CN115340688B - Preparation method of shell-like composite material with sandwich structure - Google Patents

Preparation method of shell-like composite material with sandwich structure Download PDF

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CN115340688B
CN115340688B CN202211082066.0A CN202211082066A CN115340688B CN 115340688 B CN115340688 B CN 115340688B CN 202211082066 A CN202211082066 A CN 202211082066A CN 115340688 B CN115340688 B CN 115340688B
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CN115340688A (en
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郭林
赵赫威
汪少雄
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Beihang University
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Abstract

The invention relates to the field of materials, and mainly relates to a preparation method of a shell-like composite material with a sandwich structure. The composite material consists of graphene oxide, aluminum oxide nanowires, polyvinyl alcohol and a small amount of glutaraldehyde, and is assembled by a vacuum auxiliary suction filtration method, and the thickness, the diameter and the shape of the composite material can be adjusted by a vacuum suction filtration device. The preparation process is simple, common workers can master the academic society, the prepared composite material has the characteristics of high strength and high toughness, and the composite material can maintain good appearance and mechanical property after being soaked in acid, alkali and organic solvents or being subjected to ultrasonic treatment, can always maintain good self-supporting property and structural stability in a humid environment, can be used as a structural material in an extreme environment, and has great application prospect in the fields of aerospace and engineering.

Description

Preparation method of shell-like composite material with sandwich structure
Technical Field
The invention belongs to the field of materials, and relates to preparation of gamma-hydroxy aluminum oxide nanowires, amorphous aluminum oxide nanowires, crystal-amorphous coexisting (biphase) aluminum oxide nanowires and completely crystallized gamma-aluminum oxide nanowires, in particular to preparation of shell-like composite materials with sandwich structures reinforced by the nanowires.
Background
Strength and toughness are the most basic properties of structural materials, and provide a main reference for evaluating mechanical properties of structural materials. In general, strength and toughness are contradictory, high strength materials always exhibit brittleness, and high toughness materials generally exhibit low strength. Thus, developing structural materials that combine high strength and toughness is one of the major challenges in the engineering arts.
Over millions of years of victory and defeat, the natural organism evolved almost perfect structure and function. Therefore, in the past decades, a large number of researchers have produced biomimetic materials with different functions by learning naturally and mimicking their intrinsic structure. In terms of structural materials, shells are the typical object in which they are simulated. The nacreous layer of the shell is composed of about 95% of typical brittle material Wen Danpian (calcium carbonate micrometer tablet) and about 5% of organic matter (protein and chitin fiber), and has strength comparable to aragonite, but has toughness improved by more than 3000 times. Based on this, the structure and composition of the nacreous layer were studied in detail by researchers and found that its ultra-high toughness results from the unique "brick-mud structure" built up of Wen Danpian (bricks) and organics (mud). In light of this, researchers have produced a series of layered composites with high strength and toughness over the shells themselves by varying the composition of the "bricks" and "mud" therein. Among them, graphene Oxide (GO) is the most popular inorganic nanosheets (serving as bricks) due to its platelet-like morphology, excellent mechanical properties, and abundant oxygen-containing functional groups on the surface. Since the first GO-based layered composite was successfully prepared by vacuum filtration, a number of strategies such as interfacial crosslinking, nanoplatelet reinforcement, bridging, etc. have been developed to improve its mechanical properties. However, most strategies or concerns have focused on the layered "brick-mud" structure present in the nacre coating and the interfacial modification therein, and lack novel structural designs. Thus, in order to pursue higher mechanical properties, researchers have only been able to increase the mechanical properties of such structural materials by looking for stronger flakes or organics on the basis of the "brick-mud" structure of the layered structure, which greatly limits its application.
Detailed characterization of natural nacreous layers is known in which there are also one-dimensional rigid nanofibers (chitin) and ceramic bridges immersed in the layered structure of stacks of aragonite and organic matter, which can hinder the sliding of the layered structure and the generation, propagation, etc. of cracks when the nacreous layer is subjected to damage. According to the inspired, the rigid nanowire is introduced into the traditional shell-like composite material, and the construction of a novel sandwich structure with one-dimensional nanowire support is an effective way for further improving the strength and toughness of the structural material.
Disclosure of Invention
Aiming at the problem that the strength and toughness of the existing structural material cannot be achieved, the preparation of the shell-like composite material with the sandwich structure reinforced by the one-dimensional ceramic nanowire with high strength and toughness is realized by adopting low-cost metal salt, buffer solution and the like as raw materials, obtaining the one-dimensional alumina nanowire through a hydrothermal method and high-temperature calcination, then uniformly mixing the one-dimensional alumina nanowire with graphene oxide nanosheets and organic polymers and utilizing a vacuum-assisted suction filtration mode. The method comprises the following steps:
in the first step, 17.5mL of sodium hydroxide-ammonia buffer (the concentration of sodium hydroxide and ammonia water are 2.5mol/L and mixed in equal volume) was prepared, and 17.5mL of colorless transparent AlCl prepared was added dropwise thereto 3 The solution is kept in a state of intense stirring during the dripping process, and the color of the solution is gradually changed into milky colloid. Then, after the sodium hydroxide-ammonia water is added dropwise, stirring is continued for 10min;
transferring the white emulsion obtained in the first step into a high-pressure reaction kettle with a Teflon lining, and then placing the reaction kettle into a high-temperature oven at the temperature of 160-220 ℃ for 12-36 h;
thirdly, centrifugally separating the product obtained in the second step, alternately washing the product with ethanol and water for 3 times, removing impurities and residual solvents, dispersing the product with ultrapure water, and freeze-drying the product to obtain white one-dimensional gamma-hydroxy aluminum oxide nanowires;
fourth, the third step is carried outCalcining the one-dimensional gamma-hydroxy alumina nano wire at 400-500 deg.c (preferably 500 deg.c) for 1-360 min to obtain amorphous alumina nano wire, biphasic alumina nano wire and gamma-Al according to the different calcining temperature and time 2 O 3 A nanowire;
fifthly, ultrasonically dispersing graphene oxide in deionized water and preparing 2-4 mg/mL Graphene Oxide (GO) dispersion liquid; 1-10 mg of biphasic alumina nano wire is taken and ultrasonically dispersed in deionized water to obtain the concentration of 0.2-2 mg/mL; weighing solid polyvinyl alcohol (PVA), heating in a water bath at 75 ℃ for 4 hours, and gradually dissolving and dispersing in deionized water under stirring to obtain a polyvinyl alcohol solution with the concentration of 2.5 mg/mL; dispersing 50wt% glutaraldehyde in deionized water to obtain glutaraldehyde diluent with concentration of 0.5 mg/mL;
and step six, adding 2-20mg of alumina nanowires into 5mL of GO solution on the basis of the step five, stirring for 12-36 h, fully mixing the alumina nanowires with GO, and adsorbing the wires on the surface of GO. Then, firstly, carrying out ultrasonic treatment for 20-30 min, sequentially adding 4mL of polyvinyl alcohol with the concentration of 2.5mg/mL and glutaraldehyde with the concentration of 0.2mL and the concentration of 0.5mg/mL into the mixture, stirring the mixture for 12-18 h, carrying out ultrasonic treatment for 20-30 min, and obtaining the shell-like composite material with the sandwich structure and reinforced by the alumina nano wire through a vacuum auxiliary suction filtration method.
In the present invention, the preparation conditions (e.g., temperature, humidity, apparatus, materials, processes, methods, etc.) are all common in the art or readily available to one of ordinary skill in the art according to conventional techniques in the art, without being specifically stated.
In the present invention, the dissolution or reaction temperature is 15 to 35℃at normal temperature, normal pressure, etc., unless otherwise specified.
In the invention, the graphene oxide is synthesized by a modified Hummers method, the preparation method can be referred, the thickness of the graphene is below 1nm, and the transverse dimension is between 10 and 50 mu m, but the graphene oxide is not limited to the graphene oxide.
Furthermore, the length range of the gamma-hydroxyl alumina nano wire prepared by the invention is 0.5-1.2 mu m, the diameter range is 25-30 nm, and the specific length and diameter are determined by the reaction conditions and are adjustable.
Furthermore, the length range of the prepared biphasic alumina nanowire is 0.5-1.2 mu m, the diameter range is 20-25 nm, and the specific length and diameter are determined by reaction conditions and are adjustable.
Furthermore, the length range of the gamma-alumina nano wire prepared by the invention is 0.5-1.2 mu m, the diameter range is 20-25 nm, and the specific length and diameter are determined by the reaction conditions and are adjustable.
Furthermore, the thickness of the GO-based shell-like composite material with the sandwich structure reinforced by the one-dimensional biphase (crystal-amorphous) alumina nanowires is determined by the amount of samples added during vacuum assisted suction filtration and the diameter of the sand core suction filtration device, and the transverse dimension is determined by the diameter of the sand core suction filtration device. The typical diameter of the GO-based shell-like composite material with the sandwich structure is 5cm, the thickness is 5-20 mu m, but the thickness and the diameter are not limited to the above.
Further, the concentration of sodium hydroxide in the second step is preferably in the range of 0.4 to 0.6mol/L, and the concentration of ammonia water is preferably in the range of 0.4 to 0.6mol/L.
Further, the temperature range of the hydrothermal process in the fourth step is 180-200 ℃, the preferable reaction time is 24-36 h, and any combination of them is acceptable.
Further, the seventh step preferably has a calcination temperature of 500 ℃ and a calcination time of 1 to 5 minutes to obtain the biphasic alumina nanowires.
The invention has the advantages that:
the invention provides a method for preparing gamma-aluminum hydroxide nanowire, which is simple and easy to implement and easy to popularize, can not be converted into gamma-aluminum hydroxide after being calcined at 350 ℃ for more than 12 hours, has good thermal stability, and has the yield of more than 70 percent by calculating the mole number (namely, more than 0.7 mole of aluminum hydroxide can be obtained by adding 1 mole of aluminum chloride hexahydrate), so that the method is hopeful to realize industrial application and mass production.
2 the present invention provides a very simple method for preparing dual phase alumina nanowires and gamma-alumina nanowires. The method is characterized in that the gamma-hydroxy aluminum oxide nanowire prepared by the method is subjected to heat treatment at 500 ℃ for 1-120 min, so that the biphase aluminum oxide nanowire with different crystallinity can be obtained. The gamma-aluminum oxide nanowire prepared by the method can be subjected to heat treatment for more than 360 minutes at the temperature of 500 ℃ to obtain the gamma-aluminum oxide nanowire with all crystallization. The mole number of the biphasic alumina or the fully crystallized gamma-alumina nano-wire obtained by heat treatment is unchanged.
The invention creatively constructs the GO-based shell-like composite material with the sandwich structure and reinforced by the alumina nano wire, the method is simple and convenient and is convenient to popularize, the components of the GO-based shell-like composite material can be replaced by a combination with similar morphology, and the composite material with the sandwich structure, such as a combination of a one-dimensional hydroxyapatite nano wire, an MXene two-dimensional sheet and polymer sodium carboxymethyl fiber, can also be prepared.
4, the invention creatively introduces the alumina nanowire to strengthen and construct the GO-based shell-like composite material with a sandwich structure, so that the mechanical property and long-term service stability of the composite material are obviously improved, and the composite material has good application prospects in the fields of engineering, aerospace and the like.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of a dual-phase alumina nanowire obtained in example 1 of the present invention;
FIG. 2 is an X-ray diffraction pattern (XRD) of a biphasic alumina nanowire obtained in example 1 of the present invention;
FIG. 3 is an SEM photograph of a two-phase alumina nanowire-reinforced GO-based shell-like composite material with a sandwich structure obtained in example 1 of the present invention;
FIG. 4 shows the mechanical test results of example 1 of the present invention;
Detailed Description
The invention will be further described in detail with reference to the drawings and examples, wherein solvents, medicines and instruments used in the following are not specifically described and are considered to be available in the ordinary laboratory or market. Furthermore, the examples in this embodiment are for the reader to understand the specific contents of the present invention, not the whole contents, and do not limit the scope of the present invention in any way. Further, optimization or regulation which can be conceived by those skilled in the art without departing from the scope of the idea of the present invention is included in the present invention.
Example 1
Preparation method of double-phase alumina nanowire reinforced shell-like composite material with sandwich structure
In the first step, 0.875g of sodium hydroxide solution was weighed and dissolved in 8.75mL of water to obtain 2.5mol/L of sodium hydroxide solution, which was then added to an equal volume of 2.5mol/L of aqueous ammonia to obtain 17.5mL of sodium hydroxide-aqueous ammonia buffer. Then, 4.2g of aluminum chloride hexahydrate was dissolved in 17.5mL of water and stirred vigorously to obtain a clear and transparent aluminum chloride solution having a concentration of 1 mol/L. Subsequently, 17.5mL of sodium hydroxide-ammonia buffer was added dropwise to a clear and transparent aluminum chloride solution prepared to 17.5mL using a constant pressure separatory funnel, and the solution gradually became milky white with vigorous stirring. After the dropwise addition of the buffer solution is completed, stirring is continued for 10min;
and secondly, transferring the white emulsion obtained in the first step into a high-pressure reaction kettle with a Teflon lining, and then placing the reaction kettle in a high-temperature oven for reaction for 24 hours at 200 ℃. After the reaction, the product was transferred to a centrifuge tube and centrifuged to leave a solid product. Then, ethanol and water are used for alternately centrifuging and washing for 3 times to remove impurities and residual solvents, and then ultrapure water is used for dispersing and freeze-drying the impurities and the residual solvents, so that white gamma-hydroxy aluminum oxide nanowires can be obtained;
thirdly, calcining the gamma-hydroxy aluminum oxide nanowire obtained in the second step in an air atmosphere at 500 ℃ for 1-120 min to obtain a biphasic aluminum oxide nanowire;
fourthly, weighing solid polyvinyl alcohol (PVA), heating in a water bath at 75 ℃ for 4 hours, and gradually dissolving and dispersing in deionized water under the condition of stirring to obtain a polyvinyl alcohol solution with the concentration of 2.5 mg/mL; dispersing 50wt% glutaraldehyde in deionized water to obtain glutaraldehyde diluent with concentration of 0.5 mg/mL;
and fifthly, on the basis of the fourth step, adding 7mg of the biphasic alumina nanowire into 5mL of 4mg/mL GO solution, stirring for 36h, fully mixing the biphasic alumina nanowire with GO, and fully adsorbing the nanowire on the surface of GO. Then, firstly, carrying out ultrasonic treatment for 30min, sequentially adding 4mL of 2.5mg/mL polyvinyl alcohol and 0.2mL of 0.5mg/mL glutaraldehyde into the mixture, stirring the mixture for 12 to 18h, carrying out ultrasonic treatment for 20 to 30min, and obtaining the double-phase alumina nanowire reinforced shell-like composite material with a sandwich structure through a vacuum assisted suction filtration method. The thickness of the composite material is about 10 mu m, the diameter of the composite material is 5cm, the microstructure of the composite material is in a sandwich structure, and the biphase alumina nanowires are mixed between the graphene oxide sheets. It should be noted in particular that the thickness and diameter or even the shape can be adjusted, depending on the amount of sample added, the concentration of the sample, the size and shape of the suction filtration device;
and sixthly, stretching the double-phase alumina nanowire reinforced shell-like composite material with the sandwich structure by using a universal stretcher, wherein the strength and the strain of the shell-like composite material are respectively more than 800MPa and 7 percent, and are higher than those of the existing bridge steel. In addition, the film is respectively soaked in solvents or solutions such as organic solvents, acids, alkalis, ethanol, water and the like, or is kept stand or subjected to ultrasonic vibration, and good self-supporting property and good structural stability can be still maintained.
Example 2
Preparation method of gamma-alumina nanowire reinforced shell-like composite material with sandwich structure
In the first step, 0.875g of sodium hydroxide solution was weighed and dissolved in 8.75mL of water to obtain 2.5mol/L of sodium hydroxide solution, which was then added to an equal volume of 2.5mol/L of aqueous ammonia to obtain 17.5mL of sodium hydroxide-aqueous ammonia buffer. Then, 4.2g of aluminum chloride hexahydrate was dissolved in 17.5mL of water and stirred vigorously to obtain a clear and transparent aluminum chloride solution having a concentration of 1 mol/L. Subsequently, 17.5mL of sodium hydroxide-ammonia buffer was added dropwise to a clear and transparent aluminum chloride solution prepared to 17.5mL using a constant pressure separatory funnel, and the solution gradually became milky white with vigorous stirring. After the dropwise addition of the buffer solution is completed, stirring is continued for 10min;
and secondly, transferring the white emulsion obtained in the first step into a high-pressure reaction kettle with a Teflon lining, and then placing the reaction kettle in a high-temperature oven for reaction for 24 hours at 200 ℃. After the reaction, the product was transferred to a centrifuge tube and centrifuged to leave a solid product. Then, ethanol and water are used for alternately centrifuging and washing for 3 times to remove impurities and residual solvents, and then ultrapure water is used for dispersing and freeze-drying the impurities and the residual solvents, so that white gamma-hydroxy aluminum oxide nanowires can be obtained;
thirdly, calcining the gamma-aluminum hydroxide nanowire obtained in the second step in an air atmosphere at 500 ℃ for 360 minutes to obtain the gamma-aluminum hydroxide nanowire;
fourthly, weighing solid polyvinyl alcohol (PVA), heating in a water bath at 75 ℃ for 4 hours, and gradually dissolving and dispersing in deionized water under the condition of stirring to obtain a polyvinyl alcohol solution with the concentration of 2.5 mg/mL; dispersing 50wt% glutaraldehyde in deionized water to obtain glutaraldehyde diluent with concentration of 0.5 mg/mL;
and fifthly, on the basis of the fourth step, adding 7mg of gamma-alumina nanowires into 5mL of 4mg/mL of GO solution, and stirring for 36h to fully mix the gamma-alumina nanowires with GO and enable the gamma-alumina nanowires to be fully adsorbed on the surface of the GO. Then, firstly, carrying out ultrasonic treatment for 30min, sequentially adding 4mL of 2.5mg/mL polyvinyl alcohol and 0.2mL of 0.5mg/mL glutaraldehyde into the mixture, stirring the mixture for 12 to 18h, carrying out ultrasonic treatment for 20 to 30min, and obtaining the gamma-alumina nanowire reinforced shell-like composite material with a sandwich structure through a vacuum assisted suction filtration method. The thickness of the composite material is about 10 mu m, the diameter of the composite material is 5cm, the microstructure of the composite material is in a sandwich structure, and gamma-alumina nanowires are mixed between graphene oxide sheets. It should be noted in particular that the thickness and diameter or even the shape can be adjusted, depending on the amount of sample added, the concentration of the sample, the size and shape of the suction filtration device;
and sixthly, stretching the gamma-alumina nanowire reinforced shell-like composite material with the sandwich structure by using a universal stretcher, and measuring the strength and the strain of the shell-like composite material to be respectively more than 500MPa and 5%. In addition, the film is respectively soaked in solvents or solutions such as organic solvents, acids, alkalis, ethanol, water and the like, or is kept stand or subjected to ultrasonic vibration, and good self-supporting property and good structural stability can be still maintained.
Example 3
Preparation method of amorphous alumina nanowire reinforced shell-like composite material with sandwich structure
In the first step, 0.875g of sodium hydroxide solution was weighed and dissolved in 8.75mL of water to obtain 2.5mol/L of sodium hydroxide solution, which was then added to an equal volume of 2.5mol/L of aqueous ammonia to obtain 17.5mL of sodium hydroxide-aqueous ammonia buffer. Then, 4.2g of aluminum chloride hexahydrate was dissolved in 17.5mL of water and stirred vigorously to obtain a clear and transparent aluminum chloride solution having a concentration of 1 mol/L. Subsequently, 17.5mL of sodium hydroxide-ammonia buffer was added dropwise to a clear and transparent aluminum chloride solution prepared to 17.5mL using a constant pressure separatory funnel, and the solution gradually became milky white with vigorous stirring. After the dropwise addition of the buffer solution is completed, stirring is continued for 10min;
and secondly, transferring the white emulsion obtained in the first step into a high-pressure reaction kettle with a Teflon lining, and then placing the reaction kettle in a high-temperature oven for reaction for 24 hours at 200 ℃. After the reaction, the product was transferred to a centrifuge tube and centrifuged to leave a solid product. Then, ethanol and water are used for alternately centrifuging and washing for 3 times to remove impurities and residual solvents, and then ultrapure water is used for dispersing and freeze-drying the impurities and the residual solvents, so that white gamma-hydroxy aluminum oxide nanowires can be obtained;
thirdly, calcining the gamma-hydroxy aluminum oxide nanowire obtained in the second step in the air atmosphere for 10s at the temperature of 500 ℃ to obtain an amorphous aluminum oxide nanowire;
fourthly, weighing solid polyvinyl alcohol (PVA), heating in a water bath at 75 ℃ for 4 hours, and gradually dissolving and dispersing in deionized water under the condition of stirring to obtain a polyvinyl alcohol solution with the concentration of 2.5 mg/mL; dispersing 50wt% glutaraldehyde in deionized water to obtain glutaraldehyde diluent with concentration of 0.5 mg/mL;
and fifthly, on the basis of the fourth step, adding 7mg of amorphous alumina nanowires into 5mL of 4mg/mL of GO solution, and stirring for 36h to fully mix the amorphous alumina nanowires with GO and fully adsorb the amorphous alumina nanowires on the surface of GO. Then, firstly, carrying out ultrasonic treatment for 30min, sequentially adding 4mL of 2.5mg/mL polyvinyl alcohol and 0.2mL of 0.5mg/mL glutaraldehyde into the mixture, stirring the mixture for 12 to 18h, carrying out ultrasonic treatment for 20 to 30min, and obtaining the amorphous alumina nanowire reinforced shell-like composite material with a sandwich structure through a vacuum assisted suction filtration method. The thickness of the composite material is about 10 mu m, the diameter of the composite material is 5cm, the microstructure of the composite material is in a sandwich structure, and amorphous alumina nanowires are mixed between graphene oxide sheets. It should be noted in particular that the thickness and diameter, or even the shape, may be adjusted depending on the amount of sample added, the concentration of the sample, and the size and shape of the suction filtration device.
And sixthly, stretching the amorphous aluminum oxide nanowire reinforced shell-like composite material with the sandwich structure, which is prepared in the fifth step, by using a universal stretcher, and measuring the strength and the strain of the shell-like composite material to be respectively more than 600MPa and 5% (shown in figure 4). In addition, the film is respectively soaked in solvents or solutions such as organic solvents, acids, alkalis, ethanol, water and the like, or is kept stand or subjected to ultrasonic vibration, and good self-supporting property and good structural stability can be still maintained.

Claims (3)

1. A preparation method of a shell-like composite material with a sandwich structure is characterized by comprising the following steps:
firstly, adjusting the concentration range of aluminum chloride hexahydrate to be 0.1-2 mol/mL; the NaOH-ammonia water mixed solution is used as a precipitator, wherein the ammonia water regulating concentration range is 0.5-3.5 mol/mL, the NaOH solution regulating concentration range is 0.5-3.5 mol/mL, and then the ammonia water and the NaOH solution with the same volume are fully mixed and can be used as the precipitator for precipitating aluminum salt in the aluminum chloride solution;
secondly, dripping 17.5mL of the NaOH-ammonia water mixed solution prepared in the first step into 17.5mL of aluminum chloride solution, stirring for 5-60 min, and transferring to a 100mL high-temperature reaction kettle for reaction for 12-48 h at 140-240 ℃;
thirdly, removing the solvent in the sample after the reaction in the second step, leaving solid products, then alternately washing the products with ethanol and deionized water for 3 times, then ultrasonically dispersing the obtained products into deionized water, and then freeze-drying to obtain clean white gamma-aluminum hydroxide nanowires;
fourthly, placing the gamma-hydroxy aluminum oxide nanowire obtained in the third step in a high-temperature furnace to calcine for 1-10s at 500 ℃ to obtain an amorphous aluminum oxide nanowire; calcining the gamma-hydroxy alumina nanowire in a high temperature furnace at 500 ℃ for 1-120 min to obtain a crystal-amorphous coexisting biphasic alumina nanowire; calcining gamma-hydroxy alumina nanometer wire in high temperature furnace for 360min to obtain completely crystallized gamma-alumina nanometer wire, and calcining in air, oxygen or inert gas;
fifthly, dispersing dry Graphene Oxide (GO) in deionized water to obtain GO solution with the concentration of 2-10 mg/mL; heating and dispersing solid polyvinyl alcohol in deionized water, heating at 60-90 ℃ and vigorously stirring for 4 hours until the polyvinyl alcohol is completely dissolved, then stopping heating, and cooling to room temperature for standby in stirring to obtain a polyvinyl alcohol solution with the concentration of 2.5 mg/mL; dispersing 50wt% glutaraldehyde in deionized water to obtain glutaraldehyde diluent with concentration of 0.5 mg/mL;
step six, on the basis of the step five, adding 2-20mg of crystal-amorphous coexisting biphasic alumina nanowires into 5mL of 2-10 mg/mL GO solution, and then stirring for 12-36 h to enable the biphasic alumina nanowires to be fully mixed with GO and enable the crystal-amorphous coexisting biphasic alumina nanowires to be adsorbed on the surface of GO; then, ultrasonic treatment is carried out for 20-30 min, 4mL of 2.5mg/mL of polyvinyl alcohol and 0.2mL of 0.5mg/mL of glutaraldehyde are sequentially added into the mixture, stirring is carried out for 12-18 h, ultrasonic treatment is carried out for 20-30 min, and then the shell-like composite material with a sandwich structure and enhanced by the crystal-amorphous coexisting biphasic alumina nano wire is obtained by a vacuum auxiliary suction filtration method.
2. The method for preparing the shell-like composite material with the sandwich structure according to claim 1, wherein the method comprises the following steps: the shell-like composite material with sandwich structure and reinforced by the crystal-amorphous coexisting biphase alumina nano wire prepared in the sixth step has good performanceGood mechanical property, tensile strength exceeding 800MPa, breaking strain exceeding 7%, breaking work exceeding 30MJ/m 3 。
3. Use of a shell-like composite material with a sandwich structure prepared according to any one of the methods of claims 1-2 in engineering and materials.
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