CN114956771B - 一种无机复合型矿用注浆加固材料 - Google Patents

一种无机复合型矿用注浆加固材料 Download PDF

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CN114956771B
CN114956771B CN202210475341.9A CN202210475341A CN114956771B CN 114956771 B CN114956771 B CN 114956771B CN 202210475341 A CN202210475341 A CN 202210475341A CN 114956771 B CN114956771 B CN 114956771B
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陈晓祥
郑钧予
王兵建
王成
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Shanxi Zhongkuang Weite Mining Technology Development Co ltd
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Abstract

本发明提供一种无机复合型矿用注浆加固材料，首次将碳纳米管和纳米二氧化硅复合材料加到浆料中，不仅仅通过填充效应使得水泥结石体的孔隙率低，更加密实，而且纳米二氧化硅可以促进生成更多的C‑S‑H凝胶作为注浆加固材料的胶结相，提高材料的力学性能和耐久性；通过酸处理不仅仅使得两端开口从而方便将二氧化硅内嵌到管体中，同时也利用纳米管的限域效应使得二氧化硅体积不再增大从而增大其比表面积减少使用量，复合材料通过与基体协同变形，提高水泥基材料本身的抗拉强度的同时也使结石体更加密实，同时，对纳米无机材料进行表面改性使其与浆料有更好的相容性提高其分散性能无需使用表面活性剂。

Description

一种无机复合型矿用注浆加固材料
技术领域
本发明属于注浆充填材料技术领域，尤其涉及一种无机复合型矿用注浆加固材料。
背景技术
煤炭是我国的主要能源，煤炭资源的开采在我国具有举足轻重的作用，现有煤层注浆材料主要分为普通硅酸盐水泥类和有机高分子材料类两种。普通硅酸盐水泥具有价格低廉，施工操作简单，粘结煤体后具有一定抵抗巷道变形的能力成为注浆加固破碎岩石的首选材料。
中国专利CN103553489B公开了一种粉煤灰水泥基充填材料及其制备方法，该充填材料由粉煤灰、水泥、复合外加剂、铝粉和水配比组合而成，对生产设备及人员要求低，生产周期短，生产成本低，虽然粉煤灰的加入可以提高浆体流动性，改善颗粒级配，但是浆液的强度也会降低。中国专利CN112679168A公开了一种高强度矿用无机发泡充填材料，主要应用于煤矿散碎岩体加固和巷道孔洞充填，一维材料碳纳米管的加入，使充填材料更加致密化，进而极大增强材料发泡固化后的抗压强度、抗折强度和韧性，但是通常由电弧法或者CVD法制备得到的碳纳米管由于两端封闭形成的空管效应，造成在水泥结石体毛细孔中的填充效应强度降低，且由于碳纳米管本身具有团聚效应，加固后的力学性能可能难以达到预期效果。
因此，如何提供一种性能指标更好的矿用注浆加固材料是人们一直希望能够得到解决的问题。
发明内容
针对上述现有技术，本发明提供了提供一种无机复合型矿用注浆加固材料，所包含组份及对应的重量份为：水泥 20~33重量份，粉煤灰 22~38重量份，内嵌有二氧化硅的改性碳纳米管 0.1~0.3重量份，微硅粉 25~35重量份，减水剂0.2-8份，速凝剂1.5-3.5份，膨胀剂1.5-3.5份。
优选的，所述水泥为硅酸盐水泥、磷酸盐水泥、硫铝酸盐水泥或磷铝酸盐水泥中的至少一种；作为优选，所述水泥为硫铝酸盐水泥。
优选的，所述粉煤灰粒径为1~50μm。
优选的，所述微硅粉粒径为0.1~0.5μm。
优选的，所述减水剂为市售FDN-8000、FDN-03、FDN-C或者KS-20减水剂；膨胀剂为铝酸盐类膨胀剂或硫铝酸盐类膨胀剂；速凝剂为市售J85或8880型速凝剂。
所述内嵌有二氧化硅的改性碳纳米管制备方法包括以下步骤：
1）将称量好的碳纳米管加入体积比3：1的浓硫酸与浓硝酸混合溶液中，然后将碳纳米管和混酸转移至搅拌反应器中，在80-120℃下回流1-3h，经稀释、抽滤、清洗数次后干燥得到两端开口且有羧基修饰的碳纳米管；
2）将步骤1）得到的产物置于反应管中部，程序升温至600 ℃然后向反应管中通入气相二氧化硅，流速为200-1000 ml/min，保持2-4 h，得到内嵌有二氧化硅的改性碳纳米管。
优选的，所述气相二氧化硅通过四氯化硅火焰水解法制备得到。
优选的，所述碳纳米管为短多壁碳纳米管，其长度为0.5-2μm，管内径5-10 nm，外径10-20 nm，比表面积>200 m2/g，堆积密度为0.22 g/cm3，真实密度约2.1 g/cm3，导电率>100 s/cm。
与现有技术相比，本发明所提供的无机复合型矿用注浆加固材料首次将碳纳米管和纳米二氧化硅复合材料加到浆料中，不仅仅通过填充效应使得水泥结石体的孔隙率低，更加密实，而且纳米二氧化硅可以促进生成更多的C-S-H凝胶作为注浆加固材料的胶结相，提高材料的力学性能和耐久性；通过酸处理不仅仅使得两端开口从而方便将二氧化硅内嵌到管体中，同时也利用纳米管的限域效应使得二氧化硅体积不再增大从而增大其比表面积减少使用量，复合材料通过与基体协同变形，提高水泥基材料本身的抗拉强度的同时也使结石体更加密实，同时，对纳米无机材料进行表面改性使其与浆料有更好的相容性提高其分散性能无需使用表面活性剂。
附图说明
图1是实施例1制备得到的内嵌有二氧化硅的改性碳纳米管TEM图。
具体实施方式
以下通过具体实施例详细说明本发明技术方案的实施和所具有的有益效果，但不能认定为对本发明的可实施范围的任何限定。
实施例1
一种无机复合型矿用注浆加固材料，所包含组份及对应的重量份为：硫铝酸盐水泥 25重量份，粉煤灰 28重量份，内嵌有二氧化硅的改性碳纳米管 0.1重量份，微硅粉 30重量份，减水剂2份，速凝剂2.5份，膨胀剂3份，其中，粉煤灰粒径为1~50μm，所述微硅粉粒径为0.1~0.5μm，所述减水剂为KS-20减水剂；膨胀剂为硫铝酸盐类膨胀剂；速凝剂为8880型速凝剂。
所述内嵌有二氧化硅的改性碳纳米管制备方法包括以下步骤：
1）将称量好的碳纳米管加入体积比3：1的浓硫酸与浓硝酸混合溶液中，然后将碳纳米管和混酸转移至搅拌反应器中，在100℃下回流2h，经稀释、抽滤、清洗数次后干燥得到两端开口且有羧基修饰的碳纳米管；
2）将步骤1）得到的产物置于反应管中部，以10 ℃/min升温速率升至600 ℃然后向反应管中通入气相二氧化硅，流速为800 ml/min，保持3 h，得到内嵌有二氧化硅的改性碳纳米管（见图1）。
对比例1
一种无机复合型矿用注浆加固材料，所包含组份及对应的重量份为：硫铝酸盐水泥 25重量份，粉煤灰 28重量份，碳纳米管 0.08重量份，纳米二氧化硅0.02中两份，微硅粉30重量份，减水剂2份，速凝剂2.5份，膨胀剂3份，其中，粉煤灰粒径为1~50μm，所述微硅粉粒径为0.1~0.5μm，所述减水剂为KS-20减水剂；膨胀剂为硫铝酸盐类膨胀剂；速凝剂为8880型速凝剂。
将实施例1和对比例1的两种注浆加固材料分别通过自流平施工，硬化后抗压强度提高20%以上，拉伸强度提高10%以上。

Claims (8)

1.一种无机复合型矿用注浆加固材料，其特征在于，包含组份及对应的重量份为：水泥20～33重量份，粉煤灰 22～38重量份，内嵌有二氧化硅的改性碳纳米管 0.1～0.3重量份，微硅粉 25～35重量份，减水剂0.2-8份，速凝剂1.5-3.5份，膨胀剂1.5-3.5份；
所述内嵌有二氧化硅的改性碳纳米管制备方法包括以下步骤：
1）将称量好的碳纳米管加入体积比3：1的浓硫酸与浓硝酸混合溶液中，然后将碳纳米管和混酸转移至搅拌反应器中，在80-120℃下回流1-3h，经稀释、抽滤、清洗数次后干燥得到两端开口且有羧基修饰的碳纳米管；
2）将步骤1）得到的产物置于反应管中部，程序升温至600℃然后向反应管中通入气相二氧化硅，流速为200-1000ml/min，保持2-4h，得到内嵌有二氧化硅的改性碳纳米管。
2.根据权利要求1所述一种无机复合型矿用注浆加固材料，其特征在于，所述水泥为硅酸盐水泥、磷酸盐水泥、硫铝酸盐水泥或磷铝酸盐水泥中的至少一种。
3.根据权利要求2所述一种无机复合型矿用注浆加固材料，其特征在于，所述水泥为硫铝酸盐水泥。
4.根据权利要求1所述一种无机复合型矿用注浆加固材料，其特征在于，所述粉煤灰粒径为1～50μm。
5.根据权利要求1所述一种无机复合型矿用注浆加固材料，其特征在于，所述微硅粉粒径为0.1～0.5μm。
6.根据权利要求1所述一种无机复合型矿用注浆加固材料，其特征在于，所述减水剂为市售FDN-8000、FDN-03、FDN-C或者KS-20减水剂；膨胀剂为铝酸盐类膨胀剂或硫铝酸盐类膨胀剂；速凝剂为市售J85或8880型速凝剂。
7.根据权利要求1所述一种无机复合型矿用注浆加固材料，其特征在于，
所述气相二氧化硅通过四氯化硅火焰水解法制备得到。
8.根据权利要求1所述一种无机复合型矿用注浆加固材料，其特征在于，所述碳纳米管为短多壁碳纳米管，其长度为0.5-2μm，管内径5-10nm，外径10-20nm，比表面积>200m2/g，堆积密度为0.22g/cm3，真实密度2.1g/cm3，导电率>100s/cm。
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