CN111470862A - Ceramic slurry, preparation method of ceramic casting film and chip multilayer ceramic capacitor - Google Patents
Ceramic slurry, preparation method of ceramic casting film and chip multilayer ceramic capacitor Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 174
- 239000002002 slurry Substances 0.000 title claims abstract description 116
- 238000005266 casting Methods 0.000 title claims abstract description 52
- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 42
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 34
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims abstract description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 30
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 25
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000004359 castor oil Substances 0.000 claims abstract description 20
- 235000019438 castor oil Nutrition 0.000 claims abstract description 20
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 20
- 238000010345 tape casting Methods 0.000 claims abstract description 20
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims abstract description 9
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
- C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
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- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
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Abstract
The invention belongs to the technical field of ceramic capacitors, and particularly relates to a ceramic slurry, a preparation method of a ceramic tape-casting film and a chip multilayer ceramic capacitor. The ceramic slurry provided by the invention comprises barium titanate powder, castor oil, polyvinyl butyl acetal, di-n-butyl phthalate, n-butyl alcohol, ethylene glycol and absolute ethyl alcohol which have a specific weight part ratio, wherein the absolute ethyl alcohol is used as a solvent, the castor oil is used as a dispersing agent, the polyvinyl butyl acetal is used as a binder, the di-n-butyl phthalate is used as a plasticizer, and the n-butyl alcohol and the ethylene glycol are used as defoaming agents, and the ceramic slurry is endowed with good rheological property under the synergistic effect of the components, so that the surface of a ceramic casting film formed by casting the ceramic slurry is flat and compact.
Description
Technical Field
The invention belongs to the technical field of ceramic capacitors, and particularly relates to a ceramic slurry, a preparation method of a ceramic tape-casting film and a chip multilayer ceramic capacitor.
Background
M L CC (Multi-layer Ceramic Capacitors) is an acronym for chip multilayer Ceramic Capacitors, which is a monolithic structure formed by stacking Ceramic dielectric films with printed electrodes in a staggered manner, sintering the stacked Ceramic dielectric films at a high temperature to form a Ceramic chip, and packaging metal layers at two ends of the chip.
In recent years, the multilayer ceramic capacitor is one of the chip elements which are manufactured in a mode of alternating dielectric and electrode, is widely applied to coupling, filtering, oscillating and bypass circuits in an electronic complete machine of industrial automatic control equipment, and is most widely applied to high-frequency circuits, and the demand of M L CC is increased day by day along with the rapid development of industries such as domestic and foreign electronic information and surface mounting technology, so that the performance and the production cost of M L CC are gradually valued by various manufacturers.
The casting process is a forming method for preparing large-area flat and thin ceramic materials in a large area, comprises the processes of slurry preparation, forming, drying, base band stripping and the like, is applied to the production of single-layer or multi-layer ceramic materials since the emergence of the casting process, slurry prepared in the M L CC technology can obtain a ceramic film which is thin enough through the casting process so as to further reduce the single-layer thickness of the M L CC dielectric medium, and is an important technology for producing chip multilayer capacitors and multilayer ceramic substrates.
However, the existing casting process still has various defects, for example, most of the currently used casting processes are mainly organic casting, and the organic solvent contains many toxic and volatile components, which easily causes operator's poisoning.
Disclosure of Invention
The invention mainly aims to provide ceramic slurry, and aims to solve the problem that workers are easily poisoned due to the fact that an organic solvent is adopted in the existing casting process.
Another object of the present invention is to provide a method for preparing a ceramic casting film and a chip type multilayer ceramic capacitor.
In order to achieve the purpose, the invention adopts the following technical scheme:
a ceramic slurry is used for preparing a ceramic casting film, and comprises the following components in parts by weight, based on 100 parts by weight of the total ceramic slurry:
the ceramic slurry provided by the invention comprises barium titanate powder, castor oil, polyvinyl butyl acetal, di-n-butyl phthalate, n-butyl alcohol, ethylene glycol and absolute ethyl alcohol which have the specific weight part ratio, wherein the absolute ethyl alcohol is used as a solvent, the castor oil is used as a dispersing agent, the polyvinyl butyl acetal is used as a binder, the di-n-butyl phthalate is used as a plasticizer, the n-butyl alcohol and the ethylene glycol are used as defoaming agents, and the ceramic slurry is endowed with good rheological property under the synergistic effect of the components, so that the surface of a ceramic casting film formed by casting the ceramic slurry is flat and compact.
Compared with the prior art, the ceramic slurry provided by the invention only takes the absolute ethyl alcohol as the solvent of the slurry, so that toxic organic solvents such as butanone and the like are avoided, the ceramic slurry is green and environment-friendly, the absolute ethyl alcohol is low in price, and the production cost can be greatly saved; meanwhile, the ceramic slurry provided by the invention has excellent rheological property, and can be matched with a tape casting process to obtain an ultrathin ceramic tape casting film with a flat and compact surface and a film thickness of less than 10 micrometers.
Correspondingly, the preparation method of the ceramic casting film comprises the following steps:
providing the ceramic slurry;
and carrying out tape casting on the ceramic slurry to obtain the ceramic tape casting film.
According to the preparation method of the ceramic casting film, the ceramic slurry is matched with a casting forming process to prepare the ceramic casting film, so that the ultrathin ceramic casting film with a smooth and compact surface can be obtained.
Correspondingly, the chip type multilayer ceramic capacitor comprises a ceramic chip, wherein the ceramic chip is formed by overlapping and sintering a plurality of ceramic dielectric diaphragms;
wherein, the ceramic dielectric membrane is a ceramic tape-casting film prepared by the preparation method.
According to the chip multilayer ceramic capacitor provided by the invention, the ceramic dielectric diaphragm is the ceramic tape-casting film prepared by the preparation method, the surface is flat and compact, the film thickness is small, the preparation of the miniaturized and high-performance chip multilayer ceramic capacitor is facilitated, and the application range of the chip multilayer ceramic capacitor is expanded.
Drawings
FIG. 1 is a flow chart of a method of preparing a ceramic slurry according to an embodiment of the present invention;
FIG. 2 is a flow chart illustrating a method for preparing a ceramic slurry according to another embodiment of the present invention;
FIG. 3 is SEM images of cast ceramic films obtained in example 1 and example 9, respectively, the left image is the SEM image of the cast ceramic film obtained in example 1, and the right image is the SEM image of the cast ceramic film obtained in example 9;
FIG. 4 is an AFM image of the ceramic cast films obtained in example 1 and example 9, respectively, the left image being an AFM image of the ceramic cast film obtained in example 1, and the right image being an AFM image of the ceramic cast film obtained in example 9;
FIG. 5 is an SEM image of cast ceramic films prepared in examples 1-4;
FIG. 6 is an AFM image of cast ceramic films prepared in examples 1-4
FIG. 7 is a graph of density and variation for cast ceramic films prepared in examples 1-4;
FIG. 8 is the results of the laser particle size test of the ceramic slurries prepared in examples 5-8;
FIG. 9 is a graph of particle size distribution for ceramic slurries prepared in examples 5-8;
FIG. 10 is a Zeta potential distribution plot of ceramic slurries prepared in examples 5-8;
FIG. 11 is a graph of viscosity versus shear rate for ceramic slurries prepared in examples 5-8;
FIG. 12 is a graph of viscosity versus shear rate for ceramic slurries prepared in examples 1-4.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The mass of each component mentioned in the description of the embodiment of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the mass between each component, therefore, it is within the scope of the disclosure of the description of the embodiment of the present invention to scale up or down the content of each component of the composition according to the description of the embodiment of the present invention. Specifically, the mass described in the description of the embodiment of the present invention may be a unit of weight known in the medical field such as μ g, mg, g, kg, etc.
A ceramic slurry is used for preparing a ceramic casting film, and comprises the following components in parts by weight, based on 100 parts by weight of the total ceramic slurry:
the ceramic slurry provided by the embodiment of the invention comprises barium titanate powder, castor oil, polyvinyl butyl acetal, di-n-butyl phthalate, n-butyl alcohol, ethylene glycol and absolute ethyl alcohol which have the specific weight part ratio, wherein the absolute ethyl alcohol is used as a solvent, the castor oil is used as a dispersing agent, the polyvinyl butyl acetal is used as a binder, the di-n-butyl phthalate is used as a plasticizer, the n-butyl alcohol and the ethylene glycol are used as defoaming agents, and the ceramic slurry is endowed with good rheological property under the synergistic action of the components, so that the surface of a ceramic casting film formed by casting the ceramic slurry is flat and compact.
In the present specification, the term "the balance of ethanol" refers to the amount of ethanol remaining in the ceramic slurry, for example, when the ceramic slurry only includes barium titanate powder and absolute ethanol, the weight percentage of barium titanate is 49.46% based on 100% of the total weight of the ceramic slurry, and the balance of absolute ethanol is the weight percentage of absolute ethanol: 100% -49.46% ═ 50.54%.
As an embodiment, the ceramic slurry comprises the following components in parts by weight, based on 100 parts by weight of the total weight of the ceramic slurry:
the ceramic slurry is detected to have the viscosity of 0.947Pas, the roughness of the prepared ceramic casting film is 51.5nm, the thickness of the film is as small as 44 microns, and the density is as high as 3.79g/cm3The ceramic slurry provided by the embodiment of the invention has good rheological property and can be used for preparing a ceramic casting film with a flat and compact surface.
The capacitance of M L CC has the formula C × S × (N-1)/d, where dielectric constant (F/M) of the dielectric is given, and S is the area of the internal electrode (M)2) D is the thickness (M) of the dielectric layer, therefore, the thickness of the dielectric layer is a limiting factor for limiting the M L CC capacitive performance, the thickness of the film prepared by casting the ceramic slurry is less than 10 microns, and the ceramic slurry provided by the embodiment of the invention is combined with the casting forming processIt is beneficial to obtaining a miniaturized and high-performance chip multilayer ceramic capacitor.
Specifically, barium titanate powder (BTO powder) has a high dielectric constant and ferroelectric properties, and is a typical class ii dielectric material as a base material of the ceramic slurry.
In order to realize the miniaturization and high performance of M L CC, a ceramic dielectric layer must be as thin as possible and the electrical property is excellent, so that the BTO powder used by flow casting is selected to have the smallest split diameter and excellent square.
In one embodiment, the barium titanate powder has a particle size of 90 to 150 nm. In some embodiments, the barium titanate powder is selected from Chinese porcelain 100nm, and has an actual particle size of 134.22nm and a specific surface area of 10.9208m2The squareness c/a is 1.0067.
In order to realize the miniaturization and high performance of M L CC, the solid content of the ceramic slurry needs to be optimized, wherein the solid content of the ceramic slurry depends on the using amount of barium titanate powder.
In one embodiment, the weight of the barium titanate powder is 34 to 50 parts, preferably 49.49 parts. When the weight part of the barium titanate powder is 49.49 parts, the obtained ceramic slurry has excellent rheological property.
And the castor oil is used as an anionic dispersant and is used as a dispersant of the ceramic slurry to disperse the BOT powder in cooperation with the absolute ethyl alcohol.
The amount of castor oil affects the dispersion degree of barium titanate powder in absolute ethyl alcohol and affects the rheological property of ceramic slurry to a certain extent.
In one embodiment, the castor oil is 0.5 to 2 parts by weight, preferably 1.58 parts by weight, and when the content of castor oil in the ceramic slurry is 1.58%, the dispersibility of the BTO powder is the best.
Polyvinyl butyral (PVB) is used as a binder of ceramic slurry and is used for preventing powder segregation or improving the strength of a green body prepared by subsequent sintering, so that the density of the film is improved to a certain extent and the thickness of the film is reduced.
The di-n-butyl phthalate (DBP) is used as a plasticizer of ceramic slurry, is used for reducing the plastic limit temperature Tg of PVB (polyvinyl butyral), prevents the slurry from coagulating at room temperature or below, can play a role in bridging barium titanate particles and lubricating to reduce the viscosity of the slurry, is beneficial to improving the rheological property of the slurry, and promotes the preparation of a ceramic casting film with a smooth, compact and ultrathin surface.
N-butanol and ethylene glycol as defoaming agents for ceramic slurries. After the mixed solution of n-butanol and ethylene glycol is sufficiently dispersed in the solvent, the mixed solution adheres to the bubble membrane, and adsorbs a part of the surfactant of the bubble membrane, resulting in poor surface tension and bubble breakage.
The barium titanate powder, castor oil, absolute ethyl alcohol, PVB, DBP, n-butanol, and ethylene glycol may be commercially available products, or may be products prepared by conventional techniques in the art, and the embodiment of the present invention is not particularly limited thereto.
Compared with the conventional method that anhydrous ethanol and a medium-low polarity organic solvent (such as butanone) are compounded to serve as a solvent of the ceramic slurry, the solvent of the ceramic slurry disclosed by the embodiment of the invention only contains the anhydrous ethanol, so that the ceramic slurry is green and environment-friendly, and the anhydrous ethanol is low in price, so that the production cost can be greatly saved; meanwhile, the ceramic slurry is endowed with excellent rheological property through the synergistic effect among the barium titanate powder, the castor oil, the absolute ethyl alcohol, the PVB, the DBP, the n-butyl alcohol and the ethylene glycol, when the ceramic slurry is matched with a tape casting process, an ultrathin ceramic tape casting film with a flat and compact surface and a film thickness of less than 10 micrometers can be obtained, and when the film is applied to the preparation of a chip multilayer ceramic capacitor, the capacitive performance of the chip multilayer ceramic capacitor is improved, and the preparation of a miniaturized chip multilayer ceramic capacitor is facilitated.
Based on the technical scheme, the embodiment of the invention also provides a preparation method of the ceramic casting film and a chip multilayer ceramic capacitor.
Correspondingly, the preparation method of the ceramic casting film comprises the following steps:
s01, providing the ceramic slurry;
s02, carrying out tape casting on the ceramic slurry to obtain the ceramic tape casting film.
According to the preparation method of the ceramic casting film provided by the embodiment of the invention, the ceramic slurry is matched with a casting forming process to prepare the ceramic casting film, so that the ultrathin ceramic casting film with a smooth and compact surface can be obtained.
The raw material composition and the action effect of the ceramic material in step S01 are the same as those of the ceramic slurry described above, and are not repeated herein for brevity.
As an embodiment, as shown in fig. 1, the method for preparing the ceramic slurry includes the steps of:
s011, mixing barium titanate powder, castor oil and absolute ethyl alcohol, and carrying out first mixing treatment to obtain a first mixture;
s012, mixing polyvinyl butyl acetal, di-n-butyl phthalate, n-butyl alcohol and ethylene glycol with the first mixture, and carrying out second mixed material treatment.
In step S011, barium titanate powder and castor oil are dispersed in absolute ethyl alcohol, barium titanate particles carry negative ions and counter ions in a solvent, castor oil is ionized into surface ions and counter ions in the solvent, barium titanate powder and castor oil synergistically form a double electric layer dispersion system, and when powder particles having adsorbed negative charges approach each other, repulsion is generated to make them slide and stagger each other, thereby preventing the powder from aggregating to form large aggregates. In step S012, PVB and DBP are fully contacted with the powder particles through a second mixing process, PVB performs a binding function, and DBP reduces a plastic limit temperature Tg of PVB to ensure that the slurry does not condense at room temperature, and simultaneously bridges and lubricates barium titanate particles, thereby reducing the viscosity of the slurry and improving the rheological property of the ceramic slurry to a certain extent.
The steps of performing the first mixing treatment and performing the second mixing treatment may refer to the conventional operations in the art, such as mechanical stirring, ultrasonic dispersion, and the like, so that the components can be uniformly mixed. In some embodiments, the first compounding process and/or the second compounding process comprises: ball milling is carried out for 3-5 hours.
Further, as shown in fig. 2, the step of performing the second mixed material processing further includes: and carrying out vacuum degassing treatment to obtain the ceramic slurry. In some embodiments, the vacuum degas for 40 minutes.
In step S02, the ceramic slurry is subjected to tape casting to obtain the ceramic cast film.
The step of casting the ceramic slurry may be performed by a conventional procedure in the art, for example, a ceramic slurry is flowed onto the base tape from the rear of the slurry tank, deposited on the base tape by a relative movement between the base tape and the doctor blade, and dried to form a ceramic thin film.
More specifically, the height of the doctor blade is adjusted to below 500 microns. In one embodiment, in the step of casting the ceramic slurry by a casting process, the height of the doctor blade is adjusted to 90 to 110 μm.
More specifically, the speed of the base tape with respect to the blade is a casting line speed, and as an embodiment, the casting line speed is 0.2 to 0.3cm/s, the drying temperature is 30 to 50 ℃, and the drying time is 7 to 10 hours. In some examples, the casting line speed was 0.25cm/s, the drying temperature was 40 ℃ and the drying time was 8 hours.
Correspondingly, the chip type multilayer ceramic capacitor comprises a ceramic chip, wherein the ceramic chip is formed by overlapping and sintering a plurality of ceramic dielectric diaphragms;
wherein, the ceramic dielectric membrane is a ceramic tape-casting film prepared by the preparation method.
According to the chip multilayer ceramic capacitor provided by the embodiment of the invention, the ceramic dielectric diaphragm is the ceramic tape-casting film prepared by the preparation method, the surface is flat and compact, the film thickness is small, the preparation of a miniaturized and high-performance chip multilayer ceramic capacitor is facilitated, and the application range of the chip multilayer ceramic capacitor is expanded.
In order that the above-described details and operation of the present invention will be clearly understood by those skilled in the art, and the advanced performance of a ceramic slurry, a method for producing a ceramic casting film and a chip type multilayer ceramic capacitor according to the embodiments of the present invention will be remarkably shown, the embodiments of the present invention will be exemplified by the following examples.
Example 1
The embodiment provides a ceramic casting film for preparing M L CC, and the preparation method of the ceramic casting film specifically comprises the following steps:
s11, providing ceramic slurry;
(1) the preparation of the slurry is carried out according to the following slurry formula:
(2) preparation of the slurry
Mixing barium titanate powder, castor oil and absolute ethyl alcohol, and performing ball milling for 4 hours to obtain a first mixture;
mixing polyvinyl butyl acetal, di-n-butyl phthalate, n-butanol and ethylene glycol with the first mixture, ball-milling for 4 hours, and then vacuum degassing for 40 minutes to obtain ceramic slurry.
S12, adjusting the height of a scraper to be 100 microns, enabling the ceramic slurry obtained in the step S11 to flow to a base band, and carrying out tape casting molding, wherein the tape casting linear velocity is 0.25cm/S, the drying temperature is 40 ℃, and the drying time is 8 hours, so that the ceramic tape casting film is obtained.
Examples 2-10 the differences between the method of making cast ceramic films and example 1 are shown in table 1:
TABLE 1
| Barium titanate | Castor oil | PVB | DBP | N-butanol | Ethylene glycol | Anhydrous ethanol | Height of the scraper | |
| Example 2 | 34.62 portions | - | - | - | - | - | 54.4 parts of | - |
| Example 3 | 39.56 portions | - | - | - | - | - | 49.46 parts | - |
| Example 4 | 44.51 parts | - | - | - | - | - | 44.51 parts | - |
| Example 5 | 39.56 portions | 0.79 portion | - | - | - | - | 50.25 parts | - |
| Example 6 | 39.56 portions | 1.19 parts | - | - | - | - | 49.85 parts | - |
| Example 7 | 39.56 portions | 1.58 parts of | - | - | - | - | 49.46 parts | - |
| Example 8 | 39.56 portions | 1.98 portions | - | - | - | - | 49.06 parts | - |
| Example 9 | - | - | - | - | - | - | - | 450μm |
Note: "-" means the same as in example 1.
Test example 1
1. The ceramic casting films prepared in examples 1 and 9 were measured for film thickness, and the surface morphology of the films was observed by Scanning Electron Microscope (SEM) and Atomic Force Microscope (AFM), respectively, and fig. 3 and 4 are the results of the measurements.
The film thickness of example 1 was 21.3 μm, the film thickness of example 9 was 88.6 μm, and the 100 μm blade height was better than 450 μm for pursuing miniaturization and thinning of the product; as shown in fig. 3, the surface colloid of example 1 is significantly less, and the density of the powder particles is high; as shown in FIG. 4, the film of example 1 had a surface roughness of 51.5nm, and the film of example 9 had a surface roughness of 99.9 nm.
In conclusion, it is shown that the overall properties of the ceramic cast film obtained when the blade height is lowered to 100 μm are excellent.
2. The surface morphology of the ceramic casting films prepared in examples 1 to 4 was observed by a Scanning Electron Microscope (SEM) and an Atomic Force Microscope (AFM), respectively.
FIG. 5 is an SEM image of the ceramic cast films prepared in examples 1-4, and as the results show, the solid contents of the ceramic slurries used in examples 2, 3, 4 and 1 are sequentially increased, and the surface of the cast film becomes denser and less organic colloid and void are formed as the solid contents are increased; FIG. 6 is an AFM image of the ceramic cast films prepared in examples 1-4, as the results show the relative flatness of the ceramic cast films prepared in examples 1-4.
3. Five samples each having a length and width of 2cm were cut transversely on the cast ceramic films prepared in examples 1 to 4, and the average thickness and mass thereof were measured, and then the density deviation value thereof was calculated, and the results are shown in table 2.
The results of the density and deviation shown in fig. 7 were obtained by calculation, and as the solid content increased, the density of the cast film was continuously increased, and the density deviation thereof reached a peak at the solid contents of 40 wt% and 45 wt%, and reached a minimum in the selected sample at the solid content of 49.46 wt%.
TABLE 2
Test example 2
1. The ceramic slurries prepared in examples 5 to 8 were tested for particle size and Zeta potential using a laser light scattering potentiostat model 90Plus Zeta from brueck heim, usa, as follows:
when preparing a test sample, firstly transferring the prepared slurry into a Zeta potential sample cell by a dropper for one to two drops, and then continuously adding absolute ethyl alcohol to dilute the slurry. The average counting rate of the instrument is controlled to be about 300kcps, so that the instrument is prevented from being damaged due to overlarge light intensity of laser scattered light during testing. For the Zeta potential test, the electrode special for the test needs to be soaked for more than 5 minutes to ensure the accuracy of the test.
FIG. 8 is a result of a laser particle size test of the ceramic slurries prepared in examples 5 to 8, as a result of which it is shown that the average particle diameters of the ceramic slurries of examples 5, 6, 7 and 8 are 525.857nm, 471.322nm, 302.106nm and 446.618nm, respectively.
FIG. 9 is a particle size distribution diagram of the ceramic slurries prepared in examples 5 to 8, and as a result, it was shown that the ceramic slurry of example 7, in which D10, D50 and D90 were all smaller than the ceramic slurries of examples 5, 6 and 8, showed excellent powder dispersibility at a dispersant content of 1.58 wt%.
FIG. 10 is a Zeta potential distribution diagram of the ceramic slurries prepared in examples 5 to 8, and as a result, it was shown that the Zeta potential of the slurry was the maximum at a dispersant content of 1.58 wt%, and the Zeta potential was in positive correlation with the stability of the system, indicating that the stability of the slurry system was excellent at a dispersant content of 1.58 wt%.
2. The ceramic slurries prepared in examples 1 to 8 were used as HAAKE from Saimer Feishel, USATMMARSTMThe type rotational rheometer is used for testing the viscosity of the ceramic slurry, and the specific testing process is as follows:
in the experiment, a PP35ti platform and a rotor are used for testing the viscosity-shear rate corresponding relation of the configured slurry in a shear rate range of 0-1001/s. The height of the sample is 1mm, the test temperature is 25 ℃, the number of recording points is 100, and the time is 30 s.
FIG. 11 is a graph of viscosity versus shear rate for the ceramic slurries prepared in examples 5-8, as the results show that the viscosities of the ceramic slurries prepared in examples 5-8 are very close.
FIG. 12 is a graph of viscosity versus shear rate for the ceramic slurries prepared in examples 1-4, and the results show that the ceramic slurries of examples 1, 3, 4 all have viscosities between 0.2Pas and 1.0Pas, and slurries within this viscosity range are more amenable to casting, wherein the closer the viscosity value is to the upper limit of this interval, the more amenable to casting, indicating that the ceramic slurries have excellent rheological properties when the slurry solids content is 49.49%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The ceramic slurry is used for preparing a ceramic casting film, and comprises the following components in parts by weight, based on 100 parts by weight of the total ceramic slurry:
2. the ceramic slurry according to claim 1, wherein the barium titanate powder is 34 to 50 parts by weight; and/or
The weight of the castor oil is 0.5-2 parts.
3. The ceramic slurry according to claim 1, wherein the barium titanate powder has a particle size of 90 to 150 nm.
4. The ceramic slurry according to any one of claims 1 to 3, wherein the ceramic slurry comprises the following components in parts by weight, based on 100 parts by weight of the total ceramic slurry:
5. a method for preparing a ceramic casting film is characterized by comprising the following steps:
providing a ceramic slurry according to any one of claims 1 to 4;
and carrying out tape casting on the ceramic slurry to obtain the ceramic tape casting film.
6. The manufacturing method according to claim 5, wherein in the step of casting the ceramic slurry by a casting process, a height of a doctor blade is adjusted to 90 to 110 μm.
7. The method for preparing the ceramic slurry according to claim 5, comprising the steps of:
mixing barium titanate powder, castor oil and absolute ethyl alcohol, and carrying out first mixing treatment to obtain a first mixture;
and mixing polyvinyl butyl acetal, di-n-butyl phthalate, n-butanol and ethylene glycol with the first mixture, and carrying out second mixed material treatment.
8. The method for preparing a master batch according to claim 7, wherein the step of performing the second batch processing further comprises: and carrying out vacuum degassing treatment to obtain the ceramic slurry.
9. A production method according to claim 7, characterized in that the first compounding process and/or the second compounding process includes: ball milling is carried out for 3-5 hours.
10. A chip type multilayer ceramic capacitor is characterized by comprising a ceramic chip, wherein the ceramic chip is formed by overlapping and sintering a plurality of ceramic dielectric diaphragms;
wherein the ceramic dielectric membrane is a ceramic cast film prepared by the preparation method of any one of claims 5 to 9.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112723879A (en) * | 2021-01-05 | 2021-04-30 | 贵州大学 | Barium calcium zirconate titanate piezoelectric ceramic tape-casting slurry and application thereof |
| CN113314340A (en) * | 2021-06-01 | 2021-08-27 | 山东国瓷功能材料股份有限公司 | Ultrathin medium slurry for casting ceramic superfine powder and ceramic film formed by ultrathin medium slurry |
| CN114804841A (en) * | 2022-04-30 | 2022-07-29 | 北京智感度衡科技有限公司 | Alumina green ceramic chip for particulate matter sensor and preparation method thereof |
-
2020
- 2020-03-09 CN CN202010158888.7A patent/CN111470862A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112723879A (en) * | 2021-01-05 | 2021-04-30 | 贵州大学 | Barium calcium zirconate titanate piezoelectric ceramic tape-casting slurry and application thereof |
| CN113314340A (en) * | 2021-06-01 | 2021-08-27 | 山东国瓷功能材料股份有限公司 | Ultrathin medium slurry for casting ceramic superfine powder and ceramic film formed by ultrathin medium slurry |
| CN114804841A (en) * | 2022-04-30 | 2022-07-29 | 北京智感度衡科技有限公司 | Alumina green ceramic chip for particulate matter sensor and preparation method thereof |
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