CN1572753A - Manufacturing method for ceramic composition - Google Patents
Manufacturing method for ceramic composition Download PDFInfo
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- CN1572753A CN1572753A CNA2004100488736A CN200410048873A CN1572753A CN 1572753 A CN1572753 A CN 1572753A CN A2004100488736 A CNA2004100488736 A CN A2004100488736A CN 200410048873 A CN200410048873 A CN 200410048873A CN 1572753 A CN1572753 A CN 1572753A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/475—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on bismuth titanates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
Abstract
The invention provides a method for producing a ceramic composition, by which the amount of residual alkalis in an obtained ceramic composition can be reduced, synthesis can be performed sufficiently, and the size of obtained crystal grains can be made small while utilizing hydrothermal reaction. The method for producing the ceramic composition comprises performing a first process for obtaining a hydroxide slurry in which ions of elements constituting the ceramic composition are converted into respective hydroxides, a second process for obtaining a cleaned material by washing the hydroxides in the hydroxide slurry and controlling pH to be >6 and <=9, a third process for obtaining a reaction product by adding an alkali hydroxide solution to the washed material obtained in the second process and subjecting the resulting mixture to hydrothermal reaction, a fourth process for stirring and washing the reaction product obtained in the third process, and a fifth process for adding an aqueous solvent to the reaction product after the fourth process, controlling the pH of the slurry to be >5 and <7, and again subjecting the slurry to hydrothermal reaction, and thereafter drying the reaction product.
Description
Technical field
The present invention relates to the manufacture method of ceramic composition, particularly adopt the manufacture method of the ceramic composition of hydro-thermal reaction.
Background technology
The thin layerization of contained dielectric ceramic layer and multiple stratification are constantly progressive in the multi-layer ceramic capacitor.Particularly in recent years, also can produce and have the multi-layer ceramic capacitor that the hundreds of layer thickness is the dielectric ceramic layer of 1 μ m.When making such multi-layer ceramic capacitor, use following particulate and ceramic powder barium titanate class that crystallinity is high of 0.1 μ m to be used as constituting the material of dielectric ceramic layer.
Equally, for piezo ceramic element, people also constantly require its miniaturization and high performance in recent years.In order to satisfy such requirement, people wish to realize the high crystalline of particulate and few impurity, for example, realize lead titanate (PT) class powder.
As PT class manufacturing method of power, people are known usually has the aqueous solution and the alkaline aqueous solution that make each composition to mix the method (hydrothermal method) of carrying out hydro-thermal reaction.
This hydrothermal method is because of needing pyroprocessing, and brings into play liquid reactive characteristic, the gained particle fine and form also even, the best synthetic method of all saying so.
But, utilize hydrothermal method, carry out hydro-thermal reaction because of using alkaline aqueous solution, so a large amount of residual fatal problems that the problem of alkali metal is arranged in the PT class powder after existence is synthesized as mineralizer (reaction promotor).
(pre-original text collection is given a lecture in the annual meeting of 1993 annual Japanese pottery associations to Non-Patent Document 1, p.24-25) has put down in writing the method for lead titanate (PT) powder that utilizes hydrothermal method to make several micron level, but is 700 ppm by weight as the remaining quantity of alkali-metal potassium.
In addition, it is synthetic to disclose the hydro-thermal of carrying out PT under alkali free condition in Patent Document 1 (the open flat 11-335122 communique of communique of Japan's special permission) and 2 (the open flat 9-286617 communiques of communique of Japan's special permission), but the crystallinity of the PT after synthetic may be low.
People also are devoted to research and develop the material that can be used in the above-mentioned PT of replacement.Can replace wherein a kind of material of PT is bismuth layer-like compound.But bismuth layer-like compound is subjected to the restrictions of 2 dimensions because of spontaneous utmost point polar orientation, so, making usually when ceramic, even polarize processings, also existence can not make the fatal shortcoming of a large amount of remnant polarization.
Therefore, as Non-Patent Document 2 (Tadashi Takenaka, Journal of the Ceramic Societyof Japan, 110[41] 2002, p.215-224) described, adopt the technology of the particle mix heat forged etc., make orientation ceramic, make it piezoelectric property occur.In addition, also, attempting in high-intensity magnetic field, making particle orientation as described in the Non-Patent Document 3 (p.111 the annual meeting of 2002 annual Japanese pottery associations gives a lecture pre-original text collection).
Utilize aforesaid particle orientation technology, when making orientation ceramic, can realize usually disperseing and single crystalloid particle as single.Particularly under the situation of bismuth layer-like compound, this monocrystalline has tabular and so on the special shape than large aspect ratio.
As wherein a kind of useful method that can make bismuth layer-like compound, available above-mentioned hydrothermal method with above-mentioned special shape.At Non-Patent Document 4 (A.V.Prasda rao and S.Komarneni, ISAF ' 96, Proc.IEEE Int.Symp.Appl.Ferroelect., 10th, Vol.2, Pub.Inst.E1ectro.Engineers, NY, 1996, the hydro-thermal reaction of carrying out under 240 ℃ temperature 7 days is disclosed in p.923-925), make Bi
4Ti
3O
12Single-phase particle.Non-Patent Document 5 (Yanhui Shi, Changsheng Cao, Shouhua Feng, Materials Letters 46 (2000), disclose the hydro-thermal reaction of carrying out 3 days in p.270-273) under 240 ℃ temperature, can make Bi
4Ti
3O
12Single-phase particle.
But the method for record in these Non-Patent Documents 4 and 5, long hydro-thermal reaction because of needs 7 days or 3 days, so they can not be applied to reality, and these methods are because of using a large amount of potassium hydroxide, so may have a large amount of alkali metals in the powder of gained, and this possibility is not documented in directly in the above-mentioned document.
As mentioned above, must solve a large amount of residual problems of alkali metal in the conventional art.Why? this is that alkali metal can make the coking property of pottery and the electrical characteristic of the sintered compact that makes significantly descend because well-known.
As the technology that can address the above problem, the described method of Patent Document 3 (open the flat 7-69634 of communique number of Japan's special permission) is for example arranged.In Patent Document 3, embodiment has disclosed the synthetic of barium titanate powder and strontium titanate powder, has also put down in writing and has carried out hydro-thermal reaction processing, the method that residual alkali number is reduced once more to make the hydro-thermal synthetic powder through hydro-thermal reaction.
In above-mentioned Patent Document 3, as embodiment, the synthetic of perovskite-type compounds that contains alkali earth metal with regard to barium titanate etc. put down in writing.But when the perovskite-type compounds that contains lead element of PT etc. is synthetic, perhaps under bismuth layer-like compound synthetic situation, directly use the method shown in the Patent Document 3, also differing obtains good result surely.
In fact, in Patent Document 3, disclose in hydro-thermal reaction treatment process once more, adopting pH is the solvent of 7-10, but present inventor's test-results shows the occasion at perovskite-type compounds that contains lead element and bismuth layer-like compound, and the only pH of the aqueous solvent when the hydro-thermal reaction once more that remaining alkali number is lowered is handled is different from Patent Document 3 described 7-10.
Therefore the manufacture method that the purpose of this invention is to provide a kind of ceramic composition, this method adopts hydro-thermal reaction, reduce the remaining alkali number in the ceramic composition of gained simultaneously, even reduced the addition that promotes the alkali of hydro-thermal reaction, also can fully synthesize, and the crystalline particle of gained can be reduced.
Other specific purpose of the present invention is: in the manufacture method of the ceramic composition with the single-phase tabular particle as bismuth layer-like compound, provide a kind of method that remaining alkali number can be reduced.
Summary of the invention
In order to solve the problems of the technologies described above, the manufacture method of ceramic composition of the present invention has the feature that comprises following operation:
At first, have with contain draw up ceramic composition the formation element solution and make the ion of above-mentioned formation element form oxyhydroxide and the alkali hydroxide soln that takes out mixes, make the 1st operation of hydroxide slurry.In the 1st operation, constitute element ion and be formed oxyhydroxide.
Then, clean contained oxyhydroxide in the above-mentioned hydroxide slurry that makes in above-mentioned the 1st operation, the pH that adjusts above-mentioned hydroxide slurry is 9 below but not below 6 and make the 2nd operation of clean thing; Then in the above-mentioned clean thing of above-mentioned the 2nd operation gained, add alkali hydroxide soln as mineralizer (reaction promotor), make it carry out hydro-thermal reaction and make the 3rd operation of reactant.
Above-mentioned the 2nd operation is because of being the integrant of key character of the present invention, by implementing the 2nd operation, can remove attached to the impurity on the oxyhydroxide (mainly being to constitute element alkali metal hydroxide in addition), also make simultaneously constitute element can uniform mixing on molecular level, thus, improved the reactivity of carrying out the clean thing of hydro-thermal reaction in the 3rd operation.From then on as can be known, as a result of, the addition of the alkali metal hydroxide that added in the 3rd operation can be reduced.In the 3rd operation, by hydro-thermal reaction, each constitutes element and is synthesized and is composition.
Carry out again the above-mentioned reactant that above-mentioned the 3rd operation makes is stirred the 4th clean operation, in the 4th operation, removed in the 3rd operation attached to the impurity on the reactant.
After above-mentioned the 4th operation, carry out above-mentioned reactants dry is made the drying process of dry thing.
The manufacture method of ceramic composition of the present invention is preferably between above-mentioned the 4th operation and the above-mentioned drying process, also comprises adding aqueous solvent to above-mentioned reactant, adjusts the pH of slurries so that it above 5 and less than 7, carries out the 5th operation of hydro-thermal reaction again.By between the 4th operation and drying process, carrying out above-mentioned the 5th operation, can also further remove impurity.
Ceramic composition by the present invention's production, be when containing the bismuth layer-like compound of bismuth, titanium and alkali earth metal, be suitable for the embodiment of above-mentioned the best, simultaneously, in the 1st operation, constitute first cellulose solution and better contain bismuth and titanium, in the 3rd operation, in the clean thing of the 2nd operation gained, better add solution or the oxyhydroxide that contains alkali earth metal again.
In above-mentioned specific embodiment, in the 1st operation, constitute first cellulose solution and can contain alkali earth metal, but best alkali-free earth metals element.This is because the clean meeting carried out of the 2nd operation makes the alkali earth metal stripping, in fact not remaining alkali earth metal in the clean thing of wire gained thereafter, and the alkali earth metal that is added in the 1st operation wastes.Moreover, for example Ca of stripping or Sr can form the single-phase or bismuth oxide phase of by product bismuth titanates.
In the 3rd operation, the amount of the alkali metal hydroxide that adds as mineralizer reduced so that the equivalent concentration of alkali hydroxide soln (equivalent concentration) below 0.01N, and the time of carrying out hydro-thermal reaction better shorten to below 1 hour.
The heat treatment step that drying process preferably also is included in more than 400 ℃ and the temperature below 700 ℃ is heat-treated the particle that is made by dried dry thing.
By the present invention, in the 2nd operation before carrying out the 3rd operation of hydro-thermal reaction, adjust to the pH of hydroxide slurry below 9 and, and make clean thing less than below 6, can will remove, can on molecular level, carry out uniform mixing with constituting element simultaneously attached to the impurity on the oxyhydroxide.Thus, the reactivity of the clean thing that carries out hydro-thermal reaction in the 3rd operation can be improved, addition can be reduced like this as the alkali metal hydroxide of the mineralizer (reaction promotor) that is added in the 3rd operation.Its result not only can reduce the crystalline particle of the ceramic composition of gained, and remaining alkali number is reduced, and can effectively avoid the problem that the electrical characteristic of the coking property of the caused pottery of alkali metal or sintered compact descend.
In the present invention, after the reactant of gained stirs the 4th clean operation in to the 3rd operation, add aqueous solvent in reactant, adjust the pH of slurries so that it surpasses 5, and less than 7, implement to carry out the 5th operation of hydro-thermal reaction again, can further remove impurity, the electrical characteristic of sintered compact of the ceramic composition of gained are improved more.
Particularly the ceramic composition that will produce in the present invention is for containing for example bismuth calcium titanate (CBT:CaBi
4Ti
4O
15) or bismuth titanates strontium (SBTi:SrBi
3Ti
4O
15) during the bismuth layer-like compound of such bismuth-containing, titanium and alkali earth metal, carry out above-mentioned 1-the 5th operation, in the 1st operation, contain bismuth and titanium by constituting first cellulose solution, in the 3rd operation, in the clean thing of the 2nd operation gained, add the words of the solution or the oxyhydroxide that contain alkali earth metal again, can not produce the single-phase or bismuth oxide phase of by product bismuth titanates, in addition, can make electrical insulating property alkali earth metal higher, that contain Ca and Sr and so on as the single-phase compound of bismuth stratiform that constitutes element.
In addition, in the 3rd operation, the equivalent concentration that makes alkali hydroxide soln is below 0.01N, and make the time of carrying out hydro-thermal reaction below 1 hour, in drying process, also be implemented in more than 400 ℃ and the heat treatment step of under the temperature below 700 ℃, the particle that is formed by dried dry thing being heat-treated, just the crystalline particle of the ceramic composition of gained can be controlled at for example minimum level of 15nm degree.
To this, the equivalent concentration of alkali hydroxide soln surpasses 0.01N, or the hydro-thermal reaction time surpass 1 hour, can directly generate the ceramic composition crystalline particle of the greater particle size more than the 30nm.
In addition, if the equivalent concentration of alkali hydroxide soln is low excessively, perhaps the hydro-thermal reaction time too short, even after heat-treat, can only make amorphous particle.Thus, obtain above-mentioned effect conscientiously, it is above and below the 0.01N that the equivalent concentration of alkali hydroxide soln is preferably in 0.001N, and the hydro-thermal reaction time is preferably in more than 5 minutes and below 1 hour.
The employed temperature of heat treatment step behind the drying process is preferably in more than 450 ℃ and below 600 ℃.In addition, this thermal treatment better is high speed thermal treatment, for example, carries out heating and cooling with the speed more than 5 ℃/minute, and thermal treatment is held time below 10 minutes.
To this, warming and cooling rate is less than 5 ℃/minute, and thermal treatment temp surpasses 700 ℃, and thermal treatment is held time and surpassed 10 minutes, the above particle growth of 50nm can occur.
Do not have special restriction for heat-treating atmosphere, but compare with air atmosphere, the neutral atmosphere of nitrogen one class can make has the more ceramic composition of small particle size.
Description of drawings
Fig. 1 has shown the analytical results of the single-phase particle of bismuth titanates of gained among the embodiment 6, (a) has shown XRD figure; (b) shown the SEM photo.
The top of Fig. 2 has shown the XRD figure of the bismuth titanate orientation ceramic sintered compact of gained among the embodiment 7, and the bottom has shown the XRD figure of the single-phase particle of bismuth titanates of embodiment 6 gained.
Fig. 3 has shown the observations of SEM of the bismuth titanate orientation ceramic sintered compact of embodiment 7 gained, (a) show the surface of taking ceramic sintered bodies and the SEM photo; (b) the SEM photo of the cross section gained of ceramic sintered bodies is taken in demonstration.
The top of Fig. 4 has shown the XRD figure of the single-phase particle of bismuth calcium titanate of embodiment 8 gained; The bottom has shown the XRD figure of the powder after the hydro-thermal reaction in the 3rd operation among the embodiment 8.
Fig. 5 has shown the SEM photo of the single-phase particle of bismuth calcium titanate of embodiment 8 gained.
The top of Fig. 6 has shown the XRD figure of the bismuth calcium titanate orientation ceramic sintered compact of embodiment 9 gained; The bottom has shown the XRD figure of the single-phase particle of bismuth calcium titanate of embodiment 8 gained.
Fig. 7 has shown the SEM observations of the bismuth calcium titanate orientation ceramic sintered compact shown in the embodiment 9, (a) be take the ceramic post sintering surface and the SEM photo, (b) be take the ceramic post sintering body section and the SEM photo.
Embodiment
Followingly describe with regard to embodiments of the present invention according to embodiment.
Embodiment 1
Take by weighing the tetraisopropoxy titanium of 28.34g (containing 0.1 mole) and the Virahol (IPA) of 118.15g, make the IPA solution of tetraisopropoxy titanium as titanium elements.In addition lead nitrate 34.95g (containing 0.105 mole as lead element) is dissolved in the pure water of 170.37g, makes the lead nitrate aqueous solution.
Utilize homogenizer that the IPA solution of tetraisopropoxy titanium is carried out high-speed stirring, utilize miniature tubing sucker-rod pump that the lead nitrate aqueous solution is dripped simultaneously, make the mixed serum of the oxyhydroxide of the lead nitrate aqueous solution and titanium.Then, utilize homogenizer that this mixed serum is carried out high-speed stirring, utilize miniature tubing sucker-rod pump that the potassium hydroxide solution of the 8N of 34.86g (containing 0.21 mole as potassium hydroxide) is dripped simultaneously, make the hydroxide slurry that is mixed with lead element and titanium elements (more than be the 1st operation).
The prepared hydroxide slurry fluid dewatering of the 1st operation is obtained dewatered cake.The pure water that adds 300g then is in this dewatered cake, make slurries, utilize homogenizer that these slurries are carried out high-speed stirring about 30 minutes, thereafter, repeat dehydration operation 3 times and make lead element and titanium elements on molecular level, carry out uniform mixing, and the potassium hydroxide and the saltpetre of impurity are removed.The pH of the filtrate of the dehydration gained that this operation is last is 6.8.(more than be the 2nd operation).
To the dewatered cake of the clean thing of the 2nd operation gained, add the potassium hydroxide solution of 8N of 0.498g (containing 0.003 mole) and the pure water of 299.625g as potassium hydroxide, make slurries.Basic solvent equivalent concentration during the hydro-thermal reaction of these slurries is 0.01N.Utilize homogenizer that these slurries are carried out high-speed stirring about 30 minutes, thereafter, the tetrafluoroethylene system of putting into beaker, it is in 0.5 liter the stirring-type reactor that this beaker is configured in internal volume, in the hydro-thermal reaction (more than be the 3rd operation) of carrying out 4 hours under the condition of 200 ℃ and 200rpm.
After the 3rd operation was finished, slurries are dewatered made dewatered cake as reactant.Then, the pure water to dewatered cake interpolation 300g makes slurries.Utilize homogenizer that these slurries are carried out high-speed stirring about 30 minutes, repeat dehydration operation thereafter 3 times (more than be the 4th operation).
The dewatered cake that the 4th operation is made is added the pure water of 300g, makes slurries, utilizes homogenizer that these slurries are carried out high-speed stirring about 30 minutes.Then, put into tetrafluoroethylene system beaker, it is in 0.5 liter the stirring-type reactor that this beaker is configured in internal volume, in the hydro-thermal reaction (more than be the 5th operation) of carrying out 4 hours under the condition of 200 ℃ and 200rpm again.
Then, after the 5th operation is finished, dewater, the dewatered cake of gained is put into the baking oven that is set at 100 ℃ of temperature, make its dry 12 hours., utilize 40 purpose sieves carry out whole grain, make needed ceramic composition powder thereafter.
The ceramic composition powder that makes is as mentioned above estimated, obtained following result.
At first, the XRD qualitative result that particle carried out to the ceramic composition powder that constitutes gained is the single-phase particle of lead titanate (PT) of tetragonal lattice.Carry out simultaneously finding after the accurate XRD determining c/a axial ratio for and during integral body (bulk) the same 1.065.The result of SEM and tem observation is that the particle that constitutes ceramic composition has anisotropic rectangular shape, and particle diameter is 30nm.Carry out again finding that observe clear and definite spot, this particle is a monocrystalline sample lead titanate particle after the observation of electron rays diffractogram.Remaining potassium amount in the particle being analyzed the back find that it is few, is 40 ppm by weight.
As mentioned above, it is few to make remaining potassium amount by embodiment 1, be 40 ppm by weight and form be uniformly, particle diameter is the monocrystalline sample lead titanate particle of 30nm.
To remove impurity is that the particle that cleaning of purpose generated can repeatedly carry out usually, is equivalent to the 4th operation in the foregoing description 1.In the foregoing description 1, clean operation except carrying out this, carry out the 5th operation again, under hydrothermal condition, clean operation once more, just can reduce remaining potassium amount more, reach 40 ppm by weight.
In the clean operation of under above-mentioned hydrothermal condition, being carried out, add aqueous solvent and preferably make pH surpass 5 and less than 7.If pH surpasses 7, the effect of removing of alkali metals such as potassium weakens; If pH is below 5, lead element can stripping.Relevant with this is, has disclosed the method for utilizing once more hydrothermal treatment consists can reduce remaining alkali number in above-mentioned Patent Document 3, and the solvent of this moment is preferably neutral or alkalescence (pH is 7-10).In this Patent Document 3, mainly disclosed the perovskite-type compounds synthetic example that barium titanate etc. contains alkali earth metal.To this, in the foregoing description 1, contain perovskite-type compounds synthetic of lead element, disclosed pH is different in the best pH that implements the aqueous solvent in the 5th operation of hydrothermal treatment consists once more and the Patent Document 3, should arouse attention.Temperature of reaction under the hydrothermal condition is more fortunately more than the hydrothermal temperature of the 3rd operation.Consider that from the thermotolerance of the beaker of used tetrafluoroethylene system this temperature should be the upper limit with about 250 ℃ in addition.
Shown in above-mentioned embodiment 1, it should be noted that also the basic solvent equivalent concentration can be with the hydro-thermal reaction implemented in the 3rd operation time becomes minimum.More particularly, the equivalent concentration of the basic solvent the during hydro-thermal reaction of embodiment 1 becomes minimum, is 0.01N.And common hydro-thermal synthetic in, the basic solvent equivalent concentration during hydro-thermal reaction is more than 1N.For example, shown in disclose in the Patent Document 1 and carried out the main points that hydro-thermal reaction is the scope that requires of special permission in the basic solvent more than 1N.To this, in the foregoing description 1, carry out the 2nd operation, when removing potassium hydroxide and saltpetre, carry out mixed uniformly operation on molecular level with lead element and titanium elements.Basic solvent equivalent concentration when its result can make the hydro-thermal reaction of the 3rd operation becomes less.
As mentioned above, the basic solvent equivalent concentration during hydro-thermal reaction among the embodiment 1 is 0.01N, and this is equivalent to pH and is about 12.The hydro-thermal reaction of such the 3rd operation is not limited to pH and is about 12, implements all comparatively ideal in pH is the alkalescence zone of 8-14.
Carry out clean operation that the 2nd operation implements so that the pH of the filtrate of dehydration gained below 9, not below 6.If carry out unnecessary clean operation, the stripping of lead composition can take place below 6 in the pH that makes filtrate, becomes the reason of forming deviation.In addition, if it is not enough to clean operation, the pH of filtrate surpasses 9, can not obtain the single-phase particle of lead titanate, and the amount of remaining potassium amount in the end product powder can surpass 100 ppm by weight.In addition, comparatively it is desirable to, cleaning operation is 7-8 up to the pH of filtrate.
Embodiment 2
The same with embodiment 1, take by weighing the tetraisopropoxy titanium of 28.34g (containing 0.1 mole) and the Virahol (IPA) of 118.15g as titanium elements, make the IPA solution of tetraisopropoxy titanium.In addition lead nitrate 34.95g (containing 0.105 mole as lead element) is dissolved in the pure water of 170.37g, makes the lead nitrate aqueous solution.
Utilize homogenizer that the IPA solution of tetraisopropoxy titanium is carried out high-speed stirring, utilize miniature tubing sucker-rod pump that the lead nitrate aqueous solution is dripped simultaneously, make the mixed serum of the oxyhydroxide of the lead nitrate aqueous solution and titanium.Then, utilize homogenizer that this mixed serum is carried out high-speed stirring, utilize miniature tubing sucker-rod pump that the potassium hydroxide solution of the 8N of 34.86g (containing 0.21 mole as potassium hydroxide) is dripped simultaneously, make the hydroxide slurry that is mixed with lead element and titanium elements (more than be the 1st operation).
After removing the about 200ml of the prepared hydroxide slurry supernatant liquor of the 1st operation, add the pure water of 200g, make slurries, utilize homogenizer that these slurries are carried out high-speed stirring about 30 minutes, thereafter, repeat this operation 6 times and make lead element and titanium elements on molecular level, carry out uniform mixing, and make the slurries of having removed impurities H potassium oxide and saltpetre.The pH of the solvent in the slurries of final gained is 7.1.(more than be the 2nd operation).
To the slurries of the clean thing of the 2nd operation gained, remove the supernatant liquor of 0.498g after, add the potassium hydroxide solution of the 8N of 0.498g (containing 0.003 mole) as potassium hydroxide, make slurries.Utilize homogenizer that these slurries are carried out high-speed stirring about 30 minutes, thereafter, the tetrafluoroethylene system of putting into beaker, it is in 0.5 liter the stirring-type reactor that this beaker is configured in internal volume, carry out 4 hours hydro-thermal reaction under the condition of 200 ℃ and 200rpm, the basic solvent equivalent concentration the during hydro-thermal reaction of these slurries is 0.01N.(more than be the 3rd operation).
For the slurries of the 3rd operation gained as reactant, remove the about 200ml of supernatant liquor after, the pure water that adds 200g makes slurries.Utilize homogenizer that these slurries are carried out high-speed stirring about 30 minutes, repeat this operation 6 times (more than be the 4th operation).
Then, the slurries of the 4th operation gained are put into tetrafluoroethylene system beaker, it is in 0.5 liter the stirring-type reactor that this beaker is configured in internal volume, in the hydro-thermal reaction (more than be the 5th operation) of carrying out 4 hours under the condition of 200 ℃ and 200rpm again.
Then, for the slurries of the 5th operation gained, remove the supernatant liquor of about 200ml after, the pure water that adds 200g makes slurries.Utilize homogenizer that these slurries are carried out high-speed stirring about 30 minutes, repeat this operation 3 times.Carry out evaporation drying by slurries and make dried powder, thereafter, utilize 40 purpose sieves that this dried powder is carried out whole grain, make required ceramic composition powder final gained.
To the ceramic composition powder of above-mentioned gained, find with the embodiment 1 the same back of estimating: at first, the XRD qualitative result is the single-phase particle of lead titanate (PT) of tetragonal lattice.Carry out simultaneously finding that the c/a axial ratio is 1.063 after the accurate XRD determining.The result of SEM and tem observation is that the particle that constitutes ceramic composition has anisotropic rectangular shape, and particle diameter is 32nm.Carry out again finding that observe clear and definite spot, this particle is a monocrystalline sample lead titanate particle after the observation of electron rays diffractogram.Be found to be 43 ppm by weight after remaining potassium amount in the particle analyzed, few.
Except in the 3rd operation of the foregoing description 1, dewatered cake is added 4.98g (containing 0.03 mole as the potassium hydroxide) potassium hydroxide solution of 8N and the pure water of 296.25g makes beyond the slurries, all the other all with the foregoing description 1 the same ceramic composition powder that makes.Basic solvent equivalent concentration during the hydro-thermal reaction of the 3rd operation of this embodiment 3 is 0.1N.
To the ceramic composition powder of gained, equally with embodiment 1 estimate discovery: at first the XRD qualitative result is the single-phase particle of lead titanate (PT) of tetragonal lattice.Carry out finding that the c/a axial ratio is 1.067 after the accurate XRD determining, and the situation of whole (bulk) is with value.The result of SEM and TEM gained is that the particle of observation ceramic composition is to have anisotropic rectangular shape, and particle diameter is 100nm (0.1 μ m).Carry out again finding that observe clear and definite spot, this particle is a monocrystalline sample lead titanate particle after the observation of electron rays diffractogram.Be found to be 60 ppm by weight after remaining potassium amount in the particle analyzed, few.
Embodiment 4
Except in the 3rd operation of the foregoing description 1, dewatered cake is added 0.3984g (containing 0.0024 mole as the potassium hydroxide) potassium hydroxide solution of 8N and the pure water of 299.602g make beyond the slurries, all the other all carry out until the 4th operation under the condition identical with the foregoing description 1.Basic solvent equivalent concentration during the hydro-thermal reaction of the 3rd operation of this embodiment 4 is 0.008N.
After this, be not equivalent to the operation of the 5th operation of embodiment 1, the dewatered cake of the 4th operation gained is put into the baking oven that is set at 100 ℃ of temperature, carry out 12 hours drying.With 40 purpose sieves carry out whole grain thereafter.The result who the particle of this drying process gained is analyzed by X-ray diffraction distinguishes and is the amorphousness particle.The result that SEM observes is: size is consistent, and particle diameter is the particle of 10nm.
Then, in nitrogen atmosphere, under 500 ℃ of temperature to above-mentioned drying process in the particle of gained carry out 1 minute thermal treatment, make required ceramic composition powder.
To the ceramic composition powder of gained, equally with embodiment 1 estimate discovery: at first the XRD qualitative result is the single-phase particle of lead titanate (PT) of tetragonal lattice.Carry out finding that the c/a axial ratio is 1.065 after the accurate XRD determining, and the situation of whole (bulk) is with value.The result that SEM and TEM constitute is that the particle of observing ceramic composition has anisotropic rectangular shape, and particle diameter is 15nm.Carry out again finding that observe clear and definite spot, this particle is a monocrystalline sample lead titanate particle after the observation of electron rays diffractogram.Be found to be 38 ppm by weight after remaining potassium amount in the particle analyzed, few.
Embodiment 5
Except in the last heat treatment step of the foregoing description 4, in atmosphere, implement thermal treatment and replace beyond the thermal treatment in the nitrogen atmosphere, all the other all with the embodiment 4 the same ceramic composition powder that make.
When being obtained the particle diameter of lead titanate particle, gained ceramic composition powder finds that it is 20nm.
Embodiment 6
26.07g (containing 0.1 mole as bismuth element) bismuthyl chloride is dissolved in 200cm
3The hydrochloric acid soln of 3N in, make the hydrochloric acid soln of bismuthyl chloride.In addition the tetraisopropoxy titanium (as titanium elements, containing 0.075 mole) of 21.108g and the IPA of 124.11g are mixed, make the IPA solution of tetraisopropoxy titanium.
With the IPA solution high-speed stirring of homogenizer with tetraisopropoxy titanium, utilize miniature tubing sucker-rod pump that the potassium hydroxide solution of the 8N of 498g (containing 3 moles as potassium hydroxide) is dripped simultaneously, then, utilize miniature tubing sucker-rod pump that the hydrochloric acid soln of bismuthyl chloride is dripped equally, make the hydroxide slurry that is mixed with bismuth element and titanium elements (more than be the 1st operation).
The prepared hydroxide slurry fluid dewatering of the 1st operation is obtained dewatered cake.The pure water that adds 800g then is in this dewatered cake, make slurries, utilize homogenizer that these slurries are carried out high-speed stirring about 30 minutes, thereafter, repeat dehydration operation 5 times and make bismuth element and titanium elements on molecular level, carry out uniform mixing, and impurities H potassium oxide and Repone K are removed.The pH of the filtrate of the dehydration gained that this operation is last is 8.5.(more than be the 2nd operation).
To the dewatered cake of the 2nd operation gained, the potassium hydroxide solution of the 8N of interpolation 74.7g (containing 0.45 mole as potassium hydroxide) and the pure water of 543.75g make slurries.Basic solvent equivalent concentration during the hydro-thermal reaction of these slurries is 0.75N.Utilize homogenizer that these slurries are carried out high-speed stirring about 30 minutes, thereafter, the tetrafluoroethylene system of putting into beaker, it is in 1.1 liters the stirring-type reactor that this beaker is configured in internal volume, in the hydro-thermal reaction (more than be the 3rd operation) of carrying out 24 hours under the condition of 220 ℃ and 500rpm.
After the 3rd operation was finished, slurries are dewatered made dewatered cake.Then, the pure water to dewatered cake interpolation 800g makes slurries.Utilize homogenizer that these slurries are carried out high-speed stirring about 30 minutes, repeat dehydration operation thereafter 2 times (more than be the 4th operation).
The dewatered cake that the 4th operation is made is added the pure water of 600g, makes slurries, utilizes homogenizer that these slurries are carried out high-speed stirring about 30 minutes.Then, put into tetrafluoroethylene system beaker, it is in 1.1 liters the stirring-type reactor that this beaker is configured in internal volume, in the hydro-thermal reaction (more than be the 5th operation) of carrying out 24 hours under the condition of 220 ℃ and 500rpm again.
Then, after the 5th operation is finished, dewater, the dewatered cake of gained is put into the baking oven that is set at 100 ℃ of temperature, make its dry 12 hours., utilize 40 purpose sieves carry out whole grain, make the ceramic composition powder that needs thereafter.
The ceramic composition powder that makes is as mentioned above estimated, obtained following result.
At first, the XRD qualitative result that the ceramic composition powder of gained is carried out is confirmed to be the single-phase particle of bismuth titanates (BIT) of rhombic system shown in Fig. 1 (a).The result that SEM observes observes this particle and has tabularly shown in Fig. 1 (b), and particle diameter is about 5 μ m.In addition, the more remaining potassium amount in the particle being analyzed the back and find, is 90 ppm by weight, few.
As mentioned above, it is few to make remaining potassium amount by embodiment 6, be 90 ppm by weight and have a single-phase particle of tabular bismuth titanates that particle diameter is about 5 μ m.
With respect to carrying out 7 days or 3 days long hydro-thermal reactions in 240 ℃ in above-mentioned Non-Patent Document 4 and 5, the very practical hydrothermal synthesizing condition in 220 ℃ and 24 hours in the foregoing description 6 just can make the single-phase particle of bismuth titanates down.This be because and embodiment 1 described like that, in the 2nd operation, when potassium hydroxide and Repone K are removed, implemented the cause of bismuth element and the titanium elements uniform mixing operation on molecular level.Consequently, compare with 5 report example, can under the hydrothermal reaction condition of more low temperature and shorter time, make the single-phase particle of bismuth titanates with Non-Patent Document 4.
In the foregoing description 6, the clean number of times of the 2nd operation is 5 times.This is because used more potassium hydroxide solution (containing 3 moles as potassium hydroxide) in the 1st operation, the cause that the hydrochloric acid soln of bismuthyl chloride is hydrolyzed.For the clean operation in the 2nd operation, compared with clean number of times, the degree that the pH of filtrate is cleaned how is even more important.In the above embodiments 1,3 and 4,,, in this embodiment 6, be synthetic bismuth titanates, so in the 2nd operation, cleaning up to the pH of filtrate is 8.5 so in the 2nd operation, the pH of filtrate is 6.5 or 6.8 because of PT is synthesized.This is because of the difference according to the purpose compound, and the optimal ph of filtrate is also different.
In embodiment 6, the same with the situation of embodiment 1-3, the equivalent concentration of the potassium hydroxide solution of the 3rd operation surpasses 0.01N, the hydro-thermal reaction time was above 1 hour, and do not carry out the thermal treatment behind the drying process, handle preceding clean operation (the 2nd operation) and carry out hydro-thermal reaction, under hydrothermal condition, clean operation (the 5th operation).For this reason, remaining potassium amount can be reduced to below 100 ppm by weight.By the way, though within the scope of the invention, only be implemented under the situation of the 4th operation, remaining potassium amount is the 200-300 ppm by weight.
For above-mentioned hydrothermal treatment consists of carrying out once more, in Patent Document 3, also disclose, but in Patent Document 3, the hydrothermal treatment consists of carrying out is to carry out in pH is the aqueous solvent of 7-10 once more.And utilize pH is adjusted into 7 barium hydroxide solution, finds when carrying out hydrothermal treatment consists once more that remaining potassium amount is 180 ppm by weight, can not drop to below 100 ppm by weight.In the aqueous solvent below 5, carry out hydrothermal treatment consists once more at pH, the problem of the remarkable stripping of bismuth element can occur.The pH of the aqueous solvent the during hydrothermal treatment consists that therefore, must carry out once more is set at and surpasses 5 and less than 7.
Embodiment 7
With etc. weight ratio with the single-phase mix particles of BIT of the single-phase particle of BIT and the solid state reaction gained of the foregoing description 6 gained, add pure water and tackiness agent to this mixed powder, mixing through ball mill makes slurries.Then, utilize the scraping blade method that these slurries are shaped and make the ceramic raw material sheet.
To make living lamination body behind the multi-disc ceramic raw material sheet lamination of above-mentioned gained and the extrusion, then, the lamination type of this life become prescribed level after, make living lamination body substrate (chip).
After the lamination body substrate of giving birth to carried out the processing of unsticking mixture, in atmosphere, 1000 ℃ of temperature roastings made ceramic sintered bodies in 2 hours.
The analytical results of the XRD of the ceramic sintered bodies of gained is shown in the top (" BIT orientedceramics ") of Fig. 2.For easily and the XRD analysis result of ceramic sintered bodies shown in the top compare, shown the XRD analysis result of the single-phase particle of BIT of embodiment 6 gained shown in Fig. 1 (a) in the bottom of Fig. 2 (" BIT particle by hydrothermal method ").The SEM observations on the surface of the ceramic sintered bodies of these embodiment 7 gained is shown in Fig. 3 (a).And the SEM observations in cross section is shown in Fig. 3 (b).
From Fig. 2 and Fig. 3 as can be known: utilize embodiment 7 can make good BIT orientation ceramic.
Embodiment 8
26.07g (containing 0.1 mole as bismuth element) bismuthyl chloride is dissolved in 200cm
3The hydrochloric acid soln of 3N in, make the hydrochloric acid soln of bismuthyl chloride.In addition the tetraisopropoxy titanium (as titanium elements, containing 0.1 mole) of 28.31g and the IPA of 118.18g are mixed, make the IPA solution of tetraisopropoxy titanium.
Drip in the IPA solution of above-mentioned tetraisopropoxy titanium with the pure water of miniature tubing sucker-rod pump 100g, then with homogenizer with its high-speed stirring, utilize miniature tubing sucker-rod pump that the potassium hydroxide solution of the 8N of 498g (containing 3 moles as potassium hydroxide) is dripped simultaneously, then, utilize the hydrochloric acid soln of the bismuthyl chloride that miniature tubing sucker-rod pump will make as described above to drip equally, make the hydroxide slurry that is mixed with bismuth element and titanium elements (more than be the 1st operation).
The prepared hydroxide slurry fluid dewatering of the 1st operation is obtained dewatered cake.The pure water that adds 800g then is in this dewatered cake, make slurries, utilize homogenizer that these slurries are carried out high-speed stirring about 30 minutes, thereafter, repeat dehydration operation 5 times and make bismuth element and titanium elements on molecular level, carry out uniform mixing, and impurities H potassium oxide and Repone K are removed.Dewater the at last pH of filtrate of gained of this operation is 8.6.(more than be the 2nd operation).
To the dewatered cake of the 2nd operation gained, the potassium hydroxide solution of the 8N of interpolation 133.215g (containing 0.8025 mole as potassium hydroxide) and the pure water of 399.69g make slurries.These slurries are carried out high-speed stirring about 15 minutes, thereafter, on one side these slurries of high-speed stirring, on one side with the miniature tubing sucker-rod pump calcium chloride solution (0.02625 mole calcium chloride is dissolved in the pure water of 100g) that drips.After dripping, the slurries that high-speed stirring is about 15 minutes are put into tetrafluoroethylene system beaker, and it is in 1.1 liters the stirring-type reactor that this beaker is configured in internal volume, carry out 24 hours hydro-thermal reaction (more than be the 3rd operation) under the condition of 220 ℃ and 500rpm.
After the 3rd operation was finished, slurries are dewatered made dewatered cake.Then, the pure water to dewatered cake interpolation 600g makes slurries.Utilize homogenizer that these slurries are carried out high-speed stirring about 30 minutes, repeat dehydration operation thereafter 3 times (more than be the 4th operation).
The pure water that the dewatered cake that makes to the 4th operation is added 600g makes slurries, utilizes homogenizer that these slurries are carried out high-speed stirring about 30 minutes.Then, put into tetrafluoroethylene system beaker, it is in 1.1 liters the stirring-type reactor that this beaker is configured in internal volume, carries out 24 hours hydro-thermal reaction (more than be the 5th operation) under the condition of 220 ℃ and 500rpm again.
Then, after the 5th operation is finished, dewater, the dewatered cake of gained is put into the baking oven that is set at 100 ℃ of temperature, make its dry 12 hours., utilize 40 purpose sieves carry out whole grain, make the ceramic composition powder that needs thereafter.
The ceramic composition powder that as above makes is estimated, obtained following result.
At first, the XRD qualitative result that the ceramic composition powder of gained is carried out is confirmed to be bismuth calcium titanate (CBT:CaBi shown in the top (" product after hydrothermal treatment ") of Fig. 4
4Ti
4O
15) single-phase particle.The bottom of Fig. 4 (" product after hydrothermalreaction ") expression is to the XRD qualitative result that powder carried out after the hydro-thermal reaction of the 3rd operation.
The SEM observations as shown in Figure 5, this particle has tabular, particle diameter is 0.2-0.3 μ m.To finding after the remaining potassium component analysis in the particle that remaining potassium amount is few, be 95 ppm by weight.
As mentioned above, it is few to make remaining potassium amount by embodiment 8, be 95 ppm by weight and have a single-phase particle of tabular bismuth calcium titanate that particle diameter is about 0.2-0.3 μ m.
In the foregoing description 6, confirmed after the 3rd operation, can make the single-phase particle of required bismuth titanates.To this, in the time of will obtaining the single-phase particle of bismuth calcium titanate as embodiment 8, after the 3rd operation, shown in the bottom of Fig. 4, like that, generated bismuth titanates (Bi as by product
4Ti
3O
12) phase and bismuth oxide (Bi
4O
7) phase, and can not obtain the single-phase of bismuth calcium titanate.In embodiment 8, after the 5th operation of carrying out once more hydro-thermal reaction is finished, just obtain the single-phase particle of bismuth calcium titanate.
Shown that in embodiment 6 the 5th operation has unusual effect to reducing remaining potassium amount, has also shown same effect in embodiment 8.Therefore, if only when proceeding to the 4th operation, remaining potassium amount is about 400 ppm by weight.
In addition, from embodiment 8 as can be known, in order to obtain the single-phase particle of bismuth calcium titanate, carry out again the 5th operation that hydro-thermal reaction handles and be removing bismuth titanates mutually with bismuth oxide mutually, obtain the requisite operation of the single-phase particle of bismuth calcium titanate.
Not in the 3rd operation, but in the 1st operation, add the solution that contains calcium, once attempt synthetic bismuth calcium titanate, but cleaned the stripping that can cause calcium hydroxide, not remaining in fact calcium in the dewatered cake of thereafter dehydration gained, the particle that is generated is a principal phase with bismuth titanates mutually.In order to address this problem, estimate the calcium hydroxide amount of institute's stripping, when making the solution reaction that contains excessive calcium, generate the calcium titanate phase as by product, and can not obtain single-phase particle.
In embodiment 8, make the excessive 5 moles of % of calcium add-on with respect to the chemical theory amount.If feed in raw material by the chemical theory amount, it is obvious that the by-product of bismuth titanates phase becomes.If than the superfluous 10 moles of % of chemical theory amount, the crystallinity that generates particle reduces.Therefore, with respect to the chemical theory amount, the preferably superfluous 5 moles of % of calcium amount.Different with the situation of embodiment 8, not only in the 3rd operation, when also in the 1st operation, adding calcium, can consider this point, determine suitable calcium amount.
Be used for the pH of aqueous solvent of the hydrothermal treatment consists again of the 5th operation, the same with embodiment 6, must be set at: surpass 5 and less than 7.If pH is below 5, the bismuth element stripping is obvious; If more than 7, can influence the minimizing effect of remaining potassium amount.
Embodiment 9
After adding pure water and the tackiness agent single-phase particle of CBT that extremely above-mentioned embodiment 8 makes, carry out the mixing slurries that make with ball mill.Then, use the scraping blade method that these slurries are configured as the ceramic raw material sheet.
Make living lamination body after the multi-disc ceramic raw material sheet lamination of above-mentioned gained and pressure removed, then, the lamination type of this life become prescribed level after, make living lamination body substrate (chip).
After meticulously the lamination body substrate of giving birth to being carried out the processing of unsticking mixture, in atmosphere, 120 ℃ of temperature roastings made ceramic sintered bodies in 2 hours.
The analytical results of the XRD of the ceramic sintered bodies of gained is shown in the top (" CBT orientedceramics ") of Fig. 6.For easily and the XRD analysis result of ceramic sintered bodies shown in the top compare, shown the XRD analysis result of the single-phase particle of CBT of embodiment 8 gained in the bottom of Fig. 6 (" CBT particle by hydrothermal method ").The SEM observations on the surface of the ceramic sintered bodies of these embodiment 9 gained is shown in Fig. 7 (a).And the SEM observations in cross section is shown in Fig. 7 (b).
From Fig. 6 and Fig. 7 as can be known: utilize embodiment 9 can make good CBT orientation ceramic.
Embodiment 10
The same hydroxide slurry that is mixed with bismuth element and titanium elements (more than be the 1st operation) that makes with embodiment 8.
Then, with the embodiment 8 the same hydroxide slurry fluid dewaterings that the 1st operation is made, after making dewatered cake, this dewatered cake is added pure water, the operation of stirring and dewatering, repeat 5 times, make bismuth element and titanium elements uniform mixing on molecular level, remove the potassium hydroxide and the Repone K of impurity simultaneously.The pH of the filtrate that makes by last dehydration in this operation is 8.4 (more than be the 2nd operation).
To the dewatered cake of the 2nd operation gained, the potassium hydroxide solution of the 8N of interpolation 124.5g (containing 0.75 mole as potassium hydroxide) and the pure water of 506.25g make slurries.These slurries are carried out high-speed stirring about 15 minutes, thereafter, in these slurries, add 6.983g (as strontium, contain 0.02625 mole) 8 hydrates of strontium hydroxide, after the interpolation, the tetrafluoroethylene system of putting into beaker, it is in 1.1 liters the stirring-type reactor that this beaker is configured in internal volume, carries out 24 hours hydro-thermal reaction (more than be the 3rd operation) under the condition of 220 ℃ and 500rpm.
The same with embodiment 8, carry out the 4th operation and the 5th operation, after the 5th operation was finished, dehydration was put into the baking oven that is set at 100 ℃ of temperature with the dewatered cake of gained, made its dry 12 hours., utilize 40 purpose sieves carry out whole grain, make the ceramic composition powder that needs thereafter.
The ceramic composition powder that makes is as mentioned above estimated, obtained following result.
At first, the XRD qualitative result that the ceramic composition powder of gained is carried out is: confirmed it is bismuth titanates strontium (SBTi:SrBi
4Ti
4O
15) single-phase particle.In addition, the observations of SEM is: this particle has tabular, is that particle diameter is the particle of 0.2-0.3 μ m.Remaining potassium amount in the particle is analyzed the back to be found: be 87 ppm by weight, and few.
As mentioned above, utilize embodiment 10 can obtain the effect the same with the foregoing description 8.
Embodiment 8-10 carries out when containing calcium and strontium as alkali earth metal respectively, under the situation of the alkali earth metal that contains other, utilizes the method the same with the employed method of embodiment 8-10 can obtain same effect.
Claims (5)
1. the manufacture method of a ceramic composition, it is characterized in that, comprise following operation: the alkali hydroxide soln that the solution of the formation element of the ceramic composition that will contain draws up is equipped with takes out with the ion formation oxyhydroxide that makes above-mentioned formation element mixes, and makes the 1st operation of hydroxide slurry; Clean contained oxyhydroxide in the above-mentioned hydroxide slurry that makes in above-mentioned the 1st operation, the pH that adjusts above-mentioned hydroxide slurry is 9 below but not below 6 and make the 2nd operation of clean thing; In the above-mentioned clean thing of above-mentioned the 2nd operation gained, add alkali hydroxide soln as mineralizer, make it carry out hydro-thermal reaction and make the 3rd operation of reactant; The above-mentioned reactant that above-mentioned the 3rd operation is made stirs the 4th clean operation; After above-mentioned the 4th operation, above-mentioned reactants dry is made the drying process of dry thing.
2. the manufacture method of ceramic composition according to claim 1, it is characterized in that, between above-mentioned the 4th operation and above-mentioned drying process, also comprise and add aqueous solvent to above-mentioned reactant, adjust the pH of slurries so that it above 5 and less than 7, carries out the 5th operation of hydro-thermal reaction once more.
3. the manufacture method of ceramic composition according to claim 2 is characterized in that, above-mentioned ceramic composition is the bismuth layer-like compound that contains bismuth, titanium and alkali earth metal, and in above-mentioned the 1st operation, the first cellulose solution of above-mentioned formation contains bismuth and titanium; In above-mentioned the 3rd operation, in the above-mentioned clean thing that above-mentioned the 2nd operation makes, add solution or the oxyhydroxide that contains alkali earth metal again.
4. according to the manufacture method of each described ceramic composition among the claim 1-3, it is characterized in that in above-mentioned the 3rd operation, the equivalent concentration of above-mentioned alkali hydroxide soln is below 0.01N, the time of carrying out above-mentioned hydro-thermal reaction is below 1 hour.
5. according to the manufacture method of each described ceramic composition among the claim 1-3, it is characterized in that, also be included in more than 400 ℃ and the temperature below 700 ℃, the heat treatment step that the particle of the above-mentioned dry thing gained that forms by being dried in the above-mentioned drying process is heat-treated.
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| JP2004112952A JP4375092B2 (en) | 2003-06-04 | 2004-04-07 | Method for producing ceramic composition |
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| JP5013671B2 (en) * | 2004-12-28 | 2012-08-29 | 日揮触媒化成株式会社 | Method for producing metal oxide sol and metal oxide sol |
| KR100703077B1 (en) * | 2005-06-03 | 2007-04-06 | 삼성전기주식회사 | Method for Manufacturing Crystalline Dielectric Thin Film, Crystalline Dielectric Thin Film Manufactured Thereby and Thin Film Capacitor Having the Same |
| KR101268883B1 (en) | 2010-12-06 | 2013-05-29 | 한국세라믹기술원 | High strength organic-inorganic composite having mineral bridge structure and preparation method thereof |
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