KR100808472B1 - Dielectric ceramic compositions and manufacturing method thereof - Google Patents
Dielectric ceramic compositions and manufacturing method thereof Download PDFInfo
- Publication number
- KR100808472B1 KR100808472B1 KR1020060120341A KR20060120341A KR100808472B1 KR 100808472 B1 KR100808472 B1 KR 100808472B1 KR 1020060120341 A KR1020060120341 A KR 1020060120341A KR 20060120341 A KR20060120341 A KR 20060120341A KR 100808472 B1 KR100808472 B1 KR 100808472B1
- Authority
- KR
- South Korea
- Prior art keywords
- composition
- dielectric
- sintering
- mixture
- zno
- Prior art date
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/12—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances ceramics
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/6261—Milling
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/6303—Inorganic additives
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3409—Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
Abstract
Description
본 발명은 유전손실이 작고 유전율이 크며 온도 안정적인, 또한 저온 소결이 가능한 유전체 세라믹 조성물에 관한 것으로서, 더욱 상세하게는 은, 구리, 은/팔라듐 등의 금속전극과 동시에 소성하여 캐패시터, 필터 등의 전자부품 또는 그것을 내장한 기판 등 내부 도체를 갖는 전자부품에 적합한 유전체 세라믹 조성물과 이를 제조하는 방법에 관한 것이다.The present invention relates to a dielectric ceramic composition having a low dielectric loss, a high dielectric constant, temperature stability, and low temperature sintering. More specifically, the present invention relates to a method of manufacturing a ceramic, such as silver, copper, silver / palladium, and the like. The present invention relates to a dielectric ceramic composition suitable for an electronic component having an internal conductor such as a component or a substrate containing the same, and a method of manufacturing the same.
최근 전자 및 통신기기들의 소형화가 급격히 진행되면서 여기에 사용되는 전자부품들도 적층화 또는 칩(chip)화 되고 있다. 다시 말해, 휴대 전화, 위성 방송 등 전자파를 이용한 통신의 발전에 따라 단말기기의 소형화가 요구되며 이로 인해 기기를 구성한 개별 부품의 소형화가 필요하다.Recently, as the miniaturization of electronic and communication devices has progressed rapidly, the electronic components used therein have also been stacked or chipped. In other words, with the development of communication using electromagnetic waves such as mobile phones and satellite broadcasts, miniaturization of terminal devices is required, which requires miniaturization of individual components constituting the device.
대표적인 적층 부품으로는 캐패시터(capacitor)를 들 수 있으며, 이동통신용 단말기 등에는 필터(filter), 커플러(Coupler), 듀플렉서(duplexer), 오실레이 터(oscillator), MCM(Multichip Module) 등이 이용되고 있다.Representative laminated parts include a capacitor, and a mobile communication terminal includes a filter, a coupler, a duplexer, an oscillator, and a multichip module. have.
이러한 적층 부품들은 여러 층의 유전체와 내부전극(inner electrode)으로 이루어져 있으며, 이들 부품을 제조하기 위해서는 유전체층을 얇은 테입(tape)으로 만들고 그 위에 내부전극을 인쇄(printing)한 후 이들을 여러 층 적층하여 소결(firing)하는 과정을 거쳐야 한다.These laminated parts consist of several layers of dielectric and inner electrode. To manufacture these parts, the dielectric layer is made into a thin tape, and the internal electrode is printed on it, and then the layers are laminated. It must go through the process of firing.
따라서, 적층소자에 사용되는 유전체는 응용에 적합한 유전특성을 가져야 함과 동시에 전극과 함께 소성할 수 있어야 한다. 유전체에 요구되는 유전특성으로는 캐패시턴스에 관계되는 높은 유전율(εr)과, 유전손실(tanδ), 그리고 온도변화에 따른 캐패시턴스의 변화(TCC)가 작아야 하는 것 등이 있다.Therefore, the dielectric used for the laminated device must have dielectric properties suitable for the application and be able to be fired together with the electrode. Dielectric properties required for dielectrics include a high permittivity (ε r ) related to capacitance, a dielectric loss (tanδ), and a change in capacitance (TCC) with temperature change.
한편, 적층소자에 사용되는 내부전극으로는 은, 구리, 니켈, 팔라듐, 백금, 금 및 이들의 합금이 사용되며, 이들 금속 전극재료와 함께 소성하는 세라믹 유전체의 소결온도와 특성에 따라 사용하는 금속 전극재료가 정해진다.On the other hand, silver, copper, nickel, palladium, platinum, gold, and alloys thereof are used as internal electrodes used in the stacked devices, and metals are used according to the sintering temperature and characteristics of ceramic dielectrics fired together with these metal electrode materials. The electrode material is determined.
예를 들면 은(Ag) 전극은 그 특성이 가장 낮은 비저항(1.62×10-4Ωcm)을 가지고 있으면서 저가이기는 하지만 융점이 961℃로 낮기 때문에 소결온도가 950℃ 이상인 세라믹 유전체에는 사용할 수 없다. 한편, 금(Au), 백금(Pt) 또는 팔라듐(Pd)의 경우는 융점은 높지만 가격이 비싼 단점이 있기 때문에 그 사용이 제한적이다. 그리고 구리(Cu)나 니켈 전극은 산화저항(oxidation resistance)이 급격히 떨어지므로 10-9 atm 정도의 낮은 산소분압(oxygen partial pressure)에서 소성이 이루어져야 하지만, 대부분의 유전체 세라믹 조성물은 낮은 산소분압 하에서 열처 리할 경우 유전손실(dielectric loss)이 급격히 증가하여 캐패시터로 사용할 수 없다는 문제점이 있다. For example, silver (Ag) electrodes have the lowest specific resistance (1.62 x 10 -4 Ωcm) and are inexpensive, but they cannot be used in ceramic dielectrics with sintering temperatures above 950 ° C because they have a low melting point of 961 ° C. On the other hand, gold (Au), platinum (Pt) or palladium (Pd) is a high melting point, but the price is expensive because of its disadvantages, its use is limited. And since copper (Cu) and nickel electrodes have a sharp drop in oxidation resistance, they should be fired at a low oxygen partial pressure (10 -9 atm), but most dielectric ceramic compositions are heated under low oxygen partial pressure. In this case, there is a problem in that the dielectric loss is rapidly increased and it cannot be used as a capacitor.
한편, 현재 적층부품에 사용되고 있는 세라믹 유전체 조성물은 대부분 BaTiO3가 기본조성이며, 순수 BaTiO3은 소결온도가 1350℃ 이상에서 열처리하여도 90% 이상의 높은 밀도를 얻기 힘들고 소결 중에 미세입자 성장이 일어나 유전특성이 떨어지는 문제가 있다. 소결첨가제를 사용하면 950℃까지 저온소성으로 치밀한 유전체를 얻을 수 있으나 이상 입성장으로 물성은 저하된다. 일반적으로 저온 소성을 위한 소결첨가제로는 저온에서 점도가 낮고 액상이 균일하게 분포하여야 하며 소결 후 액상이 BaTiO3과 반응하지 않아야 하고, 이차상을 형성하는 경우 이차상이 높은 유전율을 가지는 것이 바람직한데 이를 위해서 첨가되는 유전체 소결조제는 Pb계 첨가물과 무연조성의 Bi계 첨가물이 알려져 있다. 하지만 Pb계 유리는 저온소결할 경우 저유전율의 이차상이 형성되며 현저한 입자 성장을 일으키는 문제점이 있으며, Bi계 유리는 저온 소결후에 밀도가 낮고 유전율이 낮아진다는 문제가 있다. 이에 따라, BaTiO3를 주 조성으로 하지 않고 낮은 온도에서 소성하여 치밀한 소결체를 얻으면서도 높은 유전특성이 발현할 수 있는 새로운 유전체 조성물 및 그 제조방법이 요구되고 있다.On the other hand, the ceramic dielectric composition that is currently being used for lamination parts are most BaTiO 3 has a basic composition, the pure BaTiO 3 is the fine particles grow up in the hard sintered to obtain a high density of 90% or more by heat treatment above 1350 ℃ sintering temperature oil There is a problem of falling characteristics. When the sintering additive is used, it is possible to obtain a dense dielectric with low temperature firing up to 950 ° C, but the physical properties decrease due to abnormal grain growth. In general, as a sintering additive for low-temperature firing, low viscosity at low temperature and the liquid phase should be uniformly distributed, and after sintering, the liquid phase should not react with BaTiO 3 , and when the secondary phase is formed, the secondary phase has a high dielectric constant. Dielectric sintering aids added for this purpose are known Pb-based additives and lead-free Bi-based additives. However, when Pb-based glass is sintered at low temperature, a low dielectric constant secondary phase is formed and there is a problem of remarkable grain growth. Bi-based glass has a problem of low density and low dielectric constant after low temperature sintering. Accordingly, there is a need for a new dielectric composition and a method of manufacturing the same, which can exhibit high dielectric properties while obtaining a compact sintered body by baking at a low temperature without using BaTiO 3 as a main composition.
유전체로서 BaO-TiO2-Nb2O5계는 BaTiNb4O13, Ba3Ti4Nb4O21, Ba3Ti5Nb6O28, Ba6Ti2Nb8O30 등이 알려져 있는데, 이중 Ba6Ti2Nb8O30은 1,350℃에서 소결되며 유전율 이 68.6으로 처음 보고되었다("Dielectric properties of barium titanium niobates", G. L. Roberts et al., Journal of Materials Research, Vol. 12 (1997), pp. 526-530). 또한 양이온 Nb 자리에 Ta를 소량 첨가하면 유전율이 증가하고 온도계수가 조절되는 것으로 알려졌다. 최근에 Ba6Ti2Nb8O30은 1,325℃에서 소결한 경우 밀도가 98%이고 측정주파수 1Hz에서 유전율이 800, 유전손실이 0.035의 값을 갖는 것으로 보고되었다("Diffused ferroelectrics of Ba6Ti2Nb8O30 and Sr6Ti2Nb8O30 with filled tungsten-bronze structure", Y. Yuan, X. M. Chen, and Y. J. Wu, Journal of Applied Physics, Vol. 98 (2005), 084110).BaO-TiO 2 -Nb 2 O 5 is known as a dielectric, BaTiNb 4 O 13 , Ba 3 Ti 4 Nb 4 O 21 , Ba 3 Ti 5 Nb 6 O 28, Ba 6 Ti 2 Nb 8 O 30, etc. Ba 6 Ti 2 Nb 8 O 30 is sintered at 1,350 ° C. and first reported a dielectric constant of 68.6 (“Dielectric properties of barium titanium niobates”, GL Roberts et al., Journal of Materials Research, Vol. 12 (1997), pp 526-530). It is also known that adding a small amount of Ta to the cation Nb site increases the dielectric constant and controls the temperature coefficient. Recently, Ba 6 Ti 2 Nb 8 O 30 has been reported to have a density of 98%, a dielectric constant of 800 and a dielectric loss of 0.035 at a measurement frequency of 1 Hz when sintered at 1,325 ° C ("Diffused ferroelectrics of Ba 6 Ti 2 Nb 8 O 30 and Sr 6 Ti 2 Nb 8 O 30 with filled tungsten-bronze structure ", Y. Yuan, XM Chen, and YJ Wu, Journal of Applied Physics, Vol. 98 (2005), 084110).
따라서, 상기 조성물은 유전율이 큰 반면, 유전손실은 현저히 낮으나, 저온 소결특성에 대해서는 알려진 것이 없기 때문에 이를 개선할 필요가 있다.Therefore, the composition has a high dielectric constant, while the dielectric loss is significantly low, but there is no known about low temperature sintering properties, it is necessary to improve it.
한편, BaO-TiO2-Nb2O5계 유전체 중 Ba3Ti5Nb6O28를 주 조성으로 하고 여기에 소결조제로서 B2O3-ZnO계 유리를 포함한 유전체 세라믹 조성물이 본 발명자에 의해 기 출원되어 특허된 바 있다(대한민국 공개특허 특2002-0038333). 그러나, 여기에서 소결조제로서 사용할 수 있는 B2O3-ZnO를 함유한 유리는 무작위적으로 B2O3와 ZnO의 함량을 조절하여 첨가한 것으로서 특정의 조성식을 한정하여 그 효과의 차이를 규명하지 못했으며, 이와 같은 유리가 다른 주 조성을 갖는 BaO-TiO2-Nb2O5계 유전체 모두에 동일한 효과를 가짐을 유추할 개연성을 갖지 못하였다. On the other hand, a dielectric ceramic composition containing Ba 3 Ti 5 Nb 6 O 28 as the main composition among BaO-TiO 2 -Nb 2 O 5 based dielectrics and containing B 2 O 3 -ZnO based glass as a sintering aid is provided by the present inventors. It has been filed and patented (Korean Patent Laid-Open No. 2002-0038333). However, the glass containing B 2 O 3 -ZnO, which can be used as a sintering aid, is added by adjusting the content of B 2 O 3 and ZnO randomly, and the specific compositional formula is limited to identify the difference in the effect. It was not possible to infer that such glass had the same effect on all of the BaO—TiO 2 —Nb 2 O 5 based dielectrics having different main compositions.
또한 다른 소결조제로서 ZnO, CuO 등의 산화물 첨가제가 알려져 있는데 특정 의 조합이 특정 주 조성의 유전체에 바람직함을 인식하지 못하였다. In addition, oxide additives such as ZnO and CuO are known as other sintering aids, but it was not recognized that certain combinations are preferred for dielectrics of specific main composition.
이에, 본 발명자는 상기와 같은 종래 세라믹 유전체 조성물(BaTiO3)의 문제점을 해결하기 위해 연구노력하던 중, 유전체로서 Ba6Ti2Nb8O30를 주성분으로 하되 여기에 소결조제를 첨가한 결과, 품질계수의 향상을 도모하며 저온소결이 가능하여 은(Ag), 은/팔라듐, 구리 등의 저융점 금속전극과 동시에 소성하여 적층 또는 평면형 소자를 만들 수 있음을 알게 되어 본 발명을 완성하게 되었다.Thus, the inventors of the present invention, while trying to solve the problems of the conventional ceramic dielectric composition (BaTiO 3 ) as described above, Ba 6 Ti 2 Nb 8 O 30 as the main component, but as a result of adding a sintering aid, In order to improve the quality factor and to be sintered at a low temperature, the present invention has been found to be able to produce a laminated or planar device by simultaneously firing with low melting metal electrodes such as silver (Ag), silver / palladium, and copper.
또한, 본 발명자는 Ba6Ti2Nb8O30를 주 조성으로 하는 유전체 세라믹 조성물의 소결온도를 낮추면서 높은 유전율과 낮은 유전손실을 손상시키지 않는 방법을 모색하던 중, B2O3-ZnO 계 유리 중 특정의 조성식을 만족할 때, 또는 산화물을 혼합물로서 첨가할 때 저온소결 시 우수한 유전특성을 가짐을 알게 되어 본 발명을 완성하게 되었다. In addition, the present inventors Ba 6 Ti 2 Nb 8 O 30 for lowering the sintering temperature of the dielectric ceramic composition as the main composition while trying to find a way that does not impair the high-dielectric constant and low dielectric loss, B 2 O 3 -ZnO-based The present invention has been completed by knowing that it has excellent dielectric properties when sintering at a low temperature when satisfying a specific compositional formula in glass, or when an oxide is added as a mixture.
따라서, 본 발명의 목적은 유전율이 큰 Ba6Ti2Nb8O30를 주성분으로 하는 유전체의 높은 유전율과 낮은 유전손실 및 저온 소결특성을 만족시킬 수 있는 유전체 세라믹 조성물을 제공하는 데 있다.Accordingly, an object of the present invention is to provide a dielectric ceramic composition capable of satisfying high dielectric constant, low dielectric loss, and low temperature sintering characteristics of a dielectric material having a high dielectric constant of Ba 6 Ti 2 Nb 8 O 30 as a main component.
또한, 본 발명은 이와 같은 유전체 세라믹을 제조하는 방법을 제공하는 데도 그 목적이 있다.It is also an object of the present invention to provide a method for producing such a dielectric ceramic.
이와 같은 목적을 달성하기 위한 본 발명은 6BaO·2TiO2·4Nb2O5(Ba6Ti2Nb8O30)로 표현되는 주 조성 100중량부; 및 ZnB2O4 또는 Zn3B2O6 조성을 갖는 ZnO-B2O3계의 유리, B2O3와 CuO의 혼합물 및 B2O3와 ZnO의 혼합물 중에서 선택된 산화물 혼합물, 및 이들의 혼합물로 이루어진 군으로부터 선택된 소결조제 0.01 내지 30중량부를 포함하는 유전체 세라믹 조성물에 그 특징이 있다.
또한 본 발명은 Ba6Ti2Nb8O30로 표현되는 주 조성물을 하소하는 단계; 하소된 주 조성물에, ZnB2O4 또는 Zn3B2O6 조성을 갖는 ZnO-B2O3계의 유리, B2O3와 CuO의 혼합물 및 B2O3와 ZnO의 혼합물 중에서 선택된 산화물 혼합물 및 이들의 혼합물로 이루어진 군으로부터 선택된 소결조제를 동시에 첨가하여 혼합하는 단계; 상기 혼합물을 분쇄하여 성형하는 단계; 및 상기 성형물을 1,000℃ 이하에서 소결하는 단계를 포함하는 유전체 세라믹의 제조방법에도 그 특징이 있다.The present invention for achieving the object, the main composition is 100 parts by weight, expressed as 6BaO · 2TiO 2 · 4Nb 2 O 5 (Ba 6 Ti 2 Nb 8 O 30); And ZnO-B 2 O 3 based glass having a ZnB 2 O 4 or Zn 3 B 2 O 6 composition, B 2 O 3 and Mixture of CuO and with B 2 O 3 The dielectric ceramic composition comprises 0.01 to 30 parts by weight of an sintering aid selected from the group consisting of oxide mixtures selected from the mixture of ZnO, and mixtures thereof.
In addition, the present invention comprises the steps of calcining the main composition represented by Ba 6 Ti 2 Nb 8 O 30 ; In the calcined main composition, a ZnO-B 2 O 3 based glass having a ZnB 2 O 4 or Zn 3 B 2 O 6 composition, B 2 O 3 and Mixture of CuO and with B 2 O 3 Simultaneously adding and mixing an sintering aid selected from the group consisting of an oxide mixture selected from the mixture of ZnO and a mixture thereof; Pulverizing and molding the mixture; And a method of manufacturing a dielectric ceramic including sintering the molding at 1,000 ° C. or less.
삭제delete
삭제delete
이와 같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.
본 발명에 따른 마이크로파 유전체 세라믹 조성물은 BaO와 TiO2, 그리고 Nb2O5가 6 : 2 : 4의 비율로 이루어진 Ba6Ti2Nb8O30을 주 조성으로 하고, 여기에 특정의 조성식을 갖는 ZnO-B2O3 유리, 산화물 혼합물 또는 이들의 혼합물을 첨가하여 제 조된다. In the microwave dielectric ceramic composition according to the present invention, BaO, TiO 2 , and Ba 6 Ti 2 Nb 8 O 30 having a ratio of 6: 2: 4 of BaO, TiO 2 , and Nb 2 O 5 have a specific compositional formula. Prepared by the addition of ZnO-B 2 O 3 glass, oxide mixtures or mixtures thereof.
여기서 특정의 조성식을 갖는 유리는 ZnO와 B2O3가 일정 몰비를 가지면서 혼합될 경우 ZnB2O4, Zn3B2O6 또는 ZnB4O7의 결정화 조성을 가질 수 있는데, 이들 중에서도 ZnB2O4 또는 Zn3B2O6를 의미한다. Here, the glass having a specific compositional formula is ZnB 2 O 4 , when ZnO and B 2 O 3 are mixed with a certain molar ratio, It may have a crystallization composition of Zn 3 B 2 O 6 or ZnB 4 O 7 , among these means ZnB 2 O 4 or Zn 3 B 2 O 6 .
ZnO-B2O3 유리는 통상 ZnO와 B2O3를 건식혼합한 후 900 내지 1,400℃ 정도의 온도에서 녹인 후 급냉시켜 제조되는 것으로서, 이때 두 산화물의 몰비에 따라서 여러 종류의 조성식을 갖는 유리가 얻어질 수 있다. ZnO-B 2 O 3 glass is usually manufactured by dry mixing ZnO and B 2 O 3 at a temperature of about 900 to 1,400 ° C. and then quenching the glass, and having various kinds of compositional formulas depending on the molar ratio of the two oxides. Can be obtained.
본 발명에서는 다양한 ZnO-B2O3 유리 중에서 Ba6Ti2Nb8O30을 주 조성에 가장 적합한 유리를 선택한 것으로서, 모든 ZnO-B2O3 계 유리가 Ba6Ti2Nb8O30 유전체의 고유전율을 손상시키지 않으면서 저온소결을 가능하게 하지는 못하였다. In the present invention, the glass most suitable for the main composition of Ba 6 Ti 2 Nb 8 O 30 among various ZnO-B 2 O 3 glass is selected, and all ZnO-B 2 O 3 based glass is Ba 6 Ti 2 Nb 8 O 30 dielectric Low temperature sintering was not possible without compromising the high dielectric constant of.
가장 효과적인 ZnO-B2O3 계 유리는 ZnB2O4 와 Zn3B2O6 조성을 갖는 유리였으며, ZnB4O7 조성의 유리의 경우 B2O3 함량이 높아 소결밀도가 현저히 낮아졌다. The most effective ZnO-B 2 O 3 -based glasses were glasses with ZnB 2 O 4 and Zn 3 B 2 O 6 compositions, and the ZnB 4 O 7 glass had a high B 2 O 3 content, resulting in a significantly lower sintered density.
이와 같이 선택된 유리를 주 조성 100중량부에 대해 0.01 내지 30중량부로 첨가하는 것이 바람직하며, 더욱 바람직하기로는 15중량부 이내인 것이다. 소결조제의 첨가량이 상기 범위를 만족하는 경우 조성물의 소결을 촉진시키고 동시에 원래 조성의 유전특성을 향상시킬 수 있으나, 이 범위를 벗어나 과량으로 첨가될 경우 소결특성과 유전특성의 증가 효과를 기대할 수 없었다.The glass thus selected is preferably added in an amount of 0.01 to 30 parts by weight based on 100 parts by weight of the main composition, more preferably within 15 parts by weight. If the addition amount of the sintering aid satisfies the above range, it is possible to promote the sintering of the composition and at the same time to improve the dielectric properties of the original composition. .
만일 Ba6Ti2Nb8O30계 조성물에 소결조제를 첨가하지 않은 경우는 1,300℃ 이상에서 소결이 이루어지며, 이로 인해 은(Ag), 구리, 은/팔라듐 합금과 같은 저융점 금속전극과는 함께 소성할 수 없다. If the sintering aid is not added to the Ba 6 Ti 2 Nb 8 O 30 based composition, the sintering is performed at 1,300 ° C. or higher, which is why the low melting point metal electrode such as silver (Ag), copper, and silver / palladium alloy It cannot be fired together.
그러나, 주 조성인 Ba6Ti2Nb8O30에 소결조제로서 특정의 ZnO-B2O3 유리를 첨가하여 소결할 경우 850∼1,000℃에서 소결이 가능하므로 저융점 금속전극과 함께 소성할 수 있게 된다.However, when sintering by adding a specific ZnO-B 2 O 3 glass as a sintering aid to Ba 6 Ti 2 Nb 8 O 30 which is the main composition, it can be sintered at 850 to 1,000 ° C, so that it can be fired together with the low melting point metal electrode. Will be.
또한 본 발명에서는 상기한 유리를 대체하거나 이들과 혼합하여, 산화물 혼합물을 첨가할 수 있는데, 산화물 혼합물로는 B2O3와 CuO의 혼합물 및 B2O3와 ZnO와의 혼합물이 바람직하다. Further, in the present invention, an oxide mixture may be added by replacing or mixing with the above-described glasses. As the oxide mixture, a mixture of B 2 O 3 and CuO and a mixture of B 2 O 3 and ZnO are preferable.
그 함량은 주 조성 100중량부에 대해 0.01 내지 30중량부인 것이 바람직하다. It is preferable that the content is 0.01-30 weight part with respect to 100 weight part of main compositions.
만일 유리와 산화물 혼합물을 혼합 사용할 경우라면 유리를 소량으로 혼합하는것이 유전특성에 있어서 바람직하다. If glass and oxide mixtures are used in admixture, mixing the glass in small amounts is desirable for dielectric properties.
혼합시 총량은 주 조성 100중량부에 대해 0.01 내지 30중량부인 것이 바람직하다. It is preferable that the total amount at the time of mixing is 0.01-30 weight part with respect to 100 weight part of main compositions.
한편 본 발명의 유전체 세라믹 조성물을 제조하는 방법을 구체적으로 살펴보면 다음과 같다.Meanwhile, a method of manufacturing the dielectric ceramic composition of the present invention will be described in detail.
순도 99.9%의 BaCO3, TiO2, 및 Nb2O5를 몰비율이 6 : 2 : 4 가 되도록 칭량하 고, 이를 폴리에틸렌 병에 증류수와 무게비로 1 : 1 이 되도록 넣은 다음, 원활한 혼합을 위해 분산제를 1 중량부 첨가하였다. 이렇게 준비된 시료를 볼밀에 넣고 안정화 지르코니아 볼(Yttria stabilized Zirconia)을 사용하여 24시간 혼합(mixing)하였다.BaCO 3 , TiO 2 , and Nb 2 O 5 with a purity of 99.9% are weighed so that the molar ratio is 6: 2: 4, and this is placed in a polyethylene bottle at a ratio of 1: 1 by distilled water and weight ratio, for smooth mixing. 1 part by weight of dispersant was added. The sample thus prepared was placed in a ball mill and mixed for 24 hours using a stabilized zirconia ball (Yttria stabilized Zirconia).
혼합된 슬러리를 오븐에서 100℃로 가열하여 수분을 제거한 후 알루미나 도가니에 담아서 1100℃에서 2시간 동안 하소하였다. 하소된 분말에 소결조제 및 첨가제를 원하는 중량비로 혼합하고 위의 혼합공정과 동일한 방식으로 24시간 분쇄(milling)하였다. 이와 같이 제조한 상기 유전체 조성물은 유전율이 크고 유전손실이 작기 때문에 적층부품에 직접 응용할 수 있다. 그러나 상기 조성물은 저온 소결특성이 떨어지므로 저온 소결특성을 부여하기 위하여 다음과 같은 방법으로 저온 소결용 유전체 조성물을 제조한다.The mixed slurry was heated to 100 ° C. in an oven to remove moisture, and then placed in an alumina crucible and calcined at 1100 ° C. for 2 hours. The calcined powder was mixed with the sintering aid and the additive in the desired weight ratio and milled for 24 hours in the same manner as the above mixing process. The dielectric composition thus prepared has a high dielectric constant and a low dielectric loss, which can be directly applied to a laminated component. However, since the composition has low temperature sintering characteristics, a dielectric composition for low temperature sintering is prepared by the following method in order to give low temperature sintering characteristics.
즉, Ba6Ti2Nb8O30 조성에 특정 조성의 ZnO-B2O3 유리를 첨가하거나 또는 산화물 혼합물로서 B2O3와 CuO, B2O3와 ZnO를 첨가하거나, 유리와 산화물 혼합물을 혼합하여 소결조제로 첨가하여 혼합한 후, 수분을 제거하고, 이를 분쇄하고 여기에 결합제를 첨가하여 성형 및 소결하여 유전체 조성물을 제조한다.That is, ZnO-B 2 O 3 glass of a specific composition is added to the Ba 6 Ti 2 Nb 8 O 30 composition, or B 2 O 3 and CuO, B 2 O 3 and ZnO as the oxide mixture, or the glass and oxide mixture After mixing and adding to the sintering aid and mixing, water is removed, it is ground and the binder is added thereto to form and sinter to prepare a dielectric composition.
이하, 본 발명의 실시예를 상세히 설명한다. 그러나 하기의 실시예들은 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐 본 발명이 하기의 실시예에 한정되는 것은 아니다.Hereinafter, embodiments of the present invention will be described in detail. However, the following examples are merely provided to more easily understand the present invention, and the present invention is not limited to the following examples.
실시예 1∼22 및 비교예 1~6Examples 1-22 and Comparative Examples 1-6
본 실시예 및 비교예에서는 Ba6Ti2Nb8O30계 조성물에 유리 첨가제를 첨가한 경우 이에 따른 유전특성과 소결특성의 변화를 확인한 것이다.In the present Example and Comparative Example, when the glass additive is added to the Ba 6 Ti 2 Nb 8 O 30- based composition, the dielectric properties and the sintering properties according to this are confirmed.
먼저, Ba6Ti2Nb8O30계 조성물에 유리를 첨가한 경우 이에 따른 유전특성과 소결특성의 변화를 확인하기 위하여 저온소성 유전체 조성물을 제조하였다. First, when glass is added to the Ba 6 Ti 2 Nb 8 O 30- based composition to prepare a low-temperature fired dielectric composition to confirm the change in dielectric properties and sintering properties accordingly.
먼저 출발물질로 순도 99.9%의 BaCO3, TiO2, 및 Nb2O5를 몰비율이 6 : 2 : 4 가 되도록 칭량하고, 이를 폴리에틸렌 병에 증류수와 무게비로 1 : 1이 되도록 넣은 다음, 원활한 혼합을 위해 분산제를 1 중량부 첨가하였다. 이렇게 준비된 시료를 볼밀에 넣고 안정화 지르코니아 볼(Yttria stabilized Zirconia)을 사용하여 24시간 혼합(mixing)하였다.First, BaCO 3 , TiO 2 , and Nb 2 O 5 with a purity of 99.9% were weighed so as to have a molar ratio of 6: 2: 4, and the mixture was placed in a polyethylene bottle with a ratio of distilled water and a weight of 1: 1. 1 part by weight of dispersant was added for mixing. The sample thus prepared was placed in a ball mill and mixed for 24 hours using a stabilized zirconia ball (Yttria stabilized Zirconia).
혼합된 슬러리를 오븐에서 100℃로 가열하여 수분을 제거한 후 알루미나 도가니에 담아서 1100℃에서 2시간 동안 하소하였다. 하소된 분말에 소결조제 및 첨가제를 원하는 중량비로 혼합하고 위의 혼합공정과 동일한 방식으로 24시간 분쇄(milling)하였다. 소결조제로 ZnB2O4, Zn3B2O6 또는 ZnB4O7 유리를 1-30 중량부로 첨가하였다. The mixed slurry was heated to 100 ° C. in an oven to remove moisture, and then placed in an alumina crucible and calcined at 1100 ° C. for 2 hours. The calcined powder was mixed with the sintering aid and the additive in the desired weight ratio and milled for 24 hours in the same manner as the above mixing process. ZnB 2 O 4 , Zn 3 B 2 O 6 or ZnB 4 O 7 glass was added in an amount of 1-30 parts by weight as a sintering aid.
상기에 사용된 유리는 ZnO와 B2O3 원료를 1:1, 3:1 혹은 1:2 몰비로 혼합하여 1000℃에서 급랭하여 유리를 얻은 후 플래네터리 밀(Planetary Mill, Netsh PM400, German)을 사용하여 분쇄하여 얻어진 것이다. The glass used above is obtained by mixing ZnO and B 2 O 3 raw materials at a molar ratio of 1: 1, 3: 1 or 1: 2 and quenching the glass at 1000 ° C. to obtain a planetary mill (Planetary Mill, Netsh PM400, German). Obtained by grinding).
혼합된 슬러리에 결합제로서 폴리비닐알콜(PVA, Polyvinyl alcohol)을 1중량부 첨가한 후 조립화하였다. 조립화된 분말은 1000 kg/㎠의 압력으로 지름 10mm, 높이 1∼2 mm의 실린더형으로 성형하여 이들을 850∼1000℃ 범위에서 공기 분위기 하에서 소결(sintering)하였다. 승온속도는 분당 5℃이며 냉각은 로냉하였다.1 parts by weight of polyvinyl alcohol (PVA, Polyvinyl alcohol) was added to the mixed slurry and then granulated. The granulated powder was molded into a cylindrical shape having a diameter of 10 mm and a height of 1 to 2 mm at a pressure of 1000 kg / cm 2, and they were sintered in an air atmosphere in the range of 850 to 1000 ° C. The rate of temperature increase was 5 ° C. per minute and the cooling was furnace cooled.
이와 같이 제조된 소결 시편에 대하여 다음과 같은 유전특성을 조사하였다. 제조된 소결체의 상온 유전율 및 유전손실을 임피던스 분석기 (Impedance/Gain analyzer, HP4194A)를 이용하여 주파수 1 kHz에서 측정하였다.The dielectric properties of the sintered specimens thus prepared were investigated as follows. The room temperature dielectric constant and dielectric loss of the prepared sintered body were measured at an frequency of 1 kHz using an impedance analyzer (Impedance / Gain analyzer, HP4194A).
다음 표 1은 Ba6Ti2Nb8O30로 이루어진 주조성에 소결조제를 혼합한 유전체 조성물을 공기중에서 850-950℃에 소결하였을 때의 소결특성과 유전특성을 나타내었다.Table 1 shows the sintering characteristics and dielectric characteristics when the dielectric composition mixed with a sintering aid in a castability consisting of Ba 6 Ti 2 Nb 8 O 30 at 850-950 ℃ in air.
상기 표 1의 결과로부터, Ba6Ti2Nb8O30 유전체 조성물에 ZnB2O4, Zn3B2O6 또는 ZnB4O7 유리를 첨가하는 경우 소결조제를 첨가하지 않은 경우에 비해 소결 온도를 크게 낮출 수 있음을 볼 수 있다. From the results in Table 1 above, when ZnB 2 O 4 , Zn 3 B 2 O 6, or ZnB 4 O 7 glass is added to the Ba 6 Ti 2 Nb 8 O 30 dielectric composition, the sintering temperature is compared with the case where no sintering aid is added. It can be seen that can be greatly reduced.
구체적으로, 비교예 1과 같이 소결 조제가 첨가되지 않은 Ba6Ti2Nb8O30 유전체 조성물은 1,350℃에서 소결이 되며 유전율은 1072이며 유전 손실은 0.05를 갖는다.Specifically, as in Comparative Example 1, the Ba 6 Ti 2 Nb 8 O 30 dielectric composition to which the sintering aid was not added is sintered at 1,350 ° C., and the dielectric constant is 1072 and the dielectric loss is 0.05.
저온 소결체의 밀도에 있어서, ZnB4O7 유리가 첨가된 경우 3.12~4.52 정도의 낮은 값을 가져서 저온소결특성이 저하되었다. ZnB4O7 유리는 ZnO : B2O3 = 36.9 : 63.1 (중량비)로 B2O3 함량이 상대적으로 크고, 미세조직 관찰결과 보론 함량이 많은 시편의 경우 표면이 거칠고 기공이 상당히 많이 관찰되었다. 따라서 ZnO-B2O3 계의 유리조성 중 보론 함량이 많은 ZnB4O7 유리의 경우 주 조성물의 저온소결 조제로 적합하지 않음을 알 수 있다. In the density of the low-temperature sintered compact, when ZnB 4 O 7 glass was added, it had a low value of about 3.12 to 4.52, thereby lowering the low-temperature sintering characteristics. ZnB 4 O 7 glass was ZnO: B 2 O 3 = 36.9: 63.1 (weight ratio), and the B 2 O 3 content was relatively high. . Therefore, it can be seen that ZnB 4 O 7 glass having high boron content in the glass composition of ZnO-B 2 O 3 system is not suitable as a low temperature sintering aid of the main composition.
반면, ZnB2O4 또는 Zn3B2O6 유리가 첨가되었을 경우 4.9~5.24로 상당히 큰 값을 가졌고, 미세조직 관찰 결과 상당히 치밀한 미세조직을 보였다. On the other hand, when ZnB 2 O 4 or Zn 3 B 2 O 6 glass was added, it had a very large value of 4.9 to 5.24, and the microstructure observation showed a very dense microstructure.
따라서, 상대적으로 보론 함량이 많은 ZnB4O7 유리 보다 ZnB2O4 또는 Zn3B2O6 유리가 소결조제로 주 조성에 첨가되었을 경우 소결성 증진에 더 큰 역할을 함을 알 수 있다. Therefore, when ZnB 2 O 4 or Zn 3 B 2 O 6 glass is added to the main composition as a sintering aid than ZnB 4 O 7 glass having a relatively high boron content, it can be seen that it plays a greater role in improving sinterability.
상기 표 1의 실시예에서 나타낸 바와 같이, Ba6Ti2Nb8O30계 조성물에 ZnB2O4 유리 또는 Zn3B2O6 유리를 첨가할 경우 소결은 1,000℃ 이하에서 이루어지며 높은 유전율을 유지할 수 있다. 따라서 은, 구리 또는 은/팔라듐과 같이 저융점 전극과 함께 소성하여 적층소자를 만들 수 있다.As shown in the examples of Table 1, when ZnB 2 O 4 glass or Zn 3 B 2 O 6 glass is added to the Ba 6 Ti 2 Nb 8 O 30- based composition, the sintering is performed at 1,000 ℃ or less and high dielectric constant I can keep it. Therefore, it is possible to produce a laminated device by firing together with a low melting electrode such as silver, copper, or silver / palladium.
실시예 23∼46 및 비교예 7~12Examples 23-46 and Comparative Examples 7-12
본 실시예는 조성물 제조시에 유리조성이 아닌, B2O3-CuO 혹은 B2O3-ZnO의 산화물 혼합물을 첨가한 경우의 유전특성과 소결특성의 변화를 확인한 것으로, Ba6Ti2Nb8O30계 조성물에 B2O3와 CuO 혹은 B2O3와 ZnO의 두 가지 산화물을 동시에 첨가할 경우 유전특성이 향상됨을 보였다. 다만 소결온도에 있어서는 유리의 첨가보다는 다소 높아짐을 알 수 있다. This example confirmed that the change in the dielectric properties and sintered properties of the addition of the oxide mixture, B 2 O 3 -CuO, or B 2 O 3 -ZnO than the glass composition at the time of producing the composition, Ba 6 Ti 2 Nb When the two oxides of B 2 O 3 and CuO or B 2 O 3 and ZnO were added to the 8 O 30 based composition at the same time, dielectric properties were improved. However, it can be seen that the sintering temperature is somewhat higher than the addition of glass.
유리를 첨가한 공정과 마찬가지로 1100도에서 하소된 Ba6Ti2Nb8O30에 B2O3-CuO 혹은 B2O3-ZnO의 두 가지 산화물을 동시에 첨가한 후, 밀링과 성형의 과정을 거친 후 950도에서 2시간 소결하였다.As in the glass addition process, two oxides of B 2 O 3 -CuO or B 2 O 3 -ZnO are simultaneously added to Ba 6 Ti 2 Nb 8 O 30 calcined at 1100 ° C. After roughing it was sintered at 950 degrees for 2 hours.
다음 표 2에는 이와 같이 제조한 유전체 조성물의 소결 특성과 유전특성을 나타내었다.Table 2 shows the sintering characteristics and dielectric characteristics of the dielectric composition thus prepared.
상기 표 2의 결과로부터, B2O3-CuO 혹은 B2O3-ZnO의 산화물 혼합물을 첨가할 경우 소결 온도를 크게 낮출 수 있음을 알 수 있다. 유리를 첨가하였을 경우보다 소결온도는 약간 높아 졌지만, 더 높은 유전율과 낮은 유전손실을 가짐을 확인할 수 있다. From the results of Table 2, the addition of the oxide mixture of B 2 O 3 -CuO, or B 2 O 3 -ZnO it can be seen that significantly lower the sintering temperature. The sintering temperature is slightly higher than that of glass, but it has higher dielectric constant and lower dielectric loss.
또한, 산화물의 혼합물이 30 중량부 이상 첨가될 경우 첨가물의 낮은 유전율로 인해 저온소결체의 유전율이 현저히 낮아지거나 유전손실 또한 더 커짐을 확인할 수 있었다. In addition, when more than 30 parts by weight of the mixture of the oxide due to the low dielectric constant of the low temperature sintered body due to the low dielectric constant was significantly lower or even more dielectric loss was confirmed.
실시예 47∼53 Examples 47-53
본 실시예는 조성물 제조시에 유리조성과 함께, B2O3-CuO 또는 B2O3-ZnO의 산화물 혼합물을 첨가한 경우의 유전특성과 소결특성의 변화를 확인한 것으로, Ba6Ti2Nb8O30계 조성물에 상기 실시예 1 내지 22에서와 같이 ZnB2O4 유리 또는 ZnB2O6유리를 사용하고, 이것과 B2O3와 CuO 혹은 B2O3와 ZnO의 두 가지 산화물을 첨가할 경우 소결특성과 유전특성이 향상됨을 보였다. 구체적으로 소결온도는 산화물 혼합물만을 첨가한 경우보다는 다소 낮아지고, 유전특성은 유리만을 사용한 경우에 비해 향상되는 결과를 보였다. This example confirmed that the change in the dielectric properties and sintered properties of the addition of the oxide mixture with a glass composition, B 2 O 3 -CuO, or B 2 O 3 -ZnO when the composition prepared, Ba 6 Ti 2 Nb ZnB 2 O 4 glass or ZnB 2 O 6 glass was used in the 8 O 30 based composition as in Examples 1 to 22, and two oxides of B 2 O 3 and CuO or B 2 O 3 and ZnO were used. The addition showed that the sintering and dielectric properties were improved. Specifically, the sintering temperature was slightly lower than the case where only the oxide mixture was added, and the dielectric properties were improved compared to the case of using only glass.
상기 실시예들의 공정과 마찬가지로 1100도에서 하소된 Ba6Ti2Nb8O30에 유리와, B2O3-CuO 또는 B2O3-ZnO 산화물을 동시에 첨가한 후, 밀링과 성형의 과정을 거친 후 950도에서 2시간 소결하였다.In the same manner as in the above embodiments, glass and B 2 O 3 -CuO or B 2 O 3 -ZnO oxides are simultaneously added to Ba 6 Ti 2 Nb 8 O 30 calcined at 1100 degrees, followed by milling and molding. After roughing it was sintered at 950 degrees for 2 hours.
다음 표 3에는 이와 같이 제조한 유전체 조성물의 소결 특성과 유전특성을 나타내었다.Table 3 shows the sintering characteristics and dielectric characteristics of the dielectric composition thus prepared.
상기 표 3의 결과로부터, B2O3-CuO 혹은 B2O3-ZnO의 산화물 혼합물에 소량의 유리를 첨가할 경우 산화물 혼합물만을 사용한 경우보다 소결온도는 다소 낮아지고, 유전손실을 다소 높아짐을 알 수 있다. From the results of Table 3, B 2 O 3 B 2 O 3 -CuO, or the addition of a small amount of glass to the oxide mixture of -ZnO sintering than that only with the oxide mixture the temperature is somewhat lower, a dielectric loss somewhat higher Able to know.
상기 표 1 내지 3의 결과로부터, 유리, 산화물 화합물 및 이들의 혼합물을 첨가하면 Ba6Ti2Nb8O30계의 1000℃ 이하에서의 소결을 가능하게 함을 알 수 있다. 그러므로 Ba6Ti2Nb8O30계 조성물에 소결조제 및 첨가제만을 첨가하여 제조한 유전체 조성물은 그 자체로 고주파용 마이크로파 적층부품에 응용할 수 있을 뿐만 아니라 저융점 전극과 동시에 소성할 수 있다.From the results of Tables 1 to 3, it can be seen that addition of glass, oxide compounds, and mixtures thereof enables sintering at 1000 ° C. or lower of the Ba 6 Ti 2 Nb 8 O 30 system. Therefore, the dielectric composition prepared by adding only a sintering aid and additives to the Ba 6 Ti 2 Nb 8 O 30 based composition can be applied to microwave laminated parts for high frequency, and can be fired simultaneously with the low melting point electrode.
이상에서 상세히 설명한 바와 같이, 본 발명에 의한 Ba6Ti2Nb8O30계 세라믹 유전체 조성물에 ZnB2O4 또는 Zn3B2O6 조성의 유리, 산화물 혼합물 및 이들의 혼합물을 첨가한 결과, 1,000℃ 이하에서 소결이 가능해지며 이로써 은(Ag)과 같은 저융점 전극과 동시소성이 가능하고, 이렇게 제조된 세라믹 유전체 조성물은 적층캐패시터(MLCC)에 유전체로 사용이 가능하며 특히, 유전손실이 작고 유전율 크기 때문에 PCS등의 이동통신용 부품을 제조하기에 적합하다.As described above in detail, ZnB 2 O 4 to the Ba 6 Ti 2 Nb 8 O 30- based ceramic dielectric composition according to the present invention Or as a result of the addition of Zn 3 B 2 O 6 glass, oxide mixtures and mixtures thereof, sintering is possible up to 1,000 ° C., thereby enabling simultaneous firing with low melting electrodes such as silver (Ag). The ceramic dielectric composition can be used as a dielectric in a multilayer capacitor (MLCC), and is particularly suitable for manufacturing mobile communication components such as PCS due to its low dielectric loss and large dielectric constant.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020060120341A KR100808472B1 (en) | 2006-12-01 | 2006-12-01 | Dielectric ceramic compositions and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020060120341A KR100808472B1 (en) | 2006-12-01 | 2006-12-01 | Dielectric ceramic compositions and manufacturing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR100808472B1 true KR100808472B1 (en) | 2008-03-03 |
Family
ID=39397235
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020060120341A KR100808472B1 (en) | 2006-12-01 | 2006-12-01 | Dielectric ceramic compositions and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR100808472B1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170121254A (en) * | 2015-02-27 | 2017-11-01 | 페로 코포레이션 | Low-K and Mid-K LTCC dielectric compositions and devices |
| KR101920887B1 (en) * | 2017-06-30 | 2018-11-21 | (주)알엔투테크놀로지 | Sintered structure by sintering bonding for dielectric layer and metal ferrite magnetic layer and method of manufacturing the same |
| CN109803941A (en) * | 2016-10-17 | 2019-05-24 | 昭荣化学工业株式会社 | Dielectric ceramic composition and ceramic electronic component |
| EP3778531A4 (en) * | 2018-04-11 | 2022-04-27 | Shoei Chemical Inc. | Dielectric ceramic composition and ceramic electronic component |
| EP3778530A4 (en) * | 2018-04-11 | 2022-04-27 | Shoei Chemical Inc. | Dielectric ceramic composition and ceramic electronic component |
| CN116081953A (en) * | 2023-01-03 | 2023-05-09 | 武汉理工大学 | Zinc-boron binary ultralow-temperature sintered microcrystalline glass and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06103813A (en) * | 1991-12-11 | 1994-04-15 | Tdk Corp | High frequency dielectric ceramic composition |
| JP2000058367A (en) | 1998-08-10 | 2000-02-25 | Taiyo Yuden Co Ltd | Ceramic laminated electronic component |
| JP2000086337A (en) | 1998-09-14 | 2000-03-28 | Sharp Corp | Dielectric porcelain composition for low-temperature firing |
| KR20010110577A (en) * | 2000-06-07 | 2001-12-13 | 남상임 | Dielectric Ceramic Compositions |
-
2006
- 2006-12-01 KR KR1020060120341A patent/KR100808472B1/en not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06103813A (en) * | 1991-12-11 | 1994-04-15 | Tdk Corp | High frequency dielectric ceramic composition |
| JP2000058367A (en) | 1998-08-10 | 2000-02-25 | Taiyo Yuden Co Ltd | Ceramic laminated electronic component |
| JP2000086337A (en) | 1998-09-14 | 2000-03-28 | Sharp Corp | Dielectric porcelain composition for low-temperature firing |
| KR20010110577A (en) * | 2000-06-07 | 2001-12-13 | 남상임 | Dielectric Ceramic Compositions |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170121254A (en) * | 2015-02-27 | 2017-11-01 | 페로 코포레이션 | Low-K and Mid-K LTCC dielectric compositions and devices |
| KR102005291B1 (en) | 2015-02-27 | 2019-07-30 | 페로 코포레이션 | Low-K and Mid-K LTCC dielectric compositions and devices |
| CN109803941A (en) * | 2016-10-17 | 2019-05-24 | 昭荣化学工业株式会社 | Dielectric ceramic composition and ceramic electronic component |
| EP3527546A4 (en) * | 2016-10-17 | 2020-10-07 | Shoei Chemical Inc. | Dielectric porcelain composition and ceramic electronic component |
| US11066332B2 (en) | 2016-10-17 | 2021-07-20 | Shoei Chemical Inc. | Dielectric ceramic composition and ceramic electronic component |
| CN109803941B (en) * | 2016-10-17 | 2022-01-11 | 昭荣化学工业株式会社 | Dielectric ceramic composition and ceramic electronic component |
| KR101920887B1 (en) * | 2017-06-30 | 2018-11-21 | (주)알엔투테크놀로지 | Sintered structure by sintering bonding for dielectric layer and metal ferrite magnetic layer and method of manufacturing the same |
| EP3778531A4 (en) * | 2018-04-11 | 2022-04-27 | Shoei Chemical Inc. | Dielectric ceramic composition and ceramic electronic component |
| EP3778530A4 (en) * | 2018-04-11 | 2022-04-27 | Shoei Chemical Inc. | Dielectric ceramic composition and ceramic electronic component |
| US11524923B2 (en) | 2018-04-11 | 2022-12-13 | Shoei Chemical Inc. | Dielectric ceramic composition and ceramic electronic components |
| US11702368B2 (en) | 2018-04-11 | 2023-07-18 | Shoei Chemical Inc. | Dielectric ceramic composition and ceramic electronic component |
| CN116081953A (en) * | 2023-01-03 | 2023-05-09 | 武汉理工大学 | Zinc-boron binary ultralow-temperature sintered microcrystalline glass and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100426219B1 (en) | Dielectric Ceramic Compositions and Manufacturing Method of Multilayer components thereof | |
| US6743744B1 (en) | Low temperature sinterable and low loss dielectric ceramic compositions and method thereof | |
| US6579817B2 (en) | Dielectric ceramic composition and method for producing the same, and device for communication apparatus using the same | |
| KR100444230B1 (en) | Nonreducible dielectric ceramic composition | |
| US7655588B2 (en) | Dielectric porcelain composition and method for production thereof | |
| KR100808472B1 (en) | Dielectric ceramic compositions and manufacturing method thereof | |
| JP2000044341A (en) | Dielectric ceramic composition | |
| KR100401942B1 (en) | Dielectric Ceramic Compositions and Manufacturing Process the same | |
| JP3737774B2 (en) | Dielectric ceramic composition | |
| KR100557853B1 (en) | Phosphate Ceramic Compositions with Low Dielectric Constant | |
| KR100401943B1 (en) | Dielectric Ceramic Compositions and Manufacturing Method using the same compositions | |
| JPWO2005085154A1 (en) | Dielectric particle aggregate, low-temperature sintered dielectric ceramic composition using the same, and low-temperature sintered dielectric ceramic manufactured using the same | |
| KR20070103642A (en) | Low-fire dielectric ceramics compositions with adjustable temperature coefficient | |
| CN110304916B (en) | Anti-reduction BaTiO3Base medium ceramic and preparation method thereof | |
| KR100359721B1 (en) | Dielectric Ceramic Compositions able to be cofired with metal | |
| JP2781501B2 (en) | Dielectric ceramic composition for low temperature firing | |
| JP2005213138A (en) | Low temperature firing high dielectric constant ceramic composition | |
| KR100478127B1 (en) | Dielectric Ceramic Composition | |
| JP2004026543A (en) | Dielectric porcelain composition and laminated ceramic component using the same | |
| KR100373694B1 (en) | Dielectric Ceramic Compositions | |
| KR100823217B1 (en) | Dielectric porcelain composition and method for production thereof | |
| JP4174668B2 (en) | DIELECTRIC CERAMIC COMPOSITION, PROCESS FOR PRODUCING THE SAME, DIELECTRIC CERAMIC USING THE SAME, AND MULTILAYER CERAMIC COMPONENT | |
| JP3193157B2 (en) | Dielectric porcelain composition for low-temperature firing, dielectric resonator or dielectric filter obtained using the same, and methods for producing them | |
| KR20040078525A (en) | Dielectric Ceramic Compositions for High Frequency Applications | |
| KR100454711B1 (en) | Microwave dielectric ceramic compositions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| N231 | Notification of change of applicant | ||
| N231 | Notification of change of applicant | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| LAPS | Lapse due to unpaid annual fee |