CN102392329A - Method for pre-oxidizing polyacrylonitrile-based protofilament - Google Patents
Method for pre-oxidizing polyacrylonitrile-based protofilament Download PDFInfo
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- CN102392329A CN102392329A CN2011102747398A CN201110274739A CN102392329A CN 102392329 A CN102392329 A CN 102392329A CN 2011102747398 A CN2011102747398 A CN 2011102747398A CN 201110274739 A CN201110274739 A CN 201110274739A CN 102392329 A CN102392329 A CN 102392329A
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Abstract
The invention relates to a method for pre-oxidizing a polyacrylonitrile-based protofilament. In the method, aiming at the distribution of temperature ranges, multi-section stretching is performed in the preoxidation process so as to adapt to the conversion of fiber structures in different stages. In the initial stage of preoxidation, a thermoplastic polyacrylonitrile (PAN) protofilament is subjected to positive stretching to control chemical contraction and keep the orientation degree of a macromolecular chain on a fiber axis; the degree of the positive stretching is reduced together with the continuous preoxidation and the aggravation of cyclation reaction, so that the positive stretching is transited to zero stretching and negative stretching; and in the later stage of the preoxidation, fibers are subjected to negative stretching to control and keep necessary chemical contraction, so that the preferred orientation of the macromolecular chain on the fiber axis is realized, the orientation degree of the preoxidized fibers is improved effectively and a linear molecular chain of the PAN protofilament is converted into a heat-resistant trapezoid structure; therefore, the uniform diffusion of oxygen is realized, a ratio of a fibrocortex is increased, the compacting degree of the preoxidized fibers is increased, the homogeneous preoxidized fibers are obtained, a molecular structure of the preoxidized fibers is improved, and the mechanical strength of carbon fibers is improved effectively.
Description
Technical field
The present invention relates to carbon fiber pre-oxidation field, specifically is a kind of method of polyacrylonitrile-based precursor pre-oxidation.
Background technology
Carbon fiber has a series of excellent properties such as high specific strength, high ratio modulus, endurance, creep resistant, corrosion-resistant and thermal coefficient of expansion be little; Thereby in national defence sophisticated technologies such as space flight, aviation, be widely used in the enhancing body of carbon fiber enhancement resin base composite material (CFRP), also be the new material that civilian industry updates.Prepare in the process at polyacrylonitrile (PAN) base carbon fibre, the pre-oxidation stage is absolutely necessary one of stage, also is violent structure conversion stage, and it carries out in air atmosphere, and the control temperature is usually between 180 ℃～300 ℃.Main cyclisation, dehydrogenation and the oxidation reaction of taking place in the pre-oxidation stage; The thaumatropy of thermoplasticity PAN chain macromolecule is nonplastic heat-resisting trapezoidal-structure; Making fiber can not melt at the carbonation stage of high temperature does not fire; And the maintenance fibre morphology, chemical reaction complicacy and technical process be consuming time grows (reaching more than 1 hour) most, is that the PAN base carbon fibre prepares in the process one of focus of research and difficult point both at home and abroad.
It is a complex physicochemical process that process pre-oxidation of PAN precursor and carbonization are converted into carbon fiber.In this process, the PAN precursor becomes the fragile material carbon fiber by flexible material.The TENSILE STRENGTH of fragile material is controlled by defective, and all kinds of defect and impurities all will obviously reduce the mechanical property of carbon fiber, becomes the main factor that restriction improves the carbon fiber TENSILE STRENGTH.Therefore, the process of raising carbon fiber mechanical property is exactly to reduce defects count and the process that reduces flaw size.The defective of carbon fiber mainly comes from three aspects: the one, by spinning cause PAN precursor defective and heredity to carbon fiber; The 2nd, produce in the preoxidation process; The 3rd, form in the carbonisation.In the pre-oxidation stage; The chemical constitution of optimizing the PAN fiber in conjunction with pre-oxidation process transforms, and suitable pre-oxidation drawing-off can realize the even diffusion of oxygen, increased fiber cortex ratio; Increase the densification degree of pre-oxidized fibers; Reducing fiber defective number and reduce flaw size, thereby obtain the pre-oxidized fibers of homogeneous, is one of effective means of preparation high-performance carbon fibre.
Influence the PAN fibre structure in the preoxidation process and change the drawing-off that technological parameter with performance indications has pre-oxidation temperature and temperature range distribution, preoxidation time and fiber is applied; Wherein the following draw ratio that fiber is applied is distributed with the pre-oxidation structure closely relatedly in certain oxidizing temperature interval, is determining the finally structure and the performance of carbon fiber product largely.Bigger thermal contraction takes place in the PAN fiber in preoxidation process, on the one hand, curling naturally of macromolecular chain produced the physics contraction; On the other hand, produced chemical shrinkage in the big molecule cyclization process.Fiber in the preoxidation process is applied the thermal contraction of suitable drawing-off with the restriction fiber, favourable to the pre-oxidation reaction, can keep the preferred orientation of macromolecular main chain structure to fiber axis, make fiber obtain excellent orientation, and improve the intensity and the modulus of carbon fiber.In addition, the differentiation of institutional framework has taken place in the skin-core structure of PAN precursor formation stage generation when fiber preoxidation." skin " portion of oxygen silk skin-core structure is fine and close in advance, the degree of orientation is high, and " core " portion is loose and disorderly, and the intensity of fiber mainly is the contribution of " skin " in the skin-core structure, and the intensity that " core " contributed is not as good as 1/2 of skin.Fiber is applied suitable drawing-off the content of " skin " in the skin-core structure is increased, thereby improve the intensity of carbon fiber.
To the distribution of temperature range, preoxidation process generally carries out the multistage drawing-off, transforms with the fibre structure that adapts to different phase.In general, at pre-oxidation initial stage (180 ℃～220 ℃), apply positive drawing-off with the control chemical shrinkage, to keep the degree of orientation of macromolecular chain to fiber axis for thermoplasticity PAN precursor; Along with constantly carrying out of pre-oxidation, cyclization has begun acutely, should be gradually than the degree of Shaozheng drawing-off and progressively carry out the transition to zero drawing-off and negative drawing-off; Especially at pre-oxidation later stage (220 ℃～300 ℃); Because the cyclisation of the molecular structure that cyclization causes and crosslinked applies negative drawing-off to fiber, with control and the necessary chemical shrinkage of maintenance; Keep the preferred orientation of macromolecular main chain structure, and make the linear molecule chain of PAN precursor transform to heat-resisting trapezium structure to fiber axis.Simultaneously, the multiplying power that in the preoxidation process fiber is applied drawing-off should be controlled within the specific limits, and the drawing-off that applies is excessive, will cause bigger internal stress, causes the generation of inner tensile defective, and leaves in the final carbon fiber product; The drawing-off that applies is too small, and the fiber orientation degree is low, can not get high-intensity carbon fiber equally.
Aspect the pre-oxidation theoretical research; Chemical reaction, the institutional framework of PAN fiber in preoxidation process developed the various countries scholar and a large amount of research has been carried out in molecule cyclisation behavior; And set up numerous reaction mechanism models; But because the difficulty that the complexity of preoxidation process itself and pre-oxidized fibers characterize, its theory study is very little to the directive function of concrete technology.Aspect pre-oxidation process; There is a small amount of document to inquire into the influence of pre-oxidation Temperature Distribution, heating rate and time to fibre structure; But receive pre-oxidation Equipment for Heating Processing shortage afterwards and the single restriction of analytical test means; The draft process aspect of pre-oxidation is only limited to the research for this single-point of pre-oxidation itself,, seldom relates to and the mechanical property of final carbon fiber product is influenced this overall situation of field the research of pre-oxidized fibers effect on structure like it.And the improvement of the research of all methods and technology finally all is to be purpose with the mechanical property that will improve carbon fiber product.Therefore, the reasonable setting of PAN precursor pre-oxidation stage process parameter distributes like the science of draw ratio, and is most important for the mechanical property that improves carbon fiber.
Summary of the invention
For overcoming the preoxidation process drawing-off that exists in the prior art when excessive or too small, influence the deficiency of the mechanical property of carbon fiber product, the present invention proposes a kind of method of polyacrylonitrile-based precursor pre-oxidation.
Detailed process of the present invention comprises the steps:
Step 1 is carried out pre-oxidation at No. 1 warm area.The temperature of No. 1 warm area pre-oxidation is 180 ℃～200 ℃, and the time of pre-oxidation is 10min.In No. 1 warm area preoxidation process, at first confirm the linear velocity V of No. 1 drawing roller
1With rotating speed RPM
1, the linear velocity V of No. 1 drawing roller wherein
1=pre-oxidation coverage/pre-oxidation total time, preoxidation time are 60min, and the pre-oxidation coverage is 18m.Rotating speed RPM
1=(V
1/ S) * 100.
Step 2 is carried out pre-oxidation at No. 2 warm areas.The temperature that No. 2 warm areas carry out pre-oxidation is 215 ℃～230 ℃, and the time of pre-oxidation is 10min.In No. 2 warm area preoxidation processes, at first confirm the linear velocity V of No. 2 drawing roller
2With rotating speed RPM
2, the linear velocity V of No. 2 drawing roller wherein
2=V
1(1+R
1), rotating speed RPM
2=(V
2/ S) * 100.In the formula, R
1Be the draw ratio of the 1st warm area, R
1Be 0 ‰.
Step 3 is carried out pre-oxidation at No. 3 warm areas.The temperature that No. 3 warm areas carry out pre-oxidation is 235 ℃～250 ℃, and the time of pre-oxidation is 10min.In No. 3 warm area preoxidation processes, at first confirm the linear velocity V of No. 3 drawing roller
3With rotating speed RPM
3, linear velocity V wherein
3=V
2(1+R
2), rotating speed RPM
3=(V
3/ S) * 100, and in the formula, R
2Be the draw ratio of the 2nd warm area, R
2Be 0 ‰～60 ‰.
Step 4 is carried out pre-oxidation at No. 4 warm areas.The temperature that No. 4 warm areas carry out pre-oxidation is 245 ℃～260 ℃, and the time of pre-oxidation is 10min.In No. 4 warm area preoxidation processes, at first confirm the linear velocity V of No. 4 drawing roller
4With rotating speed RPM
4, linear velocity V wherein
4=V
3(1+R
3), rotating speed RPM
4=(V
4/ S) * 100.In the formula, R
3Be the draw ratio of the 3rd warm area, R
3Be 0 ‰.
Step 5 is carried out pre-oxidation at No. 5 warm areas.The temperature that No. 5 warm areas carry out pre-oxidation is 255 ℃～270 ℃, and the time of pre-oxidation is 10min.In No. 5 warm area preoxidation processes, at first confirm the linear velocity V of No. 5 drawing roller
5With rotating speed RPM
5, linear velocity V wherein
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 ‰.
Step 6 is carried out pre-oxidation at No. 6 warm areas.The temperature that No. 6 warm areas carry out pre-oxidation is 270 ℃～290 ℃, and the time of pre-oxidation is 10min.In No. 6 warm area preoxidation processes, at first confirm the linear velocity V of No. 6 drawing roller
6And RPM
6, linear velocity V wherein
6=V
5(1+R
5), rotating speed RPM
6=(V
6/ S) * 100.In the formula, R
5Be the draw ratio of the 5th warm area, R
5Be-12.5 ‰～0 ‰, r/min.
Through step 1～6, obtain pre-oxidized fibers.
Step 7 is confirmed the linear velocity V of No. 7 drawing roller
7With rotating speed RPM
7Linear velocity V
7=V
6(1+R
6), rotating speed RPM
7=(V
7/ S) * 100, and in the formula, R
6Be the draw ratio of the 1st warm area, R
6Be-12.5 ‰～0 ‰.
Step 8, the pre-oxidized fibers carbonization.Pre-oxidized fibers gets into carbide furnace through the carbonization drawing roller.In the pre-oxidized fibers carbonization, pre-oxidized fibers is respectively through low temperature warm area and high temperature warm area, and the carbonization time of low temperature warm area is 2min, and the carbonization time of high temperature warm area is 1min, obtains the finished product carbon fiber.The linear velocity V of carbonization drawing roller
CarbonLinear velocity V with No. 7 drawing roller
7Identical.The rotating speed RPM of pre-oxidized fibers carbonization
Carbon=(V
Carbon/ S) * 100.
Described low temperature warm area is 750 ℃～850 ℃, and described high temperature warm area is 1350 ℃～1450 ℃.
The unit of described rotating speed RPM is r/min.S is drawing roller girth m/r.
For verifying effect of the present invention; The present invention has carried out the Mechanics Performance Testing of carbon fiber product, and testing equipment is 3365 serial universal testing machines, gauge length 200mm; 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 more than 4164MPa～4441MPa by 3563MPa through analytical test gained carbon fiber strength value.
The present invention has carried out the science setting through proposing the method for polyacrylonitrile fibril pre-oxidation to technological parameters such as pre-oxidation temperature and draw ratios, and to the distribution of temperature range, preoxidation process has carried out the multistage drawing-off, transforms with the fibre structure that adapts to different phase.At pre-oxidation initial stage (180 ℃～220 ℃), apply positive drawing-off with the control chemical shrinkage for thermoplasticity PAN precursor, to keep the degree of orientation of macromolecular chain to fiber axis; Along with constantly carrying out of pre-oxidation, cyclization has begun acutely, should be gradually than the degree of Shaozheng drawing-off and progressively carry out the transition to zero drawing-off and negative drawing-off; At pre-oxidation later stage (220 ℃～300 ℃), fiber is applied negative drawing-off especially, with control and the necessary chemical shrinkage of maintenance; Keep the preferred orientation of macromolecular main chain structure, effectively improve the degree of orientation of pre-oxidized fibers, and make the linear molecule chain of PAN precursor transform to heat-resisting trapezium structure to fiber axis; Thereby realize the even diffusion of oxygen, increased fiber cortex ratio, the densification degree of increase pre-oxidized fibers; Reduce fiber defective number and reduce flaw size, thereby obtain the pre-oxidized fibers of homogeneous, improve the pre-oxidized fibers molecular structure; Technological operation is simple, can effectively improve the mechanical strength of carbon fiber.Advantages such as the present invention has that treatment process is simple, easy operating, raising finished product carbon fiber mechanical property effect are remarkable are the methods that through engineering approaches is produced tool practical value.
The specific embodiment
Embodiment one
Present embodiment is the method for a kind of PAN based precursor pre-oxidation.
The pre-oxidation furnace that present embodiment was suitable for is divided into 3 groups, and 6 warm areas are arranged.The temperature of pre-oxidation furnace is elevated to 270 ℃ gradually by 180 ℃, before and after each warm area 1 drawing roller is arranged respectively, has 7 drawing roller.Polyacrylonitrile fibril drives through drawing roller and is moved gradually to high temperature by low temperature, is 10min in the time of each warm area pre-oxidation, and pre-oxidation total time is 60min, and whole pre-oxidation effective length is 18m.
The detailed process of present embodiment comprises the steps:
Step 1 is carried out pre-oxidation at No. 1 warm area.At first confirm the linear velocity V of No. 1 drawing roller
1With rotating speed RPM
1
The linear velocity V of No. 1 drawing roller
1=pre-oxidation effective length/pre-oxidation total time.In the present embodiment, preoxidation time is 60min, and whole pre-oxidation effective length is 18m.The linear velocity V of No. 1 drawing roller
1=18m/60min=0.300m/min.
Rotating speed formula: RPM
1=(V
1/ S) * 100=95.54r/min
In the formula: RPM is a rotating speed, r/min; S is drawing roller girth m/r, and its numerical value is 0.314m/r.
The temperature that No. 1 warm area carries out pre-oxidation is 180 ℃, and the time of pre-oxidation is 10min.
Step 2 is carried out pre-oxidation at No. 2 warm areas.At first confirm the linear velocity V of No. 2 drawing roller
2With rotating speed RPM
2
Linear velocity formula: V
2=V
1(1+R
1)=0.300 (1+0 ‰)=0.300m/min is in the formula: R
1Be the draw ratio of the 1st warm area, R
1Be 0 ‰.
Rotating speed formula: RPM
2=(V
2/ S) * and 100=95.54r/min, in the formula: RPM is a rotating speed, r/min; S is drawing roller girth m/r, and in the present embodiment, S is 0.314m/r.
The temperature that No. 2 warm areas carry out pre-oxidation is 215 ℃, and the time of pre-oxidation is 10min.
Step 3 is carried out pre-oxidation at No. 3 warm areas.At first confirm the linear velocity V of No. 3 drawing roller
3With rotating speed RPM
3
Linear velocity formula: V
3=V
2(1+R
2)=0.300 (1+9 ‰)=0.303m/min is in the formula: R
2Be the draw ratio of the 2nd warm area, R
2Be 9 ‰.
Rotating speed formula: RPM
3=(V
3/ S) * and 100=96.50r/min, in the formula: RPM is a rotating speed, r/min; S is drawing roller girth m/r, and in the present embodiment, S is 0.314m/r.
The temperature that No. 3 warm areas carry out pre-oxidation is 235 ℃, and the time of pre-oxidation is 10min.
Step 4 is carried out pre-oxidation at No. 4 warm areas.At first confirm the linear velocity V of No. 4 drawing roller
4With rotating speed RPM
4
Linear velocity formula: V
4=V
3(1+R
3)=V
3(1-2.5 ‰)=0.302m/min is in the formula: R
3Be the draw ratio of the 3rd warm area, R
3Value is for-2.5 ‰.
Rotating speed formula: RPM
4=(V
4/ S) * and 100=96.18r/min, in the formula: RPM is a rotating speed, r/min; S is drawing roller girth m/r, and in the present embodiment, S is 0.314m/r.
The temperature that No. 4 warm areas carry out pre-oxidation is 245 ℃, and the time of pre-oxidation is 10min.
Step 5 is carried out pre-oxidation at No. 5 warm areas.At first confirm the linear velocity V of No. 5 drawing roller
5With rotating speed RPM
5
Linear velocity formula: V
5=V
4(1+R
4)=V
4(1-2.5 ‰)=0.301m/min is in the formula: R
4Be the draw ratio of the 4th warm area, R
4Be-2.5 ‰.
Rotating speed formula: RPM
5=(V
5/ S) * and 100=95.86r/min, in the formula: RPM is a rotating speed, r/min; S is drawing roller girth m/r, and in the present embodiment, S is 0.314m/r.
The temperature that No. 5 warm areas carry out pre-oxidation is 255 ℃, and the time of pre-oxidation is 10min.
Step 6 is carried out pre-oxidation at No. 6 warm areas.At first confirm the linear velocity V of No. 6 drawing roller
6And RPM
6
Linear velocity formula: V
6=V
5(1+R
5)=V
5(1-12.5 ‰)=0.297m/min is in the formula: R
5Be the draw ratio of the 5th warm area, R
5Be-12.5 ‰.
Rotating speed formula: RPM
6=(V
6/ S) * and 100=94.59r/min, in the formula: RPM is a rotating speed, r/min; S is drawing roller girth m/r, and in the present embodiment, S is 0.314m/r.
The temperature that No. 6 warm areas carry out pre-oxidation is 270 ℃, and the time of pre-oxidation is 10min.
Through step 1～6, obtain pre-oxidized fibers.
Step 7 is confirmed the linear velocity V of No. 7 drawing roller
7With rotating speed RPM
7
Linear velocity formula: V
7=V
6(1+R
6)=V
6(1-12.5 ‰)=0.293m/min, in the formula: R6 is the draw ratio of the 6th warm area, R
6Be-12.5 ‰.
Rotating speed formula: RPM
7=(V
7/ S) * and 100=93.31r/min, in the formula: RPM is a rotating speed, r/min; S is drawing roller girth m/r, and S is 0.314m/r.
Step 8, the pre-oxidized fibers carbonization.Pre-oxidized fibers gets into carbide furnace through the carbonization drawing roller.In the pre-oxidized fibers carbonisation, pre-oxidized fibers is respectively through low temperature warm area and high temperature warm area, and is 2min at the carbonization time of low temperature warm area, is 1min at the carbonization time of high temperature warm area, obtains the finished product carbon fiber.The linear velocity V of carbonization drawing roller
CarbonLinear velocity V with No. 7 drawing roller
7Identical, i.e. V
Carbon=V
7=0.293m/min.
Rotating speed formula: RPM
Carbon=(V
Carbon/ S) * and 100=93.31r/min, in the formula: RPM is a rotating speed, r/min; S is drawing roller girth m/r, and in the present embodiment, S is 0.314m/r.
Described low temperature warm area is 750 ℃, and described high temperature warm area is 1350 ℃.
Present embodiment through setting the different rotating speeds of each drawing roller, brings the variation of the linear velocity of each warm area front and back drawing roller under certain pre-oxidation temperature and time condition; Thereby realize the positive drawing-off or the negative drawing-off of each oxidation stage through linear differential; Thereby realize the even diffusion of oxygen, increased fiber cortex ratio, the densification degree of increase pre-oxidized fibers; Reduce fiber defective number and reduce flaw size; Thereby obtain the pre-oxidized fibers of homogeneous, improve the pre-oxidized fibers molecular structure, improve the carbon fiber product mechanical property.Through the test of mechanical strength analyzer, present embodiment gained carbon fiber product tensile strength is respectively: 3618MPa, and 3908MPa, 3468MPa, 3551MPa, 3050MPa, 3657MPa, 3711MPa, 3678MPa, 3848MPa, 3145MPa, its mean value are 3563MPa.
Embodiment two
Present embodiment is the method for a kind of PAN based precursor pre-oxidation.
The pre-oxidation furnace that present embodiment was suitable for is divided into 3 groups, and 6 warm areas are arranged.The temperature of pre-oxidation furnace is elevated to 270 ℃ gradually by 180 ℃, before and after each warm area 1 drawing roller is arranged respectively, has 7 drawing roller.Fiber drives through drawing roller and is moved gradually to high temperature by low temperature, and pre-oxidation total time is 60min, and whole pre-oxidation effective length is 18m.
The detailed process of present embodiment comprises the steps:
Step 1 is carried out pre-oxidation at No. 1 warm area.At first confirm the linear velocity V of No. 1 drawing roller
1With rotating speed RPM
1
The linear velocity V of No. 1 drawing roller
1=pre-oxidation effective length/pre-oxidation total time.In the present embodiment, preoxidation time is 60min, and whole pre-oxidation effective length is 18m.The linear velocity V of No. 1 drawing roller
1=18m/60min=0.300m/min.
Rotating speed formula: RPM
1=(V
1/ S) * 100=95.54r/min
In the formula: RPM is a rotating speed, r/min; S is drawing roller girth m/r, and its numerical value is 0.314m/r.
The temperature that No. 1 warm area carries out pre-oxidation is 195 ℃, and the time of pre-oxidation is 10min.
Step 2 is carried out pre-oxidation at No. 2 warm areas.At first confirm the linear velocity V of No. 2 drawing roller
2With rotating speed RPM
2
Linear velocity formula: V
2=V
1(1+R
1)=0.300 (1+0 ‰)=0.300m/min is in the formula: R
1Be the draw ratio of the 1st warm area, R
1Be 0 ‰.
Rotating speed formula: RPM
2=(V
2/ S) * and 100=95.54r/min, in the formula: RPM is a rotating speed, r/min; S is drawing roller girth m/r, and in the present embodiment, S is 0.314m/r.
The temperature that No. 2 warm areas carry out pre-oxidation is 225 ℃, and the time of pre-oxidation is 10min.
Step 3 is carried out pre-oxidation at No. 3 warm areas.At first confirm the linear velocity V of No. 3 drawing roller
3With rotating speed RPM
3
Linear velocity formula: V
3=V
2(1+R
2)=0.300 (1,+20 ‰)=0.306m/min is in the formula: R
2Be the draw ratio of the 2nd warm area, R
2Be 20 ‰.
Rotating speed formula: RPM
3=(V
3/ S) * and 100=97.45r/min, in the formula: RPM is a rotating speed, r/min; S is drawing roller girth m/r, and in the present embodiment, S is 0.314m/r.
The temperature that No. 3 warm areas carry out pre-oxidation is 245 ℃, and the time of pre-oxidation is 10min.
Step 4 is carried out pre-oxidation at No. 4 warm areas.At first confirm the linear velocity V of No. 4 drawing roller
4With rotating speed RPM
4
Linear velocity formula: V
4=V
3(1+R
3)=V
3(1+0 ‰)=0.306m/min is in the formula: R
3Be the draw ratio of the 3rd warm area, R
3Value is 0 ‰.
Rotating speed formula: RPM
4=(V
4/ S) * and 100=97.45r/min, in the formula: RPM is a rotating speed, r/min; S is drawing roller girth m/r, and in the present embodiment, S is 0.314m/r.
The temperature that No. 4 warm areas carry out pre-oxidation is 255 ℃, and the time of pre-oxidation is 10min.
Step 5 is carried out pre-oxidation at No. 5 warm areas.At first confirm the linear velocity V of No. 5 drawing roller
5With rotating speed RPM
5
Linear velocity formula: V
5=V
4(1+R
4)=V
4(1+0 ‰)=0.306m/min is in the formula: R
4Be the draw ratio of the 4th warm area, R
4Be 0 ‰.
Rotating speed formula: RPM
5=(V
5/ S) * and 100=97.45r/min, in the formula: RPM is a rotating speed, r/min; S is drawing roller girth m/r, and in the present embodiment, S is 0.314m/r.
The temperature that No. 5 warm areas carry out pre-oxidation is 275 ℃, and the time of pre-oxidation is 10min.
Step 6 is carried out pre-oxidation at No. 6 warm areas.At first confirm the linear velocity V of No. 6 drawing roller
6And RPM
6
Linear velocity formula: V
6=V
5(1+R
5)=V
5(1-7.5 ‰)=0.304m/min is in the formula: R
5Be the draw ratio of the 5th warm area, R
5Be-7.5 ‰.
Rotating speed formula: RPM
6=(V
6/ S) * and 100=96.82r/min, in the formula: RPM is a rotating speed, r/min; S is drawing roller girth m/r, and in the present embodiment, S is 0.314m/r.
The temperature that No. 6 warm areas carry out pre-oxidation is 280 ℃, and the time of pre-oxidation is 10min.
Through step 1～6, obtain pre-oxidized fibers.
Step 7 is confirmed the linear velocity V of No. 7 drawing roller
7With rotating speed RPM
7
Linear velocity formula: V
7=V
6(1+R
6)=V
6(1-7.5 ‰)=0.302m/min, in the formula: R6 is the draw ratio of the 6th warm area, R
6Be-7.5 ‰.
Rotating speed formula: RPM
7=(V
7/ S) * and 100=96.18r/min, in the formula: RPM is a rotating speed, r/min; S is drawing roller girth m/r, and S is 0.314m/r.
Step 8, the pre-oxidized fibers carbonization.Pre-oxidized fibers gets into carbide furnace through the carbonization drawing roller.In the pre-oxidized fibers carbonization, pre-oxidized fibers is respectively through low temperature warm area and high temperature warm area, and is 2min at the carbonization time of low temperature warm area, is 1min at the carbonization time of high temperature warm area, obtains the finished product carbon fiber.The linear velocity V of carbonization drawing roller
CarbonLinear velocity V with No. 7 drawing roller
7Identical, i.e. V
Carbon=V
7=0.302m/min.
Rotating speed formula: RPM
Carbon=(V
Carbon/ S) * and 100=96.18r/min, in the formula: RPM is a rotating speed, r/min; S is drawing roller girth m/r, and in the present embodiment, S is 0.314m/r.
Described low temperature warm area is 800 ℃, and described high temperature warm area is 1400 ℃.
Present embodiment through setting the different rotating speeds of each drawing roller, brings the variation of the linear velocity of each warm area front and back drawing roller under certain pre-oxidation temperature and time condition; Thereby realize the positive drawing-off or the negative drawing-off of each oxidation stage through linear differential; Thereby realize the even diffusion of oxygen, increased fiber cortex ratio, the densification degree of increase pre-oxidized fibers; Reduce fiber defective number and reduce flaw size; Thereby obtain the pre-oxidized fibers of homogeneous, improve the pre-oxidized fibers molecular structure, improve the carbon fiber product mechanical property.Through the test of mechanical strength analyzer, present embodiment gained carbon fiber product tensile strength is respectively: 3884MPa, and 3915MPa, 4398MPa, 4065MPa, 4036MPa, 4265MPa, 4460MPa, 4017MPa, 4129MPa, 4474MPa, its mean value are 4164MPa.
Embodiment three
Present embodiment is the method for a kind of PAN based precursor pre-oxidation.
The pre-oxidation furnace that present embodiment was suitable for is divided into 3 groups, and 6 warm areas are arranged.The temperature of pre-oxidation furnace is elevated to 270 ℃ gradually by 180 ℃, before and after each warm area 1 drawing roller is arranged respectively, has 7 drawing roller.Polyacrylonitrile fibril drives through drawing roller and is moved gradually to high temperature by low temperature, and pre-oxidation total time is 60min, and whole pre-oxidation effective length is 18m.
The detailed process of present embodiment comprises the steps:
Step 1 is carried out pre-oxidation at No. 1 warm area.At first confirm the linear velocity V of No. 1 drawing roller
1With rotating speed RPM
1
The linear velocity V of No. 1 drawing roller
1=pre-oxidation effective length/pre-oxidation total time.In the present embodiment, preoxidation time is 60min, and whole pre-oxidation effective length is 18m, the linear velocity V of No. 1 drawing roller
1=18m/60min=0.300m/min.
Rotating speed formula: RPM
1=(V
1/ S) * 100=95.54r/min
In the formula: RPM is a rotating speed, r/min; S is drawing roller girth m/r, and its numerical value is 0.314m/r.
The temperature that No. 1 warm area carries out pre-oxidation is 200 ℃, and the time of pre-oxidation is 10min.
Step 2 is carried out pre-oxidation at No. 2 warm areas.At first confirm the linear velocity V of No. 2 drawing roller
2With rotating speed RPM
2
Linear velocity formula: V
2=V
1(1+R
1)=0.300 (1+0 ‰)=0.300m/min is in the formula: R
1Be the draw ratio of the 1st warm area, R
1Be 0 ‰.
Rotating speed formula: RPM
2=(V
2/ S) * and 100=95.54r/min, in the formula: RPM is a rotating speed, r/min; S is drawing roller girth m/r, and in the present embodiment, S is 0.314m/r.
The temperature that No. 2 warm areas carry out pre-oxidation is 230 ℃, and the time of pre-oxidation is 10min.
Step 3 is carried out pre-oxidation at No. 3 warm areas.At first confirm the linear velocity V of No. 3 drawing roller
3With rotating speed RPM
3
Linear velocity formula: V
3=V
2(1+R
2)=0.300 (1,+60 ‰)=0.318m/min is in the formula: R
2Be the draw ratio of the 2nd warm area, R
2Be+60 ‰.
Rotating speed formula: RPM
3=(V
3/ S) * and 100=101.27r/min, in the formula: RPM is a rotating speed, r/min; S is drawing roller girth m/r, and in the present embodiment, S is 0.314m/r.
The temperature that No. 3 warm areas carry out pre-oxidation is 250 ℃, and the time of pre-oxidation is 10min.
Step 4 is carried out pre-oxidation at No. 4 warm areas.At first confirm the linear velocity V of No. 4 drawing roller
4With rotating speed RPM
4
Linear velocity formula: V
4=V
3(1+R
3)=V
3(1+0 ‰)=0.318m/min is in the formula: R
3Be the draw ratio of the 3rd warm area, R
3Value is 0 ‰.
Rotating speed formula: RPM
4=(V
4/ S) * and 100=101.27r/min, in the formula: RPM is a rotating speed, r/min; S is drawing roller girth m/r, and in the present embodiment, S is 0.314m/r.
The temperature that No. 4 warm areas carry out pre-oxidation is 260 ℃, and the time of pre-oxidation is 10min.
Step 5 is carried out pre-oxidation at No. 5 warm areas.At first confirm the linear velocity V of No. 5 drawing roller
5With rotating speed RPM
5
Linear velocity formula: V
5=V
4(1+R
4)=V
4(1+0 ‰)=0.318m/min is in the formula: R
4Be the draw ratio of the 4th warm area, R
4Be 0 ‰.
Rotating speed formula: RPM
5=(V
5/ S) * and 100=101.27r/min, in the formula: RPM is a rotating speed, r/min; S is drawing roller girth m/r, and in the present embodiment, S is 0.314m/r.
The temperature that No. 5 warm areas carry out pre-oxidation is 270 ℃, and the time of pre-oxidation is 10min.
Step 6 is carried out pre-oxidation at No. 6 warm areas.At first confirm the linear velocity V of No. 6 drawing roller
6And RPM
6
Linear velocity formula: V
6=V
5(1+R
5)=V
5(1-7.5 ‰)=0.316m/min is in the formula: R
5Be the draw ratio of the 5th warm area, R
5Be-7.5 ‰.
Rotating speed formula: RPM
6=(V
6/ S) * and 100=100.64r/min, in the formula: RPM is a rotating speed, r/min; S is drawing roller girth m/r, and in the present embodiment, S is 0.314m/r.
The temperature that No. 6 warm areas carry out pre-oxidation is 290 ℃, and the time of pre-oxidation is 10min.
Through step 1～6, obtain pre-oxidized fibers.
Step 7 is confirmed the linear velocity V of No. 7 drawing roller
7With rotating speed RPM
7
Linear velocity formula: V
7=V
6(1+R
6)=V
6(1-7.5 ‰)=0.314m/min, in the formula: R6 is the draw ratio of the 6th warm area, R
6Be-7.5 ‰.
Rotating speed formula: RPM
7=(V
7/ S) * and 100=100.00r/min, in the formula: RPM is a rotating speed, r/min; S is drawing roller girth m/r, and S is 0.314m/r.
Step 8, the pre-oxidized fibers carbonization.Pre-oxidized fibers gets into carbide furnace through the carbonization drawing roller.In the pre-oxidized fibers carbonisation, pre-oxidized fibers is respectively through low temperature warm area and high temperature warm area, and is 2min at the carbonization time of low temperature warm area, is 1min at the carbonization time of high temperature warm area, obtains the finished product carbon fiber.The linear velocity V of carbonization drawing roller
CarbonLinear velocity V with No. 7 drawing roller
7Identical, i.e. V
Carbon=V
7=0.314m/min.
Rotating speed formula: RPM
Carbon=(V
Carbon/ S) * and 100=100.00r/min, in the formula: RPM is a rotating speed, r/min; S is drawing roller girth m/r, and in the present embodiment, S is 0.314m/r.
Described low temperature warm area is 850 ℃, and described high temperature warm area is 1450 ℃.
Present embodiment through setting the different rotating speeds of each drawing roller, brings the variation of the linear velocity of each warm area front and back drawing roller under certain pre-oxidation temperature and time condition; Thereby realize the positive drawing-off or the negative drawing-off of each oxidation stage through linear differential; Thereby realize the even diffusion of oxygen, increased fiber cortex ratio, the densification degree of increase pre-oxidized fibers; Reduce fiber defective number and reduce flaw size; Thereby obtain the pre-oxidized fibers of homogeneous, improve the pre-oxidized fibers molecular structure, improve the carbon fiber product mechanical property.Through the test of mechanical strength analyzer, present embodiment gained carbon fiber product tensile strength is respectively: 4555MPa, and 4352MPa, 4401MPa, 4352MPa, 4539MPa, 4594MPa, 4532MPa, 4217MPa, 4357MPa, 4514MPa, its mean value are 4441MPa.
Claims (2)
1. the method for a polyacrylonitrile-based precursor pre-oxidation is characterized in that, its detailed process comprises the steps:
Step 1 is carried out pre-oxidation at No. 1 warm area; The temperature of No. 1 warm area pre-oxidation is 180 ℃～200 ℃, and the time of pre-oxidation is 10min; In No. 1 warm area preoxidation process, at first confirm the linear velocity V of No. 1 drawing roller
1With rotating speed RPM
1, the linear velocity V of No. 1 drawing roller wherein
1=pre-oxidation coverage/pre-oxidation total time, preoxidation time are 60min, and the pre-oxidation coverage is 18m; Rotating speed RPM
1=(V
1/ S) * 100;
Step 2 is carried out pre-oxidation at No. 2 warm areas; The temperature that No. 2 warm areas carry out pre-oxidation is 215 ℃～230 ℃, and the time of pre-oxidation is 10min; In No. 2 warm area preoxidation processes, at first confirm the linear velocity V of No. 2 drawing roller
2With rotating speed RPM
2, the linear velocity V of No. 2 drawing roller wherein
2=V
1(1+R
1), rotating speed RPM
2=(V
2/ S) * 100; In the formula, R
1Be the draw ratio of the 1st warm area, R
1Be 0 ‰;
Step 3 is carried out pre-oxidation at No. 3 warm areas; The temperature that No. 3 warm areas carry out pre-oxidation is 235 ℃～250 ℃, and the time of pre-oxidation is 10min; In No. 3 warm area preoxidation processes, at first confirm the linear velocity V of No. 3 drawing roller
3With rotating speed RPM
3, linear velocity V wherein
3=V
2(1+R
2), rotating speed RPM
3=(V
3/ S) * 100, and in the formula, R
2Be the draw ratio of the 2nd warm area, R
2Be 0 ‰～60 ‰;
Step 4 is carried out pre-oxidation at No. 4 warm areas; The temperature that No. 4 warm areas carry out pre-oxidation is 245 ℃～260 ℃, and the time of pre-oxidation is 10min; In No. 4 warm area preoxidation processes, at first confirm the linear velocity V of No. 4 drawing roller
4With rotating speed RPM
4, linear velocity V wherein
4=V
3(1+R
3), rotating speed RPM
4=(V
4/ S) * 100; In the formula, R
3Be the draw ratio of the 3rd warm area, R
3Be 0 ‰;
Step 5 is carried out pre-oxidation at No. 5 warm areas; The temperature that No. 5 warm areas carry out pre-oxidation is 255 ℃～270 ℃, and the time of pre-oxidation is 10min; In No. 5 warm area preoxidation processes, at first confirm the linear velocity V of No. 5 drawing roller
5With rotating speed RPM
5, linear velocity V wherein
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 ‰;
Step 6 is carried out pre-oxidation at No. 6 warm areas; The temperature that No. 6 warm areas carry out pre-oxidation is 270 ℃～290 ℃, and the time of pre-oxidation is 10min; In No. 6 warm area preoxidation processes, at first confirm the linear velocity V of No. 6 drawing roller
6And RPM
6, linear velocity V wherein
6=V
5(1+R
5), rotating speed RPM
6=(V
6/ S) * 100; In the formula, R
5Be the draw ratio of the 5th warm area, R
5Be-12.5 ‰～0 ‰, r/min;
Through step 1～6, obtain pre-oxidized fibers;
Step 7 is confirmed the linear velocity V of No. 7 drawing roller
7With rotating speed RPM
7Linear velocity V
7=V
6(1+R
6), rotating speed RPM
7=(V
7/ S) * 100, and in the formula, R
6Be the draw ratio of the 1st warm area, R
6Be-12.5 ‰～0 ‰;
Step 8, the pre-oxidized fibers carbonization; Pre-oxidized fibers gets into carbide furnace through the carbonization drawing roller; In the pre-oxidized fibers carbonization, pre-oxidized fibers is respectively through low temperature warm area and high temperature warm area, and the carbonization time of low temperature warm area is 2min, and the carbonization time of high temperature warm area is 1min, obtains the finished product carbon fiber; The linear velocity V of carbonization drawing roller
CarbonLinear velocity V with No. 7 drawing roller
7Identical; The rotating speed RPM of pre-oxidized fibers carbonization
Carbon=(V
Carbon/ S) * 100; Described low temperature warm area is 750 ℃～850 ℃, and described high temperature warm area is 1350 ℃～1450 ℃.
2. a kind of according to claim 1 method of polyacrylonitrile-based precursor pre-oxidation is characterized in that, the unit of rotating speed RPM is r/min; S is drawing roller girth m/r.
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