CN100344810C - Production and apparatus for graphite carbon - Google Patents
Production and apparatus for graphite carbon Download PDFInfo
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- CN100344810C CN100344810C CNB2005100129070A CN200510012907A CN100344810C CN 100344810 C CN100344810 C CN 100344810C CN B2005100129070 A CNB2005100129070 A CN B2005100129070A CN 200510012907 A CN200510012907 A CN 200510012907A CN 100344810 C CN100344810 C CN 100344810C
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Abstract
The present invention relates to a method for producing a graphitic fiber. The method is as follows: a carbon fiber is dipped into acetone solution to remove slurry, then dried, and enters a graphitizing furnace to be graphitized by hot stretching in the protection of inactive gas after dried; the fiber graphitization temperature is from 2000 to 3500 DEG C, the dwell time of the fiber at a high temperature zone is 5 to 120 seconds, the stretching ratio of the fiber in a graphitizing process is maintained with the range of-5 to 5 percent, and the tension is displayed through a tensiometer on line. After graphitized, the fiber uses epoxy resin acetone solution of which the concentration is form 0.5 to 2.5 wt percent to starch for 10 to 180 seconds; after starched, the fiber is dried at the temperature of 150 to 350 DEG C for 1 to 5 minutes to obtain the graphitic fiber. The present invention has the advantages of reasonable technological process, high automation and low energy consumption, and is suitable for large scale industrial production.
Description
Technical field
The invention belongs to a kind of method and device of producing graphitized fibre, be specifically related to a kind of carbon fiber continuous graphitization production method and special-purpose high temperature annealing device thereof.
Technical background
Carbon fiber is fibrous raw material of wood-charcoal material, has high specific strength, high ratio modulus, high temperature resistant, anti-ablation, endurance, creep resistant, conduction, heat conduction, a series of excellent properties such as density is low and thermal coefficient of expansion is little, be the most important reinforcing material of advanced configuration composite, having a wide range of applications aspect spaceship, aerospace craft, satellite, military project and the high-grade sports goods.
Graphite fibre carries out graphitization in 2000 ℃～3000 ℃ by carbon fiber and makes under the protection of inert gas; in graphitizing process; carbon fiber can further remove the non-carbon about 5%; carbon atom carries out the arrangement of graphite-like structure simultaneously; on microcosmic, change to ordered 3 D structure by two-dimentional random graphits structure; crystalline size increases, and the degree of orientation increases, thereby the modulus of carbon fiber is improved.
At present the suitability for industrialized production of high-performance graphite fibre and the country that forms series of products are the Japan and the U.S..The first place, the output tool world of toray company (Toray) graphite fibre, kind has M and MJ series.Wherein the tensile strength of M65J type PAN base carbon fibre is that 3.63GPa, tensile modulus reach 640GPa, has represented the highest level of PAN foundation stone China ink fiber.The tensile strength of the asphaltic base graphite fibre of the P-120S of U.S. A Moke company (BPAmoco) model is that 2.2GPa, tensile modulus are up to 827GPa.Because abroad to backward in technique from this field of the blockade of China's high-tech technology and China, the highest level of China's present PAN base carbon fibre Small Scale Industry production is T-300.The high-performance graphite fibre still is in the development stage, and level has a long way to go with abroad comparing.
The key factor that influences carbon fiber and graphiteization is high-temperature service and high-temperature heat treatment technical matters.Wherein the high-temperature service graphitizing furnace is particularly crucial, and the temperature of superelevation and stable Temperature Distribution are the bases of preparation high-performance graphite fibre.Aspect the high-temperature service graphitizing furnace, divide batch (-type) and continous mode according to the difference of the mode of production; Divide directly heating and indirect according to the difference of mode of heating; Difference according to thermal source is divided into resistance furnace again, induction furnace, solar furnace and plasma technique.
At the high-temperature heat treatment technical elements, multiple factor can influence the microstructure and the mechanical property of graphite fibre, as factors such as temperature, Temperature Distribution, drawing-off, catalysis, pressure, graphitization time, neutron irradiation, precursor, clean environments.In recent years, breakthrough progress has been obtained to the research of carbon fiber and graphiteization in carburizing, magnetic field.Wherein drawing-off Technology for Heating Processing runs through in the overall process of carbon fiber production, because it not only helps improving the tensile modulus of carbon fiber, can also improve the tensile strength of carbon fiber, reason is that drawing-off can improve the degree of the aspect of crystallite in the carbon fiber along the preferred orientation of fiber axis.And HTT is high more, and this influence is obvious more.
At present, the industrial abroad carbon fiber and graphite equipment that generally adopts mostly is the high-temperature tubular electric resistance furnace for graphitization, its feature is: carbon fiber passes in the middle of graphite-pipe, add at the graphite-pipe two ends and to apply direct current, when electric current during by graphite heater, graphite heater is heated as resistance, because the resistivity of graphite-pipe is lower, so electric current is trained to several Wan An up to several thousand, cause the low-voltage and high-current heating, meanwhile form the high-temperature region in the inside of graphite-pipe.Because the heavy DC electric current is difficult to regulate, thus reach the purpose of control power usually by the coupling efficiency of the AC transformer before the adjusting rectification circuit, and then the control heating-up temperature.Carbon fiber is carried out high-temperature heat treatment and graphitization formation graphite fibre takes place in graphite-pipe under inert gas argon gas or protection of nitrogen gas.The shortcoming of this method is that power consumption is big, and the heater life-span is short, and cost is higher.Short main cause of heater graphite-pipe life-span is that in loading current, the inhomogeneities of resistance can cause the overheated of heater part to rupture until heater because the inhomogeneities of graphite-pipe resistance causes.
Summary of the invention
The purpose of this invention is to provide that a kind of energy consumption is low, the life-span is long is the production method and the special-purpose high temperature annealing device thereof of the continuous production high-performance of raw material graphitized fibre with the carbon fiber.
The present invention is that method that raw material is produced graphite fibre continuously comprises the steps: carbon fiber soaked at acetone soln and removed slurry in 1～10 minute with the carbon fiber, dries then, and bake out temperature is 150～350 ℃, and drying time is 1～5 minute; The oven dry back is under inert gas shielding atmosphere, enter graphitizing furnace and carry out hot drawing-off graphitization, the fiber graphitization temperature is 2000～3000 ℃, fiber is 5～120 seconds in the high-temperature region time of staying, fiber remains on-5～5% in the draw ratio of graphitizing process, and carries out the on-line tension demonstration by tensiometer; Fiber employing concentration is that 0.5-2.5wt% epoxy resin acetone soln carries out starching after the graphitization, and the starching time is 10～180 seconds; Fiber after the starching is dried under 150～350 ℃ of temperature, and drying time is 1～5 minute, obtains graphite fibre.
In order to finish the present invention, designed the isolated plant graphitizing furnace.This graphitizing furnace comprises body of stainless steel and graphite-pipe heater, it is characterized in that outside the graphite-pipe heater, insulating tube being arranged, the outstanding outward helical form air core coil that is placed with of insulating tube, air core coil cools off with cold water, it between body of stainless steel and the insulating tube insulation material, the body of stainless steel two ends advance silk mouthful and filament mouth employing labyrinth plate air seal set, on the plate air seal set of labyrinth the inert gas air inlet is arranged, at the middle part of graphite-pipe heater and body of stainless steel thermometer hole is arranged.
Aforesaid helical form air core coil is made of copper.
Aforesaid helical form air core coil is 5～20 circles.
The length of aforesaid graphite heater is 0.5～2 meter.
When using this graphitizing furnace, the sealing of employing argon gas, under argon gas atmosphere, carbon fiber passes in graphite-pipe, and adopting the power of power supply is 20～200KW, frequency is 2.5～400KHz, the energising after-current produces high-frequency induction magnetic field in copper coil, because the graphite-pipe conduction is heated graphite-pipe so produce induced-current (eddy current) on the tube wall of graphite-pipe, be warming up to 2000 ℃～3000 ℃, 5～120 seconds graphitization time of staying; Because argon gas meeting ionization produces plasma state, so carbon fiber can be carried out graphitization by indirect under plasma atmosphere under the high temperature.
The present invention compares with existing correlation technique has that technology is reasonable, automaticity is high, energy consumption is low and advantage such as suitable large-scale industrial production.Its special equipment graphitizing furnace adopts the eddy-current heating plasma to heat, and has temperature field and Temperature Distribution ratio and is easier to advantages such as control, heater graphite-pipe long service life, is easy to obtain to produce the required condition of different performance graphite fibre.Utilize the method heating graphite heater to 3000 ℃ only to need half an hour, only need 30KW/h 3000 ℃ of following constant temperature work power consumptions, 2800 ℃ of following heater working lives were greater than 6 months.Utilize the graphite fibre stability of this explained hereafter high, coefficient of dispersion is less than 5%.
Description of drawings
Fig. 1 is a carbon fiber continuous graphitizing furnace structural representation of the present invention.
As shown in the figure, the 1st, carbon fiber, the 2nd, graphite heater, the 3rd, stainless steel body of heater, the 4th, induction coil, the 5th, power supply, the 6th, thermometer hole, the 7th, insulating tube, the 8th, insulation material, the 9th, inert gas air inlet, the 10th, labyrinth plate air seal set.
The outstanding copper helical form air core coil 4 that is placed with outside insulating tube 7, air core coil 4 usefulness cold water cool off, be insulation material 8 between body of stainless steel 3 and the graphite-pipe heater 2, advance silk mouthful and filament mouth employing labyrinth plate air seal set 10 at body of stainless steel 3 two ends, on the labyrinth plate air seal set 1 inert gas air inlet 9 is arranged, thermometer hole 6 is arranged at the middle part of insulating tube 7 and body of stainless steel 3.
The specific embodiment
Carbon fiber with the 3K silk is a raw material, the time of staying of carbon fiber in acetone soln is 3 minutes, dried 3 minutes through 200 ℃, carry out the high temperature graphitization stove then and carry out graphitization, argon gas enters from inert gas air inlet 9, carbon fiber passes in graphite-pipe 2, adopting the power of power supply is 200KW, and frequency is 20KHz; Graphite furnace temperature is 2400 ℃, and 20 seconds time of staying, the draw ratio of fiber is-1%; Fiber employing concentration is that 2wt% epoxy resin acetone soln carries out starching after the graphitization, and the starching time is 80 seconds; Fiber after the starching was dried 3 minutes under 200 ℃ of temperature, obtained graphite fibre.The performance of graphite fibre sees Table 1.
Embodiment 2
Carbon fiber with the 3K silk is a raw material, the time of staying of carbon fiber in acetone soln be 10 minutes, through 250 ℃ the oven dry 5 minutes, carry out the high temperature graphitization stove then and carry out graphitization, argon gas enters from inert gas air inlet 9, carbon fiber passes in graphite-pipe 2; Adopting the power of power supply is 100KW, and frequency is 5KHz, and graphite furnace temperature is 2600 ℃, and 50 seconds time of staying, the draw ratio of fiber is 1%; Fiber employing concentration is that 0.5wt% epoxy resin acetone soln carries out starching after the graphitization, and the starching time is 60 seconds; Fiber after the starching was dried 5 minutes under 250 ℃ of temperature, obtained graphite fibre.The performance of graphite fibre sees Table 1.
Embodiment 3
Carbon fiber with the 3K silk is a raw material, the time of staying of carbon fiber in acetone soln be 6 minutes, through 300 ℃ the oven dry 1 minute, carry out the high temperature graphitization stove then and carry out graphitization, argon gas enters from inert gas air inlet 9, carbon fiber passes in graphite-pipe 2; Adopting the power of power supply is 100KW, and frequency is 10KHz, and graphite furnace temperature is 2800 ℃, and 80 seconds time of staying, the draw ratio of fiber is 1%; Fiber employing concentration is that 1wt% epoxy resin acetone soln carries out starching after the graphitization, and the starching time is 70 seconds; Fiber after the starching was dried 1 minute under 300 ℃ of temperature, obtained graphite fibre.The performance of graphite fibre sees Table 1.
Embodiment 4
Carbon fiber with the 3K silk is a raw material, the time of staying of carbon fiber in acetone soln be 6 minutes, through 150 ℃ the oven dry 4 minutes, carry out the high temperature graphitization stove then and carry out graphitization, argon gas enters from inert gas air inlet 9, carbon fiber passes in graphite-pipe 2; Adopting the power of power supply is 200KW, and frequency is 10KHz, and graphite furnace temperature is 3000 ℃, and 80 seconds time of staying, the draw ratio of fiber is 3%; Fiber employing concentration is that 1wt% epoxy resin acetone soln carries out starching after the graphitization, and the starching time is 10 seconds; Fiber after the starching was dried 4 minutes under 150 ℃ of temperature, obtained graphite fibre.The performance of graphite fibre sees Table 1.
Embodiment 5
Carbon fiber with the 3K silk is a raw material, the time of staying of carbon fiber in acetone soln be 1 minute, through 320 ℃ the oven dry 2 minutes, carry out the high temperature graphitization stove then and carry out graphitization, argon gas enters from inert gas air inlet 9, carbon fiber passes in graphite-pipe 2; Adopting the power of power supply is 80KW, and frequency is 300KHz, and graphite furnace temperature is 2800 ℃, and 100 seconds time of staying, the draw ratio of fiber is 5%; Fiber employing concentration is that 2wt% epoxy resin acetone soln carries out starching after the graphitization, and the starching time is 20 seconds; Fiber after the starching was dried 2 minutes under 320 ℃ of temperature, obtained graphite fibre.The performance of graphite fibre sees Table 1.
The performance of graphite fibre under the different embodiment of table 1
| Heat treatment temperature (℃) | TENSILE STRENGTH (Gpa) | Stretch modulus (Gpa) | Elongation (%) | Line density (g/1000m) | Volume density (g/cm 3) |
| | 2.78 | 380 | 0.7 | 182.2 | 1.78 |
| Embodiment 2 | 2.53 | 402 | 0.6 | 182.0 | 1.83 |
| Embodiment 3 | 2.39 | 420 | 0.6 | 181.2 | 1.86 |
| Embodiment 4 | 2.30 | 446 | 0.5 | 179.5 | 1.89 |
| Embodiment 5 | 2.46 | 487 | 0.5 | 177.5 | 1.89 |
Claims (1)
1, a kind of method of producing graphitized fibre, it is characterized in that comprising the steps: with carbon fiber acetone soln soak went in 1～10 minute the slurry, dry then, bake out temperature is 150～350 ℃, drying time is 1～5 minute; The oven dry back is under inert gas shielding atmosphere, enter graphitizing furnace and carry out hot drawing-off graphitization, the fiber graphitization temperature is 2000～3000 ℃, fiber is 5～120 seconds in the high-temperature region time of staying, fiber remains on-5～5% in the draw ratio of graphitizing process, and carries out the on-line tension demonstration by tensiometer; Fiber employing concentration is that 0.5-2.5wt% epoxy resin acetone soln carries out starching after the graphitization, and the starching time is 10～180 seconds; Fiber after the starching is dried under 150～350 ℃ of temperature, and drying time is 1～5 minute, obtains graphite fibre.
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| CNB2005100129070A CN100344810C (en) | 2005-10-12 | 2005-10-12 | Production and apparatus for graphite carbon |
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| CNB2005100129070A CN100344810C (en) | 2005-10-12 | 2005-10-12 | Production and apparatus for graphite carbon |
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| CN 200610164483 Division CN100491613C (en) | 2005-10-12 | 2005-10-12 | Method and equipment for producing graphitized fiber |
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| CN100344810C true CN100344810C (en) | 2007-10-24 |
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| CN1329567C (en) * | 2005-10-12 | 2007-08-01 | 中国科学院山西煤炭化学研究所 | Continuous carbon fibre graphitizing method and apparatus |
| CN100450316C (en) * | 2006-04-14 | 2009-01-07 | 李家俊 | Modified processing method of carbon fibre electrothermal wire |
| CN102061531A (en) * | 2010-12-03 | 2011-05-18 | 西安航科等离子体科技有限公司 | Fiber pressure-retaining drawing device under pressurized steam |
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| CN1746344A (en) * | 2005-10-12 | 2006-03-15 | 中国科学院山西煤炭化学研究所 | A kind of continuous carbon fibre graphitizing method and device thereof |
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Granted publication date: 20071024 Termination date: 20131012 |