KR20010008807A - A Method for Preparing Barium Titanate Powder by Oxalate Synthesis - Google Patents

A Method for Preparing Barium Titanate Powder by Oxalate Synthesis Download PDF

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KR20010008807A
KR20010008807A KR1019990026817A KR19990026817A KR20010008807A KR 20010008807 A KR20010008807 A KR 20010008807A KR 1019990026817 A KR1019990026817 A KR 1019990026817A KR 19990026817 A KR19990026817 A KR 19990026817A KR 20010008807 A KR20010008807 A KR 20010008807A
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barium titanate
oxalate
oxide powder
powder
producing
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KR1019990026817A
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KR100360118B1 (en
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허강헌
이재준
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이형도
삼성전기 주식회사
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
    • F21S6/00—Lighting devices intended to be free-standing
    • F21S6/002—Table lamps, e.g. for ambient lighting
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
    • F21S6/00—Lighting devices intended to be free-standing
    • F21S6/004—Lighting devices intended to be free-standing with a lamp housing in direct contact with the floor or ground
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
    • F21V3/00—Globes; Bowls; Cover glasses
    • F21V3/02—Globes; Bowls; Cover glasses characterised by the shape
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
    • F21V9/00—Elements for modifying spectral properties, polarisation or intensity of the light emitted, e.g. filters
    • F21V9/08—Elements for modifying spectral properties, polarisation or intensity of the light emitted, e.g. filters for producing coloured light, e.g. monochromatic; for reducing intensity of light

Abstract

PURPOSE: Provided is an easy and economic preparation method of BaTiO3-based oxides by modified oxalate method which is characterized by having more steps, primary milling, calcination, and secondary milling compared with a conventional oxalate method. The resultant BaTiO3-based oxide powder has spherical shape, mono-size and reproducible Ba/Ti control required for ceramic condensers, PTC and piezoelectrics. CONSTITUTION: The preparation method comprises the steps of: preparing BaCl2/TiCl4 solution by mixing 0.2-2.0mol/l of BaCl2 with 0.2-2.0mol/l of TiCl4 aqueous solution in a molar ratio of 1-1.5; preparing 0.2-5.0mol/l of oxalic acid((COOH)2), where a molar ratio of (COOH)2/TiCl4 is 1-3.0; adding BaCl2/TiCl4 solution at a 1-50ml/l rate to 50-100deg.C of oxalic acid solution for precipitating barium titanic oxalate(BTO, BaTi(C2O4)24H2O); aging for 1-100hrs.; drying at 50-200deg.C; thermal decomposing by heating at 2-10deg.C/min and holding at 600-1000deg.C; optionally substituting one or at least two element selected from Sr, Ca, Mg, Pb for Ba, and substituting one or at least two element selected from Zr, Hf, Sn for Ti; primary milling to 0.1-0.3micrometer of particle diameter; calcining at 800-1200deg.C; secondary milling to 0.2-1micrometer of particle diameter.

Description

옥살레이트법에 의한 티탄산바륨계 산화물 분말 제조방법{A Method for Preparing Barium Titanate Powder by Oxalate Synthesis}A method for preparing barium titanate powder by oxalate synthesis

본 발명은 강유전체, 압전체 등 여러분야에 사용되는 페롭스카이트형 산화물 분말, 특히 티탄산바륨계 분말을 옥살레이트법에 의해 제조하는 방법에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing perovskite-type oxide powders, especially barium titanate-based powders used in ferroelectrics, piezoelectrics and the like by the oxalate method.

일반적으로, 티탄산바륨(BaTiO3)파우더는 강유전체로서 페라이트와 함께 전자세라믹스의 중요한 구성재료로, 세라믹 콘덴서, PTC(정특성써미스터) 및 압전체등의 원료로서 광범위하게 사용되고 있다.BACKGROUND ART In general, barium titanate (BaTiO 3 ) powder is used as a ferroelectric and ferrite as an important constituent material of an electronic ceramic, and is widely used as a raw material for ceramic capacitors, PTC (static thermistors) and piezoelectric materials.

이러한 티탄산바륨파우더는 종래에는 산화티탄과 탄산바륨을 고상반응에 의해 합성시켜 제조하였지만, 최근 MLCC의 소형대용량화(고유전율조성, 유전체 박층화 및 고적층화), 저온소성화, 고주파화, 고성능화 등에 따라, 티탄산바륨파우더는 고순도/조성균일성, 미립/입도균일성, 비응집성/고분산성 등이 요구되고 있으며, 이러한 특성을 만족할 수 있는 파우더 제조방법으로 액상합성법의 수요가 증가하고 있다. 상기 액상합성법으로 예를들면 수열합성법, 공침법(옥살레이트법), 알콕사이드법(졸겔법)등이 개발되어 그 사용이 급증하고 있다.The barium titanate powder is conventionally manufactured by synthesizing titanium oxide and barium carbonate by solid phase reaction, but recently, due to the small capacity of MLCC (high dielectric constant, dielectric thinning and high lamination), low temperature firing, high frequency, high performance, etc. The barium titanate powder is required to have high purity / composition uniformity, fine granularity / particle size uniformity, non-aggregation / high dispersibility, and the demand for liquid synthesis is increasing as a powder manufacturing method that can satisfy these characteristics. For example, hydrothermal synthesis, co-precipitation (oxalate method), alkoxide method (sol-gel method), and the like have been developed as the liquid phase synthesis method.

특히, 액상합성법중에서 옥살레이트법은 Ba과 Ti이온이 함유된 혼합용액에 옥살산을 첨가하여 바륨티탄옥살레이트(BTO) 화합물로 침전시킨 후 이것을 건조, 열분해하여 티탄산바륨파우더를 제조하는 방법으로, 공정이 단순하고 원료비와 설비투자비가 싸다는 장점이 있어 가장 먼저 상용화되었으나, 파우더 조성(Ba/Ti) 및 입도제어가 어렵고 열분해시 입자간에 강한 응결체를 형성하여 분쇄후 입자가 파쇄상으로 되며, 미분쇄된 입자가 잔존하여 혼합/성형시 분산성이 좋지 않고 소결시 소결성이 좋지 않고 비정상결정립이 생성되기 쉬운 문제점이 있다. 또한 입자간의 강한 응결로 인하여 입자를 크게 키울수 없으며 결정성도 나빠 MLCC B특성용으로는 적합하지 않으므로 최근에는 MLCC의 박층화, 고적층화 추세에 따라 수열합성법으로 제조한 파우더로 대체되고 있는 실정이다. 그러나, 수열합성법은 분체 특성적인 장점에도 불구하고 합성공정이 복잡하고 오토클레이브를 사용하므로 생산성이 좋지않으며, 파우더 가격이 비싸기 때문에 MLCC의 가격 경쟁력을 높이기 위해서는 합성공정이 단순하고 가격이 저렴한 파우더 합성법의 개발이 필요하다.In particular, in the liquid phase synthesis method, the oxalate method is a method of preparing barium titanate powder by adding oxalic acid to a mixed solution containing Ba and Ti ions, precipitating it with a barium titanium oxalate (BTO) compound, and drying and thermally decomposing it. This product was commercialized first because of its simplicity and low cost of raw materials and equipment investment, but it was difficult to control powder composition (Ba / Ti) and particle size, and formed a strong coagulum between particles during pyrolysis. There is a problem that the pulverized particles remain and thus have poor dispersibility in mixing / molding, poor sintering in sintering, and abnormal grains. In addition, due to the strong coagulation between the particles can not grow large particles and poor crystallinity is not suitable for the MLCC B characteristics, the recent situation is being replaced by a powder prepared by the hydrothermal synthesis method according to the trend of MLCC thinning, high lamination. However, in spite of the powder characteristics, the hydrothermal synthesis method is not very productive due to the complex synthesis process and the use of autoclave. Since the powder price is high, the synthesis process is simple and inexpensive to increase the price competitiveness of MLCC. Need development

기존의 옥살레이트법의 제조공정은 도 1과 같이 나타낼 수 있다. 염화바륨과 염화티탄 수용액을 Ba:Ti비가 1:1이 되도록 혼합하고, 여기에 옥살산(Oxalic acid)을 첨가하면 바륨티탄옥살레이트[BTO, BaTiO(C2O4)2·4H2O]가 하기식 1과 같은 반응에 의해 침전되는데, 이를 잘 세척한 후 여고, 건조하여 800-900℃에서 열분해하여 하기식 2-4의 과정을 거쳐 티탄산바륨파우더를 얻는다.The manufacturing process of the conventional oxalate method can be represented as shown in FIG. Barium chloride and titanium chloride solution are mixed so that the Ba: Ti ratio is 1: 1, and when oxalic acid is added, barium titanium oxalate [BTO, BaTiO (C 2 O 4 ) 2 .4H 2 O] It is precipitated by the reaction as shown in Equation 1 below, which is washed well, dried, dried and pyrolyzed at 800-900 ° C. to obtain a barium titanate powder through the process of Equation 2-4.

BaCl2+ TiCl4+ (COOH)2→ BaTiO(C2O4)2·4H2OBaCl 2 + TiCl 4 + (COOH) 2 → BaTiO (C 2 O 4 ) 2 4H 2 O

BaTiO(C2O4)2·4H2O → BaTiO(C2O4)2+ 4H2OBaTiO (C 2 O 4 ) 2 4H 2 O → BaTiO (C 2 O 4 ) 2 + 4H 2 O

BaTiO(C2O4)2+ 1/2O2→ BaCO3+ TiO2+ CO +2CO2 BaTiO (C 2 O 4 ) 2 + 1 / 2O 2 → BaCO 3 + TiO 2 + CO + 2CO 2

BaCO3+ TiO2→ BaTiO3 BaCO 3 + TiO 2 → BaTiO 3

하지만, 이 방법은 파우더 조성(Ba/Ti) 및 입도제어가 어렵고 열분해시 입자간에 강한 응결체를 형성하여 분쇄후 입자가 파쇄상으로 되며, 미분쇄된 입자가 잔존하여 혼합/성형시 분산성이 좋지 않고 소결시 소결성이 좋지 않고 비정상결정립이 생성되기 쉬운 문제점이 있다. 또한, 입자간의 강한 응결체 형성으로 인하여 입자를 크게 키울수 없으며 결정성도 나빠서 MLCC B특성용으로는 적합하지 않은 문제점도 있다.However, this method is difficult to control the powder composition (Ba / Ti) and particle size, and forms a strong agglomerate between particles during pyrolysis, and the particles become crushed after pulverization. There is a problem that the poor sinterability is not good when sintering and abnormal grains are easily generated. In addition, due to the formation of strong agglomerates between particles, the particles cannot be largely grown, and the crystallinity is also poor, which is not suitable for MLCC B properties.

이에 본 발명자들은 상기 문제점들을 해결하기 위해 연구와 실험을 거듭하고 그 결과에 근거하여 본 발명을 제안하게 된 것으로, 본 발명은 옥살레이트법에 의해 파우더 제조시 열분해 후, 1차분쇄, 하소, 2차분쇄를 거침으로써, 품질이 우수한 파우더가 얻어지고, 또한 생산성, 가격측면에서 우수한 티탄산바륨계 파우더 제조방법을 제공하고자 하는데, 그 목적이 있다.In order to solve the above problems, the present inventors have repeatedly studied and experimented and proposed the present invention based on the results. The present invention, after the thermal decomposition during powder production by the oxalate method, primary grinding, calcining, 2 It is an object of the present invention to provide a method for producing a barium titanate-based powder which is excellent in terms of productivity and price, by obtaining a powder having a differential grinding.

도 1은 종래의 옥살레이트법에 의한 티탄산바륨분말 제조 공정도1 is a process chart of the production of barium titanate powder by the conventional oxalate method

도 2는 본 발명의 방법에 의한 티탄산바륨분말 제조 공정도2 is a process chart of the production of barium titanate powder by the method of the present invention

도 3(a-d)는 본 발명에 의해 얻어진 분말의 하소후 SEM사진 및 분쇄후 SEM사진Figure 3 (a-d) is a SEM photograph after calcination of the powder obtained by the present invention and a SEM photograph after grinding

도 4(a-d)는 기존방식에 의해 얻어진 분말의 하소후 SEM사진 및 분쇄후 SEM사진Figure 4 (a-d) is a SEM picture after calcination and SEM image of the powder obtained by the conventional method

상기 목적을 달성하기 위한 본 발명은 염화바륨수용액과 염화티탄수용액을 옥살산 수용액에 첨가하여 바륨티탄산옥살레이트(BTO)를 침전시킨 후, 에이징하고 세척, 여과, 건조하여 바륨티탄산옥살레이트 파우더를 제조하는 단계; 제조된 티탄산바륨파우더를 열분해한 후, 1차분쇄하여 미립의 파우더를 제조하는 단계; 및 상기 미립의 파우더를 하소한 후, 2차 분쇄하는 단계를 포함하는 옥살레이트법에 의한 티탄산바륨계 산화물 분말 제조방법에 관한 것이다.In order to achieve the above object, the present invention adds an aqueous barium chloride solution and an aqueous titanium chloride solution to an oxalic acid solution to precipitate barium titanate oxalate (BTO), and then prepares barium titanate oxalate powder by aging, washing, filtration and drying. step; Thermally decomposing the prepared barium titanate powder, and then pulverizing the powder to prepare fine powder; And after calcining the fine powder, it relates to a method for producing a barium titanate oxide powder by the oxalate method comprising the step of secondary grinding.

이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.

본 발명에서는 염화바륨수용액과 염화티탄수용액을 옥살산 수용액에 첨가하여 바륨티탄산옥살레이트(BTO)를 침전시킨 후, 에이징하고 세척, 여과, 건조하여 바륨티탄산옥살레이트 파우더를 제조하는 과정을 거친다.In the present invention, barium chloride solution and titanium chloride solution are added to an aqueous solution of oxalic acid to precipitate barium titanate oxalate (BTO), followed by aging, washing, filtration and drying to prepare barium titanate oxalate powder.

상기 염화바륨 수용액은 보통 BaCl2·2H2O를 물에 녹여 사용하는데, 바람직한 농도범위는 0.2-2.0mol/l이다.The barium chloride aqueous solution is usually used by dissolving BaCl 2 · 2H 2 O in water, the preferred concentration range is 0.2-2.0 mol / l.

상기 염화티탄 수용액은 보통 TiCl4용액을 희석하여 사용하는데, 바람직한 농도범위는 0.2-2.0mol/l이다.The aqueous titanium chloride solution is usually used by diluting the TiCl 4 solution, the preferred concentration range is 0.2-2.0 mol / l.

상기 염화바륨 수용액과 상기 염화티탄 수용액은 염화바륨과 염화티탄의 몰비가 1-1.5으로 되도록 하는 것이 바람직하다.The barium chloride solution and the titanium chloride solution is preferably such that the molar ratio of barium chloride and titanium chloride is 1-1.5.

상기 옥살산 수용액은 0.2-5.0mol/l의 농도를 갖는 것을 사용하는 것이 바람직하며, 상기 옥살산과 상기 염화티탄의 몰비는 1-3.0인 것이 바람직하다. 또한, 상기 옥살산 수용액은 온도가 50-100℃인 것을 사용하는 것이 바람직하고, 이러한 온도범위에서는 교반속도가 10-1000rpm/min인 것이 바람직하다.The oxalic acid aqueous solution is preferably used having a concentration of 0.2-5.0 mol / l, the molar ratio of the oxalic acid and the titanium chloride is preferably 1-3.0. In addition, the oxalic acid aqueous solution is preferably used that the temperature is 50-100 ℃, in this temperature range it is preferable that the stirring speed is 10-1000rpm / min.

상기 염화바륨 수용액과 염화티탄수용액은 상기 옥살산에 투입하는데, 이들은 미리 섞어서 투입하는 것이 바람직하며, 그 첨가속도는 1-50ml/l인 것이 바람직하다.The aqueous barium chloride solution and aqueous titanium chloride solution are added to the oxalic acid, which is preferably mixed and added in advance, and the addition rate is preferably 1-50 ml / l.

상기 에이징은 1-100시간 정도 행하는 것이 바람직하다.It is preferable to perform the said aging about 1-100 hours.

상기 건조는 50-200℃정도에서 행하는 것이 바람직하다.It is preferable to perform the said drying at about 50-200 degreeC.

또한, 본 발명에서는 상기 제조된 티탄산바륨파우더를 열분해하는 과정을 거치며, 상기 열분해 후, Ba 또는/및 Ti의 자리에 치환되는 원소를 함유하는 첨가제를 혼합하는 과정을 거칠 수도 있다.In addition, in the present invention, the barium titanate powder is thermally decomposed, and after the thermal decomposition, an additive containing an element substituted in place of Ba or / and Ti may be mixed.

상기 열분해는 가열속도를 2-10℃/min정도로 하는 것이 바람직하고, 유지온도는 600-1000℃정도로 하는 것이 바람직하다.Preferably, the pyrolysis is at a heating rate of about 2-10 ° C / min, and a holding temperature of about 600-1000 ° C.

상기 Ba자리에 치환되는 원소는 예를들면, Sr, Ca, Mg, Pb 중에서 선택된 것을 사용할 수 있고, 또한 이들을 2종이상 선택하여 사용할 수 있다. 이같은 원소의 투입은 산화물, 탄산화물, 수산화물 등의 형태로 1차분쇄전에 투입하는 것도 가능하다.As the element substituted at the Ba site, for example, one selected from Sr, Ca, Mg, and Pb may be used, and two or more kinds thereof may be selected and used. Such element may be added before primary grinding in the form of oxide, carbonate, hydroxide, or the like.

상기 Ti자리에 해당하는 원소는 예를들면, Zr, Hf, Sn 중에서 선택된 것을 사용할 수 있고, 또한 이들을 2종이상 선택하여 사용할 수 있다. 이같은 원소의 투입은 산화물, 탄산화물, 수산화물 등의 형태로 1차분쇄전에 투입하는 것도 가능하다.As the element corresponding to the Ti site, for example, one selected from Zr, Hf, and Sn may be used, and two or more thereof may be selected and used. Such element may be added before primary grinding in the form of oxide, carbonate, hydroxide, or the like.

또한, 본 발명에서는 상기 혼합물을 1차분쇄하여 미립의 파우더를 제조하는 과정, 및 상기 미립의 파우더를 하소한 후, 2차 분쇄하는 과정을 거친다.In addition, in the present invention, the mixture is first ground to prepare a fine powder, and the powder is calcined, and then subjected to a second grinding process.

상기 1차 분쇄 및 2차 분쇄는 그 분쇄방식이 예를들면, 비드밀, 볼밀, 플라너터리밀 등의 강제교반 습식분쇄방식으로 행할 수 있고, 볼의 크기는 0.2-5.0mm인 것이 바람직하고, 분쇄시간은 10-300분 행하는 것이 바람직하다. 상기 1차 분쇄에 의해 얻어진 입자의 평균입경은 0.1-0.3μm인 것이 바람직하다. 상기 2차 분쇄에 의해 얻어진 입자의 평균입경은 0.2-1.0μm인 것이 바람직하다.The primary grinding and secondary grinding may be performed by a forced stirring wet grinding method such as a bead mill, a ball mill, or a planetary mill, and the size of the balls is preferably 0.2-5.0 mm. The grinding time is preferably 10-300 minutes. It is preferable that the average particle diameter of the particle | grains obtained by the said 1st grinding | pulverization is 0.1-0.3 micrometer. It is preferable that the average particle diameter of the particle | grains obtained by the said secondary grinding | pulverization is 0.2-1.0 micrometer.

상기 하소는 800-1200℃의 온도에서 행하는 것이 바람직하다.It is preferable to perform the said calcination at the temperature of 800-1200 degreeC.

한편, 상기한 바와같은 본 발명의 파우더 제조공정을, 도 1과 같은 종래공정과 비교하기 위해 도 2에 간략하게 나타내었다.On the other hand, the powder manufacturing process of the present invention as described above is briefly shown in Figure 2 to compare with the conventional process as shown in FIG.

이하, 실시예를 통하여 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.

실시예Example

(발명예 1)(Invention example 1)

Ti 0.5몰, Ba/Ti가 1.1몰인 BaCl2와 TiCl4혼합용액을 농도 2.0몰, 용액온도 80℃ 옥살산 수용액에 5ml/분의 속도로 격렬하게 교반하면서 첨가하여 침전시킨 후, 1일 동안 에이징하였다.BaCl 2 and TiCl 4 mixed solution having 0.5 mol of Ti and 1.1 mol of Ba / Ti was added to precipitate 2.0 ml, 80 ° C solution temperature of oxalic acid with vigorous stirring at a rate of 5 ml / min, and then aged for 1 day. .

에이징하여 얻어진 침전용액을 순수로 잘 세척한 후 오븐에서 100℃로 3시간 건조하여 BTO파우더를 제조하였다. 이 BTO파우더를 전기로에 5℃/분 속도로 850℃에서 열분해한 후, 플라너터리밀(볼크기 2.0mm)로 30분, 180분 1차 분쇄하였다. 이를 다시 전기로에서 1050℃로 하소한 후 플라너터리밀 (볼크기 2.0mm)로 30분 동안?? 2차 분쇄, 건조하여 티탄산바륨파우더 샘플 ⓐ, ⓑ를 제조하였다.The precipitated solution obtained by aging was washed well with pure water and then dried at 100 ° C. in an oven for 3 hours to prepare a BTO powder. The BTO powder was pyrolyzed in an electric furnace at 850 ° C. at a rate of 5 ° C./min, and firstly pulverized with a planetary mill (ball size 2.0 mm) for 30 minutes and 180 minutes. It was calcined again at 1050 ℃ in an electric furnace and then 30 minutes with planetary mill (ball size 2.0mm) ?? Secondary grinding and drying to prepare barium titanate powder samples ⓐ and ⓑ.

이 파우더의 분체 및 유전체(X7R332, 1300℃소결)특성을 측정하여 하기 표1에 나타내었다. 또한, 하소 및 분쇄 후 파우더 조직을 도 3에 나타내었는데, 도 3(a)는 샘플 ⓐ의 하소후 조직이고, 도 3(b)는 샘플 ⓐ의 분쇄후 조직이고, 도 3(c)는 샘플 ⓑ의 하소후 조직이고, 도 3(d)는 샘플 ⓑ의 분쇄후 조직이다.The powder and dielectric properties (X7R332, sintered at 1300 ° C.) of the powder were measured and shown in Table 1 below. In addition, the powder structure after calcination and pulverization is shown in Figure 3, Figure 3 (a) is the post-calcination of the sample ⓐ, Figure 3 (b) is the post-calcination of the sample ⓐ, Figure 3 (c) is a sample After calcination of ⓑ, Fig. 3 (d) shows the post-crushing tissue of sample ⓑ.

하기 표1 및 도 3에서 알 수 있는 바와같이, 특성이 기존방식에 의해 것에 비하여 우수하였으며, 하소후 입자사이에 넥(Neck)을 형성하여 분쇄시 이 넥부분이 쉽게 끊어지므로 입자모양이 구형이며 입도 분포가 균일하고 미분쇄상이 적게 잔조함을 알 수 있었다.As can be seen in Table 1 and Figure 3, the characteristics were superior to those by the conventional method, since the neck portion is easily broken during crushing by forming a neck (neck) between the particles after calcination is spherical shape It was found that the particle size distribution was uniform and the fine pulverized phase remained low.

(비교예)(Comparative Example)

상기 발명예1에서 제조한 BTO파우더를 전기로에서 5℃/분 속도로 850℃, 1050℃에서 열분해하여 플라너터리밀(볼크기 2.0mm)로 60분 동안 분쇄, 건조하여 티탄산바륨파우더 샘플 ①,②를 제조하였다.The BTO powder prepared in Inventive Example 1 was thermally decomposed at 850 ° C. and 1050 ° C. at a rate of 5 ° C./min in an electric furnace, pulverized and dried for 60 minutes with a planetary mill (ball size 2.0 mm), and samples of barium titanate powder ①, ② was prepared.

이 파우더의 분체 및 유전체(X7R332, 1300℃소결)특성을 측정하여 하기 표1에 나타내었다. 또한, 하소 및 분쇄 후 파우더 조직을 도 4에 나타내었는데, 도 4(a)는 샘플 ①의 하소후 조직이고, 도 4(b)는 샘플 ①의 분쇄후 조직이고, 도 4(c)는 샘플 ②의 하소후 조직이고, 도 4(d)는 샘플 ②의 분쇄후 조직이다.The powder and dielectric properties (X7R332, sintered at 1300 ° C.) of the powder were measured and shown in Table 1 below. In addition, the powder structure after calcination and pulverization is shown in Figure 4, Figure 4 (a) is a post-calcination of the sample ①, Figure 4 (b) is a post-crushing structure of the sample ①, Figure 4 (c) is a sample ② is the structure after calcination, Figure 4 (d) is a structure after the grinding of the sample ②.

하기 표1 및 도 4에서 알 수 있는 바와같이, 발명예 1에서 제조한 파우더에 비하여 유전특성이 떨어지고 하소후 입자간의 강한 응결체 형성으로 인하여 분쇄후의 입자형상이 파쇄상이며 입도분포도 균일하지 않았다.As can be seen in Table 1 and Figure 4, the dielectric properties are lower than the powder prepared in Inventive Example 1 and due to the formation of strong aggregates between the particles after calcination, the particle shape after grinding is crushed and the particle size distribution was not uniform.

특성characteristic 샘플ⓐSample ⓐ 샘플ⓑSample ⓑ 샘플①Sample ① 샘플②Sample ② 공정fair 열분해:850℃1차분쇄:30분하소:1050℃2차분쇄:30분Pyrolysis: 850 ° C Primary grinding: 30 minutes Calcining: 1050 ° C Secondary grinding: 30 minutes 열분해:850℃1차분쇄:180분하소:1050℃2차분쇄:30분Pyrolysis: 850 ° C Primary grinding: 180 minutes Calcining: 1050 ° C Secondary grinding: 30 minutes 열분해:850℃분쇄:60분Pyrolysis: 850 ° C Grinding: 60 minutes 열분해:1050℃분쇄:60분Pyrolysis: 1050 ° C Grinding: 60 minutes 분체특성Powder characteristics 평균입경(μm)Average particle size (μm) 0.50.5 0.40.4 0.250.25 0.80.8 비표면적(m2/g)Specific surface area (m 2 / g) 1.901.90 2.662.66 3.943.94 1.301.30 입도분포(μm)Particle size distribution (μm) 0.37,0.80,1.440.37,0.80,1.44 0.31,0.71,1,280.31,0.71,1,28 0.10,0.55,4.190.10,0.55,4.19 0.13,1.21,4.520.13,1.21,4.52 결정화도Crystallinity 4.664.66 2.512.51 2.062.06 5.55.5 Ba/Ti몰Ba / Ti Mall 0.9990.999 0.9990.999 0.9990.999 0.9990.999 BaTiO3순도(wt%)BaTiO 3 Purity (wt%) 99.999.9 99.999.9 99.999.9 99.999.9 유전특성(X7R332)Dielectric Properties (X7R332) 상온유전율Room temperature dielectric constant 31013101 30503050 36823682 30423042 유전손실(%)Dielectric loss (%) 0.810.81 0.800.80 1.421.42 2.512.51 온도계수(%)Temperature coefficient (%) -4.51~5.75-4.51 ~ 5.75 -2.87~3.45-2.87-3.45 -27.6~10.2-27.6-10.2 -10.7~21.1-10.7 ~ 21.1 소결밀도(g/cm3)Sintered Density (g / cm 3 ) 5.775.77 5.805.80 5.615.61 5.555.55 절연저항(1011Ω)Insulation resistance (10 11 Ω) 5.35.3 4.24.2 2.82.8 1.31.3 비고Remarks 발명예Inventive Example 발명예Inventive Example 비교예Comparative example 비교예Comparative example

상기 표1에서 알 수 있는 바와같이, 본 발명에 의한 경우는 기존방법에 의한 비교예는 유전손실, 온도계수, 소결밀도에서 열악하였다. 즉, 비교예는 일반적인 스팩(Spec)인 유전손실 1.0%이하, 온도계수 ±15이내, 소결밀도 5.7g/cm3에 미달되었다.As can be seen in Table 1, in the case of the present invention, the comparative example by the conventional method was poor in dielectric loss, temperature coefficient, and sintered density. That is, the comparative example was less than 1.0% or less of dielectric loss, a temperature coefficient of ± 15 or less, and a sintered density of 5.7 g / cm 3 which is a general specification.

(발명예 2)(Invention example 2)

상기 발명예 1에서 제조한 BTO파우더를 전기로에서 5℃/분 속도로 850℃에서 열분해한 후, 여기에 Ba/(Ba+Ca)=0.95, Ti/(Ti+Zr)=0.95, (Ba+Ca)/(Ti+Zr)=1.003의 조성이 되도록, BaCO3, CaCO3와 ZrO2를 첨가하였다. 이것을 플라너터리밀(볼크기 2.0mm)로 180분 동안 1차분쇄한 후, 전기로에서 1050℃로 하소한 후 플라너터리밀(볼크기 2.0mm)로 30분동안 2차 분쇄, 건조하여 0.5μm의 균일한 구상입자의 BCTZ 복합 파우더(Ba0.95Ba0.05)1.003(Ti0.95Zr0.05)O3를 제조하였다. 제조한 파우더의 특성을 측정한 결과 매우 우수하였다.The BTO powder prepared in Inventive Example 1 was pyrolyzed at 850 ° C. at a rate of 5 ° C./min in an electric furnace, followed by Ba / (Ba + Ca) = 0.95, Ti / (Ti + Zr) = 0.95, (Ba + BaCO 3 , CaCO 3 and ZrO 2 were added so as to have a composition of Ca) / (Ti + Zr) = 1.003. This was first pulverized with a planetary mill (ball size 2.0 mm) for 180 minutes, calcined at 1050 ° C. in an electric furnace, and then crushed and dried for 30 minutes with a planetary mill (ball size 2.0 mm) for 0.5 minutes. BCTZ composite powder (Ba 0.95 Ba 0.05 ) 1.003 (Ti 0.95 Zr 0.05 ) O 3 having a uniform spherical particle size of μm was prepared. As a result of measuring the properties of the powder, it was very excellent.

상술한 바와같은 본 발명에 의하면, 티탄산바륨파우더의 Ba/Ti를 1.000±0.002로 재현성있게 제어할 수 있고, 또한, 입자형상이 구형이고 입도가 균일하며 응결체(Hard Aggromerate) 형성이 적은 파우더를 제조할 수 있어, 이로인하여 입자크기를 크게할 수 있어 MLCC F특성 뿐만아니라 B특성에 적용할 수 있고, 또한, 1차분쇄전에 첨가제를 혼합함으로서 복합페롭스카이트 티탄산바륨계 파우더, 예를 들어, BTZ, BCTZ, BSCTZ 등을 손쉽게 제조할 수 있고, 또한, 수열합성법이나 졸겔법등 다른 액상합성법에 비하여 제조공정이 간단하고 원료비 및 설비투자비가 적게 들어 생산성 및 수율이 좋아 파우더를 싸게 제조할 수 있는 효과가 제공된다.According to the present invention as described above, Ba / Ti of the barium titanate powder can be reproducibly controlled to 1.000 ± 0.002, and powder having a spherical shape, uniform particle size, and low agglomerate formation is obtained. It can be produced, thereby increasing the particle size can be applied to not only MLCC F characteristics but also B characteristics, and also by mixing the additive before the first milling composite perovskite barium titanate-based powder, for example, BTZ, BCTZ, BSCTZ, etc. can be easily manufactured, and the production process is simpler compared to other liquid synthesis methods such as hydrothermal synthesis method and sol gel method, and raw material cost and equipment investment cost are low. The effect is provided.

Claims (17)

염화바륨수용액과 염화티탄수용액을 옥살산 수용액에 첨가하여 바륨티탄산옥살레이트(BTO)를 침전시킨 후, 에이징하고 세척, 여과, 건조하여 바륨티탄산옥살레이트 파우더를 제조하는 단계;Adding barium chloride aqueous solution and titanium chloride aqueous solution to an aqueous solution of oxalic acid to precipitate barium titanate oxalate (BTO), and then aging, washing, filtering and drying to prepare barium titanate oxalate powder; 제조된 티탄산바륨파우더를 열분해한 후, 1차분쇄하여 미립의 파우더를 제조하는 단계; 및Thermally decomposing the prepared barium titanate powder, and then pulverizing the powder to prepare fine powder; And 상기 미립의 파우더를 하소한 후, 2차 분쇄하는 단계를 포함하는 옥살레이트법에 의한 티탄산바륨계 산화물 분말 제조방법Method for producing barium titanate oxide powder by oxalate method comprising calcining the fine powder, and then secondary grinding 제 1 항에 있어서,The method of claim 1, 상기 염화바륨 수용액의 농도가 0.2-2.0mol/l인 것을 특징으로 하는 옥살레이트법에 의한 티탄산바륨계 산화물 분말 제조방법Method for producing barium titanate-based oxide powder by the oxalate method, characterized in that the concentration of the barium chloride aqueous solution is 0.2-2.0 mol / l 제 1 항에 있어서,The method of claim 1, 상기 염화티탄 수용액의 농도가 0.2-2.0mol/l인 것을 특징으로 하는 옥살레이트법에 의한 티탄산바륨계 산화물 분말 제조방법Method for producing a barium titanate-based oxide powder by the oxalate method, characterized in that the concentration of the aqueous titanium chloride solution is 0.2-2.0 mol / l 제 1 항에 있어서,The method of claim 1, 상기 염화바륨과 염화티탄의 몰비가 1-1.5인 것을 특징으로 하는 옥살레이트법에 의한 티탄산바륨계 산화물 분말 제조방법Method for producing barium titanate oxide powder by oxalate method, characterized in that the molar ratio of barium chloride and titanium chloride is 1-1.5 제 1 항에 있어서,The method of claim 1, 상기 옥살산 수용액의 농도가 0.2-5.0mol/l인 것을 특징으로 하는 옥살레이트법에 의한 티탄산바륨계 산화물 분말 제조방법Method for producing barium titanate oxide powder by oxalate method, characterized in that the concentration of the oxalic acid aqueous solution is 0.2-5.0 mol / l 제 1 항에 있어서,The method of claim 1, 상기 옥살산과 상기 염화티탄의 몰비가 1-3.0인 것을 특징으로 하는 옥살레이트법에 의한 티탄산바륨계 산화물 분말 제조방법Method for producing barium titanate oxide powder by oxalate method, characterized in that the molar ratio of oxalic acid and titanium chloride is 1-3.0. 제 1 항에 있어서,The method of claim 1, 상기 옥살산 수용액의 온도가 50-100℃이고, 교반속도는 10-1000rpm/min인 것을 특징으로 하는 옥살레이트법에 의한 티탄산바륨계 산화물 분말 제조방법Method for producing barium titanate oxide powder by the oxalate method, characterized in that the temperature of the oxalic acid aqueous solution is 50-100 ℃, the stirring speed is 10-1000rpm / min 제 1 항에 있어서,The method of claim 1, 상기 염화바륨 수용액과 염화티탄수용액의 첨가속도가 1-50ml/l인 것을 특징으로 하는 옥살레이트법에 의한 티탄산바륨계 산화물 분말 제조방법Method for producing barium titanate-based oxide powder by oxalate method, characterized in that the addition rate of the barium chloride aqueous solution and aqueous titanium chloride solution is 1-50ml / l 제 1 항에 있어서,The method of claim 1, 상기 에이징 시간이 1-100시간인 것을 특징으로 하는 옥살레이트법에 의한 티탄산바륨계 산화물 분말 제조방법Method for producing barium titanate oxide powder by oxalate method, characterized in that the aging time is 1-100 hours 제 1 항에 있어서,The method of claim 1, 상기 건조는 50-200℃에서 행해지는 것임을 특징으로 하는 옥살레이트법에 의한 티탄산바륨계 산화물 분말 제조방법Method for producing barium titanate oxide powder by the oxalate method characterized in that the drying is carried out at 50-200 ℃ 제 1 항에 있어서,The method of claim 1, 상기 열분해는 가열속도가 2-10℃/min이고 유지온도가 600-1000℃인 것을 특징으로 하는 옥살레이트법에 의한 티탄산바륨계 산화물 분말 제조방법The pyrolysis is a barium titanate-based oxide powder manufacturing method by the oxalate method, characterized in that the heating rate is 2-10 ℃ / min and the holding temperature is 600-1000 ℃ 제 1 항에 있어서,The method of claim 1, 상기 파우더의 열분해 후, Ba 또는/및 Ti의 자리에 치환되는 원소를 함유하는 첨가제를 혼합하는 것을 특징으로 하는 옥살레이트법에 의한 티탄산바륨계 산화물 분말 제조방법After pyrolysis of the powder, a method for producing barium titanate oxide powder by the oxalate method, characterized by mixing an additive containing an element substituted in place of Ba or / and Ti. 제 12 항에 있어서,The method of claim 12, 상기 Ba 자리에 치환되는 원소는 Sr, Ca, Mg, Pb 중에서 선택된 1종 또는 2종이상인 것임을 특징하는 티탄산바륨계 산화물 분말 제조방법The element substituted at the Ba site is Sr, Ca, Mg, Pb barium titanate-based oxide powder manufacturing method characterized in that one or two or more selected from 제 12 항에 있어서,The method of claim 12, 상기 Ti 자리에 치환되는 원소는 Ti, Zr, Hf, Sn 중에서 선택된 1종 또는 2종이상인 것임을 특징하는 티탄산바륨계 산화물 분말 제조방법The element substituted at the Ti site is a barium titanate-based oxide powder production method characterized in that one or two or more selected from Ti, Zr, Hf, Sn. 제 12 항 내지 제 14 항 중 어느 한항에 있어서,The method according to any one of claims 12 to 14, 상기 첨가제는 산화물, 탄산화물, 수산화물, 염화물, 질산화물의 형태인 것을 특징으로 하는 티탄산바륨계 산화물 분말 제조방법The additive is a method for producing barium titanate oxide powder, characterized in that the form of oxides, carbonates, hydroxides, chlorides, nitrates 제 1 항에 있어서,The method of claim 1, 상기 1, 2차 분쇄는 크기가 0.2-5.0mm인 볼을 이용하여 10-300분 행하는 강제교반 습식방식에 의한 것임을 특징으로 하는 옥살레이트법에 의한 티탄산바륨계 산화물 분말 제조방법The first and second grinding is a method for producing barium titanate-based oxide powder by the oxalate method, characterized in that by the forced stirring wet method performed for 10-300 minutes using a 0.2-5.0mm ball size 제 1 항에 있어서,The method of claim 1, 상기 하소는 800-1200℃의 온도에서 행하는 것임을 특징으로 하는 옥살레이트법에 의한 티탄산바륨계 산화물 분말 제조방법The calcination is a method for producing barium titanate oxide powder by the oxalate method, characterized in that at a temperature of 800-1200 ℃
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