CN100528808C - 浇铸稀土合金用的耐火材料和其生产方法以及浇铸稀土合金的方法 - Google Patents

浇铸稀土合金用的耐火材料和其生产方法以及浇铸稀土合金的方法 Download PDF

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CN100528808C
CN100528808C CNB2006101689746A CN200610168974A CN100528808C CN 100528808 C CN100528808 C CN 100528808C CN B2006101689746 A CNB2006101689746 A CN B2006101689746A CN 200610168974 A CN200610168974 A CN 200610168974A CN 100528808 C CN100528808 C CN 100528808C
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casting
rare earth
earth alloy
tundish
equal
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CN1990425A (zh
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长谷川宽
河村伸彦
佐佐木史郎
广濑洋一
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Resonac Holdings Corp
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Showa Denko KK
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Abstract

采用浇口盘(3，13)，将稀土合金浇铸成片材(6)等。浇铸使用的浇口盘的耐火材料不必为提高熔融体(2)的流动性能而预热。所采用的耐火材料基本上是由等于或大于70%(重量)的Al2O3，和等于或小于30%(重量)的SiO2，或等于或大于70%(重量)的ZrO2，和等于或小于30%(重量)的一种或多种选自Y2O3、Ce2O3、CaO、MgO、Al2O3、TiO2或SiO2的材料组成的。耐火材料的堆密度等于或小于1g/cm3，在温度1200-1400℃下的导热率等于或小于0.5kcal/(mh℃)，在1400℃加热1小时的灼烧重量损失率等于或小于0.5%(重量)。

Description

浇铸稀土合金用的耐火材料和其生产方法以及浇铸稀土合金的方法
本申请是申请号为99809914.7母案的分案申请。该母案的申请日为1999年6月22日；发明名称为“浇铸稀土合金用的耐火材料和其生产方法以及浇铸稀土合金的方法”。
技术领域
本发明涉及浇铸稀土合金，例如R-Fe-B基磁体合金、R-Ni基吸收氢的合金以及Sm-Co基磁体合金的耐火材料，该稀土合金包含稀土元素(R)，作为稀土合金的主要成分之一。本发明还涉及耐火材料的生产方法和浇铸稀土合金的方法。
背景技术
近来，为了利用稀土合金极好的磁性，人们一直在关注稀土烧结磁体或稀土熔合磁体。特别是对R-Fe-B基磁体，一直进行进一步提高磁性的研究。在R-Fe-B基磁体中，具有铁磁性的R2Fe14B相和富R相(具有高浓度稀土元素，例如Nd的非磁性相)，前者是磁性的基础，后者是液相烧结的基础并对磁性的增强具有很大的作用。
为了得到较好的磁体性能，提高具有铁磁性的R2Fe14B相的体积份额是必要的。这必然降低富R相的体积份额。因此，当采用常规方法进行浇铸时，富R相分散得很差，以致局地部缺乏富R相，在许多情况下不能得到令人满意的性能。
一方面，在磁体组成中R2Fe14B相的体积份额较高时，在磁体合金中比较容易生成α-Fe。这种α-Fe能严重降低磁体合金的可破碎性，因而在破碎加工时能引起组成的变化。这又引起磁性的降低和磁性变化的增加。
因此，有人提出解决涉及高性能磁体的这些问题的方法。在日本未审定的专利公报5-222488和5-295490中，提出一种浇铸带材的方法。由于这种方法在固化时的冷却速度，高于常规叠箱铸模浇铸方法的冷却速度，所以能够制造具有精确结构和细分散的富R相的合金。在这种合金中α-Fe是很难生成的。
在日本未审定的专利公报5-222488中所述的浇铸带材的方法在于：通过使稀土金属-铁-硼合金熔融体固化，生产用于制造永磁体的合金锭；在生产过程中，使合金熔融体在冷却速度为10-500℃/s的条件下冷却，过冷程度为10-500℃；合金熔融体均匀地凝固成厚度为0.05-15mm的铸锭。具体的浇铸方法是使熔融体从浇口盘向下流到旋转的轧辊上。
日本未审定的专利公报5-295490举例说明了一种制造鳞片状合金的旋转盘方法，和制造带材或片材形式合金的双轧辊方法。
与此同时，作为蓄电池电极材料的，具有极好的吸收氢性能的R-Ni基吸收氢的合金最近已经引起人们的关注。将Co、Mn和Al等之类的元素加入这种合金中，能增强吸收氢的性能和其它的材料性能。在采用常规叠箱铸模浇铸方法的浇铸过程中，添加的元素容易发生微观离析。为了使晶体组成均匀化，延长热处理时间是必要的。
此外，通常在粉碎步骤中将吸收氢的合金粉碎到几十微米。由叠箱铸模浇铸方法制造的合金很难粉碎，颗粒直径大，其中含有富添加的元素的相。因此，粉碎后粉末的粒度分布不均匀，对吸收氢的性能产生不利的影响。最终制得的吸收氢的合金粉末具有吸收氢的性能低的缺点。
有人提出采用浇铸带材的方法解决上述的问题(日本未审定的专利公报5-3207920)。由于在浇铸带材的方法中，固化的冷却速度高于常规叠箱铸模浇铸方法的冷却速度，所制合金的组成和结构的均匀性得到改善。采用这种合金，能够制造具有初始充电速度快、电池寿命长和电容量大之类特性的蓄电池。
图1示出浇铸带材的方法。将熔融体2先从熔炉(未示出)放到可倾斜的浇包1中，再注入浇口盘3中。然后在预定的加料速度下，从其中将熔融体加到水冷式铜轧辊(单轧辊)4上。通过轧辊的转动，在水冷式铜轧辊4上将熔融体2铸造成片材5。然后使片材5与轧辊分离，采用锤式(未示出)破碎，制成薄的碎片6，储存在金属储池7中。
如上所述，将熔融体少量地加到轧辊上，使合金的厚度一般等于或小于1mm。熔融体的热量不应被将熔融体从坩埚引到冷轧辊上的浇口盘等引出，所以能防止熔融体凝固。
在将熔融体少量地加入由普通的耐火材料，例如氧化铝、富铝红柱石、氧化铝-富铝红柱石、氧化镁、二氧化锆或calsia制造的浇口盘时，浇口盘引出了熔融体的热量，使熔融体凝固，不能进行浇铸。在这种情况下，如果通过降低浇口盘的厚度来减少引出的热量，就能维持熔融体良好的流动。然而，这种薄的浇口盘不仅很难制造，而且很难处理，因为它容易破裂。
为了防止在由上述普通耐火材料制造的浇口盘中发生上述的问题，需要至少将浇口盘的表面加热到大致与熔融体相同的温度。然而，浇口盘的加热涉及下列问题。
(1)由于熔融温度通常为1200-1500℃，加热整个浇口盘的设备具有复杂的结构。能在这种温度下加热的加热器是很贵的。
(2)加热整个浇口盘的设备很复杂。
(3)由于浇口盘的热容大，加热时间长，因而降低了生产效率。
(4)加热器可能放电，这视熔炉的真空度而定。因此会造成安全问题。
本申请人在欧洲专利公报EP 0784350A1中提出：一种将熔融体浇注到旋转的圆筒形铸模中的迅速冷却和离心浇铸吸收氢的合金的方法；一种使浇注的熔融体与旋转的铸模一起旋转并在旋转一周的过程中凝固在铸模的表面上，接着逐次在凝固的表面上进行浇注的浇铸方法；和一种从二个或多个设在铸模上的铸口，将熔融体加到铸模内表面上的方法。实现这些方法的设备示于图2。
在图2中，在真空室10内安装一个可倾斜的熔炉12、第一级固定式的浇口盘13a、第二级往复式的浇口盘13b、和一个旋转的圆筒形铸模14。由旋转机构16使旋转的圆筒形铸模14旋转。
熔融体从熔炉12，流过第一级固定式浇口盘13a和第二级往复式浇口盘13b，然后浇注到旋转的圆筒形铸模14中。铸锭15是圆筒状材料，它被浇铸在旋转的圆筒形铸模14的内表面上。伸入圆筒形铸模14内的浇口盘13b，设有几个浇铸口17。浇口盘13b往复移动，迅速和均匀地将熔融体加到铸模的内表面上。
本发明人研究了下列耐火材料：在浇铸带材的方法中用于稳定供入稀土合金熔融体的耐火材料；在离心浇铸方法中，将少量熔融体加到旋转铸模上的耐火材料；在单轧辊熔融体骤冷方法中，通过细浇铸口供入熔融体的耐火材料；此外，还有用于减少以少量加入的熔融体温度下降的耐火材料。结果，本发明人发现，在熔融体和Al2O3-SiO2基耐火材料或ZrO2基耐火材料之间，实际上未发生任何反应；而且在浇铸时预热是不必要的。因此，曾实现本发明。
发明内容
根据本发明第一方面的用于浇铸稀土合金的耐火材料，其特征在于下列(1)-(3)项。
(1)Al2O3和SiO2的含量
根据本发明第一方面的耐火材料，是基于Al2O3-SiO2。按包含粘合剂等在内的总成分的重量计算，Al2O3的含量等于或大于70％(重量)。SiO2的含量等于或小于30％(重量)。由于耐热性随耐火成分Al2O3含量的增加而增大，所以，为了使耐火材料在1200-1500℃下具有足够的耐热性，Al2O3的含量等于或大于70％(重量)是必要的。另一方面，耐火材料成形后的可模塑性随SiO2含量的增加而提高，在浇铸过程中受到热冲击时，耐火材料很难发生破裂。然而，由于Al2O3的含量随SiO2含量的增加而下降，所以耐火材料的耐热温度降低。因此，SiO2的含量应该等于或小于30％。优选Al2O3的含量等于或大于80％(重量)，SiO2的含量等于或小于20％(重量)。
在本发明第一方面的耐火材料中，Al2O3和SiO2优选等于或大于总耐火材料的90％(重量)，其余的是杂质和相关元素。
(2)堆密度和导热率
稀土合金熔融体的热量被耐火材料所吸收。在浇铸过程中，熔融体的温度发生明显的降低。在极端情况下，会出现完全凝固或半凝固状态。为了防止这种情况，耐火材料应尽可能是多孔的，以便降低导热率。在浇铸稀土合金时，在具有代表性的熔融体温度1200-1400℃下，导热率是特别重要的。因此，将耐火材料的堆密度调节到等于或小于1g/cm3，将在温度1200-1400℃内的导热率调节到等于或小于0.5kcal/(mh℃)。优选耐火材料的堆密度等于或小于0.5g/cm3。
为了将导热率降低到尽可能低的水平，与容易紧密压实的氧化铝粉末相比，更优选氧化铝纤维(真密度为3.87g/cm3)。氧化铝纤维的含量优选等于或大于70％(重量)。特别是，氧化铝纤维的方向不应是有序排列的，氧化铝纤维应是不规则排列和盘绕的。调节耐火材料成分，以使耐火材料中包含等于或大于总量70％(重量)的氧化铝纤维和富铝红柱石纤维(真密度3.16g/cm3)，同样可以降低导热率。附带地说在富铝红柱石纤维中含有SiO2。此外，SiO2可以以胶体二氧化硅或胶体富铝红柱石的形式包含在耐火材料中。
(3)灼烧的重量损失
耐火材料一般是采用树脂之类的有机粘结剂和水玻璃之类的无机粘结剂成形的。不用除去这些粘结剂就可使用如此成形的耐火材料。所以在使用成形的耐火材料时，有机的粘结剂就会分解成N2、CO和CO2之类的有机气体和H2O，它们与熔融体发生反应，使熔融体的流动性下降。此外，还会从容易分解的无机化合物中分解出结合水和二氧化碳等，它们也有类似的影响。在熔融体的流动性严重降低时，熔融体会在浇口盘内凝固。因此，事先从耐火材料中尽可能完全地除去有机粘结剂等是极其重要的。因此，本发明的特征在于，在1400℃加热1h的条件下，灼烧重量损失率等于或小于0.5％(重量)。偶而也用ZrO2、TiO2、CaO和MgO代替一部分Al2O3，前提是满足上述的堆密度、导热率和灼烧重量损失率条件。优选这些成分的上限为总量的5％(重量)。耐火材料可以包含一些杂质，例如FeO、Fe2O3、Fe3O4、Na2O、K2O和其它不可避免的杂质，其量不超过5％(重量)。
其次，根据本发明第二方面的浇铸稀土合金的耐火材料，其特征在于下列(4)-(6)项。
(4)ZrO2和Y2O3、Ce2O3、CaO、MgO、Al2O3、TiO2或SiO2的含量
本发明第二方面的耐火材料，是基于ZrO2。按包含粘结剂等在内的总成分计算，ZrO2含量等于或大于70％(重量)，而一种或多种选自Y2O3、Ce2O3、CaO、MgO、Al2O3、TiO2和SiO2的含量等于或小于30％(重量)。纯ZrO2在室温至1170℃下，具有单斜晶系结构，在1170-2370℃下，是畸变的正方晶系结构，在等于或高于2370℃下，是萤石结构形式的立方晶系结构。在冷却到1170℃时，随从正方晶系转变到单斜晶系结构，体积膨胀4％。只要ZrO2保持纯态，ZrO2就会发生裂缝并最后破裂(例如，K.Nakajima，S.Shimada：固态离子学(Solid State Ionics)，Vol.101-103，p131-135(1997))。因此，为了防止破裂，将其结构转变成立方晶系，在这种情况下不会发生任何体积膨胀。为此，将一种或多种选自Y2O3、Ce2O3、CaO或MgO加入并取代溶解在ZrO2中。优选采用如此稳定的二氧化锆。此外，加入一种或多种Al2O3、TiO2和SiO2对提高耐热性和机械性能的耐久性也是有效的。它们的加入量被限制在等于或小于30％(重量)，这是由于下列原因：令人满意地防止破裂；限制这些成分在ZrO2中的溶质量；Y2O3和Ce2O3是较贵的；和更大量地加入CaO、MgO、Al2O3、TiO2和SiO2会提高与熔融体的反应性。这些成分以大量成分的加入量，更优选为1-15％(重量)。
实际上SiO2能与ZrO2结合，以ZrSiO4的形式存在。在本发明第二方面的耐火材料中，按耐火材料的总量计算，ZrO2与一种或多种Y2O3、Ce2O3、CaO、MgO、Al2O3、TiO2和SiO2的总量优选等于或大于85％(重量)。其余为杂质和相关元素。
(5)堆密度和导热率
这些与本发明的第一方面相同，因此省略对它们的说明。
(6)灼烧的重量损失
耐火材料可以包含一些杂质，例如FeO、Fe2O3、Fe3O4、Na2O、k2O、hfO2、C和其它不可避免的杂质，其量不超过5％(重量)。除此以外，其它与上述的项(3)相同。
耐火材料的生产方法
其次，根据本发明第一方面的生产耐火材料的方法，其中包括将一种或多种选自氧化铝、富铝红柱石和二氧化硅的材料，与一种或多种选自无机粘结剂和有机粘结剂的粘结剂混合，制成一种混合物，使耐火材料中具有等于或大于70％(重量)的Al2O3，和等于或小于30％(重量)的SiO2，将混合物成形、干燥，再在1000-1400℃下进行热处理。
虽然氧化铝、二氧化硅和富铝红柱石不限于纤维材料，但在混合物中，优选采用至少一种选自氧化铝纤维、二氧化硅纤维和富铝红柱石纤维的纤维材料。
根据本发明的生产方法的一个实施方案，首先混合一种或多种选自氧化铝纤维、富铝红柱石纤维和二氧化硅纤维的纤维材料。例如，可制成氧化铝纤维与二氧化硅纤维的混合物，和氧化铝纤维与富铝红柱石纤维的混合物。再使其与一种或多种选自有机粘结剂和无机粘结剂的粘结剂混合，制成一种混合物，然后使混合物成形。必须使混合物中相应成分的混入量为，如在耐火材料中，Al2O3等于或大于70％(重量)，和SiO2等于或小于30％(重量)。在采用包含SiO2的粘结剂如水玻璃的场合，粘结剂和纤维中的SiO2总量，应该达到预定量。
例如，可将水玻璃、胶体二氧化硅等作为无机粘结剂使用。例如，可将硅酸乙酯、乙基纤维素和三甘醇作为有机粘结剂使用。这二类粘结剂可以一起使用。在这种情况下，可进一步增强成形体的干燥强度及其在高温下的熔合强度。此处以纤维重量为100份计算，优选粘结剂量为1-30份(重量)。至于粘结剂之间的比例，按总粘结剂重量为100份计算，优选有机粘结剂量为50-100份(重量)。
然后利用压制、冲压成形等方法，将纤维和粘结剂的混合物制成浇口盘、流槽和铸口等形状。采用另一种方案，可将混合物制成简单的形状如片状、圆柱或圆筒形状，它们在加热后能制成浇口盘、流槽和铸口等。然后进行充分地自然干燥，得到能耐随后处理的硬度。接着进行热处理，借此促进纤维的熔合，此外，还能分解成形体中的有机物，形成多孔的结构。由于有机物在约400-800℃下分解，所以在此温度下进行热处理能获得多孔的结构。然而，为了充分地除去有机粘结剂，成形体必须在1000-1400℃下热处理。当加热温度低于1000℃时，有机物分解不完全，造成熔融体的流动性降低。另一方面，在加热温度超过1400℃时，成形体烧结并变脆，从而使其处理变得困难。此外，在熔融体流动时，成形体不耐热冲击，容易破裂。
因此，根据本发明第二方面生产耐火材料的方法，将一种或多种选自二氧化锆纤维、二氧化锆晶须、稳定的二氧化锆纤维和稳定的二氧化锆晶须的材料，与无机和/或有机的粘结剂混合，使耐火材料中具有等于或大于70％(重量)的ZrO2，和等于或小于30％(重量)的一种或多种选自Y2O3、Ce2O3、CaO、MgO、Al2O3、TiO2和SiO2的材料，使混合物成形、干燥和硬化，然后在1000-1400℃下进行热处理。
在根据本发明的方法中，将选自二氧化锆和稳定的二氧化锆的一种或多种材料混合。二氧化锆或稳定的二氧化锆或二者的一部分或全部，优选是纤维和/或晶须。例如可只采用稳定的二氧化锆纤维，或将二氧化锆纤维与稳定的二氧化锆纤维组合。在混合物中混入一种或多种无机和有机的粘结剂以后，再将混合物成形。混合物中相应成分的混入量，必须使耐火材料中具有等于或大于70％(重量)的ZrO2，和总量等于或小于30％(重量)的一种或多种选自Y2O3、Ce2O3、CaO、MgO、Al2O3、TiO2和SiO2的材料。当采用包含SiO2的粘结剂如水玻璃时，粘结剂、纤维和晶须中的SiO2总量，应达到预定量。
其它材料与本发明的第一方面相同。
根据本发明第一和第二方面的浇铸稀土合金熔融体的耐火材料，受到上述组成、堆密度、导热率和灼烧重量损失方面的限制。因此能满足对耐热性、熔融体的流动性、耐破裂性和耐热冲击性能的要求。
浇铸方法
根据本发明的浇铸稀土合金的方法，其特征在于，通过一个浇注装置，例如本发明第一和第二方面的成形的耐火材料的浇口盘、流槽和铸口，将稀土合金熔融体浇注到旋转轧辊的表面上，从而制成片材、带材和薄的碎片等，优选厚度为0.1-1mm。此外，根据本发明的方法，其特征还在于，通过将熔融体浇注到旋转圆筒的内表面上，制成圆筒形材料，优选厚度为1-20mm。
稀土合金是指用于稀土磁体的合金，特别是用于R-Fe-B基磁体的合金、R-Ni基吸收氢的合金和Sm-Co基磁体合金等。R-Fe-B基磁体合金的组成为：23.0％Nd、6.0％Pr、1.0％Dy、1.0％B、0.9％Co、0.1％Cu和0.3％Al，其余部分是Fe。R-Ni基吸收氢的合金的组成为：8.7％La、17.1％Ce、2.0％Pr、5.7％Nd、1.3％Co、5.3％Mn和1.9％Al，其余部分是Ni。Sm-Co磁体合金的组成为：25.0％Sm、18.0％Fe、5.0％Cu和3.0％Zr，其余部分是Co。然而本发明并不限于这些组成。
上述的浇口盘，是一个接受来自熔炉或浇包的稀土合金熔融体的容器，容器上具有调节浇注速度的浇注口，以便制造薄的铸造产品。由于在离心浇铸方法或浇铸带材的方法中，在浇口盘上流动的熔融体量小，所以会发生上述吸收熔融体热量的问题。其次，流槽是离心浇注方法和浇铸带材的方法中所使用的浇口盘的一种形式，在熔炉与浇口盘有相当距离的场合，用其将熔融体引到浇口盘中。铸口是设在上述浇口盘或流槽上的浇注口，或者是将熔融体引到旋转轧辊上的通道装置。特别是离心浇铸使用的浇口盘的铸口，能控制熔融体在旋转圆筒内表面上的积累速度。此外，浇铸带材采用浇口盘时，可将熔融体以层流形式浇注在恒速的单轧辊或双轧辊上。当每次浇注的熔融体量少至1kg的十分之几时，可将熔融体直接从容器如浇包加到旋转轧辊等上，而不通过浇口盘或流槽。当采用根据本发明的耐火材料制造浇口盘等时，由于熔融体的流动性能得到改善，所以浇铸生产的薄片的厚度分布及其结构是均匀的。此外，粉碎这些薄片制备的用于制造磁体的合金粉末的粒度是恒定的。可以预料，最终产品即磁体，能达到磁性稳定的效果。此外，就浇铸带材的方法而言，例如通过控制熔融体的加料速度，很容易使薄片薄到等于或小于0.3mm。在这种情况下，由于稀土合金的凝固速度很快，可以生成细的微观结构。
下面将说明这种浇铸方法的优选条件。将熔融体浇注到浇口盘等中的适宜温度为1300-1600℃。对于R-Fe-B磁体合金，优选温度为1350-1500℃，上面已给出一个其组成的实例，对于R-Ni基吸收氢的合金，该温度为1350-1500℃，上面已给出一个其组成的实例，对于Sm-Co基磁体合金，该温度为1350-1500℃，上面已给出一个其组成的实例。
在浇铸带材的情况下，熔融体进入浇口盘等的出炉温度如下：对于R-Fe-B磁体合金，为1300-1450℃，上面已给出一个其组成的实例，对于R-Ni基吸收氢的合金，该温度为1300-1450℃，上面已给出一个其组成的实例，对于Sm-Co基磁体合金，该温度为1300-1450℃，上面已给出一个其组成的实例。
熔融体的浇注量，是由旋转圆筒的面积、圆筒的转速和所要求的铸造厚度决定的。在浇铸熔融体以后，可将片材、带材和圆筒形材料等粉碎成絮片的形式。
在本发明中，虽然熔融体的浇注速度很低，但可在不预热浇口盘、流槽等的条件下，浇铸稀土合金熔融体。而且，在浇铸过程中，能在不使浇口盘、流槽等绝热的情况下，改善熔融体的流动。预热之类的准备操作，需要相当长的时间，而且需要非常小心。在常规浇铸方法的情况下，为了维持浇铸条件，必须凭经验使浇口盘绝热。在考虑这些因素时，可以说根据本发明的浇铸方法，在操作性能和稳定性方面，是相当先进的。
附图说明
图1是说明浇铸带材方法的示意图。
图2是说明常规离心浇铸方法的示意图。
图3是在实施例和对比例中采用的浇口盘的示意图。
具体实施方式
本发明第一方面的实施例和对比例
下面通过一些实施例更详细地说明本发明。
在下面所述的实施例1-4和对比例中，所采用的耐火材料的组成成分具有下列性质。
氧化铝纤维：平均直径5μm，平均长度0.5mm。
富铝红柱石纤维：平均直径5μm，平均长度0.5mm。
胶体二氧化硅：平均直径3-4μm。
胶体富铝红柱石：平均直径3-4μm。
氧化铝颗粒：平均直径3-4μm。
富铝红柱石颗粒：平均直径3-4μm。
硅酸乙酯40，是一种典型的用作粘结剂的硅酸乙酯。
实施例1
将氧化铝、富铝红柱石和二氧化硅混合，使其具有表1所示的耐火材料组成。将15份(重量)粘结剂与100份(重量)所制的纤维混合物混合。将纤维混合物与粘结剂混合充分，制成浆液混合物。然后采用模压装置成形，制成流槽状的浇口盘形式的材料。在自然干燥硬化以后，在表1所示的热处理温度下进行热处理。浇口盘1具有图3所示的形状。相应部件的尺寸是：宽度(w)360mm，高度(h)125mm，长度(1)900mm，熔融体流动部分的深度(h1)100mm，上部宽度(w1)310mm，底部宽度(w2)300mm。
Al2O3和SiO2的化学分析结果、堆密度和在1200-1400℃下的最大导热率示于表1。此外，从浇口盘取样，在1400℃下灼烧1小时。测定的重量损失也示于表1。
使就在浇铸前温度为1450℃(出炉温度)的NdFeB合金，从浇口盘3的一端流入，同时调节熔融体的加料量，使熔融体2的厚度达到0.5mm。从浇口盘的另一端，将总量100kg的熔融体浇铸到浇铸带材的轧辊上。熔融体能在浇口盘上正常地流动而不凝固。在浇铸时，浇口盘不进行预热。在完成浇铸以后，检查浇口盘的情况时确认，既没有沾污浇口盘，也没有显示浇口盘与熔融体发生反应的外来物质。
此外，熔融体流动的顺畅程度是由下式决定的。确定的流动系数是0.67。
流动系数＝熔融体通过铸口的实际流速，这些熔融体是储存在浇口盘内的，采用伯努力定理计算其产生的恒定排出压力/在同样条件下熔融体流过铸口的理论流速。
在这个方程式中示出的理论流速(v)是由下式计算的，设g表示重力加速度，h表示在浇口盘中储存的熔融体高度。
V = ( 2 gh )
实施例2
采用与实施例1相同的浇铸带材的方法，使用由与实施例1相同的耐火材料组成的浇口盘，浇铸Mm(混合金属)Ni-基合金(出炉温度1450℃)。熔融体能在浇口盘上正常流动，而不凝固在浇口盘上。这时流动系数为0.67。
在完成浇铸以后，检查浇口盘的情况时确认，既没有沾污浇口盘，也没有显示浇口盘与熔融体发生反应的外来物质。
实施例3
采用与实施例1相同的浇铸带材的方法，使用由与实施例1相同的耐火材料组成的浇口盘，浇铸Sm Co-基合金(出炉温度1450℃)。熔融体能在浇口盘上正常流动，而不凝固在浇口盘上。这时流动系数为0.71。
在完成浇铸以后，检查浇口盘的情况时确认，浇口盘未与熔融体反应。
对比例1
采用与实施例1相同的方法，制成由表1所示的耐火材料组成的浇口盘。试图采用与实施例1相同的浇铸带材的方法，浇铸NdFeB-基合金。然而，在浇铸过程中，熔融体的流动性逐渐减小，最终发生凝固。在熔融体流动困难时，流动系数为0.26。在这种情况下，这种耐火材料的加热条件是800℃下加热1小时。在1400℃下的灼烧重量损失率为4.0％(重量)。
对比例2
将具有与实施例1相同组成的耐火材料，制成与实施例1相同的浇口盘。耐火材料的加热温度为1500℃，保持1小时。在加工过程中，耐火材料经常发生破裂。
实施例4
采用与实施例1相同的方法，制成由表1所示的耐火材料组成的浇口盘，采用与实施例1相同的浇铸带材的方法，使用这种浇口盘浇铸NdFeB-基合金。熔融体能在浇口盘上正常流动，而不凝固在浇口盘上。浇铸前熔融体的温度(出炉温度)是1450℃。这时的流动系数是0.77。浇口盘不进行预热。
在完成浇铸以后，检查浇口盘的情况时确认，浇口盘未与熔融体反应。
对比例3
采用与实施例1相同的方法，制成由表1所示对比例3的耐火材料组成的浇口盘。试图采用与实施例1相同的浇铸带材的方法，使用这种浇口盘浇铸NdFeB基合金。然而，在浇铸过程中，熔融体的流动性逐渐减小，最终发生凝固。在熔融体流动困难时，流动系数为0.29。在这种情况下，这种耐火材料的加热条件是800℃下加热1小时。在1400℃下的灼烧重量损失率为4.0％(重量)。
对比例4
采用与实施例1相同的方法，将具有表1所示对比例4组成的耐火材料制成浇口盘。耐火材料的热处理条件是1500℃下加热1小时。在加工过程中，耐火材料经常发生破裂。
对比例5
采用与实施例1相同的方法，使用表1所示对比例5的耐火材料制成浇口盘。采用与实施例1相同的浇铸带材的方法，浇铸NdFeB-基合金。熔融体能在浇口盘上流动而不凝固。然而，在浇铸过程中，熔融体从浇口盘的底部泄漏。在修正熔融体泄漏以后，流动系数为0.45。在完成浇铸以后，检查浇口盘的情况时发现，浇口盘已经损坏，形成一个孔眼。在孔眼的周围，沾污范围很大。在将浇口盘打破，检查破裂面时发现，几乎浇口盘与熔融体发生接触的所有部分，但除孔眼部位外均有沾污。这证明，在浇铸过程中，在熔融体和浇口盘之间发生了反应。根据这一事实推测，流动系数比实施例1低的原因是由于熔融体与浇口盘发生反应引起的，该反应降低了熔融体的流动性。
对比例6
表2所示对比例6的耐火材料是由氧化铝纤维、胶体富铝红柱石和粉碎的普通氧化铝耐火材料颗粒组成的。采用与实施例1相同的方法，将耐火材料制成浇口盘。采用与实施例1相同的浇铸带材的方法，同时采用上述的浇口盘，浇铸NdFeB-基合金。从一开始起，熔融体的流动性就很差，在大部分熔融体浇铸之前就凝固了。在熔融体流动困难时，流动系数为0.24。
对比例7
表2所示对比例7的耐火材料，是由氧化铝纤维、富铝红柱石纤维、胶体富铝红柱石和粉碎的普通氧化铝耐火材料颗粒组成的。采用与实施例1相同的方法，将耐火材料制成浇口盘。采用与实施例1相同的浇铸带材的方法，浇铸NdFeB合金。从一开始起，熔融体的流动性就很差，在大部分熔融体浇铸之前就凝固了。在熔融体流动困难时，流动系数为0.24。
对比例8
按照实施例1的方法，将表3所示对比例8的普通耐火材料，制成浇口盘。试图采用与实施例1相同的浇铸带材的方法，浇铸NdFeB-基合金。然而，在熔融体刚开始在浇口盘上流动时，就发生凝固。因此不能进行浇铸。此后，除去留在浇口盘上的合金，检查浇口盘的情况。确认浇口盘与熔融体未发生反应。
对比例9
按照实施例1的方法，将表3所示对比例9的普通耐火材料，制成浇口盘。试图采用与实施例1相同的浇铸带材的方法，浇铸NdFeB-基合金。然而，在熔融体刚开始在浇口盘上流动时，就发生凝固。因此不能进行铸造。此后，除去留在浇口盘上的合金，打破浇口盘以观测浇口盘的破裂面。沾污局部地扩大到浇口盘的内部。因此确认，浇口盘与熔融体发生了反应。
Figure C20061016897400171
Figure C20061016897400181
本发明第二方面的实施例和对比例
在下述实施例5-26和对比例10-29中，所采用的耐火材料的组成成分具有下列性质。
二氧化锆纤维：平均直径5μm，平均长度1.5mm。
二氧化锆晶须：平均直径5μm，平均长度500μm。
稳定的二氧化锆纤维：平均直径5μm，平均长度1.5mm。
稳定的二氧化锆晶须：平均直径5μm，平均长度500μm。
硅酸乙酯40，是一种典型的用作粘结剂的硅酸乙酯。
实施例5
混合ZrO2、Y2O3和SiO2，使其具有表4所示的耐火材料组成。将15份(重量)粘结剂与100份(重量)所制的纤维混合物混和。使纤维混合物与粘结剂充分混合，制成浆液混合物。然后采用模压装置将混合物成形，制成流槽状的浇口盘形式的材料。在自然干燥硬化后，在表4所示的热处理温度下进行热处理。浇口盘3具有图3所示的形状。相应部件的尺寸与本发明第一方面的实施例和对比例相同。
在表4中示出ZrO2、Y2O3和SiO2的化学分析结果、堆密度和在1200-1400℃下的最大导热率。此外，从浇口盘上取样，在1400℃下灼烧1小时。测定的重量损失也示于表4。
使浇铸前温度为1450℃(出炉温度)的NdFeB合金，从浇口盘的一端流入，同时调节熔融体的加料量，使熔融体2的厚度达到0.5mm。从浇口盘的另一端，将总量100kg的熔融体浇铸到浇铸带材的轧辊上。熔融体在浇口盘上正常流动而不凝固。在这种情况下，浇口盘不进行预热。在完成浇铸以后，检查浇口盘的情况时确认，浇口盘既没有沾污，也没有显示浇口盘与熔融体发生反应的外来物质。
此外，以实施例1中定义的流动系数表示熔融体流动的容易程度，流动系数为0.71。
实施例6
采用与实施例5相同的浇铸带材的方法，使用与实施例5相同的耐火材料组成的浇口盘，浇铸Mm(混合稀土)Ni-基合金(出炉温度1450℃)。熔融体能在浇口盘上正常流动，而不凝固在浇口盘上。这时流动系数为0.71。
在完成浇铸以后，检查浇口盘的情况时确认，浇口盘未与熔融体反应。
实施例7
采用与实施例5相同的浇铸带材的方法，使用由与实施例5相同的耐火材料组成的浇口盘，浇铸Sm Co-基合金(出炉温度1450℃)。熔融体能在浇口盘上正常流动，而不在浇口盘上凝固。这时流动系数为0.77。
在完成浇铸以后，检查浇口盘的情况时确认，浇口盘未与熔融体反应。
实施例8-26
采用与实施例5相同的方法，制造由表4所示的耐火材料组成的浇口盘，采用与实施例5相同的浇铸带材的方法，使用所制的浇口盘浇铸NdFeB-基合金。熔融体能在每种浇口盘上正常流动，而不凝固在浇口盘上。出炉温度为1450℃。在这些浇铸时的流动系数示于表4。在这些情况下，浇口盘不进行预热。
在完成浇铸以后，检查浇口盘的情况时确认，浇口盘未与熔融体反应。
对比例10-17
使用由表5所示的耐火材料组成的浇口盘。试图采用与实施例5相同的浇铸带材的方法，浇铸NdFeB-基合金。然而，对于每一种浇口盘，在浇铸过程中，熔融体的流动性都逐渐减小，最终发生凝固。在熔融体流动困难时，流动系数为0.27-0.30。在这些情况下，这些耐火材料的加热条件是800℃下加热1小时。每种浇口盘在1400℃下的灼烧重量损失是0.4％(重量)。
对比例18-25
按照实施例5的方法，将具有表5所示组成的耐火材料制成浇口盘。耐火材料的加热温度为1500℃，加热1小时。在加工过程中，每种浇口盘都经常破裂。
对比例26
使用由表5所示对比例26的耐火材料组成的浇口盘。采用与实施例5相同的浇铸带材的方法，浇铸NdFeB-基合金。熔融体能在浇口盘上流动而不凝固。然而，在浇铸过程中，熔融体从浇口盘的底部泄漏。在修正熔融体泄漏以后，流动系数为0.43。在完成浇铸以后，检查浇口盘的情况时发现，浇口盘已损坏，形成一个孔眼。在孔眼的周围，沾污范围很大。在将浇口盘打破，检查浇口盘的破裂面时发现，几乎浇口盘的所有部分都与熔融体发生接触，但孔眼部分却没有沾污。因而证明，在浇铸过程中，熔融体与浇口盘之间发生了反应。根据这一事实推断，流动系数比实施例5低的原因是由于熔融体与浇口盘发生反应引起的，该反应降低了熔融体的流动性。
对比例27-28
按照实施例5的方法，将表6所示对比例27-28的普通耐火材料制成浇口盘。试图采用与实施例5相同的浇铸带材的方法，浇铸NdFeB-基合金。然而，在熔融体刚开始在浇口盘上流动时，就发生凝固，不能进行浇铸。然后，除去留在浇口盘上的合金，检查浇口盘的情况。确认浇口盘未与熔融体反应。
对比例29
按照实施例5的方法，将表6所示对比例29的普通耐火材料制成浇口盘。试图采用与实施例5相同的浇铸带材的方法，浇铸NdFeB-基合金。然而，在熔融体刚开始在浇口盘上流动时，就发生凝固，不能进行浇铸。
工业应用范围
根据本发明，不用复杂的方法和设备，就能稳定地生产用作制造稀土磁体的最佳原料合金。因此，本发明是极其有用的。除了生产这种合金以外，在浇铸各种稀土合金时，很容易进行质量控制。
Figure C20061016897400221
Figure C20061016897400231
Figure C20061016897400241

Claims (14)

1.一种用于浇铸稀土合金的耐火材料，其特征在于，它基本上是由等于或大于70％重量的ZrO2和等于或小于30％重量的一种或多种选自Y2O3、Ce2O3、CaO、MgO、Al2O3、TiO2或SiO2的材料组成的，该耐火材料的堆密度等于或小于1g/cm3，在温度1200-1400℃下的导热率等于或小于0.5kcal/(mh℃)，在1400℃加热1小时的灼烧重量损失率等于或小于0.5％重量。
2.根据权利要求1的用于浇铸稀土合金的耐火材料，其特征在于，它包含等于或大于70％重量的一种或多种选自二氧化锆纤维、二氧化锆晶须、稳定的二氧化锆纤维和稳定的二氧化锆晶须的材料。
3.一种用于生产浇铸稀土合金的耐火材料的方法，其特征在于，将一种或多种选自二氧化锆、稳定的二氧化锆的材料与一种或多种选自无机粘结剂和有机粘结剂的粘结剂混合，以制备一种混合物，使耐火材料中具有等于或大于70％重量的ZrO2和等于或小于30％重量的一种或多种选自Y2O3、Ce2O3、CaO、MgO、Al2O3、TiO2或SiO2的材料，将混合物成形，干燥硬化，再在1000-1400℃下进行热处理，借此分解所述的粘结剂，从而制成堆密度等于或小于1g/cm3的多孔结构。
4.根据权利要求3的用于生产浇铸稀土合金的耐火材料的方法，其中所述的二氧化锆和稳定的二氧化锆的至少之一是纤维形式的。
5.根据权利要求3或4的用于生产浇铸稀土合金的耐火材料的方法，其中所述的二氧化锆和稳定的二氧化锆的至少之一是晶须形式的。
6.一种用于浇铸稀土合金的方法，其特征在于，采用浇注装置，将稀土合金熔融体浇注到旋转轧辊的表面上，或浇注到旋转圆筒的内表面上，浇注装置是由基本上由等于或大于70％重量的ZrO2和等于或小于30％重量的一种或多种选自Y2O3、Ce2O3、CaO、MgO、Al2O3、TiO2或SiO2的材料组成的耐火材料制造，其堆密度等于或小于1g/cm3，在温度1200-1400℃下的导热率等于或小于0.50kcal/(mh℃)，灼烧的重量损失率等于或小于0.5％重量，将熔融体冷却，使其凝固。
7.根据权利要求6的用于浇铸稀土合金的方法，其中所述的浇注装置是浇口盘3、流槽或铸口。
8.根据权利要求6或7的用于浇铸稀土合金的方法，其中所述的旋转轧辊是浇铸带材的单轧辊4或双轧辊。
9.根据权利要求8的用于浇铸稀土合金的方法，其特征在于，将所述的稀土合金浇铸成厚度为0.1-1mm的片材或带材。
10.根据权利要求6或7的用于浇铸稀土合金的方法，其中所述的旋转圆筒是用于离心浇铸的旋转铸模。
11.根据权利要求10的用于浇铸稀土合金的方法，其特征在于将所述的稀土合金浇铸成厚度为1-20mm的圆筒形材料。
12.根据权利要求7-11任一项的用于浇铸稀土合金的方法，其特征在于，在不预热所述浇口盘、流槽或铸口的条件下，浇铸稀土合金熔融体。
13.一种稀土合金材料，该材料是粉碎在权利要求9中所述的稀土合金片材制备的很薄的碎片或鳞片。
14.一种稀土合金材料，该材料是粉碎在权利要求10中所述的稀土合金圆筒形材料制备的很薄的碎片或鳞片。
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CN1303035C (zh) 2007-03-07
EP1659102B1 (en) 2010-05-26
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EP1659102A1 (en) 2006-05-24
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CA2335827A1 (en) 1999-12-29
EP1118601A1 (en) 2001-07-25
EP1118601A4 (en) 2005-01-26
JP4366015B2 (ja) 2009-11-18
ATE384028T1 (de) 2008-02-15
ATE469108T1 (de) 2010-06-15
DE69938004D1 (de) 2008-03-06
DE69938004T2 (de) 2009-01-15

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