阅读说明：本技术 一种超声辅助均匀化连续纤维表面热气流反应的方法及装置 (Method and device for ultrasonic-assisted homogenization of continuous fiber surface hot air flow reaction ) 是由 王延相 崔博文 王成国 王成娟 岳阳 姚志强 魏化震 王启芬 陈刚 于 2021-08-25 设计创作，主要内容包括：本发明涉及连续纤维热表面处理领域,公开了一种超声辅助均匀化连续纤维表面热气流反应的方法及装置。该方案在管式炉两侧适当位置加入了连接在超声波换能器上的陶瓷滑轮组,通过在连续纤维中传播的超声振动波达到使大丝束纤维的内部纤维表面充分接触反应气体的效果,解决了大丝束纤维内部纤维表面反应不足的问题。本发明的装置能够制备出与目前常用的连续化处理方案相比表面反应更加均匀的纤维丝束。本发明所需设备简单、实用性强,可适用于对多种现有工艺方案进行改进,且既适合单一设备的改进,也可用于多工序的连续化生产线,能够适配多种纤维和多种热气流表面反应改性的工艺要求,占用空间小,使用灵活方便且可定制性强。(The invention relates to the field of continuous fiber thermal surface treatment, and discloses a method and a device for ultrasonic-assisted homogenization of continuous fiber surface hot air flow reaction. According to the scheme, the ceramic pulley blocks connected to the ultrasonic transducers are added at appropriate positions on two sides of the tube furnace, the effect of enabling the surface of the internal fiber of the large tow fiber to be in full contact with reaction gas is achieved through the ultrasonic vibration waves propagated in the continuous fiber, and the problem of insufficient reaction of the surface of the internal fiber of the large tow fiber is solved. The device of the invention can prepare fiber tows with more uniform surface reaction compared with the prior common continuous processing scheme. The device is simple in required equipment and strong in practicability, can be suitable for improving various conventional process schemes, is suitable for improving single equipment, can also be used for a multi-process continuous production line, can adapt to the process requirements of surface reaction modification of various fibers and various hot air flows, and is small in occupied space, flexible and convenient to use and strong in customizability.)

1. An apparatus for ultrasonically assisted homogenization of a continuous fiber surface hot gas flow reaction, comprising: the two ends of the ultrasonic pulley block are opened, and the ultrasonic pulley block is connected with the traction device; both sides are provided with draw gear around heating device, be provided with at least a set of supersound assembly pulley between draw gear and the heating device, the supersound assembly pulley includes: the device comprises an ultrasonic transmitting device and a pulley block, wherein the pulley block comprises at least one upper pulley and at least one lower pulley, and the upper pulley is contacted with the upper surface of the fiber; the lower pulley is in contact with the lower surface of the fiber; the ultrasonic transmitting device is connected with the upper pulley and the lower pulley, and the heating device is also provided with an air inlet device and an air exhaust device.

2. The apparatus for ultrasonically assisted homogenizing of a continuous fiber surface hot gas flow reaction of claim 1, wherein the front and back sides of the heating means are provided with ultrasonic pulley sets, respectively.

3. The apparatus for ultrasonically assisted homogenizing of a continuous fiber surface hot gas flow reaction of claim 1, wherein the shaft of the upper pulley or the lower pulley is fixedly connected to the vibrating member of the ultrasonic wave emitting device.

4. The apparatus for ultrasonically assisted homogenizing of a continuous fiber surface hot gas flow reaction of claim 1 wherein the upper or lower pulley is disposed perpendicular to the fiber axis.

5. The apparatus for ultrasonically assisted homogenizing of continuous fiber surface hot gas flow reactions as claimed in claim 1 wherein the distance between the upper or lower pulley and the port of the air intake or air exhaust is 10-80 cm; preferably 20-40 cm.

6. The device for the ultrasonic-assisted homogenization of the hot gas flow reaction on the surface of a continuous fiber according to claim 1, wherein the distance between the upper pulley or the lower pulley and the traction device is 5-100cm, preferably 10-50cm, and more preferably 20-30 cm.

7. The apparatus for ultrasonically assisted homogenizing of a continuous fiber surface hot gas stream reaction of claim 1, wherein the spacing between adjacent upper and lower pulleys is 1-30 cm; preferably 3-10 cm.

8. The apparatus for ultrasonically assisted homogenizing of a continuous fiber surface hot gas stream reaction according to claim 1, wherein the heating means is a tube furnace, preferably a quartz tube furnace;

or the upper pulley or the lower pulley is a ceramic pulley;

or, the ultrasonic wave emitting device is an ultrasonic transducer.

9. A method for ultrasonic-assisted homogenization of continuous fiber surface hot air flow reaction is characterized by comprising the following steps:

carrying out thermal surface treatment on the surface of the fiber by adopting chemical vapor deposition;

and in the chemical vapor deposition, transmitting the vibration of ultrasonic waves to the surface of the fiber through a solid medium to obtain the fiber.

10. Use of the device according to any one of claims 1-8 for the preparation of a functional material.

Technical Field

The invention relates to the field of continuous fiber thermal surface treatment, in particular to a process scheme for promoting the full contact of the surface of a large tow fiber with reaction gas to obtain uniform surface modification by using equipment such as an ultrasonic transducer and the like for assistance. The field of application to which the present invention is applicable includes various continuous fiber surface modifications including, without limitation, multi-scale reinforcement, coating deposition, surface activation, and the like. Process recipes associated with the present invention include, without limitation, chemical vapor deposition, elemental doping, pre-oxidation, and the like.

Background

The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.

Fiber reinforced composites are one of the most widely used forms of composites at present, and are the most predominant form of application of various high performance fibers in structural components and the like. In order to reinforce the bonding interface between the fiber and the composite material and to sufficiently exert the performance of the fiber in the composite material, it is necessary to modify the surface of the fiber. Besides the application of mechanical properties, various modification means of the fiber also play an important role in the development and preparation of new functional materials such as electromagnetic properties, thermal properties, photocatalysis and the like. Among various surface modification processes, many processes involving the reaction of fibers with gases at high temperatures, such as chemical vapor deposition and the like, have received much attention because of the ability to introduce a variety of specific complex structures (such as carbon nanotubes, ceramic whiskers, nanoparticles, and the like) on the fiber surface. However, in the process of continuously treating large tow fibers by such a process, the fiber reaction may be insufficient due to dense adhesion of the fiber bundle itself. The fibers located at the outer layer of the tow can be sufficiently exposed to the reaction gas, while the fibers located at the inner layer are difficult to be sufficiently exposed to the reaction gas due to physical barrier, which is a main cause of insufficient reaction.

There are many methods for promoting uniform dispersion of fibers for different processes. In the resin impregnation and other processes, in order to ensure that the fibers are fully contacted with the resin, spreading equipment is often adopted to spread and arrange the fibers into a lamellar shape, but the method needs huge equipment and cannot be used for continuous treatment; or the yarn spreading can be realized only in a short length range, and the long fiber heating section in the tube furnace can not be ensured to be kept in a spreading state. Traditional mechanical stirring, ultrasonic and centrifugal methods are often used to promote uniform distribution or sufficient reaction of the fibers within the liquid, but these methods cannot cope with the treatment requirements of continuous fibers on the one hand, and on the other hand, require high-density media such as liquid and cannot be used in a gas-filled reaction environment. Since most gas-fiber reactions also require high temperature conditions to be carried out, continuous heat treatment of the fibers needs to be carried out in a tube furnace or oven with open ends, and the narrow furnace chamber and high temperature environment both constitute important limitations for the apparatus and method for dispersing the fibers. At present, no effective method for solving the problem of insufficient reaction of large tow fibers under the conditions is available.

Ultrasonic waves are mechanical waves of extremely short wavelength, generally referred to as waves whose lower bound exceeds the human hearing. The frequency of the ultrasonic wave is more than 1 kilohertz, and the ultrasonic wave is widely applied to a plurality of fields of cleaning, crushing, disinfection, detection and the like at present. Compared with sound waves, the ultrasonic wave has shorter wavelength, poor penetration force in air and fast loss, but has stronger propagation force in a high-density medium, and can cause a small-range high-frequency vibration of an object. The ultrasonic cleaner is one of the most common application forms of ultrasonic waves, and utilizes liquid as a medium to uniformly transmit ultrasonic vibration to the surface of a cleaning object to promote impurity peeling to achieve a cleaning effect. For example: ultrasonic transducers are electronic devices that convert electrical energy into mechanical energy in the form of ultrasonic waves and are currently used in a wide variety of ultrasonic equipment, including ultrasonic cleaners, ultrasonic welding equipment, and trichloro machines. But the inventor researches and discovers that: at present, no ultrasonic-assisted fiber surface hot air flow reaction research exists.

Disclosure of Invention

The invention mainly provides an improved scheme based on ultrasonic wave on the basis of a high-temperature gas reaction treatment process for the surface of continuous fibers. Compared with the prior art, the method has unique advantages, and is embodied in that the problem of uneven surface treatment among fibers caused by difficult contact between the fiber surface inside the large tow fiber and reaction gas can be effectively solved, so that the large tow fiber can be uniformly and fully modified. These advantages enable better performance enhancement of the treated fibers.

In order to achieve the technical purpose, the invention adopts the following technical scheme:

in a first aspect of the present invention, there is provided an apparatus for ultrasonically assisted homogenizing of a continuous fiber surface hot gas flow reaction, comprising: the two ends of the ultrasonic pulley block are opened, and the ultrasonic pulley block is connected with the traction device; both sides are provided with draw gear around heating device, be provided with at least a set of supersound assembly pulley between draw gear and the heating device, the supersound assembly pulley includes: the device comprises an ultrasonic transmitting device and a pulley block, wherein the pulley block comprises at least one upper pulley and at least one lower pulley, and the upper pulley is contacted with the upper surface of the fiber; the lower pulley is in contact with the lower surface of the fiber; the ultrasonic transmitting device is connected with the upper pulley and the lower pulley, and the heating device is also provided with an air inlet device and an air exhaust device.

The invention takes the ultrasonic transducer as an ultrasonic emission source, takes a pulley commonly used in a continuous treatment process as a medium, transmits ultrasonic waves to the fiber bundle, guides the fiber bundle to generate local high-frequency vibration to promote the full contact between the surface of the internal fiber and reaction gas, can realize the uniform reaction of the gas on the surface of the continuous fiber bundle in a high-temperature environment, and avoids the problem of insufficient reaction of the internal fiber.

In a second aspect of the present invention, there is provided a method for ultrasonically-assisted homogenizing a hot air flow reaction on a surface of a continuous fiber, comprising:

carrying out thermal surface treatment on the surface of the fiber by adopting chemical vapor deposition;

and in the chemical vapor deposition, transmitting the vibration of ultrasonic waves to the surface of the fiber through a solid medium to obtain the fiber.

Compared with the conventional continuous treatment scheme, the method has the advantages that the fiber surface reaction effect is more uniform, and the phenomenon of partial surface reaction deficiency caused by mutual contact of fibers is reduced. Compared with the prior common fiber dispersion method, the method provided by the invention is suitable for a continuous high-temperature treatment process, and the improved method is simple, convenient and easy to implement and is suitable for various fiber types.

In a third aspect of the invention there is provided the use of any of the above apparatus for the preparation of a functional material.

The invention has the beneficial effects that:

(1) the invention provides a scheme for fully contacting the surface of a large tow fiber with a reaction gas in a high-temperature environment so as to realize uniform modification. The invention can overcome the problem of uneven modification caused by insufficient contact between the fiber surface inside the large tow and gas when the hot air surface reaction is carried out on the large tow fiber in the prior art, and correspondingly improves the performance of the large tow fiber after modification.

(2) The invention has the advantages of simple required equipment, strong practicability, no need of structural modification of equipment such as a tube furnace and the like, suitability for improving various existing process schemes, suitability for multi-process production lines, small occupied space, flexible and convenient use, strong customizability and capability of adjusting parameters according to different process requirements.

(3) The operation method is simple, low in cost, universal and easy for large-scale production.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.

Fig. 1 is a schematic view of the installation of the device according to the technical solution of the present invention. (A) A top view of the apparatus; (B) side view of the device.

Wherein, the device comprises a 1-a fiber traction device, a 1-b fiber traction device, a 2-a ceramic pulley block, a 2-b ceramic pulley block, a 3-rod-shaped ultrasonic transducer, a 4-ceramic pulley shaft, a 5-quartz tube furnace, a 6-inert gas protection device, a reactor gas inlet pipe, a 7-inert gas inlet pipe, an 8-a inert gas protection sleeve, an 8-b inert gas protection sleeve and a 9-air extraction device;

FIG. 2 is a scanning electron microscope image of secondary electrons of carbon fiber samples according to various embodiments of the present invention. (A) The carbon fiber sample obtained in the comparative example 1 of the invention is subjected to secondary electron scanning electron microscopy; (B) the carbon fiber sample obtained in the comparative example 2 of the invention is subjected to secondary electron scanning electron microscopy; (C) the secondary electron scanning electron microscope image of the carbon fiber sample obtained in example 1 of the invention.

Fig. 3 is a photograph of carbon fiber samples according to various examples of the present invention. (A) The surface photograph of the carbon fiber tow obtained in comparative example 1 of the present invention; (B) the surface photograph of the carbon fiber tow obtained in comparative example 2 of the present invention; (C) the surface photograph of the carbon fiber tow obtained in the embodiment 1 of the invention; (D) the surface photograph of the carbon fiber tow obtained in comparative example 3 of the present invention.

Fig. 4 is a photograph of a sample of a unidirectional composite of carbon fibers according to various embodiments of the present invention. (A) The surface photograph of the carbon fiber unidirectional composite material obtained in the comparative example 1 of the invention; (B) the surface photograph of the carbon fiber unidirectional composite material obtained in the comparative example 2 of the invention; (C) the surface photograph of the carbon fiber unidirectional composite material obtained in the embodiment 1 of the invention.

Detailed Description

It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

As introduced by the background art, aiming at the problems of uneven treatment effect and insufficient fiber surface reaction inside large tow fibers which are common when the high-temperature gas reaction treatment is carried out on the surface of continuous fibers in the prior art, the invention provides an improved scheme of a continuous fiber treatment process based on ultrasonic assistance, which comprises the following steps:

an apparatus for ultrasonic-assisted homogenization of a hot gas flow reaction on the surface of a continuous fiber, the related equipment comprising:

a quartz tube furnace with two open ends;

a running tractor for the continuous fiber bundle;

and a ceramic pulley fixed with an ultrasonic transducer.

Inert gas protection devices, corresponding gas inlet pipelines and corresponding gas extraction devices are arranged at two ends of the quartz tube furnace;

in some embodiments, the inert gas is nitrogen, argon, or the like that does not participate in the relevant reaction;

one end of the quartz tube furnace is provided with a gas inlet pipeline for reaction gas, so that the reaction gas directly enters the furnace chamber between the inert gases at the two sides;

the running traction devices are respectively positioned at two sides of the tube furnace, so that the fiber can pass through the furnace chamber and be wound on the furnace chamber, the device at one end releases the fiber at a constant speed in the process, and the device at the other end collects the fiber at a corresponding speed;

if the process is used as one process in a multi-process continuous production line, the operation traction device is a fiber traction device which is connected with the front process and the rear process in the middle of the production line;

the ceramic pulleys are arranged on two sides of the tube furnace in a group respectively and are positioned at the proper position between the inert gas protection device and the operation traction device;

in some embodiments, the set of ceramic pulleys should include at least two and be located on both upper and lower sides of the continuous fiber bundle, at least one on each side;

in some embodiments, the first pulley of the set of ceramic pulleys near the quartz tube furnace should be located below the fiber bundle.

In some embodiments, the shaft of the ceramic pulley should be fixed with a vibrating component (such as piezoelectric ceramic) in the ultrasonic transducer, so that the mechanical vibration generated when the ultrasonic transducer is operated is transmitted to the shaft of the ceramic pulley;

in some embodiments, the operating frequency of the ultrasonic transducer is 20-50 kHz; preferably 25-35 kHz.

In some embodiments, the ceramic pulley should apply some pressure to the fibers perpendicular to the axial direction of the fibers to ensure intimate contact of the fibers with the pulley;

in some embodiments, the groove width of the ceramic pulley is 0.5-3 cm; preferably 1-2 cm.

In some embodiments, the distance between the ceramic pulley and the port of the inert gas protection device is 10-80 cm; preferably 20-40 cm; the distance should avoid the position of the air extractor.

In some embodiments, the spacing between pulleys in the set of ceramic pulleys is 1-30 cm; preferably 3-10 cm.

In some embodiments, the spacing between the ceramic pulley and the running traction device is 5-100 cm; preferably 10 to 50cm, and more preferably 20 to 30 cm.

The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.

Embodiment 1: the embodiment is described by combining the attached figure 1 of the specification, and comprises a fiber traction device (1-a, 1-b), an ultrasonic pulley block and a reaction device, wherein the ultrasonic pulley block comprises a ceramic pulley block (2-a, 2-b) and a rod-shaped ultrasonic transducer (3), the rod-shaped ultrasonic transducer (3) is fixed with a ceramic pulley shaft (4), the reaction device comprises a quartz tube furnace (5), an inert gas protection device and a reactor gas inlet tube (6), and the inert gas protection device comprises an inert gas inlet tube (7), an inert gas protective sleeve (8-a, 8-b) and an air exhaust device (9). The implementation mode is realized according to the following steps:

step 1: continuous fibers as raw materials are fed into the subsequent step from a fiber traction device (1-a) at one end of the device at a uniform speed in a tensioning state, and the traction speed is determined according to corresponding reaction conditions;

step 2: the continuous fibers are wound on a ceramic pulley block (2-a), pulleys in the ceramic pulley block, which are close to a tube furnace (5), are positioned at the lower side of the fibers, the pulleys are respectively arranged at the upper side and the lower side of the fibers and tightly attached to the fibers, pressure is applied to the fibers along the direction vertical to the fiber axis, the fibers are kept in a tensioning state, and the fiber bundles are spread in pulley grooves as much as possible; each ceramic pulley shaft (4) is connected to the rod-shaped ultrasonic transducer (3);

and step 3: sending the continuous fiber into a quartz tube furnace (5), sequentially passing through an inert gas protective sleeve (8-a), a quartz tube and an inert gas protective sleeve (8-b) on the other side, and allowing the inert gas to enter the protective sleeve (8) through a gas inlet pipe (7) and be exhausted from a gas exhaust device (9) arranged at an opening; reaction gas required by fiber surface modification enters a reaction area from a gas inlet pipe (6), the temperature required by the reaction is provided by a heater arranged in the tubular furnace, and the reaction temperature and the reaction gas are determined according to corresponding reaction conditions;

and 4, step 4: after the modified continuous fibers leave the inert gas protective sleeve (8-b), the continuous fibers are wound on a ceramic pulley block (2-b), the ceramic pulley block (2-b) is symmetrical to the ceramic pulley block (2-a), and the positions, the number and the like of the pulleys are consistent with those in the step 2;

and 5: the continuous fiber is wound on a fiber traction device (1-b) at the other end of the device, keeps a uniform tension state, and enters a subsequent process or is collected by a filament collecting machine.

Wherein, the width of the groove of the ceramic pulley block (2) in the step 2 and the step 4 is 0.5-3cm, preferably 1-2 cm.

Wherein, the ceramic pulley block (2) in the step 2 and the step 4 comprises at least two pulleys, the pulley close to the tube furnace (5) is positioned at the lower side of the fiber, and the distance between the pulley and the port of the inert gas protective sleeve (8) is 10-80cm, preferably 20-40 cm; the rest pulleys are distributed at the upper side and the lower side of the fiber at intervals, and the interval between the pulleys is 1-30cm, preferably 3-10 cm; the distance between the pulley closest to the fiber traction device (1) and the traction device (1) is 5-100cm, preferably 10-50cm, and further preferably 20-30 cm;

wherein, the working frequency of the rod-shaped ultrasonic transducer (3) in the step 2 and the step 4 is 20-50kHz, preferably 25-35 kHz.

Embodiment 2: the embodiment is described with reference to fig. 1 of the specification, and the embodiment is different from embodiment 1 in that the composition of an ultrasonic pulley block is different, a rod-shaped ultrasonic transducer (3) in embodiment 1 is replaced by a cylindrical ultrasonic transducer, a bearing inner ring of a ceramic pulley (2) is welded with a vibrating head of the ultrasonic transducer, a bearing outer ring can freely rotate, and a pulley shaft (4) in embodiment 1 is eliminated.

In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.

Example 1

This example was carried out according to the process requirements of continuous carbon fiber surface catalyzed chemical vapor deposition for growing carbon nanotubes, see patent (CN 201811601589.5).

Step 1: according to the continuous process requirement, continuous carbon fibers with catalyst particles uniformly loaded on the surfaces are obtained in the first several processes of a production line, the standard of the fibers is Dongli T700, the specification of tows is 12K, the fibers are sent to a chemical vapor deposition process through a traction roller, and the running speed of the fibers is 3 cm/min;

step 2: putting continuous carbon fibers on two ultrasonic pulleys, wherein the first ceramic pulley is positioned 30cm behind a traction roller and above the fibers; the second ceramic pulley is positioned 10cm behind the first ceramic pulley, is positioned below the fiber and is 25cm away from the opening of the rear inert gas protective sleeve; the width of the groove of the selected ceramic pulley is 2cm, and the fibers are spread on the pulley as far as possible; the working frequency of an ultrasonic transducer connected with the pulley shaft is 28 kHz;

and step 3: feeding the continuous carbon fiber loaded with the catalyst into a quartz tube furnace with two opened ends and under the protection of inert gas, wherein the fiber sequentially passes through an inert gas protective sleeve, a quartz tube furnace chamber and an inert gas protective sleeve on the other side; the inflow rate of inert gas in the protective sleeves at the two sides is 1L/min, the reaction gas fed into the middle furnace cavity is hydrogen and acetylene which are fully mixed in advance, the inflow rate of the hydrogen is 0.4L/min, and the inflow rate of the acetylene is 0.2L/min; the temperature inside the tube furnace was set to 650 ℃;

and 4, step 4: putting the continuous carbon fiber on which the growth of the carbon nano tube on the surface is finished in the step 3 on two ultrasonic pulleys, wherein the first ceramic pulley is positioned 25cm behind the opening of the inert gas protective sleeve and below the fiber; the second ceramic pulley is positioned 10cm behind the first ceramic pulley, is positioned above the fibers and has a distance of 30cm from the rear traction roller; all parameters of the two pulleys and the ultrasonic transducers connected with the pulleys are kept consistent with those in the step 2;

and 5: winding the continuous carbon fiber obtained in the step 4 on a traction roller, and keeping the running speed of the traction roller at 3 cm/min; connecting a take-up machine behind the traction roller to collect the modified carbon fibers, wherein the collection speed is consistent with the fiber running speed, and obtaining a carbon fiber tow sample with carbon nanotubes growing on the surface;

step 6: and impregnating the obtained fiber with epoxy resin to prepare a unidirectional prepreg, then laying the prepreg in a mould in a laminating way, and obtaining a platy unidirectional composite material sample through a hot press molding process.

The carbon fiber sample obtained in step 5 was measured according to BS ISO 11566: 1996, tensile strength of the filaments was measured, 40 filaments per group and the average was taken. The monofilament tensile strength of the carbon fiber obtained in this example was 5.18 GPa.

And (4) carrying out interlaminar shear strength test on the composite material sample obtained in the step (6) according to the standard of JC/T773-2010, testing 5 samples in each group, and averaging. The interlaminar shear strength of the composite material obtained in this example was 114 MPa.

FIG. 2(C) is a scanning electron microscope image of secondary electrons of a carbon fiber sample obtained in example 1 of the present invention; FIG. 3(C) is a photograph of the surface of the carbon fiber tow obtained in example 1 of the present invention; fig. 4(C) is a surface photograph of the carbon fiber unidirectional composite obtained in example 1 of the present invention.

Example 2

This example was carried out according to the process requirements of glass fiber coating on the surface of carbon fiber proposed by Wuzhiyun et al, and reference is made to the paper (research on continuous glass fiber coating on the surface of carbon fiber by chemical vapor deposition [ J ] & Tianjin textile science 2015).

Step 1: the commercial large-tow carbon fiber is degummed and wound on a traction roller, the specification of the tow is 12K, and the wire feeding speed of the traction roller is 1.2 m/min;

step 2: sequentially lapping continuous carbon fibers on three ultrasonic pulleys, wherein a first ceramic pulley is positioned 20cm behind a traction roller and below the fibers; the second ceramic pulley is positioned 5cm behind the first ceramic pulley and above the fiber; the third ceramic pulley is positioned 5cm behind the second ceramic pulley, is positioned below the fiber and is 20cm away from the opening of the rear inert gas protective sleeve; the width of the groove of the selected ceramic pulley is 1.5cm, and the fibers are spread on the pulley as far as possible; the working frequency of an ultrasonic transducer connected with the pulley shaft is 25 kHz;

and step 3: feeding continuous carbon fibers into a tubular furnace with two opened ends and inert gas protection, wherein the fibers sequentially pass through an inert gas protection sleeve, a furnace chamber and an inert gas protection sleeve on the other side; the inflow rates of inert gases in the protective sleeves on the two sides are both 1.5L/min, the reaction gases fed into the middle furnace cavity are hydrogen, methane and boron trichloride which are fully mixed in advance, and the inflow rates of the hydrogen, the methane and the boron trichloride are respectively 0.8L/min, 0.4L/min and 0.2L/min; the temperature inside the tube furnace was set to 1150 ℃;

and 4, step 4: sequentially lapping the continuous carbon fibers coated in the step 3 on three ultrasonic pulleys, wherein the first ceramic pulley is positioned 20cm behind the opening of the inert gas protective sleeve and below the fibers; the second ceramic pulley is positioned 5cm behind the first ceramic pulley and above the fiber; the third ceramic pulley is positioned 5cm behind the second ceramic pulley, is positioned below the fibers and is 20cm away from the rear traction roller; all parameters of the two pulleys and the ultrasonic transducers connected with the pulleys are kept consistent with those in the step 2;

and 5: winding the continuous carbon fiber obtained in the step 4 on a traction roller, and keeping the running speed of the traction roller at 1.2 m/min; and connecting a take-up machine behind the traction roller to collect the coated carbon fibers, wherein the collecting speed is consistent with the fiber running speed, and obtaining the finished carbon fiber tows coated with glass fibers on the surface.

Example 3

This example was carried out according to the process requirements of continuous carbon fiber surface catalyzed chemical vapor deposition for growing carbon nanotubes, see patent (CN 201811601589.5).

Step 1: sending the 12K continuous carbon fiber with the surface uniformly loaded with catalyst particles into a chemical vapor deposition process through a traction roller, wherein the fiber running speed is 5 cm/min;

step 2: sequentially lapping carbon fibers on two ultrasonic pulleys, wherein a first ceramic pulley is positioned at the position 40cm behind a traction roller and above the fibers; the second ceramic pulley is positioned 8cm behind the first ceramic pulley, is positioned below the fiber and is 30cm away from the opening of the rear inert gas protective sleeve; the width of the groove of the selected ceramic pulley is 1cm, and the fibers are spread on the pulley as much as possible; the vibration heads of the ultrasonic transducers are welded on the bearing inner ring of the pulley, and the working frequency is 35 kHz;

and step 3: feeding the continuous carbon fiber loaded with the catalyst into a quartz tube furnace with two opened ends and under the protection of inert gas, wherein the fiber sequentially passes through an inert gas protective sleeve, a quartz tube furnace chamber and an inert gas protective sleeve on the other side; the inflow rate of inert gas in the protective sleeves at the two sides is 0.6L/min, the reaction gas fed into the middle furnace cavity is hydrogen and acetylene which are fully mixed in advance, the inflow rate of the hydrogen is 0.5L/min, and the inflow rate of the acetylene is 0.3L/min; the temperature inside the tube furnace was set to 700 ℃;

and 4, step 4: putting the continuous carbon fiber on which the growth of the carbon nano tube on the surface is finished in the step 3 on two ultrasonic pulleys, wherein the first ceramic pulley is positioned 30cm behind the opening of the inert gas protective sleeve and below the fiber; the second ceramic pulley is positioned 8cm behind the first ceramic pulley, is positioned above the fibers and is 40cm away from the rear traction roller; all parameters of the two pulleys and the ultrasonic transducers connected with the pulleys are kept consistent with those in the step 2;

and 5: winding the continuous carbon fiber obtained in the step 4 on a traction roller, and keeping the running speed of the traction roller at 5 cm/min; and connecting a take-up machine behind the traction roller to collect the modified carbon fibers, wherein the collection speed is consistent with the fiber running speed, and obtaining a carbon fiber tow finished product with carbon nanotubes growing on the surface.

Comparative example 1

The difference from example 1 is that: and the ultrasonic transducers in the step 2 and the step 4 are not started.

The carbon fiber sample obtained in step 5 was measured according to BS ISO 11566: 1996, tensile strength of the filaments was measured, 40 filaments per group and the average was taken. The tensile strength of the filaments of the carbon fibers obtained in this example was 4.98 GPa.

And (4) carrying out interlaminar shear strength test on the composite material sample obtained in the step (6) according to the standard of JC/T773-2010, testing 5 samples in each group, and averaging. The interlaminar shear strength of the composite material obtained in this example was 83 MPa.

FIG. 2(A) is a scanning electron microscope image of secondary electrons of a carbon fiber sample obtained in comparative example 1 of the present invention; FIG. 3(A) is a photograph of the surface of a carbon fiber tow obtained in comparative example 1 of the present invention; FIG. 4(A) is a photograph showing the surface of the carbon fiber unidirectional composite obtained in comparative example 1 of the present invention.

Comparative example 2

The difference from example 1 is that: the working frequency of the ultrasonic transducer in the step 2 is 15kHz, and the working frequency of the ultrasonic transducer in the step 4 is consistent with that in the step 2.

The carbon fiber sample obtained in step 5 was measured according to BS ISO 11566: 1996, tensile strength of the filaments was measured, 40 filaments per group and the average was taken. The tensile strength of the filaments of the carbon fibers obtained in this example was 5.06 GPa.

And (4) carrying out interlaminar shear strength test on the composite material sample obtained in the step (6) according to the standard of JC/T773-2010, testing 5 samples in each group, and averaging. The interlaminar shear strength of the composite material obtained in this example was 96 MPa.

FIG. 2(B) is a scanning electron micrograph of a carbon fiber sample obtained in comparative example 2 of the present invention; FIG. 3(B) is a photograph of the surface of the carbon fiber tow obtained in comparative example 2 of the present invention; FIG. 4(B) is a photograph showing the surface of the carbon fiber unidirectional composite obtained in comparative example 2 of the present invention.

Comparative example 3

The difference from example 1 is that: the working frequency of the ultrasonic transducer in the step 2 is 60kHz, and the working frequency of the ultrasonic transducer in the step 4 is consistent with that in the step 2.

The carbon fiber sample obtained in step 5 was measured according to BS ISO 11566: 1996, tensile strength of the filaments was measured, 40 filaments per group and the average was taken. The monofilament tensile strength of the carbon fiber obtained in this example was 4.14 GPa.

Fig. 3(D) is a photograph of the surface of the carbon fiber tow obtained in comparative example 3 of the present invention.

As can be seen from the accompanying drawings 2-4 in the specification, the improved scheme of the ultrasonic-assisted homogenization of the hot airflow reaction on the surface of the continuous fiber, which is adopted by the invention, is beneficial to improving the uniformity of the process for growing the carbon nanotubes on the surface of the continuous carbon fiber and improving the problem of insufficient growth of the carbon nanotubes on the surface of the fiber inside the large tow fiber.

All the ultrasonic transducers in the comparative example 1 are not started, and the obtained carbon nanotube-carbon fiber sample is the same as the traditional process; the operating frequency of the ultrasonic transducer in comparative example 2 is lower than the requirement in the summary of the invention of the present application; the working frequency of the ultrasonic transducer in the embodiment 1 meets the requirements in the summary of the invention of the application; the operating frequency of the ultrasonic transducer in comparative example 3 is higher than the requirements in the summary of the invention of the present application. The other process parameters of the four examples described above are the same and can constitute control experiments.

FIG. 2 shows that the uniformity of the growth of the carbon nanotubes is effectively improved by using an ultrasonic transducer with a proper working frequency; FIG. 2(A) shows that there is little growth of carbon nanotubes on the surface of the bulk fiber without the assistance of ultrasound; fig. 2(B) shows that the ultrasonic assistance effectively improves the uniformity of the growth of the carbon nanotubes, but the working frequency is low, and part of the fiber surface is still exposed; fig. 2(C) shows that the improvement proposed by the present application effectively improves the uniformity of carbon nanotube growth.

Fig. 3 illustrates that the ultrasonic transducer with proper working frequency is adopted to effectively improve the uniformity of the growth of the carbon nano tube, the fiber in which the carbon nano tube grows in the figure shows black due to rough surface, and the fiber in which the carbon nano tube does not grow reflects light due to smooth surface; fig. 3(a) shows that the carbon nanotubes inside the obtained fiber tow grow very insufficiently without ultrasonic assistance, and part of the fibers reflect light seriously; fig. 3(B) shows that the ultrasonic assistance effectively improves the uniformity of the growth of the carbon nanotubes, and the tow is darker in color than fig. 3(a), but still has few fibers with smooth surface and bright reflected light; FIG. 3(C) shows that the fiber obtained according to the modification proposed in the present application has a uniform black color as a whole, and has no portion that reflects light significantly, illustrating that carbon nanotubes are uniformly grown on the surface of the fiber; fig. 3(D) shows that too high ultrasonic frequency easily causes the phenomena of broken filaments and broken filaments of the fiber, and is not suitable for production.

TABLE 1 comparison table of tensile properties of carbon fiber samples with carbon nanotubes grown on the surface of each example

Example/comparative example numbering	Working frequency of ultrasonic transducer	Tensile strength of fiber filaments
			Comparative example 1	0kHz (not opened)	4.98GPa
Comparative example 2	15kHz	5.06GPa
			Example 1	28kHz	5.18GPa
Comparative example 3	60kHz	4.14GPa

As can be seen from Table 1, the uniformity of the growth of the carbon nanotubes is effectively improved by adopting the ultrasonic transducer with proper working frequency; growing carbon nanotubes can repair the defects on the surface of the carbon fibers, and the tensile strength of the fibers is improved in a small range, so that reference can be made to a paper (a multi-scale carbon nanotube reinforcement is grown on the surface of the carbon fibers by loading a metal catalyst [ J ] & lt, the Proc. of materials research & gt 2018); the tensile strength of the fiber obtained in example 1 is remarkably improved, which indicates that the number of the fibers subjected to reaction repair in the carbon fiber tow obtained according to the improved scheme provided by the application is more, and indicates that more fiber surfaces are fully reacted; the substantial reduction in tensile strength of the fiber filaments obtained in comparative example 3 indicates that too high an ultrasonic frequency impairs the strength of the fibers.

FIG. 4 illustrates that the use of an ultrasonic transducer with a suitable operating frequency effectively improves the uniformity of carbon nanotube growth; fig. 4(a) shows that the carbon nanotube-carbon fiber obtained by the conventional process (i.e. the comparative example 1) shows a stripe pattern when being made into a unidirectional prepreg due to uneven growth of the carbon nanotubes, and the composite material obtained by pressing has rough surface, is easy to wrinkle, and has inconsistent gloss; FIG. 4(B) shows that the small power ultrasonic assistance of the comparative example 2 effectively improves the uniformity of the growth of the carbon nanotubes, and the obtained unidirectional composite material has improved surface smoothness, but the uniformity is still insufficient to eliminate patterns; fig. 4(C) shows that the surface of the unidirectional composite material obtained according to the modification proposed in the present application (example 1) exhibits a uniform black color with few patterns, indicating that carbon nanotubes are sufficiently grown even on the surface of the fibers inside the tows, and thus the prepreg prepared has a uniform texture perpendicular to the axial direction of the fibers.

TABLE 2 comparison table of interlaminar shear strength of unidirectional composite material sample prepared from carbon nanotube-carbon fiber in each example of the present application

Example/comparative example numbering	Working frequency of ultrasonic transducer	Interlaminar shear strength of composite material
			Comparative example 1	0kHz (not opened)	83MPa
Comparative example 2	15kHz	96MPa
			Example 1	28kHz	114MPa

As can be seen from Table 2, the uniform modification of the fiber bundle surface has an important influence on the performance of the composite material; the material properties obtained with the improved process (example 1) assisted by ultrasound of the appropriate frequency are significantly improved over the conventional process (comparative example 1).

The ultrasonic-assisted improvement scheme provided by the application can effectively solve the problem that the surface treatment among fibers is uneven due to the fact that the fiber surface inside the large tow fiber is difficult to contact with reaction gas, so that the treated fibers can obtain better performance improvement, and the ultrasonic-assisted improvement scheme has obvious advantages compared with the conventional process; in addition, it is also explained that the requirements for the operating frequency of the ultrasonic transducer in the summary of the invention proposed in this application may be neither too high nor too low.

It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.