JPH01294557A - Production of ceramic thin film - Google Patents
Production of ceramic thin filmInfo
- Publication number
- JPH01294557A JPH01294557A JP63126681A JP12668188A JPH01294557A JP H01294557 A JPH01294557 A JP H01294557A JP 63126681 A JP63126681 A JP 63126681A JP 12668188 A JP12668188 A JP 12668188A JP H01294557 A JPH01294557 A JP H01294557A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- drying
- slurry
- ceramic thin
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 26
- 239000010409 thin film Substances 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000001035 drying Methods 0.000 claims abstract description 26
- 239000002002 slurry Substances 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 19
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 10
- 230000007062 hydrolysis Effects 0.000 claims abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims abstract description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 8
- 238000010304 firing Methods 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 4
- GYIWFHXWLCXGQO-UHFFFAOYSA-N barium(2+);ethanolate Chemical compound [Ba+2].CC[O-].CC[O-] GYIWFHXWLCXGQO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 3
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000007761 roller coating Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は金属アルコキシドを用いて塗布することにより
薄膜を作成するセラミック薄膜の製造方法に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a ceramic thin film by coating with a metal alkoxide.
［従来の技術］
従来、セラミック薄膜を製造する方法として、溶射、ス
パッタリング等の気相法が知られている。[Prior Art] Conventionally, vapor phase methods such as thermal spraying and sputtering are known as methods for producing ceramic thin films.
また金属酸化物や水酸化物の濃厚なゾルを基材に塗布し
た後、ゲルに変え、これを乾燥・焼成して薄膜を得るゾ
ル−ゲル法が知られている。Also known is a sol-gel method in which a concentrated sol of metal oxides or hydroxides is applied to a substrate, turned into a gel, dried and fired, and a thin film is obtained.
［発明が解決しようとする課題］
上記気相法は気相から固相となった粒子を基材上に順次
付着させて或いは積もらせて薄膜を作成するため緻密な
膜が得がたい。またゾル−ゲル法では固形分の含有量を
一定量以上増やすことができないためやはり緻密な膜が
得がたく、シかも乾燥時に塗膜にひび割れを生じやすい
問題点がある。[Problems to be Solved by the Invention] In the above-mentioned gas phase method, a thin film is created by sequentially attaching or piling particles that have changed from a gas phase to a solid phase onto a base material, so it is difficult to obtain a dense film. Furthermore, in the sol-gel method, since the solid content cannot be increased beyond a certain amount, it is difficult to obtain a dense film, and the coating film tends to crack when drying.
本発明の目的は、緻密でひび割れのないセラミック薄膜
の製造方法を提供することにある。An object of the present invention is to provide a method for producing a dense and crack-free ceramic thin film.
［課題を解決するための手段］
上記目的を達成するために、本発明のセラミック薄膜の
製造方法は、金属アルコキシドを加水分解し、この加水
分解生成物を乾燥して得られたセラミック粉末を有機バ
インダと乾燥助剤とともに溶媒に分散してスラリーを調
製し、このスラリーを基材に塗布し、乾燥した後、焼成
してセラミック薄膜を得る方法である。[Means for Solving the Problems] In order to achieve the above object, the method for producing a ceramic thin film of the present invention involves hydrolyzing a metal alkoxide, drying the hydrolyzed product, and then converting the resulting ceramic powder into an organic material. In this method, a slurry is prepared by dispersing it in a solvent together with a binder and a drying aid, and this slurry is applied to a base material, dried, and then fired to obtain a ceramic thin film.
本発明を工程順に詳述する。The present invention will be explained in detail in order of steps.
（ａ）セラミック粉末の生成
本発明のセラミック粉末は、金属アルコキシドＭ （Ｏ
Ｒ）ｎの加水分解により生成される。ここでＭは有機金
属が合成可能な金属元素、Ｒは炭素数１〜２０のアルキ
ル基である。金属アルコキシドの加水分解は１種類のア
ルコキシド又は２種以上のアルコキシドをベンゼン、ア
ルコール等の有機溶媒に所定の比率で混合したものに、
脱炭酸した蒸留水、又は希アンモニア水その他のアルカ
リ水溶液を添加して行われる。(a) Production of ceramic powder The ceramic powder of the present invention comprises metal alkoxide M (O
R) Produced by hydrolysis of n. Here, M is a metal element capable of synthesizing an organic metal, and R is an alkyl group having 1 to 20 carbon atoms. Hydrolysis of metal alkoxide involves mixing one type of alkoxide or two or more types of alkoxide in an organic solvent such as benzene or alcohol in a predetermined ratio.
This is done by adding decarboxylated distilled water, dilute ammonia water, or other alkaline aqueous solution.
この添加により粉末状の沈殿物が生成する。この沈殿物
を濾過、遠心分離等の適当な方法により母液から分離す
る。分離された沈殿物は減圧下又は大気圧下の１００℃
前後の温度で沈殿物の表面に付着した溶液がほぼ蒸発す
るまで乾燥される。沈殿物の表面に付着した有機溶媒等
の溶液が乾燥で消散しない場合には、有機溶媒を含む溶
液で沈殿物を洗浄してから乾燥することが望ましい。This addition produces a powdery precipitate. This precipitate is separated from the mother liquor by a suitable method such as filtration or centrifugation. The separated precipitate is heated at 100°C under reduced pressure or atmospheric pressure.
The precipitate is dried at a temperature between 1 and 2 until the solution adhering to the surface of the precipitate is almost evaporated. If a solution such as an organic solvent attached to the surface of the precipitate does not disappear by drying, it is desirable to wash the precipitate with a solution containing an organic solvent and then dry it.
上記製法により得られたセラミック粉末は、金属アルコ
キシドの加水分解で他の陽イオンや陰イオンの添加が不
要であるため、高純度で粒径が数１０人から数１００人
の微粒の粉末となる。The ceramic powder obtained by the above manufacturing method is a fine powder with high purity and a particle size of several tens to hundreds of particles, since the addition of other cations and anions is not necessary due to the hydrolysis of metal alkoxide. .
（ｂ）スラリーの調製
上記セラミック粉末を有機バインダと乾燥助剤とともに
溶媒に分散してスラリーを調製する。有機バインダは親
水性有機バインダであればよいが、特にポリビニルアル
コール又はポリビニルブチラールが好ましい。また乾燥
助剤には二価アルコール、三価アルコール等を用いるこ
とができるが、特にエチレングリコールが好ましい。更
に溶媒には上記有機バインダ及び乾燥助剤と相溶性のあ
る水又は脂肪族炭化水素系、芳香族炭化水素系の有機溶
媒を用いることができる。分散性を高めるため、上記ス
ラリー成分に更に界面活性剤を加えてもよい。(b) Preparation of slurry A slurry is prepared by dispersing the above ceramic powder in a solvent together with an organic binder and a drying aid. The organic binder may be any hydrophilic organic binder, but polyvinyl alcohol or polyvinyl butyral is particularly preferred. Further, as a drying aid, dihydric alcohol, trihydric alcohol, etc. can be used, but ethylene glycol is particularly preferred. Further, the solvent may be water, an aliphatic hydrocarbon-based organic solvent, or an aromatic hydrocarbon-based organic solvent that is compatible with the organic binder and drying aid. In order to improve dispersibility, a surfactant may be further added to the slurry component.
本発明のスラリーは、上記溶媒にセラミック粉末と有機
バインダと乾燥助剤を加え攪拌し、３本ロール、ボール
ミル等で混線し脱気した後、超音波装置等で分散させて
調製される。次の塗布方法に応じて、スラリー成分の配
合比はスラリー総量１００重量部に対して、セラミック
粉末が４０〜７０重量部、有機バインダが２〜２０重量
部、乾燥助剤が２〜２０重量部、溶媒が２０〜５０重量
部の範囲からそれぞれ選ばれ、粘度調整が行われる。The slurry of the present invention is prepared by adding ceramic powder, an organic binder, and a drying aid to the above-mentioned solvent, stirring, cross-mixing with a three-roll mill, a ball mill, etc., deaerating the mixture, and then dispersing the mixture with an ultrasonic device or the like. Depending on the following application method, the mixing ratio of the slurry components is 40 to 70 parts by weight of ceramic powder, 2 to 20 parts by weight of organic binder, and 2 to 20 parts by weight of drying aid, based on 100 parts by weight of the total amount of slurry. , a solvent is selected from a range of 20 to 50 parts by weight, and the viscosity is adjusted.
（ｃ）スラリーの塗布
上記スラリーが塗布される基材は表面が平滑であって、
次の乾燥・焼成時にひび割れ、そり、うねり等の変質、
変形しない耐熱性のあるものであればよい。(c) Application of slurry The base material to which the slurry is applied has a smooth surface,
Deterioration such as cracking, warping, and waviness during the next drying and firing.
Any material may be used as long as it is heat resistant and does not deform.
また塗布方法はドクタブレード・コーティング、スプレ
ーコーティング、ローラコーティング、ディッピング等
のいずれの方法でもよい。Further, the coating method may be any method such as doctor blade coating, spray coating, roller coating, or dipping.
（ｄ）スラリーの乾燥・焼成
基材に塗布されたスラリーは室温〜１００’Ｃの温度範
囲で大気圧或いは減圧下に放置して乾燥される。昇温加
熱により、又は加熱【７た気体で乾燥してもよい。(d) Drying and firing of slurry The slurry applied to the substrate is dried by leaving it under atmospheric pressure or reduced pressure at a temperature ranging from room temperature to 100'C. Drying may be performed by heating at an elevated temperature or by using heated gas.
スラリーが１００℃以下で調製されることから、焼成温
度は従来の１３５０℃より低い８００〜１３００℃の温
度範囲で従来法より高い焼結度のセラミック薄膜が得ら
れる。Since the slurry is prepared at 100°C or lower, a ceramic thin film with a higher degree of sintering than the conventional method can be obtained at a firing temperature in the range of 800 to 1300°C, which is lower than the conventional 1350°C.
セラミック薄膜の厚みはスラリー粘度、塗布回数に応じ
て０．ｌｔｔｍから数ｌＯμｍ程度まで調整することが
できる。The thickness of the ceramic thin film varies depending on the slurry viscosity and the number of applications. It can be adjusted from lttm to several lOμm.
［発明の効果］
以上述べたように、本発明によれば、均一で微粒のセラ
ミック粉末を有機バインダと乾燥助剤とともにスラリー
にして基材に塗布するため、焼成した後に基材上にピン
ホールのない極めて緻密でひび割れのないセラミック薄
膜を製造することができる。[Effects of the Invention] As described above, according to the present invention, uniform, fine-grained ceramic powder is made into a slurry together with an organic binder and a drying aid and applied to a base material, so that pinholes are formed on the base material after firing. It is possible to produce extremely dense and crack-free ceramic thin films.
［実施例］
次に本発明の詳細な説明する。以下に用いる「部」は「
重量部」を示す。[Example] Next, the present invention will be explained in detail. “Department” used below is “
Parts by weight.
〈実施例１〉
高純度のＢａ金属とエタノールとを直接反応させバリウ
ムエトキシドを調製した。このバリウムエトキシドに市
販のチタニウムエトキシドをＢａ：Ｔｉの比が１−１に
なるように混合し、７０℃で還流反応させた。更に２時
間還流させながら脱炭酸した蒸留水を少量ずつ滴下して
加水分解させると沈殿物が得られた。得られた沈殿物を
遠心分離機にかけ、エタノールと水を除き７０℃で乾燥
すると、ＢａＴｉｅ、粉末が得られた。<Example 1> Barium ethoxide was prepared by directly reacting high purity Ba metal with ethanol. Commercially available titanium ethoxide was mixed with this barium ethoxide so that the Ba:Ti ratio was 1-1, and the mixture was refluxed at 70°C. Further, while refluxing for 2 hours, decarbonated distilled water was added dropwise little by little to cause hydrolysis, and a precipitate was obtained. The obtained precipitate was centrifuged to remove ethanol and water and dried at 70°C to obtain BaTie powder.
このＢａＴｉＯ３粉末に溶媒として水を加えた混合液に
、界面活性剤、有機バインダ及び乾燥助剤を次の配合比
で加え、ボールミルにより均一に混合してスラリーを調
製した。A surfactant, an organic binder, and a drying aid were added to a mixture of BaTiO3 powder and water as a solvent in the following mixing ratio, and mixed uniformly using a ball mill to prepare a slurry.
・ＢａＴｉ０．粉末 ５５
．０部・セルモＤ−１３４（界面活性剤、第−工業側製
）０．５部・有機バインダ（ポリビニルアルコール）
ｓ、ｏｌ・乾燥助剤（エチレングリコール）５．０部
・溶媒（水） ３４
．５部このスラリーを脱気及び粘度調整した後、ローラ
コーティングによりアルミナ基板に塗布した。・BaTi0. powder 55
．． 0 parts Celmo D-134 (surfactant, manufactured by Dai-Kogyo) 0.5 parts Organic binder (polyvinyl alcohol)
s, ol・Drying aid (ethylene glycol) 5.0 parts・Solvent (water) 34
．． 5 parts This slurry was degassed and viscosity-adjusted and then applied to an alumina substrate by roller coating.
この基板を乾燥器に入れ５０℃の温度で乾燥した後、１
３００℃で焼成したところ厚み０．５μｍのＢａＴｉ０
ｚ薄膜が得られた。After putting this substrate in a dryer and drying it at a temperature of 50°C,
When fired at 300℃, the thickness of BaTi0 was 0.5 μm.
A z thin film was obtained.
このＢａＴｉ０＊薄膜を走査電子顕微鏡で観察し、薄膜
がひび割れを起こすことなく緻密化していることを確認
した。This BaTi0* thin film was observed with a scanning electron microscope, and it was confirmed that the thin film was densified without cracking.
〈実施例２〉
実施例１で得られたＢａＴｉ０．粉末に溶媒としてアル
コールを加えた混合液に、界面活性剤、有機バインダ及
び乾燥助剤を次の配合比で加え、ボールミルにより均一
に混合してスラリーを調製した。<Example 2> BaTi0. obtained in Example 1. A surfactant, an organic binder, and a drying aid were added in the following mixing ratio to a mixture of powder and alcohol as a solvent, and the mixture was uniformly mixed using a ball mill to prepare a slurry.
・ＢａＴｉ０．粉末 ５０
．０部・有機バインダ（ポリビニルブチラール）５８０
部・乾燥助剤（エチレングリコール） １０．
０部・溶媒（ｎ−ブタノール） ３５
．０部このスラリーを実施例１と同様にアルミナ基板に
塗布し、乾燥した後、焼成したところＢａＴｉＯｓ薄膜
が得られた。・BaTi0. powder 50
．． 0 parts/Organic binder (polyvinyl butyral) 580
Part/Drying aid (ethylene glycol) 10.
0 parts/Solvent (n-butanol) 35
．． 0 parts This slurry was applied to an alumina substrate in the same manner as in Example 1, dried, and then fired to obtain a BaTiOs thin film.
このＢａＴｉＯｓ薄膜を走査電子顕微鏡で観察し、薄膜
がひび割れを起こすことなく緻密化していることを確認
した。This BaTiOs thin film was observed with a scanning electron microscope, and it was confirmed that the thin film was densified without cracking.
Claims (1)
物を乾燥してセラミック粉末を得る工程と、前記セラミ
ック粉末と有機バインダと乾燥助剤とを溶媒に分散して
スラリーを調製する工程と、前記スラリーを基材に塗布
する工程と、 前記基材に塗布したスラリーを乾燥した後、焼成してセ
ラミック薄膜を得る工程と を含むセラミック薄膜の製造方法。 ２）有機バインダはポリビニルアルコール又はポリビニ
ルブチラールである請求項１記載のセラミック薄膜の製
造方法。 ３）乾燥助剤はエチレングリコールである請求項１記載
のセラミック薄膜の製造方法。[Claims] 1) A step of hydrolyzing a metal alkoxide and drying the hydrolysis product to obtain a ceramic powder, and dispersing the ceramic powder, an organic binder, and a drying aid in a solvent to form a slurry. A method for producing a ceramic thin film, comprising: preparing the slurry; applying the slurry to a base material; and drying the slurry applied to the base material and then firing it to obtain a ceramic thin film. 2) The method for producing a ceramic thin film according to claim 1, wherein the organic binder is polyvinyl alcohol or polyvinyl butyral. 3) The method for producing a ceramic thin film according to claim 1, wherein the drying aid is ethylene glycol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63126681A JPH01294557A (en) | 1988-05-24 | 1988-05-24 | Production of ceramic thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63126681A JPH01294557A (en) | 1988-05-24 | 1988-05-24 | Production of ceramic thin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01294557A true JPH01294557A (en) | 1989-11-28 |
Family
ID=14941223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63126681A Pending JPH01294557A (en) | 1988-05-24 | 1988-05-24 | Production of ceramic thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01294557A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002114576A (en) * | 2000-10-03 | 2002-04-16 | Murata Mfg Co Ltd | Method and device for removing coarse ceramic particle |
| KR100616512B1 (en) * | 2003-10-06 | 2006-08-29 | 삼성전기주식회사 | Ceramic Composition for Green Sheet Having Superior Strength, Preparing Method of Green Sheet And Green Sheet Prepared Thereby |
| CN112980260A (en) * | 2021-03-24 | 2021-06-18 | 南京信息职业技术学院 | Preparation method of car paint polyvinyl alcohol-titanium dioxide composite coating |
| CN113644379A (en) * | 2021-01-18 | 2021-11-12 | 华南理工大学 | Porous ceramic fiber diaphragm material for thermal battery and preparation method thereof |
-
1988
- 1988-05-24 JP JP63126681A patent/JPH01294557A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002114576A (en) * | 2000-10-03 | 2002-04-16 | Murata Mfg Co Ltd | Method and device for removing coarse ceramic particle |
| KR100616512B1 (en) * | 2003-10-06 | 2006-08-29 | 삼성전기주식회사 | Ceramic Composition for Green Sheet Having Superior Strength, Preparing Method of Green Sheet And Green Sheet Prepared Thereby |
| CN113644379A (en) * | 2021-01-18 | 2021-11-12 | 华南理工大学 | Porous ceramic fiber diaphragm material for thermal battery and preparation method thereof |
| CN112980260A (en) * | 2021-03-24 | 2021-06-18 | 南京信息职业技术学院 | Preparation method of car paint polyvinyl alcohol-titanium dioxide composite coating |
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