CN111763086A - Piezoelectric ceramic composite material slurry system, preparation method and 3D printing method - Google Patents
Piezoelectric ceramic composite material slurry system, preparation method and 3D printing method Download PDFInfo
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Abstract
The invention discloses a photocurable 0-3 type PZT/resin-based piezoelectric composite material slurry system and a preparation method thereof, and a method for quickly printing a strong 0-3 type PZT/resin-based piezoelectric composite material in high-precision 3D, the photosensitive piezoelectric ceramic resin slurry is prepared by mixing piezoelectric ceramic particles, oligomer, monomer, photoinitiator, light absorbent, conductive phase and other additives and adjusting the material ratio, the particles are aligned in a polymer matrix based on the electrophoresis principle to achieve the strong 0-3 compounding, and then the rapid high-precision printing and molding of the piezoelectric ceramic composite material are realized by adopting the continuous rapid surface exposure printing technology, and then, the strong 0-3 type piezoelectric composite material with high precision, low cost and high piezoelectric constant is formed by post-treatment processes such as polarization and the like.
Description
Technical Field
The invention belongs to the technical field of 3D printing, and relates to a photocuring molded 0-3 type PZT/resin-based piezoelectric composite material slurry system, a preparation method thereof and a 3D printing method of a strong 0-3 type PZT/resin-based piezoelectric composite material.
Background
The existing widely used polycrystalline piezoelectric ceramics have the defects of difficult impedance matching with air, water and other media, large brittleness, high density, poor impact resistance, complex forming process and the like, and although the high-molecular piezoelectric material has good flexibility and easy processing, the problems of small piezoelectric coefficient and electromechanical coupling coefficient, limited use temperature, material aging and the like exist. The piezoelectric composite material is formed by compounding a polymer matrix with high viscoelasticity and piezoelectric ceramics according to a certain connection mode. The piezoelectric composite material has the advantages of both piezoelectric ceramics and piezoelectric polymers: high piezoelectric coefficient, good toughness and ductility, convenient molding, low density, easy matching of acoustic impedance and wide application environment. At present, the piezoelectric composite material is widely applied to sensors, transducers and acoustic imaging equipment.
The 0-3 type piezoelectric composite material is formed by dispersing discontinuous ceramic particles in a three-dimensionally communicated polymer matrix, is the simplest piezoelectric composite material, has the advantages of strong adaptability, no influence of hydrostatic pressure and the like, but has the problems of relatively low piezoelectric strain constant, difficult polarization and the like compared with other communicated forms in the 0-3 type piezoelectric composite material.
The existing 0-3 type piezoelectric composite material forming methods such as cold/hot pressing method forming, solution blending forming and the like can only process simple structures or can only prepare complex structures by means of specific molds, and cannot meet the increasing market demands, so that a novel forming technology, namely a 3D printing technology, needs to be developed.
Researches find that the composite material formed by directly mixing lead zirconate titanate (PZT) piezoelectric ceramic particles and a photosensitive resin matrix in proportion belongs to a 0-3 type piezoelectric composite material in a communication classification mode, the material can be manufactured and processed by a 3D printing process while the material characteristics of the PZT piezoelectric ceramic and the photosensitive resin are maintained, and the composite material has the advantages of simple forming process, large-area forming, meeting the complexity and precision requirements which are not met by the traditional manufacturing mode and the like. Meanwhile, the 3D printing process for forming the 0-3 type piezoelectric composite material can easily solve the problems of relatively low piezoelectric constant, difficult polarization and the like of the 0-3 type piezoelectric composite material in the process flow. Therefore, the 0-3 type PZT/photosensitive resin based piezoelectric composite material has wide application prospect in the application field of piezoelectric materials according to the material characteristics.
Disclosure of Invention
Aiming at the problem that the existing technologies such as solution blending molding, cold/hot pressing molding and the like can not rapidly process a 0-3 type piezoelectric composite material with high precision, low cost and high piezoelectric constant and complex structure, the invention aims to provide a photocurable 0-3 type PZT/resin-based piezoelectric composite material slurry system, a preparation method thereof and a method for rapidly printing a strong 0-3 type PZT/resin-based piezoelectric composite material by high precision 3D. The device with the high-precision complex structure is quickly formed on the basis of the oxygen inhibition principle, the working efficiency is greatly improved, the production cost is reduced, the conductive performance of the formed composite material is enhanced through the addition of the conductive phase of the slurry system, and the polarization difficulty is reduced.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for 3D printing of a strong 0-3 type piezoelectric composite material comprises the following steps:
s1: establishing a three-dimensional model corresponding to a three-dimensional structure to be manufactured;
s2: slicing a three-dimensional model of a three-dimensional structure to be manufactured to obtain a series of two-dimensional section slices;
s3: preparing printing slurry for manufacturing a three-dimensional structure to be manufactured;
s4: placing the prepared printing slurry into a resin tank of a photocuring printer, applying a sinusoidal alternating current electric field on the side wall of the resin tank to polarize the powder in the slurry, and carrying out orientation arrangement in a resin matrix to achieve 0-3 composite strength;
s5: irradiating by adopting a curing light source, projecting a mask image of a two-dimensional section slice of a three-dimensional structure to be manufactured to the surface of the printing paste, and curing and forming to obtain a blank;
s6: and drying, plating an electrode and carrying out polarization treatment on the obtained blank to obtain the three-dimensional structure to be manufactured.
Further, the printing paste in step S3 includes solid particles, monomers, oligomers, photoinitiators, light absorbers, surface modifiers, dispersants, conductive phases, and defoaming agents, and filling the conductive phases in the matrix of the 0-3 type piezoelectric composite material can polarize the piezoelectric phases in the material more sufficiently when the piezoelectric phase is polarized in step S6.
Further, the diameter of the solid particles was 100-500 nm.
Further, the method of preparing the printing paste in the step S3 includes steps S31-S34:
s31: selecting commercial PZT-5H powder particles, crushing the powder particles to be 100-500nm through ball milling, and drying;
s32: carrying out surface modification on the dry-ground PZT-5H powder particles by adopting a silane coupling agent;
s33: mixing a photoinitiator, acrylic resin, a monomer, a light absorbent and a defoaming agent, and ultrasonically stirring to form a premixed solution;
s34: stirring and mixing the modified PZT-5H powder, the premixed liquid, the conductive phase and the dispersing agent, adding the mixture into a ball mill for wet grinding, and vacuumizing the mixture after uniform mixing to obtain the printing slurry.
Further, the photoinitiator includes, but is not limited to, 1-hydroxycyclohexyl phenyl ketone (184), phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (819), 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide (TPO), and the like, which are commonly used initiators;
monomers include, but are not limited to, acrylic acid, 1, 6-hexanediol diacrylate (HDDA), triethylene glycol diacrylate (TEGDA), tripropylene glycol diacrylate (TPGDA), cyclohexyl methacrylate, ethoxylated trimethylolpropane triacrylate (EM2380), and the like;
conductive phases include, but are not limited to, conductive carbon black, conductive carbon nanotubes, conductive polymers, and the like;
dispersants include, but are not limited to, sodium polyacrylate, ammonium polyacrylate, sodium stearate, and the like;
light absorbers include, but are not limited to, 2- (2-hydroxy-3, 5-dibutylphenyl) -5-chlorobenzotriazole, 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole, and the like;
defoamers include, but are not limited to, silicone defoamers and the like.
Furthermore, the mass fractions of the photoinitiator, the acrylic resin, the monomer, the light absorber and the defoaming agent in the premix liquid are respectively 1-5%, 30-40%, 54.75-64.75%, 0.1-0.2% and 0.01-0.05%; the mass fractions of the modified PZT-5H powder, the premixed liquid, the conductive phase and the dispersant in the printing slurry are respectively 55-70%, 28.8-43.8%, 0.3-0.6% and 0.3-0.6%.
Further, the sinusoidal AC electric field in step S4 is 500-.
Further, the time for applying the sinusoidal AC electric field to the side wall of the resin tank in step S4 is 40-60 min.
Further, the step S5 further includes steps S51-S53:
s51: starting a curing light source, projecting a mask image of a two-dimensional section slice of a three-dimensional structure to be manufactured to the surface of the printing paste, curing and forming a single layer of the printing paste in the irradiation range of the mask image, and closing the curing light source after the single layer is cured and formed;
s52: moving the forming platform, switching the projection image to the next layer, starting a curing light source, projecting the mask image of the two-dimensional section of the next layer to the surface of the printing paste formed by single-layer curing, and curing the surface of the printing paste;
s53: and repeating the step S52 until the three-dimensional structure to be manufactured is formed in an accumulated mode, and obtaining a biscuit of the three-dimensional structure to be manufactured.
Further, the polarization DC voltage in step S6 is 3000-.
The invention has the beneficial effects that: compared with the prior art, the invention discloses a photo-curable 0-3 type PZT/resin-based piezoelectric composite material slurry system, a preparation method thereof and a method for quickly printing a strong 0-3 type piezoelectric composite material by high precision 3 D.A micro-stereolithography technology is adopted, and the electrophoresis principle is utilized to realize the orientation arrangement of powder in the slurry, thereby achieving the strong 0-3 type composition between the piezoelectric ceramic powder and the resin matrix, realizing the covalent bonding between the piezoelectric ceramic particles and the resin matrix through particle modification, enhancing the connection strength between two phases and improving the integral piezoelectric performance of the formed part; and the rapid printing and forming are realized based on the oxygen inhibition effect, the step effect in 3D printing is inhibited, the high-precision requirement of rapidly manufacturing devices with complex structures is realized, and the working efficiency is greatly improved.
Drawings
FIG. 1 is a schematic representation of the steps of a ceramic 3D printing method of an embodiment of the present invention;
FIG. 2 is a schematic flow chart of a process for preparing a printing paste for ceramic 3D printing according to an embodiment of the present invention;
FIG. 3 is a schematic structural diagram of a ceramic 3D printer according to an embodiment of the present invention;
FIG. 4 is a partial schematic view of a resin tank of a ceramic 3D printer according to an embodiment of the invention;
FIG. 5 is a schematic representation of the strong bond of the modified PZT to the resin matrix of an embodiment of the present invention;
FIG. 6 is a schematic diagram of an embodiment of the present invention in which an applied electric field is used to prepare a strong 0-3 type piezoelectric composite;
FIG. 7 is a graphical representation of strong type 0-3 recombination versus type 0-3, type 1-3 piezoelectric constants for an embodiment of the present invention;
fig. 8 is a comparison view of the micro electron microscope of the surface of the rapid continuous print based on the oxygen inhibition effect and the general micro-stereolithography print according to the embodiment of the present invention, wherein (a) is a micro electron microscope of the surface of the general micro-stereolithography print, and (b) is a micro electron microscope of the rapid continuous print using the oxygen inhibition effect.
Description of reference numerals:
1. side supporting plates, 2. a forming platform, 3. a resin tank, 31, 32. an external electric field electrode, 4. a micro-mirror array, 5. a feeding device, 6. a resin tank bracket, 7. a base and 8. a curing light source; 9. the forming chamber comprises a forming chamber frame, 10 printing slurry, 11 supporting plates, 12 polymerization inhibition areas, 13 newly cured layers, 14 polymerization inhibition gas and 15 printing area air-permeable groove bottoms.
Detailed Description
For a better understanding of the present invention, the following examples are given in order to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
A method of making an underwater acoustic transducer, as shown in fig. 1-2, the process comprising the steps of:
s1: establishing a three-dimensional model corresponding to the three-dimensional structure of the underwater acoustic transducer;
s2: slicing the three-dimensional model of the underwater acoustic transducer to obtain a series of two-dimensional section slices;
s3: preparing printing slurry for manufacturing the underwater acoustic transducer:
s31: ball-milling commercial PZT-5H powder particles at 350rpm for 3H, crushing the powder particles to 100-500nm and drying at 80 ℃ for 12H;
s32: carrying out surface modification on dry-ground PZT-5H powder particles by adopting a silane coupling agent: preparing a mixed solution by using 2 parts by mass of water and 38 parts by mass of ethanol; adjusting the ph of the mixed solution to 3-4 by using acetic acid, adding 5 parts by mass of PZT powder and 1 part by mass of trimethoxy silane propyl acrylate, refluxing, stirring and heating for 3 hours at 78 ℃, performing centrifugal separation, washing for 3 times by using deionized water, and drying for 12 hours at 100 ℃;
s33: mixing phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (819), polyurethane acrylate, 1, 6-hexanediol diacrylate (HDDA), 2- (2-hydroxy-3, 5-dibutyl-tert-butylphenyl) -5-chlorobenzotriazole and an organic silicon defoaming agent, and ultrasonically stirring for 30min to form a premixed solution, wherein the mass fractions of the phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (819), the polyurethane acrylate, the 1, 6-hexanediol diacrylate (HDDA), the 2- (2-hydroxy-3, 5-dibutyl-tert-butylphenyl) -5-chlorobenzotriazole and the organic silicon defoaming agent are 5%, 30%, 64.75%, 0.2% and 0.05%, respectively;
s34: stirring and mixing the modified PZT-5H powder, the premixed liquid, the conductive carbon black and the ammonium polyacrylate, adding the mixture into a ball mill, wet-milling the mixture for 3 hours at 350rpm, uniformly mixing the mixture, and vacuumizing the mixture for 10 minutes at room temperature to obtain printing slurry, wherein the mass fractions of the modified PZT-5H powder, the premixed liquid, the conductive carbon black and the ammonium polyacrylate are 70%, 28.8%, 0.6% and 0.6% respectively;
s4: placing the prepared printing slurry into a resin tank of a photocuring printer, and applying a sinusoidal alternating current electric field (500v/mm, 4kHz) on the side wall of the resin tank for 60min to polarize the powder in the slurry, and carrying out orientation arrangement in the resin matrix to achieve strong 0-3 compounding;
s5: the resin tank is provided with a printing area breathable tank bottom, gas is prevented from being in gas-liquid contact with printing slurry, a 405nm ultraviolet curing light source is adopted for irradiation, the curing light source projects a mask image of a two-dimensional section slice of an underwater acoustic transducer to the surface of the printing slurry through a micro-mirror array, curing molding is carried out, a blank is obtained, a feeding device continuously forms a piezoelectric ceramic composite material curing piece at the speed of 0.8-1 s/layer, and the method comprises the following specific steps:
s51: starting a curing light source, projecting a mask image of the two-dimensional section slice of the underwater acoustic transducer to the surface of the printing paste, curing and molding a single layer of the printing paste in the irradiation range of the mask image, and closing the curing light source after the single layer is cured and molded;
s52: moving the forming platform, switching the projection image to the next layer, starting a curing light source, projecting the mask image of the two-dimensional section of the next layer to the surface of the printing paste formed by single-layer curing, and curing the surface of the printing paste;
s53: repeating the step S52 until the underwater acoustic transducer is cumulatively molded to obtain a biscuit of the underwater acoustic transducer;
s6: and washing the obtained blank by using deionized water, drying the blank in a forced air drying oven at 50 ℃ for 2h, plating an electrode, and carrying out polarization treatment (the polarization direct current voltage is 4000V/mm, the polarization time is 60min, and the polarization temperature is 90 ℃) to obtain the strong 0-3 type PZT/resin-based piezoelectric composite material underwater acoustic transducer.
The photosensitive piezoelectric ceramic resin paste (printing paste) prepared by the embodiment can be used for preparing a piezoelectric ceramic composite material with a high-performance unconventional structure and realizing near-net-size forming. As shown in figure 5, covalent bonding of piezoelectric ceramic particles and a resin matrix is realized by adopting a micro-stereolithography technology and using a particle modification process, as shown in figures 6-7, the particles are oriented and arranged in the polymer matrix based on the electrophoresis principle to achieve strong 0-3 compounding, and the formed strong 0-3 type composite structure greatly enhances the piezoelectric performance of a formed part. The conductive performance of the formed composite material is enhanced by adding the conductive phase of the slurry system, the polarization difficulty is reduced, and the polarization is simpler and more sufficient. As shown in fig. 8, (a) is a microscopic electron microscope image of the surface of a general micro-stereolithography print, and (b) is a microscopic electron microscope image of a rapid and continuous print using the oxygen inhibition effect, and a comparison of the two shows that the surface roughness of a device printed by the invention is greatly improved, the step effect is effectively inhibited, and the precision of a formed part is greatly improved.
The ceramic 3D printer used in the embodiment of the present invention, as shown in fig. 3-4, includes a side supporting plate 1, a forming platform 2, a resin tank 3, an external electric field electrode 31(32), a micromirror array 4, a feeding device 5, a resin tank bracket 6, a base 7, a curing light source 8, and a supporting plate 11; the side supporting plate 1 is vertical to the base 7; the resin tank 3 is used for containing printing slurry 10, the resin tank 3 comprises a forming chamber frame 9 and a printing region air-permeable tank bottom 15, and the printing slurry positioned on the printing region air-permeable tank bottom 15 is in gas-liquid contact under the action of the polymerization inhibiting gas 14; the side wall of the resin tank 3 is provided with an external electric field electrode 31 (32); the resin tank 3 is connected to the vertical side support plate 1 through a resin tank bracket 6; the curing light source 8 is used for emitting curing light; the micromirror array 4 is used to controllably irradiate the printing paste 10 with curing light; the curing light source 8 and the micro-mirror array 4 are arranged on the base 7; a pallet 11 for carrying the pallet 11 of the ceramic solidified pieces on the forming platform 2 and moving the solidified ceramic solidified pieces through the feeding device 5; a polymerization-inhibiting zone 12 is formed between a newly cured layer 13 of the ceramic pre-cured piece on the forming table 2 carried by the pallet 11 and the printing paste 10 provided on the printing zone air-permeable trough bottom 15. The ceramic 3D printer further comprises a controller to control the printing process, the controller comprising a memory including one or more of a read only memory ROM, a random access memory RAM, a flash memory or an electronically erasable programmable read only memory EEPROM.
The above description is only a specific embodiment of the present invention, and not all embodiments, and any equivalent modifications of the technical solutions of the present invention, which are made by those skilled in the art through reading the present specification, are covered by the claims of the present invention.
Claims (10)
1. A method for 3D printing of a strong 0-3 type piezoelectric composite material is characterized by comprising the following steps:
s1: establishing a three-dimensional model corresponding to a three-dimensional structure to be manufactured;
s2: processing the three-dimensional model slice of the three-dimensional structure to be manufactured to obtain a series of two-dimensional section slices;
s3: preparing printing slurry for manufacturing the three-dimensional structure to be manufactured;
s4: placing the prepared printing slurry into a resin tank of a photocuring printer, applying a sinusoidal alternating current electric field on the side wall of the resin tank to polarize the powder in the slurry, and carrying out orientation arrangement in a resin matrix to achieve 0-3 recombination;
s5: irradiating by adopting a curing light source, projecting the mask image of the two-dimensional section slice of the three-dimensional structure to be manufactured to the surface of the printing paste, and curing and forming to obtain a blank;
s6: and drying, plating an electrode and carrying out polarization treatment on the obtained biscuit to obtain the three-dimensional structure to be manufactured.
2. The method of 3D printing a strong 0-3 type piezoelectric composite according to claim 1, wherein the printing paste in step S3 comprises solid particles, monomers, oligomers, photoinitiators, light absorbers, surface modifiers, dispersants, conductive phases, defoamers.
3. The method for 3D printing of a strong 0-3 piezoelectric composite material as claimed in claim 2, wherein the diameter of the solid particles is 100-500 nm.
4. The method of 3D printing a strong 0-3 type piezoelectric composite according to claim 2, wherein the method of preparing the printing paste in step S3 includes steps S31-S34:
s31: selecting commercial PZT-5H powder particles, crushing the powder particles to be 100-500nm through ball milling, and drying;
s32: carrying out surface modification on the dry-ground PZT-5H powder particles by adopting a silane coupling agent;
s33: mixing a photoinitiator, acrylic resin, a monomer, a light absorbent and a defoaming agent, and ultrasonically stirring to form a premixed solution;
s34: and stirring and mixing the modified PZT-5H powder, the premixed liquid, the conductive phase and the dispersing agent, adding the mixture into a ball mill for wet grinding, uniformly mixing, and vacuumizing to obtain the printing slurry.
5. The method of 3D printing a strong 0-3 type piezoelectric composite of claim 4, wherein the photoinitiator is 1-hydroxycyclohexyl phenyl ketone, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, or 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide;
the monomer is acrylic acid, 1, 6-hexanediol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, cyclohexyl methacrylate or ethoxylated trimethylolpropane triacrylate;
the conductive phase is conductive carbon black, conductive carbon nanotubes or conductive polymers;
the dispersant is sodium polyacrylate, ammonium polyacrylate or sodium stearate;
the light absorbent is 2- (2-hydroxy-3, 5-dibutyl tert-phenyl) -5-chlorobenzotriazole or 2'- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole;
the defoaming agent is an organic silicon defoaming agent.
6. The method for 3D printing of a strong 0-3 type piezoelectric composite material according to claim 4 or 5, wherein the mass fractions of the photoinitiator, the acrylic resin, the monomer, the light absorber and the defoaming agent in the premix are 1-5%, 30-40%, 54.75-64.75%, 0.1-0.2% and 0.01-0.05%, respectively;
the printing slurry comprises 55-70% of modified PZT-5H powder, 28.8-43.8% of premixed liquid, 0.3-0.6% of conductive phase and 0.3-0.6% of dispersing agent by mass.
7. The method for 3D printing of a strong 0-3 piezoelectric composite material as claimed in claim 1, wherein the sinusoidal AC electric field in step S4 is 500-1000v/mm, 3-5 kHz.
8. The method for 3D printing of a strong 0-3 type piezoelectric composite material according to claim 1, wherein the time for applying the sinusoidal AC electric field to the side wall of the resin tank in step S4 is 40-60 min.
9. The method for 3D printing a strong 0-3 type piezoelectric composite according to claim 1, wherein the step S5 further comprises the steps S51-S53:
s51: starting a curing light source, projecting a mask image of the two-dimensional section slice of the three-dimensional structure to be manufactured to the surface of the printing paste, curing and forming a single layer of the printing paste within the irradiation range of the mask image, and closing the curing light source after the single layer is cured and formed;
s52: moving a forming platform, switching a projection image to a next layer, starting a curing light source, projecting a mask image of a two-dimensional section of the next layer to the surface of the printing paste subjected to single-layer curing forming, and curing the surface of the printing paste;
s53: and repeating the step S52 until the three-dimensional structure to be manufactured is formed in an accumulated mode, and obtaining the biscuit of the three-dimensional structure to be manufactured.
10. The method for 3D printing of strong 0-3 piezoelectric composite material as claimed in claim 1, wherein the polarization DC voltage is 3000-5000V/mm, the polarization time is 30-60min, and the polarization temperature is 70-110 ℃ in step S6.
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| CN115179387A (en) * | 2022-05-26 | 2022-10-14 | 中南大学 | 3D printing preparation method for composite material driver with wood pile type PZT support structure |
| WO2023003814A1 (en) * | 2021-07-22 | 2023-01-26 | Xerox Corporation | Piezoelectric powder particulates for additive manufacturing and methods associated therewith |
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