CN1267377C - Microwave medium ceramic and preparing method thereof - Google Patents

Microwave medium ceramic and preparing method thereof Download PDF

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CN1267377C
CN1267377C CN 200310111238 CN200310111238A CN1267377C CN 1267377 C CN1267377 C CN 1267377C CN 200310111238 CN200310111238 CN 200310111238 CN 200310111238 A CN200310111238 A CN 200310111238A CN 1267377 C CN1267377 C CN 1267377C
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mole
microwave
oven dry
ball milled
tio
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CN1528705A (en
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周东祥
龚树萍
黄国华
徐建梅
梁飞
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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Abstract

The present invention discloses microwave dielectric ceramics which comprises the main constituent of p(m(aCaO. bNd2O3). cMgO. TiO2). q(1/4Li2O. 1/4Sm2O3. TiO2), wherein according to the molar percentage, p plus q is 100 mol%, m plus c is 1 a plus 3b is 1, q is from 30 to 55 mol%, a is from 0.3 to 0.75 mol%, and m is 0.8 to 0.95 mol%; ZnO is used as an accessory constituent, and the content u of the accessory constituent accounts for 0.5 to 2.0 wt% of the main constituent. The present invention also provides a preparing method for the microwave dielectric ceramics. The dielectric constant of the prepared microwave dielectric ceramics is from 90 to 120, and simultaneously, the microwave dielectric ceramics have low loss, and adjustable temperature coefficient of resonance frequency; microwave components such as dielectric resonators, filters, etc., can be suitable for high frequency by using the microwave dielectric ceramics provided by the present invention. Simultaneously, the ceramics provided by the present invention can also be applied to high-frequency ceramic capacitors, or temperature compensating ceramic capacitors, etc.

Description

A kind of microwave-medium ceramics and preparation method thereof
Technical field
The invention belongs to the microwave-medium ceramics technical field, be specifically related to a kind of microwave-medium ceramics and preparation method thereof.This microwave-medium ceramics can be used for microwave devices such as the dielectric resonator, wave filter in the communication system.
Background technology
In recent years, along with the fast development of mobile communication and satellite communication technology, the demand of the microwave-medium ceramics that microwave devices such as dielectric resonator and wave filter are used constantly increases.
For high performance microwave-medium ceramics, at first require it that low dielectric loss (high Q value, under the application corresponding frequency, Q＞3000) is arranged and approach (20ppm/ ℃＜τ of zero temperature coefficient of resonance frequency f＜20ppm/ ℃, for the lower material series of specific inductivity, requirement-10ppm/ ℃＜τ f＜10ppm/ ℃), simultaneously, for the needs that satisfy high frequencyization require the Q value of trying one's best high, for the needs that satisfy the microwave device miniaturization require microwave-medium ceramics high DIELECTRIC CONSTANT is arranged, and high Q value is coordinated mutually with high-k ε, for reducing manufacturing cost, the sintering temperature of microwave-medium ceramics is reduced.
The CaO-Li that has developed at present 2O-Nd 2O 3-TiO 2The high-permittivity microwave medium ceramics of series, its specific inductivity can reach more than 100, but its dielectric loss and temperature coefficient of resonance frequency are bigger than normal.How to realize the high Q value of high-permittivity microwave medium ceramics and a great problem that adjustableization of temperature factor is still this field.These have just limited the expansion of the further high frequencyization of microwave device, miniaturization and range of application widely.
Summary of the invention
The purpose of this invention is to provide a kind of microwave-medium ceramics that can overcome above-mentioned defective, it has low-dielectric loss, and temperature stability is good, and sintering temperature is lower, the dielectric coefficient height; Its invention also provides the manufacture method of this microwave-medium ceramics.
A kind of microwave-medium ceramics provided by the invention comprises principal constituent and minor component, wherein,
The expression formula of principal constituent is:
P[m (aCaObNd 2O 3) cMgOTiO 2] q[1/4Li 2O1/4Sm 2O 3TiO 2], calculate with molar percentage, wherein: p+q=100 mole %, m+c=100 mole %, a+3b=100 mole %, 30 moles of %≤q≤55 mole %, 30 moles of %≤a≤75 mole %, 80 moles of %≤m≤95 mole %;
Minor component is ZnO, the content u of minor component be principal constituent 0.5 to 2.0wt%.
The preparation method of above-mentioned microwave-medium ceramics may further comprise the steps successively:
(1) with CaCO 3, Nd 2O 3, MgCO 3, TiO 2By above-mentioned m (aCaObNd 2O 3) cMgOTiO 2Ratio mix with ball milled, oven dry back is 1050～1150 ℃ of pre-burnings 2～4 hours, and then mixes oven dry afterwards with ball milled;
(2) with Li 2CO 3, Sm 2O 3, TiO 2By above-mentioned 1/4Li 2O1/4Sm 2O 3TiO 2Ratio mix with ball milled, oven dry back is 950～1050 ℃ of pre-burnings 2～4 hours, and then mixes oven dry afterwards with ball milled;
(3) will mix with ball milled in proportion with powder and the ZnO that step (1), (2) make respectively, again oven dry;
(4) add binding agent and granulation in the powder that makes, compression moulding 1250～1400 ℃ of following sintering 3～5 hours, promptly obtains required microwave-medium ceramics again.
Microwave-medium ceramics of the present invention, its specific inductivity are 90～120, have low-loss and adjustable temperature coefficient of resonance frequency simultaneously, utilize microwave-medium ceramics provided by the invention can make microwave devices such as dielectric resonator and wave filter adapt to higher frequency.Simultaneously, pottery provided by the invention also can be applicable to radio ceramics electrical condenser or temperature compensating ceramic capacit etc.
Embodiment
Table 1 shows several specific exampless and the microwave dielectric property thereof that constitutes each component content of the present invention.Its preparation method as mentioned above, wherein its purity of the raw material that is adopted is more than 99.9%.With the cylindrical dielectric resonator method carry out microwave dielectric property (be DIELECTRIC CONSTANT, dielectric loss characteristics Qf value, temperature coefficient of resonance frequency τ f) evaluation.
Sample No.1-4 prepares by the following method:
1. with purity the CaCO more than 99.9% 3, Nd 2O 3, MgCO 3, TiO 2By above-mentioned m (aCaObNd 2O 3) cMgOTiO 2Ratio mix with ball milled, solvent is a deionized water, oven dry back pre-burning 4 hours in 1050 ℃, air atmosphere, and then mix oven dry afterwards with ball milled.
2. with purity the Li more than 99.9% 2CO 3, Sm 2O 3, TiO 2By above-mentioned 1/4Li 2O1/4Sm 2O 3TiO 2Ratio mix with ball milled, solvent is a deionized water, oven dry back pre-burning 4 hours in 950 ℃, air atmosphere, and then mix oven dry afterwards with ball milled.
3 powders that will make respectively with 1,2 methods and purity are that the ZnO more than 99.9% mixes with ball milled according to the above ratio, and solvent is a deionized water, afterwards oven dry.
4 in the powder that makes, add binding agent and granulation after, compression moulding, it is 5% polyvinyl alcohol (PVA) solution that binding agent adopts concentration, and its dosage is 10% of powder total amount, at last in 1250 ℃, air atmosphere sintering 5 hours to prepare required microwave-medium ceramics.
Sample No.5-16 prepares by the following method:
1. with purity the CaCO more than 99.9% 3, Nd 2O 3, MgCO 3, TiO 2By above-mentioned m (aCaObNd 2O 3) cMgOTiO 2Ratio mix with ball milled, solvent is a deionized water, oven dry back pre-burning 3 hours in 1100 ℃, air atmosphere, and then mix oven dry afterwards with ball milled.
2. with purity the Li more than 99.9% 2CO 3, Sm 2O 3, TiO 2By above-mentioned 1/4Li 2O1/4Sm 2O 3TiO 2Ratio mix with ball milled, solvent is a deionized water, oven dry back pre-burning 3 hours in 1000 ℃, air atmosphere, and then mix oven dry afterwards with ball milled.
3 powders that will make respectively with 1,2 methods and purity are that the ZnO more than 99.9% mixes with ball milled according to the above ratio, and solvent is a deionized water, afterwards oven dry.
4 in the powder that makes, add binding agent and granulation after, compression moulding, it is 5% polyvinyl alcohol (PVA) solution that binding agent adopts concentration, and its dosage is 10% of powder total amount, at last in 1300 ℃, air atmosphere sintering 4 hours to prepare required microwave-medium ceramics.
Sample No.17-24 prepares by the following method:
1. with purity the CaCO more than 99.9% 3, Nd 2O 3, MgCO 3, TiO 2By above-mentioned m (aCaObNd 2O 3) cMgOTiO 2Ratio mix with ball milled, solvent is a deionized water, oven dry back pre-burning 3 hours in 1100 ℃, air atmosphere, and then mix oven dry afterwards with ball milled.
2. with purity the Li more than 99.9% 2CO 3, Sm 2O 3, TiO 2By above-mentioned 1/4Li 2O1/4Sm 2O 3TiO 2Ratio mix with ball milled, solvent is a deionized water, oven dry back pre-burning 3 hours in 1000 ℃, air atmosphere, and then mix oven dry afterwards with ball milled.
3 powders that will make respectively with 1,2 methods and purity are that the ZnO more than 99.9% mixes with ball milled according to the above ratio, and solvent is a deionized water, afterwards oven dry.
4 in the powder that makes, add binding agent and granulation after, compression moulding, it is 5% polyvinyl alcohol (PVA) solution that binding agent adopts concentration, and its dosage is 10% of powder total amount, at last in 1350 ℃, air atmosphere sintering 3 hours to prepare required microwave-medium ceramics.
Sample No.25-28 prepares by the following method:
1. with purity the CaCO more than 99.9% 3, Nd 2O 3, MgCO 3, TiO 2By above-mentioned m (aCaObNd 2O 3) cMgOTiO 2Ratio mix with ball milled, solvent is a deionized water, oven dry back pre-burning 2 hours in 1150 ℃, air atmosphere, and then mix oven dry afterwards with ball milled.
2. with purity the Li more than 99.9% 2CO 3, Sm 2O 3, TiO 2By above-mentioned 1/4Li 2O1/4Sm 2O 3TiO 2Ratio mix with ball milled, solvent is a deionized water, oven dry back pre-burning 2 hours in 1050 ℃, air atmosphere, and then mix oven dry afterwards with ball milled.
3. powder that will make respectively with 1,2 methods and purity are that ZnO more than 99.9% mixes with ball milled according to the above ratio, and solvent is a deionized water, afterwards oven dry.
4. after in the powder that makes, adding binding agent and granulation, compression moulding, it is 5% polyvinyl alcohol (PVA) solution that binding agent adopts concentration, and its dosage is 10% of powder total amount, at last in 1400 ℃, air atmosphere sintering 3 hours to prepare required microwave-medium ceramics.
Table one
Sample No. a (mol) b (mol) c (mol) m (mol) p (mol％) q (mol％) u (wt％) ε Qf (GHz) τ f (ppm/℃)
1 0.75 0.083 0.20 0.80 70 30 2 120 5700 +15
2 0.75 0.083 0.20 0.80 45 55 2 102 4900 +7
3 0.75 0.083 0.05 0.95 45 55 2 107 5600 +2
4 0.75 0.083 0.05 0.95 55 45 2 113 6100 +8
5 0.70 0.100 0.10 0.90 50 50 1.0 118 6000 +12
6 0.70 0.100 0.10 0.90 55 45 1.0 120 6300 +14
7 0.70 0.100 0.16 0.84 50 50 1.0 110 7000 +10
8 0.70 0.100 0.16 0.84 55 45 1.0 112 7200 +12
9 0.62 0.127 0.10 0.90 50 50 1.0 114 5700 +4
10 0.62 0.127 0.10 0.90 55 45 1.0 117 6000 +8
11 0.62 0.127 0.16 0.84 50 50 1.0 108 6300 +2
12 0.62 0.127 0.16 0.84 55 45 1.0 110 6700 +6
13 0.55 0.150 0.10 0.90 50 50 1.0 104 4000 -4
14 0.55 0.150 0.10 0.90 55 45 1.0 108 5100 -1
15 0.55 0.150 0.16 0.84 50 50 1.0 102 4100 -6
16 0.55 0.150 0.16 0.84 55 45 1.0 106 4700 -2
17 0.50 0.167 0.10 0.90 50 50 1.0 98 3700 -7
18 0.50 0.167 0.10 0.90 55 45 1.0 103 4200 -4
19 0.50 0.167 0.16 0.84 50 50 1.0 92 4000 -10
20 0.50 0.167 0.16 0.84 55 45 1.0 95 4800 -7
21 0.40 0.200 0.10 0.90 50 50 1.0 93 3700 -12
22 0.40 0.200 0.10 0.90 55 45 1.0 96 3200 -9
23 0.40 0.200 0.16 0.84 50 50 1.0 91 3600 -15
24 0.40 0.200 0.16 0.84 55 45 1.0 93 3400 -13
25 0.30 0.233 0.20 0.80 70 30 0.5 106 4500 +10
26 0.30 0.233 0.20 0.80 45 55 0.5 94 5100 +3
27 0.30 0.233 0.05 0.95 70 30 0.5 102 4700 +13
28 0.30 0.233 0.05 0.95 45 55 0.5 98 4600 +6
From above-mentioned example as can be seen, a is 40-70 mole %, and m is 84-90 mole %, and p is 50-55 mole %, and technique effect of the present invention was better when u was 1.00 moles of %.

Claims (4)

1, a kind of microwave-medium ceramics comprises principal constituent and minor component, wherein,
The expression formula of principal constituent is:
P[m (aCaObNd 2O 3) cMgOTiO 2] q[1/4Li 2O1/4Sm 2O 3TiO 2], calculate with molar percentage, wherein: p+q=100 mole %, m+c=100 mole %, a+3b=100 mole %, 30 moles of %≤q≤55 mole %, 30 moles of %≤a≤75 mole %, 80 moles of %≤m≤95 mole %;
Minor component is ZnO, the content u of minor component be principal constituent 0.5 to 2.0wt%.
2, microwave-medium ceramics according to claim 1 is characterized in that:
A is 40-70 mole %, and m is 84-90 mole %, and p is 50-55 mole %, and u is 1.00 moles of %.
3, a kind of method for preparing claim 1 or 2 described microwave-medium ceramics may further comprise the steps successively:
(1) with CaCO 3, Nd 2O 3, MgCO 3, TiO 2By above-mentioned m (aCaObNd 2O 3) cMgOTiO 2Ratio mix with ball milled, oven dry back is 1050～1150 ℃ of pre-burnings 2～4 hours, and then mixes oven dry afterwards with ball milled;
(2) with Li 2CO 3, Sm 2O 3, TiO 2By above-mentioned 1/4Li 2O1/4Sm 2O 3TiO 2Ratio mix with ball milled, oven dry back is 950～1050 ℃ of pre-burnings 2～4 hours, and then mixes oven dry afterwards with ball milled;
(3) will mix with ball milled in proportion with powder and the ZnO that step (1), (2) make respectively, again oven dry;
(4) add binding agent and granulation in the powder that makes, compression moulding 1250～1400 ℃ of following sintering 3～5 hours, promptly obtains required microwave-medium ceramics again.
4, method according to claim 3 is characterized in that: pre-burning in the above steps and sintering all carry out in air atmosphere.
CN 200310111238 2003-10-15 2003-10-15 Microwave medium ceramic and preparing method thereof Expired - Fee Related CN1267377C (en)

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Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1317226C (en) * 2005-09-09 2007-05-23 华中科技大学 Low dielectric constant microwave dielectric ceramic material
CN102070338B (en) * 2010-11-25 2013-01-09 成都理工大学 Process for preparing CaO-Li2O-Sm2O3-TiO2 microwave dielectric materials by using liquid-phase method
CN102718475B (en) * 2012-05-30 2014-08-13 深圳光启创新技术有限公司 Dielectric ceramic and preparation method thereof and harmonic oscillator
CN111384570A (en) * 2018-12-31 2020-07-07 深圳市大富科技股份有限公司 Dielectric filter, communication equipment, dielectric resonator and preparation method
CN111470861B (en) * 2020-04-22 2022-03-01 吴坚强 Microwave dielectric ceramic material and method for preparing microwave ceramic filter device by using same

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