KR0148065B1 - Manufacturing method of zirconia sheet - Google Patents

Manufacturing method of zirconia sheet

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Publication number
KR0148065B1
KR0148065B1 KR1019950040878A KR19950040878A KR0148065B1 KR 0148065 B1 KR0148065 B1 KR 0148065B1 KR 1019950040878 A KR1019950040878 A KR 1019950040878A KR 19950040878 A KR19950040878 A KR 19950040878A KR 0148065 B1 KR0148065 B1 KR 0148065B1
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zirconia
sheet
present
solvent
powder
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KR1019950040878A
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Korean (ko)
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KR970027006A (en
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오영제
정형진
심인보
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김은영
한국과학기술연구원
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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
    • C04B35/622—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
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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
    • C04B35/622—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
    • C04B35/62625—Wet mixtures
    • C04B35/6264—Mixing media, e.g. organic solvents
    • 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
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/6342—Polyvinylacetals, e.g. polyvinylbutyral [PVB]
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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
    • C04B35/622—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
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63488—Polyethers, e.g. alkylphenol polyglycolether, polyethylene glycol [PEG], polyethylene oxide [PEO]
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    • 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
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3229—Cerium oxides or oxide-forming salts thereof
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    • 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
    • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
    • C04B35/62655—Drying, e.g. freeze-drying, spray-drying, microwave or supercritical drying

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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  • Inorganic Chemistry (AREA)
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  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

본 발명은 폴리비닐부티랄 79 3.0-9.0wt%, 폴리에틸렌글리콜 2.0-5.0wt% 및 디부틸프탈레이트 1.0-4.0wt%로 이루어지며 이들의 비율이 중량비로 3.0-9.0 : 2.0-5.0 :1.0-4.0 인, 자르코니아 시트 제조에 사용되는 유기물 첨가제 조성물 및 그것을 이용하여 닥터 블레이드 성형 방법으로 지르코니아 쉬트를 제조하는 방법에 관한 것이다. 본 발명의 방밥에서는 첨가제의 첨가량을 줄임으로써 밀도가 향상되고, 탈지 또는 소결시 균열이나 휨의 발생이 없는 그린쉬트를 제조할 수 있으며, 혼합 공정을 1단계로 할 수 있어 공정을 단순화시킨다.The present invention is composed of polyvinyl butyral 79 3.0-9.0wt%, polyethylene glycol 2.0-5.0wt% and dibutyl phthalate 1.0-4.0wt% and their ratio is 3.0-9.0: 2.0-5.0: 1.0-4.0 by weight It relates to an organic additive composition used for the production of phosphorus, zirconia sheet and a method for producing a zirconia sheet by a doctor blade molding method using the same. In the Bangbang of the present invention, by reducing the amount of the additive added, the density can be improved, and a green sheet can be produced without the occurrence of cracks or warping during degreasing or sintering, and the mixing process can be performed in one step, thereby simplifying the process.

Description

지르코니아 쉬트 제조방법Zirconia Sheet Manufacturing Method

본 발명은 지르코니아 쉬트 제조에 사용되는 유기물 첨가제 조성물 및 그것을 사용하여 닥터 블레이드 성형방법으로 지르코니아 쉬트를 제조하는 방법에 관한 것이다. 본 발명의 밥법으로 제조된 지르코니아 쉬트는 고밀도 지르코니아 쉬트이므로 연료전지분야, 고체전해질형 및 한계전류형 산소센서분야 등의 다양한 분야에 응용할 수 있다.The present invention relates to an organic additive composition used in the production of zirconia sheets and a method for producing a zirconia sheet by a doctor blade molding method using the same. Since the zirconia sheet produced by the rice method of the present invention is a high density zirconia sheet, it can be applied to various fields such as fuel cell field, solid electrolyte type and limit current type oxygen sensor field.

닥터 블레이드 세라믹스 성형방법은 미세한 세라믹스 분말을 수계 또는 비수계 용매를 혼합한 후, 여기에 결합제, 가소제, 분산제, 소포제 등을 적정한 비율로 혼합하여 세라믹스 슬러리를 제조하고, 움직이는 블레이드 또는 움직이는 운반 필름 위에 일정한 두께로 목적하는 바에 따라서 성형하고, 용매를 제거하여 그린 쉬트를 제조하는 과정으로 이루어지며, 테이프 캐스팅법이라고도 불려진다.Doctor blade ceramics molding method is to prepare a ceramic slurry by mixing a fine ceramic powder with an aqueous or non-aqueous solvent, and then mixing a binder, a plasticizer, a dispersant, an antifoaming agent and the like in an appropriate ratio, and a constant on a moving blade or a moving carrier film. Forming as desired by thickness, and removing the solvent to produce a green sheet, also called a tape casting method.

일반적으로, 세라믹스 분말과 여러 유기 첨가제를 혼합하는 과정은, 먼저 용매와 세라믹스 분말만을 혼합하여 20시간 이상 1차 볼밀을 수행한 후, 결합제, 가소제, 분산제 등의 유기 첨가제를 첨가 혼합하여 20시간 이상 2차 볼밀을 수행하는 과정을 거치게 된다.In general, the process of mixing the ceramic powder and the various organic additives, first mixing only the solvent and the ceramic powder to perform the first ball mill 20 hours or more, and then add and mix the organic additives such as binders, plasticizers, dispersants 20 hours or more The second ball mill goes through the process.

일반적으로 세라믹스 성형에 첨가되어지는 유기물 첨가제는 기능에 따라서 결합제, 가소제, 분산제, 소포제, 용매 등 여러 가지로 구분가능하다. 이들 유기물 첨가제는 실제 공정중에서 최소한 3가지 이상이 첨가되어지며, 유기물 첨가제의 첨가 순서, 첨가량 등은 닥터 블레이드 성형 공정에 지대한 영향을 미치는 요소이다. 세라믹스 슬러리 제조시 첨가되는 유기물 첨가제와 첨가량이 많으면 세라믹스 그린쉬트의 그린 밀도가 낮아질 뿐 아니라, 탈지과정에서 균열이나 휨이 발생하거나 파괴되는 문제점, 소결 후 소결밀도가 낮아지는 문제점이 발생한다.In general, organic additives added to ceramic molding may be classified into various types such as binders, plasticizers, dispersants, antifoaming agents, solvents, and the like, depending on their functions. At least three or more of these organic additives are added in the actual process, and the order of addition and amount of the organic additives have a great influence on the doctor blade forming process. If the organic additives and the amount of the additives added during the manufacture of the ceramic slurry are not only lower the green density of the ceramic green sheet, but also cause problems such as cracking or warping occurring or breaking during degreasing, and sintering density after sintering.

본 발명은 종래 기술에 있어서 문제점으로 남아있던 밀도 저하문제, 탈지시 균열이나 휨 발생, 소결시 균열 문제 등이 현저히 개선된 세라믹스 슬러리를 제조 할 수 있는 유기물 첨가제 조성물을 제공한다.The present invention provides an organic additive composition capable of producing a ceramic slurry, which is a marked improvement in density reduction problem, crack or warpage during degreasing, crack problem during sintering, etc., which remains a problem in the prior art.

또한 본 발명은 종래의 경우보다 유기물 첨가제의 첨가량을 줄임으로써, 지르코니아 제조 단가를 낮출 수 있고 소결 후 고밀도를 얻을 수 있는 지르코니아 그린 쉬트를 제조하는 방법을 제공한다.In addition, the present invention provides a method for manufacturing a zirconia green sheet which can lower the production cost of zirconia and obtain a high density after sintering by reducing the addition amount of the organic additive than the conventional case.

또한 본 발명은 세라믹스 분말과 유기 첨가제의 혼합과정을 한 과정으로 단순화시킨 지르코니아 쉬트 제조방법을 제공한다.The present invention also provides a method for producing a zirconia sheet which simplifies the mixing process of the ceramic powder and the organic additive in one process.

본 발명의 방법은 일반적으로 1차, 2차의 혼합과정을 거쳐 제조하는 종래의 방법에서 탈피하여 1차 혼합과정만을 수행함으로써 제조 공정의 단순화로 실용화에 있어서 경제적 잇점이 크고, 유기물 첨가제의 첨가량을 줄임으로써 종래의 것보다 고밀도인 지르코니아 그린쉬트를 제조할 수 있다.The method of the present invention is largely economically advantageous in practical use as a simplification of the manufacturing process by performing only the first mixing process by eliminating the conventional method of manufacturing through the mixing process of the first and second generally, and the addition amount of the organic additives By reducing, it is possible to produce zirconia green sheets of higher density than conventional ones.

본 발명에 따른 유기물 첨가제 조성물은 폴리비닐부티랄(polyvinylbutyral)폴리에틸렌글리콜(polyethyleneglycol) 및 디부틸프탈레이트(dibutylphthalate)로 이루어지며 이들의 비율이 중량비로 3.0-9.0 : 2.0-5.0 : 1.0-4.0이다.The organic additive composition according to the present invention is composed of polyvinylbutyral polyethyleneglycol and dibutylphthalate and their ratio is 3.0-9.0: 2.0-5.0: 1.0-4.0 by weight.

본 발명의 유기물 첨가제 조성물을 이용한 지르코니아 쉬트 제조방법은 다양한 세라믹스 분말에 적용할 수 있으며, 예를 들어, 안정화 8Y-ZrO2분말 또는 (8Y-ZrO2)1-x(CeO2)x분말(0.1X0.6)을 출발물질로 하여 지르코니아 쉬트를 제조할 수 있다.Zirconia sheet production method using the organic additive composition of the present invention can be applied to a variety of ceramic powder, for example, stabilized 8Y-ZrO 2 powder or (8Y-ZrO 2 ) 1-x (CeO2) x powder (0.1X0 .6) can be used as starting material for the production of zirconia sheets.

본 발명의 방법에서는 닥터 블레이드 방법을 응용하여, 세라믹스 분말, 유기물 첨가제 조성물과 용매를 한꺼번에 혼합, 분쇄하여 슬러리를 만든 후, 건조, 소결하여 지르코니아 소결체를 얻는다.In the method of the present invention, the doctor blade method is applied, and the ceramic powder, the organic additive composition and the solvent are mixed and pulverized at the same time to form a slurry, followed by drying and sintering to obtain a zirconia sintered body.

용매로는 닥터 블레이드 성형공정에 일반적으로 사용되는 용매는 어느 것이나 사용할 수 있다. 용매는 건조공정에 영향을 미치므로 단일 용매보다도 휘발도가 다른 2 가지 용매의 공비(azeotropic) 용매를 혼합하여 사용하는 것이 좋으며, 예를 들어 메틸에틸케톤(40wt%) + 에탄올(60wt%)의 혼합용매를 사용할 수 있다.As the solvent, any solvent generally used in the doctor blade forming step may be used. Since the solvent affects the drying process, it is preferable to use azeotropic solvents of two solvents having different volatilities than a single solvent, for example, methyl ethyl ketone (40 wt%) + ethanol (60 wt%). Mixed solvents can be used.

이하 실시예를 통해 본 발명을 더욱 자세히 설명할 것이나, 실시예에 의해 본 발명의 범위가 제한되지는 않는다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited by Examples.

[실시예 1]Example 1

세라믹스 분말인 8Y-ZrO272wt%, 폴리비닐부티랄 7wt%, 폴리에틸렌글리콜 5wt%, 디부틸프탈레이트 4wt% 와 메틸에틸케톤(40wt%) + 에탄올(60wt%)] 12wt% 을 칭량하였다. 이들을 지르코니아 볼밀에 동시에 넣어 145rpm 으로 24시간 혼합, 분쇄하였다. 혼합물 내의 기포를 제거하기 위하여 통상적인 방법에 따라 진공펌프를 이용하여 탈포과정을 거쳤으며, 원하는 두께의 그린 쉬트를 얻기 위하여 슬러리 점도를 21,000cps로 조절하였다.72 wt% of ceramic powder 8Y-ZrO 2, 7 wt% of polyvinyl butyral, 5 wt% of polyethylene glycol, 4 wt% of dibutyl phthalate and 12 wt% of methyl ethyl ketone (40 wt%) + ethanol (60 wt%)] were weighed. These were simultaneously put into a zirconia ball mill and mixed and ground at 145 rpm for 24 hours. In order to remove bubbles in the mixture, a defoaming process was performed using a vacuum pump according to a conventional method, and the slurry viscosity was adjusted to 21,000 cps to obtain a green sheet having a desired thickness.

닥터 블레이드 성형 장치로 지르코니아 쉬트를 성형한 후 실온에서 3일간 건조 공정을 거쳐 안정화 8Y-ZrO2을 제조하였다. 유기물을 제조하기 위하여 600℃에서 탈지시키고, 1500℃에서 소결하여 완전한 지르코니아 소결체를 얻었다.After the zirconia sheet was molded by the doctor blade molding apparatus, a stabilized 8Y-ZrO 2 was produced through a drying process at room temperature for 3 days. In order to manufacture an organic substance, it degreased at 600 degreeC and sintered at 1500 degreeC, and obtained the complete zirconia sintered compact.

그린 쉬트에 외관 검사를 통하여 쉬트내 기포나 균열이 존재하지 않음을 확인하였으며 측정 결과를 표1에 제시한다.Visual inspection of the green sheet confirmed that there were no bubbles or cracks in the sheet and the measurement results are shown in Table 1.

[실시예 2]Example 2

세라믹스 분말인 8Y-ZrO 72wt%, CeO23wt%, 폴리비닐부티랄 9wt%, 폴리에틸렌글리콜 5wt%, 디부틸프탈레이트 4wt%, 메틸에틸케톤(40wt%) + 에탄올(60wt%)]11wt%을 칭량하였다. 이들을 지르코니아 볼밑에 동시에 넣어 145rpm 으로 24시간 혼합, 분쇄하였다. 혼합물내의 기포를 제거하기 위하여 탈포과정을 거쳤으며, 원하는 두께의 그린 쉬트를 얻기 위하여 슬러리 점도를 25,000cps로 조절하였다. 실시예1과 같은 방법을 성형, 건조, 탈지 및 소결시켜 CeO2를 함유하는 지르코니아 소결체를 얻었다.Weighing ceramics powder 8Y-ZrO 72wt%, CeO 2 3wt%, polyvinyl butyral 9wt%, polyethylene glycol 5wt%, dibutyl phthalate 4wt%, methyl ethyl ketone (40wt%) + ethanol (60wt%)] 11wt% It was. These were simultaneously put under zirconia balls, mixed and ground at 145 rpm for 24 hours. Defoaming was performed to remove bubbles in the mixture, and the slurry viscosity was adjusted to 25,000 cps to obtain a green sheet of a desired thickness. In Example 1 by molding, drying, degreasing and sintering the same way as to obtain a sintered body of zirconia containing CeO 2.

그린쉬트의 외관 검사를 통하여 쉬트네 기포나 균열이 존재하지 않음을 확인하였으며 측정 결과를 표1에 제시한다.Examination of the green sheet confirmed that no sheet bubbles or cracks existed, and the measurement results are shown in Table 1.

Claims (3)

세라믹스 분말 72.5-60.0wt%, 폴리비닐부티랄 3.0-9.0wt%, 폴리에틸렌글리콜 2.0-5.0wt%, 디부틸프탈레이트 1.0-4.0wt% 및 용매 10-22wt%를 동시에 분쇄하며 혼합한 후 성형하고 건조하는 것으로 이루어지는 지르코니아 쉬트 제조방법.Ceramics powder 72.5-60.0wt%, polyvinyl butyral 3.0-9.0wt%, polyethylene glycol 2.0-5.0wt%, dibutyl phthalate 1.0-4.0wt% and solvent 10-22wt% are simultaneously pulverized, mixed, molded and dried The zirconia sheet manufacturing method which consists of doing. 제2항에 있어서, 상기 세라믹스 분말이 8Y-ZrO2분말 또는 (8Y-ZrO2)1-x(CeO2)x분말(0.1X0.6)인 제조방법.The method of claim 2, wherein the ceramic powder is 8Y-ZrO 2 powder or (8Y-ZrO 2 ) 1-x (CeO 2) x powder (0.1 × 0.6). 제2항에 있어서, 상기 용매가 메틸에틸케톤(40wt%)과 에탄올(60wt%)의 혼합용매인 제조방법.The method of claim 2, wherein the solvent is a mixed solvent of methyl ethyl ketone (40 wt%) and ethanol (60 wt%).
KR1019950040878A 1995-11-11 1995-11-11 Manufacturing method of zirconia sheet KR0148065B1 (en)

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