CN101456746B - 具有低膨胀性、高强度、耐裂纹扩展性的不定形耐火物 - Google Patents

具有低膨胀性、高强度、耐裂纹扩展性的不定形耐火物 Download PDF

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CN101456746B
CN101456746B CN2008100828280A CN200810082828A CN101456746B CN 101456746 B CN101456746 B CN 101456746B CN 2008100828280 A CN2008100828280 A CN 2008100828280A CN 200810082828 A CN200810082828 A CN 200810082828A CN 101456746 B CN101456746 B CN 101456746B
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古宫山常夫
山川治
本庄哲博
樋口阳人
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NGK Adrec Co Ltd
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Abstract

本发明涉及一种适用于陶瓷产品的不定形耐火物，特别提供以保护、改性质低膨胀的陶瓷产品的表面为目的而使用的具有低膨胀性、高强度、耐裂纹扩展性的不定形耐火物。该不定形耐火物是将堇青石粉末、水及氧化铝溶胶或硅溶胶溶液构成的溶剂混练而成，其中，堇青石粉末具有中位径为10～50μm范围、不到10μm的粒子的含量为1％以下36％以上、10μm以上50μm以下的粒子的含量为50％以上75％以下、51μm以上的粒子的含量为1％以上14％以下的尖细的山形状的粒度分布。

Description

具有低膨胀性、高强度、耐裂纹扩展性的不定形耐火物
技术领域
本发明涉及一种适用于耐火物等的有耐火性的陶瓷产品的不定形耐火物，特别涉及在将低膨胀的耐火砖及耐火陶瓷产品的表面和粘结面或界面或砌缝进行修补、保护、改性、填充、成形的目的下使用的具有低膨胀性、高强度、耐裂纹扩展性的不定形耐火物。
背景技术
以往，作为耐火物之间的粘结剂，周知是使用不定形耐火物。如专利文献1和专利文献2所示，这样的不定形耐火物一般是将根据用途所选择的无机骨料及微粉末用水进行混练。但是，问题是由于用水作为溶剂，所以不能实现充分的强度，另外，为了重视耐火性和耐侵蚀性而使用高熔点的骨料，现状是还不存在全部满足低膨胀性、高强度、耐裂纹扩展性的不定形耐火物。
另一方面，也推出了将不定形耐火物作为用于修补、保护、改性、充填低膨胀的陶瓷产品的表面的修补材料、保护材料、改性、填充材料等使用的方案。在这样的灰浆中添加炭化硅来调整热膨胀，从而维持低膨胀。但是，由于炭化硅是非氧化物，所以有氧化的问题，不能恒久维持低膨胀，并还有氧化劣化造成的接合强度的降低的问题。进而，由于在溶剂中使用水，所以还有接着强度降低的问题。因此，为了实现强度的改善，进行了氧化物添加剂的添加，但这种场合，会产生热膨胀变大的问题。
如专利文献1所示，推出了配合了粒径2mm以上的骨料和硅酸盐水泥等的超高韧性灰浆，虽能够实现高强度，却不能够改善低膨胀性、耐裂纹进展性。
另外，如专利文献3所示，作为用于将陶瓷产品的表面改性的涂层材料，提出了堇青石粉末与水的构成物，但虽能够实现低膨胀性、高强度，却不能改善耐裂纹扩展性。
专利文献1  特开2005-67945号公报
专利文献2  特开平3-75275号公报
专利文献3  特开2004-231506号公报
发明内容
本发明的目的在于：解决上述问题，提供一种具有低膨胀、高强度、耐裂纹扩展性的不定形耐火物，该不定形耐火物是以保护、改性低膨胀的陶瓷产品的表面的目的而使用的不定形耐火物，其具有低膨胀性、高强度，且还具有耐裂纹扩展性，能够维持良好的组织状态。
为解决上述问题而成的本发明的具有低膨胀性、高强度且还具有耐裂纹扩展性的灰浆的特征在于：由对堇青石粉末和水及硅溶胶溶液构成的溶进行混练而成，其中堇青石粉末的中位径为10～50μm范围，具有尖细的山状的粒度分布，即0.50μm以上不到10μm的粒子的含量为1％以上36％以下、10μm以上50μm以下的粒子的含量为50％以上75％以下、51μm以上200μm以下的粒子的含量为1％以上14％以下。
另外，上述氧化铝溶胶或硅溶胶溶液的硅含量或氧化铝含量分别优选为10～70％的范围，将其作为技术方案2及技术方案3涉及的发明，进而，氧化铝溶胶或硅溶胶溶液中的碱氧化物含量优选为0.01％以上2％以下，将其作为技术方案4涉及的发明。
在本发明中，由于混合了中位径为10～50μm范围、具有尖细的山形状的粒度分布的堇青石粉末和由水及硅溶胶溶液构成的溶剂，其中的堇青石粉末中0.5μm以上不到10μm的粒子的含量为1％以上36％以下，10μm以上50μm以下的粒子的含量为50％以上75％以下，51μm以上200μm以下的粒子的含量为1％以上14％以下，由此，通过堇青石粉末确保低膨胀性，并通过用氧化铝溶胶或硅溶胶溶液作为溶剂来实现高强度。进而，在通过使用具有尖细的山形状的粒度分布的堇青石粉末来实现高强度的同时，还能够防止不定形耐火物的裂纹扩展。
另外，通过使氧化铝溶胶或硅溶胶溶液的氧化铝或硅含量分别为10～70％的范围，并使氧化铝溶胶或硅溶胶溶液中的碱氧化物含量为0.01％以上2％以下，能够实现高强度。
附图说明
图1是显示本发明的堇青石粉末的粒度分布的图。
图2是显示现有例的堇青石粉末的粒度分布的图。
具体实施方式
以下显示本发明的优选实施方式。
在本发明中，为了确保低膨胀性而使用了堇青石材料。由于堇青石的热膨胀系数在900℃下低至1.6～2.0×10-6，所以，在用于低膨胀的陶瓷产品的表面时，膨胀率的差小，能够防止破裂等发生，另外，堇青石本身是不易产生裂纹的材质，能够防止不定形耐火物的裂纹发生。
另外，堇青石粉末的中位径为10～50μm范围。通过控制中位径，能够得到施工性、强度、耐裂纹扩展性良好的灰浆。如果中位径不到10μm，则会使溶剂的添加量变多、强度降低，如果大于50μm，虽然施工性良好，但强度会降低。此外，使得0.5μm以上不到10μm的粒子的含量为1％以上36％以下、10μm以上50μm以下的粒子的含量为50％以上75％以下、51μm以上200μm以下的粒子的含量为1％以上14％以下，如果堇青石粉末的不足0.5μm的粒子的量多，则溶剂的量增大，强度下降，不优选。此外优选不含有200μm以上的粒子，因为粗大的粒粒子会成为缺陷导致强度下降。
进而，堇青石粉末具有0.5μm以上不到10μm的粒子的含量为1％以上36％以下、10μm以上50μm以下的粒子的含量为50％以上75％以下、51μm以上200μm以下的粒子的含量为1％以上14％以下的尖细的山形状的粒度分布。本发明者根据研究的结果发现，通过控制堇青石粉末的粒度分布，能够提高接着强度及耐裂纹扩展性。
在图1中，显示本发明的堇青石粉末的粒度分布，在图2中显示现有技术的堇青石粉末的粒度分布。中位径在图1中为16.367±5μm，中位径频率为7.5％以上，而图2中的中位径为17.573μm，中位径频率为5.0％以下。而且，根据本发明者的研究，判明按现有的粒径各异的宽大的山形状的粒度分布，在作为不定形耐火物时，空隙变多，不能得到充分的强度，而与此相对，如本发明的粒径均匀的尖细山形状的粒度分布的场合，能够成为最密充填，可实现充分的强度，且还能够防止裂纹的扩展。
另外，中位径频度的上限优选为11％以下。
另外，在本发明中，作为溶剂是使用水及氧化铝溶胶或硅溶胶构成的溶液。
这是因为查明了以往在仅使用水作为溶剂的场合，不能得到充分的强度，而在使用胶质状态的氧化铝或硅作为溶剂的场合，能够得到充分的强度。
上述氧化铝或硅溶胶溶液的氧化铝或硅含量分别优选为10～70％。这是因为如果不到10％，则难以确保充分的强度，而如果多于70％，则在价格上变贵，背离实用基础。
另外，硅溶胶溶液中的Na2O和K2O等的碱氧化物含量优选为0.01％以上2％以下。这是因为如果多于2％，则强度会降低。
除此之外，也能够根据需要，在数％以下的范围适当含有粘性调整用的有机粘结剂和用于防止涂层材料的“塌边”和弹性率降低用的纤维等。
从以上的说明中可以明确，本发明的灰浆通过使用低膨胀的堇青石和作为溶剂的硅溶胶溶液，且将上述堇青石粉末的粒度分布控制在规定范围，能够确保低膨胀性和高强度，作为低膨胀的陶瓷产品的表面保护、改性用涂层材料发挥优越的效果。另外，还能够抑制耐裂纹的扩展性，所以其可作为能维持良好的组织状态的不定形耐火物的发挥效果。
实施例
由表1所示的组成构成，且使用堇青石粉末做成不定形耐火物，该堇青石粉末具有中位径为10～50μm范围，具有0.5μm以上不到10μm的粒子的含量为1％以上36％以下、10μm以上50μm以下的粒子的含量为50％以上75％以下、51μm以上200μm的粒子的含量为1％以上14％以下的尖细山形状的粒度分布。将其涂敷在低膨胀的多孔质陶瓷产品的表面，实现了保护、改性。在表1中显示测定的得到的不定形耐火物强度、施工性、裂纹发生数量等的结果。另外，关于抗弯强度及热膨胀系数，在使不定形耐火物干燥后进行了测定。
作为比较例，在表1中显示测定了使用中位径频度为5％以下的具有宽大的山形状的粒度分布的现有的堇青石粉末作成了灰浆时的不定形耐火物的强度、施工性、裂纹发生数量等的结果。
该结果能够确认本发明的不定形耐火物与现有例相比，在低膨胀性、高强度性、耐裂纹扩展性上具有优越的特性。
表1
  比较例1   实施例1   实施例2   实施例3   实施例4   实施例5   实施例6   实施例7   实施例8   实施例9   实施例10   实施例11
  现有堇青石   100
  改性堇青石   100   100   100   100   100   100   100   100   100   100   100
  水   29   29
  硅溶胶浓度5％液   30
  硅溶胶浓度10％液   32
  硅溶胶浓度30％液   35   35   35   35   35
  硅溶胶浓度50％液   37
  硅溶胶浓度70％液   40
  硅溶胶浓度80％液   42
  0.5μm以上、不足10μm的粒子的含量   31   22   22   21   22   22   11   8   27   27   20   25
  10μm以上、50μm以下的粒子的含量   44   61   62   63   62   63   73   74   70   55   54   54
  51μm以上、200μm以下的粒子的含量   22   14   14   15   14   14   14   14   2   15   14   13
  碱含有率   0   0   1   1   1   1   1   2   3   1   1   1
  抗弯强度Mpa   1.0   1.5   1.6   2.1   3.5   4.5   5.0   3.3   2.5   5.5   1.7   2.8
  中位径μm   25   25   25   25   25   25   25   25   25   25   38   45
  裂纹发生数量   150   50   48   30   25   20   15   30   35   10   15   20
  施工性   ○   ○   ○   ○   ○   ○   ○   ○   ○   ○   ○   ○

Claims (3)

1.一种具有低膨胀性、高强度、耐裂纹扩展性的不定形耐火物，其特征在于：将具有尖细的山形状的粒度分布的陶瓷粉末与由水及非晶体胶体溶液构成的溶剂进行混练，该陶瓷粉末的中位径为10～50μm的范围，0.5μm以上不到10μm的粒子的含量为1％以上36％以下，10μm以上50μm以下的粒子的含量为50％以上75％以下，51μm以上200μm以下的粒子的含量为1％以上14％以下，
所述陶瓷粉末是堇青石粉末，
所述非晶体胶体溶液是氧化铝溶胶溶液或硅溶胶溶液。
2.根据权利要求1所述的具有低膨胀性、高强度、耐裂纹扩展性的不定形耐火物，其特征在于：所述氧化铝溶胶溶液或硅溶胶溶液的氧化铝或二氧化硅含量分别为10～70％。
3.根据权利要求1或2所述的具有低膨胀性、高强度、耐裂纹扩展性的不定形耐火物，其特征在于：所述非晶体胶体溶液中的碱氧化物含量为0.01％以上2％以下。
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