JPS59179145A - Preparation of emulsified slurry - Google Patents

Preparation of emulsified slurry

Info

Publication number
JPS59179145A
JPS59179145A JP58053273A JP5327383A JPS59179145A JP S59179145 A JPS59179145 A JP S59179145A JP 58053273 A JP58053273 A JP 58053273A JP 5327383 A JP5327383 A JP 5327383A JP S59179145 A JPS59179145 A JP S59179145A
Authority
JP
Japan
Prior art keywords
dispersion
liq
slurry
emulsifier
inorg
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.)
Granted
Application number
JP58053273A
Other languages
Japanese (ja)
Other versions
JPH028772B2 (en
Inventor
Migiwa Ando
安藤 汀
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Tokushu Togyo KK
Niterra Co Ltd
Original Assignee
NGK Spark Plug Co Ltd
Nippon Tokushu Togyo KK
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by NGK Spark Plug Co Ltd, Nippon Tokushu Togyo KK filed Critical NGK Spark Plug Co Ltd
Priority to JP58053273A priority Critical patent/JPS59179145A/en
Publication of JPS59179145A publication Critical patent/JPS59179145A/en
Publication of JPH028772B2 publication Critical patent/JPH028772B2/ja
Granted legal-status Critical Current

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  • Compositions Of Oxide Ceramics (AREA)
  • Preparation Of Clay, And Manufacture Of Mixtures Containing Clay Or Cement (AREA)
  • Colloid Chemistry (AREA)

Abstract

PURPOSE:To obtain stable emulsified slurry by stirring a liquid dispersion of inorg. powder, emulsifier, and boric acid in a water-insoluble liq. alcohol after adding a liquid dispersion consisting of inorg. powder, polyvinyl alcohol, and water, thereto. CONSTITUTION:A liquid dispersion W is prepd. by mixing inorg. powder, polyvinyl alcohol and water. Separate liquid dispersion O is prepd. by admixing inorg. powder, emulsifier, and boric acid to a water-insoluble liquid alcohol. An emulsified slurry is obtd. by stirring after pouring said liq. dispersion W into the liq. dispersion O. In the mixing stage of both liq. dispersions, the liq. dispersion W, as soon as it is dispersed in the liq. dispersion O in the particulate state, is surrounded by the emulsifier and boric acid contained in the liq. dispersion O to form gelled film of polyvinyl alcohol. While the intrusion of inorg. Particles into the dispersion O is prevented by the gelled film, the film of the emulsifier is regenerated and restored.

Description

【発明の詳細な説明】 本発明は、エマルジョン状態の安定性に優れたエマルジ
ョン型スラリーの調整方法に関するものである。
DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for preparing an emulsion-type slurry with excellent emulsion state stability.

近年、金属、セラミックス及びガラスのうちから選ばれ
る二種以上の物質を含むスラリーから出発して複合焼結
体を作る技術において、該スラリーをエマルジョン型に
調整することによって、スラリーに含まれる各物質の有
する特性のうち必要なもののみを複合焼結体に引き継が
せる技術が注目されている。熱伝導性の良い金属粒子が
、高絶縁性セラミックスの層を介して結合している金属
・セラミックス複合焼結体はその一例であり、このよう
な焼結体は各物質単独又は均一化合物では達成できなか
った特徴すなわち高熱伝導性及び高絶縁性の併有性を具
備したものである。しかしながら従来上記のようなエマ
ルジョン型スラリーは主として次の理由によってそのエ
マルジョン状態の安定性を欠いていた。すなわち、水系
スラリーと乳化剤を含む油系スラリーとを混合し攪拌す
ることによって、水系スラリーが部系スラリー中に乳化
分散した構成を有するエマルジョン型スラリーが生成さ
れるが、攪拌時に機械的に加わる力によって乳化剤の分
子膜が破れ、水系スラリー中の無機質粉末粒子が部系ス
ラリー中へ浸入する場合が少なくなかったからである。
In recent years, in the technology of making a composite sintered body starting from a slurry containing two or more substances selected from metals, ceramics, and glasses, each substance contained in the slurry is prepared by adjusting the slurry to an emulsion type. A technology that allows a composite sintered body to inherit only the necessary characteristics of the composite sintered body is attracting attention. One example is a metal-ceramic composite sintered body in which metal particles with good thermal conductivity are bonded through a layer of highly insulating ceramic, and such a sintered body cannot be achieved with each material alone or with a homogeneous compound. It has characteristics that were previously unavailable, namely the combination of high thermal conductivity and high insulation properties. However, the conventional emulsion-type slurry as described above lacks stability in its emulsion state mainly due to the following reasons. That is, by mixing and stirring a water-based slurry and an oil-based slurry containing an emulsifier, an emulsion-type slurry having a structure in which the water-based slurry is emulsified and dispersed in the partial slurry is produced, but the mechanical force applied during stirring is This is because the molecular membrane of the emulsifier is broken and the inorganic powder particles in the aqueous slurry often penetrate into the slurry.

またスラリー中成分の組み合わせが不適当であるために
、本質的にエマルジョン状態が不安定となり、時間の経
過に伴い分散していた水系スラリー粒子が合体し始め最
終的には水相スラリーと油相スラリーとの二層に分離し
てしまうこともあった。以上の様にエマルジョン状態の
破壊されたスラリーから出発して得られた焼結体は、前
記エマルジョン型スラリーから出発して得られた複合焼
結体の具備する緒特性の併有性を失っているだけでなく
、機械的強度、均一性等焼結体としての基本的特性にお
いても劣ったものとなる。従って従来のエマルジシン型
スラリー調整方法によれば、スラリー中成分の比重やお
互いの濡れ性を考慮してその組み合わせを選定し、注意
して攪拌する必要があった。
In addition, due to an inappropriate combination of components in the slurry, the emulsion state essentially becomes unstable, and over time, the dispersed aqueous slurry particles begin to coalesce, eventually resulting in the aqueous slurry and oil phase. Sometimes it separated into two layers with the slurry. As described above, the sintered body obtained by starting from the slurry in the emulsion state has lost the properties of the composite sintered body obtained by starting from the emulsion-type slurry. Not only this, but also the basic properties of a sintered body such as mechanical strength and uniformity are inferior. Therefore, according to the conventional emulsion-type slurry preparation method, it is necessary to select a combination of components in the slurry in consideration of their specific gravity and mutual wettability, and to carefully stir the components.

発明者はポリビニルアルコール水溶液が微量の硼酸と接
触することによって瞬時にゲル化する現象を利用し、i
量の硼酸を含有した部系スラリーとポリビニルアルコー
ルを含有した水系スラリーとを混合しIW M’するこ
とによって安定なエマルジョン型スラリーが得られるこ
とを見い出したのである。
The inventor utilized the phenomenon that polyvinyl alcohol aqueous solution instantaneously gels when it comes into contact with a trace amount of boric acid, and
It has been discovered that a stable emulsion-type slurry can be obtained by mixing a partial slurry containing a certain amount of boric acid with an aqueous slurry containing polyvinyl alcohol and subjecting the mixture to IWM'.

本発明は上記の知見にもとづいて得られたもので、その
要旨とするとごろは (a)無機質粉末、ポリビニルアルコール(以下rPV
Ajと略称)及び水を混合して分散液Wを作る工程。
The present invention was obtained based on the above findings, and the gist thereof is (a) inorganic powder, polyvinyl alcohol (hereinafter referred to as rPV),
A process of mixing Aj) and water to create a dispersion W.

(b)無機質粉末、乳化剤及び硼酸を非水溶性液体アル
コールに添加し混合して分散液○を作る工程。
(b) Step of adding inorganic powder, emulsifier, and boric acid to non-aqueous liquid alcohol and mixing to create dispersion liquid ○.

(C)前記WをOに注ぎ、攪拌する工程。(C) A step of pouring the W into O and stirring.

からなるエマルジョン型スラリーの調整方法に存する。The invention consists in a method for preparing an emulsion-type slurry consisting of:

本発明方法によって得られたスラリーのエマルジョン状
態が安定である理由を以下に詳述する。
The reason why the emulsion state of the slurry obtained by the method of the present invention is stable will be explained in detail below.

すなわち、上記(c)工程の段階でWはO中を粒子状に
分散すると同時に0中の乳化剤と硼酸とに囲まれるので
、仮に機械的な力によってW粒子中の無機質粒子が乳化
剤分子膜を破ってO中へ浸出しようとしてもその瞬間に
PVA分子と硼酸との反応が生しPVAのゲル化膜が生
成し、このゲル化膜が無機質粒子のO中への浸出を防止
している間に乳化剤分子膜が再生修復されるが故に、W
粒子の安定分散が長時間維持されるのである。
That is, in step (c) above, W is dispersed in O in the form of particles and at the same time is surrounded by the emulsifier in O and boric acid. Even if the inorganic particles are to be broken and leached into O, at that moment a reaction between PVA molecules and boric acid occurs and a PVA gel film is formed, and this gel film prevents inorganic particles from leaching into O. Because the emulsifier molecular film is regenerated and repaired, W
Stable dispersion of particles is maintained for a long time.

本発明方法によって調整されたエマルジョン型スラリー
は、上記の理由によりそのエマルジョン状態が極めて安
定であるので、このスラリーから出発して得られる複合
焼結体は均一性が良く、各成分の優れた特性を併有した
ものとなるのである。
The emulsion-type slurry prepared by the method of the present invention has an extremely stable emulsion state for the above reasons, so the composite sintered body obtained starting from this slurry has good uniformity and excellent characteristics of each component. It becomes something that has both.

従ってこのようなは複合焼結体のうち、モリブデン、タ
ングステン、鉄、白金、珪素等の金属又は窒化硼素、へ
りリア、窒化アルミニウム、炭化珪素、マグネシア等の
高熱伝導性セラミックスを含む分散液Wとアルミナ、ム
ライト、フォルステライト、ジルコン、ワラストナイト
、ガラスセラミックス等の高絶縁性セラミックスを含む
分散液0とからなるエマルジョン型スラリーから出発し
たものはIC基板やヒートシンク等の電子部品に好適で
ある。また、フォルステライト、ムライト、ジルコン、
ジルコニア、ガラスセラミックス等の断熱性、耐摩耗性
に優れたセラミ・ンクスを含む分散液Wと上記金属を含
む分散液Oとからなるエマルジョン型スラリーから出発
したものはガスヶ、7トやシールリング等の機械部品に
好適である。
Therefore, among such composite sintered bodies, dispersion W containing metals such as molybdenum, tungsten, iron, platinum, and silicon, or highly thermally conductive ceramics such as boron nitride, herria, aluminum nitride, silicon carbide, and magnesia, An emulsion-type slurry starting from a dispersion containing highly insulating ceramics such as alumina, mullite, forsterite, zircon, wollastonite, and glass ceramics is suitable for electronic components such as IC boards and heat sinks. Also, forsterite, mullite, zircon,
Products starting from an emulsion-type slurry consisting of a dispersion W containing ceramics with excellent heat insulation and wear resistance such as zirconia and glass ceramics and a dispersion O containing the above-mentioned metals include gas rings, 7-pieces, seal rings, etc. Suitable for mechanical parts.

以下実施例を示す。Examples are shown below.

実施例1 (a)蒸留水               82cc
PVA (デンカB−17)3g 平均粒径0.3μmの酸化第二鉄    53g平均粒
径0.5μmの二酸化マンガン  3gを内容積300
m#のポリエチレン製ボールミルで15時間混合し、こ
れを分散液W1とした。
Example 1 (a) Distilled water 82cc
PVA (Denka B-17) 3g ferric oxide with an average particle size of 0.3μm 53g manganese dioxide with an average particle size of 0.5μm 3g with an internal volume of 300
The mixture was mixed for 15 hours using a m# polyethylene ball mill, and this was used as a dispersion W1.

中)試薬−級硼酸            0.5gn
−ブチルアルコール       180cc平均粒径
0.5μmのフォルステライト(シランカップリング処
理品)】7g 乳化剤(日本油脂@製ノニオン0P−8OR)  2.
4gエチルセルロース           2g可塑
剤(ジオクチルフタレート)     6gを内容積5
00m1!のポリエチレン製ボールミルで15時間混合
し、これを分散液01  とした。分散液01 を50
0m1のビーカーに移し、これをプロペラ攪拌機で攪拌
しながら分散液W、を注ぎ込むことによってエマルジョ
ン型スラリーS、を得た。
Middle) Reagent-grade boric acid 0.5gn
-Butyl alcohol 180cc Forsterite with average particle size of 0.5μm (silane coupling treated product) 7g Emulsifier (Nonion 0P-8OR manufactured by NOF@) 2.
4g ethyl cellulose 2g plasticizer (dioctyl phthalate) 6g internal volume 5
00m1! The mixture was mixed in a polyethylene ball mill for 15 hours, and this was used as Dispersion 01. Dispersion liquid 01 50
The slurry was transferred to a 0 ml beaker, and the dispersion W was poured thereinto while stirring with a propeller stirrer to obtain an emulsion-type slurry S.

スラリー81  のエマルジョン状態は1日放置後も安
定に維持されていた。このSlをポリエステル製キャリ
アーフィルム」二に流し、ドクターブレード法によって
シー1−成形した後、15時間自然乾燥させることによ
って厚さ0.8mmのグリーンシートを製造した、シー
トの断面を電子顕微鏡を用いて観察すると、図に示す如
く酸化第二鉄及び二酸化マンガンからなる集金法1がフ
ォルステライト磁器2によって囲まれた構造を呈してい
た。このグリーンシートを水素ガス雰囲気中露点15℃
、温度1350℃、保持時間1時間の条件で焼成するこ
とによって、焼結フォルステライト磁器を基幹とし、そ
の中に酸化第二鉄の還元によって生じた焼結鉄球が均一
に分散した構造を有する金属・セラミックス複合焼結体
を製造した。
The emulsion state of Slurry 81 remained stable even after being left for one day. This Sl was poured onto a polyester carrier film, formed into a sheet using a doctor blade method, and air-dried for 15 hours to produce a green sheet with a thickness of 0.8 mm.The cross section of the sheet was examined using an electron microscope. When observed, it was found that the collection method 1 made of ferric oxide and manganese dioxide was surrounded by forsterite porcelain 2 as shown in the figure. This green sheet was placed in a hydrogen gas atmosphere with a dew point of 15°C.
By firing at a temperature of 1,350°C and a holding time of 1 hour, it has a structure based on sintered forsterite porcelain, in which sintered iron balls produced by reduction of ferric oxide are uniformly dispersed. A metal/ceramic composite sintered body was manufactured.

尚、本実施例では、シート成形を容易にするために、結
合剤及び可塑剤を分散液01に添加したが、これらは本
発明方法に必須の成分ではなく、次の実施例2に示す鋳
込み成形の場合は熱論のこと、噴霧乾燥や凍結乾燥を利
用する場合にもこれらを添加することなく本発明の効果
を奏するこが可能である。
In this example, a binder and a plasticizer were added to the dispersion liquid 01 in order to facilitate sheet forming, but these are not essential components for the method of the present invention, and the casting shown in Example 2 below. In the case of molding, it is possible to achieve the effects of the present invention without adding these materials even when using thermal theory, spray drying or freeze drying.

実施例2 (al蒸留水               82cc
PVA (デンカB−17)3g 平均粒径0.3μmの酸化第二鉄    22g平均粒
径0.5μmの三酸化モリブデン 40g平均粒径0.
2μmの酸化アルミニウム 1gを内容積300m!!
のポリエチレン製ボールミルで15時間混合し、これを
分散液W とした。
Example 2 (al distilled water 82cc
PVA (Denka B-17) 3g Ferric oxide with an average particle size of 0.3 μm 22g Molybdenum trioxide with an average particle size of 0.5 μm 40g Average particle size of 0.
1g of 2μm aluminum oxide has an internal volume of 300m! !
The mixture was mixed for 15 hours using a polyethylene ball mill, and this was used as a dispersion W.

(1))試薬−級硼酸           0.5μ
m−ブチルアルコール       180cc平均粒
径0.2μmの酸化アルミニウム(シランカップリング
処理品)17g 試薬特級水酸化アルミニウム (シランカップリング処理品)      5g試薬−
級珪酸化マグネシウムカルシウムg 乳化剤(日本油脂■製ノニオン0P−801?)  2
.4gを内容積500m1のポリエチレン製ボールミル
で15時間混合し、これを分散液02とした。
(1)) Reagent-grade boric acid 0.5μ
m-Butyl alcohol 180 cc Aluminum oxide with an average particle size of 0.2 μm (silane coupling treated product) 17 g Reagent special grade aluminum hydroxide (silane coupling treated product) 5 g Reagent -
Grade magnesium calcium silicate g Emulsifier (Nonion 0P-801 manufactured by NOF ■) 2
.. 4 g was mixed for 15 hours in a polyethylene ball mill with an internal volume of 500 m1, and this was used as dispersion liquid 02.

実施例1と同様に分散液W2を分散液02に注ぎ込むこ
とによってエマルジョン型スラリーS2を得た。このS
2を石膏型に流し込み、20分間放置後、型から取り出
し、水素雰囲気中温度1520’C,露点5℃、保持時
間1時間の条件で焼成することによって、50ΦX2m
の焼結体を得た。得られた焼結体は、アルミナ磁器を基
幹とし、その中に鉄及びモリブデンからなる粒径10〜
20μmの焼結粒子が均一に分散した構造を有する金属
・セラミックス複合焼結体であった。
As in Example 1, dispersion W2 was poured into dispersion 02 to obtain emulsion-type slurry S2. This S
2 was poured into a plaster mold, left for 20 minutes, removed from the mold, and baked in a hydrogen atmosphere at a temperature of 1520'C, a dew point of 5°C, and a holding time of 1 hour.
A sintered body was obtained. The obtained sintered body has alumina porcelain as its core, and contains particles of iron and molybdenum with a diameter of 10 to 10.
The metal/ceramic composite sintered body had a structure in which sintered particles of 20 μm were uniformly dispersed.

【図面の簡単な説明】[Brief explanation of the drawing]

図は本発明のエマルジョン型スラリーの調整方法の一実
施例に従って得られたグリーンシートの一部断面図であ
る。
The figure is a partial sectional view of a green sheet obtained according to an embodiment of the emulsion-type slurry preparation method of the present invention.

Claims (1)

【特許請求の範囲】 (a)無機質粉末、ポリビニルアルコール及び水を混合
して分散液Wを作る工程。 (b)無機質粉末、乳化剤及び硼酸を非水溶性液体アル
コールに添加し混合して分散液Oを作る工程。 (C)前記Wを0に注ぎ、攪拌する工程。 からなるエマルジョン型スラリーの調整方法。
[Claims] (a) A step of mixing an inorganic powder, polyvinyl alcohol, and water to prepare a dispersion W. (b) A step of adding an inorganic powder, an emulsifier, and boric acid to a water-insoluble liquid alcohol and mixing them to form a dispersion O. (C) Step of pouring the W into 0 and stirring. A method for preparing an emulsion-type slurry consisting of:
JP58053273A 1983-03-29 1983-03-29 Preparation of emulsified slurry Granted JPS59179145A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP58053273A JPS59179145A (en) 1983-03-29 1983-03-29 Preparation of emulsified slurry

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP58053273A JPS59179145A (en) 1983-03-29 1983-03-29 Preparation of emulsified slurry

Publications (2)

Publication Number Publication Date
JPS59179145A true JPS59179145A (en) 1984-10-11
JPH028772B2 JPH028772B2 (en) 1990-02-27

Family

ID=12938125

Family Applications (1)

Application Number Title Priority Date Filing Date
JP58053273A Granted JPS59179145A (en) 1983-03-29 1983-03-29 Preparation of emulsified slurry

Country Status (1)

Country Link
JP (1) JPS59179145A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106003639A (en) * 2016-06-13 2016-10-12 北京汽车股份有限公司 Method for manufacturing seal ring, seal ring and vehicle
JP2018538398A (en) * 2015-12-22 2018-12-27 ローム アンド ハース カンパニーRohm And Haas Company Droplets dispersed in an aqueous medium

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018538398A (en) * 2015-12-22 2018-12-27 ローム アンド ハース カンパニーRohm And Haas Company Droplets dispersed in an aqueous medium
CN106003639A (en) * 2016-06-13 2016-10-12 北京汽车股份有限公司 Method for manufacturing seal ring, seal ring and vehicle

Also Published As

Publication number Publication date
JPH028772B2 (en) 1990-02-27

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