CN101391890A - Mid-low temperature sintered medium dielectric constant microwave dielectric ceramics and preparation method thereof - Google Patents
Mid-low temperature sintered medium dielectric constant microwave dielectric ceramics and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 238000005245 sintering Methods 0.000 claims abstract description 44
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 17
- 238000009413 insulation Methods 0.000 claims abstract description 10
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 5
- 239000003989 dielectric material Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 42
- 239000011787 zinc oxide Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- -1 polyethylene Polymers 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims 2
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 239000004698 Polyethylene Substances 0.000 claims 1
- 150000004996 alkyl benzenes Chemical class 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims 1
- 238000000498 ball milling Methods 0.000 abstract description 24
- 239000000203 mixture Substances 0.000 abstract description 10
- 239000003985 ceramic capacitor Substances 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 22
- 229960000935 dehydrated alcohol Drugs 0.000 description 14
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 10
- 238000009766 low-temperature sintering Methods 0.000 description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 6
- 239000004141 Sodium laurylsulphate Substances 0.000 description 6
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 6
- 229960004418 trolamine Drugs 0.000 description 5
- 238000004891 communication Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 3
- 238000010295 mobile communication Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001149 thermolysis Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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- Inorganic Insulating Materials (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
本发明公开了一种中低温烧结的中介电常数微波介质陶瓷及其制备方法。制备时，先将ZnO、Nb2O5混合后添加助磨剂球磨；烘干后在900～1000℃下预烧2～8小时；再将预烧后的粉料与TiO2、烧结助剂、助磨剂球磨后烘干；然后添加粘结剂并造粒，压制成型，再在900～1000℃的范围内烧结2～8小时，得到微波介质陶瓷。本发明提供的微波介质陶瓷材料具有良好的微波介电性能：介电常数为35～50，Q×f＝10000～30000GHz，以及小且可调的谐振频率温度系数和高的绝缘电阻率，可用于制备谐振器、滤波器、移相器等，也可用做多层片式陶瓷电容器介质材料，具有重要的工业应用价值。The invention discloses a mid-low temperature sintered medium dielectric constant microwave dielectric ceramic and a preparation method thereof. When preparing, first mix ZnO and Nb 2 O 5 and then add grinding aids for ball milling; after drying, pre-fire at 900-1000°C for 2-8 hours; then mix the pre-fired powder with TiO 2 and sintering aids 1. Grinding aids are dried after ball milling; then adding binder and granulating, pressing and forming, and then sintering at 900-1000°C for 2-8 hours to obtain microwave dielectric ceramics. The microwave dielectric ceramic material provided by the present invention has good microwave dielectric properties: the dielectric constant is 35-50, Q×f=10000-30000 GHz, and the small and adjustable resonant frequency temperature coefficient and high insulation resistivity can be used It can be used to prepare resonators, filters, phase shifters, etc., and can also be used as a dielectric material for multilayer chip ceramic capacitors, which has important industrial application value.
Description
Technical field
The invention belongs to microwave dielectric material and make the field, particularly a kind of medium dielectric constant microwave medium microwave-medium ceramics that is applicable to the low temperature sintering for preparing resonator and electrical condenser and preparation method thereof.
Background technology
Microwave-medium ceramics is a new trend of in the world dielectric substance being studied in recent years, and this mainly is the growth requirement that adapts to the microwave mobile communication.20 th century later, the information processing technology combine with the electronic information digitizing technique communication system have been pushed to a unprecedented new height.The ultimate aim of communication is to accomplish the information transmission and the exchange of full-time sky, thereby makes the height mobility of communication machine become the inexorable trend of development.Current, mobile communication is promoted to the whole people, is the expansion capacity, just must improve carrier frequency.For this reason, the new focus that exploitation a series ofly is suitable for having high-performance in the microwave range, the electronic material of high reliability performance characteristics and components and parts rise to the stupalith field.
In recent years, the trend of device miniaturization makes people more and more pay close attention to high-end medium dielectric constant microwave medium microwave-medium ceramics input.Though existing at present 0.42 (La
1/2Na
1/2) TiO
3-0.58Ca (Fe
1/2Nb
1/2) O
3, Pb
0.45Ca
0.6[(Mg
1/3Nb
2/3)
0.99Sn
0.01] O
3At 42～80, the temperature coefficient of resonance frequency high-end medium dielectric constant microwave medium microwave-medium ceramics between ± 10ppm/ ℃, but there are shortcomings such as Q * f value generally lower (being lower than 10000GHz), composition complexity Deng specific inductivity.In addition, also have Ba
2Ti
9O
20And Ba
1.85Sm
4.1Ti
9O
26With the gluing pottery that is connected into two-layer composite of low-loss and insulating, high Q * f value and near-zero resonance frequency temperature coefficient have been obtained having, specific inductivity can be at 42～80 continually varying seriation medium dielectric constant microwave medium microwave-medium ceramics.But, Ba
2Ti
9O
20Synthetic difficulty, to burn temperature higher, need adopt during with such material preparation laminated device costliness and resistance high Ag
70Pd
30Or Ag
35Pd
65Electrode materials, cost height, high-frequency loss are big.
ZnNb
2O
6(Q * f=83700GHz) causes people's interest, but has specific inductivity (ε less than normal because high quality factor
r=25), the undesirable (τ of temperature coefficient of resonance frequency
f=-56ppm/ ℃) shortcoming.Comparatively speaking, TiO
2High relatively specific inductivity and positive temperature coefficient are arranged, its ε
r=100, τ
f=400ppm/ ℃.Therefore, ZnO-Nb
2O
5-TiO
2Series ceramic material is expected to obtain a kind of microwave-medium ceramics of medium dielectric constant microwave medium, be expected on the basis that guarantees its high dielectric property, its sintering temperature is reduced to below 1000 ℃ by the mode of adding an amount of sintering aid again, it be applicable to make high-quality multiplayer microwave device.Use ZnNb
2O
6With TiO
2Compound, if do not add sintering aid, sintering temperature is then higher, reach 1200 ℃ and just can burn till, and is unfavorable for industrialization.(" low-temperature sintering ZnNb such as Zhang Qilong
2O
6/ TiO
2The preparation of composite ceramics and the research of dielectric properties ", Materials Science and Engineering journal 2003,21 (5): 694～696) studied ZnO:Nb
2O
5: TiO
2=1:1:x system is with the binary oxide V that has than eutectoid point (630 ℃)
2O
5-CuO finds that as sintering aid when x=1.92, the microwave material dielectric properties that obtain at 930 ℃ of sintering are: ε
r=37.71, τ
f=-2ppm/ ℃, but its Q * the f value is on the low side (Q * f=10370GHz), and V
2O
5Expensive and severe toxicity is arranged, do not meet environmental requirement.Subsequently, Wang Huan equality (" SnO
2Doping ZnO-Nb
2O
5-TiO
2Microwave-medium ceramics ", electronic component and material, 2004,23 (7): 4～6) introduce, when the mol ratio of material component is ZnO: Nb
2O
5: TiO
2: SnO
2During=1:1:1.92:0.08, the dielectric properties of the microwave material that obtains at 1150 ℃ of sintering are: ε
r=50.3, Q * f=14892GHz, but τ
f(τ bigger than normal
f=25.12ppm/ ℃), and sintering temperature is higher.
Summary of the invention
The objective of the invention is in order to satisfy the requirement of mobile communication, provide that a kind of sintering temperature that can overcome the prior art shortcoming is lower, the medium dielectric constant microwave medium microwave dielectric ceramic materials of production environmental protection and preparation method thereof microwave device miniaturization, radio frequencyization.
The present invention is with ZnO-Nb
2O
5-TiO
2Series ceramic material is an object, adopts one or more oxide compounds as sintering aid, the collaborative sintering temperature that reduces pottery, the microwave dielectric property of comprehensive regulation material.
To achieve these goals, the medium dielectric constant microwave medium microwave dielectric ceramic materials and the preparation method of a kind of low temperature sintering that the present invention proposes comprise following content:
A kind of preparation method of medium dielectric constant microwave medium microwave-medium ceramics of low temperature sintering may further comprise the steps:
(1) takes by weighing ZnO, Nb in proportion
2O
5, mix 0.1～1.0% the grinding aid that the raw material gross weight is added in the back, with deionized water and zirconium ball ball milling 3～6 hours on planetary ball mill; The oven dry back was 900～1000 ℃ of following pre-burnings 2～8 hours;
(2) with powder and TiO after step (1) pre-burning
2, sintering aid weighing in proportion again, mix 0.1～1.0% the grinding aid that the raw material gross weight is added in the back, with deionized water and zirconium ball ball milling 3～6 hours on planetary ball mill, oven dry again;
(3) but in the powder that makes, add binding agent to granulation, compression moulding, sintering 2～8 hours in 900～1000 ℃ scope obtains microwave-medium ceramics again;
In mole percent level, this ceramic raw material is made up of following component: ZnO 22～33%, Nb
2O
520～30%, TiO
240～55%; By weight percentage, sintering aid is 0.1～8% of a raw material gross weight; Described sintering aid is CuO, B
2O
3, 3ZnOB
2O
3, ZnOB
2O
3, 2ZnO3B
2O
3, Cu (BO
2)
2In one or more.
The source of described ZnO is the ZnO compound or can thermolysis is the compound of zinc oxide.
The thermolysis of described energy is that the compound of zinc oxide is preferably zinc acetate or zinc subcarbonate.
Described grinding aid is to comprise in sodium alkyl benzene sulfonate, sodium alkyl sulfate, trolamine, ethanol, the isopropylcarbinol one or more.
Described binding agent is preferably polyvinyl alcohol for binding agent commonly used, and its concentration is 0.1～0.2g/ml.
A kind of medium dielectric constant microwave medium microwave dielectric ceramic materials by the method for preparing low temperature sintering, its specific inductivity is 35～50, Q * f=10000～30000GHz, temperature coefficient of resonance frequency τ
f=0 ± 30ppm/ ℃, insulation resistivity ρ is 2.0 * 10
11Ω cm～5.0 * 10
13Ω cm.
With respect to prior art, the present invention has following characteristics:
1. low temperature sintering: according to the difference of forming proportioning, sintering temperature is between 900～1000 ℃, and sintering atmosphere is air or inert atmosphere, and the prior art sintering temperature is more than 1150 ℃.
2. has good microwave dielectric property: the microwave-medium ceramics ε of the present invention's preparation
rAdjustable between=35～50, and Q * f=10000～30000GHz (resonant frequency f=4～6GHz), τ
f=0 ± 30ppm/ ℃; Insulation resistivity ρ is 2.0 * 10
11Ω cm～5.0 * 10
13Ω cm.As seen the microwave-medium ceramics Q * f of the present invention's preparation is generally higher, and prior art is about 10000GHz, and is not high enough.
3. this material compliance with environmental protection requirements has no side effect, environmentally safe, and raw materials cost is low, and marketable value is arranged.
Embodiment
The present invention is further illustrated below in conjunction with embodiment, but it is pointed out that embodiment does not limit protection scope of the present invention.
Embodiment 1:
Take by weighing 6.5g ZnO, 21.3gNb
2O
5, the trolamine of interpolation 0.0834g after mixing (0.3wt.% is with respect to the starting material gross weight, down together), ball milling 4 hours 950 ℃ of following pre-burnings 2 hours, synthesizes ZnNb after the oven dry
2O
6
Take by weighing the ZnNb after the 27.8g pre-burning more respectively
2O
6, 11.2gTiO
2, 0.78g CuO, mix the back and add 0.1193g trolamine (0.3wt.%), ball milling 4 hours, the oven dry back is the polyvinyl alcohol solution granulating and forming of 0.1g/ml with 1ml concentration, 1000 ℃ of following sintering 4 hours, obtains microwave-medium ceramics at last.
Embodiment 2:
Take by weighing 6.5g ZnO, 21.3gNb
2O
5, mixing the trolamine (0.3wt.%) that 0.0834g is added in the back, ball milling 4 hours is dried the back 950 ℃ of following pre-burnings 2 hours, synthetic ZnNb
2O
6
Take by weighing the ZnNb after the 27.8g pre-burning more respectively
2O
6, 11.2gTiO
2, 1.17g CuO, mix the trolamine (0.3wt.%) that 0.1205g is added in the back, ball milling 4 hours, the oven dry back is polyvinyl alcohol (PVA) the solution granulating and forming of 0.1g/ml with 1ml concentration, 1000 ℃ of following sintering 4 hours, obtains microwave-medium ceramics at last.
Embodiment 3:
Take by weighing 8.2g ZnO, 26.6g Nb
2O
5, mixing Sodium dodecylbenzene sulfonate (0.1wt.%) and 0.5ml dehydrated alcohol that 0.0348g is added in the back, ball milling 4 hours is dried the back 1000 ℃ of following pre-burnings 2 hours, synthetic ZnNb
2O
6
Take by weighing the ZnNb after the 34.7g pre-burning more respectively
2O
6, 12.0g TiO
2, 1.6345gCu (BO
2)
2Mix Sodium dodecylbenzene sulfonate (0.1wt.%) and 0.5ml dehydrated alcohol that 0.0483g is added in the back, ball milling 4 hours, the oven dry back is the polyvinyl alcohol solution granulating and forming of 0.1g/ml with 1ml concentration, 950 ℃ of following sintering 8 hours, obtain microwave-medium ceramics at last.
Embodiment 4:
Take by weighing 8.0g ZnCO
32Zn (OH)
2H
2O, 18.6g Nb
2O
5, mixing sodium lauryl sulphate (0.8wt.%) and 3ml isopropylcarbinol that 0.2128g is added in the back, ball milling 4 hours is dried the back 900 ℃ of following pre-burnings 2 hours, synthetic ZnNb
2O
6
Take by weighing the ZnNb after the 24.3g pre-burning more respectively
2O
6, 10.6gTiO
2, 0.698g CuO, 0.349g B
2O
3, mixing the back and add 0.2876g sodium lauryl sulphate (0.8wt.%) and 3ml isopropylcarbinol, ball milling 4 hours is the polyvinyl alcohol solution granulating and forming of 0.1g/ml with 1ml concentration after the oven dry, 975 ℃ of following sintering 4 hours, obtains microwave-medium ceramics at last.
Embodiment 5:
Take by weighing 8.0g ZnCO
32Zn (OH)
2H
2O, 18.6g Nb
2O
5, mixing sodium lauryl sulphate (0.2wt.%) and 1ml dehydrated alcohol that 0.0532g is added in the back, ball milling 4 hours is dried the back 1000 ℃ of following pre-burnings 2 hours, synthetic ZnNb
2O
6
Take by weighing the ZnNb after the 24.3g pre-burning more respectively
2O
6, 9.8gTiO
2, 0.682g CuO, 0.682g B
2O
3, mixing sodium lauryl sulphate (0.2wt.%) and 1ml dehydrated alcohol that 0.0709g is added in the back, ball milling 4 hours is the polyvinyl alcohol solution granulating and forming of 0.1g/ml with 1ml concentration after the oven dry, 975 ℃ of following sintering 4 hours, obtains microwave-medium ceramics at last.
Embodiment 6:
Take by weighing 8.2g ZnO, 26.6g Nb
2O
5, mixing Sodium dodecylbenzene sulfonate (0.2wt.%) and 1ml dehydrated alcohol that 0.0696g is added in the back, ball milling 4 hours is dried the back 1000 ℃ of following pre-burnings 2 hours, synthetic ZnNb
2O
6
Take by weighing the ZnNb after the 34.7g pre-burning more respectively
2O
6, 14g TiO
2, 0.974g CuO, 0.877g 2ZnO3B
2O
3Mix Sodium dodecylbenzene sulfonate (0.2wt.%) and 1ml dehydrated alcohol that 0.1011g is added in the back, ball milling 4 hours, the oven dry back is 10% polyvinyl alcohol solution granulating and forming with the 1ml weight percent concentration, 975 ℃ of following sintering 4 hours, obtain microwave-medium ceramics.
Embodiment 7:
Take by weighing 8.2g ZnO, 26.6g Nb
2O
5, mixing Sodium dodecylbenzene sulfonate (0.2wt.%) and 1ml dehydrated alcohol that 0.0696g is added in the back, ball milling 4 hours is dried the back 1000 ℃ of following pre-burnings 2 hours, synthetic ZnNb
2O
6
Take by weighing the ZnNb after the 34.7g pre-burning more respectively
2O
6, 14g TiO
2, 0.974g CuO, 2.63g2ZnO3B
2O
3Add Sodium dodecylbenzene sulfonate (0.2wt.%) and the 1ml dehydrated alcohol of 0.1046g after the mixing respectively, ball milling 4 hours, the oven dry back is the polyvinyl alcohol solution granulating and forming of 0.1g/ml with 1ml concentration, 975 ℃ of following sintering 4 hours, obtain microwave-medium ceramics respectively.
Embodiment 8:
Take by weighing 8.2g ZnO, 26.6g Nb
2O
5, mixing Sodium dodecylbenzene sulfonate (0.2wt.%) and 1ml dehydrated alcohol that 0.0696g is added in the back, ball milling 4 hours is dried the back 1000 ℃ of following pre-burnings 2 hours, synthetic ZnNb
2O
6
Take by weighing the ZnNb after the 34.7g pre-burning more respectively
2O
6, 14g TiO
2, 0.974g CuO, 2.63g 2ZnO3B
2O
3, mixing Sodium dodecylbenzene sulfonate (0.2wt.%) and 1ml dehydrated alcohol that 0.1046g is added in the back, ball milling 4 hours is the polyvinyl alcohol solution granulating and forming of 0.1g/ml with 1ml concentration after the oven dry, 950 ℃ of following sintering 4 hours, obtains microwave-medium ceramics.
Embodiment 9:
Take by weighing 8.2g ZnO, 26.6g Nb
2O
5, mixing Sodium dodecylbenzene sulfonate (0.2wt.%) and 1ml dehydrated alcohol that 0.0696g is added in the back, ball milling 4 hours is dried the back 1000 ℃ of following pre-burnings 2 hours, synthetic ZnNb
2O
6
Take by weighing the ZnNb after the 34.7g pre-burning more respectively
2O
6, 14g TiO
2, 0.974g CuO, 1.461g 3ZnOB
2O
3Add Sodium dodecylbenzene sulfonate (0.2wt.%) and the 1ml dehydrated alcohol of 0.1023g after the mixing respectively, ball milling 4 hours, the oven dry back is the polyvinyl alcohol solution granulating and forming of 0.2g/ml with 1ml concentration, 950 ℃ of following sintering 6 hours, obtain microwave-medium ceramics respectively.
Embodiment 10:
Take by weighing 8.0g ZnCO
32Zn (OH)
2H
2O, 18.6g Nb
2O
5, mixing sodium lauryl sulphate (0.2wt.%) and 1ml dehydrated alcohol that 0.0532g is added in the back, ball milling 4 hours is dried the back 1000 ℃ of following pre-burnings 2 hours, synthetic ZnNb2O6;
Take by weighing the ZnNb after the 24.3g pre-burning more respectively
2O
6, 9.8gTiO
2, 0.682g CuO, 0.682g B
2O
3, mixing sodium lauryl sulphate (0.2wt.%) and 1ml dehydrated alcohol that 0.0709g is added in the back, ball milling 4 hours is the polyvinyl alcohol solution granulating and forming of 0.1g/ml with 1ml concentration after the oven dry, 925 ℃ of following sintering 6 hours, obtains microwave-medium ceramics at last.
Performance test:
The sample surfaces of the foregoing description preparation with diamond polishing after, (vector network analyzer of 300kHz～8.5GHz) is according to the microwave dielectric property of Hakki-Coleman parallel plate resonator method test material to adopt AglientE5071B.Concrete test procedure is as follows: network analyzer is arranged on transmission mode, and the cylindrical sample that two ends are parallel places between metal sheet, determines TE0
11Resonance peak is carefully adjusted the shape at peak, reads loaded Q and resonant frequency, measures the diameter and the height of sample then, utilizes RESONATE software can calculate the specific inductivity and the nonloaded Q of microwave-medium ceramics.Temperature coefficient of resonance frequency τ
f=(f
80-f
25)/(f
25* 55) ppm/ ℃ (f wherein
80And f
25Be respectively the resonance mid-frequency under 80 ℃ and 25 ℃).Under 500V, record the insulation resistance of material, calculate insulation resistivity.The concrete electrical property of sample sees table 1 for details.
The test result of table 1 embodiment of the invention
| Embodiment | Sintering aid content (wt.%) | Diameter D (mm) | Height h (mm) | Sintering temperature (℃) | Q×f (GHz) | ε r | τ f (ppm/℃) | ρ (Ω·cm) |
| 1 | 2.0％CuO | 11.67 | 6.84 | 1000 | 13739 | 42.79 | -3.98 | >6.0×10 11 |
| 2 | 3.0％CuO | 11.52 | 6.74 | 1000 | 10773 | 43.98 | -1.49 | >2.0×10 11 |
| 3 | 3.5％Cu(BO 2) 2 | 11.70 | 6.30 | 950 | 12868 | 41.12 | -8.85 | >1.0×10 12 |
| 4 | 2.0％CuO+ 1.0％B 2O 3 | 11.68 | 6.58 | 975 | 15071 | 48.85 | +19.77 | >3.4×10 11 |
| 5 | 2.0％CuO+ 2.0％B 2O 3 | 11.70 | 5.98 | 975 | 17009 | 40.37 | -11.67 | >1.5×10 12 |
| 6 | 2.0％CuO+1.8％ 2ZnO·3B 2O 3 | 11.59 | 6.84 | 975 | 11003 | 41.01 | -15.68 | >1.7×10 13 |
| 7 | 2.0％CuO+5.4％ 2ZnO·3B 2O 3 | 11.52 | 6.03 | 975 | 12324 | 38.06 | -12.82 | >3.0×10 13 |
| 8 | 2.0％CuO+5.4％ 2ZnO·3B 2O 3 | 11.53 | 5.18 | 950 | 18717 | 37.55 | -16.25 | >3.0×10 13 |
| 9 | 2.0％CuO+3.0％ 3ZnO·B 2O 3 | 11.56 | 5.78 | 950 | 21438 | 38.25 | -14.65 | >5.0×10 13 |
| 10 | 2.0％CuO+ 2.0％B 2O 3 | 11.66 | 6.48 | 925 | 14319 | 41.03 | +2.72 | >1.0×10 12 |
As known from Table 1, all samples all can be at middle low temperature (Ts≤1000 ℃) sintering down; The DIELECTRIC CONSTANT of sample
rGreater than 37, and, change little along with the change of sintering aid content; Q * f value is 10000～22000GHz.By the data of sample 1～3 as can be known, when a kind of sintering aid CuO of independent interpolation, τ
fNear zero, but sintering temperature is higher, and insulation resistivity is relatively low; Add Cu (BO
2)
2Can significantly reduce sintering temperature and improve insulation resistivity, but Q * the f value is on the low side.From the result of sample 4,5 and 10, compound interpolation CuO and B
2O
3Can effectively reduce sintering temperature, Q * f value higher relatively (greater than 14000GHz), temperature coefficient of resonance frequency τ
fJust becoming by negative with the increase of titanium dioxide amount (as embodiment 4) or the decline (as embodiment 10) of sintering temperature, having near zero temperature coefficient of resonance frequency at 925 ℃ of agglomerating samples 10.From sample 6～9, compound interpolation CuO and 2ZnO3B
2O
3Or 3ZnOB
2O
3The time, the insulation resistivity of sample significantly improves (1～2 order of magnitude), and the variation of sample temperature coefficient of resonance frequency is little; With the decline of sintering temperature, Q * f value increases; Additive ZnO-B
2O
3Composition little to the influence of the dielectric properties of sample.Kind by regulating principal phase component, additive and add-on, sintering temperature, we can obtain medium dielectric constant microwave medium (ε
r〉=37), high Q * f value, nearly zero temperature coefficient of resonance frequency and the high microwave ceramic material of insulation resistivity.
The replacement that all are similar and change apparent to those skilled in the artly, they are regarded as being included in the protection domain of the present invention.
Claims (7)
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