CN1496961A - Manufacturing method of perovskite barium titanate powder - Google Patents
Manufacturing method of perovskite barium titanate powder Download PDFInfo
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- CN1496961A CN1496961A CNA03127269XA CN03127269A CN1496961A CN 1496961 A CN1496961 A CN 1496961A CN A03127269X A CNA03127269X A CN A03127269XA CN 03127269 A CN03127269 A CN 03127269A CN 1496961 A CN1496961 A CN 1496961A
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Abstract
Provided is a method for manufacturing perovskite-type barium titanate powder having a small mean particle diameter of <=1 [mu]m, little dispersion in particle diameter, a Ba to Ti molar ratio of about 1 with little dispersion in the ratio, high purity and excellent crystallinity. The method for manufacturing perovskite-type barium titanate powder includes: a first step of washing barium titanyl oxalate having a mean particle diameter of 50 to 300 [mu]m with water; a second step of obtaining barium titanyl oxalate having a mean particle diameter of 0.05 to 1 [mu]m by slurrying and wet-grinding the washed barium titanyl oxalate; and a third step of calcining the obtained barium titanyl oxalate having a mean particle diameter of 0.05 to 1 [mu]m at 700 to 1,200[deg.]C.
Description
Technical field
The invention relates to the manufacture method of perovskite-type barium titanate powder made, particularly about manufacture method as the useful perovskite-type barium titanate powder made of the raw material of functionality ceramics such as piezoelectrics, photoelectric material, dielectric material, semi-conductor, sensing member.
Background technology
Perovskite-type barium titanate powder made, the raw material as functionality ceramics such as piezoelectrics, laminated ceramic compacitors uses at present.; in recent years; laminated ceramic compacitor for high capacity, and requires to increase lamination number or high-dielectric constantization; for this reason; for perovskite-type barium titanate powder made as raw material, require the following fluctuation fine, particle diameter of 1 μ m little, Ba to the mol ratio (following also be called " Ba/Ti mol ratio ") of Ti be approximately 1 and also its fluctuation little; high purity, excellent in crystallinity.
Manufacture method as perovskite-type barium titanate powder made, for example open in the clear 61-146710 communique and propose the spy, the aqueous solution that mixes water soluble barium salt and water-soluble titanium salt and oxalic acid simultaneously carries out the powerful broken fine barium titanium oxalate (BaTiO (C that obtains that stirs by the gel that will obtain in the short period of time
2O
4) 4H
2O) crystallization is carried out calcining method at 700～900 ℃.In addition, Clabaugh, people such as W.S. propose, at about 80 ℃ H
2C
2O
4The high degree of agitation TiCl that drips on one side on one side in the aqueous solution
4And BaCl
2The aqueous solution, obtain barium titanium oxalate, this barium titanium oxalate is calcined, the size distribution of making primary particle is that 0.3～1.5 μ m, Ba/Ti mol ratio are 0.987～1.003 BaTiO
3Method.
[patent documentation 1]
The spy opens clear 61-146710 communique (page 1)
[non-patent literature 1]
Clabaugh, W.S., et al. work " is converted to the precipitation (Precipitation of Barium Titanyl Oxalate Tetrahydrate forConversion to Barium Titanate of High Purity) of the barium titanium oxalate tetrahydrate that high purity metatitanic acid barium uses " (Journal of Research of theNational Bureau of Standards), (U.S.), 1956, the 56th volume (Vol56), No. 5 (No.5), p.289-291.
But, the perovskite-type barium titanate powder made that uses the special method of opening clear 61-146710 communique record to obtain, in its manufacturing processed, in crystal, enter the chlorine of a great deal of, even therefore clean, also be difficult to make cl content fully to be reduced to below hundreds of ppm, and exist purity not enough, owing to clean, the fluctuation of composition also becomes big such problem easily.In addition, at Clabaugh, in the method that people such as W.S. propose, it is that the following fluctuation fine, particle diameter of 1 μ m is little that existence can not get median size, the Ba/Ti mol ratio be about 1 and also its fluctuation little, the problem that the perovskite-type barium titanate powder made of excellent in crystallinity is such.
Summary of the invention
Therefore, the object of the present invention is to provide a kind ofly, median size is that the following fluctuation fine, particle diameter of 1 μ m is little, the Ba/Ti mol ratio be about 1 and also its fluctuation little, high purity, the manufacture method of the perovskite-type barium titanate powder made of excellent in crystallinity.
The inventor, under such practical situation, that furthers investigate repeatedly found that, clean processing if will have the barium titanium oxalate of specified particle size characteristic, just can remove impurity such as chlorine easily, if the barium titanium oxalate that will clean again after handling carries out the case of wet attrition processing to specific particle diameter, calcine, just can access median size is that the following fluctuation fine, particle diameter of 1 μ m is little, the Ba/Ti mol ratio be about 1 and also its fluctuation little, high purity, the perovskite-type barium titanate powder made of excellent in crystallinity, thus finish the present invention.
That is, the invention provides a kind of manufacture method of perovskite-type barium titanate powder made, it is characterized in that having: first operation that washes the barium titanium oxalate of median size 50～300 μ m; After barium titanium oxalate after cleaning made slurry, carry out case of wet attrition and handle, obtain second operation of the barium titanium oxalate of median size 0.05～1 μ m; With, in the 3rd operation of the barium titanium oxalate of this median size of 700～1200 ℃ of temperature lower calcinations 0.05～1 μ m.
In addition, above-mentioned case of wet attrition is handled and is preferably carried out in organic solvent, and this organic solvent is more preferably ethanol.
Description of drawings
Fig. 1 is the synoptic diagram of the X-ray diffraction curve of a that uses in mathematical expression 1 of explanation and b.
Fig. 2 is near the X-ray diffractogram 2 θ=44～46 ° of the barium titanate that obtains in embodiment 1.
Fig. 3 is near the X-ray diffractogram 2 θ=44～46 ° of the barium titanate that obtains in comparative example 1.
Embodiment
[manufacture method of perovskite-type barium titanate powder made]
(first operation)
First operation of the manufacture method of perovskite-type barium titanate powder made of the present invention is the barium titanium oxalate (BaTiO (C that washes specified particle diameter
2O
4) 4H
2O), remove the operation that enters the impurity such as chlorine in this titanium oxyoxalate titanate particle.The barium titanium oxalate of Shi Yonging in the present invention, median size is 50～300 μ m normally, preferably 100～200 μ m.If median size is in this scope, then crystal grain is big, thereby when washing, and the wash-out of Ba and Ti is just few, and can remove impurity such as chlorine effectively, is best therefore.Moreover, the titanium oxyoxalate titanate particle is the sugared shape particle of gold rice, but in the present invention, the median size of so-called barium titanium oxalate, expression with maximum diameter observed with scanning electronic microscope (SEM), that comprise to the sugared shape particulate protrusion tip of gold rice portion as a sugared shape particle grain size of gold rice, for the addition mean value of a plurality of gold meter sugared these particle diameters of shape particulate.
If the median size of barium titanium oxalate is in above-mentioned scope, if wash, just make the content that enters the impurity such as chlorine in the titanium oxyoxalate titanate particle be reduced to hundreds of ppm levels easily, and resulting perovskite-type barium titanate powder made is when clean, the wash-out of Ba and Ti is few, it in 0.998～1.002 scope approximately is 1 that the Ba/Ti mol ratio becomes easily, is preferred therefore.
On the other hand, if the median size of barium titanium oxalate is less than 50 μ m, even wash, also be difficult to make the impurity such as chlorine that enter in the particle to be reduced to hundreds of ppm levels, and because the wash-out of Ba and Ti, so the Ba/Ti mol ratio of the perovskite barium titanate that obtains is difficult to become in 0.998～1.002 the scope, is worthless therefore.In addition, if median size surpasses 300 μ m, crush efficiency reduces, and in second operation described later, it is big that the fluctuation of the particle diameter after the case of wet attrition becomes easily, is worthless therefore.
In addition, the barium titanium oxalate that in first operation, uses, Ba/Ti mol ratio normally 0.998～1.002.If the Ba/Ti mol ratio of barium titanium oxalate is in this scope, the Ba/Ti mol ratio that just obtains resulting perovskite barium titanate is 0.998～1.002 to be approximately 1 perovskite barium titanate, is preferred therefore.
Employed water in cleaning does not pollute barium titanium oxalate with ion etc. and is as the criterion, therefore preferably ion exchanged water, pure water, ultrapure water etc.Have again, in order to improve clean effect, after beginning to clean, can be again clean with ion exchanged water etc. with process water etc.
Method of cleaning as in first operation has no particular limits, if but use pulp again etc. to clean, clean respond wellly, be preferred therefore.So-called pulp again is after giving up supernatant liquor, add the method that pure water is cleaned again.In addition, cleaning if the cl concn that contains in this barium titanium oxalate is fully cleaned to 500ppm, preferably below the 200ppm, just obtain highly purified perovskite-type barium titanate powder made easily, is preferred therefore.
After cleaning processing, carry out drying as requested, the barium titanium oxalate after obtaining cleaning.In the present invention, the rerum natura of the barium titanium oxalate after cleaning, median size is 50～300 μ m normally, preferably 100～200 μ m.In addition, the Ba/Ti mol ratio normally 0.998～1.002.And the barium titanium oxalate after cleaning, cl content is normally below the 500ppm, preferably below the 200pm.Moreover clean number of times is not limited to once, for the cl content of the barium titanium oxalate after cleaning becomes in the above-mentioned scope, also can carry out repeatedly repeatedly.
(second operation)
Second operation is after the barium titanium oxalate after cleaning in first operation is made slurry, to carry out case of wet attrition and handle, and obtaining median size is the operation of the barium titanium oxalate in the specified range.
As the solvent that in the modulation of above-mentioned slurry, uses, use is the inert solvent to barium titanium oxalate, for example can enumerate water, methyl alcohol, ethanol, propyl alcohol, butanols, toluene, dimethylbenzene, acetone, methylene dichloride, ethyl acetate, dimethyl formamide and Anaesthetie Ether etc.Wherein, if use the few solvent of wash-out of organic solvent such as methyl alcohol, ethanol, propyl alcohol, butanols, toluene, dimethylbenzene, acetone, methylene dichloride, ethyl acetate, dimethyl formamide and Anaesthetie Ether and Ba and Ti, just can access the high perovskite-type barium titanate powder made of crystallinity, be preferred therefore.Especially, if use ethanol, just can make the perovskite-type barium titanate powder made of excellent in crystallinity at the cold zone about 800～950 ℃ at an easy rate, be particularly preferred therefore.Above-mentioned solvent can use a kind of or be used in combination more than two kinds.
In second operation, at first modulation is starched.By in above-mentioned solvent, mixing the barium titanium oxalate after cleaning, disperse uniformly, and obtain slurry.The concentration of slurry so long as the degree of can case of wet attrition handling is just, has no particular limits, but 10～70 weight % normally, 30～50 weight % preferably, if this concentration, crush efficiency is just high.
Then, using this slurry to carry out case of wet attrition handles.As the method that case of wet attrition is handled, for example can enumerate this slurry of in the case of wet attrition device, packing into, carry out the method for pulverization process.As the case of wet attrition device, for example can enumerate ball mill, bead grinding machine etc.
Case of wet attrition is handled the median size proceed to the barium titanium oxalate of obtaining from scanning electronic microscope (SEM) becomes 0.05～1 μ m usually, preferably becomes 0.05～0.8 μ m.If median size is less than 0.05 μ m, pulverizing is difficult technically, and operates the difficulty that becomes, and is worthless therefore.In addition, if median size surpasses 1 μ m, the particle diameter fluctuation of resulting perovskite barium titanate becomes big easily, thereby is worthless.
As the material of the bead in the case of wet attrition device of packing into when the pulverization process, for example can enumerate zirconium white, aluminum oxide, silicon-dioxide, zeolite, silicon carbide, silicon nitride etc.Wherein because when case of wet attrition impurity sneak into few, so be best with the zirconium white.
The diameter of above-mentioned bead is 0.3～5mm normally, preferably 0.3～2mm.If diameter is that then crush efficiency is good in this scope, be preferred therefore.
After the case of wet attrition processing finishes, intactly dry resulting fine titanium oxyoxalate barium dust or slurry.Drying means is if can reclaim the method for solvent, just can reduce manufacturing cost, therefore be preferred, in addition, if use the spray-drier etc. of the slurry after can the dry wet type pulverization process of full dose to carry out, the wash-out composition is included in the titanium oxyoxalate barium dust again, is most preferred therefore.
Moreover, in the slurry after slurry before the case of wet attrition in second operation is handled or case of wet attrition are handled, also can add mixing as required and contain the minor component element compound.Mix the compound that contains the minor component element if add like this, just obtain roughly being evenly dispersed in the perovskite-type barium titanate powder made of the state solid solution of particle surface with the minor component element, for example can adjust this ceramic specific inductivity of making after the perovskite-type barium titanate powder made potteryization etc., be desirable therefore.
As containing the minor component element compound, for example can enumerate the compound that is selected from least a element among Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu rare earth element, Ba, Li, Bi, Zn, Mn, Al, Si, Ca, Sr, Co, Ni, Cr, Fe, Mg, Ti, V, Nb, Mo, W and the Sn.
Contain the minor component element compound and can be inorganics or organic any, for example can enumerate oxide compound, oxyhydroxide, muriate, nitrate, oxalate, carboxylate salt and the alkoxide etc. that contain above-mentioned element.Moreover, be to contain under the situation of compound of Si element containing the minor component element compound, except that above-mentioned oxide compound, also can use silicon sol or water glass etc.Have again, at the element that contains the minor component element compound is under the situation of metallic element, as containing the minor component element compound, if use alkoxide, just can access the perovskite-type barium titanate powder made that the minor component element is evenly dispersed in particle surface especially, be preferred therefore.The above-mentioned minor component element compound that contains can use a kind of or is used in combination more than two kinds.
Mix the method that contains the minor component element compound as adding in the slurry before case of wet attrition is handled, for example can enumerate: modulation in advance makes and contains the minor component element compound and be dissolved in the solution in the above-mentioned solvent or make and contain the minor component element compound and be dispersed in slurry in the above-mentioned solvent, this solution or slurry and case of wet attrition is handled the slurry blended method of preceding barium titanium oxalate; Directly add in the slurry of the barium titanium oxalate before case of wet attrition is handled and mix the method that contains the minor component element compound; Be blended in barium titanium oxalate after the cleaning that first operation obtains simultaneously, contain minor component element compound and above-mentioned solvent and the method for modulation slurry etc.In addition, mix the method that contains the minor component element compound as adding in the slurry of the barium titanium oxalate after case of wet attrition is handled, for example can enumerate: be modulated in advance and dissolve the solution that contains the minor component element compound in the above-mentioned solvent, the slurry blended method of the barium titanium oxalate after this solution and the case of wet attrition processing; Directly add in the slurry of the barium titanium oxalate after case of wet attrition is handled and mix the method that contains the minor component element compound.Wherein, the former method disperses to become easily, is preferred therefore.
The addition that contains the minor component element compound cooperates the dielectric characteristics as purpose, can at random set, but the cumulative amount of the element in containing the minor component element compound, and with respect to the barium titanium oxalate of 100 weight parts, 0.01～10 weight part normally for example.
(the 3rd operation)
The 3rd operation is the operation of the titanium oxyoxalate barium dust of median size 0.05～1 μ m that calcining obtains in above-mentioned second operation under specified temperature, through this operation, obtains perovskite-type barium titanate powder made.
Calcination condition, calcining temperature are 700～1200 ℃, preferably 800～1100 ℃.If the reason that calcining temperature is defined as in the above-mentioned scope is because less than 700 ℃, just be difficult to obtain monophasic perovskite-type barium titanate powder made, therefore be worthless, on the other hand, if above 1200 ℃, it is big that the fluctuation of particle diameter becomes easily, is worthless therefore.In addition, in the present invention, as required, calcination processing can be carried out several times.
After the calcining, suitably cool off, pulverize as required, just obtain perovskite-type barium titanate powder made.Moreover the pulverizing of carrying out as required is adapted at calcining the perovskite-type barium titanate powder made that obtains and is fragile bonded and carry out when block etc., but the particle of perovskite-type barium titanate powder made itself is to have following specific median size, the particle of BET specific surface area.
That is, the perovskite-type barium titanate powder made that obtains after the 3rd operation finishes is to be generally 0.05～1 μ m, to be preferably 0.05～0.8 μ m from the median size that scanning electronic microscope (SEM) is obtained, and the BET specific surface area is 1m
2/ g is above, be preferably 2～15m
2/ g, the powder that the fluctuation of particle diameter is few.And, except that above-mentioned rerum natura, be cl content be generally 500ppm following, be preferably below the 200ppm, and the mol ratio of Ba and Ti is 0.998～1.002 to be approximately the powder of 1 excellent in crystallinity.
The perovskite-type barium titanate powder made that obtains like this, as mentioned above, median size is fine to 0.05～1 μ m, and the poor highly purified powder of impurity such as chloride ion is that the fluctuation of particle diameter is little, the powder of excellent in crystallinity.
Perovskite-type barium titanate powder made of the present invention, for example for making laminated ceramic compacitor, be mixed together with Synergist S-421 95s such as present known additive, organic system binding agent, softening agent, dispersion agents and be dispersed in the suitable solvent, starch and form, be shaped by carrying out thin slice, just can access the ceramic sheet that in the manufacturing of laminated ceramic compacitor, uses.
For making laminated ceramic compacitor from this ceramic sheet, at first to stick with paste with conduction in the one side printing internal electrode formation of this ceramic sheet, after the drying, the above-mentioned ceramic sheet of lamination multi-disc by in the thickness direction crimping, forms layered product.Then, this layered product of heat treated takes off adhesive treatment, burns till then, obtains sintered body.Coating Ni paste, Ag paste, nickelalloy paste, copper paste, copper alloy paste etc. on this sintered compact if toast, just can obtain the lamination electrical condenser again.
In addition, for example in resins such as Resins, epoxy, vibrin, polyimide resin, cooperate perovskite-type barium titanate powder made of the present invention, if form resin flake, resin film, binding agent etc., just can be, be used to suppress same material, electrode ceramic circuit substrate, glass-ceramic circuit substrate and the use of circuit material around of the contraction difference of internal electrode and dielectric layer as the material of printing distributing board or multi-layer printed circuit board etc.
In addition, the resulting perovskite-type barium titanate powder made of the present invention, the employed catalyzer or the surface modifying material of giving the printing colorant of anti-static electrification, cleaning effect are used in the time of can being suitable as reaction such as exhaust removal, chemosynthesis.
Moreover the barium titanium oxalate that uses in first operation of perovskite-type barium titanate powder made manufacture method of the present invention for example can use the manufacture method of following barium titanium oxalate to make.
[manufacture method of barium titanium oxalate]
The B liquid that the A liquid that the dissolving titanium tetrachloride is formed with bariumchloride forms with dissolving oxalic acid in water contacts, carry out slaking after, by solid-liquid separation, just can be manufactured on the barium titanium oxalate of the specified particle size that uses in first operation.
The titanium tetrachloride that can use in the method, bariumchloride and oxalic acid, if can obtain, just have no particular limits, but, preferably use foreign matter content few in order to obtain highly purified barium titanium oxalate or perovskite-type barium titanate powder made. industrially
Operation at first, is modulated in the water dissolving titanium tetrachloride and bariumchloride and the A liquid that forms and dissolving oxalic acid and the B liquid that forms in water.A liquid is the aqueous solution that contains titanium tetrachloride and bariumchloride, but the dissolving of titanium tetrachloride and bariumchloride has no particular limits in proper order, can dissolve simultaneously, dissolves another again after also can dissolving one.
A liquid, the Ba in the bariumchloride is to the mol ratio (Ba/Ti) of the Ti in the titanium tetrachloride normally 1.0～1.5, and preferably 1.0～1.2, if such mol ratio, the Ba/Ti mol ratio of barium titanium oxalate just becomes 0.998～1.002 easily, is preferred therefore.
In addition, the concentration of the bariumchloride in the A liquid is converted into BaCl
2Concentration, 1～10 weight % normally, preferably 5～8 weight % if such concentration just obtains barium titanium oxalate with high yield, are preferred therefore.In addition, the concentration of the titanium tetrachloride in the A liquid is converted into TiCl
4Concentration, 1～10 weight % normally, preferably 5～8 weight % if such concentration just obtains barium titanium oxalate with high yield, are preferred therefore.
In addition, above-mentioned B liquid, the concentration of oxalic acid is 5～70 weight % normally, and preferably 10～40 weight % if such concentration just obtains barium titanium oxalate with high yield, are preferred therefore.
As the contact method of A liquid and B liquid, can enumerate the method for under A liquid stirs, adding the method for B liquid or under agitation in B liquid, adding A liquid.B liquid is to the addition of above-mentioned A liquid or the A liquid addition to B liquid, and (oxalic acid/Ti), add if become 2.1～2.3 ground usually just can obtain barium titanium oxalate with high yield, so be preferred the oxalic acid in the B liquid to the mol ratio of the Ti in the A liquid.In addition, stirring velocity shows that often mobile state is just passable so long as comprise from adding beginning to the slurry that reacts the barium titanium oxalate that generates during the end of a period, has no particular limits.
In the present invention, by or make to reaction system continuously or the interpolation time of interrupted A liquid of supplying with or B liquid elongated, or owing to improve and add temperature, it is big that the particle diameter of the barium titanium oxalate of generation just becomes easily.For this reason, in the present invention, contacting of this A liquid and B liquid, the interpolation temperature of the another kind of solution that in A liquid or B liquid, adds, normally 50～90 ℃, preferably 50～70 ℃, the interpolation time is more than 0.5 hour, preferably more than 1 hour, carry out continuously, if like this with certain speed, it approximately is 1 and the barium titanium oxalate of the little stay in grade that fluctuates that resulting barium titanium oxalate just becomes the Ba/Ti mol ratio, and, in slaking reaction described later, can obtain median size in the above-mentioned scope with the short period of time, be preferred therefore.Moreover the temperature of the another kind of solution that adds in A liquid or B has no particular limits, if but in the scope identical with above-mentioned interpolation temperature, operation just becomes easily, and be preferred therefore.
After the contacting of A liquid and B liquid ended, carry out slaking reaction.If carry out this slaking reaction, grain growth along with the barium titanium oxalate that promotes to be generated, and finish reaction, the little barium titanium oxalate of fluctuation that therefore to access the median size, the Ba/Ti mol ratio that have in the above-mentioned scope be 0.998～1.002, form.
Slaking condition, curing temperature be normally more than 50 ℃, and 50～90 ℃ temperature is preferably carried out more than 0.5 hour, preferred slaking reaction more than 1 hour.Moreover, all temperature of mixture after so-called curing temperature is meant A liquid and B liquid contacts.After slaking finishes, use ordinary method to carry out solid-liquid separation, obtain median size normally 50～300 μ m, the barium titanium oxalate of 100～200 μ m preferably.
The manufacture method of above-mentioned barium titanium oxalate, for example the median size that can use in first operation of above-mentioned perovskite-type barium titanate powder made manufacture method is to use in the modulation of barium titanium oxalate of 50～300 μ m.
[embodiment]
Below, illustrate in greater detail the present invention by embodiment, but the present invention is not subjected to the restriction of these embodiment.
Embodiment 1
(manufacturing process of barium titanium oxalate)
Be modulated at the mixing solutions that dissolves 600g (2.456mol) bariumchloride two water salt and 444g (2.342mol) titanium tetrachloride in the 4100ml water, with this as A liquid.Then, be modulated at the oxalic acid aqueous solution of dissolving 620g oxalic acid in 70 ℃ of warm water of 1500ml, with this as B liquid.Make B liquid remain on 70 ℃ on one side, Yi Bian, stir under 1 hour at 70 ℃ again and carry out slaking under agitation with the 120 fens B liquid that drips among the clockwise A.After the cooling, filter, reclaim barium titanium oxalate.Physics value at resulting barium titanium oxalate shown in the table 1.Obtain median size according to scanning electronic microscope (SEM) photo.
Table 1
| The physics value of barium titanium oxalate | |
| Median size | ????120μm |
(first operation)
With 4.5 liters of distilled water the barium titanium oxalate that reclaims is carried out three pulps again, carefully clean.Then, under 105 ℃, carry out drying, obtain the 1000g barium titanium oxalate.Physics value at resulting barium titanium oxalate shown in the table 2.
Value based on x-ray fluorescence analysis calculates the Ba/Ti mol ratio.In addition, obtain median size according to scanning electronic microscope (SEM) photo.Use the ion-chromatographic determination chlorine ion concentration.
Table 2
| The physics value of barium titanium oxalate | |
| The Ba/Ti mol ratio | ????1.000 |
| Median size | ????120μm |
| Cl content | ????100ppm |
(second operation)
Pack in the ball mill of capacity 700ml adding slurry that 60g synthetic barium titanium oxalate and 140ml ethanol in first operation forms,, carry out case of wet attrition and handle to the 5mm zirconia ball of wherein putting into 1070g.Follow the slurry after 105 ℃ of dry wet type pulverization process of following full dose, obtaining median size is the barium titanium oxalate of 0.7 μ m.
(the 3rd operation)
With 10g at barium titanium oxalate sample that second operation obtains carrying out 4 hours calcination processing under the atmosphere, under 900 ℃, obtain the barium titanate sample.
Obtain Ba/Ti mol ratio, BET specific surface area, degree of crystallinity, the median size of resulting barium titanate sample, the fluctuation and the cl content of particle diameter.The results are shown in table 3 and the table 4.In addition, the X-ray diffractogram of barium titanate shown in Figure 2.
Have again, calculate the Ba/Ti mol ratio based on the x-ray fluorescence analysis value.In addition, use Cu-K α line as gamma ray source, (Japanese Off イ リ Star プ ス Co., Ltd. system, model is that X ' PartMPD) measures the barium titanate sample, obtains degree of crystallinity according to following calculating formula to utilize the X-ray diffraction device.Degree of crystallinity, the value that obtains is big more, and the expression crystallinity is good more.In Fig. 1, be shown schematically in a in the following formula and the method for obtaining of b.
Degree of crystallinity=a/b
Near (the intensity of the diffraction peak c of lattice plane (200) face a:2 θ=45.38 °.The intensity of the e of paddy portion between near the diffraction peak d of lattice plane (002) face b:2 θ=44.86 ° and the diffraction peak c of above-mentioned lattice plane (200) face).Utilize the machinery conversion means of X-ray diffraction device to obtain diffraction peak c, diffraction peak d and the e of paddy portion.
When carrying out the electron microscope observation sample with 20000 times of multiplying powers, the standard deviation when measuring 200 above particle grain size of arbitrary extracting is estimated the fluctuation of particle diameter.The little person of this standard deviation represents that the fluctuation of particle diameter is few.In addition, utilize the cl content of ion-chromatographic determination barium titanate.
Embodiment 2 and 3
In the 3rd operation, except the calcining temperature of barium titanium oxalate sample is defined as 920 ℃ (embodiment 2) or 940 ℃ (embodiment 3), make in the same manner with embodiment 1, obtain the barium titanate sample, obtain the fluctuation and the cl content of Ba/Ti mol ratio, BET specific surface area, degree of crystallinity, median size, particle diameter.The results are shown in table 3 and the table 4.
Comparative example 1
(manufacturing process of barium titanium oxalate and first operation)
Implement the manufacturing process and first operation of barium titanium oxalate in the same manner with embodiment 1, obtain the barium titanium oxalate sample of rerum natura shown in the 1000g table 2.
(operation after first operation)
This barium titanium oxalate sample of 200g carrying out 4 hours calcination processing under the atmosphere, under 900 ℃, is obtained the barium titanate sample.
Then, in the ball mill of capacity 700ml, add resulting barium titanate sample of 60g and 140ml ethanol formation slurry,, carry out case of wet attrition and handle to the 5mm zirconia ball of wherein putting into 1070g.Then the slurry after 105 ℃ of dry wet type pulverization process of following full dose obtains the barium titanate sample.
About resulting barium titanate sample, obtain the fluctuation and the cl content of Ba/Ti mol ratio, BET specific surface area, degree of crystallinity, median size, particle diameter with the gimmick identical with embodiment 1.The results are shown in table 3 and the table 4.In addition, the X-ray diffractogram of resulting barium titanate shown in Figure 2.
Comparative example 2～4
In the operation after first operation, except the calcining temperature with the barium titanium oxalate sample is defined as 920 ℃ (comparative examples 2), 940 ℃ (comparative example 3) or 1000 ℃ (comparative example 4), make in the same manner with comparative example 1, obtain the barium titanate sample, obtain the fluctuation and the cl content of Ba/Ti mol ratio, BET specific surface area, degree of crystallinity, median size, particle diameter.The results are shown in table 3 and the table 4.
Table 3
| Calcining temperature (℃) | The Ba/Ti mol ratio | BET specific surface area (m 2/g) | Degree of crystallinity | |
| Embodiment 1 | ???900 | ????1.000 | ??????5.7 | ????2.4 |
| Embodiment 2 | ???920 | ????1.000 | ??????4.6 | ????3.2 |
| Embodiment 3 | ???940 | ????1.000 | ??????3.6 | ????4.2 |
| Comparative example 1 | ???900 | ????1.000 | ??????5.4 | ????- |
| Comparative example 2 | ???920 | ????1.000 | ??????4.5 | ????- |
| Comparative example 3 | ???940 | ????1.000 | ??????4.3 | ????- |
| Comparative example 4 | ???1000 | ????1.000 | ??????4.1 | ????0.5 |
Table 4
| Median size (μ m) | The fluctuation standard deviation of particle diameter | Cl content (ppm) | |
| Embodiment 1 | ???0.39 | ????0.12 | ????85 |
| Embodiment 2 | ???0.43 | ????0.13 | ????84 |
| Embodiment 3 | ???0.48 | ????0.11 | ????81 |
| Comparative example 1 | ???0.44 | ????0.25 | ????89 |
| Comparative example 2 | ???0.48 | ????0.26 | ????87 |
| Comparative example 3 | ???0.53 | ????0.24 | ????85 |
| Comparative example 4 | ???0.60 | ????0.25 | ????81 |
Result according to table 3 and table 4 knows the following fact.That is, by embodiment 1～3 as can be known, the barium titanate that utilizes manufacture method of the present invention to obtain is the following subparticle of particle diameter 1 μ m, high purity, and crystallinity is good, and the fluctuation of particle diameter is few.In addition, by comparative example 1～4 as can be known, do not carrying out under the situation of second operation of the present invention,, just can not get the good barium titanate of crystallinity if do not carry out heat treated at the high temperature more than 1000 ℃.In addition, by comparative example 1～4 as can be known, do not carrying out under the situation of second operation of the present invention; even after calcining, carry out pulverization process; because coarse particles or subparticle are many, thus in barium titanate the also skeleton of residual barium titanium oxalate, in addition; even carry out pulverization process; because coarse particles or subparticle are many, so the fluctuation of particle diameter is also big, in addition; do not detect near 2 θ=44.86 ° 002 diffraction peak with X-ray diffraction analysis, crystallinity is poor.
Embodiment 4
(manufacturing process of barium titanium oxalate and first operation)
Implement the manufacturing process and first operation of barium titanium oxalate in the same manner with embodiment 1, obtain the barium titanium oxalate sample of rerum natura shown in the 1000g table 2.
(second operation)
In the ball mill of capacity 700ml, add 140ml ethanol and butanols yttrium, the add-on of this butanols yttrium, with respect to the barium titanate that generates, being converted into yttrium oxide is 1 weight %.Then, in ball mill, be placed in the 5mm zirconia ball of synthetic 60g barium titanium oxalate and 1070g in first operation, carry out case of wet attrition and handle.
Then, the slurry after 105 ℃ of dry wet type pulverization process of following full dose, obtaining in median size is the barium titanium oxalate of the surface attachment yttrium of 0.7 μ m.
(the 3rd operation)
10g is carried out 4 hours calcination processing at the barium titanium oxalate of surface attachment yttrium under the atmosphere, under 1100 ℃, obtaining the barium titanate sample of yttrium oxide solid solution.
For this barium titanate sample, use the method identical to obtain fluctuation, cl content and the yttrium content of Ba/Ti mol ratio, BET specific surface area, degree of crystallinity, median size, particle diameter with embodiment 1.Utilize ICP (inductively coupled plasma) analytical method to obtain the amount of Y in addition.The results are shown in the table 5.
Embodiment 5
(front travel and first operation)
Implement the front travel and first operation in the same manner with embodiment 1, obtain the barium titanium oxalate sample of rerum natura shown in the 1000g table 2.
(second operation)
In the ball mill of capacity 700ml, put into the 5mm zirconia ball of barium titanium oxalate sample, 0.6g yttrium oxide (median size 0.1 μ m), 140ml ethanol and 1070g that 60g obtains in first operation, carry out case of wet attrition and handle.Then, the slurry after 105 ℃ of dry wet type pulverization process of following full dose obtains the mixture that yttrium oxide and median size are the barium titanium oxalate of 0.7 μ m.
(the 3rd operation)
Then, the mixture with resulting yttrium oxide and barium titanium oxalate is carrying out 4 hours calcination processing under the atmosphere, under 1100 ℃.Obtain barium titanate sample at the surface attachment yttrium oxide.
For this barium titanate sample, use the method identical to obtain fluctuation, cl content and the yttrium content of Ba/Ti mol ratio, BET specific surface area, degree of crystallinity, median size, particle diameter with embodiment 1.Utilize ICP (inductively coupled plasma) analytical method to obtain the amount of Y in addition.The results are shown in the table 5.
Table 5
| Embodiment 4 | Embodiment 5 | |
| The Ba/Ti mol ratio | ????1.000 | ????1.000 |
| ??Y 2O 3Content (weight %) | ????0.98 | ????1.01 |
| Cl content (ppm) | ????87 | ????83 |
| BET specific surface area (m 2/g) | ????4.4 | ????4.0 |
| Median size (μ m) | ????0.41 | ????0.58 |
| The standard deviation of particle diameter | ????0.08 | ????0.13 |
| Degree of crystallinity | ????5.3 | ????4.8 |
For the barium titanate sample that contains the yttrium that embodiment 4 and embodiment 5 obtain, the result who uses SEM-EDX (NEC society system) to carry out the drawing of yttrium, embodiment 4 and embodiment 5 do not see the segregation of yttrium, be evenly dispersed in powder surface, but embodiment 4 one sides and embodiment 5 compare as can be known, and yttrium disperses more equably.
The effect of invention
Manufacture method according to perovskite-type barium titanate powder made of the present invention, can make average grain diameter is that the following fluctuation fine, particle diameter of 1 μ m is little, the Ba/Ti mol ratio approximately be 1 and also its fluctuation little, high-purity, the perovskite-type barium titanate powder made of excellent in crystallinity.
Claims (5)
1. the manufacture method of a perovskite-type barium titanate powder made is characterized in that, has: washing median size is first operation of the barium titanium oxalate of 50～300 μ m; After barium titanium oxalate after this is cleaned is made slurry, carry out case of wet attrition and handle, obtaining median size is second operation of the barium titanium oxalate of 0.05～1 μ m; With, be that the barium titanium oxalate of 0.05～1 μ m carries out incinerating the 3rd operation with this median size under 700～1200 ℃.
2. the manufacture method of perovskite-type barium titanate powder made according to claim 1, it is characterized in that, described median size be the barium titanium oxalate of 50～300 μ m be make in water the dissolving titanium tetrachloride contact at 50～90 ℃ with the formed B liquid of dissolving oxalic acid in water with the formed A liquid of bariumchloride, carry out more than 0.5 hour after the slaking at 50～90 ℃, to carry out solid-liquid separation resulting.
3. the manufacture method of perovskite-type barium titanate powder made according to claim 1 and 2 is characterized in that, the solvent of described slurry is an organic solvent.
4. the manufacture method of perovskite-type barium titanate powder made according to claim 3 is characterized in that, described organic solvent is an ethanol.
5. according to the manufacture method of each described perovskite-type barium titanate powder made in the claim 1～4, it is characterized in that, in the slurry after slurry before case of wet attrition in second operation is handled or case of wet attrition are handled, add mixing and contain the minor component element compound, this contains the minor component element compound is the compound that is selected from least a element among rare earth element, Ba, Li, Bi, Zn, Mn, Al, Si, Ca, Sr, Co, Ni, Cr, Fe, Mg, Ti, V, Nb, Mo, W and the Sn.
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| JP2002288673A JP4759211B2 (en) | 2002-10-01 | 2002-10-01 | Method for producing perovskite-type barium titanate powder |
| JP2002288673 | 2002-10-01 |
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| JPS61146710A (en) * | 1984-12-19 | 1986-07-04 | Central Glass Co Ltd | Production of fine barium titanate particle of high purity |
| DE3635532A1 (en) * | 1986-10-18 | 1988-04-28 | Philips Patentverwaltung | METHOD FOR PRODUCING BARIUM TITANATE BATIO (DOWN ARROW) 3 (DOWN ARROW) |
| JPS63218512A (en) * | 1987-03-05 | 1988-09-12 | Sekisui Plastics Co Ltd | Production of tabular particle of metal titanate |
| JPH08236818A (en) * | 1995-03-01 | 1996-09-13 | Denki Kagaku Kogyo Kk | Thermoelectric material |
| TW527321B (en) * | 2000-08-09 | 2003-04-11 | Samsung Electro Mech | A method for producing barium titanate based powders by oxalate process |
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| JP4759211B2 (en) | 2011-08-31 |
| CN100484879C (en) | 2009-05-06 |
| JP2004123431A (en) | 2004-04-22 |
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