CN109825087B - Protective material for 3D printing of high-negative Poisson ratio interwoven structure - Google Patents
Protective material for 3D printing of high-negative Poisson ratio interwoven structure Download PDFInfo
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Abstract
The invention discloses a novel protective material for a 3D printing high-negative Poisson ratio interwoven structure, which is formed by printing a shape memory material and common rubber through a microdroplet jet additive manufacturing technology; triangular structures (1) are uniformly distributed in the structure of the protective material, and the triangular structures (1) connect triangular nodes through linear structures (3); non-closed hexagonal structures are formed between the adjacent linear structures (3). The invention utilizes 3D printing technology, and the improved photosensitive material is stimulated by temperature to make 3D printing out a real object with excellent characteristics of memory, response, recovery, shock resistance, adaptability and the like.
Description
Technical Field
The invention relates to the technical field of protective materials, in particular to a novel protective material for 3D printing of a high-negative Poisson's ratio interwoven structure.
Background
The negative poisson ratio material is applied to safety protection at present. Chinese utility model patent specifications CN206336247U, CN206782464U respectively disclose an automobile energy-absorbing box filled with a negative Poisson's ratio structure and an energy-absorbing anti-falling packing box based on a negative Poisson's ratio material. Both of these patents utilize the energy absorbing properties of a negative poisson's ratio material to make a protective material. But the problem is that it is difficult to achieve high negative poisson's ratio (NP < -0.5) not only due to the structure but also the materials from which the high negative poisson's ratio structure is made;
at present, the soft material with the negative Poisson ratio structure is difficult to realize 3D printing for developing the protective material with the negative Poisson ratio interweaving structure. The general negative poisson ratio material is prepared with chemical polymer material (such as CN105860379B and CN107474303A) or through certain weaving process to produce negative poisson ratio fabric (such as CN104911804B and CN 207091629U). There are also negative poisson's ratio fabrics produced by making negative poisson's ratio yarns (e.g., CN103361811B), and there are other negative poisson's ratio materials made by some other physicochemical processes (e.g., CN 105965930A). Direct 3D printing of negative poisson's ratio material has not been achieved.
Disclosure of Invention
Aiming at the problems in the prior art, the applicant of the present invention provides a novel protective material for 3D printing of a high negative poisson's ratio interlaced structure. The invention utilizes 3D printing technology, and the improved photosensitive material is stimulated by temperature to make 3D printing out a real object with excellent characteristics of memory, response, recovery, shock resistance, adaptability and the like.
The technical scheme of the invention is as follows:
a novel protective material with a high negative Poisson ratio interwoven structure for 3D printing is formed by printing a shape memory material and common rubber through a microdroplet jet additive manufacturing technology; triangular structures (1) are uniformly distributed in the structure of the protective material, and the triangular structures (1) connect triangular nodes through linear structures (3); non-closed hexagonal structures are formed between the adjacent linear structures (3).
Three sides of the triangular structure (1) are made of common rubber.
The nodes of the triangular structure (1) are made of shape memory materials.
The distance between the centers of the circumscribed circles of the triangular structures (1) is 10mm, and the side length of each triangle is 1-4 mm.
The shape memory material is a photosensitive resin material; namely bisphenol F epoxy acrylate resin, pentaerythritol triacrylate or modified stearyl acrylate.
The bisphenol F epoxy acrylate resin is prepared by reacting epoxy resin and acrylic acid for 3.5-4 hours at the temperature of 100-110 ℃ by taking tetramethylammonium chloride as a catalyst and hydroquinone as a polymerization inhibitor; the dosage of the catalyst is 1.0wt%, and the dosage of the polymerization inhibitor is 0.1 wt%; the mass ratio of the epoxy resin to the acrylic acid is 1: 0.8-1.2.
The pentaerythritol triacrylate is prepared by reacting pentaerythritol and acrylic acid for 5-6 hours in a toluene environment by taking p-toluenesulfonic acid as a catalyst; the using amount of the catalyst is 4% of the mass of pentaerythritol, and the mass ratio of the pentaerythritol to acrylic acid to toluene is 1:3.6: 1.86; wherein, a polymerization inhibitor PMT accounting for 3.5-4% of the mass of acrylic acid and a decolorizing agent TSJ-1 accounting for 3-3.5% of the mass of pentaerythritol are also added in the reaction process.
The modified octadecyl acrylate is prepared by reacting octadecyl acrylate monomer, cross-linking agent propoxylated neopentyl glycol diacrylate and diluent under the action of a photoinitiator; the photoinitiator is benzoin ethyl ether-thionium salt initiator; the mass ratio of the monomer to the cross-linking agent is 1: 0.18.
The linear structure (3) is made of common rubber.
The beneficial technical effects of the invention are as follows:
the invention borrows the principle of shape memory for the first time, thus giving each small unit with the negative Poisson ratio structure an initial shape which has larger deformation compared with the original shape, when the prepared material with the negative Poisson ratio structure absorbs energy, the initial shape which is set at the beginning is recovered, and the high negative Poisson ratio which is wanted by people is achieved by continuously adjusting the structure through a finite element method.
The existing negative Poisson ratio structure has a certain rule but is single, particularly the chiral structure, and the hexaligament chiral structure is superior to other negative Poisson ratio structures such as a honeycomb structure and a star structure. The chiral structure material has better attenuation characteristic, has better buckling strength when receiving even flat pressure compared with common hexagonal honeycomb structure and hexagonal ligament chiral structure, and in addition, the chiral structure has outstanding capacity of bearing large-deflection deformation and good vibration isolation and sound insulation performance.
The invention adds chiral structural elements and designs a brand-new structure with better negative Poisson ratio effect. The chiral negative Poisson ratio structure has great development prospect and improvement possibility.
Drawings
FIG. 1 is a schematic view of the present invention;
in the figure: 1. a triangular structure; 2. an outer surface linear structure; 3. a straight line configuration.
FIG. 2 is a schematic diagram of a triangular structure according to the present invention.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
Example 1:
referring to fig. 1, 3D printable common materials (silica gel) with good tensile properties are used at straight lines, bisphenol F epoxy acrylate resin (containing diluents TPGDA and photoinitiators BDK) is used for triangular nodes, the structure is accurately designed by using CAD (design parameters are that the distance between the centers of circles circumscribed to the triangle is 10mm, and the side lengths of the triangle are respectively 1mm, 2.5mm and 4mm), and a complete composite structure with a high-negative poisson ratio structure is formed by using a 3D printing technology; finally, the mechanical property of the composite resin is tested by using ABAQUS software, so that the Poisson ratio of the structure with the high negative Poisson ratio combined with the shape memory material can reach-0.6, and the composite resin has the advantages of high specific strength, large specific modulus, good fatigue resistance and high tensile strength, but the elongation at break is reduced to a certain extent, and the improvement of the crystallinity of the composite resin is found, so that the flexibility of a 3D printing part can be effectively improved.
The bisphenol F epoxy acrylate resin is prepared by reacting epoxy resin and acrylic acid at a mass ratio of 1:0.8, tetramethylammonium chloride as a catalyst and hydroquinone as a polymerization inhibitor at 100 ℃ for 4 hours; the amount of the catalyst was 1.0wt% and the amount of the polymerization inhibitor was 0.1 wt%.
Example 2:
referring to fig. 1, a 3D printable common material (rubber) with good tensile properties is used in a straight line, pentaerythritol triacrylate resin is used as nodes of a triangle, and after the structure is precisely designed by CAD (the inscribed circle of the triangle is 10mm, 15mm, 20mm in diameter), a 3D printing technology (object's connex series) is used to form a complete composite structure with a high negative poisson ratio; finally, the mechanical property of the material is tested by using ABAQUS software, and the Poisson ratio of the structure with the high negative Poisson ratio combined with the shape memory material can reach-0.6.
The pentaerythritol triacrylate resin is prepared by using toluenesulfonic acid as a catalyst, adopting polymerization inhibitor PMT and decolorizing agent TSJ-1, wherein the dosage of the catalyst is 4% of the mass of pentaerythritol, the adding amount of the polymerization inhibitor is 4% of the mass of acrylic acid, the dosage of the decolorizing agent is 3% of the dosage of the pentaerythritol, the raw material feeding ratio (the ratio of the amounts of the substances) of pentaerythritol to acrylic acid and toluene is 1:3.6:1.86, and the reaction time is 5 hours.
The structure of the invention has the property of negative Poisson ratio, and the used memory material gives corresponding stimulation to the material when receiving impact and tension and compression, so that the length of the material is changed, and the negative Poisson ratio of the material is increased.
Example 3:
by the same principle as that of example 2, the modified octadecyl acrylate is adopted in the triangle node, and is prepared by reacting octadecyl acrylate monomer, propoxylated neopentyl glycol diacrylate as a cross-linking agent and a diluent under the action of a photoinitiator; the photoinitiator is benzoin ethyl ether-thionium salt initiator (6 wt%); the mass ratio of the monomer to the cross-linking agent is 1: 0.18.
The mechanical property of the material is tested by using ABAQUS software, and the Poisson ratio of the structure with high negative Poisson ratio combined with the shape memory material can reach-0.53.
Claims (4)
1. The protective material with the high negative Poisson ratio interwoven structure for 3D printing is characterized in that the protective material is formed by printing a shape memory material and common rubber through a microdroplet jet additive manufacturing technology; triangular structures (1) are uniformly distributed in the structure of the protective material, and the triangular structures (1) connect triangular nodes through linear structures (3); non-closed hexagonal structures are formed between the adjacent linear structures (3); three sides of the triangular structure (1) are made of common rubber; the nodes of the triangular structure (1) are made of shape memory materials; the linear structure (3) is made of common rubber;
the distance between the centers of the circumscribed circles of the triangular structure (1) is 10mm, and the side length of the triangle is 1-4 mm;
the shape memory material is a photosensitive resin material; namely bisphenol F epoxy acrylate resin, pentaerythritol triacrylate or modified stearyl acrylate.
2. The protective material according to claim 1, wherein the bisphenol F epoxy acrylate resin is prepared by reacting epoxy resin with acrylic acid at 100-110 ℃ for 3.5-4 h under the conditions of taking tetramethylammonium chloride as a catalyst and hydroquinone as a polymerization inhibitor; the dosage of the catalyst is 1.0wt%, and the dosage of the polymerization inhibitor is 0.1 wt%; the mass ratio of the epoxy resin to the acrylic acid is 1: 0.8-1.2.
3. The protective material according to claim 1, wherein the pentaerythritol triacrylate is prepared by reacting pentaerythritol with acrylic acid in a toluene environment for 5-6 hours in the presence of p-toluenesulfonic acid as a catalyst; the using amount of the catalyst is 4% of the mass of pentaerythritol, and the mass ratio of the pentaerythritol to acrylic acid to toluene is 1:3.6: 1.86; wherein, a polymerization inhibitor PMT accounting for 3.5-4% of the mass of acrylic acid and a decolorizing agent TSJ-1 accounting for 3-3.5% of the mass of pentaerythritol are also added in the reaction process.
4. The protective material according to claim 1, wherein the modified stearyl acrylate is prepared by reacting a monomer stearyl acrylate, a cross-linking agent propoxylated neopentyl glycol diacrylate and a diluent under the action of a photoinitiator; the photoinitiator is benzoin ethyl ether-thionium salt initiator; the mass ratio of the monomer to the cross-linking agent is 1: 0.18.
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| CN112045990B (en) * | 2020-09-10 | 2022-02-01 | 西安交通大学 | Chiral auxetic metamaterial structure with compression-shear coupling characteristic and preparation method thereof |
| CN116102873B (en) * | 2023-04-13 | 2023-06-16 | 北京航空航天大学 | Negative poisson ratio structure and manufacturing method thereof |
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