CN113621238B - Piezoelectric ceramic ultra-high filling silicone rubber composite ink material for ink direct-writing printing and preparation method and application thereof - Google Patents
Piezoelectric ceramic ultra-high filling silicone rubber composite ink material for ink direct-writing printing and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a piezoelectric ceramic ultra-high filling silicon rubber composite ink material for ink direct writing printing, and a preparation method and application thereof, wherein the composite ink material mainly comprises silicon rubber resin, piezoelectric ceramic filler and solvent components, wherein the addition amount of the piezoelectric ceramic filler can reach 90 wt%. Tests prove that the composite ink material has good printing capability, good dispersibility and strong supporting force, and a printed piezoelectric part has good flexibility and piezoelectric output.
Description
Technical Field
The invention belongs to the technical field of 3D printing high polymer materials, and particularly relates to a piezoelectric ceramic ultra-high filling silicone rubber composite ink material for ink direct-writing printing, a preparation method and application thereof, and is particularly suitable for preparing a high-performance wearable energy harvesting device.
Background
The piezoelectric material is an intelligent material capable of realizing power-electricity conversion, can collect discrete mechanical energy in the environment, is used in the fields of self-powered equipment, wearable sensors, nano generators and the like, and provides a material basis for miniaturization, light weight and wearable devices. The kinds of piezoelectric materials mainly include piezoelectric crystals such as quartz, piezoelectric ceramics such as barium titanate, lead zirconate titanate, potassium niobate, and the like; piezoelectric polymers such as polyvinylidene fluoride (PVDF), odd nylon (PA11), and the like. The piezoelectric ceramic has high piezoelectric and dielectric properties, but the brittleness and density are large, the piezoelectric polymer has the advantages of light weight, good flexibility and the like, but the piezoelectric and dielectric properties are small, the piezoelectric composite material can integrate the excellent properties of the piezoelectric ceramic and the piezoelectric ceramic, and the piezoelectric ceramic is widely researched in recent years, and the existing piezoelectric composite material system mainly comprises the piezoelectric ceramic and the non-piezoelectric polymer such as PVDF, PA11 and the like, polyvinyl alcohol (PVA), polyvinyl chloride (PVC) and the like, which are compounded to prepare the high-performance piezoelectric composite material. However, the current research is limited to the preparation process, the ceramic content of the obtained piezoelectric composite material is usually between 10 wt% and 40 wt%, the piezoelectric composite material cannot be processed smoothly when the ceramic content is high, meanwhile, the defect that the dispersibility is poor and the agglomeration is easy to occur is easily caused by high filling of the piezoelectric ceramic, and the problem that the mechanical property of the polymer matrix is deteriorated, so that the better flexibility of the composite material cannot be realized. Since the piezoelectric ceramic has higher piezoelectric and dielectric properties, higher filling content of the piezoelectric ceramic is necessary to improve the piezoelectric properties of the piezoelectric composite material.
However, most studies aim at preparing a film sample by using methods such as spin coating and cast molding, and studies on how to increase the filling content of piezoelectric ceramics are rare. For example, chinese patent publication No. CN112311275A discloses a wearable energy harvester and a method for preparing a PDMS-BT film, specifically, a ball mill is used to fully mix a proper amount of BT and PDMS; and coating the PDMS-BT film in a mold, and putting the mold into an oven for curing to obtain the PDMS-BT film. The technical scheme disclosed by the patent adopts a coating mode to prepare a simple film structure, and the mass fraction of barium titanate is only 4-7.2 wt%.
At the present stage, the 3D printing technology in the additive manufacturing field gradually realizes industrial transformation, and the 3D printing technology has the advantages of digital manufacturing, dimension reduction manufacturing, rapid molding manufacturing and the like, and has great research prospects and industrial values.
The 3D printing method mainly includes Fused Deposition Modeling (FDM), Selective Laser Sintering (SLS), Stereolithography (SLA), direct ink-write printing (DIW), and the like. DIW is also known as auto-slip (Robocasting or Robotic displacement). The Ink material (Ink) is stored in a temperature controlled cartridge (Barrel) and attached to a Nozzle (nozle) mounted on a three axis cnc (computer numerical control) platform, and the material is extruded from the Nozzle and formed on a substrate by a screw extrusion or pneumatic pressure control system. Layer by Layer construction can be carried out by analyzing model slices and compiling codes, and direct-writing parameters (pressure and speed) and direct-writing environments (temperature and direct-writing medium) can have great influence on a direct-writing process. Compared with other 3D printing technologies, the DIW 3D printing technology is based on normal temperature processing, has less strict requirements on materials, can perform direct-writing 3D printing on slurry formed by metal, ceramic, polymers and the like, is particularly suitable for printing of thermosetting materials, such as PDMS, and is widely applied to the fields of microelectronics, photovoltaics, energy, tissue engineering and the like. However, the DIW technology also has the problem of printability of ink materials, generally due to the problems of difficult adjustment and control of viscosity of printing ink, poor ink support during printing and the like, and research and development of the DIW technology in various fields are greatly limited.
Disclosure of Invention
In order to solve the problems in the background art, the invention provides a piezoelectric ceramic ultra-high filling silicone rubber composite ink material for ink direct-writing printing, and a preparation method and application thereof, wherein the addition amount of a piezoelectric ceramic filler in the composite ink material can reach 90 wt%, tests show that the composite ink material has the advantages of good printing capability, good dispersibility and strong supporting force, and a printed piezoelectric part has good flexibility and piezoelectric output.
In order to achieve the purpose, the invention adopts the technical scheme formed by the following technical measures.
A piezoelectric ceramic ultra-high filling silicone rubber composite ink material for ink direct-writing printing mainly comprises the following raw materials in parts by weight:
more than or equal to 100 parts of silicone rubber resin,
the weight of the piezoelectric ceramic filler is less than or equal to 900 parts,
200-500 parts of a solvent;
wherein the total amount of the silicone rubber resin and the piezoelectric ceramic filler is 1000 parts.
Generally, the silicone rubber resin may be selected from any type, model, or prepared according to the prior art. For better illustration and to provide a preferred technical solution, the silicone rubber resin is selected from at least one of methyl silicone rubber, methyl vinyl silicone rubber, methyl phenyl vinyl silicone rubber and fluorosilicone rubber.
The piezoelectric ceramic filler is selected from piezoelectric ceramic fillers which can be prepared by a composite material with silicone rubber resin in the prior art, and specifically, the piezoelectric ceramic filler which can be used as a silicone rubber resin matrix in the traditional processing field (such as compression molding, spin coating, cast molding, injection molding and the like) can be selected by persons skilled in the art. In order to better illustrate the present invention and provide a preferred embodiment, the piezoelectric ceramic filler includes at least one of barium titanate, potassium niobate, and lead zirconate titanate. In order to uniformly disperse the piezoelectric ceramic filler in the solvent, the piezoelectric ceramic filler is selected from powder, and preferably, the micron-sized or nano-sized piezoelectric ceramic powder with the particle size of less than 1 μm is selected. The piezoelectric ceramic powder can be directly purchased from the market or prepared by conventional crushing equipment.
Generally, the solvent is an organic solvent that is compatible with the silicone rubber resin, and in which the piezoelectric ceramic filler is sufficiently dispersed. In order to better illustrate the present invention and provide a preferred technical solution, the solvent includes at least one or more of alcohol liquid (preferably glycerol, isopropanol, ethanol), ester liquid (preferably ethyl acetate, butyl acetate, isopropyl acetate), N-dimethylformamide, and acetone.
Further, the proportion of each raw material in the ink material is optimal in terms of achieving the functionality of the ink material, and in order to improve the piezoelectric performance of the ink material, preferably, the piezoelectric ceramic ultra-high filling silicone rubber composite ink material for ink direct writing printing mainly comprises the following components in parts by weight:
100-600 parts of silicone rubber resin,
400-900 parts of piezoelectric ceramic filler,
200-500 parts of a solvent;
wherein the total amount of the silicone rubber resin and the piezoelectric ceramic filler is 1000 parts.
The inventor of the invention finds that when the addition amount of the piezoelectric ceramic filler is 800 parts by contrast experiment research results, the performance of the piezoelectric product of the prepared ink material in the aspect of piezoelectricity reaches the best after 3D printing. When the addition amount of the piezoelectric ceramic filler is further increased and exceeds 950 parts, the printable performance of the prepared ink material is greatly reduced, so that 3D printing processing of piezoelectric parts cannot be performed.
Further preferably, the piezoelectric ceramic ultra-high filling silicone rubber composite ink material for ink direct-writing printing mainly comprises the following raw materials in parts by weight:
100-300 parts of silicone rubber resin,
700-900 parts of piezoelectric ceramic filler,
200-500 parts of a solvent;
wherein the total amount of the silicone rubber resin and the piezoelectric ceramic filler is 1000 parts.
In general, other processing aids such as antioxidants, flame retardants, anti-aging agents and the like known in the prior art can be added in the invention, and other functional fillers such as carbon-based fillers, conductive fillers polyaniline and the like can be added according to factors such as actual technical purposes or processing conditions, and the addition amount of the other functional fillers can be determined by referring to the prior art by a person skilled in the art. However, it is a prerequisite that these processing aids and fillers do not adversely affect the achievement of the object of the present invention and the achievement of the excellent effects of the present invention.
The preparation method of the piezoelectric ceramic ultra-high filling silicon rubber composite ink material for ink direct-writing printing comprises the following steps:
(1) under the condition of normal temperature, adding piezoelectric ceramic filler into a solvent, and fully mixing to obtain a mixed liquid for later use;
(2) adding the silicone rubber resin into the mixed solution obtained in the step (1), and fully mixing to obtain a silicone rubber matrix mixed liquid for later use;
(3) thickening the silicone rubber matrix mixed liquid obtained in the step (2) to obtain a piezoelectric ceramic ultra-high filling silicone rubber composite ink material for ink direct-writing printing; the piezoelectric ceramic ultra-high filling silicone rubber composite ink material for ink direct-writing printing is obtained through thickening, and the shear rate is 20-200 s at normal temperature -1The viscosity is 10 to 100 mPas.
Wherein, the sufficient mixing in the step (1) is to achieve that the piezoelectric ceramic filler is fully dispersed in the solvent to form a mixed liquid, and the sufficient mixing in the step (2) is to make the silicone rubber resin fully dissolved in the solvent and the piezoelectric ceramic filler fully dispersed in the solvent to form a silicone rubber matrix mixed liquid. The mixing and stirring process in the prior art can be selected by those skilled in the art according to the actual process conditions and the weight of the raw materials to be mixed. In order to better illustrate the invention and provide a technical scheme for reference, under the laboratory condition, when the addition amount of the silicone rubber is 5-10 g, the sufficient mixing is performed by a magnetic stirring mixing process in a magnetic rotation speed of 100-500 r/min for 3-12 h.
Note that, the mixed liquid in step (1) and the silicone rubber base mixed liquid in step (2) are subjected to defoaming treatment after being sufficiently mixed in order to eliminate the influence of bubbles in the mixed liquid due to the selection of a mixing and stirring process, for example, the above-mentioned magnetic stirring and mixing process, which is likely to cause air to enter and generate bubbles in the actual stirring and mixing process. In order to better illustrate the invention and provide a referable technical scheme, the steps (1) and (2) are fully mixed, and the method further comprises the step of performing freezing defoaming after mixing, wherein the freezing defoaming is to keep the mixed liquid at a temperature of 2-4 ℃ for at least 24 hours.
Thickening treatment in the step (3) is to thicken the silicone rubber matrix mixed liquid obtained in the step (2) to normal temperature, wherein the shear rate is 20-200 s-1At first, it sticks toThe degree of the thickening agent is 10 to 100 mPas, and a person skilled in the art can select a thickening treatment mode suitable for the prior art according to actual process conditions and the weight of the raw materials to be mixed. In order to better illustrate the invention and provide a technical scheme for reference, under the laboratory conditions, the method can select the modes of vacuum oven thickening treatment or heating stirring thickening treatment and the like, and determine the process parameters such as thickening treatment time consumption and the like by means of real-time measurement or experience summary and the like, so as to ensure that the viscosity of the mixed liquid obtained after thickening treatment is 10-100 mPa & s, meet the requirement of direct writing printing of ink and have printability.
When the addition amount of the silicone rubber resin is 5-10 g, preferably, the thickening treatment in the step (3) is thickening treatment by using a vacuum oven at the temperature of 40-60 ℃ and the vacuum degree of-0.01-0.09 MPa for 20-90 min.
It is noted that the viscosity defined in the technical scheme of the invention is that the silicone rubber resin matrix/piezoelectric ceramic filler system meets the printability, and the viscosity is obtained through a large amount of exploration and experimental summary. Those skilled in the art will appreciate that the viscosity index required for a direct write ink printable ink material will vary depending on the particular ink material used, and that viscosity is not the only measure of the printability of the ink material.
The invention has the main points that the ultrahigh filling of the piezoelectric ceramic filler is realized, the ink supporting property required when the silicon rubber resin matrix is used as an ink material is met through the ultrahigh filling characteristic of the piezoelectric ceramic filler, and the silicon rubber resin is selected as the matrix, so that the piezoelectric ceramic filler has good flexibility when being filled with high materials, particularly the piezoelectric ceramic filler with ultrahigh filling rate. After thickening, the ink material has the characteristics of good printing capability, good dispersibility and strong supporting force, and can be applied to ink direct-writing printing, and the piezoelectric workpiece obtained by printing has good flexibility and piezoelectric output.
It should be noted that the above inventive features of the present invention are only applicable to ink direct-write printing, and other 3D printing processes are not applicable to the present invention, for example, when the amount of the piezoelectric ceramic filler added reaches 90 wt%, the selective laser sintering 3D printing technique cannot produce good adhesion behavior due to too high filler content, and the above defects do not occur in the present invention.
In addition, the silicone rubber-based composite ink material prepared according to the technical scheme of the invention can generally adopt the same process parameters as those of the silicone rubber-based composite material subjected to ink direct-writing printing in the prior art in the field. In order to better illustrate the invention, the invention provides a specific mode for reference, the silicone rubber-based composite ink material prepared by the technical scheme of the invention is used for ink direct writing, and the technological parameters are as follows: the diameter of the needle head is 0.6-1.2 mm, the pressure is 0.07-0.3 MPa, and the printing speed is 15-25 cm/min.
The invention has the following beneficial effects:
1. the addition amount of the piezoelectric ceramic filler in the composite ink material prepared by the invention can reach 90 wt%, and the functionality of the filler with high addition ratio can be fully exerted, so that the performance and the application range of ink direct-writing printed products are greatly expanded.
2. According to the invention, the silicone rubber matrix mixed liquid is thickened, so that the prepared composite ink material has moderate viscosity and good supporting force, is suitable for ink direct-writing printing processing, widens the preparation approach of the composite ink, and expands the forming method of the silicone rubber matrix composite.
3. The composite ink material prepared by the invention is used for ink direct-writing printing, and the obtained product is a composite material which is difficult to prepare by other printing methods, has ultrahigh filling and high elasticity, has good compression strength, and widens the selection range of piezoelectric composite materials with excellent 3D printing performance.
4. The preparation method has the advantages of mature process conditions, simple preparation process and low manufacturing cost, and is suitable for large-scale production.
Drawings
Fig. 1 is an SEM image of a sample of a porous frame article prepared in application example 1 of the present invention. It is obvious that the piezoelectric ceramic filler is uniformly distributed in the piezoelectric ceramic filler, and the agglomeration phenomenon does not occur.
FIG. 2 is a photograph of a sample of the porous frame article prepared in application example 1 of the present invention.
Fig. 3 is a photograph of a sample of the porous frame article prepared in application example 1 of the present invention when subjected to a cantilever piezoelectric impact test.
Fig. 4 is a graph showing the test results of open-circuit voltage and short-circuit current of the sample of the porous frame workpiece prepared in application example 1 of the present invention.
Fig. 5 is a graph of the cyclic compressive stress strain of samples of the porous frame articles prepared in application example 1 of the present invention.
Fig. 6 is a graph showing the open circuit voltage test results of the sample of the porous frame article prepared in application example 2 of the present invention.
Fig. 7 is a graph showing the open circuit voltage test results of the sample of the porous frame article prepared in application example 3 of the present invention.
Fig. 8 is a graph showing the open circuit voltage test results of the sample of the porous frame article prepared in application example 4 of the present invention.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the accompanying drawings. It should be noted that the examples given are not to be construed as limiting the scope of the invention, and that those skilled in the art, on the basis of the teachings of the present invention, will be able to make numerous insubstantial modifications and adaptations of the invention without departing from its scope.
The following examples contain the main experimental raw materials and reagents:
Polydimethylsiloxane (PDMS): SLYGARD 184, manufactured by Dow burning corporation of USA;
barium titanate (BaTiO)3): density 6.08g/cm3500nm average particle size, tetragonal phase, supplied by Sinocera, Shandong;
the main experimental equipment is as follows:
multifunctional constant-temperature constant-speed magnetic stirrer: model B15-3, shanghai selec instruments ltd;
and (3) vacuum drying oven: DZF-6050, Shanghai Qixin scientific instruments, Inc.;
ink direct-write printer: a B series desktop type three-axis automatic glue dispensing manipulator, Shenzhen Shangsheng Industrial Equipment Co., Ltd;
testing and characterization:
analysis by scanning electron microscope
The morphology of the samples was observed using a scanning electron microscope (INSPECT F, FEI, Japan). Quenching the printed sample in liquid nitrogen, and spraying gold on an observation surface in vacuum; the acceleration voltage was 20 kV.
Piezoelectric performance test
The corona polarization is carried out by adopting a piezoelectric material composite polarizer (HYJH-F, Shanxi province New Material science and technology Co., Ltd., China). Polarization conditions: the voltage is 2kV/mm at 25 ℃ and the time is 60 min. Using quasi-static d33The piezoelectric coefficient of the polarized material is tested by a measuring instrument (ZJ-3A). Adhering double-sided conductive aluminum foils on the front and back sides of the polarized workpiece, and testing the piezoelectric output performance of the sample by a linear motor testing system. Testing the output open-circuit voltage and short-circuit current, and the linear motor acceleration is 5m/s 2。
Compression performance test
A cyclic compression performance test is carried out on a 3D printing part by adopting an Electroforce 3220 SERIES II type material testing machine of Bose company in America and combining software Wintest7 software, wherein the cyclic frequency is 2000 times, and the frequency is 1 Hz.
Example 1
The present embodiment provides a piezoelectric ceramic ultra-high filling silicone rubber composite ink material for ink direct-writing printing, which mainly comprises the following raw materials, by weight:
200 parts of silicon rubber resin, namely 200 parts of,
800 parts of piezoelectric ceramic filler, namely piezoelectric ceramic filler,
400 parts of a solvent;
wherein the silicone rubber resin is selected from polydimethylsiloxane silicone rubber,
the piezoelectric ceramic filler is selected from barium titanate,
the solvent is selected to be ethyl acetate;
the preparation method of the piezoelectric ceramic ultra-high filling silicon rubber composite ink material for ink direct-writing printing comprises the following steps:
(1) under the condition of normal temperature, adding piezoelectric ceramic filler into a solvent, and fully mixing to obtain a mixed liquid for later use;
(2) adding the silicone rubber resin into the mixed solution obtained in the step (1), and fully mixing to obtain a silicone rubber matrix mixed liquid for later use;
(3) thickening the silicone rubber matrix mixed liquid obtained in the step (2) to obtain a piezoelectric ceramic highly-filled silicone rubber composite ink material for ink direct writing; wherein the thickening treatment is carried out by adopting a vacuum oven for thickening for 30min at the temperature of 40 ℃ and the vacuum degree of-0.09 MPa.
The piezoelectric ceramic high-filling silicone rubber composite ink material for ink direct writing obtained through thickening treatment has the shear rate of 100s at normal temperature-1The viscosity was 45 mPas.
Application example 1
The application example is that the piezoelectric ceramic high-filling silicone rubber composite ink material prepared in the embodiment 1 is used for preparing a porous frame workpiece as a sample through ink direct-writing printing, and the technological parameters of the ink direct-writing printing are as follows: the diameter of the needle is 0.8mm, the pressure is 0.2MPa, and the printing speed is 20 cm/min.
Through testing, the length, the width and the height of a sample of the prepared porous frame part are 15X 5mm, the open-circuit voltage is 22V, and the short-circuit current is 250nA, as shown in the attached figure 4 of the specification.
The test shows that the sample shows excellent fatigue resistance, good recovery and strength after 2000 times of cyclic compression, as shown in figure 5 in the specification.
Example 2
The piezoelectric ceramic high-filling silicone rubber composite ink material for ink direct writing comprises the following raw materials in parts by weight:
100 parts of silicone rubber resin, namely 100 parts of,
900 parts of piezoelectric ceramic filler,
500 parts of a solvent;
wherein the silicone rubber resin is selected from polydimethylsiloxane silicone rubber,
The piezoelectric ceramic filler is selected from barium titanate,
the solvent is selected to be ethyl acetate;
the preparation method of the piezoelectric ceramic high-filling silicone rubber composite ink material for ink direct writing comprises the following steps:
(1) under the condition of normal temperature, adding piezoelectric ceramic filler into a solvent, and fully mixing to obtain a mixed liquid for later use;
(2) adding the silicone rubber resin into the mixed solution obtained in the step (1), and fully mixing to obtain a silicone rubber matrix mixed liquid for later use;
(3) thickening the silicone rubber matrix mixed liquid obtained in the step (2) to obtain a piezoelectric ceramic high-filling silicone rubber composite ink material for ink direct writing; wherein the thickening treatment is carried out by adopting a vacuum oven for thickening for 20min at the temperature of 40 ℃ and the vacuum degree of-0.09 MPa.
The piezoelectric ceramic high-filling silicon rubber composite ink material for ink direct writing obtained by thickening treatment has the shear rate of 100s at normal temperature-1The viscosity was 47 mPas.
Application example 2
The application example is that the piezoelectric ceramic high-filling silicone rubber composite ink material prepared in the embodiment 2 is used for preparing a porous frame workpiece as a sample through ink direct-writing printing, and the technological parameters of the ink direct-writing printing are as follows: the diameter of the needle is 0.8mm, the pressure is 0.25MPa, and the printing speed is 20 cm/min.
Through testing, the prepared porous frame part sample has the length multiplied by the width multiplied by the height multiplied by 15 multiplied by 5mm, and the open-circuit voltage is 16V, as shown in the attached figure 6 of the specification.
Example 3
The piezoelectric ceramic high-filling silicone rubber composite ink material for ink direct writing comprises the following raw materials in parts by weight:
300 parts of silicone rubber resin, namely, silicone rubber resin,
700 parts of piezoelectric ceramic filler, namely 700 parts of,
350 parts of a solvent;
wherein the silicone rubber resin is selected from polydimethylsiloxane silicone rubber,
the piezoelectric ceramic filler is selected from barium titanate,
the solvent is selected to be ethyl acetate;
the preparation method of the piezoelectric ceramic high-filling silicone rubber composite ink material for ink direct writing comprises the following steps:
(1) under the condition of normal temperature, adding piezoelectric ceramic filler into a solvent, and fully mixing to obtain a mixed liquid for later use;
(2) adding the silicone rubber resin into the mixed solution obtained in the step (1), and fully mixing to obtain a silicone rubber matrix mixed liquid for later use;
(3) thickening the silicone rubber matrix mixed liquid obtained in the step (2) to obtain a piezoelectric ceramic highly-filled silicone rubber composite ink material for ink direct writing; wherein the thickening treatment is carried out by adopting a vacuum oven for thickening for 40min at the temperature of 50 ℃ and the vacuum degree of-0.09 MPa.
Application example 3
The application example is that the piezoelectric ceramic high-filling silicone rubber composite ink material prepared in the embodiment 3 is used for preparing a porous frame workpiece as a sample through ink direct-writing printing, and the technological parameters of the ink direct-writing printing are as follows: the diameter of the needle is 0.8mm, the pressure is 0.15MPa, and the printing speed is 20 cm/min.
The porous frame work sample prepared by the test has the length multiplied by the width multiplied by the height of 15 multiplied by 5mm and the open circuit voltage of 17V, as shown in the attached figure 7 of the specification.
Example 4
The piezoelectric ceramic high-filling silicone rubber composite ink material for ink direct writing comprises the following raw materials in parts by weight:
400 parts of silicon rubber resin, namely 400 parts of,
600 parts of a piezoelectric ceramic filler, namely,
300 parts of a solvent;
wherein the silicone rubber resin is selected from polydimethylsiloxane silicone rubber,
the piezoelectric ceramic filler is selected from barium titanate,
the solvent is selected to be ethyl acetate;
the preparation method of the piezoelectric ceramic high-filling silicone rubber composite ink material for ink direct writing comprises the following steps:
(1) under the condition of normal temperature, adding piezoelectric ceramic filler into a solvent, and fully mixing to obtain a mixed liquid for later use;
(2) Adding the silicone rubber resin into the mixed solution obtained in the step (1), and fully mixing to obtain a silicone rubber matrix mixed liquid for later use;
(3) thickening the silicone rubber matrix mixed liquid obtained in the step (2) to obtain a piezoelectric ceramic highly-filled silicone rubber composite ink material for ink direct writing; wherein the thickening treatment is carried out by adopting a vacuum oven for thickening for 60min at the temperature of 60 ℃ and under the vacuum degree of-0.09 MPa.
Application example 4
The application example is that the piezoelectric ceramic high-filling silicone rubber composite ink material prepared in the embodiment 4 is used for preparing a porous frame workpiece as a sample through ink direct-writing printing, and the technological parameters of the ink direct-writing printing are as follows: the diameter of the needle is 0.8mm, the pressure is 0.1MPa, and the printing speed is 20 cm/min.
Through testing, the prepared porous frame part sample has the length multiplied by the width multiplied by the height multiplied by 15 multiplied by 5mm, and the open-circuit voltage is 10V, as shown in the attached figure 8 of the specification.
Example 5
The piezoelectric ceramic high-filling silicone rubber composite ink material for ink direct writing comprises the following raw materials in parts by weight:
500 parts of silicone rubber resin, namely 500 parts of,
500 parts of piezoelectric ceramic filler, namely 500 parts of piezoelectric ceramic filler,
300 parts of a solvent;
Wherein the silicone rubber resin is selected from methyl silicone rubber,
the piezoelectric ceramic filler is selected from barium titanate,
the solvent is selected from glycerol;
the preparation method of the piezoelectric ceramic high-filling silicone rubber composite ink material for ink direct writing comprises the following steps:
(1) under the condition of normal temperature, adding piezoelectric ceramic filler into a solvent, and fully mixing to obtain a mixed liquid for later use;
(2) adding the silicone rubber resin into the mixed solution obtained in the step (1), and fully mixing to obtain a silicone rubber matrix mixed liquid for later use;
(3) thickening the silicone rubber matrix mixed liquid obtained in the step (2) to obtain a piezoelectric ceramic high-filling silicone rubber composite ink material for ink direct writing; wherein the thickening treatment is carried out by adopting a vacuum oven for thickening for 90min at the temperature of 60 ℃ and the vacuum degree of-0.09 MPa.
Application example 5
The application example is that the piezoelectric ceramic high-filling silicone rubber composite ink material prepared in the embodiment 5 is used for preparing a porous frame workpiece as a sample through ink direct-writing printing, and the technological parameters of the ink direct-writing printing are as follows: the diameter of the needle is 0.6mm, the pressure is 0.07MPa, and the printing speed is 15 cm/min.
Example 6
The piezoelectric ceramic high-filling silicone rubber composite ink material for ink direct writing comprises the following raw materials in parts by weight:
600 parts of silicon rubber resin, namely 600 parts of,
400 parts of a piezoelectric ceramic filler,
200 parts of a solvent;
wherein the silicone rubber resin is selected from methyl vinyl silicone rubber,
the piezoelectric ceramic filler is selected from lead zirconate titanate,
the solvent is selected to be isopropanol;
the preparation method of the piezoelectric ceramic high-filling silicone rubber composite ink material for ink direct writing comprises the following steps:
(1) under the condition of normal temperature, adding piezoelectric ceramic filler into a solvent, and fully mixing to obtain a mixed liquid for later use;
(2) adding the silicone rubber resin into the mixed solution obtained in the step (1), and fully mixing to obtain a silicone rubber matrix mixed liquid for later use;
(3) thickening the silicone rubber matrix mixed liquid obtained in the step (2) to obtain a piezoelectric ceramic highly-filled silicone rubber composite ink material for ink direct writing; wherein the thickening treatment is carried out by adopting a vacuum oven for thickening for 60min at the temperature of 60 ℃ and the vacuum degree of-0.01 MPa.
Application example 6
The application example is that the piezoelectric ceramic high-filling silicone rubber composite ink material prepared in the embodiment 6 is used for preparing a porous frame workpiece as a sample through ink direct-writing printing, and the technological parameters of the ink direct-writing printing are as follows: the diameter of the needle is 1.0mm, the pressure is 0.1MPa, and the printing speed is 15 cm/min.
Example 7
The piezoelectric ceramic high-filling silicone rubber composite ink material for ink direct writing comprises the following raw materials in parts by weight:
200 parts of silicon rubber resin, namely 200 parts of,
800 parts of piezoelectric ceramic filler, namely piezoelectric ceramic filler,
350 parts of a solvent;
wherein the silicone rubber resin is selected from fluorosilicone rubber,
the piezoelectric ceramic filler is selected from potassium niobate,
the solvent is selected to be ethyl acetate;
the preparation method of the piezoelectric ceramic high-filling silicone rubber composite ink material for ink direct writing comprises the following steps:
(1) under the condition of normal temperature, adding piezoelectric ceramic filler into a solvent, and fully mixing to obtain a mixed liquid for later use;
(2) adding the silicone rubber resin into the mixed solution obtained in the step (1), and fully mixing to obtain a silicone rubber matrix mixed liquid for later use;
(3) thickening the silicone rubber matrix mixed liquid obtained in the step (2) to obtain a piezoelectric ceramic highly-filled silicone rubber composite ink material for ink direct writing; wherein the thickening treatment is carried out by adopting a vacuum oven for thickening for 30min at the temperature of 50 ℃ and the vacuum degree of-0.08 MPa.
Application example 7
The application example is that the piezoelectric ceramic high-filling silicone rubber composite ink material prepared in the embodiment 7 is used for preparing a porous frame workpiece as a sample through ink direct-writing printing, and the technological parameters of the ink direct-writing printing are as follows: the diameter of the needle is 0.8mm, the pressure is 0.3MPa, and the printing speed is 25 cm/min.
Claims (6)
1. The application of the silicone rubber composite ink material as an ink direct-writing printing material is characterized in that the silicone rubber composite ink material mainly comprises the following raw materials in parts by weight:
184100-600 parts of polydimethyl silicone rubber SLYGARD,
400-900 parts of piezoelectric ceramic filler,
200-500 parts of a solvent;
wherein, the total amount of the polydimethyl silicone rubber SLYGARD 184 and the piezoelectric ceramic filler is 1000 parts;
the preparation method of the silicone rubber composite ink material comprises the following steps:
(1) under the condition of normal temperature, adding piezoelectric ceramic filler into a solvent, and fully mixing to obtain a mixed liquid for later use;
(2) adding silicon rubber into the mixed solution obtained in the step (1), and fully mixing to obtain a silicon rubber matrix mixed liquid for later use;
(3) thickening the silicone rubber matrix mixed liquid obtained in the step (2) to obtain a piezoelectric ceramic ultra-high filling silicone rubber composite ink material for ink direct-writing printing; the piezoelectric ceramic ultra-high filling silicone rubber composite ink material for ink direct-writing printing is obtained through thickening, and the shear rate is 20-200 s at normal temperature -1The viscosity is 10 to 100 mPas.
2. Use according to claim 1, characterized in that: the piezoelectric ceramic filler comprises at least one of barium titanate, potassium niobate and lead zirconate titanate.
3. Use according to claim 1, characterized in that: the solvent comprises at least one or more of alcohol liquid, ester liquid, N-dimethylformamide and acetone.
4. The application of the compound fertilizer as claimed in claim 1, characterized in that the raw materials mainly comprise the following components in parts by weight:
184100-300 parts of polydimethyl silicone rubber SLYGARD,
700-900 parts of piezoelectric ceramic filler,
200-500 parts of a solvent;
wherein, the total amount of the polydimethyl silicone rubber SLYGARD 184 and the piezoelectric ceramic filler is 1000 parts.
5. Use according to claim 1, characterized in that: and (3) thickening for 20-90 min by adopting a vacuum oven at the temperature of 40-60 ℃ and under the vacuum degree of-0.01 to-0.09 MPa.
6. Use according to claim 1, characterized in that: the technological parameters of the ink direct-writing printing are as follows: the diameter of the needle head is 0.6-1.2 mm, the pressure is 0.07-0.3 MPa, and the printing speed is 15-25 cm/min.
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