CN112789257A - 热用干式喷涂材料及干式热喷涂施工方法 - Google Patents

热用干式喷涂材料及干式热喷涂施工方法 Download PDF

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CN112789257A
CN112789257A CN201980065209.7A CN201980065209A CN112789257A CN 112789257 A CN112789257 A CN 112789257A CN 201980065209 A CN201980065209 A CN 201980065209A CN 112789257 A CN112789257 A CN 112789257A
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大野洋辅
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Krosaki Harima Corp
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Abstract

本发明的目的在于，在热用干式喷涂材料及干式热喷涂施工方法上，使耐腐蚀性提高。具体而言，本发明其特征在于，在将包含耐火材料及粘合剂的配合物通过配管而朝向喷涂喷嘴压送并在所述喷涂喷嘴的顶端部上添加水进而在热中进行喷涂的干式热喷涂施工方法上，所述配合物在所述耐火材料及所述粘合剂的总量100质量％中，包含10质量％以上50质量％以下的粒径0.075mm以上且小于1mm的苦土石灰石，且在所述耐火原料及粘合剂的总量100质量％中，粒径小于0.075mm的苦土石灰石的含量为35质量％以下(包含0)。

Description

热用干式喷涂材料及干式热喷涂施工方法
技术领域
本发明尤其涉及熔钢炉、电炉的炉体(炉壁)这样的工业窑炉的热修补所优选使用的热用干式喷涂材料(不定形耐火物)及其施工方法。
另外，“热”是指被施工面的温度为大致600℃以上的环境。
背景技术
不定形耐火物根据使用用途而施工方法不同。例如，在使用不定形耐火物来作为工业窑炉的内衬用的浇注材料时，是经过耐火材料和水的混炼工序、浇注工序、养护工序、干燥工序来进行施工。
另一方面，也存在有将不定形耐火物作为工业窑炉的筑炉或修补用的喷涂材料来使用的情况。此刻，施工方法大致分为湿式喷涂施工方法和干式喷涂施工方法。湿式喷涂施工方法为，通过混炼机等机械混炼机构事先将喷涂材料和水充分混炼，用泵将该混炼后的混炼物朝向喷涂喷嘴压送，在该喷涂喷嘴的顶端部上导入空气和速凝剂来进行喷涂的施工方法。干式喷涂施工方法为，不介由机械混炼机构，而是在喷涂喷嘴的顶端部上，向干粉状的喷涂材料中添加水来进行喷涂的施工方法。
通常，使用喷涂材料的喷涂施工在热及冷的任意的环境下均可进行，并且干式喷涂施工方法在该双方的环境下均可适用。但是，通常在热的环境下不应用湿式喷涂施工方法。这是因为，在湿式喷涂施工方法的情况下，由于需要事先的混炼作业，因此在施工后，产生有输送软管的清洗作业等后处理作业，所述输送软管为，在用混炼机、泵进行压送时所使用的输送软管。因此，在热的环境下，喷涂施工不适合使用湿式施工方法，而多是应用了施工方法简单的干式喷涂施工方法。
作为该干式喷涂施工方法所使用的喷涂材料(干式喷涂用不定形耐火物)，在专利文献1中公开有一种包含苦土石灰石的喷涂材料。然而，本发明者们发现，在使用包含苦土石灰石的喷涂材料来进行热喷涂施工时，尤其是在耐腐蚀性上存在有改善的余地。
专利文献
专利文献1：日本特开昭58-145660号公报
发明内容
本发明所要解决的技术问题是，在热用干式喷涂材料及干式热喷涂施工方法上，使耐腐蚀性提高。
为了在热用干式喷涂材料及干式热喷涂施工方法上使耐腐蚀性提高，本发明者们尤其着眼于耐炉渣渗透性而进行了反复研究，发现粒径0.075mm以上且小于1mm的苦土石灰石有助于大幅提高耐炉渣渗透性，以至于完成了本发明。
即，根据本发明的一个观点，提供了以下的热用干式喷涂材料。
一种热用干式喷涂材料，包含耐火原料和粘合剂，其特征在于，
在所述耐火材料及所述粘合剂的总量100质量％中，包含10质量％以上50质量％以下的粒径0.075mm以上且小于1mm的苦土石灰石，
在所述耐火原料及粘合剂的总量100质量％中，粒径小于0.075mm的苦土石灰石的含量为35质量％以下(包含0)。
此外，根据本发明的其他观点，提供了以下的干式热喷涂施工方法。
一种干式热喷涂施工方法，将包含耐火材料及粘合剂的配合物通过配管朝向喷涂喷嘴压送，在所述喷涂喷嘴的顶端部上添加水，并在热中进行喷涂，其特征在于，
所述配合物在所述耐火材料及所述粘合剂的总量100质量％中，包含10质量％以上50质量％以下的粒径0.075mm以上且小于1mm的苦土石灰石，
在所述耐火原料及粘合剂的总量100质量％中，粒径小于0.075mm的苦土石灰石的含量为35质量％以下(包含0)。
另外，本发明所述的粒径是指，用筛对耐火材料粒子进行筛选分离时的筛目的大小，例如粒径小于0.075mm的苦土石灰石是指，通过了筛目为0.075mm的筛的苦土石灰石，粒径0.075mm以上的苦土石灰石是指，未通过筛目为0.075mm的筛的苦土石灰石。
根据本发明，通过使粒径0.075mm以上且小于1mm的苦土石灰石的含量在特定范围内，可提高耐炉渣渗透性，其结果可提高耐腐蚀性。
附图说明
图1是表示粘接性的评价方法的说明图。
具体实施方式
本发明的热用干式喷涂材料在耐火材料及粘合剂的总量(以下称为“总量”)100质量％中，包含10质量％以上50质量％以下的粒径0.075mm以上且小于1mm的苦土石灰石(以下称为“中粒的苦土石灰石”)。
该中粒的苦土石灰石(CaCO3·MgCO3)因工作受热时的脱气反应(CaCO3·MgCO3→CaO·MgO+2CO2)，而在其内部生成有空隙，且生成高反应性的游离CaO。如此，由工作面渗透来的炉渣被捕集在所生成的空隙中，进而与游离CaO反应，生成高熔点组合物2CaO·SiO2(熔点2130℃)，从而抑制了炉渣的渗透。
当中粒的苦土石灰石的含量小于10质量％时，则无法充分发挥炉渣渗透抑制效果(耐炉渣渗透性提高效果)，从而无法得到足够的耐腐蚀性提高效果。另一方面，当苦土石灰石的含量超过50质量％时，则因脱气反应而生成有过量的空隙(开放气孔)，其结果会助长炉渣渗透并降低耐腐蚀性。
优选在总量100质量％中，中粒的苦土石灰石的含量为20质量％以上40质量％以下。
本发明的热用干式喷涂材料可包含粒径小于0.075mm的苦土石灰石(以下称为“微粒的苦土石灰石”)。
在此，虽然微粒的苦土石灰石也会因前述的脱气反应而生成CaO，但由于该CaO是由与水的接触面积较大的微粒的苦土石灰石而生成，因此容易引起水合反应(CaO+2H2O→Ca2++2OH-)，由该水合反应而产生的Ca2+与粘合剂等反应被认为有助于喷涂施工体的基质部的结合强化(高强度化)，且被认为无助于前述的高熔点组合物生成。
可是，当包含大量微粒的苦土石灰石时，则前述的脱气反应所造成的影响(空隙形成的影响)变得比前述的基质部的结合强化(高强度化)作用更强，会导致在基质部中生成过量的空隙，其结果，在引起喷涂施工体强度的显著下降的同时，还会引起耐腐蚀性的下降。因而，在总量100质量％中，微粒的苦土石灰石的含量为35质量％以下(包含0)。
另一方面，由于微粒的苦土石灰石如前所述可得到基质部的结合强化(高强度化)作用，因此从积极利用该基质部的结合强化(高强度化)作用来提高粘接性(在喷涂后，工业窑炉进行工作后的喷涂材料与被施工面的粘接性)的观点出发，优选在总量100质量％中，微粒的苦土石灰石的含量为5质量％以上35质量％以下，更优选为5质量％以上25质量％以下。
本发明的热用干式喷涂材料也可包含粒径1mm以上的苦土石灰石(以下称为“粗粒的苦土石灰石”)。可是，由于粗粒的苦土石灰石因前述的脱气反应而生成有较大的空隙，因此当包含大量粗粒的苦土石灰石时，则容易发生炉渣渗透，导致耐腐蚀性趋于下降。因而，优选在总量100质量％中，粗粒的苦土石灰石的含量为50质量％小于(包含0)。
如上，通过使各粒度的苦土石灰石之中尤其是中粒的苦土石灰石的含量在特定范围内，可得到本发明的前述的炉渣渗透抑制效果(耐炉渣渗透性提高效果)。
作为苦土石灰石以外的耐火材料，本发明的热用干式喷涂材料可包含通常用于喷涂材料的各种耐火材料，但考虑到与苦土石灰石的相容性，优选其主体为氧化镁、橄榄石(olivine)、使用后的氧化镁碳质砖碎屑等碱性耐火材料(碱性氧化物)。作为碱性耐火材料以外的耐火材料，可包含氧化铝等。
粘合剂可使用通常作为结合材料而用于干式喷涂材料的粘合剂，例如可列举磷酸盐、硅酸盐、沥青、粉末树脂、高铝水泥等，但典型而言，可使用包含选自磷酸盐及硅酸盐之中至少1种的粘合剂。作为磷酸盐，有磷酸钠、磷酸钾、磷酸锂、磷酸钙、磷酸镁、磷酸铝等，作为硅酸盐，有硅酸钠、硅酸钾、硅酸钙等。此外，粘合剂的使用量(含量)可与通常的干式喷涂材料相同，例如在总量100质量％中，为1质量％以上10质量％以下。
另外，也可以在粘合剂中使用添加剂。作为添加剂，可使用固化剂、分散剂、增粘剂等各种添加剂。例如，作为固化剂可使用熟石灰，作为分散剂可使用磷酸盐、作为增粘剂可使用粘土。
如上的本发明的热用干式喷涂材料被用于干式热喷涂施工方法，所述干式热喷涂施工方法为，将如前所述的包含耐火材料及粘合剂的配合物通过配管朝向喷涂喷嘴压送，在该喷涂喷嘴的顶端部上添加水，并在热中进行喷涂。
水的添加量可与通常的干式热喷涂施工方法相同，例如相对于总量100质量％，通过外掺为10质量％以上40质量％以下。
实施例
表1示出本发明的热用干式喷涂材料的实施例及比较例的原材料构成和评价结果。另外，在表1中，粘合剂的“其他”是指粘土、熟石灰、分散剂等。
评价项目和评价方法如下。
<耐腐蚀性>
将各例的热用干式喷涂材料从喷涂喷嘴以15kg/分钟的喷涂量朝向作为被施工面而被加热到1000℃的氧化镁砖的表面喷涂1分钟。此刻，在喷涂喷嘴的顶端部上添加的水的添加量为，相对于总量100质量％，通过外掺为20质量％。
通过实施1分钟的喷涂，得到包含大致50mm厚的喷涂材料的施工体的喷涂施工体。使用旋转侵蚀试验机，以C/S＝1.0的合成炉渣为侵蚀剂，在1650～1700℃下，使从该喷涂施工体切出的规定尺寸的试样侵蚀3小时。测定了各例的最大熔损量，并求出以实施例1的最大熔损量为100的相对量。该相对量越小则耐腐蚀性(耐炉渣渗透性)越高。在耐腐蚀性的评价中，将该相对量为100以下的情况作为◎(良)，将超过100且110以下的情况作为○(可)，将超过110的情况作为×(不可)。
<喷涂施工体强度>
遵照日本工业标准JISR2575，针对从由前述的要领而得到的各例的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◎(良)，将70以上80小于的情况作为○(可)，将70小于的情况作为×(不可)。
<粘接性>
如图1的上层所示，在羊羹状的氧化镁砖的中央设置了15mm的间隔，在该间隔中，对在各例的喷涂材料中添加了水(相对于总量100质量％，通过外掺为20质量％)并混炼后的喷涂材料进行浇注、养护、干燥，其后如图1的下层所示，在由羊羹状物的顶端施加0.25MPa的负荷的状态下，在1400℃下烧成3小时而得到试片。通过3点弯曲试验对各例的试片测定了粘接面的弯曲强度，并求出以实施例1的弯曲强度为100的相对值。该相对值越大则粘接性越高。在粘接性的评价中，将该相对值为100以上的情况作为◎(良)，将超过60且小于100的情况作为○(可)。
该粘接性的评价是表示在实际的喷涂施工时，在喷涂后，工业窑炉进行工作后的喷涂材料与被施工面的粘接强度的指标。
<综合评价>
在前述的各评价中，将全部为◎的情况作为◎(良)，将无×且在任意一项上有○的情况作为○(可)，将任意一项为×的情况作为×(不可)。该综合评价是表示实际的喷涂施工体的耐用性的指标。
表1
Figure BDA0003004157860000071
实施例1～9是处于本发明的范围内的热用干式喷涂材料。综合评价均为◎(良)或○(可)，得到了良好的结果。
比较例1是中粒的苦土石灰石的含量较少的例子。无法充分得到炉渣渗透抑制效果(耐炉渣渗透性提高效果)，耐腐蚀性的评价为×(不可)。
比较例2是中粒的苦土石灰石的含量较多的例子。因前述的脱气反应而生成有过量的空隙(开放气孔)导致助长了炉渣渗透，其结果耐腐蚀性的评价为×(不可)。
比较例3是微粒的苦土石灰石的含量较多的例子。因前述的脱气反应所造成的影响，在基质部中生成有过量的空隙，其结果耐腐蚀性及喷涂施工体强度的评价为×(不可)。

Claims (4)

1.一种热用干式喷涂材料，包含耐火原料和粘合剂，其特征在于，
在所述耐火材料及所述粘合剂的总量100质量％中，包含10质量％以上50质量％以下的粒径0.075mm以上且小于1mm的苦土石灰石，
在所述耐火原料及粘合剂的总量100质量％中，粒径小于0.075mm的苦土石灰石的含量为35质量％以下且包含0。
2.根据权利要求1所述的热用干式喷涂材料，其特征在于，所述粘合剂包含选自磷酸盐及硅酸盐之中的至少1种。
3.根据权利要求1或2所述的热用干式喷涂材料，其特征在于，所述粒径小于0.075mm的苦土石灰石的含量为5质量％以上35质量％以下。
4.一种干式热喷涂施工方法，将包含耐火材料及粘合剂的配合物通过配管朝向喷涂喷嘴压送，在所述喷涂喷嘴的顶端部上添加水，并在热中进行喷涂，其特征在于，
所述配合物在所述耐火材料及所述粘合剂的总量100质量％中，包含10质量％以上50质量％以下的粒径0.075mm以上且小于1mm的苦土石灰石，
在所述耐火原料及粘合剂的总量100质量％中，粒径小于0.075mm的苦土石灰石的含量为35质量％以下且包含0。
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