CN1100022C - Preparation of high-temperature lead metaniobate ceramic in tungsten bronzes structure - Google Patents
Preparation of high-temperature lead metaniobate ceramic in tungsten bronzes structure Download PDFInfo
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- CN1100022C CN1100022C CN00127914A CN00127914A CN1100022C CN 1100022 C CN1100022 C CN 1100022C CN 00127914 A CN00127914 A CN 00127914A CN 00127914 A CN00127914 A CN 00127914A CN 1100022 C CN1100022 C CN 1100022C
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Abstract
The present invention discloses a process for preparing lead metaniobate high-temperature ceramics in tungsten-bronze structure, which relates to a high-temperature piezoelectric ceramics. The process of the present invention comprises: nanometer raw materials are used, a powder synthesis process of compounding pressing blocks and powder at both high temperature and low temperature is adopted, the ball milling conditions are improved, the materials are mixed and milled on site many times, the heat preservation time is shortened, proper rapid cooling speed and cold working precision are adopted, the polarization power is increased, etc. When used, the process of the present invention enables the preparing quantity of the ceramic powder is increased to 10 kilograms, enhances the volume density, the insulation resistance, the piezoelectric property, the consistency, etc. of ceramic elements, and meanwhile increases the yield of the product. The present invention has the advantages of convenient process and liable operation.
Description
The preparation technology of tungsten bronze structure lead meta-columbute pyroceramic of the present invention relates to high-temperature piezoelectric pottery, PbNb
2O
6Piezoelectric ceramics has many outstanding characteristics, as the single vibration modes of low quality factor (Qm＜10) (Kt＞＞Kr) and high Curie temperature (Tc=570 ℃) etc., so very wide application prospect is being arranged aspect industrial detection, medical diagnosis and the pyrostat.But for pure PbNb
2O
6Piezoelectric ceramics, its ferroelectric phase are positioned at high-temperature zone (more than 1230 ℃), must be frozen into the normal temperature district to it with the technology of quenching or cold zone uses, thereby make PbNb
2O
6It is very difficult that the preparation of piezoelectric ceramics piezoceramic material and element becomes, moreover ferroelectric phase is very unsettled at normal temperatures, thereby limited the widespread use of this material greatly.Though on the composition of material, done many work for many years, from replacing and adding assorted angle material is carried out modification, obtained good effect, but owing to still continue to use traditional Technology, make batch process can only be limited in 100～1000 the gram scopes and can't enlarge, and performance difference is very big, the polarization yield rate is also very low, and the situation of deoxidation also can appear in element when high temperature uses, and makes the insulation resistor rate swash acute decline, so that can not use, cause when the assembling transmitter, will filling oxygen, application is caused very big difficulty, at these situations, be PbNb
2O
6Piezoelectric ceramics is sought the suitable Technology of producing superior prod in enormous quantities of a cover and is pressed for.
The objective of the invention is to provide a kind of and can produce the new preparation technology of high-quality tungsten bronze structure lead meta-columbute pyroceramic in enormous quantities.
The present invention is achieved in that the preparation technology of tungsten bronze structure lead meta-columbute pyroceramic, and the general formula of its ceramic composition is: Pb
1-xMe
xNb
2O
6(base-material)+additive ywt% (is 100 in the base-material gross weight), wherein: Me=Ca
+ 2, Ba
+ 2X=0.02～0.12; Additive is: Sm
2O
3, Ce
2O
3, Nd
2O
3And Te
2O
3, y=0.03～0.3%, the specific embodiment of its preparation is as follows:
(1), powder is synthetic: will be by the stoichiometric PbNb of described general formula
2O
6, nano level (～100nm) CaO, BaO, TiO
2With Sm
2O
3, Ce
2O
3, Nd
2O
3And Te
2O
3Mix, in agate glass ball mill, material ball ratio=1: 1.5, carried out batch mixing 6～8 hours, with powder take out briquetting (pressure 100MPa) in sintering oven with 2～5 ℃/minute of heat-up rates, be heated to 850 ℃, and be incubated after 2 hours with＞250 ℃/minute speed of cooling, be cooled to room temperature, briquetting is taken out to pulverize again and insert in the ball mill fine grinding after 6～8 hours, powder moved to the heat-up rate with 2～5 ℃/minute rises to 1260～1270 ℃ in the sintering oven, be incubated after 2 hours with＞250 ℃/minute speed of cooling, be cooled to room temperature, and moved in the ball mill fine grinding 32～48 hours, promptly get the synthetic powder of the present invention's pottery, take out standby;
(2), the burning till and polarize of pottery:
With (1) gained powder, make piezoelectric ceramics green compact of the present invention to add the dry-pressing formed mode of tackiness agent, behind the green compact plastic removal, insert in the alumina crucible, in sintering oven with the speed of 2～5 ℃/minute of heat-up rates, it is carried out sintering under 1290～1315 ℃, be incubated 0～0.5 hour, cool off, take out after the cold working finishing with 250 ℃/minute speed of cooling, place eight shelves again after 5000V/mm/180 ℃/100m carries out high-power polarization, promptly get piezoelectric ceramics finished product of the present invention.
Wherein, the sphere diameter of the agate glass abrading-ball of balls grinding machine is 5～15mm.
Wherein, the cold working precision of ceramic component is ± 0.005mm.
Advantage of the present invention is, make the powder preparation of pottery improve 10 kilograms by existing 100～1000 grams, and improved volume density, insulation resistance, piezoelectric property and the consistence etc. of ceramic component, also improved the yield rate of product simultaneously, and technology easy, be easy to grasp.
Following examples will be described further technical characterictic of the present invention:
Embodiment 1: the preparation technology of tungsten bronze structure lead meta-columbute pyroceramic comprises the synthetic of ceramic powder, the burning till, polarize of ceramic component, and its detailed process is as follows:
(1), powder is synthetic: will be by the stoichiometric PbNb of described general formula
2O
6, chemical pure CaO, BaO, TiO
2With Sm
2O
3, Ce
2O
3, Nd
2O
3And Te
2O
3Mix, in agate glass ball mill, the sphere diameter of the agate glass abrading-ball of material ball ratio=1: 1.2 balls grinding machine is 5～15mm, carries out batch mixing 4 hours, mixed powder is incubated 2 hours through 850 ℃ of low temperature, so is cooled to room temperature, send agate glass ball mill ball milling 24 hours again, get mixed powder, take out standby;
(2), the burning till and polarize of pottery:
Will be from (1) gained mixed powder, make piezoelectric ceramics green compact of the present invention to add the dry-pressing formed mode of tackiness agent, behind the green compact plastic removal, insert in the alumina crucible, in sintering oven with 2～5 ℃/minute of heat-up rates, be heated to 1315 ℃, be incubated 1 hour, naturally cooling, taking-up is after the cold working finishing, the cold working precision is ± 0.005mm, places to put horse after carrying out the monolithic polarization under the 5000V/mm/180 ℃/20mA again, promptly gets the piezoelectric ceramics finished product.
Embodiment 2:
(1), powder is synthetic:
Remove CaO, BaO, TiO
2Adopt nano level (～100nm) outside, all the other raw materials are with embodiment 1, the material ball ratio of raw material in agate glass ball mill=carry out batch mixing 6 hour at 1: 1.5, powder moved to the heat-up rate with 2～5 ℃/minute rises to 850 ℃ in the sintering oven, be incubated after 2 hours, ℃ be cooled to room temperature, and moved in the ball mill fine grinding again 32 hours with speed of cooling＞100, get mixed powder, take out standby;
(2), the burning till and polarize of pottery:
Will be from (1) gained mixed powder, make piezoelectric ceramics green compact of the present invention to add the dry-pressing formed mode of tackiness agent, behind the green compact plastic removal, insert in the alumina crucible, in sintering oven with the speed of 2～5 ℃/minute of heat-up rates, it is carried out sintering under 1315 ℃, be incubated 1 hour, speed of cooling with＞100 ℃/minute is cooled off, taking-up is after the cold working finishing, the cold working precision places and puts horse after 5000V/mm/180 ℃/20mA carries out eight polarization once with embodiment 1, promptly gets the piezoelectric ceramics finished product.
Embodiment 3:
(1), during powder is synthetic, raw material is formed with embodiment 2, ratio of grinding media to material in agate glass ball mill is with embodiment 2, batch mixing 7 hours, the gained compound is carried out briquetting under pressure=100MPa, be heated to 850 ℃ of following insulations after 2 hours, again the piece material is pulverized with 2～5 ℃/minute heat-up rates, ℃ be quickly cooled to room temperature with speed of cooling＞200, send agate glass ball mill to carry out fine grinding 40 hours, take out powder, it is moved in the sintering oven, be heated to 1270 ℃ with 2～5 ℃/minute heat-up rates, be incubated 2 hours, ℃ be quickly cooled to room temperature with speed of cooling＞200, powder is stand-by;
(2) the burning till and polarize of pottery:
To pour into the ceramic member green compact from the powder of (1) gained, send sintering oven with 2～5 ℃/minute heat-up rate in the rearmounted alumina crucible of plastic removal, be heated to 1310 ℃, be incubated 0.5 hour, ℃ be quickly cooled to room temperature with speed of cooling＞200, blank is through finishing, and the cold working precision is with embodiment 1, place again and put horse after 5000V/mm/180 ℃/100mA carries out eight polarization once, promptly get piezoelectric ceramics finished product of the present invention.
Embodiment 4:
(1), during powder is synthetic, raw material is formed with embodiment 2, the ratio of grinding media to material of raw material in agate glass ball mill is with embodiment 2, batch mixing 8 hours, the gained mixed powder is carried out briquetting under pressure=100MPa, with 2～5 ℃/minute heat-up rates be heated to 850 ℃ down insulation again the piece material is pulverized after 2 hours, ℃ be quickly cooled to room temperature with speed of cooling＞250, send agate glass ball mill to carry out fine grinding 48 hours, take out powder, be heated to 1260 ℃, be incubated 2 hours with 2～5 ℃/minute heat-up rates, ℃ be quickly cooled to room temperature with speed of cooling＞250, powder is stand-by;
(2) the burning till and polarize of pottery:
To pour into the ceramic member green compact from the powder of (1) gained, send sintering oven with 2～5 ℃/minute heat-up rate in the rearmounted alumina crucible of plastic removal, be heated to 1290 ℃, ℃ be quickly cooled to room temperature with speed of cooling＞250, blank send polarization through finishing, cold working precision and polarization condition get piezoelectric ceramics finished product of the present invention with embodiment 3.
The test result of embodiment 1～4 gained tungsten bronze structure lead meta-columbute pyroceramic end properties is listed as follows:
The element function synopsis of table 1, common preparation technology and the present invention's preparation
| Numbering | Data Source | d 33 (PC/N) | ε T 33/ε 0 | Tanδ (％) | Q M | ρ (gram/cm 3) | Tc (℃) | Kt | Kp |
| 1 | Ordinary process | 74 | 210 | 2 | 18 | 5.6 | 560 | 0.38 | 0.04 |
| 2 | The present invention | 80 | 270 | 0.9 | 12 | 6.1 | 560 | 0.40 | 0.04 |
| 3 | Chinese invention patent ZL93112369.0 | 70-89 | 174-253 | / | ＜10 | / | 530-570 | 0.38-0.45 | 0.04-0.08 |
| 4 | U.S.S.R SU.1 20307807 Jan 1986 | 68-87 | 250-1530 | / | 22-39 | / | 561 | 0.32-0.44 | 0.05-0.08 |
The Technology of table 2, each embodiment
| Embodiment | Material fineness | The batch mixing condition | Synthetic | Fine grinding (hour) | Sintering | Cooling | Polarization | |
| Low temperature | High temperature | |||||||
| One | General chemistry reagent | Material: ball=1: 1.2 batch mixing 4 hours | 850 ℃/2hv of powder | / | 24 | 1315℃ /1hv | Naturally cooling | 5000v/mm/180 ℃/20mA of monolithic polarization |
| Two | ～100nm | Material: ball=1: 1.5 batch mixing 6 hours | 850 ℃/2hv of powder | 1270 ℃/2hv of powder | 32 | 1315℃ /1hv | Speed of cooling＞100 ℃/minute | Eight polarization of 5000v/mm/180 ℃/20mA |
| Three | ～100nm | Material: ball=1: 1.5 batch mixing 7 hours | 850 ℃/2hv of briquetting | 1270 ℃/2hv of powder | 40 | 1310℃ /0.5hv | Speed of cooling＞200 ℃/minute | Eight polarization of 5000v/mm/180 ℃/100mA |
| Four | ～100nm | Material: ball=1: 1.5 batch mixing 8 hours | 850 ℃/2hv of briquetting | 1260 ℃/2hv of powder | 48 | 1290℃ /0hv | Speed of cooling＞250 ℃/minute | Eight polarization of 5000v/mm/180 ℃/100mA |
The result of table 3, each embodiment
| Embodiment | Volume density ρ (gram/cm 3) | Kt | Kp | d 33 (PC/N) | ε T 33/ε 0 | Tanδ (％) | Q M | Tc (℃) | Polarization yield rate (%) |
| One | 5.6 | 0.38 | 0.04 | 74 | 210 | 2.0 | 18 | 560 | 70 |
| Two | 5.8 | 0.40 | 0.04 | 76 | 230 | 1.6 | 16 | 560 | 85 |
| Three | 6.1 | 0.41 | 0.04 | 79 | 260 | 1.3 | 12 | 561 | 95 |
| Four | 6.1 | 0.42 | 0.04 | 80 | 270 | 0.9 | 11 | 562 | 95 |
Claims (3)
1. the preparation technology of a tungsten bronze structure lead meta-columbute pyroceramic, the general formula of its ceramic composition is: Pb
1-xMe
xNb
2O
6(base-material)+additive ywt% (is 100 in the base-material gross weight), wherein: Me=Ca
+ 2, Ba
+ 2X=0.02～0.12; Additive is: Sm
2O
3, Ce
2O
3, Nd
2O
3And Te
2O
3, y=0.03～0.3% is characterized in that: the specific embodiment of its preparation is as follows:
(1), powder is synthetic: will be by the stoichiometric PbNb of described general formula
2O
6, nano level (～100nm) CaO, BaO, TiO
2With Sm
2O
3, Ce
2O
3, Nd
2O
3And Te
2O
3Mix, in agate glass ball mill, material ball ratio=1: 5, carried out batch mixing 6～8 hours, with powder take out briquetting (pressure 100MPa) in sintering oven with 2～5 ℃/minute of heat-up rates, be heated to 850 ℃, and be incubated after 2 hours with＞250 ℃/minute speed of cooling, be cooled to room temperature, briquetting is taken out to pulverize again and insert in the ball mill fine grinding after 6～8 hours, powder moved to the heat-up rate with 2～5 ℃/minute rises to 1260～1270 ℃ in the sintering oven, be incubated after 2 hours with＞250 ℃/minute speed of cooling, be cooled to room temperature, and moved in the ball mill fine grinding 32～48 hours, promptly get the synthetic powder of the present invention's pottery, take out standby;
(2), the burning till and polarize of pottery:
With (1) gained powder, make piezoelectric ceramics green compact of the present invention to add the dry-pressing formed mode of tackiness agent, behind the green compact plastic removal, insert in the alumina crucible, in sintering oven with the speed of 2～5 ℃/minute of heat-up rates, it is carried out sintering under 1290～1315 ℃, be incubated 0～0.5 hour, speed of cooling with 250 ℃/minute is cooled off, taking-up is after the cold working finishing, place eight shelves again under 5000V/mm/180 ℃/10min condition, carry out high-power polarization after, promptly get piezoelectric ceramics finished product of the present invention.
2. the preparation technology of tungsten bronze structure lead meta-columbute pyroceramic according to claim 1 is characterized in that, the sphere diameter of the agate glass abrading-ball of balls grinding machine is 5～15mm.
3. the preparation technology of tungsten bronze structure lead meta-columbute pyroceramic according to claim 1 is characterized in that, the cold working precision of ceramic component is ± 0.005mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00127914A CN1100022C (en) | 2000-12-15 | 2000-12-15 | Preparation of high-temperature lead metaniobate ceramic in tungsten bronzes structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00127914A CN1100022C (en) | 2000-12-15 | 2000-12-15 | Preparation of high-temperature lead metaniobate ceramic in tungsten bronzes structure |
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|---|---|
| CN1295047A CN1295047A (en) | 2001-05-16 |
| CN1100022C true CN1100022C (en) | 2003-01-29 |
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|---|---|---|---|
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|---|---|---|---|---|
| CN101631754B (en) * | 2007-02-22 | 2013-08-14 | 株式会社村田制作所 | Dielectric ceramic composition and multilayer ceramic capacitor |
| CN101265093B (en) * | 2008-04-30 | 2010-06-02 | 陕西师范大学 | Tungsten bronze structure lead lanthanum niobate titanate high-temperature piezoelectric ceramic and preparation method thereof |
| CN101462878B (en) * | 2008-12-31 | 2012-04-18 | 中国科学院上海硅酸盐研究所 | Piezoelectric ceramic material for receiving acoustic logging system multipole and preparation thereof |
| CN101531511B (en) * | 2009-04-11 | 2011-11-09 | 桂林工学院 | High thermal stability microwave dielectric ceramic material sintered at low temperature and preparation method thereof |
| CN101538159B (en) * | 2009-04-11 | 2011-11-09 | 桂林工学院 | Microwave dielectric ceramic with medium dielectric constant sintered at low temperature and preparation method thereof |
| CN107337452B (en) * | 2017-07-14 | 2019-10-25 | 陕西师范大学 | The Sm of high transparency and luminous thermal stability3+Adulterate luminous ferroelectric ceramic material of tungsten bronze and preparation method thereof |
| CN109704762B (en) * | 2019-02-22 | 2021-07-13 | 中国科学院上海硅酸盐研究所 | Strontium niobate-based antiferroelectric ceramic and preparation method and application thereof |
| CN111087243A (en) * | 2019-12-11 | 2020-05-01 | 中国科学院上海硅酸盐研究所 | Compact lead metaniobate piezoelectric ceramic material and preparation method thereof |
| CN114804872A (en) * | 2022-04-29 | 2022-07-29 | 杭州瑞声海洋仪器有限公司 | Lead meta-niobate based piezoelectric ceramic material with high Curie temperature and high stability and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1092560A (en) * | 1993-03-16 | 1994-09-21 | 中国科学院上海硅酸盐研究所 | Modification lead meta-columbute high-temperature piezoelectric ceramic material and preparation method thereof |
-
2000
- 2000-12-15 CN CN00127914A patent/CN1100022C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1092560A (en) * | 1993-03-16 | 1994-09-21 | 中国科学院上海硅酸盐研究所 | Modification lead meta-columbute high-temperature piezoelectric ceramic material and preparation method thereof |
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