CN1254455C - Preparing method for temperature-stabilized dielectric ceramic materials - Google Patents
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- CN1254455C CN1254455C CN 200410026201 CN200410026201A CN1254455C CN 1254455 C CN1254455 C CN 1254455C CN 200410026201 CN200410026201 CN 200410026201 CN 200410026201 A CN200410026201 A CN 200410026201A CN 1254455 C CN1254455 C CN 1254455C
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Abstract
The present invention discloses a method for preparing Pb-series temperature-stabilized dielectric ceramic materials. The present invention is characterized in that PbO, WO<3>, TiO<2>, and Nb<2>O<5> are milled into slurry by balls in ethanol medium according to the stoichiometric ratio; the water solution of soluble nickel salt, magnesium salt and manganese salt is added into the slurry to be milled by balls, dried and ground. Then, the mixture is sintered for 1 to 4 hours at 750 DEG C to 950 DEG C and then is milled by balls so as to obtain presintering powder, and the presintering powder is molded and sintered into ceramic at 1050 DEG C to 1200 DEG C. The present invention reduces the sintering temperature and the sintering time of ceramic so as to reduce the volatilization of lead monoxide, decrease the energy consumption and the production cost and improve the working environment. The dielectric constant at room temperature of the prepared dielectric ceramic material reaches to more than 4300.
Description
Technical field
The present invention relates to a kind of preparation method of dielectric ceramic material, particularly a kind of lead is the preparation method of temperature-stable dielectric ceramic material.
Background technology
Laminated ceramic capacitor (MLCC) is that electrode materials and ceramic body is superimposed with the parallel connection of multilayer alternatively form, is fired into an integral body.Because the MLCC volume is little, capacity is big, stable performance, inexpensive, be particularly suitable for the chip type surface-assembled, can improve the circuit packing density greatly, dwindle machine volume, these outstanding characteristics make MLCC become at present consumption maximum in the world, a kind of chip type electronic component with fastest developing speed.X7R type MLCC particularly, temperature stability is best, is indispensable elements such as notebook computer, palm PC, mobile telephone, digital camera, automobile, and its market demand accounts for more than 40% of MLCC total amount.According to the international EIA of Electronic Industries Association USA standard, X7R refers between temperature range-55～+ 125 ℃, temperature coefficient of capacitance≤± 15%, dielectric loss (tg δ)≤2.5%.
At present, the material system that satisfies the X7R characteristic of research comparative maturity mainly contains two classes: a class is a lead-based relaxor ferroelectric ceramics; Another kind of right and wrong lead is BaTiO
3The base dielectric ceramic.Although BaTiO
3Be used as the main flow material of making ceramic condenser, but its specific inductivity is lower, and the upper limit is about 10000～14000, and firing temperature higher (＞1300 ℃), need higher precious metal palladium of employing cost or the silver palladium alloy inner electrode as MLCC, cost is higher.And have the relaxation sections electroceramics, particularly lead-based relaxor ferroelectric ceramics of calcium hematite structure, and its specific inductivity is up to 30000, and very wide Curie peak is arranged, and temperature stability is higher; Simultaneously, it also has advantages such as firing temperature is lower, can use the higher silver-colored palladium of silver content as inner electrode, and its production cost is reduced greatly.
Lead with " core-shell " structure be X7R type stupalith consist of xPb (Mg
1/2W
1/2) O
3-yPb (Ni
1/3Nb
2/3) O
3-(1-x-y) PbTiO
3+ aWO
3+ bMnO
2, be abbreviated as xPMW-yPNN-(1-x-y) PT+aWO
3+ bMnO
2Usually adopting two kinds of methods to prepare this ekalead is X7R type ceramic powder material: conventional oxide method (Fumio Uchikoba, Takashi Ito andShigeyuki Nakajima, Jpn.J.Appl.Phys.1995,34:2374-2379) with secondary synthesis method (Yong Zhang, ZhilunGui, Longtu Li, JiemoTian.Mater.Sci.and Eng.2001, B83:66-69).In the conventional oxide method, for preventing the green stone phase of deleterious Jiao, need to add excessive magnesium and plumbous oxide reduce in the pottery Jiao Lvshi mutually, and excessive plumbous oxide and magnesium oxide make xPMW-yPNN-(1-x-y) PT+aWO
3+ bMnO
2Pottery is difficult to satisfy the X7R characteristic.The processing step of secondary synthesis method is: earlier magnesium oxide is become niobite MgWO with tungstic oxide, nickel oxide and Niobium Pentxoxide respectively at high-temperature calcination
4And NiNb
2O
6, and then mix with plumbous oxide, titanium dioxide and Manganse Dioxide (or manganous carbonate), ball milling, get the almost xPMW-yPNN-of pure perovskite phase (1-x-y) PT+aWO through pre-burned
3+ bMnO
2The pre-burning powder is after ball milling, screening, moulding and high temperature sintering make lead is the X7R stupalith.The calcined temperature of secondary synthesis method and sintering temperature are all than higher, length consuming time, technology is loaded down with trivial details, and cause environmental pollution because of PbO is volatile, and easily produce stoichiometric ratio and depart from prescription, and reactive component is inhomogeneous etc. not enough, make that lead is that the yield rate of X7R pottery is lower, and preparation cost is higher.
The solution chemistry method has good application prospects aspect the preparation electronic ceramics powder, and wherein chemical precipitation method can be synthesized pure perovskite phase Pb (Mg
1/3Nb
2/3) O
3(being called for short PMN), Pb (Fe
1/2Nb
1/2) O
3On pottery, its principal feature is can be at next step synthetic almost pure perovskite PMN based ceramic powder body mutually of lower calcined temperature and sintering temperature, and has reduced the environmental pollution that plumbous volatilization caused thus.But because the singularity and the very high reason of cost of chemical property of the soluble salt (alkoxide or oxalate etc.) of high price niobium, and consequent technology singularity, limited the application aspect preparing of solution chemistry method in lead-based relaxor ferroelectric ceramics.In order to seek more simple and convenient preparation method, people such as the Plumb, Nathan J. of Shanghai Inst. of Silicate, Chinese Academy of Sciences propose liquid phase pack (Plumb, Nathan J. etc., the functional ceramic powder preparation, the theoretical basis of liquid phase technique for packing and application (first version), Shanghai scientific popularization press, Shanghai: 1997), promptly adopt the solution of magnesium nitrate and citric acid niobium to replace MgO and Nb in the conventional oxide method respectively
2O
5, generate MgNb in calcining reaction in early stage
2O
6, the PMN powder at later stage and PbO reaction formation perovskite structure makes the developed and simplification of chemical method.But this method still need prepare the coordination compound-citric acid niobium that contains niobium, the citric acid niobium is the hydrate that is made niobium hydroxide or niobium oxides by Niobium Pentxoxide earlier, be dissolved in oxalic acid then and obtain water miscible oxalate, come the hydrate of purified hydrogen niobium oxides or niobium oxides again with ammonia precipitation process, obtain water-soluble citric acid niobium with citric acid dissolved hydrogen niobium oxides or niobium oxides at last, cost is higher, and technological process is complicated.
Summary of the invention
The lead that the purpose of this invention is to provide a kind of X7R of satisfying characteristic is the preparation method of temperature-stable dielectric ceramic material, the room temperature dielectric constant of the dielectric ceramic material that obtains is greater than 4300, reach as high as more than 5300, dielectric loss (tg δ)≤2.5%, insulation resistivity is greater than 10
12Ω cm.This method is with low cost, and technology is simple, and environmental friendliness has good industrial applications prospect is arranged very much.
The step of preparation process of the present invention of realizing above-mentioned purpose is as follows successively:
1. press general formula xPb (Mg
1/1W
1/2) O
3-yPb (Ni
1/3Nb
2/3) O
3-(1-x-y) PbTiO
3+ aWO
3+ bMnO
2Represented stoichiometric ratio is with PbO, WO
3, TiO
2And Nb
2O
5Ball milling gets slurry A in ethanol medium, x=0.25 in the formula～0.35, y=0.35～0.45,3.0mol%≤a≤20.0mol%, 0.25mol%≤b≤1.5mol%; Wherein, a represents the WO with respect to the metering ratio
3Excessive amount of substance percentage ratio, b represents doping agent MnO
2With respect to principal constituent xPb (Mg
1/2W
1/2) O
3-yPb (Ni
1/3Nb
2/3) O
3-(1-x-y) PbTiO
3Amount of substance percentage ratio;
2. add to by the aqueous solution of represented stoichiometric soluble nickel (II) salt of above-mentioned general formula, magnesium (II) salt and manganese (II) salt that ball milling gets slurry B among the slurry A;
3. slurry B is dried down at 80～120 ℃, grind and obtain C;
4. C ball milling behind 750～950 ℃ of following roasting 1～4h is obtained pre-burning powder D;
5. pre-burning powder D with 5～10 ℃/min heat-up rate, rises to 1050～1200 ℃ through extrusion forming, and insulation 1～4h sinters pottery into.
Soluble nickel salt, magnesium salts and manganese salt are nitrate, acetate, formate or their mixture.
C ball milling after 800～850 ℃ of following roastings obtains pre-burning powder D in the above-mentioned processing step.
Pre-burning powder D sinters pottery at 1130～1170 ℃ in the above-mentioned processing step.
Add the tackiness agent press molding before the roasting of pre-burning powder, tackiness agent is 5% polyvinyl alcohol.
The pre-burning powder of perovskite structure is that preparation high dielectric property lead is the key of relaxation ferroelectric ceramic(s).The lead of pure perovskite phase is X7R type ceramic powder material to use prior art to be difficult to make almost, and major cause is that the reactive behavior and the distributing homogeneity of reaction raw materials-magnesium oxide, nickel oxide is relatively poor, reacts halfway cause; And adopting solid phase to mix also is difficult to make the small amounts of dopants manganese oxide to be evenly distributed.The present invention is to contain magnesium (II), the cheap soluble salt of nickel (II) and manganese (II) replaces its corresponding oxide, need not to add in addition precipitation agent, to have alkaline reaction raw materials plumbous oxide as precipitation agent, make soluble magnesium (II), nickel (II) and manganese (II) salt pass through hydrolysis reaction, generate corresponding oxyhydroxide or subsalt precipitation, generate " nascent state " oxide compound-magnesium oxide of polymolecularity and high reaction activity then by thermolysis, nickel oxide and manganese oxide, under lower maturing temperature, prepare the almost xPMW-yPNN-of pure perovskite phase (1-x-y) PT+aWO
3+ bMnO
2The pre-burning powder can burn till the X7R type stupalith with high dielectric property with this powder in wide temperature range.
The method of ceramic material that the X7R characteristic is satisfied in preparation of the present invention has the following advantages and positively effect:
1, magnesium oxide, nickel oxide and the manganese oxide (or manganous carbonate) in the corresponding solubility magnesium salts of use, nickel salt and the manganese salt replacement conventional oxide method in the preparation process, other component is used corresponding oxide compound, compare with chemical precipitation method, avoid alkoxide or the muriate or the coordination compound of higher high price niobium (V) of use cost and titanium (IV).
2, make water and/or ethanol as solvent in the preparation process, production safety, compliance with environmental protection requirements.
3, the use of solubility magnesium salts, nickel salt and manganese salt has improved the reactive behavior and the dispersiveness of magnesium oxide, nickel oxide and manganese oxide, the stupalith that obtains has high dielectric properties, promptly under the suitable situation of other performance, specific inductivity (5300) is higher than about 3800 of TDK report.
4, preparation method of the present invention has reduced ceramic sintering temperature and sintering time, thereby has reduced the volatilization of plumbous oxide, has also reduced energy consumption and production cost, has improved production environment.
5, the equipment that relates to of preparation method of the present invention is simple, and the pottery of preparing can satisfy the requirement of X7R type MLCC high-performance and miniaturization.
Embodiment
The preparation method of a kind of X7R type MLCC dielectric ceramic material provided by the invention can be at 1050～1200 ℃, and insulation 1～4h sintering goes out the X7R type dielectric ceramic material of excellent performance.The room temperature dielectric constant of material is up to 5300, and the temperature coefficient of capacitance in-55 ℃～+ 125 ℃ scopes is less than ± 15%, and insulation resistivity is all greater than 10
12Ω cm, dielectric loss be less than 2.5%, stable performance.
Use Japanese DMX-III type X-ray powder diffraction instrument of science to determine the thing phase of powder; The test macro that the mensuration of the temperature spectrum (change curve of dielectric constant with temperature) that is situated between adopts computer-controlled high low temperature trap and the accurate LCR tester of HP4284A type to form.
Example 1: sample 1-3 is corresponding to 1130 ℃ (samples 1), and 1150 ℃ (sample 2) and 1170 ℃ (sample 3) and soaking time are the xPMW-yPNN-that sintering makes under the 2h (1-x-y) PT+aWO
3+ bMnO
2Pottery.Wherein x=0.29 and y=0.41; A=5mol% and b=0.25mol%.
Accurate weighing PbO 13.3991g, WO
32.1190g, TiO
21.4385g and Nb
2O
52.1808g, in ethanol medium, behind the ball milling 12h, obtain PbO, WO then
3, TiO
2And Nb
2O
5Mixed slurry A; With Ni (Ac)
2, Mg (Ac)
2And Mn (NO
3)
2Be mixed with concentration and be respectively 0.20g/ml, the aqueous solution of 0.15g/ml and 0.01g/ml is measured Ni (Ac) respectively
2Solution 7.25ml, Mg (Ac)
2Solution 8.26ml, Mn (NO
3)
2Solution 2.69ml is added among the above-mentioned slurry A and continues ball milling 2h and obtain slurry B; Slurry B 100 ℃ of oven dry down, is obtained reaction precursor body C through grinding; Reaction precursor body C can obtain the almost xPMW-yPNN-of pure perovskite phase (1-x-y) PT+aWO behind 850 ℃ of following roasting 2h
3+ bMnO
2Powder body material obtains pre-burning powder D through ball milling 12h; The adhesive polyethylene alcohol extrusion forming that in pre-burning powder D, adds weight percent 0.5%; With 10 ℃/min heat-up rate, rise to 1130 ℃～1170 ℃, insulation 2h sinters pottery into.Be coated with silver in the ceramics top and bottom of burning till, measure Jie's temperature spectrum and the dielectric loss graphic representation of pottery between-55 ℃～125 ℃, main test result sees Table 1.
K represents specific inductivity in the table 1, and tg δ represents dielectric loss, and the temperature coefficient of capacitance of the relative 25 ℃ of specific inductivity of specific inductivity under the temperature is measured in TCC (%) expression.
Specific inductivity and the temperature coefficient of capacitance of table 1 sample 1-3
| Sample number | Sintering temperature/℃ | 25 ℃ of room temperatures | TCC/％ | ||||
| K | tgδ | -55℃ | -30℃ | 85℃ | 125℃ | ||
| 1 2 3 | 1130 1150 1170 | 4930 5395 4318 | 0.0084 0.0033 0.0058 | -3.69 -4.15 -0.74 | 1.92 5.81 5.81 | 3.99 -11.24 -9.62 | -13.84 -7.71 -14.69 |
Example 2:
Sample 4-6 is corresponding to xPMW-yPNN-(1-x-y) PT+aWO that makes at 1150 ℃ of (insulation 2h) sintering
3+ bMnO
2Pottery.X=0.29 wherein, y=0.41; A is respectively 5mol% (sample 4), 10mol% (sample 5) and 20mol% (sample 6); B is 0.25mol%.
Accurate weighing PbO 13.3991g, Nb
2O
52.1808g, TiO
21.4385g, WO
3Be respectively 2.1190g, 2.2199g, 2.4217g; In ethanol medium, behind the ball milling 12h, obtain mixed slurry A respectively then; With Ni (Ac)
2, Mg (Ac)
2And Mn (NO
3)
2Be mixed with concentration and be respectively 0.20g/ml, the aqueous solution of 0.15g/ml and 0.01g/ml is measured Ni (Ac) respectively
2Solution 7.25ml, Mg (Ac)
2Solution 8.26ml, Mn (NO
3)
2Solution 2.69ml adds among the above-mentioned slurry A, continues ball milling 2h and obtains slurry B.Slurry B 100 ℃ of oven dry down, is obtained reaction precursor body C through grinding; Reaction precursor body C can obtain the almost xPMW-yPNN-of pure perovskite phase (1-x-y) PT+aWO behind 850 ℃ of roasting 2h
3+ bMnO
2Powder body material obtains pre-burning powder D through ball milling 12h; The adhesive polyethylene alcohol extrusion forming that in pre-burning powder D, adds weight percent 0.5%; With 5 ℃/min speed, rise to 1150 ℃, insulation 2h sinters pottery into.Be coated with silver in the ceramics top and bottom of burning till, between-55 ℃～125 ℃, measure Jie's temperature spectrum and the dielectric loss graphic representation of pottery, mainly the results are shown in Table 2.
Specific inductivity and the temperature coefficient of capacitance of table 2 sample 4-6
| Sample number | Excessive WO 3/mol％ | 25 ℃ of room temperatures | TCC/％ | ||||
| K | tgδ | -55℃ | -30℃ | 85℃ | 125℃ | ||
| 4 5 6 | 5.0 10.0 20.0 | 5395 4782 5029 | 0.0033 0.0045 0.0058 | -4.15 -4.87 -3.92 | 5.82 4.87 3.92 | -11.29 -10.56 -9.25 | -7.71 -8.07 -7.60 |
Example 3
Sample 7-8 is corresponding to xPMW-yPNN-(1-x-y) PT+aWO that makes at 1150 ℃ of (insulation 2h) sintering
3+ bMnO
2Pottery, wherein x is respectively 0.29 (sample 7) and 0.31 (sample 8), and y is respectively 0.41 (sample 7) and 0.39 (sample 8); A=5mol% and b=0.25mol%.
Accurately weighing PbO is respectively 13.3991g and 13.3808g, WO
3Be respectively 2.1190g and 2.2616g, TiO
2Be respectively 1.4385g and 1.4370g, Nb
2O
5Be respectively 2.1808g and 2.0716g, respectively counter sample 7 and sample 8 (as follows); In ethanol medium, behind the ball milling 20h, obtain PbO, WO then
3, TiO
2And Nb
2O
5Slurry A; With Ni (Ac)
2, Mg (Ac)
2And Mn (NO
3)
2Be mixed with concentration and be respectively 0.2g/ml, the aqueous solution of 0.15g/ml and 0.01g/ml is measured Ni (Ac) respectively
2Solution 7.25ml and 6.89ml, Mg (Ac)
2Solution 8.26ml and 8.82ml, Mn (NO
3)
2Solution 2.69ml and 2.68ml are added among the above-mentioned slurry A, continue ball milling 2h and obtain slurry B.Slurry B 110 ℃ of oven dry down, is obtained reaction precursor body C through grinding; Reaction precursor body C can obtain the almost xPMW-yPNN-of pure perovskite phase (1-x-y) PT+aWO behind 820 ℃ of following roasting 3h
3+ bMnO
2Material obtains pre-burning powder D through ball milling 12h; The adhesive polyethylene alcohol extrusion forming that in pre-burning powder D, adds weight percent 0.5%; With 10 ℃/min heat-up rate, rise to 1150 ℃, insulation 2h sinters pottery into.Be coated with silver in the ceramics top and bottom of burning till, between-55 ℃～125 ℃, measure Jie's temperature spectrum and the dielectric loss figure of pottery, mainly the results are shown in Table 3.
Table 3 sample 7 and 8 specific inductivity and temperature coefficient of capacitance
| Sample number | Form | 25 ℃ of room temperatures | TCC/％ | ||||
| K | tgδ | -55℃ | -30℃ | 85℃ | 125℃ | ||
| 7 8 | x＝0.29；y＝0.41 x＝0.31；y＝0.39 | 5395 4668 | 0.0033 0.0037 | -4.15 -7.38 | 5.81 1.29 | -11.24 -2.20 | -7.71 -12.65 |
Claims (8)
1, a kind of preparation method of temperature-stable dielectric ceramic material, its preparation technology in turn includes the following steps:
A. press general formula xPb (Mg
1/2W
1/2) O
3-yPb (Ni
1/3Nb
2/3) O
3-(1-x-y) PbTiO
3+ aWO
3+ bMnO
2Represented stoichiometric ratio is with PbO, WO
3, TiO
2And Nb
2O
5Ball milling gets slurry A in ethanol medium, x=0.25 in the formula～0.35, and y=0.35～0.45,3.0mol%≤a≤20.0mol%, 0.25mol%≤b≤1.5mol%, a represent the WO with respect to the metering ratio
3Excessive amount of substance percentage ratio, b represents doping agent MnO
2With respect to principal constituent xPb (Mg
1/2W
1/2) O
3-yPb (Ni
1/3Nb
2/3) O
3-(1-x-y) PbTiO
3Amount of substance percentage ratio;
B. add to by the aqueous solution of represented stoichiometric soluble nickel (II) salt of above-mentioned general formula, magnesium (II) salt and manganese (II) salt that ball milling gets slurry B among the slurry A;
C. with slurry B oven dry, grind C;
D. C ball milling after 750～950 ℃ of following roastings is got pre-burning powder D;
E. pre-burning powder D sinters pottery at 1050～1200 ℃.
2, the preparation method of a kind of temperature-stable dielectric ceramic material according to claim 1 is characterized in that: described soluble nickel salt, magnesium salts and manganese salt are nitrate, acetate, formate or their mixture.
3, the preparation method of a kind of temperature-stable dielectric ceramic material according to claim 1, wherein maturing temperature is 800～850 ℃ in the steps d.
4, the preparation method of a kind of temperature-stable dielectric ceramic material according to claim 1, wherein maturing temperature is 1130～1170 ℃ among the step e.
5, the preparation method of a kind of temperature-stable dielectric ceramic material according to claim 1, wherein roasting 1～4h in the steps d.
6, the preparation method of a kind of temperature-stable dielectric ceramic material according to claim 1, wherein rising the speed stabilizing rate among the step e is 5～10 ℃/min, roasting 1～4h.
7, according to the preparation method of one of any described a kind of temperature-stable dielectric ceramic material among the claim 1-6, it is characterized in that: add the tackiness agent press molding in the pre-burning powder.
8, the preparation method of a kind of temperature-stable dielectric ceramic material according to claim 7, tackiness agent is that mass percent is 5% polyvinyl alcohol.
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|---|---|---|---|
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