CN107892579B - 铝酸钙质玻璃窑炉锡槽吊顶砖及其制备方法 - Google Patents
铝酸钙质玻璃窑炉锡槽吊顶砖及其制备方法 Download PDFInfo
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- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000011449 brick Substances 0.000 title claims abstract description 38
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000011521 glass Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 239000004568 cement Substances 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910001678 gehlenite Inorganic materials 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 3
- 229910052570 clay Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052882 wollastonite Inorganic materials 0.000 claims description 3
- 239000010456 wollastonite Substances 0.000 claims description 3
- 238000007580 dry-mixing Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000007547 defect Effects 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 abstract description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011819 refractory material Substances 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
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Abstract
本发明属于耐火材料技术领域，具体涉及一种铝酸钙质玻璃窑炉锡槽吊顶砖及其制备方法。所述的铝酸钙质玻璃窑炉锡槽吊顶砖原料为：6‑3mm致密铝酸钙10‑25％；3‑1mm致密铝酸钙15‑30％；1‑0.1mm致密铝酸钙20‑40％；纯铝酸钙水泥粉5‑20％；α‑氧化铝粉5‑20％；硅质化合物粉0.2‑3％。本发明制备的铝酸钙质玻璃窑炉锡槽吊顶砖，内部结构均匀，气孔率低，热传导率低，高温蠕变率低，与碱金属氧化物Na2O在使用温度下无化学反应，解决了硅铝酸质吊顶砖易产生剥离脱落、导致玻璃缺陷的问题，减少了锡槽内的热量损失，提高锡槽吊顶砖的使用寿命；其制备方法，科学合理、简单易行。
Description
技术领域
本发明属于耐火材料技术领域，具体涉及一种铝酸钙质玻璃窑炉锡槽吊顶砖及其制备方法。
背景技术
锡槽是浮法平板玻璃生产线的关键设备，其主要由锡槽底砖和锡槽吊顶砖组成。目前，锡槽吊顶砖主要采用组合式结构，市场上多数材质采用硅酸铝质制作而成。在其使用过程中，由于玻璃带在锡槽内成型时其玻璃成分中所含的Na2O有百分之五左右的量挥发，使其与盖顶硅酸铝质耐火材料中的硅、铝反应形成玻璃相，随着釉层的不断增厚，在其自身重力作用下脱落到玻璃板上从而使玻璃产生缺陷。
中国专利CN104326755A公开了一种低导热莫来石锡槽组合顶盖砖，采用低导热的莫来石粗颗粒和细颗粒为骨料，采用铝酸钙、氧化铝粉、硅微粉等为粘结剂，经振动成型，养护后烘干、烧成而得，制得的锡槽组合顶盖砖具有低导热、抗热震性好、高温强度高的特点。但是，其采用的颗粒和细粉多数为硅、铝系原料，长期使用过程中难免和玻璃蒸发出的碱金属氧化物Na2O产生反应，导致最终的脱落造成玻璃缺陷的风险。
发明内容
针对现有技术的不足，本发明的目的是提供一种铝酸钙质玻璃窑炉锡槽吊顶砖，内部结构均匀，气孔率低，热传导率低，高温蠕变率低，与碱金属氧化物Na2O在使用温度下无化学反应，解决了硅铝酸质吊顶砖易受碱金属氧化物侵蚀产生剥离脱落、导致玻璃缺陷的问题，提高锡槽吊顶砖的使用寿命；本发明还提供其制备方法。
本发明所述的铝酸钙质玻璃窑炉锡槽吊顶砖，由如下重量百分数的原料制成：
所述的致密铝酸钙为气孔率小于3％的铝酸钙，其化学组成为：以质量百分比计，CaO21-27％，Al2O3 73-79％，Fe2O3≤0.10％，其余为MgO、SiO2等常见组分。
铝酸钙原料为烧结或电熔纯铝酸钙水泥。
所述的纯铝酸钙水泥粉、α-氧化铝粉与硅质化合物粉的粒径均＜0.088mm。通过以上颗粒搭配生产出的产品，保证了稳定的理化性能。
所述的硅质化合物为硅微粉、粘土、石英或硅灰石中的一种。
优选地，所述的硅质化合物为硅微粉。
所述的铝酸钙质玻璃窑炉锡槽吊顶砖的气孔率为13-20％。
所述的铝酸钙质玻璃窑炉锡槽吊顶砖的化学组成为：
以质量百分比计，CaO 15-25％，Al2O3 72-85％，SiO2 0.5-5％，其余为MgO、Na2O等常见组分。
所述的铝酸钙质玻璃窑炉锡槽吊顶砖的XRD矿物相组成包括：二铝酸钙占70-90％、六铝酸钙占0-10％和钙黄长石占5-20％。
本发明所述的铝酸钙质玻璃窑炉锡槽吊顶砖的制备方法，将致密铝酸钙与纯铝酸钙水泥粉、α-氧化铝粉和硅质化合物粉配料干混后，加水混炼，浇注成型，经干燥、烧成，得产品。
其中：
所述的浇注成型采用振动浇注的方式成型。
所述的浇注成型后的坯体，脱模后自然干燥2-5天，再经过110℃烘干后，入窑烧成。
所述的烧成温度为1250-1450℃，烧成保温时间为6-30小时。
所述的烧成步骤如下：
10-200℃，升温速度1-2℃/分钟；
200-1250℃，升温速度1-3℃/分钟；
1250-1450℃保温，保温时间为6-30小时；
停火降温，随窑炉自然冷却。
以上烧成制度保证了烧制产品中不会因为原料的化学反应和热应力的共同作用出现开裂的现象，保证了产品能够充分的烧结。
本发明以致密的铝酸钙颗粒为原料，加入α-氧化铝粉、纯铝酸钙和硅质化合物粉为结合剂，经1250-1450℃烧结后，制成以CaO-Al2O3-SiO2系三元化合物-钙黄长石(Gehlenite，化学式为2CaO.Al2O3.SiO2)为结合相的铝酸钙锡槽吊顶砖，避免了砖体受碱金属氧化物Na2O的侵蚀，在气孔率为13-20％时，热传导率低，高温蠕变率低、能够大大提高吊顶砖寿命，避免对窑炉内玻璃造成缺陷，减少了窑炉的热量损失的特性。
综上所述，本发明的有益效果如下：
(1)本发明制备的铝酸钙质玻璃窑炉锡槽吊顶砖，内部结构均匀，气孔率低，热传导率低，高温蠕变率低，与碱金属氧化物Na2O在使用温度下无化学反应，解决了硅铝酸质吊顶砖易受碱金属氧化物侵蚀产生剥离脱落、导致玻璃缺陷的问题，减少了锡槽内的热量损失，提高锡槽吊顶砖的使用寿命。
(2)本发明所述的制备方法，科学合理、简单易行。
具体实施方式
下面结合实施例对本发明做进一步说明。
实施例中采用的所有原料均为市购。
实施例中采用的原料的理化指标见表1。
表1原料的理化指标
| 原料名称 | 铝酸钙 | α-氧化铝粉 | 版纳粘土 | 硅灰石 | 石英 | 硅微粉 |
| SiO<sub>2</sub> | 0.15 | 0.01 | 46.03 | 50.2 | 99.22 | 96.00 |
| Al<sub>2</sub>O<sub>3</sub> | 75.5 | 99.57 | 37.78 | 0.46 | 0.39 | 0.33 |
| Fe<sub>2</sub>O<sub>3</sub> | 0.09 | 0.02 | 0.30 | 0.82 | 0.03 | 0.25 |
| TiO<sub>2</sub> | 0.03 | 0.00 | 0.02 | 0.01 | 0.02 | 0.03 |
| CaO | 23.2 | 0.04 | 0.04 | 44.9 | 0.02 | 0.05 |
| MgO | 0.55 | 0.00 | 0.09 | 1.00 | 0.02 | 0.02 |
| K<sub>2</sub>O | 0.07 | 0.00 | 0.40 | 0.00 | 0.09 | 0.03 |
| Na<sub>2</sub>O | 0.21 | 0.21 | 0.86 | 0.00 | 0.06 | 0.05 |
| 其他 | 0.10 | / | 0.44 | 0.38 | / | 0.24 |
| 灼减 | 0.10 | 0.15 | 14.04 | 2.23 | 0.15 | / |
| 合量 | 100 | 100 | 100 | 100 | 100 | 100 |
| 气孔率％ | 1.33 | / | / | / | / | |
| 体积密度g/cm<sup>3</sup> | 2.67 | / | / | / | / |
实施例1-6
将表2中配方将原料按比例加入到混炼机内，混合5-15分钟后，加水混炼3-5分钟，再将泥料浇注到模型中进行振动成型，坯体脱模后自然干燥1-3天后，在110℃下烘干进行1250℃-1450℃烧成制得铝酸钙锡槽底砖样品，烧成制度如下：
10-200℃，升温速度1℃/分钟；
200-650℃，升温速度1.5℃/分钟；
650-1000℃，升温速度1.5℃/分钟；
1000-1250℃，升温速度2℃/分钟；
1250-1450℃保温，保温时间为8-30小时；
停火降温，随窑炉自然冷却。
检测其化学成分、矿物相组成、气孔率、体积密度、耐压强度、热传导率等理化指标见表2。
表2原料配方和测试结果
*铝酸钙质玻璃窑锡槽吊顶砖中的MgO、Na2O等杂质形成少量镁铝尖晶石或玻璃相，因此主要矿物相二铝酸钙、六铝酸钙、钙黄长石的合量不足100％。
Claims (7)
1.一种铝酸钙质玻璃窑炉锡槽吊顶砖，其特征在于：由如下重量百分数的原料制成：
6-3mm致密铝酸钙 10-25%；
3-1mm致密铝酸钙 15-30%；
1-0.1mm致密铝酸钙 20-40%；
纯铝酸钙水泥粉 5-20%；
α-氧化铝粉 5-20%；
硅质化合物粉 0.2-3%；
所述的铝酸钙质玻璃窑炉锡槽吊顶砖的制备方法，将致密铝酸钙与纯铝酸钙水泥粉、α-氧化铝粉和硅质化合物粉配料干混后，加水混炼，浇注成型，经干燥、烧成，得产品；其中，所述的浇注成型采用振动浇注的方式成型；
所述的铝酸钙质玻璃窑炉锡槽吊顶砖的气孔率为13-18%。
2.根据权利要求1所述的铝酸钙质玻璃窑炉锡槽吊顶砖，其特征在于：所述的致密铝酸钙为气孔率小于3%的铝酸钙。
3.根据权利要求1所述的铝酸钙质玻璃窑炉锡槽吊顶砖，其特征在于：所述的纯铝酸钙水泥粉、α-氧化铝粉与硅质化合物粉的粒径均＜0.088mm。
4.根据权利要求1所述的铝酸钙质玻璃窑炉锡槽吊顶砖，其特征在于：所述的硅质化合物为硅微粉、粘土、石英或硅灰石中的一种。
5.根据权利要求1所述的铝酸钙质玻璃窑炉锡槽吊顶砖，其特征在于：所述的铝酸钙质玻璃窑炉锡槽吊顶砖的XRD矿物相组成包括：二铝酸钙70-90%、六铝酸钙0-10%和钙黄长石5-20%。
6.根据权利要求1所述的铝酸钙质玻璃窑炉锡槽吊顶砖，其特征在于：所述的烧成温度为1250-1450℃，烧成保温时间为6-30小时。
7.根据权利要求1所述的铝酸钙质玻璃窑炉锡槽吊顶砖，其特征在于：所述的烧成步骤如下：
10-200℃，升温速度1-2℃/分钟；
200-1250℃，升温速度1-3℃/分钟；
1250-1450℃保温，保温时间为6-30小时；
停火降温，随窑炉自然冷却。
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