CN109763319B - Process method for catalytically growing carbon nanotubes on surface of PAN-based carbon fiber based on sulfur-doped modified catalyst - Google Patents
Process method for catalytically growing carbon nanotubes on surface of PAN-based carbon fiber based on sulfur-doped modified catalyst Download PDFInfo
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Abstract
The invention relates to a process method for catalytically growing carbon nanotubes on the surface of PAN-based carbon fiber based on a sulfur-doped modified catalyst, belonging to the field of carbon fiber surface modification. The process method comprises the following steps: step 1: desizing the PAN-based carbon fiber; step 2: carrying out surface oxidation treatment on the desized carbon fiber by an electrochemical anodic oxidation method; and step 3: preparing an ethanol solution of cobalt nitrate hexahydrate and thiourea with a molar ratio of 5:2 as a catalyst precursor, soaking the carbon fiber with the oxidized surface in the precursor for 5-30 min, and then placing in an oven for drying; and 4, step 4: placing carbon fibers in a tube furnace, heating to 600-800 ℃ at a speed of 5-10 ℃/min under the protection of nitrogen, and introducing a carbon fiber mixture with a flow ratio of 4: 1-1: 1H2/C2H2And (5) keeping the temperature of the mixed gas for 5-20 min, cooling to room temperature, and taking out the sample. The invention can improve the surface performance of the carbon fiber, improve the surface roughness of the fiber, effectively improve the interface performance of the carbon fiber reinforced composite material and reinforce the carbon fiber body.
Description
Technical Field
The invention relates to the field of carbon fiber surface modification treatment, in particular to a process method for growing carbon nanotubes on the surface of carbon fibers by catalysis through a chemical vapor deposition method.
Background
The carbon fiber is a high-performance fiber material with the carbon content of more than 95 percent, and mainly comprises PAN (polyacrylonitrile) -based carbon fiber, pitch-based carbon fiber and viscose-based carbon fiber, wherein the PAN-based carbon fiber is most widely applied. The carbon fiber has the characteristics of high strength, high modulus, high temperature resistance, corrosion resistance and fatigue resistance, and has excellent electrical conductivity and thermal conductivity, so that the carbon fiber becomes an irreplaceable national defense civil industry prop material. At present, carbon fibers are generally used as a reinforcement and are made into a carbon fiber reinforced composite material together with other matrix materials. Compared with pure metal materials, the carbon fiber reinforced composite material has higher fatigue strength and rigidity, higher toughness and better forming performance compared with inorganic materials, and higher temperature resistance and weather resistance compared with high polymer materials, so the carbon fiber reinforced composite material is widely applied in various fields, particularly the field of national defense and military industry. However, the carbon fiber has a smooth surface and a low polar functional group content. The inert surface of the carbon fiber causes poor interface performance of the carbon fiber reinforced composite material, and the phenomena of interface damage such as debonding, pulling-out and the like often occur under the action of load, so that further application and popularization of the carbon fiber reinforced composite material and further improvement of mechanical performance are hindered. The carbon nano tube is grafted on the surface of the carbon fiber, so that the mechanical engagement between the carbon fiber and the matrix can be enhanced, and the stress buffer layer is formed between the carbon fiber and the resin matrix to inhibit the generation of stress concentration and interlaminar failure.
At present, technologies related to grafting carbon nanotubes on the surface of carbon fibers can be roughly classified into three categories: chemical grafting, physical deposition and in-situ growth.
Zhanweiwei et al (research on mechanical properties of carbon nanotube chemical grafting and continuous carbon fiber composites [ D ]. national defense science and technology university, 2009.) use a chemical grafting method to graft carbon nanotubes on the surface of carbon fibers. By grafting the carbon nano tube, the tensile strength of the carbon fiber reinforced epoxy resin matrix composite material is improved by 9.78%, and the interlaminar shear strength of the composite material is improved by 6.2%.
Suckaki strong et al (influence of carbon fiber electrophoretic deposition carbon nanotubes on interface performance [ J ] material science and technology, 2015,23(01):45-50.) deposit carboxylated carbon nanotubes on the surface of carbon fibers by an electrophoretic deposition method, so that the surface roughness of the carbon fibers and the content of oxygen-containing functional groups are improved, and the interface performance of the composite material is greatly improved.
Fanwenxin et al (research on carbon nanotubes grown on the surface of carbon fibers and performance of reinforced composite materials thereof [ J ] functional materials 2015,46(20): 20097-. When the grafting amount of the carbon nano tube is 3.75-15.4%, the interlaminar shear strength of the composite material is also greatly improved.
Wang Xinghui et al (research on carbon fiber/carbon cloth surface growth carbon nanotubes and composite materials thereof [ J ]. Shandong university Master thesis 2018) adopt an electrochemical anodic oxidation method to treat the surface of carbon fibers, and chemically deposit (CVD) Carbon Nanotubes (CNTs) on the surfaces of the carbon fibers and the carbon cloth, explore the influence of an electrochemical treatment process on the loading of a catalyst and the mechanical properties of carbon fiber multifilaments, define the action mechanism of the CVD process on CNTs/carbon fiber reinforcement, and realize the uniform growth of the CNTs on the surface of the carbon cloth.
When the carbon nano tubes are grafted on the surface of the carbon fiber by utilizing the prior art, certain damage is inevitably generated on the carbon fiber body, so that the tensile strength of the carbon fiber body is reduced, and the process is relatively complex and is not beneficial to mass production.
Disclosure of Invention
The invention aims to solve the problem of providing a process method for catalytically growing carbon nanotubes on the surface of carbon fibers, which has a simple process, has a certain reinforcing effect on the strength of the carbon fibers and controllable yield of the carbon nanotubes. The process method can overcome the defects of the prior art, solves the problem that the carbon fiber body is greatly damaged in the prior art, has simple process and controllable yield of the carbon nano tubes, and is beneficial to batch production of the carbon fiber with the surface grafted with the carbon nano tubes.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a process method for catalytically growing carbon nanotubes on the surface of PAN-based carbon fibers based on a sulfur-doped modified catalyst comprises the following steps:
performing desizing treatment on the PAN-based carbon fiber;
performing electrochemical anodic oxidation treatment on the desized PAN-based carbon fiber to obtain pretreated PAN-based carbon fiber;
dipping the pretreated PAN-based carbon fiber into an ethanol solution of cobalt salt and thiourea, and drying to obtain carbon fiber loaded with a catalyst precursor;
and growing a carbon nano tube on the surface of the carbon fiber loaded with the catalyst precursor by adopting a CVD method to obtain the CNTs/PAN-based carbon fiber composite material.
The research of the application finds that: in order to ensure that the doping of sulfur does not affect the loading of the catalyst, the sulfur source is required to be ensured to have low volatility, be easily dissolved in ethanol, be decomposed into sulfur-containing gas at the temperature of below 400 ℃ and not react with cobalt nitrate to generate precipitate and gas. Therefore, systematic research and large-scale experimental investigation on the types and the proportions of the catalyst and the sulfur source are carried out, and the following results are found: the catalyst and the sulfur source are cobalt salt and thiourea, wherein when the molar ratio of Co to S is 3-5: 2-4, the requirements of sulfur doping and carbon nanotube growth can be simultaneously met, and the monofilament tensile strength and interlayer bonding force of the carbon nanotube are remarkably improved.
In some embodiments, the cobalt salt is Co (NO)3)2·6H2O。
The thiourea can not be replaced by urea, but can be replaced by an organic sulfur source which has low volatility, is easily dissolved in ethanol, is decomposed into sulfur-containing gas at the temperature of below 400 ℃ and does not react with cobalt nitrate to generate precipitate and gas.
The surface of the carbon fiber can be effectively activated by electrochemical anodic oxidation treatment, the oxidation etching degree of the graphite microcrystal is continuously increased along with the increase of the current intensity, and the grooves on the surface of the carbon fiber are gradually obvious. The number and size of the catalyst and sulfur particles on the surface of the carbon fiber also increase with increasing current intensity. To ensure that the interfacial shear strength between the carbon nanotubes and the carbon fibers can be effectively increased, in some embodiments, the preferred electrochemical anodization process of the present application employs ammonium dihydrogen phosphate NH4H2PO4As the electrolyte, the mass concentration of the electrolyte is 3-10%, the tensile strength of the monofilament after growing the carbon nano tube can be improved by 11.2%, and the interfacial shear strength can be improved by more than 6.4%.
The research of the application finds that: in the anodic oxidation process, if the current is overlarge, the catalyst and the sulfur particles on the surface of the carbon fiber are large, the doping of the sulfur element is uneven, and agglomeration occurs; when the current density is lower, the oxidation etching degree is weaker, the number of oxygen-containing functional groups generated on the surface of the electrolytic filament is less, the loading of the catalyst is uneven, and the doping rate of sulfur is low. Therefore, in some embodiments, the conditions of the electrochemical anodic oxidation treatment preferred in the present application are that the current intensity is 0.2A to 0.8A, and the electrochemical treatment time is 40 to 100s, so as to effectively improve the quality and uniformity of the loading/doping of the catalyst and the sulfur element, and obtain the CNTs/carbon fiber composite material with high tensile strength and interlayer bonding force.
In some embodiments, the time for the immersion is 30 to 90 min.
In some embodiments, the drying is performed at 60-90 ℃ for 30-90 min.
In some embodiments, the CVD method comprises the specific steps of: heating to 600-800 ℃ under the protection of nitrogen at normal pressure, and introducing H2/C2H2And (5) mixing the gases, keeping the temperature for 5-20 min, cooling to room temperature, and taking out the sample.
The invention also provides the CNTs/PAN-based carbon fiber composite material prepared by any one of the methods
The invention also provides application of the CNTs/PAN-based carbon fiber composite material in preparation of aerospace equipment, automobiles, ships, weaponry and civil infrastructure.
The invention has the beneficial effects that:
(1) the invention can overcome the defects of the prior art and provides the process method for catalytically growing the carbon nano tube on the surface of the PAN-based carbon fiber, which has simple process and low cost. The process method of the invention not only can improve the interface performance of the carbon fiber reinforced composite material, but also can improve the tensile strength of the carbon fiber body.
(2) The preparation method is simple, strong in practicability and easy to popularize.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 is a scanning electron micrograph of a sample of example 4;
FIG. 2 is a scanning electron micrograph of a sample of example 6.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. 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 application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As introduced in the background art, the problems that the tensile strength of the carbon fiber body is reduced and the process is relatively complex and is not favorable for mass production are solved by inevitably damaging the carbon fiber body when the carbon nanotubes are grafted on the surface of the carbon fiber in the prior art. Therefore, the invention provides a process method for catalytically growing carbon nanotubes on the surface of PAN-based carbon fibers based on a sulfur-doped modified catalyst, which comprises the following steps:
step 1: carrying out surface high-temperature desizing treatment on the PAN-based carbon fiber;
step 2: 3 to 10 mass percent of ammonium dihydrogen phosphate (NH)4H2PO4) Carrying out electrochemical anodic oxidation treatment on the carbon fiber by using electrolyte, wherein the current intensity is 0.2-0.8A, and the electrochemical treatment time is 40-100 s;
and step 3: cobalt nitrate hexahydrate (Co (NO) with a molar ratio of 5:2 is prepared3)2·6H2O) and thiourea (CN)2H4S) taking the ethanol solution as a catalyst precursor solution, soaking the carbon fiber obtained in the step 2 in the catalyst precursor solution for 5-30 min, and soaking the catalyst precursorPlacing the carbon fiber in an oven to be dried for 30-90 min at the temperature of 60-90 ℃ so that the catalyst precursor uniformly covers the surface of the carbon fiber;
and 4, step 4: placing the carbon fiber obtained in the step 3 in a tube furnace, heating to 600-800 ℃ under the protection of normal pressure nitrogen, and then introducing the carbon fiber in a ratio of 4: 1-1: 1H2/C2H2And (5) keeping the temperature of the mixed gas for 5-20 min, cooling to room temperature, and taking out the sample.
The PAN-based carbon fiber used in step 1 may be any one of 1K, 3K, 6K, and 10K, and a PAN-based carbon fiber of 3K is preferably selected.
Wherein, the carbon fiber after the electrolytic treatment in the step 2 needs to be washed by deionized water, and the washing process can be assisted by ultrasonic.
In the step 3, one or more of heating, ultrasonic treatment, stirring and the like can be adopted for assisting in the process of preparing the catalyst precursor solution. Furthermore, the carbon fiber impregnation process can also be assisted by ultrasonic and other modes.
Thiourea in the catalyst precursor is a sulfur-containing organic substance which can be decomposed into NH at about 200 DEG C3What H2S，H2S will adhere to the surface of the catalyst particles to effect sulfur doping of the catalyst particles.
In order to provide a good reaction environment, the reaction process can adopt argon protection besides nitrogen protection.
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
Step 1: carrying out surface high-temperature desizing treatment on the PAN-based carbon fiber;
step 2: 7% by mass of ammonium dihydrogen phosphate (NH)4H2PO4) Carrying out electrochemical anodic oxidation treatment on the carbon fiber for electrolyte, wherein the current intensity is 0.6A, and the electrochemical treatment time is 60 s;
and step 3: cobalt nitrate hexahydrate (Co (NO) with a molar ratio of 5:2 is prepared3)2·6H2O) and thiourea (CN)2H4S) taking the ethanol solution as a catalyst precursor solution, soaking the carbon fiber obtained in the step 2 in the catalyst precursor solution for 5min, and drying the carbon fiber soaked with the catalyst precursor in an oven at 70 ℃ for 30min to uniformly cover the catalyst precursor on the surface of the carbon fiber;
and 4, step 4: placing the carbon fiber obtained in the step 3 in a tube furnace, heating to 600 ℃ under the protection of normal pressure nitrogen, and then introducing a mixture of carbon fiber and carbon fiber in a ratio of 3: 1H2/C2H2Keeping the temperature of the mixed gas for 5min, cooling to room temperature and taking out the sample.
The samples were subjected to scanning electron microscope observation and monofilament tensile testing. A scanning electron microscope can observe that a layer of short and uniform carbon nano tubes grows on the surface of the carbon fiber. The tensile strength of the filaments was measured according to the standard BS ISO11566:1996 on carbon fibers before and after growing the CNTs, and 40 filaments were measured per sample and averaged. Compared with desized carbon fiber, the tensile strength of the carbon fiber monofilament after growing the carbon nanotube is improved to 4.08GPa from 3.91GPa, and is improved by 4.3%.
Example 2
Step 1: carrying out surface high-temperature desizing treatment on the PAN-based carbon fiber;
step 2: 7% by mass of ammonium dihydrogen phosphate (NH)4H2PO4) Carrying out electrochemical anodic oxidation treatment on the carbon fiber for electrolyte, wherein the current intensity is 0.6A, and the electrochemical treatment time is 60 s;
and step 3: cobalt nitrate hexahydrate (Co (NO) with a molar ratio of 5:2 is prepared3)2·6H2O) and thiourea (CN)2H4S) taking the ethanol solution as a catalyst precursor solution, soaking the carbon fiber obtained in the step 2 in the catalyst precursor solution for 5min, and drying the carbon fiber soaked with the catalyst precursor in an oven at 70 ℃ for 30min to uniformly cover the catalyst precursor on the surface of the carbon fiber;
and 4, step 4: placing the carbon fiber obtained in the step 3 in a tube furnace, heating to 650 ℃ under the protection of normal pressure nitrogen, and then introducing a mixture of carbon fiber and carbon fiber in a ratio of 3: 1H2/C2H2Mixing gas, keeping warmAnd 5min, cooling to room temperature and taking out the sample.
The samples were subjected to scanning electron microscope observation and monofilament tensile testing. The scanning electron microscope can observe that a layer of uniform carbon nanotubes grows on the surface of the carbon fiber. The tensile strength of the filaments was measured according to the standard BS ISO11566:1996 for carbon fibers before and after growing CNTs, and 40 filaments were measured and averaged. Compared with desized carbon fiber, the tensile strength of the monofilament after growing the carbon nanotube is improved to 4.21GPa from 3.91GPa, which is improved by 7.7%.
Example 3
Step 1: carrying out surface high-temperature desizing treatment on the PAN-based carbon fiber;
step 2: 7% by mass of ammonium dihydrogen phosphate (NH)4H2PO4) Carrying out electrochemical anodic oxidation treatment on the carbon fiber for electrolyte, wherein the current intensity is 0.6A, and the electrochemical treatment time is 60 s;
and step 3: cobalt nitrate hexahydrate (Co (NO) with a molar ratio of 5:2 is prepared3)2·6H2O) and thiourea (CN)2H4S) taking the ethanol solution as a catalyst precursor solution, soaking the carbon fiber obtained in the step 2 in the catalyst precursor solution for 5min, and drying the carbon fiber soaked with the catalyst precursor in an oven at 70 ℃ for 30min to uniformly cover the catalyst precursor on the surface of the carbon fiber;
and 4, step 4: placing the carbon fiber obtained in the step 3 in a tube furnace, heating to 700 ℃ under the protection of normal pressure nitrogen, and then introducing a mixture of carbon fiber and carbon fiber in a ratio of 3: 1H2/C2H2Keeping the temperature of the mixed gas for 5min, cooling to room temperature and taking out the sample.
And (3) observing the sample by using a scanning electron microscope, and testing the monofilament tensile strength and the interlaminar shear strength. The surface of the carbon fiber can be observed to grow uniform carbon nano tubes by a scanning electron microscope, but a small amount of lamellar graphite is included in the carbon fiber. The tensile strength of the filaments was measured according to the standard BS ISO11566:1996 for carbon fibers before and after growing CNTs, and 40 filaments were measured and averaged. Compared with desized carbon fiber, the tensile strength of the monofilament after growing the carbon nanotube is improved to 4.16GPa from 3.91GPa, which is improved by 6.4%.
Example 4
Step 1: carrying out surface high-temperature desizing treatment on the PAN-based carbon fiber;
step 2: 7% by mass of ammonium dihydrogen phosphate (NH)4H2PO4) Carrying out electrochemical anodic oxidation treatment on the carbon fiber for electrolyte, wherein the current intensity is 0.6A, and the electrochemical treatment time is 60 s;
and step 3: cobalt nitrate hexahydrate (Co (NO) with a molar ratio of 5:2 is prepared3)2·6H2O) and thiourea (CN)2H4S) taking the ethanol solution as a catalyst precursor solution, soaking the carbon fiber obtained in the step 2 in the catalyst precursor solution for 10min, and drying the carbon fiber soaked with the catalyst precursor in an oven at 70 ℃ for 30min to uniformly cover the catalyst precursor on the surface of the carbon fiber;
and 4, step 4: placing the carbon fiber obtained in the step 3 in a tube furnace, heating to 650 ℃ under the protection of normal pressure nitrogen, and then introducing a mixture of carbon fiber and carbon fiber in a ratio of 3: 1H2/C2H2Keeping the temperature of the mixed gas for 5min, cooling to room temperature and taking out the sample.
And (3) observing the sample by using a scanning electron microscope, and testing the monofilament tensile strength and the interlaminar shear strength. The growth of carbon nanotubes with short and uniform length on the surface of the carbon fiber can be observed by a scanning electron microscope. Testing the tensile strength of monofilaments of carbon fibers before and after growing the CNTs according to a standard BS ISO11566:1996, testing 40 monofilaments, and taking an average value; the carbon fiber reinforced composite was subjected to interlaminar shear strength testing according to the GB/T1446-2005 and GB/T1450.1-2005 standards for 5 specimens per specimen, and the average was taken. Compared with desized carbon fiber, the tensile strength of the monofilament after growing the carbon nanotube is improved to 4.16GPa from 3.91GPa, the tensile strength is improved by 9.4%, and the shear strength of the composite material interface is improved to 70.5MPa from 65.3MPa, and the shear strength is improved by 7.9%.
Example 5
Step 1: carrying out surface high-temperature desizing treatment on the PAN-based carbon fiber;
step 2: 7% by mass of dihydrogen phosphateAmmonium (NH)4H2PO4) Carrying out electrochemical anodic oxidation treatment on the carbon fiber for electrolyte, wherein the current intensity is 0.6A, and the electrochemical treatment time is 60 s;
and step 3: cobalt nitrate hexahydrate (Co (NO) with a molar ratio of 5:2 is prepared3)2·6H2O) and thiourea (CN)2H4S) taking the ethanol solution as a catalyst precursor solution, soaking the carbon fiber obtained in the step 2 in the catalyst precursor solution for 10min, and drying the carbon fiber soaked with the catalyst precursor in an oven at 70 ℃ for 30min to uniformly cover the catalyst precursor on the surface of the carbon fiber;
and 4, step 4: placing the carbon fiber obtained in the step 3 in a tube furnace, heating to 700 ℃ under the protection of normal pressure nitrogen, and then introducing a mixture of carbon fiber and carbon fiber in a ratio of 3: 1H2/C2H2Keeping the temperature of the mixed gas for 5min, cooling to room temperature and taking out the sample.
The samples were subjected to scanning electron microscope observation and monofilament tensile testing. The growth of carbon nanotubes with long and uniform length on the surface of the carbon fiber can be observed by a scanning electron microscope. Testing the tensile strength of monofilaments of the carbon fibers before and after growing the CNTs according to the international standard BS ISO11566:1996, testing 40 monofilaments of each sample, and averaging; the interlaminar shear strength test was carried out on the carbon fiber-reinforced composite material according to the standards GB/T1446-2005 and GB/T1450.1-2005, and 5 samples were tested and averaged. Compared with desized carbon fiber, the tensile strength of the monofilament after growing the carbon nanotube is improved to 4.25GPa from 3.91GPa, the tensile strength is improved by 8.6 percent, and the shear strength of the composite material interface is improved to 69.1MPa from 65.3MPa and is improved by 5.8 percent.
Example 6
Step 1: carrying out surface high-temperature desizing treatment on the PAN-based carbon fiber;
step 2: 7% by mass of ammonium dihydrogen phosphate (NH)4H2PO4) Carrying out electrochemical anodic oxidation treatment on the carbon fiber for electrolyte, wherein the current intensity is 0.6A, and the electrochemical treatment time is 60 s;
and step 3: cobalt nitrate hexahydrate (Co (NO) with a molar ratio of 5:2 is prepared3)2·6H2O) and thiourea (CN)2H4S) taking the ethanol solution as a catalyst precursor solution, soaking the carbon fiber obtained in the step 2 in the catalyst precursor solution for 10min, and drying the carbon fiber soaked with the catalyst precursor in an oven at 70 ℃ for 30min to uniformly cover the catalyst precursor on the surface of the carbon fiber;
and 4, step 4: placing the carbon fiber obtained in the step 3 in a tube furnace, heating to 650 ℃ under the protection of normal pressure nitrogen, and then introducing a mixture of carbon fiber and carbon fiber in a ratio of 3: 1H2/C2H2Keeping the temperature of the mixed gas for 10min, cooling to room temperature and taking out the sample.
And (3) observing the sample by using a scanning electron microscope, and testing the monofilament tensile strength and the interlaminar shear strength. The scanning electron microscope can observe that carbon nanotubes with long and uniform lengths grow on the surface of the carbon fiber, and a small amount of lamellar graphite is mixed in the carbon nanotubes. Testing the tensile strength of monofilaments of the carbon fibers before and after growing the CNTs according to the international standard BS ISO11566:1996, testing 40 monofilaments of each sample, and averaging; the interlaminar shear strength test was carried out on the carbon fiber reinforced composite material according to the standards GB/T1446-2005 and GB/T1450.1-2005, and 5 samples were tested and averaged. Compared with desized carbon fiber, the tensile strength of the monofilament after growing the carbon nanotube is improved to 4.35GPa from 3.91GPa, the tensile strength is improved by 11.2%, and the shear strength of the composite material interface is improved to 69.5MPa from 65.3MPa, and the shear strength is improved by 6.4%.
Wherein, the carbon fiber after the electrolytic treatment in the step 2 needs to be washed by deionized water, and the washing process can be assisted by ultrasonic.
In the step 3, one or more of heating, ultrasonic treatment, stirring and the like can be adopted for assisting in the process of preparing the catalyst precursor solution. Furthermore, the carbon fiber impregnation process can also be assisted by ultrasonic and other modes.
Thiourea in the catalyst precursor is a sulfur-containing organic substance which can be decomposed into NH at about 200 DEG C3What H2S，H2S will adhere to the surface of the catalyst particles to effect sulfur doping of the catalyst particles.
In order to provide a good reaction environment, the reaction process can adopt argon protection besides nitrogen protection.
Analyzing the results of the above examples, the variables such as the deposition temperature of the carbon nanotubes, the growth time of the carbon nanotubes, and the dipping time of the catalyst precursor have a great influence on the morphology of the carbon nanotubes, the tensile strength of the carbon fibers, and the interfacial properties of the composite material.
FIG. 1 is a scanning electron micrograph of a sample of example 4, which shows that a layer of dense, uniform and short carbon nanotubes grows on the surface of the carbon fiber of the sample, and the surface roughness of the carbon fiber is greatly improved due to the presence of the carbon nanotubes. By grafting the carbon nano tube, the mechanical engagement of the carbon fiber and the resin matrix interface is enhanced, and meanwhile, the carbon nano tube has certain pinning and inhibiting effects on the crack propagation, so that the interface performance of the composite material is greatly improved. In addition, in the vapor deposition process, the original defects on the surface of the carbon fibers are repaired to a certain extent, so that the tensile strength of the carbon fibers is improved.
FIG. 2 is a SEM photograph of a sample of example 6, and comparing FIG. 1, it is found that the carbon nanotubes on the surface of the sample are longer in length and some amount of graphite flakes are produced. The existence of the lamellar graphite can influence the infiltration of the resin matrix on the surface of the carbon fiber, has certain influence on the continuity of the matrix and finally influences the enhancement effect of the interface bonding performance. But the longer growth time enables the defects on the surface of the carbon fiber to be better repaired, so that the tensile strength of the carbon fiber is improved more.
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. Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the present invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive efforts by those skilled in the art based on the technical solution of the present invention.
Claims (4)
1. A process method for catalytically growing carbon nanotubes on the surface of PAN-based carbon fibers based on a sulfur-doped modified catalyst is characterized by comprising the following steps:
performing desizing treatment on the PAN-based carbon fiber;
performing electrochemical anodic oxidation treatment on the desized PAN-based carbon fiber to obtain pretreated PAN-based carbon fiber;
dipping the pretreated PAN-based carbon fiber into an ethanol solution of cobalt salt and thiourea, and drying to obtain carbon fiber loaded with a catalyst precursor;
growing a carbon nano tube on the surface of the carbon fiber loaded with the catalyst precursor by adopting a CVD method to obtain a CNTs/PAN-based carbon fiber composite material;
in the cobalt salt and the thiourea, the molar ratio of Co to S is 3-5: 2-4;
the cobalt salt is Co (NO)3)2·6H2O；
The electrochemical anodic oxidation treatment adopts ammonium dihydrogen phosphate NH4H2PO4The mass concentration of the electrolyte is 3-10%;
the conditions of the electrochemical anodic oxidation treatment are that the current intensity is 0.2-0.8A, and the electrochemical treatment time is 40-100 s;
the CVD method comprises the following specific steps: heating to 600-800 ℃ under the protection of nitrogen at normal pressure, and introducing H2/C2H2Keeping the temperature of the mixed gas for 5-20 min, cooling to room temperature, and taking out a sample;
the dipping time is 30-90 min.
2. The process method of claim 1, wherein the drying is carried out at 60-90 ℃ for 30-90 min.
3. A CNTs/PAN based carbon fiber composite prepared by the process of claim 1 or 2.
4. Use of CNTs/PAN based carbon fibre composite according to claim 3 for the preparation of aerospace equipment, automotive and marine, weaponry and civil infrastructure.
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