阅读说明：本技术 具有形状记忆功能的仿墨鱼骨轻质高强材料的制备方法 (Preparation method of cuttlefish bone-imitated light high-strength material with shape memory function ) 是由 柏浩 茅安然 高微微 于 2021-06-30 设计创作，主要内容包括：本发明公开了一种具有形状记忆功能的仿墨鱼骨轻质高强材料的制备方法。设计构建仿墨鱼骨结构的三维模型,用具有形状记忆功能的光敏树脂3D打印仿墨鱼骨结构；仿墨鱼骨结构包括层状多孔结构,由上下层板和正弦曲线型波浪板组成；多个正弦曲线型波浪板间隔平行均布在上下层板之间且垂直于上下层板；正弦曲线型波浪板以上下不对称设置。本发明提高了力学性能,在孔隙度高达90％的情况下,仍然能保持高机械稳定性,具有轻质高强的性质；发生塑性形变后仍然可通过加热的方式回复原始形状且力学性能基本不变,达到多次使用的目的。(The invention discloses a preparation method of an inkfish bone-imitated light high-strength material with a shape memory function. Designing and constructing a three-dimensional model of the bionic cuttlefish bone structure, and 3D printing the bionic cuttlefish bone structure by using photosensitive resin with a shape memory function; the cuttlefish bone-imitating structure comprises a layered porous structure and consists of an upper layer plate, a lower layer plate and a sine curve type wave plate; a plurality of sine curve wave plates are uniformly distributed between the upper and lower laminate plates at intervals in parallel and are vertical to the upper and lower laminate plates; the sine curve wave plates are arranged asymmetrically from top to bottom. The invention improves the mechanical property, can still maintain high mechanical stability under the condition that the porosity reaches 90 percent, and has the properties of light weight and high strength; after plastic deformation, the original shape can still be recovered by a heating mode, and the mechanical property is basically unchanged, so that the purpose of multiple use is achieved.)

1. A preparation method of an imitated cuttlefish bone light high-strength material with a shape memory function is characterized by comprising the following steps:

1) preparing photosensitive resin with a shape memory function;

2) designing and constructing a three-dimensional model of the inkfish bone structure;

3) 3D printing the inkfish bone-imitated structure by using photosensitive resin with a shape memory function;

4) and carrying out post-treatment on the printed material.

2. The preparation method of the cuttlefish bone-imitated lightweight high-strength material with the shape memory function according to claim 1, characterized in that:

the prepared photosensitive resin with the shape memory function is obtained according to the following steps:

mixing acrylic acid and bisphenol A ethoxy dimethacrylate (BPA) according to a mass ratio of 30: 70-70: 30, adding a photoinitiator, and magnetically stirring uniformly.

3. The preparation method of the cuttlefish bone-imitated lightweight high-strength material with the shape memory function according to claim 1, characterized in that:

the prepared photosensitive resin with the shape memory function is obtained according to the following steps:

mixing tert-butyl acrylate and aliphatic polyurethane diacrylate according to the mass ratio of 50: 50-95: 5, then adding a photoinitiator, and magnetically stirring uniformly.

4. The preparation method of the cuttlefish bone-imitated lightweight high-strength material with the shape memory function according to claim 1, characterized in that: the prepared photosensitive resin with the shape memory function is obtained according to the following steps:

mixing tert-butyl acrylate and diethylene glycol diacrylate according to the mass ratio of 50: 50-90: 10, then adding a photoinitiator, and magnetically stirring uniformly.

5. The preparation method of the cuttlefish bone-imitated lightweight high-strength material with the shape memory function according to claim 1, characterized in that: the prepared photosensitive resin with the shape memory function is obtained according to the following steps:

mixing hydroxyethyl acrylate, hydroxyethyl methacrylate, 3-sulfopropyl potassium methacrylate and polycaprolactone diacrylate according to the mass ratio of 78:10:2:10, then adding a photoinitiator, and uniformly stirring by magnetic force.

6. The preparation method of the cuttlefish bone-imitated lightweight high-strength material with the shape memory function according to claim 1, characterized in that: the prepared photosensitive resin with the shape memory function is obtained according to the following steps:

mixing hydrophobic lauryl acrylate and 1, 6-hexanediol diacrylate according to a mass ratio of 90: 10-98: 2, adding a photoinitiator, and magnetically stirring uniformly.

7. The preparation method of the cuttlefish bone-imitated lightweight high-strength material with the shape memory function according to claim 1, characterized in that: the mass fraction of the photoinitiator is 0.5-5%.

8. The preparation method of the cuttlefish bone-imitated lightweight high-strength material with the shape memory function according to claim 1, characterized in that: in the step 2), the three-dimensional model of the inkfish-bone-like structure is completed in three-dimensional modeling software, the inkfish-bone-like structure comprises at least one layer of layered porous structure, and each layered porous structure mainly comprises an upper plate, a lower plate and a sine curve type wave plate between the upper plate and the lower plate; the upper layer plate and the lower layer plate are respectively arranged in parallel up and down, a plurality of sine curve wave plates are uniformly distributed between the upper layer plate and the lower layer plate at intervals in parallel, and each sine curve wave plate is arranged perpendicular to the planes of the upper layer plate and the lower layer plate;

sinusoidal wave plate adopt the board that extends along the horizontal direction between upper plate and the lower floor board with sinusoidal wave, sinusoidal wave plate is asymmetric setting from top to bottom, specifically be: the wave section of the upper end of the sine curve wave plate connected with the upper layer plate and the wave section of the lower end of the sine curve wave plate connected with the lower layer plate have the same period but different amplitudes, and the wave section of the upper end of the sine curve wave plate and the wave section of the lower end of the sine curve wave plate are in linear smooth transition.

9. The preparation method of the cuttlefish bone-imitated lightweight high-strength material with the shape memory function according to claim 1, characterized in that: in the step 3), after the photosensitive resin is poured into the resin tank, setting the exposure time to be 0.5-20 s, curing layer by layer, and accumulating until printing is finished;

and 4) after printing is finished, cleaning with ethanol or acetone to remove excessive uncured photosensitive resin, and performing post-curing in an ultraviolet post-curing box.

10. An inkfish bone-imitated light high-strength material with a shape memory function is characterized in that: the preparation method of any one of claims 1 to 9.

Technical Field

The invention relates to a preparation method of a high-performance material, belonging to the fields of bionics and shape memory materials, in particular to a preparation method of an inkfish bone-imitated light high-strength material with a shape memory function.

Background

The shape memory polymer material is a new type of polymer material, and can change shape when being stimulated by the outside. Depending on the type of stimulus, they are generally classified into thermotropic shape memory polymers, electroluminescent shape memory polymers, and photoinduced shape memory polymers. The 3D printing is a new processing mode based on layer-by-layer accumulation to obtain a complex three-dimensional structure model, and has the advantage of accurately constructing a complex structure. The 3D printing technology is used for preparing the shape memory polymer material and is also called 4D printing, namely, the time dimension is increased on the basis of 3D printing, and the shape of the printed material can be changed along with time when the printed material is stimulated by the outside. However, the shape memory polymer material printed by 3D printing at present is often poor in mechanical property and has limitation in application.

The natural cuttlefish bone has the porosity of more than 90 percent, can bear the hydrostatic pressure of hundreds of meters under water, and is a light high-strength natural porous material. The superior mechanical property of the corrugated plate is greatly related to the unique laminated asymmetric corrugated plate hole structure. Aiming at the characteristic that the shape memory polymer material manufactured by 3D printing has poor mechanical property, the invention combines the characteristic of a natural cuttlebone structure, and uses the 3D printing shape memory polymer to obtain the cuttlebone structure imitating material which has excellent mechanical property and shape memory function. The material has great potential in the fields of aerospace and the like.

Disclosure of Invention

In order to solve the problems, the invention provides a design and preparation method of an inkfish bone-imitated light high-strength material with a shape memory function by regulating and controlling a structure and utilizing 3D printing of resin with the shape memory function.

The technical scheme of the invention is as follows:

1) preparing photosensitive resin with a shape memory function;

2) constructing a three-dimensional model of the imitated cuttlefish bone structure through CAD design;

3) 3D printing the inkfish bone-imitated structure by using photosensitive resin with a shape memory function;

4) and carrying out post-treatment on the printed material.

The prepared photosensitive resin with the shape memory function is obtained according to the following steps:

mixing acrylic acid and bisphenol A ethoxy dimethacrylate (BPA) according to a mass ratio of 30: 70-70: 30, adding a photoinitiator, and magnetically stirring uniformly.

The prepared photosensitive resin with the shape memory function is obtained according to the following steps:

mixing tert-butyl acrylate and aliphatic polyurethane diacrylate according to the mass ratio of 50: 50-95: 5, then adding a photoinitiator, and magnetically stirring uniformly.

The prepared photosensitive resin with the shape memory function is obtained according to the following steps:

mixing tert-butyl acrylate and diethylene glycol diacrylate according to the mass ratio of 50: 50-90: 10, then adding a photoinitiator, and magnetically stirring uniformly.

The prepared photosensitive resin with the shape memory function is obtained according to the following steps:

mixing hydroxyethyl acrylate, hydroxyethyl methacrylate, 3-sulfopropyl potassium methacrylate and polycaprolactone diacrylate according to the mass ratio of 78:10:2:10, then adding a photoinitiator, and uniformly stirring by magnetic force.

The prepared photosensitive resin with the shape memory function is obtained according to the following steps:

mixing hydrophobic lauryl acrylate and 1, 6-hexanediol diacrylate according to a mass ratio of 90: 10-98: 2, adding a photoinitiator, and magnetically stirring uniformly.

The photoinitiator comprises benzoin and derivatives, benzil, alkyl benzophenones, acyl phosphorus oxide, benzophenone and thioxanthone. Specifically, the antioxidant is at least one of benzophenone, 2-dimethoxy-2-phenylacetophenone, dibenzoyl peroxide, 2-diethoxyacetophenone, phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, benzophenone, 4-chlorobenzophenone, 4-phenylbenzophenone, 4-methylbenzophenone, 3-methylbenzophenone, 2-methylbenzophenone, isopropylthioxanthone and thiopropoxythioxanthone.

The mass fraction of the photoinitiator is 0.5-5%.

In the step 2), the three-dimensional model of the inkfish-imitated bone structure is completed in three-dimensional modeling software (e.g., CAD three-dimensional modeling software), as shown in fig. 1 and 4, the inkfish-imitated bone structure comprises at least one layer of layered porous structure, and each layered porous structure mainly comprises an upper plate, a lower plate and a sine wave plate between the upper plate and the lower plate; the upper layer plate and the lower layer plate are respectively arranged in parallel up and down, a plurality of sine curve wave plates are uniformly distributed between the upper layer plate and the lower layer plate at intervals in parallel, each sine curve wave plate is arranged perpendicular to the plane of the upper layer plate and the plane of the lower layer plate, and the upper end and the lower end of each sine curve wave plate are respectively connected to the bottom surface of the upper layer plate and the top surface of the lower layer plate;

sinusoidal wave plate adopt the board that extends along the horizontal direction between upper plate and the lower floor board with sinusoidal wave, sinusoidal wave plate is asymmetric setting from top to bottom, specifically be: the wave section of the upper end of the sine curve wave plate connected with the upper layer plate and the wave section of the lower end of the sine curve wave plate connected with the lower layer plate have the same period but different amplitudes, and the wave section of the upper end of the sine curve wave plate and the wave section of the lower end of the sine curve wave plate are in linear smooth transition, so that the uniformly distributed asymmetric twisted wave plates in the vertical direction are formed.

In a specific implementation, the amplitude of the upper end wave section of the sine curve wave plate is larger than that of the lower end wave section of the sine curve wave plate, but the opposite arrangement is also possible.

A one-way channel is formed between adjacent sine curve wave plates, and a hole structure is formed at a channel port of the one-way channel, so that the sine curve wave plates are uniformly distributed between the horizontal upper and lower laminate plates to form a porous structure with the one-way channel.

As shown in fig. 1, fig. 2 and fig. 4, the embodiment further includes a plurality of layered porous structures, which are arranged one above the other; after the plurality of layered porous structures are arranged in an up-and-down stacked manner, in the adjacent two layered porous structures, the upper plate of the next layered porous structure and the lower plate of the previous layered porous structure are the same plate.

The upper layer plate and the lower layer plate are the same in thickness and are 1-5 times of the plate thickness of the sine curve wave plate, the amplitude of the wave section of the lower end of the sine curve wave plate is 2-5 times of the plate thickness of the sine curve wave plate, the lower amplitude of the sine curve wave plate is 1-3 times of the plate thickness of the sine curve wave plate, the height of the sine curve wave plate is 10-100 times of the plate thickness of the sine curve wave plate, the distance between adjacent sine curve wave plates is 5-20 times of the plate thickness of the sine curve wave plate, and the period of the wave section of the sine curve wave plate is 10-30 times of the plate thickness of the sine curve wave plate.

In the step 3), after the photosensitive resin is poured into the resin tank, setting the exposure time to be 0.5-20 s, curing layer by layer, and accumulating until printing is finished; and introducing the slice data into a photocuring 3D printer, pouring the prepared photosensitive resin, projecting the slice data to the bottom of a resin tank by a projector, selectively curing by ultraviolet light, accumulating layer by layer until the manufacturing is finished, cleaning by ethanol after the printing is finished, and performing post-curing in an ultraviolet curing box.

And 4) after printing is finished, cleaning with ethanol or acetone to remove excessive uncured photosensitive resin, and performing post-curing in an ultraviolet post-curing box. The ultraviolet wavelength is 250-420 nm, and the ultraviolet illumination intensity is 5-500 mW/cm²。

The inkfish bone-imitating structure of the invention comprises: the structure design of the imitated cuttlefish bone comprises horizontal parallel laminates, and sine-curve asymmetric wave plates are uniformly distributed among the laminates to form a layered porous structure; 3D printing of the cuttlefish bone-imitated light high-strength material with the shape memory function. The material has excellent mechanical property and shape memory function.

The invention has the beneficial effects that:

(1) the cuttlefish bone-imitated light high-strength material with the shape memory function, which is prepared by the invention, greatly improves the mechanical property because of imitating the structure of a natural cuttlefish bone layered asymmetric wave plate, can still keep high mechanical stability under the condition that the porosity is up to 90 percent, and has the properties of light weight and high strength.

(2) The cuttlefish bone-imitated light high-strength material with the shape memory function, which is prepared by the invention, can still recover the original shape in a heating mode after plastic deformation, and the mechanical property is basically unchanged, so that the aim of repeated use can be fulfilled.

(3) Compared with the traditional shape memory high polymer material with poor mechanical property, the cuttlefish bone-imitated light high-strength material with the shape memory function, which is prepared by the invention, combines the shape memory function and the light high-strength property together, and greatly expands the application scenes of the shape memory high polymer material, such as the fields of aerospace and the like.

(4) The cuttlefish bone-imitated light high-strength material with the shape memory function, which is prepared by the invention, has a complex structure and is difficult to obtain by using a traditional manufacturing mode, and the required precision and quality can be obtained by applying a 4D printing technology.

(5) The cuttlefish bone-imitated light high-strength material with the shape memory function, which is prepared by the invention, can use shape memory polymers of different systems to manufacture corresponding structures, and has universality.

Drawings

FIG. 1 is a schematic wire frame diagram of the structure of the cuttlefish bone-imitated lightweight high-strength material with the shape memory function in example 1;

FIG. 2 is a schematic diagram of a three-dimensional solid structure of the cuttlefish bone-imitated lightweight high-strength material with a shape memory function in example 1;

FIG. 3 is a graph showing the comparison of the first compression and the second compression after the heating recovery of the cuttlefish bone-imitated lightweight high-strength material with the shape memory function in example 1;

FIG. 4 is a schematic diagram of the three-dimensional solid structure of the cuttlefish bone-imitated lightweight high-strength material with shape memory function in example 2;

FIG. 5 is an optical diagram of the heat recovery process of the cuttlefish bone-imitated lightweight high-strength material with shape memory function in example 2.

Detailed Description

The invention is further described with reference to the accompanying drawings and the detailed description.

The examples of the invention are as follows:

example 1

(1) Preparing photosensitive resin: 55g of acrylic monomer, 45g of bisphenol A ethoxydimethacrylate (BPA) and 2g of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (819 photoinitiator) were mixed and stirred magnetically for 24 h.

(2) A three-dimensional model of the structure of the inkfish bone was designed using CAD software, as shown in fig. 1 and 2. The model consists of five layers, wherein the upper layer plate and the lower layer plate of each layer are 50mm long, 31.5mm wide and 0.35mm thick, the height of the interlayer asymmetric wave plate is 8mm, the amplitude of the upper end wave section of the wave plate is 1.2mm, the amplitude of the lower end wave section of the wave plate is 0.6mm, the period of the sine curve wave plate is 4.5mm, the distance between adjacent sine curve wave plates is 6mm, and the thickness of the sine curve wave plate is 0.32 mm. After the design was completed, the model in STL format was derived and slicing was completed using slicing software, with a layer thickness of 50 μm.

(3) Pouring the prepared photosensitive resin into a resin tank, opening an ultraviolet curing 3D printer, introducing the slice data into the machine, setting the exposure time to be 2s, and printing.

(4) After printing, the mold was removed, cleaned with ethanol for 30s, and post-cured in an ultraviolet curing oven for 300 s.

(5) The porosity of the model is 90% through software calculation, the strength of the material when the material is compressed for the first time is 2.0MPa, after the material is compressed and subjected to plastic deformation, the material can completely return to the original shape after being heated at 90 ℃, and then a second compression test is carried out, so that the compression strength reaches 1.94MPa and returns to 97% of the initial strength. The results of the two-time compression are shown in fig. 3, and the result shows that the marmot bone structure-imitating material with shape memory can be heated to recover the shape and the mechanical property basically and completely after being subjected to plastic deformation. In addition, Table 1 summarizes some of the literature for metal foam materialsCompared with the material, the material has the advantages that the density of the inkfish bone-imitated light high-strength material with the shape memory function is very low and is only 0.15 g/cm due to higher porosity³And the specific strength (strength/density) is far higher than that of other metal foams, and the light-weight and high-strength properties of the material are reflected.

TABLE 1

Example 2

(1) Preparing photosensitive resin: 55g of acrylic monomer, 45g of bisphenol A ethoxydimethacrylate (BPA) and 2g of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (819 photoinitiator) were mixed and stirred magnetically for 24 h.

(2) And designing a three-dimensional model imitating the bone structure of the cuttlefish by using CAD software. As shown in fig. 4, the model is composed of three layers, wherein the upper and lower plates of each layer are 53mm long, 47.775mm wide, and 0.4mm thick, the height of the asymmetrical wave plate between the layers is 4.3mm, the amplitude of the upper end wave section of the wave plate is 0.52mm, the amplitude of the lower end wave section of the wave plate is 0.26mm, the period of the sine curve wave plate is 1.95mm, the interval between adjacent sine curve wave plates is 3mm, and the thickness of the sine curve wave plate is 0.3 mm. After the design was completed, the model in STL format was derived and slicing was completed using slicing software, with a layer thickness of 50 μm.

(3) Pouring the prepared photosensitive resin into a resin tank, opening an ultraviolet curing 3D printer, introducing the slice data into the machine, setting the exposure time to be 2s, and printing.

(4) After printing, the mold was removed, cleaned with ethanol for 30s, and post-cured in an ultraviolet curing oven for 300 s.

(5) The strength of the model when being compressed for the first time is 2.23MPa, after being compressed and plastically deformed, the model can be completely recovered to the original shape after being heated at 90 ℃, and the heating recovery process is shown in figure 5. And then, a second compression test is carried out, the compression strength also reaches 2.18MPa, and the initial strength is recovered to 98 percent. The result shows that the marmot bone structure-imitating material with shape memory has basically complete recovery of shape and mechanical property after being heated after plastic deformation.