CN115073886B - Preparation method of MXene/CNT composite sponge reinforced resin matrix composite material - Google Patents
Preparation method of MXene/CNT composite sponge reinforced resin matrix composite material Download PDFInfo
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- 239000011159 matrix material Substances 0.000 title claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 34
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- 239000000203 mixture Substances 0.000 claims description 32
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- 230000008569 process Effects 0.000 claims description 19
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- 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
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/921—Titanium carbide
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
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- 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
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- C08K3/10—Metal compounds
- C08K3/14—Carbides
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- 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
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- 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
- C08K9/00—Use of pretreated ingredients
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Abstract
A preparation method of an MXene/CNT composite sponge reinforced resin matrix composite material belongs to the field of material science. The method mainly solves the problems of MXene/CNT composite sponge component design, nano sheet dispersion and overlap joint of nano sheets and nano tubes. The invention is realized according to the following steps: 1. etching titanium aluminum carbide; 2. collecting alcohol washing MXene; 3. preparing an MXene/CNT porous structure composite sponge; 4. preparation of an MXene/CNT composite sponge reinforced resin matrix composite. And finally determining the optimal intensity component ratio to be 5:1 to 10:1, the reinforcing effect is larger than that of a single component in the component proportion, and the composite sponge reinforcing resin matrix composite material with the advantages of improved bending and tensile strength and modulus and increased fracture absorption work is prepared and synthesized. The preparation method is simple, easy to implement, low in cost and environment-friendly.
Description
Technical Field
The invention belongs to the field of material science, and particularly relates to a preparation method of an MXene/CNT composite sponge reinforced resin matrix composite material.
Background
The MXene nano material is used as a novel two-dimensional inorganic compound with a graphene-like structure, is based on a unique lamellar structure and has effective Young modulus and specific surface energy which are slightly higher than those of lamellar layers of graphene oxide, so that the MXene nano material becomes an ideal material of a nano reinforcing phase, and has a very good light weight reinforcing and toughening lifting space. On the basis, the intrinsic electronic structural characteristics and the surface functional groups of the composite material also endow the composite material with very unique electrical and thermal functional characteristics, and the composite material brings development prospect for the cooperative realization of enhancement and functions.
However, in the process of converting the primitive material into the reinforcing phase, how to realize the macroscopic realization of the nano phase characteristic is the key for achieving the research purpose, and the phenomenon that the nano materials such as MXene and the like are easy to agglomerate exists, which severely limits the formation of the reinforcing body and the improvement of the mechanical characteristics of the subsequent composite material. At present, aiming at the problems that the forming method of the MXene reinforced phase macroscopic body material is complex in operation, easy to introduce impurities into a system, environment-friendly, poor in designability, difficult to regulate and control a microstructure and the like, the reinforced phase needs to be explored and optimized in all aspects from three angles of components, the microstructure and a preparation process. The binary nano composite phase is introduced from the angle of the components, so that the connection characteristic of the sheet layers and the formability of the reinforcement are improved, the arrangement direction of the sheet layers is designed from the angle of the microstructure, so that the discrete state of the sheet layers is regulated and controlled, the full discrete is realized, and the preparation of the nano reinforcement macroscopic body is finished by adopting a preparation process which is easier to operate and has mild conditions from the angle of the preparation process.
Disclosure of Invention
The invention aims to solve the problems of difficult operation, poor environmental protection and poor controllability of an MXene macroscopic reinforcement prepared by the existing method, overlap joint of a two-dimensional lamellar and a one-dimensional tubular material of a composite reinforcement phase, and the like, and provides a preparation method of an MXene/CNT composite sponge reinforced resin matrix composite material, which solves the problems of component regulation and designability of the porous reinforcement of the composite material, and the problems of dispersion and full inflow impregnation of the nano lamellar reinforcement phase in the resin matrix phase.
The invention adopts a safe, reliable and easy-to-implement freeze-drying method, utilizes the in-situ directional arrangement and self-assembly of the two-dimensional lamellar in the directional freezing process, can prepare the porous spongy macroscopic body with a directional lamellar structure, avoids the agglomeration of nano lamellar, can perform the microstructure design and regulation of the reinforcing phase while retaining the nano characteristic, and can well promote the mechanical property of the composite material by introducing the porous spongy macroscopic body into a resin system, thereby realizing the synergistic design of nano-micro-macro.
The MXene aqueous phase solution has larger nucleation density under directional freezing, and the lap joint effect among the sheets and the average pore diameter of the sponge are all provided with lifting spaces. The interaction of the functional groups such as-OH and the like on the surface of the porous carbon nano-rod is utilized to interact with the groups of the one-dimensional nano-material carboxylated multi-arm carbon nano-rod, the network structure of the supporting sheet layer is utilized to promote the discrete arrangement among the sheet layers, and the gel effect is stronger, so that the nucleation density can be reduced to promote the further improvement of the porosity, and a more excellent reinforcement can be obtained through the design and comparison of the composite sponge components by utilizing the two effects, so that the mechanical property of the resin-based composite material is greatly improved and the subsequent functional characteristic is realized.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method of an MXene/CNT composite sponge reinforced resin matrix composite material comprises the following steps:
step one: etching the titanium aluminum carbide source material: the preparation of MXene is carried out by adopting a milder method for generating hydrofluoric acid in situ to etch titanium aluminum carbide: according to 0.8 g-1 g:1.6 to 2.0g: taking Ti according to the proportion of 20-25 mL 3 AlC 2 Adding lithium fluoride and concentrated hydrochloric acid into the concentrated hydrochloric acid, fully stirring, adding titanium aluminum carbide, continuing magnetic stirring, avoiding temperature change and violent generation of bubbles in the mixing process, adding all titanium aluminum carbide, and putting the mixed solution into an oil bath pot for etching for 48 hours at 50 ℃;
step two: MXene (Ti) 3 C 2 T x ) Preparation and collection of two-dimensional materials: loading 50ml of the solution obtained in the step one into a centrifuge tube for centrifugal treatment, firstly, carrying out primary water washing by 1L of 1mol/L of diluted hydrochloric acid, pouring out supernatant after centrifugation, and then continuously adding the diluted hydrochloric acid for multiple centrifugation until the 1L of diluted hydrochloric acid is completely consumed; adding absolute ethanol into the centrifuge tube, shaking, placing the centrifuge tube into a centrifuge, supplementing with deionized water after each centrifugation process, andvortex oscillating, repeating for 2-3 times to perform alcohol washing; removing supernatant fluid from the centrifugal product in the last step, continuously supplementing deionized water for washing, centrifuging again after vortex oscillation, repeatedly pouring out the supernatant fluid, and continuously adding deionized water until the pH value of the supernatant fluid is 6.5-7, wherein the centrifuged supernatant fluid is blue-black; after alcohol washing and water washing, centrifugal treatment is carried out to finish the collection of MXene, the obtained upper solution is MXene aqueous phase dispersion liquid with large lamellar size, and deionized water is added according to the requirement to prepare different concentrations;
step three: preparation of MXene/CNT composite sponge: the MXene aqueous phase slurry with different concentrations and 1mg/ml carboxylated CNT aqueous phase solution prepared in the step two are mixed according to the following ratio of 1-10: 1, mixing the materials according to the molar ratio, and performing magnetic stirring and ultrasonic treatment; magnetically stirring for 12 hours after the completion to obtain an MXene/CNT water phase mixed solution; vacuum ester is used as an adhesive and uniformly coated on the lower part of a silica gel square die, and the die is adhered to an iron disc; pouring the obtained mixed solution with different concentrations into a silica gel square mold, covering the mold, and placing an iron disc above the two porcelain squares to enable the lower surfaces of the two porcelain squares to be in a suspended state; pouring liquid nitrogen under the iron disc to uniformly spread the temperature gradient of the cold source until the mixed solution is completely frozen, putting the mixed solution into a refrigerator for one hour, taking out the mixed solution, demoulding, putting the mixed solution into a freeze dryer, freezing at the temperature of minus 40 ℃, vacuumizing a drying chamber, heating the vacuum drying chamber to 25 ℃, and keeping the vacuum drying environment for not less than 100 hours to obtain the nano-sheet MXene (Ti) 3 C 2 T x ) A three-dimensional network skeleton built by the GNT composite, namely the MXene/CNT composite porous sponge;
step four: preparation of MXene/CNT composite sponge reinforced resin matrix composite material (introduction and even distribution of MXene/CNT sponge in resin System): designing an aluminum mold, wherein the length and width of a mold groove are respectively 20cm, the height is 3mm, a section of opening (designed for demolding of subsequent resin) is formed, a homogeneous aluminum strip is used as a seal, and a double-sided adhesive tape is used for attaching the aluminum strip to a section of opening, so that the height of the aluminum strip is ensured to be consistent with the depth of the mold groove; weighing 50g of epoxy resin in a beaker, and fully soaking 0.1-0.15g of the MXene/CNT composite sponge in the third step in the epoxy resin for 24 hours under vacuum pressure maintaining; stirring the resin mixture under a mechanical stirrer by utilizing shearing flow force for 24 hours, wherein no residual particles are observed under the lamplight beating environment, so that two-dimensional sheets are fully and discretely distributed in the resin, and carrying out pressure maintaining and bubble removing treatment on the composite resin in a vacuum drying oven until bubbles on the upper layer disappear; weighing the curing agent according to the preparation proportion of the combination of the epoxy resin and the curing agent, pouring the curing agent into a beaker filled with the resin, slowly stirring the mixture by using a glass rod until the surface is free of oil, uniformly stabilizing the mixed system, putting the mixed resin into a vacuum drying oven for secondary foam removal treatment, pumping the mixed resin until the foam disappears, brushing a release agent on a mould, brushing the mould again after the mixed resin is dried, preferably brushing the mould for three times, taking out the resin, pouring the resin into the mould, evenly distributing the resin, heating the resin in an oven for heat preservation, taking out an aluminum strip, and demoulding to successfully prepare the MXene sponge reinforced resin matrix composite material consistent with the mould in size.
Further, in the first step, the lithium fluoride is stirred in hydrochloric acid for at least 15min at a rotating speed of 10r/min; the time for adding 1g of titanium aluminum carbide is 15-20min; the rotation speed of the mixed solution is 10-15r/min when the titanium aluminum carbide is added; in the etching stirring process under the oil bath environment, the magnetic stirring rotating speed is 10-15r/min.
Further, in the second step, dilute hydrochloric acid is added for preliminary washing, the rotation speed of a centrifugal machine is 3500rpm, and the duration of each centrifugation is 5-10min; the method comprises the steps of carrying out a first treatment on the surface of the In the alcohol washing process, the hands are required to be used for more than 15min, the centrifugal speed is 10000rpm, and the centrifugal time is 30min; the centrifugal speed in the water washing process is 3500rpm, and the duration time is 5-10min; vortex oscillation is carried out for more than 30min after each centrifugation process in the water washing process; the rotational speed of the centrifugal machine in the collecting process is 1500rpm, and the centrifugal time is 30-35min.
Further, in the third step, the rotating speed of the mixed solution of MXene and CNT is 10-15r/min, and the stirring time is 20min; the ultrasonic time is 10-15 min, the frequency is 80Hz, and the power is 500w; the vacuum degree of the vacuumizing is 3-10 Pa; the freezing time is 3-3.5 h at the temperature of minus 40 ℃, and the vacuum drying process retention time is 100-120 h after the temperature is raised to 25 ℃.
Further, in the fourth step, the shearing flow stirring speed of the composite resin is 1800-2000r/min; the foam discharging time of the composite resin is 20-25 min until the foam discharging is complete; the stirring time of the composite resin and the curing agent is 15-25min; the secondary foam discharging time of the composite resin is 10min-15min until the foam discharging is complete; the composite resin is heated and insulated in an oven to realize solidification, the solidification and insulation time is 24 hours, and the solidification and heating temperature is 40 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention prepares water-soluble MXene by using MILD method, which can be uniformly dispersed in water solution;
(2) The invention utilizes an alcohol washing method and a water phase mechanical stirring mixing method to promote the lap joint and bridging action of two-dimensional slices and one-dimensional tubular under the action of groups, an ultrasonic step is added between two water phase mixing, and the ultrasonic is not generated in the slice preparation process;
(3) The invention adopts a freeze drying method to prepare the MXene/CNT composite spongy macroscopic body reinforcing phase with lamellar network structure distribution, and the spongy macroscopic body has a porous structure, so that the high specific surface area characteristic of the two-dimensional material can be fully exerted, and the agglomeration effect is avoided;
(4) The invention prepares the MXene/CNT composite sponge reinforced resin matrix composite material, and the MXene/CNT sheet layer and the resin matrix have sufficient impregnated space and larger adhesive force, so that the resin material can achieve the effect of greatly improving various mechanical properties including strength, modulus, hardness, fracture absorption work and the like.
Drawings
FIG. 1 is a graph of an aqueous solution of MXene obtained in step two of example 1;
FIG. 2 is a photograph of the MXene/CNT composite sponge macroscopic body having an oriented structure obtained in step three of example 1;
FIG. 3 is a graph showing the microcosmic morphology of the MXene/CNT porous structure composite sponge sheet obtained in step three of example 1;
FIG. 4 is a graph of the MXene/CNT composite sponge reinforced resin matrix composite obtained in step four of example 1;
FIG. 5 is a graph of fracture morphology of the MXene/CNT sponge reinforced composite obtained in step four of example 1;
fig. 6 shows the bending test stress-strain curves of examples 1, 2 and 3.
Detailed Description
The following description of the present invention refers to the accompanying drawings and examples, but is not limited to the same, and modifications and equivalents of the present invention can be made without departing from the spirit and scope of the present invention.
Example 1:
1. etching titanium aluminum carbide: preparation of MXene by etching titanium aluminum carbide with hydrofluoric acid, taking 2gTi 3 AlC 2 And 4g of lithium fluoride, which was added to 40ml of 9mol/L hydrochloric acid. After hydrochloric acid and lithium fluoride are fully stirred, titanium aluminum carbide is added into the mixed solution and stirred, and temperature change and severe generation of bubbles are avoided in the mixing process. Adding all titanium aluminum carbide, and etching the mixed solution for 48 hours at 50 ℃;
2. MXene (Ti) 3 C 2 T x ) Is prepared and collected: the solution obtained in the step one is filled into a centrifuge tube, and the initial water washing is carried out by 1mol/L of diluted hydrochloric acid for 1L in total. Subsequently, absolute ethanol was added to the centrifuge tube, centrifuged after shaking for more than 15min, and repeated 3 times to perform alcohol washing, and vortexed and oscillated for more than 30min after each centrifugation process. After 3 alcohol washes, the supernatant was removed, supplemented with deionized water for washing, vortexed for 20min, and centrifuged again until the pH of the supernatant was approximately 7. After alcohol washing and water washing, MXene is collected, the rotating speed of a centrifugal machine in the collecting process is 1500rpm, the time is set to 30min, the obtained upper layer solution is the MXene aqueous phase dispersion liquid with large lamellar size, and deionized water is added according to the requirement to prepare the concentration of 6mg/ml.
3. Preparation of MXene/CNT composite sponge mix: the MXene aqueous phase slurry with different concentrations and the carboxylated CNT aqueous phase solution with the concentration of 1mg/ml prepared in the step two are mixed according to the mole fraction ratio of 10:1 into a mixture ratio ofMixing was performed, and magnetic stirring was performed at a rotational speed of 15r/min for 30min. Then carrying out ultrasonic treatment for 15min at the power of 500w and the frequency of 80 Hz; and after the completion, magnetically stirring at a rotating speed of 15r/min for 12 hours to obtain the MXene/CNT water phase mixed solution. The obtained mixed solutions with different concentrations and sizes are poured into a mould adhered to a disc, and the mould is covered. And a gasket is filled in the middle of the disc, and liquid nitrogen is poured below the disc to uniformly spread the temperature gradient of the cold source until the disc is completely frozen. Putting the mixture into a refrigerator for one hour, taking out the mixture, demolding the mixture, putting the mixture into a freeze dryer, freezing the mixture at the temperature of minus 40 ℃ for 3 hours, vacuumizing the drying chamber to the vacuum degree of 3-10Pa, and then heating a temperature control partition board for 120 hours to 25 ℃. After the drying is finished, the nano-sheet MXene (Ti) 3 C 2 T x ) The three-dimensional network skeleton built by the GNT composite, namely the MXene/CNT composite porous sponge.
4. Introduction and even distribution of MXene/CNT sponge in resin System: 50g of epoxy resin was weighed into a beaker, and 0.15g of the MXene/CNT composite sponge in step three was thoroughly impregnated into the epoxy resin with a vacuum dwell time of 24 hours. And stirring the resin mixture under the action of shearing flow force of a mechanical stirrer for 24 hours, wherein no residual particles are observed in the lamplight beating environment, so that the two-dimensional sheets are fully and discretely distributed in the resin. And (3) carrying out pressure maintaining and bubble removing treatment on the composite resin in a vacuum drying box until bubbles on the upper layer disappear.
5. Curing process and preparation of MXene/CNT composite sponge reinforced resin matrix composite material: weighing the curing agent according to the preparation example of the adopted combination of the epoxy resin and the curing agent, pouring the curing agent into a beaker filled with the resin, and slowly stirring the mixture by using a glass rod until the surface is free from oily state, and uniformly and stably mixing the mixture for 20min. And (3) placing the mixed resin into a vacuum drying box, pumping until bubbles disappear, and discharging bubbles for 10min for the second time. And brushing a release agent on the aluminum mould, and brushing once again after the release agent is dried, wherein the release agent is preferably brushed for three times. Taking out the resin, pouring the resin into a mould, enabling the resin to be distributed flatly, putting the mould in an oven, heating and preserving heat for 24 hours at 40 ℃, taking out the resin, removing the aluminum strips, and demoulding to prepare the MXene sponge reinforced resin matrix composite material which is successfully consistent with the mould in size.
The bending strength of the composite sponge reinforced resin obtained in the embodiment is 123.68MPa, and is 50.79% higher than that of the pure resin. The flexural modulus was 1745.45MPa, which is 42.79% higher than that of the pure resin. The elongation at break was 9.46%, and the work of absorption at break was increased to 8.25X10% 6 J/m 3 The tensile strength is 72.84MPa, and the tensile modulus is improved to 582.72MPa.
Example 2:
1. etching titanium aluminum carbide: preparation of MXene by etching titanium aluminum carbide with hydrofluoric acid, taking 2gTi 3 AlC 2 And 4g of lithium fluoride, which was added to 40ml of 9mol/L hydrochloric acid. After hydrochloric acid and lithium fluoride are fully stirred, titanium aluminum carbide is added into the mixed solution and stirred, and temperature change and severe generation of bubbles are avoided in the mixing process. Adding all titanium aluminum carbide, and etching the mixed solution for 48 hours at 50 ℃;
2. MXene (Ti) 3 C 2 T x ) Is prepared and collected: the solution obtained in the step one is filled into a centrifuge tube, and the initial water washing is carried out by 1mol/L of diluted hydrochloric acid for 1L in total. Subsequently, absolute ethanol was added to the centrifuge tube, centrifuged after shaking for more than 15min, and repeated 3 times to perform alcohol washing, and vortexed and oscillated for more than 30min after each centrifugation process. After 3 alcohol washes, the supernatant was removed, supplemented with deionized water for washing, vortexed for 20min, and centrifuged again until the pH of the supernatant was approximately 7. After alcohol washing and water washing, MXene is collected, the rotating speed of a centrifugal machine in the collecting process is 1500rpm, the time is set to 30min, the obtained upper layer solution is the MXene aqueous phase dispersion liquid with large lamellar size, and deionized water is added according to the requirement to prepare the concentration of 6mg/ml.
3. Preparation of MXene/CNT composite sponge mix: the MXene aqueous phase slurry with different concentrations and the carboxylated CNT aqueous phase solution with the concentration of 1mg/ml prepared in the step two are mixed according to the mole fraction ratio of 5:1, and magnetically stirring for 30min at a rotating speed of 15r/min. Then carrying out ultrasonic treatment for 15min at the power of 500w and the frequency of 80 Hz; and after the completion, magnetically stirring at a rotating speed of 15r/min for 12 hours to obtain the MXene/CNT water phase mixed solution. Pouring the obtained mixed solution with different concentrations into a container for adhesionIn the mold of the disc, and the mold is capped. And a gasket is filled in the middle of the disc, and liquid nitrogen is poured below the disc to uniformly spread the temperature gradient of the cold source until the disc is completely frozen. Putting the mixture into a refrigerator for one hour, taking out the mixture, demolding the mixture, putting the mixture into a freeze dryer, freezing the mixture at the temperature of minus 40 ℃ for 3 hours, vacuumizing the drying chamber to the vacuum degree of 3-10Pa, and then heating a temperature control partition board for 120 hours to 25 ℃. After the drying is finished, the nano-sheet MXene (Ti) 3 C 2 T x ) The three-dimensional network skeleton built by the GNT composite, namely the MXene/CNT composite porous sponge.
4. Introduction and even distribution of MXene/CNT sponge in resin System: 50g of epoxy resin was weighed into a beaker, and 0.15g of the MXene/CNT composite sponge in step three was thoroughly impregnated into the epoxy resin with a vacuum dwell time of 24 hours. And stirring the resin mixture under the action of shearing flow force of a mechanical stirrer for 24 hours, wherein no residual particles are observed in the lamplight beating environment, so that the two-dimensional sheets are fully and discretely distributed in the resin. And (3) carrying out pressure maintaining and bubble removing treatment on the composite resin in a vacuum drying box until bubbles on the upper layer disappear.
5. Curing process and preparation of MXene/CNT composite sponge reinforced resin matrix composite material: weighing the curing agent according to the preparation example of the adopted combination of the epoxy resin and the curing agent, pouring the curing agent into a beaker filled with the resin, and slowly stirring the mixture by using a glass rod until the surface is free from oily state, and uniformly and stably mixing the mixture for 20min. And (3) placing the mixed resin into a vacuum drying box, pumping until bubbles disappear, and discharging bubbles for 10min for the second time. And brushing a release agent on the aluminum mould, and brushing once again after the release agent is dried, wherein the release agent is preferably brushed for three times. And taking out the resin, pouring the resin into a mould, enabling the resin to be distributed flatly, putting the mould into an oven, heating and preserving heat for 24 hours at 40 ℃, taking out the mould, removing the aluminium strips, and demoulding to prepare the MXene sponge reinforced resin matrix composite material which is successfully consistent with the mould in size.
The flexural strength of the composite sponge reinforcing resin obtained in this example was 120.10MPa, and the flexural modulus was 1888.93MPa. The elongation at break was 9.82%, and the work of absorption at break was increased to 8.86×10 6 J/m 3 . The tensile strength is 61.98MPa, and the tensile modulus is improved to 458.16MPa.
Example 3:
1. etching titanium aluminum carbide: preparation of MXene by etching titanium aluminum carbide with hydrofluoric acid, taking 2gTi 3 AlC 2 And 4g of lithium fluoride, which was added to 40ml of 9mol/L hydrochloric acid. After hydrochloric acid and lithium fluoride are fully stirred, titanium aluminum carbide is added into the mixed solution and stirred, and temperature change and severe generation of bubbles are avoided in the mixing process. Adding all titanium aluminum carbide, and etching the mixed solution for 48 hours at 50 ℃;
2. MXene (Ti) 3 C 2 T x ) Is prepared and collected: the solution obtained in the step one is filled into a centrifuge tube, and the initial water washing is carried out by 1mol/L of diluted hydrochloric acid for 1L in total. Subsequently, absolute ethanol was added to the centrifuge tube, centrifuged after shaking for more than 15min, and repeated 3 times to perform alcohol washing, and vortexed and oscillated for more than 30min after each centrifugation process. After 3 alcohol washes, the supernatant was removed, supplemented with deionized water for washing, vortexed for 20min, and centrifuged again until the pH of the supernatant was approximately 7. After alcohol washing and water washing, MXene is collected, the rotating speed of a centrifugal machine in the collecting process is 1500rpm, the time is set to 30min, the obtained upper layer solution is the MXene aqueous phase dispersion liquid with large lamellar size, and deionized water is added according to the requirement to prepare the concentration of 6mg/ml.
3. Preparation of MXene/CNT composite sponge mix: the MXene aqueous phase slurry with different concentrations and the carboxylated CNT aqueous phase solution with the concentration of 1mg/ml prepared in the step two are mixed according to the mole fraction ratio of 1:1, and magnetically stirring for 30min at a rotating speed of 15r/min. Then carrying out ultrasonic treatment for 15min at the power of 500w and the frequency of 80 Hz; and after the completion, magnetically stirring at a rotating speed of 15r/min for 12 hours to obtain the MXene/CNT water phase mixed solution. The obtained mixed solutions with different concentrations and sizes are poured into a mould adhered to a disc, and the mould is covered. And a gasket is filled in the middle of the disc, and liquid nitrogen is poured below the disc to uniformly spread the temperature gradient of the cold source until the disc is completely frozen. Putting the mixture into a refrigerator for one hour, taking out the mixture, demolding the mixture, putting the mixture into a freeze dryer, freezing the mixture at the temperature of minus 40 ℃ for 3 hours, vacuumizing the drying chamber to the vacuum degree of 3-10Pa, and then heating a temperature control partition board for 120 hours to 25 ℃. Drying is completedAfter that, the nano-sheet MXene (Ti) 3 C 2 T x ) The three-dimensional network skeleton built by the GNT composite, namely the MXene/CNT composite porous sponge.
4. Introduction and even distribution of MXene/CNT sponge in resin System: 50g of epoxy resin was weighed into a beaker, and 0.15g of the MXene/CNT composite sponge in step three was thoroughly impregnated into the epoxy resin with a vacuum dwell time of 24 hours. And stirring the resin mixture under the action of shearing flow force of a mechanical stirrer for 24 hours, wherein no residual particles are observed in the lamplight beating environment, so that the two-dimensional sheets are fully and discretely distributed in the resin. And (3) carrying out pressure maintaining and bubble removing treatment on the composite resin in a vacuum drying box until bubbles on the upper layer disappear.
5. Curing process and preparation of MXene/CNT composite sponge reinforced resin matrix composite material: weighing the curing agent according to the preparation example of the adopted combination of the epoxy resin and the curing agent, pouring the curing agent into a beaker filled with the resin, and slowly stirring the mixture by using a glass rod until the surface is free from oily state, and uniformly and stably mixing the mixture for 20min. And (3) placing the mixed resin into a vacuum drying box, pumping until bubbles disappear, and discharging bubbles for 10min for the second time. And brushing a release agent on the aluminum mould, and brushing once again after the release agent is dried, wherein the release agent is preferably brushed for three times. Taking out the resin, pouring the resin into a mould, enabling the resin to be distributed flatly, putting the mould in an oven, heating and preserving heat for 24 hours at 40 ℃, taking out the resin, removing the aluminum strips, and demoulding to prepare the MXene sponge reinforced resin matrix composite material which is successfully consistent with the mould in size.
The bending strength of the composite sponge reinforced resin obtained in the embodiment is 106.11MPa, the bending modulus is 1577.94MPa, and the bending strength is improved by 42.79% compared with the pure resin. The elongation at break was 7.98%, and the work of absorption at break was increased to 5.72X10% 6 J/m 3 The tensile strength is 54.22MPa, and the tensile modulus is improved to 653.95MPa.
Claims (5)
1. A preparation method of an MXene/CNT composite sponge reinforced resin matrix composite material is characterized by comprising the following steps: the method comprises the following steps:
step one: etching the titanium aluminum carbide source material: according to 0.8 g-1 g:16-2.0 g: taking Ti according to the proportion of 20-25 mL 3 AlC 2 Adding lithium fluoride and concentrated hydrochloric acid into the concentrated hydrochloric acid, fully stirring, adding titanium aluminum carbide, continuing magnetic stirring, avoiding temperature change and violent generation of bubbles in the mixing process, adding all titanium aluminum carbide, and putting the mixed solution into an oil bath pot for etching for 48 hours at 50 ℃;
step two: MXene (Ti) 3 C 2 T x ) Preparation and collection of two-dimensional materials: loading 50ml of the solution obtained in the step one into a centrifuge tube for centrifugal treatment, firstly, carrying out primary water washing by 1L of 1mol/L of diluted hydrochloric acid, pouring out supernatant after centrifugation, and then continuously adding the diluted hydrochloric acid for multiple centrifugation until the 1L of diluted hydrochloric acid is completely consumed; adding absolute ethyl alcohol into a centrifuge tube, putting the centrifuge tube into the centrifuge after hand shaking treatment, supplementing the centrifuge tube with deionized water after each centrifugation process, and carrying out vortex oscillation, and repeating for 2-3 times to carry out alcohol washing; removing supernatant fluid from the centrifugal product in the last step, continuously supplementing deionized water for washing, centrifuging again after vortex oscillation, repeatedly pouring out the supernatant fluid, and continuously adding deionized water until the pH value of the supernatant fluid is 6.5-7, wherein the centrifuged supernatant fluid is blue-black; after alcohol washing and water washing, centrifugal treatment is carried out to finish the collection of MXene, the obtained upper solution is MXene aqueous phase dispersion liquid with large lamellar size, and deionized water is added according to the requirement to prepare different concentrations;
step three: preparation of MXene/CNT composite sponge: the MXene aqueous phase slurry with different concentrations and 1mg/ml carboxylated CNT aqueous phase solution prepared in the step two are mixed according to the following ratio of 1-10: 1, mixing the materials according to the molar ratio, and performing magnetic stirring and ultrasonic treatment; magnetically stirring for 12 hours after the completion to obtain an MXene/CNT water phase mixed solution; vacuum ester is used as an adhesive and uniformly coated on the lower part of a silica gel square die, and the die is adhered to an iron disc; pouring the obtained mixed solution with different concentrations into a silica gel square mold, covering the mold, and placing an iron disc above the two porcelain squares to enable the lower surfaces of the two porcelain squares to be in a suspended state; pouring liquid nitrogen under the iron disc to uniformly diffuse the temperature gradient of the cold source until the mixed solution is completely frozen, putting the mixed solution into a refrigerator for one hour,taking out, demoulding, freezing at-40deg.C, vacuumizing, heating to 25deg.C, and maintaining vacuum drying environment for at least 100 hr to obtain nanosheet MXene (Ti) 3 C 2 T x ) A three-dimensional network skeleton built by the GNT composite, namely the MXene/CNT composite porous sponge;
step four: preparation of MXene/CNT composite sponge reinforced resin matrix composite material: designing an aluminum mold, wherein the length and width of a mold groove are respectively 20cm, the height is 3mm, a section of the mold groove is provided with an opening, a homogeneous aluminum strip is used as a seal, and a double-sided adhesive tape is used for attaching the aluminum strip to a section of the opening, so that the height of the aluminum strip is ensured to be consistent with the depth of the mold groove; weighing 50g of epoxy resin in a beaker, and fully soaking 0.1-0.15g of the MXene/CNT composite sponge in the third step in the epoxy resin for 24 hours under vacuum pressure maintaining; stirring the resin mixture under a mechanical stirrer by utilizing shearing flow force for 24 hours, wherein no residual particles are observed under the lamplight beating environment, so that two-dimensional sheets are fully and discretely distributed in the resin, and carrying out pressure maintaining and bubble removing treatment on the composite resin in a vacuum drying oven until bubbles on the upper layer disappear; weighing the curing agent according to the compounding proportion of the epoxy resin and the curing agent, pouring the curing agent into a beaker filled with the resin, slowly stirring the mixture by using a glass rod until the surface is free of oil, uniformly stabilizing the mixed system, putting the mixed resin into a vacuum drying oven for secondary foam discharging treatment, pumping the mixed resin until the foam disappears, brushing a release agent on a mould, brushing the mould again after the mixed resin is dried, preferably brushing the mixed resin for three times, taking out the resin, pouring the resin into the mould, evenly distributing the resin, heating the resin in an oven for heat preservation, taking out an aluminum strip, and demoulding to prepare the MXene sponge reinforced resin matrix composite material consistent with the mould in size.
2. The method for preparing the MXene/CNT composite sponge reinforced resin matrix composite material according to claim 1, which is characterized in that: in the first step, the lithium fluoride is stirred in hydrochloric acid for at least 15min, and the rotating speed is 10r/min; the time for adding 1g of titanium aluminum carbide is 15-20min; the rotation speed of the mixed solution is 10-15r/min when the titanium aluminum carbide is added; in the etching stirring process under the oil bath environment, the magnetic stirring rotating speed is 10-15r/min.
3. The method for preparing the MXene/CNT composite sponge reinforced resin matrix composite material according to claim 1, which is characterized in that: in the second step, dilute hydrochloric acid is added for preliminary washing, the rotation speed of a centrifugal machine is 3500rpm, and the duration of each centrifugation is 5-10min; in the alcohol washing process, the hands are required to be used for more than 15min, the centrifugal speed is 10000rpm, and the centrifugal time is 30min; the centrifugal speed in the water washing process is 3500rpm, and the duration time is 5-10min; vortex oscillation is carried out for more than 30min after each centrifugation process in the water washing process; the rotational speed of the centrifugal machine in the collecting process is 1500rpm, and the centrifugal time is 30-35min.
4. The method for preparing the MXene/CNT composite sponge reinforced resin matrix composite material according to claim 1, which is characterized in that: in the third step, the rotating speed of the mixed solution of MXene and CNT is 10-15r/min, and the stirring time is 20min; the ultrasonic time is 10-15 min, the frequency is 80Hz, and the power is 500w; the vacuum degree of the vacuumizing is 3-10 Pa; the freezing time is 3-3.5 h at the temperature of minus 40 ℃, and the vacuum drying process retention time is 100-120 h after the temperature is raised to 25 ℃.
5. The method for preparing the MXene/CNT composite sponge reinforced resin matrix composite material according to claim 1, which is characterized in that: in the fourth step, the shearing flow stirring speed of the composite resin is 1800-2000r/min; the foam discharging time of the composite resin is 20-25 min until the foam discharging is complete; the stirring time of the composite resin and the curing agent is 15-25min; the secondary foam discharging time of the composite resin is 10min-15min until the foam discharging is complete; the composite resin is heated and insulated in an oven to realize solidification, the solidification and insulation time is 24 hours, and the solidification and heating temperature is 40 ℃.
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