CN103408299A - Zinc barium titanate system ceramic low temperature sintering material and preparation method thereof - Google Patents
Zinc barium titanate system ceramic low temperature sintering material and preparation method thereof Download PDFInfo
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- CN103408299A CN103408299A CN2013103002979A CN201310300297A CN103408299A CN 103408299 A CN103408299 A CN 103408299A CN 2013103002979 A CN2013103002979 A CN 2013103002979A CN 201310300297 A CN201310300297 A CN 201310300297A CN 103408299 A CN103408299 A CN 103408299A
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Abstract
The present invention discloses a zinc barium titanate system microwave dielectric ceramic material and a preparation method thereof, and relates to an electronic material technology. The chemical composition of the material is (1-x)BaTi4O9-xBaZn2Ti4O11-yM, wherein x is more than or equal to 0.15 and is less than or equal to 0.25 (molar ratio ), M is a firing reduction agent, y is more than or equal to 0.0531 and is less than or equal to 0.1005 (weight ratio), components of the firing reduction agent comprise, by weight, 44.25-53.47% of Li2CO3, 4.82-9.19% of SiO2, 33.24-37.71% of B2O3, 0.88-0.94% of ZnO, 3.75-9.83% of Al2O3, and 0.3-1% of additives such as MnCO3 and CuO, and a weight ratio of the MnCO3 to the CuO is 3:4-3:6. The present invention further provides the concrete method for producing the material. The prepared microwave dielectric ceramic has characteristics of low sintering temperature (less than or equal to 900 DEG C) and excellent dielectric property, and can be used for manufacturing of low temperature co-firing ceramic systems, multilayer dielectric resonators, microwave antennas, filters and other microwave devices, wherein the excellent dielectric property comprises that: a dielectric constant of 20-30 is adjustable, a quality factor is high, and a resonant frequency temperature coefficient is small.
Description
Technical field
The invention belongs to electronic ceramics and manufacture field thereof, relate to a kind of zinc titanate barium system microwave dielectric ceramics stupalith and preparation method thereof.
Background technology
Microwave-medium ceramics refers to and is applied in microwave (300MHz is to 300GHz) band circuitry as dielectric material and completes the pottery of one or more functions, be the key foundation material in modern communication technology, be widely used in the microwave devices such as dielectric resonator, wave filter, dielectric substrate, Medium Wave Guide loop, microwave capacitors, duplexer, antenna.
Constantly to high frequency and digitizing future development, to the miniaturization of components and parts, integrated so that modular requirement is also more and more urgent along with electronic information technology.LTCC LTCC (Low Temperature Co-fired Ceramics), with its excellent electricity, machinery, calorifics and operational characteristic, has become one of major technique of electronic-component module.
Be applied to the dielectric ceramic of microwave frequency band, should meet the demands: (1) suitable specific inductivity is beneficial to miniaturization (size of medium components and parts and the DIELECTRIC CONSTANT ε of device
rSquare root be inversely proportional to); (2) high quality factor (f is resonant frequency for Qf value, Q～1/tan δ wherein) and low loss (tan δ); (3) stable nearly zero temperature coefficient of resonance frequency.
BaO-ZnO-TiO
2BaTi in system
4O
9And BaZn
2Ti
4O
11, have good microwave dielectric property, and frequency-temperature coefficient that can be complementary,
BaTi
4O
9：ε
r=37、Q×f=22700GHz、τ
f=+15ppm/℃
BaZn
2Ti
4O
11：ε
r=30、Q×f=68000GHz、τ
f=-30ppm/℃
But the two all has high sintering temperature (>1200 ℃), can not be directly and the low melting point metals such as Ag, Cu burn altogether.
Usually the method that reduces the sintering temperature of microwave dielectric material has: add low melting point oxide or low melting glass sintering aid, introduce chemical synthesis process, and superfine powder is made raw material etc.Synthetic and the superfine powder of chemical process is made raw material and can be caused complex technical process, and manufacturing cost and cycle can rise.
Comparatively speaking, the technique of adding low melting point oxide or low melting glass sintering aid is relatively simple, is easy to batch production.Traditional method is a kind of for mixing low melting point oxide, as B
2O
3And V
2O
5Yet, free B
2O
3And V
2O
5In later stage curtain coating process, easily cause slurry viscosity excessive and unstable, limited its practical application; Another kind method is to mix low melting glass, but the existence of glassy phase has improved the dielectric loss of material greatly, and glass is unstable at the fusion process performance, and cost is higher, has greatly limited BaO-ZnO-TiO
2Development system material and the microwave multilayer device.
Summary of the invention
Goal of the invention of the present invention is to overcome the technical problem of above-mentioned existence, but a kind of low-temperature sintering (≤900 ℃) is provided, and has specific inductivity adjustable (20-30), the microwave dielectric ceramic materials that low-loss and frequency-temperature coefficient are stable and preparation method.
The chemical constitution of microwave dielectric ceramic materials of the present invention is: (1-x) BaTi
4O
9-xBaZn
2Ti
4O
11-yM, wherein: 0.15≤x≤0.25(mol ratio), M is for falling the burning agent, 0.0531≤y≤0.1005(weight ratio), described falling burnt the agent component and weight percent is: Quilonum Retard (Li
2CO
3): 44.25%～53.47%, silicon-dioxide (SiO
2): 4.82%～9.19%, boron trioxide (B
2O
3): 33.24%～37.71%, zinc oxide (ZnO): 0.88%～0.94%, aluminium sesquioxide (Al
2O
3): 3.75%～9.83%, additive manganous carbonate (MnCO
3) and cupric oxide (CuO): 0.3%～1%, both weight ratios are 3:4～3:6.
Wherein a kind of screening formulation mass percent is: 0.85BaTi
4O
9-0.15BaZn
2Ti
4O
11: 91.12%, Quilonum Retard (Li
2CO
3): 4.51%, silicon-dioxide (SiO
2): 0.44%, boron trioxide (B
2O
3): 2.98%, zinc oxide (ZnO): 0.08%, aluminium sesquioxide (Al
2O
3): 0.79%, manganous carbonate (MnCO
3): 0.03%, cupric oxide (CuO): 0.05%.
The present invention has realized following beneficial effect: do not contain the heavy metal composition, can in the product of high frequency field, apply, environmental protection is pollution-free; By 1250 ℃ of traditional sintering process, dropped to below 900 ℃, the further reduction of sintering temperature, have power savings advantages; Sintering aid is used compound eutectoid point oxide compound and additive, has further improved the shortcoming of conventional sintering auxiliary agent, as: the low melting point oxide (B that can't mate with casting technique
2O
3And V
2O
5) or the low melting glass of expensive and unstable properties; Its specific inductivity is from 20～30 adjustable, and Qf is high, and temperature coefficient of resonance frequency is little.
The invention allows for simultaneously concrete preparation method:
Step 1: by barium oxide (BaO), zinc oxide (ZnO), titanium dioxide (TiO
2) starting powder by (1-x) BaTi
4O
9-xBaZn
2Ti
4O
11Form batching;
Step 2: by the batching that step 1 prepares, the deionized water of take is solvent, and planetary ball mill mixed 3～5 hours, under 80-120 ℃, dries after taking-up, with 60 eye mesh screens, sieve, after in 800 ℃～1000 ℃ air atmosphere 5～8 hours synthetic principal crystalline phase BaTi of pre-burning
4O
9Phase and BaZn
2Ti
4O
11Phase;
Step 3: in described principal crystalline phase, add account for total mass per-cent be 5.31%～10.05% the burning agent falls, the alcohol of take is solvent, planetary ball mill mixed 3～5 hours, described total mass is that principal crystalline phase adds and falls the quality of burning agent;
Step 4: after again drying, to account for the material total mass be that 2～5% acrylic acid solution is as the binding agent granulation to additive capacity;
Step 5: dry-pressing formed, forming pressure 200～300Mpa;
Step 6: sintering is 1～3 hour in 850-900 ℃ of air atmosphere, makes microwave-medium ceramics.
The pottery that the present invention adopts oxide compound and additive mixing solid reaction process to prepare is good at 850-900 ℃ of sintering, its specific inductivity is adjustable from 20～30, Qf high (> 8000), temperature coefficient of resonance frequency is little, and domestic raw materials cost is low, industrial great using value arranged, accelerate the extensive application of domestic microwave ceramics.
In sum, owing to having adopted technique scheme, compared with prior art, the invention has the beneficial effects as follows:
1, formula of the present invention does not contain the heavy metal composition, can in the product of high frequency field, apply, and environmental protection is pollution-free, meets the strict standard requirement of RHOS and the WEEE of the up-to-date appearance of the European Community.
2, by 1250 ℃ of traditional sintering process, dropped to below 900 ℃, the further reduction of sintering temperature, have power savings advantages.
3, sintering aid is used compound eutectoid point oxide compound and additive, has further improved the shortcoming of conventional sintering auxiliary agent, as: the low melting point oxide (B that can't mate with casting technique
2O
3And V
2O
5) or the low melting glass of expensive and unstable properties.
4, its specific inductivity is from 20～30 adjustable, and the Qf value is high, and temperature coefficient of resonance frequency is little.
5, the present invention can be widely used in the low temperature high-permittivity microwave medium core material in the microwave devices such as satellite communications medium resonator, wave filter, vibrator, has the essential industry using value.
The accompanying drawing explanation
Examples of the present invention will be described by way of reference to the accompanying drawings, wherein:
Fig. 1 does not adulterate to fall the BZT that the burns agent XRD at 1350 degree sintering;
Fig. 2 is that the XRD of the BZT of burning agent at 875 degree sintering falls in doping 0.1005;
Fig. 3 is that the scanning electron microscope (SEM) photograph of the BZT of burning agent at 850 degree sintering falls in doping 0.0531;
Fig. 4 is that the scanning electron microscope (SEM) photograph of the BZT of burning agent at 850 degree sintering falls in doping 0.1005.
Embodiment
Disclosed all features in this specification sheets, or the step in disclosed all methods or process, except mutually exclusive feature and/or step, all can combine by any way.
Disclosed arbitrary feature in this specification sheets (comprising any accessory claim), unless special narration all can be replaced by other equivalences or the alternative features with similar purpose.That is, unless special narration, each feature is an example in a series of equivalences or similar characteristics.
Embodiment
Material of the present invention is 89.95%～94.69% BaO-ZnO-TiO by mass percent
2And mass percent is 5.31%～10.05% falls and burn agent and form, BaO-ZnO-TiO
2Material system consist of (1-x) BaTi
4O
9-xBaZn
2Ti
4O
11(0.15≤x≤0.25), fall the manufacture raw material that burns agent and contain: Li
2CO
3, SiO
2, B
2O
3, ZnO, Al
2O
3, MnCO
3, CuO.Table 1 shows the data of the several specific embodiments that form each component content of the present invention, and table 2 provides the microwave dielectric property of each embodiment.Its preparation method is:
Step 1: by barium oxide (BaO), zinc oxide (ZnO), titanium dioxide (TiO
2) starting powder press 0.85BaTi
4O
9-0.15BaZn
2Ti
4O
11Form batching;
Step 2: by the batching that step 1 prepares, the deionized water of take is solvent, and planetary ball mill mixed 3～5 hours, under 80-120 ℃, dries after taking-up, with 60 eye mesh screens, sieve, after in 800 ℃～1000 ℃ air atmosphere 5～8 hours synthetic principal crystalline phase BaTi of pre-burning
4O
9Phase and BaZn
2Ti
4O
11Phase;
Step 3: in described principal crystalline phase, add account for total mass per-cent be 5.31%～10.05% the burning agent falls, the alcohol of take is solvent, planetary ball mill mixed 3～5 hours; The described mass percent of burning agent of falling is:
Li
2CO
3：50.78%， SiO
2：4.91%， B
2O
3：33.59%， ZnO：0.89%，
Al
2O
3：8.93%， MnCO
3：0.34%， CuO：0.56%。
Step 4: after again drying, to account for the material total mass be that 2～5% acrylic acid solution is as the binding agent granulation to additive capacity;
Step 5: dry-pressing formed, forming pressure 200～300Mpa;
Step 6: sintering is 1～3 hour in 850-900 ℃ of air atmosphere, makes microwave-medium ceramics.
By the cylindrical dielectric resonator method, carry out the evaluation of microwave dielectric property, detection method is GB/T 7265.2-1987 open type chamber method.
Table 1:
Table 2
Fig. 1 illustrates the XRD diffractogram of unadulterated BZT, and Fig. 2 illustrates doping 0.09 and falls the BZT that the burns agent XRD diffractogram at 850 degree sintering, and contrast being found out that doping is fallen after burning agent and also having synthesized main crystalline phase BaTi
4O
9And BaZn
2.03Ti
3.93O
10.89Second-phase does not generate, Fig. 3 illustrates doping 0.0531 and falls the scanning electron microscope (SEM) photograph of the BZT of burning agent at 850 degree sintering, Fig. 4 illustrates doping 0.1005 and falls the scanning electron microscope (SEM) photograph of the BZT of burning agent at 850 degree sintering, from scanning electron microscope (SEM) photograph, can find out, along with falling the increase of burning the agent addition, pore reduces, it is fine and close that structure becomes, and illustrates that falling the burning agent has promoter action to sintering.
The present invention is not limited to aforesaid embodiment.The present invention expands to any new feature or any new combination disclosed in this manual, and the arbitrary new method disclosed or step or any new combination of process.
Claims (3)
1. a low-temperature sintering zinc titanate barium system microwave dielectric ceramic materials, is characterized in that its chemical constitution is: (1-x) BaTi
4O
9-xBaZn
2Ti
4O
11-yM, wherein: 0.15≤x≤0.25(mol ratio), M is for falling the burning agent, 0.0531≤y≤0.1005(weight ratio), described falling burnt the agent component and weight percent is:
Quilonum Retard (Li
2CO
3): 44.25%～53.47%, silicon-dioxide (SiO
2): 4.82%～9.19%, boron trioxide (B
2O
3): 33.24%～37.71%, zinc oxide (ZnO): 0.88%～0.94%, aluminium sesquioxide (Al
2O
3): 3.75%～9.83%, additive manganous carbonate (MnCO
3) and cupric oxide (CuO): 0.3%～1%, both weight ratios are 3:4～3:6.
2. microwave dielectric ceramic materials as claimed in claim 1, it is characterized in that: its chemical constitution is: 0.85BaTi
4O
9-0.15BaZn
2Ti
4O
11: 91.12%, y=0.0887, it falls burning agent component and shared weight percent hundred is:
Li
2CO
3：50.78%， SiO
2：4.91%， B
2O
3：33.59%， ZnO：0.89%，
Al
2O
3：8.93%， MnCO
3：0.34%， CuO：0.56%。
3. the preparation method of microwave dielectric ceramic materials as claimed in claim 1 is characterized in that concrete steps are:
Step 1: by barium oxide (BaO), zinc oxide (ZnO), titanium dioxide (TiO
2) starting powder by (1-x) BaTi
4O
9-xBaZn
2Ti
4O
11Form batching;
Step 2: by the batching that step 1 prepares, the deionized water of take is solvent, and planetary ball mill mixed 3～5 hours, after taking-up, dry under 80-120 ℃, after with 60 eye mesh screens, sieving in 800 ℃～1000 ℃ air atmosphere 5～8 hours synthetic principal crystalline phase BaTi of pre-burning
4O
9Phase and BaZn2Ti4O11 phase;
Step 3: in described principal crystalline phase, add account for total mass per-cent be 5.31%～10.05% the burning agent falls, the alcohol of take is solvent, planetary ball mill mixed 3～5 hours, described total mass is that principal crystalline phase adds the quality of falling the burning agent, after taking-up, dry under 80-120 ℃, add again account for the material total mass 2～5% acrylic acid solution as the binding agent granulation, compression moulding, finally sintering 1～3 hour in 850 ℃ of-900 ℃ of air atmosphere.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104108929A (en) * | 2014-05-26 | 2014-10-22 | 电子科技大学 | Low-temperature sintered composite microwave dielectric ceramic material and preparation method thereof |
| CN110317057A (en) * | 2019-05-06 | 2019-10-11 | 北京元六鸿远电子科技股份有限公司 | A kind of medium dielectric constant low-temperature co-fired ceramic and preparation method |
| CN111233460A (en) * | 2020-01-19 | 2020-06-05 | 深圳振华富电子有限公司 | Microwave dielectric ceramic material and preparation method thereof |
| CN114180956A (en) * | 2021-12-20 | 2022-03-15 | 无锡鑫圣慧龙纳米陶瓷技术有限公司 | Microwave dielectric ceramic for high-dielectric-constant 5G waveguide and preparation method and application thereof |
| CN114804857A (en) * | 2021-01-28 | 2022-07-29 | 山东国瓷功能材料股份有限公司 | Low-temperature co-fired ceramic material and preparation method thereof |
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2013
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104108929A (en) * | 2014-05-26 | 2014-10-22 | 电子科技大学 | Low-temperature sintered composite microwave dielectric ceramic material and preparation method thereof |
| CN104108929B (en) * | 2014-05-26 | 2015-08-19 | 电子科技大学 | A kind of low-temperature sintering composite microwave medium ceramic material and preparation method thereof |
| CN110317057A (en) * | 2019-05-06 | 2019-10-11 | 北京元六鸿远电子科技股份有限公司 | A kind of medium dielectric constant low-temperature co-fired ceramic and preparation method |
| CN110317057B (en) * | 2019-05-06 | 2023-03-28 | 北京元六鸿远电子科技股份有限公司 | Medium-dielectric-constant low-temperature co-fired ceramic material and preparation method thereof |
| CN111233460A (en) * | 2020-01-19 | 2020-06-05 | 深圳振华富电子有限公司 | Microwave dielectric ceramic material and preparation method thereof |
| CN111233460B (en) * | 2020-01-19 | 2022-04-19 | 深圳振华富电子有限公司 | Microwave dielectric ceramic material and preparation method thereof |
| CN114804857A (en) * | 2021-01-28 | 2022-07-29 | 山东国瓷功能材料股份有限公司 | Low-temperature co-fired ceramic material and preparation method thereof |
| CN114804857B (en) * | 2021-01-28 | 2023-03-14 | 山东国瓷功能材料股份有限公司 | Low-temperature co-fired ceramic material and preparation method thereof |
| CN114180956A (en) * | 2021-12-20 | 2022-03-15 | 无锡鑫圣慧龙纳米陶瓷技术有限公司 | Microwave dielectric ceramic for high-dielectric-constant 5G waveguide and preparation method and application thereof |
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