KR960011353B1 - Composition of ceramic slurry - Google Patents

Composition of ceramic slurry Download PDF

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KR960011353B1
KR960011353B1 KR1019930020439A KR930020439A KR960011353B1 KR 960011353 B1 KR960011353 B1 KR 960011353B1 KR 1019930020439 A KR1019930020439 A KR 1019930020439A KR 930020439 A KR930020439 A KR 930020439A KR 960011353 B1 KR960011353 B1 KR 960011353B1
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tape
slurry composition
ceramic slurry
added
ceramic
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KR950011373A (en
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이준근
김영욱
박태희
조항선
임동기
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한국과학기술연구원
김은영
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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
    • C04B35/62615—High energy or reactive ball 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
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/584—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
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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
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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
    • C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/6342—Polyvinylacetals, e.g. polyvinylbutyral [PVB]
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    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C—CHEMISTRY; METALLURGY
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    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/40—Surface-active agents, dispersants
    • C04B2103/408—Dispersants
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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
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602—Making the green bodies or pre-forms by moulding
    • C04B2235/6025—Tape casting, e.g. with a doctor blade

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
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  • Compositions Of Oxide Ceramics (AREA)

Abstract

The composition comprises a sintering agent, dispersing agent and ceramic powder as a major component, and other solvents. The process using this composition includes the addition of a binder and a plasticizer to the first slurry obtained by ball milling, followed by manufacturing tape casting. The composition provides the hindered settling of ceramic powder with the passage of time, which is less susceptible to cracking during drying after tape casting.

Description

세라믹스 슬러리 조성물Ceramic slurry composition

본 발명은 세라믹스의 테이프성형에 적합한 슬러리 조성에 관한 것으로, 특히 질화규소나 질화 알루미늄분말을 주조성으로 하고 여기에 소량의 소결조제와 분산제 및 첨가제를 첨가하여 분산특성을 향싱시킴으로써 시간의 경과에 따른 세라믹 분말의 침강을 억제하여 테이프성형 후의 건조시에 균열이 일어나지 않도록 한 세라믹스 슬러리 조성물에 관한 것이다.The present invention relates to a slurry composition suitable for tape molding of ceramics, and in particular, silicon nitride or aluminum nitride powder is castable, and a small amount of sintering aid, dispersant, and additive is added to enhance the dispersing characteristics. The present invention relates to a ceramic slurry composition in which sedimentation of powder is suppressed so that cracking does not occur during drying after tape molding.

일반적으로 세라믹스 제조공정중의 한단계인 성형공정은 대개 테이프 성형 방법이나 주입성형 방법의 어느 한 방법을 통해서 이루어지고 있다.In general, the molding process, which is one step in the ceramic manufacturing process, is usually performed through either a tape forming method or an injection molding method.

테이프성형공정은 25~1200㎛ 범위의 얇은 두께와 넓은 면적을 갖는 판상의 세라믹 박막제조에 적합한 방법으로서, 이러한 테이프성형공정을 통해 얻어지진 박막상의 테이프는 다층 축전기의 기판을 비롯한 패키지 및 발열체의 기판등으로 널리 사용되고 있다.The tape forming process is suitable for the manufacture of plate-shaped ceramic thin films having a thin thickness and a large area in the range of 25 to 1200 μm. The thin film tape obtained through the tape forming process is a substrate of a package and a heating element including a substrate of a multilayer capacitor. Widely used.

일반적으로 테이프성형공정을 미국특허 제2,966,719호, 제3,698, 923호 및 5002,710호 등에 잘 나타나 있는데, 이들 특허 명세서에 나타나 있는 테이프성형공정을 요약하면 세라믹 분말에 분산제와 용매를 함께 넣어 볼밀링하여 1차슬러리를 얻은 다음, 이 1차슬러리에 바인더와 가소제를 첨가하여 다시 밀링함으로써 2차슬러리를 제조하고, 필요시 탈포공정을 거친 후에 닥터블레이드 장치를 이용하여 테이프 형태로 성형하고 있다. 이때 1차슬러리 제조시 필요에 따라서는 젖음촉진제 및 소포제(기포제거제) 등의 첨가제가 첨가되기도 한다.Generally, the tape forming process is well described in US Pat. Nos. 2,966,719, 3,698, 923, and 5002,710. The tape forming process described in these patent specifications is summarized by ball milling with a dispersant and a solvent in a ceramic powder. After the first slurry was obtained, the secondary slurry was prepared by adding a binder and a plasticizer to the primary slurry and milling again, followed by a defoaming step if necessary, followed by molding into a tape using a doctor blade device. At this time, additives such as a wetting accelerator and an antifoaming agent (bubble removing agent) may be added as needed in the production of the primary slurry.

상기 테이프성형공정을 통해 성형된 테이프나 세라믹스 성형체는 후속공정으로서 건조공정을 거치게 되는데, 이때 슬러리의 분산상태에 따라 건조공정 도중에 균열이 발생할 수 있기 때문에 효과적으로 분산된 슬러리의 제조가 요구되고 있다.The tape or ceramic molded body formed through the tape forming process is subjected to a drying process as a subsequent process. In this case, since the cracking may occur during the drying process according to the dispersion state of the slurry, the production of the dispersed slurry is required.

이에따라 슬러리의 분산효과를 높이기 위해 각종 세라믹 분말에 적합한 분산제를 선택하여 사용하는 것이 매우 중요하다.Accordingly, it is very important to select and use a dispersant suitable for various ceramic powders in order to increase the dispersion effect of the slurry.

특히, 질화규소 및 질화알루미늄의 테이프성형을 위한 슬러지의 경우에는 아직까지 이들 세차믹스 분말에 적합한 슬러리 조성 및 분산제가 알려지고 있지 않은 실정이에서 현재 이들 세라믹스 분말에 적합한 분산제와 슬러리 조성의 개발이 절실하게 요구되고 있다.Particularly, in the case of sludge for tape forming of silicon nitride and aluminum nitride, a slurry composition and a dispersant suitable for these premixed powders are not known yet. Therefore, the development of a dispersant and a slurry composition suitable for these ceramic powders is urgently needed. It is required.

따라서, 본 발명은 질화규소 및 질화알루미늄의 테이프성형에 적합한 슬러리 조성으로서 건조시 균열이 발생하지 않는 우수한 분산특성의 세라믹스 슬러리 조성물을 제공하는데 목적이 있다.Accordingly, an object of the present invention is to provide a ceramic slurry composition having excellent dispersion characteristics in which cracking does not occur when drying as a slurry composition suitable for tape forming of silicon nitride and aluminum nitride.

본 발명에 의한 테이프성형공정에서는 일정한 범위의 입도분포를 갖는 세라믹 분말에 소결조제, 분산제 및 용매를 첨가하여 볼밀링함으로써 원료분말의 균일한 분산과 충분한 혼합이 이루어지도록 하여 1차슬러리에 제조한 후 이 1차슬러리에 바인더와 가소제를 가하여 다시 볼밀림함으로써 2차슬러리를 제조하여 이를 진공 장치중에 장입하여 탈표공정을 행한 다음 닥터블레이드 장치를 이용하여 테이프성형 및 건조공정을 거쳐 세라믹 테이프를 제조한다.In the tape molding process according to the present invention, after sintering aid, dispersant and solvent are added to the ceramic powder having a particle size distribution in a certain range, the ball mill is made to uniformly disperse the raw powder and make sufficient mixing to prepare the first slurry. A binder and a plasticizer are added to the primary slurry to ball mill again to prepare a secondary slurry, charged into a vacuum apparatus, subjected to a de-marking step, and then subjected to a tape forming and drying process using a doctor blade apparatus to produce a ceramic tape.

상기 테이프성형공정에서 슬러리를 이루고 있는 세라믹 분말은 질화규소 및 질화알루미늄이며, 소결조제로는 Ca, Al, Si, Y, Mg, Sc, Nb, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Hf, Ta 등의 산화믈 중 선택되는 1가지 이상의 산화물이 1~18%(이하, 모든 %는 중량%임) 첨가하는 것이 바람직하다.The ceramic powder constituting the slurry in the tape forming process is silicon nitride and aluminum nitride, and sintering aids include Ca, Al, Si, Y, Mg, Sc, Nb, La, Ce, Pr, Nd, Sm, Gd, Tb, At least one oxide selected from among oxides such as Dy, Ho, Er, Tm, Yb, Hf, Ta, and the like is preferably added in an amount of 1 to 18% (hereinafter, all% are by weight).

그리고 분산제는 폴리옥시카보닐펜타메틸렌을 0.1~6% 첨가하는 것이 바람직하고, 용매는 메틸에틸케톤, 메틸이소부틸케톤, 톨루엔, 아세톤, 이소프로필알콜,씨크롤헥사논 중의 하나 또는 둘 이상의 혼합물로서 건조고체량에 대하여 20~90% 첨가하는 것이 바람직하다.In addition, the dispersant is preferably 0.1 to 6% of polyoxycarbonylpentamethylene, and the solvent is methyl ethyl ketone, methyl isobutyl ketone, toluene, acetone, isopropyl alcohol, cyclohexanone, or a mixture of two or more thereof. It is preferable to add 20-90% with respect to dry solid weight.

또한, 볼밀링은 폴리프로필렌 또는 세라믹 볼밀과 세라믹 볼을 사용하여 3~72시간 행하는 것이 적당하다.Moreover, it is suitable to perform ball milling for 3 to 72 hours using a polypropylene or a ceramic ball mill and a ceramic ball.

상기 바인더는 폴리비닐부틸알을 건조고체량에 대하여 1~20% 첨가하고, 가소제는 폴리에틸렌글리콜, 벤질부틸프탈레이트, 디옥틸프탈레이트 디부틸프탈레이트 중의 하나 또는 둘 이상의 혼합물로서 건조고체량에 대하여 1~20% 첨가하는 것이 바람직하다.The binder is added 1 to 20% of polyvinyl butylal to dry solids, and the plasticizer is a mixture of one or two or more of polyethylene glycol, benzyl butyl phthalate and dioctyl phthalate dibutyl phthalate to 1 to 20 based on dry solids. It is preferable to add%.

그리고, 탈포공정은 50~2000tpm의 교반기를 사용하여 0.01~80torr의 진공에서 수행하고, 닥터블레이드 장치를 이용한 테이브성형공정은 항온, 항습조건에서 0.1~2.0m/min의 속도로 하는 것이 바람직하다.In addition, the defoaming process is carried out in a vacuum of 0.01 ~ 80torr using a stirrer of 50 ~ 2000tpm, the tape forming process using a doctor blade device is preferably at a speed of 0.1 ~ 2.0m / min at constant temperature, constant humidity conditions. .

이와같은 제조공정을 통해 얻어진 본 발명의 슬러리 조성물은 분산 특성이 우수하여 슬러리 제조 후 48시간 경과 후에도 세라믹 분말이 침강되지 않으며, 테이프성형 후의 건조단계에서 균열이 발생하지 않는 장점이 있다.The slurry composition of the present invention obtained through such a manufacturing process is excellent in dispersing characteristics, so that the ceramic powder does not precipitate even after 48 hours of slurry production, and there is an advantage that cracking does not occur in the drying step after tape molding.

본 발명 세라믹스 슬러리 조성물의 기술적 특성과 제조공정은 다음의 실시예를 통하여 보다 명확하게 이해될 것이다.Technical characteristics and manufacturing process of the ceramic slurry composition of the present invention will be more clearly understood through the following examples.

실시예 1Example 1

0.2~3.0㎛ 범위의 입도분포를 갖는 질화규소 분말에 소결조제로서 산화이르비움 및 산화규소, 분산제로서 폴리옥시카보닐 펜타메틸렌을 첨가하고, 메틸에틸케톤, 메틸이소부틸케톤, 이소프로필알콜을 용매로하여 폴리프로필렌 볼밀과 질화규소볼을 사용하여 8시간 동안 볼밀링하여 1차슬러리를 제조하였다. 이때 슬러리의 각 성분에 대한 첨가량은 아래의 표 1에 나타나 있다.To the silicon nitride powder having a particle size distribution in the range of 0.2 to 3.0 μm, yrbium oxide, silicon oxide and polyoxycarbonyl pentamethylene as dispersant are added, and methyl ethyl ketone, methyl isobutyl ketone and isopropyl alcohol are used as a solvent. The first slurry was prepared by ball milling for 8 hours using a polypropylene ball mill and silicon nitride balls. At this time, the addition amount for each component of the slurry is shown in Table 1 below.

상기 스러리를 바인더로서 표 1에서와 같은 비율의 폴리비닐부틸알과 가소제로서 폴리에틸렌글리콜 및 벤질 부틸프탈레이트를 넣고 24시간 동안 상기 볼밀과 볼을 사용하여 밀링한 다음, 진공탈포기를 사용하여 200rpm의 속도 및 1torr의 진공으로 1시간 탈포한 후, 22℃±3℃의 온도와 70%±10%의 습도에서 0.3m/min의 속도로 테이프성형공정을 거쳐서, 실온에서 7일간 건조함으로서 2m×0.12m×0.001m 크기의 질화규소 테이프를 제조하였다. 이렇게 제조된 질화규소 테이프는 54%의 성형 밀도를 가지며, 건조공정중 균열이 전혀 발생하지 않았다.Polyurethane butylal in the same ratio as shown in Table 1 and polyethylene glycol and benzyl butylphthalate as plasticizers were milled for 24 hours using the ball mill and the ball, and then the vacuum degassing machine was used at 200 rpm. After degassing for 1 hour by the speed and vacuum of 1torr, and then tape forming at 0.3m / min at 22 ℃ ± 3 ℃ and 70% ± 10% humidity, drying at room temperature for 7 days, 2m × 0.12 A silicon nitride tape of m × 0.001 m size was prepared. The silicon nitride tape thus produced had a molding density of 54% and no cracking occurred during the drying process.

실시예 2Example 2

0.8~2.5㎛ 범위의 입도분포를 갖는 질화알루미늄 분말에 소결조제로서 산화이트륨 및 산화알루미늄, 분산제로서 폴리옥시카보닐펜타메틸렌을 아래의 표 2와 같은 조성으로 첨가하고 메틸에틸케톤, 메틸이소부틸케톤, 씨틀로헥사논을 용매로하여 산화알루미늄 볼밀과 산화알루미늄 볼을 사용하여 8시간 동안 볼밀링하여 1차 슬러리를 제조하였다. 상기 슬러리에 바인더로서 표 2에서 보여준 비율의 폴리비닐부틸알과 가소제로서 폴리에틸렌글리콜 및 디부틸프탈레이트를 넣고 24시간 동안 상기 볼밀과 볼을 사용하여 밀링한 다음, 진공탈포기를 사용하여 200rpm의 속도 및 1torr의 진공으로 1시간 탈포한 후, 22℃±3℃의 온도와 70%±10%의 습도에서 0.3m/min의 속도로 테이프성형공정을 거쳐서, 실온에서 7일간 건조함으로서 2m×0.12m×0.001m 크기의 질화알루미늄 테이프를 제조하였다. 이렇게 제조된 질화알루미늄 테이프는 57%의 성형 밀도를 가지며, 건조공정중 균열이 전혀 발생하지 않았다.Yttrium oxide and aluminum oxide as a sintering aid and polyoxycarbonylpentamethylene as a dispersant were added to the aluminum nitride powder having a particle size distribution in the range of 0.8 to 2.5 μm in the composition shown in Table 2 below, and methyl ethyl ketone and methyl isobutyl ketone The first slurry was prepared by ball milling for 8 hours using an aluminum oxide ball mill and an aluminum oxide ball, using cyclohexanone as a solvent. Polyvinyl butyl al in the ratio shown in Table 2 as a binder and polyethylene glycol and dibutyl phthalate as a plasticizer were added to the slurry and milled using the ball mill and the ball for 24 hours, and then a vacuum degassing machine was used at a speed of 200 rpm and After degassing for 1 hour in a vacuum of 1 torr, and then performing tape molding at a rate of 0.3 m / min at a temperature of 22 ° C. ± 3 ° C. and a humidity of 70% ± 10%, drying at room temperature for 7 days to obtain 2 m × 0.12 m × An aluminum nitride tape having a size of 0.001 m was prepared. The aluminum nitride tape thus produced had a molding density of 57% and no cracking occurred during the drying process.

실시예 3Example 3

실시에 1과 동일한 방법으로 테이프성형용 질화규소 슬러리를 제조하였는데, 단지 소결조제를 산화이르비움 대신 산화이트륨으로, 산화규소 대신 산화알루미늄으로 대체하여 슬러리를 제조하여 실시예 1과 동일한 방법으로 테이프성형공정 및 건조공정을 거쳐 2m×0.12m×0.001m 크기의 질화알루미늄 테이프를 제조하였다. 이렇게 제조된 질화알루미늄 테이프는 57%의 성형 밀도를 가지며, 건조공정중 균열이 전혀 발생하지 않았다.Tapered silicon nitride slurry was prepared in the same manner as in Example 1, except that only the sintering aid was replaced with yttrium oxide instead of yttrium oxide and aluminum oxide instead of silicon oxide to prepare a slurry, and the tape forming process was performed in the same manner as in Example 1. And an aluminum nitride tape having a size of 2 m × 0.12 m × 0.001 m through a drying process. The aluminum nitride tape thus produced had a molding density of 57% and no cracking occurred during the drying process.

Claims (7)

세라믹 분말에 소결조제와 분산제를 첨가하고 용매를 가하여 볼밀링하여 얻어진 1차슬러리에 바인더와 가소제를 첨가하여 다시 볼밀링하여 제조되는 테이프성형용 세라믹스 슬러리 조성물.A tape molding ceramic slurry composition prepared by adding a sintering aid and a dispersing agent to a ceramic powder and adding a solvent to the first slurry obtained by ball milling to add a binder and a plasticizer. 제1항에 있어서, 세라믹 분말은 0.2~3.0㎛의 입도분포를 갖는 질화규소 분말 또는 질화알루미늄 분말인 테이프성형용 세라믹스 슬러리 조성물.The ceramic slurry composition for tape molding according to claim 1, wherein the ceramic powder is silicon nitride powder or aluminum nitride powder having a particle size distribution of 0.2 to 3.0 µm. 제1항에 있어서, 소결조제로 Ca, Al, Si, Y, Mg, Sc, Nb, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Hf, Ta 등의 산화물 중 선택되는 1가지 이상의 산화물이 1~18% 첨가된 테이프성형용 세라믹 슬러리 조성물.The method of claim 1, wherein the sintering aid is Ca, Al, Si, Y, Mg, Sc, Nb, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Hf, Ta Tape molding ceramic slurry composition to which 1 to 18% of at least one oxide selected from oxides, such as these, is added. 제1항에 있어서, 분산제로 폴리옥시카보닐펜타메틸렌이 0.1~6중량% 첨가된 테이프성형용 세라믹 슬러리 조성물.The tape-forming ceramic slurry composition according to claim 1, wherein 0.1 to 6% by weight of polyoxycarbonylpentamethylene is added as a dispersant. 제1항에 있어서, 용매로 메틸에틸케톤, 메틸이소부틸케톤, 톨루엔, 아세톤, 이소프로필알콜, 씨클로헥사논중의 하나 또는 둘 이상의 혼합물이 건조고체량에 대하여 20~90% 첨가된 테이프성형용 세라믹 슬러리 조성물.The tape forming method according to claim 1, wherein one or more mixtures of methyl ethyl ketone, methyl isobutyl ketone, toluene, acetone, isopropyl alcohol, and cyclohexanone are added in an amount of 20 to 90% with respect to dry solids. Ceramic slurry composition. 제1항에 있어서, 바인더로 폴리비닐부틸알이 건조고체량에 대하여 1~20%중량% 첨가된 테이프성형용 세라믹 슬러리 조성물.The tape-forming ceramic slurry composition according to claim 1, wherein 1 to 20% by weight of polyvinyl butylal is added to the dry solids as a binder. 제1항에 있어서, 가소제로 폴리에틸렌글리콜, 벤질부틸프탈레이트 디옥틸프탈레이트 디부틸프탈레이트 중 1가지 또는 2가지 이상이 건조고체량에 대하여 1~20중량% 첨가된 테이프성형용 세라믹 슬러리 조성물.The tape molding ceramic slurry composition according to claim 1, wherein one or two or more of polyethylene glycol and benzyl butyl phthalate dioctyl phthalate dibutyl phthalate are added in an amount of 1 to 20% by weight based on the dry solid weight.
KR1019930020439A 1993-10-04 1993-10-04 Composition of ceramic slurry KR960011353B1 (en)

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Publication number Priority date Publication date Assignee Title
KR101239356B1 (en) * 2010-12-21 2013-03-05 한국원자력연구원 Fabrication method of hydrophobic polymer coated ceramic nano powder and ceramic nano powder thereby

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101239356B1 (en) * 2010-12-21 2013-03-05 한국원자력연구원 Fabrication method of hydrophobic polymer coated ceramic nano powder and ceramic nano powder thereby

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