A bionic protective shell with self-sensing and self-healing functions, its preparation method and application

Abstract

The present invention discloses a bionic protective shell with self-sensing and self-repair functions, including a bionic protective shell composed of a protective layer and a pore regulation layer. The protective layer is composed of countless simulated cell units, and solution A and solution B are respectively contained in the simulated cell units, and each simulated cell unit is only adjacent to the simulated cell unit containing the other solution. The present invention has the following advantages: 1. Through the bionic skin, the present invention uses the reaction between solution A and solution B in the simulated cell units to repair the damaged simulated cell walls, having the function of self-repair. 2. By measuring the voltage change or current change on the bionic protective shell, the external force condition, self-damage and repair condition of the bionic protective shell can be effectively obtained. 3. The wrinkles protruding from the inner wall of the pore regulation layer in the present invention open or close to regulate the heat exchange between the inside and the outside of the bionic protective shell.

Description

Technical Field

[0001] The present invention belongs to the technical field of protective shells, and particularly relates to a bionic protective shell with self-sensing and self-repairing functions, a preparation method thereof, and an application thereof. Background Art

[0002] In space, space stations and spacecraft are inevitably impacted or scratched by some very small meteorite fragments or space debris. These often bring some tiny cracks that are invisible to the naked eye to the space stations and spacecraft. These cracks may be below the surface of the material and are imperceptible to people. Once these cracks are formed, they will spread as the material ages and is damaged. In addition, in space, the temperature difference is extremely large, the temperature changes greatly, and frequent temperature changes will also exacerbate the aging and damage of the material. These may ultimately cost us an irreparable price.

[0003] The skin is one of the most important organs. In sun plants, its leaf epidermis covers the surface. The leaf epidermis can be divided into guard cell areas and stoma cell areas according to function. They are in direct contact with the external environment and have functions such as protection, body temperature regulation, and perception of external stimuli. The guard cell area of the leaf epidermis of sun plants has the functions of protecting the main body of the leaf, sensing its own state, and repairing its own damage. The stoma cell area can adjust the size of the stoma and perform gas metabolism functions such as respiration and transpiration.

[0004] The action mechanism of the leaf epidermis of sun plants is worthy of our reference and learning. In order to prevent the generation and spread of these cracks and slow down the aging and damage of the material, it is necessary to develop a bionic protective shell imitating the skin. By adding this layer of protective shell to the outer surface of precision components such as space stations and spacecraft, it can play a role in protecting the space stations and spacecraft. When this layer of protective shell is impacted or scratched, it can sense the occurrence of this damage and quickly complete self-repair without relying on artificial assistance. At the same time, when the external temperature changes, it can sense the rise and fall of the external temperature, and then adjust the heat exchange by adjusting the size of the stoma, providing a stable or small-temperature-fluctuation environment inside the protective shell. This self-sensing and self-repairing ability is of great significance for protecting spacecraft and extending the service life of spacecraft. Summary of the Invention

[0005] In view of the above defects or improvement requirements of the prior art, the present invention provides a bionic protective shell with self-sensing and self-repairing functions based on 4D printing technology, a preparation method thereof, and an application thereof.

[0006] The technical solution provided by the present invention is as follows:

[0007] In a first aspect, the present invention provides a bionic protective shell with self-sensing and self-healing functions, including a protective layer and a pore regulation layer; the protective layer is composed of a plurality of simulated cell units, and each simulated cell unit is composed of a cavity filled with solution A or B, where the cytoplasm is solution A or solution B, and each simulated cell unit is only adjacent to a simulated cell unit filled with the other solution; electrodes are connected to both ends of the simulated cell unit.

[0008] The cavity of the simulated cell unit is composed of a hydrogel doped with carbon nanotubes; solution A is a mixed solution of acrylic isocyanate-modified cyclodextrin and carbon nanotubes; solution B is a mixed solution of acrylated-modified adamantane and carbon nanotubes.

[0009] The pore regulation layer is disposed between the protective layers and on the outer surface.

[0010] Further, the hydrogel in the hydrogel doped with carbon nanotubes includes polyacrylic acid-based and polyacrylamide-based hydrogels. Preferably, the hydrogel is polyacrylic acid, polymethacrylic acid, polyacrylamide or poly-N-substituted acrylamide, and the mass ratio of carbon nanotubes to the hydrogel is 1:9.

[0011] Further, the concentration of solution A is 1 - 5 g / ml, and the mass ratio of carbon nanotubes to acrylic isocyanate-modified cyclodextrin is 0.05 - 0.12:1.

[0012] Further, the concentration of solution B is 1 - 5 g / ml, and the mass ratio of carbon nanotubes to acrylated-modified adamantane is 0.05 - 0.18:1.

[0013] Further, the pore regulation layer has holes, and many convex folds are distributed on the inner wall of the holes. The folds are shape memory materials; when the external temperature changes, the folds will stretch and contract to reduce or increase the size of the holes, thereby regulating the heat exchange inside and outside the bionic protective shell.

[0014] Furthermore, the materials of the folds include shape memory polyurethane, fluororesin, polycaprolactone and polyamide.

[0015] The principle of self-healing and self-sensing of the bionic protective shell of the present invention is as follows:

[0016] When the simulated cell walls between the simulated cell units are damaged and ruptured due to external forces or other reasons, solution A and solution B in the simulated cell units will meet and interact at the rupture to form crosslinked methylacrylic acid gelatin. The repaired simulated cell units have elasticity, fatigue resistance, repeatability and self-healing properties.

[0017] There are connecting electrodes at both ends of the simulated cell unit filled with Solution A and Solution B. When the simulated cell unit is subjected to an external force, it will deform, and the deformation of the simulated cell unit will change its own resistance. Further, when the simulated cell wall is damaged and ruptured due to external forces or other reasons, after the Solution A and Solution B in the simulated cell unit react to repair the damaged simulated cell wall, it will also change the resistance of the simulated cell unit itself, enabling the bionic protective shell to have the ability of self-sensing. The resistance change caused by the reaction of Solution A and Solution B is different from the resistance change caused by the deformation of the simulated cell unit. By measuring the voltage change or current change of the electrodes on the simulated cell unit, the external force situation and self-repair situation of the bionic protective shell can be effectively known.

[0018] The pore regulation layer has pores, and many raised folds are distributed on the inner wall of the pores. The folds are made of shape memory material. When the external temperature changes, the folds will stretch and contract, thereby reducing or increasing the size of the pores, and further regulating the heat exchange inside and outside the bionic protective shell, so as to provide a stable or small-temperature-fluctuation environment inside the protective shell.

[0019] When the temperature is low, the shape memory restoring force of the shape memory material is small, and the pores of the pore regulation layer are in a contracted state under the overall extrusion. As the temperature rises, the shape memory restoring force of the shape memory material gradually increases, and the pores of the pore regulation layer also gradually increase, accelerating the heat exchange inside and outside the bionic protective shell. When the temperature drops, the shape memory restoring force of the shape memory material gradually decreases, slowing down the heat exchange inside and outside the bionic protective shell.

[0020] Second, the present invention provides a preparation method of the bionic protective shell described in the first aspect, including the following steps:

[0021] S1: Preparation of Solution A: Mix ethylenediamine isocyanate modified cyclodextrin and carbon nanotubes in alkaline deionized water, and after ultrasonic treatment, keep warm for a period of time to obtain it;

[0022] S2: Preparation of Solution B: Mix acrylated modified adamantane and carbon nanotubes in alkaline deionized water, and after ultrasonic treatment, keep warm for a period of time to obtain it;

[0023] S3: Model the bionic protective shell through 3D modeling software;

[0024] S4: 3D print the model to obtain it.

[0025] Further, the preparation temperature of Solution A is 30 - 60 °C; the preparation temperature of Solution B is 30 - 60 °C.

[0026] Further, the 3D modeling software includes 3D modeling software such as Magics, UG, CREO, etc.

[0027] Furthermore, the parameters of 3D printing are a layer height of 0.03 - 0.05 mm and a speed of 5 - 15 mm / s.

[0028] In a third aspect, the present invention provides the application of the bionic protective shell described in the first aspect as a protective shell for spacecraft, mobile phone shells, and automotive shells.

[0029] Generally speaking, compared with the prior art through the above technical solutions conceived by the present invention, the bionic protective shell and its preparation method provided by the present invention have the following beneficial effects:

[0030] 1) Through the bionic skin, the present invention utilizes the reaction of solution A and solution B in the simulated cell unit to repair the damaged simulated cell wall, having the function of self - repair. The repaired simulated cell unit has more excellent elasticity and fatigue resistance.

[0031] 2) When the bionic protective shell is deformed by external force, internal damage occurs, and the internal damage is repaired, its own resistance will change. By measuring the voltage change or current change on the bionic protective shell, the external force situation, self - damage, and repair situation of the bionic protective shell can be effectively known.

[0032] 3) The convex folds on the inner wall of the pore - regulating layer in the present invention are shape - memory materials, enabling the folds to open or close to regulate the heat exchange between the inside and outside of the bionic protective shell. When the external temperature changes, the folds will stretch and contract to reduce or increase the size of the holes, thereby regulating the heat exchange inside and outside the bionic protective shell, and providing a stable or small - temperature - fluctuation environment inside the protective shell. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] The drawings are only for the purpose of showing specific embodiments and are not considered as a limitation to the present invention.

[0034] Figure 1 is the cross - sectional front view of the embodiment of the present application;

[0035] Figure 2 is the structural schematic diagram of the embodiment of the present application.

[0036] Figure 3 is the structural schematic diagram of Embodiment 1.

[0037] Wherein 1 is the pore - regulating layer and 2 is the guard layer. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0038] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0039] Example 1

[0040] Figures 1-3 There is shown a bionic protective shell with self-sensing and self-healing functions. The bionic protective shell is composed of a protective layer 2 and a pore regulating layer 1. The protective layer is composed of countless simulated cell units. The simulated cell unit is composed of a cavity filled with solution A or B. Each simulated cell unit is only adjacent to a simulated cell unit filled with the other solution. Electrodes are connected to both ends of the simulated cell unit. The pore regulating layer is disposed between the protective layers and on the outer surface.

[0041] Preferably, the cavity of the simulated cell unit is composed of polyacrylic acid hydrogel doped with carbon nanotubes, where the mass ratio of carbon nanotubes to hydrogel is 1:9. Solution A is a mixed solution of isocyanatoethyl acrylate modified cyclodextrin and carbon nanotubes, and solution B is a mixed solution of acrylated modified adamantane and carbon nanotubes.

[0042] Preferably, the pore regulating layer is a microstructure imitating the stomata of spinach epidermis, and the pore regulating layer is a polyurethane shape memory material.

[0043] The preparation method of the bionic protective shell is inkjet direct writing (DIW) printing technology, and the specific steps are as follows:

[0044] S1: Preparation of solution A: Mix isocyanatoethyl acrylate modified cyclodextrin and carbon nanotubes in alkaline deionized water at 30°C. After ultrasonic treatment, keep warm for a period of time to obtain a uniform solution A. The concentration of solution A is 2 g / ml, and the mass ratio of carbon nanotubes to cyclodextrin is 0.05.

[0045] S2: Preparation of solution B: Mix acrylated modified adamantane and carbon nanotubes in alkaline deionized water at 30°C and after ultrasonic treatment, keep warm for a period of time to obtain solution B. The concentration of solution B is 2 g / ml, and the mass ratio of carbon nanotubes to adamantane is 0.05.

[0046] S3: Model the bionic protective shell through 3D modeling software such as Magics, UG, and CREO. The model structure diagram is as Figure 3 and save it as an STL format file;

[0047] S4: Input the saved STL format file into an inkjet direct writing 3D printing device (DIW), with a layer height of 0.05 mm and a speed of 5 mm / s as the printing parameters.

[0048] Example 2

[0049] A bionic protective shell with self-sensing and self-healing functions, which consists of a protective layer 2 and a pore regulation layer 1. The protective layer is composed of countless simulated cell units, and each simulated cell unit is composed of a cavity filled with solution A or B. Each simulated cell unit is only adjacent to a simulated cell unit filled with the other solution; electrodes are connected to both ends of the simulated cell unit. The pore regulation layer is disposed between the protective layers and on the outer surface.

[0050] Preferably, the cavity of the simulated cell unit is composed of polyacrylic acid hydrogel doped with carbon nanotubes, where the mass ratio of carbon nanotubes to hydrogel is 1:9. Solution A is a mixed solution of isocyanatoethyl acrylate-modified cyclodextrin and carbon nanotubes, and solution B is a mixed solution of acrylated-modified adamantane and carbon nanotubes.

[0051] Preferably, the pore regulation layer is a micro-structure of the stomata of the buttercup epidermis, and the pore regulation layer is a polycaprolactone shape memory material.

[0052] The preparation method of the bionic protective shell is an inkjet direct writing (DIW) printing technology, and the specific steps are as follows:

[0053] S1: Preparation of solution A: Mix isocyanatoethyl acrylate-modified cyclodextrin and carbon nanotubes in alkaline deionized water at 30 °C. After ultrasonic treatment, keep it warm for a period of time to obtain a uniform solution A. The concentration of solution A is 3 g / ml, and the mass ratio of carbon nanotubes to cyclodextrin is 0.05;

[0054] S2: Preparation of solution B: Mix acrylated-modified adamantane and carbon nanotubes in alkaline deionized water at 30 °C and perform ultrasonic treatment. After keeping it warm for a period of time, obtain solution B. The concentration of solution B is 3 g / ml, and the mass ratio of carbon nanotubes to adamantane is 0.05.

[0055] S3: Model the bionic protective shell using 3D modeling software such as Magics, UG, and CREO, and save it as an STL format file;

[0056] S4: Input the saved STL format file into an inkjet direct writing 3D printing device (DIW), with a layer height of 0.05 mm and a speed of 5 mm / s as the printing parameters.

[0057] Example 3

[0058] A bionic protective shell with self-sensing and self-healing functions, the bionic protective shell is composed of a protective layer 2 and a pore regulating layer 1. The protective layer is composed of countless simulated cell units. The simulated cell unit is composed of a cavity filled with solution A or B. Each simulated cell unit is only adjacent to the simulated cell unit filled with the other solution; electrodes are connected to both ends of the simulated cell unit. The pore regulating layer is arranged between the protective layers and is located on the outer surface.

[0059] Preferably, the cavity of the simulated cell unit is composed of polyacrylic acid hydrogel doped with carbon nanotubes, and the mass ratio of carbon nanotubes to hydrogel is 1:9. Solution A is a mixed solution of isocyanatoethyl acrylate modified cyclodextrin and carbon nanotubes, and solution B is a mixed solution of acrylated modified adamantane and carbon nanotubes.

[0060] Preferably, the pore regulating layer is a micro-structure imitating the stomata of Chinese cabbage epidermis, and the pore regulating layer is a fluororesin shape memory material

[0061] The preparation method of the bionic protective shell is inkjet direct writing (DIW) printing technology, and the specific steps are as follows:

[0062] S1: Preparation of solution A: Mix isocyanatoethyl acrylate modified cyclodextrin and carbon nanotubes in alkaline deionized water at 30°C. After ultrasonic treatment, keep warm for a period of time to obtain a uniform solution A. The concentration of solution A is 3 g / ml, and the mass ratio of carbon nanotubes to cyclodextrin is 0.1;

[0063] S2: Preparation of solution B: Mix acrylated modified adamantane and carbon nanotubes in alkaline deionized water at 30°C and perform ultrasonic treatment. After keeping warm for a period of time, obtain solution B. The concentration of solution B is 3 g / ml, and the mass ratio of carbon nanotubes to adamantane is 0.1.

[0064] S3: Model the bionic protective shell through 3D modeling software such as Magics, UG, and CREO, and save it as an STL format file;

[0065] S4: Input the saved STL format file into an inkjet direct writing 3D printing device (DIW), and the printing parameters are a layer height of 0.03 mm and a speed of 5 mm / s.

[0066] Example 4

[0067] A bionic protective shell with self-sensing and self-healing functions, the bionic protective shell is composed of a protective layer 2 and a stomatal regulation layer 1. The protective layer is composed of countless simulated cell units. The simulated cell units are composed of cavities filled with solution A or B. Each simulated cell unit is only adjacent to the simulated cell unit filled with the other solution. Electrodes are connected to both ends of the simulated cell unit. The stomatal regulation layer is arranged between the protective layers and is placed on the outer surface.

[0068] Preferably, the cavity of the simulated cell unit is composed of polyacrylic acid hydrogel doped with carbon nanotubes, and the mass ratio of carbon nanotubes to hydrogel is 1:9. Solution A is a mixed solution of isocyanatoethyl acrylate-modified cyclodextrin and carbon nanotubes, and solution B is a mixed solution of acrylated-modified adamantane and carbon nanotubes.

[0069] Preferably, the stomatal regulation layer is a micro-structure imitating the stomata of madder epidermis, and the stomatal regulation layer is a polyamide shape memory material

[0070] The preparation method of the bionic protective shell is the ink direct writing (DIW) printing technology, and the specific steps are as follows:

[0071] S1: Preparation of solution A: Mix isocyanatoethyl acrylate-modified cyclodextrin and carbon nanotubes in alkaline deionized water at 30 °C. After ultrasonic treatment, keep warm for a period of time to obtain a uniform solution A. The concentration of solution A is 4 g / ml, and the mass ratio of carbon nanotubes to cyclodextrin is 0.05;

[0072] S2: Preparation of solution B: Mix acrylated-modified adamantane and carbon nanotubes in alkaline deionized water at 30 °C and ultrasonic treatment, and keep warm for a period of time to obtain solution B. The concentration of solution B is 3 g / ml, and the mass ratio of carbon nanotubes to adamantane is 0.05.

[0073] S3: Model the bionic protective shell through 3D modeling software such as Magics, UG, and CREO, and save it as an STL format file;

[0074] S4: Input the saved STL format file into an ink direct writing 3D printing device (DIW), and the printing parameters are a layer height of 0.04 mm and a speed of 5 mm / s.

[0075] As Figures 1-3 shown, the bionic shell described in the present invention has three typical shapes, such as strip-shaped, square-shaped, and annular-shaped. These three shapes are only for exemplary display, and in fact, it only needs to meet that the stomatal regulation layer is arranged between the protective layers and is placed on the outer surface. Those skilled in the art can make any structural changes.

[0076] Those skilled in the art can easily understand that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent replacements, and improvements made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

[0077] As described above, it is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any modifications, equivalent replacements, and improvements made by those skilled in the art within the technical scope disclosed by the present invention shall be included within the protection scope of the invention.

Claims

1. A bionic protective shell with self-sensing and self-healing functions, characterized in that, It includes a protective layer and a stomatal regulation layer; the protective layer is composed of multiple simulated cell units, and each simulated cell unit is composed of a cavity filled with solution A or B. Each simulated cell unit is only adjacent to a simulated cell unit filled with the other solution; electrodes are connected to both ends of the simulated cell unit. The cavity of the simulated cell unit is composed of a hydrogel doped with carbon nanotubes; solution A is a mixed solution of acrylic isocyanate-modified cyclodextrin and carbon nanotubes; solution B is a mixed solution of acrylated-modified adamantane and carbon nanotubes. The stomatal regulation layer is disposed between the protective layers and on the outer surface.

2. The bionic protective shell according to claim 1, characterized in that, The hydrogel in the hydrogel doped with carbon nanotubes includes polyacrylic acid-based and polyacrylamide-based hydrogels.

3. The bionic protective shell according to claim 1, characterized in that, The concentration of solution A is 1-5 g / ml, and the mass ratio of carbon nanotubes to acrylic isocyanate-modified cyclodextrin is 0.05-0.12:

1.

4. The bionic protective shell according to claim 1, characterized in that, The concentration of solution B is 1-5 g / ml, and the mass ratio of carbon nanotubes to acrylated-modified adamantane is 0.05-0.18:

1.

5. The bionic protective shell according to claim 1, characterized in that, The stomatal regulation layer has holes, and many raised wrinkles are distributed on the inner wall of the holes. The wrinkles are shape memory materials; when the external temperature changes, the wrinkles will stretch and contract to reduce or increase the size of the holes, thereby regulating the heat exchange inside and outside the bionic protective shell.

6. The bionic protective shell according to claim 5, characterized in that, The materials of the wrinkles include shape memory polyurethane, fluororesin, polycaprolactone, and polyamide.

7. A preparation method of the bionic protective shell according to any one of claims 1-6, characterized in that, It includes the following steps: S1: Preparation of solution A: Mix acrylic isocyanate-modified cyclodextrin and carbon nanotubes in alkaline deionized water, and after ultrasonic treatment, keep it warm for a period of time to obtain it. S2: Preparation of solution B: Mix acrylated-modified adamantane and carbon nanotubes in alkaline deionized water and after ultrasonic treatment, keep it warm for a period of time to obtain it. S3: Model the bionic protective shell through 3D modeling software. S4: 3D print the model to obtain it.

8. The bionic protective shell according to claim 1, characterized in that, The preparation temperature of solution A is 30-60 °C; the preparation temperature of solution B is 30-60 °C.

9. The bionic protective shell according to claim 1, characterized in that, The parameters of 3D printing are a layer height of 0.03-0.05 mm and a speed of 5-15 mm / s.

10. Application of the bionic protective shell according to any one of claims 1-6 as a protective shell for spacecraft, an automobile shell and a mobile phone shell.

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