the molecule chain end decomposition discharges NH
3From chemical bond dissociation energy, in the low-temperature carbonization stage, the carbon-to-carbon singly-bound at first ruptures, and changes more stable two keys into, and bigger conjugated system, and develops along increasing aromatic ring number direction.And experiment shows, the reaction that takes place of low-temperature carbonization stage is to be main with pyrolysis, and this stage has 40% of fibre weight to be fallen by pyrolysis approximately, and the degree of orientation obviously reduces, and is the stage that bigger variation takes place The Nomenclature Composition and Structure of Complexes.The high temperature carbonization temperature is controlled at 1000 ℃-1400 ℃; The reaction that the high temperature carbonization stage takes place mainly is a ring opening; Carry out crosslinked between the ladder polymer structure; The structure of polymer progressively changes to the structure of polycrystalline carbon in the fiber, and non-carbon is by getting rid of in the fiber, progressively generates the carbon fiber of carbon content greater than 93% random graphits structure.
The low-temperature carbonization operation is will guarantee that the cyclized structure of pre-oxidized fibers is further complete and progressively change into random graphits structure; To control pore size and distribution, monofilament ectonexine structure, degree of molecular orientation, crystal size and crystalline orientation, specific area, the fibrous carbon content of fiber etc. simultaneously well, and prevent that fiber from producing blemish and lousiness and adhering to pollutant etc.The main technologic parameters that influences the carbon fiber mechanical property in the charing stage comprises: temperature, carbonization time and degree of draft.Drawing-off is through the overall process of producing carbon fiber.Drawing-off has positive drawing-off, negative drawing-off and decides elongation.In the low-temperature carbonization process, because fiber self weightlessness about 43.3% often causes disorientation, need just lead 1%-5%, thereby reach the purpose that suppresses disorientation.In the low-temperature carbonization process, degree of draft is low excessively, and drafting tension is when being lower than certain numerical value, and the fiber orientation degree is poor, and stretch modulus is low; Degree of draft is too high, and drafting tension is too big, causes fracture of wire, lousiness easily, causes TENSILE STRENGTH low.Therefore, should be in carbonization process according to the draft process of precursor, the charing degree of draft that selection matches should guarantee the orientation that fiber is good, reduces lousiness, fracture of wire and blemish etc. again, thereby prepares the carbon fiber of good mechanical properties.
In recent years, the experts and scholars of many carbon fiber aspects studied carbon fiber structural in the carbonization process develop with microstructure variation, and in the carbonization process variation of process conditions to the influence of carbon fiber mechanical property.But these research major parts bias toward the research of carbon fiber knowwhy; And research is the research of single-point factor in the carbon fiber carbonization process; Do not form the research of system, integral body, and because the complexity of carbonization process itself, its theory study is very little to the directive function of concrete technology.The present invention is from actual production, is target to improve the carbon fiber mechanical property, produces high performance carbon fiber through changing the technological parameter of pre-oxidized fibers in the low-temperature carbonization process.
Summary of the invention
For overcoming the deficiency of the mechanical property reduction that causes the polyacrylonitrile-based carbon fibre product when drawing-off is excessive or too small in the low-temperature carbonization process in the prior art, the present invention proposes a kind of preparation method of polyacrylonitrile-based carbon fibre.
Detailed process of the present invention comprises the steps:
Step 1, the pre-oxidation of polyacrylonitrile fibril: adopt the continous mode pre-oxidation furnace to realize the pre-oxidation of polyacrylonitrile fibril; 195 ℃～265 ℃ of pre-oxidation furnace temperature ranges are through 6 warm area formation temperature gradients; Drawing of fiber rate-2%, pre-oxidation calendar time are 60min, and effective preoxidation time of each warm area is 10min; In the preoxidation process of polyacrylonitrile fibril, the linear velocity V of the 1st warm area porch drawing roller
1=0.3m/s, rotating speed RPM
1=(V
1/ S) * 100; The 2nd warm area porch drawing roller linear velocity V
2=V
1(1+R
1), rotating speed RPM
2=(V
2/ S) * 100, and in the formula, R
1Be the draw ratio of the 1st warm area, R
1Be 0%; The 3rd warm area porch drawing roller linear velocity V
3=V
2(1+R
2), rotating speed RPM
3=(V
3/ S) * 100, R
2Be the draw ratio of the 2nd warm area, R
2Be 3%; The 4th warm area porch drawing roller linear velocity V
4=V
3(1+R
3), rotating speed RPM
4=(V
4/ S) * 100, and in the formula, R
3Be the draw ratio of the 3rd warm area, R
3Be 2%; The 5th warm area porch drawing roller linear velocity V
5=V
4(1+R
4), rotating speed RPM
5=(V
5/ S) * 100, and in the formula, R
4Be the draw ratio of the 4th warm area, R
4Be 0%; The 6th warm area porch drawing roller linear velocity V
6=V
5(1+R
5), rotating speed RPM
6=(V
6/ S) * 100, R
5Be the draw ratio of the 5th warm area, R
5Be-2%; The linear velocity V of the 6th warm area exit drawing roller
7With rotating speed RPM
7, V
7=V
6(1+R
6), R
6Be the draw ratio of the 6th warm area, R
6Be-1.5%; Obtain pre-oxidized polyacrylonitrile fiber; The unit of described rotating speed RPM is r/min; S is drawing roller girth m/r.
Step 2, low-temperature carbonization: pre-oxidized polyacrylonitrile fiber is got into low temperature carbonization furnace through low-temperature carbonization stove drawing roller carry out charing; In the charing, as the charing medium, the interior pressure of retort is 20～50Pa with high pure nitrogen; The process of low-temperature carbonization comprises 3 warm areas, and each warm area is respectively 450 ℃, 570 ℃ and 625 ℃, and by low temperature to high temperature formation temperature gradient; Drawing of fiber rate 1%～10% in the low-temperature carbonization process, the calendar time of low-temperature carbonization are 2min; Low-temperature carbonization drawing roller linear velocity V
Low charcoal=V
7(1+R
Low charcoal), rotating speed RPM
Low charcoal=(V
Low charcoal/ S) * 100, R
Low charcoalBe the draw ratio of low-temperature carbonization process, R
Low charcoalBe 1%～10%; Obtain the low-temperature carbonization fiber.
Step 3, high temperature carbonization: the low-temperature carbonization fiber that obtains is got into high temperature carbonization furnace through high temperature carbonization stove drawing roller carry out charing; In the charing, as the charing medium, the interior pressure of retort is 20～50Pa with high pure nitrogen; The process of high temperature carbonization comprises 2 warm areas, and each warm area is respectively 1050 ℃ and 1350 ℃, and by low temperature to high temperature formation temperature gradient; Drawing of fiber rate-4% in the high temperature carbonization process, the calendar time 1min of high temperature carbonization; High temperature carbonization drawing roller linear velocity V
High charcoal=V
Low charcoal(1+R
High charcoal), rotating speed RPM
High charcoal=(V
High charcoal/ S) * 100, R
High charcoalBe the draw ratio of high temperature carbonization process, R
High charcoalBe-4%; Obtain polyacrylonitrile carbon fiber.
For verifying performance of the present invention, carbon fiber has been carried out Mechanics Performance Testing.Testing equipment is 3365 serial universal testing machines, gauge length 200mm, and speed is 0.5cm/min, and comes calculating mean value with the Mechanics Performance Testing numerical value of ten carbon fiber samples.Bring up to 4621MPa through analytical test gained carbon fiber strength value by 3547MPa.
Pre-oxidation in the process of the present invention, high temperature carbonization process conditions are fixed; Under the fixing condition of low-temperature carbonization temperature and the speed of service; Through changing the low-temperature carbonization degree of draft, promptly set the different rotating speeds of low-temperature carbonization stokehold first break draft roller, realize the different degree of drafts under each low-temperature carbonization technology.The low-temperature carbonization stage takes place is to be main with pyrolysis, and the low-temperature carbonization stage has 43.3% of fibre weight to be fallen by pyrolysis approximately, chooses suitable degree of draft; Increase the carbon fiber compactness and the degree of orientation; Minimizing fiber surface defective is fiber defective number and reduces flaw size, both can avoid tension force too big, causes fracture of wire, lousiness etc.; The reaction that has caused when also having avoided tension force too big not exclusively and further increases the fiber defective, thereby improves the carbon fiber product mechanical property.The present invention chooses suitable charring process through the drawing-off amount in the adjustment low-temperature carbonization process, has prepared high performance carbon fiber, and the TENSILE STRENGTH of carbon fiber reaches 4621MPa, has reached leading domestic level, has surpassed toray T300 technical merit.Concrete performance indications are as shown in table 1:
The product of table 1 the present invention preparation and toray T300 properties of product are relatively
The specific embodiment
Embodiment one
Present embodiment is a kind of preparation method of polyacrylonitrile-based carbon fibre, and the performance indications of said polyacrylonitrile-based precursor are as shown in table 2:
The performance indications table of table 2 polyacrylonitrile fibril
The preparation detailed process of present embodiment is:
Step 1, the pre-oxidation of polyacrylonitrile fibril: adopt the continous mode pre-oxidation furnace to realize the pre-oxidation of polyacrylonitrile fibril; 195 ℃～265 ℃ of pre-oxidation furnace temperature ranges are through 6 warm area formation temperature gradients; Drawing of fiber rate-2%, pre-oxidation calendar time are 60min, and effective preoxidation time of each warm area is 10min; In the preoxidation process of polyacrylonitrile fibril, the linear velocity V of the 1st warm area porch drawing roller
1=0.3m/min, rotating speed RPM
1=(V
1/ S) * 100=95.54r/min; The 2nd warm area porch drawing roller linear velocity V
2=V
1(1+R
1)=0.3m/min, rotating speed RPM
2=(V
2/ S) * and 100=95.54r/min, in the formula, R
1Be the draw ratio of the 1st warm area, R
1Be 0%; The 3rd warm area porch drawing roller linear velocity V
3=V
2(1+R
2)=0.3* (1+3%)=0.309m/min, rotating speed RPM
3=(V
3/ S) * and 100=98.41r/min, R
2Be the draw ratio of the 2nd warm area, R
2Be 3%; The 4th warm area porch drawing roller linear velocity V
4=V
3(1+R
3)=0.309* (1+2%)=0.315m/min, rotating speed RPM
4=(V
4/ S) * and 100=100.4r/min, in the formula, R
3Be the draw ratio of the 3rd warm area, R
3Be 2%; The 5th warm area porch drawing roller linear velocity V
5=V
4(1+R
4)=0.315* (1+0%)=0.315m/min, rotating speed RPM
5=(V
5/ S) * and 100r/min=100.4r/min, in the formula, R
4Be the draw ratio of the 4th warm area, R
4Be 0%; The 6th warm area porch drawing roller linear velocity V
6=V
5(1+R
5)=0.315* (1-2%)=0.309m/min, rotating speed RPM
6=(V
6/ S) * and 100=98.41r/min, R
5Be the draw ratio of the 5th warm area, R
5Be-2%; The linear velocity V of the 6th warm area exit drawing roller
7With rotating speed RPM
7, V
7=V
6(1+R
6)=0.309* (1-1.5%)=0.304m/min, RPM
7=(V
7/ S) * and 100=96.93r/min, R
6Be the draw ratio of the 6th warm area, R
6Be-1.5%; Obtain polyacrylonitrile base preoxidized fiber; The unit of described rotating speed RPM is r/min; S is drawing roller girth m/r.
Step 2, low-temperature carbonization: pre-oxidized polyacrylonitrile fiber is got into low temperature carbonization furnace through low-temperature carbonization stove drawing roller carry out charing; In the charing, as the charing medium, the interior pressure of retort is 20～50Pa with high pure nitrogen; The process of low-temperature carbonization comprises 3 warm areas, and each warm area is respectively 450 ℃, 570 ℃ and 625 ℃, and by low temperature to high temperature formation temperature gradient; Drawing of fiber rate 1%～10% in the low-temperature carbonization process, the drawing of fiber rate is 10% in the present embodiment.The calendar time of low-temperature carbonization is 2min; Low-temperature carbonization drawing roller linear velocity V
Low charcoal=V
7(1+R
Low charcoal)=0.304* (1+10%)=0.334m/min, rotating speed RPM
Low charcoal=(V
Low charcoal/ S) * and 100=106.50r/min, R
Low charcoalBe the draw ratio of low-temperature carbonization process, R
Low charcoalBe 10%; Obtain polyacrylonitrile-radical low-temperature carbonization fiber.
Step 3, high temperature carbonization: the low-temperature carbonization fiber that obtains is got into high temperature carbonization furnace through high temperature carbonization stove drawing roller carry out charing; In the charing, as the charing medium, the interior pressure of retort is 20～50Pa with high pure nitrogen; The process of high temperature carbonization comprises 2 warm areas, and each warm area is respectively 1050 ℃ and 1350 ℃, and by low temperature to high temperature formation temperature gradient; Drawing of fiber rate-4% in the high temperature carbonization process, the calendar time 1min of high temperature carbonization; High temperature carbonization drawing roller linear velocity V
High charcoal=V
Low charcoal(1+R
High charcoal)=0.334* (1-4%)=0.321m/min, rotating speed RPM
High charcoal=(V
High charcoal/ S) * and 100=102.11r/min, R
High charcoalBe the draw ratio of high temperature carbonization process, R
High charcoalBe-4%; Obtain polyacrylonitrile-based carbon fibre.
Pre-oxidation in the present embodiment, high temperature carbonization process conditions are fixed; Under the fixing condition of low-temperature carbonization temperature and the speed of service; Through changing the low-temperature carbonization degree of draft, promptly set the different rotating speeds of low-temperature carbonization stokehold first break draft roller, realize the different degree of drafts under each low-temperature carbonization technology.Through the test of mechanical strength analyzer, present embodiment gained carbon fiber product tensile strength is respectively: 3015MPa, and 3623MPa, 3461MPa, 3843MPa, 3565MPa, 3408MPa, 3541MPa, 3408MPa, 2811MPa, its mean value of 3531MPa is 3547MPa.
Embodiment two
Present embodiment is a kind of preparation method of polyacrylonitrile-based carbon fibre, and the performance indications of said polyacrylonitrile-based precursor are as shown in table 3:
The performance indications table of table 3 polyacrylonitrile fibril
The preparation detailed process of present embodiment is:
Step 1, the pre-oxidation of polyacrylonitrile fibril: adopt the continous mode pre-oxidation furnace to realize the pre-oxidation of polyacrylonitrile fibril; 195 ℃～265 ℃ of pre-oxidation furnace temperature ranges are through 6 warm area formation temperature gradients; Drawing of fiber rate-2%, pre-oxidation calendar time are 60min, and effective preoxidation time of each warm area is 10min; In the preoxidation process of polyacrylonitrile fibril, the linear velocity V of the 1st warm area porch drawing roller
1=0.3m/min, rotating speed RPM
1=(V
1/ S) * 100=95.54r/min; The 2nd warm area porch drawing roller linear velocity V
2=V
1(1+R
1)=0.3m/min, rotating speed RPM
2=(V
2/ S) * and 100=95.54r/min, in the formula, R
1Be the draw ratio of the 1st warm area, R
1Be 0%; The 3rd warm area porch drawing roller linear velocity V
3=V
2(1+R
2)=0.3* (1+3%)=0.309m/min, rotating speed RPM
3=(V
3/ S) * and 100=98.41r/min, R
2Be the draw ratio of the 2nd warm area, R
2Be 3%; The 4th warm area porch drawing roller linear velocity V
4=V
3(1+R
3)=0.309* (1+2%)=0.315m/min, rotating speed RPM
4=(V
4/ S) * and 100=100.40r/min, in the formula, R
3Be the draw ratio of the 3rd warm area, R
3Be 2%; The 5th warm area porch drawing roller linear velocity V
5=V
4(1+R
4)=0.315* (1+0%)=0.315m/min, rotating speed RPM
5=(V
5/ S) * and 100r/min=100.40r/min, in the formula, R
4Be the draw ratio of the 4th warm area, R
4Be 0%; The 6th warm area porch drawing roller linear velocity V
6=V
5(1+R
5)=0.315* (1-2%)=0.309m/min, rotating speed RPM
6=(V
6/ S) * and 100=98.41r/min, R
5Be the draw ratio of the 5th warm area, R
5Be-2%; The linear velocity V of the 6th warm area exit drawing roller
7With rotating speed RPM
7, V
7=V
6(1+R
6)=0.309* (1-1.5%)=0.304m/min, RPM
7=(V
7/ S) * and 100=96.93r/min, R
6Be the draw ratio of the 6th warm area, R
6Be-1.5%; Obtain polyacrylonitrile base preoxidized fiber; The unit of described rotating speed RPM is r/min; S is drawing roller girth m/r.
Step 2, low-temperature carbonization: pre-oxidized polyacrylonitrile fiber is got into low temperature carbonization furnace through low-temperature carbonization stove drawing roller carry out charing; In the charing, as the charing medium, the interior pressure of retort is 20～50Pa with high pure nitrogen; The process of low-temperature carbonization comprises 3 warm areas, and each warm area is respectively 450 ℃, 570 ℃ and 625 ℃, and by low temperature to high temperature formation temperature gradient; Drawing of fiber rate 1%～10% in the low-temperature carbonization process, the drawing of fiber rate is 8% in the present embodiment.Effective total time of low-temperature carbonization is 2min; Low-temperature carbonization drawing roller linear velocity V
Low charcoal=V
7(1+R
Low charcoal)=0.304* (1+8%)=0.328m/min, rotating speed RPM
Low charcoal=(V
Low charcoal/ S) * and 100=104.56r/min, R
Low charcoalBe the draw ratio of low-temperature carbonization process, R
Low charcoalBe 8%; Obtain polyacrylonitrile-radical low-temperature carbonization fiber.
Step 3, high temperature carbonization: the low-temperature carbonization fiber that obtains is got into high temperature carbonization furnace through high temperature carbonization stove drawing roller carry out charing; In the charing, as the charing medium, the interior pressure of retort is 20～50Pa with high pure nitrogen; The process of high temperature carbonization comprises 2 warm areas, and each warm area is respectively 1050 ℃ and 1350 ℃, and by low temperature to high temperature formation temperature gradient; Drawing of fiber rate-4% in the low-temperature carbonization process, the calendar time 1min of high temperature carbonization; High temperature carbonization drawing roller linear velocity V
High charcoal=V
Low charcoal(1+R
High charcoal)=0.328* (1-4%)=0.315m/min, rotating speed RPM
High charcoal=(V
High charcoal/ S) * and 100=100.28r/min, R
High charcoalBe the draw ratio of high temperature carbonization process, R
High charcoalBe-4%; Obtain polyacrylonitrile-based carbon fibre.
Pre-oxidation in the present embodiment, high temperature carbonization process conditions are fixed; Under the fixing condition of low-temperature carbonization temperature and the speed of service; Through changing the low-temperature carbonization degree of draft, promptly set the different rotating speeds of low-temperature carbonization stokehold first break draft roller, realize the different degree of drafts under each low-temperature carbonization technology.Through the test of mechanical strength analyzer, present embodiment gained carbon fiber product tensile strength is respectively: 3261MPa, and 4032MPa, 3356MPa, 3505MPa, 3798MPa, 4107MPa, 3755MPa, 4000MPa, 3455MPa, 3784MPa, its mean value are 3705MPa.
Embodiment three
Present embodiment is a kind of preparation method of polyacrylonitrile-based carbon fibre, and the performance indications of said polyacrylonitrile-based precursor are as shown in table 4:
The performance indications table of table 4 polyacrylonitrile fibril
The preparation detailed process of present embodiment is:
Step 1, the pre-oxidation of polyacrylonitrile fibril: adopt the continous mode pre-oxidation furnace to realize the pre-oxidation of polyacrylonitrile fibril; 195 ℃～265 ℃ of pre-oxidation furnace temperature ranges are through 6 warm area formation temperature gradients; Drawing of fiber rate-2%, preoxidation time are 60min, and effective preoxidation time of each warm area is 10min; In the preoxidation process of polyacrylonitrile fibril, the linear velocity V of the 1st warm area porch drawing roller
1=0.3m/min, rotating speed RPM
1=(V
1/ S) * 100=95.54r/min; The 2nd warm area porch drawing roller linear velocity V
2=V
1(1+R
1)=0.3m/min, rotating speed RPM
2=(V
2/ S) * and 100=95.54r/min, in the formula, R
1Be the draw ratio of the 1st warm area, R
1Be 0%; The 3rd warm area porch drawing roller linear velocity V
3=V
2(1+R
2)=0.3* (1+3%)=0.309m/min, rotating speed RPM
3=(V
3/ S) * and 100=98.41r/min, R
2Be the draw ratio of the 2nd warm area, R
2Be 3%; The 4th warm area porch drawing roller linear velocity V
4=V
3(1+R
3)=0.309* (1+2%)=0.315m/min, rotating speed RPM
4=(V
4/ S) * and 100=100.4r/min, in the formula, R
3Be the draw ratio of the 3rd warm area, R
3Be 2%; The 5th warm area porch drawing roller linear velocity V
5=V
4(1+R
4)=0.315* (1+0%)=0.315m/min, rotating speed RPM
5=(V
5/ S) * and 100r/min=100.4r/min, in the formula, R
4Be the draw ratio of the 4th warm area, R
4Be 0%; The 6th warm area porch drawing roller linear velocity V
6=V
5(1+R
5)=0.315* (1-2%)=0.309m/min, rotating speed RPM
6=(V
6/ S) * and 100=98.41r/min, R
5Be the draw ratio of the 5th warm area, R
5Be-2%; The linear velocity V of the 6th warm area exit drawing roller
7With rotating speed RPM
7, V
7=V
6(1+R
6)=0.309* (1-1.5%)=0.304m/min, RPM
7=(V
7/ S) * and 100=96.93r/min, R
6Be the draw ratio of the 6th warm area, R
6Be-1.5%; Obtain polyacrylonitrile base preoxidized fiber; The unit of described rotating speed RPM is r/min; S is drawing roller girth m/r.
Step 2, low-temperature carbonization: pre-oxidized polyacrylonitrile fiber is got into low temperature carbonization furnace through low-temperature carbonization stove drawing roller carry out charing; In the charing, as the charing medium, the interior pressure of retort is 20～50Pa with high pure nitrogen; The process of low-temperature carbonization comprises 3 warm areas, and each warm area is respectively 450 ℃, 570 ℃ and 625 ℃, and by low temperature to high temperature formation temperature gradient; Drawing of fiber rate 1%～10% in the low-temperature carbonization process, the drawing of fiber rate is 3% in the present embodiment.Effective total time of low-temperature carbonization is 2min; Low-temperature carbonization drawing roller linear velocity V
Low charcoal=V
7(1+R
Low charcoal)=0.304* (1+3%)=0.313m/min, rotating speed RPM
Low charcoal=(V
Low charcoal/ S) * and 100=99.68r/min, R
Low charcoalBe the draw ratio of low-temperature carbonization process, R
Low charcoalBe 3%; Obtain polyacrylonitrile-radical low-temperature carbonization fiber.
Step 3, high temperature carbonization: the low-temperature carbonization fiber that obtains is got into high temperature carbonization furnace through high temperature carbonization stove drawing roller carry out charing; In the charing, as the charing medium, the interior pressure of retort is 20～50Pa with high pure nitrogen; The process of high temperature carbonization comprises 2 warm areas, and each warm area is respectively 1050 ℃ and 1350 ℃, and by low temperature to high temperature formation temperature gradient; Drawing of fiber rate-4% in the low-temperature carbonization process, the calendar time of high temperature carbonization are 1min; High temperature carbonization drawing roller linear velocity V
High charcoal=V
Low charcoal(1+R
High charcoal)=0.313* (1-4%)=0.305m/min, rotating speed RPM
High charcoal=(V
High charcoal/ S) * and 100=95.69r/min, R
High charcoalBe the draw ratio of high temperature carbonization process, R
High charcoalBe-4%; Obtain polyacrylonitrile-based carbon fibre.
Pre-oxidation in the present embodiment, high temperature carbonization process conditions are fixed; Under the fixing condition of low-temperature carbonization temperature and the speed of service; Through changing the low-temperature carbonization degree of draft, promptly set the different rotating speeds of low-temperature carbonization stokehold first break draft roller, realize the different degree of drafts under each low-temperature carbonization technology.Through the test of mechanical strength analyzer, present embodiment gained carbon fiber product tensile strength is respectively: 4325MPa, and 4903MPa, 4541MPa, 4873MPa, 3456MPa, 4518MPa, 4693MPa, 4599MPa, 4713MPa, 4422MPa, its mean value are 4621MPa.
Embodiment four
Present embodiment is a kind of preparation method of polyacrylonitrile-based carbon fibre, and the performance indications of said polyacrylonitrile-based precursor are as shown in table 5:
The performance indications table of table 5 polyacrylonitrile fibril
The preparation detailed process of present embodiment is:
Step 1, the pre-oxidation of polyacrylonitrile fibril: adopt the continous mode pre-oxidation furnace to realize the pre-oxidation of polyacrylonitrile fibril; 195 ℃～265 ℃ of pre-oxidation furnace temperature ranges are through 6 warm area formation temperature gradients; Drawing of fiber rate-2%, preoxidation time are 60min, and effective preoxidation time of each warm area is 10min; In the preoxidation process of polyacrylonitrile fibril, the linear velocity V of the 1st warm area porch drawing roller
1=0.3m/min, rotating speed RPM
1=(V
1/ S) * 100=95.54r/min; The 2nd warm area porch drawing roller linear velocity V
2=V
1(1+R
1)=0.3m/min, rotating speed RPM
2=(V
2/ S) * and 100=95.54r/min, in the formula, R
1Be the draw ratio of the 1st warm area, R
1Be 0%; The 3rd warm area porch drawing roller linear velocity V
3=V
2(1+R
2)=0.3* (1+3%)=0.309m/min, rotating speed RPM
3=(V
3/ S) * and 100=98.41r/min, R
2Be the draw ratio of the 2nd warm area, R
2Be 3%; The 4th warm area porch drawing roller linear velocity V
4=V
3(1+R
3)=0.309* (1+2%)=0.315m/min, rotating speed RPM
4=(V
4/ S) * and 100=100.4r/min, in the formula, R
3Be the draw ratio of the 3rd warm area, R
3Be 2%; The 5th warm area porch drawing roller linear velocity V
5=V
4(1+R
4)=0.315* (1+0%)=0.315m/min, rotating speed RPM
5=(V
5/ S) * and 100r/min=100.4r/min, in the formula, R
4Be the draw ratio of the 4th warm area, R
4Be 0%; The 6th warm area porch drawing roller linear velocity V
6=V
5(1+R
5)=0.315* (1-2%)=0.309m/min, rotating speed RPM
6=(V
6/ S) * and 100=98.41r/min, R
5Be the draw ratio of the 5th warm area, R
5Be-2%; The linear velocity V of the 6th warm area exit drawing roller
7With rotating speed RPM
7, V
7=V
6(1+R
6)=0.309* (1-1.5%)=0.304m/min, RPM
7=(V
7/ S) * and 100=96.93r/min, R
6Be the draw ratio of the 6th warm area, R
6Be-1.5%; Obtain polyacrylonitrile base preoxidized fiber; The unit of described rotating speed RPM is r/min; S is drawing roller girth m/r.
Step 2, low-temperature carbonization: pre-oxidized polyacrylonitrile fiber is got into low temperature carbonization furnace through low-temperature carbonization stove drawing roller carry out charing; In the charing, as the charing medium, the interior pressure of retort is 20～50Pa with high pure nitrogen; The process of low-temperature carbonization comprises 3 warm areas, and each warm area is respectively 450 ℃, 570 ℃ and 625 ℃, and by low temperature to high temperature formation temperature gradient; Drawing of fiber rate 1%～10% in the low-temperature carbonization process, the drawing of fiber rate is 1% in the present embodiment.Effective total time of low-temperature carbonization is 2min; Low-temperature carbonization drawing roller linear velocity V
Low charcoal=V
7(1+R
Low charcoal)=0.304* (1+1%)=0.307m/min, rotating speed RPM
Low charcoal=(V
Low charcoal/ S) * and 100=97.78r/min, R
Low charcoalBe the draw ratio of low-temperature carbonization process, R
Low charcoalBe 1%; Obtain polyacrylonitrile-radical low-temperature carbonization fiber.
Step 3, high temperature carbonization: the low-temperature carbonization fiber that obtains is got into high temperature carbonization furnace through high temperature carbonization stove drawing roller carry out charing; In the charing, as the charing medium, the interior pressure of retort is 20～50Pa with high pure nitrogen; The process of high temperature carbonization comprises 2 warm areas, and each warm area is respectively 1050 ℃ and 1350 ℃, and by low temperature to high temperature formation temperature gradient; Drawing of fiber rate-4% in the low-temperature carbonization process, effective total time 1min of high temperature carbonization; High temperature carbonization drawing roller linear velocity V
High charcoal=V
Low charcoal(1+R
High charcoal)=0.307* (1-4%)=0.295m/min, rotating speed RPM
High charcoal=(V
High charcoal/ S) * and 100=93.86r/min, R
High charcoalBe the draw ratio of high temperature carbonization process, R
High charcoalBe-4%; Obtain polyacrylonitrile-based carbon fibre.
Pre-oxidation in the present embodiment, high temperature carbonization process conditions are fixed; Under the fixing condition of low-temperature carbonization temperature and the speed of service; Through changing the low-temperature carbonization degree of draft, promptly set the different rotating speeds of low-temperature carbonization stokehold first break draft roller, realize the different degree of drafts under each low-temperature carbonization technology.Through the test of mechanical strength analyzer, present embodiment gained carbon fiber product tensile strength is respectively: 4073MPa, and 4313MPa, 4063MPa, 4131MPa, 4060MPa, 3912MPa, 4086MPa, 3905MPa, 3872MPa, 3854MPa, its mean value are 4027MPa.
Claims (1)
1. the preparation method of a polyacrylonitrile-based carbon fibre is characterized in that, detailed process is:
Step 1, the pre-oxidation of polyacrylonitrile fibril: adopt the continous mode pre-oxidation furnace to realize the pre-oxidation of polyacrylonitrile fibril; 195 ℃～265 ℃ of pre-oxidation furnace temperature ranges are through 6 warm area formation temperature gradients; Drawing of fiber rate-2%, pre-oxidation calendar time are 60min, and effective preoxidation time of each warm area is 10min; In the preoxidation process of polyacrylonitrile fibril, the linear velocity V of the 1st warm area porch drawing roller
1=0.3m/s, rotating speed RPM
1=(V
1/ S) * 100; The 2nd warm area porch drawing roller linear velocity V
2=V
1(1+R
1), rotating speed RPM
2=(V
2/ S) * 100, and in the formula, R
1Be the draw ratio of the 1st warm area, R
1Be 0%; The 3rd warm area porch drawing roller linear velocity V
3=V
2(1+R
2), rotating speed RPM
3=(V
3/ S) * 100, R
2Be the draw ratio of the 2nd warm area, R
2Be 3%; The 4th warm area porch drawing roller linear velocity V
4=V
3(1+R
3), rotating speed RPM
4=(V
4/ S) * 100, and in the formula, R
3Be the draw ratio of the 3rd warm area, R
3Be 2%; The 5th warm area porch drawing roller linear velocity V
5=V
4(1+R
4), rotating speed RPM
5=(V
5/ S) * 100, and in the formula, R
4Be the draw ratio of the 4th warm area, R
4Be 0%; The 6th warm area porch drawing roller linear velocity V
6=V
5(1+R
5), rotating speed RPM
6=(V
6/ S) * 100, R
5Be the draw ratio of the 5th warm area, R
5Be-2%; The linear velocity V of the 6th warm area exit drawing roller
7With rotating speed RPM
7, V
7=V
6(1+R
6), R
6Be the draw ratio of the 6th warm area, R
6Be-1.5%; Obtain pre-oxidized polyacrylonitrile fiber; The unit of described rotating speed RPM is r/min; S is drawing roller girth m/r;
Step 2, low-temperature carbonization: pre-oxidized polyacrylonitrile fiber is got into low temperature carbonization furnace through low-temperature carbonization stove drawing roller carry out charing; In the charing, as the charing medium, the interior pressure of retort is 20～50Pa with high pure nitrogen; The process of low-temperature carbonization comprises 3 warm areas, and each warm area is respectively 450 ℃, 570 ℃ and 625 ℃, and by low temperature to high temperature formation temperature gradient; Drawing of fiber rate 1%-10% in the low-temperature carbonization process, the calendar time of low-temperature carbonization is 2min; Low-temperature carbonization drawing roller linear velocity V
Low charcoal=V
7(1+R
Low charcoal), rotating speed RPM
Low charcoal=(V
Low charcoal/ S) * 100, R
Low charcoalBe the draw ratio of low-temperature carbonization process, R
Low charcoalBe 1%-10%; Obtain the low-temperature carbonization fiber;
Step 3, high temperature carbonization: the low-temperature carbonization fiber that obtains is got into high temperature carbonization furnace through high temperature carbonization stove drawing roller carry out charing; In the charing, as the charing medium, the interior pressure of retort is 20～50Pa with high pure nitrogen; The process of high temperature carbonization comprises 2 warm areas, and each warm area is respectively 1050 ℃ and 1350 ℃, and by low temperature to high temperature formation temperature gradient; Drawing of fiber rate-4% in the high temperature carbonization process, the calendar time 1min of high temperature carbonization; High temperature carbonization drawing roller linear velocity V
High charcoal=V
Low charcoal(1+R
High charcoal), rotating speed RPM
High charcoal=(V
High charcoal/ S) * 100, R
High charcoalBe the draw ratio of high temperature carbonization process, R
High charcoalBe-4%; Obtain polyacrylonitrile-based carbon fibre.
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| CN103184590A (en) * | 2013-04-15 | 2013-07-03 | 西安康本材料有限公司 | Preparation method of carbon fiber with strength of 4,800-5,000MPa |
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| CN103184589B (en) * | 2013-04-15 | 2015-03-04 | 西安康本材料有限公司 | Preparation method of PAN (polyacrylonitrile)-based carbon fiber for modifying protofilament through ammonification |
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| CN103184592A (en) * | 2013-04-15 | 2013-07-03 | 西安康本材料有限公司 | Manufacturing method of ternary ammonification modified T400-stage 12K carbon fiber |
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| CN103184590B (en) * | 2013-04-15 | 2014-10-29 | 西安康本材料有限公司 | Preparation method of carbon fiber with strength of 4,800-5,000MPa |
| CN103184592B (en) * | 2013-04-15 | 2015-12-09 | 西安康本材料有限公司 | Ternary ammoniation modified T400 level 12K carbon fiber production method |
| CN103184590A (en) * | 2013-04-15 | 2013-07-03 | 西安康本材料有限公司 | Preparation method of carbon fiber with strength of 4,800-5,000MPa |
| CN103184589A (en) * | 2013-04-15 | 2013-07-03 | 西安康本材料有限公司 | Preparation method of PAN (polyacrylonitrile)-based carbon fiber for modifying protofilament through ammonification |
| CN103290527A (en) * | 2013-05-22 | 2013-09-11 | 西安康本材料有限公司 | Method for lowering ash content of polyacrylonitrile-based carbon fiber |
| CN106676676A (en) * | 2016-11-21 | 2017-05-17 | 安徽佳力奇碳纤维科技股份公司 | Preparation method of polyacrylonitrile-based active carbon fibers and application of active carbon fibers |
| CN106676676B (en) * | 2016-11-21 | 2019-09-20 | 安徽佳力奇碳纤维科技股份公司 | Blood filter based on polyacrylonitrile based activated carbon fiber |
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| CN106835365B (en) * | 2017-01-20 | 2019-03-15 | 哈尔滨天顺化工科技开发有限公司 | A method of carbon fiber is prepared by polyacrylonitrile fibril carbonization |
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| CN111218733A (en) * | 2020-03-13 | 2020-06-02 | 北京化工大学 | Preparation method of large-diameter high-strength medium-modulus carbon fiber |
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Application publication date: 20121017 |