CN111635242A - Rapid preparation method and application of high-density revolving body carbon/carbon composite material - Google Patents
Rapid preparation method and application of high-density revolving body carbon/carbon composite material Download PDFInfo
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Abstract
The invention discloses a rapid preparation method and application of a high-density revolving body carbon/carbon composite material, belonging to the technical field of carbon fiber composite material manufacture, and the method comprises the following steps: (1) weaving and molding the carbon fiber preform; (2) carrying out high-temperature heat treatment on the carbon fiber preform; (3) chemical vapor deposition densification; (4) high-temperature heat treatment; (5) resin impregnationCarbonization and densification; (6) and (4) high-temperature heat treatment. The volume density of the carbon/carbon composite material prepared by the invention is more than or equal to 1.88g/cm3The method has the advantages of simple process, convenient operation, short preparation period and low comprehensive cost, and can be applied to the fields of aerospace, industrial dies and the like.
Description
Technical Field
The invention belongs to the field of carbon fiber composite material manufacturing, and particularly relates to a rapid preparation method of a carbon/carbon composite material.
Background
The carbon/carbon composite material has the excellent performances of low density, high specific strength specific modulus, low thermal expansion coefficient, high heat conduction and electric conduction capability, creep resistance, thermal shock resistance, ablation resistance, good high-temperature mechanical property and dimensional stability under the condition of a non-oxidizing medium and the like, is a structural and functional integrated core material which is relevant to strategic industrial development and national safety in China, and has unique supporting effect on development of aerospace, rail transit, nuclear industry, weaponry and equipment in the industrial field in China.
The continuous fiber reinforced carbon-based composite material can be obtained by adopting a gas phase method and a liquid phase method. For the preparation of high-density carbon/carbon composite materials, the process characteristics and advantages of the two methods are combined and the gas phase/liquid phase mixing process is adopted to realize the preparation. Generally, a high-density carbon/carbon composite material is densified in an initial stage by using a chemical vapor deposition method, so that the advantage of strong interface bonding between pyrolytic carbon and carbon fibers is fully exerted, meanwhile, damage to fibers caused by substances such as organic solvents in a precursor of a liquid phase method is avoided, and then a subsequent densification process is completed by using the carbon matrix filling characteristic of the liquid phase method. The control of the process parameters of the two carbon matrix introduction modes and the key conversion point are the key factors for determining whether the preparation of the high-density carbon/carbon composite material can be realized, and also the key factors for determining whether the batch production can be realized, and reducing the cost and the preparation period.
The invention content is as follows:
the invention aims to provide a rapid preparation method of a high-density revolving body carbon/carbon composite material; the method has the advantages of high yield, high efficiency and the like.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention relates to a rapid preparation method of a high-density revolving body carbon/carbon composite material, which mainly comprises the following steps: step (1), weaving and forming a carbon fiber preform; step (2), performing high-temperature heat treatment on the carbon fiber preform; step (3), vapor deposition densification of the carbon fiber preform; step (4), performing high-temperature heat treatment on the carbon/carbon composite material blank; step (5), impregnating/carbonizing and densifying the carbon/carbon composite material green body; and (6) carrying out high-temperature heat treatment on the carbon/carbon composite material blank.
Preferably, the bulk density of the high-density solid of revolution carbon/carbon composite material is more than or equal to 1.88g/cm3。
Preferably, the high density carbon/carbon composite material is characterized by a solid of revolution structure.
Further preferably, the high-density solid of revolution carbon/carbon composite material has an equal wall thickness cylindrical structure.
Preferably, the woven structure of the carbon fiber preform in the step (1) is a puncture preform or a needle-punched preform.
Further preferably, the carbon fiber preform in the step (1) is a puncture structure preform.
Further preferably, the step (1) of knitting and forming the carbon fiber preform is realized by alternately laminating and needling a non-woven fabric and an ultrathin mesh tire and by bidirectional penetration of Z-direction fibers. The thickness of the single layer of the ultrathin net tire is less than or equal to 150 micrometers.
Preferably, the period of the alternating lamination of the carbon fiber preform non-woven fabric in the step (1) is [0 °/60 °/120 ° ] n, and the lamination mode can improve the isotropy of the composite material and effectively improve the structural and performance stability of the product in a hot working environment.
Preferably, the carbon fiber preform in the step (1) has a bulk density of 0.65 to 0.85g/cm3(ii) a The weight percentage of the non-woven cloth to the net tire is 70:30-90: 10; the density between layers of the non-woven fabric is 16-26 layers/cm; the Z-direction fiber spacing is 2.0-2.8 mm. The volume density, the weight ratio of the non-woven cloth to the net tire and the interlaminar density of the non-woven cloth of the carbon fiber preform are limited in order to ensure the total content of the carbon fibers and the ratio of long fibers/short fibers and meet the service performance of the product.
Further preferably, the carbon fiber preform in the step (1) has a bulk density of 0.70 to 0.80g/cm3(ii) a The weight ratio of the non-woven cloth to the net tire is 75:25-85: 15; the density between layers of the non-woven fabric is 18-24 layers/cm; the spacing between the fibers in the Z direction is 2.0 x 2.0mm-2.6*2.6mm。
Preferably, the heat treatment temperature of the carbon fiber preform in the step (2) is 2000-2300 ℃, the heat preservation time is 2-3 hours, and the heating rate is 80-120 ℃/h; further preferably, the heating rate of the heat treatment in the step (2) is 100 ℃/h, the high-temperature heat treatment process adopts a segmented mode of a vacuum stage and an inert gas protection stage, and the mode conversion temperature is 1700-1800 ℃; the inert gas is high-purity argon (99.99%). Placing the carbon fiber preform obtained in the step (1) into a heating furnace; firstly, vacuumizing until the air pressure in the furnace is less than or equal to 100Pa, then heating to 1700-1800 ℃, and then filling inert gas; heating to 2000-2300 ℃ under inert atmosphere, and keeping the temperature for 2-3 h; and obtaining the carbon fiber preform after high-temperature heat treatment.
Preferably, the chemical vapor deposition densification in the step (3) is realized by the assistance of a confined reactor, wherein the confined reactor is of a cylindrical structure and consists of a gas preheating dispersion cylinder, a flow guide plate and a deposition chamber.
Further preferably, the diameter of the reaction gas preheating dispersion cylinder is 550-850mm, and the effective height is 400-500 mm.
Further preferably, the guide plate is an annular thin plate with the thickness of 20-30mm, and is connected with the reaction gas preheating and dispersing cylinder through a straight opening.
Further preferably, the baffle gas passage diameter is consistent with the carbon fiber preform internal diameter.
Preferably, the distance between the upper adjacent carbon fiber preforms and the lower adjacent carbon fiber preforms in the confined reactor is 30-60 mm.
Further preferably, single material column loading or multiple material columns loading can be selected according to the specification of the carbon fiber preform blank; the distance between the carbon fiber preforms of different material columns loaded by the multiple material columns is 50-60 mm;
further preferably, a cushion block of 30-40mm is arranged above the carbon fiber preform at the top end of the stock column, and a circular plate with the same outer diameter as the preform is covered.
Further preferably, the distance between the preform and the deposition cylinder is 80-100 mm;
preferably, the vapor deposition densification of the carbon fiber preform in the step (3) is carried out by taking propylene as a carbon source gas and nitrogen as a diluent gas, wherein the flow ratio of the propylene to the nitrogen is 5:1-3: 1;
preferably, the vapor-phase densification deposition temperature of the carbon fiber preform in the step (3) is 945-975 ℃, and the deposition pressure is 1.0-1.8 kPa;
preferably, the bulk density of the carbon/carbon composite material blank densified by chemical vapor deposition in the step (3) is 1.25-1.40g/cm3And the surface is machined and then enters a high-temperature heat treatment process.
Further preferably, the bulk density of the carbon/carbon composite material after gas phase densification is 1.28-1.36g/cm3. The invention provides necessary conditions for shortening the manufacturing period of products and improving the yield of the products by matching the steps (1), (2) and (3).
Preferably, the high-temperature heat treatment temperature of the carbon/carbon composite material blank in the step (4) is 2300 ℃.
Further preferably, the temperature rise rate of the high-temperature heat treatment of the carbon/carbon composite material blank in the step (4) is 100 ℃/h.
Further preferably, the high-temperature heat treatment of the carbon/carbon composite material blank in the step (4) adopts a vacuum + inert gas protection segmented mode, and the mode conversion temperature is 1700-1800 ℃. The processing mode is consistent with the step (2).
Further preferably, the high temperature heat treatment inert gas is high purity argon (99.99%).
Preferably, the impregnant of the carbon/carbon composite material body in the step (5) adopts furan resin, and the curing agent adopts phosphoric acid.
Further preferably, the amount of the phosphoric acid curing agent used in the step (5) is 5 to 9% by mass of the resin.
Preferably, the resin impregnation pressure of the carbon/carbon composite material blank in the step (5) is 3-5MPa, and the single impregnation time is 5-7 hours; the curing temperature is 180 ℃ and 200 ℃, the curing pressure is 3-5MPa, and the single curing time is 1-5 h.
Preferably, the carbonization temperature of the carbon/carbon composite material blank body after resin impregnation and curing in the step (5) is 800-1000 ℃, the single carbonization time is 2-3 hours, and the whole process is protected by nitrogen.
Preferably, the high-temperature heat treatment temperature of the carbonized carbon/carbon composite material blank in the step (6) is 2000-2300 ℃, and the single heat treatment time is 2-3 hours.
Preferably, the subsequent densification of the carbon/carbon composite body after deposition densification takes the form of a cyclic densification cycle of impregnation/curing/carbonization/high temperature heat treatment/process surface machining.
More preferably, in the above-described densification cycle, the carbonization step is performed for 2 to 3 cycles, and the carbonization step is omitted in the subsequent densification cycle.
Further preferably, in the densification cycle, the high-temperature heat treatment temperature is adjusted according to the densification effect of the carbon/carbon composite material blank.
Further preferably, in the densification cycle, the machining amount of the process surface machining of the carbon/carbon composite material blank is 0.5-2 mm.
Preferably, the volume density of the obtained carbon/carbon composite material can reach 1.88g/cm after 8-11 cycles of densification3The carbon/carbon composite material-blank is obtained after the surface finish machining.
Preferably, the carbon/carbon composite material prepared by the invention is suitable for aerospace thermal structural components, industrial production molds and the like;
the invention is characterized in that the steps (1), (2), (3), (4), (5) and (6) are matched; the material can meet the bearing and heat-resisting requirements, and the yield of the product can be ensured to be 100%.
The invention has the beneficial effects that:
(1) the carbon fiber preform related to the invention adopts an angle-rotating weftless fabric and ultrathin mesh tire alternate layering mode, so that on one hand, the high fiber content of the preform can be ensured, and on the other hand, the structural and performance stability of the carbon/carbon composite material member with the characteristics of a revolved body with the same wall thickness in a heated use environment can be improved.
(2) The initial densification is carried out by adopting low-temperature low-pressure chemical vapor deposition, the connectivity of open pores can be ensured to the maximum extent, the subsequent resin carbon densification period can be shortened, the preset volume density can be quickly reached, and the preparation period is greatly shortened.
(3) The reaction gas flow field is effectively regulated and controlled by adopting the limited-area reactor, so that the densification uniformity in the single carbon fiber preform and among a plurality of vertically-loaded batch preforms can be ensured.
In conclusion, the rapid preparation method of the high-density revolving body carbon/carbon composite material has the advantages of simple process, convenient operation, short preparation period and low cost, can be applied to products such as aerospace thermal structural components, industrial production molds and the like, and provides a practical and effective method for uniform densification and low-cost production of carbon/carbon composite material components with revolving body structural characteristics.
The preparation method has the production period of CVD 200-300h and the subsequent densification period of 8-11 times, and the whole period is far lower than that of the prior art. Meanwhile, the sample obtained by the method meets the requirements of bearing and heat resistance of aerospace thermal structure parts and dies in working environments; and the yield is 100%, which is far higher than the prior level.
Drawings
FIG. 1 is a schematic view of loading and flow field control of a preform monolithic column for a high-density solid-of-revolution carbon/carbon composite material.
FIG. 2 is a schematic view of the loading and flow field control of a preform three-material column for a high-density solid-of-revolution carbon/carbon composite material.
Figure 3 is a photograph of a sample of high density carbon/carbon composite material with a solid of revolution.
Detailed Description
The materials of the present invention, methods of making the components thereof, and applications thereof will be described in further detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
The high-density revolving body carbon/carbon composite material prepared in the embodiment is of an equal-wall-thickness revolving body structure, the specification is 350mm in magnitude (outer diameter), a single-material-column loading mode (shown in a schematic diagram 1) is adopted in the chemical vapor densification process, and the manufacturing method specifically comprises the following steps:
(1) alternately laying non-woven cloth and ultrathin net tire, wherein the alternate lamination period of the non-woven cloth is [0 °/60 °/120 ° ]]nIntroducing Z-direction carbon fibers through bidirectional penetration to form a three-dimensional puncture structure preform with the volume density of 0.72g/cm3The weight ratio of the non-woven cloth to the net tire is 75: 25; the density between layers of the non-woven fabric is 19-20 layers/cm; the Z-direction fiber spacing was 2.2 x 2.2 mm.
(2) Placing the carbon fiber preform into a vacuum induction furnace, heating to 1700 ℃ at the speed of 100 ℃/h under the vacuum condition, preserving heat for 1h, and gradually introducing high-purity argon (99.99%) during the heat preservation period; then, heating to 2300 ℃ at the speed of 100 ℃/h and preserving heat for 2h, wherein the pressure in the furnace is maintained in a micro-positive pressure state; and (5) keeping the temperature for 2h, stopping heating, and naturally cooling along with the furnace.
(3) A limited-area reactor (as shown in a schematic diagram 1) is arranged in a deposition furnace, carbon fiber preforms subjected to high-temperature heat treatment are loaded in a deposition chamber in a single material column mode, 4 layers of strip-shaped carbon felts are arranged below each preform and used as cushion blocks (the height of each cushion block is 30-40mm), and 4 layers of strip-shaped cover plates with the same outer diameter are arranged above the preform at the top end of each material column and covered.
(4) Starting a vacuum system after the pressure rise rate of the equipment is qualified (less than 300Pa/h), gradually heating to 975 ℃, preserving heat for 2h, and introducing reaction gas; the flow ratio of the propylene to the nitrogen is 3:1, and the pressure of a deposition system is 1.2-1.8 kPa; the gas phase densification process takes 100h as a period, and the blank is loaded in the reverse order after the first period is finished to continue densification. After the total deposition time is 300h, the carbon fiber preform is densified to a bulk density of 1.31-1.34g/cm3。
(5) Carrying out surface machining on the carbon/carbon composite material blank after gas phase densification, then placing the blank into a vacuum induction furnace, heating to 1800 ℃ at the speed of 100 ℃/h under the vacuum condition, preserving heat for 1h, and gradually introducing high-purity argon (99.99%) during the heat preservation period; then, heating to 2300 ℃ at the speed of 100 ℃/h and preserving heat for 2h, wherein the pressure in the furnace is maintained in a micro-positive pressure state; and (5) keeping the temperature for 2h, stopping heating, and naturally cooling along with the furnace.
(6) Furan resin is used as a raw material, phosphoric acid (9 wt.%) is used as a curing agent, and the carbon/carbon composite material blank subjected to high-temperature heat treatment is subjected to impregnation/curing treatment, wherein the resin impregnation pressure is 3-5MPa, and the impregnation time is 5-7 hours; the curing temperature is 180-;
(7) placing the carbonized carbon/carbon composite material blank in a vacuum induction furnace for high-temperature heat treatment at 2000 ℃ in a segmented mode, wherein the heating rate is 100 ℃/h, and the mode conversion temperature is 1700 ℃; and after the high-temperature heat treatment is finished, performing surface process machining on the carbon/carbon composite material blank.
(8) Repeating the steps (6) and (7) to complete a second liquid phase densification cycle;
(9) repeating the steps (6) and (7) after the second liquid phase densification cycle is completed, setting the heat treatment temperature in the step (7) to 2300 ℃ and the mode switching temperature to 1800 ℃, and completing the third liquid phase densification cycle.
(10) The subsequent liquid phase densification process adopts a dipping/curing/high-temperature heat treatment mode (mode without carbonization), the key process parameters in the steps (6) and (7) are generally adopted, and the fifth and eighth liquid phase densification periods refer to the key process parameters in the step (9). After ten liquid phase densification periods are accumulated, the volume density of the carbon/carbon composite material reaches 1.88g/cm3And finally, finishing to obtain the high-density revolution body carbon/carbon composite material.
The obtained high-density revolving body carbon/carbon composite material meets the requirements of bearing and heat resistance of aerospace thermal structural components and dies in working environments; example 1 was repeated to obtain samples which were all acceptable.
Example 2
The high-density revolving body carbon/carbon composite material prepared in the embodiment is of a revolving body structure with the same wall thickness, the specification is 200mm magnitude (outer diameter), a three-material-column loading mode (shown in a schematic diagram 2) is adopted in the chemical vapor densification process, and the manufacturing method specifically comprises the following steps:
(1) alternately laying non-woven cloth and ultrathin net tire, wherein the alternate lamination period of the non-woven cloth is [0 °/60 °/120 ° ]]nIntroducing Z-direction carbon fibers through bidirectional penetration to form a three-dimensional puncture structure preform with the volume density of 0.80g/cm3The weight ratio of the non-woven cloth to the net tire is 80: 20; the density between layers of the non-woven fabric is 22-23 layers/cm; the Z-direction fiber spacing was 2.6 x 2.6 mm.
(2) Placing the carbon fiber preform into a vacuum induction furnace, heating to 1700 ℃ at the speed of 100 ℃/h under the vacuum condition, preserving heat for 1h, and gradually introducing high-purity argon (99.99%) during the heat preservation period; then, heating to 2300 ℃ at the speed of 100 ℃/h and preserving heat for 2h, wherein the pressure in the furnace is maintained in a micro-positive pressure state; and (5) keeping the temperature for 2h, stopping heating, and naturally cooling along with the furnace.
(3) A limited-area reactor (as shown in a schematic diagram 2) is arranged in a deposition furnace, carbon fiber preforms subjected to high-temperature heat treatment are loaded in a deposition chamber in a three-material-column mode, 4 layers of strip-shaped carbon felts are arranged below each preform and used as cushion blocks (the height of each cushion block is 30-40mm), and 4 layers of strip-shaped cover plates with the same outer diameter are arranged above the preforms at the top ends of the material columns and covered.
(4) Starting a vacuum system after the pressure rise rate of the equipment is qualified (less than 300Pa/h), gradually heating to 965 ℃, preserving heat for 2h, and introducing reaction gas; the flow ratio of the propylene to the nitrogen is 4:1, and the pressure of a deposition system is 1.0-1.4 kPa; the gas phase densification process takes 100h as a period, and the blank is loaded in the reverse order after the first period is finished to continue densification. After the total deposition time is 250h, the carbon fiber preform is densified to a bulk density of 1.28-1.30g/cm3。
(5) Carrying out surface machining on the carbon/carbon composite material blank after gas phase densification, then placing the blank into a vacuum induction furnace, heating to 1800 ℃ at the speed of 100 ℃/h under the vacuum condition, preserving heat for 1h, and gradually introducing high-purity argon (99.99%) during the heat preservation period; then, heating to 2300 ℃ at the speed of 100 ℃/h and preserving heat for 2h, wherein the pressure in the furnace is maintained in a micro-positive pressure state; and (5) keeping the temperature for 2h, stopping heating, and naturally cooling along with the furnace.
(6) Furan resin is used as a raw material, phosphoric acid (5 wt.%) is used as a curing agent, and the carbon/carbon composite material blank subjected to high-temperature heat treatment is subjected to impregnation/curing treatment, wherein the resin impregnation pressure is 3-5MPa, and the impregnation time is 5-7 hours; the curing temperature is 180-;
(7) placing the carbonized carbon/carbon composite material blank in a vacuum induction furnace for high-temperature heat treatment at 2000 ℃ in a segmented mode, wherein the heating rate is 100 ℃/h, and the mode conversion temperature is 1700 ℃; and after the high-temperature heat treatment is finished, performing surface process machining on the carbon/carbon composite material blank.
(8) Repeating the steps (6) and (7) to complete a second liquid phase densification cycle;
(9) repeating the steps (6) and (7) after the second liquid phase densification cycle is completed, setting the heat treatment temperature in the step (7) to 2300 ℃ and the mode switching temperature to 1800 ℃, and completing the third liquid phase densification cycle.
(10) The subsequent liquid phase densification process adopts a dipping/curing/high-temperature heat treatment mode (mode without carbonization), the key process parameters in the steps (6) and (7) are generally adopted, and the fourth and seventh liquid phase densification periods refer to the key process parameters in the step (9). After nine liquid phase densification periods are accumulated, the volume density of the carbon/carbon composite material reaches 1.88g/cm3And finally, finishing to obtain the high-density revolution body carbon/carbon composite material.
The obtained high-density revolving body carbon/carbon composite material meets the requirements of bearing and heat resistance of aerospace thermal structural components and dies in working environments; example 2 was repeated and all the samples were acceptable.
Example 3
The high-density revolving body carbon/carbon composite material prepared in the embodiment is of a revolving body structure with the same wall thickness, the specification is 250mm magnitude (outer diameter), a three-material-column loading mode (shown in a schematic diagram 2) is adopted in the chemical vapor densification process, and the manufacturing method specifically comprises the following steps:
(1) alternately laying non-woven cloth and ultrathin net tire, wherein the alternate lamination period of the non-woven cloth is [0 °/60 °/120 ° ]]nIntroducing Z-direction carbon fibers through bidirectional penetration to form a three-dimensional puncture structure preform with the volume density of 0.75g/cm3The weight ratio of the non-woven cloth to the net tire is 80: 20; the density between layers of the non-woven fabric is 21-22 layers/cm; the Z-direction fiber spacing was 2.4 x 2.4 mm.
(2) Placing the carbon fiber preform into a vacuum induction furnace, heating to 1700 ℃ at the speed of 100 ℃/h under the vacuum condition, preserving heat for 1h, and gradually introducing high-purity argon (99.99%) during the heat preservation period; then, heating to 2300 ℃ at the speed of 100 ℃/h and preserving heat for 2h, wherein the pressure in the furnace is maintained in a micro-positive pressure state; and (5) keeping the temperature for 2h, stopping heating, and naturally cooling along with the furnace.
(3) A limited-area reactor (as shown in a schematic diagram 2) is arranged in a deposition furnace, carbon fiber preforms subjected to high-temperature heat treatment are loaded in a deposition chamber in a three-material-column mode, 4 layers of strip-shaped carbon felts are arranged below each preform and used as cushion blocks (the height of each cushion block is 30-40mm), and 4 layers of strip-shaped cover plates with the same outer diameter are arranged above the preforms at the top ends of the material columns and covered.
(4) Starting a vacuum system after the pressure rise rate of the equipment is qualified (less than 300Pa/h), gradually heating to 950 ℃, preserving the temperature for 2h, and introducing reaction gas; the flow ratio of propylene to nitrogen is 3:1, and the pressure of a deposition system is 1.2-1.5 kPa; the gas phase densification process takes 100h as a period, and the blank is loaded in the reverse order after the first period is finished to continue densification. After the total deposition time is 250h, the carbon fiber preform is densified to a bulk density of 1.33-1.36g/cm3。
(5) Carrying out surface machining on the carbon/carbon composite material blank after gas phase densification, then placing the blank into a vacuum induction furnace, heating to 1800 ℃ at the speed of 100 ℃/h under the vacuum condition, preserving heat for 1h, and gradually introducing high-purity argon (99.99%) during the heat preservation period; then, heating to 2300 ℃ at the speed of 100 ℃/h and preserving heat for 2h, wherein the pressure in the furnace is maintained in a micro-positive pressure state; and (5) keeping the temperature for 2h, stopping heating, and naturally cooling along with the furnace.
(6) Furan resin is used as a raw material, phosphoric acid (8 wt.%) is used as a curing agent, and the carbon/carbon composite material blank subjected to high-temperature heat treatment is subjected to impregnation/curing treatment, wherein the resin impregnation pressure is 3-5MPa, and the impregnation time is 5-7 hours; the curing temperature is 180-;
(7) placing the carbonized carbon/carbon composite material blank in a vacuum induction furnace for high-temperature heat treatment at 2000 ℃ in a segmented mode, wherein the heating rate is 100 ℃/h, and the mode conversion temperature is 1700 ℃; and after the high-temperature heat treatment is finished, performing surface process machining on the carbon/carbon composite material blank.
(8) Repeating the steps (6) and (7) to complete a second liquid phase densification cycle;
(9) repeating the steps (6) and (7) after the second liquid phase densification cycle is completed, setting the heat treatment temperature in the step (7) to 2300 ℃ and the mode switching temperature to 1800 ℃, and completing the third liquid phase densification cycle.
(10) The subsequent liquid phase densification process adopts a dipping/curing/high-temperature heat treatment mode (mode without carbonization), the key process parameters in the steps (6) and (7) are generally adopted, and the fifth and seventh liquid phase densification periods refer to the key process parameters in the step (9). After eight liquid phase densification periods are accumulated, the volume density of the carbon/carbon composite material reaches 1.88g/cm3And finally, finishing to obtain the high-density revolution body carbon/carbon composite material.
The obtained high-density revolving body carbon/carbon composite material meets the requirements of bearing and heat resistance of aerospace thermal structural components and dies in working environments; example 3 was repeated and all the samples obtained were acceptable.
Example 4
The high-density revolving body carbon/carbon composite material prepared in the embodiment is of a revolving body structure with the same wall thickness, the specification is 500mm magnitude (outer diameter), a single-material-column loading mode (shown as a schematic diagram 1) is adopted in the chemical vapor densification process, and the manufacturing method specifically comprises the following steps:
(1) alternately laying non-woven cloth and ultrathin net tire, wherein the alternate lamination period of the non-woven cloth is [0 °/60 °/120 ° ]]nIntroducing Z-direction carbon fibers through bidirectional penetration to form a three-dimensional puncture structure preform with the volume density of 0.70g/cm3The weight ratio of the non-woven cloth to the net tire is 75: 25; the density between layers of the non-woven fabric is 18-19 layers/cm; the Z-direction fiber spacing was 2.0 x 2.0 mm.
(2) Placing the carbon fiber preform into a vacuum induction furnace, heating to 1700 ℃ at the speed of 100 ℃/h under the vacuum condition, preserving heat for 1h, and gradually introducing high-purity argon (99.99%) during the heat preservation period; then, heating to 2300 ℃ at the speed of 100 ℃/h and preserving heat for 2h, wherein the pressure in the furnace is maintained in a micro-positive pressure state; and (5) keeping the temperature for 2h, stopping heating, and naturally cooling along with the furnace.
(3) A limited-area reactor (as shown in a schematic diagram 2) is arranged in a deposition furnace, carbon fiber preforms subjected to high-temperature heat treatment are loaded in a deposition chamber in a single material column mode, 4 layers of strip-shaped carbon felts are arranged below each preform and used as cushion blocks (the height of each cushion block is 30-40mm), and 4 layers of strip-shaped cover plates with the same outer diameter are arranged above the preform at the top end of each material column and covered.
(4) Starting a vacuum system after the pressure rise rate of the measuring equipment is qualified (less than 300Pa/h), gradually heating to 945 ℃, preserving the temperature for 2h, and introducing reaction gas; the flow ratio of the propylene to the nitrogen is 5:1, and the pressure of a deposition system is 1.0-1.2 kPa; the gas phase densification process takes 100h as a period, and the blank is loaded in the reverse order after the first period is finished to continue densification. After the total deposition time is 350h, the carbon fiber preform is densified to a bulk density of 1.32-1.35g/cm3。
(5) Carrying out surface machining on the carbon/carbon composite material blank after gas phase densification, then placing the blank into a vacuum induction furnace, heating to 1800 ℃ at the speed of 100 ℃/h under the vacuum condition, preserving heat for 1h, and gradually introducing high-purity argon (99.99%) during the heat preservation period; then, heating to 2300 ℃ at the speed of 100 ℃/h and preserving heat for 2h, wherein the pressure in the furnace is maintained in a micro-positive pressure state; and (5) keeping the temperature for 2h, stopping heating, and naturally cooling along with the furnace.
(6) Furan resin is used as a raw material, phosphoric acid (7.5 wt.%) is used as a curing agent, and the carbon/carbon composite material blank subjected to high-temperature heat treatment is subjected to impregnation/curing treatment, wherein the resin impregnation pressure is 3-5MPa, and the impregnation time is 5-7 hours; the curing temperature is 180-;
(7) placing the carbonized carbon/carbon composite material blank in a vacuum induction furnace for high-temperature heat treatment at 2000 ℃ in a segmented mode, wherein the heating rate is 100 ℃/h, and the mode conversion temperature is 1700 ℃; after the high-temperature heat treatment is finished, carrying out surface process machining on the carbon/carbon composite material blank;
(8) repeating the steps (6) and (7) to complete a second liquid phase densification cycle;
(9) repeating the steps (6) and (7) after the second liquid phase densification cycle is completed, setting the heat treatment temperature in the step (7) to 2300 ℃ and the mode switching temperature to 1800 ℃, and completing the third liquid phase densification cycle.
(10) The subsequent liquid phase densification process adopts a dipping/curing/high-temperature heat treatment mode (mode without carbonization), the key process parameters in the steps (6) and (7) are generally adopted, and the fifth and eighth liquid phase densification periods refer to the key process parameters in the step (9). After ten liquid phase densification periods are accumulated, the volume density of the carbon/carbon composite material reaches 1.88g/cm3And finally, finishing to obtain the high-density revolution body carbon/carbon composite material.
The obtained high-density revolving body carbon/carbon composite material meets the requirements of bearing and heat resistance of aerospace thermal structural components and dies in working environments; example 4 was repeated and all the samples obtained were acceptable.
In the technical development process, the inventor tries to solve the problem that when the minimum distance between upper and lower adjacent carbon fiber preforms in a limited-area reactor in a vapor deposition phase is less than 30 mm; the volume density of the carbon/carbon composite material blank after densification by chemical vapor deposition is more than 1.40g/cm3When the current is over; in the high-temperature heat treatment process, a segmented mode of a vacuum stage and an inert gas protection stage is not adopted, and a single vacuum heat treatment or a single inert atmosphere heat treatment is adopted; the manufacturing period of the sample is obviously longer, and the qualification rate is obviously lower.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A rapid preparation method of a high-density revolving body carbon/carbon composite material is characterized by comprising the following steps:
(1) knitting forming method of carbon fiber preform
The carbon fiber preform is punched by alternately laminating a non-woven fabric and an ultrathin net tire, and the introduction of Z-direction fibers is realized in a bidirectional penetration mode; wherein the non-woven fabric has an alternate lamination period of [0 °/60 °/120 ° ]]n(ii) a The density of the carbon fiber preform is 0.65-0.85g/cm3；
(2) High temperature heat treatment of carbon fiber preforms
Placing the carbon fiber preform obtained in the step (1) in a heating furnace; firstly, vacuumizing until the air pressure in the furnace is less than or equal to 100Pa, then heating to 1700-1800 ℃ for heat preservation, and then filling inert gas; heating to 2000-2300 ℃ under inert atmosphere, and preserving heat for 2-3h to obtain a carbon fiber preform subjected to high-temperature heat treatment;
(3) chemical vapor deposition densification
Taking the carbon fiber preform subjected to high-temperature heat treatment as a treatment object, and increasing the density of the carbon fiber preform to 1.25-1.40g/cm through chemical vapor deposition3Obtaining a blank after chemical vapor deposition densification; during chemical vapor deposition, the deposition temperature is controlled to be 945-975 ℃, and the deposition pressure is controlled to be 1.0-1.8 kPa;
the carbon fiber preform chemical vapor deposition densification is realized by the assistance of a limited-area reactor, the limited-area reactor is of a cylindrical structure and comprises a gas preheating area and a deposition reaction area, and the two areas are separated by a gas distribution plate;
(4) high temperature heat treatment after vapor deposition densification
Placing the blank obtained in the step (3) after the chemical vapor deposition densification into a heating furnace; firstly, vacuumizing until the air pressure in the furnace is less than or equal to 100Pa, then heating to 1700-1800 ℃ for heat preservation, and then filling inert gas; heating to 2000-2300 ℃ under inert atmosphere, and preserving heat for 2-3h to obtain a blank subjected to high-temperature heat treatment;
(5) resin impregnation/carbonization densification
Performing resin impregnation/carbonization densification on the blank subjected to high-temperature heat treatment; the single impregnation time is less than 8 hours, the single curing time is less than 6 hours, and the single carbonization time is less than 4 hours; obtaining a resin impregnated/carbonized densified blank;
(6) high-temperature heat treatment;
putting the resin impregnated/carbonized densified blank obtained in the step (5) into a heating furnace; firstly, vacuumizing until the air pressure in the furnace is less than or equal to 100Pa, then heating to 1700-1800 ℃ for heat preservation, and then filling inert gas; heating to 2000-2300 deg.C under inert atmosphere, and keeping the temperature for 2-3 h.
2. The method for rapidly preparing a high-density revolved body carbon/carbon composite material according to claim 1, wherein the carbon/carbon composite material is in a revolved body structure shape, and the carbon fiber preform is in a puncture structure or a needle-punched structure; the high density means that the volume density of the material is more than or equal to 1.88g/cm3。
Preferably, the carbon/carbon composite material of the revolution body is in a cylindrical shape with equal wall thickness;
preferably, the carbon fiber preform is a piercing structure.
3. The method for rapidly preparing a high-density solid of revolution carbon/carbon composite material according to claim 1, wherein the bulk density of the carbon fiber preform is 0.65 to 0.85g/cm3(ii) a The weight percentage of the non-woven cloth to the net tire is 70:30-90: 10; the density between layers of the non-woven fabric is 16-26 layers/cm; the Z-direction fiber spacing is 2.0-2.8 mm.
Preferably, the carbon fiber preform has a bulk density of 0.70 to 0.80g/cm3；
Preferably, the weight ratio of the non-woven cloth to the net tire in the carbon fiber preform is 75:25-85: 15;
preferably, the interlayer density of the carbon fiber preform non-woven fabric is 18-24 layers/cm;
preferably, the Z-direction fiber spacing is 2.0 x 2.0mm to 2.6 x 2.6 mm.
4. The method for rapidly preparing the high-density revolving body carbon/carbon composite material according to claim 1, wherein the high-temperature heat treatment temperature in the steps (2), (4) and (6) is 2000 ℃ to 2300 ℃, the holding time is 2 to 3 hours, and the heating rate is 80 to 120 ℃/h.
Preferably, the heating rate of the high-temperature heat treatment is 100 ℃/h;
preferably, the inert gas for high-temperature heat treatment adopts high-purity argon; the purity of the high-purity argon is more than or equal to 99.99 percent.
5. The method for rapidly preparing the high-density revolving body carbon/carbon composite material according to claim 1, characterized in that: the chemical vapor deposition densification adopts propylene as a carbon source gas and nitrogen as a diluent gas, and the flow ratio of the propylene to the nitrogen is 5:1-3: 1.
Preferably, the distance between the upper adjacent carbon fiber preforms and the lower adjacent carbon fiber preforms in the confined reactor is 30-40 mm.
Preferably, the distance between the carbon fiber preforms of different material columns in the confined reactor is 50-60 mm;
preferably, the distance between the carbon fiber preform and the deposition cylinder in the confinement reactor is 80-100 mm.
6. The method for rapidly preparing the high-density revolving body carbon/carbon composite material according to claim 1, characterized in that: in the step (3), the density of the carbon fiber preform is raised to 1.25-1.40g/cm through chemical vapor deposition3Obtaining a blank after chemical vapor deposition densification; and (4) processing the surface of the blank densified by the chemical vapor deposition and then entering the manufacturing link in the step (4).
7. The method for rapidly preparing the high-density revolving body carbon/carbon composite material according to claim 1, characterized in that: the resin adopted for impregnating the carbon/carbon composite material in the step (5) is furan resin; the curing agent adopts phosphoric acid, and the dosage of the phosphoric acid is 5-9% of the mass of the resin; the dipping pressure is 3-5MPa, and the single dipping time is 5-7 hours; the curing temperature is 180-200 ℃, the single curing time is 1-5 hours, and the curing pressure is 3-5 MPa; the carbonization temperature is 800-1000 ℃, the single carbonization time is 2-3 hours, and the nitrogen protection is performed in the whole carbonization process.
8. The method for rapidly preparing the high-density revolving body carbon/carbon composite material according to claim 1, characterized in that: in the step (6), the carbonized carbon/carbon composite material is subjected to high-temperature heat treatment in a high-temperature furnace, and surface process processing is performed after the heat treatment to complete a first liquid-phase densification cycle; the impregnation/carbonization/heat treatment densification cycle is repeated after processing.
In particular, in the liquid phase densification cycle, the carbonization process is canceled after 2-3 cycles, i.e. the carbonization/solidification process is directly performed in the heat treatment process after the impregnation/solidification process is completed.
9. The method for rapidly preparing the high-density revolving body carbon/carbon composite material according to claim 1, characterized in that: after the steps (5) and (6) are cyclically executed for 8-10 times, the volume density of the carbon/carbon composite material can reach 1.88g/cm3The above.
10. The application of the rapid preparation method of the high-density revolving body carbon/carbon composite material is characterized in that: the prepared composite material is suitable for the fields of aerospace, industrial molds and the like.
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