CN114956808B - MLCC ceramic dielectric material and preparation method thereof, high-temperature stable MLCC ceramic and preparation method and application thereof - Google Patents
MLCC ceramic dielectric material and preparation method thereof, high-temperature stable MLCC ceramic and preparation method and application thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 143
- 239000003989 dielectric material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 238000005245 sintering Methods 0.000 claims abstract description 50
- 239000002019 doping agent Substances 0.000 claims abstract description 38
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 18
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 28
- 238000007599 discharging Methods 0.000 claims description 26
- 239000007921 spray Substances 0.000 claims description 25
- 238000000498 ball milling Methods 0.000 claims description 22
- 238000005469 granulation Methods 0.000 claims description 21
- 230000003179 granulation Effects 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 13
- 239000000853 adhesive Substances 0.000 claims description 12
- 230000001070 adhesive effect Effects 0.000 claims description 12
- 239000002518 antifoaming agent Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 239000013530 defoamer Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 230000000630 rising effect Effects 0.000 claims description 8
- 239000012776 electronic material Substances 0.000 claims description 7
- 239000011361 granulated particle Substances 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 238000003801 milling Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 238000009740 moulding (composite fabrication) Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 25
- 239000003292 glue Substances 0.000 description 18
- 239000011805 ball Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 238000004321 preservation Methods 0.000 description 10
- 230000009286 beneficial effect Effects 0.000 description 9
- 239000013078 crystal Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 3
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Abstract
The invention provides an MLCC ceramic dielectric material and a preparation method thereof, and a high-temperature stable MLCC ceramic and a preparation method and application thereof, relating to the technical field of ceramic material manufacture 3 And a dopant, wherein the dopant comprises Al 2 O 3 、Bi 2 O 3 、Yi 2 O 3 A mixture of CuO; al (Al) 2 O 3 Occupy BaTiO 3 The mole percentage of (2) is 1-9 mol%. The invention solves the technical problems of lengthy preparation process, complex operation and poor performance of the prior MLCC ceramic, and achieves the technical effects of simple preparation process, low sintering temperature, cost saving, better electrical property stability of the MLCC ceramic at high temperature and capability of meeting the X8R requirement of the MLCC ceramic.
Description
Technical Field
The invention relates to the technical field of ceramic material manufacturing, in particular to a high-temperature stable MLCC ceramic, and a preparation method and application thereof.
Background
As an important electronic information material, the MLCC ceramic influences the development of downstream and terminal industries to a certain extent, however, the conventional technology and the MLCC ceramic prepared by the conventional technology have the problems of long preparation process, complex operation and the like, the performance of the obtained MLCC ceramic is relatively general and cannot reach the expected ideal performance, so that the MLCC ceramic has a plurality of inconveniences and defects in practical application and use, and the further development of downstream products and terminal industries is limited, so that the conventional MLCC ceramic and the preparation method thereof are necessary to be improved, the comprehensive performance of the conventional MLCC ceramic is improved, and the MLCC ceramic can be better applied to practical production.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide an MLCC ceramic dielectric material which can meet the X8R characteristic after being sintered into ceramic and has better electrical property stability at high temperature.
The second purpose of the invention is to provide a preparation method of the MLCC ceramic dielectric material, which has simple and efficient process.
The third purpose of the invention is to provide a high temperature stable MLCC ceramic with dielectric constant of 2000-3100, the capacity temperature change rate meeting the X8R requirement, and better electrical performance stability at high temperature.
The fourth purpose of the invention is to provide a preparation method of the high-temperature stable MLCC ceramic, which has short preparation process and simple operation.
The fourth object of the present invention is to provide an application of a high temperature stable MLCC ceramic, which has outstanding application effects.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
in a first aspect, an MLCC ceramic dielectric material comprises a main constituent and a dopant;
the main component is BaTiO 3 ；
The dopant includes Al 2 O 3 、Bi 2 O 3 、Yi 2 O 3 A mixture of CuO;
the Al is 2 O 3 Occupies the BaTiO 3 The mole percentage of (2) is 1-9 mol%.
Further, the dopant occupies the BaTiO 3 The mole percentages of (a) are respectively as follows:
Al 2 O 3 1～9mol％，Bi 2 O 3 0.2～2mol％，Yi 2 O 3 0.2～2mol％，CuO 1～6mol％。
in a second aspect, a method for preparing an MLCC ceramic dielectric material includes the steps of:
mixing the main components and the doping agent in proportion, grinding and granulating to obtain the MLCC ceramic dielectric material.
Further, the preparation method of the main component comprises a hydrothermal method;
preferably, the hydrothermal method comprises the steps of:
with Ti (OC) 4 H 9 ) 4 For titanium source, with Ba (OH) 2 ·8(H 2 O) is a barium source, and a mineralizer is added for reaction to obtain a main component;
preferably, the molar ratio Ba/Ti is 1-1.5: 1, a step of;
preferably, the mineralizer comprises NH 3 ·H 2 O；
Preferably, the temperature of the reaction is 180-200 ℃ and the time is 25-35 h;
preferably, the particle size of the main component is 80 to 120nm.
Further, the grinding mode comprises ball milling;
preferably, the ball milling comprises the steps of:
adding water, a binder and a defoaming agent, mixing, and then performing ball milling by using a ball mill to obtain powder slurry;
preferably, the binder comprises polyvinyl alcohol;
preferably, the addition amount of the binder accounts for 1-5% of the total mass of the main component and the doping agent;
preferably, the defoamer comprises a polyether defoamer;
preferably, the adding amount of the defoaming agent accounts for 0.01 to 0.04 percent of the total mass of the main component and the doping agent;
preferably, the ball milling time is 6-10 hours;
preferably, the ball mill comprises ZrO 2 ；
Preferably, the mass ratio of the main component, the water and the ball mill is 1 (1.25-3.5): 5;
preferably, the solid content of the powder slurry is 20-45% by mass.
Further, the granulating includes spray granulating;
preferably, the temperature of a feed inlet of the spray granulation is 180-220 ℃, and the temperature of a discharge outlet of the spray granulation is 95-105 ℃;
preferably, the rotational speed of the spray granulation is 10-30 r/s;
preferably, the particle size of the spray granulated particles is 40-80 μm;
preferably, the water content of the spray granulated particles is 0.25 to 0.8wt%.
In a third aspect, a high temperature stable MLCC ceramic is prepared from any of the MLCC ceramic dielectric materials described above.
In a fourth aspect, a method for preparing a high temperature stable MLCC ceramic, comprising the steps of:
the MLCC ceramic dielectric material of any one of the above-mentioned claims is pressed and sintered to obtain the Gao Wenwen shaped MLCC ceramic.
Further, the sintering includes two-step sintering;
preferably, the two-step sintering comprises the steps of:
starting from room temperature (the room temperature is 20-50 ℃), heating to a first sintering temperature of 1300-1450 ℃ at a heating rate of 5-20 ℃/min, preserving heat for 10-60 min, then cooling to a second sintering temperature of 1000-1100 ℃ at a cooling rate of 8-15 ℃/min, and preserving heat for 4-10 h;
preferably, the two-step sintering is preceded by a glue discharging step;
preferably, the step of removing the adhesive includes the steps of:
firstly heating up for the first time from room temperature (the room temperature is 20-50 ℃), then preserving heat for glue discharging, and then heating up for the second time, and then preserving heat for glue discharging;
preferably, the temperature after the first temperature rise is 395-405 ℃ and the heat preservation time is 110-120 min;
preferably, the temperature rising rate of the first temperature rising is 1-2 ℃/min;
preferably, the temperature after the second temperature rise is 590-600 ℃, and the heat preservation time is 110-120 min;
preferably, the temperature rising rate of the second temperature rising is 1-1.5 ℃/min.
In a fifth aspect, a high temperature stable MLCC ceramic is used in an electronic material.
Compared with the prior art, the invention has at least the following beneficial effects:
the MLCC ceramic dielectric material provided by the invention comprises a main component BaTiO 3 And a dopant, wherein the dopantComprises Al 2 O 3 、Bi 2 O 3 、Yi 2 O 3 Mixtures of CuO, al 2 O 3 Occupy BaTiO 3 The mol percent of (2) is 1-9 mol percent; in the MLCC ceramic dielectric material of the invention, baTiO is used 3 As a ceramic main crystal phase, it can provide a higher dielectric constant and lower dielectric loss; dopant Al 2 O 3 The sintering activity of the barium titanate ceramics can be promoted, so that the sintering temperature is reduced; bi (Bi) 2 O 3 And Yi 2 O 3 The dielectric constant can be used as a frequency stabilizer, and the change rate of the dielectric constant along with the temperature can be reduced at high temperature; cuO acts as a sintering aid. The material of the invention adopts BaTiO 3 ·xAl 2 O 3 The system (X is more than or equal to 0.01 and less than or equal to 0.09) can be cooperatively matched among the components, so that the MLCC ceramic dielectric material can not only meet the X8R characteristic after being sintered into ceramic, but also has better electrical property stability at high temperature, and meanwhile, the subsequent ceramic sintering temperature is reduced, and the cost is saved.
The preparation method of the MLCC ceramic dielectric material provided by the invention has simple and efficient process.
The dielectric constant of the high-temperature stable MLCC ceramic provided by the invention is 2000-3100, the capacitance-temperature change rate meets the X8R requirement, and the electrical property stability at high temperature is better.
The preparation method of the high-temperature stable MLCC ceramic provided by the invention has the advantages of short preparation process and simple operation.
The application of the high-temperature stable MLCC ceramic provided by the invention can meet the performance requirements of electronic materials, meet the use requirements of the electronic materials and has outstanding application effects.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic flow chart of a preparation process of the high temperature stable MLCC ceramic provided in embodiment 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
According to a first aspect of the present invention, there is provided an MLCC ceramic dielectric material comprising a main component and a dopant;
wherein the main component is BaTiO 3 ；
The dopant includes Al 2 O 3 、Bi 2 O 3 、Yi 2 O 3 A mixture of CuO;
Al 2 O 3 occupy BaTiO 3 The molar percentage of (2) is 1 to 9mol%, and typical but non-limiting molar percentages thereof are, for example, 1mol%, 2mol%, 3mol%, 4mol%, 5mol%, 6mol%, 7mol%, 8mol%, 9mol%.
In the MLCC ceramic dielectric material of the invention, baTiO is used 3 As the main crystal phase of the ceramic, baTiO is adopted 3 As a ceramic main crystal phase, it can provide a higher dielectric constant and lower dielectric loss; dopant Al 2 O 3 The sintering activity of the barium titanate ceramics can be promoted, so that the sintering temperature is reduced; bi (Bi) 2 O 3 And Yi 2 O 3 The dielectric constant can be used as a frequency stabilizer, and the change rate of the dielectric constant along with the temperature can be reduced at high temperature; cuO acts as a sintering aid. The ceramic material of the invention adopts BaTiO 3 ·xAl 2 O 3 The system (X is more than or equal to 0.01 and less than or equal to 0.09) can be cooperated with each other, so that after the MLCC ceramic dielectric material is sintered into ceramic, not only the temperature change rate can meet the X8R characteristic, but also the system has better electrical property stability at high temperature, and simultaneously the subsequent temperature is reducedThe ceramic sintering temperature of the ceramic is saved.
In a preferred embodiment, the MLCC ceramic dielectric material has a dopant of BaTiO 3 The mole percentages of (a) are respectively as follows:
Al 2 O 3 1～9mol％，Bi 2 O 3 0.2～2mol％，Yi 2 O 3 0.2～2mol％，CuO 1～6mol％。
in the present invention, al 2 O 3 Typical but non-limiting mole percentages are, for example, 1 mole%, 2 mole%, 3 mole%, 4 mole%, 5 mole%, 6 mole%, 7 mole%, 8 mole%, 9 mole%; bi (Bi) 2 O 3 Typical but non-limiting mole percentages are, for example, 0.2 mole%, 0.4 mole%, 0.6 mole%, 0.8 mole%, 1 mole%, 1.2 mole%, 1.4 mole%, 1.6 mole%, 1.8 mole%, 2 mole%; yi 2 O 3 Typical but non-limiting mole percentages are, for example, 0.2 mole%, 0.4 mole%, 0.6 mole%, 0.8 mole%, 1 mole%, 1.2 mole%, 1.4 mole%, 1.6 mole%, 1.8 mole%, 2 mole%; typical, but non-limiting, mole percentages of CuO are, for example, 1 mole%, 2 mole%, 3 mole%, 4 mole%, 5 mole%, 6 mole%.
The preferred dopant of the invention comprises BaTiO 3 The molar percentage of the ceramic dielectric material is favorable for improving the electrical property stability of the MLCC ceramic dielectric material at high temperature after being sintered into ceramic, and the capacity temperature change rate of the MLCC ceramic dielectric material can meet the X8R characteristic.
According to a second aspect of the present invention, there is provided a method for preparing an MLCC ceramic dielectric material, comprising the steps of:
mixing the main components and the doping agent in proportion, grinding and granulating to obtain the MLCC ceramic dielectric material.
The preparation method of the MLCC ceramic dielectric material provided by the invention has simple and efficient process.
In the present invention, baTiO as a main component 3 The preparation method of (2) comprises a hydrothermal method.
In a preferred embodiment, the present invention prepares BaTiO as a main component by a hydrothermal method 3 The method comprises the following steps:
with Ti (OC) 4 H 9 ) 4 For titanium source, with Ba (OH) 2 ·8(H 2 O) is a barium source, and a mineralizer is added for reaction to obtain a main component;
wherein, the mole ratio of Ba/Ti can be 1-1.5:1, such as 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, but not limited thereto; mineralizers include, but are not limited to NH 3 ·H 2 The reaction temperature of O may be 180 to 200 ℃, for example, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, but is not limited thereto: the reaction time may be 25 to 35 hours, for example, 25 hours, 26 hours, 27 hours, 28 hours, 29 hours, 30 hours, 31 hours, 32 hours, 33 hours, 34 hours, 35 hours, but is not limited thereto: the specific steps and the technological parameters selected by the invention are more beneficial to the main component BaTiO 3 Is successfully prepared to obtain BaTiO with better performance 3 。
In the present invention, baTiO as a main component 3 The particle size of (a) may be 80-120 nm, and typical but non-limiting particle sizes are, for example, 80nm, 90nm, 100nm, 110nm, 120nm, which may further facilitate subsequent mixing with dopants, grinding, and pelleting to produce MLCC ceramic dielectric materials with excellent properties.
In the present invention, milling means include, but are not limited to, ball milling, which facilitates adequate milling of the more intimate mixture.
In a preferred embodiment, the ball mill of the invention comprises the steps of:
adding water, a binder and a defoaming agent, mixing, and then performing ball milling by using a ball mill to obtain powder slurry;
wherein, the binder comprises, but is not limited to, polyvinyl alcohol, and the addition amount of the binder accounts for 1-5% of the total mass of the main component and the doping agent, for example, 1%, 2%, 3%, 4% and 5%; the defoamer includes but is not limited to polyether defoamer, and the addition amount of the defoamer accounts for 0.01-0.04% of the total mass of the main component and the dopant, and can be 0.01%, 0.02%, 0.03% and 0.04% for example.
The binder and the defoamer added in the invention and the dosage thereof are more beneficial to the ball milling process of the mixture.
In the present invention, the time of ball milling is not particularly limited as long asThe polishing may be sufficiently performed, and may be preferably 6 to 10 hours, for example, 6 hours, 7 hours, 8 hours, 9 hours, and 10 hours, but not limited thereto; the material of the ball mill is not particularly limited, and for example, the material may be ZrO 2 But is not limited thereto.
In a preferred embodiment, the mass ratio of the main ingredient, water and ball mill is 1: (1.25-3.5) to 5, which is typically but not limited to, for example, 1:1.25:5, 1:1.5:5, 1:2:5, 1:2.25:5, 1:2.5:5, 1:3:5, 1:3.25:5, 1:3.5:5, more conducive to adequate ball milling of the mix.
In the invention, the mass percentage of the solid content of the powder slurry obtained after ball milling is 20-45%, such as 20%, 25%, 30%, 35%, 40% and 45%, which is more beneficial to the subsequent granulation preparation process.
In a preferred embodiment, the granulation of the present invention includes, but is not limited to, spray granulation, wherein the inlet temperature of spray granulation is 180-220 ℃, typical but non-limiting inlet temperature thereof is, for example, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, outlet temperature thereof is 95-105 ℃, typical but non-limiting outlet temperature thereof is, for example, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃, 100 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃, 105 ℃; the rotational speed of the spray granulation is, for example, 10 to 30r/s, and typical but non-limiting rotational speeds thereof are, for example, 10r/s, 15r/s, 20r/s, 25r/s, 30r/s.
The temperature of the feed inlet and the temperature of the discharge outlet of the spray granulation and the rotating speed are more favorable for fully granulating the powder slurry with high quality so as to obtain the MLCC ceramic dielectric material.
The particle size of the spray granulated particles is 40 to 80. Mu.m, for example, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, but not limited thereto; the water content of the spray-granulated particles may be, for example, 0.25 to 0.8wt%, 0.3wt%, 0.35wt%, 0.4wt%, 0.45wt%, 0.5wt%, 0.55wt%, 0.6wt%, 0.65wt%, 0.7wt%, 0.75wt%, 0.8wt%, but is not limited thereto.
The particle size and the water content of the spray granulation are more beneficial to the subsequent compression molding and sintering of the MLCC ceramic dielectric material to obtain the high-temperature stable MLCC ceramic.
A typical preparation method of an MLCC ceramic dielectric material comprises the following steps:
step S101: preparation of BaTiO as main component of MLCC ceramic dielectric material 3 The preparation method is a hydrothermal method, and specifically comprises the following steps:
with Ti (OC) 4 H 9 ) 4 For titanium source, with Ba (OH) 2 ·8(H 2 O) is a barium source, and the molar ratio of Ba to Ti is 1.5:1, adding mineralizer NH 3 ·H 2 O is reacted at 185 deg.c for 30 hr to obtain main component BaTiO of MLCC ceramic dielectric material 3 The grain diameter is 80-120 nm;
step S102: adding the doping agent, the binder, the defoaming agent, water and ball mill into the main component BaTiO obtained in the step S101 according to the formula ratio 3 Ball milling and mixing to obtain powder slurry;
wherein the main component is BaTiO 3 The mass ratio of water to ball mill is 1: (1.25-3.5) to 5, and can be preferably 1:3:5;
the ball mill is made of ZrO 2 ；
The ball milling and mixing time is 6-10 h;
the binder is polyvinyl alcohol, and the addition amount of the binder accounts for 1-5% of the total mass of the main component and the doping agent;
the defoaming agent is polyether, and the addition amount of the defoaming agent accounts for 0.01-0.04% of the total mass of the main component and the doping agent;
the mass percentage of the solid content in the powder slurry obtained after ball milling is 20-45%;
step S103: granulating the powder slurry obtained in the step S102 to obtain an MLCC ceramic dielectric material;
the granulating mode comprises spray granulating;
wherein, the temperature of a feed inlet of spray granulation is 180-220 ℃ and the temperature of a discharge outlet is 95-105 ℃;
the rotational speed of spray granulation is 10-30 r/s (circle/second);
the particle size of the particles obtained by spray granulation is 40-80 mu m (micrometers), and the water content is 0.2-0.8 wt%.
Compared with the conventional MLCC powder preparation process, the MLCC ceramic powder obtained by the preparation process not only can meet the X8R characteristic in electrical property, but also can avoid the secondary ball milling process in process, and can reduce the subsequent ceramic sintering temperature and save the cost.
According to a third aspect of the present invention, there is provided a high temperature stable MLCC ceramic prepared from the MLCC ceramic dielectric material of the present invention.
The dielectric constant of the high-temperature stable MLCC ceramic provided by the invention is 2000-3100, the capacitance-temperature change rate meets the X8R requirement, and the electrical property stability at high temperature is better.
According to a fourth aspect of the present invention, there is provided a method for preparing a high temperature stable MLCC ceramic, comprising the steps of:
the MLCC ceramic dielectric material is pressed, molded and sintered to obtain the high-temperature stable MLCC ceramic.
The preparation method of the high-temperature stable MLCC ceramic provided by the invention has the advantages of short preparation process and simple operation.
In a preferred embodiment, the sintering of the present invention includes, but is not limited to, two-step sintering.
The two-step sintering of the present invention comprises the steps of:
heating to a first sintering temperature of 1300-1450 ℃ at a heating rate of 5-20 ℃/min from 20-50 ℃ and preserving heat for 10-60 min, then cooling to a second sintering temperature of 1000-1100 ℃ at a cooling rate of 8-15 ℃/min and preserving heat for 4-10 h;
typical but non-limiting rates of heating are, for example, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min, 10 ℃/min, 11 ℃/min, 12 ℃/min, 13 ℃/min, 14 ℃/min, 15 ℃/min, 16 ℃/min, 17 ℃/min, 18 ℃/min, 19 ℃/min, 20 ℃/min; typical but non-limiting temperatures for the first sintering are, for example, 1300 ℃, 1350 ℃, 1400 ℃, 1450 ℃; typical but non-limiting soak times for the first sintering are, for example, 10min, 20min, 30min, 40min, 50min, 60min;
typical but non-limiting rates of cooling are, for example, 8 ℃/min, 10 ℃/min, 12 ℃/min; typical but non-limiting temperatures for the second sintering are, for example, 1000 ℃, 1050 ℃, 1100 ℃; typical but non-limiting soak times for the second sintering are, for example, 4h, 5h, 6h, 7h, 8h, 9h, 10h.
The two-step sintering temperature program is more beneficial to improving the comprehensive performance of the MLCC ceramic, so that the capacity temperature change rate of the MLCC ceramic can meet the X8R characteristic, and the electrical performance stability at high temperature is better.
In the invention, the two-step sintering is preceded by a glue discharging step, and the glue discharging step is more beneficial to the subsequent sintering process, thereby further improving the performance of the ceramic product.
The glue discharging method comprises the following steps:
the first temperature rise is carried out from 20 ℃ to 50 ℃, then the heat preservation is carried out, the glue discharging is carried out, and then the second temperature rise is carried out, and then the heat preservation is carried out, so that the glue discharging is carried out.
In the invention, the temperature after the first temperature rise of the adhesive discharge is 395-405 ℃, the typical but non-limiting temperature is 395 ℃, 400 ℃, 405 ℃ and the heat preservation time is 110-120 min, and the typical but non-limiting heat preservation time is 110min, 111min, 112min, 113min, 114min, 115min, 116min, 117min, 118min, 119min and 120min; the first heating rate is 1-2 deg.C/min, typical but non-limiting rates are, for example, 1 deg.C/min, 1.5 deg.C/min, 2 deg.C/min;
the temperature after the second temperature rise of the adhesive discharging is 590-600 ℃, the typical but non-limiting temperature is 590 ℃, 595 ℃, 600 ℃, the heat preservation time is 110-120 min, and the typical but non-limiting heat preservation time is 110min, 111min, 112min, 113min, 114min, 115min, 116min, 117min, 118min, 119min and 120min; the second temperature is raised at a rate of 1 to 1.5 c/min, typical but non-limiting rates being, for example, 1 c/min, 1.2 c/min, 1.3 c/min, 1.4 c/min, 1.5 c/min.
The two-step temperature-rising and heat-preserving glue discharging process is more beneficial to the glue discharging effect of the pressed material, is beneficial to the subsequent sintering process, and further improves the performance of ceramic products.
A typical preparation method of the high temperature stable MLCC ceramic comprises the following steps:
pressing and forming the MLCC ceramic dielectric material to obtain a ceramic blank, discharging glue, and then sintering in two steps to obtain the high-temperature stable MLCC ceramic;
wherein, the glue discharging comprises the following steps:
starting from 20-50 ℃, heating the ceramic blank for the first time and then preserving heat, and then heating for the second time and then preserving heat; specifically, the temperature of the first heating of the glue discharging is 395-405 ℃, the heat preservation time is 110-120 min, the temperature of the second heating of the glue discharging is 590-600 ℃, and the heat preservation time is 110-120 min; wherein the heating rate of the first heating of the adhesive discharging is 1-2 ℃/min, and the heating rate of the second heating of the adhesive discharging is 1-1.5 ℃/min;
wherein the two-step sintering comprises the following steps:
starting from 20-50 ℃, heating to 1300-1450 ℃ at a heating rate of 5-20 ℃/min, preserving heat at the temperature for 10-60 min, cooling to 1000-1100 ℃ at a second sintering temperature, and preserving heat at the temperature for 4-10 h.
The preparation method provided by the invention adopts a solid-phase sintering method, has simple procedures, can reduce the production cost, and the prepared MLCC ceramic has excellent performance, meets the X8R performance requirement and meets the use requirement of MLCC devices.
According to a fifth aspect of the present invention, there is provided the use of a high temperature stable MLCC ceramic in an electronic material.
The application of the high-temperature stable MLCC ceramic provided by the invention can meet the performance requirements of electronic materials, meet the use requirements of the electronic materials and has outstanding application effects.
The invention is further illustrated by the following examples. The materials in the examples were prepared according to the existing methods or were directly commercially available unless otherwise specified.
Example 1
A preparation method of high-temperature stable MLCC ceramic, see FIG. 1, comprises the following steps:
(a) Preparation of BaTiO, the major component of MLCC ceramics 3 The preparation method of the powder is a hydrothermal method, and comprises the following steps:
with Ti (OC) 4 H 9 ) 4 For titanium source, with Ba (OH) 2 ·8(H 2 O) is a barium source, and the molar ratio of Ba to Ti is 1.5:1, and adding mineralizer NH 3 ·H 2 O, mineralizer is added dropwise until Ti (OC 4 H 9 ) 4 Hydrolysis to generate white sol, and reacting at 185 ℃ for 30 hours to obtain the main component BaTiO of the MLCC ceramic 3 Powder with the particle size of 80-120 nm;
(b) Adding a dopant, a binder, a defoaming agent, water, and ball mill to BaTiO as a main component in the step (a) 3 Ball milling and mixing are carried out on the powder to obtain powder slurry of the MLCC ceramic, wherein the mass percentage of the solid content of the powder slurry is 25%;
wherein the dopant is Al 2 O 3 、Bi 2 O 3 、Yi 2 O 3 And CuO, and contains BaTiO as a main component 3 The mole percentages of (a) are respectively as follows:
Al 2 O 3 4mol％，Bi 2 O 3 0.2mol％，Yi 2 O 3 0.2mol％，CuO 5mol％；
wherein the main component is BaTiO 3 The mass ratio of water to ball mill is 1:3:5, and the ball mill is made of ZrO 2 ；
The binder is polyvinyl alcohol, and the addition amount of the binder accounts for 3% of the total mass of the main component and the doping agent;
the defoaming agent is polyether defoaming agent, and the addition amount of the defoaming agent accounts for 0.03% of the total mass of the main component and the doping agent;
the ball milling mixing time is 8 hours;
(c) Granulating the powder slurry obtained in the step (b) and then compacting to obtain a ceramic blank;
wherein, the granulation is spray granulation;
the temperature of a feed inlet of spray granulation is 200 ℃, the temperature of a discharge outlet of spray granulation is 95 ℃, and the rotating speed of spray granulation is 20r/s;
(d) Performing two-step sintering after the ceramic blank in the step (c) is subjected to glue discharging, so as to obtain high-temperature stable MLCC ceramic;
wherein, the glue discharging comprises the following steps:
firstly heating up for the first time from the room temperature of 30 ℃, then preserving heat for glue discharging, and then preserving heat for the second time after heating up for the second time for glue discharging;
the first heating program of the adhesive discharging is 400 ℃/120min, and the heating rate is 2 ℃/min; the second heating program of the adhesive discharging is 600 ℃/120min, and the heating rate is 1.5 ℃/min;
wherein the two-step sintering comprises the following steps:
heating to the first sintering temperature 1380-1420 ℃ at a heating rate of 8 ℃/min from the room temperature of 30 ℃, preserving heat at the temperature for 30-40 min, cooling to the second sintering temperature 1000-1100 ℃ at a cooling rate of 5 ℃/min, and preserving heat at the temperature for 5-8 h.
Example 2
The difference between this example and example 1 is that the dopant in this example is BaTiO 3 The mole percentages of (a) are respectively as follows:
Al 2 O 3 1mol％，Bi 2 O 3 0.2mol％，Yi 2 O 3 0.2mol％，CuO 1mol％；
otherwise, the same as in example 1 was conducted to obtain a high-temperature stable MLCC ceramic.
Example 3
The difference between this example and example 1 is that the dopant in this example is BaTiO 3 The mole percentages of (a) are respectively as follows:
Al 2 O 3 5mol％，Bi 2 O 3 1mol％，Yi 2 O 3 1mol％，CuO 3mol％；
otherwise, the same as in example 1 was conducted to obtain a high-temperature stable MLCC ceramic.
Example 4
The difference between this example and example 1 is that the dopant in this example is BaTiO 3 The mole percentages of (a) are respectively as follows:
Al 2 O 3 9mol％，Bi 2 O 3 2mol％，Yi 2 O 3 2mol％，CuO 6mol％；
otherwise, the same as in example 1 was conducted to obtain a high-temperature stable MLCC ceramic.
Example 5
The difference between this example and example 1 is that the dopant in this example is BaTiO 3 The mole percentages of (a) are respectively as follows:
Al 2 O 3 9mol％，Bi 2 O 3 3mol％，Yi 2 O 3 3mol％，CuO 7mol％；
otherwise, the same as in example 1 was conducted to obtain a high-temperature stable MLCC ceramic.
Example 6
The difference between this example and example 1 is that the dopant in this example is BaTiO 3 The mole percentages of (a) are respectively as follows:
Al 2 O 3 1mol％，Bi 2 O 3 0.1mol％，Yi 2 O 3 0.1mol％，CuO 0.5mol％；
otherwise, the same as in example 1 was conducted to obtain a high-temperature stable MLCC ceramic.
Example 7
This example differs from example 1 in that BaTiO is the main component in step (a) of this example 3 The preparation of the catalyst is not carried out by adopting a hydrothermal method, but adopts a solid phase synthesis method to prepare the main component BaTiO 3 The disadvantage is that the ceramic component BaTiO is prepared 3 Non-uniformity, larger particle size, and poor performance uniformity.
Comparative examples 1 to 3
Comparative examples 1 to 3 differ from example 1 in that Al was used in step (b) of comparative examples 1 to 3 2 O 3 The addition amount of (C) is based on the main component BaTiO 3 The mole percentages of (a) are 0mol%, 0.5mol% and 10mol%, respectively;
the remainder was the same as in example 1, to obtain an MLCC ceramic.
Comparative example 4
The difference between this comparative example and example 1 is that Bi was not added in step (b) of this comparative example 2 O 3 ；
The remainder was the same as in example 1, to obtain an MLCC ceramic.
Comparative example 5
The difference between this comparative example and example 1 is that no Yi is added in step (b) of this comparative example 2 O 3 ；
The remainder was the same as in example 1, to obtain an MLCC ceramic.
Comparative example 6
The comparative example differs from example 1 in that CuO was not added in step (b) of the comparative example;
the remainder was the same as in example 1, to obtain an MLCC ceramic.
Test example 1
The MLCC ceramics of examples 1 to 7 and comparative examples 1 to 6 were tested for dielectric constant, dielectric loss, rate of change of capacitance temperature, and sintering temperature, and the results are shown in Table 1.
TABLE 1
In summary, the MLCC ceramic dielectric material of the invention adopts BaTiO 3 As the main crystal phase of the ceramic, al is used as 2 O 3 、Bi 2 O 3 、Yi 2 O 3 And the mixture of CuO as a doping agent, which plays the roles of a frequency stabilizer and a sintering aid; the material of the invention adopts BaTiO 3 ·xAl 2 O 3 The system (x is more than or equal to 0.01 and less than or equal to 0.09) can obtain the high-temperature electric property with higher stability through a ball milling process, granulation, dry pressing forming process and two-step sintering processThe good MLCC ceramic can meet the use requirement; compared with the conventional MLCC ceramic preparation process, the electrical property of the MLCC ceramic prepared by the preparation method can meet the X8R characteristic, the secondary ball milling process is reduced in process, the sintering temperature is reduced, and meanwhile, the solid-phase sintering method is adopted, so that the process is simple, and the cost is saved.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (26)
1. A high temperature stable MLCC ceramic is characterized in that,
the ceramic material is obtained by pressing, forming and sintering an MLCC ceramic dielectric material;
the MLCC ceramic dielectric material comprises a main component and a doping agent;
the main component is BaTiO 3 ；
The dopant includes Al 2 O 3 、Bi 2 O 3 、Y 2 O 3 A mixture of CuO;
the dopant occupies the BaTiO 3 The mole percentages of (a) are respectively as follows:
Al 2 O 3 4mol%，Bi 2 O 3 0.2mol%，Y 2 O 3 0.2mol%，CuO 5mol%；
the sintering is two-step sintering;
the two-step sintering comprises the following steps:
and (3) heating to the first sintering temperature of 1300-1450 ℃ at a heating rate of 5-20 ℃/min from 20-50 ℃, preserving heat for 10-60 min, cooling to the second sintering temperature of 1000-1100 ℃ at a cooling rate of 8-15 ℃/min, and preserving heat for 4-10 h.
2. The high temperature stable MLCC ceramic as claimed in claim 1, wherein the preparation method of the MLCC ceramic dielectric material comprises the following steps:
mixing the main components and the doping agent in proportion, grinding and granulating to obtain the MLCC ceramic dielectric material.
3. The high temperature stable MLCC ceramic as claimed in claim 2, wherein the preparation method of the main component includes a hydrothermal method.
4. The high temperature stable MLCC ceramic as claimed in claim 3, wherein the hydrothermal method comprises the steps of:
with Ti (OC) 4 H 9 ) 4 For titanium source, with Ba (OH) 2 ·8(H 2 O) is a barium source, and a mineralizer is added for reaction to obtain a main component.
5. The high temperature stable MLCC ceramic of claim 4, wherein the molar ratio of Ba/Ti is 1 to 1.5:1.
6. the high temperature stable MLCC ceramic of claim 4, wherein said mineralizer comprises NH 3 ·H 2 O。
7. The high temperature stable MLCC ceramic of claim 4, wherein said reacting is at a temperature of 180 to 200 ℃ for a time of 25 to 35 hours.
8. The high temperature stable MLCC ceramic according to claim 4, wherein the particle size of the main component is 80 to 120nm.
9. The high temperature stable MLCC ceramic of claim 2, wherein said milling means comprises ball milling.
10. The high temperature stable MLCC ceramic of claim 9, wherein said ball milling comprises the steps of:
adding water, a binder and a defoaming agent, mixing, and then performing ball milling by using a ball mill to obtain powder slurry.
11. The high temperature stable MLCC ceramic of claim 10, wherein said binder comprises polyvinyl alcohol.
12. The high temperature stable MLCC ceramic of claim 10, wherein the binder is added in an amount of 1-5% of the total mass of the main component and the dopant.
13. The high temperature stable MLCC ceramic of claim 10, wherein said defoamer comprises a polyether defoamer.
14. The high temperature stable MLCC ceramic according to claim 10, wherein the amount of the antifoaming agent added is 0.01-0.04% of the total mass of the main component and the dopant.
15. The high temperature stable MLCC ceramic of claim 10, wherein said ball milling time is 6-10 hours.
16. The high temperature stable MLCC ceramic of claim 10, wherein the ball mill material comprises ZrO 2 。
17. The high temperature stable MLCC ceramic according to claim 10, wherein the mass ratio of the main component, the water and the ball mill is 1 (1.25-3.5): 5;
the solid content of the powder slurry is 20-45% by mass.
18. The high temperature stable MLCC ceramic of claim 2, wherein said granulating comprises spray granulating.
19. The high temperature stable MLCC ceramic of claim 18, wherein said spray granulation has a feed inlet temperature of 180-220 ℃ and a discharge outlet temperature of 95-105 ℃.
20. The high temperature stable MLCC ceramic of claim 18, wherein said spray granulation has a rotational speed of 10-30 r/s.
21. The high temperature stable MLCC ceramic of claim 18, wherein said spray granulated particles have a particle size of 40-80 μm.
22. The high temperature stable MLCC ceramic of claim 18, wherein said spray granulated particles have a moisture content of 0.25 to 0.8wt%.
23. The high temperature stable MLCC ceramic of claim 1, further comprising a paste ejection step prior to said two step sintering;
the adhesive discharging comprises the following steps:
and (3) firstly heating up the adhesive for the first time from 20-50 ℃, then preserving heat for adhesive discharging, and then heating up the adhesive for the second time, and then preserving heat for adhesive discharging.
24. The high temperature stable MLCC ceramic of claim 23, wherein said first temperature ramp is at a temperature of 395-405 ℃ for a time of 110-120 minutes;
the temperature rising rate of the first temperature rising is 1-2 ℃/min.
25. The high temperature stable MLCC ceramic of claim 23, wherein said second temperature ramp is 590 to 600 ℃ and the holding time is 110 to 120 minutes;
the temperature rising rate of the second temperature rising is 1-1.5 ℃/min.
26. Use of the high temperature stable MLCC ceramic of any one of claims 1-25 in electronic materials.
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