CN114734659A - Forming method of continuous fiber reinforced thermoplastic PAKE hollow composite material product - Google Patents
Forming method of continuous fiber reinforced thermoplastic PAKE hollow composite material product Download PDFInfo
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- CN114734659A CN114734659A CN202210471604.9A CN202210471604A CN114734659A CN 114734659 A CN114734659 A CN 114734659A CN 202210471604 A CN202210471604 A CN 202210471604A CN 114734659 A CN114734659 A CN 114734659A
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- 239000002131 composite material Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 55
- 239000011199 continuous fiber reinforced thermoplastic Substances 0.000 title claims abstract description 33
- 239000000835 fiber Substances 0.000 claims abstract description 46
- 229920006260 polyaryletherketone Polymers 0.000 claims abstract description 23
- 238000001816 cooling Methods 0.000 claims abstract description 22
- 238000003825 pressing Methods 0.000 claims abstract description 13
- 238000002844 melting Methods 0.000 claims abstract description 11
- 230000008018 melting Effects 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000004804 winding Methods 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 26
- 238000000465 moulding Methods 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000007769 metal material Substances 0.000 claims description 10
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 10
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 9
- 229920002530 polyetherether ketone Polymers 0.000 claims description 9
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 8
- 239000004917 carbon fiber Substances 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 238000009966 trimming Methods 0.000 claims description 7
- 229920002379 silicone rubber Polymers 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 5
- 229920001652 poly(etherketoneketone) Polymers 0.000 claims description 5
- 229920001973 fluoroelastomer Polymers 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 4
- 238000003475 lamination Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 3
- 239000004945 silicone rubber Substances 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 229920006231 aramid fiber Polymers 0.000 claims description 2
- IYRWEQXVUNLMAY-UHFFFAOYSA-N carbonyl fluoride Chemical class FC(F)=O IYRWEQXVUNLMAY-UHFFFAOYSA-N 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 claims 1
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- 229920001657 poly(etheretherketoneketone) Polymers 0.000 claims 1
- 229920001660 poly(etherketone-etherketoneketone) Polymers 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 238000004080 punching Methods 0.000 claims 1
- 239000000741 silica gel Substances 0.000 description 12
- 229910002027 silica gel Inorganic materials 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005674 electromagnetic induction Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- -1 ether ketone Chemical class 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000009755 vacuum infusion Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
- B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
- B29C37/02—Deburring or deflashing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/54—Component parts, details or accessories; Auxiliary operations, e.g. feeding or storage of prepregs or SMC after impregnation or during ageing
Abstract
The invention discloses a method for forming a continuous fiber reinforced thermoplastic PAKE hollow composite material product, which comprises the following steps: (1) winding raw materials required by the continuous fiber reinforced PAEK composite material on a high-temperature-resistant tool to obtain a blank piece; (2) transferring the blank piece and the high-temperature-resistant tool into a forming device, and heating; (3) when the temperature rises to be higher than the melting temperature of the raw materials, preserving the heat, then applying pressure to the outside of the high-temperature resistant tool, simultaneously introducing high-pressure gas into the high-temperature resistant tool, and maintaining the pressure for a period of time; (4) and after pressure maintaining, quickly cooling, opening the mold, taking out the product, and deburring to obtain a molded product. The forming method of the continuous fiber reinforced thermoplastic PAKE hollow composite material product provided by the invention gets rid of the limitation that winding equipment and wire laying and laying equipment are required, and the continuous fiber reinforced thermoplastic PEAK hollow composite material product can be manufactured. The method of the invention has simple process and makes up for the current domestic technical shortages.
Description
Technical Field
The invention relates to the field of special engineering plastic thermoplastic composite materials, in particular to a method for forming a continuous fiber reinforced thermoplastic PAKE hollow composite material product.
Background
Polyether ketone (PAEK) is a kind of aromatic thermoplastic special engineering plastic. The molecular chain contains rigid benzene rings, soft and smooth ether bonds and carbonyl groups, the molecular structure is relatively regular, and the semi-crystalline is presented. The crystallinity varies according to the forming process, and generally ranges from 5 to 48 percent. The crystallinity varies, and the properties of the material also vary slightly. The unique molecular structure endows the PAEK material with good dimensional stability, remarkable thermal stability, good mechanical property, chemical corrosion resistance, fatigue resistance and the like. The performance of the material can be further improved by adjusting the forming process, or the PAEK crystallinity can be artificially regulated and controlled according to specific requirements.
The development and application of PAEK are mature abroad, late in initiation at home and relatively laggard in technology. The special engineering plastic thermoplastic material can be subjected to injection molding, extrusion and high-temperature compression molding according to common plastics except for high melting temperature. The pure PAEK material, the chopped fiber or the fiber powder reinforced and modified PAEK material can be molded according to conventional materials, and the set temperature of a mold is increased. For continuous fiber reinforced PAEK materials, the melting temperature exceeds 300 ℃, many continuous fiber reinforced resin matching processes, such as: vacuum infusion, hand pasting, wet bag pressing, etc. cannot be used. While autoclaves, winding and lay-down processes can be used, equipment must be upgraded to require temperatures that can be raised to 400 ℃ or above for application. Due to the lack of corresponding forming equipment in China and the research on the continuous fiber reinforced PAEK composite material, the main body stays in the development stage of the unidirectional tape and cannot be continuously extended. Otherwise, the equipment needs to be imported from foreign countries at high cost, and the equipment for laying the silk cannot be imported at present due to the trade war of China and America. Patent CN106079475B discloses a method for manufacturing a solid-headed pipe with a sealed end at one end of a composite material, which aims at the problem that two-step molding is needed to manufacture the pipe after the thermosetting resin is paved; patent CN113650273A "a light high pressure resistant composite material pipe, preparation method and preparation system" first winds continuous fiber cloth on a pipeline core mold and preheats the continuous fiber cloth, then impregnates the fiber cloth with MC nylon prepolymer, and finally heats and cures the impregnated MC nylon prepolymer to obtain the composite material pipe. These prior art patented methods are significantly different from PEAK press forming.
Disclosure of Invention
Aiming at the defects of the prior continuous fiber reinforced PAEK material production technology in China at present, the invention provides a method for molding a continuous fiber reinforced thermoplastic PAKE hollow composite material product with simple process on the basis of molding the conventional composite material pipe, and makes up the technical defects.
The invention is realized by the following technical scheme:
a method for forming a continuous fiber reinforced thermoplastic PAKE hollow composite article, comprising the steps of:
(1) winding raw materials required by the continuous fiber reinforced PAEK composite material on a high-temperature-resistant tool to obtain a blank piece;
(2) transferring the blank piece and the high-temperature-resistant tool to a cavity of a molding device together, and then starting to heat;
(3) when the temperature rises to be higher than the melting temperature of the raw materials, preserving the heat, then applying pressure to the outside of the high-temperature resistant tool, simultaneously introducing high-pressure gas into the high-temperature resistant tool, and maintaining the pressure for a period of time;
(4) after pressure maintaining, quickly cooling, opening the die, taking out the product, and trimming burrs to obtain a molded product;
wherein: the molding equipment has the functions of high-temperature pressing and rapid heating and cooling.
Further, a method for forming a continuous fiber reinforced thermoplastic PAKE hollow composite product comprises the following steps: the continuous fiber reinforced PAEK composite material in the step (1), wherein the fiber is selected from one of continuous carbon fiber, continuous glass fiber, continuous aramid fiber, continuous quartz fiber, continuous polyimide and continuous PPO fiber.
Further, a method for forming a continuous fiber reinforced thermoplastic PAKE hollow composite product comprises the following steps: the material can be in the form of unidirectional fiber prepreg, fiber fabric prepreg, alternate lamination composite of fiber and resin film, or alternate lamination composite of fiber and resin powder.
Further, a method for forming the continuous fiber reinforced thermoplastic PAKE hollow composite material product comprises the following steps: the continuous fiber reinforced PAEK composite material in the step (1), wherein the PAKE can be one or more modified compositions of PEEK (polyether ether ketone), PEK (polyether ketone), PEKK (polyether ketone), PEKEKK (polyether ketone ether ketone) and PEEKK (polyether ether ketone).
Further, a method for forming a continuous fiber reinforced thermoplastic PAKE hollow composite product comprises the following steps: transferring the blank piece and the high-temperature-resistant tool to a cavity of a molding device together, and then starting to heat; wherein the temperature rising process needs to be completed within 2 hours.
Further, a method for forming a continuous fiber reinforced thermoplastic PAKE hollow composite product comprises the following steps: the high-temperature resistant tool in the step (2) is a pipe made of a non-metal material or a soft metal material with the expansion coefficient larger than that of the continuous fiber reinforced PAEK composite material; wherein the non-metallic material is required to be instantly resistant to temperature of more than 300 ℃ and the melting point of the soft metallic material is more than 350 ℃.
Further, a method for forming a continuous fiber reinforced thermoplastic PAKE hollow composite product comprises the following steps: the non-metallic material is selected from modified silicon rubber, modified fluororubber or modified fluoroketone rubber.
Further, a method for forming a continuous fiber reinforced thermoplastic PAKE hollow composite product comprises the following steps: and (3) the forming equipment in the step (2) is one of a vulcanizing machine, a mould pressing machine or stamping equipment.
Further, a method for forming a continuous fiber reinforced thermoplastic PAKE hollow composite product comprises the following steps: and (3) preserving heat when the temperature is raised to be higher than the melting temperature of the raw materials by 20-30 ℃, then applying pressure to the outside of the high-temperature-resistant tool by 4.0-5.0MPa through a forming device, simultaneously introducing high-pressure air of 1.5-3.0MPa into the high-temperature-resistant tool, and keeping the pressure for 2-30 minutes.
Further, a method for forming a continuous fiber reinforced thermoplastic PAKE hollow composite product comprises the following steps: after pressure maintaining, quickly cooling to below 130 ℃, then opening the mold, taking out the product, and trimming burrs to obtain a molded product; wherein the rapid cooling process needs to complete rapid cooling within 60 minutes.
Specifically, the forming method of the continuous fiber reinforced thermoplastic PAKE hollow composite material product comprises the following specific steps:
(1) winding raw materials required by the continuous fiber reinforced PAEK composite material on a high-temperature-resistant tool to obtain a blank piece;
(2) transferring the blank piece and the high-temperature-resistant tool to a cavity of a molding device together, and then starting to heat;
(3) when the temperature rises to be higher than the melting temperature of the raw materials, preserving the heat, then applying pressure to the outside of the high-temperature resistant tool, simultaneously introducing high-pressure gas into the high-temperature resistant tool, and maintaining the pressure for a period of time; ensuring that the exterior of the formed product is mechanically pressurized and the interior of the formed product is pressurized by high-temperature compressed air, wherein the internal pressure of the formed product is generated by two forces, one is extrusion of the high-temperature resistant tool on the interior of the product due to thermal expansion, the other is thermal expansion force of the compressed air, and the two forces are transmitted to the interior of the composite material product pipe;
(4) after pressure maintaining, quickly cooling, opening the die, taking out the product, and trimming burrs to obtain a molded product;
wherein: the molding equipment has a high-temperature pressing function and can maintain pressure; the molding equipment also has the functions of rapid temperature rise and rapid temperature drop, and the temperature can be quickly raised to 380 ℃ or above in a short time and can also be reduced to 130 ℃ or below in a short time.
The principle of the forming method of the PAKE hollow composite material product provided by the invention is as follows:
the method is characterized in that the high-temperature compression molding and hollow blow molding principles are combined, the molding equipment has the functions of pressure application and pressure maintaining, certain small pressure is applied to the outside of a product mold in the stage of starting temperature rise to prevent the disorder of fiber grains caused by temperature rise and expansion of a resin material, when the temperature of the mold rises to be 20-30 ℃ higher than the melting temperature of the resin material, the outside and the inside gradually apply pressure at the same time, the outside applies pressure by means of the molding equipment, and the inside applies pressure by means of thermal expansion of an auxiliary material (namely a high-temperature-resistant tool material) or by means of heat expansion of high-pressure air. Under dual pressure, it was ensured that the PAEK resin in the molten state could penetrate into the fiber tows. Keeping the pressure for a certain time to ensure that the soaking is finished, and then rapidly cooling and shaping. When the temperature is reduced to below 130 ℃, the temperature is reduced to below the glass transition temperature of the PAEK resin, the PAEK resin is solidified, and the continuous fiber reinforced PAEK is formed. And finally, removing redundant sizing materials and scattered fiber tows at the joint line part to obtain the continuous fiber reinforced PAEK hollow product.
The invention has the beneficial effects that:
(1) the forming method of the continuous fiber reinforced thermoplastic PAKE hollow composite material product provided by the invention has a simple process and makes up for the technical shortages in China at present.
(2) The forming method of the continuous fiber reinforced thermoplastic PAKE hollow composite material product provided by the invention gets rid of the limitation that winding equipment and wire laying and laying equipment are required, and the continuous fiber reinforced thermoplastic PEAK hollow composite material product can be manufactured. In view of production continuity, although the process of the invention belongs to intermittent production and does not achieve the effect of continuous and rapid production, the process at least can produce products for experimental research and analysis and application of small-volume products, and is an obvious step progress.
(3) The composite material prepared by the invention can be applied to the field with high temperature resistance and high toughness requirements, and is mainly applied to the fields of aerospace and military industry.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
Example 1
A forming method of a continuous fiber reinforced thermoplastic PAKE hollow composite material product (specifically, a 990mm phi 45 phi 42mm continuous carbon fiber reinforced thermoplastic PEEK composite material pipe is manufactured) comprises the following specific steps:
(1) preparing a continuous carbon fiber reinforced PEEK material prepreg with the width of 980mm and the length of 700mm, and uniformly applying force to wind the prepreg on a high-temperature-resistant tool with the outer diameter phi of 41.8 phi of 36mm (the high-temperature-resistant tool is a pipe made of modified fluororubber) to obtain a blank piece; meanwhile, the edge part of the prepreg is welded and fixed by using an electric soldering iron, so that unwinding is avoided; then, the two ends of the high-temperature resistant tool are modified to ensure that the length of the high-temperature resistant tool is between 1050 plus 1100mm, and meanwhile, the outer sides of the two ends of the high-temperature resistant tool are sealed by using high-temperature resistant films;
(2) transferring the blank piece and the high-temperature-resistant tool into a cavity of a molding device together, closing a mold, and then starting to heat; wherein: the used mould is a mould press, the pressure application and pressure maintaining of the mould press are controlled by programs, the temperature rise and cooling can be controlled by the programs, and the temperature of the pressing plate can be raised to 450 ℃ at most;
(3) raising the temperature to 370 ℃ by program control for 110 minutes, preserving the heat, then applying pressure to the outside of the high-temperature resistant tool by 5.0MPa, and simultaneously introducing high-pressure gas by 2.0MPa from two ends of the high-temperature resistant tool to ensure that the outside of the formed pipe is mechanically pressed by a press and the inside of the formed pipe is pressed by high-temperature compressed air; the pressure in the formed pipe comes from two forces, one is the force of the thermal expansion of the modified fluororubber tool, the other is the force of the thermal expansion of compressed air, the two forces are transmitted to the inside of the formed composite pipe, the outside is 5.0MPa, the inside is 2.0MPa, and the pressure is kept constant for 10 minutes;
(4) and after the pressure maintaining is finished, rapidly cooling to below 130 ℃ within 60 minutes, then decompressing and opening the die, cleaning fibers and excess materials overflowing from resin at the position of a joint line outside the product, taking out the fibers and excess materials, and trimming burrs to obtain the phi 45 x phi 42mm continuous carbon fiber reinforced thermoplastic PEEK composite material pipe.
Example 2
A molding method of a continuous fiber reinforced thermoplastic PAKE hollow composite product (specifically, a 1000mm phi 40 x phi 37mm continuous carbon fiber reinforced thermoplastic PEKK composite pipe is manufactured), and the preparation process comprises the following specific steps:
(1) preparing a continuous carbon fiber reinforced PEKK material prepreg with the width of 990mm and the length of 630mm, uniformly applying force to wind the prepreg on a high-temperature-resistant tool with the outer diameter phi of 36.8 phi 31mm (wherein the high-temperature-resistant tool is a pipe made of modified silicon rubber), and obtaining a blank piece; meanwhile, the edge part of the prepreg is welded and fixed by using an electric soldering iron, so that unwinding is avoided; then, both ends of the silica gel high-temperature resistant tool pipe are modified to ensure that the length of the silica gel high-temperature resistant tool pipe is between 1030 and 1050mm, and simultaneously, both ends of the silica gel high-temperature resistant tool pipe are wound and sealed by using high-temperature resistant films;
(2) placing the blank with the silica gel tool in a forming die, closing the die, and then starting to heat up; wherein: the used mould is a mould press, the pressure application and pressure maintaining of the mould can be controlled by a program, heating and cooling are not controlled, heating and cooling are arranged in the mould, and the mould is externally connected with an electromagnetic induction heating system and a refrigerator water cooling system;
(3) raising the temperature to 360 ℃ by program control for 20 minutes, preserving the heat, then applying pressure to the outside of the high-temperature-resistant silica gel tool by 4.5MPa, and simultaneously introducing high-pressure air by 2.0MPa from two ends of the high-temperature-resistant silica gel tool to ensure that the outside of the formed pipe is mechanically pressed by a press and the inside of the formed pipe is pressed by high-temperature compressed air; the pressure in the formed pipe comes from two forces, one is the force of the thermal expansion of the modified silicone rubber tool, the other is the force of the thermal expansion of compressed air, the two forces are transmitted into the formed composite material pipe, the external part is 4.5MPa, the internal part is 2.0MPa, and the pressure is kept constant for 5 minutes;
(4) after the pressure maintaining is finished, rapidly cooling to below 125 ℃ within 60 minutes, then decompressing and opening the die, cleaning the fibers and the excess materials overflowing from the resin at the external joint line part of the product, taking out the fibers and the excess materials, and trimming burrs to obtain the phi 40 x phi 37mm continuous carbon fiber reinforced thermoplastic PEKK composite material pipe.
Example 3
A method for forming a continuous fiber reinforced thermoplastic PAKE hollow composite material product (specifically, a horn-shaped continuous carbon fiber reinforced thermoplastic PEK composite material pipe which is 200mm long, 80X phi 78mm at one end and 40mm at the other end) comprises the following specific steps:
(1) preparing a continuous carbon fiber reinforced PEK material prepreg with the width of 630mm, the length of 1010mm at one end and the height of 195mm, uniformly applying force to wind the prepreg on a high-temperature-resistant tool with one end phi 77.8 phi 72mm, the other end phi 38 phi 33mm and the length of 230mm (wherein the high-temperature-resistant tool is a pipe made of modified silicon rubber), and thus obtaining a blank; meanwhile, welding and fixing the edge part of the prepreg by using an electric iron; then, both ends of the silica gel high-temperature resistant tool pipe are modified to ensure that the length of the silica gel high-temperature resistant tool pipe is between 210 and 200mm, and simultaneously, both ends of the silica gel high-temperature resistant tool pipe are wound and sealed by using high-temperature resistant films;
(2) placing the blank with the silica gel tool in a forming die, closing the die, and then starting to heat up; wherein: the used mould is a mould press, the pressure application and pressure maintaining of the mould can be controlled by a program, heating and cooling are not controlled, heating and cooling are arranged in the mould, and the mould is externally connected with an electromagnetic induction heating system and a refrigerator water cooling system;
(3) the temperature is raised to 335 ℃ within 18 minutes through program control, then the temperature is kept, the pressure is applied to the outside of the high-temperature-resistant silica gel tool by 4.5MPa, and simultaneously 2.0MPa of high-pressure air is introduced from the two ends of the high-temperature-resistant silica gel tool, so that the pressure is mechanically applied to the outside of the formed pipe by a press, and the pressure is applied to the inside of the formed pipe by high-temperature compressed air; the pressure in the formed pipe comes from two forces, one is the force of the thermal expansion of the modified silicone rubber tool, the other is the force of the thermal expansion of compressed air, the two forces are transmitted into the formed composite material pipe, the external part is 4.5MPa, the internal part is 2.0MPa, and the pressure is kept constant for 5 minutes;
(4) after the pressure maintaining is finished, rapidly cooling to below 120 ℃ within 60 minutes, then decompressing and opening the die, cleaning the fiber and the excess material overflowing from the resin at the position of a joint line outside the product, taking out and trimming burrs to obtain the horn-shaped continuous carbon fiber reinforced thermoplastic PEK composite material pipe with the dimension length of 200mm, the diameter of one end of 80 phi 78mm and the diameter of the other end of 50 phi 40 mm.
Comparative example 1
Comparative example 1 differs from example 1 in that the prepreg in example 1 was prepared as a PEEK film, and glass fibers were used as fibers, and the remaining conditions were not changed.
Comparative example 2
Comparative example 2 is different from example 1 in that the prepreg of example 1 is prepared as a carbon fiber unidirectional prepreg, and the unidirectional prepreg is wrapped and wound in layers at a certain angle, for example, 0 °/45 °/-45 °, and the splice part is welded by heat and pressure, and the other conditions are the same as example 1.
The composites obtained in examples 1-3 and comparative examples 1-2 were tested for their properties, and the results of the tests are shown in Table 1 below.
The test results show that the raw materials and process parameters of the process can ensure that the prepared continuous fiber reinforced thermoplastic PAKE hollow composite material has excellent mechanical properties. According to the test results of the comparative examples 1 and 2, it is demonstrated that the present invention can be applied to the common continuous carbon fiber prepreg, and the two materials of the resin film and the fiber can be alternately stacked, and in addition, the unidirectional fiber prepreg can be used under the condition of a certain lay-up angle. According to the test result, different materials can form the composite pipe through the compounding, the fibers have different directions and are combined in different directions, and the test result is different. In addition, there are differences in properties due to the differences in glass fiber and carbon fiber materials.
The forming method provided by the invention gets rid of the limitation that winding equipment and wire laying and laying equipment are required, and can be used for manufacturing a continuous fiber reinforced thermoplastic PEAK hollow composite material product with excellent mechanical property. In view of production continuity, although the process belongs to an intermittent production mode and cannot achieve the purpose of continuous and rapid production, the process can produce specific products for experimental research and analysis and application of small-volume products, and has obvious step progress.
The above-mentioned preferred embodiments of the present invention are provided for illustration only and not for the purpose of limiting the invention. Obvious variations or modifications of the present invention are within the scope of the present invention.
Claims (10)
1. A method for forming a continuous fiber reinforced thermoplastic PAKE hollow composite article, comprising the steps of:
(1) winding raw materials required by the continuous fiber reinforced PAEK composite material on a high-temperature-resistant tool to obtain a blank piece;
(2) transferring the blank piece and the high-temperature-resistant tool to a cavity of a molding device together, and then starting to heat;
(3) when the temperature rises to be higher than the melting temperature of the raw materials, preserving the heat, then applying pressure to the outside of the high-temperature resistant tool, simultaneously introducing high-pressure gas into the high-temperature resistant tool, and maintaining the pressure for a period of time;
(4) after pressure maintaining, quickly cooling, opening the die, taking out the product, and trimming burrs to obtain a molded product;
wherein: the molding equipment has the functions of high-temperature pressing, rapid heating and rapid cooling.
2. The method for forming a continuous fiber reinforced thermoplastic PAKE hollow composite product according to claim 1, wherein the continuous fiber reinforced PAEK composite material in step (1) is selected from one of continuous carbon fiber, continuous glass fiber, continuous aramid fiber, continuous quartz fiber, continuous polyimide, and continuous PPO fiber.
3. The method for forming a continuous fiber reinforced thermoplastic PAKE hollow composite material product according to claim 2, wherein the material form can be unidirectional fiber prepreg, fiber fabric prepreg, alternate lamination and composite of fiber and resin film, and alternate lamination and composite of fiber and resin powder.
4. The method of claim 1, wherein the continuous fiber reinforced PAKE composite material in step (1) is a modified composition of one or more of PEEK, PEK, PEKK, PEKEKK, and PEEKK polyether ketones.
5. The method for molding the continuous fiber reinforced thermoplastic PAKE hollow composite material product according to claim 1, wherein in the step (2), the blank and the high temperature resistant tool are transferred to a molding equipment cavity together, and then the temperature is raised; wherein the temperature rising process needs to be completed within 2 hours.
6. The method for forming the continuous fiber reinforced thermoplastic PAKE hollow composite material product according to claim 1 or 5, wherein the high temperature resistant tool in the step (2) is a pipe made of a non-metallic material or a soft metallic material with an expansion coefficient larger than that of the continuous fiber reinforced PAEK composite material; wherein the non-metallic material is required to be instantly resistant to temperature exceeding 300 ℃, and the melting point of the soft metallic material exceeds 350 ℃.
7. The method as claimed in claim 6, wherein the non-metallic material is selected from modified silicone rubber, modified fluoro rubber or modified fluoro ketone rubber.
8. The method of claim 1 or 5, wherein the forming device in step (2) is one of a vulcanizing machine, a molding machine or a punching device.
9. The method for molding the continuous fiber reinforced thermoplastic PAKE hollow composite material product according to claim 1, wherein in the step (3), when the temperature is raised to be higher than the melting temperature of the raw material by 20-30 ℃, the heat preservation is carried out, then the molding equipment is used for pressurizing the outside of the high temperature resistant tool by 4.0-5.0MPa, and simultaneously high-pressure air with the pressure of 1.5-3.0MPa is introduced into the high temperature resistant tool, and the pressure is maintained for 2-30 minutes.
10. The method for molding the continuous fiber reinforced thermoplastic PAKE hollow composite material product according to claim 1, wherein after the pressure maintaining in the step (4), the temperature is rapidly reduced to below 130 ℃, then the mold is opened, the product is taken out, and burrs are removed to obtain a molded product; wherein the rapid cooling process needs to complete rapid cooling within 60 minutes.
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