CN110230124B - Method for oiling mesophase pitch fibers - Google Patents
Method for oiling mesophase pitch fibers Download PDFInfo
- Publication number
- CN110230124B CN110230124B CN201910422062.4A CN201910422062A CN110230124B CN 110230124 B CN110230124 B CN 110230124B CN 201910422062 A CN201910422062 A CN 201910422062A CN 110230124 B CN110230124 B CN 110230124B
- Authority
- CN
- China
- Prior art keywords
- oiling
- mesophase pitch
- solution
- nitrogen
- carbon fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011302 mesophase pitch Substances 0.000 title claims abstract description 57
- 239000000835 fiber Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 42
- 239000004917 carbon fiber Substances 0.000 claims abstract description 42
- 239000000843 powder Substances 0.000 claims abstract description 40
- 239000010426 asphalt Substances 0.000 claims abstract description 36
- 239000000084 colloidal system Substances 0.000 claims abstract description 23
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 238000004804 winding Methods 0.000 claims abstract description 16
- 238000009736 wetting Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000011295 pitch Substances 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract 4
- 239000003607 modifier Substances 0.000 claims abstract 3
- 239000002994 raw material Substances 0.000 claims abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 56
- 229910002804 graphite Inorganic materials 0.000 claims description 48
- 239000010439 graphite Substances 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 48
- 238000005868 electrolysis reaction Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- ICLYJLBTOGPLMC-KVVVOXFISA-N (z)-octadec-9-enoate;tris(2-hydroxyethyl)azanium Chemical compound OCCN(CCO)CCO.CCCCCCCC\C=C/CCCCCCCC(O)=O ICLYJLBTOGPLMC-KVVVOXFISA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- 239000002096 quantum dot Substances 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 6
- 239000000344 soap Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000005087 graphitization Methods 0.000 claims 1
- 238000003763 carbonization Methods 0.000 abstract description 7
- 238000009941 weaving Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 11
- 239000008041 oiling agent Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 5
- 229940117013 triethanolamine oleate Drugs 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
Classifications
-
- 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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
- D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
- D01F11/125—Carbon
-
- 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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
- D01F11/14—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with organic compounds, e.g. macromolecular compounds
-
- 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
- D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Fibers (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a method for oiling mesophase pitch fibers, which comprises the steps of oiling in two steps, wherein the first oiling step is surface wetting modifier modified by nitrogen-doped graphene quantum dots, and the contact length of oiling is 5-20 mm; the second step is water-soluble colloid of the intermediate phase pitch-based carbon fiber ultrafine powder, the intermediate phase pitch-based carbon fiber is used as a raw material for preparation, the second step of oiling is carried out after the first step of oiling, the contact length of the second step of oiling is 2-10cm, the temperature of the two steps of oiling is 10-40 ℃, and the oiling interval of the asphalt filaments on the two oil rollers is 5-30 cm; after oiling, the mixture is wound on a winding machine at the winding speed of 50-300 m/min. After two oiling steps, the bundling property of the mesophase pitch fiber bundle is good, the mesophase pitch fiber bundle can be fully oxidized in the subsequent oxidation process, the bundling property of the filament bundle is good after low-temperature carbonization at the temperature of 400 ℃ and 600 ℃, and the subsequent high-temperature heat treatment and weaving manufacturability of the filament bundle are improved.
Description
Technical Field
The invention designs a secondary oiling method suitable for a mesophase pitch fiber bundle.
Background
The oil agent can protect the surface of the mesophase pitch fiber from being damaged, and also has the functions of bundling, separating and antistatic property and the like, and the oil agent can be ashed and has a small amount of residues after carbonization. For mesophase pitch fiber, a small amount of oil solution residues can play a role in bundling, and carbon filaments can be directly collected on a filament tube without sizing. At present, a spinning oil agent is mainly a silicon-based oil agent with a single component, point contact between filaments is realized through silicon-containing residues, but the surface of carbon fibers is corroded in the subsequent carbonization process, so that the surface structure of the carbon fibers is inevitably damaged, and the mechanical property of the mesophase pitch-based carbon fibers is finally influenced.
Disclosure of Invention
The invention aims to provide a method for oiling mesophase pitch fibers.
The invention optimizes the bundling performance of the mesophase pitch fiber after low-temperature carbonization and reduces the surface damage of the fiber by designing two oiling processes. The first step is a surface wetting modifying oil agent modified by nitrogen-doped graphene quantum dots, firstly, the surface wetting modifying agent modified by the nitrogen-doped graphene quantum dots is prepared by a constant potential electrolysis method, the voltage is 1-5V, the electrolyte is 1-10mol/L ammonia water solution, the anode of an electrolysis system is a high-purity graphite rod, the cathode is a Pt electrode, the current intensity is 0.05-0.2mA, the electrolysis time is 1-3h, the electrolysis solution is filtered by a 10nm microporous filtering membrane to obtain filtrate, and the filtrate is washed, dried and vacuum-dried by deionized water to obtain the solid of the nitrogen-doped graphene quantum dots. The particle size of the prepared nitrogen-doped graphene quantum dot is 2-10 nm; then, 0.5-2% by mass of triethanolamine oleate soap is added to prepare an aqueous solution, the molar concentration of the nitrogen-doped graphene quantum dots in the prepared solution is 0.01-0.1mol/L, and a first oiling agent is prepared, wherein the oiling contact length is 5-20 mm. The second step is water soluble colloid of superfine mesophase pitch-based carbon fiber powder, which is prepared with mesophase pitch-based carbon fiber as material. Firstly, mechanically crushing the intermediate phase asphalt-based carbon fiber into short fibers with the length of 2-5mm, graphitizing at 2600-3000 ℃ to obtain intermediate phase asphalt-based graphite short fibers, and then continuously crushing the intermediate phase asphalt-based graphite short fibers into intermediate phase asphalt-based graphite fine powder with the diameter of 3-10 microns by using an airflow mill. And (3) carrying out oxidation treatment on the intermediate phase asphalt-based graphite fine powder, wherein the oxidizing atmosphere is steam, air, oxygen or a mixture of the steam, the air and the oxygen, and the oxidation temperature is 500-800 ℃. Carrying out oxidation treatment on the intermediate phase asphalt-based graphite fine powder, carrying out ultrasonic crushing, screening 0.1-5 mu m superfine intermediate phase asphalt-based graphite fine powder according to particle size classification, adding deionized water and sodium oleate to prepare a solution, adding ammonia water to adjust the pH value of the solution to 9-11, wherein the concentration of sodium oleate in the obtained solution is 0.1-5wt%, the concentration of graphite colloid is 1-5wt%, the stirring rate is 2000-5000 r/min, and the water bath temperature of the solution is 30-70 ℃ to obtain the water-soluble colloid of the intermediate phase asphalt-based carbon fiber superfine powder. After the first oiling, performing second oiling, wherein the contact length of the second oiling is 2-10cm, the temperature of the two oiling agents is 10-40 ℃, and the oiling interval of the asphalt filaments on the two oiling rollers is 5-30 cm; after oiling, the mixture is wound on a winding machine at the winding speed of 50-300 m/min.
According to the invention, the bundling performance of the mesophase pitch fiber after low-temperature carbonization is optimized by two oiling processes, the first process is a surface wetting modified oil agent modified by nitrogen-doped graphene quantum dots, the nitrogen-doped graphene quantum dots can be enriched at surface active point positions of the pitch fiber in the first oiling process, and become an intermediate body for connecting the mesophase pitch-based carbon fiber and the ultrafine pitch-based carbon fiber in the second oiling process, so that the oiling effect of the second process is optimized. The second step is water-soluble colloid of mesophase pitch-based carbon fiber ultrafine powder, the carbon fiber surface basically has no non-carbon element residue except a small amount of nitrogen elements after carbonization, and the carbon fibers are bundled by Van der Waals force, so that the structural damage of the fiber surface is reduced, and the subsequent high-temperature heat treatment and weaving manufacturability of the carbon fiber are improved. After two oiling steps, the intermediate phase asphalt fiber bundle has good bundling property, can be fully oxidized in the subsequent oxidation process, has good bundling property after low-temperature carbonization at the temperature of 400 ℃ and 600 ℃, has less broken filaments during fiber winding, and is favorable for secondary unwinding and fiber weaving processes.
Detailed Description
And performing two-pass oiling on the spun mesophase pitch-based carbon fiber. The first step is a surface wetting modifying oil agent modified by nitrogen-doped graphene quantum dots, firstly, the surface wetting modifying agent modified by the nitrogen-doped graphene quantum dots is prepared by a constant potential electrolysis method, the voltage is 1-5V, the electrolyte is 1-10mol/L ammonia water solution, the anode of an electrolysis system is a high-purity graphite rod, the cathode is a Pt electrode, the current intensity is 0.05-0.2mA, the electrolysis time is 1-3h, the electrolysis solution is filtered by a microporous filtering membrane to obtain filtrate, and the filtrate is washed, dried and vacuum-dried by deionized water to obtain the solid of the nitrogen-doped graphene quantum dots. The particle size of the prepared nitrogen-doped graphene quantum dot is 2-10 nm; then, 0.5% -2% triethanolamine oleate soap is added into the solution to prepare aqueous solution, the concentration of nitrogen-doped graphene quantum dots in the prepared solution is 0.01-0.1mol/L, and first oiling agent is prepared, wherein the oiling contact length is 5-20 mm. The second step is water soluble colloid of superfine mesophase pitch-based carbon fiber powder, which is prepared with mesophase pitch-based carbon fiber as material. Firstly, mechanically crushing the intermediate phase asphalt-based carbon fiber into short fibers with the length of 2-5mm, graphitizing at 2600-3000 ℃ to obtain intermediate phase asphalt-based graphite short fibers, and then continuously crushing the intermediate phase asphalt-based graphite short fibers into intermediate phase asphalt-based graphite fine powder with the diameter of 3-10 microns by using an airflow mill. And (3) carrying out oxidation treatment on the intermediate phase asphalt-based graphite fine powder, wherein the oxidizing atmosphere is steam, air, oxygen or a mixture of the steam, the air and the oxygen, and the oxidation temperature is 500-800 ℃. Carrying out oxidation treatment on the intermediate phase asphalt-based graphite fine powder, carrying out ultrasonic crushing, screening 0.1-5 mu m superfine intermediate phase asphalt-based graphite fine powder according to particle size classification, adding deionized water and sodium oleate to prepare a solution, adding ammonia water to adjust the pH value of the solution to 9-11, wherein the concentration of sodium oleate in the obtained solution is 0.1-5wt%, the concentration of graphite colloid is 1-5wt%, the stirring rate is 2000-5000 r/min, and the water bath temperature of the solution is 30-70 ℃ to obtain the water-soluble colloid of the intermediate phase asphalt-based carbon fiber superfine powder. After the first oiling, performing second oiling, wherein the contact length of the second oiling is 2-10cm, the temperature of the two oiling agents is 10-40 ℃, and the oiling interval of the asphalt filaments on the two oiling rollers is 5-30 cm; after oiling, the mixture is wound on a winding machine at the winding speed of 50-300 m/min.
Example 1: and performing two-pass oiling on the spun mesophase pitch-based carbon fiber. The first step is a surface wetting modifying oil agent modified by nitrogen-doped graphene quantum dots, firstly, the surface wetting modifying agent modified by the nitrogen-doped graphene quantum dots is prepared by a constant potential electrolysis method, the voltage is 1V, the electrolyte is 1mol/L ammonia water solution, the anode of an electrolysis system is a high-purity graphite rod, the cathode is a Pt electrode, the current intensity is 0.05mA, the electrolysis time is 1h, the electrolysis is carried out, the electrolysis solution is filtered by a 10nm microporous filtering membrane to obtain filtrate, and deionized water is washed, dried and vacuum-dried to obtain the solid of the nitrogen-doped graphene quantum dots. The particle size of the prepared nitrogen-doped graphene quantum dot is 8-10 nm; then, 0.5% triethanolamine oleate soap is added into the solution to prepare an aqueous solution, the concentration of nitrogen-doped graphene quantum dots in the prepared solution is 0.01mol/L, and a first oiling agent is prepared, wherein the oiling contact length is 5 mm. The second step is water soluble colloid of superfine mesophase pitch-based carbon fiber powder, which is prepared with mesophase pitch-based carbon fiber as material. Firstly, mechanically crushing the mesophase pitch-based carbon fiber into short filaments with the length of 2mm, graphitizing at 2600 ℃ to obtain mesophase pitch-based graphite short filaments, and then continuously crushing the mesophase pitch-based carbon fiber into 3 mesophase pitch-based graphite fine powder by using an air jet mill. And (3) carrying out oxidation treatment on the intermediate phase asphalt-based graphite fine powder, wherein the oxidizing atmosphere is water vapor, and the oxidation temperature is 500 ℃. Carrying out oxidation treatment on the intermediate phase asphalt-based graphite fine powder, carrying out ultrasonic crushing, screening superfine intermediate phase asphalt-based graphite micropowder with the particle size of 0.1 mu m in a grading manner, adding deionized water and sodium oleate to prepare a solution, adding ammonia water to adjust the pH value of the solution to 9, wherein the concentration of sodium oleate in the obtained solution is 0.1wt%, the concentration of graphite colloid is 1wt%, the stirring rate is 2000 r/min, and the water bath temperature of the solution is 30 ℃ to obtain the water-soluble colloid of the intermediate phase asphalt-based carbon fiber superfine powder. Immediately performing second oiling on the first oiling, wherein the contact length of the second oiling is 2cm, the temperature of the two oiling agents is 40 ℃, and the oiling interval of the asphalt filaments on the two oiling rollers is 30 cm; after oiling, the mixture is wound on a winding machine at the winding speed of 300 m/min.
Example 2 two coats were applied to the spun mesophase pitch-based carbon fiber. The first step is a surface wetting modified oil agent modified by nitrogen-doped graphene quantum dots. Firstly, nitrogen-doped graphene quantum dots are prepared by a constant potential electrolysis method, the voltage is 3V, the electrolyte is 5mol/L ammonia water solution, the anode of an electrolysis system is a high-purity graphite rod, the cathode is a Pt electrode, the current intensity is 0.1mA, the electrolysis time is 1.5h, after electrolysis, the anode is filtered by a 10nm microporous filtering membrane to obtain filtrate, and the filtrate is washed by deionized water, dried and dried in vacuum to obtain the solid of the nitrogen-doped graphene quantum dots. The particle size of the prepared nitrogen-doped graphene quantum dot is 4-5 nm; then, 1% triethanolamine oleate soap is added to the solution to prepare an aqueous solution, the concentration of the nitrogen-doped graphene quantum dots in the prepared solution is 0.05mol/L, and a first oiling agent is prepared, wherein the oiling contact length is 15 mm. . The second step is water soluble colloid of superfine mesophase pitch-based carbon fiber powder, which is prepared with mesophase pitch-based carbon fiber as material. Firstly, mechanically crushing the mesophase pitch-based carbon fiber into short filaments with the length of 3mm, then graphitizing at 2800 ℃ to obtain mesophase pitch-based graphite short filaments, and then continuously crushing the mesophase pitch-based graphite short filaments into mesophase pitch-based graphite fine powder with the diameter of 6 microns by utilizing an air jet mill. And (3) carrying out oxidation treatment on the intermediate phase asphalt-based graphite fine powder, wherein the oxidizing atmosphere is air, and the oxidizing temperature is 600 ℃. Carrying out oxidation treatment on the intermediate phase asphalt-based graphite fine powder, carrying out ultrasonic crushing, screening 2-micron superfine intermediate phase asphalt-based graphite fine powder according to particle size classification, adding deionized water and sodium oleate to prepare a solution, adding ammonia water to adjust the pH value of the solution to 10, wherein the concentration of sodium oleate in the obtained solution is 2wt%, the concentration of graphite colloid is 3wt%, the stirring speed is 3500 revolutions per minute, and the water bath temperature of the solution is 50 ℃ to obtain the water-soluble colloid of the intermediate phase asphalt-based carbon fiber superfine powder. Immediately performing second oiling on the first oiling, wherein the contact length of the second oiling is 6cm, the temperature of the two oiling agents is 25 ℃, and the oiling interval of the asphalt yarns on the two oiling rollers is 20 cm; after oiling, the mixture is wound on a winding machine at the winding speed of 200 m/min.
Example 3 two coats were applied to the spun mesophase pitch-based carbon fiber. The first step is a surface wetting modifying oil agent modified by nitrogen-doped graphene quantum dots, firstly, the surface wetting modifying agent modified by the nitrogen-doped graphene quantum dots is prepared by a constant potential electrolysis method, the voltage is 5V, the electrolyte is 10mol/L ammonia water solution, the anode of an electrolysis system is a high-purity graphite rod, the cathode is a Pt electrode, the current intensity is 0.2mA, the electrolysis time is 3h, the electrolysis is carried out, the electrolysis solution is filtered by a 10nm microporous filtering membrane to obtain filtrate, and deionized water is washed, dried and vacuum-dried to obtain the solid of the nitrogen-doped graphene quantum dots. The particle size of the prepared nitrogen-doped graphene quantum dot is 2-3 nm; then, 2% triethanolamine oleate soap is added into the solution to prepare an aqueous solution, the concentration of nitrogen-doped graphene quantum dots in the prepared solution is 0.1mol/L, and a first oiling agent is prepared, wherein the oiling contact length is 20 mm. The second step is water soluble colloid of superfine mesophase pitch-based carbon fiber powder, which is prepared with mesophase pitch-based carbon fiber as material. Firstly, mechanically crushing the mesophase pitch-based carbon fiber into short filaments with the length of 5mm, then graphitizing at 3000 ℃ to obtain mesophase pitch-based graphite short filaments, and then continuously crushing the mesophase pitch-based graphite short filaments into 10 mu m mesophase pitch-based graphite fine powder by using an air jet mill. And (3) carrying out oxidation treatment on the intermediate phase asphalt-based graphite fine powder, wherein the oxidizing atmosphere is oxygen, and the oxidizing temperature is 800 ℃. Carrying out oxidation treatment on the intermediate phase asphalt-based graphite fine powder, carrying out ultrasonic crushing, screening superfine intermediate phase asphalt-based graphite micro powder of 5 micrometers according to particle size classification, adding deionized water and sodium oleate to prepare a solution, adding ammonia water to adjust the pH value of the solution to 11, wherein the concentration of sodium oleate in the obtained solution is 5wt%, the concentration of graphite colloid is 5wt%, the stirring speed is 5000 r/min, and the water bath temperature of the solution is 70 ℃, so that the water-soluble colloid of the intermediate phase asphalt-based carbon fiber superfine powder is obtained. Immediately performing second oiling on the first oiling, wherein the contact length of the second oiling is 10cm, the temperature of the two oiling agents is 10 ℃, and the oiling interval of the asphalt yarns on the two oiling rollers is 5 cm; after oiling, the mixture is wound on a winding machine at the winding speed of 50 m/min.
Claims (7)
1. A method for oiling mesophase pitch fibers is characterized by comprising the following steps: oiling is carried out in two steps, wherein the first step is a surface wetting modified oil agent modified by nitrogen-doped graphene quantum dots, and the second step is a water-soluble colloid of mesophase pitch-based carbon fiber ultrafine powder; the first oiling is surface wetting modifier modified by nitrogen-doped graphene quantum dots, and the contact length of the oiling is 5-20 mm; the second step is water-soluble colloid of the intermediate phase pitch-based carbon fiber ultrafine powder, the intermediate phase pitch-based carbon fiber is used as a raw material for preparation, the second step of oiling is carried out after the first step of oiling, the contact length of the second step of oiling is 2-10cm, the temperature of the two steps of oiling is 10-40 ℃, and the oiling interval of the asphalt filaments on the two oil rollers is 5-30 cm; after oiling, winding on a winding machine at the winding speed of 50-300 m/min; the first oiling is a surface wetting modifier modified by nitrogen-doped graphene quantum dots, and the preparation process is as follows:
firstly, preparing nitrogen-doped graphene quantum dots by a constant potential electrolysis method, wherein the voltage is 1-5V, the electrolyte is 1-10mol/L ammonia water solution, the anode of an electrolysis system is a high-purity graphite rod, the cathode is a Pt electrode, the current intensity is 0.05-0.2mA, the electrolysis time is 1-3h, filtering is carried out by a 10nm microporous filtering membrane after electrolysis to obtain filtrate, the filtrate is dried, washed by deionized water and dried in vacuum to obtain a solid of the nitrogen-doped graphene quantum dots, then adding oleic acid triethanolamine soap with the mass concentration of 0.5-2% to prepare an aqueous solution, and preparing the first oil solution, wherein the concentration of the nitrogen-doped graphene quantum dots in the prepared solution is 0.01-0.1 mol/L;
the second step is water-soluble colloid of mesophase pitch-based carbon fiber ultrafine powder, and the preparation process comprises the following steps:
firstly, mechanically crushing a mesophase pitch-based carbon fiber into short fibers with the length of 2-5mm, graphitizing at 2600 DEG and 3000 ℃ to obtain mesophase pitch-based graphite short fibers, continuously crushing the mesophase pitch-based graphite fine powders into 3-10 mu m by using an airflow mill, oxidizing the mesophase pitch-based graphite fine powders, then performing ultrasonic crushing on the mesophase pitch-based graphite fine powders, classifying and screening 0.1-5 mu m superfine mesophase pitch-based graphite fine powders according to particle sizes, then adding deionized water and sodium oleate to prepare a solution, adding ammonia water to adjust the pH value of the solution to 9-11, wherein the mass concentration of sodium oleate in the solution is 0.1-5wt%, the mass concentration of graphite colloid is 1-5wt%, the stirring rate is 2000-5000 r/min, the water bath temperature of the solution is 30-70 ℃, obtaining the water-soluble colloid of the mesophase pitch-based carbon fiber ultrafine powder.
2. A method of oiling mesophase pitch fibers as defined in claim 1, wherein: the concentration of the nitrogen-doped graphene quantum dots in the prepared solution is 0.02-0.1 mol/L.
3. A method of oiling mesophase pitch fibers as defined in claim 1, wherein: the particle size of the prepared nitrogen-doped graphene quantum dot is 2-10 nm.
4. A method of oiling mesophase pitch fibers as defined in claim 1: the mass concentration of the graphite colloid is 2-5wt%, and the stirring speed is 3000 and 5000 r/min.
5. A method of oiling mesophase pitch fibers as defined in claim 1: the water bath temperature of the solution is 35-70 ℃.
6. A method of oiling mesophase pitch fibers as defined in claim 1, wherein: and (3) carrying out oxidation treatment on the mesophase pitch-based graphite fine powder in an oxidizing atmosphere of steam, air, oxygen or a mixture of the steam, the air and the oxygen.
7. A method of oiling mesophase pitch fibers as defined in claim 1, wherein: the graphitization temperature is 2700 ℃ and 3000 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910422062.4A CN110230124B (en) | 2019-05-21 | 2019-05-21 | Method for oiling mesophase pitch fibers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910422062.4A CN110230124B (en) | 2019-05-21 | 2019-05-21 | Method for oiling mesophase pitch fibers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110230124A CN110230124A (en) | 2019-09-13 |
| CN110230124B true CN110230124B (en) | 2021-08-31 |
Family
ID=67860847
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910422062.4A Active CN110230124B (en) | 2019-05-21 | 2019-05-21 | Method for oiling mesophase pitch fibers |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110230124B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103276477A (en) * | 2013-06-09 | 2013-09-04 | 东莞市比比克电子科技有限公司 | Preparation technology of intermediate phase pitch-based carbon fiber |
| CN104213253A (en) * | 2014-09-15 | 2014-12-17 | 北京化工大学常州先进材料研究院 | Preparation method of novel mesophase pitch-based composite carbon fibers |
| CN105088420A (en) * | 2015-09-14 | 2015-11-25 | 陕西天策新材料科技有限公司 | Preparation method for high-heat-conduction asphalt graphite fibers |
| CN105256409A (en) * | 2015-11-17 | 2016-01-20 | 安徽弘昌新材料有限公司 | Mesophase-pitch-based carbon fiber and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05214613A (en) * | 1991-07-18 | 1993-08-24 | Petoca:Kk | Production of mesophase pitch-based carbon fiber |
-
2019
- 2019-05-21 CN CN201910422062.4A patent/CN110230124B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103276477A (en) * | 2013-06-09 | 2013-09-04 | 东莞市比比克电子科技有限公司 | Preparation technology of intermediate phase pitch-based carbon fiber |
| CN104213253A (en) * | 2014-09-15 | 2014-12-17 | 北京化工大学常州先进材料研究院 | Preparation method of novel mesophase pitch-based composite carbon fibers |
| CN105088420A (en) * | 2015-09-14 | 2015-11-25 | 陕西天策新材料科技有限公司 | Preparation method for high-heat-conduction asphalt graphite fibers |
| CN105256409A (en) * | 2015-11-17 | 2016-01-20 | 安徽弘昌新材料有限公司 | Mesophase-pitch-based carbon fiber and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110230124A (en) | 2019-09-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10450674B2 (en) | Process for preparing a silicon-carbon nanocomposite nanofiber | |
| CN109524648B (en) | Porous carbon nanofiber flexible battery material containing nano-silicon and preparation method thereof | |
| JP2004532937A (en) | Spinning, processing, and utilizing carbon nanotube filaments, ribbons, and yarns | |
| CN112458553A (en) | High-performance carbon nano/MXene composite fiber and preparation method thereof | |
| CN110576193B (en) | Method for preparing superfine silver nanowires by using citrate as reducing agent | |
| CN105696114A (en) | Preparation method of carbon fiber material with adjustable pore diameter and porosity and carbon fiber material | |
| CN106140162B (en) | A kind of preparation method of the copper nano-particle for electrocatalytic hydrogen evolution/carbon nano-fiber hybrid material | |
| CN112265981A (en) | Method for preparing carbon nano tube by lignin nano micelle | |
| Chavez et al. | Recent developments in centrifugally spun composite fibers and their performance as anode materials for lithium-ion and sodium-ion batteries | |
| KR101631300B1 (en) | Manufacturing method of SiO2/CNFs composite and Lithium Secondary battery using of Ni-Cu catalysts | |
| CN102605468A (en) | Method for preparing nickel sulfide nano-fibers | |
| CN102817107B (en) | Preparation method for silver nano-sphere loaded LiFePO4 nano-fibers | |
| CN109585808B (en) | Silicon-based nano-fibrous material with core-shell structure, and preparation and application thereof | |
| CN110230124B (en) | Method for oiling mesophase pitch fibers | |
| CN103212422A (en) | Preparation method of carbon nanofiber composite material loaded with palladium-cobalt alloy nanometer particles and electro-catalytic oxidation method for formic acid or methyl alcohol | |
| CN109755528B (en) | Preparation method and application of manganese selenide/carbon fiber energy storage material | |
| CN104532405A (en) | Vanadium nitride (VN) porous hollow nano-fiber and preparation method thereof | |
| CN111962183B (en) | Preparation method of hollow carbon sphere fiber | |
| CN110400916A (en) | A kind of carbon fibre composite preparation method of two selenizings molybdenum nanometer sheet modification | |
| CN114551986A (en) | High-conductivity composite solid electrolyte and preparation method thereof | |
| CN110284218B (en) | Method for oiling mesophase pitch fibers | |
| CN114530573B (en) | Flexible self-supporting positive electrode for sodium ion battery and preparation method and application thereof | |
| KR101328525B1 (en) | Continuous apparatus for increasing strength of nano carbon fiber by mechano-electrospinning and method thereof | |
| CN110257957B (en) | Sodium vanadium molybdate nano fiber and preparation method thereof | |
| AU2020100844A4 (en) | A Preparation Method and Application Of Graphene Nanotubes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: Room 2202, building F1, Lugu Yuyuan, No.27 Wenxuan Road, high tech Development Zone, Changsha City, Hunan Province Patentee after: Hunan Dongying Carbon Materials Technology Co.,Ltd. Address before: Room 2202, building F1, Lugu Yuyuan, No.27 Wenxuan Road, high tech Development Zone, Changsha City, Hunan Province Patentee before: HUNAN DONGYING CARBON MATERIAL TECHNOLOGY CO.,LTD. |
|
| CP01 | Change in the name or title of a patent holder |