CN113338027A - Surface treatment method of carbon fiber - Google Patents
Surface treatment method of carbon fiber Download PDFInfo
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- CN113338027A CN113338027A CN202110515584.6A CN202110515584A CN113338027A CN 113338027 A CN113338027 A CN 113338027A CN 202110515584 A CN202110515584 A CN 202110515584A CN 113338027 A CN113338027 A CN 113338027A
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- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
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Abstract
The application discloses a surface treatment method of carbon fibers, which comprises the following steps: obtaining carbon fibers; carrying out plasma treatment on the surface of the carbon fiber to obtain the carbon fiber after the plasma treatment; and putting the carbon fiber subjected to the plasma treatment into a chromium ion solution prepared in advance for chromium ion modification treatment to obtain the modified carbon fiber. The plasma treatment of the surface of the carbon fiber can improve the surface tension and surface activity of the carbon fiber, and increase functional groups, such as hydroxyl functional groups, on the surface of the carbon fiber. Since the hydroxyl group and the chromium ion can be combined, the deposition rate of the chromium ion on the surface of the carbon fiber is also improved. After the carbon fiber is soaked in the chromium ion solution, a large amount of chromium ions are deposited on the surface of the carbon fiber, so that the interface bonding force between the carbon fiber and the resin matrix is enhanced.
Description
Technical Field
The application relates to the technical field of carbon fiber surface treatment, in particular to a carbon fiber surface treatment method, and simultaneously relates to a modified carbon fiber and a composite material.
Background
The global ocean area accounts for about 71 percent of the earth surface, and various mineral products, energy sources and biological resources in the ocean far exceed the land. With the increasing population, the shortage of land resources and the more serious environmental pollution, people look at the sea like treasury. With the development and progress of science and technology, more and more resources such as petroleum, combustible ice and the like are discovered in the ocean. The reasonable application of ocean energy can greatly reduce the exhaustion speed of various resources on land. However, the difficulty of developing ocean resources is very high, and the deep ocean is often harsh and the environment is complex, which is a great challenge.
In recent years, the sea has been more and more deeply explored. At present, there have been some developments in deep sea, where necessary instruments are installed on a deep sea underwater vehicle, and operations such as detection, recording, and sampling are performed in a deep sea environment, and underwater operations are performed. Because the working site of the deep sea submersible is on the seabed of thousands of meters or even thousands of meters, the environment is complex, the water pressure is extremely high, and the unpowered floating technology is adopted, so that the submersible is required to meet the requirements of water pressure resistance and low density at the same time, and the personal and property safety is protected. In order to achieve the aim, the light-weight high-strength composite material enters the sight of people, can provide buoyancy for the underwater vehicle, improves the effective load of the underwater vehicle, reduces the external size of the underwater vehicle and saves the cost.
Carbon fiber is a new type reinforcing material developed recently, and is an ideal reinforcing body which can be used as a functional material and a structural material. The carbon fiber reinforced light composite material has the advantages of low density, high strength, high modulus, low expansion coefficient, high temperature resistance, corrosion resistance, electric conduction, heat conduction, shock absorption and the like, so that the carbon fiber reinforced light composite material has the irreplaceable excellent performance of other composite materials and is widely applied to the civil industry and the military field. However, the carbon fiber is carbonized in high-temperature inert gas in the preparation process, and the carbon element is gathered along with the escape of non-carbon elements in the process, so that the surface tension and the surface activity of the carbon fiber are reduced due to the structure, so that the untreated carbon fiber has few surface functional groups, is not easy to be compounded with other polymers, is easy to generate defects after being mixed, and can reduce the mechanical property of the composite material, thereby greatly limiting the application of the composite material.
Therefore, how to treat the surface of the carbon fiber to improve the surface tension, surface activity and surface functional group of the carbon fiber is a problem to be solved.
Disclosure of Invention
The application provides a surface treatment method of carbon fibers, which aims to solve the problems of low surface tension, low surface activity and few surface functional groups of the carbon fibers in the prior art.
The application provides a surface treatment method of carbon fibers, which comprises the following steps: obtaining carbon fibers; carrying out plasma treatment on the surface of the carbon fiber to obtain the carbon fiber after the plasma treatment; and putting the carbon fiber subjected to the plasma treatment into a chromium ion solution prepared in advance for chromium ion modification treatment to obtain the modified carbon fiber.
Optionally, the step of putting the carbon fiber after the plasma treatment into a chromium ion solution prepared in advance to perform chromium ion modification treatment to obtain a modified carbon fiber includes: immersing the carbon fiber subjected to plasma treatment into a chromium ion solution to form a chromium ion layer on the surface of the carbon fiber; drying the impregnated carbon fibers; and cutting the dried carbon fiber to obtain the modified carbon fiber with the preset length.
Optionally, the performing plasma treatment on the surface of the carbon fiber includes: placing continuous carbon fibers in a target gas environment, and carrying out plasma treatment on the surfaces of the continuous carbon fibers according to preset plasma treatment conditions; sizing the carbon fiber after the plasma treatment; and drying the carbon fiber subjected to sizing treatment.
Optionally, the target gas in the target gas environment is a gas that is ejected to the continuous carbon fibers through a spray gun according to a preset gas flow rate.
Optionally, the target gas includes at least one of the following gases: air, oxygen, hydrogen, and argon.
Optionally, the preset gas flow includes: more than 0.3L/min and less than or equal to 3L/min.
Optionally, the preset plasma processing conditions include: the processing time ranges from more than 15s to less than or equal to 600 s; and processing power, wherein the processing power range is more than 200W and less than or equal to 900W.
Optionally, the sizing agent for sizing the carbon fiber after the plasma treatment is an aqueous epoxy sizing agent.
Optionally, the drying temperature range for drying the sized carbon fiber is greater than 20 ℃ and less than or equal to 300 ℃.
Optionally, the chromium ion solution comprises: a solute containing chromium ions and a volatile solvent with a low boiling point, wherein the concentration range of the chromium ions in the chromium ion solution is less than 0.1mol/L and more than or equal to 10 mol/L.
Optionally, the solute comprising chromium ions comprises: chromium acetate or chromium acetylacetonate; the volatile solvent having a low boiling point includes acetone, methyl ethyl ketone and ethanol.
The application also provides a modified carbon fiber, which is obtained by adopting the surface treatment method.
The present application also provides a composite material comprising: the modified carbon fiber obtained by the surface treatment method described above.
Compared with the prior art, the method has the following advantages:
the application provides a surface treatment method of carbon fibers, which comprises the following steps: obtaining carbon fibers; carrying out plasma treatment on the surface of the carbon fiber to obtain the carbon fiber after the plasma treatment; and putting the carbon fiber subjected to the plasma treatment into a chromium ion solution prepared in advance for chromium ion modification treatment to obtain the modified carbon fiber.
In the method, the surface of the carbon fiber is subjected to plasma treatment and chromium ion modification, and the surface appearance and the surface functional groups of the carbon fiber are influenced by adjusting the size of airflow, the treatment power, the treatment time and the treatment temperature. The plasma treatment of the surface of the carbon fiber can improve the surface tension and surface activity of the carbon fiber and increase the functional groups, such as hydroxyl functional groups, on the surface of the carbon fiber. Since the hydroxyl and the chromium ions can be combined, the deposition rate of the chromium ions on the surface of the carbon fiber is improved. After the carbon fiber is soaked in the chromium ion solution, a large amount of chromium ions are deposited on the surface of the carbon fiber, so that the interface bonding force between the carbon fiber and the resin matrix is enhanced.
Further, a composite material comprises the modified carbon fiber obtained by the surface treatment method of the carbon fiber. Because the composite material is prepared by the modified carbon fiber and the resin matrix. Thus, the compressive strength and density of the composite material are increased, while the water absorption of the composite material at high hydrostatic pressures is reduced. Wherein, the high hydrostatic pressure means that the pressure range of the hydrostatic pressure is more than or equal to 100 MPa. The composite material is used for preparing equipment for deep sea, such as a submarine, so that the pressure resistance of the submarine in the deep sea field can be improved, and the water absorption rate can be reduced.
Drawings
Fig. 1 is a flow chart of a method for surface treatment of carbon fibers provided herein.
Fig. 2 is a scanning electron microscope image of the interface bonding of carbon fiber and resin matrix without plasma treatment and chromium ion modification provided by the present application.
FIG. 3 is a scanning electron microscope image of the interface bonding of the carbon fiber modified by plasma treatment and chromium ions and the resin matrix provided by the present application.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application. This application is capable of implementation in many different ways than those herein set forth and of similar import by those skilled in the art without departing from the spirit of this application and is therefore not limited to the specific implementations disclosed below.
The experimental methods used in the examples of the present application are all conventional methods unless otherwise specified; reagents, materials and the like used in the examples of the present application are commercially available unless otherwise specified.
Referring to fig. 1, fig. 1 is a flow chart illustrating a surface treatment method for carbon fibers according to the present disclosure. The application provides a surface treatment method of carbon fiber, which comprises the following steps:
step S101: and (5) obtaining the carbon fiber.
In the step S101, the carbon fiber may be dry-jet wet-spun polyacrylonitrile-based carbon fiber, or commercially available carbon fiber, such as T700 grade polyacrylonitrile-based carbon fiber, which is commonly used in the production of the prior art. In addition, the carbon fiber used in the present application is not limited to the above-mentioned carbon fiber.
The present step of obtaining carbon fibers is for preparing the surface of the carbon fibers for plasma treatment and chromium ion modification in step S102 and step S103.
Step S102: and carrying out plasma treatment on the surface of the carbon fiber to obtain the carbon fiber after the plasma treatment.
In step S102, plasma treatment is performed on the surface of the carbon fiber, wherein the specific plasma treatment method includes:
step 1: placing continuous carbon fibers in a target gas environment, and carrying out plasma treatment on the surfaces of the continuous carbon fibers according to preset plasma treatment conditions.
The target gas in the target gas environment is gas which is sprayed out of the continuous carbon fibers through a spray gun according to a preset gas flow rate.
The target gas includes at least one of the following gases: air, oxygen, hydrogen, and argon.
The preset gas flow rate comprises: more than 0.3L/min and less than or equal to 3L/min.
The preset plasma processing conditions include:
the processing time ranges from more than 15s to less than or equal to 600 s;
and processing power, wherein the processing power range is more than 200W and less than or equal to 900W.
In step 1, the carbon fiber is subjected to plasma treatment on the surface of the continuous carbon fiber according to the preset plasma treatment conditions, specifically, the continuous carbon fiber is placed at a driving position, and a spray gun sprays gas according to a preset gas flow to create a target gas environment, so that the continuous carbon fiber is subjected to contact reaction with the target gas in the target gas environment, and the plasma treatment on the surface of the carbon fiber is completed.
Step 2: and sizing the carbon fiber after the plasma treatment.
Wherein, the sizing agent for sizing the carbon fiber comprises a water-based epoxy sizing agent.
And step 3: and drying the carbon fiber subjected to sizing treatment.
Wherein the drying temperature range for drying the carbon fiber after sizing treatment is more than 20 ℃ and less than or equal to 300 ℃.
The step S102 is to perform plasma treatment on the surface of the carbon fiber, so as to improve the surface activity of the carbon fiber, and introduce a proper amount of functional groups, such as hydroxyl functional groups, on the surface of the carbon fiber, so that the deposition rate of the carbon fiber surface modified by the chromium ions can be improved because the hydroxyl groups can be combined with the chromium ions.
Step S103: and putting the carbon fiber subjected to the plasma treatment into a chromium ion solution prepared in advance for chromium ion modification treatment to obtain the modified carbon fiber.
Step S103 is to combine the hydroxyl functional groups on the surface of the carbon fibers after the plasma treatment with the chromium ions to enhance the interfacial bonding force between the carbon fibers and the resin matrix.
The step of putting the carbon fiber after the plasma treatment into a chromium ion solution prepared in advance for chromium ion modification treatment to obtain the modified carbon fiber comprises the following steps:
immersing the carbon fiber subjected to plasma treatment into a chromium ion solution to form a chromium ion layer on the surface of the carbon fiber; drying the impregnated carbon fibers; and cutting the dried carbon fiber to obtain the modified carbon fiber with the preset length.
Wherein, because a proper amount of hydroxyl functional groups are introduced to the surface of the carbon fiber after plasma treatment, the carbon fiber is placed in a chromium ion solution, and the hydroxyl and chromium ions can be combined, thereby forming a chromium ion layer on the surface of the carbon fiber. The chromium ion layer can increase the interface bonding force of the carbon fiber and the resin matrix.
After drying the impregnated carbon fibers, cutting the carbon fibers into short carbon fibers with preset lengths, wherein the short carbon fibers with the lengths of 1mm are adopted in the embodiment of the application. In addition, the preset length of the carbon fiber to be cut in the present application may be determined according to specific situations, and is not limited herein.
Wherein the chromium ion solution comprises: a solute containing chromium ions and a volatile solvent with a low boiling point, wherein the concentration range of the chromium ions in the chromium ion solution is less than 0.1mol/L and more than or equal to 10 mol/L.
The solute comprising chromium ions comprises: chromium acetate or chromium acetylacetonate; the volatile solvent having a low boiling point includes acetone, methyl ethyl ketone and ethanol.
The application provides a surface treatment method of carbon fibers, which comprises the following steps: obtaining carbon fibers; carrying out plasma treatment on the surface of the carbon fiber to obtain the carbon fiber after the plasma treatment; and putting the carbon fiber subjected to the plasma treatment into a chromium ion solution prepared in advance for chromium ion modification treatment to obtain the modified carbon fiber.
In the method, the surface of the carbon fiber is subjected to plasma treatment and chromium ion modification, and the surface appearance and the surface functional groups of the carbon fiber are influenced by adjusting the size of the airflow, the treatment power, the treatment time and the treatment temperature. The plasma treatment of the carbon fiber can improve the surface activity of the carbon fiber and increase the functional groups, such as hydroxyl functional groups, on the surface of the carbon fiber. Since the hydroxyl group and the chromium ion can be combined, the deposition rate of the chromium ion on the surface of the carbon fiber is also improved. After the carbon fiber is soaked in the chromium ion solution, a large amount of chromium ions are deposited on the surface of the carbon fiber, so that the interface bonding force between the carbon fiber and the resin matrix is enhanced.
Furthermore, the composite material prepared by combining the carbon fiber subjected to plasma treatment and chromium ion modification with the resin matrix can improve the mechanical property and water absorption of the composite material. The composite material is used for preparing equipment for deep sea, such as a submarine, so that the pressure resistance of the submarine in the deep sea field can be improved, and the water absorption rate can be reduced.
Taking an epoxy resin as an example, the epoxy resin has a relatively high water absorption capacity because of the presence of-OH groups in the epoxy chain of the epoxy resin, which attract polar water molecules. However, the method for treating the surface of the carbon fiber provided by the embodiment of the present application is to subject the surface of the carbon fiber to plasma treatment and chromium ion modification, so that the surface of the carbon fiber generates an interface where the chromium ion-containing epoxy resin having improved moisture resistance is bonded to the carbon fiber, wherein the chromium ion prevents absorption of water molecules by coordinating itself to the epoxy chain and — OH group on the carbon fiber. Meanwhile, the operation method for carrying out plasma treatment and chromium ion modification on the surface of the carbon fiber is simple, the cost is low, the continuous production is conveniently achieved by matching with a production line, the modification effect is very obvious, and the method has the characteristics of economy, practicability and the like.
For a better understanding of the properties of the composite material formed by modified carbon fibers and a resin matrix in the present application, please refer to fig. 2 and fig. 3, wherein fig. 2 is a scanning electron microscope image of the interface bonding between the carbon fibers and the resin matrix provided in the present application without plasma treatment and chromium ion modification. Fig. 3 is a scanning electron microscope image of the interface bonding of the carbon fiber modified by plasma treatment and chromium ions and the resin matrix provided by the application.
As can be seen from fig. 2, before the carbon fibers were not treated, the surfaces of the carbon fibers were smooth, and the interfaces between the carbon fibers and the resin matrix at the fracture surfaces were almost disappeared, and voids were generated between them. As can be seen from fig. 3, after the carbon fiber is subjected to plasma treatment and chromium ion modification, the surface of the carbon fiber becomes rough, and a large number of oxygen-containing functional groups are generated, so that the carbon fiber can be bonded to the resin matrix better, and the scanning electron microscope image thereof also shows good interface bonding performance.
The above is a description of a composite material provided in the present application, wherein the relevant description of the modified carbon fiber can refer to the explanation of the surface treatment of the carbon fiber. In order to better understand the present application, the following examples are given to illustrate the surface treatment method of the composite material and the carbon fiber. In the following examples, "parts" are "parts by mass" unless otherwise specified. The following examples all use dry jet wet spun continuous carbon fibers of grade T700, but the invention is not limited to such carbon fibers.
Comparative example 1 (carbon fiber without any treatment)
Taking 3 parts of untreated carbon fiber with the length of 1mm, mixing the carbon fiber with epoxy resin, acid anhydride and N, N-dimethylbenzylamine, uniformly stirring, heating and curing, keeping the temperature at 50 ℃ for 2 hours, curing at 80 ℃ for 3 hours, and curing at 120 ℃ for 5 hours to prepare the composite material.
Comparative example 2 (plasma surface-treated carbon fiber)
Plasma treatment of the surface of the carbon fiber:
the continuous carbon fiber is placed at a driving position, the spray gun sprays gas according to a preset gas flow to create a target gas environment, so that the continuous carbon fiber and the target gas are subjected to contact reaction in the target gas environment, and plasma treatment on the surface of the carbon fiber is completed. Sequentially carrying out sizing treatment, drying treatment, rolling and cutting on the carbon fiber subjected to the plasma treatment into modified carbon fiber with the length of 1 mm; wherein the set air flow rate is set to 0.5L/min, the treatment time is 60s, and the treatment power is 600W.
The modified carbon fiber is adopted to prepare a composite material:
and (3) mixing the treated modified carbon fiber with epoxy resin, acid anhydride and N, N-dimethylbenzylamine, uniformly stirring, heating and curing, keeping the temperature at 50 ℃ for 2 hours, curing at 80 ℃ for 3 hours, and curing at 120 ℃ for 5 hours to obtain the composite material.
Comparative example 3 (chromium ion modified carbon fiber)
Carrying out chromium ion modification on the surface of the carbon fiber:
soaking carbon fibers in a chromium ion solution for 24 hours, taking out the carbon fibers, drying, rolling and cutting the carbon fibers into modified carbon fibers with the length of 1mm, wherein chromium ions in the chromium ion solution are derived from chromium acetate, the concentration of the chromium ions in the chromium ion solution is 0.1mol/L, and the solvent is acetone.
The modified carbon fiber is adopted to prepare a composite material:
and (3) mixing the treated modified carbon fiber with epoxy resin, acid anhydride and N, N-dimethylbenzylamine, uniformly stirring, heating and curing, keeping the temperature at 50 ℃ for 2 hours, curing at 80 ℃ for 3 hours, and curing at 120 ℃ for 5 hours to obtain the composite material.
Example 1 (plasma surface treatment and chromium ion modified carbon fiber)
Plasma treatment of the surface of the carbon fiber:
the continuous carbon fiber is placed at a driving position, the spray gun sprays gas according to a preset gas flow to create a target gas environment, so that the continuous carbon fiber and the target gas are subjected to contact reaction in the target gas environment, and plasma treatment on the surface of the carbon fiber is completed. Sequentially carrying out sizing treatment, drying treatment and winding on the carbon fiber subjected to the plasma treatment; wherein the set air flow rate is set to 0.5L/min, the treatment time is 60s, and the treatment power is 700W.
Carrying out chromium ion modification on the carbon fiber after plasma treatment:
and (2) soaking the carbon fiber subjected to plasma treatment in a chromium ion solution for 24 hours, taking out, drying, rolling and cutting into modified carbon fiber with the length of 1mm, wherein chromium ions in the chromium ion solution are derived from chromium acetate, the concentration of the chromium ions in the chromium ion solution is 0.1mol/L, and the solvent is acetone.
The modified carbon fiber is adopted to prepare a composite material:
and (3) mixing the treated modified carbon fiber with epoxy resin, acid anhydride and N, N-dimethylbenzylamine, uniformly stirring, heating and curing, keeping the temperature at 50 ℃ for 2 hours, curing at 80 ℃ for 3 hours, and curing at 120 ℃ for 5 hours to obtain the composite material.
Example 2 (plasma surface treatment and chromium ion modified carbon fiber)
Subjecting the surface of the carbon fiber to plasma treatment:
the continuous carbon fiber is placed at a driving position, the spray gun sprays gas according to a preset gas flow to create a target gas environment, so that the continuous carbon fiber and the target gas are subjected to contact reaction in the target gas environment, and plasma treatment on the surface of the carbon fiber is completed. Sequentially carrying out sizing treatment, drying treatment and winding on the carbon fiber subjected to the plasma treatment; wherein the set air flow rate is set to 0.5L/min, the treatment time is 120s, and the treatment power is 300W.
Carrying out chromium ion modification on the carbon fiber after plasma treatment:
and (2) soaking the carbon fiber treated by the plasma in a chromium ion solution for 24 hours, then taking out, drying, rolling and cutting into modified carbon fiber with the length of 1mm, wherein chromium ions in the chromium ion solution are from chromium acetylacetonate, the concentration of the chromium ions in the chromium ion solution is 0.5 mol/L%, and the solvent is acetone.
The modified carbon fiber is adopted to prepare a composite material:
and (3) mixing 3 parts of the treated chopped carbon fibers with epoxy resin, acid anhydride and N, N-dimethylbenzylamine, uniformly stirring, heating and curing, keeping the temperature at 50 ℃ for 2 hours, curing at 80 ℃ for 3 hours, and curing at 120 ℃ for 5 hours to obtain the composite material.
Example 3 (plasma surface treatment and chromium ion modified carbon fiber)
Subjecting the surface of the carbon fiber to plasma treatment:
the continuous carbon fiber is placed at a driving position, the spray gun sprays gas according to a preset gas flow to create a target gas environment, so that the continuous carbon fiber and the target gas are subjected to contact reaction in the target gas environment, and plasma treatment on the surface of the carbon fiber is completed. Sequentially carrying out sizing treatment, drying treatment and winding on the carbon fiber subjected to the plasma treatment; wherein the set air flow rate is set to 1L/min, the treatment time is 120s, and the treatment power is 600W.
Carrying out chromium ion modification on the carbon fiber after plasma treatment:
and (2) soaking the carbon fiber treated by the plasma in a chromium ion solution for 24 hours, then taking out, drying, rolling and cutting into modified carbon fiber with the length of 1mm, wherein chromium ions in the chromium ion solution are from chromium acetylacetonate, the concentration of the chromium ions in the chromium ion solution is 0.8 mol/L%, and the solvent is acetone.
The modified carbon fiber is adopted to prepare a composite material:
and (3) mixing the treated modified carbon fiber with epoxy resin, acid anhydride and N, N-dimethylbenzylamine, uniformly stirring, heating and curing, keeping the temperature at 50 ℃ for 2 hours, curing at 80 ℃ for 3 hours, and curing at 120 ℃ for 5 hours to obtain the composite material.
Example 4 (plasma surface treatment and chromium ion-modified carbon fiber)
Subjecting the surface of the carbon fiber to plasma treatment:
the continuous carbon fiber is placed at a driving position, the spray gun sprays gas according to a preset gas flow to create a target gas environment, so that the continuous carbon fiber and the target gas are subjected to contact reaction in the target gas environment, and plasma treatment on the surface of the carbon fiber is completed. Sequentially carrying out sizing treatment, drying treatment and winding on the carbon fiber subjected to the plasma treatment; wherein the set air flow rate is set to 0.2L/min, the treatment time is 180s, and the treatment power is 500W.
Carrying out chromium ion modification on the carbon fiber after plasma treatment:
and (2) soaking the carbon fiber subjected to plasma treatment in a chromium ion solution for 24 hours, taking out, drying, rolling and cutting into modified carbon fiber with the length of 1mm, wherein chromium ions in the chromium ion solution are from chromium acetylacetonate, the concentration of the chromium ions in the chromium ion solution is 1mol/L, and the solvent is acetone.
The modified carbon fiber is adopted to prepare a composite material:
and (3) mixing the treated modified carbon fiber with epoxy resin, acid anhydride and N, N-dimethylbenzylamine, uniformly stirring, heating and curing, keeping the temperature at 50 ℃ for 2 hours, curing at 80 ℃ for 3 hours, and curing at 120 ℃ for 5 hours to obtain the composite material.
The properties of the composite materials of the above comparative examples and examples were compared and the results are shown in table 1.
Table 1:
the performance testing methods in table 1 are as follows:
1) the density was measured according to the drainage method.
2) Interlaminar shear strength refers to the strength limit of the laminate under pure shear loading between layers. The test method comprises the following steps: preparing a mixed solution by using epoxy resin as a matrix and triethylene tetramine as a curing agent, coating and immersing a carbon fiber test sample strip on the mixed solution, and curing the carbon fiber sample strip coated with the mixed solution at the curing temperature of 120 ℃ for 2 hours. Wherein, the carbon fiber test sample strip before being treated by the mixed solution is made into a CFRP (carbon fiber reinforced composite) test sample strip according to the method of GB 3357-82.
3) Uniaxial compressive strength test method:
the carbon fiber samples were cut into 10X 25mm columnar bars and their uniaxial compressive strength was measured according to the method for measuring the compressive property of GB/T8813-2008 rigid foam.
Wherein, the calculation formula of the uniaxial compressive strength is as follows:
P＝F/(B×L)
wherein, P is uniaxial compressive strength, MPa;
f is the maximum stress of the sample at yield, and the unit is N;
b refers to the width of the sample, and the unit is mm;
l is the length of the sample in mm.
4) Isostatic crush strength is the hydrostatic strength of the synthetic foam tested according to ASTM D2736.
5) The water absorption of 121MPa @168h refers to the water absorption of the composite material after the composite material is placed under the water pressure of 121MPa for 168 hours.
From the tests in table 1, it can be seen that, compared with the untreated carbon fiber reinforced lightweight composite material, after the carbon fibers are subjected to plasma surface treatment, the interlaminar shear strength of the composite material is improved by 16.3%, the uniaxial compressive strength is improved by 10.1%, the isostatic fracture strength is improved by 3.2%, and the water absorption of 121MPa @168h is reduced by 20.7%, while after the carbon fibers are subjected to plasma surface treatment and chromium ion modification, the interlaminar shear strength of the composite material is improved by 15.5%, the uniaxial compressive strength is improved by 16.1%, the isostatic fracture strength is improved by 7.7%, and the water absorption of 121MPa @168h is reduced by 72.0%.
The modified carbon fiber provided by the application can improve the mechanical property of the light composite material (the uniaxial compressive strength is improved from 108.4MPa to 145.5MPa, the isostatic compressive failure strength is improved from 156MPa to 199MPa), and simultaneously reduce the water absorption of the light composite material (the water absorption of 121MPa @168h is reduced from 0.82% to 0.19%). The light composite material is used for preparing equipment for deep sea, such as a submarine, so that the pressure resistance of the submarine in the deep sea field can be improved, and the water absorption rate can be reduced.
Although the present application has been described with reference to the preferred embodiments, it is not intended to limit the present application, and those skilled in the art can make variations and modifications without departing from the spirit and scope of the present application, therefore, the scope of the present application should be determined by the claims that follow.
Claims (10)
1. A surface treatment method for carbon fibers, characterized by comprising:
obtaining carbon fibers;
carrying out plasma treatment on the surface of the carbon fiber to obtain the carbon fiber after the plasma treatment;
and putting the carbon fiber subjected to the plasma treatment into a chromium ion solution prepared in advance for chromium ion modification treatment to obtain the modified carbon fiber.
2. The method according to claim 1, wherein the step of putting the plasma-treated carbon fiber into a chromium ion solution prepared in advance to perform chromium ion modification treatment to obtain a modified carbon fiber comprises the following steps:
immersing the carbon fiber subjected to plasma treatment into a chromium ion solution to form a chromium ion layer on the surface of the carbon fiber;
drying the impregnated carbon fibers;
and cutting the dried carbon fiber to obtain the modified carbon fiber with the preset length.
3. The method of claim 1, wherein the plasma treating the surface of the carbon fiber comprises:
placing continuous carbon fibers in a target gas environment, and carrying out plasma treatment on the surfaces of the continuous carbon fibers according to preset plasma treatment conditions;
sizing the carbon fiber after the plasma treatment;
and drying the carbon fiber subjected to sizing treatment.
4. The method according to claim 3, wherein the target gas in the target gas environment is a gas ejected at a preset gas flow rate through a spray gun toward the continuous carbon fibers.
5. The method of claim 4, wherein the target gas comprises at least one of: air, oxygen, hydrogen, and argon.
6. The method of claim 3, wherein the pre-set plasma processing conditions comprise:
the processing time ranges from more than 15s to less than or equal to 600 s;
and processing power, wherein the processing power range is more than 200W and less than or equal to 900W.
7. The method according to claim 3, wherein the drying temperature range for drying the sized carbon fiber is greater than 20 ℃ and less than or equal to 300 ℃.
8. The method of claim 2, wherein the chromium ion solution comprises:
a solute containing chromium ions and a volatile solvent with a low boiling point, wherein the concentration range of the chromium ions in the chromium ion solution is less than 0.1mol/L and more than or equal to 10 mol/L.
9. A modified carbon fiber, characterized in that it is obtained by the surface treatment method according to any one of claims 1 to 8.
10. A composite material, comprising: modified carbon fiber obtained by the surface treatment method according to any one of claims 1 to 8.
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