CN115109281B - Carbon nanotube reinforced co-curing damping composite material and preparation method thereof - Google Patents

Carbon nanotube reinforced co-curing damping composite material and preparation method thereof Download PDF

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CN115109281B
CN115109281B CN202211028749.8A CN202211028749A CN115109281B CN 115109281 B CN115109281 B CN 115109281B CN 202211028749 A CN202211028749 A CN 202211028749A CN 115109281 B CN115109281 B CN 115109281B
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CN115109281A (en
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郑长升
李强
王瑞春
李延昭
翟彦春
刘炳昌
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Weifang University of Science and Technology
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Abstract

The application provides a carbon nanotube reinforced co-curing damping composite material and a preparation method thereof. The method firstly proposes that hydrogenated carboxyl nitrile rubber is used as a viscoelastic damping sandwich material to be embedded into the composite material, and the hydrogenated carboxyl nitrile rubber viscoelastic material can form an interpenetrating network structure with an epoxy resin matrix through physical fusion and chemical crosslinking in the co-curing process, so that the composite material has excellent interlayer bonding performance. In addition, the carbon nanotubes are introduced into the surface of the carbon fiber, and the epoxy resin-based carbon fiber prepreg with different carbon nanotube contents can form a composite material in functional gradient distribution through superposition and curing. Compared with the traditional composite material, the structure can greatly improve the interface bonding strength and reduce the residual stress and the thermal stress; eliminating the stress singularity of the interface cross point and the stress free end point in the connecting material; the joint strength is enhanced, and the crack driving force is reduced, so that the overall mechanical property of the co-curing damping composite material is improved.

Description

Carbon nanotube reinforced co-curing damping composite material and preparation method thereof
Technical Field
The invention relates to the technical field of structural functional composite materials, in particular to a carbon nano tube reinforced co-curing damping composite material and a preparation method thereof.
Background
The composite material has the advantages of high specific strength, large specific rigidity, high specific modulus, fatigue resistance and the like, so that the composite material gradually replaces wood and metal alloy materials and is widely applied to the fields of aerospace, automobiles, electronics and electrics, buildings, body-building equipment and the like. The matrix of the non-metal composite material mainly comprises synthetic resin, rubber, ceramic, graphite, carbon and the like, and the reinforcing material mainly comprises glass fiber, carbon fiber, boron fiber, aramid fiber, silicon carbide fiber, asbestos fiber, whisker, metal and the like.
In order to further improve the damping performance of the non-metal composite material, the damping material can be embedded into the composite material in a manner of co-curing with resin on the basis of the traditional resin-based fiber reinforced composite material. At present, the commonly used damping material is vulcanized rubber, the surface molecular activity of the damping material is low, the aging resistance and the bonding mechanical property are poor, the interface bonding property and the overall mechanical property of the composite material are obviously reduced, the damping material is easy to age and fall off in the using process, the bearing capacity of a composite structure is lost, and the application of the damping material is severely limited.
Disclosure of Invention
The invention provides a carbon nano tube reinforced co-curing damping composite material and a preparation method thereof, aiming at the defects in the prior art.
In a first aspect, the invention provides a preparation method of a carbon nanotube reinforced co-cured damping composite material, which comprises the following steps:
step 1: growing carbon nanotubes on the surfaces of carbon fibers, combining the carbon fibers on which the carbon nanotubes are grown with epoxy resin to prepare carbon nanotube modified epoxy resin-based carbon fiber prepregs, and paving the epoxy resin-based carbon fiber prepregs with different carbon nanotube contents according to a gradient sequence to form a composite material preformed body in functional gradient distribution;
step 2: plasticating and mixing the cut hydrogenated carboxyl nitrile rubber to obtain raw rubber which is mixed uniformly;
and step 3: dissolving the uniformly mixed virgin rubber in an organic solvent which is easy to exert to form rubber cement, and uniformly coating the rubber cement on a substrate to prepare a viscoelastic damping film;
and 4, step 4: and embedding the viscoelastic damping film as a middle layer between the two composite material preformed bodies through an autoclave co-curing process.
Preferably, the growing of the carbon nanotubes on the surface of the carbon fiber further comprises the following steps:
adding carbon fiber in N 2 Carrying out heat treatment in the atmosphere to obtain desized carbon fibers;
adding the desized carbon fiber into 5 wt% NH 4 H 2 PO 4 Electrolyzing in the aqueous solution to obtain modified carbon fibers;
immersing the modified carbon fiber into ethanol solution with different catalyst precursors to obtain the carbon fiber with a precursor coating, wherein the different catalysts comprise: ferric nitrate nonahydrate, nickel nitrate hexahydrate, cobalt nitrate hexahydrate;
subjecting the carbon fiber with the precursor coating to N 2 Heating to 440 deg.C under protection, maintaining the temperature for 20min, and introducing H 2 Heating to 460 deg.C, keeping the temperature, and finally introducing C 2 H 2 。
Preferably, the step 2 further comprises the following steps:
adding the cut hydrogenated carboxyl nitrile rubber into an open mill for plastication for 2-3 min;
adding the antioxidant p, p-diisopropylphenyl diphenylamine and the reinforcing agent N330 carbon black into the plasticated hydrogenated carboxylated nitrile rubber, mixing for 5-7min, then adding the crosslinking agent BIBP, the vulcanization aid gamma-aminopropyltriethoxysilane and the accelerator ZnO-80, and mixing for 3-4min to obtain the pre-vulcanized hydrogenated carboxylated nitrile rubber;
adding the tackifier RS into the pre-vulcanized hydrogenated carboxylated nitrile rubber, mixing for 4-5min, and calendering to obtain uniformly mixed virgin rubber.
Preferably, the mass ratio of the hydrogenated carboxylated nitrile rubber to the antioxidant pair to the p-diisopropylphenyl diphenylamine, the reinforcing agent N330 carbon black, the crosslinking agent BIBP, the vulcanization aid gamma-aminopropyltriethoxysilane and the accelerator ZnO-80 is 100:1.5:60:2:1:6.
Preferably, the step 3 further comprises the following steps:
dissolving the uniformly mixed virgin rubber in tetrahydrofuran to form rubber cement, wherein the proportion of the virgin rubber to the tetrahydrofuran is 1g;
and dripping the adhesive cement on a substrate rotating at a high speed, and preparing the adhesive cement into a viscoelastic damping film by using centrifugal force.
Preferably, the step 4 further comprises the following steps:
placing a viscoelastic damping film between the two composite material preformed bodies, and pressurizing to 2-3 MPa;
heating to 70-90 deg.C at a heating rate of 1-2 deg.C/min, maintaining for 30-60min, heating to 120 deg.C, 150 deg.C and 180 deg.C respectively, maintaining for 30-60min, and cooling to room temperature at a cooling rate of 1-2 deg.C/min.
Preferably, C 2 H 2 、H 2 And N 2 The flow rates of (A) are respectively 5L/min, 5L/min and 10L/min.
In a second aspect, the invention also provides a carbon nanotube reinforced co-cured damping composite material, which is prepared by any one of the methods.
The beneficial effects of this application are as follows:
the application firstly proposes that hydrogenated carboxyl nitrile rubber is used as a viscoelastic damping sandwich material to be embedded into the composite material, and the hydrogenated carboxyl nitrile rubber viscoelastic material can form an interpenetrating network structure with an epoxy resin matrix through physical fusion and chemical crosslinking in the co-curing process, so that the composite material has excellent interlayer bonding performance. In addition, the carbon nanotubes are introduced to the surface of the carbon fiber, and the epoxy resin-based carbon fiber prepreg with different carbon nanotube contents can be formed into a composite material with functional gradient distribution through superposition and solidification. Compared with the traditional composite material, the carbon nano tube reinforced co-curing damping composite structure has the following advantages: 1) The functional gradient composite material is used as an interface layer to connect two incompatible materials, so that the interface bonding strength can be greatly improved; 2) The use of the functionally graded composite material as the interface layer can reduce residual stress and thermal stress; 3) The functional gradient composite material is used as an interface layer, so that stress singularity of an interface intersection point and a stress free endpoint in the connecting material can be eliminated; 4) The functional gradient carbon nanotube reinforced co-cured damping composite structure is used for replacing the traditional composite material, so that the connection strength can be enhanced, the crack driving force can be reduced, and the overall mechanical property of the co-cured damping composite material is improved. Under the combined action of the carbon nano tubes with the function gradient distribution and the interface molecular chemical bonds, the material has the advantages of designable mechanical property, high damping, strong interface bonding property, large integral bending rigidity, aging resistance and the like, and has wide application prospect in the fields of light weight, vibration reduction and noise reduction, such as aerospace, high-speed rail, automobile manufacturing, household appliances, fan blades and the like.
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For a clearer explanation of the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
FIG. 1 is a flow chart of a method for preparing a carbon nanotube reinforced co-cured damping composite according to an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of a carbon nanotube reinforced co-cured damping composite according to an embodiment of the present invention;
FIG. 3 is a scanning electron micrograph of a composite containing a viscoelastic damping film;
FIG. 4 is a scanning electron micrograph of a composite containing carbon nanotubes;
FIG. 5 is a vulcanization curve of HXNBR at 180 ℃ after kneading;
FIG. 6 is a graph of the variation of the damping loss factor of HXNBR with temperature;
FIG. 7 is a schematic drawing of tensile strengths of test pieces 1 to 7;
fig. 8 is a schematic view of the bending strength of test pieces 1 to 7;
fig. 9 is a free vibration damping change curve of the test piece 1;
fig. 10 is a free vibration damping change curve of the test piece 4;
FIG. 11 shows a functionally graded distribution pattern of carbon nanotubes.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making creative efforts based on the embodiments of the present invention, shall fall within the protection scope of the present invention.
Aiming at the defects of the prior art, the scheme provides a carbon nano tube reinforced co-curing damping composite material and a preparation method thereof. Referring to fig. 1, a flow chart of a method for preparing a carbon nanotube reinforced co-cured damping composite according to an embodiment of the present invention is shown. As can be seen from fig. 1, the method comprises the following steps:
step S1: growing carbon nanotubes on the surfaces of carbon fibers, combining the carbon fibers on which the carbon nanotubes are grown with epoxy resin to prepare carbon nanotube modified epoxy resin-based carbon fiber prepregs, and paving the epoxy resin-based carbon fiber prepregs with different carbon nanotube contents according to a gradient sequence to form a composite material preformed body in functional gradient distribution;
step S2: plasticating and mixing the cut hydrogenated carboxyl nitrile rubber to obtain raw rubber which is mixed uniformly;
and step S3: dissolving the uniformly mixed virgin rubber in an organic solvent which is easy to exert to form rubber cement, and uniformly coating the rubber cement on a substrate to prepare a viscoelastic damping film;
and step S4: and embedding the viscoelastic damping film as a middle layer between the two composite material preformed bodies through an autoclave co-curing process.
Referring to fig. 2, a schematic structural diagram of a carbon nanotube reinforced co-cured damping composite according to an embodiment of the present invention is shown. As can be seen from FIG. 2, the carbon nanotube reinforced co-cured damping composite material is formed by alternately superposing a viscoelastic damping film and a composite material pre-forming body. Wherein the composite material pre-forming body can be prepared from epoxy resin-based carbon fiber pre-preg with different carbon nanotube contentsAnd the layers are sequentially paved in a gradient way. The layering sequence of the viscoelastic damping film and the composite material preformed body can be [0 ] 4 d0 4 ]Wherein 0 represents that the direction of the carbon fiber is 0 degree, d represents a viscoelastic damping film as an intermediate layer, and 4 represents that the composite material preformed bodies on the upper surface and the lower surface of the viscoelastic damping film are composed of 4 layers of epoxy resin-based carbon fiber prepregs.
The matrix material used in the invention is epoxy resin-based carbon fiber prepreg. The viscoelastic damping material is mainly composed of a high molecular polymer hydrogenated carboxyl nitrile rubber HXNBR, wherein the HXNBR is a terpolymer formed by copolymerizing conjugated diene, acrylonitrile and unsaturated carboxylic acid, and is prepared by selective hydrogenation. The carboxyl groups in the HXNBR are substantially unhydrogenated and are randomly distributed along the backbone. The carboxylic acid group can be used as an active point to form a chemical bond by itself or with a matrix, and can supplement the carbon-carbon crosslinking bond formed by a peroxide curing system. The HXNBR has excellent mechanical property, wear resistance and adhesive property. The high polymer can exhibit higher damping properties when the HXNBR transitions from a glassy state to a highly elastic state. Therefore, HXNBR is used as the best choice for damping layer of co-cured composite material due to its excellent mechanical properties. The HXNBR has the advantages of high vulcanization speed, high reaction speed and better heat resistance besides maintaining mechanical property and aging resistance. The epoxy group of the epoxy resin can generate etherification reaction with hydroxyl (as shown in a reaction formula (1)), the epoxy group of the epoxy resin can generate esterification reaction with carboxyl (as shown in a reaction formula (2)) to form an IPN structure, and the chemical crosslinking reactions are the co-curing theoretical basis for preparing the carbon nanotube reinforced co-curing damping composite material.
Figure 411328DEST_PATH_IMAGE002
Reaction formula (1)
Figure 572DEST_PATH_IMAGE004
Reaction type (2)
Referring to fig. 3 and 4, a scanning electron microscope image of the composite material containing the viscoelastic damping film and a scanning electron microscope image of the composite material containing the carbon nanotubes are respectively shown. As can be seen from fig. 3 and 4, the viscoelastic material and the resin matrix and the carbon nanotubes and the resin matrix are tightly combined, no obvious interface exists between the two, a stable transitional cross-linked structure is formed between different phases, and good physical compatibility is microscopically shown. Meanwhile, on one hand, the excellent compatibility between the HXNBR and the matrix epoxy resin is demonstrated, and on the other hand, the excellent interlayer mechanical property of the co-cured damping composite structure is proved to be derived from the physical and chemical effects among different materials.
In the application, co-curing means that the curing time and temperature of the embedded viscoelastic material HXNBR are matched with the curing time and temperature of the matrix epoxy resin, and the HXNBR and the epoxy resin form a microscopic interpenetrating network structure on a bonding interface through physical and chemical actions under the action of an additive and high temperature and high pressure so as to ensure that the composite material has higher interlayer bonding strength, so that the material has excellent structural rigidity and damping characteristics. The epoxy resin-based carbon fiber prepreg with the curing temperature of 180 ℃ has the advantages of good mechanical property, high temperature resistance and the like.
(1) The damping mechanism of the co-cured damping composite structure is as follows: the loss factor of the HXNBR is related to the melting and glass transition of the nitrile rubber, the internal viscosity of the HXNBR is higher due to the fact that the HXNBR is in a viscous state at the temperature near the glass transition temperature, rubber molecules are hindered by internal chain segments of the rubber during movement, strain lags behind stress, and hysteresis loss is generated, at the moment, the friction force inside the rubber molecules reaches the maximum, and therefore the loss factor near the glass transition temperature is the maximum. In addition, the internal friction between the reinforcing agent and the reinforcing agent or between the HXNBR molecular chain and the reinforcing agent can cause strong damping loss.
(2) The functional gradient distribution can improve the mechanical property of the traditional co-curing damping composite structure: compared with the traditional composite material, the carbon nano tube reinforced co-curing damping composite material has the following advantages: 1) The functional gradient material is used as an interface layer to connect two incompatible materials, so that the interface bonding strength can be greatly improved; 2) The use of functionally graded materials as the interfacial layer can reduce residual and thermal stresses; 3) The stress singularity of interface cross points and stress free end points in the connecting material can be eliminated by using the functional gradient material as the interface layer; 4) The functional gradient carbon nanotube reinforced co-curing damping composite structure is used for replacing the traditional composite material, so that the connection strength can be enhanced, and the crack driving force can be reduced.
The following examples are provided to illustrate specific methods for preparing the present materials.
Step 1: preparing a composite material preformed body in functional gradient distribution:
the carbon fibers are first placed in a vertical CVD furnace in N 2 Heat treatment is carried out for 2 hours in the atmosphere to remove the sizing agent, and the desized carbon fiber is obtained, wherein the heat treatment temperature is 400 ℃. Subsequently, the surface of the carbon fiber is modified by selective electrochemical anodic oxidation to obtain 5 wt% NH 4 H 2 PO 4 The aqueous solution was used as the electrolyte, the current intensity was 0.4A, and the modification time was 90S. And (3) soaking the modified carbon fiber into ethanol solutions with different catalyst precursors for 9min to obtain a uniform catalyst precursor coating on the surface of the carbon fiber. The carbon fibers coated with the catalyst precursor were then placed on a sample holder at N 2 Raising the temperature of the furnace to 440 ℃ under protection, preserving the temperature for 20min, and introducing H 2 And (3) converting the catalyst precursor into metal nano particles, then heating the furnace to 460 ℃, preserving the temperature, and introducing a carbon source to directly grow carbon nano tubes on the surfaces of the carbon fibers. Wherein H is in a reducing atmosphere 2 And N 2 The flow rates of the carbon dioxide gas and the nitrogen gas are respectively set to be 5L/min and 10L/min, and C is in the growth atmosphere 2 H 2 、H 2 And N 2 The flow rates of (2) are set to 5L/min, 5L/min and 10L/min, respectively. During the preparation process, N is continuously used 2 And (4) performing gas seal protection, ensuring that gas in the tubular furnace is isolated from air, adjusting the wire moving speed, and controlling the growth time so as to control the growth rate of the carbon nano tube. In addition, in the embodiment, the carbon fiber on which the carbon nanotube grows is combined with the epoxy resin by using a hand-pasting method to prepare the carbon nanotube modified epoxy resin-based carbon fiber prepreg, and the hand-pasting method is a common method in the field and is not described herein again.And paving the epoxy resin-based carbon fiber prepregs with different carbon nanotube contents according to a gradient sequence to form the composite material preformed body in functional gradient distribution. In other embodiments of the present application, the layering sequence may also be [0 ] 3 d0 3 ]And the like.
Step 2: preparation of HXNBR virgin rubber:
(1) And (4) cutting the HXNBR. Firstly, cutting 100 parts of HXNBR into rubber strips with the thickness of 100 mm multiplied by 20mm multiplied by 20mm, so that the rubber strips can be easily placed in an open mill, and finally, the volume fraction of the HXNBR rubber materials accounts for more than 80 percent of the capacity of the open mill;
(2) Plasticating of HXNBR. Because the HXNBR has higher hardness, the roller spacing of the open mill is adjusted to 2mm to calender the HXNBR, then the size of the roller spacing is gradually adjusted according to the hardness change of the HXNBR, the HXNBR is plasticated for 2-3 min, and finally the HXNBR is subjected to thin pass for 4-6 times;
(3) And (4) mixing the HXNBR. Controlling the temperature of a roller of an open mill at 50-60 ℃ by a water cooling method, firstly adding 1.5 parts of an anti-aging agent 445 (p, p-diisopropylphenyl diphenylamine) and 60 parts of reinforcing agent N330 carbon black into HXNBR, and mixing for 5-7min to ensure that the N330 carbon black is completely penetrated by rubber; then adding 2 parts of crosslinking agent BIBP, 1 part of vulcanization aid KH550 (gamma-aminopropyltriethoxysilane) and 6 parts of accelerator ZnO-80 into the HXNBR, and mixing for 3-4min to complete the pre-vulcanization of the HXNBR; then adding an adhesion promoter RS (a mixture of resorcinol and stearic acid) into the rubber compound, and mixing for 4-5min to enhance the adhesion performance of the HXNBR; then, calendering the primarily mixed HXNBR, adjusting the roll spacing to be the minimum for 5-6 times of triangular bag making, then adjusting the roll spacing to be 1.2-1.5 mm for rolling the rubber material and removing air bubbles in the rubber material to obtain the HXNBR which is uniformly mixed, and finally enabling the damping material to have excellent mechanical property and damping property through a mixing process. In the embodiment, the addition amount of each material is in parts by mass, and the proportion is the optimal proportion obtained by testing the components of the designed materials and the related mechanical properties and damping properties.
The invention selects an organic peroxide curing system to cure the HXNBR, and the cross-linking agent of the HXNBR can be sulfur or peroxide. The HXNBR after sulfur vulcanization has higher tensile strength and elongation at break and excellent comprehensive mechanical property, but is suitable for medium and low temperature vulcanization; the peroxide-cured HXNBR has a high crosslinking temperature and a relatively good compression set resistance. By contrast, the vulcanization temperature of the peroxide system is more suitable than that of a sulfur vulcanization system, so that the epoxy resin matrix and the HXNBR can be better mutually infiltrated during curing and forming, and an interpenetrating network structure can be formed between two phase joint surfaces, so that the interface joint strength of the epoxy resin matrix co-curing damping composite structure is improved. Therefore, the BIBP is adopted as a cross-linking agent of the HXNBR, the BIBP carries out vulcanization on the HXNBR, when the HXNBR is vulcanized by peroxide, the BIBP can be decomposed under the action of high temperature and high pressure to generate free radicals, and the free radicals capture free atoms from the HXNBR molecules to form polymer groups.
In order to accelerate the formation process of polymer free radicals, znO-80 is added in the scheme to promote the decomposition of BIBP free radicals and the formation of cross-linked polymers. Furthermore, KH550 can be used as a vulcanization aid to increase the degree of crosslinking of HXNBR and prevent scorching of the rubber. The anti-aging agent 445 is used for preventing the damping material from aging and also can improve the high temperature resistance and corrosion resistance of the rubber. The tackifier RS can further increase the interlayer bonding force, and N330 carbon black is an excellent reinforcing agent.
In this example, the physical properties of the HXNBR were tested:
the vulcanization characteristic is tested according to the standard ASTM-D-2084-07, and the vulcanization test result shows that the HXNBR with the components in parts by mass meets the requirement of the 180 ℃ high-temperature co-curing process. Referring to FIG. 5, the vulcanization curve of the HXNBR at 180 ℃ after kneading is shown. As can be seen from FIG. 5, the scorching time of the vulcanized rubber is 0.35 min, the vulcanization time to reach 50% torque is 3.6 min, the vulcanization time of 90% is 33min, and the rubber material has no reversion phenomenon after vulcanization for 200min, which indicates that the viscoelastic material has good aging resistance; the maximum torque is 52N.m; the torque fluctuation range is 6.5 N.m-52N.m, and the high-temperature co-curing requirement of the co-curing large-damping composite material for aerospace can be met.
Vulcanizing the mixed virgin rubber for 60min at 180 ℃ by using a flat vulcanizing machine to obtain a strong test piece with the thickness of 2mm, and cutting the test piece into a standard tensile sample by using a special cutter. And (3) putting the HXNBR subjected to the one-step vulcanization into a hot air aging oven for two-step vulcanization, wherein the vulcanization temperature is 180 ℃, the vulcanization pressure is normal pressure, and the vulcanization time is 1 h. The storage modulus represents the capability of the HXNBR in storing elastic deformation energy, the loss modulus refers to the energy dissipated by the HXNBR through internal friction heat generation by means of self viscoelasticity, and the size of a loss factor determines the damping performance of the HXNBR. Referring to FIG. 6, the variation of the damping loss factor of HXNBR with temperature is shown. As can be seen from FIG. 6, in the glass transition temperature region, the loss factor of HXNBR is relatively large, while in the glassy state and the high elastic state, the loss factor is relatively small; the peak loss factor of the damping material corresponds to a temperature of 5 ℃ which is related to the melting and glass transition of the HXNBR. The peak value of the loss factor of the HXNBR is 0.73, the effective damping temperature range is-10-20 ℃, and more importantly, the peak value temperature is close to the ambient temperature. Furthermore, the HXNBR has an asymmetric loss factor peak, which is caused by local dynamic changes in the HXNBR over the glass transition range. The above analysis shows that HXNBR has excellent damping properties.
And step 3: preparing a viscoelastic damping film:
(1) Mixing uniformly mixed HXNBR virgin rubber fragments and tetrahydrofuran organic solvent according to the proportion of 1g:4ml of the mixture is prepared into mucilage;
(2) And dripping glue solution on the substrate rotating at high speed, and uniformly coating the glue solution dripped on the substrate by using centrifugal force to prepare the viscoelastic damping film. The thickness of the viscoelastic damping film can be controlled by the rotation speed and the rotation time of the substrate, and is also related to the viscosity coefficient between the glue solution and the substrate. In other embodiments of the present application, tetrahydrofuran may be replaced by ethyl acetate, acetone, formaldehyde, and the like.
And 4, step 4: preparing a carbon nano tube reinforced co-curing damping composite material:
placing a viscoelastic damping film between carbon nanotube prepregs in functional gradient distribution, and pressurizing to 2-3 MPa;
heating to 70-90 deg.C at a rate of 1-2 deg.C/min, maintaining for 30-60min, heating to 120 deg.C, 150 deg.C, and 180 deg.C, respectively, maintaining for 30-60min, and cooling to room temperature at a rate of 1-2 deg.C/min.
According to the preparation method, the test pieces 2, 3, 4, 5, 6 and 7 are prepared, wherein the carbon nanotubes of the preformed body of the composite material in the test pieces 4 to 7 are prepared in an O-shaped functional gradient distribution mode (as shown in fig. 11), the test pieces 4 to 7 are optimized through the modification of the carbon nanotubes, and the thickness of the damping film of each test piece 4 to 7 is gradually increased from 0.1mm to 0.4mm. The composite material pre-forming body comprises 4 layers of epoxy resin-based carbon fiber pre-forming materials, wherein the mass fractions of carbon nano tubes in the 4 layers of epoxy resin-based carbon fiber pre-forming materials are respectively 4%, 3%, 2% and 1%, and the mass fractions are gradually decreased. The application also provides three comparison pieces, namely a test piece 1, a test piece 2 and a test piece 3, wherein the test piece 1 is not optimized by the carbon nano tube and is not added with a viscoelastic damping film intermediate layer; the test piece 2 is a comparison piece added with carbon nano tubes in O-shaped functional gradient distribution but not added with a viscoelastic damping film middle layer; test piece 3 is a comparative piece to which a viscoelastic damping film intermediate layer of 0.1mm thickness was added, but not optimized with carbon nanotubes. The total thicknesses of the test pieces 1 to 7 were 2mm,2.1mm, 2.2mm,2.3mm and 2.4mm, respectively, and the thicknesses of the viscoelastic damping films of the test pieces 1 to 7 were 0mm,0.1mm, 0.2mm,0.3mm and 0.4mm, respectively.
In order to further illustrate the performance of the carbon nanotube reinforced co-cured damping composite material, in this example, a static mechanical performance test and a damping performance test were performed on test pieces 1 to 5, respectively.
1. And (3) testing the static mechanical property:
referring to fig. 7 and 8, a schematic diagram of tensile strength of the test pieces 1 to 7 and a schematic diagram of bending strength of the test pieces 1 to 7 are shown, respectively. As can be seen from fig. 7 and 8, the tensile strength and the bending strength of the test piece 2 to the test piece 7 are improved to different degrees relative to the test piece 1, and the static mechanical properties of the embedded viscoelastic damping film are optimal when the embedded thickness is 0.3 mm. The tensile property and the bending property of the co-curing damping composite structure are not only related to the content of resin and fiber in the composite material, but also obviously influenced by the interface bonding property of the composite material and the carbon nano tubes with functionally graded distribution. The HXNBR viscoelastic damping films embedded in the test pieces 3 to 7 have high hardness and high rigidity, and have excellent interface bonding performance with epoxy resin, and the epoxy resin and the HXNBR can form a compact micro-crosslinking structure; in addition, the functionally graded structure can enhance the overall mechanical strength of the composite material. Therefore, the tensile property and the bending property of the functionally graded carbon nanotube reinforced co-cured damping composite structure test piece are improved.
2. And (3) testing the damping performance:
the relative damping coefficients of test pieces 1 to 7 were tested by a free vibration damping test according to the standard ASTM E756-05 to find the loss factor of the material. Referring to fig. 9 and 10, a free vibration damping change curve of the test piece 1 and a free vibration damping change curve of the test piece 4 are shown, respectively. As can be seen from fig. 9 and 10, the embedding of the viscoelastic damping film can greatly increase the amplitude attenuation rate of the carbon nanotube reinforced co-cured damping composite material. The loss factors of the test pieces 1 to 7 are 1.98%, 1.76%, 2.91%, 2.87%, 3.56%, 4.12% and 4.34% respectively, and the loss factor of the test piece 2 is reduced by 12.5% relative to the loss factor of the test piece 1, which is caused by the increase of the integral rigidity of the composite structure due to the addition of the carbon nano tube; the loss factors of the test pieces 4 to 7 are respectively improved by 44.95%, 79.80%, 108.10% and 119.20% compared with the test piece 1, and the embedding of the viscoelastic material greatly improves the damping performance of the composite material. Therefore, the carbon nano tube reinforced co-curing damping composite material with high temperature resistance and high mechanical property designed in the invention has excellent damping property and high utilization value.
In order to make those skilled in the art better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making creative efforts based on the embodiments of the present invention, shall fall within the protection scope of the present invention.

Claims (8)

1. A preparation method of a carbon nano tube reinforced co-cured damping composite material is characterized by comprising the following steps:
step 1: growing carbon nanotubes on the surfaces of carbon fibers, combining the carbon fibers on which the carbon nanotubes are grown with epoxy resin to prepare carbon nanotube modified epoxy resin-based carbon fiber prepregs, and paving the epoxy resin-based carbon fiber prepregs with different carbon nanotube contents according to a gradient sequence to form a composite material preformed body in functional gradient distribution;
step 2: plasticating and mixing the cut hydrogenated carboxyl nitrile rubber to obtain uniformly mixed virgin rubber;
and step 3: dissolving the uniformly mixed virgin rubber in an organic solvent which is easy to exert to form rubber cement, and uniformly coating the rubber cement on a substrate to prepare a viscoelastic damping film;
and 4, step 4: and embedding the viscoelastic damping film serving as an intermediate layer between the two composite material preformed bodies through an autoclave co-curing process.
2. The method for preparing carbon nanotubes according to claim 1, wherein the growing of carbon nanotubes on the surface of carbon fibers further comprises the steps of:
adding carbon fiber in N 2 Carrying out heat treatment in the atmosphere to obtain desized carbon fibers;
adding the desized carbon fiber into 5 wt% NH 4 H 2 PO 4 Electrolyzing in the aqueous solution to obtain modified carbon fibers;
immersing the modified carbon fiber into ethanol solution with different catalyst precursors to obtain the carbon fiber with a precursor coating, wherein the different catalysts comprise: ferric nitrate nonahydrate, nickel nitrate hexahydrate and cobalt nitrate hexahydrate;
subjecting the carbon fiber with the precursor coating to N 2 Heating to 440 deg.C under protection, maintaining the temperature for 20min, and introducing H 2 Heating to 460 deg.C, keeping the temperature, and finally introducing C 2 H 2 。
3. The method of claim 1, wherein the step 2 further comprises the steps of:
adding the cut hydrogenated carboxyl nitrile rubber into an open mill for plasticating for 2-3 min;
adding the antioxidant p, p-diisopropylphenyl diphenylamine and the reinforcing agent N330 carbon black into the plasticated hydrogenated carboxylated nitrile rubber, mixing for 5-7min, then adding the crosslinking agent BIBP, the vulcanization aid gamma-aminopropyltriethoxysilane and the accelerator ZnO-80, and mixing for 3-4min to obtain the pre-vulcanized hydrogenated carboxylated nitrile rubber;
adding the tackifier RS into the pre-vulcanized hydrogenated carboxylated nitrile rubber, mixing for 4-5min, and calendering to obtain uniformly mixed virgin rubber.
4. The preparation method according to claim 3, wherein the mass ratio of the hydrogenated carboxylated nitrile rubber, the antioxidant pair, p-diisopropylphenyl diphenylamine, the reinforcing agent N330 carbon black, the crosslinking agent BIBP, the vulcanization aid gamma-aminopropyltriethoxysilane, and the accelerator ZnO-80 is 100:1.5:60:2:1:6.
5. The method of claim 1, wherein the step 3 further comprises the steps of:
dissolving the uniformly mixed virgin rubber in tetrahydrofuran to form rubber cement, wherein the proportion of the virgin rubber to the tetrahydrofuran is 1g;
and dripping the adhesive cement on a substrate rotating at a high speed, and preparing the adhesive cement into a viscoelastic damping film by using centrifugal force.
6. The method for preparing a composite material according to claim 1, wherein the step 4 further comprises the steps of:
placing a viscoelastic damping film between the two composite material preformed bodies, and pressurizing to 2-3 MPa;
heating to 70-90 deg.C at a heating rate of 1-2 deg.C/min, maintaining for 30-60min, heating to 120 deg.C, 150 deg.C and 180 deg.C respectively, maintaining for 30-60min, and cooling to room temperature at a cooling rate of 1-2 deg.C/min.
7. The method of claim 2, wherein C is 2 H 2 、H 2 And N 2 The flow rates of (A) are respectively 5L/min, 5L/min and 10L/min.
8. A carbon nanotube reinforced co-cured damping composite, prepared by the method of any one of claims 1-7.
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