JPS6154742B2 - - Google Patents
Info
- Publication number
- JPS6154742B2 JPS6154742B2 JP51006432A JP643276A JPS6154742B2 JP S6154742 B2 JPS6154742 B2 JP S6154742B2 JP 51006432 A JP51006432 A JP 51006432A JP 643276 A JP643276 A JP 643276A JP S6154742 B2 JPS6154742 B2 JP S6154742B2
- Authority
- JP
- Japan
- Prior art keywords
- temperature
- ceramics
- shows
- pbo
- amount
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 4
- 229910021193 La 2 O 3 Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 238000009700 powder processing Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 description 19
- 230000007704 transition Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 230000005684 electric field Effects 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Inorganic Insulating Materials (AREA)
- Compositions Of Oxide Ceramics (AREA)
Description
【発明の詳細な説明】
＜梗概＞
セラミクスでありながら透光性を有し、電気と
光の相互作用をもつ強誘電体として、Pb
（ZrTi）O3に種々の元素を導入したものが考えら
れている。特に（PbLa）（ZrTi）O3、（PLZTと
略す）が脚光を浴びている。このPLZTは大きな
電気光学効果を示し、メモリー動作を示すため画
像表示素子として有望である。鉛を含むセラミク
スを作る場合、鉛は低温から蒸気として飛び出す
ので、焼結方法や、出発原料の鉛量等を考慮する
必要がある。[Detailed Description of the Invention] <Summary> Although it is a ceramic, Pb has translucency and is a ferroelectric material that interacts with electricity and light.
Various elements have been introduced into (ZrTi)O 3 . In particular, (PbLa)(ZrTi)O 3 (abbreviated as PLZT) has been in the spotlight. This PLZT exhibits a large electro-optic effect and exhibits memory operation, making it promising as an image display element. When making ceramics containing lead, it is necessary to consider the sintering method, the amount of lead in the starting material, etc., since lead escapes as vapor at low temperatures.
本発明は鉛を含む透光性セラミクスの特性を制
御するための手段として、焼結時に新規な手段を
とることによつてセラミクスの特性を変化させた
ものであり、特に、強誘電的性質と反強誘電的性
質の遷移に関する温度（Transition
Temperature）（Ttと略す）に関して、細かく制
御し、また、キユリー点（Tc）は変動させない
ようにしたものである。 The present invention is a means for controlling the properties of translucent ceramics containing lead, in which the properties of the ceramics are changed by taking a new method during sintering, and in particular, the properties of the ceramics are changed by taking new measures during sintering. Temperature related to the transition of antiferroelectric property (Transition
Temperature (abbreviated as Tt) is finely controlled, and the Curie point (Tc) is not allowed to fluctuate.
＜従来の技術＞
透光性セラミクスを表示装置に組み込む場合、
透光性セラミクスは温度雰囲気によつてその特性
が変化するので遷移温度Tt（Transition
Temperate）やTc（Curie点）が動作駆動に適し
た温度になるようにその組成を決定しなければな
らない。<Conventional technology> When incorporating translucent ceramics into a display device,
The characteristics of translucent ceramics change depending on the temperature atmosphere, so the transition temperature Tt (Transition
The composition must be determined so that the temperature (Temperate) and Tc (Curie point) are suitable for operation.
従来ではPLZTの製造の際にLa量の組成を変え
ることによりTt、Tcを決定していた。しかし、
La量の組成を変えると、Ttの他にTcも変化する
し、セラミクスの結晶構造も大きく変化させるの
で、分極量の変化も生じてくる。このように従来
の方法によれば、遷移温度Ttをかえようとする
と、キユリー温度Tcや分極量もそれに伴つて変
化し、メモリーの大きさもかわつてしまうので、
任意の特性をもつセラミクスを得られなかつた。 Conventionally, Tt and Tc were determined by changing the composition of La amount during the production of PLZT. but,
When the composition of the amount of La is changed, not only Tt but also Tc changes, and the crystal structure of the ceramics also changes significantly, resulting in a change in the amount of polarization. In this way, according to the conventional method, if you try to change the transition temperature Tt, the Kyrie temperature Tc and the amount of polarization will change accordingly, and the size of the memory will also change.
Ceramics with arbitrary properties could not be obtained.
本発明は真空中での低温度処理によつて再現性
よく、Ttを制御するもので任意のTtをもつセラ
ミクスを製造する方法を提供するものである。 The present invention provides a method for manufacturing ceramics having a desired Tt by controlling Tt with good reproducibility through low-temperature treatment in vacuum.
＜実施例＞
第１図は本発明に係る製造方法の一実施例の温
度制御工程を示す。最初の真空中での1300℃／６
時間／3000psiのホツトプレス処理で粒径が決定
され、次の真空中での1100℃の処理では粒成長は
ほとんどないがその継続時間（Ｘ時間）によつて
焼結体中に鉛の変動が生じた。<Example> FIG. 1 shows a temperature control step in an example of the manufacturing method according to the present invention. 1300℃/6 in initial vacuum
The grain size is determined by hot press treatment at 3000 psi for 300 psi, and there is almost no grain growth in the next treatment at 1100 ℃ in vacuum, but depending on the duration (X hours), lead fluctuations occur in the sintered body. Ta.
第２図に本発明のために用いたホツトプレス前
の粉体処理過程を示す。２１は秤量、２２は混
合、２３は一次焼成、２４は粉砕、２５は混合、
２６は成型、２７は二次焼成、２８はホツトプレ
スである。 FIG. 2 shows the powder treatment process used for the present invention before hot pressing. 21 is weighing, 22 is mixing, 23 is primary firing, 24 is crushing, 25 is mixing,
26 is molding, 27 is secondary firing, and 28 is hot pressing.
第３図は本発明で行つた結果の平均粒径を示し
たもので上記Ｘ時間にかかわらずほとんど一定で
あつた。 FIG. 3 shows the average particle diameter as a result of the present invention, which was almost constant regardless of the above-mentioned X time.
第４図は本発明におけるキユリー温度Tcの変
化を示すもので、上記Ｘ時間にかかわらずほとん
ど一定であつた。 FIG. 4 shows the change in the Curie temperature Tc in the present invention, which remained almost constant regardless of the above-mentioned X time.
即ち、ホツトプレス処理で粒径、Tcが決定さ
れることを示している。 That is, it is shown that the particle size and Tc are determined by the hot press treatment.
第５図は本発明の最も強調している特性で、真
空下での1100℃低温度処理の保持時間を制御する
ことにより、Ttが細かく制御できることを示し
ている。 FIG. 5 shows the most emphasized characteristic of the present invention, and shows that Tt can be finely controlled by controlling the holding time of the 1100°C low temperature treatment under vacuum.
第６図は透光性セラミクスの光学的測定を行つ
た図を示す。６１は光源、６２は検光子、６３は
PLZT測定素子、６４は受光素子である。この測
定では検光子を直交ニコルにし、電界を印加して
光量を測定した。 FIG. 6 shows a diagram of optical measurement of translucent ceramics. 61 is a light source, 62 is an analyzer, 63 is
PLZT measurement element 64 is a light receiving element. In this measurement, the analyzer was set to crossed nicols, an electric field was applied, and the amount of light was measured.
第７図は検光子を平行ニコルにし、電界を印加
しないときの透過光量をIoとし素子に直交ニコル
で電界を印加して最も透過光量の大きいときをＩ
としたもので、室温25℃におけるＩ／IoはTtの
変化とともにかわることを示している。 Figure 7 shows the analyzer in parallel Nicols, the amount of transmitted light when no electric field is applied is Io, and the amount of transmitted light when the electric field is applied to the element in crossed Nicols and the maximum amount of transmitted light is I.
This shows that I/Io at room temperature 25°C changes as Tt changes.
第８図は検光子を直交ニコルにして、電界を印
加し、光量の最小値をＮ、最大値をＳとして、
Ｓ／ＮがTtの変化とともに変化することを示し
ている。但し測定温度は室温である。 In Figure 8, the analyzer is set to crossed nicols, an electric field is applied, the minimum value of the light amount is set to N, the maximum value is set to S,
This shows that the S/N changes as Tt changes. However, the measurement temperature was room temperature.
第７図、第８図から透光性セラミクスは適用す
る目的に応じてTtを制御する必要性があること
が分る。 It can be seen from FIGS. 7 and 8 that it is necessary to control Tt of translucent ceramics depending on the purpose to which it is applied.
次に本発明に関する更に具体的実施例として
PLZTセラミクスをホツトプレス法により製作す
る場合について述べる。 Next, as a more specific example of the present invention
We will discuss the case of manufacturing PLZT ceramics using the hot press method.
出発原料は高純度（99.99％）のPbO、La2O3、
ZrO2、TiO2粉体であり、これらを第２図に示す
ような粉体処理工程で（Pb0.91La0.09）
（Zr0.35Ti0.35）O3の組成に合成した。尚、PbO蒸
発を補うため、2.5wt％のPbOを過剰に加えてい
る。 The starting materials are high purity (99.99%) PbO, La 2 O 3 ,
These are ZrO 2 and TiO 2 powders, and they are processed in a powder processing process as shown in Figure 2 (Pb 0 . 91 La 0 . 09 ).
(Zr 0 . 35 Ti 0 . 35 )O 3 was synthesized. In addition, in order to compensate for PbO evaporation, 2.5 wt% of PbO was added in excess.
セラミクスの結晶粒径の大きさはホツトプレス
時の温度、圧力、時間により決定される。第１図
は代表的な温度プロフアイルであるが高温部で結
晶粒径をコントロールし、加圧をやめて低温部で
セラミクス中のPbO含有量をコントロールする。 The crystal grain size of ceramics is determined by the temperature, pressure, and time during hot pressing. Figure 1 shows a typical temperature profile in which the grain size is controlled in the high temperature section, and the PbO content in the ceramic is controlled in the low temperature section after the pressure is stopped.
第３図は高温部で1300℃、６時間、3000psi、
低温部で1100℃とし真空時間をＸ時間とし、その
後酸素雰囲気を導入してセラミクスを作成したも
のについて平均粒径を調べたもので、粒径は3.2
μｍの平均粒径となり、1100℃に保持しても粒径
が変化しないことを示している。 Figure 3 shows the high temperature section at 1300℃, 6 hours, 3000psi,
The average particle size was investigated for ceramics created by heating the temperature to 1100°C in the low temperature part, setting the vacuum time to X hours, and then introducing an oxygen atmosphere, and the particle size was 3.2
The average particle size is μm, indicating that the particle size does not change even when held at 1100°C.
第４図はＸ時間を変化させてもキユリー温度
Tcはほとんど変化しないことを示している。 Figure 4 shows the Curie temperature even if X time is changed.
This shows that Tc hardly changes.
次に上記真空中における約1100℃の低温度処理
の時間制御よつてTcを略一定にしたままTtを制
御できる理由について考察すれば次の通りであ
る。 Next, the reason why Tt can be controlled while keeping Tc approximately constant by controlling the time of the low temperature treatment at about 1100° C. in vacuum is as follows.
PbO、La2O3、ZrO2及びTiO2の各原料の粉体を
上記PbOを過剰に加えて合成する粉体処理を行な
い、次に真空中で加圧及び高温度加熱処理するホ
ツトプレスを行なうと、PbOは粒界において偏析
した状態で存在するものと考えられる。この状態
で次に真空中で加圧せずに約1100℃（この程度の
温度では粒成長が促進されないことが確認されて
いる）で低温度加熱すると、上記粒界に存在する
過剰のPbOが分解され粒界の状態が変化するもの
と考えられ、上記Ttの変化はこれに帰因するも
のと考察される。即ち遷移温度TtはInduced
Phase状態で現われ、強誘電体域内の敏感な相変
態に係る値であるので、セラミクス中の鉛の結合
状態に影響されるものと考えられる。因に上記Ｘ
時間を変えた時のセラミクス中のPbOの量の変化
と、遷移温度Ttの変化とはその傾向に一致が見
られる。 PbO, La 2 O 3 , ZrO 2 and TiO 2 raw material powders are synthesized by adding an excess amount of the above PbO, followed by hot pressing, which involves pressure and high-temperature heat treatment in a vacuum. Therefore, PbO is considered to exist in a segregated state at grain boundaries. If this state is then heated at a low temperature of about 1100℃ (it has been confirmed that grain growth is not promoted at this temperature) without applying pressure in a vacuum, the excess PbO present at the grain boundaries will be removed. It is thought that the state of grain boundaries changes due to decomposition, and the above change in Tt is considered to be attributable to this. That is, the transition temperature Tt is Induced
It appears in the phase state and is a value related to sensitive phase transformation within the ferroelectric region, so it is thought to be influenced by the bonding state of lead in the ceramic. Incidentally, the above
The tendency of the change in the amount of PbO in the ceramics and the change in the transition temperature Tt when the time is changed is consistent.
＜効果＞
以上の本発明によれば透光性セラミクスのキユ
リー点を変動させずに遷移温度を細かく制御する
ことができ、表示装置その他の用途に応じて最適
の電気光学素子材料を提供することができるもの
である。<Effects> According to the present invention, the transition temperature of translucent ceramics can be finely controlled without changing the Curie point, and an electro-optical element material optimal for display devices and other uses can be provided. It is something that can be done.
第１図は本発明の一実施例の温度制御を表す工
程図、第２図は工程ブロツク図、第３図乃至第５
図は時間Ｘに対する特性を示す線図、第６図は測
定の光学系を示す配置図、第７図及び第８図は遷
移温度Ttに対する特性を示す線図である。
６３……PLZT素子。
Fig. 1 is a process diagram showing temperature control in an embodiment of the present invention, Fig. 2 is a process block diagram, and Figs.
6 is a diagram showing the characteristics with respect to time X, FIG. 6 is a layout diagram showing the optical system for measurement, and FIGS. 7 and 8 are diagrams showing the characteristics with respect to transition temperature Tt. 63...PLZT element.
Claims (1)
を上記PbOをやや過剰に加えて合成する粉体処理
工程と、次に真空中で加圧及び約1300℃の高温度
加熱処理するホツトプレス工程と、次に真空中で
加圧せずに約1100℃で所定時間低温度加熱して透
光性セラミクスの遷移温度を調整する遷移温度調
整工程とにより、透光性の（PbLa）（ZrTi）O3
を製造する方法。1 Powder processing step in which the raw material powders of PbO, La 2 O 3 , ZrO 2 and TiO 2 are synthesized by adding a slight excess of the above PbO, followed by pressurization in a vacuum and high temperature of about 1300°C. The translucent ( PbLa)(ZrTi) O3
How to manufacture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP643276A JPS5289106A (en) | 1976-01-20 | 1976-01-20 | Manufacture of light permeable ceramics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP643276A JPS5289106A (en) | 1976-01-20 | 1976-01-20 | Manufacture of light permeable ceramics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5289106A JPS5289106A (en) | 1977-07-26 |
| JPS6154742B2 true JPS6154742B2 (en) | 1986-11-25 |
Family
ID=11638222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP643276A Granted JPS5289106A (en) | 1976-01-20 | 1976-01-20 | Manufacture of light permeable ceramics |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5289106A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63129558U (en) * | 1987-02-13 | 1988-08-24 |
-
1976
- 1976-01-20 JP JP643276A patent/JPS5289106A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63129558U (en) * | 1987-02-13 | 1988-08-24 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5289106A (en) | 1977-07-26 |
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