CN1071722C - Dielectric ceramic compositions - Google Patents
Dielectric ceramic compositions Download PDFInfo
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- CN1071722C CN1071722C CN98100378A CN98100378A CN1071722C CN 1071722 C CN1071722 C CN 1071722C CN 98100378 A CN98100378 A CN 98100378A CN 98100378 A CN98100378 A CN 98100378A CN 1071722 C CN1071722 C CN 1071722C
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01P—WAVEGUIDES; RESONATORS, LINES, OR OTHER DEVICES OF THE WAVEGUIDE TYPE
- H01P7/00—Resonators of the waveguide type
- H01P7/10—Dielectric resonators
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/495—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
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Abstract
A dielectric ceramic composition for microwave applications, comprises compound of formula: B'B''2O6 (I) (where B' = metal selected from Mg, Co, Mn, Ni and Zn; and B'' = Nb or Ta;) and contains 0.05-2 wt% of an additive; preferably comprising one or more selected from: CuO, V2O5, La2O3, Sb2O5, WO3, MgO, SrCO3, ZnO and Bi2O3.
Description
The present invention relates to be used for the dielectric ceramic composition of microwave, particularly the dielectric ceramic composition of on such as microwave equipment, using with the dielectric resonator of working in certain microwave frequency band.
Recently, the development of telecommunication such as mobile communication and satellite communication has caused growing interest to the dielectric ceramic equipment that is used for microwave.The mobile communication scheme that particularly comprises automobile telephone, cell phone, pager and GPS (global positioning system (GPS)) has adopted microwave dielectric material and has required these materials to have various electricity and physicals, as high-k ε, high quality factor Q, little temperature coefficient of resonance frequency (Tf) and good sintering character.
In the past, the research of the dielectric combination used of relevant microwave concentrated on TiO
2The type dielectric materials.Therefore, this has just determined TiO
2The dielectric materials of type such as Ba
2Ti
9O
20, (Zr, Sn) TiO
4, BaO-Re
2O
3-TiO
2Rare earth element) and BaO-Nd (Re:
2O
3-TiO
2(BNT type) and dielectric material such as Ba (Mg with complicated perovskite structure
1/3Ta
2/3) O
3, Ba (Zn
1/3Ta
2/3) O
3And Ba (Mg
1/3Nb
2/3) O
3Equally become the material that is suitable for above-mentioned application.In addition, recently very active for the research of novel dielectric materials.This type material is made of two or more sosoloid with ceramics component of perovskite structure.
Yet,,, cause in application, existing a lot of problems under high frequency because it has less than the quality factor q of other dielectric material and the resonant frequency below 1GHz limitedly for the dielectric material of BNT type.In addition, Nb
2O
3It is a kind of relatively costly rare-earth oxide.
(Zr, Sn) TiO)
4The dielectric material of type is because its high quality factor Q and stable temperature profile have obtained widespread use.Its specific inductivity is 30～40, and the Q value is about 8000 at 4GHz, the temperature factor (ε of resonant frequency
f) be-30～+ 30ppm/ ℃.But, adopt this kind material of common solid reaction process preparation to need at ability sintering more than 1600 ℃, and at no sintering agent such as CuO, CO
2O
3, ZnO and analogue situation under be difficult to realize low-temperature sintering.Yet the physicals that adds affiliation deterioration stupalith of sintering agent.
Although many liquid phase process are used to micro mist synthetic (as sol-gel, alkoxide and coprecipitation method), these methods are too complicated and be difficult to realize economically, thereby cause the raising of product cost.
The dielectric material of complicated perovskite type ceramic composition is as Ba (Zn
1/3Ta
2/3) O
3Also be difficult to sintering, because of its sintering temperature is higher than 1550 ℃.In addition, when adding such as BaZrO
3With Mn etc. when reducing sintering temperature, many processing parameters are restive.
When the size of electronics such as delectric filter diminished gradually, multilayer device just arose at the historic moment at miniaturization.But the production requirement dielectric materials and the electrode of this device can burn altogether.In order to adopt the low dielectric utmost points such as Ag, Cu, dielectric materials must have the low frit performance.Therefore, still need develop and have good sintering character and simple composition and possess simultaneously and the suitable novel dielectric ceramic material of traditional dielectric ceramic performance that is used for microwave.
This research concentrates on ABO
3Type binary system material, there is a kind of ion in this kind material and has three-dimensional complicated perovskite structure in the B position.Therefore, dielectric ceramic composition of the present invention has and the similar dielectric properties of the ceramic composition of complicated perovskite structure such as specific inductivity and quality factor q, but its sintering temperature is lower than the sintering temperature of traditional complicated perovskite structure.
Therefore, the purpose of this invention provides the dielectric ceramic composition with the required electricity of microwave application and physicals, and it can overcome above-mentioned restriction on related process with not enough.
Other characteristic and advantage of the present invention will be illustrated in the following description, and a part wherein is apparent or understand by the practice of invention by description.Purpose of the present invention and other advantage will be elaborated and realize by specification sheets and the specified structure of claims in this article.
In order to obtain above-mentioned purpose and advantage, the invention provides a kind of dielectric ceramic composition that is used for microwave.This kind composition is basically by Formula B ' B
2" O
6Form, wherein B ' element is at least a element among Mg, Ca, Co, Mn, Ni and the Zn, B, and " element is at least a among Nb and the Ta.
B ' B shown in table 1 and the table 2 "
2O
6The experimental result of type dielectric ceramic material shows, B ' Ta
2O
6The temperature coefficient of resonance frequency of section bar material is B ' Nb just
2O
6Type for negative.Therefore, by design B ' Nb
2O
6Type and B ' Ta
2O
6The suitable mole proportioning of type dielectric material prepare sosoloid can adjust temperature coefficient of resonance frequency be approach zero on the occasion of or negative value.
In order to improve dielectric characteristics and to reduce sintering temperature, in dielectric ceramic composition, add various additives usually.For example, MnCO
3, MgO, SrCO
3Or additive such as ZnO improves dielectric characteristics, and the oxide compound of some other low-melting material such as glass Pb, Bi, V can reduce sintering temperature and make the composition that will be sintered form liquid phase.
When the addition of oxide compound be less than the said composition gross weight 0.05% the time be inoperative, but when the content of oxide compound is higher than 2.0%, may cause the dielectric properties deterioration mutually because of forming second.Therefore, content of additive is preferably 0.05%～2.0% of dielectric combination gross weight of the present invention in the present invention.
More than general description and below to elaborate be exemplary and indicative, purpose is for the invention provides a deep explanation.
Elaborating of preferred embodiment
Embodiment 1
With the pure Nb of atomizing
2O
3Or Ta
2O
5, B ' O (B '=Mg, Zn, Co, Ni), Mn
3O
4Or Ca-CO
3Be raw material, mix with the pure water ball milling back of weighing, and abrading-ball adopts ZrO
2Ball.After the wet-milling 24 hours, with the particle layering to suppress to press proportion to the hot plate of mixture fast spraying.Dried powder is calcined 2 hours down to obtain B ' Nb at 900 to 1050 ℃ in aluminum oxide pincers pot
2O
6Or B ' Ta
2O
6Powder.And then the powder after will calcining in same ball mill with pure water ball milling 24 hours.In baking oven under 100 ℃ after drying under the appropriate humidity, base-material is at 1000kg/cm
2Forming under the pressure is the disk of 10mm * 3～4mm and 1150～1160 ℃ of following sintering 2 hours.Calcining and agglomerating temperature rise rate are 5 ℃ of per minutes, cool off powder then.
Can prepare the various composite sample shown in table 1 and the table 2 by above technology.The Q value of each sample and specific inductivity (ε) record by the post resonance method of network analyzer (HP8510) with Hakki-Coleman, and the high Q value of some samples is to record with the cavity method.
Table 1 B ' Nb
2O
6Dielectric characteristics
| Mixture | Sintering temperature (℃) | Specific inductivity | Q×f | Temperature factor (the T of resonant frequency f) |
| MgNb 2O 6 | 1300 | 21.4 | 93800 | -51.4 |
| CaNb 2O 6 | 1400 | 19.6 | 21500 | 13.3 |
| MnNb 2O 6 | 1150 | 22.4 | 34300 | -59.6 |
| CoNb 2O 6 | 1100 | 22.8 | 11300 | -44.7 |
| NiNb 2O 6 | 1150 | 22.6 | 40100 | -38.0 |
| ZnNb 2O 6 | 1150 | 25.0 | 83700 | -61.3 |
Table 2 B ' Ta
2O
6Dielectric characteristics
| Mixture | Sintering temperature (℃) | Specific inductivity | Q×f | Temperature factor (the T of resonant frequency f) |
| MgTa 2O 6 | 1550 | 30.3 | 59600 | 30.2 |
| CaTa 2O 6 | 1600 | 21.2 | 11600 | 1.0 |
| MnTa 2O 6 | 1350 | 20.3 | 16500 | -43.9 |
| CoTa 2O 6 | 1500 | 29.0 | 2300 | 3.0 |
| NiTa 2O 6 | 1600 | 25.0 | 31000 | 35.0 |
| ZnTa 2O 6 | 1350 | 37.6 | 65300 | 10.8 |
The Q value changes obviously because of sintering temperature is different, and therefore, sintering temperature is defined as obtaining through repeated experiments the temperature of the highest Q value.DIELECTRIC CONSTANT is measured under the fixed sintering temperature, because it does not change with sintering temperature.
Table 1 and table 2 show, B ' Nb
2O
6The dielectric material of type has little Q value, is approximately 20～25; ZnNb
2O
6And MgNb
2O
6The Q value (Q * f) and the dielectric Q value of complicated uhligite are quite.Complicated uhligite dielectric material is at 1500 ℃ of following sintering and ZnNb
2O
6And MgNb
2O
6Sintering under 1100～1130 ℃ lesser temps then.Specifically, ZnNb wherein
2O
6Because of its excellent dielectric properties is suitable for being used as dielectric medium and can realizing low-temperature sintering under high frequency.As ZnNb
2O
6Specific inductivity can reach 25, the Q value reaches 83700 (10GHz), sintering temperature is 1150 ℃.
B ' Ta
2O
6The type dielectric material is with respect to B ' Nb
2O
6Type has higher sintering temperature, lower slightly Q value and slightly high specific inductivity.For example, ZnTa
2O
6Specific inductivity be 38, the Q value is 65000 (10GHz), with traditional (Zr, Sn) TiO
4Material is compared, and has better dielectric characteristics and lower sintering temperature.In addition, expection ZnTa
2O
6Sintering temperature and (Zr, Sn) TiO
4Sintering temperature when material adds sintering agent or adopts as complicated technologies such as sol-gel methodes is similar.
Embodiment 2
B ' Nb
2O
6The preparation of type powder and metering system are identical with embodiment 1.Powder after the calcining according to predetermined proportioning weighing and in above-mentioned same ball grinding machine with pure water ball milling 24 hours.After drying under the appropriate humidity, base-material is at 1000kg/cm in temperature is 100 ℃ baking oven
2Forming under the pressure is the disk of 10mm * 3～4mm and 1200～1400 ℃ of following sintering 2 hours.Calcining and agglomerating temperature rise rate are 5 ℃ of per minutes, cool off powder then.
The sample that can prepare the various mixtures shown in table 3 and the table 4 by above technology.The Q value of each sample and DIELECTRIC CONSTANT record by the post resonance method of network analyzer (HP8510) with Hakki-Coleman, and the high Q value of some samples records with the cavity method.
The dielectric characteristics of table 3 solid solution composition of the present invention
| Mixture | Specific inductivity | Q×f | Temperature factor (the T of resonant frequency f) |
| Mg(Nb 0.1Ta 0.9) 2O 6 | 21.7 | 80100 | -23.2 |
| Mg(Nb 0.2Ta 0.9) 2O 6 | 18.8 | 56300 | -45.5 |
| Mg(Nb 0.4Ta 0.6) 2O 6 | 19.4 | 64400 | -45.7 |
| Mg(Nb 0.6Ta 0.4) 2O 6 | 20.0 | 69600 | -51.5 |
| Mg(Nb 0.8Ta 0.2) 2O 6 | 20.3 | 93000 | -53.7 |
| Zn(Nb 0.1Ta 0.9) 2O 6 | 37.1 | 38000 | -5.7 |
| Zn(Nb 0.3Ta 0.7) 2O 6 | 33.6 | 48100 | 3.4 |
| Zn(Nb 0.4Ta 0.6) 2O 6 | 33.6 | 45000 | -5.8 |
| Zn(Nb 0.5Ta 0.5) 2O 6 | 30.5 | 53000 | -8.0 |
| Zn(Nb 0.6Ta 0.4) 2O 6 | 24.0 | 54000 | -51.6 |
| Ni(Nb 0.4Ta 0.6) 2O 6 | 23.6 | 27000 | 5.9 |
| Ni(Nb 0.5Ta 0.5) 2O 6 | 23.1 | 29000 | 1.3 |
| Ni(Nb 0.6Ta 0.4) 2O 6 | 22.7 | 35000 | -3.6 |
The dielectric characteristics of table 4 solid solution composition of the present invention
| Mixture | ε | Q×f | Temperature factor (the T of resonant frequency f) |
| Ca 1/3Zn 2/3Nb 2O 6 | 19.5 | 24000 | -52.5 |
| Ca 1/3Ni 2/3Nb 2O 6 | 19.0 | 30000 | -46.8 |
| Mg 1/3Zn 2/3(Nb 0.5Ta 0.5) 2O 6 | 30.4 | 56000 | -51.3 |
| Mg 1/2Zn 1/2(Nb 0.5Ta 0.5) 2O 6 | 28.7 | 59200 | -52.5 |
| Mg 2/3Zn 1/3(Nb 0.5Ta 0.5) 2O 6 | 25.9 | 57600 | -53.0 |
The Q value changes obviously because of sintering temperature is different, and therefore, sintering temperature is defined as obtaining through repeated experiments the temperature of the highest Q value, and this temperature is between 1250 to 1350 ℃.Sintering temperature improves with the increase of Ta content.
In B ' NbTa type sosoloid, B ' shown in the table 3 is the monometallic ion, and B ' shown in the table 4 is the bimetal ion.
Clearly, for the sosoloid of ZnNbTa and NiNbTa, its temperature coefficient of resonance frequency is between-10 ℃～+ 10 ℃.Zn (Nb
0.6Ta
0.4)
2O
6Specific inductivity extremely low because of the transformation of crystalline structure.When the molfraction of Ta was 0.5, crystalline structure had tangible influence to the temperature factor of specific inductivity and resonant frequency, but it does not influence the Q value.
Embodiment 3
When adopting as after the same way as of embodiment 1 and embodiment 2 prepares the dielectric ceramic composition of powder-type adding La
2O
3, Sb
2O
5, Bi
2O
3, CuO, ZnO, MgO, SrCO
3, MnCO
3, WO
3And V
2O
5In at least a.Powdered mixture and water with 1: 1 mixed after, at ZrO
2Wet-milling is 24 hours in the ball crusher.Calcined 2 hours at 900～1050 ℃ with mixture rapid drying and in aluminum oxide pincers pot then.Ball milling 24 hours and be sprayed on the hot plate after, base-material is at 1000kg/cm
2Forming under the pressure is the disk of 10mm * 3mm and 1150～1400 ℃ of following sintering 2～6 hours.Calcining and agglomerating temperature rise rate are 5 ℃ of per minutes, dried powder then.
By above technology, can prepare the sample of the different composite thing shown in the table 5.The Q value of each sample and DIELECTRIC CONSTANT record by the post resonance method of network analyzer (HP8510) with Hakki-Coleman, and the high Q value of some samples records with the cavity method.
Table 5 the present invention adds the dielectric characteristics of the dielectric ceramic composition of additive
| Mixture | Additive (wt%) | ε | T f | Q×f | Sintering temperature (℃) |
| ZnNb 2O 6 | CuO(1) | 21.5 | -60.7 | 61700 | 950 |
| ZnNb 2O 6 | CuO(2) | 19.0 | -70.5 | 29400 | 900 |
| ZnNb 2O 6 | Sb 2O 5(1) | 19.8 | -32.5 | 25000 | 875 |
| ZnNb 2O 6 | Bi 2O 3(1) | 22.3 | -60.9 | 63200 | 1000 |
| ZnNb 2O 6 | V 2O 5(1) | 20.0 | -81.0 | 16880 | 900 |
| Zn(Nb 0.4Ta 0.6) | V 2O 5(1) | 28.2 | -19.0 | 21000 | 950 |
| Zn(Nb 0.4Ta 0.6) | CuO(1) | 30.1 | -40.6 | 20500 | 950 |
| Zn(Nb 0.4Ta 0.6) 2O 6 | CuO+Bi 2O 3(1) | 32.3 | -5.2 | 19800 | 950 |
| Zn(Nb 0.5Ta 0.5) 2O 6 | MnCO 3(0.1) | 36.2 | -3.1 | 59000 | 1350 |
| Zn(Nb 0.5Ta 0.5) 2O 6 | La 2O 3(1) | 35.5 | -5.0 | 44700 | 1350 |
| Zn(Nb 0.5Ta 0.5) 2O 6 | WO 3(0.1) | 30.6 | 2.5 | 45500 | 1350 |
| Zn(Nb 0.5Ta 0.5) 2O 6 | MgO(0.1) | 30.2 | -6.4 | 56300 | 1350 |
| Zn(Nb 0.5Ta 0.5) 2O 6 | ZnO(0.1) | 33.5 | -1.4 | 45400 | 1300 |
| Zn(Nb 0.5Ta 0.5) 2O 6 | SrCO 3(0.1) | 38.2 | 5.9 | 48900 | 1350 |
As shown in table 5, by to ZnNb
2O
6Or Zn (Nb, Ta)
2O
6Add such as CuO, V in the dielectric material
2O
5, Bi
2O
3Or Sb
2O
5Deng oxide compound, sintering temperature can successfully be reduced to below 900 ℃.Resulting composition has splendid Q value, is about 2000 (10GHz), is higher than the sintering temperature of other any compound that obtains under identical sintering temperature.
In other cases, by adding glass, sintering temperature is 1300 ℃ BaOPbO-Nd
2O
3-TiO
2Dielectric material can be at 900 ℃ of sintering, and its specific inductivity is 67, and the Q value is 2900 (5.1GHz), and the temperature factor of resonant frequency is 20ppm/ ℃.In addition, sintering temperature is 1350 CaZrO
3Dielectric material adds that its sintering temperature is 980 ℃ behind the glass, and its specific inductivity is 25, and the Q value is 3500 (5GHz), and the temperature factor of resonant frequency is ± 10ppm/ ℃.Because Bi itself has 825 ℃ low melting point, by adding CuO, V
2O
5Can be successfully with BiNbO
4The sintering temperature of dielectric material is reduced to 875 ℃.The specific inductivity of resulting composition is 43, and the Q value is 10000 (4.3GHz), and the temperature factor of resonant frequency is approximately 38.
In addition, add such as MnCO
3, oxide compounds such as MgO, ZnO can improve Zn (Nb, Ta)
2O
6The Q value of sosoloid.Therefore, with respect to used routine (Zn, Sn) TiO
4Dielectric material, the present invention has extremely excellent dielectric characteristics.
By reducing below the sintering temperature to 900 ℃, just might in microminiaturized electronics, use cheaply metal electrode realization multilayer technology such as Ag or Cu.
As mentioned above, compare with the traditional dielectric ceramic composition that comprises complicated perovskite structure that is used for microwave, dielectric combination of the present invention has similar dielectric characteristics, and as the Q value, and it can and can easily prepare by open-and-shut prescription at low relatively sintering temperature.
For those skilled in the art, under the situation that does not depart from essence of the present invention and scope, can carry out various adjustment and change to high frequency dielectric ceramic composition of the present invention, therefore, the present invention will be encompassed in adjustment and the change that this invention is made in claims scope.
Claims (9)
1. dielectric ceramic composition that is used for microwave, it is B ' B by formula basically
2" O
6Mixture form, wherein B ' element is at least a element of selecting from Mg, Ca, Co, Mn, Ni and Zn, " element is Nb or Ta to B, and said composition comprises also that to account for composition weight per-cent be 0.05%～2.0% additive, and described additive is by following compounds CuO, V
2O
5, La
2O
3, Sb
2O
3, WO
3, MgO, SrCO
3, ZnO, Bi
2O
3And MnCO
3In at least a composition.
2. dielectric ceramic composition that is used for the microwave frequency section is basically by B ' Nb
2O
6And B ' Ta
2O
6By certain molfraction, 0.1～0.8: 0.2～0.9, mixing the sosoloid that forms constitutes, wherein B ' element is at least a element of selecting from Mg, Ca, Co, Mn, Ni and Zn, said composition comprises that also accounting for composition weight per-cent is 0.05%～2.0% additive, and described additive is by following compounds CuO, V
2O
5, La
2O
3, Sb
2O
5, WO
3, MgO, SrCO
3, ZnO, Bi
2O
3And MnCO
3In at least a composition.
3. dielectric ceramic composition as claimed in claim 2 is basically by B ' Nb
2O
6And B ' Ta
2O
6Mix the sosoloid that forms by certain molfraction and constitute, wherein B ' element is the Zn element, and said composition comprises that also accounting for composition weight per-cent is 0.05%～2.0% additive.
4. dielectric ceramic composition as claimed in claim 3, wherein ZnNb
2O
6Molfraction be 0.2～0.5.
5. dielectric ceramic composition as claimed in claim 2 is basically by B ' Nb
2O
6And B ' Ta
2O
6Mix the sosoloid that forms by certain molfraction and constitute, wherein B ' is the Mg element, and said composition comprises that also accounting for composition weight per-cent is 0.05%～2.0% additive.
6. dielectric ceramic composition as claimed in claim 5, wherein MgNb
2O
6Molfraction less than 0.1.
7. dielectric ceramic composition as claimed in claim 2 is basically by B ' Nb
2O
6And B ' Ta
2O
6Mix the sosoloid that forms by certain molfraction and constitute, wherein B ' element is at least a element among Zn, the Mg, and said composition comprises that also accounting for composition weight per-cent is 0.05%～2.0% additive.
8. dielectric ceramic composition as claimed in claim 3, wherein additive comprises following compounds CuO, V
2O
5, La
2O
3, Sb
2O
5, WO
3, MgO, SrCO
3, ZnO, Bi
2O
3In at least a.
9. dielectric ceramic composition as claimed in claim 5, wherein additive comprises following compounds CuO, V
2O
5, La
2O
3, Sb
2O
3, WO
3, MgO, SrCO
3, ZnO, Bi
2O
3In at least a.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1942/97 | 1997-01-23 | ||
| KR1019970001942A KR100203846B1 (en) | 1996-06-11 | 1997-01-23 | Dielectric ceramic composition |
| KR1942/1997 | 1997-01-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1189480A CN1189480A (en) | 1998-08-05 |
| CN1071722C true CN1071722C (en) | 2001-09-26 |
Family
ID=19495400
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|---|---|---|---|
| CN98100378A Expired - Fee Related CN1071722C (en) | 1997-01-23 | 1998-01-23 | Dielectric ceramic compositions |
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|---|---|
| CN (1) | CN1071722C (en) |
| DE (1) | DE19800353C2 (en) |
| IN (1) | IN190005B (en) |
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|---|---|---|---|---|
| KR100199301B1 (en) * | 1997-04-09 | 1999-06-15 | 김병규 | Dielectric ceramic composition |
| CN1298668C (en) * | 2004-12-31 | 2007-02-07 | 清华大学 | Low-temperature sintered sosoloid microwave dielectric ceramic material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5274913A (en) * | 1975-10-15 | 1977-06-23 | Dresser Europe Sa | Fluid distributing means |
| JPH046632A (en) * | 1990-04-24 | 1992-01-10 | Olympus Optical Co Ltd | Focus detector |
-
1997
- 1997-12-26 IN IN752BO1997 patent/IN190005B/en unknown
-
1998
- 1998-01-07 DE DE19800353A patent/DE19800353C2/en not_active Expired - Fee Related
- 1998-01-23 CN CN98100378A patent/CN1071722C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5274913A (en) * | 1975-10-15 | 1977-06-23 | Dresser Europe Sa | Fluid distributing means |
| JPH046632A (en) * | 1990-04-24 | 1992-01-10 | Olympus Optical Co Ltd | Focus detector |
Also Published As
| Publication number | Publication date |
|---|---|
| DE19800353C2 (en) | 2001-10-11 |
| CN1189480A (en) | 1998-08-05 |
| IN190005B (en) | 2003-05-31 |
| DE19800353A1 (en) | 1998-07-30 |
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