JPH0143708B2 - - Google Patents
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- Publication number
- JPH0143708B2 JPH0143708B2 JP58110366A JP11036683A JPH0143708B2 JP H0143708 B2 JPH0143708 B2 JP H0143708B2 JP 58110366 A JP58110366 A JP 58110366A JP 11036683 A JP11036683 A JP 11036683A JP H0143708 B2 JPH0143708 B2 JP H0143708B2
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- Prior art keywords
- binder
- weight
- parts
- molded
- molding
- Prior art date
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- Compositions Of Oxide Ceramics (AREA)
Description
【発明の詳細な説明】
〔発明の技術分野〕
本発明は窒化珪素、窒化アルミニウム、サイア
ロンなどの窒化系セラミツクスの成形に用いられ
るバインダの改良に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to improvements in binders used for molding nitride ceramics such as silicon nitride, aluminum nitride, and sialon.
近年、窒化珪素、サイアロンなどの窒化系セラ
ミツクスはアルミナ等の汎用のセラミツクスに比
べて耐熱性、耐腐食性等が格段に優れているた
め、タービンブレード、自動車のシリンダ、ピス
トン等のエンジニアリング材料として注目されて
いる。
In recent years, nitride ceramics such as silicon nitride and Sialon have been attracting attention as engineering materials for turbine blades, automobile cylinders, pistons, etc. because they have much better heat resistance and corrosion resistance than general-purpose ceramics such as alumina. has been done.
ところで、従来、上述した窒化系セラミツクス
製品はホツトプレス法により製造されているが、
複雑形状の製品の製造が困難である上、量産性の
点でも問題があつた。 By the way, conventionally, the above-mentioned nitride ceramic products have been manufactured by hot pressing method,
Not only is it difficult to manufacture products with complex shapes, but there are also problems in terms of mass production.
このようなことから、最近、ポリオレフインや
炭化水素、ワツクス等をベースとする種々のバイ
ンダが開発され、このバインダを窒化系セラミツ
クス粉末に添加することによつて、射出成形によ
り成形体を造ることを可能とし、複雑形状の窒化
系セラミツクス製品を量産的に製造することが試
みられている。しかしながら、こうした方法にあ
つては、バインダに起因する種々の問題がある。 For this reason, various binders based on polyolefins, hydrocarbons, waxes, etc. have been recently developed, and by adding these binders to nitrided ceramic powder, molded bodies can be made by injection molding. Attempts are being made to make it possible to mass-produce nitride ceramic products with complex shapes. However, these methods have various problems caused by the binder.
即ち、窒化系セラミツクスに従来のバインダを
添加した混練物の流動特性logη−logγ（粘性係数
−せん断速度）を測定すると、ダイラタンシー性
が認められ、射出成形により得られたグリーン成
形体内にボイドを発生したり、多大な成形歪が生
じる。その結果、成形されたグリーン成形体のバ
インダ除去（脱脂）工程において、前記多大な成
形歪やバインダの熱分解の不均一が影響してクラ
ツクが発生する。また、脱脂後の成形体の焼結時
にも前記成形歪に起因するクラツクが発生する。 In other words, when measuring the flow characteristics logη-logγ (viscosity coefficient - shear rate) of a kneaded product made by adding a conventional binder to nitride-based ceramics, dilatancy was observed, and voids were generated in the green molded body obtained by injection molding. Otherwise, a large amount of molding distortion occurs. As a result, cracks occur in the binder removal (degreasing) step of the molded green body due to the large molding distortion and non-uniform thermal decomposition of the binder. Cracks due to the molding distortion also occur during sintering of the molded body after degreasing.
本発明はボイド発生がなく、かつ脱脂後におい
てもクラツク発生のない成形体を得ることができ
る窒化系セラミツクス成形用バインダを提供しよ
うとするものである。
The present invention aims to provide a binder for molding nitrided ceramics that does not generate voids and can produce molded products that do not generate cracks even after degreasing.
本発明者は上記バインダについて鋭意研究した
結果、アンモニウム塩形界面活性剤及びアミノ変
成ポリオレフインのうちの少なくとも１種を含有
する構成にすることによつて、窒化系セラミツク
ス粉末に対するぬれ性が良好で、かつ均一な熱分
解性を有するバインダを見い出した。しかして、
本発明のバインダを窒化系セラミツクス粉末に添
加することにより流動性が著しく改善された混練
物を造ることができ、この混練物を射出成形する
ことによりボイドがなく成形歪が低減されたグリ
ーン成形体を得ることができ、ひいては脱脂後の
成形体、焼結後のセラミツクス製品のクラツク発
生を防止できる効果を発揮し得る。
As a result of intensive research on the above-mentioned binder, the inventors of the present invention have found that by making the binder contain at least one of an ammonium salt type surfactant and an amino-modified polyolefin, it has good wettability with respect to nitrided ceramic powder. We have also discovered a binder that has uniform thermal decomposition properties. However,
By adding the binder of the present invention to nitrided ceramic powder, a kneaded product with significantly improved fluidity can be produced, and by injection molding this kneaded product, a green molded product is free of voids and has reduced molding distortion. In turn, it is possible to achieve the effect of preventing the occurrence of cracks in molded bodies after degreasing and ceramic products after sintering.
次に、本発明の実施例を説明する。 Next, examples of the present invention will be described.
実施例 １
下記組成の窒化珪素／バインダの混合物をニー
ダを用いて150℃±５℃、約60分間混練して混練
物を調製した。つづいて、この混練物を射出成形
機を用いて下記条件で成形して円形ブロツク状の
グリーン成形体を造つた。Example 1 A mixture of silicon nitride/binder having the following composition was kneaded using a kneader at 150°C±5°C for about 60 minutes to prepare a kneaded product. Subsequently, this kneaded product was molded using an injection molding machine under the following conditions to produce a circular block-shaped green molded product.
＜窒化珪素／バインダの組成＞
●窒化珪素ドライミリング調整物 100重量部
●（ジアリルアンモニウムモノマ＋スチレンモノ
マ）の共重合体 ５重量部
●ポリスチレン ５重量部
●ジオクチルフタレート（DOP） ４重量部
●その他の添加剤 13重量部
＜成形条件＞
●金型温度 30℃〜35℃
●混練物の温度 150℃±５℃
●射出時間 1.5sec〜5sec
●射出圧 950Kg／cm2〜1300Kg／cm2
実施例 ２
下記組成の窒化珪素／バインダの混合物をニー
ダにて150℃±５℃、60分間混練した後、この混
練物を射出成形機を用いて下記条件で成形して円
形ブロツク状のグリーン成形体を造つた。<Silicon nitride/binder composition> ●Silicon nitride dry milling preparation 100 parts by weight●Copolymer of (diallylammonium monomer + styrene monomer) 5 parts by weight●Polystyrene 5 parts by weight●Dioctyl phthalate (DOP) 4 parts by weight●Others Additive 13 parts by weight <Molding conditions> ●Mold temperature 30℃~35℃ ●Kneaded material temperature 150℃±5℃ ●Injection time 1.5sec~5sec ●Injection pressure 950Kg/cm 2 ~1300Kg/cm 2 Examples 2 After kneading a silicon nitride/binder mixture with the following composition in a kneader at 150°C ± 5°C for 60 minutes, this kneaded product was molded using an injection molding machine under the following conditions to form a circular block-shaped green molded body. I built it.
＜窒化珪素／バインダの組成＞
●窒化珪素ドライミリング調整物 100重量部
●ポリ−２−メタクリロキシエチルトリメチルア
ンモニウム ２重量部
●ジアルキルアミノアルキルメタリクリ酸エステ
ル ５重量部
●ポリメチルメタクリレート ５重量部
●DOP ４重量部
●その他の添加剤 11重量部
＜成形条件＞
●金型温度 30℃〜40℃
●混練物の温度 150℃±５℃
●射出時間 ２〜8sec
●射出圧 1100〜1300Kg／cm2
比較例
まず、下記組成の窒化珪素／バインダの混合物
をニーダにて190℃±５℃、約60分間混練して混
練物を調製した。つづいて、この混練物を射出成
形機を用いて下記条件で成形し円形ブロツク状の
グリーン成形体を造つた。<Silicon nitride/binder composition> ●Silicon nitride dry milling preparation 100 parts by weight●Poly-2-methacryloxyethyltrimethylammonium 2 parts by weight●Dialkylaminoalkyl methacrylic acid ester 5 parts by weight●Polymethyl methacrylate 5 parts by weight● DOP 4 parts by weight ●Other additives 11 parts by weight <Molding conditions> ●Mold temperature 30℃~40℃ ●Kneaded material temperature 150℃±5℃ ●Injection time 2~8sec ●Injection pressure 1100~1300Kg/cm 2 Comparative Example First, a mixture of silicon nitride/binder having the following composition was kneaded in a kneader at 190°C±5°C for about 60 minutes to prepare a kneaded product. Subsequently, this kneaded product was molded using an injection molding machine under the following conditions to produce a circular block-shaped green molded product.
＜窒化珪素／バインダの組成＞
●窒化珪素ドライミリング調整物 100重量部
●ポリスチレン ６重量部
●DOP ４重量部
●ステアリン酸 ３重量部
●その他の添加剤 14重量部
＜成形条件＞
●金型温度 40℃±５℃
●混練物の温度 180℃±５℃
●射出時間 1.5sec〜7sec
●射出圧 950Kg／cm2〜1300Kg／cm2
しかして、本実施例１〜２及び比較例で調製し
た混練物について、オリフイスＬ／Ｒ：10mmＬ／
１mmφの粘度測定器（東洋精機社製キヤピログラ
フ）を用いて粘度測定を行なつた結果が図面に示
す特性図を得た。なお、測定温度は実施例１、実
施例２それぞれについて120℃で行なつた。図中
のA1は実施例１で調製された混練物の粘度特性
図、A2は実施例２で調製された混練物の同特性
線、Ｂは比較例で調製された混練物の同特性線、
である。この特性図より明らかな如く、本発明の
バインダを添加した混練物はほとんどダイラタン
シー性が認められないのに対し、従来のバインダ
を添加した混練物（比較例）はダイラタンシー性
が認められた。<Silicon nitride/binder composition> ●Silicon nitride dry milling preparation 100 parts by weight●Polystyrene 6 parts by weight●DOP 4 parts by weight●Stearic acid 3 parts by weight●Other additives 14 parts by weight<Molding conditions> ●Mold temperature 40℃±5℃ ●Temperature of kneaded material 180℃±5℃ ●Injection time 1.5sec to 7sec ●Injection pressure 950Kg/cm 2 to 1300Kg/cm 2 However, the kneading material prepared in Examples 1 and 2 and Comparative Example Regarding the item, orifice L/R: 10mmL/
The viscosity was measured using a 1 mmφ viscosity meter (Capirograph manufactured by Toyo Seiki Co., Ltd.), and the characteristic diagram shown in the drawing was obtained. Note that the measurement temperature was 120° C. for each of Example 1 and Example 2. In the figure, A 1 is a viscosity characteristic diagram of the kneaded product prepared in Example 1, A 2 is the same characteristic line of the kneaded product prepared in Example 2, and B is the same characteristic line of the kneaded product prepared in Comparative Example. line,
It is. As is clear from this characteristic diagram, the kneaded product to which the binder of the present invention was added had almost no dilatancy property, whereas the kneaded product to which the conventional binder was added (comparative example) had dilatancy property.
また、得られた実施例１〜２及び比較例のグリ
ーン成形体について、脱脂試験を行なつたとこ
ろ、実施例１〜２の脱脂後の成形体にはクラツク
発生は全く認められたかつたのに対し、比較例の
脱脂後の成形体にはクラツク発生やボイド発生が
認められた。 Furthermore, when a degreasing test was conducted on the obtained green molded bodies of Examples 1 and 2 and Comparative Examples, no cracks were observed in the degreased molded bodies of Examples 1 and 2. On the other hand, cracks and voids were observed in the molded product of Comparative Example after degreasing.
更に、本実施例１〜２の脱脂後の成形体につい
て、60℃で30分間、−30℃で30分間保持する急熱
急冷試験を５回繰り返し行なつたところ、いずれ
の成形体もクラツク発生は認められなかつた。 Furthermore, when the degreased molded bodies of Examples 1 and 2 were repeatedly subjected to a rapid heating and cooling test of 60°C for 30 minutes and -30°C for 30 minutes, no cracks occurred in any of the molded bodies. was not recognized.
なお、上記実施例では窒化系セラミツクスとし
て窒化珪素ドライミリング調整物を用いたが、こ
れに代つて窒化アルミニウム粉末、サイアロン粉
末を用いても同様な効果が確認された。 In the above example, a dry milled silicon nitride preparation was used as the nitride ceramic, but similar effects were confirmed when aluminum nitride powder or sialon powder was used instead.
上記実施例ではアミノ変成ポリオレフインとし
て（ジアリルアンモニウムモノマ＋スチレンモノ
マ）共重合体を用いたが、これ以外のアミノ変成
ポリオレフイン、例えばポリ−α−プロピルアミ
ノスチレン、ポリ−β−プロピルアミノスチレ
ン、ポリ−β−ブチルアミノスチレンを用いても
同様な効果が確認された。 In the above examples, a copolymer (diallylammonium monomer + styrene monomer) was used as the amino-modified polyolefin, but other amino-modified polyolefins such as poly-α-propylaminostyrene, poly-β-propylaminostyrene, poly- A similar effect was confirmed using β-butylaminostyrene.
上記実施例ではアンモニウム塩形界面活性剤と
してポリ−２−メタクリロキシエチルトリメチル
アンモニウムを用いたが、これに代つて他の界面
活性剤、例えばポリ−３−メタクリロキシ−２−
ヒドロキシプロピルトリアルキルアンモニウム、
ポリ−メタアクリルアミドアルキルアンモニウ
ム、ポリ−メタアリルアンモニウム、ポリ−ビニ
ルベンジルアンモニウム、ポリ−アルキル化アン
モニウムを用いても同様な効果が確認された。 In the above examples, poly-2-methacryloxyethyltrimethylammonium was used as the ammonium salt type surfactant, but other surfactants such as poly-3-methacryloxy-2-
hydroxypropyl trialkylammonium,
Similar effects were confirmed using poly-methacrylamidoalkylammonium, poly-methallylammonium, poly-vinylbenzylammonium, and poly-alkylated ammonium.
以上詳述した如く、本発明の窒化系セラミツク
ス成形用バインダによれば窒化系セラミツクス粉
末に添加することによりダイランシー性がほとん
ど認められない流動性の優れた混練物を調製で
き、これを射出成形することによつてボイドがな
く、成形歪が低減されたグリーン成形体を得るこ
とができ、ひいては脱脂後の成形体、焼結後のセ
ラミツクス製品のクラツク発生を防止して歩留り
の向上を達成できる等顕著な効果を有する。
As detailed above, according to the binder for molding nitrided ceramics of the present invention, by adding it to nitrided ceramic powder, it is possible to prepare a kneaded material with excellent fluidity in which hardly any dilancy is observed, and this can be injection molded. As a result, it is possible to obtain a green molded body without voids and with reduced molding distortion, and in turn, it is possible to prevent the occurrence of cracks in the molded body after degreasing and ceramic products after sintering, thereby achieving an improvement in yield, etc. Has a remarkable effect.
図面は本発明の実施例１〜２及び比較例により
調製された混練物の粘度特性を示す線図である。
The drawing is a diagram showing the viscosity characteristics of kneaded products prepared according to Examples 1 and 2 of the present invention and a comparative example.
Claims (1)
ポリオレフインのうちの少なくとも１種を含む窒
化系セラミツクス成形用バインダ。1. A binder for molding nitrided ceramics containing at least one of an ammonium salt type surfactant and an amino-modified polyolefin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58110366A JPS605064A (en) | 1983-06-20 | 1983-06-20 | Binder for forming nitride ceramics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58110366A JPS605064A (en) | 1983-06-20 | 1983-06-20 | Binder for forming nitride ceramics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS605064A JPS605064A (en) | 1985-01-11 |
| JPH0143708B2 true JPH0143708B2 (en) | 1989-09-22 |
Family
ID=14533968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58110366A Granted JPS605064A (en) | 1983-06-20 | 1983-06-20 | Binder for forming nitride ceramics |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS605064A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5648665A (en) * | 1994-04-28 | 1997-07-15 | Ngk Insulators, Ltd. | Semiconductor device having a plurality of cavity defined gating regions and a fabrication method therefor |
| JP3245308B2 (en) * | 1994-08-26 | 2002-01-15 | 日本碍子株式会社 | Method for manufacturing semiconductor device |
| JP3214987B2 (en) * | 1994-09-05 | 2001-10-02 | 日本碍子株式会社 | Semiconductor device and method of manufacturing the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5941949B2 (en) * | 1979-02-27 | 1984-10-11 | 旭硝子株式会社 | Method of forming ceramic powder |
-
1983
- 1983-06-20 JP JP58110366A patent/JPS605064A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS605064A (en) | 1985-01-11 |
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