CN109056121B - Preparation method of six-branch structure carbon fiber - Google Patents
Preparation method of six-branch structure carbon fiber Download PDFInfo
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- CN109056121B CN109056121B CN201810852394.1A CN201810852394A CN109056121B CN 109056121 B CN109056121 B CN 109056121B CN 201810852394 A CN201810852394 A CN 201810852394A CN 109056121 B CN109056121 B CN 109056121B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
Abstract
The invention relates to a preparation method of six-branch structure carbon fiber, which is characterized in that a copper/amorphous carbon catalyst precursor is prepared by a hydrothermal method and subsequent heat treatment, and then the six-branch structure carbon fiber is obtained by a chemical vapor deposition method, and the preparation steps are as follows: dissolving copper chloride in polyacrylamide solution (5% by mass), adding appropriate amount of resorcinol, formaldehyde (37-40% by mass), sodium citrate and hydrochloric acid, and stirring. And transferring the solution into a polytetrafluoroethylene lining, sealing the polytetrafluoroethylene lining by using a high-pressure kettle, placing the sealed polytetrafluoroethylene lining into a drying oven at a certain temperature, preserving the heat for a certain time to obtain a copper chloride/crosslinked polyacrylamide composite product, and freeze-drying the copper chloride/crosslinked polyacrylamide composite product. And (3) carrying out heat treatment on the freeze-dried sample at 800 ℃ in a nitrogen atmosphere to obtain a catalyst precursor. The six-branch structure carbon fiber is prepared by using a catalyst precursor, hydrogen and acetylene as heat treatment gas and carbon source gas and using a chemical vapor deposition method.
Description
Technical Field
The invention relates to a preparation method of six-branch structure carbon fiber, belonging to the technical field of carbon fiber preparation.
Background
Carbon fibers are one of the allotropes of carbon element, which have excellent properties and performance in many respects, such as: physical, chemical, magnetic, mechanical, etc., which means that carbon fibers have a wide and important development prospect in many application fields, such as: aerospace, military industry, automotive industry, marine vessels, wind power generation, sports and leisure products, public infrastructure and the like. On the basis of excellent property performance of the material, the application effect of the material can be further improved by regulating and controlling the structural characteristics of the material, and the application field of the material is widened. Therefore, the carbon fiber with a novel structure is prepared by analyzing and researching the types of preparation methods and process parameter data while fully researching and knowing the excellent characteristics and properties of the carbon fiber.
The chemical vapor deposition method is an important preparation method of vapor-grown carbon fibers, and has the advantages of simple and easily-accessible operation procedure, high product repetition rate, easily-enlarged production scale and the like, so the chemical vapor deposition method is a carbon fiber production method with bright industrial industrialization prospect.
In the patent, a high molecular polymer three-dimensional structure is used for fixing the dispersion state of copper catalyst particles, so that the loss of catalytic efficiency caused by the aggregation and growth of the catalyst particles is reduced, acetylene is used as a carbon source gas, a six-branch structure carbon fiber is prepared by a chemical vapor deposition method, and the branch structure of the six-branch structure carbon fiber can greatly widen the application field of the six-branch structure carbon fiber and improve the application effect of the six-branch structure carbon fiber, so that the successful preparation of the structure carbon fiber has certain theoretical and practical significance for research and exploration and practical application of the carbon fiber.
Disclosure of Invention
1. A preparation method of six-branch structure carbon fiber is characterized in that a catalyst precursor is prepared by a hydrothermal method and subsequent heat treatment, and then the carbon fiber with the six-branch structure is prepared by a chemical vapor deposition method, the whole preparation process is simple to operate, the product purity is high, and the method mainly comprises the following steps:
(1) dissolving a proper amount of copper chloride and sodium citrate in deionized water, uniformly stirring, adding a certain amount of polyacrylamide solution (5% by mass), resorcinol, formaldehyde (37-40% by mass) and hydrochloric acid (3M, molar ratio), and stirring at room temperature for 2 hours to obtain a uniform solution.
(2) And transferring the mixed solution into a polytetrafluoroethylene lining, then placing the polytetrafluoroethylene lining into an autoclave for sealing, placing the autoclave into an oven with the set temperature for heat preservation for a certain time, naturally cooling to room temperature after the reaction is finished to obtain a copper chloride/crosslinked polyacrylamide compound, and then carrying out freeze drying at the temperature of-40 ℃.
(3) And (3) placing the frozen and dried sample in a tube furnace, introducing nitrogen for 30min to replace air in the tube, wherein the flow rate is 100mL/min, heating to 800 ℃ at the heating rate of 1 ℃/min, and keeping for 2h, wherein the flow rate of the nitrogen is reduced to 50 mL/min. And after the reaction is finished, naturally cooling to room temperature, and collecting a product to obtain the catalyst precursor.
(4) Placing the porcelain boat loaded with a proper amount of catalyst precursor in a tube furnace, vacuumizing, introducing hydrogen to atmospheric pressure, heating to reaction temperature and keeping for a certain time, then removing the hydrogen in the tube, introducing acetylene gas to atmospheric pressure and keeping for a certain reaction time, naturally cooling to room temperature after the reaction is finished, and taking out the final product.
Drawings
Fig. 1 is a scanning electron micrograph of a six-branched carbon fiber. From this figure, it can be observed that six carbon fibers having a structure of six branches are centered on the catalyst particle, and six carbon fibers are simultaneously grown radially outward.
Fig. 2 is an XRD spectrum of the six-branched structure carbon fiber. From the analysis of the XRD spectrum, carbon fibers and a metallic copper catalyst (JCPDS 04-0836) can be identified. In this spectrum, no other diffraction peaks appeared.
Detailed Description
The first embodiment is as follows:
(1) 0.3g of copper chloride and 0.69g of sodium citrate are dissolved in 30mL of deionized water and stirred uniformly, 20mL of polyacrylamide solution (5% by mass), 0.3g of resorcinol, 16 μ L of formaldehyde (37% -40% by mass) and 300 μ L of hydrochloric acid (3M, molar ratio) are added, and stirring is carried out at room temperature for 2 hours to obtain a uniform solution.
(2) And transferring the uniform solution into a polytetrafluoroethylene lining, sealing the polytetrafluoroethylene lining in an autoclave, putting the autoclave into an oven heated to 130 ℃, preserving the temperature for 15h, naturally cooling to room temperature after the reaction is finished to obtain a copper chloride/crosslinked polyacrylamide compound, and then carrying out freeze drying at-40 ℃.
(3) And (3) placing the freeze-dried sample in a tube furnace, introducing nitrogen for 30min to remove air in the tube, wherein the flow rate is 100mL/min, heating to 800 ℃ at the heating rate of 1 ℃/min, and keeping for 2h, wherein the flow rate of nitrogen is 50 mL/min. After the reaction is finished, naturally cooling to room temperature, and collecting a product to obtain the catalyst precursor.
(4) Placing the ceramic boat loaded with the catalyst precursor in a tube furnace, vacuumizing, introducing hydrogen to atmospheric pressure, heating to 270 ℃, keeping for 10min, then removing the hydrogen, introducing acetylene gas to atmospheric pressure, keeping for 20min, naturally cooling to room temperature after the reaction is finished, and taking out the final target product.
The second embodiment is as follows:
(1) 0.3g of copper chloride and 0.69g of sodium citrate are dissolved in 30mL of deionized water and stirred uniformly, 20mL of polyacrylamide solution (5% by mass), 0.3g of resorcinol, 16 μ L of formaldehyde (37% -40% by mass) and 300 μ L of hydrochloric acid (3M, molar ratio) are added, and stirring is carried out at room temperature for 2 hours to obtain a uniform solution.
(2) And transferring the uniform solution into a polytetrafluoroethylene lining, sealing the polytetrafluoroethylene lining in an autoclave, putting the autoclave into an oven heated to 130 ℃, preserving the temperature for 18h, naturally cooling to room temperature after the reaction is finished to obtain a copper chloride/crosslinked polyacrylamide compound, and then carrying out freeze drying at the temperature of-40 ℃.
(3) And (3) placing the freeze-dried sample in a tube furnace, introducing nitrogen for 30min to remove air in the tube, wherein the flow rate is 100mL/min, heating to 800 ℃ at the heating rate of 1 ℃/min, and keeping for 2h, wherein the flow rate of nitrogen is 50 mL/min. After the reaction is finished, naturally cooling to room temperature, and collecting a product to obtain the catalyst precursor.
(4) Placing the ceramic boat loaded with the catalyst precursor in a tube furnace, vacuumizing, introducing hydrogen to atmospheric pressure, heating to 290 ℃, keeping for 10min, then removing the hydrogen, introducing acetylene gas to atmospheric pressure, keeping for 15min, naturally cooling to room temperature after the reaction is finished, and taking out the final target product.
The third concrete implementation mode:
(1) 0.3g of copper chloride and 0.69g of sodium citrate are dissolved in 30mL of deionized water and stirred uniformly, 20mL of polyacrylamide solution (5% by mass), 0.3g of resorcinol, 16 μ L of formaldehyde (37% -40% by mass) and 300 μ L of hydrochloric acid (3M, molar ratio) are added, and stirring is carried out at room temperature for 2 hours to obtain a uniform solution.
(2) And transferring the uniform solution into a polytetrafluoroethylene lining, sealing the polytetrafluoroethylene lining in an autoclave, putting the autoclave into an oven heated to 130 ℃, preserving the temperature for 15h, naturally cooling to room temperature after the reaction is finished to obtain a copper chloride/crosslinked polyacrylamide compound, and then carrying out freeze drying at-40 ℃.
(3) And (3) placing the freeze-dried sample in a tube furnace, introducing nitrogen for 30min to remove air in the tube, wherein the flow rate is 100mL/min, heating to 800 ℃ at the heating rate of 1 ℃/min, and keeping for 2h, wherein the flow rate of nitrogen is 50 mL/min. After the reaction is finished, naturally cooling to room temperature, and collecting a product to obtain the catalyst precursor.
(4) Placing the ceramic boat loaded with the catalyst precursor in a tube furnace, vacuumizing, introducing hydrogen to atmospheric pressure, heating to 290 ℃, keeping for 15min, then removing the hydrogen, introducing acetylene gas to atmospheric pressure, keeping for 15min, naturally cooling to room temperature after the reaction is finished, and taking out the final target product.
The fourth concrete implementation mode:
(1) 0.3g of copper chloride and 0.75g of sodium citrate are dissolved in 40mL of deionized water and stirred uniformly, then 24mL of polyacrylamide solution (5% by mass), 0.4g of resorcinol, 18 μ L of formaldehyde (37% -40% by mass) and 350 μ L of hydrochloric acid (3M, molar ratio) are added, and stirred at room temperature for 2 hours to obtain a uniform solution.
(2) And transferring the uniform solution into a polytetrafluoroethylene lining, sealing the polytetrafluoroethylene lining in an autoclave, putting the autoclave into an oven heated to 150 ℃, preserving the temperature for 18h, naturally cooling to room temperature after the reaction is finished to obtain a copper chloride/crosslinked polyacrylamide compound, and then carrying out freeze drying at the temperature of-40 ℃.
(3) And (3) placing the freeze-dried sample in a tube furnace, introducing nitrogen for 30min to remove air in the tube, wherein the flow rate is 100mL/min, heating to 800 ℃ at the heating rate of 1 ℃/min, and keeping for 2h, wherein the flow rate of nitrogen is 50 mL/min. After the reaction is finished, naturally cooling to room temperature, and collecting a product to obtain the catalyst precursor.
(4) Placing the ceramic boat loaded with the catalyst precursor in a tube furnace, vacuumizing, introducing hydrogen to atmospheric pressure, heating to 270 ℃, keeping for 10min, then removing the hydrogen, introducing acetylene gas to atmospheric pressure, keeping for 20min, naturally cooling to room temperature after the reaction is finished, and taking out the final target product.
The fifth concrete implementation mode:
(1) 0.3g of copper chloride and 0.75g of sodium citrate are dissolved in 40mL of deionized water and stirred uniformly, then 24mL of polyacrylamide solution (5% by mass), 0.4g of resorcinol, 18 μ L of formaldehyde (37% -40% by mass) and 350 μ L of hydrochloric acid (3M, molar ratio) are added, and stirred at room temperature for 2 hours to obtain a uniform solution.
(2) And transferring the uniform solution into a polytetrafluoroethylene lining, sealing the polytetrafluoroethylene lining in an autoclave, putting the autoclave into an oven heated to 150 ℃, preserving the temperature for 18h, naturally cooling to room temperature after the reaction is finished to obtain a copper chloride/crosslinked polyacrylamide compound, and then carrying out freeze drying at the temperature of-40 ℃.
(3) And (3) placing the freeze-dried sample in a tube furnace, introducing nitrogen for 30min to remove air in the tube, wherein the flow rate is 100mL/min, heating to 800 ℃ at the heating rate of 1 ℃/min, and keeping for 2h, wherein the flow rate of nitrogen is 50 mL/min. After the reaction is finished, naturally cooling to room temperature, and collecting a product to obtain the catalyst precursor.
(4) Placing the ceramic boat loaded with the catalyst precursor in a tube furnace, vacuumizing, introducing hydrogen to atmospheric pressure, heating to 270 ℃, keeping for 10min, then removing the hydrogen, introducing acetylene gas to atmospheric pressure, keeping for 30min, naturally cooling to room temperature after the reaction is finished, and taking out the final target product.
The sixth specific implementation mode:
(1) 0.3g of copper chloride and 0.75g of sodium citrate are dissolved in 40mL of deionized water and stirred uniformly, then 24mL of polyacrylamide solution (5% by mass), 0.4g of resorcinol, 18 μ L of formaldehyde (37% -40% by mass) and 350 μ L of hydrochloric acid (3M, molar ratio) are added, and stirred at room temperature for 2 hours to obtain a uniform solution.
(2) And transferring the uniform solution into a polytetrafluoroethylene lining, sealing the polytetrafluoroethylene lining in an autoclave, putting the autoclave into an oven heated to 150 ℃, preserving the temperature for 18h, naturally cooling to room temperature after the reaction is finished to obtain a copper chloride/crosslinked polyacrylamide compound, and then carrying out freeze drying at the temperature of-40 ℃.
(3) And (3) placing the freeze-dried sample in a tube furnace, introducing nitrogen for 30min to remove air in the tube, wherein the flow rate is 100mL/min, heating to 800 ℃ at the heating rate of 1 ℃/min, and keeping for 2h, wherein the flow rate of nitrogen is 50 mL/min. After the reaction is finished, naturally cooling to room temperature, and collecting a product to obtain the catalyst precursor.
(4) Placing the ceramic boat loaded with the catalyst precursor in a tube furnace, vacuumizing, introducing hydrogen to atmospheric pressure, heating to 300 ℃, keeping for 15min, then removing the hydrogen, introducing acetylene gas to atmospheric pressure, keeping for 30min, naturally cooling to room temperature after the reaction is finished, and taking out the final target product.
The seventh embodiment:
(1) 0.3g of copper chloride and 0.75g of sodium citrate are dissolved in 40mL of deionized water and stirred uniformly, then 24mL of polyacrylamide solution (5% by mass), 0.4g of resorcinol, 18 μ L of formaldehyde (37% -40% by mass) and 350 μ L of hydrochloric acid (3M, molar ratio) are added, and stirred at room temperature for 2 hours to obtain a uniform solution.
(2) And transferring the uniform solution into a polytetrafluoroethylene lining, sealing the polytetrafluoroethylene lining in an autoclave, putting the autoclave into an oven heated to 150 ℃, preserving the temperature for 15h, naturally cooling to room temperature after the reaction is finished to obtain a copper chloride/crosslinked polyacrylamide compound, and then carrying out freeze drying at-40 ℃.
(3) And (3) placing the freeze-dried sample in a tube furnace, introducing nitrogen for 30min to remove air in the tube, wherein the flow rate is 100mL/min, heating to 800 ℃ at the heating rate of 1 ℃/min, and keeping for 2h, wherein the flow rate of nitrogen is 50 mL/min. After the reaction is finished, naturally cooling to room temperature, and collecting a product to obtain the catalyst precursor.
(4) Placing the ceramic boat loaded with the catalyst precursor in a tube furnace, vacuumizing, introducing hydrogen to atmospheric pressure, heating to 270 ℃, keeping for 15min, then removing the hydrogen, introducing acetylene gas to atmospheric pressure, keeping for 30min, naturally cooling to room temperature after the reaction is finished, and taking out the final target product.
The specific implementation mode is eight:
(1) 0.3g of copper chloride and 0.75g of sodium citrate are dissolved in 40mL of deionized water and stirred uniformly, then 24mL of polyacrylamide solution (5% by mass), 0.4g of resorcinol, 18 μ L of formaldehyde (37% -40% by mass) and 350 μ L of hydrochloric acid (3M, molar ratio) are added, and stirred at room temperature for 2 hours to obtain a uniform solution.
(2) And transferring the uniform solution into a polytetrafluoroethylene lining, sealing the polytetrafluoroethylene lining in an autoclave, putting the autoclave into an oven heated to 150 ℃, preserving the temperature for 15h, naturally cooling to room temperature after the reaction is finished to obtain a copper chloride/crosslinked polyacrylamide compound, and then carrying out freeze drying at-40 ℃.
(3) And (3) placing the freeze-dried sample in a tube furnace, introducing nitrogen for 30min to remove air in the tube, wherein the flow rate is 100mL/min, heating to 800 ℃ at the heating rate of 1 ℃/min, and keeping for 2h, wherein the flow rate of nitrogen is 50 mL/min. After the reaction is finished, naturally cooling to room temperature, and collecting a product to obtain the catalyst precursor.
(4) Placing the ceramic boat loaded with the catalyst precursor in a tube furnace, vacuumizing, introducing hydrogen to atmospheric pressure, heating to 320 ℃, keeping for 15min, then removing the hydrogen, introducing acetylene gas to atmospheric pressure, keeping for 20min, naturally cooling to room temperature after the reaction is finished, and taking out the final target product.
Claims (1)
1. A preparation method of six-branch structure carbon fiber is characterized in that a catalyst precursor is prepared by a hydrothermal method and subsequent heat treatment, and then the six-branch structure carbon fiber is prepared by a chemical vapor deposition method, and the preparation method mainly comprises the following steps:
(1) dissolving a proper amount of copper chloride and sodium citrate in deionized water, uniformly stirring, adding a certain amount of 5% polyacrylamide solution, resorcinol, 37-40% formaldehyde and 3M hydrochloric acid, and stirring at room temperature for 2 hours to obtain a uniform solution;
(2) transferring the uniform solution into a polytetrafluoroethylene lining, sealing the polytetrafluoroethylene lining in a high-pressure kettle, placing the high-pressure kettle into a drying oven heated to a set temperature, preserving the temperature for a certain time, naturally cooling to room temperature after the reaction is finished to obtain a copper chloride/crosslinked polyacrylamide compound, and then carrying out freeze drying on the copper chloride/crosslinked polyacrylamide compound at the temperature of-40 ℃;
(3) placing the freeze-dried sample in a tube furnace, introducing nitrogen for 30min to remove air in the tube, wherein the flow rate is 100mL/min, heating to 800 ℃ at the heating rate of 1 ℃/min, keeping the temperature for 2h, and the flow rate of nitrogen is 50mL/min, naturally cooling to room temperature after the reaction is finished, and collecting a product to obtain a catalyst precursor;
(4) placing the ceramic boat loaded with the catalyst precursor in a tubular furnace, vacuumizing, introducing hydrogen to atmospheric pressure, heating to a certain temperature, keeping for a certain time, then removing the hydrogen, introducing acetylene gas to atmospheric pressure, keeping for a certain reaction time, naturally cooling to room temperature after the reaction is finished, and taking out the final target product;
the total dosage of the deionized water in the step (1) is 25 mL-50 mL;
the using amount of the copper chloride in the step (1) is 0.25 g-0.70 g;
the using amount of the sodium citrate in the step (1) is 0.48g to 1.40 g;
the using amount of the resorcinol in the step (1) is 0.22 g-0.62 g;
the dosage of the polyacrylamide solution with the mass ratio concentration of 5% in the step (1) is 15 mL-35 mL;
the dosage of the formaldehyde solution with the mass ratio concentration of 37-40% in the step (1) is 11-32 muL;
the dosage of hydrochloric acid with the molar ratio concentration of 3M in the step (1) is 100-350 mu L;
the set temperature of the oven in the step (2) is 110-200 ℃;
the reaction time in the step (2) is 10-24 h;
the reaction temperature in the step (4) is 260-350 ℃;
the hydrogen treatment time in the step (4) is 5-20 min;
the acetylene in the step (4) is reacted for 10-40 min.
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| 具有对称结构的螺旋碳纤维和多枝状碳纤维的制备及生长机理研究;张乾;《中国博士学位论文全文数据库(电子期刊)》;20091031;B020-13 * |
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