CN114672133B - Dielectric frequency stable barium strontium titanate/polyether-ether-ketone composite material and preparation method thereof - Google Patents

Dielectric frequency stable barium strontium titanate/polyether-ether-ketone composite material and preparation method thereof Download PDF

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CN114672133B
CN114672133B CN202210269424.2A CN202210269424A CN114672133B CN 114672133 B CN114672133 B CN 114672133B CN 202210269424 A CN202210269424 A CN 202210269424A CN 114672133 B CN114672133 B CN 114672133B
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高峰
刘书航
郭艺婷
吴思晨
许杰
张萍
楼志豪
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Northwestern Polytechnical University
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Abstract

Barium strontium titanate/polyether-ether-ketone composite material with dielectric frequency stability and preparation method thereof, wherein Ba is used for preparing the composite material 0.6 Sr 0.4 TiO 3 The powder is used as a filler, the polyether-ether-ketone powder is used as a base material, the polyether-sulfone powder is used as an interface modifier, the polyether-ether-ketone is melted and cooled after sintering, and the surface of the polyether-sulfone modified barium strontium titanate powder particles is covered with the polyether-ether-ketone powder, so that the inorganic barium strontium titanate particles are uniformly coated with the polyether-ether-ketone, the ceramic phase and the polymer phase are uniformly mixed, and the surfaces are fully contacted. The application has simple operation, the dielectric constant of the obtained polyether sulfone modified barium strontium titanate/polyether ether ketone composite material has higher frequency stability, low dielectric loss and high dielectric adjustability, provides an effective way for synthesizing a novel ceramic/polymer composite material with dielectric adjustability and good dielectric property, and provides a technical basis for functional optimization, interface modification and application of the subsequent ceramic/polymer composite material.

Description

Dielectric frequency stable barium strontium titanate/polyether-ether-ketone composite material and preparation method thereof
Technical Field
The application relates to the technical field of preparation of ceramic/polymer dielectric functional composite materials, in particular to a polyether sulfone modified Ba with high dielectric frequency stability 0.6 Sr 0.4 TiO 3 A polyether-ether-ketone functional composite material and a preparation method thereof.
Background
With the continuous development of the information age, single-function ceramic materials cannot meet the demands of production and living. The ceramic/polymer functional composite material has excellent comprehensive properties of good flexibility, strong processability, small density, complex forming and the like, can be used for manufacturing electronic components such as an electric tuning filter, a phased array antenna, a dielectric phase shifter and the like, can be used as a dielectric material for manufacturing energy storage equipment and an embedded capacitor, and has wide application prospect.
Barium strontium titanate (Ba) 0.6 Sr 0.4 TiO 3 BST) is an electronic ceramic material with a typical perovskite structure, has the advantages of high dielectric constant, low dielectric loss, high dielectric adjustability, high insulation resistance and the like, can be widely applied to various electronic components such as ferroelectric memories, capacitors, phase shifters and the like, and has important roles in the field of electronic functional materials. However, the traditional BST ceramic material has large brittleness, poor impact resistance, higher sintering temperature (about 1400 ℃) and difficult manufacturing of components with complex shapes, and greatly limits the application of the traditional BST ceramic material in the fields of dielectric phase shifters, phased array antennas and the like. Compared with BST ceramic materials, the polymer material polyether ether ketone (PEEK) has the advantages of strong workability, excellent mechanical property, good chemical stability, stable dielectric constant along with frequency change and the like. However, the dielectric constant of PEEK is very small (about 3.2), if BST and PEEK polymer materials are compounded, the defects of the two materials are overcome through the composition and structural design of the materials, and the ceramic/polymer functional composite material with excellent dielectric property and easy processability is hopeful to be prepared.
However, complex interfaces exist in the ceramic/polymer functional composite material, and the interfaces have great influence on the dielectric properties of the composite material, so that the dielectric properties of the functional composite material can be improved by improving the interfaces between the inorganic filler and the polymer matrix, and how to enhance the interfacial bondability of the organic and inorganic phases becomes a difficult problem for preparing the composite material. At present, a silane coupling agent is often adopted to enhance the interface bonding between a ceramic phase and an organic phase, but the processing temperature of the BST/PEEK composite material is higher than the boiling point of the silane coupling agent on the market, so that the silane coupling agent can fail, and a new method for improving the interface bonding between the BST and the PEEK needs to be found.
Polyethersulfone (PES) is a high performance amorphous polymer that is soluble in a small number of polar solutions (e.g., N' N dimethylformamide). PES has a molecular structure similar to PEEK, and has good compatibility with PEEK at a certain content. Therefore, the PES and PEEK with proper proportion have better compatibility and interface binding force, and the PES can be used as a buffer layer between the BST and PEEK. According to the application, PES and BST are blended and modified by adopting a supersaturation method, and then the modified BST and PEEK are compounded to obtain the BST/PEEK composite material with good interface bonding property and dielectric property.
In 2015 Wenlong Jiang et al published a paper (DOI: 10.1002/app.41728) entitled Poly (ether ether ketone)/wrapped graphite nanosheets with poly (Ether sulfone) compositions, preparation, mechanical properties, and tribological behavior, and dispersed Polyethersulfone (PES) -coated Graphite Nanoplatelets (GNS) in a Polyetheretherketone (PEEK) matrix by melt blending to prepare a wear resistant composite material having excellent tribological properties and good mechanical/thermal properties. In 2017, YIng Hu et al published a paper (DOI: 10.1177/0954008317723445) entitled Improvement in the mechanical and friction performance of poly (etherether ketone) composites by addition of modificatory short carbon fibers and zinc oxide, and the use of PES to coat short carbon fibers improved the tribological, mechanical and thermal properties of the composite material. In 2018, yufei Chen et al published a paper titled Micromorphology and mechanical and dielectric properties of bismaleimide composite modified by multiwalled carbon nanotubes and polyethersulfone (DOI: 10.1155/2018/9456971), and an OMWCNT/PES-MBAE composite material was prepared by an in situ sol-gel method, which improved the toughness of the material by 53.08%. In 2018, wenhan Xu et al published under the title High-k polymer nanocomposites filled with hyperbranched phthalocyanine-coated BaTiO 3 for high-temperature and elevated field applications paper (DOI: 10.1021/acsami.8b01129), which uses polyether sulfone (PES) as a matrix and phthalocyanine molecules (CuPc) and hyperbranched phthalocyanine (HCuPc) coated barium titanate nanoparticles (BT) as fillers, a thermal stability nanocomposite is prepared, the bonding between HCuPc and PES is enhanced, and the thermal stability nanocomposite is used for high-electric field and high-temperature medium application. Comparison shows that the hyperbranched coating can be usedThe dielectric response and the breakdown strength of the composite material are improved. The dielectric loss of HCuPc/PES is 40% lower than that of BT-CuPc/PES, and the breakdown strength is about 110% higher than that of BT-CuPc/PES. In 2020, qiang Deng et al published under the name Interface Enhancement-Induced Improvement of Dielectric Traits in Poly (Ether Sulfone)/Ti 3 C 2 MXene/KH550 Nanocompositions paper (DOI: 10.1007/s 11664-020-08467-2) PES/Ti was prepared by solution casting 3 C 2 The MXene/KH550 ternary nanocomposite material has the advantages of improved dielectric constant, and reduced dielectric loss and conductivity. 2021, shuhang Liu et al published under the title Microstructure and dielectric properties of (Ba 0.6 Sr 0.4 )TiO 3 The paper/PEEK functional composites prepared via cold-pressing sintering (DOI: 10.1016/j. Compscitech. 2021.109228) used a cold press sintering process to prepare BST/PEEK functional composites, tested the dielectric properties of the materials and simulated the dielectric constants of the composites using different theoretical models. The silane coupling agent KH550 is adopted to improve the interfacial compatibility between BST and PEEK, and the fact that the sintering temperature is higher than the boiling point of KH550 to volatilize and lose efficacy is found, so that the effect of improving the interfacial compatibility of inorganic and organic phases is not achieved.
Related researches on the conventional PES modified ceramic/polymer composite material mainly concentrate on improving the mechanical property, friction and wear property, thermodynamic property, hydrophilicity and the like of the material, and related researches on the dielectric field are less. The conventional PES modified ceramic/polymer composite material has the defects of uneven microstructure, high dielectric loss, unstable dielectric constant along with frequency change and the like, and the dielectric property of the ceramic/polymer prepared by the prior art is insufficient for the subsequent dielectric application. At the same time, at present, a melt extrusion method is mostly adopted to process ceramic/polymer composite materials, the fluidity of composite powder added with ceramic particles is poor, the roughness is increased, and discontinuous phenomenon is easy to occur in the extrusion process, even machine blockage is caused. Therefore, the composite material formed by melt extrusion cannot be added with more ceramic powder, and the dielectric property of the ceramic/polymer composite material mainly comes from a ceramic phase, which limits the improvement of the dielectric property. In addition, for the existing BST/PEEK composite material, an effective means for enhancing the interfacial bonding property between an inorganic phase and an organic phase is lacked, so that the breakdown strength of the material is low, and the dielectric adjustability is low. Therefore, the preparation and modification process of the PES modified BST/PEEK composite material are very important to the development and application of ceramics/polymers.
Disclosure of Invention
In order to solve the problems of poor interfacial bonding property of inorganic and organic phases and difficult processing in the prior art, the application provides a dielectric frequency stability barium strontium titanate/polyether-ether-ketone composite material and a preparation method thereof.
The application provides a dielectric frequency stability barium strontium titanate/polyether-ether-ketone composite material which adopts Ba 0.6 Sr 0.4 TiO 3 The powder is used as a filler, the polyether-ether-ketone powder is used as a base material, and the polyether sulfone powder is used as an interface modifier; wherein the Ba is 0.6 Sr 0.4 TiO 3 The volume ratio of the powder is 35-45%, the volume ratio of the polyethersulfone powder is 2-10%, and the volume ratio of the polyetheretherketone powder is 45-63%.
The method for preparing the dielectric frequency stability barium strontium titanate/polyether-ether-ketone composite material 1 is characterized by comprising the following specific processes:
step 1, batching:
weighing Ba according to the proportion 0.6 Sr 0.4 TiO 3 Powder, polyetheretherketone powder and polyethersulfone powder;
step 2, preparing a polyether sulfone homogeneous solution:
completely dissolving the weighed polyethersulfone powder in N' N dimethylformamide solution, and magnetically stirring for 0.5-1 h at 60-80 ℃ to obtain a homogeneous phase solution of polyethersulfone;
step 3, preparing Ba 0.6 Sr 0.4 TiO 3 Suspension:
ba to be weighed 0.6 Sr 0.4 TiO 3 Adding the powder into the obtained polyether sulfone homogeneous solution, and mixing to obtain Ba 0.6 Sr 0.4 TiO 3 A suspension;
in the preparation of Ba 0.6 Sr 0.4 TiO 3 When in suspension, the ultrasonic vibration time is 4-5 h, the ultrasonic power is 150-200W, and the vibration frequency is 40kHz;
step 4, preparing polyether sulfone blended Ba 0.6 Sr 0.4 TiO 3 Powder:
the obtained Ba 0.6 Sr 0.4 TiO 3 Placing the suspension in an evaporation dish, heating in a fume hood to evaporate N' N dimethylformamide as solvent in the solution, and adhering polyethersulfone in the solvent to Ba 0.6 Sr 0.4 TiO 3 The surface of the particles; obtaining polyether sulfone blend Ba 0.6 Sr 0.4 TiO 3 Powder;
in preparing the polyethersulfone blended Ba 0.6 Sr 0.4 TiO 3 When the powder is heated, the heating temperature is 160-220 ℃; the heating rate of heating is 3-5 deg.C/min.
Step 5, preparing composite powder:
mixing the obtained polyether sulfone blended barium strontium titanate filler with the weighed polyether-ether-ketone powder to obtain a mixed material; adding ethanol into the mixture, and ball milling; drying; obtaining composite powder for dry pressing molding;
when the composite powder is prepared, the rotating speed of the ball mill is 250-300 r/min, the ball milling time is 8-12 h, and the drying temperature is 55-65 ℃.
The addition amount of the ethanol is three times of the volume of the mixed material.
Step 6, dry press molding:
filling the obtained composite powder into a mould, and performing dry press molding to obtain polyether sulfone modified Ba 0.6 Sr 0.4 TiO 3 The polyether-ether-ketone composite material blank is used for subsequent sintering;
the pressure of the dry press molding is 100 MP-150 MPa, and the pressure maintaining time is 30s.
The polyethersulfone modified Ba 0.6 Sr 0.4 TiO 3 The diameter of the polyether-ether-ketone composite material blank is 12mm, and the thickness is 1mm.
Step 7, preparing polyethersulfone modified Ba 0.6 Sr 0.4 TiO 3 Polyether-ether-ketone composite material. Preparation of polyethersulfone modified Ba by sintering 0.6 Sr 0.4 TiO 3 Heating the green body pressed in the step 6 to 340-420 ℃ at a heating rate of 3-5 ℃ per minute, preserving heat for 1-2 hours, cooling to room temperature along with a furnace, and rearranging particles in the green body to obtain sintered polyethersulfone modified Ba 0.6 Sr 0.4 TiO 3 Polyether-ether-ketone composite material;
the polyethersulfone modified Ba 0.6 Sr 0.4 TiO 3 The dielectric constant of the polyether-ether-ketone composite material at 1kHz is 8.9-15.0.2, the dielectric loss is 0.0062-0.0164, the maximum frequency dispersion factor is 0.040-0.072, and the dielectric adjustability is 22.00-34.18.
The application has simple operation and low requirement on equipment. The dielectric constant of the obtained modified BST/PEEK composite material has higher frequency stability, low dielectric loss and high dielectric adjustability, and provides an effective way for synthesizing a novel ceramic/polymer composite material with dielectric adjustability and good dielectric property.
Compared with the prior art, the application has the following beneficial technical effects:
the PES-BST/PEEK composite material prepared by the method has the advantages of good stability of dielectric constant along with frequency change, low dielectric loss and higher dielectric adjustability. FIG. 1 shows SEM pictures of PES-BST/PEEK composite materials prepared by the application, and it is obvious from the pictures that PEEK after sintering is melted and cooled, and the PEEK is covered on the surfaces of PES modified BST powder particles to form a state that PEEK uniformly wraps inorganic BST particles, and ceramic phases and polymers are uniformly mixed and are in full surface contact. As PES and PEEK both have benzene ring structures in molecular chains, the dispersion force between benzene rings makes PES and PEEK have certain attractive force, so that PEEK and PES have larger intermolecular force. And PEEK and PES are long-chain structures and are easy to crosslink and wind, so that PEEK and PES have good compatibility, and therefore, the interface combination between inorganic BST particles and organic PEEK can be enhanced by modifying a proper amount of PES, and the composite material is further improvedThe comprehensive performance of the material. FIG. 2 shows the dielectric constant and dielectric loss of PES-BST/PEEK composite material as a function of frequency, at a test frequency of 100-1 Hz. Curve 1 is the dielectric constant versus frequency for the PES-BST/PEEK composite of example 1. As can be seen from curve 1, the dielectric constants of the samples all decreased slightly with increasing frequency, but remained essentially stable. Curve 2 is a plot of dielectric loss versus frequency for the PES-BST/PEEK composite of example 1, showing that the dielectric loss decreases with increasing frequency, gradually slowing down, and eventually stabilizing around 0.006. At 1khz, the dielectric constant and dielectric loss of the material were 14.2 and 0.0091, respectively. To measure dielectric constant epsilon of ceramic/polymer composites r The degree of frequency variation defines the frequency dispersion factor F (x) The following are provided:
wherein F is (x) Is the frequency dispersion factor epsilon of the composite material r(100) Is the dielectric constant epsilon of the composite material at 100Hz r(x) Is the dielectric constant of the composite material at a frequency of x Hz. F (F) (x) The smaller the value, the better the dielectric frequency stability. FIG. 3 is a graph showing the frequency dispersion factor of PES-BST/PEEK composite material, curve 3 is a graph showing the frequency dispersion factor of PES-BST/PEEK composite material in example 2 as a function of frequency, curve 4 is a graph showing the frequency dispersion factor of PES-BST/PEEK composite material in example 4 as a function of frequency, curve 5 is a graph showing the frequency dispersion factor of PES-BST/PEEK composite material in example 1 as a function of frequency, and curve 6 is a graph showing the frequency dispersion factor of PES-BST/PEEK composite material in example 3 as a function of frequency. As can be seen from the graph, the frequency dispersion factor of the composite material generally increases with increasing frequency. The maximum frequency dispersion factor of the PES-BST/PEEK composite sample is between 0.02 and 0.07 in the range of 100Hz-1M Hz. Table 1 summarizes some of the reported dielectric properties of BST/polymer composites. The dielectric constant of the composite material is 8-75, the dielectric loss is 0.0225-0.1180, F (1M) At 0.060In the range of 6 to 0.5048, the dielectric loss of the PES-BST/PEEK composite of example 1 was only 0.009, an order of magnitude less than other composites. In addition, F of (1M) The value of (2) is also much smaller than other composites. This is because the dielectric constant of ceramic/polymer functional composites is mainly derived from dipole-oriented polarization and interface polarization within the material. When the frequency is lower, the change period of the external electric field is longer, and the two polarization phenomena have enough time response; when the frequency is higher, the period of change of the applied electric field is shortened, so that the polarization at the interface of the composite material is not as responsive, and the dielectric constant is reduced with the increase of the frequency. The interface polarization of the PES-BST/PEEK composite material prepared by the method has relatively small change along with the increase of frequency, so that the PES-BST/PEEK composite material has good dielectric frequency stability. Fig. 4 shows that the PES-BST/PEEK composite material has high dielectric adjustability, wherein curve 7 is the variation of the dielectric adjustability of the PES-BST/PEEK composite material with respect to an external electric field in example 2, curve 8 is the variation of the dielectric adjustability of the PES-BST/PEEK composite material with respect to an external electric field in example 4, curve 9 is the variation of the dielectric adjustability of the PES-BST/PEEK composite material with respect to an external electric field in example 3, and curve 10 is the variation of the dielectric adjustability of the PES-BST/PEEK composite material with respect to an external electric field in example 1. Dielectric tunability refers to the property of a material that has a dielectric constant that varies non-linearly with the change in an applied electric field. With the increase of the externally applied bias electric field, the dielectric adjustability of the composite material is increased, and the phenomenon that the composite material slowly increases and then quickly climbs is presented, wherein the mutation point is called a threshold electric field. The smaller the threshold electric field, the easier it is for the composite to reach the fast rise phase of dielectric tunability at a smaller external electric field. When the applied electric field is 6.5kV/mm, the dielectric adjustability of the PES-BST/PEEK composite material in the embodiment 1 can be up to 34.18%.
TABLE 1 dielectric Properties of BST/Polymer composite
PES-BST/PEEK composite material has good microscopic uniformity, dielectric stability and lower dielectric loss, and provides technical foundation for functional optimization, interface modification and application of subsequent ceramic/polymer composite material.
TABLE 2 test parameters at 1kHz according to the application
Dielectric constant Dielectric loss Maximum frequency dispersion factor Dielectric tunability
8.9～15.0.2 0.0062～0.0164 0.040～0.072 22.00～34.18
Drawings
FIG. 1 is an SEM photograph of PES-BST/PEEK composite material obtained in example 1;
FIG. 2 is a dielectric spectrum of the PES-BST/PEEK composite material prepared in example 1;
FIG. 3 is a schematic diagram showing the frequency stability of PES-BST/PEEK composites prepared in examples 1, 2, 3, and 4;
FIG. 4 is a schematic representation of dielectric tunability of PES-BST/PEEK composites made in examples 1, 2, 3, and 4.
Fig. 5 is a flow chart of the present application.
In the figure:
a plot of dielectric loss versus frequency for the PES-BST/PEEK composite of example 1; curve 3 is the frequency dispersion factor versus frequency curve for the PES-BST/PEEK composite of example 2; curve 4 is the frequency dispersion factor versus frequency curve for the PES-BST/PEEK composite of example 4; curve 5 is the frequency dispersion factor versus frequency curve for the PES-BST/PEEK composite of example 1; curve 6 is the frequency dispersion factor versus frequency curve for the PES-BST/PEEK composite of example 3; curve 7 is the dielectric tunability of the PES-BST/PEEK composite of example 2 as a function of external electric field; curve 8 is the dielectric tunability of the PES-BST/PEEK composite of example 4 as a function of external electric field; curve 9 is the dielectric tunability of the PES-BST/PEEK composite of example 3 as a function of external electric field; curve 10 is the dielectric tunability of the PES-BST/PEEK composite of example 1 as a function of external electric field.
Detailed Description
The application relates to a high dielectric frequency stability polyether sulfone modified barium strontium titanate/polyether ether ketone composite material, which comprises barium strontium titanate powder, polyether ether ketone powder and polyether sulfone powder, wherein the barium strontium titanate powder is used as a filler, the polyether ether ketone powder is used as a base material, and the polyether sulfone powder is used as an interface modifier. The volume fraction of the barium strontium titanate powder is 40%, the volume fraction of the polyethersulfone powder is 2.5-10%, and the volume fraction of the polyetheretherketone powder is 50-57.5%.
The average particle diameter of the barium strontium titanate powder is 0.57 mu m.
TABLE 3 Components of the examples
The specific process for preparing the high dielectric frequency stability polyether sulfone modified barium strontium titanate/polyether ether ketone composite material provided by the embodiment is as follows:
step 1, batching:
and weighing the barium strontium titanate powder, the polyether sulfone powder and the polyether ether ketone powder according to the volume fraction of each material. And (5) standby application.
Step 2, preparing a homogeneous phase solution of polyethersulfone:
completely dissolving the weighed polyethersulfone powder in N' N dimethylformamide solution; the mass ratio of the polyethersulfone to the N' N dimethylformamide solution is 1:4-9. Magnetically stirring at 60-80 deg.c for 30-40 min to obtain homogeneous polyether sulfone solution.
Table 4 parameters of step 2 of each example
Step 3, preparing a barium strontium titanate suspension:
adding the weighed barium strontium titanate powder into the obtained polyether sulfone homogeneous phase solution, and performing ultrasonic vibration for 4-5 hours at normal temperature under 160-200W power and 40kHz frequency to obtain barium strontium titanate suspension;
table 5 parameters of step 3 of each example
Step 4, preparing polyether sulfone blended barium strontium titanate filler:
the polyether sulfone blended barium strontium titanate filler is prepared in a drying mode. The method comprises the steps of placing the obtained barium strontium titanate suspension in an evaporation vessel, placing the evaporation vessel in a fume hood, heating to 180-220 ℃ at a heating rate of 3-5 ℃/min, and evaporating solvent N' N dimethylformamide in the solution, wherein polyethersulfone in the solvent is attached to the surfaces of barium strontium titanate particles; obtaining polyether sulfone blended barium strontium titanate filler;
table 6 parameters of step 4 of each example
Step 5, preparing composite powder:
mixing the obtained polyether sulfone blended barium strontium titanate filler with the weighed polyether-ether-ketone powder to obtain a mixed material; ethanol is added into the mixture. The addition amount of the ethanol is three times of the volume of the mixed material. Ball milling for 8-12 hours at the room temperature at the rotating speed of 250-300 r/min, and then drying in an oven at 55-65 ℃ to finish uniform mixing of polyether-ether-ketone powder and polyether sulfone blended barium strontium titanate filler, thus obtaining composite powder for dry pressing molding;
TABLE 7 parameters of example step 5
Step 6, dry press molding:
loading the composite powder obtained in the step 5 into a die, and performing dry pressing at normal temperature under the pressure of 100-150 MPa; and maintaining the pressure for 30s. And obtaining a green body of the polyether sulfone modified barium strontium titanate/polyether ether ketone composite material for subsequent sintering. The diameter of the blank body is 12mm, and the thickness of the blank body is 1mm.
Table 8 parameters of step 6 of each example
Step 7, preparing a polyether sulfone modified barium strontium titanate/polyether ether ketone composite material:
the polyether sulfone modified barium strontium titanate/polyether ether ketone composite material is prepared by a sintering mode, and concretely comprises the following steps:
heating the obtained blank to 360-420 ℃ at the speed of 3-5 ℃/min and preserving the heat for 60-90 min. And cooling to room temperature along with the furnace after heat preservation is finished, and rearranging particles in the green body. And obtaining the polyether sulfone modified barium strontium titanate/polyether ether ketone composite material.
Table 9 parameters of example step 7
Fig. 1 is a scanning electron microscope photograph of a polyether sulfone modified barium strontium titanate/polyether ether ketone composite material prepared by the embodiment of the application, and it can be seen from the figure that the prepared sample inorganic phase and organic phase have good uniformity and good fusion property of the two organic phases. The dielectric constant of the polyether sulfone modified barium strontium titanate/polyether ether ketone composite material obtained by the application is 8.9-15.0.2 at 1k Hz, the dielectric loss is 0.0062-0.0164, the maximum frequency dispersion factor is 0.040-0.072, and the dielectric adjustability is 22.00-34.18%.
Table 10 test parameters at 1khz for each example

Claims (9)

1. A dielectric frequency stable barium strontium titanate/polyether-ether-ketone composite material is characterized in that Ba is used for preparing 0.6 Sr 0.4 TiO 3 The powder is used as a filler, the polyether-ether-ketone powder is used as a base material, and the polyether sulfone powder is used as an interface modifier; wherein the Ba is 0.6 Sr 0.4 TiO 3 The volume ratio of the powder is 35-45%, the volume ratio of the polyethersulfone powder is 2-10%, and the volume ratio of the polyetheretherketone powder is 45-63%.
2. A method for preparing the dielectric frequency stable barium strontium titanate/polyether ether ketone composite material according to claim 1, which is characterized by comprising the following specific processes:
step 1, batching:
weighing Ba according to the proportion 0.6 Sr 0.4 TiO 3 Powder, polyetheretherketone powder and polyethersulfone powder;
step 2, preparing a polyether sulfone homogeneous solution:
completely dissolving the weighed polyethersulfone powder in N' N dimethylformamide solution, and magnetically stirring for 0.5-1 h at 60-80 ℃ to obtain a homogeneous phase solution of polyethersulfone;
step 3, preparing Ba 0.6 Sr 0.4 TiO 3 Suspension:
ba to be weighed 0.6 Sr 0.4 TiO 3 Adding the powder into the obtained polyether sulfone homogeneous solution, and mixing to obtain Ba 0.6 Sr 0.4 TiO 3 A suspension;
step 4, preparing polyether sulfone blended Ba 0.6 Sr 0.4 TiO 3 Powder:
the obtained Ba 0.6 Sr 0.4 TiO 3 Placing the suspension in an evaporation dish, heating in a fume hood to evaporate N' N dimethylformamide as solvent in the solution, and adhering polyethersulfone in the solvent to Ba 0.6 Sr 0.4 TiO 3 The surface of the particles; obtaining polyether sulfone blend Ba 0.6 Sr 0.4 TiO 3 Powder;
step 5, preparing composite powder:
mixing the obtained polyether sulfone blended barium strontium titanate filler with the weighed polyether-ether-ketone powder to obtain a mixed material; adding ethanol into the mixture, and ball milling; drying; obtaining composite powder for dry pressing molding;
step 6, dry press molding:
filling the obtained composite powder into a mould, and performing dry press molding to obtain polyether sulfone modified Ba 0.6 Sr 0.4 TiO 3 The polyether-ether-ketone composite material blank is used for subsequent sintering;
step 7, preparing polyethersulfone modified Ba 0.6 Sr 0.4 TiO 3 Polyether-ether-ketone composite material; preparation of polyethersulfone modified Ba by sintering 0.6 Sr 0.4 TiO 3 Heating the green body pressed in the step 6 to 340-420 ℃ at a heating rate of 3-5 ℃ per minute, preserving heat for 1-2 hours, cooling to room temperature along with a furnace, and rearranging particles in the green body to obtain sintered polyethersulfone modified Ba 0.6 Sr 0.4 TiO 3 Polyether-ether-ketoneA composite material.
3. The method for preparing a dielectric frequency stabilization strontium barium titanate/polyether ether ketone composite material according to claim 2, wherein the method comprises the steps of preparing Ba 0.6 Sr 0.4 TiO 3 When in suspension, the ultrasonic vibration time is 4-5 h, the ultrasonic power is 150-200W, and the vibration frequency is 40kHz.
4. The method of preparing a dielectric frequency stabilized barium strontium titanate/polyetheretherketone composite material of claim 2, wherein the polyethersulfone blended Ba is prepared in step 4 0.6 Sr 0.4 TiO 3 When the powder is heated, the heating temperature is 160-220 ℃; the heating rate of heating is 3-5 deg.C/min.
5. The method for preparing the dielectric frequency stability barium strontium titanate/polyether-ether-ketone composite material according to claim 2, wherein the rotational speed of a ball mill is 250-300 r/min, the ball milling time is 8-12 h, and the drying temperature is 55-65 ℃ when the composite powder material is prepared.
6. The method of preparing a dielectric frequency stabilized barium strontium titanate/polyetheretherketone composite as claimed in claim 2, wherein the ethanol is added in an amount of three times the volume of the mixture in step 5.
7. The method for preparing a dielectric frequency stabilization barium strontium titanate/polyether-ether-ketone composite material according to claim 2, wherein the pressure of the dry press molding is 100MP to 150MPa and the dwell time is 30s.
8. The method for preparing a dielectric frequency stabilization barium strontium titanate/polyether ether ketone composite material according to claim 2, wherein the polyether sulfone is modified with Ba 0.6 Sr 0.4 TiO 3 The diameter of the polyether-ether-ketone composite material blank is 12mm, and the thickness is 1mm.
9. Such asThe method for preparing the dielectric frequency stability barium strontium titanate/polyether ether ketone composite material according to claim 2, wherein the polyether sulfone modified Ba 0.6 Sr 0.4 TiO 3 The dielectric constant of the polyether-ether-ketone composite material at 1kHz is 8.9-15.0, the dielectric loss is 0.0062-0.0164, the maximum frequency dispersion factor is 0.040-0.072, and the dielectric adjustability is 22.00-34.18.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060116923A (en) * 2005-05-11 2006-11-16 삼성전자주식회사 Novel organic polymer semiconductor, method for forming organic polymer semiconductor thin film and organic thin film transistor using the same
CN110684222A (en) * 2019-10-14 2020-01-14 深圳市峰泳科技有限公司 Polymer-based composite dielectric material and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060116923A (en) * 2005-05-11 2006-11-16 삼성전자주식회사 Novel organic polymer semiconductor, method for forming organic polymer semiconductor thin film and organic thin film transistor using the same
CN110684222A (en) * 2019-10-14 2020-01-14 深圳市峰泳科技有限公司 Polymer-based composite dielectric material and preparation method thereof

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