WO2004074209A1 - 圧電セラミックス - Google Patents
圧電セラミックス Download PDFInfo
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- WO2004074209A1 WO2004074209A1 PCT/JP2004/001685 JP2004001685W WO2004074209A1 WO 2004074209 A1 WO2004074209 A1 WO 2004074209A1 JP 2004001685 W JP2004001685 W JP 2004001685W WO 2004074209 A1 WO2004074209 A1 WO 2004074209A1
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- piezoelectric
- ceramics
- piezoelectric ceramics
- displacement
- sintering
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/495—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
- C04B35/497—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates based on solid solutions with lead oxides
- C04B35/499—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates based on solid solutions with lead oxides containing also titanates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/495—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/853—Ceramic compositions
- H10N30/8542—Alkali metal based oxides, e.g. lithium, sodium or potassium niobates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
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- C—CHEMISTRY; METALLURGY
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
- C04B2235/3203—Lithium oxide or oxide-forming salts thereof
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
- C04B2235/666—Applying a current during sintering, e.g. plasma sintering [SPS], electrical resistance heating or pulse electric current sintering [PECS]
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
Definitions
- the present invention without the sodium niobate (NaNb0 3) and potassium niobate (KNb0 3) the main body is obtained by sintering a pair Robusukai bets solid solution composition with the addition of lead titanate (PbTi0 3) to It relates to piezoelectric ceramics.
- NaNb0 3 sodium niobate
- KNb0 3 potassium niobate
- Piezoelectric ceramics have the effect of expanding and contracting by the application of electrical signals, and have a wide range of applications as actuators, such as ultrasonic transducers, ultrasonic motors, precision positioning elements, and piezoelectric dampers that use that effect.
- actuators such as ultrasonic transducers, ultrasonic motors, precision positioning elements, and piezoelectric dampers that use that effect.
- the mainstream of piezoelectric ceramic materials that are widely used are those mainly composed of lead zirconate titanate (PZT).
- MPB lead zirconate antiferroelectric rhombohedral structure
- PbTi0 3 tetragonal phase
- PZT lead zirconate titanate
- Pb Zn 1/3 Nb 2/3) 0 3 -PbTi0 3
- the PZN-PT electrical strain (4L / L) represents at least 1%, and longitudinal effect of pressure ⁇ number d 33 is that more 2500PC / N, but has extremely excellent properties as a piezoelectric material, its single It is necessary to take special measures such as the Bridgman method with controlled atmosphere for crystal production, mass production cannot be performed, and the cost must be extremely high. At present, its use is limited to highly important special fields such as medical ultrasonic diagnostic devices.
- Non-Patent Document 1 S. E. Park and T.R.Shrout, Journal of Applied Physics, 82C1 997), 1804
- Non-Patent Document 2 R. Wang, R. Xie, T. Sekiya, Y. Shimojo, Y. Akimune, N. Hirosaki and M. Itoh, Japanese Journal of Applied Physics, 41 (2002), 7119
- the present invention has been made in view of the above-described circumstances of the prior art, and has a PZT-based cell.
- Non-Patent Document 2 the ferroelectric ceramics reported in Non-Patent Document 2 were better than conventional PZT-based piezoelectric materials. Have also found that they have dramatically higher displacement characteristics, and have completed the present invention.
- the piezoelectric ceramic according to the above (1) which is a ceramic having a composition represented by (6).
- FIG. 1 is a graph showing the relationship between the applied voltage and the electric displacement of the piezoelectric ceramic according to Example 1.
- FIG. 2 is a graph showing a relationship between an applied voltage and an electric displacement of the piezoelectric ceramic according to the second embodiment.
- FIG. 3 is a graph showing the relationship between the applied voltage and the electric displacement of the piezoelectric ceramic according to Example 3.
- FIG. 4 is a graph showing the relationship between the applied voltage and the electric displacement of the piezoelectric ceramic according to Comparative Example 1.
- FIG. 5 is a graph showing the relationship between the applied voltage and the electric displacement of the piezoelectric ceramic according to Comparative Example 2.
- FIG. 6 is an electron micrograph showing the characteristics of the domain of the piezoelectric ceramics according to Example 2.
- FIG. 7 is an electron micrograph showing the characteristics of the domain of the piezoelectric ceramic according to Comparative Example 1.
- the piezoelectric Seramidzukusu of the present invention sintering the NaNb0 3 -KNb0 3 -PbTi0 3 solid solution Is obtained by
- the sintering means is not particularly limited, but in order to obtain a high-density sintered body efficiently, it is preferable to employ a pressure heating sintering method capable of heating a single-phase perovskite calcined product under pressure. .
- Examples of such pressure heating sintering methods include spark plasma sintering (SPS), hot pressing, anvil, and HIP (hot isostatic pressing). .
- SPS spark plasma sintering
- HIP hot isostatic pressing
- the pressure heating sintering method preferably used in the present invention is the SPS method.
- This SPS method is a method in which a DC pulse current is applied to a sample in a pressurized state, and grain boundary diffusion and particle bonding are caused using the high energy of high-temperature plasma generated instantaneously by spark discharge. It has attracted attention as a high-speed sintering method for ceramics.
- NaNb0 3 -KNb0 3 -PbTi0 3 system easily evaporated components as (in particular Na, K and Pb ) Is the most preferred method for sintering materials that contain a large amount of) and whose composition may be fluctuated by heating.
- the compound material is blended to the desired stoichiometric composition and calcined until the compound is a single perovskite phase.
- the calcination conditions vary depending on the raw material composition, etc., but usually the calcination temperature is 850 to 1000 ° C and the calcination time is 2 to 10 hours.
- the calcined powder thus obtained is subjected to SPS treatment using an SPS-1030 apparatus manufactured by Sumitomo Coal Mining. Specifically, after filling an appropriate amount of sample into a carbon die (outside diameter 35 mm, inside diameter 15 mm, height 50 mm), a DC ON-OFF pulse can be applied to the upper and lower punches while applying pressure from above and below using a carbon punch. If so, a desired sintered body can be obtained.
- the sample reaches a predetermined temperature (1000 ° C or more) in about 5 minutes, and is sintered by maintaining the temperature at a constant level for about 3 to 5 minutes.
- the sintering temperature varies depending on the composition, but is in the range of 10 20 to 1100 ° C.
- the obtained sintered body has a diameter of 15 mm and a thickness of 3 to 4 mm.
- the sintered body is darkened, but by annealing in air, for example, at 950 ° C for 5 hours, it is whitened and the desired piezoelectric ceramic with a relative density of 96% or more can be obtained. .
- Reference Example 1 production of the piezoelectric ceramic by preparative ⁇ beauty SPS method NaNb0 3 -KNb0 3 -PbTi0 3 system Bae Ropusukai preparative material subjected to SPS processing
- a carbon die (outside diameter: 35 mm, inside diameter: 15 mm, height: 50 mm) is filled with about 3 g of the sample, and the top and bottom punches are pressed from above and below with a force of about 0.72 t using a force-punch punch.
- a sintered body was obtained by applying a direct current ON-OFF pulse to the sintered body.
- the sample reaches a predetermined temperature (1000 ° C or more) in about 5 minutes, and is sintered by controlling the temperature for about 3 to 5 minutes.
- the sintering temperature varies depending on the composition, but is in the range of 1020 to 1100 ° C.
- the obtained sintered body has a diameter of 15 mm and a thickness of 3 to 4 mm.
- the sintered body was darkened, but was whitened by annealing at 950 ° C in air for 5 hours. Most of the obtained sintered bodies had a relative density of 96% or more.
- FIG. 1 shows the relationship between the electrical displacement of the ceramic of Example 1 and the applied voltage.
- This strain loop shows a butterfly type peculiar to the piezoelectric body, but is asymmetric. This can be interpreted as the uneven distribution of the region with the bias potential generated inside the ceramic. Within the measured range, a displacement of 1% or more on the positive voltage side, 0.4% or more on the negative voltage side, and an average of 0.7% or more are observed. These numbers, as compared with Comparative Example 1 containing no PbTi0 3, has increased dramatically, it is evident that is due to the effect of adding a PbTi0 3.
- FIG. 2 shows the relationship between the electrical displacement of the ceramics of Example 2 and the applied voltage. Unlike the ceramics of Example 1, the symmetry of the strain loop is relatively maintained. A distortion of about 1.4% is observed on the plus side and the minus side. This amount of strain can be said to be the largest among conventional piezoelectric ceramics. This is almost comparable to the case of PZN-PT single crystal, which has the highest strain in piezoelectric materials.
- FIG. 3 shows the relationship between the electrical displacement of the ceramic of Example 3 and the applied voltage. This distortion loop is also relatively symmetric, with more than 1.2% distortion on the plus and minus sides, respectively.
- FIG. 4 shows the relationship between the electric displacement of the ceramic of Comparative Example 1 and the applied voltage.
- the displacement curve is a butterfly type and shows the behavior as a piezoelectric body, but the displacement within the measurement range is about 0.1%.
- FIG. 5 shows the relationship between the electric displacement of the ceramic of Comparative Example 2 and the applied voltage.
- the displacement curve is a butterfly type and shows the behavior as a piezoelectric body, but the displacement within the measurement range is up to about 0.2%.
- FIG. 6 shows the characteristics of the ferroelectric domain of the piezoelectric ceramic of Example 2.
- the size of the domain is around ⁇ . ⁇ ⁇ . Therefore, from the serial Comparative Example 1 after free of PbTi0 3, it is clear that the domain size was smaller summer.
- Fig. 7 shows the characteristics of the ferroelectric domain of the piezoelectric ceramic of Comparative Example 1. is there.
- the size of the domain is 1-2 ⁇ or more.
- NaNb0 3 -KNb0 3 -PbTi0 3 based piezoelectric ceramic material according to the present invention while a low lead-based material, which electrically displacement comparable to that of PZN-PT single crystal, Yu correct low lead system environment It is extremely useful as a new high-performance piezoelectric ceramic material, and can be used as an actuator for vibration control of aircraft, automobiles, railway vehicles, ships, etc., and for vibration isolation of civil engineering structures. This paves the way for further expansion of applications as a ceramic factory.
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Abstract
Description
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Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005502701A JPWO2004074209A1 (ja) | 2003-02-18 | 2004-02-17 | 圧電セラミックス |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003040125 | 2003-02-18 | ||
| JP2003-040125 | 2003-02-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2004074209A1 true WO2004074209A1 (ja) | 2004-09-02 |
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ID=32905200
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2004/001685 Ceased WO2004074209A1 (ja) | 2003-02-18 | 2004-02-17 | 圧電セラミックス |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPWO2004074209A1 (ja) |
| WO (1) | WO2004074209A1 (ja) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118930262A (zh) * | 2024-07-05 | 2024-11-12 | 长沙理工大学 | 一种高效晶粒尺寸效应的铌酸银储能陶瓷及其制备方法 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11228225A (ja) * | 1998-02-18 | 1999-08-24 | Murata Mfg Co Ltd | 圧電磁器組成物 |
-
2004
- 2004-02-17 WO PCT/JP2004/001685 patent/WO2004074209A1/ja not_active Ceased
- 2004-02-17 JP JP2005502701A patent/JPWO2004074209A1/ja active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11228225A (ja) * | 1998-02-18 | 1999-08-24 | Murata Mfg Co Ltd | 圧電磁器組成物 |
Non-Patent Citations (1)
| Title |
|---|
| WANG R. ET AL: "Piezoelectric Properties of Spark-Plasma-Sintered (Na0,5 K0,5)NbO3-PbTiO3 Ceramics", JAPANESE JOURNAL OF APPLIED PHYSICS, vol. 41, 2002, pages 7119 - 7122, XP002979761 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118930262A (zh) * | 2024-07-05 | 2024-11-12 | 长沙理工大学 | 一种高效晶粒尺寸效应的铌酸银储能陶瓷及其制备方法 |
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| Publication number | Publication date |
|---|---|
| JPWO2004074209A1 (ja) | 2006-06-01 |
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