CN107141763B - Inorganic-organic composite flexible high-dielectric film and preparation method thereof - Google Patents

Inorganic-organic composite flexible high-dielectric film and preparation method thereof Download PDF

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CN107141763B
CN107141763B CN201710364635.3A CN201710364635A CN107141763B CN 107141763 B CN107141763 B CN 107141763B CN 201710364635 A CN201710364635 A CN 201710364635A CN 107141763 B CN107141763 B CN 107141763B
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CN107141763A (en
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万维
罗俊荣
苑文香
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Huaihua University
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Abstract

An inorganic-organic composite flexible high dielectric film and a preparation method thereof, comprising the following steps: mixing the polyurethane elastomer with calcium copper titanate powder, a vulcanizing agent and a coupling agent to obtain composite raw rubber; and carrying out vulcanization and coupling reaction on the composite crude rubber to prepare a film, thus obtaining the inorganic-organic composite flexible high-dielectric film. The preparation method comprises the steps of mixing the components to form composite raw rubber, carrying out a vulcanization reaction on continuous phase polyurethane elastomers in the composite raw rubber under the action of a vulcanizing agent to form polyurethane aged rubber with a three-dimensional net structure, and carrying out a coupling reaction on dispersed phase calcium copper titanate powder filled in the polyurethane elastomers and the polyurethane elastomers under the action of a coupling agent to obtain the inorganic-organic composite flexible high-dielectric film with the polyurethane aged rubber with the three-dimensional net structure as a main structure and the calcium copper titanate powder filled in the three-dimensional net structure. The film has high dielectric constant, low dielectric loss, strong tensile property, excellent flexibility and good processing property.

Description

Inorganic-organic composite flexible high-dielectric film and preparation method thereof
Technical Field
The invention relates to the technical field of dielectric materials, in particular to an inorganic-organic composite flexible high-dielectric film and a preparation method thereof.
Background
With the rapid development of information and microelectronic industries, the application requirements of miniaturization, integration, intellectualization and high frequency of semiconductor devices are rapidly increasing. More and more electronic components, such as dielectric substrates, dielectric antennas, dynamic random access memories, embedded thin film capacitors, and the like, require dielectric materials to have excellent dielectric properties and good mechanical properties and processability.
The traditional inorganic piezoelectric ceramics have high dielectric constant and higher stability, but the application of the traditional inorganic piezoelectric ceramics is limited by the defects of large brittleness, higher processing temperature, poor compatibility with the current circuit integrated processing technology and the like.
In recent years, calcium copper titanate (CaCu) having perovskite-like structure3Ti4O12CCTO) materials have received a wide range of attention from researchers. CCTO is an oxide having a body-centered cubic perovskite-like structure. CCTO has an ultra-high dielectric constant (10)4) And the dielectric constant has good frequency stability and temperature stability. Otherwise different from BaTiO3When the ferroelectric material has phase change at the Curie point, no phase change is observed in CCTO within the temperature range of 100-600K. In addition, CCTO has good nonlinear current-voltage characteristics. The excellent characteristics of CCTO make it applicable to many fields such as capacitor, gas detector, photoluminescence device, resistive random access memory, etc.
At present, the research is more about the synthesis process of CCTO powder and the performance improvement of CCTO ceramic materials. In practical applications, however, the dielectric thin film is more suitable for use in the fabrication of various electrical devices. Although epitaxial single crystal CCTO films have been reported to grow successfully on MgO, LaAlO3On oxide single crystal substrates, polycrystalline CCTO films have also been reported to grow successfully on platinized silicon wafers, and pure inorganic CCTO films have high dielectric constants. However, pure inorganic CCTO films have high dielectric loss, low breakdown voltage, high brittleness, and low structural strength, which results in poor processability and a large gap from practical applications.
Disclosure of Invention
Therefore, it is necessary to provide an inorganic-organic composite flexible high dielectric film with high dielectric constant, low dielectric loss and good flexibility and a preparation method thereof.
A preparation method of an inorganic-organic composite flexible high-dielectric film comprises the following preparation steps:
mixing the polyurethane elastomer with calcium copper titanate powder, a vulcanizing agent and a coupling agent to obtain composite raw rubber;
and carrying out vulcanization and coupling reaction on the composite crude rubber to prepare a film, thus obtaining the inorganic-organic composite flexible high-dielectric film.
In the preparation method of the inorganic-organic composite flexible high dielectric film, the polyurethane elastomer, the calcium copper titanate powder, the vulcanizing agent and the coupling agent are mixed to form composite raw rubber, continuous phase polyurethane elastomers in the composite raw rubber are subjected to a vulcanization reaction under the action of the vulcanizing agent to form polyurethane aged rubber with a three-dimensional net structure, and dispersed phase calcium copper titanate powder filled in the polyurethane elastomers is subjected to a coupling reaction with the polyurethane elastomers under the action of the coupling agent to obtain the inorganic-organic composite flexible high dielectric film taking the polyurethane aged rubber with the three-dimensional net structure as a main structure and filling the calcium copper titanate powder in the three-dimensional net structure. Compared with the existing pure inorganic CCTO film, the inorganic-organic composite flexible high-dielectric film not only has the advantages of high dielectric constant, low dielectric loss and the like, but also has the advantages of strong tensile resistance, excellent flexibility and the like, thereby ensuring good processing performance.
In one embodiment, the mass ratio of the calcium copper titanate powder to the polyurethane elastomer is 1-5: 1.
in one embodiment, the coupling agent is at least one selected from the group consisting of coupling agent KH550, coupling agent KH560 and coupling agent A151; the mass ratio of the coupling agent to the polyurethane elastomer is 0.01-0.1: 1.
in one embodiment, the vulcanizing agent is selected from at least one of a bis-penta vulcanizing agent and dicumyl peroxide; the mass ratio of the vulcanizing agent to the polyurethane elastomer is 0.01-0.05: 1.
in one embodiment, the mixing conditions are 20-120 min in an open mill mixer.
In one embodiment, the conditions of the sulfurization and coupling reactions are: and heating and pressurizing, wherein the heating temperature is 150-200 ℃, and the pressurizing pressure is 2-6 Mpa.
In one embodiment, the method for preparing the film is a die pressing method, and the step of performing vulcanization and coupling reaction on the composite raw rubber to prepare the film specifically comprises the following steps: and placing the composite crude rubber into a mold with the thickness of 50-200 mu m, and keeping the temperature and the pressure in a vulcanizing machine for 5-20 min to obtain the inorganic-organic composite flexible high-dielectric film.
In one embodiment, the preparation method of the inorganic-organic composite flexible high dielectric film further comprises the following steps:
uniformly mixing calcium carbonate powder, copper oxide powder, titanium dioxide powder, inorganic salt and a solvent to obtain a mixed slurry, wherein the calcium carbonate powder, the copper oxide powder and the titanium dioxide powder are according to CaCu3Ti4O12The weight ratio of the inorganic salt to the calcium carbonate powder is 15-25: 1, the volume-mass ratio of the solvent to the calcium carbonate powder is 15-25 mL: 1g of a compound;
drying the mixed slurry, and calcining at 700-900 ℃ for 1-7 h to obtain inorganic salt-containing calcium copper titanate intermediate powder;
and washing the inorganic salt-containing copper calcium titanate intermediate powder to remove inorganic salt, and drying to obtain the copper calcium titanate powder.
In one embodiment, the step of uniformly mixing the calcium carbonate powder, the copper oxide powder, the titanium dioxide powder, the inorganic salt and the solvent to obtain the mixed slurry comprises:
uniformly mixing the calcium carbonate powder, the copper oxide powder, the titanium dioxide powder and the solvent, adding the inorganic salt, and continuously and uniformly mixing to obtain the mixed slurry.
Also provides an inorganic-organic composite flexible high-dielectric film prepared by the preparation method of the inorganic-organic composite flexible high-dielectric film.
Drawings
FIG. 1 is a stress-strain curve of the inorganic-organic composite flexible high dielectric film obtained in example 3;
FIG. 2 is a scanning electron micrograph of a cross section of the inorganic-organic composite flexible high dielectric thin film obtained in example 3.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the accompanying drawings and specific examples. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The method for preparing an inorganic-organic composite flexible high dielectric film according to an embodiment of the present invention includes the following steps S1 to S2.
Step S1: and mixing the polyurethane elastomer with the calcium copper titanate powder, the vulcanizing agent and the coupling agent to obtain the composite raw rubber.
CCTO has an ultra-high dielectric constant (10)4) And the dielectric constant has good frequency stability and temperature stability. The polyurethane elastomer has good adhesiveness, wide tolerance temperature (-50-150 ℃), excellent processing performance, lower processing temperature, lower dielectric loss, excellent insulativity, flexibility and high breakdown voltage, but the dielectric constant of the polyurethane elastomer is usually lower, so that the performance requirements of microelectronic components are difficult to meet. Therefore, the polyurethane elastomer and the copper calcium titanate powder are selected to form the inorganic-organic composite film through research.
Step S1, uniformly mixing the polyurethane elastomer with the calcium copper titanate powder, the vulcanizing agent and the coupling agent by adopting a mixing method, so that the calcium copper titanate powder is filled into the polyurethane elastomer, wherein the polyurethane elastomer is a continuous phase, the calcium copper titanate powder is a dispersed phase, and composite green rubber with fluidity and plasticity is formed, and the mixing is favorable for the vulcanization and coupling reaction in the subsequent step S2, the film preparation and other processes.
In the examples, the mixing conditions were 20 to 120min in an open mill.
In the embodiment, the mass ratio of the calcium copper titanate powder to the polyurethane elastomer is 1-5: 1. the ratio of the components also affects the vulcanization and coupling reactions of step S2. Within the proportion range, the calcium copper titanate powder can be filled into the polyurethane elastomer to the maximum extent, and the properties of the calcium copper titanate powder and the polyurethane elastomer can be combined best.
Preferably, the mass ratio of the calcium copper titanate powder to the polyurethane elastomer is 2-4: 1. more preferably, the mass ratio of the calcium copper titanate powder to the polyurethane elastomer is 3: 1.
in the embodiment, the polyurethane elastomer is a mixing polyurethane elastomer, and the obtained inorganic-organic composite flexible high-dielectric film has better flexibility.
In an embodiment, the coupling agent is at least one selected from the group consisting of a coupling agent KH550 (chemical name: γ -aminopropyltriethoxysilane), a coupling agent KH560 (chemical name: γ - (2, 3-glycidoxy) propyltrimethoxysilane), and a coupling agent A151 (chemical name: vinyltriethoxysilane). In the embodiment, the mass ratio of the coupling agent to the polyurethane elastomer is 0.01-0.1: 1. the coupling agent simultaneously contains an inorganic group and an organic group, the inorganic group can act with the copper calcium titanate powder, the organic group can act with the polyurethane elastomer, and the coupling agent can combine the copper calcium titanate powder with the polyurethane elastomer.
Preferably, the mass ratio of the coupling agent to the polyurethane elastomer is 0.04-0.08: 1. more preferably, the mass ratio of coupling agent to polyurethane elastomer is 0.06: 1.
in an embodiment, the vulcanizing agent is selected from at least one of a bis-penta vulcanizing agent (bis-2, 5 vulcanizing agent) and dicumyl peroxide. The mass ratio of the vulcanizing agent to the polyurethane elastomer is 0.01-0.05: 1. the vulcanizing agent enables the polyurethane elastomers to generate a vulcanization reaction to generate the polyurethane rubber with a three-dimensional network structure.
Preferably, the mass ratio of vulcanizing agent to polyurethane elastomer is 0.03: 1.
in the examples, the calcium copper titanate powder is commercially available, but currently, the calcium copper titanate powder is produced in a relatively small amount in a commercial manner and is generally manufactured by self-manufacturing.
In the examples, calcium copper titanate powder was synthesized by the molten salt method. Inorganic salts with low melting point are used as reaction media, reactants have certain solubility in molten salt, the diffusion rate of ions is greatly accelerated, atomic scale mixing of the reactants is realized in a liquid phase, and the reaction is converted from solid-solid reaction to solid-liquid reaction. Compared with the conventional solid phase method, the method has the advantages of simple process, low synthesis temperature, short heat preservation time, uniform chemical components of the synthesized powder, good crystal morphology, high phase purity and the like. In addition, the method for preparing the calcium copper titanate powder also has the advantages of easy separation of inorganic salt and reusability.
Specifically, the preparation method of the copper calcium titanate powder comprises the following steps:
uniformly mixing calcium carbonate powder, copper oxide powder, titanium dioxide powder, inorganic salt and a solvent to obtain a mixed slurry, wherein the calcium carbonate powder, the copper oxide powder and the titanium dioxide powder are according to CaCu3Ti4O12The weight ratio of the inorganic salt to the calcium carbonate powder is 15-25: 1, the volume-mass ratio of the solvent to the calcium carbonate powder is 15-25 mL: 1g of a compound; drying the mixed slurry, and calcining at 700-900 ℃ for 1-7 h to obtain inorganic salt-containing copper calcium titanate intermediate powder; and (3) washing the intermediate powder of the copper calcium titanate containing inorganic salt to remove the inorganic salt, and drying to obtain the copper calcium titanate powder.
In the preparation steps of the copper calcium titanate powder, the proportion of the inorganic salt, the solvent and the calcium carbonate powder is controlled, so that the prepared copper calcium titanate powder has good crystal morphology and high phase purity, and the dielectric property and the tensile resistance of the inorganic-organic composite flexible high-dielectric film are improved.
Preferably, the drying temperature of the mixed slurry and the drying temperature of the inorganic salt-removed copper calcium titanate intermediate powder are 60-100 ℃.
Further, the step of uniformly mixing calcium carbonate powder, copper oxide powder, titanium dioxide powder, inorganic salt and a solvent to obtain a mixed slurry comprises: the calcium carbonate powder, the copper oxide powder, the titanium dioxide powder and the solvent are uniformly mixed, and then the inorganic salt is added to be continuously and uniformly mixed, so that the mixed slurry is obtained.
Furthermore, the step of uniformly mixing adopts a ball milling method, the rotation speed of the ball milling is 160 rpm-230 rpm, and the time for uniformly mixing the calcium carbonate powder, the copper oxide powder, the titanium dioxide powder and the solvent is 1-6 h; adding inorganic salt and continuously mixing uniformly for 0.5-3 h.
Preferably, the inorganic salt is at least one of sodium chloride and potassium chloride. Preferably, the solvent is absolute ethanol.
Preferably, the step of washing the inorganic salt-containing copper calcium titanate intermediate powder is washing with hot deionized water, wherein the temperature of the hot deionized water is 60-90 ℃.
Step S2: and carrying out vulcanization and coupling reaction on the composite crude rubber to prepare a film, thus obtaining the inorganic-organic composite flexible high-dielectric film.
In the compounded raw rubber, continuous phase polyurethane elastomers are subjected to a vulcanization reaction under the action of a vulcanizing agent to form polyurethane gel with a three-dimensional network structure, and dispersed phase calcium copper titanate powder filled in the polyurethane elastomers is subjected to a coupling reaction with the polyurethane elastomers under the action of a coupling agent to obtain the inorganic-organic composite flexible high-dielectric film which takes the polyurethane gel with the three-dimensional network structure as a main structure and is filled with the calcium copper titanate powder. Namely, the inorganic-organic composite flexible high dielectric film is a calcium copper titanate-polyurethane composite dielectric film.
Compared with the existing pure inorganic CCTO film, CCTO/polyimide composite material, CCTO/epoxy resin composite film and CCTO/polyvinylidene fluoride composite film, the inorganic and organic composite flexible high-dielectric film not only has the advantages of high dielectric constant, low dielectric loss and the like, but also has the advantages of strong tensile resistance, excellent flexibility and the like, thereby having good processing performance.
The inorganic-organic composite flexible high dielectric film obtained by testing at the room temperature at the frequency of 100Hz has the dielectric constant as high as 41, the dielectric loss as low as 0.05, the tensile elongation at break as high as 150 percent and the highest as 308.9 percent.
In addition, the inorganic-organic composite flexible high-dielectric film also has the advantages of high strength, high toughness, aging resistance, excellent wear resistance, excellent oil resistance and acid and alkali resistance, good adhesion, wide temperature tolerance range (-50 ℃ -150 ℃) and the like.
In the examples, the conditions of the vulcanization and coupling reactions are: heating and pressurizing at the temperature of 150-200 ℃ and the pressure of 2-6 Mpa.
In the embodiment, the method for preparing the film is a die pressing method, and the inorganic-organic composite flexible high-dielectric film is obtained by placing the composite raw rubber in a die with the thickness of 50-200 μm and maintaining the temperature and pressure in a vulcanizing machine for 5-20 min. The thickness of the inorganic-organic composite flexible high dielectric thin film obtained by controlling the thickness of the mold is 50 to 200 μm in this embodiment.
The preparation method of the inorganic-organic composite flexible high-dielectric film is simple, and the obtained inorganic-organic composite flexible high-dielectric film has the advantages of high dielectric constant, low dielectric loss, excellent flexibility and tensile resistance, and is expected to be used as a film dielectric material to be applied to electronic components such as dynamic random access memories, embedded capacitors and the like.
The invention also provides the inorganic-organic composite flexible high-dielectric film prepared by the preparation method of the inorganic-organic composite flexible high-dielectric film.
The following are specific examples.
Example 1
Adding 10.11g of calcium carbonate powder, 24.10g of copper oxide powder, 32.27g of titanium dioxide powder, 190mL of absolute ethyl alcohol and 266g of zirconia grinding balls into a grinding tank, carrying out ball milling for 1.5h in a planetary ball mill at the rotating speed of 200rpm, adding 199g of NaCl, and continuing ball milling for 1.5h at the rotating speed of 200rpm to obtain mixed slurry; and drying the mixed slurry at 75 ℃, putting the dried mixed slurry into an alumina crucible, and then putting the alumina crucible into a high-temperature furnace to roast for 2 hours at 850 ℃ to obtain saliferous CCTO intermediate powder. And repeatedly washing the salt-containing CCTO intermediate powder by using deionization at 85 ℃ until no obvious white precipitate is observed in supernatant liquor detected by using a silver nitrate solution, and drying the washed CCTO slurry to obtain the CCTO powder.
58.88g of the synthesized CCTO powder, 30.00g of polyurethane elastomer, 0.90g of bis 2,5 vulcanizing agent and 1.18g of coupling agent are placed in an open rubber mixing mill to be repeatedly mixed for 30min to prepare the composite raw rubber. Placing the composite crude rubber into a mold with the film thickness of 80 mu m, and preserving heat and pressure for 10min in a vulcanizing machine under the pressure of 3MPa and the temperature of 160 ℃ to obtain the inorganic-organic composite flexible high-dielectric film with the thickness of about 80 mu m.
Example 2
Adding 10.11g of calcium carbonate powder, 24.10g of copper oxide powder, 32.27g of titanium dioxide powder, 190mL of absolute ethyl alcohol and 266g of zirconia grinding balls into a grinding tank, carrying out ball milling for 6 hours in a planetary ball mill at the rotating speed of 160rpm, adding 199g of KCl, and continuing ball milling for 3 hours at the rotating speed of 160rpm to obtain mixed slurry; and drying the mixed slurry at 75 ℃, putting the dried mixed slurry into an alumina crucible, and then putting the alumina crucible into a high-temperature furnace to roast for 5 hours at 750 ℃ to obtain saliferous CCTO intermediate powder. And repeatedly washing the salt-containing CCTO intermediate powder by using deionized water at 75 ℃ until no obvious white precipitate is observed in supernatant liquor detected by using a silver nitrate solution, and drying the washed CCTO slurry to obtain the CCTO powder.
And (3) putting 34.35g of the synthesized CCTO powder, 30.00g of polyurethane elastomer, 0.90g of bis 2,5 vulcanizing agent and 0.68g of coupling agent KH5600 g into an open rubber mixing mill, and repeatedly mixing for 30min to obtain the composite raw rubber. Placing the composite crude rubber into a mold with the film thickness of 50 mu m, and preserving heat and pressure for 10min in a vulcanizing machine under the pressure of 2MPa and the temperature of 180 ℃ to obtain the inorganic-organic composite flexible high-dielectric film with the thickness of about 50 mu m.
Example 3
Adding 20.22g of calcium carbonate powder, 48.20g of copper oxide powder, 64.54g of titanium dioxide powder, 380mL of absolute ethyl alcohol and 532g of zirconia grinding balls into a grinding tank, carrying out ball milling for 2h in a planetary ball mill at the rotating speed of 180rpm, adding 398g of NaCl, and continuing ball milling for 2h at the rotating speed of 180rpm to obtain mixed slurry; and drying the mixed slurry at 75 ℃, putting the dried mixed slurry into an alumina crucible, and then putting the alumina crucible into a high-temperature furnace to roast for 4 hours at 800 ℃ to obtain saliferous CCTO intermediate powder. And repeatedly washing the salt-containing CCTO intermediate powder by deionization at 80 ℃ until no obvious white precipitate is observed in supernatant liquor detected by a silver nitrate solution, and drying the washed CCTO slurry to obtain the CCTO powder.
91.59g of the synthesized CCTO powder, 30.00g of polyurethane elastomer, 0.90g of bis 2,5 vulcanizing agent and 1.83g of coupling agent KH5501 are placed in an open rubber mixing mill to be repeatedly mixed for 30min to prepare the composite raw rubber. Placing the composite crude rubber into a mold with the film thickness of 100 mu m, and preserving heat and pressure for 10min in a vulcanizing machine under the pressure of 4MPa and the temperature of 160 ℃ to obtain the inorganic-organic composite flexible high-dielectric film with the thickness of about 100 mu m.
Example 4
Adding 20.22g of calcium carbonate powder, 48.20g of copper oxide powder, 64.54g of titanium dioxide powder, 380mL of absolute ethyl alcohol and 532g of zirconia grinding balls into a grinding tank, ball-milling for 1h in a planetary ball mill at the rotating speed of 230rpm, adding 265g of NaCl and 133g of KCl, and continuing ball-milling for 0.5h at the rotating speed of 230rpm to obtain mixed slurry; and drying the mixed slurry at 75 ℃, putting the dried mixed slurry into an alumina crucible, and then putting the alumina crucible into a high-temperature furnace to roast for 7 hours at 700 ℃ to obtain the salt-containing CCTO intermediate powder. And repeatedly washing the salt-containing CCTO intermediate powder by using deionization at 65 ℃ until no obvious white precipitate is observed in supernatant liquor detected by using a silver nitrate solution, and drying the washed CCTO slurry to obtain the CCTO powder.
91.59g of the synthesized CCTO powder, 30.00g of polyurethane elastomer, 0.90g of dicumyl peroxide and 0.83g of coupling agent A1511.83are placed in an open rubber mixing mill to be repeatedly mixed for 30min to prepare the composite crude rubber. Placing the composite crude rubber in a mold with the film thickness of 150 mu m, and preserving heat and pressure for 10min in a vulcanizing machine under the pressure of 5MPa and the temperature of 180 ℃ to obtain the inorganic-organic composite flexible high-dielectric film with the thickness of about 150 mu m.
Example 5
20.22g of calcium carbonate powder, 48.20g of copper oxide powder, 64.54g of titanium dioxide powder, 380mL of absolute ethyl alcohol and 532g of zirconia grinding balls are added into a grinding tank, and are ball-milled in a planetary ball mill for 4 hours at the rotating speed of 160rpm, and then 398g of NaCl is added to continue ball-milling for 2 hours at the rotating speed of 160rpm, so that mixed slurry is obtained. And drying the mixed slurry at 75 ℃, putting the dried mixed slurry into an alumina crucible, and then putting the alumina crucible into a high-temperature furnace to roast the alumina crucible for 1 hour at 900 ℃ to obtain the salt-containing CCTO intermediate powder. And repeatedly washing the salt-containing CCTO intermediate powder by deionization at 90 ℃ until no obvious white precipitate is observed in supernatant liquor detected by a silver nitrate solution, and drying the washed CCTO slurry to obtain the CCTO powder.
91.59g of the synthesized CCTO powder, 30.00g of polyurethane elastomer, 0.90g of bis-2, 5 vulcanizing agent and 1.83g of KH550 coupling agent are placed in an open rubber mixing mill to be repeatedly mixed for 30min to prepare the composite raw rubber. Placing the composite crude rubber in a mold with the film thickness of 200 mu m, and keeping the temperature and the pressure in a vulcanizing machine at the pressure of 6MPa and the temperature of 200 ℃ for 10min to obtain the inorganic-organic composite flexible high-dielectric film with the thickness of about 200 mu m.
Example 6
Example 6 is essentially the same as example 3, except that: in the step of preparing CCTO powder, the volume of absolute ethyl alcohol is 303mL, and the mass of NaCl is 505 g; in the step of preparing the inorganic-organic composite flexible high-dielectric film, 91.59g of the synthesized CCTO powder, 18.00g of polyurethane elastomer, 0.18g of bis 2,5 vulcanizing agent and 0.18g of coupling agent are mixed for 20 min.
Example 7
Example 7 is essentially the same as example 3, except that: in the step of preparing CCTO powder, the volume of absolute ethyl alcohol is 500mL, the mass of NaCl is 400g, the mixed slurry is dried at 60 ℃, then roasted at 800 ℃ for 2h to obtain salt-containing CCTO intermediate powder, and washing adopts deionization at 60 ℃; in the step of preparing the inorganic-organic composite flexible high-dielectric film, the mass of the coupling agent KH550 is 2.4g, the mass of the bis 2,5 vulcanizing agent is 1.5g, and the mixing time is 1 h.
Example 8
Example 8 is essentially the same as example 3, except that: in the step of preparing CCTO powder, the volume of absolute ethyl alcohol is 505mL, and the mass of NaCl is 303 g; in the step of preparing the inorganic-organic composite flexible high-dielectric film, the mass of the coupling agent KH550 is 3.0g, and the mixing time is 2 h.
Comparative example 1
Reference is made to "functional hybrid films with high dielectric constant" (Dang z.m., Zhou t., Yao s.h., yuan j.j., Zha j.w., Song h.t., Li j.y., Chen q., Yang w.t., Bai j.b., advanced materials, 2009,21, 2077-: polyimide was used as the continuous phase for CCTO fill.
Comparative example 2
Comparative example 2 reference is made to "polyvinylidene fluoride/calcium copper titanate and polyvinylidene fluoride/La doped calcium copper titanate composites with high dielectric and mechanical properties" (a.srivastava, k.k.jana, p.maiti, d.kumar, promulgated materials research 2015,70, 735-: polyvinylidene fluoride is used as a continuous phase for CCTO filling.
The dielectric constant, dielectric loss and elongation at break of tensile test were measured by testing the inorganic-organic composite flexible high dielectric films obtained in examples 1 to 8 and the inorganic-organic composite dielectric films obtained in comparative examples 1 to 2 at a frequency of 100Hz at room temperature, and the obtained dielectric constant, dielectric loss and elongation at break are shown in table 1.
TABLE 1
Figure BDA0001301256260000101
Figure BDA0001301256260000111
As can be seen from Table 1, the inorganic-organic composite flexible high dielectric films of examples 1-8 have dielectric constants of 19-41, dielectric losses far lower than those of comparative examples 1-2, and elongation at break much higher than those of comparative examples 1-2. The stress (Tensile stress) -Strain (Strain) curve of the inorganic-organic composite flexible high dielectric thin film obtained in example 3 is shown in fig. 1, and the Tensile elongation at break is about 160%, which indicates that the inorganic-organic composite flexible high dielectric thin film has good flexibility and good processability.
Scanning electron microscope analysis is carried out on the section of the inorganic-organic composite flexible high dielectric thin film obtained in the embodiment 3, and a scanning electron microscope photo is obtained, as shown in fig. 2, CCTO particles are distributed in a polyurethane matrix very uniformly, so that the mechanical property and the dielectric property of the inorganic-organic composite flexible high dielectric thin film are improved.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (8)

1. The preparation method of the inorganic-organic composite flexible high-dielectric film is characterized by comprising the following preparation steps:
mixing the polyurethane elastomer with calcium copper titanate powder, a vulcanizing agent and a coupling agent to obtain composite raw rubber;
carrying out vulcanization and coupling reaction on the composite crude rubber and preparing the composite crude rubber into a film to obtain the inorganic-organic composite flexible high-dielectric film; the conditions of the vulcanization and coupling reaction are as follows: heating and pressurizing, wherein the heating temperature is 150-200 ℃, and the pressurizing pressure is 2-6 Mpa;
the mass ratio of the coupling agent to the polyurethane elastomer is 0.06-0.1: 1; the mass ratio of the vulcanizing agent to the polyurethane elastomer is 0.03-0.05: 1; the mass ratio of the calcium copper titanate powder to the polyurethane elastomer is (2-4): 1;
the preparation method of the copper calcium titanate powder comprises the following steps:
uniformly mixing calcium carbonate powder, copper oxide powder, titanium dioxide powder, inorganic salt and a solvent to obtain a mixed slurry, wherein the calcium carbonate powder, the copper oxide powder and the titanium dioxide powder are according to CaCu3Ti4O12The weight ratio of the inorganic salt to the calcium carbonate powder is 15-25: 1, the volume-mass ratio of the solvent to the calcium carbonate powder is 15-25 mL: 1g of a compound;
drying the mixed slurry, and calcining at 700-900 ℃ for 1-7 h to obtain inorganic salt-containing calcium copper titanate intermediate powder;
and washing the inorganic salt-containing copper calcium titanate intermediate powder to remove inorganic salt, and drying to obtain the copper calcium titanate powder.
2. The method for preparing the inorganic-organic composite flexible high-dielectric film according to claim 1, wherein the coupling agent is at least one selected from the group consisting of a coupling agent KH550, a coupling agent KH560 and a coupling agent A151.
3. The method according to claim 1, wherein the vulcanizing agent is at least one selected from the group consisting of dicumyl peroxide and dicumyl peroxide.
4. The method for preparing the inorganic-organic composite flexible high dielectric film according to claim 1, wherein the mixing is performed in an open mill for 20-120 min.
5. The method of claim 1, wherein the polyurethane elastomer is a hybrid polyurethane elastomer.
6. The method for preparing the inorganic-organic composite flexible high-dielectric film according to claim 1, wherein the method for preparing the film is a die pressing method, and the step of performing vulcanization and coupling reaction on the composite raw rubber to prepare the film comprises the following specific steps: and placing the composite crude rubber into a mold with the thickness of 50-200 mu m, and keeping the temperature and the pressure in a vulcanizing machine for 5-20 min to obtain the inorganic-organic composite flexible high-dielectric film.
7. The method for preparing the inorganic-organic composite flexible high dielectric film according to claim 1, wherein the step of uniformly mixing the calcium carbonate powder, the copper oxide powder, the titanium dioxide powder, the inorganic salt and the solvent to obtain the mixed slurry comprises:
uniformly mixing the calcium carbonate powder, the copper oxide powder, the titanium dioxide powder and the solvent, adding the inorganic salt, and continuously and uniformly mixing to obtain the mixed slurry.
8. The inorganic-organic composite flexible high dielectric film prepared by the preparation method of the inorganic-organic composite flexible high dielectric film according to any one of claims 1 to 7.
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