CN1264779C - Dielectric ceramic material and dielectric resonator with the material - Google Patents
Dielectric ceramic material and dielectric resonator with the material Download PDFInfo
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- CN1264779C CN1264779C CN 01137711 CN01137711A CN1264779C CN 1264779 C CN1264779 C CN 1264779C CN 01137711 CN01137711 CN 01137711 CN 01137711 A CN01137711 A CN 01137711A CN 1264779 C CN1264779 C CN 1264779C
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Abstract
The present invention provides a dielectric ceramic material which comprises a sosoloid whose main crystal phase is a perovskite crystal, wherein the perovskite crystal comprises composite oxides formed by barium (Ba), magnesium (Mg), tungsten (W) and rare earth element, and the dielectric ceramic material is preferably used for dielectric resonators. Since the dielectric ceramic material can obtain high-value epsilon r and high-value Q factors in high-frequency areas, the absolute value of a temperature factor tau f of resonance frequency can be reduced.
Description
Invention field
The present invention relates to a kind of novel dielectric ceramic material, this material shows the high relative permittivity and the high Q factor in the high-frequency region of for example microwave and millimeter wave, especially, the present invention relates to a kind of high-frequency electronic element that is suitable for making, such as dielectric resonator, wave filter and electric capacity, the dielectric ceramic material that is used for the dielectric substrate of microwave integrated circuit (MIC) and is used for the waveguide etc. of millimeter wave purposes.
Background technology
Be used to resemble the dielectric resonator of high-frequency applications of microwave and millimeter wave and the dielectric substrate that is used for microwave integrated circuit (MIC) and extensively adopted dielectric ceramic material.The banded line of dielectric medium has been applied on the millimere-wave band waveguide at present.Major requirement for dielectric ceramic material is as follows:
(1) when being used for making small-sized component, this material must have high relative permittivity, tapers to (1/ ε r) because the hertzian wave of propagating in dielectric substance has
1/2Wavelength.
(2) this material must have low-dielectric loss at high-frequency region, promptly has the high Q factor.
(3) when temperature variation, the resonant frequency of this material must also only be done very little variation, that is, relative permittivity ε r must have lower temperature dependency.
The applicant proposed in the past, had as the material that satisfies above-mentioned needs: comprise BaO, MgO and WO with a special component scope
3The dielectric ceramic composition (Japanese patent laid-open 5-205524) of barium magnesium tungsten base, comprise SrO, MgO and WO with a special component scope
3The dielectric ceramic composition (Japanese patent laid-open 6-5117) of strontium magnesium tungsten base, and have with a special component scope and comprise BaO, MgO, WO
3Dielectric ceramic composition (Japanese patent laid-open 6-236708) with (the IIIA family element of barium magnesium tungsten+periodic table of elements) base of the oxide compound of IIIA family group element.
Yet produced a kind of like this problem, it is the dielectric ceramic composition (Japanese patent laid-open 5-205524) of barium magnesium tungsten base, the dielectric ceramic composition (Japanese patent laid-open 6-5117) of strontium magnesium tungsten base, and dielectric ceramic composition (Japanese patent laid-open 6-236708) of (barium magnesium tungsten+IIIV family element) base has the Q factor between 25000 to 180000, and this Q factor is that the scope internal conversion at relative permittivity ε r from 19 to 25 is the numerical value based on 1GHz.Owing to, must improve this Q factor when this Q factor may become less than 100000.
Summary of the invention
Main order of the present invention is to provide a kind of dielectric ceramic material, and its relative permittivity is 19 between 25 the time, has to be not less than 100000 the Q factor.Particularly, its relative permittivity is 19 between 25 the time, has the dielectric ceramic material of the Q factor that is not less than 130000 high numerical value, and based on the dielectric resonator of this material.
Another object of the present invention provides the dielectric ceramic material that a kind of its relative permittivity ε r depends on temperature tinily, and promptly the temperature factor τ f of resonant frequency stablizes and has less absolute value, and the dielectric resonator based on this material is provided.
The dielectric ceramic material of the present invention of realizing above-mentioned purpose is that its principal crystalline phase is the sosoloid of perovskite crystal, and described perovskite crystal comprises the composite oxides of barium, strontium, magnesium, tungsten and RE (RE represents rare earth metal) at least.
Preferably comprise in the dielectric ceramic material of the present invention and contain the perovskite crystal of the composite oxides of barium, strontium, magnesium, tungsten and RE at least, and its content is preferably at least 90 volume %.
Dielectric ceramic material of the present invention preferably comprises at least barium, strontium, magnesium, tungsten and rare earth element as metallic element, and is expressed as aBaObSrOcMgOdWO with the mol ratio form of metal oxide when the oxide compound of this metallic element
3ERE
2O
xThe time, wherein factor a, b, c, d and e satisfy following relationship:
0.35≤a≤0.55.
0.01≤b≤0.25.
0.10≤c≤0.30.
0.15≤d≤0.35.
0.01≤e≤0.20, and
a+b+c+d+e＝1
The RE of dielectric ceramic material of the present invention is preferably ytterbium.Best in addition dielectric ceramic material of the present invention comprises manganese as metallic element, and wherein manganese is based on Manganse Dioxide (MnO
2) and content be 0.01～2 weight %.
Dielectric resonator of the present invention is configured to, and above-mentioned dielectric ceramic material is arranged between a pair of input and output terminal, so that have an effect by electromagnetic coupled.
Other purpose of the present invention and advantage will become apparent along with the detailed expansion of describing.
The accompanying drawing summary
Fig. 1 is a sectional view of showing an example of dielectric resonator of the present invention.
The concrete mode that carries out an invention
Dielectric ceramic material of the present invention relates to a kind of agglomerated material of making by the prefabricated component of firing ceramics material.In order to obtain the Q factor of a high value, importantly described material is that principal crystalline phase is the sosoloid of perovskite crystal, and described perovskite crystal comprises the composite oxides of barium, strontium, magnesium, tungsten and RE (RE represents rare earth metal) at least.
Dielectric ceramic material of the present invention preferably comprises the perovskite crystal of at least 90 volume %.The perovskite crystal that comprises at least 90 volume % can improve the factor.In order to make the Q factor higher, preferably comprise 95 volume % or more perovskite crystal.
As the crystalline phase that is different from perovskite crystal, also may there be RE
2O
x(3≤x≤4), MgO, BaWO
4, BaW
2O
9, Ba
2WO
5, MgWO
4Deng.
Determine the inclusion of the perovskite crystal in the dielectric ceramic material of the present invention jointly by the measurement of transmission electron microscope observation, selected area electron diffraction image analysis and energy dispersive spectrometry (EDS) or micro-X-ray diffraction method.When measurement is contained in the inclusion of the perovskite crystal in the dielectric ceramic material of the present invention, preferably adopt transmission electron microscope observation, selected area electron diffraction image analysis and energy dispersion X-ray energy spectrum (EDS) to measure.
Transmission electron microscope observation, selected area electron diffraction image analysis and EDS analyze by following step (A) and carry out to (C).
(A) by size is about 5 * 10
-3To 5 * 10
-2Mm
2The internal crystal structure that is amplified to 2000 to 8000 times selected diffraction image viewing dielectric ceramic material in zone, analyze each crystalline image K-M and differentiate crystalline structure.
(B) crystalline phase of identifying in step (A) is perovskite crystal and is when comprising the sosoloid that contains the composite oxides of barium, strontium, magnesium, tungsten and RE at least, and this crystal is considered to the perovskite crystal that contains in the dielectric ceramic material of the present invention.An example of the crystalline phase of the perovskite crystal that contains in the dielectric ceramic material of the present invention is Ba
2MgWO
6Ba
2MgWO
6Example can be Ba among JCPDS No.70-2023 and the 70-2404
2MgWO
6
(C) the perovskite crystal zone differentiated of determining step (B) provides the volume percent of perovskite crystal with respect to the ratio in the whole zone of crystalline in the picture of step (A).
During measurement, can adopt the transmission electron microscope JEM2010F of JEOL manufacturing and the EDS analyser Voyager IV that Noran instrument company makes.
Dielectric ceramic material of the present invention preferably comprises at least barium, strontium, magnesium, tungsten and RE as metallic element, and if the oxide compound of metallic element be expressed as aBaO.bSrO.cMgO.dWO with the form of the mol ratio of metal oxide
3.eRE
2O
xWhen (3≤x≤4, RE represents rare earth metal), factor a, b, c, d and e satisfy relational expression: 0.35≤a≤0.55,0.01≤b≤0.25,0.10≤c≤0.30,0.15≤d≤0.35,0.01≤e≤0.20 and a+b+c+d+e=1.
The present invention is limited in above-mentioned numerical range with a, b, c, d and e and is based on following reason:
The scope of selecting 0.35≤a≤0.55 is because can obtain the high Q factor under this scope.0.40 the scope of≤a≤0.50 is better.The scope of selecting 0.01≤b≤0.25 is because of the less temperature that depends on of ε r in this scope.0.10 the scope of≤b≤0.15 is better.The scope of selecting 0.10≤c≤0.30 is because can obtain the high Q factor under this scope.0.15 the scope of≤c≤0.25 is better.The scope of selecting 0.15≤d≤0.35 is because can obtain the high Q factor in this scope.0.20 the scope of≤d≤0.30 is better.Select 0.01≤e≤0.25th, because of the less temperature that depends on of ε r in this scope.0.01 the scope of≤e≤0.10 is better.
For obtaining up to 100000 or the Q factor of higher numerical value, from 19 to 25 variations of relative permittivity ε r simultaneously and relative permittivity ε r have less temperature dependency, and the temperature factor τ f of resonant frequency is stable and have a little absolute value, and the rare earth metal in the dielectric ceramic material of the present invention (RE) preferably descends at least a in the column element: yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er) and ytterbium (Yb).For the temperature factor τ f numerical stability that obtains its relative permittivity ε r and resonant frequency and less be subjected to that sintering temperature influences dielectric ceramic material, preferably select ytterbium (Yb) for use.
Dielectric ceramic material importantly of the present invention includes manganese as metallic element, and wherein manganese is based on MnO
2Form and weight ratio be 0.01% to 2%.This is because work as based on MnO
2Manganese content be less than at 0.01% o'clock, the Q factor will reduce, and when its content is equal to, or greater than 2%, will make sintering become the difficulty.
Dielectric ceramic material of the present invention may be such as the polycrystal of agglomerated material or single crystal.
Dielectric ceramic material of the present invention can make as described below.The oxide compound of preparation barium, strontium, magnesium, tungsten and RE or all as if the such metallic salt of carbonate, nitrate or acetate of barium, strontium, magnesium, tungsten and RE is used as main starting material, metallic salt wherein forms oxide compound when sintering.Weighing meets these raw materials of the quantity of above-mentioned scope, and they are mixed well.Mixture roasting in 1000 ℃ to 1300 ℃ temperature range, grind to form then average particle size particle size at 0.7 μ m to the powder between the 1.2 μ m.The sintered powder that must become forms the prefabricated component of predetermined shape such as press molding method or scraping blade method by known manufacturing process.This prefabricated component is being placed temperature from 1670 ℃ to 1700 ℃ oxidizing atmosphere air for example, after placing 2 to 10 hours, temperature is reduced to about 1200 ℃ to 800 ℃ with 5 ℃ to 100 ℃ speed per hour, thereby obtains dielectric ceramic material of the present invention.
Dielectric ceramic material of the present invention has the reason of the high Q factor, may be because barium, strontium, magnesium, tungsten and RE are combined into the solute in the perovskite crystal fully, and can reduce temperature then as described above by the maintenance at high temperature of the restriction course of processing and reduce lattice imperfection, as oxygen defect.That is, the formation of sosoloid can be quickened by heating under 1670 ℃ to 1700 ℃ high temperature in 2 to 10 hours, and by making temperature reduce to 1200 ℃ to 800 ℃ level with 5 ℃ to 100 ℃ speed per hour, lattice imperfection can be reduced.Employing is different from the manufacturing process of aforesaid method, and sosoloid may not can fully forms, and lattice imperfection can increase, thereby causes the low Q factor.
By comprising based on MnO
2The manganese of 0.01% to 2% weight can realize the raising of further the reducing of lattice imperfection and the Q factor.
Dielectric ceramic material of the present invention may contain unavoidable impurities, as chlorine (Cl), aluminium (Ae), phosphorus (P), sodium (Na), calcium (Ca) and zirconium (Zr).The weight of any these impurity is about 0.1% or still less can not cause the performance of dielectric ceramic material of the present invention to go wrong.
Dielectric ceramic material of the present invention can preferably be applied to dielectric resonator.Fig. 1 has schematically showed the situation with the dielectric resonator of TE pattern work.Dielectric resonator shown in Figure 1 comprises: be arranged in the relative lip-deep input terminal 2 of two inner casings and the output terminal 3 of can 1, and be arranged in the dielectric ceramic material of the present invention 4 between input terminal 2 and the output terminal 3.In dielectric resonator with the work of TE pattern, when microwave is imported by input terminal 2, microwave is by being limited within the dielectric resonator 4 at the boundary reflection between dielectric resonator 4 and the freeboard, thereby vibrates with a CF.Vibration is provided with output terminal 3 electromagnetic coupled and as output signal.
Dielectric ceramic material of the present invention also can be applied to other resonators, and the stripline runs resonator such as coaxial resonator or use TEM pattern certainly, also has the dielectric resonator with the work of TM pattern.Dielectric resonator also can be made input terminal 2 and output terminal 3 directly are fixed on the dielectric ceramic material 4.
Dielectric ceramic material 4, resonator, dielectric as the predetermined shape made from dielectric ceramic material of the present invention, as long as resonance is taken place, can make Any shape, such as rectangular parallelepiped, cubes, sheet, discoid, cylindrical or polygon prismatic.The high-frequency signal frequency of input is approximately 1GHz to 500GHz, and from the angle of real work, resonant frequency is preferably in about 2GHz within the scope of 80GHz.
Like this, according to the present invention, can obtain such dielectric ceramic material, it has the high Q factor and relative permittivity ε r, and this relative permittivity ε r has big numerical value, and the stable temperature that also depends on lessly.Described dielectric ceramic material is preferably applied to resonator, the dielectric substrate that is used for microwave integrated circuit (MLC), electric capacity, dielectric antenna and the dielectric waveguide in microwave and the use of millimeter wave zone.
Example
Purity is the barium carbonate (BaCO more than 99%
3), Strontium carbonate powder (SrCO
3), magnesiumcarbonate (MgCO
3), tungstic oxide (WO
3), the oxide compound and the Manganse Dioxide (MnO of rare earth element
2) powder, according to the ratio weighing shown in the table 1, and mix with water, place an internal surface to be covered with the ball mill water treatment 8 hours of rubber.After dehydrating, mixture was 1000 ℃ of following roastings 2 hours.Sintered product carries out wet lapping processing with ball mill, grinds to form average particle size particle size at the powder of 0.8 μ m in 1.0 mu m ranges.
The powder that ground becomes granular through drying, form the columniform prefabricated component of the thick 5mm of diameter 10mm.This cylindrical preform kept 2 to 10 hours down 1670 ℃ to 1700 ℃ of temperature, then temperature was reduced to about 1200 ℃ to 800 ℃ level with 5 ℃ to 100 ℃ speed per hour, thereby made dielectric ceramic material of the present invention.
The relative permittivity (ε r) when the frequency of the dielectric ceramic material that obtains with aforesaid method is 10GHz and the Q factor are with the measurement of dielectric resonator method.Temperature is the also available formula of numerical value of the temperature factor (τ f) of the resonant frequency under 25 ℃ to 85 ℃
τf＝-[(f
85-f
25)/f
25]/60×10
6(ppm/℃)
Try to achieve.Here " f
85" resonant frequency of expression 85 ℃ the time, and " f
25" resonant frequency during 25 ℃ of temperature of expression.These numerical value are shown in table 1.
Determined by transmission electron microscope observation, selected area electron diffraction image analysis and EDS analysis by the crystalline volume percent that perovskite crystal constitutes.Measure and finish to (C) by previous described step (A).
During measurement, can adopt the transmission electron microscope JEM2010F of JEOL manufacturing and the EDS analyser Voyager IV that Noran instrument company makes.
Measurement shows, the perovskite crystal that is contained among all samples No.1 to 25 for preparing according to the present invention constitutes by the sosoloid of the composite oxides of barium (Ba), strontium (Sr) magnesium (Mg), tungsten (W) and rare earth element (RE).If sample of the present invention comprises the crystalline phase that is different from perovskite crystal, the crystalline phase that then is different from perovskite crystal is Yb
2O
3, MgO etc.
Symbol in the table 1, for example " 0.1La0.9Ho " represents that the contained lanthanum (La) and the ratio of holmium (Ho) are 0.1: 0.9.
As seen from Table 1, the sample No.1 to 32 that drops in the scope of the present invention all shows good characteristic, and being included in ε r in 20 to 25 the scope, being no more than 100000 the Q factor and absolute value is 35 or lower τ f.Particularly, mole a, b, c, d and e are arranged in the specified range and the sample No.1 to 25 that makes has up to 120000 even the higher Q factor.
If the contained rare earth element of sample in the scope of the present invention is ytterbium (Yb), the temperature factor τ f that will obtain its relative permittivity ε r and resonant frequency has the dielectric ceramic material that is subjected to the very little constant value of sintering temperature variable effect.
Sample No.33 to 37 all not in scope of the present invention, has or the ε r of low numerical value, or the Q factor of low numerical value or absolute value surpass 35 τ f.
The present invention is not limited to above-mentioned example, only otherwise deviate from scope of the present invention and spirit, can do various variations.
Table 1
| The sample sequence number | The rare earth element ratio | BaO a | SrO b | MgO c | WO 3 d | RE 2O 3 e | Amount to | MnO 2(weight %) | Heat-up time under 1670 ℃ to 1700 ℃ (hour) | From 1200 ℃ to 800 ℃ speed of cooling (℃/hour) | The content of perovskite crystal (volume %) | Dielectric characteristics | ||
| εr | The Q factor | τf (ppm/℃) | ||||||||||||
| 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 *33 *34 *35 *36 *37 | Yb Yb Yb Yb Yb Yb Yb Yb Yb Yb Yb Yb Yb Yb Yb Y Y Y 0.1La-0.9Ho 0.9Lu-0.1Gd 0.1Y-0.9Yb 0.1Er-0.9Eu 0.5Nd-0.5Sm Dy Tb Yb Yb Yb Yb Yb Er Yb Yb Yb Y Yb - | 0.354 0.463 0.546 0.450 0.400 0.265 0.460 0.460 0.460 0.460 0.460 0.460 0.430 0.450 0.470 0.440 0.460 0.480 0.460 0.410 0.460 0.430 0.480 0.460 0.460 0.440 0.570 0.360 0.380 0.400 0.460 0.460 0.000 0.210 0.350 0.300 0.450 | 0.161 0.052 0.015 0.050 0.100 0.250 0.040 0.040 0.040 0.040 0.040 0.040 0.065 0.040 0.020 0.050 0.030 0.020 0.030 0.030 0.030 0.030 0.030 0.050 0.030 0.060 0.030 0.260 0.080 0.060 0.030 0.040 0.230 0.000 0.220 0.210 0.050 | 0.210 0.210 0.164 0.210 0.210 0.210 0.110 0.200 0.300 0.210 0.210 0.110 0.200 0.205 0.210 0.165 0.220 0.260 0.210 0.210 0.200 0.220 0.220 0.220 0.230 0.240 0.150 0.170 0.320 0.130 0.270 0.300 0.280 0.270 0.000 0.230 0.260 | 0.250 0.250 0.250 0.265 0.265 0.250 0.350 0.250 0.150 0.160 0.200 0.350 0.245 0.225 0.180 0.280 0.210 0.150 0.200 0.190 0.250 0.200 0.230 0.210 0.220 0.230 0.170 0.160 0.170 0.370 0.120 0.150 0.310 0.330 0.310 0.000 0.240 | 0.025 0.025 0.025 0.025 0.025 0.025 0.040 0.050 0.050 0.130 0.090 0.040 0.060 0.080 0.120 0.065 0.080 0.090 0.100 0.160 0.040 0.120 0.040 0.060 0.060 0.030 0.080 0.050 0.050 0.040 0.120 0.050 0.180 0.190 0.120 0.260 0.000 | 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 | 0.01 0.01 0.00 0.05 0.02 0.05 0.10 0.10 0.20 0.20 0.05 0.02 0.00 0.20 0.20 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.20 0.20 0.20 0.10 0.05 0.10 0.05 0.10 0.10 0.00 0.00 0.00 0.00 0.10 | 2 2 2 3 4 5 2 3 8 9 10 10 4 6 6 4 5 5 2 2 2 2 2 4 4 15 6 5 5 5 4 5 3 5 8 3 5 | 5 10 20 30 40 50 20 25 80 90 100 100 40 60 60 25 70 80 20 30 40 15 20 25 8 50 30 30 35 50 15 120 50 50 50 50 50 | 97.5 98.6 97.7 100.0 97.4 91.5 97.9 97.4 96.3 99.0 99.0 99.0 98.0 97.5 96.8 99.5 98.0 97.0 96.5 90.0 98.0 97.8 97.6 97.0 98.0 94.0 94.0 93.0 93.0 92.5 93.0 92.0 - - - - - | 23.5 21.5 20.2 20.5 21.8 24.2 21.6 21.3 20.8 22.5 23.6 21.6 22.6 21.8 22.7 20.6 21.6 22.2 22.6 24.7 20.9 22.4 21.1 21.6 21.8 22.6 25.3 22.6 26.3 20.1 23.5 19.6 22.8 22.6 26.4 31.7 20.3 | 123000 206000 160000 231000 154000 132000 180000 195000 1/6000 148000 149000 162000 154000 1/2000 143000 165000 185000 168000 152000 132000 189000 168000 196000 189000 197000 101000 103000 104000 101000 106000 110000 111000 12000 24000 13000 15000 88500 | 22.3 1.1 -8.6 -6.2 10.6 31.3 2.4 0.3 3.5 20.1 14.6 -1.6 7.2 8.6 18.6 -4.2 6.7 9.5 12.3 28.6 -11.2 12.3 -5.7 1.2 2.2 10.6 6.3 41.3 35.9 5.2 15.6 2.2 15.9 18.7 48.0 36.3 -18.6 |
The sample that indicates " * " is not within the scope of the invention.
Claims (5)
1. a dielectric ceramic material comprises the sosoloid that its principal crystalline phase contains perovskite crystal, and this perovskite crystal comprises the composite oxides of Ba, Sr, Mg, W and rare earth element at least,
Wherein the oxide compound of these metallic elements is represented as aBaObSrOcMgOdWO with the form of the mol ratio of metal oxide
3ERE
2O
x, 3≤x≤4 wherein, RE represents rare earth element, factor a, b, c, d and e satisfy following relationship:
0.35≤a≤0.55，
0.01≤b≤0.25，
0.10≤c≤0.30，
0.15≤d≤0.35，
0.01≤e≤0.20, and
a+b+d+c+e＝1。
2. according to the dielectric ceramic material of claim 1, wherein: the content of perovskite crystal is at least 90 volume %.
3. according to the dielectric ceramic material of claim 1, wherein: rare earth element is Yb.
4. according to the dielectric ceramic material of claim 1, wherein: contain as metallic element based on MnO
2Manganese, its content is 0.01～2 weight %.
5. a dielectric resonator comprises each described dielectric ceramic material in the claim 1 to 4, and wherein said dielectric ceramic material is arranged between a pair of input and output terminal, to work by electromagnetic coupled.
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|---|---|---|---|
| CN 01137711 CN1264779C (en) | 2001-10-31 | 2001-10-31 | Dielectric ceramic material and dielectric resonator with the material |
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|---|---|---|---|
| CN 01137711 CN1264779C (en) | 2001-10-31 | 2001-10-31 | Dielectric ceramic material and dielectric resonator with the material |
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|---|---|---|---|---|
| KR20180111505A (en) | 2017-03-31 | 2018-10-11 | 강릉원주대학교산학협력단 | BMW based microwave dielectric ceramics |
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| KR20180111505A (en) | 2017-03-31 | 2018-10-11 | 강릉원주대학교산학협력단 | BMW based microwave dielectric ceramics |
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