CN101448758A - 耐火制品及其生产方法 - Google Patents
耐火制品及其生产方法 Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000005350 fused silica glass Substances 0.000 claims abstract description 28
- 239000011159 matrix material Substances 0.000 claims abstract description 23
- 239000000919 ceramic Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000004411 aluminium Substances 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
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- 206010013786 Dry skin Diseases 0.000 description 1
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- 238000003723 Smelting Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
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- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- MFFVROSEPLMJAP-UHFFFAOYSA-J zirconium(4+);tetraacetate Chemical class [Zr+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O MFFVROSEPLMJAP-UHFFFAOYSA-J 0.000 description 1
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/14—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D41/00—Casting melt-holding vessels, e.g. ladles, tundishes, cups or the like
- B22D41/02—Linings
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B35/00—Transporting of glass products during their manufacture, e.g. hot glass lenses, prisms
- C03B35/14—Transporting hot glass sheets or ribbons, e.g. by heat-resistant conveyor belts or bands
- C03B35/16—Transporting hot glass sheets or ribbons, e.g. by heat-resistant conveyor belts or bands by roller conveyors
- C03B35/18—Construction of the conveyor rollers ; Materials, coatings or coverings thereof
- C03B35/181—Materials, coatings, loose coverings or sleeves thereof
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- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/42—Details of construction of furnace walls, e.g. to prevent corrosion; Use of materials for furnace walls
- C03B5/43—Use of materials for furnace walls, e.g. fire-bricks
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
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Abstract
本发明涉及通常具有改善表面性质的耐火制品。本发明的目的是提出包含熔凝石英基质的耐火制品的改进，所述耐火制品将克服一些缺点并同时保持熔凝石英基质优异的已知性质。当烧结陶瓷相存在于基质至少一表面的至少一部分的孔隙中时获得了这个目的。本发明还涉及生产这种制品的方法。
Description
技术领域
[0001]说明书
本发明涉及通常具有改良表面性质的耐火制品。特别地，本发明涉及包含熔凝石英(fused silica)基质的耐火制品，例如输送热制品的辊子、或用来处理熔融玻璃或非铁金属的制品如用于熔化或结晶硅的坩埚、处理铝的旋转脱气装置等。
背景技术
[0002]耐火材料广泛用于高要求的应用中，例如处理熔融金属或操作热制品。特别地，包含熔凝石英基质的材料因它们在高温下的优异行为而为人们所熟知，例如它们的高耐火性和低的热膨胀以及它们对于玻璃或一些熔融金属的相对惰性。
[0003]然而熔凝石英材料的某些表面性质使得它们不适于一些应用。特别地，当这些材料用作玻璃退火辊(LOR、玻璃退火炉)、作为玻璃钢化辊(GTR)或作为操作和/或处理熔融玻璃或金属的容器(例如用于熔化硅的坩埚)时，“表面吸着(pickup)”行为(材料趋于吸着所传送制品表面上的杂质或碎屑)或“表面积聚(buildup)”行为(表面趋于接收并聚集金属颗粒(例如锡、硅等)或可能氧化的颗粒(氧化锡))造成严重问题。所传送制品的印痕以及硅晶体对坩埚壁的粘附是这些问题中的例子。对于这些应用，要么需要为石英基质提供昂贵且复杂的涂层，要么需要使用其它材料(例如金属)。
[0004]文献GB 2 154 228 A涉及用于喷涂表面以原位形成耐火物质的组合物。这样的组合物例如用于修复玻璃熔炉的基体耐火砌块。文献US 4,230,498涉及用于耐火炉砌块特别是石英砌块的修补组合物。该修补组合物应粘结到其所施用于的热石英砌块。这样的组合物用于修复高温下的熔炉或炼焦炉的炉壁。在这两种情况下，喷涂或修补的表面是粗糙的并且几乎不可控。
[0005]文献FR2 707 084涉及施用于熔融金属应用的玻璃态石英耐火材料的抗腐蚀涂层。添加烧结助剂使得涂层在低于1200℃的温度下烧结；1200℃对于玻璃态石英基质是有害的。这样的烧结涂层脆弱且易碎从而不适于热循环。
[0006]文献US4 528 244涉及用于熔凝石英器具上的SiAlON涂层。SiAlON也表现出一些缺点。SiAlON材料中的玻璃相意味着可能与基质粘结或粘附。此外，SiAlON可能的高温氧化及熔凝石英不可逆的结晶使得SiAlON材料不适于热循环应用。
[0007]此外，提供涂层始终是昂贵的，因为需要额外的生产步骤，并且这仅是临时的解决方案，因为涂层材料的另外层具有从石英基质材料的表面分层的趋势，这不仅使熔凝石英材料丧失涂层的益处，而且进而产生剥落缺陷。对于输送应用或固体接触应用，由于涂层被施加在表面之上，因此通常需要在涂覆步骤后对涂覆制品进行机械加工步骤以使表面均匀化。此外，由于这个另外层的热膨胀(或通常热行为)不同于石英基质的热膨胀(或通常热行为)，因此在涂层和石英基质间的界面处产生制约(constraint)，从而不利地影响表面品质。此外，由于这个另外层的热导率不同于熔凝石英基质的热导率，因此穿过制品的热传递不均匀。将金属材料用于这样的制品也不能令人满意，因为金属与被处理或传送的制品间具有相对高的反应性。此外，与熔凝石英制品相比，金属制品具有非常高的弯曲变形，并且它们用于苛刻环境(例如玻璃退火炉或结晶炉)的有效时间相对短。
发明内容
[0008]本发明的目的是提出包含熔凝石英基质的耐火制品的改进，所述耐火制品将克服上述缺点，同时保持熔凝石英基质优异的已知性质。
[0009]根据本发明，当烧结陶瓷相存在于基质至少一表面的至少一部分的孔隙中时获得了这个目的(以及其它目的)。表面指的是基层(substrate)或活性层。与除熔凝石英外不包含任何烧结陶瓷相的制品芯部不同，制品的基层或活性层在其孔隙中包含大部分的烧结陶瓷相。
[0010]本发明人事实上已想到如下假设：上述缺陷主要是由于玻璃或金属与熔凝石英制品表面上存在的开放孔隙之间的相互作用，并试图填充这种表面孔隙。由于表面孔隙被填充，因此表面的密度高于熔凝石英基质芯部的密度。优选地，表面的开放孔隙率比熔凝石英制品芯部的开放孔隙率低至少20％；最优选低50％。
[0011]根据本发明，石英基质的初始表面保持作为完成制品的表面(仅在约200μm-1mm的范围填充表面孔隙，优选约500μm)使得在浸渍步骤后无需另外的机械加工步骤。石英基质表面的填充确保石英基质和烧结陶瓷相之间的材料连续性。填充物和基质表面层的进一步烧结确保基质和填充物之间非常高的粘合。同时，它们两者协同作用有助于显著改善制品的性质及性能。填充物均匀分散在表面层上，并且占总表面层材料的小于10重量％。以这种方式，体系保持热稳定，产生较小应力，并且减少张力、剥落或龟裂裂纹。
[0012]优选用选自硅、铝、锆和镁的氧化物，它们的组合，硼、铝及硅的氮化物以及它们的组合的陶瓷材料填充熔凝石英材料的表面孔隙。
[0013]本发明还涉及生产这种制品的方法。根据本发明的有利实施方案，用提供所需金属原子的有机金属化合物的溶液浸渍熔凝石英基质的表面。适合的有机金属化合物是硅基(原硅酸四乙酯、原硅酸甲酯、硅烷等)、锆基(锆的乙酸盐、硝酸盐、氯化物、氯氧化物等)、铝基(乙酸盐等)、镁基(氯化物)。作为替代，还可使用包含所需金属原子的树脂(例如聚硅烷、铝螯合改性树脂、多酸树脂的盐等)。
[0014]作为替代，可以将孔隙填充物以在液体载体中的悬浮液形式引入。在这种情况下，材料的微粒(平均粒径小于0.01μm)悬浮在适当的液体载体中。适当的材料是例如硅、铝、镁的金属颗粒或它们的氧化物或者硼、铝或硅的氮化物，硅铝氧氮陶瓷(sialon)。
[0015]在进一步的步骤中，然后对制品表面进行热处理以烧结陶瓷。特别适合的处理是通过火焰处理填充表面进行烧结，然而在特定情况下，简单固化产品将提供所需的处理。
[0016]已经测得表面孔隙率(开放孔隙率)能够相对于熔凝石英基质芯部的孔隙率降低至少50％。表面上的孔尺寸也从未处理熔凝石英制品的平均表面孔尺寸1μm减小到根据本发明制品的小于0.1μm。相对于现有技术的基于熔凝石英基质的制品，本发明制品的表面粗糙度也显著降低；根据本发明，粗糙度(Ra和Rz)显著降低。Ra从3μm变为小于1.5μm，而Rz从15μm变为小于6μm。视觉上，也能观察到表面结构得到改善(孔洞、划痕、气泡、针孔等减少)。表面改性不影响熔凝石英材料的抗弯强度(大于20MPa)。
具体实施方式
[0017]为了更好地描述本发明，现在将通过不意图限制本专利申请范围的实施例来说明本发明。
[0018]实施例1a-浸渍熔凝石英制品的表面。
通过混合50重量％原硅酸四乙酯(纯度99.3％)、33重量％异丙醇(纯度99.7％)及17重量％(5％水溶液)来制备硅氧烷的粘稠溶液。所得溶液的pH是约5.5。在真空下(<0.2巴持续1小时)用这种溶液浸渍熔凝石英辊(直径100mm)。然后对浸渍的辊进行加热(在60℃下强制干燥24小时)。凝胶在表面层内形成并使其稳定，使得在辊表面孔隙内原位形成原生石英的超细颗粒。
[0019]实施例1b-浸渍熔凝石英制品的表面
通过混合60重量％原硅酸四乙酯(纯度99.3％)和40重量％异丙醇(纯度99.7％)来制备第一浸渍溶液。将熔凝石英辊(直径100mm)浸入这种溶液中10分钟，以便通过毛细作用浸渍辊表面孔隙。然后将所述辊浸入盐酸溶液(5％水溶液)。然后使浸渍过的辊受热(在60℃下2小时)。如果希望进一步降低表面孔隙率，则可以重复该操作序列。一次浸渍降低表面开放孔隙率40％。第二次浸渍进一步降低表面开放孔隙率另外20％，并且第三次浸渍进一步降低表面开放孔隙率另外10％。
[0020]实施例1c-浸渍熔凝石英制品的表面
重复实施例1a，不同之处在于用56重量％原硅酸四乙酯和44重量％乙酸锆的混合物代替原硅酸四乙酯。
[0021]实施例1d-浸渍熔凝石英制品的表面
重复实施例1a，不同之处在于在浸渍熔凝石英辊之前在溶液中悬浮硅、铝、镁的金属颗粒或它们氧化物或者硼、铝或硅的氮化物或硅铝氧氮陶瓷。
[0022]实施例2-融凝石英制品的表面烧结
将实施例1a-1d制备的制品在800℃下烧制2小时。
[0023]根据本发明的耐火制品由于其优异的性能因而可以得到许多工业应用。它们可以作为输送热制品的辊例如输送玻璃片的玻璃退火辊(玻璃退火炉或LOR)或玻璃钢化辊、用于热处理不锈钢或硅基电工钢片的辊、热处理用于热浸镀锌应用的碳钢片材的辊，可作为用于处理熔融材料(玻璃、金属等)的容器例如熔化、处理和/或结晶硅的坩埚、用于熔化和/或处理高性能应用(例如光学应用的玻璃如透镜)玻璃的坩埚，或者用于处理熔融材料的制品例如用于处理铝的旋转脱气装置等。
Claims (10)
1.包含熔凝石英基质的耐火制品，该基质具有芯部和至少一表面，其中在基质至少一表面的至少一部分的孔隙中存在烧结的陶瓷相。
2.根据权利要求1的耐火制品，特征在于烧结陶瓷相在基质表面的存在深度是达到200μm-1mm，优选达到500μm。
3.根据权利要求1的耐火制品，特征在于至少部分基质表面具有高于基质芯部密度的密度以及低于基质芯部孔隙率的孔隙率。
4.根据权利要求1或2的耐火制品，特征在于烧结陶瓷相选自硅、铝、锆和镁的氧化物、其组合、硼、铝及硅的氮化物及其组合或铝或硅的氧氮化物和其组合。
5.传送热制品的辊，特征在于所述辊依照于前述权利要求中的任一项，并且特征在于与待传送的制品接触的表面部分中存在烧结的陶瓷相。
6.用于操作或处理熔融金属的坩埚，特征在于所述坩埚依照于权利要求1-4中的任一项，并且特征在于在坩埚的内表面中存在烧结的陶瓷相。
7.制备根据前述权利要求中任一项的制品的方法，包括
a)提供包含熔凝石英基质的陶瓷制品，所述基质具有芯部和至少一表面；
b)浸渍该制品至少一表面的至少一部分；
d)烧结该制品至少一表面的所述至少一部分。
8.根据权利要求7的方法，特征在于烧结步骤d)是在500-800℃下烧制所述制品。
9.根据权利要求7或8的方法，特征在于包括另一步骤c)：在浸渍步骤b)之后并且在烧结步骤d)之前干燥浸渍过的制品。
10.根据权利要求9的方法，特征在于在移到步骤d)之前重复步骤b)和c)。
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| CN111069579A (zh) * | 2019-12-31 | 2020-04-28 | 浙江红鹰铭德高温材料科技有限公司 | 长寿命中间包整体冲击桶、配方及其制作工艺 |
| CN112789258A (zh) * | 2018-08-01 | 2021-05-11 | 法商圣高拜欧洲实验及研究中心 | 用于耐火产品的保护层 |
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| DE102007049634A1 (de) * | 2007-10-17 | 2009-04-23 | Technische Universität Bergakademie Freiberg | Verfahren zur Erhöhung der Korrosionsbeständigkeit von Feuerfestmaterialien |
| DE102011087060B4 (de) * | 2011-11-24 | 2017-03-09 | N-Tec Gmbh | Mineralisches Substrat mit modifizierter Oberfläche |
| RU2515737C1 (ru) * | 2012-12-24 | 2014-05-20 | Открытое акционерное общество "Обнинское научно-производственное предприятие "Технология" | Способ изготовления изделий из кварцевой керамики |
| RU2539088C1 (ru) * | 2013-10-25 | 2015-01-10 | Российская Федерация, от имени которой выступает Министерство промышленности и торговли Российской Федерации (Минпромторг России) | Способ получения безобжиговой кварцевой керамики для стекловарения |
| TWI663126B (zh) | 2014-07-09 | 2019-06-21 | 法商維蘇威法國公司 | 包含可磨塗層之輥、其製造方法及其用途 |
| US20180222808A1 (en) * | 2015-08-07 | 2018-08-09 | Vesuvius France Sa | Refractory article resistant to non-ferrous metal and production process thereof |
| AT15262U1 (de) * | 2016-03-25 | 2017-04-15 | Plansee Se | Glasschmelz-Komponente |
| RU2717844C1 (ru) * | 2019-04-23 | 2020-03-26 | Федеральное государственное бюджетное учреждение науки Хабаровский Федеральный исследовательский центр Дальневосточного отделения Российской академии наук | Способ получения огнеупорных изделий |
| JP7394558B2 (ja) * | 2019-08-28 | 2023-12-08 | Ｊｆｅスチール株式会社 | 金属体を昇温するための金属体昇温炉 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112789258A (zh) * | 2018-08-01 | 2021-05-11 | 法商圣高拜欧洲实验及研究中心 | 用于耐火产品的保护层 |
| CN112789258B (zh) * | 2018-08-01 | 2023-02-17 | 法商圣高拜欧洲实验及研究中心 | 用于耐火产品的保护层 |
| CN111069579A (zh) * | 2019-12-31 | 2020-04-28 | 浙江红鹰铭德高温材料科技有限公司 | 长寿命中间包整体冲击桶、配方及其制作工艺 |
| CN111069579B (zh) * | 2019-12-31 | 2021-10-15 | 浙江红鹰铭德高温材料科技有限公司 | 长寿命中间包整体冲击桶、配方及其制作工艺 |
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| Publication number | Publication date |
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| KR20090008402A (ko) | 2009-01-21 |
| RU2008149260A (ru) | 2010-06-27 |
| MX2008014658A (es) | 2008-11-27 |
| EP2024298B1 (en) | 2011-01-19 |
| RU2462434C2 (ru) | 2012-09-27 |
| JP2009537431A (ja) | 2009-10-29 |
| ES2357567T3 (es) | 2011-04-27 |
| BRPI0711477A2 (pt) | 2011-11-16 |
| US20090160108A1 (en) | 2009-06-25 |
| DE602007012086D1 (de) | 2011-03-03 |
| MY144997A (en) | 2011-12-15 |
| EP2024298A1 (en) | 2009-02-18 |
| DK2024298T3 (da) | 2011-03-21 |
| WO2007131749A8 (en) | 2008-12-04 |
| ATE496015T1 (de) | 2011-02-15 |
| WO2007131749A1 (en) | 2007-11-22 |
| BRPI0711477B1 (pt) | 2018-01-23 |
| CA2651899A1 (en) | 2007-11-22 |
| CA2651899C (en) | 2014-09-02 |
| US9388081B2 (en) | 2016-07-12 |
| PL2024298T3 (pl) | 2011-06-30 |
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