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CN113354427B - 一种耐火材料的热修补料 - Google Patents

一种耐火材料的热修补料 Download PDF

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Publication number
CN113354427B
CN113354427B CN202110787639.9A CN202110787639A CN113354427B CN 113354427 B CN113354427 B CN 113354427B CN 202110787639 A CN202110787639 A CN 202110787639A CN 113354427 B CN113354427 B CN 113354427B
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silicon
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CN113354427A (zh
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杨自春
陈国兵
杨飞跃
赵爽
费志方
陈俊
李军
张磊
李昆锋
孙文彩
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Naval University of Engineering PLA
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Abstract

本发明公开了一种耐火材料的热修补料，具体为增压锅炉中的碳化硅耐火材料的快速热修补料，原料包括主材质和结合剂，主材质包括6种不同粒径等级的碳化硅粉末，按粒径由高到低对应的质量比为8：5：8：15：8：10；结合剂包括氮化硅粉、硅酸钠粉、磷酸铝粉、糠醇、有机硅树脂粉、硅溶胶粉、铝溶胶粉、氧化硅微粉、氧化钒粉、硅粉、硼砂和稀土氧化物微粉，对应的质量比为20：10：4：1：5：1：1：2：0.5：0.5：0.5：0.5。主材质中不同粒径的碳化硅粉末具有良好的协同作用，可强化修补料的强度。结合剂中包含低温、中温和高温结合剂，适用于全区段温域，可使修补料连续地获得强度，使材料没有溃点温度。

Description

一种耐火材料的热修补料
技术领域
本发明属于耐火材料快速修补技术领域，具体涉及一种耐火材料的热修补料。
背景技术
耐火材料为耐火度不低于1580℃的一类无机非金属材料，广泛用于动力、冶金、化工、石油、机械制造、硅酸盐等工业领域。船舶中增压锅炉所用碳化硅耐火材料属于易损部件，在船舶受冲击和振动时更易脱落、坍塌，将直接导致停炉和动力丧失，必须尽快进行维修。但是由于锅炉炉膛处于高温状态，即使采用强制通风，仍需在30小时以后，才能进人进行维修更换，显然不能满足连续作业的要求。因此，开展快速热修补技术研究，具有十分重要的意义。
修补料是由具有一定颗粒级配的耐火材料、化学结合剂和外加剂组成的，用喷射施工方法对热工设备(如增压锅炉)内衬进行修补时使用的不定形耐火材料。修补过程是用机械方法将特殊组成的耐火材料修补在内衬表面以防止内衬蚀损，修补的料层经受锅炉的热负荷，保护耐火内衬免受火焰等侵害。针对锅炉高温时的修补有两种情况：一种是对局部凹陷处与蚀损坑的应急性修补；一种是对全部表面进行系统修补。根据物料在修补过程中的状态，通常修补方法分为：火焰修补、干法修补、半干法修补、湿法修补。火焰修补法是使物料在火焰中行进并熔融成塑态射到受补面上，该法主要热态修补炉衬，对原衬损伤少，喷涂层易烧结，使用寿命长，但成本较高，工艺也不够成熟。干法修补是运送不含水分的的干粉，在喷嘴部位添加水分的方法，该方法应用广泛，但存在粉尘以及回弹量比较多、施工性能较差等缺点。半干法修补是将混合料与通过喷枪的水环孔眼的水混合，由压缩空气喷射到修补面上的一种方法，具有修补层体积密度大，收缩较小的特点，可获得较厚的修补层，耐用性也较好，但回弹率仍较高。
湿法修补是近年来兴起并得以广泛使用的修补方法，是指将耐火骨料、基质、结合剂、添加剂与水混合制成泥浆，通过压缩空气将泥浆喷射到修补面上的一种方法。湿法修补大约在70年代后期开始在各种类型的窑炉上得以应用，但是由于施工及材料性能的问题，仅局限于很小的应用范围，还不能被广范应用。新的湿法修补技术从90年代起，首先在钢包上开始使用，到目前为止推广到各种冶金窑炉、燃烧炉、水泥制造业等众多行业的多种用途的炉窑上，得到了广泛的好评。该修补技术具有如下特点：可以修补任意厚度的炉衬；可以确保炉衬达到与浇注法施工同样的致密度；施工效率高、回弹损耗极小，可实现无粉尘施工。因此，湿法修补是未来的发展趋势。而在湿法修补的修补过程中，修补料的品质又是影响湿法修补效果的最重要的因素。当前，用于湿法修补的修补料主要为单一组成的骨料辅以一种或两种性能相似的结合剂，现有的修补料的原料组成及配比很难满足湿法修补的热修补方式下的工程要求，且形成的修补层存在粘结强度和抗折强度较差的问题，存在很大的改进空间，迫切需要改进传统意义上的湿法修补用修补料配方。
发明内容
本发明结合增压锅炉碳化硅耐火材料的理化性能组成、损伤模式和失效机理，提供了一种碳化硅耐火材料的热修补料，配比一定的不同粒径的碳化硅，具有良好的协同作用，可强化修补料的强度，经过优选的适用于全区段温域的复合结合剂可使修补料连续地获得强度，使材料没有溃点温度，可解决快速热修补增压锅炉中碳化硅耐火材料的难题。
为实现上述目的，本发明提供如下的技术方案：
本发明的技术方案，一种耐火材料的热修补料，原料包括主材质和结合剂，所述主材质包括不同粒径等级的碳化硅粉末，所述结合剂包括氮化硅粉、硅酸钠粉、磷酸铝粉、糠醇、树脂粉、溶胶粉、氧化硅微粉、氧化矾粉、硅粉、硼砂和稀土氧化物微粉。
进一步地，所述不同粒径等级的碳化硅粉末的粒径为3～0.038mm，具体包括6种不同粒径等级的碳化硅。
进一步地，所述6种不同粒径等级为2.5～3mm、2～2.5mm、1.25～2mm、1～1.25mm、0.9～1mm、0.8～0.9mm、0.6～0.8mm、0.5～0.6mm、0.4～0.5mm、0.3～0.4mm、0.25～0.3mm、0.2～0.25mm、0.15～0.2mm、0.1～0.15mm、0.044～0.074mm、0.038～0.044mm中的6种。
进一步地，所述6种不同粒径等级的碳化硅按粒径由高到低对应的质量比为8：5：8：15：8：10。
进一步地，所述6种不同粒径等级优选为2.5～3mm、2～2.5mm、1.25～2mm、1～1.25mm的一种，0.9～1mm、0.8～0.9mm、0.6～0.8mm、0.5～0.6mm中的1种，0.4～0.5mm、0.3～0.4mm、0.25～0.3mm中的1种，0.2～0.25mm、0.15～0.2mm、0.1～0.15mm中的1种，以及0.044～0.074mm和0.038～0.044mm。
进一步地，所述树脂粉为有机硅树脂粉，所述溶胶粉为硅溶胶粉和铝溶胶粉。
进一步地，所述氮化硅粉的粒径≤0.5mm，具体包括2种不同粒径等级的氮化硅，所述2种不同粒径等级选自以下4种中的1种：≤0.044mm和0.044～0.15mm、≤0.044mm和0.15～0.25mm、≤0.044mm和0.25～0.4mm、≤0.044mm和0.4～0.5mm。
进一步地，所述2种不同粒径等级的氮化硅按粒径由高到低对应的质量比为10：10。
进一步地，所述硅酸钠粉、磷酸铝粉、树脂粉、溶胶粉、氧化钒粉、硼砂的粒径均≤0.074mm，所述硅粉的粒径≤0.044mm，所述氧化硅微粉的粒径≤5μm，所述稀土氧化物微粉的粒径≤3μm。
进一步地，氮化硅粉、硅酸钠粉、磷酸铝粉、糠醇、有机硅树脂粉、硅溶胶粉、铝溶胶粉、氧化硅微粉、氧化矾粉、硅粉、硼砂、稀土氧化物微粉对应的质量比为20：10：4：1：5：1：1：2：0.5：0.5：0.5：0.5。
进一步地，所述耐火材料为增压锅炉中的碳化硅耐火材料。
与现有技术相比，本发明具有以下有益效果：
本发明以经过优选配比的6种不同粒径等级的碳化硅作为修补料的主材质，6种不同粒径等级的碳化硅具有良好的协同作用，可强化修补料的强度。本发明配方体系中的结合剂中包含三种复合结合剂：有机硅树脂作为低温(530℃以下)结合剂；硅溶胶和铝溶胶的预混粉作为中温(530～1200℃)结合剂；氧化硅微粉和氧化钒粉则作为高温(1100℃以上)结合剂。以上三类结合剂能够适应不同的温度，三类结合剂协同作用，保证在不同温度下材料强度连续获得，使材料没有溃点温度。另外，结合剂中的氮化硅粉、硅酸钠粉、磷酸铝粉、糠醇、硅粉、硼砂、稀土氧化物微粉等可起到混合增强的作用。本发明配方体系中主材质和结合剂中的各原料都有不同的粒径等级要求，采用粒径粗细不同的原料混合搭配能起到提高原料颗粒分散效果、增强修补料强度的作用。本发明的热修补材料有效解决了快速热修补增压锅炉中碳化硅耐火材料的难题，应用前景广阔。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为实施例1配制的修补料经高温烧结后的XRD图谱。
图2为实施例2配制的修补料经高温烧结后的XRD图谱。
具体实施方式
现详细说明本发明的多种示例性实施方式，该详细说明不应认为是对本发明的限制，而应理解为是对本发明的某些方面、特性和实施方案的更详细的描述。
应理解本发明中所述的术语仅仅是为描述特别的实施方式，并非用于限制本发明。另外，对于本发明中的数值范围，应理解为还具体公开了该范围的上限和下限之间的每个中间值。在任何陈述值或陈述范围内的中间值以及任何其他陈述值或在所述范围内的中间值之间的每个较小的范围也包括在本发明内。这些较小范围的上限和下限可独立地包括或排除在范围内。
除非另有说明，否则本文使用的所有技术和科学术语具有本发明所述领域的常规技术人员通常理解的相同含义。虽然本发明仅描述了优选的方法和材料，但是在本发明的实施或测试中也可以使用与本文所述相似或等同的任何方法和材料。本说明书中提到的所有文献通过引用并入，用以公开和描述与所述文献相关的方法和/或材料。在与任何并入的文献冲突时，以本说明书的内容为准。
在不背离本发明的范围或精神的情况下，可对本发明说明书的具体实施方式做多种改进和变化，这对本领域技术人员而言是显而易见的。由本发明的说明书得到的其他实施方式对技术人员而言是显而易见的。本发明说明书和实施例仅是示例性的。
关于本文中所使用的“包含”、“包括”、“具有”、“含有”等等，均为开放性的用语，即意指包含但不限于。
实施例1
使用筛网筛选并称取粒径分别为1～1.25mm、0.5～0.6mm、0.25～0.3mm、0.1～0.15mm、0.044～0.074mm、0.038～0.044mm的碳化硅粉作为修补料主材质，对应的质量比为8：5：8：15：8：10。选取质量比为20：10：4：1：5：1：1：2：0.5：0.5：0.5：0.5的氮化硅粉、硅酸钠粉、磷酸铝粉、糠醇、有机硅树脂粉、硅溶胶粉、铝溶胶粉、氧化硅微粉、氧化钒粉、硅粉、硼砂、稀土氧化物微粉作为结合剂。其中，氮化硅粉的粒径为0.044～0.15mm、≤0.044mm，对应的质量比为10：10；硅酸钠粉、磷酸铝粉、有机硅树脂粉、硅溶胶粉、铝溶胶粉、氧化钒粉、硼砂的粒径≤0.074mm；氧化硅微粉的粒径≤5μm；稀土氧化物微粉的粒径≤3μm；硅粉的粒径≤0.044mm。
将上述粉料按比例充分混合搅拌后得到修补料，包装存放，液态原料糠醇则在使用前加入。
将本实施例配制的修补料经1300℃高温烧结4h后进行化学全分析及X射线衍射检测，经高温烧结后的修补料的成分组成如表1所示，XRD图谱如图1所示。
表1
Figure BDA0003159677600000071
实施例2
使用筛网筛选并称取粒径分别为1.25～2mm、0.6～0.8mm、0.3～0.4mm、0.15～0.2mm、0.044～0.074mm、0.038～0.044mm的碳化硅粉作为修补料主材质，对应的质量比为8：5：8：15：8：10。选取质量比为20：10：4：1：5：1：1：2：0.5：0.5：0.5：0.5的氮化硅粉、硅酸钠粉、磷酸铝粉、糠醇、有机硅树脂粉、硅溶胶粉、铝溶胶粉、氧化硅微粉、氧化钒粉、硅粉、硼砂、稀土氧化物微粉作为结合剂。其中，氮化硅粉的粒径为0.15～0.25mm、≤0.044mm，对应的质量比为10：10；硅酸钠粉、磷酸铝粉、有机硅树脂粉、硅溶胶粉、铝溶胶粉、氧化钒粉、硼砂的粒径≤0.074mm；氧化硅微粉的粒径≤5μm；稀土氧化物微粉的粒径≤3μm；硅粉的粒径≤0.044mm。
将上述粉料按比例充分混合搅拌后得到修补料，包装存放，液态原料糠醇则在使用前加入。
将本实施例配制的修补料经1400℃高温烧结4h后进行X射线衍射检测，XRD图谱如图2所示。
实施例3
使用筛网筛选并称取粒径分别为2～2.5mm、0.8～0.9mm、0.4～0.5mm、0.2～0.25mm、0.044～0.074mm、0.038～0.044mm的碳化硅粉作为修补料主材质，对应的质量比为8：5：8：15：8：10。选取质量比为20：10：4：1：5：1：1：2：0.5：0.5：0.5：0.5的氮化硅粉、硅酸钠粉、磷酸铝粉、糠醇、有机硅树脂粉、硅溶胶粉、铝溶胶粉、氧化硅微粉、氧化钒粉、硅粉、硼砂、稀土氧化物微粉作为结合剂。其中，氮化硅粉的粒径为0.25～0.4mm、≤0.044mm，对应的质量比为10：10；硅酸钠粉、磷酸铝粉、有机硅树脂粉、硅溶胶粉、铝溶胶粉、氧化钒粉、硼砂的粒径≤0.074mm；氧化硅微粉的粒径≤5μm；稀土氧化物微粉的粒径≤3μm；硅粉的粒径≤0.044mm。
将上述粉料按比例充分混合搅拌后得到修补料，包装存放，液态原料糠醇则在使用前加入。
实施例4
使用筛网筛选并称取粒径分别为2.5～3mm、0.9～1mm、0.4～0.5mm、0.2～0.25mm、0.044～0.074mm、0.038～0.044mm的碳化硅粉作为修补料主材质，对应的质量比为8：5：8：15：8：10。选取质量比为20：10：4：1：5：1：1：2：0.5：0.5：0.5：0.5的氮化硅粉、硅酸钠粉、磷酸铝粉、糠醇、有机硅树脂粉、硅溶胶粉、铝溶胶粉、氧化硅微粉、氧化钒粉、硅粉、硼砂、稀土氧化物微粉作为结合剂。其中，氮化硅粉的粒径为0.4～0.5mm、≤0.044mm，对应的质量比为10：10；硅酸钠粉、磷酸铝粉、有机硅树脂粉、硅溶胶粉、铝溶胶粉、氧化钒粉、硼砂的粒径≤0.074mm；氧化硅微粉的粒径≤5μm；稀土氧化物微粉的粒径≤3μm；硅粉的粒径≤0.044mm。
将上述粉料按比例充分混合搅拌后得到修补料，包装存放，液态原料糠醇则在使用前加入。
对比例1
同实施例1，区别在于，主材质全部选用粒径为1～1.25mm的碳化硅粉，其用量为实施例1中6种不同粒径的碳化硅粉的总用量。
对比例2
同实施例1，区别在于，氮化硅粉全部选用粒径为0.044～0.15mm的氮化硅粉，其用量为实施例1中2种不同粒径的氮化硅粉的总用量。
对比例3
同实施例1，区别在于，省略有机硅树脂粉的使用。
对比例4
同实施例1，区别在于，省略硅溶胶粉和铝溶胶粉的使用。
对比例5
同实施例1，区别在于，省略氧化硅微粉和氧化钒粉的使用。
效果验证
选取实施例1-4和对比例1-5配制的修补料进行粘结强度和抗折强度的测试。
根据GB/T 8642-2002、GB/T 4513.6-2017分别检测了修补料的粘结强度及抗折强度。具体测试结果如表2所示：
表2
粘结强度(MPa) 抗折强度(MPa)
实施例1 6.3 48.1
实施例2 5.9 46.9
实施例3 6.0 44.7
实施例4 5.5 41.9
对比例1 4.0 32.6
对比例2 5.1 40.2
对比例3 4.5 38.8
对比例4 4.1 34.7
对比例5 4.3 36.3
由表2的测试结果可以看出，选用6种不同粒径等级的碳化硅粉末作为修补料的主材质比仅选用1种粒径等级的碳化硅粉末作为修补料的主材质得到的修补料的性能更好，说明主材质中不同粒径的碳化硅粉末具有良好的协同作用，可强化修补料的强度；选用2种不同粒径等级的氮化硅粉比仅选用1种粒径等级的氮化硅粉得到的修补料的性能更好，说明结合剂中不同粒径的氮化硅粉也具有一定的协同作用，可一定程度上提高修补料的性能；省略低温结合剂有机硅树脂、中温结合剂硅溶胶和铝溶胶、高温结合剂氧化硅微粉和氧化钒粉三者中的任何一种都会使修补料的性能下降，说明修补料中的低温结合剂、中温结合剂和高温结合剂成分协同作用，保证材料在不同温度下能够连续获得强度，使修补料具有更好的使用性能；主材质中不同粒径的碳化硅粉末、结合剂中不同粒径的氮化硅粉、以及结合剂中的低温结合剂、中温结合剂、高温结合剂间协同作用，得到性能最佳的修补料。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (5)

1.一种耐火材料的热修补料，其特征在于，原料包括主材质和结合剂，所述主材质包括不同粒径等级的碳化硅粉末，所述结合剂包括氮化硅粉、硅酸钠粉、磷酸铝粉、糠醇、树脂粉、溶胶粉、氧化硅微粉、氧化钒粉、硅粉、硼砂和稀土氧化物微粉；
所述不同粒径等级的碳化硅粉末的粒径为3～0.038mm，具体包括6种不同粒径等级的碳化硅；
所述6种不同粒径等级为2.5～3mm、2～2.5mm、1.25～2mm、1～1.25mm、0.9～1mm、0.8～0.9mm、0.6～0.8mm、0.5～0.6mm、0.4～0.5mm、0.3～0.4mm、0.25～0.3mm、0.2～0.25mm、0.15～0.2mm、0.1～0.15mm、0.044～0.074mm、0.038～0.044mm中的6种；
所述氮化硅粉的粒径≤0.5mm，具体包括2种不同粒径等级的氮化硅，所述2种不同粒径等级选自以下4种中的1种：≤0.044mm和0.044～0.15mm、≤0.044mm和0.15～0.25mm、≤0.044mm和0.25～0.4mm、≤0.044mm和0.4～0.5mm；
所述2种不同粒径等级的氮化硅按粒径由高到低对应的质量比为10：10；所述6种不同粒径等级的碳化硅按粒径由高到低对应的质量比为8：5：8：15：8：10。
2.根据权利要求1所述的一种耐火材料的热修补料，其特征在于，所述树脂粉为有机硅树脂粉，所述溶胶粉为硅溶胶粉和铝溶胶粉。
3.根据权利要求1所述的一种耐火材料的热修补料，其特征在于，所述硅酸钠粉、磷酸铝粉、树脂粉、溶胶粉、氧化钒粉、硼砂的粒径均≤0.074mm，所述硅粉的粒径≤0.044mm，所述氧化硅微粉的粒径≤5μm，所述稀土氧化物微粉的粒径≤3μm。
4.根据权利要求3所述的一种耐火材料的热修补料，其特征在于，氮化硅粉、硅酸钠粉、磷酸铝粉、糠醇、有机硅树脂粉、硅溶胶粉、铝溶胶粉、氧化硅微粉、氧化钒粉、硅粉、硼砂、稀土氧化物微粉对应的质量比为20：10：4：1：5：1：1：2：0.5：0.5：0.5：0.5。
5.根据权利要求1所述的一种耐火材料的热修补料，其特征在于，所述耐火材料为增压锅炉中的碳化硅耐火材料。
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