CN101370750A - 自流动耐火混合物 - Google Patents

自流动耐火混合物 Download PDF

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CN101370750A
CN101370750A CNA2006800527757A CN200680052775A CN101370750A CN 101370750 A CN101370750 A CN 101370750A CN A2006800527757 A CNA2006800527757 A CN A2006800527757A CN 200680052775 A CN200680052775 A CN 200680052775A CN 101370750 A CN101370750 A CN 101370750A
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mortar
less
fire
quality
gravity flow
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CN101370750B (zh
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T·尚皮翁
C·C·希斯
F·M·L·威勒姆
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Saint Gobain Centre de Recherche et dEtudes Europeen SAS
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Abstract

本发明涉及耐火自流动填料砂浆，包含相对于基础耐火材料以质量计，至少1％且至多10％的中值粒径大于或等于0.1μm且小于或等于2mm的未粒化的球形颗粒，还包含相对于砂浆总的干物质以质量计，少于4.5％氧化硅(SiO2)和1－8％水，未粒化的球形颗粒尺寸的标准偏差小于100％。

Description

自流动耐火混合物
技术领域
本发明涉及自流动耐火砂浆，特别是涉及制备烧结的耐火水泥或混凝土，以及使用这种砂浆通过自流动填充孔宽小于25mm的孔洞。
背景技术
根据由ASTM C71标准“关于耐火材料的标准术语”定义的术语称为“自流动”的耐火自流动砂浆是可在无需振动又不需要外部能量输入的情况下操作进行操作，同时不引起偏析的湿混合物。
因此，这些砂浆在难以进行振动或加压，甚至不可能进行振动或加压的应用中特别有用，例如用于填充宽度小于25mm、更通常小于10mm的小的有限空隙或裂缝。实际上，振动或充填工具不能进入这种空隙。为了能够基本上完全填充这种空隙，称为“填料砂浆”的耐火自流动砂浆典型地具有大于280、优选大于300的流动性值。
耐火自流动砂浆在石油化工焚烧炉或反应器的涂层领域中特别有用，例如用于填充反应器的耐火砖和金属外壳间的空隙。在这些应用中，耐火砂浆特别确保反应器金属外壳在耐火涂层偶然损坏的情况下例如在用于覆盖的耐火砖落下情况下的最终保护。从而，保护反应器金属外壳直到修复耐火涂层。
为了制备自流动的耐火砂浆，已知添加氧化硅烟尘形式或胶体状态的氧化硅。因此，通常氧化硅颗粒基本上是球形的，直径0.3-0.5μm。它们对于耐火混合料的流动性具有作用，不仅因为它们小的尺寸，而且因为它们能够与水分子通过范德华型键进行化学结合。因此它们通过Si-O-H键形成凝胶，该凝胶提供立体化学(stereochemical)作用。因此在混合物中添加水使其有效液化。
例如，EP 0,609,868描述了包含至少4.95％氧化硅、2-30％中值粒径至多30μm的球形颗粒的混合物。如果相对于干材料所述混合物包含至少6质量％水，那么根据ASTM C1446-99试验测量的这些混合物的流动性大于180mm。
然而，在耐火砂浆中存在氧化硅，无论其以氧化硅烟尘形式或以胶体状态，或在砂浆组分中引入例如以耐火粘土形式的氧化硅，均会损害通过烧结耐火自流动混合物获得的产品的某些性质。特别地，已知存在氧化硅对于温度大于或等于1500℃下的抗蠕变性有害。在特定操作条件下，存在氧化硅也有助于加速腐蚀和磨损，因为特别是在例如化学还原环境中、甚至包含气态氢的环境中以SiO形式显著蒸发。
也已知添加分散剂和大量水代替氧化硅，相对于干物料以质量计典型地大于或等于20％。因此耐火自流动混合物必须非常缓慢干燥以避免在烧结产品中出现裂纹。实际上，烧结产品的裂纹损害其机械强度，此外能使气体或液体渗透。因此这些自流动砂浆的操作导致增加的成本。
在细颗粒即尺寸小于200μm的陶瓷领域中已知另一种改善干混合物流动性的技术。根据这种技术，特别地通过常规造粒或雾化，颗粒基本上以球形团聚物形式团聚。然而，在颗粒状的颗粒混合物中添加水对于流动性显著有害。此外，添加水并不导致固化，而是使团聚物离解。因此，这些颗粒状的混合物不能用来制备自流动砂浆。
由JP 11,092,241还已知在浇注过程中或在压力下放置时具有改善的致密化能力的耐火砂浆。相对于包含球形颗粒和耐火氧化物粉末的基础耐火材料，这些混合物包含10-35质量％的直径0.1-2mm的球形粉末和至少9.8质量％水。这种水的添加对于自流动砂浆是不可接受的，因为当反应器中温度升高时它们导致裂纹。填料砂浆的限制导致这种裂纹，对于填装物料，用于水蒸发的自由表面不充分。它们使得产品特别易受气体或液体腐蚀，并抵销砂浆的保护功能。因此，耐火自流动填料砂浆的流动性值与添加水的质量％(相对于基础耐火材料的质量)的比值必须至少35。JP 11,092,241中给出的混合物仅表现出约14-19的比值。
此外，JP 11,092,241表明添加低于10％的球形粉末导致流动性的随后恶化，直径小于0.1mm的颗粒导致有害的偏析现象。
由JP 3-115,176还已知包含1-50质量％(相对于基础耐心材料)直径0.001-0.1mm的球形粉末的耐火混合料。这些混合物意图用于注浆，JP3-115,176目的在于提供对注浆具有低阻力的混合物。能用于注浆的混合物意图在喷浆装置中进行喷涂，或者“能被喷涂的混合物”与自流动砂浆具有几点不同性能。
首先，它们的作用并不是填充间隙，而是覆盖自由表面。可喷涂的混合物必须具有高的机械强度，这就解释了酚醛树脂或基于铝酸钙的水泥的高添加量(相对于球形颗粒及其它氧化物颗粒(或“团聚物”)的矿物质量，添加10-15质量％)。因此，这些混合物具有相对高的9.5-13质量％的添加水，相对于球形颗粒及其它氧化物颗粒的质量。因此，流动性值/添加水的百分比的比值为20-32，该比值不足以使这些混合物作为填料砂浆。发明人能够证实当砂浆嵌入具有低的自由表面的间隙中时，这样的水添加实际上导致裂纹。
此外，在产品的矿物组成中，注浆混合物通常具有15％的CaO铝酸盐含量。这种量对于抗腐蚀性特别不利。
另外，球化颗粒(例如JP3-115,176或JP11-092,241中给出的那些球化颗粒)通常具有宽度大于100％的尺寸分布，如在这些申请中具体说明的，对于使用是一种限制，并导致增加的水添加。
因此，需要耐火自流动填料砂浆，即特别具有至少280的流动性值，且流动性值与添加水的质量百分比(相对于基础耐火材料的质量)的比值至少35，这种砂浆允许制造与通过已知的含有氧化硅的自流动砂浆获得的烧结产品相比具有更好抗腐蚀性的烧结产品。
发明内容
根据本发明，通过包含下面组分的耐火自流动填料砂浆实现了该目的，
相对于基础耐火材料，以质量％计：
-至少1％，优选至少5％，更优选至少7％且至多10％的中值粒径大于或等于0.1μm且小于或等于2mm，优选小于或等于1mm，更优选小于或等于100μm，更更优选小于或等于1μm的未粒化的球形颗粒，及相对于砂浆总的干物质(包括基础耐火材料和干粘合剂)以质量％计
-少于4.5％的氧化硅(SiO2)，优选少于2％，更优选少于1％，更更优选没有氧化硅，及
-1-8％的水，优选少于5％，更优选少于4％，
通过未粒化的球形颗粒尺寸分布的标准偏差和该分布平均值间的比值测定的未粒化的球形颗粒尺寸的相对标准偏差小于100％，优选小于60％，更优选小于10％。
具体实施方式
以令人惊讶的方式，发明人发现根据本发明的自流动填料砂浆具有令人满意的流动性，而无需包含氧化硅，如在下文以更为详细的方式所看到的。
氧化硅量的限制有利地提供令人满意的抗腐蚀性。这种限制也能够改善抗蠕变性和抗开裂性。根据本申请，这种限制也能改善所得产品的其它性能。
优选地，根据本发明的砂浆还包含一种或多种下列可选性能：
-球形颗粒具有大于或等于0.8，优选大于或等于0.9的球形度。
-基于干材料，且优选也基于基础耐火材料物质，氧化铝量大于95质量％。有利地，由这种砂浆获得的烧结产品具有良好的抗蠕变性，即在压力下及固定温度下具有微弱的热尺寸变化。
本发明还涉及使用根据本发明的砂浆通过自流动填充宽度小于25mm的孔洞，优选宽度小于10mm且深度小于50mm的孔洞。
所谓的“团聚物”指的是在干燥砂浆前除添加剂(添加其用于粘结功能)之外的耐火颗粒，所述耐火颗粒不是未粒化的球形颗粒，即特别是非球形颗粒。
当颗粒不是通过微粒团聚，特别是并非通过常规造粒或通过雾化形成时，颗粒被称为“未粒化的”。
“基础耐火材料”或“基础耐火材料物质”指的是在干燥砂浆前除了添加用于粘结剂功能的添加剂之外的所有非氧化物耐火组分例如碳化硅或氮化硅Si3N4，或/和耐火氧化物，特别是基于Al2O3或ZrO2的耐火氧化物，添加剂例如临时粘结剂或例如基于CaO铝酸盐的水硬性粘结剂。基础耐火材料是主要组分，提供通过烧结砂浆获得的水泥的性质。该定义也排除了并不是耐火材料的水。因此基础耐火材料由团聚物和未粒化的球形颗粒组成。
分布的“宽度”或“相对标准偏差”是标准偏差和平均值间的比值。该比值以百分比显示。因此，100％宽度相应于等于平均值的标准偏差。
颗粒的“尺寸”是在该颗粒图像上测量的其最大尺寸。由倾倒在自粘毡(felt)上的这种粉末的图像测量粉末颗粒的尺寸。
当颗粒的球形度即其最小直径与其最大直径间的比值大于或等于0.75时认为该颗粒是球形的，无论球形度是怎么获得的。
球形颗粒被称为“球形”或“球化的”取决于是否在其凝固时或凝固后例如通过磨损获得其球形度。
优选地，每个球形颗粒的最大直径和最小直径间的相对差值小于10％，优选小于5％。除此之外，认为由于存在突出或突起，球形度缺陷会影响混合物的流动性。
并不限制球形颗粒的类型，只要这些颗粒由耐火产品制得，特别是基于氧化物ZrO2、Al2O3，甚至特别是SiC的碳化物，或特别是Si3N4的氮化物。
使用的球形颗粒可稍微多孔，即具有大于理论密度90％或完全理论密度的密度。
根据本发明的砂浆还包含“团聚物”，即非球形耐火颗粒的粉末或例如氧化铝、氧化锆、锆石、碳化硅或氮化硅及其混合物、甚至颗粒状球形耐火颗粒的粉末。
优选地，基础耐火材料的大于99质量％、优选基本上100质量％由氧化硅、氧化铝、氧化锆、碳化硅或氮化硅组成。
根据目标应用，通过水、可能的添加剂和不同粉末的混合物制得根据本发明的耐火砂浆。
该混合物可现场制造。但是具有水的混合物导致引起砂浆固化的过程开始，因此这意味着快速使用制备的砂浆。优选地，粉末和可能的一种或多种添加剂这样制备并以干燥状态保存。可以将它们混合，优选进行均匀化，并包封在例如袋或“大袋”中，并以干燥状态进行传送，优选使用操作程序。
根据本发明，由未粒化的球形颗粒尺寸分布的标准偏差和该分布平均值间的比值确定的未粒化的球形颗粒尺寸分布的相对标准偏差，小于100％，优选小于60％，更优选小于10％。换句话说，所用粉末的所有球形颗粒具有彼此接近的直径。如在下文更为详细看到的，因此发明人发现为了省去对氧化硅的需要使用未粒化的球形颗粒的粉末并不足够。此外，球形颗粒的直径不能大比例变化。
可通过分析至少100个，优选200个颗粒来评价尺寸分布的标准偏差和平均值。在自粘毡上放置样品，然后通过光学显微镜或通过扫描电子显微镜(取决于颗粒尺寸)进行观察。然后使用由Soft Imaging SystemCompany提供的
Figure A200680052775D00081
软件分析获得的图像，以便测量粉末每个颗粒的尺寸并获得其分布。
混合粉末颗粒的最大尺寸优选5mm，优选2.5mm。
除了水、未粒化的球形颗粒和非球形耐火颗粒粉末外，根据本发明的耐火混合物也可包含一种或多种通常使用的成形或烧结添加剂。能够以非限制性方式提及下列添加剂作为可使用的添加剂的实例：
-临时有机粘结剂(即在烧结过程中完全或部分除去)，例如树脂、纤维素或木纤维质衍生物，例如羧甲基纤维素、糊精、聚乙烯醇等。优选地，相对于混合物干物质，临时粘结剂的量为0.1-6质量％。
-化学固化剂，例如磷酸、单磷酸铝等；
-水硬性固化剂，例如CaO铝酸盐类型的含铝水泥，例如SECAR71或CA270水泥。
-抗絮凝剂或分散剂，例如碱金属的多磷酸盐或甲基丙烯酸盐衍生物。可考虑所有已知的分散剂，纯离子的、(例如HMPNa)，纯位阻的，例如聚甲基丙烯酸钠类型或其组合。
-烧结促进剂，例如二氧化钛(相对于混合物干物质的比例不超过约2％)或氢氧化镁；
-成形剂，例如镁和钙的硬脂酸盐；
-有利于操作并有助于烧结的粘土质类型的添加物。这些添加物产生氧化硅，因此优选被限制为小于2质量％。除此以外，它们导致水的过量需要。
如果粉末混合物在加湿前制得，或将与水一起引入砂浆，则可在粉末混合物中添加添加剂。
相对于干物质以水的质量计并考虑存在的添加剂，优选地，砂浆包含至少1％且至多8％水，优选小于5％，更优选小于4％水。常规地，根据混合物中粘结剂的量确定添加的水量，取决于所需的稠度或粘度。
因此，湿混合物或“砂浆”可以被浇注到例如反应器的内壁上，然后，取决于操作条件，在反应器的预加热过程中原位烧结或制成陶瓷，以便制得耐火涂层或修复这种涂层的损坏部分。
根据本发明的砂浆特别适于通过简单的浇注填充小于25mm，甚至小于10mm的间隙。也可以用于制备烧结块。为此，可进行包括下面连续步骤的制造方法：
a)将根据本发明的耐火砂浆浇注到模具中以形成预制件，
b)从模具中取出预制件，
c)干燥所述的预制件，
d)优选在氧化性气氛中，更优选在1300-1800℃的温度下焙烧所述预制件，以形成烧结的耐火块。
给出下面的非限制性的试验以说明本发明。
根据下表1-3中的组成，如先前所述制造被测试耐火自流动砂浆。
使用下面的未粒化的球形颗粒粉末：
-由Admatech Company提供的球形铝酸盐颗粒粉末Admatech 0502，平均直径D50＝0.7μm
-由Netsch Company提供的球形氧化锆(ZrO2)粉末颗粒，中值粒径D50＝1mm
-由Saint-Gobain Zirpro Company提供的球形锆石(ZrSiO4)粉末颗粒B505NP，中值粒径D50＝20μm
这些粉末的颗粒尺寸的相对标准偏差小于100％。
以粉末形式添加分散剂。
根据ASTM C1446-99标准，通过底面分别为70和100mm，高度为80mm的中空截顶圆锥体测量流动性。将测试的砂浆从圆锥体的小底面注入圆锥体中，该圆锥体以其大底面水平放置在台面上。在用于补偿触变性现象的一分钟等待时间后，提起圆锥体使得砂浆在台面上自然展开，没有振动或其它外部能量输入。在展开后5分钟在两个正交方向上测量展开砂浆的直径。“流动性值”是这两个值的平均值，单位为mm。该值越高，流动性越大。
当流动性值小于或等于100mm时，认为砂浆是不易流动的。100-180间的流动性值相应于弱的流动性。超过该值，180-280间的流动性很好，但不足以用于填料砂浆。超过280，特别是超过300的流动性被认为是适于填料砂浆。
在添加水后，在Perrier类型捏和机中混合2kg耐火粉末混合物5分钟。将由此制得的砂浆注入50mm高且50mm直径的圆柱形模具中。在自由空气中干燥24小时后从模具中取出，然后在110℃下干燥24小时。
测量由此获得的预制件的体积密度(MVA)和开孔孔隙率(PO％)。
根据ISO 5017标准测量孔隙率。低于20％的孔隙率被认为是适于耐火应用。
为了测量抗蠕变性，将试验的砂浆注入尺寸为150×25×25mm(长度×宽度×深度)的模具中，然后在1650℃在空气中焙烧5小时。
根据使用的组分常规地计算砂浆的化学组成。这相应于在干燥并在750℃在空气中煅烧约半小时(即进行处理以便显著除去临时粘结剂以及添加的或包含在水合物中的水)后获得的基于矿物材料的砂浆组成。
下表总结了测试样品的性质及测试结果
表1
Figure A200680052775D00111
NA＝不适用；NT＝未测试；NF＝不易流动＝值＝100mm；
*含有基础耐火材料和基于Ca0铝酸盐的水泥；
**相对于基础耐火材料物质
表2
 
产品的基础混合物(以质量％配制) 1氧化铝氧化硅 2氧化铝氧化铝 3氧化铝氧化铝 4氧化铝氧化锆
烧结氧化铝(片状)T60 8-14目Alcoa 30 30 23 24
烧结氧化铝(片状)T60 -14目Alcoa 21 21 21 22
烧结氧化铝(片状)T60 -325目Alcoa 25.97 25.97 25.97 27.97
由Elkem提供的983 U氧化硅烟尘 7 0 0 0
由Alcoa提供的基于CaO铝酸盐的水泥CA270 4 4 4 4
由Almatis提供的Bayer类型氧化铝粉末中值粒径D50 # 4.3微米               12 12 19 12
由Admatech提供的球形氧化铝Admatech 0502中值粒径D50＝0.7μm                     7
由Netsch提供的球形氧化铝中值粒径D50＝1mm 7
锆石(ZrO2)球形颗粒Netsch中值粒径D50＝1mm 10
非磷酸盐分散剂：甲基丙烯酸钠类型 0.03 0.03 0.03 0.03
干材料总量 100 100 100 100
水 7.5 7.5 7.5 7.5
添加的球形或球化颗粒尺寸的相对标准偏差的(％)                                     NA 52 6 7
流动性圆锥体 355 370 340 340
流动性/添加水％的比值** 46 47 44 44
MVA(体积密度) 2.98 3.01 3.03
PO(开孔孔隙率)％ 16.3 18 19.4
计算的组合物化学组成％*％SiO2％Al2O3％ZrO2％SiC                   6.892.5NANA   <0.698.5NANA   <0.6>98NANA   <0.68910NA  
NA＝不适用；NT＝未测试；NF＝不易流动＝值＝100mm；
*含有基础耐火材料和基于铝酸钙的水泥；
**相对于基础耐火材料物质
表3
 
产品的基础混合物(以质量％配制) (α)氧化锆氧化硅 5氧化锆氧化铝 6氧化锆氧化锆 7氧化锆锆石   (β)SiC氧化硅 8SiC氧化铝
由Unitec的掺杂氧化锆CaO-12/30m目 27 27 26 27
由Unitec的CaO掺杂的氧化锆30/100目 14 14 13 13.1
由Unitec的CaO掺杂的氧化锆30目 17.97 17.97 17.97 17.77
由Unitec的CaO掺杂的氧化锆300目 21 21 21 21.5
由SG材料的SiCO颗粒，2-2mm 14/30 26 26
由SG材料的SiCO颗粒，2-2mm 36/70 13 13
由SG材料的SiCO粉末，0.2mm 80/180 17.5 17.5
由SG材料的SiC粉末，0-0.2mm 220F 20.5 20.5
由Blkem提供的氧化硅烟尘983 U 6 0 0 0 7 0
由Alcoa提供的基于CaO铝酸盐的水泥CA270                          3 3 3 2.8 4 4
由Almatis提供的Bayer类型氧化铝粉末，中值粒径D50#4.3微米                 11 11 10 10.3 12 12
由Admatech的球形氧化铝Admatech 0502中值粒径D50＝0.7μm                 0 6 0 7
氧化锆球形颗粒(ZrO2)Netsch，中值粒径D50＝1mm                            9
由Saint-Gobain Zirpro提供的锆石球形颗粒(ZrSiO4)B505NP，中值粒径D50＝20μm  7.5
非磷酸盐分散剂：甲基丙烯酸钠类型 0.03 0.03 0.03 0.03 0.03 0.03
干材料总量 100 100 100 100 100 100
水 6 6 6 6 9 8
添加的球形或球化颗粒尺寸的相对标准偏差(％)                                   NA 52 7 42 NA 52
流动性圆锥体(mm) 360 370 310 370 340 325
流动性/添加水％的比值** 58 60 50 60 36 39
MVA(体积密度) 3.71 4.2 4.12 2.62 2.62
PO(开孔孔隙率)％ 17.8 19.5 18.4 12.2 15.9
计算的组合物化学组成％*％SiO2％Al2O3％ZrO2％SiC                   61376NA <0.61976NA   <0.61283NA   31381NA 8.514.5NA75   <221NA75
NA＝不适用；NT＝未测试；NF＝不易流动＝值＝100mm；
*含有基础耐火材料和基于CaO铝酸盐的水泥；
**相对于基础材料物质
实施例A和B涉及EP 0,609,868中描述的组成。它们的比较显示了与非球化的氧化铝粉末相比，对球化的氧化铝粉末流动性的公知的积极影响。实施例A和B的流动性仍低于填料砂浆所需的值。
组成C与组成A的不同之处在于球化氧化铝粉末替代氧化硅。值得注意的是，这种替换引起流动性的恶化。因此使用任何球化的氧化铝粉末不足以补偿由缺少氧化硅烟尘而导致的流动性损失。
组成C与组成B的不同之处在于不含氧化硅。值得注意的是，这种替换也引起流动性的恶化。因此，实施例A、B与C的比较证实了技术上的偏见，即根据该偏见：缺少氧化硅导致流动性恶化。因此在EP0,609,868中描述的组成不允许制造自流动填料砂浆。
实施例D也显示了分散剂的改变并不导致组成C流动性的改善。
实施例1与2的比较显示了用中值粒径D50为0.7μm且相对标准偏差为52的球形细氧化铝粉末替换氧化硅可改善流动性。通过比较实施例2和实施例A，注意到，氧化铝粉末的球形外观的重要性：使用4.3μm的中值粒径的非球形氧化铝粉末实际上并不允许获得令人满意的结果，尽管存在氧化硅。
实施例2-4的比较显示了使用中值粒径0.7μm或1mm的球形细氧化铝粉末；或使用中值粒径1mm的球形细氧化锆粉末也允许获得与添加氧化硅获得的结果相近的结果，只要相对标准偏差小于100％。小于1μm的中值粒径给出了最好结果。
实施例3和4的比较显示了使用中值粒径1mm的球形细氧化铝粉末或球形细氧化锆粉末获得相似的结果。
实施例(α)和5-7显示了通过存在中值粒径0.7μm、20μm或1mm的球形颗粒粉末也能使不含或含极少氧化硅的基于氧化锆的耐火砂浆获得良好的流动性，无论这种粉末是氧化铝粉末、氧化锆粉末或锆石粉末。
中值粒径小于1μm，实际上小于0.7μm，给出了最好的结果(370mm圆锥体)。
使用20μm的中值粒径和锆石球形颗粒粉末也获得最好的结果(370mm圆锥体)。因此锆石允许细度较小的粉末，从而所用成本较少。然而，锆石引入少量氧化硅，如在序言中所解释的，该氧化硅会损害获得的烧结产品的某些性能。
同样，实施例(β)和8显示了，通过存在中值粒径0.7μm的球形氧化铝颗粒粉末也能使不含或含极少氧化硅的基于碳化硅的耐火砂浆获得好的流动性。
此外，孔隙率和体积密度的测量显示由根据本发明的自流动耐火砂浆制得的所有产品具有小于20％的孔隙率，即对于耐火应用是令人满意的。
下表4显示了由根据本发明的耐火砂浆制得的产品(通过焙烧和陶瓷化)与含有氧化硅的砂浆相比具有较高的抗蠕变性，正如已知。
表4
 
抗蠕变性 1(氧化铝氧化硅) 2(氧化铝氧化铝) 3(氧化铝氧化铝)
MVA(体积密度) 2.98 3.01 3.05
P0(开孔孔隙率)％ 16.3 18 17.9
根据ISO 3187标准的1500℃/0.2MPa/空气流动
5-25小时之间的尺寸变化％ -3.5 -0.2 -0.6
5-100小时之间的尺寸变化％ -7.9 -0.6 -1.2
当然，描述的实施方案仅是实施例，显然可以通过技术等同物的替换对它们进行调整，而不脱离本发明的范围。

Claims (11)

1.耐火自流动填料砂浆，包含相对于基础耐火材料计至少1质量％且至多10质量％的中值粒径大于或等于0.1μm且小于或等于2mm的未粒化的球形颗粒，还包含相对于砂浆总的干物质计少于4.5质量％的氧化硅(SiO2)和1-8质量％水，
未粒化的球形颗粒尺寸的相对标准偏差小于100％。
2.根据权利要求1的耐火自流动填料砂浆，其中未粒化的球形颗粒尺寸的相对标准偏差小于60％。
3.根据权利要求1和2中任一项的耐火自流动填料砂浆，包含至少5质量％未粒化的球形颗粒，相对于基础耐火材料。
4.根据前述权利要求中任一项的耐火自流动填料砂浆，其中未粒化的球形颗粒具有小于或等于100μm的中值粒径。
5.根据权利要求4的耐火自流动填料砂浆，其中未粒化的球形颗粒具有小于或等于1μm的中值粒径。
6.根据前述权利要求中任一项的耐火自流动填料砂浆，包含少于2质量％的氧化硅，相对于于材料。
7.根据前述权利要求中任一项的耐火自流动填料砂浆，其中球形颗粒具有大于或等于0.8的球形度。
8.根据权利要求7的耐火自流动填料砂浆，其中球形颗粒具有大于或等于0.9的球形度。
9.根据前述权利要求中任一项的耐火自流动填料砂浆，其中氧化铝含量大于95质量％，相对于干材料。
10.根据前述权利要求中任一项的耐火自流动填料砂浆，包含少于5质量％水，相对于干物质。
11.根据前述权利要求中任一项的砂浆通过自流动填充宽度小于25mm孔洞的用途。
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CN103813990A (zh) * 2011-07-20 2014-05-21 法商圣高拜欧洲实验及研究中心 用于熔融玻璃的进料槽

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