CN115748238A - Aerogel-based energy-absorbing material, and preparation method and application thereof - Google Patents
Aerogel-based energy-absorbing material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an aerogel-based energy-absorbing material, and a preparation method and application thereof. The aerogel-based energy-absorbing material comprises: the aerogel material comprises a three-dimensional porous network structure which is formed by mutually lapping nano fibers and is communicated with the nano fibers; and the energy absorbing substance and the functional additive which is selectively added or not added are loaded in the porous aerogel material, and the energy absorbing substance and the functional additive are wrapped on the nano fibers and embedded and filled in the three-dimensional porous network structure. The preparation method comprises the following steps: and filling the energy-absorbing substance and the functional additive which is optionally added or not added into the porous aerogel material in an in-situ polymerization or solution-assisted filling mode, and then drying to obtain the aerogel-based energy-absorbing material. The aerogel-based energy absorption material can be prepared into any size and shape, has designable structure, is simple in preparation process, is easy to realize large-scale production, and can be applied to the fields of shock absorption, noise resistance, impact protection, energy absorption and the like.
Description
Technical Field
The invention relates to an energy-absorbing material, in particular to an aerogel-based energy-absorbing material, a preparation method and application thereof, and belongs to the technical field of new nano materials.
Background
In recent years, with the increasing awareness of people on protection in personal protection, transportation of instruments and equipment or use, the demand of lightweight protective energy-absorbing materials is gradually increasing. For example, in a high-risk working environment, personal protection work needs to be done to ensure personal safety; in the industrial production of bridges, buildings and the like, dampers are required to dissipate energy which is unnecessary or harmful to the system; in the fields of automobiles, aerospace, and the like, a large amount of impact energy needs to be absorbed to ensure the safe and normal operation of personnel, vehicles, and spacecraft. Therefore, protective equipment having excellent energy absorbing properties and being lightweight and comfortable is in need of development.
Shear thickening materials are representative of a class of typical materials with good energy absorbing properties, and have a very wide range of application scenarios. Shear thickening materials, also known as non-newtonian fluids, generally exhibit a specific fluid behavior, and the most distinctive characteristic is the shear thickening effect, i.e., the viscosity of the shear thickening material increases sharply with increasing shear rate under a range of shear rates, and is in a light and soft state when unstressed, which is comfortable to wear and easily deformable, and the material hardens rapidly when impacted by an external force, exhibiting good absorption of impact energy, and returns to a soft state after impact. In recent years, shear thickening materials have received attention from the academic and industrial fields in terms of their excellent lightweight properties, protective properties, comfort and flexibility, for example, in the field of human body protection.
At present, shear thickening materials are mainly divided into the following two types:
(1) Shearing and thickening fluid: shear thickening fluids are prepared by dispersing particles, typically silica particles, directly in a liquid, which may be ethylene glycol, polyethylene glycol 200, or the like. CN115071237A provides a composite membrane with a sandwich structure by placing an intermediate layer of shear thickening fluid between two polymer membranes, which not only can maintain the properties of modulus, strength and flexibility of the polymer membrane itself, but also can absorb impact or vibration energy, and thus has excellent toughness. CN114921083A discloses a polyurethane-polyurea double-layer shear thickening fluid microcapsule material, which can improve the impact resistance of a high polymer material, and simultaneously improve the processing fluidity of a shear thickening fluid applied to a high polymer composite material. However, the use of shear thickening fluids tends to suffer from the following problems: (1) the particles are difficult to be uniformly dispersed in the liquid matrix, so that the performance is reduced; (2) the shear thickening fluid is liquid, the unique rheological property of the shear thickening fluid exists in a narrow concentration range, and the shear thickening fluid is difficult to be applied in practical application; (3) the shear thickening liquid is exposed in the air for a long time and is easy to absorb the moisture in the air, so that the shear thickening performance is reduced; (4) when the shear thickening fluid is used, the shear thickening fluid is often filled into the porous material, and once the porous material is damaged, the fluid is easy to flow out; (5) the requirement on temperature is more severe, and the device is easy to fail under the condition of higher or lower temperature.
(2) Shearing to harden the gel: mainly refers to an organic polyborosiloxane material, which can be freely deformed at a low shear rate, when the shear rate is sharply increased, the material is suddenly changed to show a hard solid characteristic, the viscosity is sharply increased, and the system is changed like phase transition. The shear hardening gel overcomes a plurality of defects of the shear thickening fluid, has good thermal stability, and greatly expands the application prospect of the shear thickening material. CN105385163A provides a preparation method of a shear thickening gel-based shock-absorbing and energy-absorbing material, which can spontaneously change from soft to hard when being impacted, and absorb energy, thereby effectively playing a role in protection. CN107474544A discloses a light shear thickening gel, which adopts hollow microspheres to modify the traditional shear thickening gel, so that the overall mass of the shear thickening gel is light and the viscosity is reduced. The shear thickening gel with the same mass is applied to a sample, and the protection effect is obviously enhanced by adding the hollow microspheres. CN104862975A provides a preparation method of a fracture-proof fabric with a shear thickening effect, and the fabric has a good energy absorption effect. However, shear hardening gels currently still suffer from the following problems: (1) shear hardening gels are limited by creep, lack of a fixed shape, and cannot be used alone; (2) the shear-hardening gel is immersed in the traditional material form, such as inert aramid fiber, and interface failure easily occurs due to the poor bonding strength between the interface layers, so that the performance is reduced along with the time; (3) effective shear hardening gels have too small a volume ratio to function.
Based on the above, a novel aerogel-based energy-absorbing material is developed to overcome the defects of the existing shear thickening material, so as to meet the requirements of light weight, comfort, softness and good energy-absorbing performance in the practical application of the protective material, and still be a problem to be solved urgently.
Disclosure of Invention
The invention mainly aims to provide an aerogel-based energy-absorbing material and a preparation method thereof, so as to overcome the defects of the prior art.
It is a further object of the present invention to provide the use of the aforementioned aerogel-based energy absorbing material.
In order to achieve the purpose, the invention adopts the following technical scheme:
the embodiment of the invention provides an aerogel-based energy-absorbing material, which comprises:
the porous aerogel material used as the substrate comprises a three-dimensional porous network structure which is formed by mutually lapping nano fibers and is communicated;
and the energy absorbing substance and the functional additive are loaded in the porous aerogel material, and the functional additive is selectively added or not added, so that the functional additive can enhance the base material on one hand, and can introduce the properties of electric conduction, heat conduction and the like into the base material on the other hand. The energy-absorbing substance and the functional additive are wrapped on the nano fibers and embedded and filled in the three-dimensional porous network structure, and when the external strain rate or the shear rate is changed, the energy-absorbing substance can absorb and dissipate a large amount of impact energy, so that other materials or devices are protected from being damaged. The energy absorption substance comprises one or the combination of more than two of polydimethylsiloxane, polyborosiloxane, soft and hard phase change materials, plasticine, natural rubber, chloroprene rubber and nitrile rubber.
The embodiment of the invention also provides a preparation method of the aerogel-based energy-absorbing material, which comprises the following steps:
providing a porous aerogel material;
and filling the energy-absorbing substance and the functional additive which is selectively added or not added into the porous aerogel material in an in-situ polymerization or solution-assisted filling mode, and then drying to obtain the aerogel-based energy-absorbing material.
The embodiment of the invention also provides application of the aerogel-based energy-absorbing material in the fields of shock absorption, noise resistance, impact protection, energy absorption and the like.
Compared with the prior art, the invention has the beneficial effects that:
1) The aerogel matrix structure adopted by the aerogel-based energy-absorbing material provided by the invention can be individually designed, and the energy-absorbing material is free from the limitations of creep deformation and no fixed shape;
(2) The aerogel matrix adopted by the aerogel-based energy absorption material provided by the invention is internally and externally provided with a plurality of active sites, and the bonding strength between the interface layers is high;
(3) The aerogel matrix adopted by the aerogel-based energy-absorbing material provided by the invention consists of high-performance nano fibers, and can play a role in enhancing the mechanical property of the energy-absorbing substance in a nano confinement;
(4) The mass fraction of the energy-absorbing substance in the aerogel-based energy-absorbing material provided by the invention can reach 99%, which is beneficial to fully exerting the performance of the energy-absorbing substance; meanwhile, the preparation process is simple, large-scale production is easy to realize, and the method can be applied to the fields of shock absorption, noise resistance, impact protection, energy absorption and the like.
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 some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic structural view of an aerogel-based energy absorbing material in an exemplary embodiment of the present invention;
FIG. 2 is a thermogravimetric plot of the aramid aerogel film-based energy-absorbing material obtained in example 1 of the present invention;
FIG. 3 is an infrared spectrum of an aramid aerogel fiber-based energy-absorbing material obtained in example 2 of the present invention;
FIG. 4 is an optical photograph of the aramid aerogel honeycomb-based energy-absorbing material obtained in example 3 of the present invention;
FIG. 5 is an optical photograph of a cellulose aerogel film-based energy absorbing material obtained in example 4 of the present invention;
FIG. 6 is an optical photograph of a 3D printed cellulose aerogel lattice-based energy absorbing material obtained in example 5 of the present invention;
FIG. 7 is a quasi-static stress-strain curve of the energy-absorbing material based on cellulose aerogel block obtained in example 6 of the present invention;
FIG. 8 is a photograph showing the flexibility of the polyimide aerogel fiber-based energy-absorbing material obtained in example 7 of the present invention;
FIG. 9 is an internal profile of a cellulose aerogel fiber-based energy absorbing material obtained in example 8 of the present invention;
FIG. 10 is a graph showing the high-speed impact of the fibroin aerogel film-based energy absorbing material obtained in example 9 of the present invention;
fig. 11 is a high-speed impact curve diagram of the silver nanowire aerogel block-based energy-absorbing material obtained in example 10 of the present invention.
Detailed Description
Shear hardening gels have the following problems: (1) shear hardening gels are limited by creep, lack of a fixed shape, and cannot be used alone; (2) shear-hardening gel is immersed in a traditional material form, such as inert aramid fiber, and interface failure easily occurs due to poor bonding strength between interface layers, so that the performance is reduced along with the time; (3) the effective shear hardening gel volume ratio is too small to function. These disadvantages make shear hardening gels unsatisfactory for practical applications in terms of barrier properties.
In view of the defects in the prior art, the inventor of the present invention has made a long-term study and a great deal of practice to provide the technical scheme of the present invention, and mainly develops a novel aerogel-based energy-absorbing material to overcome the defects of the prior art, so as to satisfy the requirements of light weight, comfort and good energy-absorbing performance in the practical application of the protective material, and to explain a series of applications of the aerogel-based energy-absorbing material. The technical solution, its implementation and principles, etc. will be further explained as follows.
Specifically, as one aspect of the technical scheme of the present invention, the structure of the aerogel-based energy-absorbing material is shown in fig. 1, and the aerogel-based energy-absorbing material is composed of a porous aerogel material substrate loaded with an energy-absorbing substance, and optionally added functional additives. The porous aerogel material has a designable specific arbitrary macroscopic morphology structure, is formed by mutually overlapping nano fibers in the porous aerogel material, and has a communicated three-dimensional porous network structure. The energy absorbing substance and the functional additive are wrapped on the nano-fibers and embedded and filled in the three-dimensional porous network structure.
Furthermore, the aerogel matrix adopted by the aerogel-based energy-absorbing material disclosed by the invention is composed of high-performance nano fibers, and can play a role in enhancing the mechanical property of the energy-absorbing substance in the nano confinement. And the inside and the surface of the aerogel matrix are provided with a plurality of active sites, and the bonding strength between the interface layers is high.
In some preferred embodiments, the types of the constituent unit nanofibers of the porous aerogel material include, but are not limited to, any one or a combination of two or more of aramid nanofibers, cellulose nanofibers, polyimide nanofibers, fibroin nanofibers, silver nanofibers, and the like.
In some preferred embodiments, the macrostructures of the porous aerogel material include, but are not limited to, any one or combination of two or more of honeycombs, rice-type shapes, cubic lattices, films, fibers, blocks, and the like.
In some preferred embodiments, the porous aerogel material has a hierarchical porous network structure inside, the hierarchical porous network structure is composed of micropores with a pore diameter of 2nm or less, mesopores with a pore diameter of 2nm to 50nm, and macropores with a pore diameter of 50nm to 10cm, the porous aerogel material has a porosity of 50 to 99.99% and a density of 0.1 to 1500mg/cm 3 The specific surface area is 50 to 2500m 2 Per g, pore volume of 0.1-15 cm 3 /g。
Further, the energy absorbing substance can absorb and dissipate a large amount of impact energy when the external strain rate or shear rate is changed, thereby protecting other materials or devices from damage.
In some preferred embodiments, the energy absorbing substance includes, but is not limited to, any one or a combination of two or more of polydimethylsiloxane, polyborosiloxane, soft and hard phase change material, plasticine, natural rubber, neoprene, nitrile rubber, and the like.
In some preferred embodiments, the energy absorbing substance is present in the aerogel-based energy absorbing material in an amount of 30wt% to 99wt%. The mass fraction of the energy-absorbing substance in the aerogel-based energy-absorbing material can reach 99 percent, which is beneficial to fully exerting the performance of the energy-absorbing substance.
In some preferred embodiments, the functional additive includes, but is not limited to, any one or a combination of two or more of calcium carbonate, carbon nanotubes, graphene, transition metal nitride/carbide (MXene), metal (e.g., gold nanoparticles), silica particles, and the like. Further, the functional additive can enhance the substrate material on one hand, and can introduce the properties of electric conduction, heat conduction and the like into the substrate material on the other hand.
Further, the content of the functional additive in the aerogel-based energy absorption material is 0wt% -30 wt%.
In some preferred embodiments, the aerogel-based energy absorbing material has an energy absorption value of 0.1 to 1000J/g.
Another aspect of an embodiment of the present invention provides a method for preparing an aerogel-based energy absorbing material, including:
providing a porous aerogel material;
and filling the energy-absorbing substance and the functional additive which is optionally added or not added into the porous aerogel material in an in-situ polymerization or solution-assisted filling mode, and then drying to obtain the aerogel-based energy-absorbing material.
In some preferred embodiments, the preparation method specifically comprises:
(1) Selecting a porous aerogel material with a specific macroscopic structure and super-strong capillary force as a substrate;
(2) Introducing an energy-absorbing substance and a functional additive into a three-dimensional porous network structure of the porous aerogel material in a mode of in-situ polymerization or solution-assisted filling and the like;
(3) And removing redundant energy-absorbing substances on the surface and drying to obtain the aerogel-based composite energy-absorbing material with high energy absorption.
In some specific embodiments, the method of making the porous aerogel material comprises: the porous aerogel material is prepared by at least one or more of a wet spinning method, a limited sol-gel reaction spinning method, a freeze-dry spinning method, a template method, a 3D printing method and a blade coating method, but is not limited thereto.
In some specific embodiments, the drying includes at least any one of freeze drying, vacuum drying, or atmospheric drying, but is not limited thereto.
In some specific embodiments, the in situ polymerization comprises: placing the energy-absorbing material prepolymer in a reaction container, enabling the energy-absorbing material prepolymer to be in contact with the porous aerogel material, standing for 1-24 hours, taking out and removing the redundant energy-absorbing material prepolymer on the surface, then polymerizing the energy-absorbing material prepolymer in situ, and then drying to obtain the aerogel-based energy-absorbing material.
Further, the energy-absorbing material prepolymer can comprise an energy-absorbing material precursor (such as a benzyl methacrylate monomer of the soft-hard phase-change material prepolymer), an initiator (such as a 1-hydroxycyclohexyl phenyl ketone photoinitiator), a cross-linking agent (such as ethylene glycol dimethacrylate) and an ionic liquid (such as 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt).
Further, the energy-absorbing material prepolymer can further include an energy-absorbing material precursor (such as a chloroprene monomer), an emulsifier (such as a rosin acid soap emulsifier), an initiator (such as potassium persulfate), a relative molecular weight regulator (such as n-dodecyl mercaptan), a vulcanizing agent (such as sulfur), a solvent (such as water), and the like, but is not limited thereto.
Further, the in-situ polymerization specifically comprises the following steps:
placing the energy-absorbing material prepolymer in a container, immersing the porous aerogel material in the container, standing for 1-24 h, taking out and removing the redundant energy-absorbing material prepolymer on the surface, then placing the container in a specific environment to polymerize the energy-absorbing material prepolymer in situ, and then carrying out freeze drying, vacuum drying or normal pressure drying to obtain the aerogel-based energy-absorbing material.
In some specific embodiments, the solution-assisted filling comprises: dissolving an energy absorbing substance in a selected solvent to form an energy absorbing substance solution, wherein the concentration of the energy absorbing substance solution is 1-60 wt%; and contacting the porous aerogel material with the energy absorbing substance solution, standing for 1-24 h, taking out and removing the energy absorbing substance on the surface, and then drying to obtain the aerogel-based energy absorbing material.
Further, the solution-assisted filling process specifically includes the following steps:
dissolving an energy-absorbing substance in a selected solvent, soaking the porous aerogel material in the energy-absorbing substance solution, standing for 1-24 h, taking out and removing the surface energy-absorbing substance solution, and freeze-drying, vacuum-drying or normal-pressure drying to obtain the aerogel-based energy-absorbing material.
Further, the selected solvent includes, but is not limited to, any one or a combination of two or more of water, cyclohexane, ethanol, t-butanol, acetone, tetrahydrofuran, ethyl acetate, and the like.
The aerogel-based energy-absorbing material can be prepared into any size and shape, has designability in structure, and enables energy-absorbing substances to get rid of the limitations of creep and no fixed shape; and can be cut according to different sizes and coated on irregular surfaces. Meanwhile, the preparation process is simple, the conditions are mild and controllable, and the large-scale production is easy to realize.
The embodiment of the invention also provides application of the aerogel-based energy absorption material in the fields of shock absorption, noise resistance, impact protection, energy absorption and the like.
To sum up, according to the technical scheme, the aerogel-based energy absorption material provided by the invention comprises a porous aerogel matrix loaded with an energy absorption substance and a functional additive, wherein the porous aerogel matrix is formed by mutually overlapping nano fibers, has a continuous three-dimensional porous network structure, has an adjustable macrostructure, density, porosity, specific surface area and the like, and has strong capillary action force. The energy absorbing material and the functional additive are adsorbed on the surface and in the pore canal of the nanofiber of the porous aerogel matrix. The aerogel-based energy absorption material has the advantages of high energy absorption capacity, high sensitivity and wide application prospect, and can be used in the fields of shock absorption, noise resistance, impact protection, energy absorption and the like.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are described in detail below with reference to several preferred embodiments and with reference to the accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments, and those skilled in the art can make modifications according to actual situations. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The test methods in the following examples are carried out under conventional conditions without specifying specific conditions. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
The embodiment provides an aramid aerogel film-based energy-absorbing material, and a preparation method of the aramid aerogel film-based energy-absorbing material comprises the following steps:
(1) Preparing an aramid aerogel film: preparing 0.5wt% of aramid nano-fiber dispersion liquid, and preparing the aramid aerogel film by adopting a blade coating method.
(2) Preparation of the filling material: preparing a polyborosiloxane/absolute ethyl alcohol solution with the mass fraction of 30wt%.
(3) Preparing an aramid aerogel film-based energy-absorbing material: and (3) placing the aramid nano-fiber aerogel film into the solution, standing for 12h, taking out, removing the redundant polyborosiloxane/absolute ethyl alcohol solution on the surface, and drying at normal pressure to obtain the aerogel-based composite energy-absorbing film.
Fig. 2 is a thermogravimetric curve of the aramid aerogel film-based energy-absorbing material obtained in example 1, and other parameters are shown in table 1.
Example 2
The embodiment provides an aramid aerogel fiber-based energy-absorbing material, and a preparation method of the aramid aerogel fiber-based energy-absorbing material comprises the following steps:
(1) Preparing aramid aerogel fiber: preparing 10wt% of aramid nano-fiber dispersion liquid, and preparing the aramid aerogel fiber by adopting a wet spinning method.
(2) Preparation of the filling material: preparing a polyborosiloxane/tertiary butanol solution with the mass fraction of 60 wt%.
(3) Preparing an aramid aerogel fiber-based energy-absorbing material: and (3) placing the aramid nano-fiber aerogel fiber in the solution, standing for 1h, taking out, removing the redundant polyborosiloxane/tert-butyl alcohol solution on the surface, and drying in vacuum to obtain the aerogel-based composite energy-absorbing fiber.
Fig. 3 is an infrared spectrum of the aramid aerogel fiber-based energy-absorbing material obtained in example 2, and other parameters are shown in table 1.
Example 3
The embodiment provides an aramid aerogel honeycomb-based energy-absorbing material, and a preparation method of the aramid aerogel honeycomb-based energy-absorbing material comprises the following steps:
(1) Preparing an aramid aerogel honeycomb: preparing 5wt% of aramid nano-fiber dispersion liquid, and preparing the aramid aerogel honeycomb by adopting a template method.
(2) Preparation of the filling material: preparing a plasticine/cyclohexane solution with the mass fraction of 10wt%, and adding 5wt% of gold nanoparticles as a functional additive.
(3) Preparing an aramid aerogel honeycomb-based energy absorption material: and (3) placing the aramid nano-fiber aerogel honeycomb into the solution, standing for 24h, taking out, removing redundant filling liquid on the surface, and performing vacuum drying to obtain the aramid aerogel-based composite energy-absorbing honeycomb.
Fig. 4 is an optical photograph of the aramid aerogel honeycomb based energy absorbing material obtained in example 3, with other parameters being shown in table 1.
Example 4
The embodiment provides a cellulose aerogel film-based energy-absorbing material, and a preparation method of the cellulose aerogel film-based energy-absorbing material comprises the following steps:
(1) Preparation of cellulose aerogel film: preparing 0.1wt% of cellulose nano-fiber dispersion liquid, and preparing the cellulose aerogel film by adopting a blade coating method.
(2) Preparation of the filling material: 10wt% of polyborosiloxane/acetone solution is prepared, and 10wt% of silicon dioxide powder is added as a functional additive.
(3) Preparing a cellulose aerogel film-based energy-absorbing material: and placing the cellulose nanofiber aerogel film into the energy-absorbing material, standing for 8 hours, taking out, removing redundant substances on the surface, and drying in vacuum to obtain the aerogel-based composite energy-absorbing film.
FIG. 5 is an optical photograph of the cellulose aerogel film-based energy absorbing material obtained in example 4, with other parameters as shown in Table 1.
Example 5
The embodiment provides a three-dimensional lattice-based energy-absorbing material for 3D printing cellulose aerogel, and the preparation method comprises the following steps:
(1) Preparation of 3D printing cellulose aerogel three-dimensional lattice: preparing 2wt% of cellulose nanofiber dispersion liquid, and preparing the 3D printing cellulose aerogel three-dimensional lattice structure by adopting a direct-writing forming 3D printing method.
(2) Preparation of the filling material: uniformly mixing a soft phase change material prepolymer benzyl methacrylate monomer, a 1-hydroxycyclohexyl phenyl ketone photoinitiator, an ethylene glycol dimethacrylate cross-linking agent, 1-ethyl-3-methylimidazole bistrifluoromethanesulfonylimide salt, 30wt% calcium carbonate powder and the like.
(3) Preparing a 3D printing cellulose aerogel three-dimensional lattice base energy absorption material: and (3) placing the 3D printed cellulose aerogel three-dimensional lattice in the mixed solution, standing for 6 hours, taking out, removing redundant substances on the surface, and then placing the material under ultraviolet light for curing for 10 hours to obtain the aerogel-based composite energy-absorbing material.
Fig. 6 is an optical photograph of the 3D printed cellulose aerogel lattice-based energy absorbing material obtained in example 5, with other parameters as shown in table 1.
Example 6
The embodiment provides a cellulose aerogel block-based energy-absorbing material, and a preparation method of the cellulose aerogel block-based energy-absorbing material comprises the following steps:
(1) Preparing a cellulose aerogel block: preparing 8wt% of cellulose nanofiber dispersion liquid, and preparing the cellulose aerogel block by adopting a direct freeze-drying method.
(2) Preparation of the filling material: the preparation method comprises the steps of chopping nitrile rubber, preparing a nitrile rubber/ethyl acetate solution with the mass fraction of 10wt%, adding a graphene additive with the mass fraction of 1wt%, and stirring uniformly.
(3) Preparing a cellulose aerogel block-based energy-absorbing material: and placing the cellulose nanofiber aerogel block in the mixed solution, standing for 1h, taking out, removing redundant substances on the surface, washing, and then placing the material in a 90 ℃ oven for 15h to obtain the aerogel-based composite energy-absorbing block.
FIG. 7 is a quasi-static stress-strain curve of the cellulose aerogel block-based energy absorbing material obtained in example 6, with other parameters shown in Table 1.
Example 7
The embodiment provides a polyimide aerogel fiber-based energy-absorbing material, and a preparation method of the polyimide aerogel fiber-based energy-absorbing material comprises the following steps:
(1) Preparing polyimide aerogel fibers: polyimide aerogel fiber with solid content of 10wt% is prepared by a limited spinning method.
(2) Preparation of the filling material: cutting the natural rubber into pieces, and preparing a natural rubber/tetrahydrofuran solution with the mass fraction of 10 wt%.
(3) Preparing a polyimide aerogel fiber-based energy-absorbing material: and (2) placing the polyimide aerogel fiber in the mixed solution, standing for 6h, taking out, removing redundant substances on the surface, washing, and then placing the material in a 90 ℃ oven for 15h to obtain the aerogel-based composite energy-absorbing block.
FIG. 8 is a photograph showing the flexibility of the polyimide aerogel fiber-based energy absorbing material obtained in example 7, and other parameters are shown in Table 1.
Example 8
The embodiment provides a cellulose aerogel fiber-based energy-absorbing material, and a preparation method of the cellulose aerogel fiber-based energy-absorbing material comprises the following steps:
(1) Preparation of cellulose aerogel fibers: preparing 0.1wt% of cellulose nano-fiber dispersion liquid, and preparing the cellulose aerogel fiber by adopting a wet spinning method.
(2) Preparation of the filling material: adding a sulfur vulcanizing agent and a rosin acid soap emulsifier into chloroprene to prepare an oil phase; preparing water and sodium hydroxide into a water phase; and emulsifying the oil phase and the water phase, adding a relative molecular weight regulator of n-dodecyl mercaptan and a potassium persulfate initiator solution, and uniformly stirring the system in an ice bath at 4 ℃.
(3) Preparing a cellulose aerogel fiber-based energy-absorbing material: and placing the cellulose nanofiber aerogel fibers in the mixed solution, standing for 10min, taking out, removing redundant substances on the surface, then placing the material in an environment at 40 ℃ for 3h, cooling, and performing chain termination, condensation, washing and normal-pressure drying to obtain the aerogel-based composite energy-absorbing fiber.
FIG. 9 shows the internal morphology of the cellulose aerogel fiber-based energy absorbing material obtained in example 8, with other parameters as shown in Table 1.
Example 9
The embodiment provides a fibroin aerogel film-based energy absorption material, and a preparation method thereof comprises the following steps:
(1) Preparing a silk protein aerogel film: preparing 0.5wt% of fibroin nanofiber dispersion liquid, and preparing the fibroin aerogel film by adopting a blade coating method.
(2) Preparation of the filling material: 1wt% of carbon nano tube is added after 1wt% of polydimethylsiloxane/absolute ethyl alcohol solution is prepared.
(3) Preparing a silk protein aerogel film-based energy absorption material: and (3) placing the silk fibroin nanofiber aerogel film into the solution, standing for 12h, taking out, removing the excessive polydimethylsiloxane/absolute ethyl alcohol solution on the surface, and drying at normal pressure to obtain the aerogel-based composite energy absorption film.
FIG. 10 is the high-speed impact curve of the fibroin aerogel film-based energy-absorbing material obtained in example 9, with other parameters shown in Table 1.
Example 10
The embodiment provides a silver nanowire aerogel block-based energy-absorbing material, and a preparation method of the energy-absorbing material comprises the following steps:
(1) Preparing a silver nanowire aerogel block: preparing 10wt% of silver nanowire dispersion liquid, and preparing the silver nanowire aerogel block by adopting a direct drying method.
(2) Preparation of the filling material: preparing 20wt% of polydimethylsiloxane/absolute ethyl alcohol solution, and adding 1wt% of transition metal nitride/carbide (Ti) 3 C 2 T x MXene)。
(3) Preparing a silver nanowire aerogel film-based energy-absorbing material: and (3) placing the silver nanowire aerogel film in the solution, standing for 12h, taking out, removing redundant polydimethylsiloxane/absolute ethyl alcohol solution on the surface, and then washing and freeze-drying to obtain the aerogel-based composite energy-absorbing block.
Fig. 11 is the high-speed impact curve of the energy-absorbing material based on silver nanowire aerogel block obtained in example 10, and other parameters are shown in table 1.
TABLE 1 energy absorption values of the aerogel-based energy absorbing materials obtained in examples 1 to 10
Comparative example 1
The comparison example provides an aramid aerogel film material, and compared with the comparison example 1, the poly-borosiloxane/absolute ethyl alcohol solution is not added in the comparison example. The resulting material had an absorption value of 30J/g.
Through the embodiments 1 to 10, it can be found that the aerogel-based energy-absorbing material obtained by the technical scheme of the invention has the excellent performances of designable structure, high load, excellent energy-absorbing effect, simple process and the like.
In addition, the inventor also refers to the mode of examples 1-10, and carries out experiments with other raw materials and conditions listed in the specification, and also prepares the aerogel-based energy-absorbing material which has the advantages of designable structure, high load capacity, excellent energy-absorbing effect and wide application.
Although the present invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (10)
1. An aerogel-based energy absorbing material, comprising:
the porous aerogel material serving as the substrate comprises a three-dimensional porous network structure which is formed by mutually lapping nano fibers and is communicated with each other;
and the energy absorbing substance and the functional additive are loaded in the porous aerogel material, and the energy absorbing substance and the functional additive are selectively added or not added, the energy absorbing substance and the functional additive are wrapped on the nano fibers and embedded and filled in the three-dimensional porous network structure, wherein the energy absorbing substance comprises any one or a combination of more than two of polydimethylsiloxane, polyborosiloxane, soft-hard phase change materials, plasticine, natural rubber, chloroprene rubber and nitrile rubber.
2. An aerogel-based energy absorbing material as claimed in claim 1, wherein: the nano-fiber comprises any one or the combination of more than two of aramid nano-fiber, cellulose nano-fiber, polyimide nano-fiber, silk protein nano-fiber and silver nano-fiber;
and/or the macroscopic structure of the porous aerogel material comprises any one or the combination of more than two of honeycomb, chinese character 'mi' -shaped, three-dimensional lattice, film, fiber and block material;
and/or the porous aerogel material is internally provided with a hierarchical porous network structure, the hierarchical porous network structure consists of micropores with the pore diameter of below 2nm, mesopores with the pore diameter of between 2nm and 50nm and macropores with the pore diameter of between 50nm and 10cm, the porosity of the porous aerogel material is between 50 and 99.99 percent, and the density of the porous aerogel material is between 0.1 and 1500mg/cm 3 The specific surface area is 50 to 2500m 2 Per g, pore volume of 0.1-15 cm 3 /g。
3. The aerogel-based energy absorbing material of claim 1, wherein: the content of the energy absorption substance in the aerogel-based energy absorption material is 30-99 wt%; and/or the content of the functional additive in the aerogel-based energy absorption material is 0-30 wt%; and/or the functional additive comprises any one or the combination of more than two of calcium carbonate, carbon nano tubes, graphene, transition metal nitride, transition metal carbide, metal and silicon dioxide particles.
4. The aerogel-based energy absorbing material of claim 1, wherein: the energy absorption value of the aerogel-based energy absorption material is 0.1-1000J/g.
5. The method of making the aerogel-based energy absorbing material of any of claims 1-4, comprising:
providing a porous aerogel material;
and filling the energy-absorbing substance and the functional additive which is optionally added or not added into the porous aerogel material in an in-situ polymerization or solution-assisted filling mode, and then drying to obtain the aerogel-based energy-absorbing material.
6. The method of claim 5, comprising: the porous aerogel material is prepared by at least adopting any one or more of a wet spinning method, a limited sol-gel reaction spinning method, a freeze-dry spinning method, a template method, a 3D printing method and a blade coating method.
7. The method of claim 5, comprising: placing the energy-absorbing material prepolymer in a reaction container, enabling the energy-absorbing material prepolymer to be in contact with the porous aerogel material, standing for 1-24 hours, taking out and removing the redundant energy-absorbing material prepolymer on the surface, then polymerizing the energy-absorbing material prepolymer in situ, and then drying to obtain the aerogel-based energy-absorbing material;
preferably, the energy-absorbing material prepolymer comprises an energy-absorbing substance precursor, an initiator, a cross-linking agent and an ionic liquid, or the energy-absorbing material prepolymer comprises an energy-absorbing substance precursor, an emulsifier, an initiator, a relative molecular weight regulator, a vulcanizing agent and a solvent.
8. The method of claim 5, comprising: dissolving an energy-absorbing substance in a selected solvent to form an energy-absorbing substance solution, contacting the porous aerogel material with the energy-absorbing substance solution, standing for 1-24 h, taking out and removing the energy-absorbing substance on the surface, and then drying to obtain the aerogel-based energy-absorbing material;
preferably, the concentration of the energy-absorbing substance solution is 1wt% -60 wt%;
preferably, the selected solvent includes any one or a combination of two or more of water, cyclohexane, ethanol, tert-butanol, acetone, tetrahydrofuran and ethyl acetate.
9. The method of claim 5, wherein: the drying includes at least any one of freeze drying, vacuum drying or atmospheric drying.
10. Use of the aerogel-based energy absorbing material of any of claims 1-4 in the fields of vibration damping, noise damping, impact protection or energy absorption.
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