CN1159257C - Middle-temp sintered ceramic material - Google Patents
Middle-temp sintered ceramic material Download PDFInfo
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- CN1159257C CN1159257C CNB001175459A CN00117545A CN1159257C CN 1159257 C CN1159257 C CN 1159257C CN B001175459 A CNB001175459 A CN B001175459A CN 00117545 A CN00117545 A CN 00117545A CN 1159257 C CN1159257 C CN 1159257C
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Abstract
The present invention relates to a porcelain material, particularly to a middle temperature sintered porcelain material. The porcelain material comprises the components with the percentages by weight: 70 to 76% of Ba2Ti 9 as a main crystal phase, 10 to 15% of lead borosilicate, 9 to 14% of zirconium dioxide, 0.6 to 1.2% of calcium zirconate and 0.1 to 0.3% of manganese carbonate, wherein the lead borosilicate comprises 20 to 40 wt% of B2O3, 15 to 30 wt% of SiO2 and 30 to 55 wt% of PbO. The porcelain material has the advantages that the consistency, the reliability and the hit rate of the product can be improved when high frequency capacitors with small volume and high accuracy are manufactured by the NPO sheet type multi-layer porcelain dielectric capacitor porcelain material with low price, the porcelain material can also be used in wider and higher frequency bands, the porcelain material can be developed for microwave frequency bands with hundreds or even thousands of MHz, etc.
Description
The present invention relates to porcelain, particularly a kind of Middle-temp sintered ceramic material.
Along with developing rapidly of modern electronic technology, the particularly arrival of whole world information age, and the rise of microwave communication, the demand of high frequency capacitor that to temperature factor is 0 ± 30ppm/ ℃ (hereinafter to be referred as NPO) is increasing, require more and more higher, use the microwave frequency band development of frequency range to hundreds of even several gigabits, its chip multilayer ceramic capacitor extensively applies in the circuit such as filtering, bypass, vibration, compensation, wherein based on the high frequency monolithic capacitor of NPO material then with its high stable in circuit, high precision and be celebrated.
Laminated ceramic capacitor has been carried out big quantity research with the NPO material both at home and abroad, and dropped into production in enormous quantities, in the intermediate sintering temperature field, with BaO-TiO
2-Nd
2O
3System is that height Jie NPO porcelain of principal crystalline phase has entered ripe operational phase, and the component of Adjustment System and add suitable modifying agent can make the ε of porcelain powder adjust arbitrarily between 50-100.And, MgTiO is arranged at low Jie NPO porcelain system aspects
3/ CaTiO
3System, Zr/Sn/Ti system and BaTi
4O
9/ Ba
2Ti
9O
20Corresponding research and production in enormous quantities have been carried out in system.Abroad, as the MgTiO of U.S. TAM company
3/ CaTiO
3System, the Middle-temp sintered ceramic material about ε=15 has obtained use in enormous quantities, and U.S. Ferro company has also released BaTi
4O
9/ Ba
2Ti
9O
20Low Jie NPO porcelain about the ε of system=30, but it is reported that this system does not also have fully matured, the chip multilayer ceramic capacitor processing performance is poor.
Purpose of the present invention is exactly at above-mentioned the deficiencies in the prior art part, providing a kind of can make low Jie NPO chip multilayer ceramic capacitor porcelain make low capacity, high-precision high frequency capacitor, homogeneity of product, reliability and hit rate improve, can also under more wide higher frequency range, use the Middle-temp sintered ceramic material that can develop to the microwave frequency band of hundreds of even several thousand MHz.
The object of the present invention is achieved like this: a kind of ferroelectrics composition, it comprises oxidation nine titaniums two barium principal crystalline phases, lead borosilicate, zirconium dioxide, calcium zirconate, manganous carbonate composition, its weight percent is: oxidation nine titaniums two barium principal crystalline phases 70～76%, lead borosilicate 10～15%, zirconium dioxide 9～14%, calcium zirconate 0.6～1.2%, manganous carbonate 0.1～0.3%, wherein lead borosilicate consists of (wt%): B
2O
320～40%, SiO
215～30%, PbO30～55%; A kind of Middle-temp sintered ceramic material, it is to be formed at sintering below 1040 ℃ or 1040 ℃ by described ferroelectrics composition; Described ferroelectrics composition can also form at 1000 ℃ of sintering; The ferroelectrics composition can also form at 1020 ℃ of sintering; A kind of preparation method of Middle-temp sintered ceramic material, comprise described ferroelectrics composition, its weight percent is: oxidation nine titaniums two barium principal crystalline phases 70～76%, lead borosilicate 10～15%, zirconium dioxide 9～14%, calcium zirconate 0.6～1.2%, manganous carbonate 0.1～0.3%, wherein lead borosilicate consists of (wt%): B
2O
320～40%, SiO
215～30%, PbO30～55%, behind the mix → ball milling → sand milling → dry and sieve → forming and sintering → electric physicals → sampling observation; Described ball milling be agate ball in: material: ball=1: the ratio of (2～3) adds in the ball mill, ball milling 15 hours; Described ball milling be agate ball in: material: ball=1: the ratio of (2～3) adds in the sand mill, sand milling 20 hours; Described oven dry is being carried out under 250 ℃: after the described porcelain oven dry, treat naturally cooling, beat powder, sieve.
Purpose of the present invention can also realize like this: a kind of ferroelectrics composition, it comprises oxidation nine titaniums two barium principal crystalline phases, lead borosilicate, zirconium dioxide, calcium zirconate, manganous carbonate composition, its weight percent is: oxidation nine titaniums two barium principal crystalline phases 70～76%, lead borosilicate 10～15%, zirconium dioxide 9～14%, calcium zirconate 0.6～1.2%, manganous carbonate 0.1～0.3%, wherein lead borosilicate consists of (wt%): B
2O
320～40%, SiO
215～30%, PbO30～55%; A kind of Middle-temp sintered ceramic material, it is to be formed at sintering below 1040 ℃ or 1040 ℃ by described ferroelectrics composition: described ferroelectrics composition can also form at 1000 ℃ of sintering: the ferroelectrics composition can also form at 1020 ℃ of sintering; A kind of preparation method of Middle-temp sintered ceramic material, comprise described ferroelectrics constituent, its weight percent is: oxidation nine titaniums two barium principal crystalline phases 70～76%, borosilicic acid 10～15%, zirconium dioxide 9～14%, calcium zirconate 0.6～1.2%, manganous carbonate 0.1～0.3%, wherein lead borosilicate consists of (wt%): B
2O
320～40%, SiO
215～30%, PbO30～55%, behind the mix → ball milling → sand milling → dry and sieve → forming and sintering → electric physicals → sampling observation; Described ball milling be agate ball in: material: ball=1: the ratio of (2～3) adds in the ball mill, ball milling 15 hours; Described ball milling be agate ball in: material: ball=1: the ratio of (2～3) adds in the sand mill, sand milling 20 hours; Described oven dry is carried out under 250 ℃; After the described porcelain oven dry, treat naturally cooling, beat powder, sieve.
The drawing of accompanying drawing is described as follows:
Fig. 1,2,3, the 4th, the pairing X-ray diffraction analysis figure of the present invention,
Fig. 5,6,7, the 8th, electrical condenser porcelain body section sem analysis figure of the present invention,
Fig. 9,10, the 11st, TiO of the present invention
2The synthetic Ba of institute
2Ti
9O
20The situation comparison diagram,
Fig. 12 is that Tcc of the present invention is with CsZrO
3The content graphic representation,
Figure 13 is the SEM photo analysis of the capacitor chip that burns till under 1020 ℃ of the present invention,
Figure 14 is the frequency characteristic figure of the chip multilayer ceramic capacitor that burns till under 1020 ℃ of the present invention, and Figure 15 is a process flow sheet of the present invention.
Table 1 is Ba
2Ti
9O
20The synthetic degree of crystalline phase,
Table 2 is Ba
2Ti
9O
20The MLCC electrical property of the porcelain that powder is joined that the synthetic degree of crystalline phase is different,
Table 3 is Ba
2Ti
9O
20The synthesis temperature difference of microwave material is to the influence of porcelain electrical property,
Table 4 is TiO
2The starting material size-grade distribution,
Table 5 is TiO that different grain size distributes
2Synthetic Ba
2Ti
9O
20The degree of crystalline phase,
Table 6 is different Ti O
2The size-grade distribution synthetic burns piece to porcelain MLCC Effect on Performance,
Table 7 is borate glass major ingredient,
Table 8 is to add borate glass to burn till the result under 1020 ℃,
Table 9 is that the present invention has broad firing range.
The present invention is described in further detail below in conjunction with accompanying drawing, form and embodiment: a kind of ferroelectrics composition, it comprises oxidation nine titaniums two barium principal crystalline phases, lead borosilicate, zirconium dioxide, calcium zirconate, manganous carbonate composition, its weight percent is: oxidation nine titaniums two barium principal crystalline phases 70～76%, borosilicic acid 10～15%, zirconium dioxide 9～14%, calcium zirconate 0.6～1.2%, manganous carbonate 0.1～0.3%, wherein lead borosilicate consists of (wt%): B
2O
320～40%, SiO
215～30%, PbO30～55%; It is to be formed at sintering below 1040 ℃ or 1040 ℃ by described ferroelectrics composition; It is can also be formed at 1000 ℃ of sintering by described ferroelectrics composition; It is can also be formed at 1020 ℃ of sintering by described ferroelectrics composition; Comprise described ferroelectrics composition, its weight percent is: oxidation nine titaniums two barium principal crystalline phases 70～76%, lead borosilicate 10～15%, zirconium dioxide 9～14%, calcium zirconate 0.6～1.2%, manganous carbonate 0.1～0.3%, its lead borosilicate consists of (wt%): B
2O
320～40%, SiO
215～30%, PbO30～55%, behind the mix → ball milling → sand milling → dry and sieve → forming and sintering → electric physicals → sampling observation; Described ball milling be agate ball in: material: ball=1: the ratio of (2～3) adds in the ball mill, ball milling 15 hours; Described ball milling be agate ball in: material: ball=1: the ratio of (2～3) adds in the sand mill, sand milling 20 hours; Described oven dry is carried out under 250 ℃; After the described porcelain oven dry, treat naturally cooling, beat powder, sieve.
Ba
2Ti
9O
20Owner's crystalline phase material+5～7wt% borate glass+0.1～0.8 (MnCO that fluxes
3, NiO, CaZrO
3Deng modifying agent).With the native system porcelain by only lapicide moulding of planting, behind the binder removal, sintering under 10204 ± 20 ℃/2hr, be divided into sample and sample, with U.S. HP4278A bridge test capacity, loss, with the quick Insulation Resistance Tester measurement insulation resistance of Nantong SF2512, measure withstand voltage with Nanjing CJ2671 tester, with 2300 type Tc stoves and HP4278A bridge measurement Jie temperature characteristics, measure the size-grade distribution of powder with the Ku Erte particle size analyzer, with full-automatic X-ray diffractometer of D/MAX-2000 of science and Philip XL-30 scanning electron microscope porcelain phase structure and porcelain body fracture apperance are carried out microanalysis, with the frequency response characteristic of HP4291A bridge measurement porcelain.
Ba
2Ti
9O
20The synthetic influence that reaches synthetic degree to the porcelain electrical property of crystalline phase:
The selected starting material of the present invention are BaCO
3, TiO
2Deng, press BaO/TiO
2Than be between 0.420 to 0.428 and add different mineralizers respectively, synthesis accelerant is done a large amount of experiments, find by different B aO/TiO
2When add different mineralizers, synthesis accelerant to Ba
2Ti
9O
20The synthetic influence that has in various degree, wherein, with BaO/TiO
2=0.426, add micro-WO simultaneously
3, ZnO synthetic ideal.Listed as table 1 is to add micro-WO separately
3, ZnO, and add micro-WO simultaneously
3, synthetic Ba during ZnO
2Ti
9O
20Comparing result.It shown in Fig. 1,2,3,4 pairing X-ray diffraction analysis.
Annotate: numbering " 1. " is by BaO/Ti
2=0.426 preparation
" 2. " be by BaO/TiO
2=0.426 and add trace Zn O preparation
" 3. " be by BaO/TiO
2=0.426 adds micro-WO
3Preparation
" 4. " be by BaO/TiO
2=0.426 adds micro-WO
3, ZnO preparation
In addition, find in the experiment, with the synthetic degree Ba that has nothing in common with each other
2Ti
9O
20The porcelain that microwave material is produced, its chip capacitor chip is at 1020 ℃ of following sintering, and the gained electrical property has nothing in common with each other, and is wherein, ideal, as shown in table 2 to number the porcelain that 4. synthetics prepared.
There are different its electrical condenser porcelain body grain growing homogeneities of synthetic degree also inconsistent again.Shown in Fig. 5,6,7,8 electrical condenser porcelain body section sem analysis.Show through the SEM photographic analysis, contain a small amount of BaTi
4O
9The Ba of crystalline phase
2Ti
9O
20System porcelain electrical condenser porcelain body surface is except there being the little crystal grain of a large amount of rectangles, also contains a small amount of square big crystal grain, and the existence of sintering porcelain body coarse grain cause the DF of MLCC ↑, BDV ↓, IR ↓, the porcelain electric property is reduced worsens.Therefore, make every effort to obtain to synthesize 100% Ba in the production
2Ti
9O
20Crystalline phase.
Annotate: number the 1. porcelain body SEM picture of synthetics preparation
2. the porcelain body SEM picture of synthetics preparation
3. the porcelain body SEM picture of synthetics preparation
4. the porcelain body SEM picture of synthetics preparation
Ba
2Ti
9O
20The synthesis temperature difference of microwave material is to the influence of porcelain electrical property
Press BaO/TiO
2=0.426 and add micro-WO simultaneously
3, ZnO, through art breading, synthetic Ba under different temperature
2Ti
9O
20, and make the electrical condenser raw cook at 1020 ℃ of following sintering by the chip multilayer ceramic capacitor manufacturing process.As seen from Table 3, be lower than 1210 ℃ of synthetic burning pieces, because it is higher that its synthesis temperature burns the piece activity, easily causes the supernormal growth of porcelain body crystal grain, density is descended, this is from monolithic capacitor. and DF suddenly increases behind the moisture test can prove, coarse-grain also causes the withstand voltage decline of capacitor chip simultaneously, and synthesis temperature is more suitable between 1230～1250 ℃, and this moment, porcelain body crystal grain was than uniformity, density is better, and it is all more satisfactory to show as each unit for electrical property parameters.When synthesis temperature during greater than 1270 ℃, burn that piece is active significantly to be reduced, because porcelain body brilliant position growth is slow and less, cause that density descends, the porcelain body porous, DF increases.Unit for electrical property parameters is selected 1230～1250 ℃ of synthesis temperature the bests.
TiO
2Starting material are to the influence of porcelain powder electrical property
The TiO that selects for use different grain size to distribute
2, press BaO/TiO
2Than being 0.426 and adding micro-WO simultaneously
3, ZnO handles through technological process, and is synthetic under 1240 ℃/2.5hr of same temperature.Through a large amount of experiments,, find to adopt same raw material, only at granularity D by X-ray diffraction analysis
50≤ 1.204 μ m reach specific surface area BET=3.25m down
2During/g, synthetic Ba
2Ti
9O
20Fully.See Table 4,5 three kind of different grain size distributes the TiO of (seeing Fig. 9,10,11)
2The synthetic Ba of institute
2Ti
9O
20The situation contrast.And at D
50≤ 1.590 μ m, not exclusively synthetic, part BaTi is arranged
4O
2Occur, at D
50≤ 1.85 μ m except containing part BaTi
4O
9Still have a small amount of other to exist mutually outward.
Table 6 is different Ti O
2The size-grade distribution synthetic burns the influence of piece to porcelain MLCC electrical property.Because synthetic Ba
2Ti
9O
20Used BaCO
3And TiO
2In the starting material, BaCO
3Meeting produces decomposition and has big activity in building-up process, and TiO
2Do not have to produce and decompose, therefore, under the same conditions, TiO
2Granularity is to Ba
2Ti
9O
20Synthesizing has very big influence.
Borate glass and fluxing action thereof
Because the Ba of porcelain
2Ti
9O
20The synthesis temperature of main burning piece own is quite high, and it is warm higher to bring porcelain body to burn, and for this reason, must add the glass fusing assistant of 5～7% weight in the experiment, to reach the middle temperature stable sintering within 1020 ± 20 ℃ temperature range.
Multiple glass fusing assistant is studied and experiment shows, the borate glass system of table 7 has fluxing action preferably to this porcelain, and this glass dielectric loss tg δ is low.Resistivity (ρ) height, chemical stability, intensity are good.This borate glass begins liquid phase at 550 ℃, and along with the raising of temperature, amount of liquid phase increases, and in higher temperature range, then its amount of liquid phase keeps relative stability, and adds this borate glass the porcelain Effect on Performance is shown in Table 8:
This borate glass performance perameter:
Density (g/m
3): 2.53
Dielectric loss (25 ℃, 1MHz): (1～2) * 10
-4
Specific inductivity (25 ℃, 1MHz): 5～6
Resistivity (Ω cm):＞10
12
Coefficient of thermal expansion (* 10
-7): 3～4 (30 ℃～350 ℃)
Bending strength (Kg/cm
2): 1600
Table 8 is that chip multilayer ceramic capacitor burns till under 1020 ℃, by the electrical property contrast as can be known, add an amount of this borate glass, this porcelain is had wetting preferably, fluxing action, promoted that this porcelain system solid phase particles is filled, tension, improved densified sintering product.Later experiment has further proved and has added an amount of borate glass, can make this system assign dense sintering at 1020 ± 20 ℃ low temperature.Therefore, the borate glass of this experiment makes this Ba
2Ti
9O
20System's porcelain has reached the good result of intermediate sintering temperature.And in capacitor fabrication process, make porcelain good coupling be arranged with the interior electrode of low palladium content.
The present invention is meant the further improvement of the temperature factor and the electrical property of porcelain to the modification of porcelain, promptly on the one hand by adding the CaZrO of positive temperature coefficient
3Adjust the negative temperature coefficient of porcelain, the temperature factor of porcelain is controlled at ± 30ppm/ ℃ in.As shown in figure 12, add CaZrO
3The relation of content and Tcc.
In addition, CaZrO
3Enter lattice and the effect of activation lattice in addition, Zr
4+Be difficult for appraising at the current rate, more stable, Zr
4+Can suppress grain growing and become big crystal grain, help the sintering porcelain body and obtain fine crystalline structure.Experiment shows, adds proper C aZrO
3Can improve the sintering state of porcelain body and obtain superior dielectric properties.
On the other hand, add a spot of MnCO
3, can reduce the firing temperature of porcelain, improve the effect of porcelain body intensity and insulation resistance, from the above, at this Ba
2Ti
9O
20In the porcelain system, add suitable MnCO
3, can make the porcelain performance better, and further improve insulation resistivity.Therefore, CaZrO of the present invention
3, MnCO
3The interpolation modification obtained good result.
Firing temperature is to the influence of porcelain electrical property, as shown in Table 9, porcelain of the present invention system has broad firing range, and best firing range is between 1000～1040 ℃, Figure 13 is the SEM photo analysis of the capacitor chip that burns till under 1020 ℃, from figure, find, porcelain body densification, uniform crystal particles, the electrical property good with it matches.
For measuring the frequency response characteristic of porcelain of the present invention, utilize the chip multilayer ceramic capacitor that burns till under 1020 ℃ to do the test of its frequency response characteristic, see Figure 14, as seen, porcelain of the present invention also has good frequency response characteristic under the situation greater than 200MHz, can be fit to higher frequency range and use.
The present invention has following advantage compared to existing technology: capacity is little, the precision height, and homogeneity of product and reliability height can use or the like under more wide higher frequency range.
Embodiment 1: a kind of ferroelectrics composition, it comprises oxidation nine titaniums two barium principal crystalline phases, lead borosilicate, zirconium dioxide, calcium zirconate, manganous carbonate composition, its weight percent is: oxidation nine titaniums two barium principal crystalline phases 70%, lead borosilicate 15%, zirconium dioxide 14%, calcium zirconate 1.2%, manganous carbonate 0.3%, wherein lead borosilicate consists of (wt%): B
2O
320%, SiO
230%, PbO55%; A kind of Middle-temp sintered ceramic material, it is to be formed at sintering below 1040 ℃ or 1040 ℃ by described ferroelectrics composition; A kind of preparation method of Middle-temp sintered ceramic material, comprise described ferroelectrics constituent, its weight percent is: oxidation nine titaniums two barium principal crystalline phases 70%, lead borosilicate 15%, zirconium dioxide 14%, calcium zirconate 1.2%, manganous carbonate 0.3%, wherein lead borosilicate consists of (wt%): B
2O
320%, SiO
215%, PbO30%, behind the mix → ball milling → sand milling → dry and sieve → forming and sintering → electric physicals → sampling observation gets final product.
Embodiment 2: a kind of ferroelectrics composition, it comprises oxidation nine titaniums two barium principal crystalline phases, lead borosilicate, zirconium dioxide, calcium zirconate, manganous carbonate composition, its weight percent is: oxidation nine titaniums two barium principal crystalline phases 76%, lead borosilicate 10%, zirconium dioxide 9%, calcium zirconate 0.6%, manganous carbonate 0.1%, wherein lead borosilicate consists of (wt%): B
2O
340%, SiO
215%, PbO30%, a kind of Middle-temp sintered ceramic material, it is can also be formed at 1000 ℃ of sintering by described ferroelectrics composition: a kind of preparation method of Middle-temp sintered ceramic material, comprise described ferroelectrics composition, its weight percent is: oxidation nine titaniums two barium principal crystalline phases 76%, lead borosilicate 10%, zirconium dioxide 9%, calcium zirconate 0.6%, manganous carbonate 0.1%, wherein lead borosilicate consists of (wt%): B
2O
340%, SiO
215%, PbO30%, behind the mix → ball milling → sand milling → dry and sieve → forming and sintering → electric physicals → sampling observation gets final product.
Embodiment 3: a kind of ferroelectrics composition, it comprises oxidation nine titaniums two barium principal crystalline phases, lead borosilicate, zirconium dioxide, calcium zirconate, manganous carbonate composition, its weight percent is: oxidation nine titaniums two barium principal crystalline phases 75%, lead borosilicate 10%, zirconium dioxide 14%, calcium zirconate 0.7%, manganous carbonate 0.3%, wherein lead borosilicate consists of (wt%): B
2O
330%, SiO
220%, PbO50%; A kind of Middle-temp sintered ceramic material, it is can also be formed at 1020 ℃ of sintering by described iron variant compositions; A kind of preparation method of Middle-temp sintered ceramic material, comprise described ferroelectrics constituent, its weight percent is: oxidation nine titaniums two barium principal crystalline phases 25%, lead borosilicate 10%, zirconium dioxide 14%, calcium zirconate 0.7%, manganous carbonate 0.3%, wherein lead borosilicate consists of (wt%): B
2O
330%, SiO
220%, PbO50%, behind the mix → ball milling → sand milling → dry and sieve → forming and sintering → electric physicals → sampling observation gets final product.
Embodiment 4: a kind of ferroelectrics composition, it comprises oxidation nine titaniums two barium principal crystalline phases, lead borosilicate, zirconium dioxide, calcium zirconate, manganous carbonate composition, its weight percent is: oxidation nine titaniums two barium principal crystalline phases 73%, lead borosilicate 13%, zirconium dioxide 13%, calcium zirconate 0.8%, manganous carbonate 0.2%, wherein lead borosilicate consists of (wt%): B
2O
335%0, SiO
225%, PbO40%; A kind of Middle-temp sintered ceramic material, it is to be formed at sintering below 1040 ℃ or 1040 ℃ by described ferroelectrics composition: a kind of preparation method of Middle-temp sintered ceramic material, comprise described iron variant compositions, its weight percent is: oxidation nine titaniums two barium principal crystalline phases 72%, lead borosilicate 14%, zirconium dioxide 13%, calcium zirconate 0.8%, manganous carbonate 0.2%, wherein lead borosilicate consists of (wt%): B
2O
330%, SiO
230%, PbO40%, behind the mix → ball milling → sand milling → dry and sieve → forming and sintering → electric physicals → sampling observation; Described ball milling be agate ball in: material: ball=1: the ratio of (2～3) adds in the ball mill, ball milling 15 hours; Described ball milling be agate ball in: material: ball=1: the ratio of (2～3) adds in the sand mill, sand milling 20 hours; Described oven dry is carried out under 250 ℃.
Embodiment 5: a kind of ferroelectrics composition, it comprises oxidation nine titaniums two barium principal crystalline phases, lead borosilicate, zirconium dioxide, calcium zirconate, manganous carbonate composition, its weight percent is: oxidation nine titaniums two barium principal crystalline phases 72%, lead borosilicate 15%, zirconium dioxide 12%, calcium zirconate 0.7%, manganous carbonate 0.3%, wherein lead borosilicate consists of (wt%) .:B
2O
33 8%, SiO
220%, PbO42%, a kind of Middle-temp sintered ceramic material, it is can also be formed at 1000 ℃ of sintering by described ferroelectrics composition; A kind of preparation method of Middle-temp sintered ceramic material, comprise described ferroelectrics composition, its weight percent is: oxidation nine titaniums two barium principal crystalline phases 72%, lead borosilicate 15%, zirconium dioxide 12%, calcium zirconate 0.7%, manganous carbonate 0.3%, wherein lead borosilicate consists of (wt%): B
2O
338%, SiO
220%, PbO42%, behind the mix → ball milling → sand milling → dry and sieve → forming and sintering → electric physicals → sampling observation; Described ball milling be agate ball in: material: ball=1: the ratio of (2～3) adds in the ball mill, ball milling 15 hours: described ball milling be agate ball in: material: ball=1: the ratio of (2～3) adds in the sand mill, sand milling 20 hours; Described oven dry is carried out under 250 ℃.
Table 1
Table 2
Table 3
Table 4
Table 5
Table 6
Table 7
| Composition | B 2O 3 | SiO 2 | PbO | ZnO | Al 2O 3 | Other |
| Weight (wt%) | 30.76 | 24.53 | 4.17 | 27.13 | 9.13 | 4.28 |
Table 8
Table 9
Claims (9)
1, a kind of ferroelectrics composition, it comprises oxidation nine titaniums two barium principal crystalline phases, lead borosilicate, zirconium dioxide, calcium zirconate, manganous carbonate composition, its weight percent is: oxidation nine titaniums two barium principal crystalline phases 70～76%, lead borosilicate 10～15%, zirconium dioxide 9～14%, calcium zirconate 0.6～1.2%, manganous carbonate 0.1～0.3%, wherein lead borosilicate consists of (wt%): B
2O
3: 20～40%, SiO
215～30%, PbO30～55%.
2, a kind of Middle-temp sintered ceramic material is characterized in that it is that ferroelectrics composition by claim 1 forms at sintering below 1040 ℃ or 1040 ℃.
3, Middle-temp sintered ceramic material according to claim 2 is characterized in that it is that ferroelectrics composition by claim 1 forms at 1000 ℃ of sintering.
4, Middle-temp sintered ceramic material according to claim 2 is characterized in that it is that ferroelectrics composition by claim 1 forms at 1020 ℃ of sintering.
5, a kind of preparation method of Middle-temp sintered ceramic material, it is characterized in that comprising the described ferroelectrics composition of claim 1, its weight percent is: oxidation nine titaniums two barium principal crystalline phases 70～76%, lead borosilicate 10～15%, zirconium dioxide 9～14%, calcium zirconate 0.6～1.2%, manganous carbonate 0.1～0.3%, wherein lead borosilicate consists of (wt%): B
2O
320～40%, SiO
215～30%, PbO
30～55%, behind the mix → ball milling → sand milling → dry and sieve → forming and sintering → electric physicals → sampling observation.
6, the preparation method of Middle-temp sintered ceramic material according to claim 5, it is characterized in that described ball milling be agate ball in: material: ball: 1: the ratio of (2～3) adds in the ball mill, ball milling 15 hours,
7, the preparation method of Middle-temp sintered ceramic material according to claim 5 is characterized in that described sand milling is the zirconium ball, sand milling 20 hours.
8, the preparation method of Middle-temp sintered ceramic material according to claim 5 is characterized in that described oven dry carries out under 250 ℃.
9, the preparation method of Middle-temp sintered ceramic material according to claim 8, it is characterized in that the oven dry of described porcelain after, treat naturally cooling, beat powder, sieve.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001175459A CN1159257C (en) | 2000-10-30 | 2000-10-30 | Middle-temp sintered ceramic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001175459A CN1159257C (en) | 2000-10-30 | 2000-10-30 | Middle-temp sintered ceramic material |
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| CN1304906A CN1304906A (en) | 2001-07-25 |
| CN1159257C true CN1159257C (en) | 2004-07-28 |
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