CN112266497A - Shell-like light high-strength composite material and preparation method thereof - Google Patents
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Abstract
The invention belongs to the technical field of composite material preparation, and relates to a preparation method of a shell-like light high-strength composite material, which comprises the following steps of (1) using a leaf-shaped amorphous-crystal heterogeneous manganese dioxide nanosheet prepared by an oxidation-reduction method and graphene oxide obtained by a Hummers oxidation method as main construction units, combining a small amount of biological macromolecules, and preparing a high-strength composite film material by an evaporation-induced self-assembly method; (2) a large amount of composite film materials are assembled into a whole by coating a cross-linking agent layer by layer, and the light high-strength block layered micro-nano composite material is obtained by combining a hot-pressing process. The preparation process is simple and convenient to operate, the process is green and environment-friendly, and the strength of the finally prepared bulk composite material is far superior to that of most other graphene oxide-based bulk composite materials.
Description
Technical Field
The invention relates to the technical field of composite material preparation, in particular to preparation of a three-dimensional shell-like light high-strength composite material with high bending strength and toughness.
Background
Massive lightweight structural materials with high load bearing capacity and large volume in three dimensions (3D) have received attention from researchers due to their wide application in fields such as engineering construction, aerospace, etc. Graphene Oxide (GO) serving as a two-dimensional ultrathin graphite material is widely considered as an ideal micro-nano basic building unit for assembling GO-based materials due to good water solubility, excellent mechanical properties and abundant surface functional groups. However, the preparation of large-scale, high mechanical properties GO-based bulk structural materials remains a challenge. This is mainly due to the difficulty in assembling the GO material from two-dimensional (2D) micro-nano dimensions to three-dimensional (3D) block macro dimensions, and the difficulty in ensuring that the excellent mechanical properties of GO are not sacrificed. The core of the method is that a firm and controllable strong micro-nano interface is difficult to construct to harden the graphene oxide construction unit and strengthen the crosslinking effect between the graphene oxide construction unit and other construction units. The reason for this is that the graphene oxide nanosheets have super-strong flexibility, so that the improvement of the mechanical properties of the finally prepared GO-based 3D bulk material is limited, and especially the improvement of the bending strength, the fracture toughness and the rigidity of the GO-based 3D bulk material is limited.
In nature, the creatures are optimized by continuous evolution so that they can survive under extreme conditions of high mechanical stress, fatigue and wear, natural shells being among the most widely known examples of perfect combinations of high strength and high toughness. Besides its special "brick-mud" structure, the specific crystalline/amorphous interface structure in the shell nacreous layer is also one of the important reasons for its excellent mechanical properties. Therefore, a specific brick-mud structure and an amorphous/crystalline multi-element complex heterogeneous interface structure in the shell material are deeply understood and simulated, and an effective way for preparing a light high-strength GO-based 3D bulk composite material is provided.
Disclosure of Invention
In view of this, the present invention provides an amorphous/crystalline hardening strategy to effectively overcome the super-flexibility of GO itself. Specifically, we first utilized nanoscale amorphous/crystalline heterogeneous phase "lobed" MnO2Hexagonal plates (A/C-LMH) and GO are compounded through Mn-O bonds, hydrogen bonds and intermolecular forces, and then the A/C-LMH/GO reinforced assembly units are assembled into the 3D bulk artificial shell material by combining a polymer multi-level interface synthesis cross-linking design and a layer-by-layer assembly strategy from bottom to top.
The invention develops a collaborative multiphase design strategy for preparing a high-mechanical-property composite block material which can be applied to practical production. The strategy is simple to operate, low in cost and environment-friendly. Thanks to this kind of cooperation heterogeneous design strategy, GO base 3D block artificial shell through optimizing has the bending mechanical properties higher than other GO base's block composite, outstanding fracture toughness and shock resistance, and material size, thickness and microstructure are all controllable.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a shell-like light high-strength composite material comprises the following steps:
(1) preparing graphene oxide by using an improved Hummers oxidation method, dissolving the graphene oxide with deionized water to prepare a colloidal graphene oxide solution for later use;
(2) preparation of foliated amorphous/crystalline heterogeneous phase MnO by redox method2Hexagonal nano sheet, dissolving with deionized water to obtain amorphous/crystalline heterogeneous phase MnO2Hexagonal nanosheet solution for later use;
(3) MnO of amorphous/crystalline heterogeneous phase2Mixing the hexagonal nanosheet solution and the graphene oxide solution with the biomacromolecule to obtain a stable mixed solution;
(4) transferring the mixed solution obtained in the step (3) into a culture dish, and carrying out evaporation self-assembly in an oven at 60 ℃;
(5) stripping the assembled composite film to obtain a high-mechanical-property composite film;
(6) and (4) assembling a plurality of composite films obtained in the step (5) into a whole by using a cross-linking agent in a layer-to-layer brushing manner, and performing hot-pressing treatment to obtain the shell-like light high-strength composite material.
Preferably, in the above preparation method of the seashell-like lightweight high-strength composite material, the concentration of the graphene oxide solution in step (1) is about 1 mg/mL.
The beneficial effects of the above technical scheme are: the low-concentration graphene oxide solution is beneficial to full and close layer-by-layer stacking of graphene oxide nano sheets and full reaction between the graphene oxide nano sheets and other microscopic construction units comprising manganese dioxide, biological macromolecules and the like.
Preferably, in the preparation method of the shell-like lightweight high-strength composite material, the amorphous/crystalline heterogeneous phase MnO in the step (2)2The preparation of hexagonal nanosheets follows the chemical equation:
KMnO4+NaH2PO2·H2O＝MnO2+NaH3PO4+KOH，
wherein the amount of the sodium hypophosphite prepared in a single time is 40mg, the amount of the potassium permanganate is 50mg, and a certain amount of deionized water is 100 mL.
If the amorphous/crystalline heterogeneous phase structure manganese dioxide hexagonal nanosheet required by the invention is difficult to obtain by other methods, the flexible graphene oxide cannot be effectively hardened.
Preferably, in the preparation method of the seashell-like light high-strength composite material, the biomacromolecules in the step (3) comprise sodium alginate and/or regenerated silk protein;
wherein the concentration of the sodium alginate solution is 0.30 wt%, and the concentration of the regenerated silk protein solution is 1 mg/mL.
The beneficial effects of the above technical scheme are: the concentration of the defined biological macromolecules can be matched with the concentration of the graphene oxide solution required in the step (1), so that each construction unit can be fully dispersed and reacted to generate strong interaction.
Preferably, in the preparation method of the seashell-like light high-strength composite material, the mass percentages of the raw materials in the step (3) are as follows: 74.40 wt% of graphene oxide, 24.80 wt% of manganese dioxide, 0.30 wt% of regenerated silk protein and 0.50 wt% of sodium alginate.
The beneficial effects of the above technical scheme are: the material ratio is the optimal ratio obtained after a series of comparative experiments (see attached table 1), and the performance of the final composite material can be optimized at the optimal ratio.
Preferably, in the above method for preparing the seashell-like lightweight high-strength composite material, the stirring and mixing in step (3) is: ultrasonic vibration is carried out for 0.5h, and then magnetic stirring is carried out for 6 h.
The beneficial effects of the above technical scheme are: after ultrasonic oscillation and magnetic stirring for a proper time, the establishment of the interaction force between the building units can be accelerated, the reaction is insufficient after the time is short, and the formed interaction force between the building units can be destroyed after the time is too long.
Preferably, in the preparation method of the seashell-like light high-strength composite material, the evaporation self-assembly time in the step (4) is 10-12 hours.
The beneficial effects of the above technical scheme are: the evaporative self-assembly for a suitable period of time will allow the building units to fully integrate with each other and expel excess moisture. If the time is too short, the acting force among the formed construction units is distributed unevenly due to too fast assembly process, and the microstructure of the material is damaged; too long a time can cause excessive evaporation of water from the material, resulting in wrinkling or even destruction of the material.
Preferably, in the above method for preparing the seashell-like lightweight high-strength composite material, the culture dish in step (4) has a specification of 5 × 5 × 2cm3。
Preferably, in the preparation method of the shell-like light high-strength composite material, the thickness of the composite film in the step (5) is 10-20 μm, and the macroscopic color is dark brown.
The beneficial effects of the above technical scheme are: the appropriate thickness will facilitate subsequent layer-by-layer brush assembly. If the thickness is too thick, the interlayer compactness of the final block composite material is influenced, so that the mechanical property of the material is influenced; if the thickness is too thin, the difficulty of assembly is increased, and the operation is difficult.
Preferably, in the preparation method of the seashell-like lightweight high-strength composite material, the cross-linking agent in the step (6) comprises a mixed solution of sodium alginate and sodium tetraborate;
wherein the concentration of the sodium alginate solution is 0.30 wt%, and the concentration of the sodium tetraborate solution is 1 mg/mL.
The beneficial effects of the above technical scheme are: the proper concentration can increase the bonding effect of the cross-linking agent, thereby realizing effective bonding between the layers of the composite film.
Preferably, in the preparation method of the seashell-like light high-strength composite material, the step (6) is specifically as follows: and (3) assembling a plurality of composite films obtained in the step (5) into a whole by using a sodium alginate solution in a layer-by-layer brushing mode, soaking and crosslinking the composite films by using a mixed solution of the sodium alginate solution and a sodium tetraborate solution, and carrying out hot pressing treatment to obtain the shell-like light high-strength composite material.
Preferably, in the preparation method of the shell-like light high-strength composite material, the temperature of the hot pressing treatment is 35-45 ℃, and the pressure is 100 MPa.
The beneficial effects of the above technical scheme are: the hot pressing condition can effectively increase the density and the interaction force between layers of the block composite material.
The invention also discloses the shell-like light high-strength composite material prepared by the method.
In the present invention, the solution to be used is prepared under ordinary conditions, for example, by dissolving the substance in an aqueous solution at room temperature, unless otherwise specified.
In the present invention, if not specifically stated, the devices, apparatuses, materials, processes, methods, procedures, preparation conditions, etc. used are those conventionally used in the art or can be easily obtained by those of ordinary skill in the art according to the techniques conventionally used in the art.
According to the technical scheme, compared with the prior art, the invention discloses a preparation method of a shell-like light high-strength composite material, and compared with other light high-strength composite materials, the invention has the following advantages:
(1) the invention utilizes the 'leafy' amorphous/crystalline heterogeneous phase MnO for the first time2The GO nano sheets are hardened and enhanced, the problem that the GO-based bulk block material is difficult to prepare is effectively solved, and the bending strength of the finally obtained GO-based artificial shell material is far higher than that of other GO-based block composite materials;
(2) the raw materials adopted in the preparation process are simple and easy to obtain, the cost is lower, no pollution is caused to the environment, the process is simple, and the operation is simple and convenient;
(3) the block composite material prepared by the method has excellent mechanical property, and the size, thickness and microstructure of the material are controllable;
(4) the invention can prepare different types of high-strength and high-toughness 3D scale block composite materials by adjusting the types of added biological macromolecules, thereby having universality.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a representation of a "leaf-shaped" amorphous/crystalline manganese dioxide hexagonal nanosheet: (a-c, e) transmission electron microscopy characterization plots at different magnifications; (d) electron diffraction patterns under a transmission electron microscope; (f) atomic force microscopy characterization.
FIG. 2 is a composite film topography characterization: (a) evaporating and self-assembling to obtain a two-dimensional composite film macroscopic electronic photograph; (b) a representation of the composite film preparation solution under an environmental scanning electron microscope; (c) fracture section characterization diagrams of the composite film under an environmental scanning electron microscope.
Fig. 3 is a comparison graph of tensile mechanical properties of a composite film and a pure graphene oxide film: the composite film and the pure graphene oxide film are respectively shown in (a) a stress-strain curve comparison graph, (b) a maximum tensile fracture stress comparison graph, (c) a fracture work comparison graph and (d) a maximum Young modulus comparison graph.
Fig. 4 is a diagram of an assembly process from a two-dimensional composite film to a three-dimensional bulk artificial shell.
FIG. 5 is a representation of the morphology and mechanical properties of a block shell replica. (a) Finally, obtaining a macroscopic electronic photograph of the block artificial shell; (b) the appearance of the fracture section of the block artificial shell under an environment scanning electron microscope; (c) a fracture section profile diagram of a natural shell pearl layer; the block artificial shell (d) three-point bending strength-strain curve, (e) maximum bending strength and maximum bending modulus graph, (f) bending toughness KIc and KJc result graph.
Detailed Description
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 derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that, since the graphene oxide material is prepared according to the modified Hummer method reported in the literature, the preparation process thereof is not repeated in the following specific examples.
(1) Accurately weighing 500mg of prepared graphene oxide powder in advance, dissolving the graphene oxide powder in 500mL of deionized water, stirring for 2h, and then performing ultrasonic dispersion for 1min to obtain a uniformly dispersed 1mg/mL colloidal Graphene Oxide (GO) solution;
accurately weighing 1.5g of Sodium Alginate (SA), dissolving in deionized water to prepare 500mL of solution, fully stirring for 8 hours to completely dissolve the solution, and preparing into 0.3 wt% of dilute SA solution;
accurately weighing 0.5g of regenerated silk protein (rSF), dissolving in deionized water to prepare 500mL of solution, fully stirring for 8 hours to completely dissolve the regenerated silk protein to prepare 1mg/mL of rSF dilute solution;
0.5g of sodium tetraborate (Borate) is accurately weighed and dissolved in deionized water to prepare 500mL of solution, and the solution is fully stirred for 2 hours to be completely dissolved to prepare 1mg/mL of Borate solution.
(2) 40mg of sodium hypophosphite (NaH)2PO2·H2O) and 50mg of potassium permanganate (KMnO)4) Respectively dissolving in 100ml of deionized water, and fully stirring for 2h to obtain 100ml of NaH2PO2·H2O solution and 100ml KMnO4A solution; then, 100ml of KMnO4 solution was slowly added dropwise to 100ml of NaH at 35 ℃ using a constant pressure dropping funnel2PO2·H2In O solution, and simultaneously fully stirring by a magnetic stirrer to fully perform the oxidation-reduction reaction (the process lasts for about 2 hours). Immediately after the reaction, the product mixture solution was washed with deionized water by centrifugation (centrifugation rate 13000rmp)4 times. And then pouring out the supernatant to remove residual salt impurities, collecting the precipitate to obtain a leafy amorphous/crystalline manganese dioxide hexagonal nanosheet (A/C-LMH), freeze-drying the precipitate into powder, adding the powder into a certain amount of deionized water, fully stirring and centrifugally dispersing, and finally preparing a 1mg/mL A/C-LMH solution.
(3) 200.0mL of the prepared GO solution, 57.0mL of the A/C-LMH solution, 21.0mL of the rSF solution and 2.6mL of the SA solution are respectively measured, mixed and stirred for 6 hours in a 500mL beaker to be uniform, so that a uniform mixed solution with the mass ratio of 'GO (74.40 wt%) @ A/C-LMH (24.80 wt%) @ rSF (0.30 wt%) @ SA (0.50 wt%)' is obtained.
(4) Adding the mixed solution into 5 × 5 × 2cm3And putting the culture dish into an oven to perform evaporation drying self-assembly at 60 ℃, wherein the process lasts for 10-12 hours, and finally the two-dimensional composite film with high mechanical property is obtained.
(5) Repeating the above steps to prepare about 200 sheets of 5X 5cm2A composite film of uniform dimensions, as shown in fig. 2 (a).
(6) 200 prepared sheets of 5X 5cm2The composite films with uniform sizes are assembled together in a mode of brushing 0.3 wt% of SA solution layer by layer, and then the whole is soaked in the SA and Borate mixed solution for 0.5h to obtain the 3D body composite material precursor.
(7) And (3) carrying out hot pressing treatment on the obtained 3D block composite material precursor for 48h at the pressure of 100MPa and the temperature of 40 ℃ by using a hot press to finally obtain the bionic laminar composite block with low density, high bending strength and high bending toughness, as shown in fig. 4 (e).
FIG. 1 shows the "leafy" amorphous/crystalline manganese dioxide nanoplates obtained by redox methods characterized under a transmission electron microscope. The "leaf-shaped" is represented by the amorphous and crystalline regions shown in fig. 1a and 1b, which exhibit a structure similar to a vein, and the "vein" region is an amorphous region and the others are crystalline regions (fig. 1d, e). Fig. 1c shows that the prepared manganese dioxide nanosheet is of a porous structure, and fig. 1f is an atomic force microscope characterization diagram of the manganese dioxide nanosheet, and it can be seen that the thickness of the obtained 'leafy' amorphous/crystalline heterogeneous phase manganese dioxide nanosheet is about 2 nm.
From FIG. 2a, it can be seen that the composite film obtained by the evaporative self-assembly method has a smooth and flat surface and a tan color. Fig. 2b is an environmental scanning electron microscope characterization of the composite film assembly solution, which embodies the successful compounding of graphene oxide and "leafy" amorphous/crystalline manganese dioxide nanoplates. FIG. 2c is an environmental scanning electron microscope characterization of the composite film at the fracture section, which shows that the fracture section shows a corrugated staggered layered structure.
FIG. 3 is a graph comparing the mechanical properties of a composite film with that of a pure graphene oxide film, and it can be seen from the graph that the mechanical properties of the composite film are better than those of the pure graphene oxide film, the tensile strength of 368.1 + -9.9 MPa, the Young's modulus of 7.5 + -1.4 GPa and the Young's modulus of 13.8 + -2.6 MJ/m3The fracture toughness of the composite film is superior to that of similar bionic composite films.
The preparation process from the two-dimensional composite film to the three-dimensional block artificial shell is shown in fig. 4, and the preparation process is simple in steps, low in cost and environment-friendly.
The 3D bulk composite material obtained by the preparation method is subjected to a macroelectron photograph such asFIG. 5a shows a tan color of 5X 0.2cm3The composite block of (1). The appearance characterization result of the fracture section of the 3D bulk shell-like material by an environmental scanning electron microscope is shown in fig. 5b, and is similar to the fracture section of a natural shell (fig. 5c), which shows that the prepared bulk artificial shell has a natural shell 'brick-mud' structure.
In addition, the results of three-point bending tests are shown in fig. 5d-f, and the ultimate bending strength is as high as 204MPa (fig. 5d, e), which is incomparable with other graphene oxide-based bulk artificial shells at present. The ultimate bending modulus is up to 7.3GPa (figure 5e), and the fracture toughness KIcIs 0.90 +/-0.07 MPa m1/2，KJcUp to 5.44 +/-0.4 MPam1/2(FIG. 5 f).
The graphene oxide-based bulk artificial shell material prepared by the method has extremely excellent mechanical properties, and the problem that graphene oxide is difficult to assemble into a high-mechanical-property bulk composite material is solved.
In addition, the invention carries out detailed experimental study on the values of the mass percentages of the raw materials in the step (3), and the results are shown in the following table:
TABLE 1
As can be seen from the data in Table 1, when the mass percentages of the raw materials in step (3) are respectively: 74.40 wt% of graphene oxide, 24.80 wt% of manganese dioxide, 0.30 wt% of regenerated silk protein and 0.50 wt% of sodium alginate, the composite material prepared by the method has the optimal performance.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. For the scheme disclosed by the embodiment, the scheme corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of a shell-like light high-strength composite material is characterized by comprising the following steps:
(1) preparing graphene oxide by using an improved Hummers oxidation method, dissolving the graphene oxide with deionized water to prepare a colloidal graphene oxide solution for later use;
(2) preparation of foliated amorphous/crystalline heterogeneous phase MnO by redox method2Hexagonal nano sheet, dissolving with deionized water to obtain amorphous/crystalline heterogeneous phase MnO2Hexagonal nanosheet solution for later use;
(3) MnO of amorphous/crystalline heterogeneous phase2Mixing the hexagonal nanosheet solution and the graphene oxide solution with the biomacromolecule to obtain a stable mixed solution;
(4) transferring the mixed solution obtained in the step (3) into a culture dish, and carrying out evaporation self-assembly in an oven at 55-65 ℃;
(5) stripping the assembled composite film to obtain a high-mechanical-property composite film;
(6) and (4) assembling a plurality of composite films obtained in the step (5) into a whole by using a cross-linking agent in a layer-to-layer brushing manner, and performing hot-pressing treatment to obtain the shell-like light high-strength composite material.
2. The preparation method of the seashell-like lightweight high-strength composite material according to claim 1, wherein the concentration of the graphene oxide solution in the step (1) is 1 mg/mL.
3. The method for preparing the seashell-like lightweight high-strength composite material according to claim 1, wherein the amorphous/crystalline heterogeneous phase MnO in the step (2)2The preparation of hexagonal nanosheets follows the chemical equation:
KMnO4+NaH2PO2·H2O＝MnO2+NaH3PO4+KOH。
4. the preparation method of the seashell-like lightweight high-strength composite material according to claim 1, wherein the biomacromolecules in the step (3) comprise sodium alginate and/or regenerated silk protein;
wherein the concentration of the sodium alginate solution is 0.2-0.4 wt%, and the concentration of the regenerated silk protein solution is 1 mg/mL.
5. The preparation method of the shell-like lightweight high-strength composite material according to claim 4, wherein the raw materials in the step (3) are as follows in percentage by mass: 74.40 wt% of graphene oxide, 24.80 wt% of manganese dioxide, 0.30 wt% of regenerated silk protein and 0.50 wt% of sodium alginate.
6. The preparation method of the seashell-like lightweight high-strength composite material according to claim 1, wherein the evaporation self-assembly time in the step (4) is 10-12 hours.
7. The preparation method of the seashell-like lightweight high-strength composite material according to claim 1, wherein the cross-linking agent in the step (6) is a mixed solution of sodium alginate and sodium tetraborate;
wherein the concentration of the sodium alginate solution is 0.30 wt%, and the concentration of the sodium tetraborate solution is 1 mg/mL.
8. The preparation method of the seashell-like lightweight high-strength composite material according to claim 7, wherein the step (6) is specifically as follows: and (3) assembling a plurality of composite films obtained in the step (5) into a whole by using a sodium alginate solution in a layer-by-layer brushing mode, soaking and crosslinking the composite films by using a mixed solution of the sodium alginate solution and a sodium tetraborate solution, and carrying out hot pressing treatment to obtain the shell-like light high-strength composite material.
9. The preparation method of the shell-like light high-strength composite material according to claim 1 or 8, wherein the hot-pressing treatment temperature is 35-45 ℃ and the pressure is 100 MPa.
10. The shell-like lightweight high-strength composite material prepared by the method of any one of claims 1 to 9.
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