CN1074393C - 硅质耐火材料的生产方法和耐火砖 - Google Patents
硅质耐火材料的生产方法和耐火砖 Download PDFInfo
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Abstract
提供了一种制造结晶硅质耐火材料的方法，它是将气体氧、固体难熔颗粒和由硅颗粒组成的固体可燃颗粒向着一个表面喷射，使该可燃颗粒和气体氧之间对着该表面而发生反应，从而向着该表面释放出反应热量，由此形成由方石英组成的粘附耐火材料，其中该固体难熔颗粒由玻璃态二氧化硅形式的二氧化硅组成并且其中用来喷射的表面其温度至少1000℃。该方法可以用于现场修复高温窑炉，如玻璃制造窑炉，或用于制造高质量耐火砖。
Description
本发明涉及由方石英组成的结晶硅质耐火材料的制造方法。该方法可用于制造耐火材料，如用于建筑或修复窑炉的耐火砖或块的目的，也可以是用于现场修复工业窑炉，如玻璃制造窑炉中硅质耐火材料受损表面的一种方法。
该方法采用通常作为“陶瓷焊接”而为人们已知的技术，其中固体难熔颗粒和金属或半金属，如铝和硅的固体可燃烧颗粒的混合物向着要修复的表面喷射，并在那儿与富氧气体，通常为基本上纯净的氧起反应，从而使该燃料反应的热量向着该表面释放，由此形成粘附耐火修复物。
这种“陶瓷焊接”描述于英国专利1330894(Glaverbel)和英国专利2170191(Glaverbel)中，其中通过在氧的存在下向一个表面喷射难熔颗粒和可燃烧颗粒的混合物而形成粘附耐火物。该可燃烧颗粒是其组成及颗粒性可以使它们以放热方式与氧起反应形成一种难熔氧化物同时释放出至少使所喷射的难熔颗粒表面熔化所必需的热量的颗粒。颗粒的喷射可以通过采用氧气作为颗粒混合物的携带气体而方便、安全地实现。以这种方式，可以在喷射颗粒的表面上形成粘附耐火材料。
这些已知的陶瓷焊接方法可以用来形成耐火制品，如具有特定形状的耐火块，但它们最常用来形成形成涂层或修复耐火砖或壁，并且特别适用于修复或加强现有的耐火结构，如玻璃制造或焦炭窑炉的炉壁。
该方法特别适用于修复热基体表面。还可以在设备基本保持在工作温度下并且在许多情况下在窑炉作为一个整体仍处于操作过程中的同时修复受损表面。在窑炉仍处于使用过程中的同时进行修复特别适用于玻璃制造和焦炭窑炉，这是因为这些窑炉的寿命是以年计算的，常常长达20年，在整个时期内，窑炉一直连续保持在操作过程中。
该陶瓷焊接混合物的组成通常选择成可以产生化学组成与基础耐火材料相似或接近的修复物。这有助于确保新材料和基础材料之间配匹和粘接。
即使具有这些化学匹配，仍然存在使该修复物与基体粘接的问题，特别是在需要将该粘接维持相当长的一段时间的时候。如果所修复的表面受到非常高的温度，则问题将会增加。在这种情况下，就必需要用高级耐火材料，例如用于玻璃窑炉窑顶。
如果可能的话，必需避免使修补物破裂。在玻璃制造中，破裂的物质可能会落到熔融玻璃中并且会引起不需要的杂质。有时还会造成大批熔融玻璃被倒掉。
现在我们发现由方石英组成的高级耐火材料可以很容易地由固体难熔颗粒材料形成，只要其温度保持在非常高的数值下，这些难熔颗粒材料以前一直是人们要避免的，它们可能会与基础材料不匹配。更进一步地说，根据本发明可以用来成功修补的材料是玻璃态二氧化硅。
根据本发明，它提供了一种制造结晶硅质耐火材料的方法，它是将气体氧、固体难熔颗粒和由硅颗粒组成的固体可燃颗粒向着一个表面喷射，使该可燃颗粒和气体氧之间对着该表面而发生反应，从而向着该表面释放出反应热量，由此形成由方石英组成的粘附耐火材料，其特征在于该固体难熔颗粒由玻璃态二氧化硅形式的二氧化硅组成并且其特征在于用来喷射的表面其温度至少1000℃。
表面的高温可以使由于硅粒子的燃烧而形成的二氧化硅导入耐火材料中的晶体晶格中。
晶体晶格的存在在耐火材料的内部粘接和它与修复下面的表面的粘接(如果需要)方面产生几个优点。在本文中所给出的关于这些优点是如何实现的解释是假设性的。不管该假设是否准确，这些优点在本发明实际运用中已经清楚地显示出来。
可以相信晶体晶格起着一种粘接相的作用，它在该耐火材料中延伸。晶格产生了在整个耐火材料上延伸的连续结构。形成具有高力学强度的致密结构。如果将该方法用来修复受损的耐火材料表面，则该晶体晶格将会延伸到该表面并与之粘接。
所喷射的难熔颗粒可以具有与粘接相不同的结构。与该表面的粘接基本上是通过粘结相产生的。
将耐火材料在高温窑炉中当场向非常高的温度暴露使得该耐火材料转化成方石英。在形成单个耐火块或砖，例如喷射到一种模具中时，优选将所形成的耐火材料在至少1000℃下烧结。较高的窑炉温度和烧结将残余的玻璃相转变成方石英。方石英在高温下是稳定的，这具有特别的优点。
本发明的方法特别适用于当场修复玻璃制造窑炉，这是因为在该窑炉中会遇到非常高的温度。例如，在玻璃制造窑炉中窑顶的表面温度可以超过1500℃。
用于本发明的颗粒混合物，即固体可燃颗粒与由玻璃态二氧化硅组成的固体难熔颗粒的混合物可以用于在低于1000℃的温度下修复表面，只要该混合物含有在英国专利申请2257136(Glaverbel)中所限定的添加剂。
用于本发明的二氧化硅应该具有高纯度，例如至少95％重量纯氧化物，优选地为至少99％纯氧化物。所达到的耐火物质具有较高的耐火性并且降低了如果任何耐火物质落入玻璃中而使玻璃制造窑炉污染的危险。
玻璃态二氧化硅作为固体难熔颗粒用于本发明的方法中是有利的，其原因在于它很容易得到并且很容易以高纯度获得。
硅的总量优选地不超过15％重量。对可能存在于所形成的耐火材料中的未反应燃料的量进行限定是需要的，这是因为在所形成的耐火材料中存在相当比例的未反应燃料可能损害其质量。
该难熔颗粒优选地基本上由尺寸不超过4毫米，最好不超过2.5毫米的颗粒组成，以使该粉末很容易流畅地喷射。该难熔颗粒的尺寸范围扩散因子f(G)优选地不小于1.2。所说的因子f(G)在本文中用来针对一种给定的颗粒，代表因子：
其中G80代表该颗粒的80％颗粒尺寸，G20代表该颗粒的20％颗粒尺寸。
优选地，硅的平均颗粒直径不超过50微米。术语“平均颗粒直径”用于本文时是指50％重量的颗粒具有低于该平均值的尺寸。
根据本发明的方法获得的耐火材料的熔点接近纯二氧化硅的。由本发明制得的耐火砖的变形系数T0.5根据ISO标准R1893为1650℃以上。该值可以与通过常规方法制得的普通硅砖的约1550℃的T0.5相比。根据US专利4073655(Owens-Illinois,Inc.)通过反玻璃化制得的主要由稳定化的高方石英固溶体组成的耐火砖适合用于最高约达1250℃的温度。
下面参照实施例对本发明进行描述。应该强调本发明不限于其中所说的特定数量和工艺。
实施例1
将88％纯度为99.7％二氧化硅的玻璃态二氧化硅颗粒和12％硅粒子在工业纯氧气流中喷射到玻璃制造窑炉的窑顶，以形成一种耐火材料。该窑顶的温度为约1600℃。玻璃态二氧化硅的最大颗粒尺寸为2毫米。其G80为950微米，其G20为225微米，尺寸范围扩散因子f(G)为1.23。硅粒子的平均颗粒直径小于45微米，比表面积为2500-8000平方厘米/克。6天以后，取出所形成的耐火材料的样品进行分析，发现它具有下列性能：
熔点 1723℃
结构 方石英
T0.5(ISOR1893) 约1700℃*通常用于窑顶中此位置的最好的市售耐火砖(Hepworth Refractories“HEPSIL SV”高纯硅砖)其T0.5为1640℃。
实施例2
将具有与实施例1相同的组成的粉末混合物在工业纯氧气流中喷射到一种模具中以形成一种砖。将模具预加热到1600℃以接收该粉末混合物。在砖形成后，将其在1450℃下保持6天。然后对该砖进行分析，发现它与实施例1具有相同的熔点、结构和T0.5。
耐火砖，如根据实施例2制得的耐火砖可以直接地、没有任何特定条件地用于修复玻璃熔炉的受损窑顶，如果需要，还可以进行额外焊接。任何其它的结晶硅砖在没有条件(如小心地加热)用于相同位置时会立即产生大范围破裂。
Claims (7)
1．一种制造结晶硅质耐火材料的方法，它是将气体氧、固体难熔颗粒和由硅颗粒组成的固体可燃颗粒向着一个表面喷射，使该可燃颗粒和气体氧之间对着该表面而发生反应，从而向着该表面释放反应热量，由此形成由方石英组成的粘附耐火材料，其特征在于该固体难熔颗粒由玻璃态二氧化硅形式的纯度至少为95％重量的二氧化硅组成，硅的总量为不超过所喷射颗粒总重量的15％，并且用来喷射的表面其温度至少1000℃。
2．如权利要求1所说的方法，其中在喷射颗粒以后，将所得到的耐火材料在至少1000℃下烧结。
3．如权利要求1或2所说的方法，其中该固体难熔颗粒由纯度为至少99％重量的二氧化硅组成。
4．如权利要求1或2所说的方法，其中硅的平均颗粒直径不超过50微米。
5．如权利要求1或2所说的方法，其中该固体难熔颗粒基本上不合有尺寸超过4毫米的颗粒。
6．如权利要求1或2所说的方法，其中该难熔颗粒的尺寸范围扩散因子f(G)不小于1.2，其中f(G)定义如下： 式中G80代表该颗粒的80％颗粒尺寸，G20代表该颗粒的20％颗粒尺寸。
7．一种耐火砖，它由以下方法制得，并且变形系数T0.5高于1650℃，所述方法包括：将气体氧、固体难熔颗粒和由硅颗粒组成的固体可燃颗粒喷射到已预加热到至少1000℃的模具中，使该可燃颗粒和气体氧之间在模具中发生反应并释放反应热量，由此形成由方石英组成的耐火砖，然后将所得耐火砖在至少1000℃下烧结，其中所述的固体难熔颗粒由玻璃态二氧化硅形式的纯度至少为95％的二氧化硅组成，并且硅的总量不超过所喷射颗粒总重量的15％。
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9423984A GB9423984D0 (en) | 1994-11-28 | 1994-11-28 | Process for making a crystalline siliceous refractory mass |
| GB9423984.5 | 1994-11-28 | ||
| GBGB9425927.2A GB9425927D0 (en) | 1994-12-22 | 1994-12-22 | Process for making a crystalline siliceous refractory mass |
| GB9425927.2 | 1994-12-22 |
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| Publication Number | Publication Date |
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| CN1166818A CN1166818A (zh) | 1997-12-03 |
| CN1074393C true CN1074393C (zh) | 2001-11-07 |
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| HR (1) | HRP950552B1 (zh) |
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| RO (1) | RO115156B1 (zh) |
| RU (1) | RU2141929C1 (zh) |
| SI (1) | SI9520143A (zh) |
| SK (1) | SK281531B6 (zh) |
| TR (1) | TR199501507A2 (zh) |
| TW (1) | TW371651B (zh) |
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| CA2548959A1 (en) * | 2004-02-06 | 2005-09-15 | George Jay Lichtblau | Process and apparatus for highway marking |
| US6969214B2 (en) * | 2004-02-06 | 2005-11-29 | George Jay Lichtblau | Process and apparatus for highway marking |
| US7449068B2 (en) | 2004-09-23 | 2008-11-11 | Gjl Patents, Llc | Flame spraying process and apparatus |
| US20070113781A1 (en) * | 2005-11-04 | 2007-05-24 | Lichtblau George J | Flame spraying process and apparatus |
| US20070116865A1 (en) * | 2005-11-22 | 2007-05-24 | Lichtblau George J | Process and apparatus for highway marking |
| US20070116516A1 (en) * | 2005-11-22 | 2007-05-24 | Lichtblau George J | Process and apparatus for highway marking |
| CZ297828B6 (cs) * | 2006-03-09 | 2007-04-04 | Famo - Servis, Spol. S R. O. | Prásková smes pro horké opravy zdiva koksárenských komor |
| KR101788275B1 (ko) | 2011-08-04 | 2017-10-19 | 주식회사 인텍 | 세라믹 용접재 조성물 |
| LU92340B1 (fr) * | 2013-12-19 | 2015-06-22 | Fib Services Intellectual Sa | Composition pulvérulante à base de silice poreuse pour soudure céramique et son procédé d'obtention |
| LU92339B1 (fr) * | 2013-12-19 | 2015-06-22 | Fib Services Intellectual Sa | Composition siliceuse et procédé d'obtention |
| KR101663204B1 (ko) | 2015-02-24 | 2016-10-07 | 주식회사 금강알씨 | 내화보수재의 제조방법 및 상기 제조방법에 의한 내화보수재 |
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