CN111032596B - 热修补用喷涂材料 - Google Patents

热修补用喷涂材料 Download PDF

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CN111032596B
CN111032596B CN201880052866.3A CN201880052866A CN111032596B CN 111032596 B CN111032596 B CN 111032596B CN 201880052866 A CN201880052866 A CN 201880052866A CN 111032596 B CN111032596 B CN 111032596B
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本田和宽
白曼统一
赤井哲
中道翼
大野洋辅
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Krosaki Harima Corp
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Abstract

本发明的目的在于，在热修补用喷涂材料上，提高喷涂瞬间的向被修补面的附着性。具体而言，本发明的热修补用喷涂材料含有65质量％以上95质量％以下的氧化镁质原料、0.5质量％以上10质量％以下的酚醛树脂，且粒径小于20μm的氧化镁质原料的含量为5质量％以上30质量％以下，粒径小于20μm的酚醛树脂的含量为0.3质量％以上9质量％以下，所述粒径小于20μm的氧化镁质原料的含量/所述粒径小于20μm的酚醛树脂的含量为0.6以上30以下。

Description

热修补用喷涂材料
技术领域
本发明涉及热修补用喷涂材料，所述热修补用喷涂材料例如被用于转炉、脱气炉、浇包、其他窑炉的内衬的热修补，并与施工水一起被喷涂到被修补面。
另外，在本发明中“热修补”是指，被修补面的温度大约为600℃以上的状态下的修补。
背景技术
例如，在转炉中，进行有通过热来修补内衬的熔损部位的情况。作为热修补的方法，已知有一种将包含耐火原料和结合剂的喷涂材料与施工水一起喷涂到内衬的熔损部位的方法。
以往，在该方法所使用的喷涂材料中，多为将磷酸盐、硅酸盐用于结合剂，但由于磷酸盐、硅酸盐与炉渣一起形成低熔点化合物，由此带有耐用性差这样的缺点。
因此，近年，为了赋予喷涂施工体以耐炉渣渗透性及强度的目的，而使用有通过热来形成碳键的物质具体而言为酚醛树脂等碳质树脂(例如，参照专利文献1)，来替代磷酸盐、硅酸盐。
专利文献
专利文献1：日本国特开2010-235340号公报
发明内容
虽然在专利文献1中，为了抑制碳质树脂的软化的延迟，而将一部分碳质树脂在形成造粒物的状态下与被造粒粉体配合，但形成造粒物后，难以将热传导到碳质树脂。因此，无法避免碳质树脂的软化延迟，从而导致喷涂材料在到达被修补面时发生反弹，因而存在有向被修补面的附着性不佳这样的问题。
本发明所要解决的技术问题在于，在热修补用喷涂材料上，提高向被修补面的附着性。
本发明人认为，在提高向被修补面的附着性(以下仅称为“附着性”)上，将酚醛树脂用作碳质树脂是有效的。即，这是因为酚醛树脂在被喷涂到被修补面的瞬间发生凝集，因而容易发挥适当的粘性(粘接性)。此外，从提高耐炉渣渗透性等耐用性的观点出发，本发明人选择了氧化镁质原料来作为耐火原料。并且，为了解决所述课题，本发明人着眼于氧化镁质原料和酚醛树脂的配合比例尤其是超微粉区域的配合比例而进行了反复研究，其结果想出了本发明。
即，根据本发明的一个观点，可提供下述热修补用喷涂材料。
含有65质量％以上95质量％以下的氧化镁质原料、0.5质量％以上10质量％以下的酚醛树脂，
且粒径小于20μm的氧化镁质原料的含量为5质量％以上30质量％以下，粒径小于20μm的酚醛树脂的含量为0.3质量％以上9质量％以下，
“所述粒径小于20μm的氧化镁质原料的含量/所述粒径小于20μm的酚醛树脂的含量”为0.6以上30以下的热修补用喷涂材料。
根据本发明，由于超微粉区域内的氧化镁质原料和酚醛树脂的配合比例处于特定的范围内，所述超微粉区域为粒径小于20μm这样的活性非常高的超微粉区域，且在超微粉区域中均衡地存在有氧化镁质原料和酚醛树脂，因此在喷涂的瞬间，可形成具有适当粘性(粘接性)的基质，并且在该基质内形成均匀的碳键。由此提高了附着性。
具体实施方式
本发明的热修补用喷涂材料含有65质量％以上95质量％以下的氧化镁质原料、0.5质量％以上10质量％以下的酚醛树脂。
当氧化镁质原料的含量小于65质量％时，则耐腐蚀性(耐炉渣渗透性)等耐用性降低。当氧化镁质原料的含量超过95质量％时，则酚醛树脂的含量相对变少，导致附着性降低。
此外，当酚醛树脂的含量小于0.5质量％时，则形成碳键的效果减弱，导致附着性降低。当酚醛树脂的含量超过10质量％时，则由于从酚醛树脂的挥发较多，因此喷涂施工体的组织成为多孔性，会导致喷涂施工体强度降低。
如前所述，本发明对粒径小于20μm这样的超微粉区域中的氧化镁质原料和酚醛树脂的配合比例进行了限制。即，粒径小于20μm的氧化镁质原料的含量为5质量％以上30质量％以下，粒径小于20μm的酚醛树脂的含量为0.3质量％以上9质量％以下，其含量比“所述粒径小于20μm的氧化镁质原料的含量/所述粒径小于20μm的酚醛树脂的含量”(以下将该含量比仅称为“含量比”)为0.6以上30以下。这样限制含量比等配合比例的原因如下。
当粒径小于20μm的氧化镁质原料的含量小于5质量％时，则该超微粉的氧化镁质原料所具有的凝集效果(因凝集而形成的附着性保持功能)减弱，导致附着性降低。当粒径小于20μm的氧化镁质原料的含量超过30质量％时，则由于凝集效果过大而粘性升高，因此喷涂施工时的吐出性变差，其结果导致附着性也降低。
当粒径小于20μm的酚醛树脂的含量小于0.3质量％时，则导致形成碳键的反应变慢，进而附着性降低。当粒径小于20μm的酚醛树脂的含量超过9质量％时，则会在喷涂施工时因产生粉尘而漂浮，导致附着性降低。并且，由于漂浮的超微粉的酚醛树脂发生燃烧，因此还存在有变得看不到施工部位的问题。
在含量比小于0.6(超微粉的酚醛树脂较多时)时，酚醛树脂的挥发速度变快，会导致喷涂施工体一下子收缩，进而喷涂施工体在粘接界面上浮起，从而附着性降低。而后，随着附着力降低，因喷涂施工体自重、喷涂压力而会产生剥落。另一方面，在含量比超过30时(超微粉的酚醛树脂较少时)，则无法保持附着后的强度，会导致喷涂施工体脱落。该含量比的优选范围为0.6以上20以下。
作为本发明所使用的氧化镁质原料及酚醛树脂，可使用通常用作热修补用喷涂材料的原材料(市售)的原材料。而后，只需将这些氧化镁质原料及酚醛树脂的粒度构成调整为，粒径小于20μm的原材料的含量、含量比处于前述的规定的范围内即可。在此，由于在本发明的热修补用喷涂材料中，氧化镁质原料的一部分可作为骨料，因此例如只需在粒径小于4mm的粒度区域内进行粒度调整，以便粒径小于20μm的原材料的含量、含量比处于前述的规定的范围内即可。
另外，本发明中所述“氧化镁质原料”是指，MgO含量为60质量％以上的原材料，除天然的氧化镁原材料以外，也包含氧化镁砖、镁碳砖的碎屑。
此外，本发明中所述“粒径”是指筛目，例如粒径小于20μm是指通过20μm的筛目。
除氧化镁质原料及酚醛树脂以外，本发明的热修补用喷涂材料可含有0.5质量％以上10质量％以下的沥青。通过含有0.5质量％以上10质量％以下的沥青，可提高喷涂施工体强度，进而提高耐用性。
另外，除氧化镁质原料、酚醛树脂及沥青以外，本发明的热修补用喷涂材料可适当含有白云石原料、碳原料等其他耐火原料、金属粉末、有机纤维等通常用作热修补用喷涂材料原料的原材料。
与现有的热修补用喷涂材料相同，本发明的热修补用喷涂材料与施工水一起被喷涂到被修补面，但施工水的添加量等喷涂条件、喷涂方法可与现有情况相同。
实施例
表1示出本发明的实施例及比较例的原材料配合和评价结果。实施例及比较例中的评价项目和评价方法如下。另外，表1中“其他原材料”为白云石原料、碳原料及金属粉末。
(附着性)
使用常用的干式喷涂机将各例子的喷涂材料喷涂到加热到约1000℃的镁碳砖的垂直面(被修补面)上，形成了喷涂施工体。施工水的添加量为，相对于喷涂材料100质量％，通过外掺而成为20～40质量％。
用向被修补面的喷涂材料的附着比例来评价附着性，将向被修补面的附着量相对于喷涂材料的使用量的比例为80质量％以上的情况作为〇(良)，将60质量％以上且小于80质量％的情况作为△(可)，将小于60质量％的情况作为×(不可)。
(耐腐蚀性)
将C/S＝3.4的转炉炉渣和钢片作为侵蚀剂，使用旋转侵蚀试验机，使从喷涂施工体切出的规定尺寸的试样在1650～1700℃下侵蚀了5小时。测定了各例子的最大熔损量并求出其倒数，且求出了以实施例1的该倒数为100的相对值。该相对值越大则耐腐蚀性越优异。在耐腐蚀性的评价中，将该相对值为80以上的情况作为〇(良)，将70以上且小于80的情况作为△(可)，将小于70作为×(不可)。
(喷涂施工体强度)
遵照日本工业标准JISR 2575，对从喷涂施工体切出的规定尺寸的试样测定了常温下的压缩强度，并求出了以实施例1的压缩强度为100的相对值。该相对值越大则喷涂施工体强度越高。在喷涂施工体强度的评价中，将该相对值为80以上的情况作为〇(良)，将70以上且小于80的情况作为△(可)，将小于70作为×(不可)。
(吐出性)
在喷涂时对干式喷涂机的喷嘴顶端进行了目视观察，将无脉动吐出的情况作为〇(良)，将有脉动的情况作为×(不可)。
(综合评价)
将所述各评价项目的评价全部为○的情况作为○(良)，将△为1～3个且其他为〇的情况作为△(可)，将任意1项为×的情况作为×(不可)。
(表1)
Figure BDA0002384134680000061
如表1所示，处于本发明的范围内的实施例1～6的附着性的评价为○(良)或△(可)因而良好，综合评价也良好。
比较例1为氧化镁质原料的含量较少的例子。由于有助于提高耐腐蚀性(耐炉渣渗透性)的氧化镁质原料较少，因此未得到足够的耐腐蚀性。
比较例2为氧化镁质原料的含量较多的例子。酚醛树脂的含量相对变少，因而附着性降低，以至于未得到足够的喷涂施工体。因此，未取得用于评价耐腐蚀性及喷涂施工体强度的试样。
比较例3为粒径小于20μm的氧化镁质原料的含量较少的例子。粒径小于20μm的氧化镁质原料所具有的凝集效果减弱，导致附着性降低。
比较例4为粒径小于20μm的氧化镁质原料的含量较多的例子。凝集效果变得过大，导致喷涂施工时的吐出性恶化，其结果附着性降低，以至于未得到足够的喷涂施工体。因此，未取得用于评价耐腐蚀性及喷涂施工体强度的试样。
比较例5为酚醛树脂的含量较少且含量比较高(粒径小于20μm的酚醛树脂的含量较少)的例子。由于有助于提高附着性的酚醛树脂较少，因此附着性降低，以至于未得到足够的喷涂施工体。因此，未取得用于评价耐腐蚀性及喷涂施工体强度的试样。
比较例6为酚醛树脂的含量较多且含量比较低(粒径小于20μm的酚醛树脂的含量较多)的例子。酚醛树脂的挥发速度变快，此外粒径小于20μm的酚醛树脂在喷涂施工时因产生粉尘而漂浮，其结果导致附着性降低。

Claims (3)

1.一种热修补用喷涂材料，其特征在于，
含有65质量%以上95质量%以下的氧化镁质原料、0.5质量%以上10质量%以下的酚醛树脂，
且相对于所述热修补用喷涂材料100质量%，粒径小于20μm的氧化镁质原料的含量为5质量%以上30质量%以下，粒径小于20μm的酚醛树脂的含量为0.3质量%以上9质量%以下，
所述粒径小于20μm的氧化镁质原料的含量／所述粒径小于20μm的酚醛树脂的含量为0.6以上30以下；
所述粒径小于20μm是指通过20μm的筛目。
2.根据权利要求1所述的热修补用喷涂材料，其特征在于，含有0.5质量%以上10质量%以下的沥青。
3.根据权利要求1或2所述的热修补用喷涂材料，其特征在于，所述粒径小于20μm的氧化镁质原料的含量／所述粒径小于20μm的酚醛树脂的含量为0.6以上20以下。
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