A low-temperature sintered explosive transducer material

Abstract

This invention discloses a low-temperature sintered explosive electrostatic transducer material, comprising: a% lead, b% lithium, c% silver, d% potassium, and e% sodium in the low-valence ion component; x% zirconium, y% titanium, f% niobium, g% antimony, and h% tungsten in the high-valence ion component; and 0.50% to 1.50% lead oxides or lead salts as a compensating volatile component. The sum of the average valence states of the cations in the low-valence and high-valence ion components is between 5.80 and 5.995. Thus, without reducing the performance of the finished product, the sintering temperature during processing is reduced to no more than 970°C based on the material ratio. This significantly reduces the high-temperature resistance requirements of the internal electrode when processing multi-layer co-fired structures, thereby reducing the palladium content in the internal electrode, lowering raw material costs, and enabling large-scale mass production.

Description

Technical Field

[0001] This invention relates to the field of explosive electric energy conversion materials, and in particular to a low-temperature sintered explosive electric energy conversion material. Background Technology

[0002] Explosion-electric transducers utilize polarized ferroelectric ceramics, which release charge instantaneously during a phase transition caused by an explosion. This charge then supplies current and voltage to an external circuit, serving as the primary power source for a pulse current or voltage source. Explosion-electric transducers typically employ PZT (lead zirconate titanate) material. When the zirconium-to-titanium ratio is approximately 95 / 5, it lies at the phase boundary between the ferroelectric and antiferroelectric phases. During the polarization process under certain external conditions with an applied electric field, the disordered initial domains undergo orientation polarization, resulting in a residual polarization intensity P0 greater than 0. The PZT material, perpendicular to the polarization direction, accumulates bound charges on its outer surface, thus enabling energy storage. The energy storage density is related to the residual polarization intensity and the dielectric constant.

[0003] When polarized PZT materials are subjected to an external load and impact force, a phase transition will occur within microseconds, and the electric domains will depolarize, thereby releasing the stored energy. Due to the extremely short release time, strong current pulses or voltage pulses can be generated.

[0004] Traditional PZT95 / 5 materials have a relatively high sintering temperature, generally in the range of 1250℃~1350℃. The high sintering temperature will cause a large amount of lead to volatilize during the sintering process, which will affect the compressive strength of the finished product and thus affect its application in electronic components.

[0005] Therefore, when a multilayer co-fired structure is used in the design of components, the internal electrode needs to be sintered together with the PZT material. Therefore, the internal electrode material needs to be able to withstand the sintering temperature of the PZT material. In this case, an alloy with a high palladium content is usually selected, such as a silver-palladium alloy with a palladium content of not less than 30%. However, at this time, the amount of palladium used is large, the raw material cost is high, and it is difficult to apply it to the mass production of high-performance components on a large scale. Summary of the Invention

[0006] This invention discloses a low-temperature sintered explosive electrostatic transducer material, specifically comprising: Low-valence ion components, high-valence ion components, and compensating volatile components; The average valence state of the cations in the low-valence ion component is between 1.970 and 1.995, and the average valence state of the cations in the high-valence ion component is between 4.00 and 4.06. The components and molar percentage content of the low-valence ion composition are as follows: lead a%, lithium b%, silver c%, potassium d%, sodium e%; Where a%+b%+c%+d%+e%=1.00, 0.005≤b%+c%+d%+e%≤0.030; The components and molar percentage content of the high-valence ion composition are: zirconium x%, titanium y%, niobium f%, antimony g%, tungsten h%; Where x%+y%+f%+g%+h%=1.00, 0.945≤x%≤0.980, 0.020≤y%≤0.055, 0.00≤f%+g%+h%≤0.030; The sum of the average valence states of the low-valence ion components and the high-valence ion components is between 5.80 and 5.995; The compensating volatile components are lead oxides or lead salt compounds accounting for 0.50% to 1.50% of the total mass.

[0007] As an optional implementation, in the low-valent ionic components, lead exists as a divalent cation, while lithium, silver, potassium, and sodium exist as monovalent cations.

[0008] As an optional implementation, in the high-valence ion component, zirconium and titanium exist as tetravalent cations, niobium and antimony exist as pentavalent cations, and tungsten exists as hexavalent cations.

[0009] As an optional implementation method, the raw material particle size of the explosive electric transducer is D50 < 0.70 μm and D90 < 1.00 μm. As an alternative implementation method, ceramic blanks are prepared by casting or pressing.

[0010] As an optional implementation, the dielectric constant of the crystalline compound is 200~350, the piezoelectric constant d33 is 60~75 pC / N, and the Curie temperature is 230~260℃.

[0011] As an optional implementation, the low-valence ion component and the metal ion in the high-valence ion component are prepared based on the oxide or carbonate corresponding to the metal ion.

[0012] Compared with the prior art, this embodiment has the following beneficial effects: In this embodiment, without reducing the performance of the finished product, the sintering temperature of the processing is reduced to no more than 970°C based on the material ratio. Accordingly, when processing multi-layer co-fired structures, the requirements for the high-temperature resistance of the internal electrode are greatly reduced, thereby reducing the palladium content of the internal electrode, reducing raw material costs, and enabling large-scale mass production. Detailed Implementation

[0013] The technical solutions in this embodiment will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0014] This embodiment discloses a low-temperature sintered explosive transducer material, comprising: Low-valence ion components, high-valence ion components, and compensating volatile components; The average valence state of cations in the low-valence ion component is between 1.970 and 1.995, while the average valence state of cations in the high-valence ion component is between 4.00 and 4.06. The components and molar percentages of the low-valence ion composition are: lead a%, lithium b%, silver c%, potassium d%, sodium e%; Where a%+b%+c%+d%+e%=1.00, 0.005≤b%+c%+d%+e%≤0.030; The components and molar percentages of the high-valence ion composition are: zirconium x%, titanium y%, niobium f%, antimony g%, tungsten h%; Where x%+y%+f%+g%+h%=1.00, 0.945≤x%≤0.980, 0.020≤y%≤0.055, 0.00≤f%+g%+h%≤0.030; The sum of the average valence states of the cations in the low-valence ion components and the high-valence ion components is between 5.80 and 5.995; The compensating volatile components are lead oxides or lead salt compounds, accounting for 0.50% to 1.50% of the total mass.

[0015] In this embodiment, the obtained crystalline compound has a perovskite structure.

[0016] The addition of low-valence ions occupies some of the positions of high-valence ions, but electrically, the two cannot balance the valence state of oxygen, thus causing lattice distortion, thereby achieving a significant reduction in sintering temperature.

[0017] If the sum of the average valence states of the low-valence ion components and the high-valence ion components is less than 5.80, the material properties of the finished product will be significantly lower, which will lead to damage and disintegration during further finishing processes, or inability to be well assembled with other structures, or the resulting components will have a poor service life and will experience structural aging or performance fluctuations during long-term use.

[0018] Furthermore, if the sum of the overall valence states is greater than 5.995, the sintering temperature will be difficult to lower than 1050℃, making low-temperature sintering impossible. This will increase the cost of raw materials and affect the practical application.

[0019] Based on the above composition and proportion of the explosive electro-electric transducer material, the explosive electro-electric transducer substrate can be prepared through the following steps: Low-valence ion components, high-valence ion components, and compensating volatile components are milled and mixed to obtain particulate materials; Seal particulate materials and place them at a high temperature of 800℃~850℃ to synthesize crystalline compounds; The crystalline compound is finely ground and shaped into a ceramic blank. The ceramic blank is then subjected to debinding and sintering at 900℃~970℃ to obtain the explosive power conversion substrate.

[0020] Specifically, the following proposes several feasible components and their corresponding molar percentage content or percentage of total mass content: Example 1: Low-valence ion components (lead 0.995, potassium 0.005), high-valence ion components (zirconium 0.950, titanium 0.050), lead oxide 0.50~1.50wt%.

[0021] Here, a single substitution of low-valence ions was used, with only potassium ions replacing lead. No elements such as niobium, antimony, or tungsten were added to the high-valence ion component. The valence state of the low-valence ions was 1.995, the valence state of the high-valence ions was 4.000, and the total valence state was 5.995.

[0022] Based on the above composition, the ceramic body of the explosive transducer is obtained by grinding and shaping and sintering at 970℃. After subsequent metallization and polarization processes, the following material parameters can be obtained: dielectric constant of 230, piezoelectric constant of d33: 62pC / N, and Curie temperature of 258℃.

[0023] Example 2 Low-valence ion components (lead 0.990, sodium 0.010), high-valence ion components (zirconium 0.945, titanium 0.050, niobium 0.005), and lead oxide 0.50~1.50wt%.

[0024] Here, a single substitution with low-valence ions was employed, using only sodium ions to replace lead, while niobium was added to the high-valence ion component. The valence state of the low-valence ions was 1.990, the valence state of the high-valence ions was 4.005, and the total valence state was 5.995. Due to the addition of high-valence niobium in the high-valence region, the material performance parameters improved.

[0025] Based on the above composition, the materials are synthesized and ground into shape. After sintering at 970℃, another ceramic body for the explosive transducer can be obtained. After subsequent metallization and polarization processes, the following material parameters can be obtained: dielectric constant of 250, piezoelectric constant of d33: 70pC / N, and Curie temperature of 250℃.

[0026] It is evident that by adding appropriate amounts of high-valence ion components, material properties can be improved and the adaptability to special working conditions can be enhanced without increasing sintering temperature and material strength.

[0027] Example 3 Low-valence ion components (lead 0.99, potassium 0.005, lithium 0.005), high-valence ion components (zirconium 0.945, titanium 0.050, niobium 0.005), lead oxide 0.50~1.50wt%.

[0028] Here, a low-valence ion composite substitution was implemented, using potassium and lithium ions to replace lead, while niobium was added to the high-valence ion component. The low-valence ion component had a valence state of 1.990, the high-valence ion component had a valence state of 4.005, and the total valence state was 5.995. Because two elements were used for composite substitution in the low-valence ion component, the sintering temperature was further reduced.

[0029] Based on the above composition, the materials are synthesized and ground into shape. After sintering at 950℃, another ceramic body for the explosive transducer can be obtained. After subsequent metallization and polarization processes, the following material parameters can be obtained: dielectric constant of 260, piezoelectric constant of d33: 68pC / N, and Curie temperature of 252℃.

[0030] It is evident that by adjusting the composition of low-valence ions in the agent, the sintering temperature can be further reduced without affecting the material properties. This allows for a further reduction in the amount of palladium used in the internal electrode when firing multi-layer co-fired products, thereby lowering the overall material cost without affecting the material strength and properties.

[0031] Therefore, by flexibly adjusting the metal composition and composition ratio according to the requirements of the components for precision, sensitivity, conversion efficiency, etc., specific component performance can be achieved under low-temperature sintering conditions.

[0032] As an optional implementation, in the low-valent ion component, lead exists as a divalent cation, while lithium, silver, potassium, and sodium exist as monovalent cations.

[0033] As an optional implementation method, in the high-valence ion component, zirconium and titanium exist as tetravalent cations, niobium and antimony exist as pentavalent cations, and tungsten exists as hexavalent cations.

[0034] Here, the addition of high-valence metal cations to the high-valence ion component can compensate for the overall low valence state caused by the excessively high low-valence ion component, and eliminate the negative impact of the low valence state on performance.

[0035] As an optional implementation, the lead oxide is lead oxide.

[0036] To combat lead volatilization during the sintering process, lead oxides such as lead oxide or lead salt compounds are added.

[0037] Understandably, lead oxides or lead salts can be added in excess, provided that the performance of the crystalline compound meets the standards, to ensure that the finished product has sufficient pressure resistance and can be reliably used in the manufacturing and processing of components.

[0038] As an optional implementation method, the raw material particle size of the explosive electric transducer is D50 < 0.70 μm and D90 < 1.00 μm.

[0039] Here, grinding tools such as ball mills, vibratory mills, and planetary mills can be used to grind the proportioned components. The grinding process is also a process of mixing low-valence ion components, high-valence ion components, and compensating volatile components.

[0040] As an alternative implementation method, ceramic blanks are prepared by casting or pressing.

[0041] Here, individual blanks of corresponding specifications can be manufactured directly according to the specifications of the components, and then fine-processed after sintering to obtain the explosive energy conversion material that can be used to assemble specific components.

[0042] It is also possible to produce a large, integral blank, which can then be further cut into several smaller structures for finishing after sintering, thereby improving production efficiency.

[0043] As an alternative implementation, the crystalline compound has a dielectric constant of 200~350, a piezoelectric constant of d33: 60~75pC / N, and a Curie temperature of 230~260℃.

[0044] Here, low-temperature sintering is performed at a maximum temperature of 970℃. Compared with the traditional process of high-temperature sintering at 1250℃~1350℃, the sintering temperature is significantly reduced while the main properties of the resulting crystalline compound, such as dielectric constant, piezoelectric constant, and Curie temperature, are not reduced, which shows significant performance advantages.

[0045] As an alternative implementation method, the metal ions in the low-valence ion component and the high-valence ion component are prepared based on the oxides or carbonates corresponding to the metal ions.

[0046] Here, based on the oxides of the corresponding metal ions, by accurately calculating the content of metal ions in the raw materials and the reaction efficiency of the processing, the corresponding mass of raw materials can be converted and weighed for subsequent processing.

[0047] Compared with the prior art, this embodiment has the following beneficial effects: In this embodiment, without reducing the performance of the finished product, the sintering temperature of the processing is reduced to no more than 970°C based on the material ratio. Accordingly, when processing multi-layer co-fired structures, the requirements for the high-temperature resistance of the internal electrode are greatly reduced, thereby reducing the palladium content of the internal electrode, reducing raw material costs, and enabling large-scale mass production.

Claims

1. A low-temperature sintered explosive electrostatic transducer material, characterized in that, include: Low-valence ion components, high-valence ion components, and compensating volatile components; The average valence state of the cations in the low-valence ion component is between 1.970 and 1.995, and the average valence state of the cations in the high-valence ion component is between 4.00 and 4.

06. The components and molar percentage content of the low-valence ion composition are as follows: lead a%, lithium b%, silver c%, potassium d%, sodium e%; Where a%+b%+c%+d%+e%=1.00, 0.005≤b%+c%+d%+e%≤0.030; The components and molar percentage content of the high-valence ion composition are: zirconium x%, titanium y%, niobium f%, antimony g%, tungsten h%; Where x%+y%+f%+g%+h%=1.00, 0.945≤x%≤0.980, 0.020≤y%≤0.055, 0.00≤f%+g%+h%≤0.030; The sum of the average valence states of the low-valence ion components and the high-valence ion components is between 5.80 and 5.995; The compensating volatile components are lead oxides or lead salt compounds accounting for 0.50% to 1.50% of the total mass.

2. The low-temperature sintered explosive transducer material according to claim 1, characterized in that: Among the low-valent ionic components, lead exists as a divalent cation, while lithium, silver, potassium, and sodium exist as monovalent cations.

3. The low-temperature sintered explosive transducer material according to claim 1, characterized in that, include: Among the high-valence ion components, zirconium and titanium exist as tetravalent cations, niobium and antimony exist as pentavalent cations, and tungsten exists as hexavalent cations.

4. The low-temperature sintered explosive transducer material according to claim 1, characterized in that: The raw material particle size of the explosive electrostatic transducer is D50 < 0.70 μm and D90 < 1.00 μm.

5. The low-temperature sintered explosive transducer material according to claim 1, characterized in that: Ceramic blanks are prepared by casting or pressing.

6. The low-temperature sintered explosive transducer material according to claim 1, characterized in that: The dielectric constant of the crystalline compound is 200~350, the piezoelectric constant d33 is 60~75 pC / N, and the Curie temperature is 230~260℃.

7. The low-temperature sintered explosive transducer material according to claim 1, characterized in that: The low-valence ion component and the metal ions in the high-valence ion component are prepared based on the oxides or carbonates corresponding to the metal ions.