JPS62274503A - Composite pyroelectric material - Google Patents
Composite pyroelectric materialInfo
- Publication number
- JPS62274503A JPS62274503A JP61116051A JP11605186A JPS62274503A JP S62274503 A JPS62274503 A JP S62274503A JP 61116051 A JP61116051 A JP 61116051A JP 11605186 A JP11605186 A JP 11605186A JP S62274503 A JPS62274503 A JP S62274503A
- Authority
- JP
- Japan
- Prior art keywords
- pyroelectric
- plzt
- composite
- ceramic
- pvdf
- 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.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims description 18
- 239000000463 material Substances 0.000 title description 20
- 239000000919 ceramic Substances 0.000 claims description 16
- 239000002033 PVDF binder Substances 0.000 claims description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 3
- 239000010419 fine particle Substances 0.000 description 3
- 230000005616 pyroelectricity Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000035922 thirst Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
３、発明の詳細な説明
Ａ 産業上の利用分野
本発明は、ポリフッ化ビニリデンの高分子系焦電材料の
マットリックス中にセラミックス系焦電材料の微粒子を
分散させてなる複合焦電材料に関するものである。[Detailed Description of the Invention] 3. Detailed Description of the Invention A Industrial Application Field The present invention is a method of dispersing fine particles of a ceramic pyroelectric material in a matrix of a polymeric pyroelectric material of polyvinylidene fluoride. The present invention relates to a composite pyroelectric material.
Ｂ 発明の概要
本発明は、焦電性セラミックス微粒子を、高分子特にポ
リフッ化ビニリデン（ＰＶＤＦ）中に分散してなる焦電
性複合材料であり、セラミックスにＰＬＺＴ （チタン
酸ジルコン酸鉛にＬｌを添加したものを言い、以下ＰＬ
ＺＴと称す。）を用い、そのセラミックスの配合割合が
９０ｗｔに以上で、該セラミックの粒子の大きさが１〜
ｌＯμｍであり、且つ前記ＰＬＺＴの組成式が（ｐｂ、
−ｘ、 Ｌａ−） （Ｚｒ＋−、、Ｔｉ、）０３で且つ
Ｘ及びｙが０．０２＜ｘ＜０．０６． ０．３＜ｙ＜０
．５ の範囲にある複合焦電材料である。B. Summary of the Invention The present invention is a pyroelectric composite material made by dispersing pyroelectric ceramic fine particles in a polymer, particularly polyvinylidene fluoride (PVDF). What is added is the following PL
It is called ZT. ), the blending ratio of the ceramic is 90 wt or more, and the particle size of the ceramic is 1 to 1.
lOμm, and the compositional formula of the PLZT is (pb,
-x, La-) (Zr+-,,Ti,)03, and X and y are 0.02<x<0.06. 0.3<y<0
．． It is a composite pyroelectric material in the range of 5.
Ｃ従来の技術
複合焦電材料特に？！合焦電シー１−とは、焦電性セラ
ミックス徹粒子を、高分子中に分散させたものを称する
。C Conventional technology Composite pyroelectric materials in particular? ! The term "Focused Electric Sea 1-" refers to a product in which pyroelectric ceramic particles are dispersed in a polymer.
従来、焦電材料として用いられるセラミックスの無機焦
電材料としては、クンクル酸リチウム、チクン酸鉛、チ
タン酸ジルコン酸鉛等力（ある。−万有機高分子材料と
ては、ポリフッ化ビニリデン（ＰＶＤＦ）が一般に用い
られている。Conventionally, inorganic pyroelectric materials for ceramics used as pyroelectric materials include lithium cuncurate, lead ticunate, lead zirconate titanate, etc. - Organic polymer materials include polyvinylidene fluoride (PVDF), etc. ) is commonly used.
また、これら焦電材料の適用例として（よ、赤外線セッ
サー・が基本であるが、大口径の２次元センサー（焦電
ビジコン）や火災検知器、侵入検知器等の非接触センサ
ー等に用いられる。In addition, examples of applications of these pyroelectric materials include infrared sensors, but also large-diameter two-dimensional sensors (pyroelectric vidicon), non-contact sensors such as fire detectors, intrusion detectors, etc. .
次にこれら焦電材料に用いられる高分子材料１’Ｖ［Ｉ
Ｆ ト、無ｐｉ Ｐ ｂ Ｔ ｉ Ｏｓ及ヒＬ、１Ｔａ
Ｏ）特性を夫々第１表に示す。Next, the polymer material 1'V[I
F t, no pi P b T i Os and hi L, 1Ta
O) Properties are shown in Table 1.
第１表 焦電材料の特性
焦電材料に用いられる、従来の高分子材料は第１表に示
す如く焦電係数が小さ０こと力（欠、ａであり、また従
来の無機焦電材料としてのセラミックスの欠点としては
、
■薄くすると破損し易い。Table 1 Characteristics of pyroelectric materials Conventional polymeric materials used for pyroelectric materials have a small pyroelectric coefficient of 0 and a, as shown in Table 1. Disadvantages of ceramics include: - They tend to break easily when made thin.
■大面積化が出来ない。■It is not possible to increase the area.
■熱拡散係数が大きいために、熱像の滲みが大きい。■Due to the large thermal diffusion coefficient, there is a large amount of blurring in the thermal image.
等が挙げられる。etc.
Ｄ０発明が解決すべき問題点
本発明は、前述の従来の焦電材料の欠点を解消する為に
、焦電性セラミックス微粒子を高分子中に分散させてな
る複合焦電材料において、セラミックスにＰＬＺＴを用
い、そのＰＬＺＴの組成を限定することにより、高い焦
電性を有し、室温で安定な焦？４性を有する複合材料を
提供することを目的とするものである。D0 Problems to be Solved by the Invention In order to eliminate the drawbacks of the conventional pyroelectric materials described above, the present invention provides a composite pyroelectric material in which pyroelectric ceramic fine particles are dispersed in a polymer, in which PLZT is added to the ceramic. By using PLZT and limiting the composition of the PLZT, a pyroelectric material with high pyroelectricity and stable at room temperature can be obtained. The object is to provide a composite material having four properties.
Ｅ０問題点を解決するための手段
本発明は、焦電特性を有するセラミックス粒子と高分子
のポリフッ化ビニリデン（ＰＶＤＦ）とからなる焦電性
複合材料において、該セラミックスがＰＬＺＴでありそ
の配き割合が９０ｗＬに以上で、該セラミックスの粒子
の大きさが１〜１０μｍであり、且つ前記ＰＬＺＴの組
成式が
（ｐｂ、−、ル＆−） （Ｚｒ ＋−ｙ−Ｔ’ｙ）Ｏｓ
で、上記組成式中のＸ及びｙが、０．０２＜ ｘ ＜
０．０８０．３＜ ｙ ＜ ０．５の範囲にある複合焦
電材料である。Means for Solving the E0 Problem The present invention provides a pyroelectric composite material consisting of ceramic particles having pyroelectric properties and a polymer polyvinylidene fluoride (PVDF), in which the ceramic is PLZT and its distribution ratio is is 90 wL or more, the particle size of the ceramic is 1 to 10 μm, and the compositional formula of the PLZT is (pb, -, le & -) (Zr + -y - T'y)Os
So, X and y in the above composition formula are 0.02<x<
It is a composite pyroelectric material in the range of 0.080.3<y<0.5.
Ｆ 作用
本発明に用いる、組成式が（Ｐｂ、−ｘＬａｘ） （Ｚ
ｒ１−、。F Effect Used in the present invention, the compositional formula is (Pb, -xLax) (Z
r1-,.
Ｔ ｉ ｙ ｌ ＯｉであるＰＬＺＴは、組成式中のＸ
とｙの変化に伴う状態図を示す。PLZT, which is T i y l Oi, is
A state diagram accompanying changes in and y is shown.
第１図に示す如（、菱面体晶と正方品の境界付近で圧電
性、焦電性が高いことが知ら第１て１する。As shown in FIG. 1, it is known that piezoelectricity and pyroelectricity are high near the boundary between rhombohedral and tetragonal crystals.
まｔ二し＆の添加型Ｘが増加する（こつｉｌで、メ東電
性が高くなることも知られている。It is also known that the added type
第２図は、ＰＬＺＴの組成式
％式％）
の室温の比誘電率ε／１．と前記組成式中のＸとの関係
グラフである。Figure 2 shows the relative permittivity at room temperature of PLZT composition formula %) ε/1. It is a relationship graph between and X in the compositional formula.
第２図に示す如く、前記組成式中のＸが増加すると、誘
電率が増加するので、複合材料としての良好な焦電係数
を与えるための適切な値が存在する。As shown in FIG. 2, as X in the compositional formula increases, the dielectric constant increases, so there is an appropriate value for providing a good pyroelectric coefficient as a composite material.
詰まゆ、ＰＶＤＦ （比誘電率Ｃ／ε。−１１）中に分
散されたＰＬＺＴに印加される分極時の分担電圧がＰＬ
ＺＴの誘電率に逆比例して減少し、分散しているＰＬＺ
Ｔの焦電性が減少するので、複合化するための適切なＸ
の値が存在する。PL
PLZ decreases and disperses in inverse proportion to the dielectric constant of ZT
Since the pyroelectricity of T is reduced, a suitable
The value of exists.
本発明は、前述のＰＬＺＴの組成式におけるＸ及びｙを
後述する実施例の第２表に示す如く、本発明のＰＬＺＴ
＋ＰＶＤＦの複合焦電材料は、Ｘが０．０２＜ ｘ ＜
０．０６の範囲で焦電係数が大きいので、Ｘを上記の範
囲に、更に第１図のＸとｙとの関係から、ｙの範囲を限
定したものである。The present invention provides the PLZT of the present invention, as shown in Table 2 of Examples below, where
+PVDF composite pyroelectric material has an X of 0.02<x<
Since the pyroelectric coefficient is large in the range of 0.06, X is limited to the above range, and the range of y is further limited from the relationship between X and y in FIG.
次に本発明の実施例について述べる。Next, examples of the present invention will be described.
Ｇ 実施例
ＰＶＤＦ（Ｄ ＤＭＦ＠液ト１キト１〜１０ ｍｉｃ
微粉砕しりＰＬＺＴとをＰＶＤＦＰＬＺＴ−ＩＱ゛９０
（重量）の割キテ、ホー ｋ ミに中で２時間混合する
。G Example PVDF (D DMF@Liquid 1-10 mic
Finely ground PLZT and PVDF PLZT-IQ゛90
(by weight) and mix in a large pot for 2 hours.
この混合溶液をドクターブレード法でガラス板上でに成
膜する。This mixed solution is formed into a film on a glass plate using a doctor blade method.
これを真空乾燥炉中で、ＤＭＦを揮発させ、この膜をガ
ラス板から脱離させ、膜の密度を上げるために、２００
℃、１００ｋｇ／ｃ−でプレスし、膜厚２０〜１００μ
諷の複合焦電シートを製造した。This was placed in a vacuum drying oven to volatilize DMF, detach the film from the glass plate, and increase the density of the film at 200°C.
℃, press at 100kg/c-, film thickness 20-100μ
A similar composite pyroelectric sheet was manufactured.
また製造した複合焦電シートの分極条件は、銀電極を両
回に蒸着した後、７０〜１００℃で１時間１０〜１５Ｋ
Ｖ／ｍｍの電圧を印加したままで冷却放置し、室温にな
ってから電圧を解除することで行った。In addition, the polarization conditions of the manufactured composite pyroelectric sheet were as follows: 10 to 15K at 70 to 100℃ for 1 hour after depositing silver electrodes on both times.
This was done by leaving the sample to cool while applying a voltage of V/mm, and then removing the voltage after the temperature reached room temperature.
斯かる方法でＰＬＺＴの組成式中のＸ及びｙの範囲を変
えて、ＰＬＺＴとＴ’ＶＤＦの複合焦電シートの特性を
調べた結果を第２表に示す。Table 2 shows the results of investigating the properties of a composite pyroelectric sheet of PLZT and T'VDF by changing the ranges of X and y in the composition formula of PLZT using this method.
第２表から０．０２＜ ｘ ＜ ０．０６で複合焦電材
料の焦電係数が大きいことは明らかである。From Table 2, it is clear that the pyroelectric coefficient of the composite pyroelectric material is large when 0.02<x<0.06.
第 ２ 表
本ＰＬＺＴとＰＶＤＦとの配合割合は、ＰＬＺＴ９０ｗ
ｔＸ： ＰＶＤＦｌｏｗｔＸとした。Table 2 The blending ratio of PLZT and PVDF is PLZT90w
tX: PVDFlowtX.
Ｈ０発明の効果
本発明の複合焦電材料は、Ｌａの添加量ＸとＴｉの添加
量ｙの値を特定したことにより、セラミックスの比誘電
率が低下し、複合した場合、セラミックスへの分担電圧
を大きくすることが出来、従って複合材料の焦電係数を
１１．５ Ｃ０ＵＬ／℃、ｃｄ以上とＰＶＤＦに比べて
大きくすることが出来、 且つ２０〜１００μｍと薄く
しても可撓性を有し、大面積化の可能な焦電材料である
。H0 Effects of the Invention In the composite pyroelectric material of the present invention, by specifying the values of the addition amount X of La and the addition amount y of Ti, the relative dielectric constant of the ceramic is reduced, and when combined, the shared voltage to the ceramic is reduced. Therefore, the pyroelectric coefficient of the composite material can be made larger than 11.5 C0UL/℃, cd, compared to PVDF, and it has flexibility even if it is thinned to 20 to 100 μm. , is a pyroelectric material that can be made into a large area.
第１図は、ＰＬＺＴ組成中のＸとｙとの変化に伴う状態
図、第２図は、ＰＬＺＴ （Ｐｂ、、Ｌａ、） （Ｚｒ
ｏｓｓＴｉｏ＊５）０３の室渇の比ｇ電率とＸとの関係
グラフである。Figure 1 is a phase diagram accompanying changes in X and y in the PLZT composition, and Figure 2 is a phase diagram of PLZT (Pb,, La,) (Zr
It is a graph of the relationship between the specific g-electricity of room thirst and X for ossTio*5)03.
Claims (1)
ッ化ビニリデン（ＰＶＤＦ）とからなる焦電性複合材料
において、該セラミックスがＰＬＺＴであり、その配合
割合が９０ｗｔ％以上、該セラミックス粒子の大きさが
１〜１０μｍであり、且つ前記ＰＬＺＴの組成式が、 （Ｐｂ＿１＿−＿ｘ、Ｌａ＿ｘ）（Ｚｒ＿１＿−＿ｙ、
Ｔｉ＿ｙ）Ｏ＿３で、上記組成式中のｘ及びｙが、０．
０２＜ｘ＜０．０６、０．３＜ｙ＜０．５の範囲にある
ことを特徴とする複合焦電材料。[Claims] A pyroelectric composite material comprising ceramic particles having pyroelectric properties and a polymer polyvinylidene fluoride (PVDF), wherein the ceramic is PLZT, the blending ratio of which is 90 wt% or more; The particle size is 1 to 10 μm, and the compositional formula of the PLZT is (Pb_1_-_x, La_x)(Zr_1_-_y,
Ti_y)O_3, where x and y in the above composition formula are 0.
02<x<0.06, 0.3<y<0.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61116051A JPS62274503A (en) | 1986-05-22 | 1986-05-22 | Composite pyroelectric material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61116051A JPS62274503A (en) | 1986-05-22 | 1986-05-22 | Composite pyroelectric material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62274503A true JPS62274503A (en) | 1987-11-28 |
Family
ID=14677489
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61116051A Pending JPS62274503A (en) | 1986-05-22 | 1986-05-22 | Composite pyroelectric material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62274503A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007182554A (en) * | 2005-11-23 | 2007-07-19 | General Electric Co <Ge> | Antiferroelectric polymer composite, method of manufacture thereof, and article comprising the same |
-
1986
- 1986-05-22 JP JP61116051A patent/JPS62274503A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007182554A (en) * | 2005-11-23 | 2007-07-19 | General Electric Co <Ge> | Antiferroelectric polymer composite, method of manufacture thereof, and article comprising the same |
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