JPS603008B2 - Manufacturing method of ceramic substrate made of amorphous lead zirconate - Google Patents

Description

[Detailed Description of the Invention] The present invention relates to a method for producing a ceramic base material containing substantially amorphous lead zirconate, and more specifically, as a dielectric ceramic, a piezoelectric ceramic, a resistive ceramic, a semiconductor ceramic, etc. The present invention relates to a method for producing the useful ceramic base.

Lead zirconate is widely used as a porcelain material for the electronic components mentioned above, but the most common manufacturing method for synthesizing such lead-containing post-oxides is to combine lead oxide and zirconium dioxide components at high temperatures. It consists of an oxide method that involves a solid phase reaction.

However, when the product obtained by such a solid phase reaction is subjected to x-line diffraction, in addition to the x-line diffraction image characteristic of lead zirconate, the It shows a diffraction pattern and has the drawback of being extremely compositionally heterogeneous. Furthermore, the double oxide obtained by this solid phase reaction method has a coarse particle size and lacks intimate miscibility with other raw materials and auxiliary raw materials due to the fact that it has been subjected to a thermal history at high temperatures. It also has the disadvantage of poor reactivity. In order to improve the above-mentioned drawbacks of the solid phase reaction method, it is already known to produce lead zirconate or a lead zirconate/lead titanate composite (hereinafter sometimes simply referred to as a lead zirconate composite) by a solution method. ing. The typical method is
As described in U.S. Pat. No. 3,352,632, zirconium oxynitrate or titanium oxynitrate is reacted with a water-soluble lead salt such as lead nitrate or lead acetate in an aqueous medium containing oxalic acid, and The method consists of linearly forming a crystalline composite oxalate, and thermally decomposing the crystalline composite oxalate at a temperature of 700° C. or higher to obtain lead zirconate or a zirconate composite. In this method, when producing lead zirconate or lead zirconate composite,
Heating at a high temperature of 700° C. or higher promotes particle growth, which inevitably causes the disadvantage that the particle size of the target product becomes larger and non-uniform. Also, Can. Ceram. Soc.
Jour. 34103 (1965) describes an alkaline solution containing a mixture of ammonia and ammonium carbonate in a solution containing water-soluble salts such as zirconium oxynitrate and titanium oxynitrate and water-soluble lead salts such as lead nitrate. to precipitate a coprecipitate of X-ray crystalline zirconium and titanium hydroxides and a basic carbonate of lead;
It is disclosed that a lead zirconate composite powder is produced by temporarily holding this crystalline coprecipitate at a temperature of 700 to 800°C.

This method, like the method of the above-mentioned US patent, has the disadvantage that the grain size tends to coarsen due to calcination at a high temperature of 700°C or higher. When pseudorise is carried out at a low temperature, carbonate radicals and the like remain in the lead zirconate composite, making it unsatisfactory for use as a raw material for ceramics in terms of purity and the like.

3 The inventors selected lead monoxide (hereinafter sometimes simply referred to as wet process lead monoxide), which the inventors proposed in U.S. Patent No. 4,117,104, as a raw material for the lead component, and Select zirconium oxynitrate or its hydrolyzate as the raw material4
When selected, both of these components readily react to form an amorphous lead zirconate with novel particle size and crystallization properties and which is highly useful as a ceramic base. I discovered that. That is,
According to the invention, a summer density of 83 to 9.2 ta'cc;
Primary particle size of 0.2 microns or less, wave number 1400 to 14
It has an infrared absorption peak with a ratio of 1 to 1, and a chromic anhydride reaction rate of 1% or more. and the combination with the hydrolyzate in a ratio such that the molar ratio of P:MO2 (in the formula, M represents zirconium or a combination of zirconium and titanium) is in the range of 6:1 to 1:1.1, Provided is a method for producing a ceramic base containing amorphous lead zirconate, characterized in that the reaction is carried out in an aqueous medium.

The lead zirconate or zirconate composite for ceramics of the present invention is amorphous and consists of fine particles having an apparent grain size of 5 grains or less, particularly preferably 2 grains or less, and a crystallization temperature of 500 to 600°C. It has the following characteristics.

The coprecipitates of oxalates of zirconium and lead, zirconium, titanium, and lead, or the coprecipitates of hydroxide basic carbonates obtained by the oxalic acid method or ammonium carbonate method described above are all linear. This fact is easily understood from the X-ray diffraction diagrams of curve B-1 and curve C-1 in FIG.

On the other hand, in the lead zirconate or lead zirconate composite according to the present invention, solid particles of green method lead monoxide, which has extremely fine particles and is easily reactive, react directly with the zirconium component or even the titanium component. Therefore, although it is amorphous, it does not exhibit the cohesive continuous phase characteristic of gel-like materials, and takes the form of non-cohesive, tens (dense) fine particles. The fact that the lead zirconate or lead zirconate composite according to the present invention is amorphous and non-agglomerated fine particles can be seen in the curve A-2-1 or the first curve of the x-ray diffraction diagram in FIG. This will be easily understood by referring to the curve A-1 of the X-ray diffraction diagram and the optical micrographs of FIGS. 3-1 and 3-2. Furthermore, in the amorphous lead zirconate or lead zirconate composite according to the present invention, the lead oxide component, the zirconium oxide component, and the titanium oxide component exist in a compositionally extremely homogeneous form, and are extremely easy to crystallize. The fact that this product has a crystallization temperature as a velopskite-type composite oxide is significantly lower than that of zirconyl-lead or zirconyl-titanium-lead conjugates produced by the conventional crystalline oxalic acid method and ammonium carbonate method. It is clear from the X-ray diffraction diagrams of curve A-2-2 in FIG. 2 and curve A-4 in FIG. 4 that it is in the range of 500 to 60 pi.

As mentioned above, in the coprecipitate obtained by the oxalic acid method, 7
The decomposition of the complex oxalic acid occurs only at a high temperature of 00°C or higher, and on the other hand, the co-pillowed material produced by the ammonium carbonate method also shows the curve C-4Z (600°C) in the X-ray diffraction diagram in Figure 3 and the curve in Figure 5. As is clear from CM5 (800°C), the lead zirconate complex crystallizes only at a temperature of 700°C or higher.

Comparing these facts, the lead zirconate or lead zirconate composite according to the present invention has a remarkable feature of lower crystallization temperature than the lead zirconate or lead zirconate composite produced by the conventional Z solution method. It is understood that
In addition to these advantages, the lead zirconate or lead zirconate composite according to the invention has the advantage that the crystallinity of the formed crystals is significantly high upon heat treatment at a constant temperature for a period of 12 hours.

That is, in FIG. 5, the molar ratio of Pb○:Z to 2:Ti02 is 2:
It is an X-ray diffraction diagram of a 1:1 amorphous lead zirconate composite heat-treated at 820 ° C. for 10 minutes, curve A-5 is according to the present invention, curve B-5 is according to the ammonium carbonate method, Figure 6 shows the amorphous lead zirconate composite with a molar ratio of Pb○:Zr0:Ti02 of 2:1:1.
1 at °C. This is an X-ray diffraction diagram of a sample subjected to heat treatment for an extended period of time.
Curve A-6 shows the result according to the present invention, and curve C3-6 shows the result according to the ammonium carbonate method. Comparing the heights of the diffraction peaks in these figures, it becomes clear that the crystallization according to the present invention is more highly crystallized.

Furthermore, the amorphous lead zirconate or lead zirconate composite (hereinafter also simply referred to as "coalescence") fine particles according to the present invention can be obtained by dehydrating the aqueous slurry under reduced pressure (50 cm Hg absolute) to form a wet cake. Dry the cake and use your fingertips to roll it into a cube about 1 skin on each side or into a sphere about 1 skin in diameter.
When fired at 600°C to form a molded product, the pore volume is extremely small, that is, the pore radius is 75A to 4.7× by mercury intrusion method.
It exhibits a pore volume of less than 0.15'', in particular less than 0.10'', measured in the range of 1 pore A.

As is clear from the pore distribution curve in Figure T, lead zirconate or its composite obtained by the conventional solution method, ie, the oxalic acid method or the ammonium carbonate method, has no effect when measured under the conditions described above. also indicates a pongee hole volume of 0.5 I/ta or less (curve D-7・
... Oxide method, Curve C-7 ... Ammonium carbonate method, Curve B-7 ... Oxalic acid method).

On the other hand, lead zirconate according to the present invention or its subsequent coalescence shows curves A-7-1, A-7-2 (sample No. 1-10 of the example described later...A-7-1, 1-1). ...A-7
As is clear from Figure 12), the volume of the pongee pores is significantly small, and in particular, the volume of macropores with a radius of 430 to 147 × 1 A is suppressed to a significantly small level of less than 0.12 ['ta]. It is being done.・The fact that the amorphous lead zirconate molded product of the present invention exhibits such an extremely small pongee pore volume is because the amorphous lead zirconate has fine grain size, uniform grain size, and the fact that the molded product This proves the fact that the packing state is close to close-packed.

Since the amorphous lead zirconate according to the present invention has the above-mentioned novel properties, it brings about excellent effects when used as a ceramic base material.

When producing a composite body such as a ceramic using a powder such as lead zirconate as a raw material, the particle size and crystallization characteristics of the raw material powder are determined by the various physical properties of the composite structure and its manufacturing process. It is known that this has a significant impact on the workability of the process.

That is, the phosphor bodies are produced by using the powder raw materials mentioned above as they are, or by adding various compounding agents or additives, and then pressure-molding them into the desired shape, and then subjecting this molded body to normal pressure or under pressure. , produced by heating to a temperature below the melting point. In this coagulation process, by heating, bonds are formed between the particles, and at the same time, the pores interposed between the particles diffuse through the grain boundaries and leave the system, making the molded object densified and increasing its mechanical strength. is brought about. Although the lead zirconate according to the present invention is amorphous as described above, its apparent particle size is extremely fine.
The surface energy that is the driving force for scale formation is large, and this makes it possible to increase the competitive streak speed.

Furthermore, since the grain size is fine, there are many grain boundaries, which promotes the diffusion of pores and has the advantage of increasing the densification rate. Furthermore, it is known that ceramic bodies generally exhibit superior physical properties when their constituent crystal grains have a finer and finer structure.

As mentioned above, the amorphous lead zirconate according to the present invention has a fine grain size, a low crystallization temperature, and a high crystallization rate, so it can be formed at a lower temperature and in a shorter time. It is possible to suppress the growth of grains into coarse grains and to produce Akatsuki compacts having a fine and uniform structure. In particular, in the production of ceramic bodies based on lead zirconate, it is often observed that the composition of the ceramic body differs from the blended composition due to the generation of lead oxide fumes during sintering. When the lead zirconate of the invention is used as a base material, crystallization and firing can be performed at low temperatures in a short time, and the composition is homogeneous, so the generation of lead oxide fume can be suppressed and the composition can be strictly controlled. control is possible. Moreover, since the amorphous lead zirconate particles used in the present invention have a significantly small pore volume when formed into a molded body, a ceramic body having an extremely fine microstructure can be obtained.

All the properties and advantages mentioned above apply exactly not only to the lead zirconate according to the invention, but also to the lead zirconate titanate composite according to the invention.

That is, the aforementioned dielectric ceramic, piezoelectric ceramic,
In the field of resistor ceramics, etc., products containing lead zirconate and lead titanate in various arbitrary ratios are known.Thus, in the composite of the present invention, Z
The weight ratio of the Ti component and the Ti component is 99:1 to 1.
:99.

In the lead zirconate or lead zirconate composite of the present invention, it is desirable that Pb0 and M02 (M is Zr or a combination of Zr and Tj) exist in equimolar amounts, but depending on the various usages described below, The molar ratio of P:M02 is
It may vary within the range of 6:1 to 1:1.1, especially 4:1 to 1:1.

In this case, when the content of the lead oxide component is large, the X-ray diffraction image of this product may show peaks characteristic of wet lead monoxide, but the lead zirconate formed, lead titanate, or even lead monoxide may be formed. It should be noted that the lead zirconate complex itself is amorphous. The amorphous lead zirconate or complex thereof of the present invention has a poly(crystalline) content of 8.3 to 9.2/c.
True density of c, primary particle size less than 0.2 microns, wave number 14
Infrared absorption peak from 00 to 1410 arc-1, and 94
Lead monoxide having an anhydrous chromium reactivity of %L and zirconium oxynitrate or its hydrolyzate, or a combination of these and titanium oxynitrate or its hydrolyzate, are mixed in an aqueous solution at the above-mentioned molar ratio. Produced by reaction in a medium.

The above-mentioned lead monoxide raw material is prepared by filling a rotating mill with granular metal lead, a liquid medium, and oxygen gas; at least a part of the granular metal lead moistened with the liquid medium is lower than the surface of the liquid medium. is exposed in the upper gas phase, forming an ultra-thin film layer of lead oxide on the surface of the metallic lead particles, and then the metallic lead particles forming the lead oxide layer interact with each other in the liquid medium. Rotating the rotary mill under frictional conditions, thereby forming a dispersion in which ultrafine particles of lead monoxide are dispersed in a liquid medium; separating the dispersion from the particles of metallic lead; , if desired, by recovering lead monoxide produced from the dispersion in the form of fine powder, the details of which are described in US Pat. No. 4,117,104 proposed by the present inventors. ``This wet process lead monoxide has fine grains and excellent dispersibility in water. In addition, this wet method lead monoxide has extremely superior monoreactivity compared to conventional lead monoxide, and can react with various acids without using a catalyst. There are three types of green lead monoxide, namely:
7.23.11 100 2.81 386 2.51 20.5' 1. Moth 29.81.67
25.51.55
10.0 1. It shows an x-ray diffraction image that is substantially the same as that of 14.2 and 8.80 to 9.
Lead monoxide having a true density of 17 mm/cc, a primary particle size of 0.01 to 0.05 mm, and an orange to lemon hue.

{B} The following X-ray diffraction image plane spacing d(A) Relative intensity (1 nolo) 3.07
30.52.95
100 2.74 7.4 2.38 5.2 and has substantially the same x-twill diffraction pattern as 835 to Z9.
Lead monoxide having a true density of 2 m/cc, a primary particle size of 0.01 to 0.05 mm, and a white to yellow hue.

[C} The following X-line diffraction image plane spacing d(A) Relative intensity (1/lo) Z3.6
2 1003.38
34.6 3.14 11.6 3.05 74.3 2.95 11.6
22.91 17.12.86
75.6 2.55 34.9 2.46 21.1 2.33 20.4
2, with a true density of 8.80 to 9.1 e/cc and 0.01 to 0.05
There is lead monoxide which has a mountainous primary particle size, a hydration water content of 0.2 to 0.8 mole per mole of Pb0, and a white hue, and all of these are used for the purpose of the present invention. It is possible.

In the present invention, the oxynitrate or hydrolyzate of zirconium or titanium used as the other raw material is represented by the following formula M.

2. m resistance 205. "...{1) In the formula, M represents zirconium or titanium, and m is a number from 0 to 1, particularly from 0.1 to 0.5.

Those having the chemical composition of are preferably used. The oxynitrate of zirconium or titanium is water-soluble or acid-soluble, but if it can be dispersed into fine particles or colloidally in an aqueous medium, it can be partially or completely decomposed by water. can also be used for the purposes of the present invention. Such hydrolysis products can be obtained, for example, in the form of zirconic acid or titanic acid, by heating and hydrolyzing an aqueous solution of zirconium or titanium oxynitrate or by neutralizing the nitrate radical with an alkali IJ agent. When producing a composite, it is desirable to use a solution or dispersion in which the zirconium component and the titanium component are mixed in advance. Amorphous lead zirconate or a composite thereof can be easily produced by mixing and reacting both raw materials in an aqueous medium.

At this time, it is preferable to add an aqueous solution or aqueous dispersion of zirconium or titanium oxynitrate or its hydrolysis product all at once to an aqueous slurry containing lead monoxide using the green method, and carry out the reaction, but the order may be reversed. An aqueous slurry of lead monoxide may be added to the raw material slurry of zirconium or titanium, or both raw materials may be simultaneously added to an aqueous medium to carry out the reaction. In the reaction, there is no particular restriction on the concentration of raw materials in the aqueous medium, but from the viewpoint of operation it is preferable that the solid content concentration is 50 to 450 (ta'). Room temperature is sufficient for the reaction temperature, but if desired, it may be heated to a temperature below the boiling point. The reaction time may be any time as long as the two raw materials are mixed evenly and uniformly, and is generally in the range of 1 minute to 6 minutes. It is desirable to maintain the pH of the mixture in the range of 5.5 to 1, especially 6 to 9 during the reaction, and this pH can be easily adjusted by adding an alkaline agent, especially aqueous ammonia, to the mixture system. be exposed. In the present invention, the above-mentioned aqueous slurry of wet lead monoxide and an aqueous solution or dispersion of zirconium or titanium oxynitrate or its hydrolyzate are rapidly mixed under high-speed acid cutting. It is desirable to carry out the reaction.

That is, ammonium nitrate is mixed in this mixed reaction system due to the ammonia and zirconium components added for feed adjustment, or the nitrate radicals accompanying the tatitan component.
There is a tendency for the size of lead zirconate or a composite of lead zirconate and lead titanate to become larger due to the coexistence of ammonium nitrate. For example, when carrying out a reaction by gradually adding zirconium and/or titanium components to an aqueous slurry of lead monoxide using the overflow method, ammonium nitrate acts as a crystallizing agent, and the unreacted overflow The cause is thought to be the growth of lead monoxide particles. This conflict can be effectively overcome by rapidly mixing both raw materials. In the present invention, it is particularly important to use a combination of the above-mentioned wet process lead monoxide and zirconium or titanium oxynitrate or a hydrolyzate thereof.

That is, when lead monoxide produced by a normal dry method is used as a raw material, the x-ray diffraction peak of lead monoxide remains in the mixture, and the amorphous lead zirconate, which is the object of the present invention, remains as it is. cannot be obtained at all. This tendency is similarly observed when ordinary dioxide or hydroxide is used as the zirconium raw material. In the method of the present invention, the fact that lead monoxide reacts with the zirconium component or even the titanium component means that, as mentioned above, the characteristic X-ray diffraction peak of these raw materials disappears and an amorphous product is produced. This can be easily confirmed by the fact that the reaction product settles and separates from its mother liquor aqueous medium.

Wet lead monoxide is extremely difficult to separate by precipitation from an aqueous medium, but the products reacted with the zirconium component or even with the titanium component exhibit the new property of being easily precipitated from the aqueous medium. The amorphous lead zirconate or lead zirconate composite according to the present invention can be used as various ceramic bases in the form of aqueous slurry, wet cake, or dry powder, or if necessary, after crystallization by firing, it can be used as various ceramic bases. Can be used as a ceramic base.

Of course, this amorphous lead zirconate or its composite contains
Ceramic additives known per se, such as Zr02,
Ti02, Ni○, Mn02, W03, Bi203, L
a203, Nb2Q, Ta2Q, Sb203, Tho2
, K20, Li2CQ, AI203, Sr203, Cr
203, Fe203, Coo, Mg○, ZN0, Cd○
, P, oTa03, and other rare element oxides can be combined to form a ceramic composition. The production of ceramics can be carried out under conditions known per se, except for the use of the above-mentioned base materials, but it has the various advantages mentioned above, both in terms of production operations and in terms of the properties of the ceramic body. is achieved. The invention is illustrated by the following example.

Reference Example 1 Lead oxide prepared by a wet method (Hereinafter, in this example, lead oxide prepared by a wet method may be abbreviated as W1Pb○.

) was manufactured in accordance with the method described in US Pat. No. 4,117,104. i.e. 8.3 to 9
．． Density of 2 particles/cc, number average particle size of 0.2 peaks or less, infrared absorption peak at wave number 1400 to 1410 -1,
More than 94% anhydrous. A method for producing lead monoxide having a muic acid reactivity will be outlined. ol 200k9 granules of metallic lead (electrolytic lead purity 99.99%) with a diameter of 2 to 7 mm are milled in a rotary stainless steel tube mill (inner diameter: 5 mm, length: 13 mm).
0 arc, content of about 120 m), filled with 30 k of water and oxygen (2 k9 gauge pressure), and by rotating this tube mill, some of the metal lead moistened with water was brought to the water surface. The ultra-thin film layer of water around the metal lead particles absorbs oxygen, producing lead monoxide, and the metal lead particles are suspended in the water by centrifugal force. The ultrafine particles of lead monoxide generated by friction with each other are dispersed in the water, and the concentration P is increased. A dispersion of [sample number W-P-1] was obtained at 5 min/100.

The wet process lead monoxide slurry obtained here was filtered in an oven, then dried at about 8 psi, and then pulverized to prepare a wet process lead monoxide dry powder product (sample number W-Pb0-2). The lead monoxide slurry recovered here was measured for its true density, number average particle diameter, composition of metallic lead components, chromic acid reaction rate, infrared absorption spectrum, and x-ray diffraction, and the results were reported in the first They are also shown in the table. In addition, each measurement method followed the method below.

{a- Fill the true density pygnometer with benzene solution, measure the weight (W) and the temperature (Ti
) to measure.

Next, the benzene is discharged, and a predetermined amount of the sample (M (evening)
), further benzene was added, the mixture was placed in a vacuum dessicator, the pressure was reduced by 3 Hg using a vacuum pump for 3 hours, the cock was closed, the vacuum pump was removed, and the temperature was brought to Ti and left overnight. Open the cock and take out the pycnometer, replenish it with benzene and fill it up with weight (W') and temperature (Ti).
is measured and calculated using the following formula (■). da: Sample density d: Ti Specific gravity of benzene at °C {b' Number average grain The size of 200 to 300 particles was measured at a sonic magnification of 1000 to 300, and the average particle diameter (r) was determined from the number average of the size of each particle.

'c} Metallic lead content The acetic acid-insoluble content, that is, the metallic lead content, was determined in accordance with the method described in JISK-1456 (Lissage's quantitative method), and the content was expressed in (%).

'd' Chromic acid reaction rate 2 Add 500% water to the peak
A sample of lead oxide powder (69.06 mm) was accurately weighed into the solution, and slowly poured into the solution while stirring thoroughly to be sufficiently dispersed in water.Then, this dispersion was flooded to 65.degree. On the other hand, slowly add the prepared aqueous solution of chromic acid anhydride (30.0g/100 [water)] under the dark frame.
The mixture was injected for 0 minutes, and further maintained at 65°C.
The legs are aged for 60 minutes to form crystals of dilead chromate. Next, NO. The crystals of lead chromate are filtered through furnace paper in step 3, washed with water, the lead chromate produced here is dried at 11 pi○, and the amount of chromic acid fixed as lead chromate is anhydrous. The amount of chromic acid (CrQ) was divided into three quantitative amounts, and from this result it was determined that the fixed chromic acid (C3
) amount (AC) and the amount (TC) of chromic acid (C) of the raw material used, from the following formula {31, RC
=AT/TCxloo(%)...,. ．． 、． ．． [3,
The trichromic acid reaction rate (RC%) was determined.

'c} Infrared absorption spectrum measurement Under reduced pressure vacuum (3 Capes 4 Hg) 400k9' using an infrared absorption spectrum measuring device manufactured by JASCO Corporation (Type IR-G)
Molded in a KBr tablet molding machine under ground pressure, 4000
The absorption spectra were subjected to self-recording diffraction in the wavelength range of ~40 min.

In addition, the intensity of the diffraction peak of the absorption spectrum was expressed using the following six-level symbol.

VS: Strongest S: Strong M: Normal W: Weak b: Minute Sh: Minute {f' X-ray diffraction measurement is wide angle Ca
t, NO. The sample was measured by the powder measurement method using a Matsu 27 (Proportional Counter) according to the following diffraction conditions.

Diffraction condition target Cu filter Ni voltage
3 female V current
15mA count range
50 ratio pS high voltage
1450V time constant
ISeC chart speed 1 skin/mi
n Scanning speed 10/min Diffraction angle (20) 1? ~60. ? During slitting
10-10-0.3 (g) Composition analysis of lead oxide The composition was analyzed in accordance with the method described in JIS K1456 (Litharge quantitative method).

In this specification, slurries are often used as target samples, but unless otherwise specified, all compositions are expressed in weight percent on a dry matter basis. (g-1) Lead monoxide (Pb○) Weigh the sample accurately, measure the moisture content, and after converting the moisture content, (
If the sample was a powder, it was moistened with water beforehand.

) Add 6N acetic acid, heat, dissolve, and then cool.
Adjust the pH of the sample solution to 5.0 with aqueous ammonia and buffer.
0 to 5.5, and then bottled with a 1/20 molar EDTA (disodium ethylenediaminetetraacetic acid) solution using Xynol Orange as an indicator to determine the lead monoxide (Pb○) content. The amount (%) was determined on a dry matter basis. (g-2) Komyotan (Pb304) After sampling using the same machine as in the case of lead monoxide in the above Sasa-1), dissolve the sample in 6N acetic acid and sodium acetate, then add a certain amount of 1/1 Add a specified sodium thiosulfate solution, and after a certain period of time, use the starch solution as an indicator and back titrate with a 1/1 specified iodine solution to determine the content (%) of Komyotan (Pb304) on a dry matter basis. I asked for it.

(g-3) Metallic lead (Pb) After sampling in the same manner as in the case of lead monoxide (1) above, 6N acetic acid was added and dissolved by heating, and at the same time, 1 molar concentration of hydroxylamine hydrochloride was added. Add a small amount,
The lead peroxide compound present in the sample is dissolved, and then the sample is separated using furnace paper, washed with warm water, and washed until no lead component is detected. After washing, the furnace paper and the residue on the furnace paper are placed in an Erlenmeyer flask. Transfer the metal lead on the furnace paper to 6N nitric acid and 30%
After dissolving with 2-3 drops of % hydrogen peroxide solution and adjusting the pH to approximately 5 using a buffer solution of aqueous ammonia and sodium acetate, titration was performed with a 1'100 molar EDTA solution using xylenol orange as an indicator. , metallic lead (Pb)
The content (%) was determined on a dry matter basis.

(g-Phantom impurities (Fe, Cu) Sample preparation obtained by sampling in the same manner as in the case of lead monoxide in Sasa-1) above, adding nitric acid and hydrogen peroxide solution to dissolve, and repeating evaporation to dryness. The liquid was extracted with Fe (iron) and C according to JISKO120 “General Rules for Atomic Absorption Spectrometry”.
u (copper) was quantified and its content was determined on a dry matter basis (trace).

Reference example 2 According to the method described in Tokudo Sho 52-13590,
Another method for producing lead monoxide using a wet method using zinc oxide powder as a raw material will be described.

As the zinc oxide powder used as a raw material, gray-green lead zinc oxide powder manufactured by the Shimadzu lead powder method was selected.

As the Shimadzu lead powder method, as used in Reference Example 1, a method is adopted in which lead powder is produced by dry-pulverizing preformed metal lead grains in a rotary mill.
A lead oxide powder having a cap of 72 [−'] was recovered.

The zinc oxide powder is prepared into an aqueous slurry using water prior to entering the oxidation step.

At this time, the concentration of leech lead oxide component in the aqueous slurry was 202
/100' concentration. Next, a liquid cyclone applying centrifugal force classification is used to classify and separate the coarse metallic lead powder contained in the raw material lead zinc oxide powder and the coarse particles of the lead oxide powder, into a homogeneous lead zinc oxide powder. An aqueous slurry was prepared.

The liquid cyclone used for this) is a stainless steel liquid cyclone with a diameter of 55 ribs, a conical apex angle of 2, an inlet of 8 ribs, a downstream/zip of 6 0, and a discharge pressure of 1.8 k9/ground. did.

The composition of the aqueous slurry of homogeneous lead zinc oxide whose coarse particles were classified and separated using this liquid cyclone was 12.4 min/100 min as a solid content, and the metallic lead component in this solid content was The amount was 10.5% by weight.

A contact method based on the Horikimanshiki method was used to bring the homogenized aqueous slurry of lead zinc oxide into contact with molecular oxygen.

Next, a liquid cyclone was attached to separate and classify unreacted zinc oxide components after an aeration type contact tower attached to a bubble column.

. This liquid cyclone classifies and separates the unoxidized lead zinc oxide component remaining in the aqueous slurry after the oxidation process, and the lead monoxide slurry (raw material number W -POO-3) was collected. The aqueous slurry recovered here had a Pbo concentration of 18.4/100M. In addition, each item was measured in the same manner as in Reference Example 1, and the results are also shown in Table 1. Reference example 3
, The conventional dry method for producing lead monoxide is
It was manufactured according to the method described in Japanese Patent No. 7-11801.

First, an ingot of electrolytic lead with a diameter of 2.
After molding into a cylindrical shape with 5 arcs x 2.0 arcs in length, it was molded into a cylindrical shape with Genzo Shimazu's research report, Journal of the Japan Society of Mechanical Engineers, Volume 28 (No. 100) 4.
In accordance with the so-called Shimadzu lead powder method described on pages 89 to 516 (1925), metallic lead was ground using a dry grinding method in a rotary mill to produce "gray-green zinc oxide powder (so-called lead powder)". Next, the recovered lead zinc oxide powder was placed in a rotary furnace, oxygen was added, and the zinc oxide was combusted in a concentrated manner to produce a powder of approximately 630 to 7
The temperature rise due to the heat of combustion of zinc oxide is measured under a temperature condition of 20℃, and as soon as the temperature rise due to combustion competition is no longer observed, it is quickly discharged into a cooling chamber and cooled down. Granular lead oxide is bound. Next, this yellow granular lead oxide was crushed** and classified using a gas cyclone system to prepare an orange yellow lead monoxide powder (raw material number D-POO). Reference Example 4 in Table 1 A method for preparing titanium oxynitrate or its hydrolyzate will be described.

As a basic preparation method, five types of homogeneous dispersion sol liquids of titanium hydrate were prepared in accordance with the methods described in Tsubaki-Batsu Sho-Nezumi Kazuhiro No. 914 and Tarukai Sho-54-180297.

The preparation process includes A: blending raw materials and alkali, B
: Reaction with alkali, C: Removal of alkali-soluble components,
The preparation process was carried out in a five-step process in the following order: D: leaching of titanium with nitric acid, E: hydrolysis and, if necessary, partial neutralization of nitrate radicals.

Four types of raw materials containing titanium metal components were selected: iron sand slag, ilmenite ore, high titanium slag, and titanium oxide. As the iron sand slag, Nippon Koshuha Co., Ltd. selected deep-watered iron sand slag having the composition shown in Table 2 below, which is a by-product during iron sand smelting, and used this iron sand slag to turn water into soot and crush alumina balls. Wet-pulverize using a rotary mill as a medium to obtain a fine powder that passes through 320 mesh (TVer), then dehydrate,
Dry and prepared iron sand slag powder was used.

As the ilmenite ore, ilmenite ore having the composition shown in Table 2 below from the Soviet Union was selected, and as in the case of iron sand slag, it was wet-pulverized to 320 mesh, dehydrated, and dried to produce pulverized ilmenite. I used things.

As a high titanium slug, Canadian QPe is cIro
A high titanium slag with the composition shown in Table 2 below, which was produced by removing iron from ilmenite ore as a naMT ship niumCo product, was selected, and this high titanium slag was subjected to wet crushing in the same manner as iron sand slag. te 320
A high titanium slag powder prepared by pulverizing the entire mesh, dehydrating and drying was used.

As the titanium oxide, anatase type titanium oxide (Ti02) powder shown in Table 2 below, manufactured by Tohoku Kagaku Kogyo ■, was used.

As the second flux, caustic soda (NaOH), which is commercially available as an industrial raw material, was selected, and a caustic soda solution having a concentration of 5% by weight was prepared to facilitate homogeneous mixing with the titanium raw material powder.

That is, commercially available solid caustic soda as it is cannot be homogeneously mixed with raw material powder, and industrial mixing could not be performed, so caustic soda was once liquefied. The mixing ratio of each raw material powder and the brooding agent caustic soda (NaOH) is the chemical reaction equivalent of the acidic component that reacts with the alkali contained in the raw material. Choose an amount corresponding to 1.3 volume of chemical reaction equivalent with NaOH,
It was blended with a caustic soda solution (5 skin t%).

At this time, the amount of NaOH was limited to 1.5 times the chemical reaction equivalent, so the mixing ratio of the raw material and water (day 20) differs depending on the raw material, and the amount ratio is 10 times the dry weight of the raw material.
Table 3 shows each part by weight relative to 0 part by weight. The method for blending and forming granules is to use a bag mill with an internal volume of 60 kg, add a predetermined amount of caustic soda solution as a flux to about 10 kg of raw materials, mix for about 1 hour, and then pour this mixture into a bag mill with a diameter of 5. Pelletize into a columnar shape using a vertical granulator equipped with a perforated plate with holes, and
By drying at 0° C., granules containing raw materials and brood additives were prepared.

In addition, when titanium oxide is used as a raw material, it is mixed in the bag mill mentioned above, and the mixture is discharged in the form of a base.
A paste-like mixture was prepared.

Next, as a granular melting reaction method, a rotary kiln type heating furnace was used.

The rotary kiln type heating furnace is made of iron with a diameter of 5 mm.
The inside of the kiln with 0 ratio mosquito x length 200W vessel is lined with caster pull 160) made of refractory cement whose main ingredient is alumina (Japan-America Roza Manufacturing ■), and the inner diameter is 300mm. I made it.
This circular kiln is placed on a rotary table, and is driven by a motor so that it can rotate at 6 sub-rotations/hour.A rod-shaped silicon carbide heating element (length 220 mm, Toshiba Ceramic) is placed in the center of the kiln. (manufactured by Teco Random) were set to allow the temperature inside this rotary kiln to rise to approximately 1200 qo. In addition, the mixed granules are made to have a slight slope so that the mixed and prepared granules are continuously fed into the heating rotary kiln from one inlet of the heating rotary kiln and continuously discharged from the other outlet. The material is rolled and moved in the rotary kiln until it reaches a predetermined temperature of approximately I.
The temperature was maintained for Q minutes, a melting reaction took place, and the granular reaction products after the reaction were easily and continuously removed from the reaction system, i.e., from the rotary kiln. The granular melting reaction is carried out using the above-mentioned heating rotary kiln, with the temperature inside the kiln reaching the 3rd level.
While maintaining the temperature at the specified temperature shown in the table, the above-mentioned mixed granular material is continuously introduced into the kiln, and as the granular material rolls and rotates inside the kiln, it passes from the inlet to the outlet for about 1 hour.
The granular melting reaction was carried out by moving while accumulating for 0 minutes, and 14 pupils of granular reaction products were collected in each case.

The granulator of the reaction product recovered here is shown in Table 3 in the form of a melted reaction. In addition, in the case of a paste-like mixture using titanium oxide as a raw material, the paste-like mixture was
A melting reaction was carried out by heat treatment for 5 hours in an electric furnace maintained at a soil temperature of 1.0 mm to obtain a crumbly granular reaction product.

The granular and granular reactants recovered in this step were green in the case of iron sand slag, greenish-brown in the case of ilmenite and high titanium slag, and grayish-brown white in the case of titanium oxide. In addition, the shape of the collected particulate matter was expressed by the following four-level symbol, and the results are shown in Table 3. The reaction products bound by this) are added to the next aqueous leaching step to remove colored harmful metal components contained in each raw material as well as alkali-soluble components.
Ta.

Equipment for the aqueous leaching process of alkali-soluble components includes:
Stainless steel leaching tank (inner diameter 60 mm x
At a height of 700 mm), a steam pipe is installed to heat the inside of the leaching tank.
It was kept warm.

Pour 80 liters of water into this leaching tank, and use the steam pipe to add approximately 80 liters of water.
℃, maintained at 60°C during the leaching process, and thoroughly mixed inside the leaching tank using a locking machine. The slurry is then roughly pulverized in a wet process using water so as to pass through the slurry, and the alkali-soluble components such as colored toxic metal components are leached into warm water for about 30 minutes. was recovered.

Each leaching slurry collected in this process is separated into its field liquid by a filter press method, separated into furnace liquid and water-containing cake, and then overflowed with an amount equivalent to about half of the recovered furnace liquid (approximately 8 and ○), and the recovered mother liquor of the above-mentioned furnace liquor and washing liquor were respectively collected, and on the other hand, the water-containing cake containing titanium as a main component was respectively collected.

Next, the recovered water-containing cake containing the titanium component as a main component is subjected to a leaching process using nitric acid to make it soluble in nitric acid.

As the apparatus for the nitric acid leaching process, a stainless steel leaching tank equipped with the same tomaji as used in the aqueous leaching process described above was used.

This stainless steel leaching tank is filled with a nitric acid solution having a concentration of about 25% HN03, and the dried leached shallow liquid of about 13k9 is gradually poured into the tank.

After adding the leached residue, leaching with nitric acid for 1 to 2 hours under slow lighting will turn the silica component into a silica hydride gel with good sedimentation properties, allowing titanium, calcium, magnesium, The aluminum and iron components form a clear nitrate solution. When this was fractionated using a furnace, a nitric acid solution containing titanium as the main component was recovered, having the composition shown in Table 4 below (each metal component contained is expressed on an oxide basis). . Next, the nitric acid solution of titanium recovered here is heated or hydrolyzed from Alka River, and if necessary, the nitrate radicals are removed.
A portion of the titanium hydrate was neutralized from Alka River, and a homogeneously dispersed sol of titanium hydrate was recovered.

The thermal hydrolysis method involves heating a nitric acid solution of titanium at a temperature of 70°C or higher under normal pressure or 60°C or higher under 1 to 3 atmospheres to produce hydrated titanium hydrate. After settling the decomposition product and separating the mother liquor in a furnace to remove most of the nitric acid, the titanium hydrate is hydrated with a slightly alkaline solution (for example, dilute aqueous ammonia) to a size of 6 or more. The decomposed product was dispersed and passed through a 325-mesh silk knot to prepare a homogeneously dispersed sol of titanium hydrate.

In addition, as a hydrolysis method by Koyo Alkagawa, a 10% aqueous ammonia solution is added to a nitric acid solution of titanium at room temperature (3
0°C or below) to form a gel-like precipitate of titanium hydrate, and after separating most of the nitric acid and ammonia content using the furnace filtration method, the gel-like precipitate was recovered. The material was redispersed in water using a high-speed lamp (for example, a household mixer), and a homogeneously dispersed sol of titanium hydrate having a pH of at least 2.0 was recovered through a 325-mesh silk filter.

Table 3 Reference Example 5 A method for preparing zircon oxynitrate or its hydrolyzate will be explained.

As a basic preparation method, a homogeneous dispersion sol of zircon hydrate was prepared according to the method described in Hakama Seki Sho 54-54914.

The preparation process includes A: blending raw materials and alkali, B
: Reaction with alkali, C: Removal of alkali-soluble components,
The preparation process was carried out in a five-step process in the following order: D: leaching of zirconium with nitric acid, E: hydrolysis and, if necessary, partial neutralization of the nitrate radicals. Zircon sand was selected as the raw material containing the zirconium metal component.

As the zircon sand, we selected a commercially available product from Nippon Sangyo ■, and wet-pulverized this zircon sand using a rotary mill using alumina balls as the grinding medium, making the water sooty, and grinding the zircon sand into a 320-mesh (Tyler) Zircon sand powder was used, which was prepared by passing it through to make a fine powder, then dehydrating and drying it.

(Table 4 shows the analytical values of this powdered zircon sand). Table 4 As the flux, caustic soda (NaOH), which is commercially available as an industrial raw material, was selected, and a caustic soda solution having a concentration of 5% by weight was prepared to facilitate homogeneous mixing with the zircon sand raw material powder.

That is, commercially available solid caustic soda as it is cannot be homogeneously mixed with raw material powder, and industrial mixing could not be performed, so caustic soda was first made into a liquid state. The mixing ratio of the zircon sand raw material powder and the fluxing agent caustic soda (NaOH) is the chemical reaction equivalent of the acidic component that reacts with the alkali contained in the raw material.
An amount corresponding to 1.5 times the chemical reaction equivalent with NaOH was selected, and mixed with a caustic soda solution (5 skin t%).

At this time, the blending was carried out using a bag mill with a 60-meter capacity, adding a predetermined amount of caustic soda solution as an enemy agent to about 10k9 of the raw material, mixing for about 10 minutes, and then pouring this mixture into a stainless steel vat. The mixture was poured and dried at 100-200 pm to form a paste-like dry mixture of raw materials and flux. Next, this dry pasty mixture was pulverized using an atomizer, and a rotary kiln type heating furnace was used to melt and react the crushed material. Reference example 4 is a rotary kiln type heating furnace.
Using the same heating furnace as in Reference row 4, this crushed material was continuously fed into the kiln and kept at a temperature of 500 to 700°C for about 10 minutes to cause a melting reaction, and the crushed material after the reaction was completed. The reaction product can be easily and continuously taken out of the reaction system, ie, the rotary kiln. In the crushing melting reaction, the temperature inside the kiln is maintained at the predetermined temperature described above using the heating rotary kiln described above, and the mixed granular material described above is continuously introduced into the kiln. A granular melting reaction was carried out by moving the crushed material from the input port to the discharge port for about 10 minutes while rolling and rotating, and the crushed reaction product was collected.

The melted and reacted crushed reaction product collected in this step) had a grayish-white color. The reaction product obtained in this) was prepared in Reference Example 4.
In the same manner as above, it was added to the next aqueous leaching step to remove colored components and alkali-soluble components.

As a counterfeit bag for the aqueous leaching process of alkali-soluble components,
It is exactly the same as Reference Example 4. Fill this leaching tank with 80°C of water, heat it to about 80°C with a steam pipe, and keep it at 10°C during the leaching process. After the reaction product 25k9 is coarsely ground using a green method using water so that it passes through 12 mesh, this slurry is added to remove alkali-soluble components such as colored harmful metal components. After leaching into the overflowing water for about three generations, the leaching slurry was recovered.

The leached slurry collected in this step is separated into liquid by a filter press method, separated into furnace liquid and water-containing cake, and then heated with hot water (approximately 80°C) in an amount equivalent to about half of the recovered furnace liquid. ), and the recovered mother liquors of the furnace liquid and washing liquid were recovered, respectively, and the water-containing cakes containing zirconium as a main component were recovered. Next, the water-containing cake containing the recovered zirconium component as a main component is subjected to an acid leaching step to make it soluble in nitric acid.

As the apparatus for the nitric acid leaching process, a stainless steel leaching tank equipped with the same tomaji as used in the aqueous leaching process described above was used.

This stainless steel leaching tank is filled with a nitric acid solution having a concentration of about 25% HN03, and about 13k9 of the dried leached liquid is gradually poured into the tank while stirring.

After adding the leached residual bamboo, if necessary, heat the temperature to 40°C or higher and leaching it with nitric acid for 1 to 2 hours while slowly heating it. The silica component in the raw material becomes a silica hydrogel with good sedimentation properties, and zirconium and The titanium, aluminum and iron components of the sample form a clear nitrate solution. This was subjected to furnace separation using a sifter, and a nitric acid solution containing zirconium as a main component was recovered. Next, the recovered zircon nitric acid solution is heated and concentrated, free nitric acid is distilled and recovered, and crystals of zircon nitrate are recovered. If necessary, purified zirconium oxynitrate is produced from this crystal by a recrystallization method. This crystallized material was dissolved in water and subjected to high-speed coagulation to produce a homogeneous sol solution of zirconium oxynitrate (raw material number S-
ZrQ-1) or hydrolyzed from the Alka River, and if necessary, a part of the nitrate radicals were neutralized from the Alka River to recover a homogeneously dispersed sol of zircon hydrate.

In addition, as for the hydrolysis method using an alkali, a 10% ammonia aqueous solution is added to a nitric acid solution of zircon at room temperature (
Add in a controlled manner so that the amount is 3 pi○ or less,
A gel-like precipitate of zirconium hydrate is generated, and after separating most of the nitric acid and ammonia content using a furnace separation method, the gel-like precipitate collected here is placed under a high-speed lamp (for example, a household mixer). The homogeneous dispersion sol of zirconium hydrate with a bait of at least 2.0 was recovered through a 325-mesh silk knot, and the material number S-Z was collected.
It was set as d02-2.

Example 1 Substantially amorphous lead zirconate or lead zirconium titanate composite obtained from a homogeneous dispersion sol of a hydrate of lead oxide group cryo and zirconium and a homogeneous dispersion sol of a hydrate of titanium by a wet method The ceramic base material consisting of a body will be explained.

The lead oxide diagonal particle slurry prepared by the Green method was prepared using lead oxide (raw material number W) prepared by the method described in Reference Examples 1 and 2 above.
-P's -1, W-Pb0-2, and W-P's -3) were selected.

As the homogeneous dispersion sol of titanium hydrate, the titanium sol prepared by the method described in Reference Example 4 (raw material number S-Ti02-1, S-TiQ-2, S-TiQ-
3, S-T 2-4 and S-Ti02-5) were selected.

As the homogeneously dispersed sol of zircon hydrate, the zircon sol prepared by the method described in Reference Example 5 (
Raw material numbers S-Zr02-1 and S-Z 2-2) were selected.

The manufacturing conditions can be arbitrarily selected within the range shown in Table 5.

Table 5 Production of fine-grained amorphous lead zirconate and lead zirconate titanate composites Specific combinations of these production conditions are shown in Table 5, and each amorphous lead zirconate or lead zirconate composite is manufactured according to the conditions shown in Table 5. was manufactured.

As a comparative example, powdered litharge (
(DP) was selected, and when lead nitrate was used as the lead oxide raw material, the reagent lead nitrate (Pb(N03)2) was selected.

Commercially available rutile-type titanium oxide (
R-TiQ) powder and reagent titanium oxynitrate (Ti
0(N03)2) and zirconium oxynitrate (Z(N0
3) I chose 2). As a specific manufacturing method, a predetermined amount of each sol dispersion of a zirconium component with a predetermined concentration and a titanium component with a predetermined concentration is placed in a stainless steel container (inner scope 10 or 20Z) equipped with a fly-sinking machine, and then heated to room temperature (20± 5° C.) and subjected to a high-speed reel at 100 pm in the homogeneous zircon component alone and mixed sol dispersion of the zircon component and titanium component as described above. A predetermined amount of the lead component slurry liquid is added all at once, and then continuous stirring is continued for 10 minutes to carry out reaction ripening, resulting in substantially amorphous lead zirconate and lead zirconate composites with good sedimentation properties. reaction product slurry 1
(The reaction may be carried out by adding the above sol dispersion liquid to the lead component slurry liquid in the reverse manner of the above method, but in this example, sample number 1- All procedures except steps 4 and 1-16 were performed as described above).

Further, the lead zirconate or lead zirconate composite of the comparative example was manufactured according to the following methods. The following three types (H-1, Hiichi 2 and H-3) were selected as comparative examples. H-1: Based on the method described in Samurai Kosho No. 52-42760; and U.S. Patent No. A compound tate salt was formed by pressing a light from an acid or the like.

H-2:V. M. McNamara, Rono Can. Ce
ram. S ratio. Jour. 34, 103 (1965), using lead nitrate, titanium oxynitrate, and zirconium oxynitrate as raw materials, titanium and zirconium hydroxides and basic carbonic acid of lead were prepared from a mixed alkaline solution of ammonia and ammonium carbonate, etc. A consortium of salts was formed.

H-3: According to the method described in the specification of Hakama Kosho No. 54-106514, oxide raw materials of lead, titanium, and zircon were wet-mixed, and a mixed slurry was recovered.

The following physical property values were measured for the slurry produced by the reaction of a composite consisting of zirconium and lead components or zirconium, titanium, lead components, etc. produced by each of the above methods.

The above results are shown in Table 6.

■Uniformity of composition by chemical analysis, ■Shape and particle size measured under optical and electron microscopes, ■Crystal form by x-ray diffraction, ■Reaction analysis by DTA, ■Fibers measured by mercury intrusion porosimeter and BET method. Seven items, such as density and lead fume generation amount, were measured using the measurement methods shown below, and the results are shown in Table 6 and attached figures 1, 2, 4, 5, and 6.
, 7 and Photo 3.

■ Uniformity of composition Pour 100' of each reaction product slurry into a 100' measuring cylinder, stir for 10 minutes, and then pour it onto the sediment layer (u).
), middle (m) and bottom (1), each of 10'
Each sample was collected with a pipette, passed through a furnace, and used as a sample of a water-containing cake. Approximately 2 hours of this wet sample was accurately weighed, and T
The i component was dissolved and the Ti component was analyzed by a conventional metal AI reduction method, and the Zr component was analyzed by a conventional EDTA method.

On the other hand, the Pb component is separated in a furnace as a precipitate of PbS04, and then the C
After dissolving with QCOONH, Pb was dissolved using the conventional EDTA method.
The molar ratio of these three components was calculated, and from this molar ratio, the average deviation rate (%) of the molar ratio of each material was determined from the following formula 5, and the uniformity of the composition was evaluated using this value. Uniformity; Mq (%) small o (-2X=u, trivial: Pb
The molar ratio m of O and Ti○ is: The molar ratio of POO and Ti02 formed on the top, middle and bottom of the sedimentation layer. Confirm that there are no soluble components by chemical analysis,
Wash thoroughly if necessary, then bake each of these light yellow cakes at 200 to 100 picoC. For wet cakes, rinse with a small amount of water, spread on a glass plate, and heat-treat the cakes. , lightly pulverized in a milk dish, diluted with a small amount of water, and then coated on a glass plate, and directly examined under an optical microscope with a magnification of 40 x 1 and the particle size (indicated by Gidai particle size). was measured.

In particular, regarding the shape, we confirmed the presence or absence of a continuous phase characteristic of gel-like amorphous materials. A portion of the sample was also measured using a scanning electron microscope. ∎ Crystal form test ③ X-ray diffraction was performed on the sample subjected to ③ at the same time using a powder method to determine the crystal form of the wet sample and its heat-treated product, as well as P-3 or Pb (Zr).
The crystallinity of Ti)03 was compared and studied.

■ Reaction analysis using DTA After heating each sample to a specified temperature at a rate of 10 qo/min using a tabletop DTA80 intensifying layer manufactured by Rigaku Denki ■, draw a DTA curve.
Next, the temperature of the raw material sample was raised again in the same apparatus in accordance with the peak of the curve, and the heat-treated sample was then taken out and subjected to X-ray diffraction to examine the state of the crystallization reaction.

■ Formability and Sensitivity Test ■ The sample subjected to the test (i.e., the cake passed through a vacuum oven at a reduced pressure of 50 mHg) was rolled with fingertips into a cube with about 1 side or a sphere with a diameter of about 1 side, and baked at 600°C. The pongee pore volume, pongee pore distribution and specific surface area of the obtained shape were measured using a mercury intrusion type MODEL 5-7118 porosimeter and the BET method,
From this value, the moldability of the shaped object and the tightness during heat treatment were evaluated.

■ Amount of lead fume generated After each powder sample was temporarily held at 80 pi○ for 1 hour, it was weighed (the weight was W,), and then the weight after firing at 100 pi○ for 1 hour (W2) was calculated to determine the lead fume generation rate. Fume generation amount Lv (weight%
) was defined by the following formula.

LV=Semi-life ZX・oo As a result of the above, both W-POO and S-Z 2 used in the present invention, W-Pdo, S-Z Nu 2, and S-Ti02Z were combined using the high-speed Kenazusa mixed method. The lead and zircon and lead and zircon and titanium components of the reaction slurry obtained by reacting with Tsubaki are free from the compositional defects that tend to occur in the conventional oxide wet method (Comparative Example Sample No. H-3). There is almost no homogeneity, and even when compared with Z, which is said to be a homogeneous pillow method (Comparative Example Sample No. H-1) and (Comparative Example Sample No. H-2), the homogeneity is very low. I found it to be excellent.

From this, it has been found that it is easier to produce a complex chemical composition that is more delicate and highly homogeneous than lead zirconate or lead zirconate composites made by any conventional method. More specifically, the apparent particle size in the optical microscope photographs shown in Figures 3-1 and 3-2, and the X in Figure 1-A-1, Figure 2-A-2-1, etc.
As is clear from the one-line diffraction diagram, the lead zirconate or lead zirconate composite according to the present invention is x-ray amorphous, but it forms individual fine particles. It is a shape characteristic of the composite body which consists of amorphous lead zirconate of this invention.

Also, the X-
As is clear from the ray diffraction diagram, the composition is homogeneous among the conventional oxide method, oxalic acid method, and ammonium carbonate method, and lead zirconate (P-board 3) and lead zirconate composite (Pb ( The conventional oxalic acid method (H-1 of Comparative Example 1) and carbonic acid method, which are said to be superior to the oxide method (Comparative Example 3 Hiichi 3) in terms of crystallinity as ZrTi)03) Even compared to the coprecipitation method with the ammonium method (H-2 in Comparative Example 2), the crystallization temperature as PbZrQ or Pb(ZrTW03 is 600°C or less, which is lower than that seen in conventional methods). In particular, as can be seen from the x-ray diffraction diagrams in Figures 5 and 6, the degree of crystallinity under a certain thermal history is also significantly higher than that of the conventional method. As shown, in the curve A-4 of the present invention, Pb(ZrT
i) There is only the x-line diffraction peak of 03, but in curve C-4 of Comparative Example 2, in addition to the weak peak of Pb(ZrTi)Q, there is a rusty peak that is clearly thought to be lead oxide at a diffraction angle of 28-2860. It is well understood that the amorphous lead zirconate composite according to the present invention is superior in structural and compositional homogeneity under thermal history compared to conventional methods.

Furthermore, as is clear from Table 6 and FIG. 7, the pongee hole volume value measured by a mercury intrusion porosimeter of the calcined molded lead zirconate or its composite obtained by the present invention and the conventional method at 600 pm. Therefore, lead zirconate or its composite 5 according to the present invention exhibits a much smaller amount of macropores with a diameter of 400 (A) or more than any of the conventional methods. It is easily understood that a molded body with extremely excellent fineness can be obtained from the composite during molding and opening.

0 Furthermore, it is easily understood from the above-mentioned characteristics of the fine-grained amorphous lead zirconate or its composite according to the present invention that the amount of lead fume generated during heat treatment shown in Table 6 is significantly lower than that of conventional methods. It is something.

Table 6

[Brief explanation of drawings]

Curve A-1 in FIG. 1 is a x-line diffraction diagram of the amorphous lead zirconate composites according to the present invention (samples 1 to 10) dried at 110°C, and curve B-1 in FIG. This is an X-ray diffraction diagram of a 110 qo dry product of a zirconium-titanium-lead oxalate co-preparation method (sample number H-1) obtained by the ammonium carbonate method, and curve C-1 in FIG. - An X-bran diffraction diagram of a coprecipitate of lead hydroxide monobasic carbonate (sample number H-2) dried at 110°C,
Figure 2 shows amorphous lead zirconate (Subject 1-
1) X-ray diffraction diagrams of the 110°C dried product (curve A-2-1), the 55pi0 calcined product (curve A-2-2), and the 850°C calcined product (curve A-2-3), respectively. 3-1
Figure and Figure 3-2 respectively show amorphous lead zirconate (
These are optical micrographs of undried specimens of sample numbers 1-1) and amorphous lead zirconate composites (sample numbers 1-10), and curve A-4 in Fig. 4 represents the amorphous lead zirconate composite according to the present invention. 600 qo calcined product of body (sample number 1-10), curve B
14 is an oxalate precipitate obtained by the oxalic acid method (sample number H
-1) and curve C-4 are the X one-line diffraction patterns of the 600°C calcined product of hydroxide-carbonate coprecipitate (sample number Hiichi 2) obtained by the ammonium carbonate method. 5
Curve A-5 in the figure is an 800°C calcined product of the amorphous lead zirconate composite (sample number 1-10) according to the present invention, and curve C-5 is a hydroxide-carbonate co-calcined product (sample number 1-10) produced by the ammonium carbonate method. This is an X-line diffraction diagram for the 800°C calcined product of No. H-2), and the curve A-6 in FIG. The product baked for 1.5 hours and curve C-6 are 1 of the hydroxide-carbonate co-pillow product (sample number H-2) produced by the ammonium carbonate method.
00 pi○ 1. This is a x-line diffraction diagram of the calcined product of insect time, and Figure 7 shows the shaped calcined body (curve C-7) of the co-pillowed product (sample number H-2) produced by the ammonium carbonate method, and the sample produced by the oxide method. Formed pseudoscale body of number H-3 (curve D-7), formed pseudoscale body of copillar material (sample number H-1) by oxalic acid method (
Curve B-7), molding of a lead zirconate composite according to the invention (sample no. 1-10) (curve A-7-1) and molding of lead zirconate according to the invention (sample no. 1-1) The pongee hole distribution curves of pseudoscale bodies (curves A-7-2) are shown. Figure 7 Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6

Claims (1)

[Claims] 1 True density of 8.3 to 9.2 g/cc, primary particle size of 0.2 microns or less, wave number 1400 to 1410 cm^
- Lead monoxide having an infrared absorption peak at 1 and a chromic anhydride reaction rate of 94% or more, zirconium oxynitrate or its hydrolyzate, or these and titanium oxynitrate or its hydrolyzate. The combination is Pb
O:MO_2 (in the formula, M represents zirconium or a combination of zirconium and titanium) is reacted in an aqueous medium at a molar ratio in the range of 6:1 to 1:1.1. A method for producing a ceramic base containing a regular zirconate. 2. Zirconium oxynitrate or hydrolyzate has a chemical composition of the following formula ZrO_2.mN_2O_5, where m is a number from 0 to 1, and is dispersible in an aqueous medium. The method described in Section 1. 3 The aqueous slurry of lead monoxide and an aqueous solution or dispersion of zirconium oxynitrate or its hydrolyzate, or a combination of this and titanium oxynitrate or its hydrolyzate, are stirred with high-speed shearing. 2. The method according to claim 1, wherein the reaction is carried out by rapid mixing. 4. The method according to claim 1, wherein the reaction is carried out under conditions such that the solid content concentration in the aqueous medium is 50 to 490 g/l. 5. The method according to claim 1, wherein the reaction is carried out while maintaining the pH of the mixture in the range of 5.5 to 10.