RU2695917C1 - Composite piezoelectric material and method of its production - Google Patents

Abstract

FIELD: manufacturing technology.

SUBSTANCE: invention relates to composite piezoelectric materials (CPM) and can be used for making hydroacoustic receivers, medical ultrasonic diagnostics sensors, emission control, flaw detectors and other volumetric-sensitive piezoelectric transducers, as well as to the technology of making said materials. Composite piezoelectric material includes porous ceramic films of ferroelectric lead zirconate/titanate, or lead methanobate, or lead titanate, or solid solutions based thereon, connected to porous polymer films based on a silicone compound with electric resistance of not less than 10¹⁰ Ohm·cm. Ceramic film is obtained from a slurry composition, wt%: ultrafine powder of lead zirconate/titanate, or lead methanobate, or lead titanate, or solid solutions based thereon (active phase) 45.50-62.20, pore-forming agent: benzoic acid powder 2.95–12.40 or ammonium oxalate 3.20–13.8, distilled water 12.40–18.55, binder (50–65 % aqueous dispersion of ethyl acrylate, methyl acrylate copolymer and dibasic unsaturated carboxylic acid) 8.05–12.40, plasticizer (ethylene glycol or hexylene glycol) 1.10–4.20, dispersant (7–12 % aqueous solution of a copolymer of vinyl acetate and maleic acid, in which 0.8–1.5 equivalent carboxyl groups is neutralized with ammonia) 0.36–0.95, nonionic SAS1 (monoalkyl ethers of polyethylene glycol with molecular weight of 560–1,000) 0.07–0.15, nonionic SAS 2 (oxyethylated isononylphenol) 0.10–0.25, thickener (42–50 % aqueous dispersion of a copolymer of vinyl acetate, butyl acrylate and methacrylic acid or polyvinyl alcohol) 0.16–0.52, an antifoaming agent (alcohols propoxylate of fraction C₇-C₁₂) 0.03–0.33. Porous polymer film is obtained from mixture of composition, vol%: silicone compound with electric resistance of not less than 10¹⁰ Ohm·cm 70–80, foam stabilizer 0.001–0.005, white spirit and cresol – the rest at ratio of white spirit: cresol from 2:1 to 3:1 and 9:1. Method of proposed CPM manufacturing includes production of ceramic films (plates with thickness of up to 0.12–0.18 mm) from ultrafine powders of lead-containing ferroelectric phases with subsequent stepwise annealing, depositing electrodes on the lower and upper surfaces of the films, making porous polymer films based on the silicone compound, assembling the CPM by connecting the ceramic films with the partially polymerized polymer films, formation of two single parallel electrodes and terminal conductors connecting upper electrodes of separate active elements (AE) and lower electrodes of separate AE, followed by polarization of CPM AE and external sealing of CPM.

EFFECT: improving its elastic flexibility and reducing dielectric permittivity while simplifying its production method.

19 cl, 1 dwg, 1 tbl, 1 ex

Description

The invention relates to composite piezomaterials (KPM), and can be used for the manufacture of hydroacoustic receivers, sensors for medical ultrasonic diagnostics, emission monitoring, flaw detectors and other volume-sensitive piezoelectric transducers, as well as to technology (methods) for manufacturing these materials.

KPMs are known, which are a set of parallelly located polarized ceramic rods (type of connectivity 1-3) or plates (type of connectivity 2-2) in a polymer matrix [1 - 4].

The disadvantages of KPM with connectivity 1 - 3 and 2 - 2 include the fact that the maximum values of their volumetric piezoelectric parameters are achieved only when the volumetric content of the piezoelectric phase in the system is about 10 - 12 vol. % This, even with a parallel electrical connection of ceramic plates in the system, leads to a KPM sample with a low electric capacity, which leads to problems associated with its inclusion in the recording circuit. In addition, such KPMs have low mechanical strength, which decreases as the thickness of ceramic plates decreases [5–12].

Currently, several technologies are known for the production of rod and plate KPM. The first of them [3, 13 - 17]. involves the manufacture of ceramic plates or rods, round or rectangular cross-section, which, at the second stage, according to the specified algorithm, are placed in technological form, and then filled in it with an oligomer (with its subsequent polymerization) or a polymer solution (followed by evaporation of the solvent). After that, the form is destroyed, the workpiece is removed, and its active elements are polarized.

In the framework of the second type of technology [3, 13, 16, 18], a monolithic, rectangular, ceramic billet is partially sawn in two mutually perpendicular directions with the formation of a kind of three-dimensional “comb”. At the next stage, the space between the “teeth” of the “comb” is filled with polymer, and the monolithic base of the “comb” is sawn off. Similar technologies are used for the manufacture of KPM with connectivity of type 2 - 2.

The third technology [13, 19] requires the manufacture of technological forms from materials that, when the macrostructure of the CPM is formed, are destroyed by oxidation or evaporation. As an example, we can name forms made of various polymeric materials, lithography, casting, etc. [20]. At the next stage, the technological form, which has the necessary macrostructure, is filled with a suspension containing finely divided ferro-phase powder (for example, the PZT system). After evaporation of the liquid phase from a suspension (slip), the form is heated in air, which leads to its destruction and evaporation of the polymer decomposition (oxidation) products. A further increase in temperature to the optimum (for sintering the intermediate product) values makes it possible to fabricate a piezoceramic framework of arbitrary shape, the density of individual elements of which can reach 98% (of x-ray density) [5 - 7]. In particular, as part of this process, a set of hexagonal rods with a diameter of about 50 μm and a height of about 400 μm, spaced apart at a distance of 50 μm [7], as well as complex shapes (in the form of honeycombs, a set of rods and plates) having various sizes and geometry [5, 19]. If the technological mold is made of refractory material, then, at the optimum temperature, the whole composition is sintered, which, after cooling, is filled with polymer, and after its curing, the mold is destroyed (sawn) and the CPM sample is polarized [21].

  However, despite its attractiveness, the method under consideration is technologically sophisticated, characterized by the presence of environmental problems, the duration and high cost of production units, and also has a fairly low reproducibility of the electrophysical parameters (EFP) of KPM samples [5 - 7, 13].

 Also, for the manufacture of KPM with a connectivity of type 2-2 and 1-3, the injection molding method can be used [22, 23]. The method under consideration, like the previous one, (alone or together with the first method) used for the manufacture of KPM with a different volume fraction of active elements, which may take the form of rods or plates (of various sizes and shapes). Its shortcomings are similar to the shortcomings of the third method, the “soluble form method”,except for less acute environmental problems.

Sufficiently effective, for the manufacture of type 2 - 2 piezocomposites, is the slip casting method, based on the formation of thin ribbons from suspensions (ferro-phase powder - polymer binder), which are called cast slip. Within the framework of this method, multilayer composites are made in which the layers of polymer and monolithic ceramic film alternate with each other. If the film contains gas bubbles, a composite with a type 2 - 0 - 2 connection is formed. In other versions of this technology, polymer films are conductive, while the electrodes of the active element (AE) are applied not to the end parts of the plates, but to their plane, i.e. KPM of this type operates on a planar mode [8, 9, 24].

The main idea of the automatic layered method of manufacturing, for example, layered KPMs [9, 10] is the formation of their desired macrostructure using 3D printers (sequential, layered, controlled supply of slip and binder). The resulting billet at the next stage is fired (removal of polymer components and sintering of ceramic plates). The resulting ceramic frame is polarized, and its interlayer spaces are filled with a binder. At the last stage of the technology, the electrodes of the individual plates are connected and conduct surface sealing of the sample.

As follows from the above analysis of technological processes for the manufacture of rod and plate KPM, they are all multi-stage. In addition, most technologies require the manufacture of complex, usually disposable, technological forms and additional mechanical processing of primary workpieces [3, 6, 7, 13–20, 23] or complex and expensive technological equipment [8–10].

  The closest to implementation is a layered-type CPM consisting of ceramic plates (ceramic films) polarized in thickness, the planes of which, on both sides, are coated with polymer [24].

A method of obtaining such a CPM is that AE (active elements) are placed parallel to each other in a technological rectangular shape. The gap between the AE is set using rectangular columns (gaskets, stoppers), which are placed at the bottom of the technological form. AE electrodes are switched, and then, the space between the AE (directly in the form) is filled with epoxy. After the polymerization of epoxy, the lower part of the mold (bottom, process gaskets and lower parts of AE blanks) are cut off [24 fig. 9A to 9D].

 The disadvantage of this KPM is its low elastic compliance with high dielectric constant. These drawbacks are associated with the use of a dense ceramic film (it is known that dense ceramic has a sufficiently high dielectric constant up to 10,000 and a sufficiently low elastic compliance) [3 - 7, 9 - 13, 25].

The disadvantage of the method of obtaining such a KPM is its complexity, due to the need to install stoppers between the plates and to trim the lower parts of the mold and blanks.

The technical result of KPM is to increase its elastic compliance and decrease the dielectric constant, and the technical result of the method of its manufacture is its simplification.

The technical result is achieved by the fact that the composite piezomaterial includes porous ceramic films of ferroelectric zirconate / lead titanate or lead methaniobate or lead titanate or solid solutions based on them, connected to a porous polymer film based on a silicone compound with an electrical resistance of at least 10 ¹⁰ Ohm · cm while the ceramic film is obtained from a slip composition, wt. %:

ultrafine powder of lead zirconate / titanate or lead methaniobate or lead titanate or solid solutions based on them (active phase) 45.50 - 62.20

blowing agent:

benzoic acid powder 2.95 - 12.40

 or ammonium oxalate 3.20 - 13.8

distilled water 12.40 -18.55

binder: 50-65 wt. % aqueous dispersion of a copolymer of ethyl acrylate, methyl acrylate and dibasic unsaturated carboxylic acid

                                                                                               8.05-12.40

plasticizer: ethylene glycol or hexylene glycol 1.10-4.20

dispersant: 7-12% aqueous solution of a copolymer of vinyl acetate and maleic acid, in which 0.8-1.5 equivalents of carboxyl groups are neutralized with ammonia 0.36-0.95

nonionic surfactant 1: monoalkyl ethers of polyethylene glycols with a molecular weight of 560-1000 0.07-0.15

non-ionic surfactant 2: hydroxyethylated isononylphenol 0.10-0.25

thickener: 42-50% aqueous dispersion of a copolymer of vinyl acetate, butyl acrylate and methacrylic acid 0.16-0.52

antifoam: propoxylate alcohols fraction C ₇ -C ₁₂ 0,03-0,33,

and the porous polymer film is obtained from a mixture of the composition, vol.%:

silicone compound with an electrical resistance of at least 10 ¹⁰ Ohm · cm 70 - 80

foam stabilizer 0.001-0.005

white spirit and cresol rest

with a ratio of white spirit / cresol from 2: 1 to 3: 1 and 9: 1

The AK-260 product according to TU 6-02-0209917 / -90 can be taken as a binder in the manufacture of porous ceramic films, manufacturers: Vitebsk Production Association "Monolith", or "Synthesis of Surfactants", Russia, or LLC "Simplex", Russia .

Ethylene glycol according to GOST 10164-75 or hexylene glycol according to TU 6-02-0209913-89 from the manufacturer Renaissance Oil Russia or the manufacturer Katrosa Reaktiv, Russia can be taken as a plasticizer.

As a dispersant, a copolymer obtained by precipitating polymerization of vinyl acetate and maleic anhydride in an organic solvent, followed by dissolution in water and neutralization of carboxyl groups, for example, MKM-50 VM according to TU 5850767 / -88 from NPO Synthesis SAW, can be taken.

As a nonionic surfactant 1, a product obtained by esterification of acids with polyethylene glycols can be taken, for example, according to a known method (Dyment, O. N. Kazansky, K. S. and A. M. Miroshnikov. Glycols and other derivatives of ethylene and propylene oxides. M. Chemistry, 1976, p. 237).

The product Neonol AF 9-25 obtained according to TU 38.50716-87 “PO Volga Region” can be taken as a non-ionic surfactant 2.

As a thickener, AK-215 product obtained according to TU 6-02-02099134-83 of the manufacturer AKRIPOL LLC or polyvinyl alcohol according to GOST 10779-78 can be taken.

As an antifoam agent, the product ГДП-1 according to TU 38.10777-88 of manufacturers can be taken: Vitebsk production association "Monolith" or "Synthesis of surfactants".

In the manufacture of a porous polymer film, a pentelast®-712 compound may be used as a silicone compound, or"Vicksint ", or"Silagerm, or Silicon SK-419.

Organosilicon liquids, for example, ethyl silicates (ethyl silicate-32, or ethyl silicate-40, or ethyl silicate-50) according to GOST 26371-84 or products according to TU 2435-397-05763441-2003, can be taken as a foam stabilizer in the manufacture of a porous polymer film. TU 2435-427-05763441-2004 of the manufacturer of LLC Silan.

A change in the content of the components that make up the slip (in the manufacture of a porous ceramic film), outside the range of the declared values, worsens its molding properties, i.e. leads to: a) problems associated with the uniformity of the wet film, with the difficulty of separating it from the substrate, as well as with restrictions on its minimum and maximum thickness; b) to the deterioration of the strength and structural-mechanical properties of the products of its firing (cracking, warping, chips, etc.).

The technical result is also achieved by the fact that the method of manufacturing the proposed KPM involves the manufacture of ceramic films (plates with a thickness of up to 0.10 - 0.15 mm) from ultrafine powders (UDP) of lead-containing ferro-phases, applying electrodes to the end (lower and upper) surfaces of the films, manufacturing porous polymer films based on silicone compound, KPM assembly by combining ceramic films with partially polymerized polymer films, the formation of two single parallel electrodes and current output Connecting the individual top electrodes AE and lower individual electrodes AE, AE followed QPM polarization and outer sealing CPM.

The manufacture of a porous ceramic film includes the formation of raw films of ferroelectric zirconate / lead titanate or lead methaniobate or lead titanate or solid solutions based on them (slip casting) from a slip based on ultrafine powders of ferroelectric with their subsequent firing.

Porous ceramic film plates are prepared predominantly with a thickness (0.10 - 0.15 mm) in the form of squares or rectangles with sides from 3 to 20 mm.

The manufacture of a polymer film involves diluting the silicone compound with a mixture of white spirit and cresol and adding a stabilizer to it, followed by foaming the mixture by passing air under it under pressure, mixing and forming the film.

Dilution of the silicone compound with a mixture of white spirit and cresol is carried out mainly in their ratio from 2: 1 to 3: 1, in accordance with the required viscosity of the compound and the speed of its polymerization.

Organosilicon liquids, for example, ethyl silicates (ethyl silicate-32, or ethyl silicate-40, or ethyl silicate-50) are added to the mixture as a foam stabilizer.

Air, under pressure, is passed through a diluted compound with a stabilizer, preferably for 30-60 seconds, using a nozzle with an outlet diameter of less than 1 mm.

Stirring is preferably carried out for 5-15 minutes. Due to mixing, a uniform distribution of the air absorbed by the mixture is achieved (in the form of bubbles with a radius of about ten microns). In the process of mixing due to the partial evaporation of the diluent and the beginning polymerization of silicone rubber, the mixture increases its viscosity, which allows you to start pouring it through a die on a teflon surface.

The formation of the film is carried out by spilling it on a teflon surface.

The time required (at temperature 25-35 ° ^C) to form on the surface of the porous PTFE film suitable assembly for CPM is from 12 to 14 hours (depending on its thickness in the range 150 - 300 microns). Reduction of polymerization temperatures (below 25 ° ^C) leads to increased process time and its rise (above 35 ° ^C) - to the formation of "bubbles" or surface cavities.

The thickness of the poured film is determined by the parameters of the die gap and the viscosity of the poured mixture.

The change in the porosity (∆P _vol ) of the film due to the variation within the specified limits of the volume fraction of the foam stabilizer (0.01-0.05 vol.%) And the duration of foaming and mixing of the foamed mixture can be changed in the range from 12 to 50 vol.%.

The difference between the proposed KPM and the prototype [24] is that the ceramic component is dense in the known material, and the ceramic and polymer components are porous in the proposed material, which improves the piezoelectric characteristics of the material, including those determining elastic compliance and dielectric constant (growth of the volumetric piezomodule , volume piezoelectric sensitivity, and reception factor increase as the elastic compliance of the material increases and its dielectric constant decreases [5 - 9, 13 - 15]).

The used composition of the slip for producing a ceramic film differs from the known slip [26] by using lead zirconate / titanate or lead methaniobate or lead titanate or solid solutions based on them instead of titanate powders (Ca, Ba, Mg), carbonates (Mn , Ba) and zirconate Ca, and oxides Nd ₂ O ₃ , Nb ₂ O ₅ and Sm ₂ O ₃ , as well as the presence of a pore former and, accordingly, a slightly different ratio of components.

The difference between the method and the prototype [24] is that the assembly of the CPM is carried out by connecting ceramic films of lead-containing ferro-phases with partially polymerized polymer films based on silicone compound, which contributes to their “bonding” (formation of a surface transition layer) upon completion of the polymerization of the compound, as well as the fact that the electrodes are applied to the parallel ends of the films, and not on the plane, as is done for the prototype.

Figure 1 presents: a) 1 - blank of the active element (AE); b) AE with an electrode and a polymer film, where 2 is an electrode, 3 is a film; c) KPM blank type 2 - 0 - 2.

The following is an example embodiment of the invention.

 Example 1

The lead component of the slurry was the lead phase titaniumate-zirconate (PZT) phase composition Pb _0.95 Sr _0.05 Ti _0.45 Zr _0.53 Cd _0.01 W _0.01 O ₃ . Mass fraction of UDP in slip 55.7 wt. % The UDP of the ferroelectric phase together with a pore former - benzoic acid powder (9.40 wt.%), Distilled water (17.50 wt.%), A binder - an aqueous (50%) dispersion of a copolymer of ethyl acrylate, methyl acrylate and dibasic unsaturated carboxylic acid (12.10 wt.%), plasticizer - hexylene glycol (3.80 wt.%), dispersant - 8% aqueous solution of a copolymer of vinyl acetate and maleic acid (0.80 wt.%), nonionic surfactant 1 - monoalkyl ethers of polyethylene glycols with a molecular weight 560-1000 (0.10 wt.%), Surfactant 2 - hydroxyethylated isononylphenol (0.18 wt.%,), Thicken Lem - water (45%) dispersion of a copolymer of vinyl acetate, butyl acrylate and methacrylic acid (0.22 wt.%), antifoam - propoxylate of alcohols of the C ₇ -C ₁₂ fraction (0.20 wt.%), were placed in a ball mill (mixing time 2 to 5 hours, depending on the mass of the suspension being made), and then to a mixer with a turbine mixer, followed by removal of air from the slip at a residual pressure of about 0.01 atm.

The production of raw films included a set of standard operations carried out according to the instructions within the framework of the Keko equipment complex of injection equipment (CAM-L25 injection machine, SD and SC type installations for drying and cutting the film, respectively). The sequence of operations: casting a film through a die onto a lavsan substrate, rolling the film through rolls (rolling), separating the film from the lavsan substrate, cutting the resulting film into blanks of a given configuration and size (rectangles 0.12 - 0.18 mm thick, 5 mm wide and length 12 mm). The blanks are placed on a dense zirconia ceramic substrate coated with a thin layer of this oxide powder (to prevent the films from sticking to the substrate). The substrates, together with the films, are placed in a rectangular corundum cuvette, filled with coarse-grained zirconium oxide powder and heated to 125 ^° C at a speed of 3 ^° C / min. The heating rate of the films in the range of 125 - 250 ^° C is not more than 2 ^° C / min. Samples were maintained at 250 ^{° C} for 25 - 30 minutes to complete the complete removal of porogen and binder system. After closure of the isothermal sintering until the sintering temperature (1100 - 1120 ° ^C), the average rate of change of temperature of the system is, on the average 5.1 ° ^C / min. Sintering at 1100 - 1120 ^{° C} is performed for 70 - 90 minutes. The samples are cooled to room temperature within 5-6 hours.

The average porosity of the manufactured films, measured in accordance with GOST 2409-2014 [27], amounted to 49 vol.%. Silver electrodes were applied to the parallel end planes of the films by annealing. Due to the porosity of the material, the paste penetrated into the surface layer of the material to a depth of 0.4 mm. Samples were polarized in a cassette with a field of 2.5 kV / mm.

In parallel, films of a porous polymer are made. For this, the two-component silicone compound pentelast®-712, in a volume ratio of 3: 1, was diluted with a mixture of white spirit and cresol (the content of the white spirit mixture was 90 vol.%, Cresol 10 vol.%). The mixture of compound and diluent was placed in a tank with a hemispherical bottom. Ethyl silicate-40 (0.005 wt.%) Was added to it as a foam stabilizer. The components were preliminarily mixed (paddle mixer) for 10 min, the mixture, and then the mixture (for 45 sec) were foamed by passing air through it (under pressure). The foamed liquid was again intensively mixed using a powerful paddle mixer. 12 minutes after the start of repeated mixing, the mixture, through a die, was poured onto a Teflon surface. The time required (at 32 ° ^C) to form on the surface of the porous PTFE film thickness of 180 - 200 microns, it is 12 hours. Its porosity, estimated by the change in density, relative to the film made according to the instructions for the compound pentelast®-712 [28] (density: 1.26 g / cm ³ ), averaged 37 vol.%.

 The assembly of the CPM was carried out by alternately connecting ceramic and polymer plates due to the compound pentelast®-712 (figure 1). In this example, the amount of AE in the stack (average thickness of porous ceramic plates 0.12 mm) and polymer layers (average thickness 0.27 mm), the size of which in the direction perpendicular to the plane of the plates is 10 mm, an average of 25 pieces, taking into account the thickness of the AE wafers and polymer layers, the volume fraction of AE in the system is about 30 vol.%, (for the block - fig. 1b - the volume ratio of ceramic: polymer is 1: 2) and taking into account that the porosity of each AE wafer (49 vol.%) , the content of the ferroelectric phase in the system is about 15 vol.% .. Electrophysical properties of this material compared with the properties of similar CPM connectivity presented in the table.

                                                                                                             Table

SF vol%
AE Polymer KPM type g _v • 10 ³
V • m / N d _v
pK / H d _v • g _v • 10 ¹²
m ² / N Lit.
links PZT thirty UCS 2 - 0 - 2 - 0 112 151 17.4 proposed KPM PZT <10 EP 13 70 63 4.1 [eleven] PZT 10 - 15 PPU 1 - 3 - 0 69-108 72 - 140 5,4 -15,1 [13] PZT 29th PVF 3 - 3 ten thirty 0.3 [22] PZT 6 - 10 EP 13 30 - 35 20 - 30 0.7 - 0.9 [21] PZT 76 EP 2 - 2 6 - 7 67 - 69 407 - 486 [12]

* PSK - porous silicone rubber, EP - epoxy; PUF - porous polyurethane.

Similar results were obtained using the other specified components and within the indicated amounts.

As can be seen from the table, the piezoelectric parameters obtained are determined by the dielectric constant of the material and its elastic compliance [7, 11], i.e. volumetric piezosensitivity (g _v ) volumetric piezoelectric module (d _v ) and reception factor (d _v • g _v ) surpass the known analogs of the rod and plate type. Compared with the prototype [24], these characteristics will also have higher values, taking into account that the material of the prototype is formed on the basis of dense ceramic films, which have a higher dielectric constant and low elastic compliance than porous films [3 - 7, 9 - 13, 25]. The proposed method compared to the prototype is simpler, since ceramic and polymer plates are interconnected by “gluing” during the polymerization of polymer films (that is, it is not necessary to carry out additional operations to connect the films, and also it is not necessary to carry out operations to remove technological forms, grinding and cutting samples).

Literature

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28. Two-component sealants pentelast®-711 and 712, instructions for use, penta@penta-junior.ru

Claims (38)

1. Composite piezoelectric material, characterized in that it includes porous ceramic films of ferroelectric zirconate / lead titanate, or lead methaniobate, or lead titanate, or solid solutions based on them, connected to porous polymer films based on silicone compound with an electrical resistance of at least 10 ¹⁰ Ohm · cm, while the ceramic film is obtained from a slip composition, wt. %: active phase: ultrafine powder of lead zirconate / titanate, or lead methaniobate, or lead titanate, or solid solutions based on them 45.50-62.20, blowing agent: benzoic acid powder 2.95-12.40 or ammonium oxalate 3.20-13.8, distilled water 12.40-18.55, binder: 50-65 wt. % aqueous dispersion of a copolymer of ethyl acrylate, methyl acrylate and dibasic unsaturated carboxylic acid  8.05-12.40, plasticizer: ethylene glycol or hexylene glycol 1.10-4.20, dispersant: 7-12% aqueous solution of a copolymer of vinyl acetate and maleic acid, in which 0.8-1.5 equivalents of carboxyl groups are neutralized with ammonia 0.36-0.95, nonionic surfactant 1: monoalkyl ethers of polyethylene glycols with a molecular weight of 560-1000 0.07-0.15, non-ionic surfactant 2: hydroxyethylated isononylphenol 0.10-0.25, thickener: 42-50% aqueous dispersion of a copolymer of vinyl acetate, butyl acrylate and methacrylic acid  or polyvinyl alcohol 0.16-0.52, antifoam: propoxylate alcohols fraction C ₇ -C ₁₂ 0,03-0,33, and the porous polymer film is obtained from a mixture of the composition, vol.%: silicone compound with an electrical resistance of at least 10 ¹⁰ Ohm · cm 70-80, foam stabilizer 0.001-0.005, white spirit and cresol rest with a volume ratio of white spirit / cresol from 2: 1 to 3: 1 and 9: 1. 2. The composite piezoelectric material according to claim 1, characterized in that the product AK-260 is taken as a binder. 3. The composite piezoelectric material according to claim 1, characterized in that ethylene glycol or hexylene glycol is taken as a plasticizer. 4. The composite piezoelectric material according to claim 1, characterized in that the copolymer obtained by precipitating polymerization of vinyl acetate and maleic anhydride in an organic solvent is used as a dispersant, followed by dissolution in water and neutralization of the carboxyl groups. 5. The composite piezoelectric material according to claim 1, characterized in that the product obtained by the esterification of acids with polyethylene glycols is taken as a nonionic surfactant. 6. The composite piezoelectric material according to claim 1, characterized in that the product Neonol AF 9-25 is taken as a non-ionic surfactant 2. 7. The composite piezoelectric material according to claim 1, characterized in that the product AK-215 is taken as a thickener. 8. The composite piezoelectric material according to claim 1, characterized in that the product GDP-1 is taken as a defoamer. 9. The composite piezoelectric material according to claim 1, characterized in that the compound pentelast®-712, or Vixint, is taken as a silicone compound, or"Silagerm ", or Silicon SK-419. 10. The composite piezoelectric material according to claim 1, characterized in that organosilicon liquids, for example ethyl silicates, are taken as a foam stabilizer. 11. A method of manufacturing a composite piezomaterial (KPM) according to claim 1, characterized in that it includes the manufacture of ceramic films from ultrafine powders (UDP) of lead-containing ferro-phases with their subsequent step-firing and sintering according to conventional piezoceramic technology, applying electrodes to the end surfaces of the films, manufacturing porous polymer films based on silicone compound, CPM assembly by joining ceramic films with partially polymerized polymer films, the formation of two units other parallel electrodes and current outputs connecting the upper electrodes of the individual active elements (AE) and the lower electrodes of the individual AEs, followed by polarization of the AE KPM and external sealing KPM. 12. The method according to claim 11, characterized in that the manufacture of a porous ceramic film includes the formation of crude films of ferroelectric zirconate / lead titanate, or lead methaniobate, or lead titanate, or solid solutions based on them from a slip based on ultrafine powders of ferroelectric. 13. The method according to claim 11, characterized in that porous ceramic films with a thickness of 0.12-0.18 mm are prepared in the form of squares or rectangles with sides from 3 to 20 mm. 14. The method according to claim 11, characterized in that the manufacture of the polymer film comprises diluting the silicone compound with a mixture of white spirit and cresol and adding a stabilizer to it, followed by foaming the mixture by passing air through it under pressure, mixing and forming the film. 15. The method according to 14, characterized in that the dilution of the silicone compound with a mixture of white spirit and cresol is carried out in their volume ratio from 2: 1 to 3: 1 and 9: 1. 16. The method according to 14, characterized in that as a stabilizer of the foam, organosilicon liquids, for example ethyl silicates, are added to the mixture. 17. The method according to 14, characterized in that the air is passed under pressure for 30-60 using a nozzle with an outlet diameter of less than 1 mm 18. The method according to 14, characterized in that the mixing is carried out for 5-15 minutes 19. The method according to 14, characterized in that the formation of the film is carried out by spilling it on a teflon surface.

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