JPH01301203A - Preparation of high-strength cast molding - Google Patents
Preparation of high-strength cast moldingInfo
- Publication number
- JPH01301203A JPH01301203A JP63132355A JP13235588A JPH01301203A JP H01301203 A JPH01301203 A JP H01301203A JP 63132355 A JP63132355 A JP 63132355A JP 13235588 A JP13235588 A JP 13235588A JP H01301203 A JPH01301203 A JP H01301203A
- Authority
- JP
- Japan
- Prior art keywords
- polyvinyl alcohol
- molding
- slush
- alcohol polymer
- cast molding
- 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
Links
- 238000000465 moulding Methods 0.000 title abstract description 11
- 238000002360 preparation method Methods 0.000 title 1
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 27
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 14
- 239000000919 ceramic Substances 0.000 claims abstract description 10
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000002002 slurry Substances 0.000 claims description 18
- 238000005266 casting Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 229910052726 zirconium Inorganic materials 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract 2
- 230000001143 conditioned effect Effects 0.000 abstract 1
- 230000003750 conditioning effect Effects 0.000 abstract 1
- 229910052602 gypsum Inorganic materials 0.000 abstract 1
- 239000010440 gypsum Substances 0.000 abstract 1
- 239000011505 plaster Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000007582 slurry-cast process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Producing Shaped Articles From Materials (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、泥漿鋳込み成形法により生強度の高い成形体
を得る方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for obtaining a molded article with high green strength by a slurry casting method.
（従来の技術）
泥漿鋳込み成形法は陶磁器分野で従来から広く使用され
てきたが、複雑な形状のものが容易に均質に成形できる
こと、設備費が少なく多種少量生産に適していることな
どの利点があるため、近年ファインセラミックス分野で
の用途が広まりつつある。(Conventional technology) The slurry casting method has been widely used in the ceramics field, but its advantages include the ability to easily mold complex shapes into uniform shapes, low equipment costs, and suitability for high-mix, low-volume production. Because of this, its use in the fine ceramics field has been expanding in recent years.
（発明が解決しようとする課題）
しかし、鋳込み成形では成形体の生強度を高めることが
難しく、とくにファインセラミックス分野のように粘土
を用いない素地では大きな生強度を得ることが困難であ
る。(Problems to be Solved by the Invention) However, it is difficult to increase the green strength of the molded product by cast molding, and it is particularly difficult to obtain a large green strength for materials that do not use clay, such as in the field of fine ceramics.
生強度を大きくする方法としては、有機結合剤、例えば
カルボキシメチルセルロース（ＣＭＣ）、ポリビニルア
ルコール（ＰＶＡ）、アルギン酸ソーダ、アクリル系樹
脂、でんぷんなどの添加が考えられるが、これらの結合
剤は泥漿の流動特性を損ねたり、着肉速度を小さくする
など、泥漿の特性に大きな影響を与えるだけでなく、型
に吸収されて目詰まりを起こし、型を劣化させるなどの
欠点があり、そのために添加量に限界があり有効な方法
とは言い難いものであった。Possible ways to increase green strength include adding organic binders such as carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), sodium alginate, acrylic resin, and starch; Not only does it have a large effect on the properties of the slurry, such as impairing its properties and reducing the deposition rate, but it also has the disadvantage of being absorbed into the mold, causing clogging, and deteriorating the mold. This method had its limitations and could hardly be called an effective method.
したがって、本発明の目的は泥漿の特性や型の性質に大
きな影響を与えることなしに、生強度の大きな成形体を
得ることのできる鋳込み方法を見出す点にある。Therefore, an object of the present invention is to find a casting method that can obtain a molded article with high green strength without significantly affecting the characteristics of the slurry or the properties of the mold.
（課題を解決するための手段）
本発明は、この目的達成のため鋭意研究の結果見出され
たもので、この高強度鋳込み成形体の製造方法は、ポリ
ビニルアルコールまたはその誘導体に塩化ジルコニウム
を添加してなるポリビニルアルコール系重合体を、セラ
ミックス鋳込み泥漿に、０．１〜５重景％混合して鋳込
み成形した後、得られた成形体を５０〜１５０℃で熱処
理することを特徴とするものである。(Means for Solving the Problems) The present invention was discovered as a result of intensive research to achieve this objective, and a method for producing a high-strength cast molded product includes adding zirconium chloride to polyvinyl alcohol or a derivative thereof. A polyvinyl alcohol-based polymer formed by mixing 0.1 to 5 % of a ceramic casting slurry to a ceramic casting slurry and casting the mixture, and then heat-treating the resulting molded product at 50 to 150°C. It is.
以下本発明の詳細な説明する。The present invention will be explained in detail below.
本発明による鋳込み成形体の製造方法において使用され
るポリビニルアルコール系重合体は、ポリビニルアルコ
ールまたはその誘導体に塩化ジルコニウムを添加したも
の（特公昭５０−３８６５２号公報）で、これをセラミ
ックス鋳込み泥漿の調製時に原料と一緒に添加してボー
ルミルで混合するか、あるいは調製された泥漿中に添加
して攪拌機により混合する。この添加物はポリビニルア
ルコール系重合体を主体とするため、泥漿状態での保存
安定性に優れ長時間放置しても粘度上昇やゲル化を起こ
すことがなく極めて安定である。しかし、泥漿がｐ Ｈ
８以上のアルカリ性になるとゲル化するため、泥漿を常
にｐＨ８以下の中性または弱酸性に保つことが重要であ
る。The polyvinyl alcohol polymer used in the method for producing a cast molded body according to the present invention is polyvinyl alcohol or a derivative thereof to which zirconium chloride is added (Japanese Patent Publication No. 38652/1983), and this is used to prepare a ceramic casting slurry. Sometimes it is added together with the raw materials and mixed in a ball mill, or it is added into the prepared slurry and mixed with a stirrer. Since this additive is mainly composed of a polyvinyl alcohol polymer, it has excellent storage stability in a slurry state and is extremely stable without increasing viscosity or gelling even when left for a long time. However, the pH of the slurry
It is important to always keep the slurry at a neutral or slightly acidic pH of 8 or less, as it will gel if it becomes alkaline to pH 8 or higher.
ポリビニルアルコール系重合体の泥漿に対する添加量は
０．１〜５重量％であり、より望ましくは０．２〜２重
量％が適当である。添加量が０．１％未満では強度増大
の効果が充分でなく、また５重量％を超えると乾燥が困
難になるだけでなく、焼成過程で有機物を分解するのに
長時間を必要とするようになる。The amount of the polyvinyl alcohol polymer added to the slurry is 0.1 to 5% by weight, more preferably 0.2 to 2% by weight. If the amount added is less than 0.1%, the effect of increasing strength will not be sufficient, and if it exceeds 5% by weight, not only will drying become difficult, but it will take a long time to decompose the organic matter during the firing process. become.
ポリビニルアルコール系重合体を添加した泥漿は、つぎ
に石膏型に流し込み、ｖＪ込み成形を行う。The slurry to which the polyvinyl alcohol polymer has been added is then poured into a plaster mold to perform VJ molding.
すなわち、石膏型の吸水力を利用して石膏型の表面に素
地を着肉させ、成形体を得る。That is, a molded body is obtained by applying the base material to the surface of the plaster mold by utilizing the water absorption power of the plaster mold.
得られた成形体は含水状態でそのまま常温に放置するか
、５０〜１５０℃で加熱処理することにより、素地中の
ポリビニルアルコール系重合体はジルコニウムがポリビ
ニルアルコール分子間の架橋剤となって架橋構造を形成
するため、成形体を高強度のものにする。The obtained molded body is left in a water-containing state at room temperature or heat-treated at 50 to 150°C, so that the polyvinyl alcohol polymer in the base material has a cross-linked structure as zirconium acts as a cross-linking agent between polyvinyl alcohol molecules. In order to form a molded body, the molded body is made to have high strength.
この方法では乾燥過程で切れが生じるもの、例えば厚肉
のもの、形状が複雑なもの、素地の乾燥収縮が大きいも
のなどでは、６０℃以上の飽和湿度の空気中で加熱した
後、乾燥をすればよい、また成形体強度が極めて小さい
ために１石膏型から取り出す過程で切れを生じ易いよう
なものでは、石膏型ごと６０℃以上の飽和湿度の空気中
で加熱処理を行い、その上で脱型するのが適当である。With this method, for items that break during the drying process, such as items that are thick, have a complicated shape, or have large drying shrinkage, the drying process is performed after heating in air with a saturated humidity of 60°C or higher. In addition, if the strength of the molded product is extremely low and it is likely to break during the process of removing it from the plaster mold, heat treatment the entire plaster mold in air with saturated humidity of 60°C or higher, and then remove it. It is appropriate to mold it.
以下、本発明の具体的態様を実施例および比較例により
説明するが、例中、部および％とあるのは、それぞれ重
量部および重量％を表わす。Hereinafter, specific embodiments of the present invention will be explained with reference to Examples and Comparative Examples. In the Examples, parts and % represent parts by weight and % by weight, respectively.
実施例。Example.
平均粒径０．５−の微粒アルミナ１００部に、解膠剤と
しての特殊ポリアクリル酸共重合体（商品名Ｃ−２４、
日本化薬■製）０．６部、と水３１部とを添加し、ボー
ルミルで混合してアルミナ泥漿を作り、これに結合剤と
してポリビニルアルコール系重合体に塩化ジルコニウム
を添加したもの（商品名ＺＩＭ−１００、高松油脂曲製
）を、それぞれ０．４部および１部加えて、さらにボー
ルミルで充分に混合した後、石膏型に流し込んで１４＋
ｍφＸ １４（ｈ＋ｎの丸棒状試料を成形し、脱型後６
０℃の乾燥器に入れ乾燥した。A special polyacrylic acid copolymer (trade name C-24,
(manufactured by Nippon Kayaku ■) and 31 parts of water were mixed in a ball mill to make an alumina slurry, to which a polyvinyl alcohol polymer and zirconium chloride were added as a binder (trade name). After adding 0.4 parts and 1 part of ZIM-100 (made by Takamatsu Yushikyoku), and mixing thoroughly with a ball mill, the mixture was poured into a plaster mold and 14+
MφX 14 (h + n round bar sample was molded, and after demolding
It was placed in a dryer at 0°C and dried.
他に、結合剤としてそれぞれポリビニルアルコール（商
品名ＰＡ−０５、信越化学工業ｗＩ製）、アクリルエマ
ルジョン（商品名ＷＡ−３２０、三井東圧化学■ＩＫ）
、水溶性アクリル樹脂（商品名にＳ−９００、日本化薬
＠製）を添加した泥漿についての性質を調べ、比較例と
した。In addition, as binders, polyvinyl alcohol (product name PA-05, manufactured by Shin-Etsu Chemical wI) and acrylic emulsion (product name WA-320, manufactured by Mitsui Toatsu Chemical IK) are used.
The properties of a slurry to which a water-soluble acrylic resin (product name: S-900, manufactured by Nippon Kayaku@) was added were investigated and used as a comparative example.
着肉速度は石膏型に泥漿を流し込んで２０分後の石膏に
着肉した厚みで示す。また鋳込み成形体の乾燥強度を表
に示した。The deposition rate is indicated by the thickness of the plaster 20 minutes after pouring the slurry into the plaster mold. In addition, the dry strength of the cast molded product is shown in the table.
なお、表中結合剤の種類の項において、ＰＶＡ、ＡＥ、
ＳＡＲとあるのは、それぞれ上記のポリビニルアルコー
ル、アクリルエマルジョン、水溶性アクリル樹脂を表わ
す。In addition, in the section of the type of binder in the table, PVA, AE,
SAR represents the above-mentioned polyvinyl alcohol, acrylic emulsion, and water-soluble acrylic resin, respectively.
結合剤のないものの乾燥強度は１０．Ｏｋｇｆ／ａＪと
著しく小さく、生成品の取扱いに難点があった。ポリビ
ニルアルコールの０．４％の添加によって乾燥強度は２
５．Ｏｋｇｆ／ａ＃と増大するが、着肉速度が小さく実
用面に問題があった。また、近年多用されているアクリ
ル樹脂系結合剤では、添加量が１〜２％ないと、 ４０
〜５０ｋｇｆ／ａＪの乾燥強度が得ら九ない。The dry strength of the product without binder is 10. The product was extremely small at Okgf/aJ, making it difficult to handle the product. The addition of 0.4% polyvinyl alcohol increased the dry strength to 2.
5. Although it increased to Okgf/a#, the ink deposition speed was low and there was a problem in practical use. In addition, with acrylic resin binders that have been widely used in recent years, if the amount added is less than 1 to 2%, 40
It is difficult to obtain a dry strength of ~50 kgf/aJ.
これに対して１本発明のポリビニルアルコール系重合体
を用いたものでは、泥漿粘度１着肉速度共に他に比較し
て劣ることがなく、０．４％の少量添加で乾燥強度が６
１．０ｋｇｆ／ｄと大声＜、ｉ、ｏ％の添加ではさらに
９０ｋｇｆ／ｃｄとなった。On the other hand, in the case of using the polyvinyl alcohol polymer of the present invention, there is no inferiority in both slurry viscosity and inking speed compared to other products, and the dry strength is increased to 6.
With addition of 1.0 kgf/d and i,o%, it became further 90 kgf/cd.
さらに１本試料を１６２０℃で２時間焼成したところ、
相対密度９９．５％の焼結体が得られ、ポリビニルアル
コール系重合体の添加が成形体の緻密化に何の悪影響を
ももたらさないことが判った。Furthermore, when one sample was fired at 1620℃ for 2 hours,
A sintered body with a relative density of 99.5% was obtained, and it was found that the addition of the polyvinyl alcohol polymer had no adverse effect on the densification of the molded body.
（発明の効果）
以上の実施例の結果から明らかなように１本発明によれ
ば鋳込み泥漿の水分や着肉速度などの泥漿性状を大きく
変化させることなく、成形体の生強度のみを著しく向上
させることができ、したがって、とくに生強度の不足が
生じやすいファインセラミックスなどの非粘土系素地の
鋳込み成形に有用である。(Effects of the Invention) As is clear from the results of the above examples, according to the present invention, only the green strength of the molded body is significantly improved without significantly changing the properties of the slurry such as the water content of the casting slurry and the deposition rate. Therefore, it is particularly useful for casting non-clay bases such as fine ceramics, which tend to lack green strength.
Claims (1)
コニウムを添加してなるポリビニルアルコール系重合体
を、セラミックス鋳込み泥漿に、０．１〜５重量％混合
して鋳込み成形した後、得られた成形体を５０〜１５０
℃で熱処理することを特徴とする高強度鋳込み成形体の
製造方法。1. A polyvinyl alcohol polymer made by adding zirconium chloride to polyvinyl alcohol or a derivative thereof is mixed in a ceramic casting slurry in an amount of 0.1 to 5% by weight and cast.
A method for producing a high-strength cast molded body, which is characterized by heat treatment at ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63132355A JPH0818299B2 (en) | 1988-05-30 | 1988-05-30 | High-strength cast molding manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63132355A JPH0818299B2 (en) | 1988-05-30 | 1988-05-30 | High-strength cast molding manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01301203A true JPH01301203A (en) | 1989-12-05 |
| JPH0818299B2 JPH0818299B2 (en) | 1996-02-28 |
Family
ID=15079422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63132355A Expired - Lifetime JPH0818299B2 (en) | 1988-05-30 | 1988-05-30 | High-strength cast molding manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0818299B2 (en) |
-
1988
- 1988-05-30 JP JP63132355A patent/JPH0818299B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0818299B2 (en) | 1996-02-28 |
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