CN108004621B - Carbon fiber for polyamide resin matrix composite material and preparation method thereof - Google Patents
Carbon fiber for polyamide resin matrix composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a carbon fiber for a polyamide resin matrix composite material and a preparation method thereof. The invention selects the polyamide resin-based suspension sizing agent and realizes sizing by an impregnation method. Meanwhile, the carbon fiber is heated by a steam hot roller during sizing; and drying after sizing by adopting a drying mode of a vertical hot air drying box. The invention has the beneficial effects that: the preparation method is simple, the prepared carbon fiber is suitable for preparing the polyamide resin matrix composite material, and the prepared composite material has excellent process performance, high interface mechanical property and good wear resistance.
Description
Technical Field
The invention belongs to the field of carbon fiber preparation, and particularly relates to a carbon fiber for a polyamide resin matrix composite material and a preparation method thereof.
Background
With the increasing prominence of the problems of energy shortage, environmental pollution and the like in recent years, the development of lightweight technology, recycling technology and rapid forming technology of carbon fiber composite materials is accelerated, and the carbon fiber composite materials are particularly concerned in the industrial fields of automobiles, pressure tanks and the like. With this as a breakthrough, carbon fiber reinforced thermoplastic composites have been rapidly developed. The carbon fiber reinforced polyamide resin is widely concerned about excellent wear resistance, mechanical property and the like, but the composite material prepared by the prior art has a plurality of technical difficulties such as difficult resin impregnation, serious hole defects, unstable composite material performance and the like, and the reason is that on one hand, the prior processing and forming technology is not enough, and on the other hand, the prior carbon fiber is mainly developed aiming at a thermosetting epoxy resin composite material system, and most of epoxy resin or modified epoxy resin sizing agents are coated on the surface of the carbon fiber. The sizing agent is placed for too long time or can be partially or completely cured at higher drying and processing temperatures, so that fiber tows are hardened, hardened and agglomerated, and further matrix resin is difficult to impregnate, defect gaps are easy to generate, and the composite material has local mechanical defects. Particularly, carbon fibers prepared from polyamide resin-based composite materials are rare. Chinese patent (application No. 201310052755.1) provides a modified polyamide-based sizing agent prepared from polyamide, an organic solvent, a surface modifier, water, etc., and carbon fibers prepared therefrom, but because of the solvent contained therein, the safety and stability thereof are poor, and thus the sizing agent is basically eliminated in the industrial application field.
Disclosure of Invention
In order to overcome the prior art, the invention aims to provide a carbon fiber for a polyamide resin matrix composite material and a preparation method thereof. The carbon fiber prepared by the method has controllable sizing amount, can be spread to form a wide-band fiber, increases the width of a tow, reduces the difficulty of processing a subsequent intermediate product, reduces the resin consumption required by the processing of the subsequent intermediate product, and improves the processing uniformity and stability of the prepreg. The surface of the prepared carbon fiber is coated with a layer of sizing agent completely prepared from polyamide resin, does not contain epoxy resin groups, is suitable for preparing polyamide resin matrix composite materials, and the prepared composite materials have excellent process performance, high interface mechanical property and good wear resistance.
The invention adopts the production processes of polymerization, spinning, pre-oxidation, low-temperature carbonization, high-temperature carbonization, surface treatment, sizing, drying, winding and yarn winding. In order to solve the problems of poor impregnation of polyamide matrix resin, aging and hardening of fibers and the like, the invention adopts polyamide resin powder as a main body, introduces polyacrylamide dispersing agent, and simultaneously introduces fatty alcohol-polyoxyethylene ether stabilizer with long-chain oleophylic group, can effectively combine with polyamide resin and polyacrylamide, has good amphipathy, and can prepare suspension sizing agent with stable and reliable performance; in order to solve the problem of drying the fibers under the condition of high sizing amount and improve the uniformity of the polyamide resin powder spread on the surface of the carbon fibers, the invention introduces a drying process of heating by a steam hot roller in the sizing process and drying by a vertical hot air drying oven in the drying process after sizing.
The invention provides a preparation method of carbon fiber for a polyamide resin matrix composite material, which comprises the steps of polymerization, spinning, pre-oxidation, low-temperature carbonization, high-temperature carbonization, surface treatment, sizing, drying, winding and filament winding; wherein: during sizing, a polyamide resin-based suspension sizing agent is adopted by an impregnation method; the polyamide resin-based suspension sizing agent consists of polyamide resin, a dispersing agent, a stabilizing agent and deionized water; according to the total mass of the solid components of 100%, the polyamide resin accounts for 60-80%, the dispersing agent accounts for 5-15%, and the stabilizing agent accounts for 15-25%.
In the invention, low-temperature carbonization is carried out in a low-temperature carbonization furnace, the low-temperature carbonization furnace has 6 temperature regions, and the temperature is controlled to be 0-650 ℃, 0-750 ℃, 0-900 ℃ and 0-900 ℃ respectively.
In the invention, high-temperature carbonization is carried out in a high-temperature carbonization furnace, the high-temperature carbonization furnace is provided with 6 temperature zones, and the temperature is controlled to be 0-1250 ℃, 0-1350 ℃, 0-1600 ℃, 0-1800 ℃, 0-2000 ℃ and 0-2000 ℃ respectively.
In the invention, the preparation method of the polyamide resin-based suspension sizing agent comprises the following steps: the polyamide resin and the dispersing agent are uniformly mixed in deionized water, then the stabilizing agent is added, and the mixture is emulsified in a high-speed emulsifying machine at the rotating speed of 2000-10000 rpm for 10-25 min to obtain the suspension sizing agent.
In the invention, the polyamide resin has a structural general formula as shown in the following formula I:
wherein p is the degree of polymerization of the polyamide and the values of m and n may be the same or different. The number average molecular weight of the polyamide resin is 1.0 to 3.0 ten thousand, preferably 1.5 to 2.5 ten thousand. The average diameter of the polyamide powder is 20-50 micrometers, and preferably 30-40 micrometers.
In the invention, the polyamide resin is selected from one or more of polyamide 6, polyamide 11, polyamide 12, polyamide 66, polyamide 610, polyamide 612, polyamide 1010 and polyamide 1012.
In the invention, the dispersant is polyacrylamide, and the number average molecular weight is between 1.0 ten thousand and 3.0 ten thousand, preferably between 1.5 ten thousand and 2.0 ten thousand. The stabilizer is fatty alcohol-polyoxyethylene ether, and has a structural general formula shown as a formula II:
wherein R is selected from saturated aliphatic groups containing 15-20 carbon atoms; the polymerization degree n of polyoxyethylene is 20-40.
In the invention, the content of solid components in the polyamide resin-based suspension sizing agent is 5-30%; the sizing amount is controlled to be 1-20 percent during sizing.
In the invention, during sizing, the sized carbon fiber passes through the steam hot roller. The temperature control range on the surface of the steam hot roller is 0-360 ℃. When the sized fiber passes through the steam hot roller, on one hand, partial moisture is removed, and the fiber is prevented from being violently vaporized to cause insecurity when entering a subsequent high-temperature drying box; on the other hand, the polyamide powder adhered on the surface is melted and spread at high temperature, and a relatively uniform and continuous layer of polyamide resin film is formed preliminarily.
In the invention, the drying is carried out by adopting a vertical hot air drying box; the temperature control of each zone is 0-350 ℃, 0-300 ℃, 0-200 ℃ and 0-150 ℃. According to the invention, a vertical drying method is adopted, so that the polyamide resin on the surface of the carbon fiber is further melted and flowed, and is slowly leveled under the action of self weight, so that the polyamide resin film on the surface of the carbon fiber is more uniform and complete; meanwhile, the surface moisture of the fiber can be completely removed under the condition of high sizing amount.
The invention also provides the carbon fiber for the polyamide resin matrix composite material prepared by the preparation method.
In the prior art, when the emulsion type epoxy resin-based sizing agent is used for sizing carbon fibers, the softening temperature of the epoxy resin is low, so that the excessively high drying temperature cannot be adopted. Under the condition that the drying temperature and the drying time are limited, the sizing amount of the carbon fiber prepared by adopting the emulsion type epoxy resin-based sizing agent cannot be too high, otherwise, the sizing fiber is difficult to dry, the surface contains a large amount of moisture, the subsequent processing and application are influenced, and the carbon fiber is limited to be prepared into cluster fiber.
Compared with the technology for producing carbon fibers by sizing with the emulsion epoxy resin-based sizing agent, the polyamide resin-based suspension liquid sizing carbon fibers can adopt higher sizing agent concentration and higher sizing amount, and the prepared carbon fibers can be spread to form wide-band fibers after adopting the drying process of heating by the steam hot roller and drying by the vertical hot air drying oven, so that the width of tows is increased, the breadth is improved by 50-130%, and the thickness of the fibers is effectively reduced. The carbon fibers can be uniformly spread better, the difficulty of permeation and infiltration of polyamide resin into the fibers during the subsequent composite material intermediate product processing is reduced, the using amount of resin films during the prepreg processing can be reduced, the prepreg processing uniformity and stability are improved, and the production cost is reduced.
Compared with the prior art, the invention has the beneficial effects that:
(1) the carbon fiber surface for the polyamide resin matrix composite material is coated with the polyamide resin matrix carbon fiber sizing agent, does not contain epoxy resin groups, does not generate aging hardening phenomenon after long-time storage, can have good infiltration and bonding capacity with polyamide matrix resin, and has excellent process performance and wear resistance.
(2) The suspension carbon fiber sizing agent provided by the invention introduces a polyacrylamide dispersing agent, and simultaneously introduces the fatty alcohol-polyoxyethylene ether stabilizer with a long-chain oleophylic group, so that the suspension carbon fiber sizing agent can be effectively combined with polyamide resin and polyacrylamide, has good amphipathy, and the prepared sizing agent has the advantages of low cost, simple and convenient process, and safety and stability which meet the requirements of engineering processes.
(3) The invention adopts the drying process of heating by the steam hot roller during sizing and drying by the vertical hot air drying box after sizing, so that the polyamide powder adhered to the surface of the carbon fiber is melted and spread at high temperature to form a uniform and continuous polyamide resin film, and the polyamide resin powder is slowly leveled under the action of self weight, so that the carbon fiber can be quickly and uniformly spread and infiltrated by the polyamide resin powder, and the carbon fiber sizing is more uniform.
(4) The carbon fiber for the polyamide resin matrix composite material has controllable surface sizing amount, can be spread to form wide-band fibers, increases the width of tows, improves the width of the tows, reduces the thickness of the fibers, reduces the difficulty of subsequent composite material intermediate product processing, reduces the resin consumption of the subsequent composite material intermediate product processing, and improves the processing uniformity and stability.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Comparative example 1
Comparative example 1 is a manufacturing method of 3K carbon fiber, and the specific process includes the production processes of polymerization, spinning, pre-oxidation, low-temperature carbonization, high-temperature carbonization, surface treatment, sizing, drying, winding and filament winding. The specific process of comparative example 1 is the same as that of examples 1 to 4, wherein the parameters of polymerization, pre-oxidation, low-temperature carbonization, high-temperature carbonization and sizing are different.
And step 1, polymerization. The polymerization production process is the same as the method described in the step 1 of the embodiment 1 to 4, wherein the parameters changed in the polymerization production process are different in the types and the mixture ratio of the comonomers of the ternary aqueous phase polymerization reaction, the weight ratio of acrylonitrile to methyl methacrylate to itaconic acid is 95.2:3.0:1.8, the feeding concentration of the total polymerization monomers is 22 wt%, the initiator adopts sodium chlorate and sodium metabisulfite, the using amount of the sodium chlorate is 0.05 wt% based on the total amount of all the polymerization monomers, and the molar ratio of the sodium metabisulfite to the sodium chlorate is 1.4: 1. the polymerization temperature was 60 ℃ and the reaction time was 102 minutes.
And 2, spinning. The spinning production process and the method described in the step 2 of the embodiment 1-4.
And step 3, pre-oxidizing. The pre-oxidation production procedure is the same as the method described in step 3 of examples 1-4. Wherein the parameters changed in the pre-oxidation production process are that the furnace zone temperatures of the No. 1 oxidation furnace, the No. 2 oxidation furnace, the No. 3 oxidation furnace, the No. 4 oxidation furnace, the No. 5 oxidation furnace and the No. 6 oxidation furnace are 223 ℃, 232 ℃, 245 ℃, 250 ℃, 256 ℃ and 264 ℃ respectively. The draft multiple between each temperature zone of the oxidation furnace is respectively-0.2%, -1.3%, -4.2%, -0.5%.
And 4, carbonizing at low temperature. The low-temperature carbonization production procedure is the same as the method described in the step 4 of the embodiments 1 to 4. Wherein the parameters changed in the low-temperature carbonization production process are that the temperatures of the 1 st zone, the 2 nd zone, the 3 rd zone, the 4 th zone, the 5 th zone and the 6 th zone of the low-temperature carbonization furnace are respectively controlled to be 450 ℃, 520 ℃, 580 ℃, 650 ℃, 720 ℃ and 760 ℃. The draft was controlled to 3.0%.
And 5, carbonizing at high temperature. The high-temperature carbonization production procedure is the same as the method described in the step 5 of the embodiment 1-4. Wherein the parameters changed in the high-temperature carbonization production process are that the temperatures of the 1 st zone, the 2 nd zone, the 3 rd zone, the 4 th zone, the 5 th zone and the 6 th zone of the high-temperature carbonization furnace are respectively controlled to be 820 ℃, 920 ℃, 1200 ℃, 1250 ℃, 1300 ℃ and 1350 ℃. The draft ratio was controlled to-4.0%.
And 6, surface treatment. The surface treatment production procedure is the same as the method described in the step 6 of the embodiment 1-4.
And 7, sizing, drying and winding to obtain the silk. The sizing agent is bisphenol A epoxy resin based emulsion type carbon fiber sizing agent (KTM-1 type produced by Shanghai organic of Chinese academy of sciences), the concentration of the sizing agent is 3.0%, and after sizing, the carbon fiber is directly dried by horizontal circulating hot air at the drying temperature of 120 ℃ and is wound under the tension of 1000-1350 cN to prepare the 3K sized carbon fiber.
Comparative example 2
Comparative example 2 is a method for manufacturing 6K carbon fiber, which comprises the steps of polymerization, spinning, pre-oxidation, low-temperature carbonization, high-temperature carbonization, surface treatment, sizing, drying, winding and filament winding. The polymerization, pre-oxidation temperature and draft multiple of each zone, low-temperature carbonization temperature and draft multiple, high-temperature carbonization temperature and draft multiple, and specific processes and parameters of surface treatment of comparative example 2 were the same as those of comparative example 1. The total residence time of pre-oxidation, the total residence time of low-temperature carbonization and the total residence time of high-temperature carbonization are the same as those in steps 3 to 5 of examples 5 to 8. The spinning parameters of comparative example 2 were the same as in step 2 of examples 5 to 8. The sizing process of comparative example 2 was the same as comparative example 1, with different sizing parameters. The sizing agent is bisphenol F epoxy resin based emulsion type carbon fiber sizing agent (KTM-2 type produced by Shanghai organic of Chinese academy of sciences), the concentration of the sizing agent is 2.5%, and after sizing, the carbon fiber is directly dried by horizontal circulating hot air at the drying temperature of 130 ℃ and wound under the tension of 1400-1650 cN to prepare the 6K sized carbon fiber.
Examples 1 to 4
The embodiment is a manufacturing method of 3K carbon fiber suitable for polyamide resin matrix composite materials, and the manufacturing method comprises the production processes of polymerization, spinning, pre-oxidation, low-temperature carbonization, high-temperature carbonization, surface treatment, sizing, drying, winding and filament winding. The specific process is as follows:
step 1: and (4) polymerizing.
Acrylonitrile, methyl methacrylate and ammonium itaconate are used as polymerization monomers, the weight ratio of the acrylonitrile to the methyl methacrylate to the ammonium itaconate is 95.3:2.8:1.9, the feeding concentration of the total polymerization monomers is 23 wt%, an initiator ammonium persulfate is added at the same time, the initiator amount is 0.53 wt% based on the total amount of all the polymerization monomers, the polymerization temperature is 63 ℃, and the reaction time is 110 minutes. Then dissolving the obtained polymer in a concentrated sodium thiocyanate solution with the concentration of 52 wt%, stirring, mixing and dissolving, defoaming and filtering the dissolved crude stock solution to prepare the polyacrylonitrile stock solution for spinning.
Step 2: and (4) spinning.
The method adopts a sodium thiocyanate (NaSCN) wet spinning production method to prepare raw silk by carrying out solidification forming, cold drawing, water washing, hot drawing, oiling, drying, steam drawing and sizing on polyacrylonitrile stock solution. The aperture of the spinneret plate is 0.062mm, the solidification forming temperature is 0 ℃, the flow rate of the solidification bath is 1500L/h, and the concentration of the solidification bath is 14.2 percent; the draft multiple of cold draft is 1.93 times; the water washing temperature is 50 ℃, and the water washing flow is 1400L/h; the hot drawing temperature is 92 ℃, and the drawing multiple of the hot drawing is 5.2 times; the concentration of oiling oil agent is 2%; the drying temperature is 125 ℃; the steam drafting multiple is 2.0 times, and the steam pressure is 100 KPa; the setting temperature is 110 ℃.
And step 3: and (4) pre-oxidizing.
The protofilament sequentially passes through an oxidation furnace No. 1, an oxidation furnace No. 2, an oxidation furnace No. 3, an oxidation furnace No. 4, an oxidation furnace No. 5 and an oxidation furnace No. 6 to be subjected to pre-oxidation treatment. The furnace zone temperatures of the No. 1 oxidation furnace, the No. 2 oxidation furnace, the No. 3 oxidation furnace, the No. 4 oxidation furnace, the No. 5 oxidation furnace and the No. 6 oxidation furnace are 215 ℃, 226 ℃, 232 ℃, 240 ℃, 250 ℃ and 260 ℃ respectively. The draft multiple between each temperature zone of the oxidation furnace is respectively-0.1%, -1.2%, -4%, -0.5%. The residence time of each oxidation furnace is 14 minutes, and the total pre-oxidation time is 84 min.
And 4, step 4: low temperature carbonization
And the pre-oxidized fiber at the outlet of the No. 6 oxidation furnace enters a low-temperature carbonization furnace through a traction device, and is carbonized at low temperature by taking nitrogen as a medium to prepare the low-temperature carbonized fiber. The temperature of the 1 st zone, the 2 nd zone, the 3 rd zone, the 4 th zone, the 5 th zone and the 6 th zone of the low-temperature carbonization furnace is controlled to be 440 ℃, 510 ℃, 560 ℃, 630 ℃, 700 ℃ and 750 ℃ respectively. The drawing multiple is controlled to be 3.5 percent, and the total residence time in the low-temperature carbonization furnace is 1.6 min.
And 5: high temperature carbonization
And (3) the tows at the outlet of the low-temperature carbonization furnace enter the high-temperature carbonization furnace through a traction device, and are carbonized at high temperature by taking nitrogen as a medium to prepare the high-temperature carbonized filament. The temperature of the 1 st zone, the 2 nd zone, the 3 rd zone, the 4 th zone, the 5 th zone and the 6 th zone of the high-temperature carbonization furnace is controlled to be 810 ℃, 900 ℃, 1150 ℃, 1200 ℃, 1250 ℃ and 1320 ℃ respectively. The draft multiple is controlled to be-3.0 percent, and the total residence time in the high-temperature carbonization furnace is 1.6 min.
Step 6: surface treatment
And the tows at the outlet of the high-temperature carbonization furnace enter a surface treatment tank through a traction device, an ammonium bicarbonate aqueous solution is used as electrolyte, the voltage is 20V, the concentration of the electrolyte is 12%, and the retention time of the tows in the electrolyte is 3 min.
And 7: sizing, drying and winding to obtain silk
Uniformly mixing quantitative polyamide resin powder and polyacrylamide for later use; adding a certain amount of water into a reaction kettle A, starting mechanical stirring, gradually adding the mixture at a certain rotating speed, and continuously stirring for a certain time after the mixture is completely added; and transferring the aqueous mixture into a reaction kettle B through a proportioning pump, adding a certain amount of fatty alcohol-polyoxyethylene ether, starting a high-speed emulsifying machine, emulsifying at a certain rotating speed for a certain time, and preparing to obtain the suspension sizing agent. Then the sizing agent is transferred into the sizing tank through the feeding pump, and the circulating pump of the sizing tank is started to make the sizing agent slowly flow in the sizing tank.
The filament bundles at the surface treatment outlet sequentially pass through a first driving roller in the sizing tank, a sizing agent first impregnation roller in the sizing tank, a second driving roller, a second impregnation roller, a steam hot roller, a third driving roller and a pressing roller. Wherein the absolute pressure of the steam inlet of the steam hot roller is 40kgf/cm2The temperature on the surface of the steam hot roller is controlled within 250 ℃. The sized carbon fiber is dried in a vertical hot air drying oven, and the temperature of 4 temperature zones is controlled to be 330 ℃, 280 ℃, 180 ℃ and 120 ℃. And (3) feeding the carbon fiber subjected to sizing and drying into a carbon fiber winding machine, and winding under the tension of 1000-1350 cN to obtain the 3K carbon fiber suitable for the polyamide resin matrix composite.
Examples 5 to 8
The embodiment is a manufacturing method of 6K carbon fiber suitable for polyamide resin matrix composite materials, and the specific process comprises the production procedures of polymerization, spinning, pre-oxidation, low-temperature carbonization, high-temperature carbonization, surface treatment, sizing, drying, winding and filament winding. The specific process of this example is the same as the specific process of examples 1 to 4, wherein the parameters of polymerization, spinning, pre-oxidation, low-temperature carbonization, high-temperature carbonization, and sizing are different.
And step 1, polymerization. The polymerization production process is the same as the method described in the step 1 of the embodiment 1-4, wherein the parameters of the polymerization production process are different in the comonomer ratio of the ternary aqueous phase polymerization reaction, the weight ratio of acrylonitrile to methyl methacrylate to ammonium itaconate is 95.0:3.3:1.7, the feed concentration of the total polymerization monomer is 21 wt%, the amount of ammonium persulfate serving as an initiator is 0.51 wt% based on the total amount of all the polymerization monomers, the polymerization temperature is 61 ℃, and the reaction time is 100 minutes.
And 2, spinning. The spinning production procedure is the same as the method described in the step 2 of the embodiment 1-4, the solidification forming temperature is 0.5 ℃, the solidification bath flow is 2000L/h, and the solidification bath concentration is 14%; the draft multiple of cold draft is 1.9 times; the washing temperature is 52 ℃, and the washing flow rate is 1800L/h; the hot drawing temperature is 95 ℃, and the drawing multiple of the hot drawing is 5.0 times; the concentration of the oiling oil agent is 2.2 percent; the drying temperature is 130 ℃; the steam drafting multiple is 1.88 times, and the steam pressure is 105 KPa; the setting temperature is 115 ℃.
And step 3, pre-oxidizing. The pre-oxidation production procedure is the same as the method described in step 3 of examples 1-4. Wherein the parameters changed in the pre-oxidation production process are that the furnace zone temperatures of the No. 1 oxidation furnace, the No. 2 oxidation furnace, the No. 3 oxidation furnace, the No. 4 oxidation furnace, the No. 5 oxidation furnace and the No. 6 oxidation furnace are 220 ℃, 230 ℃, 240 ℃, 248 ℃, 254 ℃ and 262 ℃ respectively. The draft multiple between each temperature zone of the oxidation furnace is respectively-0.1%, -1.2%, -4%, -0.5%. The residence time of each oxidation furnace is 15 minutes, and the total pre-oxidation time is 90 minutes.
And 4, carbonizing at low temperature. The low-temperature carbonization production procedure is the same as the method described in the step 4 of the embodiments 1 to 4. Wherein the parameters changed in the low-temperature carbonization production process are that the temperatures of the 1 st zone, the 2 nd zone, the 3 rd zone, the 4 th zone, the 5 th zone and the 6 th zone of the low-temperature carbonization furnace are controlled to be 455 ℃, 530 ℃, 590 ℃, 670 ℃, 710 ℃ and 760 ℃ respectively. The draft was controlled to 3.2%. The total residence time in the low temperature carbonization furnace was 1.7 min.
And 5, carbonizing at high temperature. The high-temperature carbonization production procedure is the same as the method described in the step 5 of the embodiment 1-4. Wherein the parameters changed in the high-temperature carbonization production process are that the temperatures of the 1 st zone, the 2 nd zone, the 3 rd zone, the 4 th zone, the 5 th zone and the 6 th zone of the high-temperature carbonization furnace are respectively controlled to be 826 ℃, 930 ℃, 1250 ℃, 1280 ℃, 1320 ℃ and 1360 ℃. The draft was controlled to-3.5%. The total residence time in the high temperature carbonization furnace was 1.7 min.
And 6, surface treatment. The surface treatment production procedure is the same as the method described in the step 6 of the embodiment 1-4.
And 7, sizing, drying and winding to obtain the silk.
The preparation method, the sizing method, the drying method and the winding and reeling method of the suspension sizing agent are the same as those described in the step 7 of the embodiment 1-4. Wherein the absolute pressure introduced into the steam inlet of the steam hot roller is 48kgf/cm2Saturated steam, the temperature of the steam on the roll surface of the hot roll was 260 ℃. Vertical hot air drying oven 4 temperature zones temperature controlRespectively 320 deg.C, 275 deg.C, 175 deg.C, 120 deg.C. And controlling the winding tension to be 1400-1650 cN, and finally preparing the 6K carbon fiber suitable for the polyamide resin matrix composite material.
The solid components of the suspension sizing agents prepared in the above examples 1 to 8 are shown in table 1, the composition amount and concentration of the sizing agent are shown in table 2, the preparation process parameters of the sizing agent are shown in table 3, and the performance evaluation results of the obtained carbon fibers are shown in table 4. The invention adopts an SP10 high-temperature sizing amount tester to test the sizing amount of the sized carbon fiber; testing the width of the sizing carbon fiber by using a ruler; testing the complete infiltration time of the polyamide resin liquid drop from the beginning of contacting the carbon fiber to the complete immersion in the carbon fiber by adopting an OCA20 contact angle measuring instrument; the interfacial shear strength between polyamide resin and carbon fiber was measured by using a MODEL HM410 interfacial property evaluation apparatus, a Japan Dongrong industries Co., Ltd.
As can be seen from the test results of the 3K carbon fibers in the examples 1-4, compared with the comparative example 1 (carbon fiber sized by epoxy resin-based sizing agent), the sized carbon fiber prepared by using the suspension sizing agent has higher sizing amount, obviously increased breadth and low sizing amount dispersion coefficient, which indicates that more polyamide sizing agent is uniformly coated on the surface of the fiber and the fiber obtains sufficient spreading effect. The polyamide resin has the advantages of less wetting time of the sizing carbon fiber, better process performance, higher interface shear strength, and better wetting effect and bonding capability between the fiber and the polyamide matrix resin. The same improvement effect was obtained for 6K carbon fibers in examples 5 to 8.
TABLE 1 solid components of sizing agent
TABLE 2 sizing agent composition amounts and concentrations
TABLE 3 sizing agent preparation Process parameters
Table 4 evaluation results of carbon fiber properties
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (6)
1. A preparation method of carbon fiber for polyamide resin matrix composite is characterized in that the preparation process comprises the steps of polymerization, spinning, pre-oxidation, low-temperature carbonization, high-temperature carbonization, surface treatment, sizing, drying, winding and filament winding; wherein: during sizing, a polyamide resin-based suspension sizing agent is adopted by an impregnation method; the polyamide resin-based suspension sizing agent consists of polyamide resin, a dispersing agent, a stabilizing agent and deionized water; according to the total mass of the solid components of 100%, the polyamide resin accounts for 60-80%, the dispersant accounts for 5-15%, and the stabilizer accounts for 15-25%;
the dispersant is polyacrylamide, and the number average molecular weight is between 1.0 ten thousand and 3.0 ten thousand; the stabilizer is fatty alcohol-polyoxyethylene ether, and has a structural general formula shown as a formula II:
wherein R is selected from saturated aliphatic groups containing 15-20 carbon atoms; the polymerization degree n of the polyoxyethylene is 20-40;
the polyamide resin has a structural general formula as shown in the following formula I:
wherein p is the degree of polymerization of the polyamide, and the values of m and n can be the same or different;
in the polyamide resin-based suspension sizing agent, the content of solid components is 5-30%; the sizing amount is controlled to be 1-20% during sizing;
when the carbon fiber is subjected to a sizing procedure, introducing steam hot rollers for heating;
drying is carried out by adopting a vertical hot air drying box; the temperature control of each zone is 330-350 ℃, 280-300 ℃, 180-200 ℃ and 120-150 ℃.
2. The method according to claim 1, wherein the low-temperature carbonization is performed in a low-temperature carbonization furnace having 6 temperature zones, and the temperature is controlled to be 440 to 650 ℃, 510 to 650 ℃, 560 to 750 ℃, 630 to 900 ℃, 700 to 900 ℃ and 750 to 900 ℃.
3. The method according to claim 1, wherein the high temperature carbonization is performed in a high temperature carbonization furnace having 6 temperature zones controlled to 810 to 1250 ℃, 900 to 1350 ℃, 1150 to 1600 ℃, 1200 to 1800 ℃, 1250 to 2000 ℃ and 1320 to 2000 ℃, respectively.
4. The method of claim 1, wherein the polyamide resin based suspension sizing is prepared as follows: the polyamide resin and the dispersing agent are uniformly mixed in deionized water, then the stabilizing agent is added, and the mixture is emulsified in a high-speed emulsifying machine at the rotating speed of 2000-10000 rpm for 10-25 min to obtain the suspension sizing agent.
5. The method for preparing the polyamide resin composition according to claim 1, wherein the polyamide resin is selected from any one or more of polyamide 66, polyamide 610, polyamide 612, polyamide 1010 and polyamide 1012.
6. A carbon fiber for a polyamide resin-based composite material obtained by the production method according to any one of claims 1 to 5.
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