A 3D printed barium titanate ceramic and preparation method thereof

Abstract

The present invention discloses a 3D-printed barium titanate ceramic, which is composed of a plurality of three-dimensional structures, including a 'M'-shaped structure and a cage-shaped structure connected to the end points of the 'M'-shaped structure and composed of a plurality of plane connections. A preparation method of a 3D-printed barium titanate ceramic is also provided, wherein after forming a slurry with a photocurable resin system, a 3D printing process is used to design the structure of a lead-free piezoelectric material, and a piezoelectric material that is not environmentally harmful and has a controllable structure is prepared. The edge points of the three-dimensional structure of the present application are evenly connected, and the piezoelectric signal can be well conducted; when the three-dimensional structure is stacked, an overall signal conduction structure can be obtained, and the barium titanate powder is connected and shaped by photocurable resin, and the ceramic is densified by degreasing and sintering, which solves the problem that the structure in the prior art is mainly solid, and the piezoelectric performance parameters cannot be increased by structural regulation, and there is a structural constraint.

Description

Technical Field

[0001] The present invention relates to the field of preparation of barium titanate ceramics, and in particular to a 3D printed barium titanate ceramic and a preparation method thereof. Background Art

[0002] Barium titanate is a strong dielectric compound material with high dielectric constant and low dielectric loss. It is one of the most widely used materials in electronic ceramics. Barium titanate is the basic raw material of electronic ceramic materials and is known as the pillar of the electronic ceramics industry. It has high dielectric constant, low dielectric loss, excellent ferroelectric, piezoelectric, pressure resistance and insulation properties, and is widely used in the manufacture of ceramic sensitive components, especially positive temperature coefficient thermistors, multilayer ceramic capacitors, thermoelectric elements, piezoelectric ceramics, sonar, infrared radiation detection elements, crystal ceramic capacitors, electro-optical display panels, memory materials, polymer-based composite materials and coatings. In addition, 3D printing is a technology based on digital model files, using fluid, powder, wire (rod) and other curable, bonded, fused materials to construct objects by curing, bonding and fusing layer by layer. It is often used to make models in the fields of mold manufacturing, industrial design, etc., and then gradually used for the direct manufacture of some products. There are already parts printed using this technology.

[0003] Moreover, with the development of society, the demand for fine components in mechanical design and automation equipment is showing an increasing trend, among which sensors have a large market demand among fine components. Among them, pressure sensors are devices or apparatuses that sense pressure signals and convert tiny deformations into observable electrical signal outputs according to certain rules. They are widely used in various industrial automatic control environments, including water conservancy and hydropower, railway transportation, intelligent buildings, production automatic control, aerospace and many other industries. Most of the key piezoelectric materials of pressure sensors are composed of inorganic ceramics, which exhibit large piezoelectric constants. Among ceramic piezoelectric materials, most materials are lead-containing materials, such as lead zirconate titanate, lead magnesium niobate titanate, etc. Although these materials have good piezoelectric properties, they are very easy to harm the environment when used. The structures made by traditional methods are mainly solid, and it is impossible to increase the piezoelectric performance parameters through structural regulation, and there is a problem of structural constraints. Summary of the invention

[0004] Based on this, in order to solve the problem that the structure prepared by the traditional preparation method is mainly solid, the piezoelectric performance parameters cannot be increased by structural regulation, and there is a problem of structural constraints, the present invention provides a three-dimensional structure, and the specific technical solution is as follows:

[0005] A 3D-printed barium titanate ceramic, the barium titanate ceramic is composed of a plurality of three-dimensional structures, wherein the three-dimensional structure comprises a 'M'-shaped structure and a cage-shaped structure connected to the end points of the 'M'-shaped structure and composed of a plurality of plane connections.

[0006] In addition, the present application also provides a method for preparing 3D printed barium titanate ceramics, the preparation method comprising the following steps:

[0007] Adding the prepolymer, diluent and initiator into a stirring device and stirring them evenly to obtain a light-curing resin;

[0008] Adding barium titanate powder to the photocurable resin, stirring evenly and degassing to obtain a slurry;

[0009] The slurry is added to the material box of the 3D printer, and under the condition of ultraviolet light with a wavelength of 405 nm, the printing parameters are adjusted according to the curing condition of the slurry, the set three-dimensional structure model is imported, and the light-curing 3D printing device is started to obtain a blank of the printed part;

[0010] The green body is degreased and sintered to obtain barium titanate ceramics.

[0011] Furthermore, the prepolymer is a mixture of at least one or more of epoxy acrylate resin bisphenol A type, dipentaerythritol hexaacrylate and polyurethane acrylate.

[0012] Furthermore, the added amount of the prepolymer is 30 wt% to 55 wt% of the mass of the photocurable resin.

[0013] Furthermore, the diluent is a mixture of at least one or more of 1,6-hexanediol diacrylate, tripropylene glycol pure diacrylate and neopentyl glycol polymethyl ethylene oxide diacrylate.

[0014] Furthermore, the filler amount of the diluent is 15 wt% to 45 wt% of the mass of the photocurable resin.

[0015] Furthermore, the photoinitiator is a mixture of at least one or more of diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, PI-184 and 819.

[0016] Furthermore, the added amount of the photoinitiator is 4 wt% to 6 wt% of the mass of the photocurable resin.

[0017] Furthermore, the particle size of the barium titanate powder is 2.4 μm to 4 μm, and the added amount accounts for 65% to 75% of the mass of the slurry.

[0018] Furthermore, the light intensity of the light condition is 1.83 mw / cm 2 ~7.32 mw / cm 2 , the curing time is 2s~10s.

[0019] In the above scheme, after forming a slurry with barium titanate powder and photocurable resin, the structure of the lead-free piezoelectric material is designed through a 3D printing process to prepare a piezoelectric material that is not environmentally harmful and has a controllable structure. The edge points of the three-dimensional structure of the present application are evenly connected, and the piezoelectric signal can be well transmitted. When the three-dimensional structure is stacked, an overall signal transmission structure can be obtained, and the barium titanate powder is connected and shaped by photocurable resin. The ceramic is densified by exhausting and sintering, which solves the problem that the structure in the prior art is mainly solid, the piezoelectric performance parameters cannot be increased by structural regulation, and there is a structural constraint. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 is a schematic structural diagram of the three-dimensional structure in Example 1 of the present invention;

[0021] Figure 2 Schematic diagram 1 of the structure after the three-dimensional structure in Example 1 of the present invention is stacked;

[0022] Figure 3 This is a second structural diagram of the three-dimensional structure after stacking in Example 1 of the present invention;

[0023] Figure 4 It is a schematic diagram of the product after the three-dimensional structure in Example 1 of the present invention is stacked. DETAILED DESCRIPTION

[0024] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with its embodiments. It should be understood that the specific implementation methods described herein are only used to explain the present invention and do not limit the protection scope of the present invention.

[0025] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more related listed items.

[0026] A 3D-printed barium titanate ceramic in one embodiment of the present invention is composed of a plurality of three-dimensional structures, wherein the three-dimensional structure includes a 'M'-shaped structure and a cage-shaped structure connected to the end points of the 'M'-shaped structure and composed of a plurality of plane connections.

[0027] In addition, the present application also provides a method for preparing 3D printed barium titanate ceramics, the preparation method comprising the following steps:

[0028] Adding the prepolymer, diluent and initiator into a stirring device and stirring them evenly to obtain a light-curing resin;

[0029] Adding barium titanate powder to the photocurable resin, stirring evenly and exhausting the mixture to obtain a slurry;

[0030] The slurry is added to the material box of the 3D printer, and under light conditions, the printing parameters are defined and set according to the curing condition of the slurry, the set three-dimensional structure model is imported, and the light-curing 3D printing device is started to obtain the blank of the printed part;

[0031] The green body is subjected to degreasing treatment and sintering treatment to obtain barium titanate ceramics.

[0032] In one embodiment, the prepolymer is a mixture of at least one or more of epoxy acrylate resin bisphenol A type, dipentaerythritol hexaacrylate and polyurethane acrylate.

[0033] In one embodiment, the amount of the prepolymer added is 30 wt% to 55 wt% of the mass of the photocurable resin.

[0034] In one embodiment, the diluent is a mixture of at least one or more of 1,6-hexanediol diacrylate, tripropylene glycol pure diacrylate, and neopentyl glycol polymethyl ethylene oxide diacrylate.

[0035] In one embodiment, the filler amount of the diluent is 15 wt%~45 wt% of the mass of the photocurable resin.

[0036] In one embodiment, the photoinitiator is a mixture of at least one of diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, PI-184 and 819.

[0037] In one embodiment, the amount of the photoinitiator added is 4 wt% to 6 wt% of the mass of the photocurable resin.

[0038] In one embodiment, the particle size of the barium titanate powder is 2.4 μm to 4 μm, and the added amount accounts for 65% to 75% of the mass of the slurry.

[0039] In one embodiment, the particle size of the barium titanate powder is 2.5 μm to 3.5 μm.

[0040] In one embodiment, the stirring time of the slurry is 4h~6h.

[0041] In one of the embodiments, the exhaust gas treatment uses a planetary gravity mixer at room temperature.

[0042] In one embodiment, the light intensity of the light condition is 1.83 mw / cm 2 ~7.32 mw / cm 2 , the curing time is 2s~10s.

[0043] In one embodiment, the light intensity of the light condition is 1.85 mw / cm 2 ~6.55 mw / cm 2 , the curing time is 2s~8s.

[0044] In one of the embodiments, the thickness of the first layer slice of the 3D printer is 30 μm to 50 μm.

[0045] In one of the embodiments, the thickness of the first layer slice of the 3D printer is 35 μm to 45 μm.

[0046] In one embodiment, the degreasing treatment temperature is 550°C to 600°C.

[0047] In one embodiment, the temperature of the degreasing treatment is 560°C to 580°C.

[0048] In one embodiment, the sintering temperature is 1300°C to 1400°C.

[0049] In one embodiment, the sintering temperature is 1350°C to 1380°C.

[0050] In one embodiment, the barium titanate ceramic stacking process can be applied to the preparation of a signal conduction structure.

[0051] In the above scheme, after forming a slurry with barium titanate powder and photocurable resin, the structure of the lead-free piezoelectric material is designed through a 3D printing process to prepare a piezoelectric material that is not environmentally harmful and has a controllable structure. The edge points of the three-dimensional structure of the present application are evenly connected, and the piezoelectric signal can be well transmitted. When the three-dimensional structure is stacked, an overall signal transmission structure can be obtained, and the barium titanate powder is connected and shaped by photocurable resin. The ceramic is densified by exhausting and sintering, which solves the problem that the structure in the prior art is mainly solid, the piezoelectric performance parameters cannot be increased by structural regulation, and there is a structural constraint.

[0052] The embodiments of the present invention will be described in detail below with reference to specific examples.

[0053] Embodiment 1:

[0054] A method for preparing 3D printed barium titanate ceramics comprises the following steps:

[0055] Add epoxy acrylate resin bisphenol A type, 1,6-hexanediol diacrylate and diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide into a stirring device, stir evenly, and obtain a photocurable resin. In this embodiment, the addition amount of epoxy acrylate resin bisphenol A type accounts for 50 wt% of the mass of the photocurable resin, the addition amount of 1,6-hexanediol diacrylate accounts for 45 wt% of the mass of the photocurable resin, and the addition amount of diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide accounts for 5wt% of the mass of the photocurable resin.

[0056] Adding barium titanate powder with a particle size of 4 μm into the photocurable resin, stirring for 6 hours, and exhausting the mixture at room temperature using a planetary gravity mixer to obtain a slurry, wherein the barium titanate powder accounts for 75% of the mass of the slurry;

[0057] The slurry was added to the material box of the 3D printer, and the light intensity was 7.32 mw / cm 2 , the curing time is 5s, the first layer slice thickness of the 3D printer is 45μm, the set three-dimensional structure model is imported, and the light-curing 3D printing equipment is started to obtain the blank of the printed part;

[0058] The green body is degreased at 550° C. and sintered at 1300° C. to obtain barium titanate ceramics.

[0059] The barium titanate ceramic prepared in Example 1 has an excellent degreasing effect, and the structural design is controllable, and can conduct piezoelectric signals well, and the piezoelectric performance parameters can be increased through structural regulation.

[0060] Embodiment 2:

[0061] A method for preparing 3D printed barium titanate ceramics comprises the following steps:

[0062] Epoxy acrylate resin bisphenol A type, 1,6-hexanediol diacrylate and diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide are added to a stirring device and stirred evenly to obtain a photocurable resin. In this embodiment, the amount of epoxy acrylate resin bisphenol A type added accounts for 49 wt % of the mass of the photocurable resin, the amount of 1,6-hexanediol diacrylate added accounts for 45 wt % of the mass of the photocurable resin, and the amount of diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide added accounts for 6 wt % of the mass of the photocurable resin.

[0063] Adding barium titanate powder with a particle size of 4 μm into the photocurable resin, stirring for 5 hours, and exhausting the mixture at room temperature using a planetary gravity mixer to obtain a slurry, wherein the barium titanate powder accounts for 72% of the mass of the slurry;

[0064] The slurry was added to the material box of the 3D printer, and the light intensity was 6.55mw / cm 2 , the curing time is 8s, the first layer slice thickness of the 3D printer is 45μm, the set three-dimensional structure model is imported, and the light-curing 3D printing equipment is started to obtain the blank of the printed part;

[0065] The green body is degreased at 600° C. and sintered at 1350° C. to obtain barium titanate ceramics.

[0066] The barium titanate ceramic prepared in Example 2 has an excellent degreasing effect, and the structural design is controllable, and can conduct piezoelectric signals well, and the piezoelectric performance parameters can be increased through structural regulation.

[0067] Embodiment 3:

[0068] A method for preparing 3D printed barium titanate ceramics comprises the following steps:

[0069] Epoxy acrylate resin bisphenol A type, 1,6-hexanediol diacrylate and diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide are added to a stirring device and stirred evenly to obtain a photocurable resin. In this embodiment, the amount of epoxy acrylate resin bisphenol A type added accounts for 50 wt % of the mass of the photocurable resin, the amount of 1,6-hexanediol diacrylate added accounts for 44 wt % of the mass of the photocurable resin, and the amount of diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide added accounts for 6 wt % of the mass of the photocurable resin.

[0070] Adding barium titanate powder with a particle size of 3.5 μm to the photocurable resin, stirring for 6 hours, and exhausting the mixture at room temperature using a planetary gravity mixer to obtain a slurry, wherein the barium titanate powder accounts for 75% of the mass of the slurry;

[0071] The slurry was added to the material box of the 3D printer, and the light intensity was 7.32 mw / cm 2 , the curing time is 8s, the first layer slice thickness of the 3D printer is 46μm, the set three-dimensional structure model is imported, and the light-curing 3D printing equipment is started to obtain the blank of the printed part;

[0072] The green body is degreased at 580° C. and sintered at 1350° C. to obtain barium titanate ceramics.

[0073] The barium titanate ceramic prepared in Example 3 has an excellent degreasing effect, and the structural design is controllable, and can conduct piezoelectric signals well, and the piezoelectric performance parameters can be increased through structural regulation.

[0074] It should be noted that: the barium carbonate ceramics in Examples 1 to 3 are composed of several three-dimensional structures, including a M-shaped structure and a cage-shaped structure connected to the end points of the M-shaped structure and composed of multiple plane connections. The 3D printing method of customizing the three-dimensional structure breaks through the constraints of the structure; the barium titanate ceramics prepared in Examples 1 to 3 are environmentally friendly compared to lead-containing piezoelectric materials; the prepared photocurable resin and high-refractive index barium titanate powder can be better degreased and sintered, which is more conducive to enhancing the piezoelectricity of the barium titanate ceramics.

[0075] Comparative Example 1:

[0076] The difference from Example 3 is that in Comparative Example 1, the added amount of epoxy acrylate resin bisphenol A type accounts for 35wt% of the mass of the photocurable resin, the added amount of 1,6-hexanediol diacrylate accounts for 55wt% of the mass of the photocurable resin, and the added amount of diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide accounts for 10wt% of the mass of the photocurable resin. The rest is the same as Example 3.

[0077] The barium titanate ceramic prepared in Comparative Example 1 has a composition ratio of the photocurable resin that is quite different from that in Example 3, and when the obtained photocurable resin is used in the preparation of barium titanate ceramics, the subsequent degreasing process is not ideal. This indicates that the composition and composition ratio of the photocurable resin of the present application can be optimized to facilitate the subsequent degreasing process.

[0078] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0079] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A 3D printed barium titanate ceramic, characterized in that: The barium titanate ceramic is composed of a plurality of three-dimensional structures, wherein the three-dimensional structure includes a cross-shaped structure and a cage-shaped structure connected to the end points of the cross-shaped structure and composed of a plurality of planes connected; The preparation method of the 3D printed barium titanate ceramic comprises the following steps: Adding the prepolymer, diluent and photoinitiator into a mechanical stirring device and stirring them evenly to obtain a photocurable resin; Adding barium titanate powder to the photocurable resin, stirring evenly and degassing to obtain a slurry; The slurry is added to the material box of the 3D printer, and under the condition of ultraviolet light with a wavelength of 405nm, the printing parameters are adjusted according to the curing condition of the slurry, the set three-dimensional structure model is imported, and the light-curing 3D printing device is started to obtain the blank of the printed part; The green body is subjected to degreasing treatment and sintering treatment to obtain barium titanate ceramics; Among them, the added amount of the prepolymer is 30wt%~55wt% of the mass of the photocurable resin; the added amount of the diluent is 15wt%~45wt% of the mass of the photocurable resin; the added amount of the photoinitiator is 4wt%~6wt% of the mass of the photocurable resin; the particle size of the barium titanate powder is 2.4μm~4μm, and the added amount accounts for 65wt%~75wt% of the mass of the slurry.

2. The 3D printed barium titanate ceramic according to claim 1, characterized in that: The prepolymer is a mixture of one or more of epoxy acrylate resin bisphenol A type, dipentaerythritol hexaacrylate and polyurethane acrylate.

3. The 3D printed barium titanate ceramic according to claim 1, characterized in that: The diluent is a mixture of one or more of 1,6-hexanediol diacrylate, tripropylene glycol pure diacrylate and neopentyl glycol polymethyl ethylene oxide diacrylate.

4. The 3D printed barium titanate ceramic according to claim 1, characterized in that: The photoinitiator is a mixture of one or more of diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, PI-184 and 819.

5. The 3D printed barium titanate ceramic according to claim 1, characterized in that: The light intensity of the ultraviolet light condition is 1.83mw / cm 2 ~7.32mw / cm 2 , the curing time is 2s~10s.

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