JP2003136201A - Exothermic material for casting and exothermic formed article for casting using it - Google Patents
Exothermic material for casting and exothermic formed article for casting using itInfo
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- JP2003136201A JP2003136201A JP2001332231A JP2001332231A JP2003136201A JP 2003136201 A JP2003136201 A JP 2003136201A JP 2001332231 A JP2001332231 A JP 2001332231A JP 2001332231 A JP2001332231 A JP 2001332231A JP 2003136201 A JP2003136201 A JP 2003136201A
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- casting
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- exothermic
- heat
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、燃え残りを著しく
低減化した鋳造用発熱材及び鋳造用発熱性造形品に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-generating material for casting and a heat-generating molded article for casting in which unburned residue is significantly reduced.
【０００２】[0002]
【従来の技術】鋳造において引け巣を無くすため、溶融
金属の凝固を制御するのに発熱スリーブ、発熱パッド、
発熱鋳型等の鋳造用発熱性造形品が使用されている。こ
れらの鋳造用発熱性造形品は、アルミニウム粉末・粒状
・片状物などの易酸化性金属、金属酸化物や過酸化物な
どの酸化剤、フッ素化合物などの助燃剤、及びアルミナ
シリケート等の繊維状又は粒状の耐火性物質を水中又は
空気中で分散させ、バインダーで硬化させて製造してい
る。アトマイズアルミニウムなどの良質な易酸化性金属
は着火のために必須であるが高価なため、安価な派生品
アルミニウム粉末、粒状物等を併用している。この安価
な派生品アルミニウム粉末・粒状物は、一部が燃え残
る。この燃え残りは、鋳物に対しピンホールを発生させ
る等の弊害を引き起こす。2. Description of the Related Art In order to eliminate shrinkage cavities in casting, a heating sleeve, a heating pad,
Exothermic shaped articles for casting such as exothermic molds are used. These heat-generating shaped articles for casting are easily oxidizable metals such as aluminum powder, granules and flakes, oxidizing agents such as metal oxides and peroxides, combustion improvers such as fluorine compounds, and fibers such as alumina silicate. It is manufactured by dispersing a refractory material in the form of particles or particles in water or air and curing it with a binder. A high quality easily oxidizable metal such as atomized aluminum is indispensable for ignition, but it is expensive. Therefore, inexpensive derivative aluminum powder, granular material, etc. are used together. Part of this cheap derivative aluminum powder / granulate remains unburned. This unburned residue causes harmful effects such as generation of pinholes in the casting.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、鋳物製品に
生ずる上記の弊害を無くすため、易酸化性金属の燃え残
りを低減化した鋳造用発熱材及び鋳造用発熱性造形品を
提供することを目的とする。DISCLOSURE OF THE INVENTION The present invention provides a heat-generating material for casting and a heat-generating molded article for casting in which the unburned residue of easily oxidizable metal is reduced in order to eliminate the above-mentioned adverse effects occurring in a cast product. With the goal.
【０００４】[0004]
【課題を解決するための手段】前記目的を達成するため
に、本発明は、易酸化性金属と粒径５０μｍ以下の粒子
を１０重量％以上含む酸化剤とを含有すること、を特徴
とする鋳造用発熱材である。To achieve the above object, the present invention is characterized by containing an easily oxidizable metal and an oxidizing agent containing 10% by weight or more of particles having a particle size of 50 μm or less. It is a heat generating material for casting.
【０００５】本発明は、骨材及びバインダーを更に含有
する、前記鋳造用発熱材である。The present invention is the above-mentioned heat-generating material for casting, which further contains an aggregate and a binder.
【０００６】本発明は、助燃剤を更に含有する、前記鋳
造用発熱材である。The present invention is the above-mentioned heat-generating material for casting, which further contains a combustion improver.
【０００７】また本発明は、前記第２又は第３の鋳造用
発熱材を成形してなる鋳造用発熱性造形品である。Further, the present invention is a heat-generating molded article for casting, which is formed by molding the second or third heat-generating material for casting.
【０００８】[0008]
【発明の実施の形態】以下、本発明を詳しく説明する。
本発明における易酸化性金属としては、例えば、アルミ
ニウム、マグネシウム、シリコンが挙げられる。これら
は単独で或いは２種以上を混合して使用できる。これら
のうちアルミニウムが好ましく、アトマイズアルミニウ
ム、派生品アルミニウムの粉末、粒状物、片状物、或い
はこれらの任意の混合物であってもよいが、アトマイズ
アルミニウムと派生品アルミニウムとの混合物が燃え残
りが少なく、経済的にも有利であるため更に好ましい。
また、アルミニウムなどの易酸化性金属は、平均粒径１
０００μｍ以下のものが好ましく、平均粒径１〜５００
μｍの範囲のものがさらに好ましい。特に、燃焼性のよ
いアトマイズアルミニウムは平均粒径１〜５００μｍ、
更に１０〜２００μｍのものが好ましく、アトマイズア
ルミニウムに混合して使用する派生品アルミニウムは平
均粒径１０００μｍ以下、更に５０〜５００μｍのもの
が好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
Examples of the easily oxidizable metal in the present invention include aluminum, magnesium and silicon. These can be used alone or in admixture of two or more. Of these, aluminum is preferable, and atomized aluminum, derivative aluminum powder, granules, flakes, or any mixture thereof may be used, but the mixture of atomized aluminum and derivative aluminum has less unburned residue. It is more preferable because it is economically advantageous.
Further, an easily oxidizable metal such as aluminum has an average particle size of 1
000 μm or less is preferable, and average particle diameter is 1 to 500
The range of μm is more preferable. Particularly, atomized aluminum having good flammability has an average particle size of 1 to 500 μm,
Further, those having an average particle diameter of 1000 μm or less, and more preferably 50 to 500 μm are preferable as the derivative aluminum used by mixing with atomized aluminum.
【０００９】易酸化性金属の燃焼のために使用される酸
素の供給源は、大気から供給される酸素と添加される酸
化剤である。酸化剤の使用量を増やすとその還元によっ
て吸熱の増加をもたらし、また発熱材密度の増加を招
き、注湯時の吸熱のため着火が遅れる。そのため、酸化
剤の使用量を大きく変動させず、その微粉品を使用する
ことが初期の高温発熱をもたらし、その高温度が大気中
の酸素による燃焼持続、燃え残りの削減に寄与する。The source of oxygen used for the combustion of easily oxidizable metals is oxygen supplied from the atmosphere and an oxidant added. Increasing the amount of the oxidizer used results in an increase in heat absorption due to its reduction, and also causes an increase in the density of the heating material, which delays ignition due to the heat absorption during pouring. Therefore, the use of the finely divided product does not greatly change the amount of the oxidant used, and the initial high temperature heat is generated, and the high temperature contributes to the continuous burning of oxygen in the atmosphere and the reduction of the unburned residue.
【００１０】このような目的で使用される本発明におけ
る酸化剤としては、例えば、酸化鉄、二酸化マンガン、
硝酸ナトリウム、硝酸カリウム、塩素酸ナトリウム、塩
素酸カリウムが挙げられる。これらは単独で或いは２種
以上を混合して使用できる。これらのうち燃焼効率、経
済性などの点から酸化鉄が好ましく、酸化鉄のうち更に
四三酸化鉄が好ましい。本発明における酸化剤は、粒径
５０μｍ以下の粒子を１０重量％以上含有する必要があ
る。更に、粒径２５μｍ以下の粒子を１０重量％以上含
有するものが好ましく、粒径１０μｍ以下の粒子を１０
重量％以上含有するものが特に好ましい。また本発明に
おける酸化剤は平均粒径６０μｍ以下のものが最も好ま
しい。酸化剤は、易酸化性金属１００重量部に対して、
５〜２００重量部、更に１０〜１００重量部の範囲で配
合するのが好ましい。Examples of the oxidizing agent used in the present invention for such purposes include iron oxide, manganese dioxide,
Examples include sodium nitrate, potassium nitrate, sodium chlorate, and potassium chlorate. These can be used alone or in admixture of two or more. Of these, iron oxide is preferable from the viewpoint of combustion efficiency and economy, and among iron oxides, ferrosoferric oxide is more preferable. The oxidizing agent in the present invention must contain particles having a particle diameter of 50 μm or less in an amount of 10% by weight or more. Further, it is preferable to contain 10% by weight or more of particles having a particle diameter of 25 μm or less, and 10 particles having a particle diameter of 10 μm or less are preferable.
Those containing at least wt% are particularly preferable. The oxidizing agent in the present invention most preferably has an average particle size of 60 μm or less. The oxidizer is 100 parts by weight of the easily oxidizable metal,
The amount is preferably 5 to 200 parts by weight, more preferably 10 to 100 parts by weight.
【００１１】本発明においては更に、発熱材を具体的に
発熱スリーブ、発熱パッド、発熱鋳型などの鋳造用発熱
性造形品に成形するために、骨材及びバインダーを使用
する。この骨材としては、発熱スリーブや発熱パッド用
には、例えば、シラスの他に、黒曜石、真珠岩、モライ
トなどの発泡中空微小球が挙げられ、発熱鋳型用には、
例えば、珪砂、アルミナ砂、クロム鉄鉱砂、ジルコン
砂、かんらん石砂などの耐火性粒状砂の他に、粘土質の
砂、再生砂が挙げられる。バインダーとしては、例え
ば、フェノール樹脂、フェノール樹脂とイソシアネート
硬化剤を併用したフェノール・ウレタン樹脂、尿素樹
脂、アクリル樹脂、水ガラス、アラビアゴムが挙げられ
る。フェノール樹脂とは、フェノール、クレゾール、レ
ゾルシノールなどのフェノール類と、ホルムアルデヒド
などのアルデヒド類とを反応させて得られるものであ
る。本発明においてはフェノール・ウレタン樹脂が好ま
しい。これらのバインダーは、成形後、有機酸エステル
系硬化剤、炭酸ガスなどの硬化剤や、第三級アミン（ガ
ス）などの硬化促進触媒を通気させて硬化させる。骨材
は、易酸化性金属１００重量部に対して、１０〜１００
０重量部、更に５０〜５００重量部配合して使用するの
が好ましい。バインダーは、易酸化性金属１００重量部
に対して、０．５〜５０重量部、更に１〜３０重量部配
合して使用するのが好ましい。Further, in the present invention, an aggregate and a binder are used to specifically form the heat-generating material into a heat-generating shaped article for casting such as a heat-generating sleeve, a heat-generating pad and a heat-generating mold. As this aggregate, for heating sleeves and heating pads, for example, in addition to Shirasu, obsidian, pearlite, foamed hollow microspheres such as Morite, for heating molds,
For example, in addition to refractory granular sand such as silica sand, alumina sand, chromite sand, zircon sand, olivine sand, clay sand and reclaimed sand can be mentioned. Examples of the binder include a phenol resin, a phenol / urethane resin in which a phenol resin and an isocyanate curing agent are used in combination, a urea resin, an acrylic resin, water glass, and gum arabic. Phenolic resin is obtained by reacting phenols such as phenol, cresol and resorcinol with aldehydes such as formaldehyde. In the present invention, phenol-urethane resin is preferable. After molding, these binders are cured by passing a curing agent such as an organic acid ester-based curing agent or a carbon dioxide gas, or a curing-accelerating catalyst such as a tertiary amine (gas). Aggregate is 10 to 100 relative to 100 parts by weight of easily oxidizable metal.
It is preferable to use 0 part by weight, further 50 to 500 parts by weight in combination. The binder is preferably used in an amount of 0.5 to 50 parts by weight, more preferably 1 to 30 parts by weight, based on 100 parts by weight of the easily oxidizable metal.
【００１２】本発明に使用することができる助燃剤とし
ては、無機フッ素系化合物の塩が好適であり、具体的に
は例えば、フッ化ナトリウム、フッ化マグネシウム、珪
フッ化ナトリウム、珪フッ化カリウム、フッ化アルミニ
ウムナトリウム、フッ化アルミニウムカリウムが挙げら
れる。助燃剤は、易酸化性金属１００重量部に対して、
５〜５０重量部、更に１０〜４０重量部配合して使用す
るのが好ましい。As the combustion improver which can be used in the present invention, a salt of an inorganic fluorine compound is suitable, and specifically, for example, sodium fluoride, magnesium fluoride, sodium silicofluoride, potassium silicofluoride. , Sodium aluminum fluoride, and potassium aluminum fluoride. The combustion improver is based on 100 parts by weight of the easily oxidizable metal.
It is preferable to use 5 to 50 parts by weight, more preferably 10 to 40 parts by weight.
【００１３】本発明においては、易酸化性金属、酸化
剤、場合により骨材や助燃剤などをバインダーにて造粒
することで、微粉分増加による強度低下の弊害を回避す
ることができる。造粒法としてはバインダー添加攪拌硬
化、バインダー溶剤希釈液に分散し、噴霧乾燥法いずれ
でも良い。In the present invention, by granulating an easily oxidizable metal, an oxidizing agent, and in some cases, an aggregate or a combustion improver with a binder, it is possible to avoid the adverse effect of a decrease in strength due to an increase in fine powder content. As a granulation method, any of a spray addition method and a binder addition stirring curing method, a dispersion in a binder solvent diluting solution, and a spray drying method may be used.
【００１４】[0014]
【実施例】以下、実施例により本発明を更に詳しく説明
する。
実施例１
下記アルミニウム配合（１）、（２）又は（３）それぞ
れ３０ｇと、粒径５０μｍ以下の粒子を４４重量％（粒
径２５μｍ以下の粒子を２６重量％、粒径１０μｍ以下
の粒子を１０．５重量％）含む（平均粒径４８．３μｍ
の）微粒四三酸化鉄１０ｇと、骨材としてモライト５０
ｇと、助燃剤としてクリオライト（六フッ化アルミン酸
ナトリウム）１０ｇと、バインダーとしてフェノール・
ウレタン樹脂（保土谷アシュランド（株）製イソキュ
ア）８ｇとを混合して分散させ、これを発熱スリーブ鋳
型内に充填して成形し、次いで硬化ガスとしてトリエチ
ルアミンを常温で０．５分間通気して、この充填物を硬
化させて、押湯用発熱スリーブを製造した。
アルミニウム配合（１）：平均粒径４０μｍのアトマイ
ズアルミニウムと平均粒径１００〜２００μｍのアトマ
イズアルミニウムの重量比１：１混合
アルミニウム配合（２）：平均粒径４０μｍのアトマイ
ズアルミニウムと機械加工で派生した平均粒径２００〜
３００μｍのアルミニウム切り粉の重量比１：１混合
アルミニウム配合（３）：平均粒径４０μｍのアトマイ
ズアルミニウムと機械加工で派生した平均粒径２００〜
５００μｍのアルミニウム切り粉の重量比１：１混合
〔燃焼試験〕製造した発熱スリーブから切り出した直径
３０ｍｍ×１５ｍｍの大きさのサンプル（約７ｇ）を電
気炉中で１０００℃で燃焼させ、燃焼残物中のアルミニ
ウムの重量を測定した。発熱スリーブの燃え残り率（重
量％）を次式により求めた。
燃え残り率（重量％）＝燃焼残物中のアルミニウム重量
÷燃焼前のアルミニウム含有量×１００
但し、
燃焼残物中のアルミニウム重量の測定：スリーブ燃焼残
物を乳鉢で摺りつぶし、水封入の密閉系容器内で約１０
％苛性ソーダ水溶液に分散・溶解させ、水素ガスを発生
させた。均圧管を用い、容器内を１気圧とし、水素ガス
発生により膨張した容積を目盛りゲージで読み取った。
この水素ガスを発生させたアルミニウムの量を次式で算
出した。
アルミニウム量（ｇ）＝標準気体ガス量（ｃｃ）×０．
０００８
その際、シリコンが妨害物質となるため、温度を１５℃
以下に保ち、且つ分析を３時間以内で終了させた。これ
らの結果をまとめて表１に示す。The present invention will be described in more detail with reference to the following examples. Example 1 30 g of each of the following aluminum formulations (1), (2) or (3) and 44% by weight of particles having a particle size of 50 μm or less (26% by weight of particles having a particle size of 25 μm or less and particles having a particle size of 10 μm or less) were prepared. 10.5% by weight) (average particle size 48.3 μm)
No.) 10g of fine iron oxide black and 50 molite as aggregate
g, 10 g of cryolite (sodium hexafluoroaluminate) as a combustion improver, and phenol as a binder.
8 g of urethane resin (Isocure manufactured by Hodogaya Ashland Co., Ltd.) was mixed and dispersed, and this was filled into a heat-generating sleeve mold to be molded, and then triethylamine was aerated as a curing gas at room temperature for 0.5 minutes. Then, the filling was cured to produce a heating sleeve for a feeder. Aluminum compound (1): Atomized aluminum having an average particle size of 40 μm and atomized aluminum having an average particle size of 100 to 200 μm in a weight ratio of 1: 1 Mixed aluminum compound (2): Atomized aluminum having an average particle size of 40 μm and an average derived by machining Particle size 200 ~
Weight ratio of aluminum chips of 300 μm 1: 1 mixed aluminum blend (3): atomized aluminum having an average particle size of 40 μm and average particle size of 200 to 200 derived from machining
A 1: 1 weight ratio mixture of aluminum chips of 500 μm [combustion test] A sample (about 7 g) having a diameter of 30 mm × 15 mm cut out from a manufactured heating sleeve was burned at 1000 ° C. in an electric furnace to produce a combustion residue. The weight of the aluminum inside was measured. The unburned residue rate (% by weight) of the heat generating sleeve was determined by the following formula. Unburned residue rate (% by weight) = Aluminum weight in combustion residue / Aluminum content before combustion x 100 However, measurement of aluminum weight in combustion residue: Sleeve combustion residue is ground with a mortar and sealed with water. About 10 in the system container
Hydrogen gas was generated by dispersing and dissolving it in an aqueous solution of caustic soda. Using a pressure equalizing tube, the pressure in the container was adjusted to 1 atm, and the volume expanded by the generation of hydrogen gas was read with a scale gauge.
The amount of aluminum that generated this hydrogen gas was calculated by the following formula. Aluminum amount (g) = standard gas amount (cc) × 0.
[0008] At that time, the temperature becomes 15 ° C because silicon becomes an interfering substance.
The following was kept and the analysis was completed within 3 hours. The results are summarized in Table 1.
【００１５】比較例１
実施例１において、微粒四三酸化鉄のかわりに粒径５０
μｍ以下の粒子を０．５重量％（粒径２５μｍ以下の粒
子を０．２重量％、粒径１０μｍ以下の粒子を０．１重
量％）含む（平均粒径５００μｍの）粗粒四三酸化鉄を
使用した以外は同様にして、混合物を調製し、燃焼試験
を行った。これらの結果をまとめて表１に示す。Comparative Example 1 In Example 1, a particle size of 50 was used in place of the finely divided ferric tetroxide.
Coarse-grained tetrasodium oxide (having an average particle size of 500 μm) containing 0.5% by weight of particles having a particle size of μm or less (0.2% by weight of particles having a particle size of 25 μm or less, 0.1% by weight of particles having a particle size of 10 μm or less) A mixture was prepared and a combustion test was conducted in the same manner except that iron was used. The results are summarized in Table 1.
【００１６】実施例２
実施例１において、微粒四三酸化鉄のかわりに粒径５０
μｍ以下の粒子を１００重量％（粒径２５μｍ以下の粒
子を１００重量％、粒径１０μｍ以下の粒子を９９．０
重量％）含む（平均粒径２．４μｍの）微粒二酸化マン
ガンを使用した以外は同様にして、混合物を調製し、燃
焼試験を行った。これらの結果をまとめて表１に示す。Example 2 In Example 1, a particle size of 50 was used in place of the fine iron (III) tetroxide particles.
100% by weight of particles having a particle size of 25 μm or less (100% by weight of particles having a particle size of 25 μm or less, 99.0 particles having a particle size of 10 μm or less
% By weight) and a mixture was prepared and a combustion test was performed in the same manner except that fine manganese dioxide (having an average particle size of 2.4 μm) was used. The results are summarized in Table 1.
【００１７】比較例２
実施例１において、微粒四三酸化鉄のかわりに粒径５０
μｍ以下の粒子を９．５重量％（粒径２５μｍ以下の粒
子を５．１重量％、粒径１０μｍ以下の粒子を４．１重
量％）含む（平均粒径６４．９μｍの）粗粒二酸化マン
ガンを使用した以外は同様にして、混合物を調製し、燃
焼試験を行った。これらの結果をまとめて表１に示す。Comparative Example 2 In Example 1, a particle size of 50 was used in place of the finely divided iron (III) tetraoxide.
Coarse-grained dioxide (having an average particle size of 64.9 μm) containing 9.5% by weight of particles having a size of μm or less (5.1% by weight of particles having a particle size of 25 μm or less and 4.1% by weight of particles having a particle size of 10 μm or less) A mixture was prepared and a combustion test was conducted in the same manner except that manganese was used. The results are summarized in Table 1.
【００１８】[0018]
【表１】 [Table 1]
【００１９】[0019]
【発明の効果】以上説明した通り、本発明により初め
て、易酸化性金属の燃え残りを低減化して鋳物にピンホ
ールなどを発生させない鋳造用発熱材、及びそれを用い
た鋳造用発熱性造形品を提供することが可能となった。
特に、安価な派生品アルミニウムなどを併用した易酸化
性金属を使用しても、その燃え残りを低減化することが
できるので、経済的に極めて有利である。As described above, according to the present invention, for the first time, a heat-generating material for casting which reduces the unburned residue of easily oxidizable metal and does not generate pinholes in the casting, and a heat-generating molded article for casting using the same. It has become possible to provide.
In particular, even if an easily oxidizable metal that is used in combination with an inexpensive derivative such as aluminum is used, the unburned residue can be reduced, which is extremely economically advantageous.
Claims (4)
を１０重量％以上含む酸化剤とを含有すること、を特徴
とする鋳造用発熱材。1. A heat generating material for casting, comprising an easily oxidizable metal and an oxidizing agent containing 10% by weight or more of particles having a particle diameter of 50 μm or less.
求項１に記載の鋳造用発熱材。2. The heat-generating material for casting according to claim 1, further comprising an aggregate and a binder.
の鋳造用発熱材。3. The heat-generating material for casting according to claim 2, further comprising a combustion improver.
成形してなる鋳造用発熱性造形品。4. A heat-generating molded article for casting, which is obtained by molding the heat-generating material for casting according to claim 2 or 3.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107252872A (en) * | 2017-05-18 | 2017-10-17 | 西峡县众德汽车部件有限公司 | One kind heating precoated sand and preparation method thereof |
-
2001
- 2001-10-30 JP JP2001332231A patent/JP3696821B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107252872A (en) * | 2017-05-18 | 2017-10-17 | 西峡县众德汽车部件有限公司 | One kind heating precoated sand and preparation method thereof |
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