CN114891165B - Piezoelectric composite photosensitive resin material for three-dimensional photocuring molding printing and preparation method and application thereof - Google Patents

Abstract

The invention discloses a piezoelectric composite photosensitive resin material for stereolithography printing and its preparation method and application. The inorganic piezoelectric filler is chemically modified on the surface to realize its combination between ethylene glycol diacrylate and acrylic acid. Isobornyl ester is uniformly dispersed in a photosensitive resin solvent, and a functional piezoelectric composite photosensitive resin material that can be used for SLA 3D printing is obtained. Inorganic piezoelectric powder is uniformly dispersed in the composite resin as an active material with piezoelectric properties. The composite piezoelectric material after photocuring printing has good flexibility and impact resistance, and has excellent piezoelectric output performance. The piezoelectric parts printed and prepared by this method can be used as energy harvesters, sensors, drivers, etc. in the field of artificial intelligence.

Description

A piezoelectric composite photosensitive resin material for stereolithography printing and its preparation method and application

technical field

The invention belongs to the technical field of 3D printing, and in particular relates to a piezoelectric composite photosensitive resin material for stereolithography printing and its preparation method and application.

Background technique

3D printing technology is different from the traditional "equal material manufacturing" and "subtractive manufacturing" processing methods, and is an "additive manufacturing" technology. The core idea of 3D printing technology is to transform the complex three-dimensional structure model into a combination of simple two-dimensional cross-sections, so it can be realized through digital design of computer software (CAD, 3DMax) without using molds and machine tools. Compared with traditional processing technology, 3D printing technology has the characteristics of fast product forming speed, short production cycle and simple processing technology. 3D printing technology has developed to the present, and many types have been developed, but they can be roughly divided into three categories according to their molding characteristics, namely, laser sintering technology, represented by selective laser sintering (SLS); fusion deposition molding technology, based on molten layer Integrative molding (FDM) is the representative; stereolithography molding technology is represented by stereolithography (SLA).

Stereo-curing 3D printing technology is an earlier developed 3D printing technology. It is based on the principle of photopolymerization and uses photosensitive liquid resin as the printing material. Resin can be cured under light conditions, while the unirradiated parts remain liquid. Therefore, the printed 3D model can be easily and quickly extracted from the resin. The model printed by light curing technology has the characteristics of high precision and rapid prototyping.

For piezoelectric energy harvesting devices, inorganic piezoelectric materials are mostly hard and brittle materials, and the intrinsic brittleness of inorganic materials limits their applications. The flexibility of devices needs to be realized by modifying materials and designing structures. The current method to solve the problem of device flexibility is to attach low-dimensional inorganic piezoelectric materials to flexible substrates, and uniformly disperse inorganic piezoelectric materials as fillers in organic polymer matrices to construct flexible composite piezoelectric materials. Therefore, the construction and preparation of flexible composite piezoelectric materials will become a cutting-edge trend, which combines the high-voltage characteristics of inorganic materials and the advantages of flexibility of polymer materials, improves the comprehensive mechanical properties and electrical output performance of materials, and broadens the scope of piezoelectric materials and devices. range of use and application areas. Inorganic piezoelectric ceramics and semiconductor materials have the characteristics of high piezoelectric coefficient, high dielectric coefficient, etc., and the composite piezoelectric material made of piezoelectric active phase uniformly dispersed in flexible polymer can effectively guarantee the stability of piezoelectric energy harvesting devices. Flexible and high voltage electrical output characteristics.

Contents of the invention

The purpose of the present invention is to provide a piezoelectric composite photosensitive resin material for stereolithography printing and its preparation method and application, which has the advantages of simple process, flexible design of printing structure, flexibility, toughness, and high piezoelectric conversion efficiency. , which can meet its application requirements in many functional devices.

In order to achieve the above object, the present invention provides a piezoelectric composite photosensitive resin material for stereolithography printing, comprising the following components: a monomer solvent, a functional inorganic piezoelectric filler and a photoinitiator, and the monomer solvent includes a mass ratio of 1:1-9:2 isobornyl acrylate and polyethylene glycol diacrylate, the mass fraction of the functional inorganic piezoelectric filler accounts for 1-15% of the piezoelectric composite photosensitive resin material; the mass fraction of the photoinitiator accounts for 1-3% of the piezoelectric composite photosensitive resin material.

Preferably, the functional inorganic piezoelectric filler is a modified material, and the modification process of the functional inorganic piezoelectric filler includes the following steps:

After oxidizing the inorganic piezoelectric filler, hydroxylated inorganic piezoelectric powder is prepared, and after reacting with the mixed solution, the surface-modified inorganic piezoelectric powder that can be dispersed in the photosensitive resin is obtained, which is the functional inorganic piezoelectric filler.

Preferably, the mixed solution is a mixed solution of 3-(methacryloyloxy)propyl trimethoxy silicon and absolute ethanol, and the hydroxylated inorganic piezoelectric powder is mixed with 3-(methacryloyl oxygen) propyl trimethoxy silicon and anhydrous The mass ratio of ethanol is 1:1.25:60-1:1.8:80.

Preferably, the inorganic piezoelectric filler is piezoelectric ceramic or piezoelectric semiconductor powder particles with piezoelectric effect, and the inorganic piezoelectric filler includes barium titanate, lead titanate, lead zirconate titanate, lead magnesium niobate, zinc oxide, tellurium At least one of cadmium chloride and cadmium selenide.

Preferably, the oxidation process specifically includes the following steps: mix the inorganic piezoelectric filler and hydrogen peroxide according to a mass ratio of 1:30-50, stir and disperse for 1-2 hours, and then thermally react at 50-80°C for 60-100 minutes to obtain The mixed liquid is naturally cooled to room temperature, filtered, washed and dried in sequence to obtain the hydroxylated inorganic piezoelectric powder.

Preferably, the photoinitiator is photoinitiator 184, photoinitiator TPO, photoinitiator 127, photoinitiator 500, photoinitiator 754, photoinitiator MBF or photoinitiator ITX.

Preferably, the light intensity of the piezoelectric composite photosensitive resin material during 3D printing is 150-250 mW/dm ² .

The invention also discloses a method for preparing a piezoelectric composite photosensitive resin material for stereolithography printing, which includes the following steps: co-dissolving functional inorganic piezoelectric fillers and photoinitiators in a monomer solvent, ultrasonically dispersing 4 -6h, prepared.

The invention also discloses the application of a piezoelectric composite photosensitive resin material, which is used as a piezoelectric energy harvesting device after the piezoelectric composite photosensitive resin material is photocured and molded.

In summary, the present invention has the following advantages:

1. The surface-treated inorganic piezoelectric powder is conducive to its uniform dispersion in the photosensitive resin liquid solvent, and at the same time enhances the interaction between the inorganic particles and the polymer matrix, and enhances the printability of the piezoelectric composite photosensitive resin material.

2. The photosensitive resin monomer polyethylene glycol diacrylate (PEGDA) and isobornyl acrylate (IBA) are polymerized to realize photocuring and polymerization. The composite material has excellent flexibility and enhances the mechanical properties of the material.

Description of drawings

In order to illustrate the technical solutions of the embodiments of the present invention more clearly, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention, and thus It should be regarded as a limitation on the scope, and those skilled in the art can also obtain other related drawings based on these drawings without creative work.

Fig. 1 is the X-ray diffraction spectrum (XRD) of inorganic piezoelectric ceramic material barium titanate (BTO) powder;

Fig. 2 is the scanning electron microscope (SEM) figure of inorganic piezoelectric ceramic material barium titanate (BTO) powder;

Fig. 3 is the flexibility of the piezoelectric composite material of the piezoelectric composite photosensitive resin material system with inorganic piezoelectric ceramic barium titanate (BTO) as the filler of SLA printing;

Figure 4 is a structural drawing of a piezoelectric composite photosensitive resin material system printed by SLA with inorganic piezoelectric ceramic barium titanate (BTO) as a filler;

Fig. 5 is a graph of the open-circuit voltage of piezoelectric composite materials printed by SLA and filled with inorganic piezoelectric ceramic barium titanate (BTO) as a piezoelectric energy harvesting device.

Detailed ways

The principles and features of the present invention are described below in conjunction with the examples, which are only used to explain the present invention, and are not intended to limit the scope of the present invention. Those who do not indicate the specific conditions in the examples are carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments used were not indicated by the manufacturer, and they were all conventional products that could be purchased from the market.

Example 1

This embodiment provides a method for preparing a piezoelectric composite photosensitive resin material for stereolithography printing, including the following steps:

(1) Mix BTO powder and hydrogen peroxide at a mass ratio of 1:40, then stir and disperse with a magnetic stirrer for 2 hours, then transfer the dispersed mixed liquid to a reaction kettle, and react at 60°C for 60 minutes to obtain Mix the liquid, cool the mixed liquid naturally to room temperature, then filter, wash and dry in sequence to obtain hydroxylated BTO powder;

(2) The hydroxylated BTO powder is added to 3-(methacryloyloxy)propyltrimethoxysilane (TMSPM) and absolute ethanol mixed solution, wherein the mass ratio of hydroxylated BTO, TMSPM and absolute ethanol is 1: 1.25:60, and ultrasonically disperse for 10 hours to obtain surface-modified f-BTO powder that can be dispersed in photosensitive resin.

(3) Add surface-modified f-BTO powder and photoinitiator (TPO) to polyethylene glycol diacrylate (PEGDA) and isobornyl acrylate (IBA) mixed solvent, wherein the mass ratio of PEGDA to IBA 5:4, f-BTO accounts for 10% of the total mass of the piezoelectric composite photosensitive resin material, photoinitiator (TPO) accounts for 1% of the total mass of the piezoelectric composite photosensitive resin material, and the mixed resin is ultrasonically dispersed for 6h to obtain a Piezoelectric composite photosensitive resin material with barium titanate as inorganic piezoelectric filler for SLA3D printing.

(4) SLA 3D printing is used to prepare the piezoelectric composite photosensitive resin material with BTO as the inorganic piezoelectric filler, and the light intensity in 3D printing is 180mW/dm ² .

The structural parts of the composite piezoelectric material with BTO as the inorganic piezoelectric filler can be used as piezoelectric energy harvesting devices.

It can be seen from Figure 1 that the barium titanate used as the inorganic piezoelectric filler is tetragonal barium titanate with piezoelectric effect; it can be seen from Figure 2 that the barium titanate powder used as the inorganic piezoelectric filler has a micron flower-like structure ; It can be seen from Figure 3 that the piezoelectric composite material printed by SLA 3D has good flexibility.

Test example 1

(1) Use the barium titanate (BTO) obtained in Example 1 as the piezoelectric composite photosensitive resin material suitable for stereolithography (SLA) printing as an inorganic piezoelectric filler, and use SLA 3D printing to construct a piezoelectric composite with a three-dimensional structure. Parts, the light intensity in printing and molding is 180mW/dm ² , and the designed three-dimensional customized structure is shown in Figure 4.

(2) Use a universal compressor and Labview system to conduct piezoelectric tests on the printed three-dimensional piezoelectric parts, paste electrodes on the upper and lower sides of the parts, and press the compressor to shock them, and perform a cyclic pressure test at 10N Under this condition, a stable voltage output signal is obtained, and its curve is shown in Figure 5. It can be seen from Fig. 5 that the piezoelectric composite material can obtain a stable output voltage of 4V under the pressure of 10N.

Example 2

This embodiment provides a method for preparing a piezoelectric composite photosensitive resin material for stereolithography printing, including the following steps:

(1) Mix BTO powder and hydrogen peroxide at a mass ratio of 1:50, then stir and disperse with a magnetic stirrer for 1 hour, then transfer the dispersed mixed liquid to a reaction kettle, and react at 60°C for 70 minutes to obtain Mix the liquid, cool the mixed liquid naturally to room temperature, then filter, wash and dry in sequence to obtain hydroxylated BTO powder;

(2) Add hydroxylated BTO powder to the mixed solution of TMSPM and absolute ethanol, wherein the mass ratio of hydroxylated BTO, TMSPM and absolute ethanol is 1:1.5:70, and ultrasonically disperse for 10 hours to obtain Surface modified f-BTO powder in photosensitive resin.

(3) Add the surface-modified f-BTO powder and photoinitiator (184) into the mixed solvent of PEGDA and isobornyl acrylate, wherein the mass ratio of PEGDA to IBA is 5:4, and f-BTO accounts for the piezoelectric 1% of the total mass of the composite photosensitive resin material, photoinitiator 184 accounted for 1% of the total mass of the piezoelectric composite photosensitive resin material, and ultrasonically dispersed for 5 hours to obtain a barium titanate inorganic piezoelectric filler that can be used for SLA 3D printing Piezoelectric composite photosensitive resin material.

(4) SLA 3D printing is used to prepare the piezoelectric composite photosensitive resin material with BTO as the inorganic piezoelectric filler, and the light intensity in 3D printing is 150mW/dm ² .

Using the method provided in Test Example 1 and using the barium titanate matrix composite material in Example 2 as the raw material, the highest output voltage of the custom-made three-dimensional piezoelectric part obtained under the action of 10N cyclic pressure was 1.4V.

Example 3

This embodiment provides a method for preparing a piezoelectric composite photosensitive resin material for stereolithography printing, including the following steps:

(1) Mix BTO powder and hydrogen peroxide at a mass ratio of 1:40, then stir and disperse with a magnetic stirrer for 2 hours, then transfer the dispersed mixed liquid to a reaction kettle, and react at 70°C for 100 minutes to obtain Mix the liquid, cool the mixed liquid naturally to room temperature, then filter, wash and dry in sequence to obtain hydroxylated BTO powder;

(2) Add the hydroxylated BTO powder to the mixed solution of quantitative 3-(methacryloyloxy)propyltrimethoxysilane and absolute ethanol, wherein the mass ratio of hydroxylated BTO, TMSPM and absolute ethanol is 1:1.8 :80, and ultrasonic dispersion reaction 8h, obtain the f-BTO powder that can be used for the surface modification of being dispersed in the photosensitive resin.

(3) The surface-modified f-BTO powder and photoinitiator (127) are added in polyethylene glycol diacrylate and isobornyl acrylate (IBA) mixed solvent, wherein the mass ratio of PEGDA and IBA is 5: 4. f-BTO accounts for 15% of the total mass of the piezoelectric composite photosensitive resin material, the photoinitiator (127) accounts for 1.5% of the total mass of the piezoelectric composite photosensitive resin material, and the mixed resin is ultrasonically dispersed for 5 hours to obtain a 3D printed piezoelectric composite photosensitive resin material with barium titanate as inorganic piezoelectric filler.

(4) SLA 3D printing is used to prepare the piezoelectric composite photosensitive resin material with BTO as the inorganic piezoelectric filler, and the light intensity in 3D printing is 250mW/dm ² .

Using the method provided in Test Example 1 and using the barium titanate matrix composite material in Example 3 as the raw material, the highest output voltage of the custom-made three-dimensional piezoelectric part obtained under a cyclic pressure of 10N was 3.4V.

Example 4

This embodiment provides a preparation method and application of a piezoelectric composite photosensitive resin material suitable for stereolithography (SLA) printing using barium titanate (BTO) as an inorganic piezoelectric filler, including the following steps:

(1) Mix BTO powder and hydrogen peroxide at a mass ratio of 1:50, then stir and disperse with a magnetic stirrer for 2 hours, then transfer the dispersed mixed liquid to a reaction kettle, and react at 60°C for 70 minutes to obtain Mix the liquid, cool the mixed liquid naturally to room temperature, then filter, wash and dry in sequence to obtain hydroxylated BTO powder;

(2) Add the hydroxylated BTO powder to the mixed solution of quantitative 3-(methacryloyloxy)propyltrimethoxysilane and absolute ethanol, wherein the mass ratio of hydroxylated BTO, TMSPM and absolute ethanol is 1:1.6 :80, and ultrasonic dispersion reaction 10h, obtains the f-BTO powder that can be used for the surface modification of being dispersed in the photosensitive resin.

(3) Add surface-modified f-BTO powder and photoinitiator (754) to polyethylene glycol diacrylate (PEGDA) and isobornyl acrylate (IBA) mixed solvent, wherein the mass ratio of PEGDA to IBA 5:4, f-BTO accounts for 10% of the total mass of the piezoelectric composite photosensitive resin material, photoinitiator (754) accounts for 1.5% of the total mass of the piezoelectric composite photosensitive resin material, and the mixed resin is ultrasonically dispersed for 6h to obtain a Piezoelectric composite photosensitive resin material with barium titanate as inorganic piezoelectric filler for SLA 3D printing.

(4) SLA 3D printing is used to prepare the piezoelectric composite photosensitive resin material with BTO as the inorganic piezoelectric filler, and the light intensity in 3D printing is 220mW/dm ² .

Using the method provided in Test Example 1 and using the barium titanate matrix composite material in Example 4 as the raw material, the custom-made three-dimensional piezoelectric part obtained under a cyclic pressure of 10 N obtained a stable output voltage of 2.9V.

Although the specific implementation of the present invention has been described in detail, it should not be construed as limiting the protection scope of this patent. Within the scope described in the claims, various modifications and deformations that can be made by those skilled in the art without creative work still belong to the protection scope of this patent.

Claims (6)

1. The piezoelectric composite photosensitive resin material for three-dimensional photocuring molding printing is characterized by comprising the following components: the piezoelectric composite photosensitive resin material comprises a monomer solvent, a functional inorganic piezoelectric filler and a photoinitiator, wherein the monomer solvent comprises isobornyl acrylate and polyethylene glycol diacrylate in a mass ratio of 1; the mass fraction of the photoinitiator accounts for 1 to 3 percent of the piezoelectric composite photosensitive resin material;

the functional inorganic piezoelectric filler is a modified material, and the modification process of the functional inorganic piezoelectric filler comprises the following steps:

oxidizing the inorganic piezoelectric filler to obtain hydroxylated inorganic piezoelectric powder, and reacting the hydroxylated inorganic piezoelectric powder with the mixed solution to obtain surface-modified inorganic piezoelectric powder which is dispersed in photosensitive resin and is the functional inorganic piezoelectric filler;

wherein the mixed solution is a mixed solution of 3- (methacryloyloxy) propyl trimethoxy silicon and absolute ethyl alcohol, and the mass ratio of the hydroxylated inorganic piezoelectric powder to the 3- (methacryloyloxy) propyl trimethoxy silicon and the absolute ethyl alcohol is 1.25;

wherein the oxidation process specifically comprises the steps of: mixing the inorganic piezoelectric filler with hydrogen peroxide according to the mass ratio of 1-50, stirring and dispersing for 1-2h, then carrying out thermal reaction for 60-100min at 50-80 ℃ to obtain a mixed liquid, naturally cooling to room temperature, and then sequentially filtering, washing and drying to obtain the hydroxylated inorganic piezoelectric powder.

2. The piezoelectric composite photosensitive resin material for stereolithographic printing according to claim 1, wherein said inorganic piezoelectric filler is a piezoelectric ceramic or a piezoelectric semiconductor powder particle having a piezoelectric effect, and said inorganic piezoelectric filler comprises at least one of barium titanate, lead zirconate titanate, lead magnesium niobate, zinc oxide, cadmium telluride, and cadmium selenide.

3. The piezoelectric composite photosensitive resin material for stereolithographic printing as claimed in claim 1, wherein said photoinitiator is photoinitiator 184, photoinitiator TPO, photoinitiator 127, photoinitiator 500, photoinitiator 754, photoinitiator MBF or photoinitiator ITX.

4. The piezoelectric composite photosensitive resin material for stereolithography printing according to claim 1, wherein the light intensity of said piezoelectric composite photosensitive resin material in 3D printing lithography is 150 to 250mW/dm ² 。

5. The method for preparing the piezoelectric composite photosensitive resin material for stereolithographic printing as claimed in any one of claims 1 to 4, comprising the steps of:

and co-dissolving the functional inorganic piezoelectric filler and a photoinitiator in a monomer solvent, and performing ultrasonic dispersion for 4-6h to obtain the material.

6. The use of the piezoelectric composite photosensitive resin material for stereolithographic printing as claimed in any one of claims 1 to 4, wherein the piezoelectric composite photosensitive resin material is used as a piezoelectric energy harvesting device after being photocured and patterned.

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