JPS6022442B2 - Pyroelectric porcelain material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a stable, durable porcelain material that has a high durability coefficient, a low dielectric constant, excellent dew performance, and excellent practicality.

As a method of measuring the surface temperature of objects near room temperature or the skin temperature of the human body without directly touching them, the intensity of infrared rays emitted from the objects to be detected according to the temperature is detected using an advanced infrared detection element. This method is widely used.

This pyroelectric detection element absorbs infrared rays emitted from the object to be detected, and uses changes in spontaneous polarization caused by temperature changes in the fish matrix material as a signal.
The surface temperature of the object to be detected can be detected easily and accurately.

The maximum intensity of infrared rays corresponding to temperatures near room temperature is around a wavelength of 10 microns, and pyroelectric infrared detection elements that detect this are generally widely used. The material used for such a tortoise-shaped infrared detecting element has a larger change in spontaneous polarization with respect to temperature change, that is, a larger tortoise coefficient (s/dT), and a higher specific electric constant (Es). The smaller the value, the better, and it is desirable from both practical and industrial standpoints to provide a material with a high Curie point (Tc), which is the temperature at which toughness disappears, at a low cost. Conventionally, glycine sulfate, lithium niobate (LINO03), lithium tantalate (LI
Single crystal materials such as lead titanate (PbTi0)
3) Magnetic materials such as lead zirconate titanate (PrTi03) are known. However, glycine sulfate crystals are water-resistant and brittle, and it is difficult to process them, making it difficult to manufacture durable materials.Furthermore, the temperature at which their resistance disappears, that is, the curie temperature, is extremely low. This significantly limits its operating temperature range. Also,
Although lithium niobate crystal has good workability, it is not preferred in practice because it has a hardness coefficient (s/dT) of 4. Although it is a preferable material because it is relatively large, it is industrially disadvantageous because it is expensive. Furthermore, although iron titanate has a large dps/dt and a relative permittivity of 4.0, it is difficult to freeze, the lead component evaporates during firing, and it has stable exposure characteristics with a uniform composition. It has the disadvantage that it is difficult to obtain a porcelain material, and lead zirconate titanate has good workability and high dps/dt, but has the disadvantage of large Es. The inventors of the present invention have conducted extensive research to provide an inexpensive material that possesses the advantages of lead zirconate titanate-based porcelain materials and has significantly improved drawbacks, and has found that the dielectric constant is extremely small. , dps depending on the amount of strontium contained
We have found a very convenient material that allows us to change and select /dt and Tc, and have accomplished the present invention.

That is, the present invention is based on the formula {Gei (PQNb207)}X{(Pb・MaSrZ) (Koge Tiy).

3}・～, where X in the formula is 0.01 to 0.00
The main component is a compound having a composition in which Y is 0.10 to 0.30 and Z is 0.01 to 0.10, and further contains manganese dioxide in the range of 0.1 to 1.5% by weight of the compound. The present invention provides a pyroelectric magnetic material characterized by:

Sr expressed by the above formula used in the porcelain material of the present invention
The containing lead zirconate titanate compound has a formula in which X is 0.
It is important that Y is within the range of 0.10 to 0.30 and Z is within the range of 0.01 to 0.10, and compounds that deviate from the combination range. So,
The pyroelectric coefficient (dps/dt) becomes smaller or the relative permittivity (E
s) becomes large and the pyroelectric performance deteriorates, making it unsuitable as a pyroelectric material.

The preferred range of X, Y, and Z is 0.03 to 0.0, respectively.
05 0.15-0.20 and 0.03-0.05. In addition, manganese dioxide (
Mn02) is 0.0 for the compound represented by the above formula.
It is used in an amount of 1 to 1.5% by weight.

If the amount of the added component is too small or too large, the strength performance will deteriorate, so it is not preferable. The high-voltage ceramic material of the present invention contains, for example, Pb0, NQ05, Zr as components for forming a metal oxide composite having the composition represented by the above formula.
Chemically pure powder of 03 is conveniently used for 02, Ti02 and S, and the amounts of each of the above metal oxide components are weighed so that x, y and z in the formula are the desired values. , Further, 0.1 to 1.5% by weight of powdered MnQ is added to these, based on the total weight, and preferably these mixed powders are further pulverized and mixed to form a mixture as fine and uniform as possible. Afterwards, it is pre-fired at a temperature of about 1000 oo, for example.
The pre-fired mixture is again pulverized and strained using a pulverizer, an organic binder commonly used in the production of ceramics is added thereto, and after kneading, it is press-molded into a desired shape and then heated at a higher temperature, for example 1200°C, for 2 hours. It can be manufactured by firing to a certain extent.

In order to impart toughness to this material, electrodes are attached to both sides of a fired molded body, for example a disc, and this is heated to a temperature of 50 to 150 q
It is polarized by applying, for example, a high DC voltage in the oil flooded with water. The reinforced porcelain material of the present invention thus provided is easy to manufacture, its compact is extremely dense, has good water resistance and heat resistance, and has a relatively high variable Curie point. It is the cornerstone of high-density performance, combining a large pyroelectric coefficient and a small dielectric constant.
It is an extremely useful material industrially. Next, the present invention will be explained in more detail with reference to Examples. Examples 1-6 Chemically high purity PO0, Nb2Q, Zr02, Ti0
2 and CrC03 powder, Nh02 powder was further added as an additive component to these metal oxides, the mixture was placed in a ball mill and mixed thoroughly, and then pre-calcined at a temperature of about 1000°C for about 2 hours. I did it.

This calcined product was sufficiently pulverized and mixed again using a ball mill, and then an organic binder was added and mixed, and then 2bn
/A disk with a diameter of 2 and a thickness of 1 was formed by pressure using water. After the obtained disc was fired for about 2 hours at a temperature of about 120 psi, electrodes were contacted on both sides of the disc, and the disc was placed in oil at a temperature of about 80 to 100 oo. A direct current voltage of 100 mL was applied to polarize the sample. By such a method, X in the formula of the silk compound represented by the above formula is kept constant (0.0
3), and with Z set to 0.05 or 0.10, various durable porcelain materials whose main components are compounds with different values of Y are created, and the exposure coefficient (dps/dt) and dielectric constant of each are determined. (E
s) and Curie point (Tc) were measured.

The amount of M as an additive component relative to the compound of formula 2 is all 0.5% by weight. The varied values of Y and the measurement results for each material are summarized in Table 1.

In addition, the table shows the performance index [(dps/dt)/Es]
are also shown. Table 1 Examples 7 to 11 A disc whose main component is a compound having a composition represented by the above formula, in which the values of X and Y in the formula are 0.03 and 0.15, respectively, and the value of Z is different. Porcelain material and Y are 0
．． A disk magnetic material having values of 15 and Z of 0.05, with only the value of X changed, was prepared in the same manner as in the previous example, and examined for the same measurement items as before.

Note that each material contains 0.5% by weight of the Mm02 additive component based on the composition compound. The results of each measurement are shown in Table 2 below, along with the compound composition. Table 2 Examples 12 to 14 High purity Pbo, Nb2Q, Zr
Using each powder of Q, Ti02, and C203, various types of electromagnetic porcelain materials were created in which the amount of Nn02 added as an additive component was changed without changing the weighed amount of the metal oxide.

X in the above formula of compounds formed from these metal oxides
, Y, and Z are 0.03 for X, 0.15 for Y, and 0.05 for Z, and the same compositional compounds are formed in all the materials. The measurement results of the scorching characteristics and Tc of three types of porcelain materials with only the added amount of Mm02 changed are shown in the third section.
Shown in the table.

3. For reference, the following Table 4 shows the exposure characteristics and practicality of various conventionally known durable materials.

Table 4

Claims (1)

[Claims] 1 Formula {1/2(Pb_2Nb_2O_7)}_x・{(Pb
_1_-_zSr_z) (Zr_1_-_yTi_y)
O_3}_1_-_x, where x in the formula is 0.01
~0.06, y is 0.10-0.30 and z is 0.01
1. A pyroelectric magnetic material characterized in that the main component is a compound having a composition of 0.10 to 0.10, and further contains manganese dioxide in an amount of 0.1 to 1.5% by weight of the compound.