CN1271653C - Dielectric ceramic material for piece type capacitor and preparing method thereof - Google Patents
Dielectric ceramic material for piece type capacitor and preparing method thereof Download PDFInfo
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- CN1271653C CN1271653C CN 200410027743 CN200410027743A CN1271653C CN 1271653 C CN1271653 C CN 1271653C CN 200410027743 CN200410027743 CN 200410027743 CN 200410027743 A CN200410027743 A CN 200410027743A CN 1271653 C CN1271653 C CN 1271653C
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Abstract
The present invention relates to a dielectric ceramic material preparation method for a chip capacitor. The present invention comprises that step one, components of a third accessory component are mixed, heated and melted, glass fragments are made by a water cooling quenching method and are pulverized by a ball milling method to glass state material, and the particle diameter D50 of particles is not greater than 0.6 Mu m; step two, a main component and a first accessory component are mixed and are homogeneously made into material slurry by ball milling or mixing with water, and then, the material slurry is dried to powder material; step three, the dried powder material is calcined under 1100 to 1250 DEG C in air, is kept temperature for 0.5 to 5 hours, and is watered and milled by balls until the particle diameter D50 of particles is not greater than 0.7 Mu m, and then, the powder material is dried to obtain main material; step four, the main material, a second accessory component and the obtained glass state material are evenly mixed to obtain dielectric ceramic material which is especially suitable for making cheap metal electrode multilayer chip capacitors. The present invention has the advantages of high dielectric coefficient and small crystal particles, and besides, the temperature characteristic of the dielectric coefficient conforms to X7R characteristic requirements which are provided by EIA standard.
Description
Technical field
The present invention relates to the chip capacitor technology, specifically be a kind of can with the base-metal inner-electrode material under reducing atmosphere co-sintered, the dielectric coefficient temperature characterisitic meets the dielectric ceramic materials for chip capacitor that the X7R characteristic of EIA standard code requires.
The invention still further relates to the preparation method of described medium ceramic material.
Background technology
In order to adapt to the requirement of miniaturization, sheets type ceramic dielectric capacitor medium and inner electrode layer number constantly increase, and the shared cost of interior electrode improves constantly.Adopt base metal nickel (Ni), copper (Cu) to replace expensive palladium-Yin (Pd-Ag) can reduce the chip capacitor manufacturing cost greatly as electrode material.
Because metallic nickel or copper at high temperature are easy to oxidation, and since interior electrode must with dielectric material sintering together, so sintering process must be carried out in reducing atmosphere.The dielectric material of Cai Yonging can only be with noble metal electrode sintering in oxidizing atmosphere in the past, if be placed on sintering in the reducing atmosphere, then semiconducting can take place, material does not have the insulation property of dielectric material behind the sintering, is not suitable for cooperating electrodes in base metal to make chip capacitor.
The X7R property slice type capacitor that present dielectric property meet the EIA of EIA standard code is one of most widely used a kind of capacitor, capacitance when being meant with 25 ℃ by this standard x 7R characteristic is a benchmark, in-55～+ 125 ℃ of temperature ranges, rate of change of capacitance is no more than ± and 15%.Prior art, as U.S. Pat 006243254B1, US006245433B1, the X7R property slice type capacitor medium ceramic material dielectric coefficient lower (less than 2000) that disclosed technology such as US006205015B1 is made, and that the X7R characteristic dielectric material insulation resistance of the disclosed technology manufacturing of Japan Patent JP-A-63-103861 and dielectric coefficient temperature characterisitic are influenced by the material grains size is very big, is difficult to obtain the dielectric material that thin brilliant and dielectric coefficient temperature characterisitic meets above-mentioned standard-required.
Summary of the invention
The objective of the invention is to overcome the shortcoming that prior art exists, the dielectric ceramic materials for chip capacitor that provides a kind of suitable making electrodes in base metal multilayer chip capacitor to use, its dielectric coefficient height, the dielectric coefficient temperature characterisitic meets the X7R characteristic requirement of EIA standard code, crystal grain is tiny, is fit to make the chip capacitor of deielectric-coating thickness less than 8 μ m.
The present invention also aims to provide the preparation method of described dielectric ceramic materials for chip capacitor.
The preparation method of dielectric ceramic materials for chip capacitor of the present invention comprises the steps:
The first step: each component of the 3rd accessory ingredient is mixed, be heated to fusion after, it is broken and be crushed to particle diameter D50 in the particle≤0.6 μ m with ball-milling method and promptly make the glassy state material to adopt the water hardening method to make glass;
Second step: principal component, first accessory ingredient mix and add water for ball milling or stir makes slip, and this slip is dried to powder;
The 3rd step: with dry powder 1100～1250 ℃ of calcinings in air that obtain of second step, be incubated 0.5～5 hour, add water for ball milling particle diameter D50≤0.7 μ m to the particle, dry back acquisition major ingredient;
The 4th step: the glassy state mixing of materials that above-mentioned major ingredient, second accessory ingredient, the first step are obtained evenly promptly obtains dielectric ceramic materials for chip capacitor.
The 4th step, described mixed method can adopt dry type to mix method, but also seasoning after the wet mixed.
To account for total amount ratio accessory ingredient seldom and be uniformly dispersed in major ingredient in order to make, the above-mentioned second accessory ingredient granularity preferably guarantees particle diameter D50 in the particle≤0.6 μ m.
Described principal component expression formula: Ba
m(Ti
1-xZr
x) O
3, wherein, m=1.005～1.02, x=0～0.02;
First accessory ingredient is MgO or its presoma;
Second accessory ingredient is MnO
2, rare earth oxide Re
2O
3Or its presoma;
The 3rd accessory ingredient is BaCO
3, CaCO
3, B
2O
3, SiO
2
Each composition consumption is as follows:
Principal component 100mol%
First accessory ingredient, 0.5～1.5mol%;
The second accessory ingredient MnO
2Be 0.05～0.15mol%,
Re
2O
3Be 0.3～2.0mol%;
The 3rd accessory ingredient 1.0～3.0wt% (is 100wt% in main composition), wherein
BaCO
3, CaCO
3, B
2O
3, SiO
2Mol ratio be: 1.0: (0.1～1.0): (1.0～2.0): (0.5～1.5);
Described principal component Ba
m(Ti
1-xZr
x) O
3The BaTiO that adopts wet method (for example oxalate method, hydrothermal synthesis method or sol-gel process) to produce
3With BaCO
3, ZrO
2Mix in proportion, can carry out synchronously with second step.
Because the domestic oxalate method that adopted is produced BaTiO in batches
3, its cost and the BaTiO of price than hydro thermal method and collosol and gel manufactured
3Much lower, so the present invention preferentially adopts the BaTiO of oxalate method production
3To reduce cost;
Described drying means can adopt spray drying process or other drying means, guarantees evenly dispersion, not stratified in each composition dry run in the powder;
Described rare earth oxide Re
2O
3Be to comprise Y
2O
3, Sc
2O
3, Dy
2O
3, Ho
2O
3, Er
2O
3, Tm
2O
3, Yb
2O
3, Lu
2O
3In one or more mixtures.
The presoma of described metal oxide is meant nitrate, carbonate, oxalates or the acetate of this metal.
The media ceramic powder that adopts the inventive method to make is suitable for making the electrodes in base metal chip multilayer ceramic capacitor.The process of making chip capacitor is as follows:
(1) dielectric ceramic materials for chip capacitor that said method is made and organic carrier mixing and ball milling are made slurry.
Described organic carrier comprises organic bond and solvent, organic bond and solvent types are not done qualification, organic bond can be selected from polyvinyl butyral resin, ethyl cellulose or other common adhesive, and solvent can be selected one or more of organic solvents such as toluene, butyl carbitol, terpineol for use.Described organic carrier also can comprise dispersant, plasticizer, defoamer etc. as required, and one or more add material.
(2) the above-mentioned slurry of making curtain coating on the film casting machine is made into medium green compact film.
(3) electrode pattern in employing nickel electrode slurry and method for printing screen print on above-mentioned green compact film.
(4) the green compact film lamination behind the electrode in the above-mentioned printing is made laminate blank, institute's lamination number is decided by required capacitance requirement, and the most beneath and the most surperficial should each folded on the aforementioned medium green compact film that do not print electrode of one deck at least.
(5) adopt hot pressing and the method that waits static pressure that above-mentioned laminate blank is compressed, discharges interlayer air.
(6) cut apart base substrate.
(7) get rid of adhesive.Binder removal under can air atmosphere, also can be under nitrogen atmosphere or hydrogen-nitrogen reducing atmosphere binder removal.The binder removal maximum temperature can not surpass 300 ℃ in air, otherwise can make the inner electrode oxidation, and in nitrogen or hydrogen nitrogen reducing atmosphere during binder removal maximum temperature can rise to 500 ℃ or higher.
(8) sintering.Sintering carries out in reducing atmosphere, and sintering temperature is decided on prescription composition and powder granularity, and suitable sintering temperature can be in 1230～1320 scopes.Partial pressure of oxygen is 10 in the control sintering atmosphere
-9～10
-12Mpa, reducing atmosphere adopts the hydrogen-nitrogen mixture gas of humidification, and the hydrogen ratio can be controlled in 1～5% scope, can adopt the method for regulating hydrogen ratio and humidifier water temperature to regulate partial pressure of oxygen in the sintering atmosphere under guaranteeing the bubble-tight condition of body of heater.
(9) heat treatment.The porcelain spare that sintering obtains places weak oxide atmosphere oxidizing thermal treatment to improve the dielectric voltage withstand ability of dielectric material.Heat treatment can be carried out by temperature-fall period in sintering furnace, also can carry out behind sintering again.Partial pressure of oxygen is controlled at 10 in the heat-treating atmosphere
-7～10
-8Mpa, treatment temperature is 1100 ± 30 ℃, temperature retention time 1～3 hour.Heat treatment step can improve product voltage load aging life-span.
(10) make the ground floor termination electrode.Adopt dip-coating or the printing way porcelain spare two electrode leads to client coating upper end electrode slurry after sintering and heat treatment.Terminal electrode paste can adopt copper slurry or silver slurry.Be placed in the nitrogen atmosphere proper temperature after end slurry coating is good and handle, treatment temperature decide on the termination electrode material behavior, and treatment temperature is 750～850 ℃ during the employing copper termination, and treatment temperature is 550～850 ℃ when adopting silver-colored termination electrode.Termination electrode is communicated with nickel inner electrode by over-over mode, make each monolithic capacitor parallel connection in the sample.
(11) adopt electro-plating method to make the second layer and the 3rd layer of termination electrode.
So far promptly produce nickel inner electrode multilayer sheet type ceramic capacitor sample, this sample can be for test, analysis.
The present invention has following advantage with respect to prior art:
The medium ceramic material of the fabrication techniques that the present invention is open is fit to burn altogether with nickel electrode material, makes deielectric-coating thickness less than multilayer porcelain Jie chip capacitor of 8 microns.
The present invention adopts special principal crystalline phase treatment technology, makes a small amount of ION Mg
2+, Zr
4+At first enter barium titanate crystal grain inside, when material in reducing atmosphere during sintering, other additives are as rare earth oxide Re
2O
3And MnO
2Only react with the principal crystalline phase particle surface, make crystal grain inner not quite identical with its top layer chemical composition, thereby make ceramic dielectric crystal grain actual for mixing phase, crystal grain inside and grain surface dielectric property be difference to some extent, the inner dielectric coefficient temperature characterisitic of crystal grain Curie's peak value occurs near the barium titanate self character about 120 ℃, the crystal grain top layer is then because the part ion metalepsis on the crystal structure makes dielectric Curie peak shift near the room temperature.Like this, on macroscopic view, it is comparatively smooth that the temperature characterisitic of dielectric material coefficient becomes, and satisfies the X7R characteristic of EIA standard-required easily.
The medium ceramic material dielectric coefficient of the inventive method preparation bears endurance test (ageing test) the back good insulation preformance of standard-required greater than 2500, and failure rate is low.
Can cooperate when medium ceramic material of the present invention is used to make chip capacitor and adopt nickel inner electrode and copper termination, the chip capacitor production cost is reduced greatly.
The BaTiO that the present invention preferentially adopts Oxalic Acid Method to produce
3Raw material is because the domestic Oxalic Acid Method mass production BaTiO that adopted
3, so the medium ceramic material cost of the inventive method preparation is low.
Description of drawings
Fig. 1 is the nickel inner electrode chip capacitor profile scanning electromicroscopic photograph (embodiment 1-101) that adopts medium ceramic material of the present invention to make, Fig. 1 a is the whole section photo (scale is 500 microns) of capacitor, and Fig. 1 b is the local enlarged photograph (scale is 10 microns) of section;
Fig. 2 is medium ceramic material of the present invention (embodiment 1-101) particle size distribution testing result.
Embodiment
Below by embodiment the present invention is done further concrete description, but embodiments of the present invention are not limited thereto.
Principal component expression formula Ba
m(Ti
1-xZr
x) O
3In, m=1.01, x=0.015; First accessory ingredient is selected Mg (NO for use
3)
26H
2O is 100mol% in the principal component, Mg (NO
3)
26H
2The addition of O is 1.0mol%.
The BaTiO that adopts Oxalic Acid Method to make
3And analyze pure raw material: BaCO
3, ZrO
2, Mg (NO
3)
26H
2It is even that O adds the pure water mixing and ball milling in above-mentioned chemical composition ratio, with the spray drying process drying be placed in the resistance furnace, down calcining of air atmosphere, calcining heat is 1200 ℃, is incubated 2 hours, add water after the cooling and placed the high speed ball mill ball milling 5 hours, dry back obtains major ingredient.
The making of the 3rd accessory ingredient: with BaCO
3, CaCO
3, B
2O
3, SiO
2Be in molar ratio: 1.0: 0.5: 1.5: 1.0 weighings mix, place crucible to be heated to 1350 ℃ of fusions after, it is broken to adopt the water hardening method to make glass, and adopts high speed ball mill to pulverize 5 hours, promptly makes the 3rd adding ingredient (glassy state material).The 3rd accessory ingredient addition in each prescription of present embodiment is 1.5wt%.
In the present embodiment, as the MnO of one of second accessory ingredient
2Addition is 0.1mol%, and rare earth oxide is selected Y for use
2O
3, Dy
2O
3, Ho
2O
3, Er
2O
3And adjust the addition (seeing Table 1) of these four kinds of oxides.Selected MnO
2With the rare earth oxide particles degree less than 0.6 micron.
With above-mentioned major ingredient, second accessory ingredient and the 3rd accessory ingredient mixing and water adding ball milling after 5 hours drying be the media ceramic powder of cost of manufacture invention.
Adopt the particle size distribution of laser particle size analyzer test material, the results are shown in Figure 2.
Adopt the aforementioned techniques method produce dimensions be 0805 (2 * 1.25mm) chip capacitor sample, the effective medium number of plies of sample is 100 layers, every layer thickness is about 6～7 microns (seeing Fig. 1 b).Sintering temperature is 1260 ℃ in the technical process, and partial pressure of oxygen is controlled to be 10
-11Mpa is incubated 2 hours; Heat treatment temperature is 1100 ℃, and partial pressure of oxygen is controlled to be 10
-6MPa is incubated 2 hours.
The sample of making carries out electrical property as follows and measures.
Capacitance, dielectric loss and dielectric coefficient: adopt HP4288 capacitance measuring tester specimen capacitance and dielectric loss, calculate medium ceramic material dielectric coefficient ε.
Ageing test (endurance test): apply 2.0V/ micron direct voltage 1000 hours at 85 ℃ of samples of ambient temperature.
Insulation property after the ageing test: the sample two ends apply the insulation resistance of 2.0V/ micron dc voltage measurement sample after ageing test, adopt insulation resistance and sample capacitance product to weigh the medium ceramic material insulation property.
Capacitance temperature characterisitic: the temperature test chamber (ESPEC:MC-710P) that sample is placed precision temperature control, measure the interior sample capacitance value of-55 ℃～+ 125 ℃ scopes every 10 ℃ of temperature spot places, the rate of change of capacitance when calculating relative 25 ℃ of each temperature spot capacitance, but the most important thing is-55 ℃, the rate of change of capacitance of+85 ℃ and+125 ℃ of three key temperatures points.
Present embodiment sample electric performance test the results are shown in table 2.Comparative sample 106 in the table 2
*Adopt and sample 101 identical chemical compositions of the present invention, but do not carry out the major ingredient high-temperature calcination in the manufacture craft process, but directly adopt BaTiO
3And the BaCO of respective component
3, ZrO
2As principal component and first accessory ingredient (adopting the MgO of 1.0mol%), and second, third accessory ingredient mixing and ball milling pulverize, follow-up manufacture craft process is identical with present embodiment.Sample temperature characteristic of capacitance of the present invention as seen from Table 2 is better than comparative sample.
Table 1, materials chemistry are formed (embodiment 1)
| Main composition: Ba 1.01(Ti 0.985Zr 0.015)O 3First accessory ingredient [Mg (NO 3) 2·6H 2O]:: 1.0mol% the 3rd accessory ingredient (glassy state material): 1.5wt% | Second accessory ingredient (mol%) | |||||
| Numbering | MnO 2 | Y 2O 3 | Dy 2O 3 | Ho 2O 3 | Er 2O 3 | |
| 101 | 0.1 | 0.4 | 0.4 | |||
| 102 | 0.1 | 0.4 | 0.4 | |||
| 103 | 0.1 | 1.0 | ||||
| 104 | Manganese nitrate *0.05 | Yttrium nitrate **：0.3 | ||||
| 105 | 0.1 | 1.0 | 1.0 | |||
| 106 * | 0.1 | 1.0 | ||||
*Adopt manganese nitrate Mn (NO
3)
2: 0.05mol%,
*Adopt yttrium nitrate [Y (NO
3)
36H
2O]: 0.3mol%
Table 2, sample electrical property (embodiment 1)
| Numbering | Dielectric coefficient ε | Dielectric loss tg δ | Rate of change of capacitance Δ C/C % | Insulation property C * R after the ageing test | ||
| (25℃) | (25℃) | -55℃ | +85℃ | +125℃ | MΩ·μF | |
| 101 | 2850 | ≤1.5％ | -9.0 | -11.5 | -8.2 | ≥3000 |
| 102 | 3020 | ≤1.5％ | -8.2 | -12.3 | -7.8 | ≥5000 |
| 103 | 2920 | ≤1.5％ | -10.5 | -10.8 | -6.9 | ≥3000 |
| 104 | 3050 | ≤1.5％ | -11.2 | -11.9 | -7.5 | ≥4000 |
| 105 | 2780 | ≤1.5％ | -11.0 | -10.5 | -8.5 | ≥4000 |
| 106 * | 2820 | ≤1.5％ | -8.5 | -11.5 | -14.5 | ≥3000 |
*Comparative sample
Make the glassy state material (the 3rd accessory ingredient in the material composition) of four kinds of chemical compositions with embodiment 1 same process, its chemical composition mol ratio is respectively:
Glassy state material A: BaCO
3: CaCO
3: B
2O
3: SiO
2=1.0: 0.5: 1.5: 1.0
Glassy state material B:BaCO
3: CaCO
3: B2O
3: SiO
2=1.0: 1.0: 2.0: 1.0
Glassy state material C: BaCO
3: CaCO
3: B
2O
3: SiO
2=1.0: 0.1: 1.0: 0.5
Glassy state material D:BaCO
3: CaCO
3: B
2O
3: SiO
2=1.0: 0.5: 1.5: 1.5
Principal component expression formula Ba
m(Ti
1-xZr
x) O
3In, make m=1.01, x=0.015
First accessory ingredient is selected magnesium nitrate [Mg (NO for use
3)
26H
2O], its addition is 1.0mol%.
MnO as one of second accessory ingredient
2With MnCO
3Form adds, and addition is 0.12mol%, as the Re of one of second accessory ingredient
2O
3Select Y for use
2O
3And Dy
2O
3Each adds 0.4mol%.
The BaTiO that adopts Oxalic Acid Method to make
3And analyze pure BaCO
3, ZrO
2And the first accessory ingredient magnesium nitrate [Mg (NO
3)
26H
2O] to add the pure water mixing and ball milling in above-mentioned chemical composition ratio even, with the spray drying process drying be placed in the resistance furnace, down calcining of air atmosphere, calcining heat is 1250 ℃, is incubated 2 hours, add water after the cooling and placed the high speed ball mill ball milling 3 hours, dry back obtains major ingredient.
With above-mentioned major ingredient, second accessory ingredient and the 3rd accessory ingredient mixing and water adding ball milling after 3 hours drying be the media ceramic powder of cost of manufacture invention.
The process and the electric performance test method of making the sheet capacitor sample are identical with embodiment 1.The materials chemistry composition is listed in table 3, and the sample electric performance test the results are shown in table 4.
Table 3, materials chemistry are formed (embodiment 2)
| Main composition: Ba 1.01(Ti 0.985Zr 0.015)O 3First accessory ingredient [Mg (NO 3) 2·6H 2O]:: 1.0mol% second accessory ingredient: MnCO 3：0.12mol％ Y 2O 3：0.4mol％ Dy 2O 3：0.4mol％ | The 3rd secondary composition (glassy state material) | ||
| Numbering | The glassy state stock number | Addition wt% | |
| 107 | A | 1.5 | |
| 108 | B | 1.5 | |
| 109 | C | 1.5 | |
| 110 | D | 1.5 | |
| 111 | A | 1.0 | |
| 112 | A | 3.0 | |
Table 4, sample electrical property (embodiment 2)
| Dielectric coefficient ε | Dielectric loss tg δ | Rate of change of capacitance Δ C/C % | Insulation property C * R after the ageing test | |||
| Numbering | (25℃) | (25℃) | -55℃ | +85℃ | +125℃ | MΩ·μF |
| 107 | 2850 | ≤1.5％ | -10.3 | -11.6 | -9.5 | ≥3000 |
| 108 | 2820 | ≤1.5％ | -9.6 | -11.5 | -10.3 | ≥4000 |
| 109 | 2920 | ≤2.0％ | -8.6 | -9.8 | -10.9 | ≥3000 |
| 110 | 2950 | ≤2.0％ | -10.9 | -11.3 | -11.0 | ≥3000 |
| 111 | 2780 | ≤1.5％ | -10.6 | -11.5 | -10.8 | ≥4000 |
| 112 | 2860 | ≤2.0％ | -9.5 | -8.5 | -5.6 | ≥1000 |
Make glassy state material A (the 3rd accessory ingredient in the material composition) with embodiment 2 same process, addition is: 1.5wt%.
MnO as one of second accessory ingredient
2With MnCO
3Form adds, and addition is 0.15mol%, as the Re of one of second accessory ingredient
2O
3Select Y for use
2O
3And Dy
2O
3Each adds 0.4mol%.
Be numbered the BaTiO that 113 material selection hydro thermal method is produced
3Raw material, its powder granule are observed granularity less than 200nm. under scanning electron microscopy
As first accessory ingredient, numbering 113 is selected MgO for use, and consumption is 1.0mol%, other numbering material selection magnesium nitrates [Mg (NO
3)
26H
2O], it is 5 listed that consumption sees Table.
With BaTiO
3And analyze pure BaCO
3, ZrO
2, it is even that first accessory ingredient adds the pure water mixing and ball milling in the listed chemical composition ratio of table 5, with the spray drying process drying be placed in the resistance furnace, down calcining of air atmosphere, calcining heat is 1150 ℃, be incubated 2 hours, add water after the cooling and placed the high speed ball mill ball milling 3 hours, dry back obtains major ingredient.
With above-mentioned major ingredient, second accessory ingredient and the 3rd accessory ingredient mixing and water adding ball milling after 3 hours drying be the media ceramic powder of cost of manufacture invention.
The process and the electric performance test method of making the sheet capacitor sample are identical with embodiment 1.The materials chemistry composition is listed in table 5, and the sample electric performance test the results are shown in table 6.
Table 5, materials chemistry are formed (embodiment 3)
| Numbering | Second accessory ingredient: MnCO 3：0.15mol％ Y 2O 3：0.4mol％ Dy 2O 3: 0.4mol% the 3rd accessory ingredient: glassy state material A addition: 1.5wt% | Main composition Ba m(Ti 1-xZr x)O 3 | First accessory ingredient | ||
| BaTiO 3Production method | m | x | |||
| 113 | Hydro thermal method | 1.005 | 0 | MgO：1.0mol％ | |
| 114 | Oxalic Acid Method | 1.01 | 0.02 | [Mg(NO 3) 2·6H 2O]：1.0mol％ | |
| 115 | Oxalic Acid Method | 1.01 | 0.015 | [Mg(NO 3) 2·6H 2O]：0.5mol％ | |
| 116 | Oxalic Acid Method | 1.02 | 0.015 | [Mg(NO 3) 2·6H 2O]：1.5mol％ | |
Table 6, sample electrical property (embodiment 3)
| Numbering | Dielectric coefficient ε | Dielectric loss tg δ | Rate of change of capacitance Δ C/C % | Insulation property C * R after the ageing test | ||
| (25℃) | (25℃) | -55℃ | +85℃ | +125℃ | MΩ·μF | |
| 113 | 2950 | ≤1.5％ | -10.5 | -11.0 | -9.8 | ≥3000 |
| 114 | 2860 | ≤1.5％ | -9.6 | -7.6 | -6.5 | ≥2000 |
| 115 | 2900 | ≤2.0％ | -11.2 | -10.6 | -8.9 | ≥2000 |
| 116 | 2750 | ≤1.5％ | -10.6 | -9.6 | -8.0 | ≥4000 |
Claims (7)
1, a kind of preparation method of dielectric ceramic materials for chip capacitor is characterized in that comprising the steps:
The first step: each component of the 3rd accessory ingredient is mixed, be heated to fusion after, it is broken and be crushed to particle diameter D50 in the particle≤0.6 μ m with ball-milling method and promptly make the glassy state material to adopt the water hardening method to make glass;
Second step: principal component, first accessory ingredient mix and add water for ball milling or stir makes slip, and this slip is dried to powder;
The 3rd step: with dry powder 1100～1250 ℃ of calcinings in air that obtain of second step, be incubated 0.5～5 hour, add water for ball milling particle diameter D50≤0.7 μ m to the particle, dry back acquisition major ingredient;
The 4th step: the glassy state mixing of materials that above-mentioned major ingredient, second accessory ingredient, the first step are obtained evenly promptly obtains dielectric ceramic materials for chip capacitor;
Described principal component expression formula: Ba
m(Ti
1-xZr
x) O
3, wherein, m=1.005～1.02, x=0～0.02;
First accessory ingredient is MgO or its presoma;
Second accessory ingredient is MnO
2, rare earth oxide Re
2O
3Or its presoma, particle diameter in the particle
D50≤0.6μm；
The 3rd accessory ingredient is BaCO
3, CaCO
3, B
2O
3, SiO
2
Each composition consumption is as follows:
Principal component 100mol%
First accessory ingredient, 0.5～1.5mol%;
The second accessory ingredient MnO
2Be 0.05～0.15mol%,
Re
2O
3Be 0.3～2.0mol%;
The 3rd accessory ingredient 1.0～3.0wt% is 100wt% in main composition, wherein
BaCO
3, CaCO
3, B
2O
3, SiO
2Mol ratio be: 1.0: 0.1～1.0:
1.0～2.0∶0.5～1.5。
2, the preparation method of dielectric ceramic materials for chip capacitor according to claim 1 is characterized in that described principal component Ba
m(Ti
1-xZr
x) O
3Adopt the BaTiO of wet production
3With BaCO
3, ZrO
2Mix in proportion.
3, the preparation method of dielectric ceramic materials for chip capacitor according to claim 1 is characterized in that described principal component Ba
m(Ti
1-xZr
x) O
3Adopt the BaTiO of wet production
3With BaCO
3, ZrO
2Mix in proportion, carry out synchronously with second step.
4, according to the preparation method of claim 1 or 2 or 3 described dielectric ceramic materials for chip capacitor, the presoma that it is characterized in that described metal oxide is meant nitrate, carbonate, oxalates or the acetate of this metal.
5, the preparation method of dielectric ceramic materials for chip capacitor according to claim 4 is characterized in that described rare earth oxide Re
2O
3Be to comprise Y
2O
3, Sc
2O
3, Dy
2O
3, Ho
2O
3, Er
2O
3, Tm
2O
3, Yb
2O
3, Lu
2O
3In one or more mixtures.
6, the preparation method of dielectric ceramic materials for chip capacitor according to claim 5 is characterized in that described mixed method of the 4th step adopts dry type to mix method or wet mixed seasoning again.
7, the dielectric ceramic materials for chip capacitor of the described method preparation of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410027743 CN1271653C (en) | 2004-06-23 | 2004-06-23 | Dielectric ceramic material for piece type capacitor and preparing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410027743 CN1271653C (en) | 2004-06-23 | 2004-06-23 | Dielectric ceramic material for piece type capacitor and preparing method thereof |
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| CN104291808A (en) * | 2014-09-26 | 2015-01-21 | 天津大学 | Preparation method of medium temperature sintered X7R type ceramic capacitor dielectric |
| CN104761257B (en) * | 2015-03-16 | 2016-12-07 | 吴江华诚复合材料科技有限公司 | A kind of pressure ceramic material and preparation method thereof |
| CN113800902B (en) * | 2021-09-18 | 2022-08-09 | 福建火炬电子科技股份有限公司 | BME ceramic dielectric capacitor with high dielectric constant and preparation method thereof |
| CN114605145A (en) * | 2022-03-11 | 2022-06-10 | 太原师范学院 | Stable ceramic dielectric material and preparation method thereof |
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