CN111647252B - Carbon honeycomb and preparation method thereof - Google Patents
Carbon honeycomb and preparation method thereof Download PDFInfo
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- CN111647252B CN111647252B CN202010348455.8A CN202010348455A CN111647252B CN 111647252 B CN111647252 B CN 111647252B CN 202010348455 A CN202010348455 A CN 202010348455A CN 111647252 B CN111647252 B CN 111647252B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 125
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 96
- 239000004917 carbon fiber Substances 0.000 claims abstract description 96
- 229920005989 resin Polymers 0.000 claims abstract description 61
- 239000011347 resin Substances 0.000 claims abstract description 61
- 239000004744 fabric Substances 0.000 claims abstract description 49
- 238000009958 sewing Methods 0.000 claims abstract description 29
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 52
- 239000003292 glue Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 238000009941 weaving Methods 0.000 claims description 16
- 238000002347 injection Methods 0.000 claims description 15
- 239000007924 injection Substances 0.000 claims description 15
- 239000011302 mesophase pitch Substances 0.000 claims description 11
- 239000003822 epoxy resin Substances 0.000 claims description 9
- 229920000647 polyepoxide Polymers 0.000 claims description 8
- 229920001187 thermosetting polymer Polymers 0.000 claims description 7
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 6
- 241000264877 Hippospongia communis Species 0.000 description 117
- 238000009745 resin transfer moulding Methods 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000835 fiber Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 238000004026 adhesive bonding Methods 0.000 description 3
- -1 but not limited to Polymers 0.000 description 3
- 239000011162 core material Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- 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
- B29C70/48—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 and impregnating the reinforcements in the closed mould, e.g. resin transfer moulding [RTM], e.g. by vacuum
-
- 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 provides a carbon honeycomb, wherein the honeycomb wall of the carbon honeycomb is two-dimensional carbon cloth; the adjacent two-dimensional carbon cloth is sewed by sewing carbon fibers; the two-dimensional carbon cloth is woven by high-modulus carbon fibers and high-thermal-conductivity carbon fibers; the surfaces of the honeycomb walls of the carbon honeycomb are coated with RTM resin. The carbon honeycomb not only has the characteristic of high rigidity, but also has the characteristic of high heat conduction along the height direction of the honeycomb. The heat of the spacecraft can be effectively conducted, and the structural stability and the service life of the spacecraft are further improved. The invention also provides a preparation method of the carbon honeycomb, which has the advantages of simple preparation process, accurate control of resin content, good surface quality of the carbon honeycomb and regular arrangement of hexagonal cells of the carbon honeycomb.
Description
Technical Field
The invention relates to a carbon honeycomb and a preparation method thereof, belonging to the field of carbon materials.
Background
Structural materials used in the field of spacecraft have very high requirements on physical and chemical properties. The structural material is required to have the properties of light weight, high strength, high modulus, high and low temperature alternation resistance and the like, and also needs to have good heat-conducting property so as to quickly dredge heat generated by each component of a satellite system and ensure the stability of the size of each structure and the normal operation of electronic components.
The invention patent CN106626438A discloses a carbon fiber honeycomb core supporting structure and a preparation method thereof. The invention adopts prepreg to coat the surface of the soft mould, and then the prepreg is arranged one by one to form a honeycomb structure. The method has the advantages that the process is complicated, the workload is huge for the honeycomb structure with a slightly large plane size, and the position deviation is easy to generate in the arrangement process, so that the honeycomb structure is irregular. Secondly, only the resin layers are adhered in the longitudinal direction and the transverse direction of the honeycomb plane, so that carbon fibers are discontinuous, the longitudinal tensile strength and the transverse tensile strength of the honeycomb are low, and the requirement of high modulus is difficult to meet. Thirdly, the direct laying of the prepreg on the surface of the soft mold easily causes defects such as poor and rich glue, pores and the like on the surface of the honeycomb wall after molding, and influences various performances of the honeycomb.
The invention patent CN107379644A discloses a method for preparing a carbon fiber honeycomb core material. The carbon fiber honeycombs are prepared by aligning carbon fiber cloth with equal width, bonding two adjacent layers of cloth at the same interval by using bonding glue, stretching the cloth into a honeycomb shape and dipping the honeycomb. The carbon honeycomb prepared by the method is bonded in the transverse direction through the adhesive, so that the transverse tensile strength and modulus of the honeycomb are low, the resin content is difficult to control in the gum dipping process, and the components of the honeycomb wall are uneven.
The carbon fiber honeycomb can be prepared by the preparation method of the carbon honeycomb, but the prepared carbon honeycomb has poor heat conduction in the height direction, so that the application of the carbon fiber honeycomb in the structural field which has high heat conduction and heat dissipation requirements and needs to consider heat control design is limited. Therefore, the problem that the heat conductivity of the carbon honeycomb is ensured while the rigidity of the carbon honeycomb is ensured is to be solved urgently.
Disclosure of Invention
It is a first object of the present invention to provide a highly rigid carbon honeycomb having a high thermal conductivity in the height direction.
The second purpose of the invention is to provide a preparation method of the carbon honeycomb with high rigidity and high thermal conductivity along the height direction.
The present invention provides a carbon honeycomb which is,
the honeycomb walls of the carbon honeycomb are two-dimensional carbon cloth;
the adjacent two-dimensional carbon cloth is sewed by sewing carbon fibers;
the two-dimensional carbon cloth is obtained by weaving carbon fibers I and carbon fibers II;
the weaving is carried out by taking the carbon fiber I as the warp direction and the carbon fiber II as the weft direction;
the carbon fiber I is carbon fiber with tensile modulus of 377-600 GPa;
the carbon fiber II is carbon fiber with the heat conductivity coefficient of 500-1000W/m.K;
the surfaces of the honeycomb walls of the carbon honeycomb are coated with RTM resin.
The carbon fiber with the tensile modulus of 377-600GPa comprises PAN-based carbon fiber.
The stitched carbon fiber comprises one of T300, T700, or T800.
The carbon fiber with the thermal conductivity of 500-1000W/m.K comprises mesophase pitch-based carbon fiber.
The wall thickness of the carbon honeycomb is 0.1-0.5mm, and the height of the carbon honeycomb is 5-50 mm.
The honeycomb side length of the carbon honeycomb is 5-20 mm.
The volume density of the carbon honeycomb is 30-300kg/m3。
The row spacing of the sewing carbon fiber is 0.5 mm-1.5 mm.
The sewing width of the sewing is 0.95 to 1.05 times of the side length of the honeycomb.
The sewing distance is 2.95 to 3.05 times of the sewing width.
The PAN-based carbon fiber is one selected from M40J, M55J or M60J.
The tows of the PAN-based carbon fibers are 1K-6K.
The tows of the mesophase pitch-based carbon fibers are 1K-6K.
The two-dimensional carbon cloth comprises plain cloth, twill cloth or satin cloth.
The RTM resin is a thermosetting resin.
The thermosetting resin comprises one of epoxy resin or bismaleimide resin.
The invention also provides a preparation method of the carbon honeycomb,
the method comprises the following steps:
(1) weaving by taking the carbon fiber I as a warp direction and the carbon fiber II as a weft direction to obtain two-dimensional carbon cloth, aligning, overlapping and sewing the two-dimensional carbon cloth to obtain a honeycomb-shaped prefabricated body;
(2) RTM resin is preheated by adopting an RTM method, and then the RTM resin is injected from the bottom of the honeycomb preform, so that the RTM resin infiltrates the honeycomb preform along the height direction of the honeycomb preform.
(3) And curing the RTM resin to obtain the carbon honeycomb.
The pressure of the glue injection is 0.1MPa-1 MPa.
The temperature of the RTM resin after preheating is 39-42 ℃;
the viscosity of the RTM resin after preheating is 0.1-1 Pa.s;
the curing temperature is 140-180 ℃.
Drawings
FIG. 1 is a schematic view showing the sewing of two-dimensional carbon cloths adjacent to each other in a carbon honeycomb according to the present invention
FIG. 2 is a schematic view of a carbon honeycomb according to the present invention
Detailed Description
The carbon honeycomb and the method for manufacturing the same according to the present invention will be described in further detail with reference to the accompanying drawings and specific examples.
The invention provides a carbon honeycomb, wherein the honeycomb wall of the carbon honeycomb is two-dimensional carbon cloth, and the two-dimensional carbon cloth is obtained by weaving carbon fibers I with high tensile modulus in the warp direction and carbon fibers II with high thermal conductivity in the weft direction. The two-dimensional carbon cloth is high in strength, and meanwhile, the heat conduction speed in the weft direction is high, so that the gathered heat can be effectively conducted, and a heat transfer path is provided for the carbon honeycomb while the high rigidity of the carbon honeycomb is ensured. Therefore, the carbon honeycomb can have a high rigidity and also has an extremely high thermal conductivity in the height direction. In the carbon honeycomb, adjacent two-dimensional carbon cloth is also sewed by sewing carbon fibers; the stitching may reinforce the carbon honeycomb, improving the mechanical properties of the honeycomb in the transverse direction, which further improves the rigidity of the carbon honeycomb. The surfaces of the honeycomb walls of the carbon honeycomb are coated with RTM resin. The RTM resin is coated on the surface of the honeycomb wall of the carbon honeycomb, is filled in the pores among the fiber bundles, and forms a whole with the fibers, so that the two-dimensional carbon cloth is compact and not loose, and meanwhile, the fibers can be protected and loads can be transferred, and the carbon honeycomb is more uniformly stressed. In some embodiments of the present invention, the carbon fiber I has a modulus of 377-600 GPa. The modulus of carbon fiber I directly determines to some extent the rigidity of the carbon honeycomb.
In some embodiments of the present invention, the carbon fiber II has a thermal conductivity of 500-1000W/m.K.
In certain embodiments of the invention, the carbon honeycomb has a wall thickness of 0.1 to 0.5 mm.
In certain embodiments of the invention, the carbon honeycomb has a height of 5-50 mm.
In certain embodiments of the present invention, the carbon honeycomb has internal hexagonal cell sides of 5-20mm in length.
In certain embodiments of the invention, the carbon honeycomb has a bulk density of 30 to 300kg/m3。
Those skilled in the art will appreciate that too low a thermal conductivity may result in poor designability of the carbon honeycomb.
The designability refers to the design of the side length, the wall thickness and the height of the carbon honeycomb. If the thermal conductivity of the carbon fibers II is less than 500W/m.K, the thermal conductivity of the carbon honeycomb may be less than 1W/m.K in extreme cases, such as when the honeycomb has a side length of more than 20mm and a wall thickness of less than 0.1 mm. If the thermal conductivity of the carbon fiber II is more than 500W/m.K, the thermal conductivity of the carbon honeycomb in the height direction can reach 30W/m.K or more in some cases. In some extreme cases, the thermal conductivity of the carbon honeycomb in the height direction can be as high as 30W/m.K or more when the wall thickness is greater than 0.5mm and the side length is less than 5 mm. In some embodiments of the present invention, PAN-based carbon fibers are used for the carbon fibers with the modulus of 377-600 GPa. The PAN-based carbon fiber is low in cost and good in manufacturability, and cannot be damaged at the bent position of the honeycomb. It will be appreciated by those skilled in the art that the present invention may be practiced with other types of high tensile modulus carbon fibers including, but not limited to, PAN-based carbon fibers.
In some embodiments of the present invention, the PAN-based carbon fiber is a PAN-based carbon fiber having a model number of M40J, M55J, or M60J. The model is the model of carbon fiber produced by Dongli carbon fiber. Where M refers to graphite grade carbon fibers and the number refers to the tensile modulus J refers to the type of fiber surface sizing agent.
In certain embodiments of the invention, the high modulus carbon fiber tow is 1K to 6K.
In some embodiments of the invention, the carbon fiber having a thermal conductivity of 500W/mK to 1000W/mK is a mesophase pitch-based carbon fiber. It will be appreciated by those skilled in the art that the present invention may be practiced with other types of high thermal conductivity carbon fibers including, but not limited to, mesophase pitch-based carbon fibers.
In certain embodiments of the present invention, the tow of the highly thermally conductive carbon fibers is 1K to 6K.
In some embodiments of the present invention, the suture fibers are T300, T700 or T800 carbon fibers. The T300, T700 or T800 type carbon fiber has low cost and good weaving manufacturability. It will be appreciated by those skilled in the art that the present invention may be practiced with other types of carbon fibers including, but not limited to, T300, T700 or T800 type carbon fibers. The above-mentioned model is a model of carbon fiber produced by Dongli carbon fiber known to those skilled in the art.
In some embodiments of the invention, the stitching is in the warp direction, the stitching width is 0.95-1.05 times the length of the honeycomb side, and the stitching pitch is 2.95-3.05 times the length of the honeycomb side. The stitching is layer by layer. The pitch of the rows of the stitched carbon fibers is 0.5 mm-1.5 mm.
In certain embodiments of the present invention, the RTM resin is selected from thermosetting resins. The adoption of thermosetting resin facilitates the molding of the vacuum assisted RTM process.
In some embodiments of the present invention, the thermosetting resin is an epoxy resin or a bismaleimide resin. The epoxy resin or bismaleimide resin has good heat resistance, higher rigidity and high structural stability, and is suitable for being applied to the aerospace field. It will be appreciated by those skilled in the art that the present invention may be practiced with other types of thermoset resins including, but not limited to, epoxy resins, bismaleimide resins.
In some embodiments of the present invention, the two-dimensional carbon cloth may be plain cloth, twill cloth, satin cloth.
As can be seen from certain examples of the present invention and comparative examples, the carbon honeycomb produced by the sewing process has significantly improved shear modulus and shear strength relative to the carbon honeycomb produced without the sewing process.
The invention also provides a preparation method of the carbon honeycomb.
The preparation method of the carbon honeycomb is a Rubber-assisted vacuum resin transfer molding method (Rubber-VARTM), and comprises the following steps:
(1) weaving the prefabricated body: the carbon fiber with high modulus is used as the warp direction, the carbon fiber with high thermal conductivity is used as the weft direction to weave and manufacture two-dimensional carbon cloth, the two-dimensional carbon cloth is aligned and overlapped, the honeycomb side length is used as the sewing width in the warp direction, and the honeycomb side length is used as the interval to sew layer by layer to manufacture the carbon honeycomb prefabricated body.
(2) And (3) putting the core mold into the carbon honeycomb prefabricated body, placing the carbon honeycomb prefabricated body in a mold cavity of a forming mold, flatly placing the carbon honeycomb prefabricated body, and then fastening and sealing the mold. The resin injection port is designed at the bottom of the mold, so that RTM resin is injected from the bottom of the carbon honeycomb preform, flows uniformly along the height direction of the carbon honeycomb preform, and infiltrates carbon fibers. When RTM resin is injected from the bottom of the carbon honeycomb prefabricated part, the flowing resistance of the resin is small, the glue injection process is easy to realize, and simultaneously, the resin content of the honeycomb wall is uniform after the resin is cured. In addition, the RTM process is realized by firstly weighing the weight of the carbon honeycomb preform, then calculating the weight of the required resin according to the content of the resin to be achieved, and controlling the proportion of the weight of the resin in the glue injection tank and the glue injection amount.
(3) Checking air tightness: and vacuumizing the tightly sealed die for more than 10min, closing a vacuumizing valve, injecting compressed air, observing whether gas leaks or not, and keeping the gas tightness qualified if no leakage exists for more than 5 min.
(4) Injecting glue: and opening vacuum, and injecting glue after glue injection pressure adjustment. Different glue injection process parameters are selected according to the RTM resin with a specific mark.
(5) And (3) curing: the tightly sealed mold is moved into an oven or autoclave to cure the RTM resin. Different curing temperatures, heat preservation times and heating rates are set for different RTM resins.
(6) Demolding: and opening the mold to obtain the carbon honeycomb.
In some embodiments of the invention, the injection pressure is 0.1MPa to 1 MPa. Too large glue injection pressure can improve the requirements of tooling equipment, and too low glue injection pressure cannot meet the technological requirements.
In some embodiments of the present invention, the RTM resin is preheated before injecting the resin. The viscosity of the preheated resin is 0.1-1 Pa.s. The viscosity is too high, the resin is difficult to flow during glue injection, and pores are easily caused; the viscosity is too low, and the resin is easily sucked into the vacuum pipeline, so that the vacuum pipeline is blocked.
In summary, compared with the prior art, the invention has the following beneficial effects:
1. compared with the existing carbon honeycomb, the carbon honeycomb provided by the invention not only has the characteristic of high rigidity, but also has the characteristic of high heat conduction system along the height direction of the honeycomb. The heat of the spacecraft can be effectively conducted, and the structural stability and the service life of the spacecraft are further improved.
2. The antenna reflector and the like composed of the honeycomb sandwich composite material structure have the characteristics of high structural efficiency, large specific stiffness, strong vibration resistance and the like, the composite material structure can maintain the requirements of high-precision performance, structural bearing and the like of the antenna, and in the in-orbit operation process of the spacecraft, sunlight sun-shade difference and heat of a satellite-borne instrument are large, so that the rationality of the thermal control design of the spacecraft needs to be considered.
3. The RTM forming process and the die form adopted by the invention have the advantages of simple preparation process, accurate control of resin content, good honeycomb surface quality and regular honeycomb hexagonal cell arrangement.
Examples
For better understanding of the above technical solutions, the following detailed descriptions will be made with reference to the drawings and specific embodiments of the specification, but the present invention is not limited to these specific embodiments.
In the embodiment of the invention, the heat conductivity of the carbon honeycomb is measured by a laser flash method. Before testing, the carbon honeycomb was embedded with epoxy resin and its surface was machined flat.
The shear properties of the carbon honeycombs in the examples of the invention were tested using the method described in ASTM C273 standard.
Example 1
Selecting 1K mesophase pitch-based carbon fibers with the thermal conductivity of 600W/m.K as weft and M55J carbon fibers with the tensile modulus of 540GPa as specification 1K as warp, weaving the warp into two-dimensional twill cloth with the thickness of 0.15mm, cutting the warp into woven cloth with the width of 10mm, aligning the woven cloth, sewing the warp with T700 carbon fibers layer by taking 5mm as sewing width and 15mm as sewing interval to prepare a carbon honeycomb prefabricated body, then placing the carbon honeycomb prefabricated body in a mold and keeping the vacuum, selecting RTM epoxy resin to perform the steps of
And Hshand 2098R is preheated to 40 ℃, the viscosity is kept at 0.5 +/-0.05 Pa.s, when the pressure reaches 0.1MPa, resin is injected from the bottom of the carbon honeycomb prefabricated body, the pressure is kept for 10min, then the pressure is increased to 0.3MPa, the pressure is kept for 10min, the pressure is continuously increased to 0.6MPa, the pressure is kept for 30min, and when residual glue appears in a vacuum pipeline, glue injection is stopped. Transferring the die into an oven, heating to 180 deg.C at 2 deg.C/min, maintaining for 4 hr, naturally cooling to below 60 deg.C, and demolding to obtain honeycomb with side length of 5mm, wall thickness of 0.15mm, height of 10mm, and volume density of 42kg/m3The high thermal conductivity carbon honeycomb.
Example 2
Selecting mesophase pitch-based carbon fibers with the thermal conductivity coefficient of 700W/m.K as weft and M55J carbon fibers with the tensile modulus of 540GPa as warp, weaving the mesophase pitch-based carbon fibers into two-dimensional plain cloth with the thickness of 0.2mm, cutting the woven cloth with the width of 15mm, aligning the woven cloth, sewing the woven cloth layer by using T300 carbon fibers with the sewing width of 6mm and the sewing distance of 18mm to prepare a carbon honeycomb prefabricated body, then placing the carbon honeycomb prefabricated body in a mold and keeping the mold in vacuum, selecting RTM epoxy resin to perform vacuum
Hshand 2080R is preheated to 40 ℃, the viscosity is kept at 0.2 +/-0.05 Pa.s, when the pressure reaches 0.1MPa, resin is injected from the bottom of the carbon honeycomb preform and kept for 10min, then the pressure is increased to 0.3MPa and kept for 30min, and when residual glue appears in a vacuum pipeline, glue injection is stopped. Transferring the mold into an oven, heating to 140 deg.C at 2 deg.C/min, maintaining for 2 hr, naturally cooling to below 60 deg.C, and demolding to obtain honeycomb with side length of 6mm, wall thickness of 0.2mm, height of 15mm, and volume density of 47kg/m3The high thermal conductivity carbon honeycomb.
Example 3
Selecting 3K mesophase pitch-based carbon fibers with the thermal conductivity coefficient of 800W/m.K as the weft direction, selecting M60J carbon fibers with the tensile modulus of 588GPa of specification 3K as the warp direction, weaving into two-dimensional satin cloth with the thickness of 0.3mm, cutting the weaving cloth with the width of 20mm, aligning the weaving cloth, sewing the weaving cloth layer by using T800 carbon fibers with the sewing width of 8mm and the sewing distance of 24mm to prepare a carbon honeycomb prefabricated body, then placing the carbon honeycomb prefabricated body in a mould and keeping the vacuum, selecting QY8911-IV bismaleimide resin, preheating to 100 ℃, keeping the pressure at 0.6-1 Pa.s, starting injecting the resin when the pressure reaches 0.1MPa, keeping the pressure for 10min, then increasing the pressure to 0.3MPa, keeping the pressure for 10min, continuously increasing the pressure to 0.6MPa, keeping the pressure for 20min, and stopping injecting the resin when residual glue appears in a vacuum pipeline. Transferring the die into an oven, heating to 160 deg.C at 3 deg.C/min, holding for 2 hr, heating to 180 deg.C at 2 deg.C/min, holding for 2 hr, heating to 200 deg.C at 1 deg.C/min, holding for 4 hr, naturally cooling to below 60 deg.C, and demolding to obtain honeycomb with side length of 8mm, wall thickness of 0.3mm, height of 20mm, and volume density of 52.5kg/m3The high thermal conductivity carbon honeycomb.
Comparative example
Selecting 1K mesophase pitch-based carbon fibers with the thermal conductivity coefficient of 600W/m.K as weft and M55J carbon fibers with the tensile modulus of 540GPa as specification 1K as warp, weaving the warp into two-dimensional twill cloth with the thickness of 0.15mm, cutting the warp into woven cloth with the width of 10mm, aligning the woven cloth, gluing the warp with hot melt epoxy film layer by taking 5mm as gluing width and 15mm as gluing interval to prepare a carbon honeycomb preform, then placing the carbon honeycomb preform in a mold and keeping the vacuum, selecting RTM epoxy resin
Hshand 2098R is preheated to 40 ℃, the viscosity is kept at 0.5 +/-0.05 Pa.s, when the pressure reaches 0.1MPa, resin is injected, the pressure is kept for 10min, then the pressure is increased to 0.3MPa, the pressure is kept for 10min, the pressure is continuously increased to 0.6MPa, the pressure is kept for 30min, and when residual glue appears in a vacuum pipeline, glue injection is stopped. Transferring the die into an oven, heating to 180 deg.C at 2 deg.C/min, maintaining for 4 hr, naturally cooling to below 60 deg.C, and demolding to obtain honeycomb with side length of 5mm, wall thickness of 0.15mm, height of 10mm, and volume density of 41.5kg/m3The high thermal conductivity carbon honeycomb.
The following table shows the thermal conductivity, shear strength and shear modulus data of the carbon honeycombs prepared in the examples of the present invention.
Claims (11)
1. A carbon honeycomb, characterized by:
the honeycomb walls of the carbon honeycomb are two-dimensional carbon cloth;
the adjacent two-dimensional carbon cloth is sewed by sewing carbon fibers;
the two-dimensional carbon cloth is obtained by weaving carbon fibers I and carbon fibers II;
the weaving is carried out by taking the carbon fiber I as the warp direction and the carbon fiber II as the weft direction;
the carbon fiber I is carbon fiber with tensile modulus of 377-600 GPa;
the carbon fiber II is carbon fiber with the heat conductivity coefficient of 500-1000W/m.K;
the surfaces of the honeycomb walls of the carbon honeycomb are coated with RTM resin.
2. The carbon honeycomb of claim 1, wherein:
the carbon fiber with the tensile modulus of 377-600GPa comprises PAN-based carbon fiber;
the stitched carbon fiber comprises one of T300, T700, or T800;
the carbon fiber with the thermal conductivity of 500-1000W/m.K comprises mesophase pitch-based carbon fiber.
3. The carbon honeycomb of claim 1, wherein:
the wall thickness of the carbon honeycomb is 0.1-0.5mm, and the height of the carbon honeycomb is 5-50 mm;
the side length of the carbon honeycomb is 5-20mm, and the volume density of the carbon honeycomb is 30-300kg/m 3 。
4. The carbon honeycomb of claim 2, wherein:
the row spacing of the sewing carbon fibers is 0.5 mm-1.5 mm;
the sewing width of the sewing is 0.95-1.05 times of the side length of the honeycomb;
the sewing distance is 2.95 to 3.05 times of the sewing width.
5. The carbon honeycomb of claim 2, wherein:
the PAN-based carbon fiber is one selected from M40J, M55J or M60J;
the tows of the PAN-based carbon fibers are 1K-6K.
6. The carbon honeycomb of claim 2, wherein:
the tows of the mesophase pitch-based carbon fibers are 1K-6K.
7. The carbon honeycomb of claim 1, wherein:
the two-dimensional carbon cloth comprises plain cloth, twill cloth or satin cloth.
8. The carbon honeycomb of claim 1, wherein:
the RTM resin is thermosetting resin;
the thermosetting resin comprises one of epoxy resin or bismaleimide resin.
9. The method of making a carbon honeycomb of any one of claims 1-8, wherein: the method comprises the following steps:
(1) weaving by taking the carbon fiber I as a warp direction and the carbon fiber II as a weft direction to obtain two-dimensional carbon cloth, aligning, overlapping and sewing the two-dimensional carbon cloth to obtain a honeycomb-shaped prefabricated body;
(2) RTM resin is preheated by adopting an RTM method, and then the RTM resin is injected from the bottom of the honeycomb preform, so that the RTM resin infiltrates the honeycomb preform along the height direction of the honeycomb preform;
(3) and curing the RTM resin to obtain the carbon honeycomb.
10. The method of making a carbon honeycomb of claim 9, wherein:
in the step of injecting the RTM resin from the bottom of the honeycomb preform, the pressure of the adopted glue injection is 0.1-1 MPa.
11. The method of making a carbon honeycomb of claim 9, wherein:
the temperature of the RTM resin after preheating is 39-42 ℃;
the viscosity of the RTM resin after preheating is 0.1-1 Pa.s;
the curing temperature is 140-180 ℃.
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| US6114006A (en) * | 1997-10-09 | 2000-09-05 | Alliedsignal Inc. | High thermal conductivity carbon/carbon honeycomb structure |
| US20080286522A1 (en) * | 2006-12-15 | 2008-11-20 | Subhotosh Khan | Honeycomb having a low coefficient of thermal expansion and articles made from same |
| CN103408315B (en) * | 2013-08-09 | 2015-04-22 | 航天材料及工艺研究所 | Three-dimensional mesophase pitch-based carbon/carbon composite material with high heat conductivity and preparation technology thereof |
| CN106316437A (en) * | 2015-06-26 | 2017-01-11 | 上海航天设备制造总厂 | Satellite high-thermal-conductivity carbon/carbon composite material honeycomb preparation method |
| CN108314458B (en) * | 2018-02-09 | 2020-07-21 | 陕西天策新材料科技有限公司 | Preparation method of high-thermal-conductivity carbon/carbon composite material |
| CN110282994B (en) * | 2019-06-24 | 2021-08-17 | 湖南东映碳材料科技有限公司 | Preparation method of carbon fiber reinforced carbon-based composite material honeycomb |
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