CN87104006A - Barium titanate coforms - Google Patents

Barium titanate coforms Download PDF

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CN87104006A
CN87104006A CN87104006.9A CN87104006A CN87104006A CN 87104006 A CN87104006 A CN 87104006A CN 87104006 A CN87104006 A CN 87104006A CN 87104006 A CN87104006 A CN 87104006A
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barium titanate
complex body
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CN1017421B (en
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詹米尔·门纳希
罗伯特·C·里德
劳伦斯·P·瓦格纳
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Cabot Corp
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Abstract

General formula is Ba (1-x-x '-x ")Pb xCa X 'Sr X "Ti (1-y-y '-y ")Sn yZr Y 'Hf Y "O 3The dielectric composition of barium titanate substrate, wherein X, X ', X " with Y, Y ', Y " represent the molar fraction of divalence and quadrivalent cation, and each leisure is greater than zero, less than value independently in 0.3 the scope, make (X+X '+X ") adds and is worth and (Y+Y '+Y ") adds and be worth and all be no more than 0.4.No matter choose which kind of specific composition, the mean size of complex body primary particle of the present invention is all in the scope of 0.05 to 0.4 μ m, and Unusually narrow particle size distribution.Product is dispersible.Divalence is 1.000 ± 0.015 to the mol ratio of quadrivalent cation in this complex body.

Description

The invention relates to the dielectric composition of barium titanate substrate, exactly about becoming the barium titanate or the complex body of stoichiometric ratio, dispersible, submicron particles, its size-grade distribution is very narrow.
The specific inductivity of barium titanate and physical strength are all very high, and this makes it become the material that is specially adapted to make electrical condenser and other electron component.Noticeable especially is can be with generating mixed crystal and the adulterated method electrical properties at the scope inner control barium titanate of broad.
Barium titanate presents very simple cubic perovskite type structure, and this is many kinds of ABO 3The high temperature crystal formation of type mixed oxide.This crystalline structure is a regular octahedron array that is made of shared oxygen on the angle, and wherein less titanium (IV) positively charged ion of volume occupies octahedral central position B, and barium (II) positively charged ion is filled out place, brilliant crack, those bigger 12-coordinate A positions between octahedron.Such crystalline structure has special importance, and this is because it can allow several positively charged ions replace on position A and B, thereby can make the more complicated FE compound of many kinds easily.
The lattice structure that barium titanate is fairly simple is characterized in TiO 6-octahedron, because their polarizability height, so in fact just determined the dielectric properties of this structure.The polarizability height is because the little Ti(IV of volume) ion occupied bigger comparatively speaking space in oxygen octahedra.Yet, this cubic units structure cell can only be about be only more than 130 ℃ the Curie-point temperature stable.Below 130 ℃, Ti(IV) the position deviation center that occupies of ion.This change that departs from the central position causes crystalline structure to become tetragonal system between 5 ℃ and 130 ℃, becomes rhombic system at 5 ℃ between-90 ℃, becomes trigonal system at last when temperature is lower than-90 ℃.Self-evident, be accompanied by such temperature variation and changes of crystal, specific inductivity and intensity also all descend thereupon.
The specific inductivity and the temperature of barium titanate ceramics are relative, and near Curie temperature or its, specific inductivity has a tangible maximum value.Because lower, the pure BaTiO of specific inductivity when relation that specific inductivity and temperature are such and room temperature 3Seldom be used for the manufacturing of commercial dielectric composition.Therefore, in fact to adopt additive to improve the dielectric properties of barium titanate.For example, technically know: if with strontium with (or) calcium partly replaces barium, and with zirconium and (or) tin partly replaces titanium, then Curie temperature can be moved on to lower temperature and widen its scope, thereby make that the specific inductivity of material just reaches maximum value 10000 to 15000 under the room temperature.On the contrary, come part to replace barium, Curie temperature is raise with plumbous (II).In addition, with a little volume is suitable and valence state is different from other metal ion of barium, titanium replaces, can cause dielectric properties wide variation in essence, its summary can fly (Jaffee), the little Cork (Cook of W.R. approximately referring to B., Jr.) and H. fly " piezoelectric ceramics " book (U.S. Science Press that (Jaffe) shown approximately, New York, 1971).
In industrial practice, the production of barium titanate substrate dielectric medium powder can be that needed pure titanate, zirconate, stannate and adulterating agent are mixed and made into, or the uniform mixture of the precursor compound (for example carbonate, oxyhydroxide or nitrate) of oxide compound such as the barium of suitable stoichiometric ratio consumption, calcium, titanium or oxide compound is directly made the dielectric medium powder that needs by high temperature solid state reaction.Pure titanate, zirconate and stannate etc. are also all produced with high-temperature solid phase reaction method in general.In these roasting process, with need with the reactant wet-milling make uniform mixture.With the slurry dried that obtains and at high temperature, be about 700 ℃ to 1200 ℃, desired solid state reaction is finished in roasting.After this, calcining matter obtains making the dispersible powders that green thing piece will be used through grinding again.
Though the barium titanate substrate dielectric medium prescription of producing with solid state reaction is an acceptable for many electric purposes in fact, they have some shortcomings.At first, grinding step is the source of electric property being caused the impurity of undesirable action.The inhomogeneous meeting of forming on the microcosmic causes that generation do not wish the phase that occurs, titanic hydroxide barium for example, and it can cause the susceptibility of performance to humidity.Moreover, particle can take place during the roasting increase agglomerating phenomenon between a lot of and the particle.As a result, to be that size-grade distribution is wide reach the particle aggregate in irregular shape up to about 10 μ m from 0.2 μ m to the product of wearing into.The result of study of having delivered shows that the green thing piece with the poly-even particle powder of this broad particle distribution is made needs higher sintering temperature, and the size-grade distribution of the sintered compact of making is broad also.Yet, producing complicated dielectric medium thing piece, during as the one chip multi-layer capacitor, adopt lower sintering temperature than very big economic benefit being arranged with higher sintering temperature, reason is the reduction owing to sintering temperature, can improve the percentage composition of the silver that price is cheaper in silver-palladium electrode.
Technically know that the electrical capacity of dielectric layer is inversely proportional to its thickness.In present multi-layer capacitor, medium thickness is in the magnitude of 25 μ m.Though such thickness is wished very much can attenuate be a little greatly again, does not accomplish that reason is that along with the attenuate of medium thickness, the number of the fault on the dielectric film (as pinprick etc.) can increase.These faults can play bad influence to the performance of electrical condenser.A main source of these faults be exist the thickness difference of granularity and film not many not broken from the poly-particle that connects.Because this poly-existence that connects particle is arranged, shrink during sintering inhomogeneous, so pinprick occurs.Thereby, adopt the dielectric medium prescription of the barium titanate substrate of solid reaction process generation can increase the total manufacturing cost of one chip multi-layer capacitor greatly.
In view of the limitation of the product made from traditional solid reaction process, prior art has been developed several other methods and has been produced barium titanate.These methods comprise, the thermal decomposition method of titanous oxalate acyl barium and citric acid titanium acyl barium and being dissolved in alcoholic acid dealing with alcohol barium and dealing with alcohol titanium or water-soluble barium lactate and lactic acid titanium solution carry out high temperature oxidation under atomizing state method.In addition, barium titanate also can be made from fused salt, makes with being dissolved in barium in the ethanol and titanium and hydrolysis of alkoxide method, and also useful hydrated barta and titanium dioxide react by hydrothermal method and the reaction in water prepares.Because wherein the product that obtains of some method on particle shape, approach desirable here, so prior art attempts to use the method identical with producing pure barium titanate to produce the composition of barium titanate substrate.For example, " the Citrate trianion coprecipitation method prepares BaTiO to B.J. Gadamer moral (Mulder) in the alcohol being entitled as 3With other ceramic powder " (Ceramic Bulletin, 49 the volume, o. 11th, 990-993 page or leaf, 1970) article in disclose and can prepare BaTiO with coprecipitation method 3The composition of matrix or complex body.This method is the Ti(IV), the Zr(IV) and the Citrate trianion and the Ba(II of (or) Sn(IV)), the Mg(II), the Ca(II), the Sr(II) and the aqueous solution of the formate of (or) Pb(II) spray into and make it to take place co-precipitation in the alcohol.To be deposited in and use N 2Make it to decompose in 700-800 ℃ of following roasting in the airflow of gas dilution, obtain mean particle size at the spherical or strip particle of 3 μ m to 10 μ m.
Gallacher people such as (Gallagher) is entitled as " chemical process prepares the semi-conductor titanate " (J.Amer.Ceramic at one piece, Soc., 46 volumes, the 8th phase, the 359-365 page or leaf, 1963) article in disclose with the titanous oxalate acyl of basic metal and (or) Pb(II) and (or) mixing salt of oxalic acid zirconium acyl is precipitated out, the method for calcination then, made the barium titanate substrate complex body.These workers have confirmed to make so class BaTiO 3Substrate composition, Ba has wherein been replaced the 0-50%(mole by Sr or Pb), Ti(IV wherein) by the Zr(IV) replaced the 0-20%(mole).
Fa Kesang people such as (Faxon) discloses a kind of synthetic BaTiO on No. the 3637531st, United States Patent (USP) 3The method of substrate complex, this is to contain the solution heating of inner complex or the alkoxide of titanium, a kind of alkaline earth salt and a kind of lanthanide metal salt of titanium, to obtain the semi-solid material.Then, with this material roasting, make desired titanate complex body.
But, in the document of every kind of above-mentioned prior art, all to come the synthesis of barium titanate substrate complex with roasting.Owing to said, what this step warming temperature generated is the poly-product that connects, and it will become the less poly-even particle particle of granularity after grinding, and its size-grade distribution is very wide.
Prior art was also once attempted to overcome traditional method and make BaTiO by the synthetic a kind of blended titanates of alkali-earth metals of fused salt reaction-zirconate composition 3The shortcoming of powder.This method is published in No. the 4293534th, United States Patent (USP) investing A Lante (Arendt).This method is actually, and with titanium dioxide or zirconium dioxide or its mixture and barium oxide, strontium oxide or its mixture, mixes with alkali metal hydroxide again, and being heated to is enough to make oxyhydroxide flux fused temperature.Reactant is dissolved in the fused flux, is Ba with the titanate of alkaline-earth metal, zirconate or with the general formula again xSr (1-x)Ti yZr (1-y)O 3The sosoloid form precipitate.It chemically is homogeneous that product has, and the monodispersity and the submicron order crystalline characteristics of certain degree are arranged.But, the limitation of this method be it can only make contain Sr and (or) complex body of Zr.
The report of producing complex body with hydrothermal method was also once arranged.In No. the 715762nd, English Patent, Bo Erduqi (Balduzzi) and Shi Taineiman (Steinemann) report are with hydration TiO 2And or the aqueous slurry of the alkaline earth metal hydroxides of stoichiometric ratio consumption is heated to the temperature between 200 ℃ to 400 ℃, generation blended titanates of alkali-earth metals.Though claiming, this patent can make particle requires granularity arbitrarily under about 100 μ m product, but except the complex body that contains strontium, it still is doubt whether making the product with particle shape characteristic of the present invention.The fact of this view basis is, Ba(OH) 2In aqueous media solubility, and Ca(OH) 2And Mg(OH) 2Be insoluble more in fact, especially Ba(OH arranged) 2Under the situation about existing.Therefore, under the situation that contains the Ca complex body, have been found that under the experiment condition of Bo Erduqi and Shi Taineiman, in being heated to 200-400 ℃ process, at first generated BaTiO 3, Ca(OH then) 2Generate CaTiO with the unreacted titanium dioxide reaction of remainder 3
The people such as (Matsushita) of Panasonic confirms in No. the 34306926.1st, european patent application, the dilute slurry of hydrous titanium oxide when the temperature that is heated to 110 ℃ can and Ba(OH) 2(or) Sr(OH) 2Reaction generates BaTiO 3Or contain the complex body of Sr.The characteristic of these complex bodys on particle shape and of the present invention similar.This method still is only limited to and produces the complex body that contains Sr.
Ah portion people such as (Abe) is at " the easy agglomerating BaTiO that is entitled as of Zuo Hai (Sakai) chemical industrial company publication 3Powder " in the literary composition, disclosing a kind of hydrothermal method, to be used for synthetic general formula be BaTi (1-x)Sn xO 3The barium titanate substrate complex body.This method is that handle is by SnOCl 2And TiCl 4The 0.6MTi that aqueous solution neutralization makes (1-x)Sn xO 2Pulpous state liquid and 0.9MBa(OH) 2Mix, under 200 ℃, carried out hydrothermal treatment consists at least 5 hours again.Though people such as Ah portion specifically are not illustrated, have hinted and will be heated to certain temperature to slurries.Though do not mention the particle shape of complex body, the BaTiO that makes with identical method 3The specific surface of product is 11m 2/ g, granularity is 0.1 μ m, and is dispersible.May, contain the Sn complex body and have similar particle shape with the present invention.But, people's such as Ah portion limitation is, only having said can be the Sn(IV) be synthesized in the barium titanate complex body and go.Perhaps, it has enlightened available other quadrivalent cation, for example Zr(IV similarly), perhaps also can use divalence Sr(II) because Sr(OH) 2With Ba(OH) 2Equally solubleness is higher in aqueous media.Yet people's such as Ah portion method can not be used for the replacement of Curie-point temperature divalence displacement body (divalentshifter), and for example pb and Ca are to the replacement of divalence Ba.
Thereby, prior art can not be produced any such barium titanate complex body, wherein contain calcium and (or) plumbous or multiple divalence and quaternary positively charged ion substituent, and be into stoichiometric ratio, its particle is dispersible sphere and the narrow sub-micron grade particle of size-grade distribution.
It is dispersible to the present invention relates to many kinds, be spheric basically, become stoichiometric ratio with submicron order and the narrow barium titanate complex body of size-grade distribution.The most important thing is, barium titanate substrate dielectric composition of the present invention comprised divalence barium by divalence plumbous and (or) those complex bodys of partly replacing of divalent calcium, comprised equally also that wherein divalence barium is partly replaced by plumbous, calcium and strontium, and those complex bodys of partly being replaced by tin, zirconium and hafnium of titanic.
In an important embodiment of the present invention, the barium titanate substrate complex body can be used Formula B a (1-x '-x '-x ")Pb xCa X 'Sr X "Ti (1-y-y '-y ")Sn yZr Y 'Hf Y "O 3Represent, wherein x, x ' and x " represent the molar fraction of divalent cation; they are value in 0 to 0.3 scope independently; x+x '+x " and add and numerical value in 0 to 0.4 scope, simultaneously y, y ' and y " represent the molar fraction of quadrivalent cation; value in 0 to 0.3 scope independently, y+y '+y " and add and numerical value in 0 to 0.4 scope.
Among another important embodiment of the present invention, the barium titanate substrate complex body can be used Formula B a (1-x ')Ca X 'Ti (1-y-y '-y ")Sn yZr Y 'Hf Y "O 3Represent that wherein divalence barium positively charged ion is replaced by calcium partially.Among the another important embodiment of the present invention, barium titanate dielectric medium mixture is to use Formula B a (1-x)Pb xTi (1-y-y '-y ")Sn yZr Y 'Hf Y "O 3Expression, wherein replace divalence barium with lead.In the several embodiment in back, the numerical value of the independently molar fraction x of each embodiment, x ', x " and y, y ', y " is Ba with above-mentioned more complicated general formula all (1-x-x '-x ")Pb xCa X 'Sr X "Ti (1-y-y '-y ")Sn yZr Y 'H Y "O 3Complex body in the numerical value unanimity.
Regardless of the Chemical Composition of complex body, each barium titanate substrate complex body all has identical unique chemistry and physical properties among the present invention.The dielectric medium prescription of barium titanate substrate is by stoichiometric ratio, that is, making divalence in the complex body of heterogeneity is 1.000 ± 0.015 to the mol ratio of quadrivalent cation, and it is irrelevant with the species number and the molar percentage of any divalence and quadrivalent cation substituent.Also can make composition not according to stoichiometric ratio, wherein in the heterogeneity complex body divalence to the mol ratio of quadrivalent cation in 0.9 to 1.1 scope.The mean size of the primary particle of this barium titanate substrate complex body is in 0.05 to 0.4 mu m range.In addition, the numerical value of the mean particle size that records with image analytical method and the numerical difference between of the mean particle size that settling process records are few, and this shows that these complex bodys are dispersible.Four fens (quartile) ratios of complex body size distribution curve are less than or equal to 1.5, and this shows the Unusually narrow particle size distribution of this barium titanate substrate complex body.Another important fact is, any dispersible, submicron order barium titanate substrate dielectric composition of the present invention can make with common one step hydro thermal method operation.
Therefore, main purpose of the present invention is that a kind of dispersible, submicron order barium titanate complex body that size-grade distribution is narrow will be provided.
Another object of the present invention is that this class BaTiO of many various compositions is provided 3Substrate complex, the controlled amount of its primary particle built in 0.05 μ m up to about 0.4 μ m.
Another object of the present invention is, provide multiple can just can the synthetic complex body with general one step hydro thermal method operation.
A further object of the invention is, provide a kind of do not contain by grind the impurity introduced, composition is the barium titanate substrate complex body of stoichiometric ratio.
A further object of the invention is, a kind of barium titanate complex body is provided, and wherein contains multiple additives, Curie-point temperature is displaced to and (or) be widened to specified temperature range, and the dielectric properties that makes generation weakens the dependence of temperature.
Another object of the present invention is that the BaTiO of dispersibility is provided 3The dielectric composition of matrix, can be used for making very thin thickness and in fact do not have a fault dielectric layer.
The present invention also and then a purpose is arranged provides a kind of dielectric medium prescription of barium titanate substrate, and it can evenly sinter to the density that reaches higher being significantly less than under the temperature commonly used.
The details of each side of the present invention and advantage will award introduction in conjunction with the accompanying drawings, wherein:
Fig. 1 be a kind of composition of the present invention by stoichiometric ratio, the transmission electron micrograph of 50000 times of amplifications dispersibility, submicron order complex composite body, it has following general formula: Ba 0.856Pb 0.097Ca 0.074Ti 0.830Zr 0.099Sn 0.071O 3; Also have,
Fig. 2 is 50000 times of transmission electron micrographs of a pure barium titanate powder, and its particle shape is similar to the particle shape of Fig. 1 complex composite body in fact.
Here begin earlier the present invention is done the introduction of summarizing most, then do more detailed narration. The embodiment that the present invention recommends is that a kind of general formula is
Ba （1-x-x′-x″）Pb xCa x′Sr x″Ti （1-y-y′-y″）Sn yZr y′Hf y″O 3Complex, wherein " represent the molar fraction of bivalent cation, they are value in 0 to 0.3 scope independently, and from 0 to 0.2 interior value is then better for x, x ' and x; X+x '+x " add and numerical value be value in from 0 to 0.4 scope, from 0 to 0.3 is better; Y, y ' and y " represent the molar fraction of quadrivalent cation, value in 0 to 0.3 scope independently, from 0 to 0.25 is better; Y+y '+y " add and numerical value be value in from 0 to 0.4 scope, from 0 to 0.3 is better.
When (x+x '+x ") adds and is worth and (y+y '+y ") adds and be worth all null the time, and then complex is exactly simple barium titanate powder. When x=x "=y=y '=y "=0 and x ' greater than zero the time, the product that then generates is exactly so a kind of barium titanate substrate complex, its BaTiO3In the Ba(II of x ' molar fraction) by the Ca(II) and replace, the product general formula that obtains is Ba（1-x′）Ca x′TiO 3 Another kind of situation, when x '=x "=y=y '=y "=0 and x greater than zero the time, complex consist of Ba（1-x）Pb xTiO 3。
", y, y ' and y ", each can get the numerical value (in the restriction of chatting) of relative broad range because x, x ', x, so can prepare the complex of many kinds of very wide compound modes of composition. Yet, no matter generating which kind of composition, each barium titanate substrate complex is all narrow in its unique characteristic take high-purity, sub-micron particulate and size distribution.
This dispersibility submicron order of the present invention attritive powder is preferably by wherein tetravalence and bivalent metal ion are the 0-30%(mole) the barium titanate complex of substituent consisted of. Divalence Barium ions can partly replace with lead, calcium, strontium or its mixture. On the other hand, the titanic ion can partly replace with tin, zirconium, hafnium or its mixture. Therefore, barium titanate substrate dielectric composition of the present invention had both comprised simple lead barium titanate complex or barium titanate strontium complex, had also comprised metatitanic acid barium stannate lead and the plumbous strontium of metatitanic acid zirconic acid barium stannate and so on more complicated complex. Certainly, divalence and (or) selection of the selection of quadrivalent cation substituent and the molar percentage of replacement, depend on that requirement raises Curie temperature or reduces, depend on that also requirement widens the Curie temperature peak value or be shifted. Yet no matter generate anyly in many kinds of barium titanate substrate mixtures, barium titanate complex of the present invention remains characteristic take above-mentioned particle shape and chemistry as its unique character. Therefore, simple or complicated barium titanate complex all is molecular by the dispersibility grain that basically is sphere, the size of its primary particle also all at 0.05 μ m in the scope of 0.4 μ m, size distribution is narrow, even and when wherein divalence and quadrivalent ion had all been replaced by one or more other ions, divalence and quadrivalent ion mol ratio still were 1.000 ± 0.015.
The size distribution of this class barium titanate substrate dielectric mixture is narrow, particle size is at submicron order, and this is just so that complex of the present invention is especially noticeable in the production that further is applied to complicated dielectric substance. The research that has earlier shows, connects the green thing piece that powder is made with narrow poly-of size distribution, can be under lower temperature sintering, its size distribution of the sintered body that obtains is narrow. It is obvious adopting the lower dielectric prescription strong point economically of sintering temperature, and this is because because sintering temperature reduces, can improve the percentage of silver comparatively inexpensive in the silver-palladium alloy. In addition, because this class BaTiO3The matrix dielectric composition all is dispersible and contains hardly granularity greater than the poly-particle that connects of 1 μ m, so they can be used for making the dielectric film of very thin thickness. Therefore, the barium titanate dielectric complex powder of the sort of spherical, poly-that connect, submicron order of the present invention and narrow distribution should be need to be specially adapted on dielectric purposes of those complexity of sintering processing.
For most of dielectric purposes, the product of preferentially selecting is the smaller product of the change of wherein primary particle composition. Yet in some cases, the inhomogeneities of composition but is an advantage. In these situations, the supply of the multiple product that primary particle differs in size can be used to produce so a kind of dispersoid, and it is made of the different powder of two or more compositions, wherein the number of various primary particles or almost or very not identical. These dispersoids can be made green thing piece, and then make sintered body, and their Microinhomogeneity degree can be controlled on request. In this class was used, the inhomogeneities of composition can be intrinsic in the selected barium titanate complex. Perhaps can accomplish with following methods, namely certain barium titanate complex of a small amount of selected components is added in a kind of barium titanate dispersoid, in the hope of obtaining desired uneven components. Because shortcoming divalence barium and (or) titanic complex can be made according to the present invention, so barium titanate substrate composition of the present invention also is applicable to those application facet that will utilize uneven components very much.
The recommend method of making the barium titanate substrate complex is, containing the slurries heating of hydration quadrivalent cation oxide with the divalent cation oxide of selecting or hydroxide. Generate after the titanate of divalence, slurries still contain a large amount of hydration TiO2(or) hydration SnO2、ZrO 2Or HfO2 Then, regulate temperature and the concentration of slurries, then under isothermy, add the Ba(OH excessive than stoichiometric number)2Solution. In order to guarantee tetravalent oxide is converted into fully the acyl anion of their correspondences, preferably slurries are made the final step high-temperature heat treatment.
No matter the barium titanate complex is simple BaTiO3, or general formula is
Ba 1-x-x′-x″Pb xCa x′Sr x″Ti 1-y-y′-y″Zr ySn y′Hf y″O 3Complicated complex, can obtain the present invention such primary particle size and size distribution. This is from that complex composite body of Fig. 1
Ba 0.856Pb 0.097Ca 0.074Ti 0.830Zr 0.099Sn 0.071O 3Transmission electron micrograph in just see too clearly, it show the overwhelming majority be single, be spherical primary particle basically, Although also there are indivedual dimerization particle and trimerization particles that tightly link to each other. The primary particle size of this species complex is 0.18 μ m, and size distribution is narrow. The barium titanate substrate complex (Fig. 1) of the complexity transmission electron micrograph (Fig. 2) with pure barium titanate is compared, show that the particle shape of these barium titanate substrate mixtures is closely similar. Note particle on these two microphotos basically all be spherical, poly-that connect, submicron order with of uniform size. Notice that also divalence in this product is 1.027 to the mol ratio of quadrivalent cation, a little higher than ratio 1.000 ± 0.015 to the product regulation that becomes stoichiometric proportion. Synthesis condition is done to change slightly just can easily be reduced to this ratio in the prescribed limit, and do not affect particle shape.
In order to estimate the physics and chemistry character of barium titanate substrate complex of the present invention, once carried out the test of kinds of experiments chamber. Adopt image analytical method to measure the size of product primary particle and the size distribution of primary particle. In order to measure the bulb diameter value of equal value of primary particle, in several visual fields, measure 500 sizes to 1000 particles with transmission electron microscope. The particle that contacts with each other more than two separates it with visual method, then measures the size of each primary particle. With bulb diameter of equal value calculate that the mass accumulation percentage distributes and the primary particle size between relation. The intermediate value (by weight) of getting particle size is the primary particle size of sample. The higher limit (by weight) of quartile diameter is defined as four proportions by subtraction, QR divided by the lower limit gained quotient of quartile diameter; Get its measuring as the dispersion of distribution. The QR value of monodispersity product is 1, for our test objective, the product of QR value about from 1.0 to 1.5 is classified as the narrow class of size distribution, QR value about from 1.5 to 2.0 be classified as a still narrow class of distribution, and the QR value very is classified as the wide class of size distribution greater than 2.0. Four fens ratios of barium titanate complex of the present invention record between 1.0 to 1.5, and this shows that the size distribution of these primary particles is narrow.
Calculate the numerical value of specific surface from the primary particle size of mixture, find that the specific surface value that this value and nitrogen adsorption method record is consistent, this shows that primary particle is atresia basically.Run into and N occurs 2The specific surface value of gas method substantially exceeds the situation of the specific surface value of transmission electron microscopy, and the reason that is very easy to find the difference appearance is to exist not reacted hydrous oxide, and its specific surface is very big.
Because its size-grade distribution of complex body of the present invention is narrow, so just can easily measure the mean size of primary particle by measuring 20 to 30 particles.Discovery has relational expression D=6/ ρ S, and wherein D is particle dia (μ m), and ρ is density (g/cc), and also having S is N 2Specific surface (the m that the gas method records 2/ g), this formula can be used for obtaining well measuring of complex body primary particle size.According to this formula, find: no matter tested the composition of complex body be what, the primary particle size of barium titanate substrate complex body always at 0.05 μ m between the scope of 0.4 μ m.
The evaluation of the dispersibility of complex body product can recently be accomplished by the imaging method measured value of primary particle size and size-grade distribution and settling process measured value are opposed.Settling process provides stokes (Stokes) diameter of particle, and it is equivalent to spherical diameter of equal value haply.Once used two kinds of settling process, it is tall Jennifer boolean (Joyce Loebl) disc centrifuge (Wei Keersi (Vickers) Instr Ltd., London, Britain) and micrometer sedimentometer (this (Norcross) company of Nore clo, the Georgia), measure the mass accumulation percentage of representing with Stokes diameter and distribute, just can calculate the intermediate value and the QR value of Stokes diameter thus.
When measuring size of particles with settling process, be in the water that contains the 0.08g/L tripoly phosphate sodium STPP of pH10, or contain 0.08 or 0.12%(weight) organic chemicals portion of No. 520 Witter companies in Madison Avenue, Emphos PS-21A(New York (Witco)) Virahol in, powder is used sonic treatment 15 to 30 minutes, make it to spread out.
Because it is according to different principles that image analytical method and settling process are measured size of particles, so the size of particles that these two kinds of methods record always can not be mapped exactly.Moreover just as saying, in the image analytical method, the particle that contacts with each other separates with visual method and measures.In settling process, be sticked together or several particle behaviors agglomerated together on as single entity.The appearance of these entities is owing to occur certain adhesion (connecting as neck) between the primary particle, make it to become the coherent poly-particle that connects, it is not easy broken under sonic treatment, also can cause certain coacervation owing to not being in best dispersion system steady state.Therefore, as in accordance with expectation, QR value that settling process records is bigger than the value that imaging method records.
For barium titanate substrate complex body of the present invention, the numerical value of the primary particle size that primary particle size and the settling process that imaging method records records meets well.The measured value difference of size of particles intermediate value is no more than 1 times.This shows that this complex body is dispersible.
Estimating dispersing property can also be with other two measure.First method is got Stokes diameter in the product and is used as being difficult to that dispersive is poly-connects measuring of particle deal greater than the massfraction of 1 μ m.In second method, if most of primary particle occurs with single particle in transmission electron microscopy, just then this product is classified as a dispersible class.Have considerable neck to connect phenomenon when seeing, then product is classified as a class of poly-company property.Barium titanate substrate complex body product all is classified as a dispersible class once more through these two tests.
The composition of this complex body product and the mensuration of stoichiometric ratio are finished do ultimate analysis with the inductively coupled plasma spectrography after sample dissolution.The tolerance range of analyzing is approximately ± and 1%.No matter how many species number and molar percentages of divalence and quadrivalent cation substituent be, divalent cation all equals 1.000 ± 0.015 to the mol ratio of quadrivalent cation in the complex body.Such ratio shows that barium titanate complex body of the present invention becomes stoichiometric ratio.
Below each non-limiting instance will show further that the character of this barium titanate substrate complex body is unique.
Used in the example all is SILVER REAGENT or the pharmaceutical chemicals that is equivalent to this one-level.Used SILVER REAGENT Ba(OH) 28H 2Contained the 1%(mole among the O) Sr.Experiment shows the Sr(II) than Ba(II) the easier complex body that enters into goes.For this reason, all said here complex body all contains the Sr(II).This positively charged ion accounts for about 1% (mole) of divalent cation total amount in the complex body.For the sake of simplicity, molar fraction Sr(II) is calculated in the Ba(II) molar fraction among.Ba(OH) 2(or) Sr(OH) 2Solution maintains 70-100 ℃, removes by filter earlier any carbonate wherein before using.With CaCO 3Roasting obtains CaO in the time of 800 ℃.The latter contacted with water obtain Ca(OH) 2Pb(OH) 2Be to use NH 3In the water and Pb(NO 3) 2Solution is made.Through washing, the experiment after the wet piece of oxyhydroxide is provided with is used.
TiO 2, SnO 2And ZrO 2Hydrous oxide be at room temperature to use NH 3Water is made their aqueous chloride solution neutralizations separately.Product is through filtering, and washes with water and do not have chlorion in the filtrate and (use AgNO 3Check).Hydrous oxide is measured its specific surface 110 ℃ of dry backs, records TiO 2, SnO 2And ZrO 2Specific surface be respectively 380,290 and 150m 2/ g.In addition, hydration TiO 2With ZrO 2Coprecipitated product or hydration TiO 2With SnO 2Coprecipitated product, its preparation is to use the IV with Ti() with the Zr(IV) or the Ti(IV) with the Sn(IV) aqueous chloride solution neutral method.
All experiment all is to carry out in 2 liters autoclave.In order to prevent product contamination, all apply polytetrafluorethylecoatings coatings as the position of all contact liqs of pressing still, and be at pains all local CO of system 2All exclude.Ba(OH) 2Solution or Ba(OH) 2And Sr(OH) 2Solution injects in the autoclave with high-pressure pump, perhaps will be placed on a kind of or several hydroxide solutions that add in the thermoelastic with high pressure nitrogen and be injected in the autoclave soon.In the entire synthesis process, the material in the autoclave always stirs with the rotating speed of 1500RPM.
Example one
Prepared a kind of calcic complex body: will contain 0.20 mole of hydration TiO 2With 0.04 mole of Ca(OH) 20.64 liter in slurries handle 200 ℃ with hydrothermal method.With the slurries cooling, then in 120 ℃ slurries, add 0.41M Ba(OH) 20.46 rise.With the slurries elevated temperature to 150 that obtains ℃, be incubated 60 minutes.With sample filtering, measure the concentration of divalent cation in the filtrate.With filtration cakes torrefaction, measure the morphological character of its specific surface, nominal stoichiometry ratio and particle.
Divalence in the filtrate solid/tetravalence specific surface
Cationic mol ratio (the N of the cationic mol ratio of g/L 2Method)
Ba Ca Ca∶Ba∶Sr∶Ti m 2/g
2.62 0.446 0.127∶0.842∶0.019∶1.00 0.988 12.0
The size granularity of primary particle distributes
(transmission type microscope method)
0.15 μ m is narrow
Example two
Prepared a kind of leaded complex body: will contain 0.2 mole of hydration TiO 2Handle with hydrothermal method for 0.64 liter with the slurries of 0.04 mole of PbO.In 150 ℃ slurries, add 0.46 liter of Ba(OH) 2Slurries are incubated 60 minutes down at 150 ℃, and elevated temperature changes into perovskite structure fully with tetravalent oxide then.From slurries, take a sample, analyze.The result who obtains is as follows:
Divalence in the filtrate solid/tetravalence specific surface
Cationic mol ratio (the N of the cationic mol ratio of g/L 2Method)
Ba Ca Ca∶Ba∶Sr∶Ti m 2/g
10.6 2.74 0.810∶0.173∶0.024∶1.000 1.007 11.5
The size of primary particle
(transmission type microscope method) size-grade distribution
0.15 μ m is narrow
Example three
The complex body that has prepared several complexity, wherein BaTiO 3The Ba(II) and the Ti(IV) partly replaced by one or more divalence and quadrivalent cation.Contain tetravalence hydrous oxide and synthetic Pb(II in advance to what be heated to 150 ℃ or 120 ℃) and the uhligite slurries of (or) Ca(II) in add the Ba(OH of preheating) 2Solution.Be incubated after about 20 to 30 minutes, slurries are elevated to last temperature, be converted into into the perovskite structure of stoichiometric ratio to guarantee the tetravalence hydrous oxide.The analytical results of last gained slurries is as follows:
Cationic mol ratio divalence/tetravalence specific surface in the solid
Cationic
Ba: Pb: Ca: Ti: Zr: Sn mol ratio m 2/ g
Sample 1 0.908: 0.090: 0.000: 0.904: 0.096: 0.000 0.998 8.0
Sample 2 0.881: 0.000: 0.123: 0.881: 0.119: 0.000 1.004 12.2
Sample 3 0.856: 0.097: 0.074: 0.830: 0.099: 0.071 1.028 9.8
The size of primary particle (transmission type microscope method) size-grade distribution
1 0.14 μ m are very narrow for sample
2 0.2 μ m are narrow for sample
3 0.2 μ m are narrow for sample
The image analytical method settling process
Granularity (μ m) QR granularity (μ m) QR
Sample 1 0.12 1.33 0.24 2.2
Sample 2 0.19 1.31 0.24 1.6
Sample 3 0.18 1.25 0.24 1.5
The quantitative data of sample 2 and sample 3 quite meets with size of particles, size-grade distribution and the dispersibility data estimated according to transmission electron micrograph., to estimate according to the QR value be medium dispersibility to sample 1.Yet the settling process data point out, in this product less than 5%(weight) be to exist with the poly-particle that connects of granularity greater than 1 μ m.
Therefore, can see from above-mentioned example and disclosed content: those barium titanate substrate complex bodys of the present invention have comprised such dielectric composition, wherein contain calcium and (or) plumbous or multiple substituent, replace in divalence barium and the titanic positively charged ion, or two replace all; The unique characteristics of these mixtures are: they are spheric, and the size of primary particle is in the scope of 0.05 to 0.4 μ m, and divalence is 1.000 ± 0.015 to the mol ratio of quadrivalent cation, and size-grade distribution is narrow.Do not have a kind of prior art in the dielectric composition of the barium titanate substrate that contains calcium, lead or complex form disclosed herein, can reach these on particle shape and chemically unique character.
Self-evident, above-described content is just for to explanation of the present invention, rather than limitation of the present invention, can make multiple variation scheme as described above, and not depart from the spirit of the present patent application authority.
Figure 87104006_IMG1

Claims (18)

1, a kind of complex body of barium titanate substrate, it is that spheroidal particle constitutes basically, general formula is Ba (1-X ')Ca X 'Ti (1-y-y '-y ")Sn yZr Y 'Hf Y "O 3, " value independently in 0 to 0.3 scope, y+y '+y " adds and be worth less than 0.4, and x ' is greater than 0 and less than 0.4 for wherein y, y ' and y.
2, according to the barium titanate complex body of claim 1, the mean size of its mesocomplex primary particle is in the scope of 0.05 to 0.4 μ m.
3, according to the barium titanate complex body of claim 1, the numerical value of the primary particle size that wherein records with record with settling process with image analytical method conform to and difference within 1 times.
4, according to the barium titanate complex body of claim 1, the size-grade distribution of its mesocomplex is narrow, and four proportions by subtraction of the primary particle size distribution curve of complex body are less than or equal to 1.5.
5, according to the barium titanate complex body of claim 1, wherein
(Ba+Ca)/(Ti+Sn+Zr+Hf) mol ratio is 1.000 ± 0.015.
6, according to the barium titanate complex body of claim 1, wherein
(Ba+Ca)/(Ti+Sn+Zr+Hf) mol ratio is in 0.9 to 1.1 scope.
7, a kind of complex body of barium titanate substrate, it is that spheroidal particle constitutes basically, general formula is Ba (1-x)Pb xTi (1-y-y '-y ")Sn yZr Y 'Hf Y "O 3, " value independently in 0 to 0.3 scope, y+y '+y " adds and be worth less than 0.4, and x is greater than zero and less than 0.4 for wherein y, y ' and y.
8, according to the barium titanate complex body of claim 7, the mean size of its mesocomplex primary particle is in the scope of 0.05 to 0.4 μ m.
9, according to the barium titanate complex body of claim 7, the numerical value of the primary particle size that wherein records with record with settling process with image analytical method conform to and difference within 1 times.
10, according to the barium titanate complex body of claim 7, the size-grade distribution of its mesocomplex is narrow, and four proportions by subtraction of the primary particle size distribution curve of complex body are less than or equal to 1.5.
11, according to the barium titanate complex body of claim 7, wherein
(Ba+Pb)/(Ti+Sn+Zr+Hf) mol ratio is 1.000 ± 0.015.
12, according to the barium titanate complex body of claim 7, wherein
(Ba+Pb)/(Ti+Sn+Zr+Hf) mol ratio is in 0.9 to 1.1 scope.
13, a kind of complex body of barium titanate substrate, it is that spheroidal particle constitutes basically, general formula is Ba (1-x-x '-x ")Pb xCa X 'Sr X "Ti (1-y-y '-y ")Sn yZr Y 'Hf Y "O 3, each value independently between greater than zero, less than 0.3 all of x, x ', x ", y, y ' and y " wherein, " add and be worth less than 0.4, y+y '+y " adds and is worth less than 0.4 x+x '+x.
14, according to the barium titanate complex body of claim 13, the mean size of its mesocomplex primary particle is in the scope of 0.05 to 0.4 μ m.
15, according to the barium titanate complex body of claim 13, the numerical value of the primary particle size that wherein records with record with settling process with image analytical method conform to and difference within 1 times.
16, according to the barium titanate complex body of claim 13, the size-grade distribution of its mesocomplex is narrow, and four proportions by subtraction of the primary particle size distribution curve of complex body are less than or equal to 1.5.
17, according to the barium titanate complex body of claim 13, wherein
(Ba+Ca+Pb+Sr)/(Ti+Sn+Zr+Hf) mol ratio is 1.000 ± 0.015.
18, according to the barium titanate complex body of claim 13, wherein
(Ba+Ca+Pb+Sr)/(Ti+Sn+Zr+Hf) mol ratio is in 0.9 to 1.1 scope.
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