JPH06340467A - Production of ceramic molded body - Google Patents

Production of ceramic molded body

Info

Publication number
JPH06340467A
JPH06340467A JP5127216A JP12721693A JPH06340467A JP H06340467 A JPH06340467 A JP H06340467A JP 5127216 A JP5127216 A JP 5127216A JP 12721693 A JP12721693 A JP 12721693A JP H06340467 A JPH06340467 A JP H06340467A
Authority
JP
Japan
Prior art keywords
mold
molded body
parts
slurry
weight
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.)
Withdrawn
Application number
JP5127216A
Other languages
Japanese (ja)
Inventor
Kiyoshi Watanabe
潔 渡辺
Shigeaki Yamamuro
繁昭 山室
Hirofumi Furukawa
洋文 古河
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.)
Mitsubishi Heavy Industries Ltd
Original Assignee
Mitsubishi Heavy Industries Ltd
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 Mitsubishi Heavy Industries Ltd filed Critical Mitsubishi Heavy Industries Ltd
Priority to JP5127216A priority Critical patent/JPH06340467A/en
Publication of JPH06340467A publication Critical patent/JPH06340467A/en
Withdrawn legal-status Critical Current

Links

Abstract

PURPOSE:To provide a method for producing a ceramic molded body fit to produce a core for precision casting, etc. CONSTITUTION:Powdery ceramic stock is blended with resol and kneaded to prepare slurry. An acid catalyst is added to the slurry and this slurry is molded by pouring into a mold and hardened. The resulting molded body is taken out of the mold, dried and fired. By this method, molding time can be shortened while adopting molding by pouring and a large-sized or thick product is easily molded without requiring a gypsum mold.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は石膏型を必要とせず、短
時間で成形可能なセラミック成形体の製造方法に関す
る。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a ceramic molded body which does not require a gypsum mold and can be molded in a short time.

【0002】[0002]

【従来の技術】セラミックの成形(形状の付与)方法と
しては、金型プレス法、泥漿鋳込み法(スリップキャス
ト法)、冷間静水圧加圧プラス機械加工法、射出成形
法、ドクターブレード法(極薄板の成形法)等があり、
製品形状、生産量及び要求機能等によって各種の成形方
法が採用されている。中でも石膏型中に流し込んで、石
膏型に水あるいはアルコール等の溶媒を吸収させて着肉
成形する泥漿鋳込み法は、比較的複雑形状品の成形が
可能である、型の製作が容易で安価である、特別に
大型、高価な設備を必要としない、等の利点があり、多
くの製品の製造に採用されている。しかし一方で、石
膏型に溶媒を吸収させて硬化、成形するために、肉厚の
製品になると成形に長時間を要する、多量の型が必要
であり、多量産には不適である、乾燥中に製品に割れ
が発生し易く、特に厚肉製品では割れが顕著に発生す
る、石膏型の寿命が短く、寸法精度上問題になる場合
がある、等の欠点も併せ持っている。
2. Description of the Related Art Ceramic molding (shape imparting) methods include die pressing, slurry casting (slip casting), cold isostatic pressing plus machining, injection molding, and doctor blade ( There is a method for forming ultra-thin plates, etc.,
Various molding methods are adopted depending on the product shape, production amount, required functions, and the like. Among them, the slurry casting method in which a plaster mold is cast into a plaster mold to absorb water or a solvent such as alcohol, and the ingot is molded, a relatively complicated shaped product can be molded, and the mold is easy and inexpensive to manufacture. It has advantages such as that it does not require specially large size and expensive equipment, and is used for manufacturing many products. On the other hand, on the other hand, it takes a long time to form a thick product because the plaster mold absorbs the solvent and hardens and molds. It requires a large amount of molds and is not suitable for mass production. In addition, the product is prone to cracking, especially in thick-walled products, which is prone to cracking, the life of the gypsum mold is short, and there is a problem in dimensional accuracy.

【0003】[0003]

【発明が解決しようとする課題】セラミックスラリを石
膏型中に流し込む泥漿鋳込み法(スリップキャスト法)
は、比較的簡便に複雑形状品の成形、製造が可能である
反面、前記のような技術的課題を有している。本発明は
流し込み成形法でありながら成形時間の短縮が可能で、
石膏型を必要とせず、大型あるいは厚肉製品の成形が容
易なセラミックの成形法を提供するものである。
[Problems to be Solved by the Invention] Sludge casting method in which ceramic slurry is poured into a plaster mold (slip casting method)
Has a technical problem as described above, though it can relatively easily mold and manufacture a product having a complicated shape. Although the present invention is a casting method, it is possible to shorten the molding time.
It is intended to provide a ceramic molding method which does not require a gypsum mold and can easily mold a large-sized or thick-walled product.

【0004】[0004]

【課題を解決するための手段】本発明はセラミック原料
粉末にレゾールを配合、混練してスラリ化し、得られた
スラリに酸触媒を添加したのち型内に流し込んで成形
し、硬化後に型内から成形体を取り出し、乾燥、焼成す
ることを特徴とするセラミック成形体の製造方法であ
る。ここで、酸触媒としてはレゾール100重量部当た
り20〜35重量部の有機酸エステルを使用するのが好
ましい。また、さらにレゾールと有機酸エステルの合計
量100重量部に対し5重量部以下のアゾジカーボンア
ミドを添加することにより乾燥時の割れを防止すること
ができる。
According to the present invention, a ceramic raw material powder is mixed with a resol, kneaded to form a slurry, an acid catalyst is added to the obtained slurry, and the mixture is poured into a mold to be molded. In the method for producing a ceramic molded body, the molded body is taken out, dried and fired. Here, as the acid catalyst, it is preferable to use 20 to 35 parts by weight of an organic acid ester per 100 parts by weight of the resole. Further, by adding 5 parts by weight or less of azodicarbonamide to 100 parts by weight of the total amount of the resole and the organic acid ester, cracking during drying can be prevented.

【0005】本発明の方法においては、セラミックをス
ラリ化する溶媒とバインダを兼ねてレゾール(アルカリ
フェノール)を使用する点に最大の特徴がある。レゾー
ルに酸触媒を配合すると化学反応により短時間で硬化
(ゲル化)するので容易に型から取り出すことができ
る。レゾールに有機酸エステル等の酸触媒を添加すると
縮合反応により硬化(ゲル化)することは公知であり、
鋳造用鋳型のバインダとして使用されている。ただし、
鋳造用鋳型の場合には鋳物砂をスラリ化する必要はな
く、バインダの添加量は鋳物砂に対し数%以下という少
量であり、本発明の方法のように原料粉末がスラリ化す
る程度に多量のレゾールを配合した例はない。
The most significant feature of the method of the present invention is that a resol (alkali phenol) is used as a solvent and a binder for slurrying the ceramic. When an acid catalyst is added to the resole, it is hardened (gelled) in a short time due to a chemical reaction, so that it can be easily taken out of the mold. It is known that when an acid catalyst such as an organic acid ester is added to a resole, it is cured (gelled) by a condensation reaction,
Used as a binder for casting molds. However,
In the case of a casting mold, it is not necessary to make the molding sand into a slurry, and the amount of the binder added is a small amount of a few% or less relative to the molding sand, and a large amount such that the raw material powder becomes a slurry like the method of the present invention. There is no example of blending the resol.

【0006】次に本発明の方法をその工程順に従って説
明する。先ずセラミックの原料粉末にレゾール配合、混
練してスラリ化する。ここで使用するレゾールは通常一
般式(化1)で表される構造を有するもので酸触媒を添
加すると縮合反応により約10分程度の短時間で硬化
(ゲル化)するものである。
Next, the method of the present invention will be described in the order of steps thereof. First, a ceramic raw material powder is mixed with a resol and kneaded to form a slurry. The resol used here usually has a structure represented by the general formula (Formula 1), and when an acid catalyst is added, it cures (gels) in a short time of about 10 minutes due to a condensation reaction.

【0007】[0007]

【化1】 [Chemical 1]

【0008】セラミック原料粉末に対するレゾールの配
合量は、流し込み時のスラリの流動性によって決まり、
得られるスラリが型に流し込める程度の流動性を有する
ような量とすればよい。この量はセラミック原料粉末の
種類や密度、形状等の物性及び製品の形状、肉厚等によ
って異なるものである。
The amount of resole to be mixed with the ceramic raw material powder is determined by the fluidity of the slurry when poured,
The amount may be such that the obtained slurry has fluidity such that it can be poured into a mold. This amount varies depending on the type and density of the ceramic raw material powder, physical properties such as shape, and the shape and thickness of the product.

【0009】得られたスラリにレゾール100重量部に
対し20〜35重量部の酸触媒を添加し混合したのち、
型内に流し込んで硬化させる。使用する酸触媒としては
各種有機カルボン酸エステル、有機スルホン酸エステル
などの有機酸エステル類が好ましい。酸触媒の使用量が
20重量部未満では硬化時間が長くなり過ぎ、また硬化
後の成形体の強度が小さくなる。一方、酸触媒の量が3
5重量%を超えるとレゾールの絶対量が不足するため、
成形後のグリーン強度が小さくなるので好ましくない。
成形用の型としては金型が一般的であるが、鋳込み用の
型としては特に限定されるものではなく、必要に応じプ
ラスチック型、木型等を使用してもよい。
After adding 20 to 35 parts by weight of an acid catalyst to 100 parts by weight of the resole and mixing the resulting slurry,
Pour into the mold to cure. As the acid catalyst to be used, organic acid esters such as various organic carboxylic acid esters and organic sulfonic acid esters are preferable. If the amount of the acid catalyst used is less than 20 parts by weight, the curing time will be too long, and the strength of the molded product after curing will be low. On the other hand, the amount of acid catalyst is 3
If it exceeds 5% by weight, the absolute amount of resole will be insufficient.
It is not preferable because the green strength after molding becomes small.
A mold is generally used as a mold for molding, but the mold for casting is not particularly limited, and a plastic mold, a wooden mold, or the like may be used if necessary.

【0010】型内に流し込んだスラリは短時間(通常約
10分程度)で硬化するので、型から取り出し、乾燥し
たのち加熱してバインダの除去及び焼成を行いセラミッ
ク成形体を得ることができる。レゾール、酸触媒として
の有機酸エステル及び後述のアゾジカーボンアミドは4
00〜600℃で分解、気化するので、焼成時にこれら
のバインダ類は完全に除去され、焼成後にセラミック成
形体内に残留してセラミックの特性を阻害することはな
い。
Since the slurry poured into the mold is hardened in a short time (usually about 10 minutes), it can be taken out from the mold, dried, and then heated to remove the binder and fire to obtain a ceramic molded body. Resol, organic acid ester as an acid catalyst and azodicarbonamide described below are 4
Since they are decomposed and vaporized at 00 to 600 ° C., these binders are completely removed during firing and do not remain in the ceramic molded body after firing to impair the characteristics of the ceramic.

【0011】なお、スラリ中にアゾジカーボンアミド等
の発泡剤を添加することにより成形体中の通気度が増大
し、乾燥時のバインダの気化によって発生したガスが容
易に成形体外に出るため、特に厚肉製品では乾燥時の成
形体内における割れの発生を防止することができる。発
泡剤としてアゾジカーボンアミドを使用する場合には、
レゾールと有機酸エステルの合計量100重量部に対し
5重量部以下の量のアゾジカーボンアミドを添加するこ
とにより、アゾジカーボンアミドが加熱乾燥時に約13
0〜140℃付近で発泡し、前記のような効果を発揮す
る。アゾジカーボンアミドの添加量が5重量部を超える
と、発泡量が多くなり、逆に割れが発生するようになる
ので好ましくない。
By adding a foaming agent such as azodicarbonamide to the slurry, the air permeability in the molded body is increased, and the gas generated by the vaporization of the binder during drying easily goes out of the molded body. Particularly for thick-walled products, it is possible to prevent cracking in the molded body during drying. When using azodicarbonamide as a foaming agent,
By adding azodicarbonamide in an amount of 5 parts by weight or less to 100 parts by weight of the total amount of the resole and the organic acid ester, the azodicarbonamide is heated to about 13 parts by weight when dried.
It foams at around 0 to 140 ° C and exhibits the above-mentioned effects. When the amount of azodicarbonamide added exceeds 5 parts by weight, the amount of foaming increases, and cracking occurs, which is not preferable.

【0012】本発明の方法は石膏型を必要とせず、しか
も短時間でセラミックの成形が可能な方法であり、各種
セラミック成形品、精密鋳造用のセラミック中子などの
成形、特に大型あるいは厚肉のセラミック成形体の製造
に有効な方法である。
The method of the present invention does not require a gypsum mold and is capable of molding ceramics in a short time. It can be used for molding various ceramic molded products, ceramic cores for precision casting, etc., especially large size or thick wall. It is an effective method for producing the ceramic molded body.

【0013】[0013]

【実施例】以下実施例により本発明の方法をさらに具体
的に説明する。 (実施例1)平均粒径が12μmの溶融石英に粒径44
μm以下のジルコン粉末を表1に示すような割合で配合
したセラミック原料粉末100重量部に、レゾール
((化1)においてmが約2、nが約1に相当するも
の)を35重量部配合して混練し、次いでエチレングリ
コールジアセテート9.8重量部を添加し約30秒混練
したのち、20×20×100mmの形状を有する金型
内へ流し込み成形した。10分後に金型から成形体を取
り出し、室内で24時間自然乾燥後、さらに図1に示し
た温度条件で加熱乾燥し、次いで図2の条件でバインダ
の除去及び焼成を実施した。焼成後のセラミック成形体
には割れは認められず、常温での3点曲げ強度は表1に
示す通りであった。いずれの試料についても精密鋳造用
中子として一般的に要求される強度である100kgf
/cm2 を満足しており、精密鋳造用中子として十分に
使用できるものであった。
EXAMPLES The method of the present invention will be described in more detail with reference to the following examples. Example 1 A fused silica having an average particle size of 12 μm has a particle size of 44
To 100 parts by weight of the ceramic raw material powder in which the zircon powder having a particle size of less than or equal to μm is mixed in the ratio shown in Table 1, 35 parts by weight of resole (corresponding to m of about 2 and n of about 1 in Chemical formula 1) is mixed. Then, 9.8 parts by weight of ethylene glycol diacetate was added and kneaded for about 30 seconds, and then the mixture was cast into a mold having a shape of 20 × 20 × 100 mm. After 10 minutes, the molded body was taken out of the mold, air-dried in a room for 24 hours, then dried by heating under the temperature conditions shown in FIG. 1, and then the binder was removed and fired under the conditions shown in FIG. No cracks were observed in the ceramic molded body after firing, and the three-point bending strength at room temperature was as shown in Table 1. 100 kgf, which is the strength generally required for precision casting cores for all samples
/ Cm 2 was satisfied, and it could be sufficiently used as a core for precision casting.

【0014】[0014]

【表1】 [Table 1]

【0015】(実施例2)実施例1で使用したのと同じ
セラミック原料粉末100重量部に対し、レゾールを3
5重量部配合して混練し、次いでエチレングリコールジ
アセテート9.8重量部及びアゾジカーボンアミド1.
3重量部を添加し約30秒混練したのち、30×30×
100mmの形状を有する金型内へ流し込み成形した。
10分後に金型から成形体を取り出し、室内で24時間
自然乾燥後、さらに図3に示した温度条件で加熱乾燥
し、次いで図2の条件でバインダの除去及び焼成を実施
した。アゾジカーボンアミドを添加しない実施例1の条
件では、成形体の形状が30×30×100mmとな
り、厚みが増すと乾燥時に微細な割れが発生したが、本
実施例では焼成後のセラミック成形体には割れは認めら
れず、常温での3点曲げ強度も略表1に示したものと同
じレベルであった。
Example 2 100 parts by weight of the same ceramic raw material powder as used in Example 1 was mixed with 3 parts of resole.
5 parts by weight were mixed and kneaded, and then 9.8 parts by weight of ethylene glycol diacetate and 1.
After adding 3 parts by weight and kneading for about 30 seconds, 30 × 30 ×
It was cast into a mold having a shape of 100 mm.
After 10 minutes, the molded body was taken out of the mold, air-dried in a room for 24 hours, and then heat-dried under the temperature conditions shown in FIG. 3, and then the binder was removed and fired under the conditions shown in FIG. Under the conditions of Example 1 in which no azodicarbonamide was added, the shape of the molded body was 30 × 30 × 100 mm, and as the thickness increased, fine cracks occurred during drying, but in this Example, the ceramic molded body after firing was formed. No cracks were observed, and the three-point bending strength at room temperature was at the same level as shown in Table 1.

【0016】[0016]

【発明の効果】本発明の方法によれば、次のような効果
がある。先ず、約10分程度の短時間でセラミックスラ
リ(ゾル)が硬化(ゲル化)するので、短時間での成形
が可能である。そのため、流し込み用の型が少数です
み、多量生産が可能である。また、石膏型を必要としな
いので型の繰り返し使用が可能であり、型の乾燥等に手
入れが不要である。さらに、アゾジカーボンアミドを微
量添加することによって乾燥時の割れが防止でき、大型
厚肉製品の高能率製造が可能となった。
The method of the present invention has the following effects. First, since the ceramic slurry (sol) is cured (gelled) in a short time of about 10 minutes, molding can be performed in a short time. Therefore, the number of casting molds is small and mass production is possible. Further, since the plaster mold is not required, the mold can be repeatedly used, and maintenance such as drying of the mold is unnecessary. Furthermore, by adding a very small amount of azodicarbonamide, it is possible to prevent cracking during drying, and it has become possible to manufacture large thick products with high efficiency.

【図面の簡単な説明】[Brief description of drawings]

【図1】実施例1における乾燥温度条件を示すグラフで
ある。
FIG. 1 is a graph showing a drying temperature condition in Example 1.

【図2】実施例1及び2における乾燥、脱バインダ及び
焼成の温度条件を示すグラフである。
FIG. 2 is a graph showing temperature conditions of drying, binder removal and firing in Examples 1 and 2.

【図3】実施例2における乾燥温度条件を示すグラフで
ある。
FIG. 3 is a graph showing a drying temperature condition in Example 2.

Claims (3)

【特許請求の範囲】[Claims] 【請求項1】 セラミック原料粉末にレゾールを配合、
混練してスラリ化し、得られたスラリに酸触媒を添加し
たのち型内に流し込んで成形し、硬化後に型内から成形
体を取り出し、乾燥、焼成することを特徴とするセラミ
ック成形体の製造方法。
1. A ceramic raw material powder is mixed with resol,
A method for producing a ceramic molded body, which comprises kneading to form a slurry, adding an acid catalyst to the obtained slurry, casting the mixture into a mold, molding the molded body, and removing the molded body from the mold after curing, drying and firing. .
【請求項2】 セラミック原料粉末にレゾールを配合、
混練してスラリ化し、得られたスラリにレゾール100
重量部当たり20〜35重量部の有機酸エステルを添加
したのち型内に流し込んで成形し、硬化後に型内から成
形体を取り出し、乾燥、焼成することを特徴とするセラ
ミック成形体の製造方法。
2. A ceramic raw material powder is mixed with resole,
Knead to make a slurry, and add 100 parts of resole to the obtained slurry.
A method for producing a ceramic molded body, comprising adding 20 to 35 parts by weight of an organic acid ester per part by weight, pouring the mixture into a mold for molding, taking out the molded body from the mold after curing, drying and firing.
【請求項3】 セラミック原料粉末にレゾールを配合、
混練してスラリ化し、得られたスラリにレゾール100
重量部当たり20〜35重量部の有機エステル及びレゾ
ールと有機酸エステルの合計量100重量部に対し5重
量部以下のアゾジカーボンアミドを添加したのち型内に
流し込んで成形し、硬化後に型内から成形体を取り出
し、乾燥、焼成することを特徴とするセラミック成形体
の製造方法。
3. Resol is mixed with ceramic raw material powder,
Knead to make a slurry, and add 100 parts of resole to the obtained slurry.
20 to 35 parts by weight per 100 parts by weight of organic ester and 5 parts by weight or less of azodicarbonamide are added to 100 parts by weight of the total amount of resole and organic acid ester, and then the mixture is poured into a mold to be molded, and after curing, in the mold. A method for producing a ceramic molded body, which comprises taking out a molded body from the product, drying and firing it.
JP5127216A 1993-05-28 1993-05-28 Production of ceramic molded body Withdrawn JPH06340467A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP5127216A JPH06340467A (en) 1993-05-28 1993-05-28 Production of ceramic molded body

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP5127216A JPH06340467A (en) 1993-05-28 1993-05-28 Production of ceramic molded body

Publications (1)

Publication Number Publication Date
JPH06340467A true JPH06340467A (en) 1994-12-13

Family

ID=14954608

Family Applications (1)

Application Number Title Priority Date Filing Date
JP5127216A Withdrawn JPH06340467A (en) 1993-05-28 1993-05-28 Production of ceramic molded body

Country Status (1)

Country Link
JP (1) JPH06340467A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160003768A (en) 2013-05-29 2016-01-11 미츠비시 쥬고교 가부시키가이샤 Core for precision casting, production method therefor, and mold for precision casting
KR20160003767A (en) 2013-05-29 2016-01-11 미츠비시 쥬고교 가부시키가이샤 Core for precision casting, production method therefor, and mold for precision casting

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160003768A (en) 2013-05-29 2016-01-11 미츠비시 쥬고교 가부시키가이샤 Core for precision casting, production method therefor, and mold for precision casting
KR20160003767A (en) 2013-05-29 2016-01-11 미츠비시 쥬고교 가부시키가이샤 Core for precision casting, production method therefor, and mold for precision casting
US10166598B2 (en) 2013-05-29 2019-01-01 Mitsubish Heavy Industries, Ltd. Precision-casting core, precision-casting core manufacturing method, and precision-casting mold

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