CN108147809A - Low temperature sintering barium-titanium series microwave dielectric material and preparation method - Google Patents

Low temperature sintering barium-titanium series microwave dielectric material and preparation method Download PDF

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CN108147809A
CN108147809A CN201810118878.3A CN201810118878A CN108147809A CN 108147809 A CN108147809 A CN 108147809A CN 201810118878 A CN201810118878 A CN 201810118878A CN 108147809 A CN108147809 A CN 108147809A
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microwave dielectric
sintering
dielectric material
preparation
low temperature
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CN108147809B (en
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宋蓓蓓
齐世顺
杨魁勇
程华容
吴爱忠
吕鹏
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Beijing Yuan Six Hongyuan Electronic Polytron Technologies Inc
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Beijing Yuan Six Hongyuan Electronic Polytron Technologies Inc
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Abstract

The invention discloses a kind of low temperature sintering barium titanium series microwave dielectric materials and preparation method, the microwave dielectric material to include：Major ingredient, secondary material, property-modifying additive and sintering aid；Wherein, the major ingredient is TiO2；The secondary material is BaTiO3；The property-modifying additive is Al2O3、MnO、SnO2、CoO、Nb2O5And ZrO2In at least three kinds.Pass through technical scheme of the present invention, realize the preparation of one-pass finished powder, and it can be sintered under middle low temperature, porcelain body densification, free from admixture and defect are few after sintering, its relative dielectric constant is adjustable, frequency-temperature characteristic is stable, quality factor are high, and production cost and period is greatly saved, it is easy to accomplish industrialized production fast, can be realized steadily and be converted from material prescription to the batch production of microwave dielectric material product.

Description

Low temperature sintering barium-titanium series microwave dielectric material and preparation method
Technical field
The present invention relates to microwave dielectric material technical field more particularly to a kind of low temperature sintering barium-titanium series microwave dielectrics Material and preparation method thereof.
Background technology
China pushing forward 5G develops in World Mobile Communications conference in 2017, strives realizing 5G network providers in the year two thousand twenty With.5G epoch most significant feature is exactly high speed Gao Rong, it is necessary to which, using higher frequency range, that before 4G is super high band (300MHz ~3GHz), 5G is then main toward the even higher frequency range development of hyperfrequency (3GHz~30GHz).Main microwave-medium ceramics device There are wave filter, dielectric resonator, duplexer, diectric antenna, dielectric substrate, capacitor and Medium Wave Guide transmission line etc., and in order to Meet the upgrading of 5G technologies, high performance microwave-medium ceramics device plays a crucial role wherein.5G communications is penetrate Frequency device industry brings new growth opportunity, and one side radio-frequency module number of frequency bands to be treated increases considerably, the opposing party Face high frequency band signal intractability increases, and system requires also to increase substantially to performance of filter, and microwave-medium ceramics are wherein Play not replaceable effect.
The microwave dielectric ceramic materials of more medium dielectric constant microwave medium, Qf values are applied in microwave current media ceramic industry It is relatively low, it concentrates between 5000~30000 substantially, sintering temperature is generally concentrated at 1250~1300 DEG C of higher range, and burns The relatively low such porcelain patent of junction temperature is then accompanied by the shortcomings that expensive, Qf is low, main as described in patent CN1609050A Body material is Ca (Li1/3Nb2/3)O3And CaTiO3, about 900 DEG C of sintering temperature, but the raw material sources of wherein Li, Nb (niobium) are held high It is expensive, and its Qf value is only 6000~10000；CN102584233A discloses a kind of middle high-k low-temperature co-fired ceramics Material, ceramic major include 15~35% Nb2O5, 10~25% ZnO, 10~25% BaO, 10~20% TiO2、1 ~10% ZrO2, 1~8% Sm2O3With a small amount of La2O3, fluxing material includes 5~10% SnO2, 5~10% CuO, 5 ~10% SiO2With 1~5% B2O3, additionally including 0~5% A12O3With 0~5% LiF, sintering temperature is 830 DEG C ~880 DEG C, but the ceramic material contains Sm and La costly, therefore, the cost of raw material is higher.
As industrial production aspect is more and more stronger to the protective awareness of environment, the energy, industrial energy consumption has become The important objectives of examination of energy conservation.Therefore, energy consumption accounts for the sintering process of very big proportion and also must during porcelain production process Corresponding adjustment must be done, i.e., while the performance of product is maintained, reduces the sintering temperature of microwave-medium porcelain as best one can, The cost of raw material of ceramic material is also required to reduce simultaneously.
Invention content
At least one of regarding to the issue above, the present invention provides a kind of low temperature sintering barium-titanium series microwave dielectric materials Material and preparation method thereof, using simple preparation process finished product powder, avoids BaO-TiO2It is the numerous of microwave ceramics burning block Trivial preparation process (need to be by suitable metering than carrying out dispensing, ball milling, drying, crushing, calcining etc.) realizes the primary system of finished powder It is standby, and can be sintered under middle low temperature (900~1170 DEG C), porcelain body densification, free from admixture and defect are few after sintering, with respect to dielectric Constant is adjustable in 28~48 ranges, and production cost and period is greatly saved, it is easy to accomplish industrialized production, can fast, stablize Ground is realized to be converted from material prescription to the batch production of microwave dielectric material product.
To achieve the above object, the present invention provides a kind of low temperature sintering barium-titanium series microwave dielectric material, including：It is main Material, secondary material, property-modifying additive and sintering aid；Wherein, the major ingredient is TiO2；The secondary material is BaTiO3；The modified addition Agent is Al2O3、MnO、SnO2、CoO、Nb2O5And ZrO2In at least three kinds；The major ingredient, the secondary material, the property-modifying additive Molfraction with the sintering aid is：The TiO2It is 50~75 parts；The BaTiO3It is 15~30 parts；The Al2O3For 1~5 part；The MnO is 0.2~0.6 part；The SnO2It is 0~2 part；The CoO is 0.2~0.8 part；The Nb2O5For 0~ 3 parts；The ZrO2It is 0~3 part；Totally 5~20 parts of the sintering aid.
In the above-mentioned technical solutions, it is preferable that the sintering aid is B2O3、SiO2、ZnO、Li2CO3, MgO, BaO and CuO It is one or more.
In the above-mentioned technical solutions, it is preferable that the sintering aid for LBS sintering aids, LMZBS sintering aids and/or BCB sintering aids；The LBS sintering aids prepare raw material include molar ratio be 3:2:6 Li2CO3、H3BO3And SiO2；Institute State LMZBS sintering aids prepare raw material include molar ratio be 3:3:2:1:1 Li2CO3、Mg(OH)2、H3BO3, ZnO and SiO2；The BCB sintering aids prepare raw material include molar ratio be 1:1:2 BaCO3, CuO and H3BO3。
The invention also provides a kind of low temperature sintering barium-titanium series microwave dielectric materials in above-mentioned technical proposal Preparation method, including：By the major ingredient TiO2, the secondary material BaTiO3, the property-modifying additive and the sintering aid according to than Example mixing；Zirconia ball is added in the mixture and carries out ball milling, is dried, is sieved later.
In the above-mentioned technical solutions, it is preferable that the sintering aid is by the B2O3、SiO2、ZnO、Li2CO3、MgO、BaO、 One or more in CuO mix in proportion, add in zirconia ball and carry out ball milling, are calcined after drying, sieving.
Further, the low temperature sintering barium described in above-mentioned technical proposal-titanium series microwave dielectric material is granulated； Green body is made in the microwave dielectric material after granulation；By the green body dumping, and by the blank sintering after dumping, protect Cooled to room temperature after temperature 2~8 hours.
In the above-mentioned technical solutions, it is preferable that green body is made in the microwave dielectric material under 4~6MPa pressure, described Green body dumping in the environment of dump temperature is 500 DEG C, heating rate is 1-3 DEG C/min, keeps the temperature 2-4 hours, the green body Sintering temperature is 900~1170 DEG C.
Compared with prior art, beneficial effects of the present invention are：
1st, it realizes and is sintered under middle low temperature (900~1170 DEG C), ceramic powder has uniform component, narrow particle size distribution, dispersion Property it is good, mouldability technique is good, porcelain body is fine and close after sintering, free from admixture and few defect, relative dielectric constant can in 28~48 ranges It adjusts, room temperature loss angle tangent ＜ 5 × 10-4, insulation resistivity>1×1013Ω cm, capacity temperature characteristic are stable, quality factor Qf values are very high.
2nd, such low dielectric microwave dielectric material is made using a step dispensing, reduces BaO-TiO2It is microwave ceramics burning block system Standby cumbersome technique (such as dispensing, ball milling, drying, crushing, calcining), simplifies finished product powder preparation technique, and sintering temperature compared with It is low, energy consumption can be reduced, greatlys save production cost and period, it is easy to accomplish industrialized production fast, can be realized steadily from material The batch production of material formula to microwave dielectric material product converts.
Specific embodiment
Purpose, technical scheme and advantage to make the embodiment of the present invention are clearer, below will be in the embodiment of the present invention Technical solution be clearly and completely described, it is clear that described embodiment be the present invention part of the embodiment, without It is whole embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work Under the premise of all other embodiments obtained, shall fall within the protection scope of the present invention.
The present invention is described in further detail below：
According to a kind of low temperature sintering barium-titanium series microwave dielectric material provided by the invention, including：Major ingredient, is modified secondary material Additive and sintering aid；Wherein, the major ingredient is TiO2；The secondary material is BaTiO3；The property-modifying additive is Al2O3、 MnO、SnO2、CoO、Nb2O5And ZrO2In at least three kinds；The sintering aid is B2O3、SiO2、ZnO、Li2CO3、MgO、BaO It is one or more with CuO；The major ingredient, the secondary material, the property-modifying additive and the sintering aid molfraction be： The TiO2It is 50~75 parts；The BaTiO3It is 15~30 parts；The Al2O3It is 1~5 part；The MnO is 0.2~0.6 part； The SnO2It is 0~2 part；The CoO is 0.2~0.8 part；The Nb2O5It is 0~3 part；The ZrO2It is 0~3 part；The burning Tie totally 5~20 parts of auxiliary agent.
In the above-mentioned technical solutions, it is preferable that the sintering aid for LBS sintering aids, LMZBS sintering aids and/or BCB sintering aids；The LBS sintering aids prepare raw material include molar ratio be 3:2:6 Li2CO3、H3BO3And SiO2；Institute State LMZBS sintering aids prepare raw material include molar ratio be 3:3:2:1:1 Li2CO3、Mg(OH)2、H3BO3, ZnO and SiO2；The BCB sintering aids prepare raw material include molar ratio be 1:1:2 BaCO3, CuO and H3BO3。
Further, the preparation method of sintering aid is as follows：
(1) preparation method of LBS sintering aids：Example is 3 in molar ratio:2:6 weigh raw material Li2CO3、H3BO3、SiO2It is mixed It closes, adds in zirconium oxide (ZrO2) ball progress ball milling, Ball-milling Time is 6 hours, and 10 hours are dried at 80 DEG C to drying, is sieved with 100 mesh sieve Afterwards, it is obtained after being calcined 4 hours at 600 DEG C.
(2) preparation method of LMZBS sintering aids：Example is 3 in molar ratio:3:2:1:1 weighs raw material Li2CO3、Mg (OH)2、H3BO3、ZnO、SiO2Mixing adds in zirconia ball and carries out ball milling, and Ball-milling Time is 6 hours, and 10 hours are dried at 80 DEG C extremely It is dry, after sieving with 100 mesh sieve, obtained after being calcined 4 hours at 560 DEG C.
(3) preparation method of BCB sintering aids：By analytically pure BaCO3, CuO and H3BO3In molar ratio 1:1:2 mixing, It adds in zirconia ball and carries out ball milling, Ball-milling Time is 5 hours, and 80 DEG C are dried 10 hours to drying, after sieving with 100 mesh sieve, then at 650 DEG C Lower heat preservation is made for 3 hours.
Specifically, with the formula in table 1, proportionally by major ingredient TiO2, secondary material BaTiO3, property-modifying additive and sintering help Agent mixes, and adds in zirconia ball and carries out ball milling, and Ball-milling Time is 5 hours, 6 hours is dried at 120 DEG C to drying, after sieving with 100 mesh sieve Low temperature sintering barium-titanium series microwave dielectric material is made.
1 low temperature sintering intermediary microwave dielectric material formula (mol%) of table
PVA (the Polyvinyl of 6.5wt% are added according to microwave dielectric material made from the formula rate of table 1 Alcohol, polyvinyl alcohol) aqueous solution bonding granulation；Disk and cylinder green body are pressed under 4Mpa and 6MPa pressure respectively, it will Green body dumping, dump temperature is 500 DEG C, heating rate is 2 DEG C/min, keeps the temperature 3 hours, removes adhesive；By the base after dumping Body is sintered at 900~1170 DEG C, keeps the temperature 2~8 hours, and with stove natually cooled to room temperature, microwave dielectric ceramic materials are made.
In the present invention, because formula components and sintering process selection are suitable, BaTiO is realized3With TiO2Low temperature combination reaction is given birth to Into BaO-TiO2Series compound, while realize ceramic material sintering densification.In general, BaO-TiO2Compound Solid phase synthesis It temperature and sinters the temperature of porcelain into and is up to 1300-1400 DEG C.Compared with existing industrial manufacture process, BaO-TiO is eliminated2Chemical combination Object synthesis technology simplifies production technology, has saved cost, more conducively the industrialized production of the microwave dielectric material.
Two surface of disk fired is coated into silver paste, fires silver electrode, its room temperature electrical property is tested after capacitor is made Can, test result is as shown in table 2：Relative dielectric constant εrIt is 28~48, loss tangent is less than 5 × 10-4, insulation resistivity More than 1 × 1013Ω cm, TCf (Temperature Coefficient of frequency, temperature coefficient of resonance frequency) are general All over smaller.
TCf is an important parameter for weighing resonator resonant frequency temperature stability, and TCf is bigger, centre frequency Variation with temperature and the drift that generates is bigger, will be unable to ensure the high stability that device works in the environment of temperature change. It, should the small dielectric material of selected frequency temperature coefficient as possible for electronic circuit is enable steadily to work.TCf calculation formula are：
In above formula, temperature T0When resonant frequency be f0, resonant frequency when temperature is T is fT。
After sintering, a diameter of 8.4 ± 0.5mm of the cylindrical sample, thickness be 5.0 ± 1.0mm, the quality of cylindrical sample Factor Qf values are 17430~40253GHz.
The performance of 2 microwave dielectric ceramic materials of table
The above is embodiments of the present invention, according to low temperature sintering barium-titanium series microwave dielectric proposed by the present invention Material and preparation method thereof is made using a step dispensing, reduces BaO-TiO2It is cumbersome technique prepared by microwave ceramics burning block (including dispensing, ball milling, drying, crushing, calcining etc.) can be sintered under middle low temperature (900~1170 DEG C), normal with respect to dielectric Number is adjustable in 28~48 ranges.Microwave material is made using simple technique in the present invention, and production cost and period is greatly saved, Production is easily industrialized, can fast, steadily realize and turn from material prescription to the batch production of microwave dielectric material product Change.
It these are only the preferred embodiment of the present invention, be not intended to restrict the invention, for those skilled in the art For member, the invention may be variously modified and varied.Any modification for all within the spirits and principles of the present invention, being made, Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.

Claims (6)

1. a kind of low temperature sintering barium-titanium series microwave dielectric material, which is characterized in that including：Major ingredient, secondary material, property-modifying additive And sintering aid；
Wherein, the major ingredient is TiO2；
The secondary material is BaTiO3；
The property-modifying additive is Al2O3、MnO、SnO2、CoO、Nb2O5And ZrO2In at least three kinds；
The BaTiO3It is 15~30 parts；
The Al2O3It is 1~5 part；
The MnO is 0.2~0.6 part；
The SnO2It is 0~2 part；
The CoO is 0.2~0.8 part；
The Nb2O5It is 0~3 part；
The ZrO2It is 0~3 part；
Totally 5~20 parts of the sintering aid.
2. a kind of preparation method of low temperature sintering barium described in claim 1-titanium series microwave dielectric material, which is characterized in that The sintering aid is B2O3、SiO2、ZnO、Li2CO3, it is one or more in MgO, BaO and CuO.
3. a kind of preparation method of low temperature sintering barium-titanium series microwave dielectric material described in claims 1 or 2, feature exist In, including：
By the major ingredient TiO2, the secondary material BaTiO3, the property-modifying additive and the sintering aid proportionally mix；
Zirconia ball is added in the mixture and carries out ball milling, is dried, is sieved later.
4. the preparation method of low temperature sintering barium according to claim 3-titanium series microwave dielectric material, which is characterized in that The sintering aid is by the B2O3、SiO2、ZnO、Li2CO3, one or more in MgO, BaO, CuO mix in proportion, add in Zirconia ball carries out ball milling, is kept the temperature after drying, sieving.
5. the preparation method of low temperature sintering barium according to claim 3-titanium series microwave dielectric material, which is characterized in that It further includes：
The powdery microwave dielectric material dried after being sieved is granulated；
Green body is made in the microwave dielectric material after granulation；
By the green body dumping, and by the blank sintering after dumping, cooled to room temperature after heat preservation 2~8 hours.
6. the preparation method of microwave dielectric material according to claim 5, which is characterized in that the microwave dielectric material exists It is made green body under 4~6MPa pressure, the green body is dump temperature is 500 DEG C, heating rate is 1-3 DEG C/min, heat preservation 2-4 is small When in the environment of dumping, the sintering temperature of the green body is 900~1170 DEG C.
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