CN110330754B - Nascent thin film, polyacrylonitrile-based carbon thin film and preparation method - Google Patents
Nascent thin film, polyacrylonitrile-based carbon thin film and preparation method Download PDFInfo
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- CN110330754B CN110330754B CN201910718868.8A CN201910718868A CN110330754B CN 110330754 B CN110330754 B CN 110330754B CN 201910718868 A CN201910718868 A CN 201910718868A CN 110330754 B CN110330754 B CN 110330754B
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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Abstract
The invention relates to a primary film, a polyacrylonitrile film and a polyacrylonitrile-based carbon film. The main technical scheme adopted is as follows: the primary film is obtained by forming a polyacrylonitrile solution into a film-shaped liquid flow and then carrying out forming treatment on the film-shaped liquid flow; wherein the cross-sectional shape of the nascent film is substantially rectangular; the ratio of the cross-sectional width to the cross-sectional thickness of the nascent film is greater than 50. The method is mainly used for preparing the polyacrylonitrile-based carbon fiber in a film form, namely the polyacrylonitrile-based carbon film; when the polyacrylonitrile-based carbon film is used as the reinforcing phase, the proportion of the reinforcing phase in the composite material can be obviously improved, and the reinforcing phase can be uniformly distributed in the composite material, so that the performance of the carbon fiber composite material is improved.
Description
Technical Field
The invention relates to the technical field of polyacrylonitrile fibers, in particular to a nascent thin film, a polyacrylonitrile-based carbon thin film and a preparation method thereof.
Background
The polyacrylonitrile-based carbon fiber is an inorganic fiber with a carbon content of 90%, has excellent performances such as high specific strength and high specific modulus, and is widely applied to the fields of aerospace, new energy and the like as a composite material of a reinforcing fiber.
In carbon fiber composites, the content of carbon fibers has a determining effect on the properties of the composite. And the volume ratio of the carbon fiber with the circular section in the composite material is below 60 percent.
In order to increase the content of polyacrylonitrile-based carbon fibers in the composite material, polyacrylonitrile-based carbon fibers having an anisotropic cross-sectional shape (i.e., a non-circular cross-sectional shape) may be prepared. However, the inventors of the present invention found that: the polyacrylonitrile-based carbon fibers with general special-shaped cross sections (such as triangles, polygons, double crosses, multi-leaf shapes and the like) are unevenly distributed in the composite material, so that the performance of the composite material is easy to fluctuate.
Disclosure of Invention
In view of the above, the present invention provides a nascent thin film, a polyacrylonitrile-based carbon thin film and a preparation method thereof, and mainly aims to make polyacrylonitrile-based carbon fibers in a thin film form, and when the polyacrylonitrile-based carbon thin film is used as a reinforcement phase, the proportion of the reinforcement phase in a composite material can be increased, and the reinforcement phase can be uniformly distributed in the composite material.
In order to achieve the purpose, the invention mainly provides the following technical scheme:
in one aspect, an embodiment of the present invention provides a primary film, wherein the primary film is obtained by forming a polyacrylonitrile solution into a film-like liquid flow, and then performing a shaping process on the film-like liquid flow; wherein the cross-sectional shape of the nascent film is substantially rectangular; the ratio of the cross-sectional width to the cross-sectional thickness of the nascent film is greater than 50.
Preferably, the light transmittance of the nascent film is greater than or equal to 60%.
Preferably, the deviation between the average pore diameter at the surface layer structure and the average pore diameter at the core layer structure of the nascent film is within 10%;
preferably, the surface structure is at a position on the cross section of the film, wherein the shortest distance between the cross section of the film and the outline of the film does not exceed 1/5 of the thickness of the cross section; the core structure is located at a position on the film cross-section where the shortest distance from the center of gravity of the cross-section does not exceed 1/5 of the cross-section thickness.
In another aspect, an embodiment of the present invention provides a method for preparing a nascent thin film, including the following steps:
1) preparing a polyacrylonitrile solution;
2) forming the polyacrylonitrile solution into a film-shaped liquid flow;
3) performing shaping treatment on the film-shaped liquid flow to obtain a primary film;
wherein the cross section of the nascent fiber is approximately rectangular; the ratio of the cross-sectional width to the cross-sectional thickness of the nascent film is greater than 50;
preferably, the light transmittance of the primary film is greater than or equal to 60%;
preferably, the polyacrylonitrile polymer in the polyacrylonitrile solution comprises one or a mixture of two of polyacrylonitrile homopolymer and polyacrylonitrile copolymer;
preferably, the polyacrylonitrile solution is formed into a film-shaped liquid flow by adopting an extrusion method or a casting method;
preferably, the film-like liquid stream is subjected to a shaping treatment by a solvent evaporation method or a coagulation bath shaping method to obtain a nascent film.
Preferably, the step 3) is specifically: subjecting the film-like liquid flow to a coagulating bath forming treatment to obtain a nascent film; wherein the coagulating bath comprises the following components in a mass ratio of 1: 0-2: 8, non-solvent and solvent; preferably, the mass ratio of the non-solvent to the solvent is 1: 0-3: 7, more preferably 9: 1-4: 6, more preferably 8: 2-4: 6; and/or the temperature of the coagulation bath is-50 ℃ to 70 ℃, preferably-20 ℃ to 5 ℃; and/or the residence time of the film-like liquid flow in the coagulation bath is 1 to 150 s.
Preferably, the non-solvent in the coagulating bath is any one or a mixture of several of formic acid, glycerol, ethylene glycol, acetic acid, ethanol, methanol, chloroform, isobutanol, isoamyl alcohol, butanediol, benzyl alcohol, carbon tetrachloride, toluene, acetone, water and dioxane.
Preferably, the solvent in the coagulation bath is a solvent capable of dissolving polyacrylonitrile, and is preferably any one of dimethyl sulfoxide, dimethylformamide, dimethylacetamide, a lithium chloride solution, an ionic liquid, a sodium thiocyanate solution, and a zinc chloride solution.
Preferably, the step 2) is specifically: extruding the polyacrylonitrile solution into a film-shaped liquid flow by adopting an extrusion die; wherein the extrusion orifice of the extrusion die is approximately in any one of a rectangle shape, a slit shape and a dog bone-like shape; preferably, the average width of the extrusion orifice of the extrusion die is 1-300 μm, and preferably 4-200 μm.
In still another aspect, an embodiment of the present invention further provides a polyacrylonitrile film, where a cross-sectional shape of the polyacrylonitrile film is substantially rectangular; the ratio of the cross-sectional width to the cross-sectional thickness of the polyacrylonitrile film is greater than 50. Wherein the deviation between the average pore diameter at the surface structure and the average pore diameter at the core structure of the polyacrylonitrile film is within 10%; preferably, the thickness of the polyacrylonitrile film is less than 1 mm; preferably, the polyacrylonitrile film is made of the primary film.
In another aspect, the preparation method of the polyacrylonitrile film is characterized by comprising the following steps:
preparing a primary film: preparing a primary film by adopting the preparation method of any one of the primary films;
and (3) post-treatment: carrying out post-treatment on the nascent film to obtain a polyacrylonitrile film;
preferably, the post-treatment comprises washing, drafting, oiling and drying the nascent film to obtain the polyacrylonitrile film;
preferably, the post-treatment comprises the steps of washing the nascent film with water, drafting in a water bath, drying and heat treating, drafting with steam, and oiling to obtain the polyacrylonitrile film.
In still another aspect, an embodiment of the present invention further provides a polyacrylonitrile-based carbon film, where a cross-sectional shape of the polyacrylonitrile-based carbon film is substantially rectangular; the ratio of the cross section width to the cross section thickness of the polyacrylonitrile film is more than 50; wherein the thickness of the polyacrylonitrile-based carbon film is 0.5-150 μm, preferably within the range of 1-10 μm, and further preferably 3-8 μm; preferably, the width of the polyacrylonitrile-based carbon film is 1-10 m; or the width of the polyacrylonitrile-based carbon film is 25 mu m-1 m, preferably 1 mm-20 cm, and more preferably 5 mm-100 mm; preferably, the longitudinal tensile strength of the polyacrylonitrile-based carbon film is 2.2-4.5 GPa;
preferably, the deviation between the average pore diameter at the surface structure and the average pore diameter at the core structure of the polyacrylonitrile-based carbon film is within 10%;
preferably, the polyacrylonitrile-based carbon film is made of the polyacrylonitrile film.
In another aspect, the preparation method of the polyacrylonitrile-based carbon film comprises the following steps:
carrying out heat treatment on the polyacrylonitrile film to obtain a polyacrylonitrile-based carbon film; preferably, the heat treatment comprises:
pre-oxidation: pre-oxidizing the polyacrylonitrile film at 185-400 ℃ to obtain a pre-oxidized film;
low-temperature carbonization: carrying out low-temperature carbonization treatment on the pre-oxidized film at the temperature of 400-1000 ℃ to obtain a low-temperature carbonized film;
high-temperature carbonization: and carrying out high-temperature carbonization on the low-temperature carbonized film at the temperature of 1100-3000 ℃ to obtain the polyacrylonitrile-based carbon film.
Compared with the prior art, the nascent thin film, the polyacrylonitrile thin film and the polyacrylonitrile-based carbon thin film and the preparation method have at least the following beneficial effects:
1. the embodiment of the invention provides a primary film, which is a film-shaped polyacrylonitrile-based primary fiber with a substantially rectangular cross section and a ratio of the width of the cross section to the thickness of the cross section of more than 50; the primary film can be used for preparing a polyacrylonitrile-based carbon film, namely polyacrylonitrile-based carbon fiber with a roughly rectangular cross section and a film shape as a whole; when the polyacrylonitrile-based carbon film is used as the reinforcing phase to prepare the composite material, the proportion of the reinforcing phase in the composite material can be obviously improved, and the reinforcing phase can be uniformly distributed in the composite material, so that the performance of the carbon fiber composite material is improved.
Further, the light transmittance of the nascent film provided by the embodiment of the invention is greater than or equal to 60%; the primary film with the light transmittance is uniform in structure, has elasticity, and is convenient for subsequent treatment such as drafting, so that the polyacrylonitrile film and the polyacrylonitrile-based carbon film with uniform structures are obtained.
2. The embodiment of the invention provides a preparation method of a primary film, which is characterized in that the light transmittance of the formed primary film is more than or equal to 60 percent as far as possible by controlling the conditions of the composition of a coagulating bath, the temperature of the coagulating bath and the like, so that the primary film has uniform structure and elasticity, and is convenient for subsequent drafting and other treatments, thereby obtaining a polyacrylonitrile film and a polyacrylonitrile-based carbon film with uniform structures.
3. The embodiment of the invention provides a polyacrylonitrile film and a preparation method thereof, wherein the polyacrylonitrile film is prepared from the nascent film, so that the polyacrylonitrile film is uniform in structure and good in performance.
4. The embodiment of the invention provides a polyacrylonitrile-based carbon film and a preparation method thereof, wherein the polyacrylonitrile-based carbon film is prepared from the polyacrylonitrile film, so that the polyacrylonitrile-based carbon film has a uniform structure and better performance; when the polyacrylonitrile-based carbon film is used as the reinforcing phase to prepare the composite material, the proportion of the reinforcing phase in the composite material can be obviously improved, and the reinforcing phase can be uniformly distributed in the composite material, so that the performance of the carbon fiber composite material is improved.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
FIG. 1 is a schematic diagram of the distribution of polyacrylonitrile-based carbon film as a reinforcing phase in a composite material prepared by the embodiment of the invention;
fig. 2 is a schematic diagram of the distribution of polyacrylonitrile-based carbon fiber with a circular cross section in the composite material as a reinforcing phase in the prior art.
Detailed Description
To further explain the technical means and effects of the present invention adopted to achieve the predetermined object, the following detailed description of the embodiments, structures, features and effects according to the present invention will be made with reference to the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
In one aspect, embodiments of the present invention provide a primary film, where the primary film is obtained by forming a polyacrylonitrile solution into a film-like liquid flow, and then performing a forming process on the film-like liquid flow; wherein the cross-sectional shape of the nascent film is substantially rectangular; the ratio of the cross-sectional width to the cross-sectional thickness of the nascent film is greater than 50.
The film in the application can be a macroscopic film or a microscopic film; wherein the cross-sectional width of the macroscopic film is greater than 1 m; the width of the cross section of the microscopic film is less than 1 m.
The microscopic films (nascent films, polyacrylonitrile-based carbon films) differ from the fibers of the prior art (nascent fibers, polyacrylonitrile carbon fibers) in that: prior art nascent fibers are generally circular in cross-section, or other generally anisotropic structures. The film of the present application is substantially a fiber having a rectangular cross section, a ratio of a cross-sectional width to a cross-sectional thickness of more than 50, and a film-like shape as a whole.
Here, the "width of the cross section", that is, the width of the film, refers to the length of the film in which the upper and lower surfaces overlap each other; "thickness of the film" means the thickness of the film: average distance of upper and lower surfaces of the film.
The primary film means that the polyacrylonitrile solution is initially formed to have a film form, and the polyacrylonitrile in the film form can be in a solidification state, a gel state, or a partial solidification state or gel state. Preferably, the nascent film is in the gel state.
Preferably, in order to obtain the polyacrylonitrile film and the polyacrylonitrile-based carbon film with good structural performance and mechanical performance: the light transmittance of the nascent film provided by the embodiment of the invention is greater than or equal to 60%. If the transmittance of the nascent film is less than 60%, the structural uniformity is poor. Here, the light transmittance refers to a light transmittance obtained by a light transmittance tester, and the light source wavelength is 500 ± 10 nm.
Preferably, the deviation between the average pore diameter at the surface layer structure and the average pore diameter at the core layer structure of the nascent film is within 10%; this means that the structure of the nascent fiber is uniform.
The surface structure is positioned at the position on the cross section of the film, wherein the shortest distance between the surface structure and the outer contour of the film does not exceed 1/5 of the thickness of the cross section; the core structure is located at a position on the film cross-section where the shortest distance from the center of gravity of the cross-section does not exceed 1/5 of the cross-section thickness.
Here, the average pore diameter of the surface layer structure and the core layer structure of the nascent fiber was measured by the following method:
1. firstly, drying the nascent fiber by using a freeze-drying method to obtain a dried nascent fiber sample;
2. the section image of the nascent fiber is obtained by using a transmission electron microscope or a scanning electron microscope and the like, and the nascent fiber sample can be subjected to gold spraying treatment before testing, or other pretreatment which can increase the observation effect but does not change the original appearance of the solidified fiber is performed on the nascent fiber;
3. and processing the micro image of the solidified filament by using image processing software to obtain the pore size distribution of different areas. Selecting a circular area with the diameter of 200nm at 1000nm inward from the surface of the primary fiber as a representative area of a surface structure area, calculating the average pore diameter at the surface structure area, and removing the first two large-diameter pores during calculation so as to reduce errors. Selecting a circular area with the diameter of 200nm at the gravity center of the transverse section of the nascent fiber as a representative area of the core layer structure, calculating the average pore diameter at the inner layer structure, and removing the first two large-diameter pores during calculation so as to reduce errors.
On the other hand, the embodiment of the invention provides a preparation method of the primary film, which specifically comprises the following steps:
1) and preparing polyacrylonitrile solution.
Here, polyacrylonitrile in the polyacrylonitrile solution means: polyacrylonitrile homopolymer, or polyacrylonitrile copolymer containing acrylonitrile as main component.
The molecular weight and distribution of the polymer are not particularly limited, and the smaller the molecular weight, the poorer the mechanical properties of the polyacrylonitrile film and the polyacrylonitrile-based carbon film, and therefore the molecular weight of polyacrylonitrile is preferably 10 ten thousand or more. The mechanical properties of the polyacrylonitrile film and the polyacrylonitrile-based carbon film obtained are better as the molecular weight is larger, but the polyacrylonitrile having a large molecular weight is poor in solubility in a solvent, so the upper limit of the molecular weight of the polyacrylonitrile is not particularly limited as long as the polyacrylonitrile can be dissolved in the solvent, and usually the polyacrylonitrile is 150 ten thousand or less.
The polyacrylonitrile solvent is not particularly limited as long as it can dissolve polyacrylonitrile, and may be a single substance or a mixture of substances such as dimethylsulfoxide, dimethylformamide, dimethylacetamide, dimethylsulfoxide/lithium chloride, an ionic liquid, a sodium thiocyanate solution, and a zinc chloride solution.
2) The polyacrylonitrile solution is formed into a film-shaped liquid flow.
Here, the polyacrylonitrile solution may be formed into a liquid flow in a film shape by an extrusion method, a casting method, or a casting-drawing method; cast draw processes are preferred.
The step is mainly carried out in a coagulating bath, and if a macroscopic film is prepared, the film needs to be transversely and longitudinally stretched, wherein the longitudinal stretching is 0.7-12 times, and the transverse stretching is 0.65-3 times. If the microcosmic film is prepared, only longitudinal drafting is needed for the film, and the drafting multiple is 0.7-12 times.
Here, a primary film in a film form can be obtained by adjusting the orifice shape of the polyacrylonitrile solution extrusion die. The polyacrylonitrile solution extrusion die port can be provided with a plurality of port combinations or only a single port. The orifice of the die may be rectangular-like or slit-like, preferably dog bone-like, and the average width of the slit of the orifice is preferably 1 to 300 μm, more preferably 4 to 200 μm.
3) The film-like liquid flow is subjected to a shaping treatment to obtain a nascent film.
Here, the method of causing the film-like liquid stream to pass through the gelation or solidification may be a method of causing the liquid stream to enter a coagulation bath to undergo gelation or solidification, or a method of causing the polyacrylonitrile liquid stream to undergo gelation or solidification in an atmosphere; preferably, the polyacrylonitrile liquid stream is passed into a coagulation bath for gelation or coagulation. The gelation process refers to a process in which a polymer solution is transformed from a solution state to a gel state. The loss modulus of the polymer solution is greater than the storage modulus, and the gel state in the invention refers to the state that the loss modulus of the polymer solution is equal to or less than the storage modulus in a certain transition process, but the polymer solution still has part of phase separation.
For this step, the forming process determines the structural uniformity of the as-formed film. In the prior art, rectangular film-shaped polyacrylonitrile fibers and polyacrylonitrile-based carbon fibers do not exist; the fundamental reason is that: the fiber having a rectangular cross section is not well drawn and the drawn fiber has a non-uniform thickness.
Therefore, the inventors of the present invention have proposed for the first time the following processes to prepare a primary film having a light transmittance of 60% or more; the primary film has uniform structure and elasticity, and subsequent drafting treatment is utilized to prepare polyacrylonitrile films and polyacrylonitrile-based carbon films with uniform structures. Specifically, the forming treatment process comprises the following steps:
the polyacrylonitrile liquid flow in the form of a film is subjected to a shaping treatment in a coagulation bath. The coagulation bath may be composed of a polyacrylonitrile non-solvent and a polyacrylonitrile solvent (here, the polyacrylonitrile non-solvent is simply referred to as a non-solvent and refers to a solvent that does not dissolve polyacrylonitrile; and the polyacrylonitrile solvent is simply referred to as a solvent and refers to a solvent that can dissolve polyacrylonitrile). Wherein, the non-solvent: solvent 1: 0-2: 8 (mass%) was mixed as a coagulation bath. Preferably, the mass ratio of the non-solvent to the solvent is 1: 0-3: 7, and further preferably, the mass ratio of the non-solvent to the solvent is 9: 1-4: 6, and more preferably, the mass ratio of the non-solvent to the solvent is 8: 2-4: 6.
preferably, the non-solvent can be a single substance or a mixture of different substances; for example, the solvent may be one or more of formic acid, glycerol, ethylene glycol, acetic acid, ethanol, methanol, chloroform, isobutanol, isoamyl alcohol, butanediol, benzyl alcohol, carbon tetrachloride, toluene, acetone, water and dioxane.
Preferably, the polyacrylonitrile liquid flow in the form of a film is caused to form a primary film in a gel state in the coagulation bath by using the components and temperature of the coagulation bath (the gelation process refers to the process of converting the polyacrylonitrile solution from a solution state to a gel state.
The primary film is formed from a flow of polyacrylonitrile in the form of a film using a coagulation bath having a temperature above the melting point of the components of the coagulation bath and below the boiling point of the components of the coagulation bath. The temperature of the coagulation bath is selected to be favorable for the easy occurrence of the gelation process of the polyacrylonitrile solution in the coagulation bath, preferably low temperature condition, specifically-50-70 ℃, preferably-20-5 ℃. When the temperature of the coagulation bath is higher than 70 ℃, the polyacrylonitrile solution is subjected to phase separation in the coagulation bath, so that the difference between the structures of the surface layer and the inner layer of the primary film structure is large, and the performance of the film is reduced; the temperature of the coagulation bath is less than-50 ℃, the energy consumption is high, in addition, the temperature of the coagulation bath is too low, the drafting property of the polyacrylonitrile solution in the film forming process is poor, and the performance of the film is not easy to improve through bidirectional drafting.
In another aspect, an embodiment of the present invention further provides a polyacrylonitrile film, where a cross-sectional shape of the polyacrylonitrile film is substantially rectangular; the ratio of the section width to the section thickness of the polyacrylonitrile film is more than 50. Preferably, the polyacrylonitrile film is made of the primary film.
In another aspect, the preparation method of the polyacrylonitrile film is characterized by comprising the following steps:
1) preparing a primary film: preparing a primary film by adopting the preparation method of the primary film;
2) and (3) post-treatment: carrying out post-treatment on the nascent film to obtain a polyacrylonitrile film;
preferably, the post-treatment comprises washing, drafting, oiling and drying the nascent film to obtain the polyacrylonitrile film.
Preferably, the post-treatment comprises the steps of washing the nascent film with water, drafting in a water bath, drying and heat treating, drafting with steam, and oiling to obtain the polyacrylonitrile film.
Preferably, the post-processing steps are as follows: a water washing step of washing the obtained film in a water bath; a water bath drafting step of drafting the obtained film in a water bath; a drying heat treatment step of subjecting the film to a drying heat treatment; a steam drawing step of drawing the film in steam; and an oiling step of applying a protective oil to the surface of the film. Preferably, after the polyacrylonitrile nascent film is formed, the polyacrylonitrile nascent film is subjected to a water washing process, a water bath drafting process, an oiling process and drying densification in sequence to obtain the polyacrylonitrile film precursor. It is further preferable to add a dry steam draft step and a dry heat draft step to the above-described process.
Preferably, the post-treatment processes (water washing process, water bath drafting process, drying heat treatment process, water vapor drafting process, oiling process, drying process, water vapor drafting process, dry heat drafting process, etc.) can be adjusted according to the process optimization.
Preferably, in the post-treatment step, the longitudinal stretching ratio of the film in the water bath stretching step is preferably 1.2 to 4 times, and more preferably 2 to 3.5 times.
In the post-treatment step, the drying heat treatment step may be performed by a known method, such as hot roll drying or flat plate drying, and the drying temperature may be selected from 85 to 170 ℃.
Preferably, in the post-treatment step, the draft ratio for longitudinally drafting the polyacrylonitrile film in the steam drafting process is 1.5 times or more, and more preferably 2 times or more.
Preferably, in the post-treatment step, after the film is drawn in the bath, in order to prevent static electricity from being generated, protect the surface of the film and influence continuous production, it is preferable to subject the film drawn in the bath to oiling treatment.
Preferably, when the drafting multiple is increased, polyacrylonitrile molecules are easy to align along the drafting direction, and the mechanical property of the film is increased. Therefore, in the preparation of the polyacrylonitrile film, the film is preferably subjected to bidirectional drawing. The specific draw down factor depends on the extrusion die and the size of the final product.
In another aspect, an embodiment of the present invention further provides a polyacrylonitrile-based carbon film, where a cross-sectional shape of the polyacrylonitrile-based carbon film is substantially rectangular; the ratio of the section width to the section thickness of the polyacrylonitrile film is more than 50;
the smaller the thickness of the polyacrylonitrile carbon film, the better the mechanical properties, but the production efficiency is lowered. In the preparation of polyacrylonitrile films, since heat treatment in oxygen is required in the post-treatment, oxygen needs to diffuse from the film surface to the film interior. In order to avoid the influence on the performance of the polyacrylonitrile-based carbon film caused by the excessive difference between the surface and the internal structure of the film, the thickness of the polyacrylonitrile-based carbon film is preferably within the range of 0.5-150 μm, more preferably within the range of 1-10 μm, and even more preferably within the range of 3-8 μm. The width of the polyacrylonitrile-based carbon film is not limited, and can be adjusted together with the subsequent process through the shape and the size of the orifice of the die opening according to the actual application, for example, the width of the polyacrylonitrile-based carbon film can be less than 10 m. The width of the polyacrylonitrile-based carbon film as the reinforcement of the composite material is preferably 25 μm to 1m, more preferably 1mm to 20cm, and still more preferably 5mm to 100 mm.
Preferably, the polyacrylonitrile-based carbon film is made of the polyacrylonitrile film.
In another aspect, the preparation method of the polyacrylonitrile-based carbon film comprises the following steps:
carrying out heat treatment on the polyacrylonitrile film to obtain a polyacrylonitrile-based carbon film; preferably, the heat treatment comprises:
pre-oxidation: pre-oxidizing the polyacrylonitrile film at 185-400 ℃ to obtain a pre-oxidized film;
low-temperature carbonization: carrying out low-temperature carbonization treatment on the pre-oxidized film at the temperature of 400-1000 ℃ to obtain a low-temperature carbonized film;
high-temperature carbonization: and carrying out high-temperature carbonization on the low-temperature carbonized film at the temperature of 1100-3000 ℃ to obtain the polyacrylonitrile-based carbon film.
In order to increase the bonding strength between the polyacrylonitrile-based carbon film and the matrix in the composite material, the surface of the polyacrylonitrile-based carbon film can be treated by electrolysis. After the electrolytic treatment, the carbon film may be subjected to sizing treatment in order to facilitate subsequent use properties. The sizing agent used in the sizing treatment is selected according to the type of the matrix in the composite material. The polyacrylonitrile carbon film after sizing treatment can be prepared into the polyacrylonitrile-based carbon film prepreg by referring to a carbon fiber prepreg technology.
Unlike the prior art, the atmosphere in the heat treatment step described above in the present application is preferably parallel to the direction of advancement of the fibers, especially when a macroscopic film is used. Only in the direction parallel to the film running direction, the waste gas generated by the chemical reaction can be smoothly taken away, and the uniform contact between the atmosphere and the film is also facilitated.
As shown in fig. 1 and 2, when the polyacrylonitrile-based carbon film of the embodiment of the present invention and the polyacrylonitrile-based carbon fiber with a circular cross section of the prior art are used to prepare the composite material: the distribution of the polyacrylonitrile-based carbon film 12 as a reinforcement in the matrix 11 of the composite material 1 is shown in fig. 1; the distribution of polyacrylonitrile-based carbon fibers 13 of circular cross-section as reinforcement in the matrix 11 of the composite material 1 is shown in fig. 1.
As is evident from fig. 1 and 2: the polyacrylonitrile-based carbon film prepared by the embodiment of the invention can increase the volume fraction of the reinforcement in the composite material, increase the contact area between the reinforcement and the matrix, effectively improve the interface bonding strength and improve the performance of the composite material. Because the polyacrylonitrile-based carbon film is in a film form, before the polyacrylonitrile-based carbon film is used for preparing the composite material, the treatment such as fiber opening and width fixing is not needed, and the process for preparing the composite material is simplified.
The following are further illustrated by specific experimental examples:
example 1
In this example, a nascent thin film, a polyacrylonitrile thin film and a polyacrylonitrile-based carbon thin film are prepared; the method specifically comprises the following steps:
1) preparing a nascent film: a polyacrylonitrile solution is prepared by using dimethyl sulfoxide as a solvent and acrylonitrile and itaconic acid as comonomers through a solution polymerization method, wherein the molecular weight of polyacrylonitrile is 20 ten thousand, and the viscosity is 120pa.s (here, the polyacrylonitrile spinning solution with the viscosity-average molecular weight of 20 ten thousand and the viscosity of 120pa.s is mainly used as an example in the embodiment and the following examples, but not limited thereto, and any polyacrylonitrile spinning solution is suitable for the present invention). Extruding the polyacrylonitrile solution from an extrusion orifice of the die to form a film-shaped liquid flow, and allowing the film-shaped liquid flow to enter a coagulating bath after passing through an air layer to form the polyacrylonitrile nascent film.
Wherein the cross-sectional shape of the extrusion orifice of the die is a dogbone shape (the average width of the extrusion orifice is 0.025 mm); the temperature of the coagulation bath was controlled at-17 ℃, the composition of the coagulation bath was dimethyl sulfoxide and water in a mass ratio of 6:4, and the draw ratio in the longitudinal direction of the film was 4.
2) Preparing a polyacrylonitrile film: washing and drafting the nascent film by using deionized water; and oiling the film subjected to water bath, drying and densifying the film by using a drying roller, and longitudinally drafting the film in high-temperature steam to obtain the polyacrylonitrile film.
3) Preparing a polyacrylonitrile-based carbon film: and pre-oxidizing the obtained polyacrylonitrile film in air with a temperature gradient in a temperature range of 185-400 ℃ to obtain a pre-oxidized film. And carrying out low-temperature carbonization on the obtained pre-oxidized fiber in a nitrogen atmosphere at the temperature of 400-1000 ℃ to obtain a low-temperature carbonized film. And carbonizing the low-temperature carbonized fiber at high temperature in a nitrogen atmosphere with the maximum temperature of 1600 ℃. Then, using an ammonium bisulfate solution as an electrolyte to carry out electrolytic treatment on the film after high-temperature carbonization; and then washing, drying and sizing the electrolyzed film to obtain the carbon film. And finally, carrying out a pre-impregnation process on the carbon film to obtain the polyacrylonitrile-based carbon film pre-impregnated tape.
Example 2
In this example, a nascent thin film, a polyacrylonitrile thin film and a polyacrylonitrile-based carbon thin film are prepared; the differences from example 1 in the overall preparation procedure are as follows:
the temperature of the coagulating bath is 8 ℃, and the composition of the coagulating bath is that the mass ratio is 7: 3 and water.
The other steps were in accordance with example 1.
Example 3
In this example, a nascent thin film, a polyacrylonitrile thin film and a polyacrylonitrile-based carbon thin film are prepared; the differences from example 1 in the overall preparation procedure are as follows:
the temperature of the coagulation bath was-20 deg.C, and the component of the coagulation bath was methanol.
The other steps were in accordance with example 1.
Example 4
In this example, a nascent thin film, a polyacrylonitrile thin film and a polyacrylonitrile-based carbon thin film are prepared; the differences from example 1 in the overall preparation procedure are as follows:
the temperature of the coagulation bath was 5 deg.C, and the component of the coagulation bath was ethanol.
The other steps were in accordance with example 1.
Example 5
In this example, a nascent thin film, a polyacrylonitrile thin film and a polyacrylonitrile-based carbon thin film are prepared; the differences from example 1 in the overall preparation procedure are as follows:
the temperature of the coagulating bath is-18 ℃, and the components of the coagulating bath are ethanol and water in a mass ratio of 9: 1.
The other steps were in accordance with example 1.
Example 6
In this example, a nascent thin film, a polyacrylonitrile thin film and a polyacrylonitrile-based carbon thin film are prepared; the differences from example 1 in the overall preparation procedure are as follows:
the temperature of the coagulation bath was 1 ℃ and the component of the coagulation bath was water.
The other steps were in accordance with example 1.
Example 7
In this example, a nascent thin film, a polyacrylonitrile thin film and a polyacrylonitrile-based carbon thin film are prepared; the differences from example 1 in the overall preparation procedure are as follows:
the film-like liquid flow enters the coagulating bath without passing through an air layer; the temperature of the coagulation bath was 10 ℃, and the composition of the coagulation bath was dimethylformamide and water in a mass ratio of 4: 6.
The other steps were in accordance with example 1.
Example 8
In this example, a nascent thin film, a polyacrylonitrile thin film and a polyacrylonitrile-based carbon thin film are prepared; the differences from example 1 in the overall preparation procedure are as follows:
the film-like liquid flow enters the coagulating bath without passing through an air layer; the temperature of the coagulation bath was 63 ℃, and the composition of the coagulation bath was dimethylformamide and water in a mass ratio of 6: 4.
The other steps were in accordance with example 1.
Example 9
In this example, a nascent thin film, a polyacrylonitrile thin film and a polyacrylonitrile-based carbon thin film are prepared; the differences from example 1 in the overall preparation procedure are as follows:
the film-like liquid flow enters the coagulating bath without passing through an air layer; the temperature of the coagulation bath is 70 ℃, and the composition of the coagulation bath is dimethyl sulfoxide and water in a mass ratio of 8: 2.
The other steps were in accordance with example 1.
Example 10
In this example, a nascent thin film, a polyacrylonitrile thin film and a polyacrylonitrile-based carbon thin film are prepared; the differences from example 1 in the overall preparation procedure are as follows:
the temperature of the coagulation bath was-50 ℃ and the components of the coagulation bath were methanol.
The other steps were in accordance with example 1.
Example 11
In this example, a nascent thin film, a polyacrylonitrile thin film and a polyacrylonitrile-based carbon thin film are prepared; the differences from example 1 in the overall preparation procedure are as follows:
the temperature of the coagulation bath is-10 ℃, and the composition of the coagulation bath is dimethyl sulfoxide with the mass ratio of 5:4: 1: water: methanol.
The other steps were in accordance with example 1.
Example 12
In this example, a nascent thin film, a polyacrylonitrile thin film and a polyacrylonitrile-based carbon thin film are prepared; the differences from example 1 in the overall preparation procedure are as follows:
the temperature of the coagulation bath is 60 ℃, and the composition of the coagulation bath is dimethyl sulfoxide and water in a mass ratio of 3: 7.
The other steps were in accordance with example 1.
Comparative example 1
Comparative example 1 a nascent fiber, polyacrylonitrile fiber and polyacrylonitrile-based carbon fiber were prepared; the differences from example 1 in the overall preparation procedure are as follows:
carbon fibers were obtained by spinning with a 6K spinneret having a spinneret orifice diameter of 150 μm in the same manner as in example 1.
The other steps were identical to those of example 1.
Comparative example 2
Comparative example 2 a nascent fiber, polyacrylonitrile fiber and polyacrylonitrile-based carbon fiber were prepared; the differences from example 2 in the overall preparation procedure are as follows:
carbon fibers were obtained by spinning with a 3K spinneret having a spinneret hole diameter of 200 μm in the same manner as in example 1.
The other steps were identical to those of example 2.
Comparative example 3
Comparative example 3 a virgin fiber, a polyacrylonitrile fiber and a polyacrylonitrile-based carbon fiber were prepared; the differences from example 3 in the overall preparation procedure are as follows:
carbon fibers were obtained by spinning with a 1K spinneret having a spinneret orifice diameter of 200 μm in the same manner as in example 1.
The other steps were identical to those of example 3.
Comparative example 4
Comparative example 4 a primary fiber, a polyacrylonitrile fiber and a polyacrylonitrile-based carbon fiber were prepared; the differences from example 7 in the overall preparation procedure are as follows:
carbon fibers were obtained by spinning with a 6K spinneret having a spinneret hole diameter of 55 μm in the same manner as in example 1.
The other steps were identical to those of example 7.
Comparative example 5
Comparative example 5 a virgin fiber, a polyacrylonitrile fiber and a polyacrylonitrile-based carbon fiber were prepared; the differences from example 8 in the overall preparation procedure are as follows:
carbon fibers were obtained by spinning with a 3K spinneret having a spinneret hole diameter of 65 μm in the same manner as in example 1.
The other steps are identical to those of example 8.
Comparative example 6
Comparative example 6 a virgin fiber, a polyacrylonitrile fiber and a polyacrylonitrile-based carbon fiber were prepared; the differences from example 9 in the overall preparation procedure are as follows:
carbon fibers were obtained by spinning with a 1K spinneret having a spinneret orifice diameter of 70 μm in the same manner as in example 1.
The other steps were identical to those of example 9.
The process parameters of examples 1 to 12 and comparative examples 1 to 6, the structures of the prepared products, and the characterization results of the performance parameters are shown in Table 1.
Table 1 shows the process parameters of examples 1 to 12 and comparative examples 1 to 6, and the structural properties of the products obtained
As can be seen from table 1, fig. 1 and fig. 2, compared with the polyacrylonitrile-based carbon fiber with a circular cross section, the polyacrylonitrile-based film prepared in the embodiment of the present invention as the reinforcing phase can significantly improve the proportion (up to 90%) of the reinforcing phase in the composite material, and the reinforcing phase can be uniformly distributed in the composite material.
In addition, the film uniformity parameters for the products prepared as described in examples 1-12 are shown in Table 2.
Table 2 is a table of structural performance parameters for films prepared in examples 1-12
As is apparent from table 2, the nascent thin film, polyacrylonitrile thin film, and polyacrylonitrile-based carbon thin film prepared in the embodiment of the present invention have good structural uniformity.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.
Claims (20)
1. A polyacrylonitrile-based carbon film, wherein the cross-sectional shape of the polyacrylonitrile-based carbon film is substantially rectangular; the ratio of the cross section width to the cross section thickness of the polyacrylonitrile film is more than 50; wherein the thickness of the polyacrylonitrile-based carbon film is 0.5-150 μm; the longitudinal tensile strength of the polyacrylonitrile-based carbon film is 2.2-4.5 Gpa;
wherein the polyacrylonitrile-based carbon film is made of polyacrylonitrile film;
the cross section of the polyacrylonitrile film is approximately rectangular; the ratio of the cross section width to the cross section thickness of the polyacrylonitrile film is more than 50; wherein the deviation between the average pore diameter at the surface structure and the average pore diameter at the core structure of the polyacrylonitrile film is within 10%;
the surface structure is positioned at the position on the cross section of the film, wherein the shortest distance between the surface structure and the outer contour of the film does not exceed 1/5 of the thickness of the cross section; the core layer structure is positioned at the position on the cross section of the film, wherein the shortest distance between the center of gravity of the cross section does not exceed 1/5 of the thickness of the cross section;
wherein the polyacrylonitrile film is made of a primary film prepared by the preparation method of the primary film;
the primary film is obtained by forming a polyacrylonitrile solution into a film-shaped liquid flow and then carrying out forming treatment on the film-shaped liquid flow;
wherein the cross-sectional shape of the nascent film is substantially rectangular; the ratio of the cross-sectional width to the cross-sectional thickness of the nascent film is greater than 50;
wherein the light transmittance of the primary film is greater than or equal to 60%;
the preparation method of the primary film comprises the following steps:
1) preparing a polyacrylonitrile solution;
2) forming the polyacrylonitrile solution into a film-shaped liquid flow;
3) performing shaping treatment on the film-shaped liquid flow to obtain a primary film;
wherein the film-like liquid flow is subjected to a forming treatment of a coagulating bath to obtain a primary film; wherein the coagulating bath comprises the following components in a mass ratio of 1: 0-4: 6, non-solvent and solvent; the temperature of the coagulating bath is-50 ℃ to 1 ℃; the residence time of the film-like liquid flow in the coagulation bath is 2 to 150 s.
2. The polyacrylonitrile-based carbon film according to claim 1, wherein the deviation between the average pore diameter at the surface layer structure and the average pore diameter at the core layer structure of the nascent film is within 10%.
3. The polyacrylonitrile-based carbon film according to claim 1,
the polyacrylonitrile in the polyacrylonitrile solution comprises one or a mixture of two of polyacrylonitrile homopolymer and polyacrylonitrile copolymer; and/or
The polyacrylonitrile solution is formed into a film-shaped liquid flow by adopting an extrusion method or a casting method.
4. The polyacrylonitrile-based carbon film according to claim 1,
the mass ratio of the non-solvent to the solvent is 9: 1-4: 6.
5. the polyacrylonitrile-based carbon film according to claim 1,
the non-solvent in the coagulating bath is one or a mixture of more of formic acid, glycerol, ethylene glycol, acetic acid, ethanol, methanol, chloroform, isobutanol, isoamyl alcohol, butanediol, benzyl alcohol, carbon tetrachloride, toluene, acetone, water and dioxane; and/or
The solvent in the coagulating bath is a solvent capable of dissolving polyacrylonitrile, and the solvent is any one or a mixture of several of dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, a lithium chloride solution, an ionic liquid, a sodium thiocyanate solution and a zinc chloride solution.
6. The polyacrylonitrile-based carbon film according to claim 1, wherein the step 2) is specifically: extruding the polyacrylonitrile solution into a film-shaped liquid flow by adopting an extrusion die;
wherein the extrusion orifice of the extrusion die is substantially any one of a rectangle, a slit shape and a dog bone-like shape.
7. The polyacrylonitrile-based carbon film according to claim 6,
the average width of an extrusion orifice of the extrusion die is 1-300 mu m.
8. The polyacrylonitrile-based carbon film according to claim 1, characterized in that the thickness of the polyacrylonitrile film is less than 1 mm.
9. The polyacrylonitrile-based carbon film according to any one of claims 1 to 8, characterized in that the preparation method of the polyacrylonitrile film comprises the following steps:
and (3) post-treatment: and carrying out post-treatment on the nascent film to obtain the polyacrylonitrile film.
10. The polyacrylonitrile-based carbon film according to claim 9,
and the post-treatment comprises the steps of washing, drafting, oiling and drying the nascent film to obtain the polyacrylonitrile film.
11. The polyacrylonitrile-based carbon film according to claim 10,
and the post-treatment comprises the steps of washing the nascent film, water bath drafting, drying heat treatment, water vapor drafting and oiling treatment to obtain the polyacrylonitrile film.
12. The polyacrylonitrile-based carbon film according to claim 1, wherein the thickness of the polyacrylonitrile-based carbon film is 1-10 μm.
13. The polyacrylonitrile-based carbon film according to claim 12, wherein the thickness of the polyacrylonitrile-based carbon film is 3 to 8 μm.
14. The polyacrylonitrile-based carbon film according to claim 12, wherein the width of the polyacrylonitrile-based carbon film is 1-10 m.
15. The polyacrylonitrile-based carbon film according to claim 12, characterized in that the width of the polyacrylonitrile-based carbon film is 25 μm to 1 m.
16. The polyacrylonitrile-based carbon film according to claim 15, wherein the width of the polyacrylonitrile-based carbon film is 1mm to 20 cm.
17. The polyacrylonitrile-based carbon film according to claim 15, wherein the width of the polyacrylonitrile-based carbon film is 5mm to 100 mm.
18. The polyacrylonitrile-based carbon film according to claim 12,
the deviation between the average pore diameter at the surface layer structure and the average pore diameter at the core layer structure of the polyacrylonitrile-based carbon film is within 10%.
19. A method for preparing a polyacrylonitrile-based carbon film as claimed in any one of claims 1 to 18, characterized by comprising the steps of: and carrying out heat treatment on the polyacrylonitrile film to obtain the polyacrylonitrile-based carbon film.
20. The method of claim 19, wherein the heat treatment comprises:
pre-oxidation: pre-oxidizing the polyacrylonitrile film at 185-400 ℃ to obtain a pre-oxidized film;
low-temperature carbonization: carrying out low-temperature carbonization treatment on the pre-oxidized film at the temperature of 400-1000 ℃ to obtain a low-temperature carbonized film;
high-temperature carbonization: and carrying out high-temperature carbonization on the low-temperature carbonized film at the temperature of 1100-3000 ℃ to obtain the polyacrylonitrile-based carbon film.
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