CN114657670A - Continuous drafting reinforcing method and equipment for carbon nano tube fiber - Google Patents
Continuous drafting reinforcing method and equipment for carbon nano tube fiber Download PDFInfo
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- CN114657670A CN114657670A CN202210436451.4A CN202210436451A CN114657670A CN 114657670 A CN114657670 A CN 114657670A CN 202210436451 A CN202210436451 A CN 202210436451A CN 114657670 A CN114657670 A CN 114657670A
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
- D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
- D02J1/228—Stretching in two or more steps, with or without intermediate steps
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- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
- D02J1/04—Compacting
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- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
- D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
- D02J1/223—Stretching in a liquid bath
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- D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
- D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
- D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
- D02J1/225—Mechanical characteristics of stretching apparatus
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Abstract
The invention discloses a continuous drafting reinforcing method and equipment for carbon nano tube fibers. The continuous draw enhancing method comprises: continuously and sequentially carrying out multi-stage drawing treatment in a protonized solvent, deprotonation treatment in a coagulating bath and high-temperature annealing treatment on the carbon nanotube fiber; and during the multistage drawing treatment, the carbon nanotube fibers are sequentially wrapped and in frictional contact with a plurality of drawing shafts in the protonized solvent, and the rotating speeds of the plurality of drawing shafts are sequentially increased along the advancing direction of the carbon nanotube fibers. The continuous drafting reinforcing method of the carbon nanotube fiber can reduce the local stress borne by the carbon nanotube fiber in the drafting treatment process, avoid the carbon nanotube fiber fracture caused by stress concentration, and greatly improve the continuity in the drafting treatment process; meanwhile, the processes of drawing, deprotonation and high-temperature annealing treatment of the carbon nanotube fiber are effectively integrated, so that continuous and efficient drawing enhancement of the carbon nanotube fiber is realized.
Description
Technical Field
The invention relates to the technical field of inorganic carbon materials, in particular to a continuous drafting reinforcing method and equipment for carbon nano tube fibers.
Background
The Carbon Nanotube (CNT) fiber is a macroscopic fiber material assembled by carbon nanotubes and tube bundles thereof, has excellent mechanical, electrical and thermal properties, and has wide prospects in the fields of composite material reinforcement and multifunctional fiber application. The carbon nanotube fiber prepared by the floating catalysis method has the characteristics of low cost, high productivity and continuity, and is the most promising technical means for realizing the application of the carbon nanotube fiber on the ground. However, the existing preparation technology still has many problems, such as more pores inside the fiber, poor orientation of the carbon nanotube, etc., which significantly reduces the mechanical properties of the carbon nanotube fiber. Therefore, an efficient post-treatment enhancing means is required to be searched for realizing the preparation of the high-strength carbon nanotube fiber.
At present, many scholars mechanically reinforce carbon nanotube fibers by drawing and densifying. Zhao Jingna et al (patent No. CN112359441A) electrify the carbon nanotube/polymer composite fiber, utilize the heat that the electric current produces to make the polymer heat up and soften and turn into the high elastic state, and through the external force effect, realize the drafting orientation and densification of the carbon nanotube/polymer composite fiber; J.N.Wang (J.N.Wang, et al., Nature Communications, 2014, 5, 3845) performs rolling compaction on the carbon nanotube fiber, and the mechanical strength of the compacted fiber is up to 9 GPa. Eugene Oh (Oh et at., ACS appl.Matr.Interfaces, 2020, 2, 11) and others expand the fibers through the protonation of chlorosulfonic acid, so that the acting force between carbon nanotube tubes is weakened, and the higher drawing rate of the fibers is realized. However, the conventional reinforcing means have problems of poor continuity, low treatment efficiency, and the like, and cannot realize the continuity reinforcement of the carbon nanotube fiber.
Specifically, the drawing and densifying method of the carbon nanotube fiber in the prior art mainly has the following disadvantages:
(1) resin composite fiber drafting reinforcement technology: the technology obtains composite fiber by introducing resin material into carbon nano tube fiber, melts the resin material by means of electric heating, and performs auxiliary drafting on the fiber, thereby improving the mechanical strength of the fiber. However, the introduction of the resin material limits the application range of the composite fiber, and the conductivity of the fiber subjected to the reinforcement treatment is significantly reduced.
(2) Fiber rolling compaction enhancing technology: the fiber is densified through rolling, and the sectional area of the fiber is reduced, so that the mechanical strength of the obtained fiber is improved. However, the internal structure of the fiber is easily damaged during the rolling process, resulting in a reduction in fiber load and difficulty in achieving continuous treatment of the fiber.
(3) Chlorosulfonic acid auxiliary drafting enhancement technology: the carbon nano tube fiber expands under the protonation action of chlorosulfonic acid, the space between the inner carbon nano tubes is increased, and the van der Waals force is weakened, so that the higher drafting rate of the fiber is realized, the internal orientation of the fiber is improved, and the mechanical strength of the fiber is greatly improved. However, the device and the process method adopted at present can not realize continuous drawing enhancement of the fiber, belong to sectional treatment and non-continuous treatment, and the single fiber treatment amount is small (the single treatment length is about 10-20 cm).
Disclosure of Invention
In view of the shortcomings of the prior art, the present invention provides a method and an apparatus for enhancing the continuous drawing of carbon nanotube fibers.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
in a first aspect, the present invention provides a method for enhancing the continuous drawing of carbon nanotube fibers, comprising:
continuously and sequentially carrying out multi-stage drawing treatment in a protonized solvent, deprotonation treatment in a coagulating bath and high-temperature annealing treatment on the carbon nanotube fiber;
and during the multistage drawing treatment, the carbon nanotube fibers are sequentially wrapped and in frictional contact with a plurality of drawing shafts in the protonized solvent, and the rotating speeds of the plurality of drawing shafts are sequentially increased along the advancing direction of the carbon nanotube fibers.
In a second aspect, the present invention also provides a continuous drawing enhancing apparatus for carbon nanotube fibers, comprising:
an unwinding device for releasing carbon nanotube fibers at a specific initial rate;
the drafting device is used for carrying out multistage drafting treatment on the carbon nanotube fiber, and comprises a drafting groove for accommodating a protonated solvent and a plurality of drafting shafts arranged in the groove body of the drafting groove along the advancing direction of the carbon nanotube fiber, wherein each drafting shaft can rotate at different specific drafting rates;
a deprotonation device for deprotonating the carbon nanotube fiber;
and an annealing device for carrying out high-temperature annealing treatment on the carbon nanotube fibers.
Based on the technical scheme, compared with the prior art, the invention has the beneficial effects that:
according to the continuous drafting reinforcing method for the carbon nanotube fiber, the drafting process of the carbon nanotube fiber is continuously carried out, and the gradual drafting of the carbon nanotube fiber is realized by adopting the gradually accelerated drafting shaft, so that the local stress on the carbon nanotube fiber in the drafting process can be reduced, the carbon nanotube fiber is prevented from being broken due to stress concentration, and the continuity in the drafting process is greatly improved; meanwhile, the processes of drawing, deprotonation and high-temperature annealing treatment of the carbon nanotube fiber are effectively integrated, so that continuous and efficient drawing enhancement of the carbon nanotube fiber is realized.
The above description is only an overview of the technical solutions of the present invention, and in order to enable those skilled in the art to more clearly understand the technical means of the present invention and to implement the technical means according to the content of the description, the following description is made with reference to the preferred embodiments of the present invention and the accompanying detailed drawings.
Drawings
FIG. 1 is a schematic diagram of a carbon nanotube fiber drawing apparatus according to an exemplary embodiment of the present invention;
FIG. 2 is a graph comparing the mechanical properties of carbon nanotube fibers before and after continuous draw enhancement provided by an exemplary embodiment of the present invention;
FIG. 3 is an electron micrograph of the surface of a carbon nanotube fiber before continuous draw enhancement according to an exemplary embodiment of the present invention;
FIG. 4 is an electron micrograph of the surface of a carbon nanotube fiber after continuous draw enhancement provided by an exemplary embodiment of the present invention;
FIG. 5 is an electron micrograph of an axial cross section of a carbon nanotube fiber before continuous draw enhancement according to an exemplary embodiment of the present invention;
fig. 6 is an electron microscope photograph of an axial cross section of a carbon nanotube fiber after continuous drawing reinforcement according to an exemplary embodiment of the present invention.
Description of reference numerals: 1. an unwinding device; 2. a wire guide wheel; 3. carbon nanotube fibers; 4. a primary drafting shaft; 5. a secondary drafting shaft; 6. a tertiary drafting shaft; 7. a protonated solvent; 8. a fixed shaft; 9. a coagulation bath; 10. an annealing device; 11. a winding device.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced otherwise than as specifically described herein, and thus the scope of the present invention is not limited by the specific embodiments disclosed below.
The inventor of the present invention found in long-term practice that when the auxiliary drafting enhancing technology in the prior art is used for drafting the continuous carbon nanotube fiber, the carbon nanotube fiber is drafted in one step in chlorosulfonic acid solution, and due to the non-uniformity of the carbon nanotube fiber and the uncontrollable factors in the one-step drafting process, the continuous carbon nanotube fiber is easily broken in chlorosulfonic acid, which causes the interruption of continuous drafting, and thus the high-strength carbon nanotube fiber with continuous high length (from ten meters to kilometers) cannot be obtained. For example: the drawing force tends to cause the elongation of the weak portion of the carbon nanotube fiber to be significantly higher than that of other portions, and thus breakage occurs at the weak portion, thereby causing interruption of continuous drawing. In addition, the multistage drafting can increase the stress sites of the fibers in the involving process, so that the internal disentanglement of the fibers is more uniform, and the internal orientation and uniformity of the fibers are further improved.
Referring to fig. 1, a method for enhancing continuous drawing of a carbon nanotube fiber 3 according to an embodiment of the present invention includes the following steps:
continuously and sequentially carrying out multi-stage drawing treatment in a protonation solvent 7, deprotonation treatment in a coagulating bath 9 and high-temperature annealing treatment on the carbon nanotube fiber 3; in the multistage drawing treatment, the carbon nanotube fiber 3 is sequentially wrapped around and in frictional contact with a plurality of drawing shafts 4 to 6 in the protonated solvent 7, and the rotation speeds of the plurality of drawing shafts 4 to 6 are sequentially increased in the advancing direction of the carbon nanotube fiber 3.
Unless otherwise specified, the process steps of the present invention are carried out at ambient temperature (e.g., 15-35 ℃) except for high temperature annealing.
In the continuous drawing enhancing process, protons are adsorbed on the surfaces of the carbon nanotubes by the protonation of the protonation solvent 7, the carbon nanotubes in the carbon nanotube fibers 3 are positively charged, electrostatic repulsion is generated between the carbon nanotubes and the carbon nanotube bundles, the distance between the carbon nanotubes and the carbon nanotube bundles in the carbon nanotube fibers 3 is further increased, and van der waals force acting forces between the carbon nanotubes are weakened, so that the carbon nanotube fibers 3 show an expanded state macroscopically.
Then, multistage drafting is carried out by adopting a multistage drafting shaft, so that the drafting degree of the carbon nanotube fiber 3 is controllable when the carbon nanotube fiber is drafted at each stage, meanwhile, the uniformity of stress distribution inside the drafted fiber is improved, excessive drafting of the weak part of the carbon nanotube fiber 3 is avoided, and the phenomenon that the carbon nanotube fiber 3 is easy to break when drafted in the protonized solvent 7 is further avoided.
Then, after the carbon nanotube fiber 3 enters the coagulation bath 9, phase separation occurs in the fiber under the drive of poor solubility, the protonated solvent 7 inside the expanded carbon nanotube fiber 3 is dissolved and separated out by the solvent in the coagulation bath 9, protonation disappears, electrostatic repulsion between carbon tubes disappears, the carbon nanotube fiber 3 shrinks compactly, and meanwhile, friction between the carbon nanotube fiber 3 and the fixed shaft 8 plays a certain micro-combing role on the carbon nanotube fiber 3 through the fixed shaft 8 in the process of shrinking and densifying (deprotonation) of the carbon nanotube fiber 3, so that fiber orientation can be further improved, and further, the mechanical property of the carbon nanotube fiber 3 is improved.
Finally, the carbon nanotube fiber 3 is annealed at a high temperature to remove various solvents and reaction residual byproducts remaining inside the carbon nanotube fiber 3, thereby obtaining the final high-strength carbon nanotube fiber 3.
In some embodiments, the carbon nanotube fiber 3 may include one of a floating catalyst carbon nanotube fiber, a wet spinning carbon nanotube fiber, and an array spinning carbon nanotube fiber, or a blend fiber of any two or more thereof. Among them, the carbon nanotube fiber 3 most suitable for the continuous draft reinforcement method is the floating catalyst carbon nanotube fiber 3, and the carbon nanotube fiber 3 of this kind has advantages of long carbon nanotube length, large fiber bundle gap, and long fiber continuous length.
In some embodiments, the protonation solvent 7 may include one or a combination of two of chlorosulfonic acid and methanesulfonic acid, but is not limited thereto, and the continuous drawing enhancement of the carbon nanotube fiber by other protonation solvents instead based on the technical idea of the present invention is within the protection scope of the present invention.
In some embodiments, the coagulation bath 9 may include any one or a combination of two or more of water, acetone, and ethanol.
In some embodiments, as shown in fig. 1, the carbon nanotube fibers 3 may preferably be wrapped around the opposite sides of adjacent drawing shafts 4-6.
In some embodiments, continuing with fig. 1, any of the drafting shafts and its neighboring drafting shaft may be arranged on different sides of a predetermined dividing plane. The preset separation plane is a virtual separation plane between the upper group of drafting shafts 4-6 and the lower group of drafting shafts 4-6 as shown in fig. 1.
In some embodiments, the material of the drafting shaft may include one or a combination of two of teflon and quartz, but is not limited thereto, and the above materials are suitable materials preferred in the present invention, and other materials that are chemically inert and have a sufficiently smooth surface may also be used. The material of the draft shaft is preferably polytetrafluoroethylene.
In some embodiments, the diameter of the drafting shaft may preferably be 20 to 70 mm.
In some embodiments, the preferred spacing of the plurality of said drafting shafts may be from 5 to 20cm, more preferably from 5 to 10 cm. The inventor of the invention finds out in repeated practice and research that a proper distance between the drafting shafts is very important for obtaining the high-strength carbon nanotube fiber 3 with high continuity, and if the distance is too large and the wrap angle between the fibers at two ends of the drafting shafts is too small, the method can be similar to the one-step drafting in place method in the prior art, so that the weak part of the carbon nanotube fiber 3 is excessively drawn; if the distance is too small and the wrap angle between the fibers at the two ends of the drafting shaft is too large, the distance of each level of drafting is too short, the drafting effect cannot be uniformly distributed in a sufficient distance, and the fiber fracture or the fiber mechanics lifting is poor; the inventors have found for a long time that the above-mentioned optimum distance between the draft axes is provided.
In some embodiments, the linear velocity difference between adjacent said draw shafts may preferably be in the range of 0.1 to 0.5 m/min.
In some embodiments, after the drawing process is finished, the drawing ratio of the carbon nanotube fiber 3 may preferably be 5 to 30%. The draft ratio is the elongation of the carbon nanotube fiber 3 as a whole, not the elongation of each stage, i.e., the ratio of the distance of the fiber elongation to the original length of the fiber.
In some embodiments, the unreeling rate of the carbon nanotube fibers may preferably be 1 to 20 m/h.
In some embodiments, the take-up rate of the carbon nanotube fibers may preferably be 1 to 20 m/h.
In some embodiments, the number of draft shafts may preferably be 3 to 7.
In some embodiments, the carbon nanotubes may preferably have a wrap angle of 90 to 150 °, preferably 90 to 120 °, on the drawing axis.
In some embodiments, the carbon nanotube fibers 3 may be wrapped in frictional contact with a stationary shaft 8 in a coagulation bath 9 during the deprotonation process.
In some embodiments, the diameter of the stationary shaft 8 may preferably be 5-15 mm.
In some embodiments, the material of the fixed shaft 8 may include any one of quartz, teflon, or a combination of the two.
The appropriate wrap angle has an important influence on the micro-carding action of the carbon nanotube fibers 3, and in some embodiments, the wrap angle of the carbon nanotube fibers 3 with respect to the fixed axis 8 may preferably be 45 to 90 °.
In some embodiments, the temperature of the high temperature annealing treatment may be preferably 200-.
Based on the above embodiments, it is clear that the present invention has the following advantages:
(1) the invention provides a method for continuously drafting and enhancing carbon nanotube fibers, which realizes the batch enhancement of the carbon nanotube fibers.
(2) The drafting process of the fiber in the protonation solvent such as chlorosulfonic acid is gradual drafting, and compared with the prior art that specific drafting rate is realized at one time, the gradual drafting can reduce drafting stress, thereby being beneficial to smooth drafting and greatly improving the drafting continuity.
(3) The invention effectively integrates the processes of carbon nano tube fiber drafting, cleaning and compacting (deprotonation) and high-temperature annealing, and realizes the continuous and efficient post-treatment reinforcement of the carbon nano tube fiber.
With continued reference to fig. 1, an embodiment of the present invention further provides a continuous drawing enhancing apparatus for carbon nanotube fibers 3, including:
an unwinding device 1 for releasing carbon nanotube fibers 3 at a specific initial rate.
The drafting device is used for carrying out multistage drafting treatment on the carbon nanotube fiber 3, and comprises a drafting groove for accommodating the protonated solvent 7 and a plurality of drafting shafts arranged in the groove body of the drafting groove along the advancing direction of the carbon nanotube fiber 3, wherein each drafting shaft can rotate at different specific drafting rates.
A deprotonation device for deprotonating the carbon nanotube fiber 3.
And an annealing device 10 for performing high-temperature annealing treatment on the carbon nanotube fibers 3.
In some embodiments, the deprotonation apparatus may include a deprotonation tank for housing a coagulation bath 9 and a plurality of stationary shafts 8 disposed within the tank body of the deprotonation tank.
In some embodiments, the continuous enhanced drawing device may further include a plurality of guide wheels 2, the guide wheels 2 being used to fix a portion of the traveling path of the carbon nanotube fiber 3 so that the carbon nanotube fiber 3 forms a specific wrap angle with a portion of the drawing shaft and/or the fixed shaft 8.
In some embodiments, the continuous enhanced drawing apparatus may further include a winding device 11 for collecting the carbon nanotube fiber 3 after the high temperature annealing treatment at a specific collection rate.
The technical scheme of the invention is further explained in detail by a plurality of embodiments and the accompanying drawings. However, the examples are chosen only for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.
Example 1
The present embodiment provides a method for continuously drawing and reinforcing a carbon nanotube fiber 3, and a used continuous drawing and reinforcing device is shown in fig. 1, which specifically includes the following steps:
releasing carbon nanotube fibers 3 at a rate of 2m/h through an unreeling device 1, wherein the carbon nanotube fibers 3 are prepared by a floating catalysis method;
the carbon nano tube fiber 3 obliquely enters chlorosulfonic acid through a guide wheel 2 to generate protonation reaction and then passes through a primary drafting shaft 4, a secondary drafting shaft 5 and a tertiary drafting shaft 6 which are arranged in a zigzag array, wherein primary drafting is carried out between the primary drafting shaft 4 and an unreeling device 1, secondary drafting is carried out between the secondary drafting shaft 5 and the primary drafting shaft 4, and tertiary drafting is carried out between the tertiary drafting shaft 6 and the secondary drafting shaft 5; the drafting shafts at all levels are made of polytetrafluoroethylene, the diameter of each drafting shaft is 20mm, and the distance between every two levels is 5 cm; the wrap angle of the fibers at two ends of the drafting shaft is 90 degrees; the rotational linear velocities of the first to third drawing shafts 6 were 2.1, 2.2, and 2.3m/h in this order, and the final drawing ratio of the carbon nanotube fiber 3 was 15.8%.
The carbon nanotube fiber 3 subjected to the multistage drafting treatment continuously enters a coagulating bath 9 for deprotonation treatment under the guidance of a guide wheel 2, the coagulating bath 9 is acetone, as shown in fig. 1, two fixed shafts 8 made of quartz and having a diameter of 5mm are arranged in the coagulating bath 9, and the fiber is wrapped around the fixed shafts 8 and then extends out of the other side of the coagulating bath 9; the wrapping angle of the fibers at two ends of the fixed shaft 8 is 45 degrees;
the deprotonated carbon nanotube fiber 3 continues to enter a high-temperature annealing device 10 shown in fig. 1, wherein the temperature of the high-temperature annealing device 10 is set to be 200 ℃, and the annealing time is 15 min;
the carbon nanotube fiber 3 subjected to the high-temperature annealing treatment is wound in a winding device 11, and the linear speed of the winding device 11 is 2.3 m/min.
The continuous draft enhancing method provided in this embodiment can achieve a continuous 500m draft enhancement of the carbon nanotube fiber 3, and as shown in fig. 2, mechanical property tests are performed on the carbon nanotube fiber 3 obtained by the continuous draft enhancement of this embodiment and the original carbon nanotube fiber 3, it can be found that the continuous draft enhancing method provided in this embodiment can continuously draft and enhance the carbon nanotube fiber 3 to a tensile strength of about 5.5GPa, a tensile modulus of about 190GPa, which is significantly higher than that of the original carbon nanotube fiber 3.
Fig. 3 and fig. 4 respectively show surface electron micrographs of the reinforced carbon nanotube fiber 3 and the original carbon nanotube fiber 3 provided in this embodiment, and fig. 5 and fig. 6 respectively show electron micrographs of axial cross sections (inside of the fiber is photographed after peeling and delaminating the carbon nanotubes) of the reinforced carbon nanotube fiber 3 and the original carbon nanotube fiber 3 provided in this embodiment, it can be found from fig. 3 to fig. 6 that the fiber surface is more dense and has better orientation after being treated by the continuous drafting reinforcing method provided in this embodiment, the internal pores of the fiber are greatly reduced, the orientation degree of the internal carbon nanotubes and the tube bundles thereof is improved, and the improvement of the overall orientation of the carbon nanotube fiber 3 and the reduction of the internal pores are important reasons for the improvement of the mechanical properties of the carbon nanotube fiber 3.
Example 2
This example provides a method for continuously drawing and reinforcing a carbon nanotube fiber 3, which is basically the same as example 1 except that:
the unreeling speed is 6 m/h;
the draft axle sets up to 3 grades, and the diameter of every grade of draft axle is 70mm, and the interval of adjacent draft axle at different levels is 30cm, and the rotational speed of draft axle does in proper order: 6.4, 6.7 and 7.1 m/h;
the diameter of the fixed shaft 8 is 10 mm;
the high-temperature annealing temperature is 500 ℃, and the annealing time is 10 min.
High strength carbon nanotube fibers similar in continuity and uniformity to those of example 1 can also be obtained.
Example 3
This example provides a method for continuously drawing and reinforcing a carbon nanotube fiber 3, which is substantially the same as example 1 except that:
the unreeling speed is 12 m/min;
the draft axle sets up to 5 grades, and the diameter of every grade of draft axle is 40mm, and the interval of adjacent draft axle at different levels is 20cm, and the rotational speed of draft axle does in proper order: 12.5, 13.0, 13.5, 14.0 and 14.6 m/min;
the diameter of the fixed shaft 8 is 10 mm;
the high-temperature annealing temperature is 350 ℃, and the annealing time is 5 min.
High strength carbon nanotube fibers similar in continuity and uniformity to those of example 1 can also be obtained.
Example 4
This example provides a method for continuously drawing and reinforcing a carbon nanotube fiber 3, which is substantially the same as example 1 except that:
the coagulating bath 9 is a mixed solution of acetone and water in a volume ratio of 1: 1.
High strength carbon nanotube fibers similar in continuity and uniformity to those of example 1 can also be obtained.
Example 5
This example provides a method for continuously drawing and reinforcing a carbon nanotube fiber 3, which is basically the same as example 1 except that:
the protonation solvent is mixed solution of chlorosulfonic acid and methanesulfonic acid in the volume ratio of 1 to 1.
High-strength carbon nanotube fibers having continuity and uniformity similar to those of example 1 can also be obtained
Comparative example 1
The comparative example differs from example 1 in that: the protonated solvent 7 only passes through the drawing shaft 4 and the drawing shaft 6 from the lower part, and the rotating speed of the drawing shafts 4 and 6 is the same as the unreeling speed, thereby realizing one-step continuous drawing. The comparison example can only realize the continuous reinforcement of the carbon nanotube fiber 3 with the length of 50-100 meters, and the mechanical strength of the reinforced carbon nanotube fiber is 4.7 GPa. The comparative example and the example 1 both adopt 20 groups of samples to carry out the fiber mechanics test, the standard deviation between the mechanics test results of the 20 groups of samples in the example 1 is 0.14, and the standard deviation between the mechanics test results of the 20 groups of samples in the comparative example is 0.36.
Comparative example 2
The comparative example differs from example 1 in that: the distance between adjacent drafting shafts at each stage is 40cm, and the wrap angle between the fiber and the drafting shafts is 60 degrees. The mechanical strength of the obtained carbon nano tube fiber is 4.7 GPa.
In this comparative example, the distance between adjacent draft shafts is too large, the acting force between the fiber and the draft shafts is weakened, and the stepwise draft effect is reduced, similar to the one-time draft enhancement in comparative example 1.
Comparative example 3
The comparative example differs from example 1 in that: the distance between adjacent drafting shafts at each stage is 3cm, and the wrap angle between the fiber and the drafting shafts is 150 degrees. The mechanical strength of the obtained carbon nano tube fiber is 4.2 GPa. The present comparative example can achieve only continuous reinforcement of the carbon nanotube fiber 3 of 30 to 50 meters.
In the comparative example, the distance between adjacent drafting shafts is too small, the distance between every two drafting shafts is too small, and the drafting force cannot act on the fiber uniformly, so that the drafting continuity is poor and the fiber mechanics is low.
Comparative example 4
The comparative example is different from example 1 in that: two quartz material fixed shafts 3 arranged in the coagulation bath 9 are replaced by ceramic bearings, polytetrafluoroethylene fiber yarn guide wheels are wrapped outside the ceramic bearings, sliding friction of fibers on the quartz fixed shafts is changed into rolling friction on the ceramic bearings, and the micro-combing effect in the coagulation bath 9 is eliminated. The mechanical strength of the obtained carbon nano tube fiber is 4.5 GPa.
According to the comparative analysis of the above embodiment and the comparative example, it is clear that the continuous drawing enhancement method of carbon nanotube fiber provided by the present invention can significantly improve the continuity and uniformity of the drawing enhancement process of carbon nanotube compared to the prior art, and can efficiently and repeatedly produce high-strength carbon nanotube fiber of hectometer level, which cannot be provided by the prior art.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A method for continuously drawing and reinforcing carbon nanotube fibers, comprising:
continuously and sequentially carrying out multi-stage drawing treatment in a protonized solvent, deprotonation treatment in a coagulating bath and high-temperature annealing treatment on the carbon nanotube fiber;
wherein, during the multistage drawing treatment, the carbon nanotube fibers are sequentially in wrap-around frictional contact with a plurality of drawing shafts in the protonated solvent, and the rotation speeds of the plurality of drawing shafts are sequentially increased in the advancing direction of the carbon nanotube fibers.
2. The continuous draw enhancement method according to claim 1, wherein the carbon nanotube fibers include any one or a combination of two or more of floating catalyst carbon nanotube fibers, liquid phase spinning fibers, and array spinning fibers;
and/or, the protonation solvent comprises any one or the combination of two of chlorosulfonic acid and methanesulfonic acid;
and/or the coagulating bath comprises any one or the combination of more than two of water, acetone and ethanol.
3. The continuous draft enhancing method according to claim 1, wherein any one of said draft shafts and its adjacent draft shaft are arranged on different sides of a predetermined dividing plane, and said carbon nanotube fiber is wrapped around the side of each of said draft shafts opposite to the other adjacent draft shafts;
and/or the material of the drafting shaft comprises any one or the combination of two of polytetrafluoroethylene and quartz;
and/or the diameter of the drafting shaft is 20-70 mm;
and/or the distance between a plurality of drafting shafts is 5-10 cm;
and/or the wrap angle between the fibers at the two ends and the drafting shaft is 90-150 degrees.
4. The continuous draw enhancement process of claim 1, wherein the linear velocity difference between adjacent said draw shafts is from 0.1 to 0.5 m/h;
and/or the unreeling speed of the carbon nano tube fiber is 1-20 m/h;
and/or the rolling rate of the carbon nano tube fiber is 1-20 m/h;
and/or after the drafting treatment is finished, the drafting rate of the carbon nano tube fiber is 5-30%.
5. The continuous draft enhancement method of claim 4, wherein said number of draft shafts is 3 to 7.
6. The continuous draw enhancement method of claim 1, wherein the carbon nanotube fibers are in wrap-around frictional contact with a stationary shaft in a coagulation bath while the deprotonation treatment is performed.
7. The continuous draft enhancing method according to claim 6, wherein said fixed shaft has a diameter of 5-15 mm;
and/or the material of the fixed shaft comprises any one or the combination of two of quartz and polytetrafluoroethylene;
and/or the wrap angle between the carbon nanotube fiber and the fixed shaft is 45-90 degrees.
8. The continuous draft enhancing method according to claim 1, wherein the temperature of said high temperature annealing treatment is 200 ℃ to 500 ℃ and the fiber annealing time is 5-20 min.
9. A continuous draw enhancing apparatus for carbon nanotube fibers, comprising:
the unwinding device is used for releasing the carbon nanotube fibers at a specific initial rate;
the drafting device is used for carrying out multistage drafting treatment on the carbon nanotube fiber, and comprises a drafting groove for accommodating a protonated solvent and a plurality of drafting shafts arranged in the groove body of the drafting groove along the advancing direction of the carbon nanotube fiber, wherein each drafting shaft can rotate at different specific drafting rates;
a deprotonation device for deprotonating the carbon nanotube fiber;
and an annealing device for carrying out high-temperature annealing treatment on the carbon nanotube fibers.
10. The continuous draw enhancement apparatus of claim 9, wherein the deprotonation device comprises a deprotonation tank for housing a coagulation bath and a plurality of fixed shafts disposed within the tank body of the deprotonation tank;
preferably, the continuous enhanced drafting device further comprises a plurality of guide wheels for fixing a part of the traveling path of the carbon nanotube fiber so that the carbon nanotube fiber forms a specific wrap angle with a part of the drafting shaft and/or the fixing shaft;
preferably, the continuous reinforced drawing device further comprises a winding device for collecting the carbon nanotube fibers subjected to the high-temperature annealing treatment at a specific collection rate.
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