CN102850055A - Manufacturing method of perovskite-type composite composite oxide and manufacturing device thereof - Google Patents
Manufacturing method of perovskite-type composite composite oxide and manufacturing device thereof Download PDFInfo
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- CN102850055A CN102850055A CN2012102159009A CN201210215900A CN102850055A CN 102850055 A CN102850055 A CN 102850055A CN 2012102159009 A CN2012102159009 A CN 2012102159009A CN 201210215900 A CN201210215900 A CN 201210215900A CN 102850055 A CN102850055 A CN 102850055A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/006—Alkaline earth titanates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/34—Three-dimensional structures perovskite-type (ABO3)
Abstract
The invention provides a manufacturing method and a manufacturing device thereof for obtaining the perovskite-type composite composite oxide containing perovskite-type composite composite oxide particles having high crystallinity. The manufacturing method for obtaining the perovskite-type composite composite oxide is the manufacturing method of the perovskite-type composite composite oxide expressed by formula ABO3 (A includes at least one among Ba, Ca and Sr, B at least includes Ti). The method includes a reaction procedure. In the reaction procedure, raw material liquid including titanium oxide powder is heated in a sealing container. Ocyhydrate containing elements of A component is added into the raw material liquid after being heated. Thus, the perovskite-type composite composite oxide particles having high crystallinity can be obtained.
Description
Technical field
The present invention relates to manufacturing installation and the manufacture method thereof of perovskite composite oxide, for example relate in particular to manufacture method and manufacturing installation thereof as the barium titanate of perovskite composite oxide.
Background technology
Along with the progress of the small-size high-capacity of in recent years cascade capacitor etc., the thin layer of dielectric material element is developed.In order to make this thin layer stack capacitor, must reduce the crystal grain of dielectric ceramic and suppress crystal grain-growth, therefore, require to be particulate and to have good crystallinity as the composite oxides of ceramic raw material.
As making this as particulate and having the method for the perovskite composite oxide of good crystalline barium titanate etc., for example, propose to have the manufacture method of perovskite composite oxide such shown in patent documentation 1 and the patent documentation 2.
The manufacture method of the perovskite composite oxide of record is by general formula ABO in the patent documentation 1
3The manufacture method of the perovskite composite oxide of expression is the manufacture method of following composite oxide power, and the manufacture method of described perovskite composite oxide comprises and will consist of oxyhydroxide element, that contain crystal water of A position composition and have 250m
2The combination treatment operation that the titanium dioxide powder of the specific surface area that/g is above mixes, this combination treatment operation comprises: only be used for by carrying out heat treated lysate that moisture with crystal water generates the lysate of A position composition dissolving and generate operation and be used for making titanium dioxide powder and lysate reaction and the reaction process of formation reaction synthetics, and dissolving generates operation and reaction process carries out continuously.
The content of the composite oxide power calcining that will obtain by above-mentioned manufacture method is disclosed in patent documentation 1 in addition.
In addition, the manufacture method of the perovskite composite oxide of record is the manufacture method with spherical barium titanate particles powder of following feature in the patent documentation 2, namely, in the presence of carboxylic acid, add the barium salt aqueous solution and make the adding composition (Ba/Ti) of titanium and barium become 1.00～1.10 to the titanium hydroxide colloid, thereby generate the barium titanate nuclear particle, next, in 100 ℃～350 ℃ temperature range, the reaction soln that contains this barium titanate nuclear particle carried out hydrothermal treatment consists and obtain the spherical barium titanate particles of cubic crystal, then in 800 ℃～1200 ℃ temperature range, this spherical barium titanate particles is calcined and formed regular crystal.
The composite oxides that the manufacture method of putting down in writing by patent documentation 1 and patent documentation 2 obtains are these as ultra micron and have the composite oxides of good crystalline cubic crystal.In addition, by the composite oxides that obtain are carried out calcination processing, have good crystalline tetragonal composite oxides thereby can produce.
[formerly technical literature]
[patent documentation]
No. 4200427 communique of [patent documentation 1] Japanese Patent
No. 4240190 communique of [patent documentation 2] Japanese Patent
[summary of invention]
[problem that invention will solve]
Yet in the composite oxides of the cubic crystal that the manufacture method put down in writing by patent documentation 1 and patent documentation 2 obtains, because having hydroxy in the lattice of these composite oxides, thereby crystallinity is possible insufficient.That is, in patent documentation 1, because all temperature of reaction process less than 100 ℃, therefore may residually have hydroxy.In addition, in patent documentation 2, because the temperature when generating the barium titanate nuclear particle is less than 100 ℃ (being in an embodiment 70 ℃), so or may hydroxy be arranged the nucleus part is residual.
Therefore, because the crystallinity of the composite oxides of cubic crystal is insufficient, so even they are calcined and make its transposition is regular crystal, also still have the inadequate problem of its crystallinity.
Summary of the invention
Therefore, main purpose of the present invention is to provide manufacture method and the manufacturing installation thereof of the perovskite composite oxide that can obtain the high perovskite composite oxide particle of crystallinity.
[being used for solving the means of problem]
According to the manufacture method of perovskite composite oxide of the present invention, these titanium ore type composite oxides are by general formula ABO
3Expression, wherein, A comprises at least a kind among Ba, Ca and the Sr, B comprises Ti at least, the manufacture method of described perovskite composite oxide is characterised in that, comprises following reaction process, in this reaction process, heat the stock liquid that contains at least titanium dioxide powder inside at sealed vessel, and the stock liquid after the described heating adds the oxyhydroxide of the element that consists of A position composition and reacts.
In addition, in the manufacture method of perovskite composite oxide of the present invention, the oxyhydroxide that preferably add to consist of the element of A position composition by the stock liquid after described heating reacts, thereby the temperature of stock liquid becomes more than 100 ℃.
In addition, in the manufacture method of perovskite composite oxide of the present invention, preferably also comprise the heat treatment step of under 800 ℃～1000 ℃ the resultant of reaction that obtains being heat-treated in described reaction process.
According to the manufacturing installation of perovskite composite oxide of the present invention, it is for the manufacture of perovskite composite oxide, and these titanium ore type composite oxides are by general formula ABO
3Expression, wherein, A comprises at least a kind among Ba, Ca and the Sr, and B comprises Ti at least, and the manufacturing installation of described perovskite composite oxide is characterised in that to possess: sealed vessel, it is used for the stock liquid that sealing contains titanium dioxide powder at least; Heating arrangements, it is used for the described stock liquid at the seal inside of described sealed vessel is heated; Injection mechanism, it is used for dropping into to described stock liquid the oxyhydroxide of the element that consists of A position composition.
[invention effect]
Manufacture method according to perovskite composite oxide of the present invention, owing to the stock liquid after the heating is dropped into the oxyhydroxide of the element that consists of A position composition, therefore can be reduced with the content of the hydroxy in the simple method acquisition perovskite composite oxide particle, and the high perovskite composite oxide particle of crystallinity.
In addition, in the manufacture method of perovskite composite oxide of the present invention, if the stock liquid after the heating drop into to consist of the oxyhydroxide of the element of A position composition, and and then under the condition of high temperature more than 100 ℃, begin reaction, then can reduce the residual of hydroxy in the crystal lattice of perovskite composite oxide.Therefore, can obtain the higher perovskite composite oxide particle of crystallinity.
In addition, manufacture method according to perovskite composite oxide of the present invention, if be included in the heat treatment step of under 800 ℃～1000 ℃ the resultant of reaction that obtains in the reaction process being heat-treated, then can obtain the high perovskite composite oxide particle of crystallinity of regular crystal.
Manufacturing installation according to perovskite composite oxide of the present invention, owing to having the injection mechanism for the oxyhydroxide input of the element that will consist of A position composition, so the internal state for sealed vessel can be kept High Temperature High Pressure, and can put into the stock liquid from the oxyhydroxide that injection mechanism will consist of the element of A position composition simultaneously.
Above-mentioned purpose of the present invention, other purposes, feature and advantage can describe following form be used to carrying out an invention by the reference accompanying drawing and obtain further clearly.
Description of drawings
Fig. 1 is the sketch of an embodiment of the manufacturing installation of expression perovskite composite oxide of the present invention.
Fig. 2 is by with hydrothermal synthesis method contrast the explanatory view of the mechanism that the crystallinity of the manufacture method of perovskite composite oxide of the present invention is improved being shown.
Fig. 3 is the rheological parameters' change with time of pressure of the inside of the temperature of slip in the reaction process of expression embodiment 1 to embodiment 3 and sealed vessel.
Fig. 4 is the figure of the relation of the specific surface area of expression embodiment 1 to embodiment 3 and comparative example 1 and comparative example 2 and lattice parameter.
[nomenclature]
The manufacturing installation of 10 perovskite composite oxides
12 sealed vessels
14 heating units
16 thermometers
18 raw material throwing devices
18a drops into and uses container
The 18b cap
18c contacts member
20 agitating wings
The 20a alar part
The 20b axial region
22 first pipe arrangements
22a the first valve
22b the first pressure warning unit
24 second pipe arrangements
The 24a second valve
24b the second pressure warning unit
The 24c pressure controlled valve
Embodiment
Below, describe for an embodiment of the manufacturing installation of perovskite composite oxide of the present invention.Fig. 1 is the schematic diagram of an embodiment of the manufacturing installation of perovskite composite oxide of the present invention.
It is few that the manufacturing installation of this perovskite composite oxide is that available easy method obtains the content of the hydroxy in the crystal lattice of perovskite composite oxide, and, the manufacturing installation of the perovskite composite oxide of the perovskite composite oxide particle that crystallinity is high.
This perovskite composite oxide is by general formula ABO
3Expression.Below, an embodiment of the manufacturing installation of perovskite composite oxide of the present invention is described in detail.
The manufacturing installation 10 of the perovskite composite oxide of putting down in writing among Fig. 1 possesses sealed vessel 12, heating unit 14, thermometer 16, raw material throwing device 18, agitating wing 20.
It is in order to be used for the stock liquid sealing with the Slurries that contains at least titanium dioxide powder of ceramic raw material that sealed vessel 12 is set.Sealed vessel 12 is to tolerate the container of making the required High Temperature High Pressure of perovskite composite oxide.
Sealed vessel 12 is connected with the first pipe arrangement 22.Two ends at the first pipe arrangement 22 are provided with peristome.One square end section of the first pipe arrangement 22 is communicated with sealed vessel 12 on the top of sealed vessel 12.Pars intermedia configuration pressure warning unit 22b and the first valve 22a at the first pipe arrangement 22.Pressure warning unit 22b and the first valve 22a configure towards the other end successively from an end of the first pipe arrangement 22.It is to open and close for the path to the first pipe arrangement 22 that the first valve 22a is set.The first pressure warning unit 22b is set is for the pressure to the inside of the inside of sealed vessel 12 and the first pipe arrangement 22 and monitor.
In addition, sealed vessel 12 is connected with the second pipe arrangement 24.Two ends at the second pipe arrangement 24 are provided with peristome.One end of the second pipe arrangement 24 connects the top of sealed vessel 12 and is communicated with raw material throwing device 18 on the top of raw material throwing device 18.In addition, as required from the other end air supply of the second pipe arrangement 24.Pars intermedia configuration second valve 24a, the second pressure warning unit 24b and pressure controlled valve 24c at the second pipe arrangement 24.Second valve 24a, the second pressure warning unit 24b and pressure controlled valve 24c configure towards the other end successively from an end of the second pipe arrangement 24.In addition, second valve 24a, the second pressure warning unit 24b and pressure controlled valve 24c are arranged on the position than sealed vessel 12 more outer sections.It is in order to be used for the path of the second pipe arrangement 24 to be opened and closed that second valve 24a is set.The second pressure warning unit 24b is set is in order to be used for the pressure of the inside of the inside of raw material throwing device 18 and the second pipe arrangement 24 is monitored.Pressure controlled valve 24c is set is for the pressure to the inside of the inside of raw material throwing device 18 and the second pipe arrangement 24 and adjust.
Heating unit 14 is set is for to heating at the sealed stock liquid in the inside of sealed vessel 12 and making its insulation.Heating unit 14 is configured in for example periphery of sealed vessel 12.
Set temperature meter 16 is for to carrying out instrumentation in the temperature of the sealed stock liquid in the inside of sealed vessel 12.Thermometer 16 is configured to for example connect the top of sealed vessel 12 and reaches stock liquid.
The oxyhydroxide of the element of the pulverous A position composition in 18 pairs of formations of raw material throwing device ceramic raw material (below, only be called " pulverous oxyhydroxide ") keep, and this pulverous oxyhydroxide is put in sealed vessel 12 interior sealed stock liquids.Raw material throwing device 18 is configured in the upper side of the inside of sealed vessel 12.Raw material throwing device 18 possesses to drop into uses container 18a, cap 18b and contact member 18c.Raw material throwing device 18 is owing to being configured in the inside of sealed vessel 12, so under the pressurized state of sealed vessel 12, can drop into pulverous oxyhydroxide towards stock liquid.In addition, raw material throwing device 18 is configured in the inside of sealed vessel 12, therefore, does not require that raw material throwing device 18 itself possesses the voltage endurance capability of sealed vessel 12 this degree.
It is in order to keep pulverous oxyhydroxide with container 18a that input is set.Drop into the pyramid type that forms the protrusion under the side-looking with container 18a.The peristome that the Powdered oxyhydroxide that is formed for keeping in the lower end side that drops into container 18a falls towards stock liquid.By making the shape that drops into container 18a form pyramid type, for example can than having and being formed on the container that drops into the cylinder shape shape of the identical floorage of the floorage of the peristome on the container 18a, can keep more pulverous oxyhydroxide.In addition, form pyramid type by the shape that will drop into container 18a, after cap 18b opens, can make to remain on to drop into to fall towards stock liquid swimmingly with the pulverous oxyhydroxide among the container 18a.So, owing to make stock liquid and the reaction of pulverous oxyhydroxide, so can obtain the neat good as a result thing of particle.
At this, as the method that drops into pulverous oxyhydroxide from raw material throwing device 18 to stock liquid, the switching of the cap 18b of raw material throwing device 18 operates from the outside of sealed vessel 12.In the present embodiment, for example, the method by following record drops into pulverous oxyhydroxide from 18 pairs of stock liquids of raw material throwing device.
That is, in raw material throwing device 18, when keeping pulverous oxyhydroxide, the pressure of the inside of sealed vessel 12 is adjusted to higher than the pressure of the inside of raw material throwing device 18 by the first valve 22a and second valve 24a.Thus, the cap 18b of raw material throwing device 18 does not open and keeps the state of closing, and can keep pulverous oxyhydroxide in raw material throwing device 18.In addition, because the diameter of the lower end of cap 18b forms greatlyr than the diameter that drops into the peristome of using container 18a, so can prevent that cap 18b subsidence by above-mentioned such pressure difference is set, can keep pulverous oxyhydroxide to dropping into among the container 18a in pressurization.
On the other hand, when opening the cap 18b of raw material throwing device 18, from the other end of the second pipe arrangement 24 towards raw material throwing device 18 air supplies.Then, adjust the internal pressure of the second pipe arrangement 24 by pressure controlled valve 24c and open second valve 24a, make the pressure of the inside of raw material throwing device 18 surpass the pressure of the inside of sealed vessel 12, cap 18b opens thus.
It is for the stock liquid in sealed vessel 12 interior sealings is stirred that agitating wing 20 is set.In addition, agitating wing 20 is arranged for and stirs the stock liquid that obtains to contain the Slurries of resultant of reaction so that after pulverous oxyhydroxide is put in the stock liquid it is reacted swimmingly.The diffusion wing 20 possesses alar part 20a and axial region 20b.Alar part 20a is configured in the lower side of the inside of sealed vessel 12.The end of the center of alar part 20a and axial region 20b links.In addition, the other end of axial region 20b connects the top of sealed vessel 12 and extends outward from sealed vessel 12, and for example is connected with engine (not shown).Alar part 20a is driven rotation via axial region 20b by engine, and thus, stock liquid is stirred.
Manufacturing installation according to perovskite composite oxide of the present invention, raw material throwing device 18 is disposed at the inside of sealed vessel 12, because pass through from the switching of controlling the cap 18b of raw material throwing device 18 than the operation of sealed vessel 12 more outer sections, so can keep High Temperature High Pressure and drop into simultaneously pulverous oxyhydroxide from raw material throwing device 18 to stock liquid the internal state of sealed vessel 12.
In addition, according to the manufacturing installation of perovskite composite oxide of the present invention, owing to possessing heating unit 14, before making the reaction of stock liquid and pulverous oxyhydroxide, can stock liquid be heated in advance by heating unit 14 temperature of expectation.
Next, an embodiment of the manufacture method of the perovskite composite oxide of the present invention of the manufacturing installation 10 that used perovskite composite oxide described.Fig. 2 is by with hydrothermal synthesis method contrast the explanatory view of the mechanism that the crystallinity of the manufacture method of perovskite composite oxide of the present invention is improved being described.
As shown in Figure 2, for for the manufacture method of the perovskite composite oxide of hydrothermal synthesis method, because the temperature the when stock liquid that contains titanium dioxide powder is reacted with pulverous oxyhydroxide is less than 100 ℃, so may be in the lattice of these composite oxides residual have a hydroxy.Therefore, the crystallinity of the resultant of reaction that obtains of the manufacture method by this perovskite composite oxide is low.
On the other hand, the manufacture method of perovskite composite oxide of the present invention is different from hydrothermal synthesis method, as shown in Figure 2, it possesses following reaction process, that is, in the inside of sealed vessel 12 stock liquid that contains at least titanium dioxide powder is heated, the oxyhydroxide of the element of the pulverous formation of input A position composition in the stock liquid after then heating to this (below, only be called " pulverous oxyhydroxide "), itself and stock liquid are reacted.
The manufacture method of perovskite composite oxide of the present invention is general formula ABO
3The manufacture method of shown perovskite composite oxide.
At first, in order to make by general formula ABO
3The perovskite composite oxide of expression is prepared ceramic raw material.Element as formation A position composition is the oxyhydroxide of Ba, for example prepares pulverous Ba (OH)
2The pulverous Ba (OH) for preparing
2Be put in the raw material throwing device 18.
In addition, the element of formation B position composition contains Ti at least.As the oxide powder of the Ti that consists of B position composition, prepare for example TiO
2Powder.Then, with TiO
2Powder and pure water are put in the sealed vessel 12, and contain TiO by stirring gently to make
2The stock liquid of the Slurries of powder.
Next, fasten the first valve 22a and the second valve 24a that are connected with sealed vessel 12, after making sealed vessel 12 become sealed state, use 14 pairs of heating units to contain TiO
2The stock liquid of powder heats.The temperature that the Heating temperature of stock liquid is set as when making reaction process becomes more than 100 ℃, for example suits to be set as 58 ℃, 80 ℃ and 100 ℃.
Reach the stage of the temperature of expectation at the stock liquid that heats, pulverous oxyhydroxide that will keep in raw material throwing device 18 is put in this stock liquid, thereby reacts with this stock liquid.Thus, when in the stock liquid that heats, dropping into pulverous oxyhydroxide, then after just dropping into, cause because of reaction as shown in Figure 2 more than the temperature steep temperature rise to 100 ℃ of stock liquid.
Need to prove, when the Heating temperature of stock liquid before the reaction is set as 58 ℃, be no more than 100 ℃ though just pulverous oxyhydroxide has been put into the temperature of the stock liquid behind the stock liquid, but after reaction process in above 100 ℃.In addition, when the Heating temperature of stock liquid before the reaction is set as 80 ℃, just pulverous oxyhydroxide has been put into the temperature of the stock liquid behind the stock liquid above 100 ℃.
Then, 14 pairs of stock liquids at the seal inside of sealed vessel 12 of use heating unit are incubated and stir by 20 pairs of stock liquids of use agitating wing.Subsequently, the first valve 22a and second valve 24a are open, and the pressure recovery of the inside of sealed vessel 12 is normal atmosphere, when stock liquid cools off, can obtain the barium titanate of Slurries.Then, take out the barium titanate of the Slurries that obtains from sealed vessel 12, and put it in the drying machine and make the moisture evaporation, thereby obtain the barium titanate powder as resultant of reaction.
Next, the resultant of reaction that obtains by above-mentioned reaction process is heat-treated under 800 ℃～1000 ℃.By this heat treatment step, the crystal system of resultant of reaction becomes regular crystal from cubic crystal, thereby obtains the barium titanate as the high perovskite composite oxide particle of the crystallinity of expectation.
Manufacture method according to perovskite composite oxide of the present invention, owing to the stock liquid that heats is dropped into the oxyhydroxide of the element that consists of A position composition, therefore under the condition of high temperature more than 100 ℃, react, thereby can react at short notice, and then can reduce the content of the hydroxy in the crystal lattice of perovskite composite oxide.Therefore, can obtain the high perovskite composite oxide particle of crystallinity.
Need to prove, in the above-described embodiment, although the method for making barium titanate is described in detail, the manufacture method of the perovskite composite oxide of present embodiment also can be applicable to as with the manufacturing of for example strontium titanate of the same perovskite composite oxide of barium titanate, barium titanate calcium in.Therefore, in the present embodiment, with general formula ABO
3In the perovskite composite oxide of expression, the element that consists of A position composition comprises at least a among Ba, Ca and the Sr.
Next, the experimental example to the manufacture method of perovskite composite oxide of the present invention below describes.
1. the making of barium titanate powder
Pair used the making method of barium titanate powder of the manufacturing installation 10 of perovskite composite oxide to describe with reference to Fig. 3 and table 1.Fig. 3 represents the rheological parameters' change with time of pressure of inside of sealed vessel 12 of the manufacturing installation 10 of the temperature of the slip (stock liquid) in the reaction process of embodiment 1 to embodiment 3 and perovskite composite oxide.In addition, the Ba (OH) of table 1 expression embodiment 1 to embodiment 3 and comparative example 1
2The input temperature, just drop into Ba (OH)
2After peak temperature and the top temperature in the reaction process.
[table 1]
(embodiment 1)
As ceramic raw material, prepared Ba (OH)
2, TiO
2(specific surface area 300cm
2/ g).At first, weigh the TiO of 35.96g
2Powder, and put into sealed vessel 12 with pure water 0.1L, then stir to make gently and contain TiO
2The slip of powder (stock liquid).Next, to weigh the Ba (OH) of 77.10g as 1: 1 mode with the mol ratio of Ti element
2Powder also puts it in the raw material throwing device 18 of the inside that is arranged on sealed vessel 12.
Then, fasten the first valve 22a of being connected with sealed vessel 12 and second valve 24a and make sealed vessel 12 become sealed state, then use heating unit 14 heating slips.Utilizing the temperature of the pressure of inside of the first pressure warning unit 22b and 16 pairs of sealed vessels 12 of thermometer and slip to monitor respectively and continue heats to slip.Then, become 58 ℃ stage in the temperature of slip, for Ba (OH)
2Powder is put in the slip, adjusts pressure controlled valve 24c and opens second valve 24a.After opening second valve 24a, rise and the rapid situation about rising of temperature consistent with the first pressure warning unit 22b and simultaneously slip if observe the value of the second pressure warning unit 24b after the several seconds, then fasten second valve 24a and make sealed vessel 12 become sealed state at once.
Next, use 14 pairs of slips at the seal inside of sealed vessel 12 of heating unit to be incubated, and use simultaneously stirring slip limit, agitating wing 20 limits to make its reaction 1 hour.Then, stopped heating is opened the first valve 22a and second valve 24a, reverts in the internal pressure of sealed vessel 12 and places slip under the atmospheric state and do not process.Subsequently, after slip cooling, take out slips from sealed vessel 12, and put into drying machine and make the moisture evaporation, thereby obtain the barium titanate powder of embodiment 1.
In Fig. 3 (a), the rheological parameters' change with time of the internal pressure of the temperature of the slip in the reaction process of embodiment 1 and sealed vessel 12 is shown.At first, be that the temperature of slip becomes moment of 58 ℃ and drops into Ba (OH) in the shown temperature of the I of Fig. 3 (a)
2When dropping into Ba (OH)
2The time, after just dropping into, shown in the II of Fig. 3 (a), because of Ba (OH)
2Solution heat and reaction heat, thereby the peak temperature of slip sharply rises to 92 ℃.Then, make its reaction 1 hour, the temperature of slip rises gradually, and shown in the II of Fig. 3 (a), the temperature of slip rises to namely 114 ℃ of top temperatures.In embodiment 1, although just dropped into Ba (OH)
2After the temperature of slip surpass 100 ℃, but in reaction process thereafter, the temperature of slip has surpassed 100 ℃.
(embodiment 2)
In embodiment 2, in order to prepare ceramic raw material similarly to Example 1, in sealed vessel 12, make and contain TiO
2The slip of powder.Then, with Ba (OH)
2Powder is put into raw material throwing device 18.
Next, fasten the first valve 22a of being connected with sealed vessel 12 and second valve 24a and make sealed vessel 12 become sealed state, then use heating unit 14 heating slips.Utilizing the temperature of the pressure of inside of the first pressure warning unit 22b and 16 pairs of sealed vessels 12 of thermometer and slip to monitor respectively and continue simultaneously heats to slip.Then, become 80 ℃ stage in the temperature of slip, for Ba (OH)
2Powder is put in the slip, pressure controlled valve 24c is adjusted and opens second valve 24a.After opening second valve 24a, after the several seconds, rise and the rapid situation about rising of temperature consistent with the first pressure warning unit 22b and simultaneously slip if observe the value of the second pressure warning unit 24b, then fasten second valve 24a and make sealed vessel 12 become sealed state at once.
Next, similarly to Example 1, use 14 pairs of slips at the seal inside of sealed vessel 12 of heating unit to be incubated, and the limit use 20 pairs of slips of agitating wing to stir the limit to make its reaction 1 hour simultaneously.Then, stopped heating and make the first valve 22a and second valve 24a open returns in the internal pressure of sealed vessel 12 and to place slip under the atmospheric state and do not process.Then, after slip cooling, take out slips from sealed vessel 12, and put it in the drying machine and make the moisture evaporation, thereby obtain the barium titanate powder of embodiment 2.
In Fig. 3 (b), the rheological parameters' change with time of the internal pressure of the temperature of the slip in the reaction process of embodiment 2 and sealed vessel 12 is shown.At first, be that the temperature of slip becomes moment of 80 ℃ and drops into Ba (OH) in the shown temperature of the I of Fig. 3 (b)
2When dropping into Ba (OH)
2The time, after just dropping into, shown in the II of Fig. 3 (b), because of Ba (OH)
2Solution heat and the reaction heat peak temperature that makes slip sharply rise to 113 ℃.Then, if reaction was carried out 1 hour, then the temperature of slip rises gradually, and shown in the III of Fig. 3 (b), the temperature of slip rises to namely 133 ℃ of top temperatures.In embodiment 2, just dropped into Ba (OH)
2After the temperature of slip surpass 100 ℃, then finishing before to reaction, the temperature of slip has all surpassed 100 ℃.
(embodiment 3)
Also be in order to prepare ceramic raw material similarly to Example 1, to make in the inside of sealed vessel 12 and contain TiO in embodiment 3
2The slip of powder.Then, with Ba (OH)
2Powder is put in the raw material throwing device 18.
Next, fasten the first valve 22a of being connected with sealed vessel 12 and second valve 24a and make sealed vessel 12 become sealed state, then use 14 pairs of slips of heating unit to heat.Utilizing the temperature of the pressure of inside of the first pressure warning unit 22b and 16 pairs of sealed vessels 12 of thermometer and slip to monitor respectively and continue simultaneously heats to slip.Then, become 100 ℃ stage in the temperature of slip, for Ba (OH)
2Powder is put in the slip, adjusts pressure controlled valve 24c and opens second valve 24a.After opening second valve 24a, after the several seconds, rise and the rapid situation about rising of the temperature of and slip consistent with the first pressure warning unit 22b if observe the value of the second pressure warning unit 24b, then fasten second valve 24a and make sealed vessel 12 become sealed state at once.
Next, similarly to Example 1, use 14 pairs of slips at sealed vessel 12 seal insides of heating unit to be incubated, and the limit use 20 pairs of slips of agitating wing to stir the limit to make its reaction 1 hour simultaneously.Then, stopped heating and make the first valve 22a and second valve 24a open reverts in the internal pressure of sealed vessel 12 and to place slip under the atmospheric state and do not process.Then, after slip cooling, take out slips from sealed vessel 12, and put it in the drying machine and make the moisture evaporation, thereby obtain the barium titanate powder of embodiment 3.
In Fig. 3 (c), the rheological parameters' change with time of the internal pressure of the temperature of the slip in the reaction process of embodiment 3 and sealed vessel 12 is shown.At first, be that the temperature of slip becomes moment of 100 ℃ and drops into Ba (OH) in the shown temperature of the I of Fig. 3 (c)
2If drop into Ba (OH)
2, after just dropping into, shown in the II of Fig. 3 (c), because of Ba (OH)
2Solution heat and reaction heat make slurry temperature sharply rise to 127 ℃.Then, if reaction has been carried out 1 hour, then the temperature of slip rises gradually, and shown in the III of Fig. 3 (c), the temperature of slip rises to namely 142 ℃ of top temperatures.In embodiment 3, just dropped into Ba (OH)
2After the temperature of slip surpass 100 ℃, then finishing before to reaction, the temperature of slip has all surpassed 100 ℃.
(comparative example 1)
At first, in order to prepare ceramic raw material similarly to Example 1, make in the inside of sealed vessel 12 and contain TiO
2The slip of powder.Then, with Ba (OH)
2Powder is put in the raw material throwing device 18.
Next, make the first valve 22a that is connected with sealed vessel 12 become open state, behind the state that second valve 24a is become fasten, use 14 pairs of slips of heating unit to heat.Utilizing the temperature of the pressure of inside of the first pressure warning unit 22b and 16 pairs of sealed vessels 12 of thermometer and slip to monitor respectively and continue heats to slip.Then, become 58 ℃ stage in the temperature of slip, for Ba (OH)
2Put in the slip, pressure controlled valve 24c is adjusted and open second valve 24a.After second valve 24a opens, after the several seconds, if observe the situation of rapid rising of the temperature of slip, then fasten second valve 24a at once and make state before sealed vessel 12 becomes the opening of second valve 24a.
Next, similarly to Example 1, use 14 pairs of slips at the seal inside of sealed vessel 12 of heating unit to be incubated, and the limit use agitating wing 20 stirring slip limits to make its reaction 1 hour simultaneously.Then, stop the heating of sealed vessel 12 and its placement is not processed.Subsequently, after slip cooling, take out slips from sealed vessel 12, and put into drying machine and make the moisture evaporation, thereby obtain the barium titanate powder in the comparative example 1.
Because comparative example 1 carries out under the open state of the first valve 22a in reaction process, therefore different from the above embodiments 1 to embodiment 3, just dropped into Ba (OH)
2After the peak temperature of slip be 95 ℃, the slurry temperature in the reaction process surpasses 100 ℃, the top temperature of the slip in the reaction process is 95 ℃.
(comparative example 2)
In comparative example 2, the making of barium titanate powder is undertaken by so-called hydrothermal synthesis method.
At first, weighing TiO
2Powder and Ba (OH)
2Powder is with BaTiO
3The mode that the lower pulp density that converts becomes 1.0 moles/L adds pure water and makes slip.
Then, finish mix slurry is put into sealed vessel 12, the limit is stirred the temperature that the limit makes slip and is risen to 200 ℃, carries out hydro-thermal reaction 200 ℃ of lower maintenances 1 hour.Then, make the internal pressure of sealed vessel 12 revert to normal atmosphere, and stop the heating of sealed vessel 12 and place slip not dealing with.Then, after the slip cooling, close and put into drying machine from sealed vessel 12 taking-up slips and make the moisture evaporation, thereby obtain the barium titanate powder of comparative example 2.
2. the evaluation of barium titanate powder
The embodiment 1 to embodiment 3 that obtains by aforesaid method and the barium titanate powder in comparative example 1 and the comparative example 2 are carried out (take CuK α as gamma ray source) X-ray diffraction, obtain crystalline texture and lattice parameter by inner Te Woerde (Rietveld) method.In addition, obtain the specific surface area of the barium titanate powder of embodiment 1 to embodiment 3 and comparative example 1 and comparative example 2 by the BET method.
Their measurement result of table 2 expression.In addition, Fig. 4 represents the relation of specific surface area and lattice parameter.
[table 2]
As shown in table 2, the crystal system of the barium titanate of embodiment 1 to embodiment 3 and comparative example 1 and comparative example 2 is cubic crystal.
In addition, if the lattice parameter in the concern table 2 can be confirmed following situation, that is, lattice parameter is along with Ba (OH)
2The input temperature rising and diminish.The reason that can expect is that because the generation temperature of the particle of barium titanate raises, thereby residual hydroxy reduces in lattice.In addition, identifiablely according to Fig. 4 be that to compare crystallinity less than 100 ℃ comparative example 1 higher with the slurry temperature of reaction process integral body.
Furthermore, the comparative example 2 of table 2 illustrates the evaluation result of the barium titanate powder that obtains by general hydrothermal synthesis method.The lattice parameter of comparative example 2 and the lattice parameter that has with the embodiment 2 of the equal specific surface area of comparative example 2 are compared, thereby can confirm following situation, that is, because the lattice parameter of comparative example 2 is larger, crystallinity is insufficient.The reason that can expect is, because with TiO
2And Ba (OH)
2At room temperature mix, then put into sealed vessel 12 and make slurry temperature rise to gradually 200 ℃, so temperature is low during the reaction beginning, therefore residual have a hydroxy.
In addition, under 800 ℃～1000 ℃ temperature, the barium titanate powder that obtains is calcined.By calcining, crystal grain-growth and crystal system transposition, thus obtain the barium titanate of regular crystal.In addition, embodiment and the comparative example of contrast table area equal extent compare, and can obtain thus the barium titanate powder of the large regular crystal of axial ratio c/a in the high embodiment of crystallinity.
3. the making of strontium titanate powder
Pair used the making method of strontium titanate powder of the manufacturing installation 10 of perovskite composite oxide to describe with reference to table 3.Table 3 illustrates the Sr (OH) of embodiment 4 and comparative example 3
2The input temperature, just drop into Sr (OH)
2After peak temperature and reaction process in top temperature.
[table 3]
| Sr(OH) 2The input temperature (℃) | Peak temperature (℃) | Top temperature (℃) | |
| |
100 | 129 | 132 |
| Comparative example 3 | 65 | 95 | 97 |
(embodiment 4)
As ceramic raw material, prepared Sr (OH)
2, TiO
2(specific surface area 300cm
2/ g).At first, weigh the TiO of 30.00g
2Powder is put into sealed vessel 12 with pure water 0.1L, stirs gently and make to contain TiO
2The slip of powder (stock liquid).Next, to weigh the Sr (OH) of 45.70g as 1: 1 mode with the mol ratio of Ti element
2Powder, and put it in the raw material throwing device 18 of the inside that is arranged on sealed vessel 12.
Next, fasten the first valve 22a of being connected with sealed vessel 12 and second valve 24a and make sealed vessel 12 become sealed state, then use 14 pairs of slips of heating unit to heat.Utilizing the temperature of the pressure of inside of the first pressure warning unit 22b and 16 pairs of sealed vessels 12 of thermometer and slip to monitor respectively and continue heats to slip.Then, become 100 ℃ stage in the temperature of slip, for Sr (OH)
2Powder is put in the slip, adjusts pressure controlled valve 24c and opens second valve 24a.After second valve 24a opens, after the several seconds, rise and situation consistent with the first pressure warning unit 22b and that slurry temperature sharply rises if observe the value of the second pressure warning unit 24b, then horse back is fastened second valve 24a and is made sealed vessel 12 become sealed state.
Next, use 14 pairs of slips at sealed vessel 12 seal insides of heating unit to be incubated, and the limit use agitating wing 20 stirring slip limits to make its reaction 1 hour simultaneously.Then, stopped heating makes the first valve 22a and second valve 24a open, reverts in the internal pressure of sealed vessel 12 and places slip under the atmospheric pressure state and do not process.Then, after slip cooling, take out slips from sealed vessel 12, and put into drying machine and make the moisture evaporation, thereby obtain the strontium titanate powder of embodiment 4.
(comparative example 3)
At first, in order to prepare ceramic raw material similarly to Example 4, contain TiO at the internal production of sealed vessel 12
2The slip of powder.Then, with Sr (OH)
2Powder is put into raw material throwing device 18.
Next, make the first valve 22a that is connected with sealed vessel 12 become open state, become the state of fastening at second valve 24a after, use 14 pairs of slips of heating unit to heat.Utilizing the temperature of the pressure of inside of the first pressure warning unit 22b and 16 pairs of sealed vessels 12 of thermometer and slip to monitor respectively and continue simultaneously heats to slip.Then, become 65 ℃ stage in the temperature of slip, for Sr (OH)
2Powder is put in the slip, adjusts pressure controlled valve 24c and opens second valve 24a.After second valve 24a opens, after several seconds, rise and situation consistent with the first pressure warning unit 22b and that the while slurry temperature sharply rises if observe the value of the second pressure warning unit 24b, then horse back is fastened second valve 24a and is made sealed vessel 12 become the open front state of second valve 24a.At this, be put to from Sr (OH) 2 powder and begin to reach the peak temperature shown in the table 3 slip and namely need 12 minutes till 95 ℃.
Next, similarly to Example 4, use 14 pairs of slips at the seal inside of sealed vessel 12 of heating unit to be incubated, and the limit use agitating wing 20 stirring slip limits to make its reaction 1 hour simultaneously.Then, stop the heating of sealed vessel 12 and place slip and do not process.Subsequently, after slip cooling, take out slips from sealed vessel 12, and put into drying machine and make the moisture evaporation, thereby obtain the strontium titanate powder in the comparative example 3.
4. the evaluation of strontium titanate powder
For the strontium titanate powder of the embodiment 4 that obtains by aforesaid method and comparative example 3, special wald's approach is obtained lattice parameter in the utilization.
About the measurement result of lattice parameter, the lattice parameter of the strontium titanate powder of embodiment 4 is 0.3914nm, and the lattice parameter of the strontium titanate powder of comparative example 3 is 0.3922nm.
So, in airtight manufacture method, observe following situation, that is, be considered to follow the temperature of reaction to rise in short period of time end, the tendency that exists in addition lattice parameter to reduce.Therefore, what can expect is can obtain evenly and the high strontium titanate powder of crystallinity by this manufacture method.
In the above-described embodiment, as the method that drops into pulverous oxyhydroxide from the raw material throwing device to stock liquid, the switching of the cap of raw material throwing device realizes by the second valve of the outside that is arranged at sealed vessel and pressure controlled valve are operated, but be not limited to this, also can use other mechanisms that can drop into pulverous oxyhydroxide from the raw material throwing device to stock liquid by operating from sealed container outside.Namely, in order by operating from sealed container outside cap to be opened and closed, for example, can make its switching by the rotation cap, adopt in addition cap is carried out power operation and it is opened and closed, perhaps can toward the outer side cap be applied hydraulic pressure and cap is opened from the inboard of raw material throwing device.
In addition, in the above-described embodiment, the raw material throwing device is disposed at the inside of sealed vessel, but is not limited to this, can drop into from the raw material throwing device to stock liquid the mode of pulverous oxyhydroxide, for example the raw material throwing device also can be disposed at the upper side of sealed vessel.
[utilizing on the industry possibility]
The manufacture method of perovskite composite oxide of the present invention and manufacturing installation thereof are particularly suited in the electronic unit such as the laminated ceramic capacitor that uses along with the miniaturization of various electronicss etc. etc.
Claims (4)
1. the manufacture method of a perovskite composite oxide, these titanium ore type composite oxides are by general formula ABO
3Expression, wherein, A comprises at least a kind among Ba, Ca and the Sr, and B comprises Ti at least, and the manufacture method of described perovskite composite oxide comprises following reaction process:
Heat the stock liquid that contains at least titanium dioxide powder inside at sealed vessel, and the stock liquid after the described heating adds the oxyhydroxide of the element that consists of A position composition and reacts.
2. the manufacture method of perovskite composite oxide according to claim 1 is characterized in that,
The oxyhydroxide that adds the element that consists of A position composition by the stock liquid after described heating reacts, thereby the temperature of stock liquid becomes more than 100 ℃.
3. the manufacture method of perovskite composite oxide according to claim 1 and 2 is characterized in that,
Also comprise the heat treatment step of under 800 ℃～1000 ℃ the resultant of reaction that obtains being heat-treated in described reaction process.
4. the manufacturing installation of a perovskite composite oxide, for the manufacture of perovskite composite oxide, these titanium ore type composite oxides are by general formula ABO
3Expression, wherein, A comprises at least a kind among Ba, Ca and the Sr, and B comprises Ti at least, and the manufacturing installation of described perovskite composite oxide possesses:
Sealed vessel, it is used for the stock liquid that sealing contains titanium dioxide powder at least;
Heating arrangements, it is used for the described stock liquid at the seal inside of described sealed vessel is heated;
Injection mechanism, it is used for dropping into to described stock liquid the oxyhydroxide of the element that consists of A position composition.
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| JP2005067940A (en) * | 2003-08-22 | 2005-03-17 | Tdk Corp | Method for producing barium titanate powder |
| TW200631918A (en) * | 2003-09-02 | 2006-09-16 | Sakai Chemical Industry Co | Process for production of composition |
| EP1978000A1 (en) * | 2005-12-28 | 2008-10-08 | Showa Denko K.K. | Complex oxide film and method for producing same, composite body and method for producing same, dielectric material, piezoelectric material, capacitor, piezoelectric element and electronic device |
| CN101549996A (en) * | 2008-03-31 | 2009-10-07 | Tdk株式会社 | Composite oxide particles and production method thereof |
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| TWI238146B (en) * | 2001-07-04 | 2005-08-21 | Showa Denko Kk | Barium titanate and production process thereof |
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| JP2005067940A (en) * | 2003-08-22 | 2005-03-17 | Tdk Corp | Method for producing barium titanate powder |
| TW200631918A (en) * | 2003-09-02 | 2006-09-16 | Sakai Chemical Industry Co | Process for production of composition |
| EP1978000A1 (en) * | 2005-12-28 | 2008-10-08 | Showa Denko K.K. | Complex oxide film and method for producing same, composite body and method for producing same, dielectric material, piezoelectric material, capacitor, piezoelectric element and electronic device |
| CN101549996A (en) * | 2008-03-31 | 2009-10-07 | Tdk株式会社 | Composite oxide particles and production method thereof |
| US20090253571A1 (en) * | 2008-03-31 | 2009-10-08 | Tdk Corporation | Composite oxide particles and production method thereof |
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| CN110302791A (en) * | 2019-04-29 | 2019-10-08 | 南京工业大学 | A kind of electrolysis water catalyst of unconventional Local Structure and preparation method thereof |
| CN110302791B (en) * | 2019-04-29 | 2022-04-01 | 南京工业大学 | Electrolytic water catalyst with unconventional local structure and preparation method thereof |
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