CN116376225B - Light high-rigidity high-damping material with self-healing function and application thereof - Google Patents
Light high-rigidity high-damping material with self-healing function and application thereof Download PDFInfo
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- 238000013016 damping Methods 0.000 title abstract description 43
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
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- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
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Abstract
The invention belongs to the field of metamaterial design, and particularly discloses a light high-rigidity high-damping material with a self-healing function and application thereof, wherein a unit cell of the light high-rigidity high-damping material comprises a matrix phase and a reinforcing phase, wherein: the reinforcing phase is a negative poisson ratio structural framework; the matrix phase is made of self-healing materials, and the self-healing materials are filled in the hole areas of the negative poisson ratio structural framework. According to the invention, through the self-healing composite material design on a microscopic scale and the structural damping metamaterial structural design on a microscopic scale, the material-structure integrated multi-scale design is completed, and the coupling effect of the self-healing material and the negative poisson ratio structure is completed, so that the dynamics performance of the material is improved on the basis of ensuring the self-healing function.
Description
Technical Field
The invention belongs to the field of metamaterial design, and particularly relates to a light high-rigidity high-damping material with a self-healing function and application thereof.
Background
Metamaterial is a material which breaks the original material limitation by micro-structural design at sub-wavelength. The metamaterial microstructure design on the sub-wave length enables the original material to have the characteristics of negative rigidity, negative refractive index, negative poisson ratio and the like, and can widen the application scene of the original material. The negative poisson ratio structure expands transversely when being axially stretched, so the negative poisson ratio structure is also called an auxetic structure, has good ductility and can be widely applied to manufacturing of electronic devices; the auxetic structure can have J-shaped stress-strain curve similar to skin, has self-adaptive characteristics, and can be used for manufacturing products such as cardiovascular stents of human bodies, wearable fabrics and the like to self-adapt to deformation of human bodies. When the negative poisson ratio structure is axially compressed, the negative poisson ratio structure transversely contracts, so that the whole structure contracts inwards, the inside of the structure deforms greatly, and the energy absorption capacity is improved, and the negative poisson ratio structure is widely applied to energy absorption equipment, such as an energy absorption box of an automobile. But the rigidity performance is poor due to the hole structure characteristic of the negative poisson ratio.
The composite material is composed of more than two phases of materials, and the damage such as cracking of a matrix phase of the composite material, interfacial failure of a reinforcing phase and the like can cause catastrophic damage. In natural life systems, self-healing is a self-protection mechanism formed by the biology world in a long evolution process to cope with external damage, and is seen in that self-healing is a self-healing mode which cures self-injury from a small mesoscopic structure (such as DNA repair) to a macroscopic level (such as self-healing of skin cracking). In self-healing polymeric materials, the bond energy of reversible covalent bonds is often weaker than that of irreversible covalent bonds, and reversible chemical bond cleavage tends to occur first when broken by a load. When the damaged parts are contacted with each other, reversible covalent bonds are formed again at the damaged interface of the polymer chain segment through local temperature excitation, the polymer chain segment is promoted to be sewn at the crack, and finally, the repair of statics and dynamic performance is realized, and the recycling of materials is realized. However, the conventional composite material such as the epoxy resin-based material reinforced by the carbon nano tube realizes high-rigidity mechanical property only through two-phase mixing, and rigidity and damping are a group of mutually exclusive properties for the material, so that it is very important how to make the composite material have a self-healing function and simultaneously give consideration to the high-rigidity high-damping mechanical property.
Disclosure of Invention
Aiming at the defects or improvement demands of the prior art, the invention provides a light high-rigidity high-damping material with a self-healing function and application thereof, and aims to realize the coupling effect of the self-healing material and a negative poisson ratio structure and improve the rigidity and damping of the material on the basis of ensuring the self-healing function.
In order to achieve the above object, according to an aspect of the present invention, there is provided a light-weight, high-rigidity and high-damping material having a self-healing function, the unit cell of which comprises a matrix phase and a reinforcing phase, wherein:
the reinforcing phase is a negative poisson ratio structural framework; the matrix phase is made of self-healing materials, and the self-healing materials are filled in the hole areas of the negative poisson ratio structural framework.
As a further preferred aspect, the negative poisson's ratio structural skeleton comprises four identical sub-parts, wherein:
Each sub-part comprises a central round node and 4 ligaments, and the 4 ligaments are uniformly and circumferentially distributed around the central round node; the ligament comprises an S-shaped ligament and a linear ligament which are vertically arranged, one end of the S-shaped ligament is connected with the central round node, and the other end of the S-shaped ligament is connected with the linear ligament;
the four sub-parts are distributed in a shape of a Chinese character 'tian', and the tail ends of a linear ligament are connected with each other between the adjacent sub-parts.
As a further preferred aspect, the S-ligament comprises three equidistant curves connected in sequence, each equidistant curve being formed by two concentric arcs.
Further preferably, the width of the equidistant curve is the width of the ligament, and the width of the ligament is 35 mm-45 mm.
As a further preference, the radius of the central circular node is not less than the width of the ligament.
As a further preference, the matrix phase material has a density less than the density of the reinforcing phase material.
As a further preferred aspect, the reinforcing phase material is steel, and the self-healing material of the matrix phase is an epoxy resin doped with multiwall carbon nanotubes.
As a further preferred option, the self-healing material is also doped with glutaric anhydride and sebacic acid.
As a further preferred aspect, the self-healing material has a multi-walled carbon nanotube ratio of 0.1wt.% to 0.5wt.%.
According to another aspect of the present invention, there is provided the use of a lightweight, high stiffness, high damping material with self-healing function as described above, combining a plurality of said cells into a complex geometry.
In general, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
1. According to the invention, the self-healing material is filled in the negative poisson ratio structural framework, firstly, the self-healing composite material is used for repairing and recycling the structural damping metamaterial, and the weight is reduced; secondly, the skeleton reinforcing phase has the basic characteristic of negative poisson ratio of an auxetic structure, and can provide relaxation driving force for the matrix phase, so that energy dissipation is increased, and material damping is improved; thirdly, the self-healing material is filled in the hole area of the framework reinforcing phase, so that potential cracks on the framework can be repaired, and the rigidity of the material is improved.
2. The invention designs the reinforced phase negative poisson ratio structure of the structural damping metamaterial unit cell, designs the ligament of the negative poisson ratio structure into an S shape, thereby ensuring that the self-healing material of the skeleton and the matrix phase has a larger contact area, and utilizes the large deformation ligament of the auxetic structure to provide relaxation driving force for the matrix phase, thereby realizing the efficient dissipation of vibration energy.
3. The invention designs the width of the ligament, improves poisson ratio and structural rigidity, and ensures that enough self-healing materials can be filled so as to realize light weight and high energy dissipation.
4. The invention provides a specific self-healing material, and due to the doping of the multi-wall carbon nano tube, a large amount of epoxy resin polymer chains can be absorbed to form an effective interface area, so that the stress is transferred to the carbon nano tube from the epoxy resin, and the rigidity performance of the self-healing material is improved; the cross-linked network topology structure of the epoxy resin can influence the interface characteristic driven by the carbon nano tube, so that the damping performance of the self-healing material is improved in an interface damping mode; accordingly, the ratio of the multi-wall carbon nano tube is designed to obtain the self-healing material with better rigidity and damping comprehensive performance.
Drawings
FIG. 1 is a schematic view of a portion of a negative Poisson's ratio bone scaffold in accordance with an embodiment of the present invention;
FIG. 2 is a schematic view of a light high stiffness high damping material unit cell with self-healing function according to an embodiment of the present invention;
FIG. 3 is a schematic diagram of the geometric parameters of the skeleton enhanced phase according to an embodiment of the present invention;
FIG. 4 is a schematic diagram of the self-healing matrix phase geometry according to an embodiment of the present invention;
FIG. 5 is a schematic diagram of a negative Poisson's ratio structure skeleton according to an embodiment of the present invention;
FIG. 6 is a schematic diagram of a unit cell structure according to an embodiment of the present invention;
FIG. 7 is a schematic diagram of a structure of a damping metamaterial according to an embodiment of the present invention;
FIG. 8 is a graph showing the loss factor of a plate structure made of different materials according to an embodiment of the present invention;
FIG. 9 is a graph comparing stiffness damping of materials according to embodiments of the present invention with other materials.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The embodiment of the invention provides a light high-rigidity high-damping material with a self-healing function, as shown in fig. 2, wherein a unit cell of the material comprises a matrix phase and a reinforcing phase, wherein:
the reinforcing phase is a negative poisson ratio structural framework; the matrix phase is made of self-healing materials, and the self-healing materials are filled in the hole areas of the negative poisson ratio structural framework.
Furthermore, the invention completes the material-structure integrated multi-scale design through the composite material design on the microscopic scale and the structural design of the structural damping metamaterial on the microscopic scale, and the following is a specific description.
On a microscopic scale, the thermosetting resin has the advantages of high specific stiffness, nonflammability, solvent resistance and the like, so that the thermosetting resin can be used as a structural material, has good damping performance and is often selected as a base material of a composite material. According to the invention, epoxy resin is used as a base material, a multiwall carbon nanotube is doped, and a self-healing function is introduced under the curing action of a curing agent, so that a self-healing material is obtained. The incorporation of the multiwall carbon nanotubes can enhance the rigidity performance of the self-healing material, and the cross-linked network topology of the epoxy resin can obviously improve the damping performance of the material through interface damping.
Further, the curing agent is preferably glutaric anhydride and sebacic acid, and the ratio of the glutaric anhydride to the sebacic acid is 3:1; the multi-walled carbon nanotubes have a ratio of 0.1wt.% to 0.5wt.%, preferably 0.1wt.%.
On the microscale, the rigidity and the damping of the material are a group of mutually exclusive mechanical properties, and the material cannot be made to have both high rigidity and high damping performance by simple material doping, so that the structural design of the structural damping metamaterial on the microscale is performed on the basis of completing the design of the microscale material. On the microscopic scale, a negative poisson ratio structural framework is taken as a reinforcing phase, a self-healing material is taken as a matrix phase, a conventional negative poisson ratio structure mainly comprises a chiral structure, a concave angle structure and a rotating rigid body structure, and ligaments of the structure are in a simple L shape and cannot contact with the matrix phase self-healing composite material to the greatest extent, so that the maximum driving force cannot be provided for the matrix phase.
Therefore, the negative poisson ratio framework enhancement phase is designed firstly, as shown in fig. 5, the negative poisson ratio framework comprises four identical sub-parts, each sub-part comprises a central round node and 4 ligaments, as shown in fig. 1, and the 4 ligaments are uniformly and circumferentially distributed around the central round node; the ligament comprises an S-shaped ligament and a linear ligament which are vertically arranged, one end of the S-shaped ligament is connected with the central round node, and the other end of the S-shaped ligament is connected with the linear ligament; the four sub-parts are distributed in a shape of a Chinese character 'tian', and the tail ends of a linear ligament are connected between the adjacent sub-parts.
Specifically, in order to utilize the large deformation ligament of the auxetic structure to provide a relaxation "driving force" for the matrix phase and realize efficient dissipation of vibration energy, the ligament of the negative poisson ratio structure needs to be designed into an S shape, so that a larger contact area is ensured, the S-shaped ligament is an equidistant curve formed by three sections of concentric arcs, and the radii of the concentric arcs are R2 and R3 respectively. Since it is necessary to ensure that the central round node of the reinforcing phase has sufficient rigidity to rotate the skeleton to generate a negative poisson's ratio effect, the radius R1 of the central round node is not smaller than the ligament width (i.e., R2-R3), which is preferably 35mm to 45mm.
Furthermore, the high-damping self-healing material with smaller density than the reinforced phase material is used as a matrix phase, so that the limitation of poor rigidity performance of the auxetic structure is overcome, higher energy dissipation is realized, and light weight is realized. Meanwhile, the self-repairing function of the self-healing material can realize the repairing and recycling of the structural damping metamaterial; specifically, the material is soaked in glycol, so that the epoxy resin is dissolved, and long polymer chains are effectively broken into short chains, thereby realizing the recovery of the carbon nanotubes.
On a macroscopic scale, the above unit cells are expanded into plates, beams, and other various complex geometries. For example, the structural damping metamaterial unit cell is designed into a plate structure along the plane direction, and the loss factor and the rigidity of the plate are also improved due to the high damping and high rigidity mechanical properties of the structural damping metamaterial unit cell.
The following are specific examples:
the unit cell comprises a negative poisson ratio skeleton reinforcing phase and a self-healing matrix phase, and the appearance basic size of the unit cell is 960mm multiplied by 30mm.
First, a material design on a microscopic scale is performed on a matrix phase self-healing material: the epoxy resin is used as a matrix, glutaric anhydride and sebacic acid with the proportion of 3:1 are used as curing agents, 0.1wt.%,0.2wt.%,0.3wt.%,0.5wt.% of multi-wall carbon nano tube are added on the basis, and experiments prove that the short multi-wall carbon nano tube doped with 0.1wt.% has better damping and rigidity performance, the maximum loss factor is 0.77, and the maximum loss modulus is 1242MPa.
Secondly, taking quarter unit cell as an example, further describing geometric parameters of the skeleton reinforced phase, wherein specific parameters are shown in fig. 3, in concentric arcs, the radius of an outer arc is R2, the radius of an inner arc is R3, the width of a ligament is R2-R3, and the radius of a central circular node is equal to the width of the ligament. To verify the effect of the skeleton reinforcing phase ligaments on poisson's ratio parameters, numerical calculations were performed with ligament widths of 35mm, 40mm and 45mm, respectively, and the calculation results are shown in table 1. As can be seen from table 1, the negative poisson ratio skeleton has a remarkable negative poisson ratio effect, when the ligament thickness is increased from 35mm to 40mm, the rigidity is increased from 60.40MPa to 100.59MPa, and the rigidity is increased by 1.67 times, but when the ligament thickness is increased from 35mm to 40mm, the absolute value of poisson ratio is improved, but the rigidity is increased slightly. Meanwhile, compared with a negative poisson ratio framework with the ligament thickness of 45mm, the framework with the ligament thickness of 40mm is more beneficial to filling more damping phase self-healing composite materials and is more beneficial to designing metamaterial unit cells with high rigidity and high damping.
TABLE 1 ligament thickness performance comparison for different negative Poisson ratios
Then, taking quarter unit cell as an example, the self-healing matrix phase geometry parameters are further described, and specific parameters are shown in fig. 4. The self-healing matrix phase is matched with the framework reinforcing phase, and the basic appearance size after matching is 960mm multiplied by 30mm.
In order to verify the influence of the framework material on the overall mechanical property, steel, aluminum and rubber are respectively used as framework reinforcing phase materials to form a structural damping metamaterial unit cell, as shown in fig. 6, and the unit cell is periodically expanded into a5×5 plate structure along the plane direction, as shown in fig. 7. The product of the rigidity and the loss factor is taken as the energy consumption modulus and is used for evaluating the comprehensive performance of the single-cell rigidity and the damping of the metamaterial, the structure is calculated by utilizing numerical analysis, and the calculation result is shown in table 2.
Table 2 comparison of various skeletal metamaterial properties
The loss factors of the plate structure under different frequencies are shown in fig. 8, steel is used as a negative poisson ratio skeleton reinforcing phase material, the loss factor of the self-healing material is about 0.20, and the loss factor is far higher than that of the skeleton reinforcing phase by 0.0006 although the loss factor is lower than that of other control groups, so that the damping performance is better, and the rigidity of the damping metamaterial of the structure is far higher than that of other control groups, so that the damping metamaterial has good rigidity performance. As shown in fig. 9, according to the energy dissipation modulus, the energy dissipation modulus of the metamaterial taking steel as the framework reinforcing phase material and taking the self-healing composite material as the matrix phase is 2837.38MPa, so that the high rigidity and the high damping performance can be simultaneously achieved, and the energy dissipation modulus figure-of-merit value of the metamaterial are remarkably higher than those of other materials.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (5)
1. A material having a self-healing function, characterized in that the unit cell of the material comprises a matrix phase and a reinforcement phase, wherein:
The reinforcing phase is a negative poisson ratio structural framework; the matrix phase is made of self-healing materials, and the self-healing materials are filled in the hole areas of the negative poisson ratio structural framework;
The negative poisson's ratio structural skeleton comprises four identical sub-portions, wherein:
Each sub-part comprises a central round node and 4 ligaments, and the 4 ligaments are uniformly and circumferentially distributed around the central round node; the ligament comprises an S-shaped ligament and a linear ligament which are vertically arranged, one end of the S-shaped ligament is connected with the central round node, and the other end of the S-shaped ligament is connected with the linear ligament;
the four sub-parts are distributed in a shape of a Chinese character 'tian', and the tail ends of a linear ligament are connected with each other between the adjacent sub-parts;
the reinforced phase material is steel or aluminum; the self-healing material of the matrix phase is epoxy resin doped with multi-wall carbon nano tubes, glutaric anhydride and sebacic acid are also doped in the self-healing material, and the ratio of the multi-wall carbon nano tubes in the self-healing material is 0.1wt.% to 0.5wt.%.
2. A self-healing material according to claim 1, wherein the S-shaped ligament comprises three equidistant curves connected in sequence, each equidistant curve being formed by two concentric circular arcs.
3. A material with self-healing function according to claim 2, wherein the width of the equidistant curve is the width of the ligament, which is 35 mm-45 mm.
4. A self-healing material according to claim 3, wherein the radius of the central circular node is not less than the width of the ligament.
5. Use of a material with self-healing function according to any of claims 1 to 4, wherein a plurality of said cells are combined into a complex geometry.
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| CN115584120A (en) * | 2022-10-14 | 2023-01-10 | 北京化工大学 | Preparation method of polyurethane elastomer composite material with negative Poisson ratio property |
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| CN103758904B (en) * | 2014-01-27 | 2016-03-09 | 重庆交通大学西南水运工程科学研究所 | A kind of damping sheet based on negative poisson ' s ratio structure |
| WO2019165583A1 (en) * | 2018-02-27 | 2019-09-06 | 苏州大学张家港工业技术研究院 | Reversible self-repairing epoxy resin and preparation and recovery remoulding method therefor |
| CN112307663B (en) * | 2020-11-06 | 2022-09-27 | 西北工业大学 | Design method of chiral metamaterial structure with preset negative Poisson ratio characteristic |
| CN113816676B (en) * | 2021-09-06 | 2022-05-31 | 青岛理工大学 | Negative Poisson's ratio cement-based composite material and preparation method thereof |
| CN114474785B (en) * | 2022-02-09 | 2023-11-21 | 烟台大学 | 3D multi-component composite auxetic super-structure material based on additive manufacturing |
| CN115819974B (en) * | 2022-11-15 | 2023-11-14 | 华南理工大学 | Composite material structural system with customizable mechanical properties and preparation method |
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| CN112852109A (en) * | 2021-01-14 | 2021-05-28 | 成都谦智明远科技有限公司 | Preparation method of high-temperature self-repairing hot-mix epoxy asphalt material |
| CN115584120A (en) * | 2022-10-14 | 2023-01-10 | 北京化工大学 | Preparation method of polyurethane elastomer composite material with negative Poisson ratio property |
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