CN101314545A - Spray coating method for producing dielectric ceramic powder body and obtained products thereof - Google Patents
Spray coating method for producing dielectric ceramic powder body and obtained products thereof Download PDFInfo
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- CN101314545A CN101314545A CNA2008100292729A CN200810029272A CN101314545A CN 101314545 A CN101314545 A CN 101314545A CN A2008100292729 A CNA2008100292729 A CN A2008100292729A CN 200810029272 A CN200810029272 A CN 200810029272A CN 101314545 A CN101314545 A CN 101314545A
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Abstract
The invention relates to a spray coating method for preparing dielectric ceramic powder and the dielectric ceramic powder prepared. The spray coating method comprises the following steps: A. main crystal phase ceramic powder and modified metallic ion composite soluble inorganic salt precursor or sol are processed into slurry with good fluidity; B. the slurry in the step A is prepared by deionized water into slurry with a solid content between 5 and 70 percent; and C. the slurry obtained in the step B is stirred and simultaneously conveyed to a spray drier by a feed pump, the feed rate is controlled to between 0.01 and 6.01 liters per minute, and the dielectric ceramic powder required is prepared after spray drying of the slurry at a hot blast temperature of between 120 and 450 DEG C; or D. the dielectric ceramic powder obtained in the step C is placed into a high temperature furnace at a temperature of between 250 and 1200 DEG C for calcinating 0.5 to 6 hours. The method is economic and simple; doped compositions and main crystal phase materials are uniformly distributed; and prepared dielectric powder crystal grains reach submicron or nano level and have superhigh evenness and dispersity.
Description
Technical field
The present invention relates to a kind of spray coating method of electronic ceramics powder and electronic ceramics powder of gained of preparing, relate in particular to the spray coating method of the dielectric ceramic powder body that a kind of electronic devices and components use and the dielectric ceramic powder body of gained.
Background technology
The preparation of fine electronic stupalith is normally burnt on the basis of piece or principal crystalline phase at synthetic main composition, realizes intended function by adding one or more doping vario-property compositions.Continuous fusion along with the rapid rising and the 3C technology of 3G mobile technology, with mobile phone, GPS, MP3, MP4, flash memory disk, DC, DV, Bluetooth, small size notebook computer the growing continuously and fast of hand-hold electronic equipments terminal of representative, electronics constantly develops to miniaturization, subminiaturization, high reliability direction, thereby promoted electronic component constantly to the development continuously and healthily of weak point, little, smart, thin direction, also just harsh all the more to fineness, homogeneity and dispersiveness and the morphology microstructure requirement thereof of electronic material.As has a typical representational chip multilayer ceramic capacitor (Multilayer Ceramic Capacitors, MLCC), realize large vol, microminiaturization for the development that adapts to complete electronic set, its dielectric thickness is less than 1 micron at present, the design number of plies is up to more than 1000 layers, for guaranteeing that it has higher reliability, often need to guarantee that each layer has 5～10 crystal grain at least, its dielectric material crystal grain of this inevitable requirement reaches submicron order even nano level, and has the homogeneity of superelevation and good dispersiveness.
Advanced material synthetic methods such as chemical synthesis even gas phase synthesis method are burnt in the piece preparation at main composition and have been obtained a large amount of application at present, the material master burns even level that piece reached molecular level still, in composition doping vario-property subsequently, at present domestic and international industrial production is mainly still continued to use oxide compound or carbonate and is the material that sets out that mixes, disperse to mix by the method for traditional solid phase ball milling, require dopant material and the main piece that burns to have very good matching, this just produces bigger difficulty to the selection of dopant material, this selects supplier to " getting a good buy by shopping around " in the big production is disadvantageous, particularly along with the rise of nano material, the coupling that realizes multiple dopant material shows difficulty, even so, when doping in 1%, even littler, realize nano material or submicron material completely homodisperse be still extremely difficult.In addition, disperse uniformly main the burning in the piece for improving each altered contents, the grinding that often will carry out the long period disperses, because the ultra-fine main particularly active height of nano powder surface of piece that burns, the long grinding tends to powder surface is produced influence greatly, even causes burning the distortion increase of piece crystal grain, simultaneously owing to grind for a long time, also be easy in process of lapping, introduce impurity, thereby finally cause the material property deterioration.Particularly will prepare below the material medium diaphragm thickness 10 μ m, as the medium layer MLCC less than 3 μ m, its insulating property and reliability thereof are doubt.For example, at publication number is in the Chinese patent of 1244514A, 1626475A, 1402275A, 1634798A, 1191594C, 1564270A, 101013618A, when making various electron ceramic material, all continued to use the principal crystalline phase and the various oxide compound solid phase ball milling blended traditional technology of solid phase method preparation.Publication number is in the Chinese patent of 1085635C and 1623955A, 1635592A for another example, though the principal crystalline phase that has adopted chemical processes such as Oxalic Acid Method and hydrothermal method to produce respectively still adopts traditional mixing procedure of main crystal phase material and doping oxide or carbonate to prepare porcelain.
Recently, though have the people softening method of modifying has been proposed in the preparation method, though be that part has been used soluble inorganic salt and principal crystalline phase powder to mix the sedimentary method of evaporate to dryness to carry out doping vario-property in the Chinese patent of 1461022A, 1461023A for example at publication number, but because in slow drying process, it still is difficult to guarantee not have the existence of segregation, and reliability and insulativity remain doubt.In the last few years, precipitation coated the sub-stupalith of legal system power backup and had also obtained bigger development, was that the Chinese patent of 1121048C, 100392779C has just adopted the technology of precipitation coating-doping modification to improve material doped homogeneity greatly as publication number.But, because various hotchpotch deposition conditions are different, to external world condition change comparatively responsive, thereby actually operating get up quite complicated, scale operation control difficulty; Simultaneously,, often will under lower solids content, precipitate coating, even be aided with repeatedly the repeated precipitation washing, thereby its efficient is lower, and need to consume a large amount of deionized waters, improved cost undoubtedly for controlling its deposition condition preferably.In addition, because it repeatedly precipitates, use a large amount of deionized water wash repeatedly, this often burns piece such as BaTiO to its many composition master
3(BT), Ba
x(Ti
1-aZr
a) O
3(BTZ), (Ba
1-bCa
b)
x(T
I-aZr
a) O
3(BCTZ), (Ca
1-cSr
c) ZrO
3(CSZ), (Ba
1-cSr
c) ZrO
3(BSZ), SrTiO
3(ST) (a=0.1-0.35, b=0.1-0.15, c=0.30-0.70, x=0.90-1.05), the individual element loss is excessive Deng causing, it is bigger to run off during nanometer grade powder that particularly surfactivity is bigger, as BT in neutrality or weakly alkaline slip, barium ion is easy to run off, under a large amount of deionized water repetitive scrubbings, Ba element among the BT is difficult to control effectively with Ti element ratio, and from literature search and actual a large amount of experiments, effective control of Ba, Ti element is the basis that realization BT sill is stablized lot production among the BT.In addition, sol-gel coats, and has also obtained report in recent years in the document, but it becomes the glue cycle long, and drying temperature is lower, thereby causes its production cycle longer, and this is unfavorable for large batch of modern production.
Summary of the invention
The technical problem that the present invention need solve provides in a kind of mass production, and economy simply and effectively realizes the preparation method of the equally distributed dielectric ceramic powder body between doping composition and the main crystal phase material; Another technical problem that the present invention need solve provides a kind of dielectric ceramic powder body by this method preparation.
Technical scheme of the present invention is achieved in that a kind of spray coating method for preparing dielectric ceramic powder body, step is successively: A, the compound soluble inorganic salt precursor of principal crystalline phase ceramic powder and modified metal ion or its colloidal sol are carried out the physics dispersion treatment become the slip of good fluidity to be about to all to need adulterated altered contents metal ions and dispersion agent to be diluted to solution with deionized water in a certain amount of deionized water, back and principal crystalline phase are mixed and carry out physics and be dispersed into slip; Perhaps earlier add the compound soluble inorganic salt precursor solution of modified metal ion or its colloidal sol again with the coordinate slip of good fluidity of a certain amount of deionized water physics dispersion treatment oikocryst, being about to principal crystalline phase carries out after physics is dispersed into slip with deionized water or the deionized water that contains certain dispersion agent, add the doping vario-property composition metal ion slip of releasing rare one-tenth with deionized water while stirring again, the crystalline form that can also directly select for use the methods such as hydrothermal method of certain solid content directly to make is perfect, finely disseminated water-based slip also can add certain amount of dispersant in case of necessity in slip; Slurry temperature is controlled at 0～90 ℃, dispersant dosage≤5%, and preferred temperature is controlled to be 10～50 ℃; Temperature＜0 ℃, feed liquid is easy to freeze, and influences the dissolving of doping composition in deionized water and disperses, and temperature＞90 ℃ produce certain difficulty to production operation.B, with the described slip of steps A, being deployed into solid content with deionized water is 5%～70% slip, solid content＜5% o'clock, inefficiency increases production cost, solid content＞70%, slip is thickness too, influence mist projection granulating, also may influence the abundant dissolving of the composition that partly mixes, cause not reaching the high homogeneity that the doping composition is scheduled in material.C, with the slip of step B gained while stirring the materials pump delivery to spray-drier, the control input speed is 0.01L/min～6.0L/min, spraying drying under 120 ℃～450 ℃ hot blast temperature, obtain the dielectric ceramic powder body of needs, gained powder granulation diameter is 500nm～200 μ m, water content≤3.0%; When hot blast temperature＜120 ℃, mist projection granulating difficulty, gained powder water content is too high, be easy to cause the material segregation, do not reach the effect of predetermined high uniformity, hot blast temperature＞450 ℃, too harsh to equipment requirements, be unfavorable for producing, powder granulation diameter＜500nm can cause inefficiency, equipment requirements is also comparatively harsh, production efficiency is too low, and powder granulation diameter＞200 μ m also can be easy to cause the material segregation, do not reach the effect of predetermined high uniformity, cause material degradation; When water content＞3.0%, can cause in the put procedure of material before calcining, the doping composition dissolves segregation again on the principal crystalline phase surface, causes material homogeneity to descend dispersed variation.Perhaps, soluble salt gross weight for doping composition and sintering agent composition accounts for material gross weight＞3%, and water content surpasses at 0.5% o'clock behind the mist projection granulating, and aforesaid method also comprises step D: the dielectric ceramic powder body that is about to step C gained is put into 250～1200 ℃ of following calcinings of High Temperature Furnaces Heating Apparatus 0.5～6 hour again.When temperature is lower than 250 ℃, gained doping composition still contains more soluble salt, very easily absorb airborne moisture content during preservation and get damp, can cause this composition to dissolve segregation again on the principal crystalline phase surface, cause material homogeneity to descend, dispersed variation, simultaneously, its volatilization composition is too high, and it is disadvantageous that the back is made components and parts, when temperature is higher than 1200 ℃, the gained material very easily produces hard aggregation, causes the dispersion of materials variation, and it is excessive to cause material grains to be grown up again even, active decline, coking property degenerates.
Further: described principal crystalline phase ceramic powder is selected a preparation by hydrothermal method, coprecipitation method, homogeneous precipitation method, Oxalic Acid Method, sol-gel method, microemulsion method, spraying decomposition method, vapor phase process, and diameter of particle is 50～1500nm.The compound soluble inorganic salt precursor of described modified metal ion comprises one or more mixing solutionss in oxyhydroxide or hydrous oxide, nitrate, acetate, Citrate trianion, oxalate or its colloidal sol, the high-dispersion nano suspension, and preferred scheme is nitrate, acetate and Citrate trianion.Described amount of deionized water: the principal crystalline phase ceramic powder is 0.7～4.0 than r: 1, when ratio r＜0.7, deionized water is difficult to cover fully principal crystalline phase, the principal crystalline phase ceramic powder is difficult to the complete wetting pulping, dispersion effect cannot guarantee, when ratio r＞4.0, go dried up too much, the slip dispersion effect is with variation, and dispersion efficiency descends;
Described principal crystalline phase ceramic powder is to select a physics dispersing mode with stirring, ball milling, sand milling, three-dimensional vibrating to handle, and preferred scheme is to carry out Ball milling with stirring, ball mill.Among the described step B, with deionized water slurry blending being become solid content is the slip of 20-50%.Among the described step C, the spraying drying temperature is 180～300 ℃, and powder granulation diameter is 5.0 μ m～80 μ m, water content＜1.0%.Among the described step D, calcining temperature is 700～1000 ℃, insulation 0.5～3h.
The present invention is a doped raw material by the metallic element soluble salt of selecting economy for use and being easy to get, use the method for spraying coating-doping, realized one or more modification hotchpotchs to the coated with uniform of ultra-fine principal crystalline phase ceramic powder or uniform distribution betwixt, success obtained one or more modification hotchpotchs to the even doping vario-property of principal crystalline phase powder and kept the hyperfine electronic ceramics of principal crystalline phase ceramic material body original powder surface pattern.This method control is easy, and production cost is low, and the cycle is short, efficient is high, good stability.Solving traditional solid phase doping method doping is difficult to evenly, select harsh and long-time ground and mixed to bring impurity and the problem that causes the principal crystalline phase lattice distortion to dopant material, also solve the precipitator method or homogeneous precipitation method technology controlling and process difficulty simultaneously, water wasting is consuming time, inefficiency, the problem of poor stability.
Dielectric ceramic powder body with above-mentioned spray coating method preparation, pass through sintering, organism has volatilized or burn off, the dielectric ceramic powder body of gained comprises principal crystalline phase ceramic powder or main piece ceramic powder, modified metal ion and the sintering agent of burning, and its prescription molecular formula is (1-m) MA-mMB-pMZ, and wherein MA represents the main piece that burns, MB is the modification composition, MZ is the sintering agent composition, m=0～15, p=0～3.Described principal crystalline phase ceramic powder or the main piece phase ceramics powder that burns are a kind of among barium titanate BT, zirconium barium titanate BTZ, barium calcium zirconate titanate BCTZ, strontium-barium titanate BST, strontium zirconate calcium CSZ, strontium zirconate barium BSZ, calcium zirconate CZ, barium zirconate BZ, tin titan zirconium ZST, magnesium titanate MT, magnesium titanate zinc ZMT, strontium titanate ST, the metatitanic acid neodymium barium BNT; Described altered contents metallic element is one or more among Ba, Sr, Ca, Mg, Sn, Zn, Cu, Ni, Co, Fe, Mn, Cr, Sc, Sb, Zr, Ti, Al, Sc, Nb, Ta or rare-earth elements La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Y, the Lu.Described sintering agent is B, Si, Li, Na, K, Bi, Sb, P, V, Zn, Cu.
The dielectric material crystal grain median size of above-mentioned dielectric ceramic material reaches micron order, submicron order even nano level, and has the homogeneity of superelevation, good dispersiveness and higher purity.This medium ceramic material is particularly suitable for preparation as multilayer monolith structure fine electronic components and parts, especially becomes highly reliable, ultra-thin, the high number of plies of film production, jumbo MLCC with casting method film forming, wet method silk screen printing.
Description of drawings
Fig. 1 is a principal crystalline phase when being BT, the dielectric medium morphology microstructure figure of gained; Fig. 2 is a principal crystalline phase when being BT, the grain growing shape appearance figure on nickel electrode laminated ceramic capacitor porcelain body surface; Fig. 3 is principal crystalline phase dielectric medium morphology microstructure figure when being BTZ; Fig. 4 is a principal crystalline phase when being BTZ, the grain growing shape appearance figure on nickel electrode laminated ceramic capacitor porcelain body surface; Fig. 5 is principal crystalline phase dielectric medium morphology microstructure figure when being ZMT; Fig. 6 is a principal crystalline phase when being ZMT, the grain growing shape appearance figure on nickel electrode laminated ceramic capacitor porcelain body surface.
Embodiment
Purport of the present invention is to utilize the liquid phase doping technology of spraying coating-doping simple and easy to control, by select for use be simple and easy to starting material, realized that altered contents metallic element Ba, Sr, Ca, Mg, Sn, Zn, Cu, Ni, Co, Fe, Mn, Cr, Sc, Sb, Zr, Ti, Al, Sc, Nb, Ta or La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, the rare earth doped material of Y, Lu and sintering agent B, Si, Li, Na, K, Bi, Sb, P, V, Zn, Cu burn piece to superfine electric material master, as BaTiO
3(BT), Ba
x(Ti
1-aZr
a) O
3(BTZ), (Ca
1-bSr
b) ZrO
3, (Ba
1-bSr
b) ZrO
3, SrTiO
3(ST), the surface of ZnO coats or evenly mixes, economy simply and effectively realizes the uniform distribution between doping composition and the main crystal phase material, solving traditional solid phase doping method mixes and is difficult to evenly and dopant material is selected harsh and long-time ground and mixed to bring impurity and caused the problem of principal crystalline phase lattice distortion, also solve simultaneously the precipitator method or homogeneous precipitation method technology controlling and process difficulty, water wasting is consuming time, inefficiency, the problem of poor stability, in addition, also solved long problem of sol-gel method production cycle.Superelevation homogeneity and dispersed nanometer or submicron fine electronic material have successfully been obtained.Below in conjunction with embodiment content of the present invention is described in further detail, mentioned content is not a limitation of the invention among the embodiment, and the selection of material and condition can be suited measures to local conditions and the result be there is no substantial effect in the method.
At first, the general planning of summary the inventive method: a kind of spray coating method for preparing dielectric ceramic powder body, step is successively: A, the compound soluble inorganic salt precursor of principal crystalline phase ceramic powder and modified metal ion or colloidal sol are put into deionized water carry out the slip that the physics dispersion treatment becomes good fluidity; Perhaps earlier become the slip of good fluidity to add the compound soluble inorganic salt precursor of modified metal ion again or colloidal sol is deployed into slip with deionized water physics dispersion treatment principal crystalline phase ceramic powder; Perhaps directly select the water-based slip for use; B, with the described slip of steps A, being deployed into solid content with deionized water is 5%～70% slip, preferred solid content is 20-50%; C, with the slip of step B gained while stirring the materials pump delivery to spray-drier, the control input speed is 0.01L/min～6.0L/min, spraying drying under 120 ℃～450 ℃ hot blast temperature, obtain the dielectric ceramic powder body of needs, gained powder granulation diameter is 500nm～200 μ m, water content≤3.0%, preferred input speed is 0.5L/min-4.0L/min, 180～300 ℃ of spraying drying temperature, powder granulation diameter are 5.0 μ m～80 μ m, water content＜1.0%.Perhaps: D, the dielectric ceramic powder body of step C gained is put into the calcining 0.5～6 hour down of 250～1200 ℃ of High Temperature Furnaces Heating Apparatuss again, preferably calcining temperature is 700～1000 ℃, insulation 0.5～3h.
Embodiment 1
Present embodiment is that the BT powder of 300nm～350nm is a principal crystalline phase with Hydrothermal Preparation, particle diameter, forms and the MLCC dielectric ceramic powder body of described spray coating method preparation temperature characteristic conforms EIA-X7R standard with following prescription.
Earlier 0.30Kg polypropylene acid amide is dissolved in 25 ℃ of deionized waters of 130Kg dissolving and it is added in ball mill, add the BT powder of 100.00Kg weight again, after seal start and disperse 5h, back discharging fully is slip A in plastic containers.Other takes by weighing the Ca (NO of 2.33Kg
3)
2.4H
2O, the Y (NO of 5.25Kg
3)
3.6H
2O, 0.31Kg concentration is 50% Mn (NO
3)
2Mg (the NO of slip, 0.88Kg
3)
26H
2Cu (the NO of O, 0.38Kg
3)
26H
2O, 1.00Kg solid content are 40% silicon sol, with being diluted to doping vario-property salt slip in the 100L deionized water, slowly add among the slip A of aforementioned stirring then, 2h is continued to keep stirring in the back that finishes, it is dispersed high finally to obtain good fluidity, and solids content is about 29.67% slip B.Start centrifugal spray-drying tower, regulating the spray drying device hot blast temperature is 230 ℃, the control input speed is 3L/min, size with the control droplet, making the average granulation diameter of final powder is 25 μ m, water content is 0.53%, to the slip B coating-doping of spraying, obtains the powder C of good fluidity.To resulting powder C, move on to and carry out 820 ℃ of calcinings in the High Temperature Furnaces Heating Apparatus, and insulation 2.5h, finally obtained powder D.To 5 of powder D random sampling, be no less than 30 points altogether and carry out electronic scanning Electronic Speculum (SEM) analysis respectively, all do not have and find to exist particle to exist, do not find that evaporate to dryness sedimentation or coprecipitation method are controlled to find the phenomenon that a large amount of small-particles are piled up when bad usually yet than big difference with original principal crystalline phase BT particle; Sampling simultaneously is no less than 10 point-like electron energy spectrum analysiss (EDS), it is very even to find that each doped element distributes between microcell, there is no the obvious enrichment phenomenon of some element, there is not the non-existent point of individual element yet, accompanying drawing 1 is the dielectric ceramic powder body pattern, and table 1 is got ten and pressed each to put doped element be 100% o'clock result for EDS analyzes institute.Thereby, can think success realization multiple doping composition be the even adulterated modification of 300nm principal crystalline phase BT to particle diameter, and successful maintenance original pattern of BT powder and dispersiveness.
For further verifying the electric property of the powder that this method prepares, to powder D, it is 6 μ m that the method for preparing nickel electrode MLCC with common casting method has been made dielectric thickness, and effectively medium is that 80 layers apparent size specification is the nickel electrode MLCC of 2.0mm * 1.25mm (0805).Get at random and be no less than 5 and observe the growing states of MLCC porcelain body surface microstructure, find the tiny regular densification of its crystal grain, there is no abnormal grain and exist with SEM; Get 30pcs at random, in temperature is 25 ℃, under the envrionment conditions of 75RH%, is 1KHz with electric bridge in frequency, voltage is that 0.5V tests its electrical capacity (C) and dielectric loss (tg δ), with measured capacity, by calculating specific inductivity (ε), under 50V, keep testing in 1 minute its resistivity (ρ) with quick Insulation Resistance Tester, test its withstand voltage properties (BDV) under direct current with Hi-pot Tester, and use high-low temperature chamber, under differing temps, use electric bridge at frequency 1KHz, voltage is that 1.0V tests its electrical capacity (C), and calculates it with respect to the volume change rate (TC) under 25 ℃, with the absolute value of the maximum velocity of variation between-55 ℃ to 125 ℃ | Max|.Respectively get 72pcs, at 1.5v low pressure and 125v high pressure,, carry out the acceleration steady state damp heat test (DSAT) of 100h under the RH85% respectively at 85 ℃, other gets 72pcs and soaks 3-5s at 270 ℃ and carry out thermal shock test (TST), all with volume change rate absolute value before and after the test | and Δ C/C|＞10%, IR＜5 * 10
9Judge number of non-compliances when Ω and examination back loss value take place greater than the arbitrary situation of the preceding value twice of examination, concrete parameter sees Table 2.Fig. 2 is the grain growing shape appearance figure on its nickel electrode laminated ceramic capacitor porcelain body surface.By the result as seen, method can obtain meeting the super even high meticulous dielectric ceramic powder body of EIA-X7R standard very easily thus.
Embodiment 2
Present embodiment is 200nm hydro-thermal superfine cubic phase Ba (Ti with the particle diameter
0.866Zr
0.134) O
3(BTZ) be principal crystalline phase, form and the dielectric ceramic powder body of described spray coating method preparation temperature characteristic conforms EIA-Y5V standard, and be equipped with the nickel electrode multilayer ceramic with conventional curtain coating legal system and carry out performance verification with following prescription.
Take by weighing the Ca (NO of 306g weight respectively
3)
24H
2O, the Y (CH of 135g weight
3COO)
33.15H
2O, the Mn (CH of 62g weight
3COO)
24H
2Mg (the CH of O, 54g weight
3COO)
24H
2Cu (the NO of O, 30g weight
3)
23H
2O, 267g solid content are the TiO 2 sol of 20wt%, and the 250g solid content is the silicon sol of 20wt% and the AK0531 macromolecule dispersing agent of 30g, the back add deionized water 8.87Kg make its fully dissolve slip A.Other takes by weighing the 20Kg solid content is the ultra-fine high-purity cube of phase BTZ of hydro-thermal that the particle diameter of 50wt% Hydrothermal Preparation is about 200nm, adds about 30 ℃ deionized water 20Kg and stirs 2h to become solid content be 25% distributed slurry B.Stir slip B on one side then, Yi Bian add feed liquid A slowly, keep quick dispersed with stirring 2h again behind reinforced the finishing, finally obtaining solids content is 20wt%, good fluidity, dispersed high slip.Start centrifugal spray-drying tower, regulating the spray drying device hot blast temperature is 200 ℃, the control input speed is 0.8L/min, size with the control droplet, making the average granulation diameter of final powder is 20 μ m, water content is 0.45%, thereby has realized the coating-doping of spraying to slip B, obtains the powder C of good fluidity.To resulting powder C, move on to and carry out 900 ℃ of calcinings in the calcining furnace, and insulation 1.5h, finally obtained powder D.To 5 of powder D random sampling, be no less than 30 points altogether and carry out electronic scanning Electronic Speculum (SEM) analysis respectively, all do not have and find to exist particle to exist, do not find that evaporate to dryness sedimentation or coprecipitation method are controlled to find the phenomenon that a large amount of small-particles are piled up when bad usually yet than big difference with original principal crystalline phase BTZ particle; Same sampling is no less than 10 point-like electron energy spectrum analysiss (EDS), it is very even to find that each doped element distributes between microcell, there is no the obvious enrichment phenomenon of some element, there is not the non-existent point of individual element yet, thereby, can think success realization multiple doping composition be the even adulterated modification of 200nm principal crystalline phase BTZ to particle diameter, and successful maintenance original pattern of BTZ powder and dispersiveness.Accompanying drawing 3 is the dielectric ceramic powder body pattern, and subordinate list 2 is got ten some doped elements (deduction principal crystalline phase element titanium) by 100% conversion result by EDS analyzes.
For further verifying the electric property of the dielectric ceramic powder body that this method prepares, to powder D, it is 10 μ m that the method for preparing the nickel electrode laminated ceramic capacitor with common casting method has been made dielectric thickness, and effectively medium is 28 layers, and dimensions is 0805 nickel electrode laminated ceramic capacitor.Get at random and be no less than 5pcs and observe the growing state of MLCC porcelain body surface microstructure, find the regular densification of its grain growing, there is no abnormal grain and exist with SEM; Get 30pcs at random, in temperature is 25 ℃, RH is under 75% the envrionment conditions, is 1KHz with electric bridge in frequency, voltage is that 1.0V tests its electrical capacity (C) and dielectric loss (tg δ), with measured capacity, by calculating specific inductivity (ε), under 50V, keep testing in 1 minute its resistivity (ρ) with quick Insulation Resistance Tester, test its withstand voltage properties (BDV) under direct current with Hi-pot Tester, and be 1KHz in frequency with high-low temperature chamber and electric bridge, voltage is conjunction measuring its capacity under differing temps under the 1.0V, calculating it with respect to the volume change rate (TC) under 25 ℃, and the absolute value of the maximum velocity of variation between-30 ℃ to 85 ℃; Respectively get 72pcs, at 1.5v low pressure and 125v high pressure,, carry out the acceleration steady state damp heat test (DSAT) of 100h under the 85RH% respectively at 85 ℃, other gets 72pcs and soaks 3-5s at 270 ℃ and carry out thermal shock test (TST), all with volume change rate absolute value before and after the test | and Δ C/C|＞30%, IR＜10
9Judge number of non-compliances when Ω and examination back loss value take place greater than the arbitrary situation of the preceding value twice of examination, concrete parameter sees Table 4.Accompanying drawing 4 is the grain growing shape appearance figure on its nickel electrode laminated ceramic capacitor porcelain body surface.By the result as seen, method can obtain meeting the meticulous dielectric ceramic powder body of super even height of EIA-Y5V standard very easily thus.
Embodiment 3
Present embodiment prepares the ultra-fine Zn that particle diameter is 300nm with coprecipitation method
0.70Mg
0.30TiO
3(ZMT) be principal crystalline phase,, and starch the preparation laminated ceramic capacitor with conventional casting method and low palladium content silver and carry out performance verification with the electron ceramic material of following prescription composition and described spray coating method preparation temperature characteristic conforms EIA-COG standard.
Taking by weighing 100Kg master earlier burns piece ZMT and goes into three-dimensional vibrating mill, the back adds 30 ℃ deionized water 100L, the back start is ground 8h and is dispersed into slip, back discharging is gone in the container of band stirring, be added with into deionized water, regulating its solid content is 45%, after take by weighing slip 30Kg and go into another and be with and be A in the well-stirred container, take by weighing in addition 97.3g concentration respectively and be 50% pin acid manganese slip and 40.5g boric acid, add deionized water 8Kg and stir into slip, after add again the 168.8g solid content be 40% silicon sol stirred 10 minutes slip B, at last again slip B is joined slowly among the slip A of stirring, after finishing, continue stirring 2h, is 35% slip thereby obtain slip solid content.Start centrifugal spray-drying tower, regulating the spray drying device hot blast temperature is 280 ℃, the control input speed is 1.8L/min, size with the control droplet, making the average granulation diameter of final powder is 50 μ m, water content is 0.36%, thereby has realized the coating-doping of spraying to slip A, obtains the powder C of good fluidity.
At this moment, directly to 5 of powder C random sampling, be no less than 30 points altogether and carry out electronic scanning Electronic Speculum (SEM) analysis respectively, all do not have the particle of finding with original principal crystalline phase ZMT particle significant difference and exist, do not find that evaporate to dryness sedimentation or coprecipitation method are controlled to find the phenomenon that a large amount of small-particles are piled up when bad usually yet; Same sampling is no less than 10 point-like electron energy spectrum analysiss (EDS), and it is very even to find that each doped element distributes between microcell, there is no the obvious enrichment phenomenon of some element, does not also have the non-existent point of individual element.Thereby, can think success realization multiple doping composition be the even adulterated modification of 300nm principal crystalline phase ZMT to particle diameter, and successful maintenance original pattern of ZMT powder and dispersiveness.Accompanying drawing 5 is the dielectric ceramic powder body pattern of principal crystalline phase ZMT after mixing, and subordinate list 5 is got ten some doped elements (deduction EDS is difficult to measure element B) and pressed 100% and convert the result for EDS analyzes.
Equally, for further verifying the electric property of the powder that this method prepares, to powder C, with low palladium content silver slurry system, it is 20 μ m that the method for preparing laminated ceramic capacitor with common casting method has been made dielectric thickness, and effectively medium is 15 layers, and dimensions is 0805 laminated ceramic capacitor.Get and be no less than 5 growing states of observing MLCC porcelain body surface microstructure with SEM, find the regular densification of its grain growing, there is no abnormal grain exists, get 30pcs, in temperature is 25 ℃, RH is under 75% the envrionment conditions, is 1MHz with the A electric bridge in frequency, voltage is that 0.5V tests its electrical capacity (C) and dielectric loss (tg δ), with measured capacity,, under 50V, keep testing in 1 minute its resistivity (ρ) with quick Insulation Resistance Tester by calculating specific inductivity (ε), test its withstand voltage properties (BDV) under direct current with Hi-pot Tester, and be 1MHz with high-low temperature chamber and electric bridge in frequency, voltage is that 1.0V cooperatively interacts down, tests its electrical capacity (C), calculating it with respect to the volume change coefficient (TCC) under 25 ℃, and the absolute value of the maximum velocity of variation between-55 ℃ to 125 ℃; Respectively get 72pcs, at 1.5v low pressure and 125v high pressure,, carry out the acceleration steady state damp heat test (DSAT) of 100h under the 85RH% respectively at 85 ℃, other gets 72pcs and soaks 3-5s at 270 ℃ and carry out thermal shock test (TST), all with volume change rate absolute value before and after the test | and Δ C/C|＞2%, ρ＜5 * 10
10Judge number of non-compliances when Ω .cm and examination back loss value take place greater than the arbitrary situation of the preceding value twice of examination, concrete parameter sees Table 6.Accompanying drawing 6 is the grain growing shape appearance figure on its laminated ceramic capacitor porcelain body surface.By the result as seen, method can obtain meeting the meticulous dielectric ceramic powder body of super even height of EIA-NPO standard very easily thus.
Table 1: principal crystalline phase is the BT powder, and EDS analyzes institute and gets ten and press each to put doped element be 100% o'clock result.Unit: %
| Element | Ca | Y | Cu | Mn | Mg | Si |
| 1 | 19.21 | 60.12 | 4.83 | 2.45 | 4.16 | 9.23 |
| 2 | 19.65 | 59.87 | 4.91 | 2.35 | 4.01 | 9.21 |
| 3 | 19.53 | 59.90 | 4.81 | 2.39 | 4.08 | 9.29 |
| 4 | 19.41 | 60.02 | 4.96 | 2.33 | 4.06 | 9.22 |
| 5 | 19.43 | 59.92 | 4.79 | 2.36 | 4.13 | 9.37 |
| 6 | 19.41 | 59.95 | 5.01 | 2.31 | 4.09 | 9.23 |
| 7 | 19.49 | 60.05 | 4.95 | 2.27 | 4.11 | 9.13 |
| 8 | 19.38 | 59.97 | 4.86 | 2.29 | 4.15 | 9.35 |
| 9 | 19.47 | 60.15 | 4.91 | 2.23 | 4.13 | 9.11 |
| 10 | 19.46 | 59.99 | 4.93 | 2.36 | 4.09 | 9.17 |
Table 2: principal crystalline phase is the BT powder, the sample test data results
Table 3: principal crystalline phase is the BTZ powder, and EDS analyzes institute and gets ten and press each to put doped element be 100% o'clock result.Unit: %
| Element | Ca | Y | Cu | Mn | Mg | Si |
| 1 | 36.96 | 26.51 | 5.60 | 9.81 | 4.38 | 16.74 |
| 2 | 37.05 | 26.53 | 5.65 | 9.98 | 4.29 | 16.50 |
| 3 | 36.99 | 26.44 | 5.61 | 9.86 | 4.33 | 16.77 |
| 4 | 36.93 | 26.49 | 5.71 | 9.95 | 4.24 | 16.68 |
| 5 | 36.95 | 26.48 | 5.59 | 9.89 | 4.36 | 16.73 |
| 6 | 36.92 | 26.55 | 5.63 | 9.94 | 4.31 | 16.65 |
| 7 | 37.00 | 26.51 | 5.61 | 9.87 | 4.32 | 16.69 |
| 8 | 36.98 | 26.49 | 5.72 | 9.96 | 4.38 | 16.47 |
| 9 | 37.06 | 26.52 | 5.53 | 9.92 | 4.28 | 16.69 |
| 10 | 36.91 | 26.47 | 5.64 | 9.90 | 4.31 | 16.77 |
Table 4: principal crystalline phase is the BTZ powder, the sample test result
Table 5: principal crystalline phase is the ZMT powder, and EDS analyzes institute and gets ten and press each to put doped element be 100% o'clock result.Unit: %
| Element | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| Mn | 32.33 | 31.97 | 32.51 | 32.15 | 32.02 | 31.87 | 32.39 | 31.96 | 32.13 | 32.06 |
| Si | 67.67 | 68.03 | 67.49 | 67.85 | 67.98 | 68.13 | 67.61 | 68.04 | 67.87 | 67.94 |
Table 6: principal crystalline phase is the ZMT powder, the sample test result
Claims (10)
1, a kind of spray coating method for preparing dielectric ceramic powder body, step is successively:
A, the compound soluble inorganic salt precursor of principal crystalline phase ceramic powder and modified metal ion or colloidal sol are put into deionized water carry out the slip that the physics dispersion treatment becomes good fluidity; Perhaps earlier become the slip of good fluidity to add the compound soluble inorganic salt precursor of modified metal ion again or colloidal sol is deployed into slip with deionized water physics dispersion principal crystalline phase ceramic powder; Perhaps directly select the water-based slip for use;
B, with the described slip of steps A, being deployed into solid content with deionized water is 5%～70% slip;
C, with the slip of step B gained while stirring the materials pump delivery to spray-drier, the control input speed is 0.01L/min～6.0L/min, spraying drying under 120 ℃～450 ℃ hot blast temperature, obtain the dielectric ceramic powder body of needs, gained powder granulation diameter is 500nm～200 μ m, moisture content≤3.0%;
Perhaps:
D, the dielectric ceramic powder body of step C gained is put into the calcining 0.5～6 hour down of 250～1200 ℃ of High Temperature Furnaces Heating Apparatuss again.
2. the spray coating method of dielectric ceramic powder body according to claim 1, it is characterized in that: described principal crystalline phase ceramic powder is selected a preparation by hydrothermal method, coprecipitation method, homogeneous precipitation method, Oxalic Acid Method, sol-gel method, microemulsion method, spraying decomposition method, vapor phase process, and diameter of particle is 50～1500nm.
3, the spray coating method of dielectric ceramic powder body according to claim 2 is characterized in that: described modified metal ionically-soluble inorganic salt or its colloidal sol comprise one or more mixing solutionss in oxyhydroxide or hydrous oxide, nitrate, acetate, Citrate trianion, oxalate or its colloidal sol, the high-dispersion nano suspension.
4, the spray coating method of dielectric ceramic powder body according to claim 3 is characterized in that: described amount of deionized water: principal crystalline phase ceramic powder mass ratio is 0.7～4.0: 1.
5, the spray coating method of dielectric ceramic powder body according to claim 4 is characterized in that: described principal crystalline phase ceramic powder is to select a physics dispersing mode with stirring, ball milling, sand milling, three-dimensional vibrating to handle.
6, the spray coating method of dielectric ceramic powder body according to claim 1 is characterized in that: among the described step B, with deionized water slurry blending being become solid content is 20～50% slip.
7, the spray coating method of dielectric ceramic powder body according to claim 6 is characterized in that: among the described step C, the spraying drying temperature is 180～300 ℃, and powder granulation diameter is 5.0 μ m～80 μ m, water content＜1.0%.
8, the spray coating method of dielectric ceramic powder body according to claim 7 is characterized in that: among the described step D, calcining temperature is 700～1000 ℃, insulation 0.5～3h.
9, a kind of according to the dielectric ceramic powder body of selecting a described spray coating method preparation in the claim 1～8, it is characterized in that: it comprises principal crystalline phase ceramic powder or main piece ceramic powder, modified metal ion and the sintering agent of burning, its prescription molecular formula is (1-m) MA-mMB-pMZ, wherein MA represents the main piece that burns, MB is the modification composition, MZ is the sintering agent composition, m=0～15, p=0～3.
10, dielectric ceramic powder body according to claim 9 is characterized in that: described principal crystalline phase ceramic powder or the main piece phase ceramics powder that burns are a kind of among barium titanate BT, zirconium barium titanate BTZ, barium calcium zirconate titanate BCTZ, strontium-barium titanate BST, strontium zirconate calcium CSZ, strontium zirconate barium BSZ, calcium zirconate CZ, barium zirconate BZ, tin titan zirconium ZST, magnesium titanate MT, magnesium titanate zinc ZMT, strontium titanate ST, the metatitanic acid neodymium barium BNT;
Described modified metal element is one or more among Ba, Sr, Ca, Mg, Sn, Zn, Cu, Ni, Co, Fe, Mn, Cr, Sc, Sb, Zr, Ti, Al, Sc, Nb, Ta or rare-earth elements La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Y, the Lu;
Described sintering agent is one or more soluble salt or its colloidal sol of B, Si, Li, Na, K, Bi, Sb, P, V, Zn, Cu.
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