CN113235304B - Aqueous solution sizing agent based on polyether-ether-ketone, preparation method thereof and preparation method of carbon fiber cloth reinforced polyether-ether-ketone composite material - Google Patents
Aqueous solution sizing agent based on polyether-ether-ketone, preparation method thereof and preparation method of carbon fiber cloth reinforced polyether-ether-ketone composite material Download PDFInfo
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Abstract
An aqueous solution sizing agent based on polyether-ether-ketone, a preparation method thereof and a preparation method of a carbon fiber cloth reinforced polyether-ether-ketone composite material; the invention belongs to the field of fiber reinforced thermoplastic composite materials. The invention aims to solve the problems that the existing modified polyether-ether-ketone has poor thermal stability and can not prepare a long-term stable aqueous solution sizing agent. The sizing agent is obtained by carrying out hydroxylation treatment on polyether-ether-ketone; then carrying out esterification treatment with concentrated phosphoric acid; adding dichloromethane or chloroform, ultrasonic dispersing, mixing with the water solution of the opacifier, ultrasonic dispersing, and magnetically stirring until dichloromethane or chloroform is completely volatilized. The sizing agent can be in an opacified state for up to 30 days.
Description
Technical Field
The invention belongs to the field of fiber reinforced thermoplastic composite materials; in particular to a water solution sizing agent based on polyether-ether-ketone, a preparation method thereof and a preparation method of a carbon fiber cloth reinforced polyether-ether-ketone composite material.
Background
The fiber-reinforced thermoplastic composite material is widely applied to the field of aerospace, energy and equipment manufacturing and the like, has excellent thermal properties, chemical and physical corrosion resistance and repeatable processing characteristics, and is concerned as a lightweight structural component. Carbon fiber cloth is a typical reinforcement and plays a significant role in the manufacturing process of composite materials. As a typical thermoplastic engineering plastic, the excellent long-term high-temperature service property and thermal stability of the polyether-ether-ketone make the polyether-ether-ketone a research hotspot. Because the surface activity of the carbon fiber cloth is low, and the polyether-ether-ketone resin is in an inert structure, the viscosity of the molten polyether-ether-ketone resin is high under the high-temperature condition, and the adverse factors act together to cause that the interface bonding condition between the carbon fiber cloth and the polyether-ether-ketone resin is weak, the mechanical property of the composite material is seriously influenced, and the application of the composite material in multiple fields is limited. Therefore, the interface modification between the carbon fiber cloth and the polyether-ether-ketone is the key for improving the further application of the composite material. Statistics shows that the carbon fiber cloth at the interface is modified by using a sizing method, so that the bonding condition of the carbon fiber cloth and the polyether-ether-ketone can be effectively solved. The sizing agent used in the sizing process mainly comprises a sizing material and sizing liquid. Common sizing materials include polyetherimides, polyamic acids (precursors of polyimides), polyetherketoneketones, polyethersulfones, and the like, while common sizing materials include N-N, dimethylformamide and N-methylpyrrolidone. However, these two common sizing solutions are organic reagents, and there is a possibility that volatilization, splashing and the like may cause damage to the research personnel and the local environment during the sizing process. If an aqueous solution is used as the sizing solution, the above conventional sizing materials cannot be effectively and stably dispersed in the aqueous solution to meet the sizing requirement. On the other hand, the preparation temperature of the carbon fiber cloth reinforced polyetheretherketone composite material is usually higher than 350 ℃, so the heat resistance of the sizing material is one of the key indexes for measuring the quality of the sizing agent. In view of the statistics and analysis, the preparation of the modified resin based on the polyetheretherketone, which has relatively excellent thermal properties and can be stably dispersed in an aqueous solution, is an effective technical measure for optimizing the interface of the carbon fiber cloth reinforced polyetheretherketone composite material.
The basis for realizing the effective technical measures is to improve the activity of the polyether-ether-ketone molecular chain and keep the excellent thermal property of the polyether-ether-ketone molecular chain. Therefore, a preparation method suitable for the modified polyether-ether-ketone aqueous solution sizing agent needs to be designed.
Disclosure of Invention
At present, the sizing agent for the carbon fiber cloth reinforced polyether-ether-ketone composite material mainly comprises two problems:
1. the modified polyether-ether-ketone has poor thermal stability;
2. common sizing materials cannot be effectively dispersed in aqueous solvents, resulting in the inability to prepare aqueous sizing agents that are stable for long periods of time. In order to solve the two problems and solve the problem that the interface bonding of the carbon fiber cloth reinforced polyether-ether-ketone composite material is weak, the invention provides the aqueous solution sizing agent based on the polyether-ether-ketone and the preparation method thereof, so that on one hand, the excellent thermal property of the modified polyether-ether-ketone is ensured, and on the other hand, the harm of the organic sizing agent to researchers and local environment is overcome.
The invention carries out two times of modification treatment on the polyether-ether-ketone, so that the polyether-ether-ketone has higher activity, and simultaneously maintains good thermal stability and lower thermal decomposition rate under high-temperature conditions. And then, preparing a relatively stable aqueous solution sizing agent containing the modified polyether-ether-ketone by using an emulsion/solvent evaporation method so as to solve the problem that the organic sizing agent may cause local damage to researchers and the environment.
The invention relates to a sizing agent for an aqueous solution based on polyether-ether-ketone, which is characterized in that the sizing agent is obtained by hydroxylation treatment of polyether-ether-ketone; then carrying out esterification treatment with concentrated phosphoric acid; adding dichloromethane or chloroform, performing ultrasonic dispersion, mixing with the aqueous solution of the opacifier, performing ultrasonic dispersion again, and performing magnetic stirring until the dichloromethane or chloroform is completely volatilized to obtain the emulsion; the method specifically comprises the following steps:
step one, performing hydroxylation treatment on polyether-ether-ketone;
step two, carrying out esterification treatment with concentrated phosphoric acid;
and step three, adding the polyether-ether-ketone treated in the step two into dichloromethane or chloroform, performing ultrasonic dispersion, then mixing with an aqueous solution of an opacifier, performing ultrasonic dispersion again, and then performing magnetic stirring until the dichloromethane or chloroform is completely volatilized, thus obtaining the sizing agent.
Further defined, the hydroxylation treatment in step one is accomplished by: pouring 20g of polyether-ether-ketone powder into 500ml of dimethyl sulfoxide solution containing 6g of sodium borohydride, reacting for 25-35 hours at 120 ℃, then pouring into absolute ethyl alcohol, filtering, washing for multiple times, and drying solid substances; thereby completing the hydroxylation treatment.
Further defined, the step two esterification treatment is completed by the following operations: pouring 1g to 5g of the polyether-ether-ketone treated in the first step into 30ml to 100ml of phosphoric acid, reacting for 1 hour to 3 hours at the temperature of 70 ℃ to 90 ℃, then pouring into deionized water, filtering, washing with the deionized water for multiple times, and finally drying solid substances; thus completing the esterification treatment.
Further defined, the opacifying agent is triton-100.
Further limit, the aqueous solution of the opacifier in the step three is obtained by adding the opacifier into deionized water according to the proportion of 0.5 to 2.5 percent and then carrying out ultrasonic dispersion for 10 minutes.
Further limiting, the concentration of the polyether-ether-ketone treated in the second step in the sizing agent in the third step is 0.1-1.0%.
The preparation method of the carbon fiber cloth reinforced polyetheretherketone composite material comprises the steps of desizing and oxidizing the carbon fiber cloth, drying, adding the oxidized carbon fiber cloth into the sizing agent of any one of claims 1 to 2 or the sizing agent prepared by the method of any one of claims 3 to 7, standing for 2 hours, taking out and drying; weighing a proper amount of polyether-ether-ketone powder, and uniformly coating the powder on the surface of the carbon fiber cloth to control the volume content of the fibers in the final composite material to be 55-60%; carrying out hot-press molding on the materials; and obtaining the carbon fiber cloth reinforced polyether-ether-ketone composite material. The method is specifically completed by the following steps:
step 3, uniformly coating the surface of the carbon fiber cloth treated in the step 2 with polyether-ether-ketone powder, and then laying 8-16 layers in a stacking manner to control the volume content of the fiber to be 55-60% to obtain a blank;
step 4, carrying out hot press molding process on the blank in the step 3, wherein the hot pressing is a three-stage type, and the first stage is as follows: raising the temperature to 150-200 ℃ at room temperature, preserving the heat for 20-35 minutes, maintaining the pressure for 2.5-5.5 MPa, and effectively removing moisture and air, wherein in the second stage: heating to 370-380 deg.C, keeping the temperature for 20-40 min, maintaining the pressure for 2.5-5.5 MPa to completely melt the PEEK substrate, and fully infiltrating carbon fiber cloth, third stage: cooling to 290-300 deg.C, maintaining for 20-40 min, maintaining at 2.5-5.5 MPa for stable crystallization of polyether-ether-ketone matrix, maintaining the mechanical properties of the composite material, and cooling to room temperature at 0 MPa; and obtaining the carbon fiber cloth reinforced polyether-ether-ketone composite material.
The invention relates to a two-step modification process of PEEK, which comprises the steps of firstly carrying out hydroxylation treatment on the PEEK, particularly carrying out reaction time; the hydroxylation time is 25-35 hours, and the hydroxylation time plays a decisive role in the number of hydroxyl groups introduced on a polyether-ether-ketone molecular chain. If the hydroxylation time is too short, a large number of hydroxyl groups cannot be introduced into a polyether-ether-ketone molecular chain, and the number of hydroxyl point sites capable of undergoing an esterification reaction with phosphoric acid in a subsequent reaction is small, so that the finally modified polyether-ether-ketone has poor dispersibility in water and cannot be stably distributed in the emulsion for a long time; on the contrary, if the hydroxylation time is too long, the number of hydroxyl groups is increased and the ketone group is gradually reduced, the main chain structure of the polyether-ether-ketone is seriously damaged, and the later thermal and mechanical stability of the polyether-ether-ketone serving as a sizing agent is influenced.
When the esterification temperature is too low, the reaction activity of the concentrated phosphoric acid and the hydroxyl of the hydroxylated polyether-ether-ketone is low, which is not beneficial to the esterification reaction, and if the same reaction degree is required, the reaction time needs to be greatly prolonged; too high a temperature, e.g., above 150 ℃, is undesirable because it poses a risk of splashing or boiling during the esterification reaction.
When the esterification time is too short, the reaction of the concentrated phosphoric acid and the hydroxylated polyetheretherketone is not completely carried out, and the thermal stability and the dispersibility in an aqueous solution of the modified polyetheretherketone cannot be effectively improved; the time is too long, and the molecular chain structure of the hydroxylated polyether-ether-ketone can be damaged under the condition of concentrated phosphoric acid, so that the property of the product is adversely affected.
Improper selection of the reactant mass or volume, if too small, the esterification reaction of the concentrated phosphoric acid and the hydroxylated polyether ether ketone is not completely carried out, and if too large, the raw materials are wasted. Therefore, the problems of reaction degree and raw material cost should be fully considered when selecting the mass and volume of the reaction substance.
In the preparation process of the phosphoric acid modified polyether-ether-ketone aqueous solution sizing agent, the ultrasonic time plays a key role in influencing the dispersibility, if the ultrasonic time is too short, a stable emulsion is not formed easily, and in addition, the short ultrasonic time cannot obtain small-particle modified polyether-ether-ketone, so that the aim of stable dispersion in water cannot be fulfilled; if the ultrasonic dispersion time is long, part of the liquid volatilizes due to the ultrasonic generation, so that the relative concentration of the modified polyether ether ketone in the liquid increases, and the stable dispersion in water becomes difficult.
The selection of the concentration of the triton plays a key role in the dispersibility of the modified polyether-ether-ketone in water. If the concentration is low, the acting force between molecules of the triton and the modified polyether-ether-ketone is small, and the modified polyether-ether-ketone can be gradually precipitated under the action of gravity, so that good aqueous solution dispersibility cannot be obtained; on the other hand, if the concentration is high, the viscosity of the aqueous solution of triton increases, which is not favorable for uniformly dispersing the modified polyetheretherketone in the interior thereof in the form of small particles, and therefore, under such conditions, good dispersibility of the aqueous solution cannot be obtained.
Dichloromethane or chloroform as the carrier of the solution carrying the modified polyetheretherketone, the choice of which is equally important. Because this solution vehicle is not miscible with water and secondly readily volatizes at room temperature, there is less liquid to satisfy both. It is therefore proposed to use either dichloromethane or chloroform as the carrier, with dichloromethane being preferred because of the lower probability of producing phosgene compared to chloroform.
In the interface modification process of the composite material, the concentration selection of the sizing agent is a key parameter. In the process of preparing the modified polyether-ether-ketone aqueous sizing agent, the high concentration means that the unit solution has more modified polyether-ether-ketone needing to be dispersed, which provides a challenge for the aqueous solution dispersibility of the modified polyether-ether-ketone which only takes an aqueous solution as a carrier and triton as an opacifier. The high concentration can result in that a uniform and turbid solution can not be obtained under the ultrasonic condition, and finally a stable aqueous solution of the modified polyetheretherketone can not be obtained. If the concentration is small, the modified polyether-ether-ketone can form small particles which are stably dispersed in an aqueous solution under an ultrasonic condition, but the interface modification method aiming at the modified carbon fiber cloth has too low concentration, so that the interface between the carbon fiber cloth and the polyether-ether-ketone cannot be effectively improved. Therefore, the concentration of the sizing agent with stable dispersibility needs to be selected according to actual conditions.
The preparation method can be used for obtaining the aqueous solution sizing agent which is harmless to research personnel and local environment;
the phosphoric acid modified polyether-ether-ketone aqueous solution sizing agent prepared by the preparation method has excellent dispersibility in water, and can be in an emulsion state for 30 days. Aqueous sizing agents for the material can be prepared in advance and applied as needed. The method is suitable for large-batch industrial production;
the phosphoric acid modified polyether-ether-ketone prepared by the method has excellent thermal stability, and the heat loss is small under the high-temperature condition;
the invention can effectively improve the problem of weak interface bonding between the carbon fiber cloth and the polyether-ether-ketone, and is beneficial to improving the mechanical property of the carbon fiber cloth reinforced polyether-ether-ketone composite material.
Drawings
FIG. 1 is thermogravimetric curves of HPEEK and p-HPEEK under nitrogen prepared in example 1;
FIG. 2(a) shows the morphology of a p-HPEEK aqueous solution sizing agent after standing for 30 days;
FIG. 2(b) shows the morphology of an aqueous solution of polyetheretherketone after standing for 12 hours;
FIG. 3(a) is a scanned topography view of a sized carbon fiber;
fig. 3(b) is a distribution diagram of elements of the sized carbon fiber, wherein red: carbon element, green: oxygen element, pink: phosphorus element
FIG. 3(c) is a phosphorus distribution plot of sized carbon fibers;
FIG. 4(a) is composite flexural performance;
FIG. 4(b) interlaminar shear performance.
Detailed Description
Example 1 the preparation method of the aqueous sizing agent based on polyetheretherketone in this example was carried out by the following steps:
step one, pouring 20g of polyether-ether-ketone powder into 500ml of dimethyl sulfoxide solution filled with 6g of sodium borohydride, and reacting for 30 hours at 120 ℃; pouring the reacted mixed solution into 3000ml of absolute ethyl alcohol, filtering, washing for 3-5 times by using 0.1mol/L hydrochloric acid solution and deionized water (to remove organic solvent among solid matters, the hydrochloric acid can effectively replace sodium ions on a polyether-ether-ketone molecular chain subjected to hydroxylation reaction with hydrogen ions to form hydroxyl groups, and washing by using the deionized water to obtain the solid matters without doping of the organic solvent and the hydrochloric acid solution), and drying the solid matters at 100 ℃ for 12h to remove moisture. The product is polyetheretherketone which undergoes a reduction reaction and is noted as HPEEK.
Step two, pouring 3g of HPEEK into 50ml of concentrated phosphoric acid (the mass concentration is 85 percent), and reacting for 2 hours at 80 ℃; pouring the reacted mixed solution into 500ml of deionized water, then filtering, washing 3-5 times by using the deionized water, and finally drying the solid substance at 100 ℃ for 12h to remove water. The product was designated p-HPEEK.
And step three, adding 0.32g of triton-100 into 20ml of deionized water, and performing ultrasonic dispersion for 10 minutes to obtain a transparent aqueous solution A. 0.14gp-HPEEK was poured into 3ml of dichloromethane and dispersed by sonication for 10 minutes to give solution B. And mixing the aqueous solution A and the solution B, and performing ultrasonic dispersion for 10 minutes again to obtain milky mixed solution. And magnetically stirring the milky white mixed solution until dichloromethane is completely volatilized to obtain the p-HPEEK aqueous solution sizing agent with the p-HPEEK concentration of 0.7 percent.
The preparation method of the carbon fiber cloth reinforced polyether-ether-ketone composite material comprises the following steps:
step 3, uniformly coating the surface of the carbon fiber cloth treated in the step 2 with polyetheretherketone powder, and then layering and paving 8 layers to control the volume content of the fiber to be 60% to obtain a blank, wherein the weight of the oxidized carbon fiber cloth in the blank is 30g, and the weight of the polyetheretherketone powder is 14.8 g;
step 4, carrying out a hot-press molding process on the blank in the step 3, wherein hot pressing is a three-stage process; a first stage: raising the temperature to 180 ℃ at room temperature, preserving the heat for 30 minutes, maintaining the pressure for 2.9 MPa, effectively removing moisture and air, and in the second stage: heating to 375 ℃ at 180 ℃, preserving heat for 30 minutes, maintaining the pressure for 2.9 MPa to completely melt the polyetheretherketone matrix, fully infiltrating the carbon fiber cloth, and carrying out a third stage: cooling to 295 ℃ at 375 ℃, preserving heat for 30 minutes, maintaining the pressure for 2.9 MPa to ensure that the polyetheretherketone matrix is stably crystallized, which is beneficial to maintaining the mechanical property of the composite material, and the fourth stage: cooling to room temperature at 300 deg.C, and 0 MPa; and preparing the carbon fiber cloth reinforced polyether-ether-ketone composite material.
The carbon fiber cloth-reinforced polyetheretherketone composite material prepared in example 1 was subjected to a bending test and an interlaminar shear test to obtain the bending strength and the interlaminar shear strength before and after modification.
The effect of the invention is verified by the following:
thermogravimetric analysis is carried out on the phosphoric acid modified polyether ether ketone (p-HPEEK), the experimental condition is that the temperature is increased to 800 ℃ at the temperature rise rate of 10 ℃/min under 30 ℃, and nitrogen is used as protective gas. The mass of the test sample was recorded during the temperature increase and plotted as shown in figure 1. It was found that at 370 ℃ the thermal decomposition of p-HPEEK was only 1.6% and its thermal stability was sufficient to satisfy the sizing conditions.
After the p-HPEEK is prepared into the aqueous sizing agent, the dispersion durability of the p-HPEEK in water is crucial to the sizing process. It was observed that the standing aqueous slurry containing p-HPEEK was stably dispersed in an opaque state for more than 30 days, as shown in FIG. 2 (a). In order to better compare the advantages of the aqueous sizing agent, under the same conditions, an aqueous solution containing pure polyetheretherketone was prepared, and it was observed that the standing aqueous solution containing pure polyetheretherketone was not stably dispersed under the standing condition, and after more than 12 hours, polyetheretherketone was completely precipitated, so that a significant delamination phenomenon occurred in the aqueous solution, as shown in fig. 2 (b).
The carbon fiber cloth is placed in a proper glass container filled with the sizing agent of the p-HPEEK aqueous solution for 2 hours to achieve the sizing effect. Because water is used as a solvent for sizing, no harm is caused to human bodies and local environment in the operation process, and the sizing agent is an environment-friendly sizing agent. Scanning and observing the appearance of the sized carbon fiber cloth as shown in fig. 3 (a); and performing energy spectrum analysis on a local region, wherein fig. 3(b) is a superimposed graph of all elements (carbon element, oxygen element, and phosphorus element except hydrogen element) contained in the region, and fig. 3(c) is a distribution graph of phosphorus element in the region. As can be seen from FIG. 3(a), p-HPEEK has been successfully attached to the surface of the carbon fiber cloth by the sizing process. As can be seen from FIGS. 3(b) and (c), the distribution of phosphorus in p-HPEEK is relatively uniform, especially in FIG. 3 (c). Thus, it can be proved that the sizing agent of the p-HPEEK aqueous solution is suitable for treating the surface of the carbon fiber cloth.
Example 1 a carbon fibre cloth reinforced polyetheretherketone composite is prepared and then the composite is subjected to mechanical testing, including bending and interlaminar shear testing, according to ASTM D7264 and ASTM D2344 standards to obtain the bending and interlaminar shear strength of the material. The results are shown in FIGS. 4(a) and (b). Compared with carbon fiber cloth (OCF) which is not sized after desizing and oxidation, the bending strength, the bending modulus and the interlaminar shear strength of the composite material prepared by the carbon fiber cloth (0.7 percent OCF) which is treated by the sizing agent of the p-HPEEK aqueous solution with the concentration of 0.7 percent are improved to a certain extent and reach 31.0 percent, 11.0 percent and 30.0 percent respectively. The lifting effect is better than the modification effect of the polyamide-based aqueous sizing agent reported in the literature (the bending strength is about 8 percent improved).
Claims (9)
1. The aqueous solution sizing agent based on the polyether-ether-ketone is characterized in that the sizing agent is prepared by hydroxylating the polyether-ether-ketone; then carrying out esterification treatment with concentrated phosphoric acid; adding dichloromethane or chloroform, performing ultrasonic dispersion, mixing with the aqueous solution of the opacifier, performing ultrasonic dispersion again, and performing magnetic stirring until the dichloromethane or chloroform is completely volatilized to obtain the emulsion; wherein the hydroxylation treatment time is 25-35 hours.
2. The aqueous polyetheretherketone-based sizing agent according to claim 1, wherein the opacifying agent is triton-100.
3. The method for preparing a sizing agent for aqueous solutions based on polyetheretherketone according to claim 1 or 2, characterized in that it is carried out by the following steps:
step one, performing hydroxylation treatment on polyether-ether-ketone;
step two, carrying out esterification treatment with concentrated phosphoric acid;
and step three, adding the polyether-ether-ketone treated in the step two into dichloromethane or chloroform, performing ultrasonic dispersion, then mixing with an aqueous solution of an opacifier, performing ultrasonic dispersion again, and then performing magnetic stirring until the dichloromethane or chloroform is completely volatilized, thus obtaining the sizing agent.
4. The method for preparing aqueous sizing agent based on polyetheretherketone according to claim 3, wherein the hydroxylation treatment in step one is performed by: pouring 20g of polyether-ether-ketone powder into 500ml of dimethyl sulfoxide solution containing 6g of sodium borohydride, reacting for 25-35 hours at 120 ℃, then pouring into absolute ethyl alcohol, filtering, washing for multiple times, and drying solid substances; thereby completing the hydroxylation treatment.
5. The method for preparing a sizing agent for aqueous solutions based on polyetheretherketone according to claim 3, characterized in that the step of di-esterification is carried out by: pouring 1g to 5g of the polyether-ether-ketone treated in the first step into 30ml to 100ml of concentrated phosphoric acid, reacting for 1 hour to 3 hours at the temperature of 70 ℃ to 90 ℃, then pouring into deionized water, filtering, washing with the deionized water for multiple times, and finally drying solid substances; thus completing the esterification treatment.
6. The method for preparing the aqueous solution sizing agent based on polyetheretherketone according to claim 3, wherein the aqueous solution of the opacifier in step three is obtained by adding the opacifier into deionized water according to the proportion of 0.5-2.5% and then performing ultrasonic dispersion for 10 minutes.
7. The method for preparing the aqueous solution sizing agent based on polyetheretherketone according to claim 3, wherein the concentration of polyetheretherketone in the sizing agent obtained in the third step is 0.1-1.0% after the treatment in the second step.
8. The preparation method of the carbon fiber cloth reinforced polyether-ether-ketone composite material is characterized by comprising the following steps of:
after desizing and oxidation treatment, drying the carbon fiber cloth, adding the oxidized carbon fiber cloth into the sizing agent of any one of claims 1 to 2 or the sizing agent prepared by the method of any one of claims 3 to 7, standing for 2 hours, taking out and drying; weighing a proper amount of polyether-ether-ketone powder and uniformly coating the powder on the surface of the carbon fiber cloth, so that the volume content of fibers in the final composite material is controlled to be 55-60%; carrying out hot-press molding on the materials; and obtaining the carbon fiber cloth reinforced polyether-ether-ketone composite material.
9. The method for preparing the carbon fiber cloth reinforced polyetheretherketone composite material according to claim 8, wherein the hot press forming process is performed in three stages, wherein the first stage comprises: heating to 150-200 deg.c at room temperature, maintaining for 20-35 min and maintaining at 2.5-5.5 MPa; and a second stage: heating to 370-380 deg.c, maintaining for 20-40 min and maintaining at 2.5-5.5 MPa; a third stage: cooling to 290-300 deg.c, maintaining for 20-40 min and maintaining at 2.5-5.5 MPa.
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