CN117362015B - 高纯刚玉砖及其制备方法 - Google Patents
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- 239000010431 corundum Substances 0.000 title claims abstract description 57
- 229910052593 corundum Inorganic materials 0.000 title claims abstract description 57
- 239000011449 brick Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000011521 glass Substances 0.000 claims abstract description 29
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 239000012535 impurity Substances 0.000 claims abstract description 16
- 239000013078 crystal Substances 0.000 claims abstract description 15
- 229910018068 Li 2 O Inorganic materials 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 9
- 238000005266 casting Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000003723 Smelting Methods 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 238000007531 graphite casting Methods 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000010891 electric arc Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 238000010583 slow cooling Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 1
- 230000003628 erosive effect Effects 0.000 abstract description 10
- 239000011819 refractory material Substances 0.000 abstract description 7
- 230000035939 shock Effects 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000523 sample Substances 0.000 description 8
- 239000006060 molten glass Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000013074 reference sample Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Abstract
本发明涉及一种高纯刚玉砖及其制备方法,涉及耐火材料的技术领域。本发明的高纯刚玉砖以原料氧化物的重量百分比计,含有:0.08~1.0%的SiO2、0.15~0.45%的Na2O、0.05~0.15%的Li2O、0.05~0.25%的P2O5、0.05~0.15%的B2O3、1.2~3.0%的Cr2O3,和余量的Al2O3以及杂质;其中:Na2O/Li2O重量比为3~5,P2O5以BPO4的形式添加;以结晶组成的重量百分比计,所述高纯刚玉砖为电熔α‑Al2O3型刚玉砖,并且结晶组成包括92~98%的α‑Al2O3和2~8%的β‑Al2O3。本发明的高纯刚玉砖不仅具有优异的抗折强度、抗热震性能,而且改进和提高了高温条件下的耐玻璃侵蚀性能,适用于玻璃窑炉冷却部池壁、澄清部等部位,体现了优异的使用性能。
Description
技术领域
本发明涉及耐火材料的技术领域,更具体地说,本发明涉及一种高纯刚玉砖及其制备方法。所述高纯刚玉砖主要应用于玻璃熔窑的澄清部、冷却部、工作池等部位。
背景技术
电熔刚玉砖是在电弧炉中将氧化铝熔融后浇铸到指定的特定形状的模型中,通过退火保温,再通过金刚石磨具的加工,得到所需要的产品。该产品根据其中氧化铝结晶形态的不同和数量的多少分为3种,第一种是以α-Al2O3为主晶相,称为α刚玉砖;第二种是以α-Al2O3与β-Al2O3晶相为主,含量基本为1:1,α相含量略高,称为αβ刚玉砖;第三种以β-Al2O3晶相为主,称为β刚玉砖。其中:电熔α-Al2O3属于六方晶系,是氧化铝在高温下唯一稳定的晶体,且仅含有少量β-Al2O3,纯度高,不污染玻璃液,在1350°以下具有良好的耐玻璃侵蚀性能,是玻璃熔窑的澄清部、冷却部等部位较理想的耐火材料。然而,近年来,随着新工艺技术的发展,对玻璃熔窑的要求也越来越高,尤其是对于与玻璃液直接接触的电熔耐火材料的性能指标。
发明内容
为了提高高纯刚玉砖的性能,尤其是改进其在高温条件下的耐玻璃侵蚀性能,本发明的目的在于提供一种高纯刚玉砖及其制备方法。
本发明的第一方面涉及一种高纯刚玉砖,以原料氧化物的重量百分比计,含有:0.08~1.0%的SiO2、0.15~0.45%的Na2O、0.05~0.15%的Li2O、0.05~0.25%的P2O5、0.05~0.15%的B2O3、1.2~3.0%的Cr2O3,和余量的Al2O3以及杂质;其中:Na2O/Li2O重量比为3~5,P2O5以BPO4的形式添加;以结晶组成的重量百分比计,所述高纯刚玉砖为电熔α-Al2O3型刚玉砖,并且结晶组成包括92~98%的α-Al2O3和2~8%的β-Al2O3。
其中,所述杂质的含量小于1.0%,优选小于0.8%,更优选小于0.5。
其中,所述杂质中Fe2O3+CaO+MgO+TiO2的总量小于0.4%,其中:Fe2O3的含量小于0.10%,TiO2的含量小于0.10%,CaO小于0.05%。
其中,所述Al2O3的含量大于95%,优选大于97%,更优选大于98%。
其中,所述SiO2的含量优选为0.15~1.0%,更优选为0.25~0.75%。
其中,所述Cr2O3的含量优选为1.2~2.5%,更优选为1.2~2.0%。
其中,所述Na2O的含量优选为0.15~0.39%,更优选为0.15~0.36%。
其中,所述P2O5的含量优选为0.05~0.15%。
其中,所述高纯刚玉砖中玻璃相的含量小于2.0%。
本发明的第二方面还涉及上述高纯刚玉砖的制备方法,所述制备方法包括以下步骤:
(5)配料:按照原料氧化物的重量百分比准备Al2O3、SiO2、Na2CO3、Li2CO3、BPO4、B2O3和Cr2O3得到原料粉末;
(6)熔炼:将所述原料粉末加入电弧炉中加热熔融,通入含氧气体进行高温熔炼;
(7)浇铸:将高温熔炼得到的熔液浇铸到铸型中,保温退火;
(8)加工:将保温退火后得到的耐火产品加工成所述高纯刚玉砖。
与现有技术相比,本发明的高纯刚玉砖具有以下有益效果:
本发明的高纯刚玉砖不仅具有优异的抗折强度、抗热震性能,而且改进和提高了高温条件下的耐玻璃侵蚀性能,适用于玻璃窑炉冷却部池壁、澄清部等部位,体现了优异的使用性能。
附图说明
图1为本发明的高纯刚玉砖的典型XRD图;
图2为本发明使用过的高纯刚玉砖的截面SEM图。
具体实施方式
以下将结合具体实施例对本发明的高纯刚玉砖做进一步的阐述,以帮助本领域的技术人员对本发明的技术方案有更完整、准确和深入的理解。
玻璃窑炉是由耐火材料制成的熔制玻璃的核心设备,玻璃生产技术以及质量的提高在很大程度上依赖于耐火材料品质的提升,同样地,玻璃窑炉的使用效率与寿命,很大程度上取决于耐火材料的品质与质量。为了适应新工艺技术发展玻璃熔窑越来越严苛的要求,本发明提供了一种高纯刚玉砖,所述高纯刚玉砖为电熔α-Al2O3型刚玉砖。本发明的高纯刚玉砖以原料氧化物的重量百分比计含有:0.08~1.0%的SiO2、0.15~0.45%的Na2O、0.05~0.15%的Li2O、0.05~0.25%的P2O5、0.05~0.15%的B2O3、1.2~3.0%的Cr2O3,和余量的Al2O3以及杂质;其中:Na2O/Li2O重量比为3~5,P2O5以BPO4的形式添加;以结晶组成的重量百分比计,包括92~98%的α-Al2O3和2~8%的β-Al2O3。在本发明中,α-Al2O3为高温稳定相结构,具有严密坚实的组织结构,少量的β-Al2O3是为了改善浇注成型而存在,图1示出了本发明的高纯刚玉砖的XRD图谱,从中可以观察到β-Al2O3的特征峰均为弱峰,此外也可以确认其中所含的非晶质的玻璃相很低,本发明中玻璃相的含量小于2.0%。所述的杂质是由原料的不纯而引入的,而非有意添加。所述杂质的含量小于1.0%,优选小于0.8%,更优选小于0.5。所述的杂质包括Fe2O3、CaO、MgO和TiO2等,所述杂质中Fe2O3+CaO+MgO+TiO2的总量小于0.4%,其中:Fe2O3的含量小于0.10%,TiO2的含量小于0.10%,CaO小于0.05%,将杂质控制在所限定范围内,对电熔刚玉砖的性能基本没有不良影响。本发明的刚玉砖中含有1.2~3.0%的Cr2O3,Cr2O3的含量优选为1.2~2.5%,更优选为1.2~2.0%,刚玉砖中通过添加BPO4和B2O3来替代部分碱性氧化物Na2O,从而可以显著降低Na2O的含量,本发明还进一步通过加入Li2O,并限定Na2O/Li2O重量比为3~5,在添加有Cr2O3的前提下保证了高纯刚玉砖的抗热震性能,而且出人预料地提高刚玉砖在高温条件下例如1500℃条件下的耐熔融玻璃侵蚀性能。所述Na2O的含量优选为0.15~0.39%,更优选为0.15~0.36%。所述P2O5的含量优选为0.05~0.15%。在本发明中,添加少量的SiO2,有利于防止制品开裂,提高成品率,所述SiO2的含量优选为0.15~1.0%,更优选为0.25~0.75%;如果原料中SiO2、P2O5、Na2O以及B2O3的含量高于限定值,将会导致玻璃相增多或β-Al2O3的显著提高,将显著影响耐熔融玻璃侵蚀性能。本发明的高纯刚玉砖可采用公知的电熔法制备,其制备方法包括以下步骤:首先,按照原料氧化物的重量百分比准备Al2O3、SiO2、Na2CO3、Li2CO3、BPO4、B2O3和Cr2O3得到原料粉末;各原料的纯度优选大于99%,原料粉末的粒径并无特殊要求,优选其中值粒径小于100μm,更优选为小于50μm。然后,将所述原料粉末加入三相电弧炉中加热熔融,并且通入氧气进行高温熔炼,熔炼温度控制在2100℃以上;熔炼后,将得到的熔液浇铸到石墨铸型中,并放入缓冷槽中用刚玉粉包埋进行保温退火并缓慢冷却至室温。最后,可根据制品规格采用金刚石工具切除浇口部位,并根据规格要求加工成制品。本发明的高纯刚玉砖适用于玻璃窑炉冷却部池壁、澄清部等部位,图2为玻璃窑炉内使用后的高纯刚玉砖的截面图,可以发现基本没有玻璃溶渣侵蚀的现象,显示了优异的耐玻璃侵蚀性能。
表1和表2分别示出了采用电熔法制备的实施例以及比较例的高纯刚玉砖的原料组成。
表1本发明实施例的高纯刚玉砖的原料组成(以氧化物计)wt%
原料 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 |
Al2O3 | 96.91 | 95.81 | 97.25 | 96.80 | 97.65 |
SiO2 | 0.15 | 0.75 | 0.60 | 0.50 | 0.25 |
Na2O | 0.45 | 0.36 | 0.30 | 0.25 | 0.15 |
Li2O | 0.15 | 0.09 | 0.08 | 0.05 | 0.05 |
P2O5 | 0.15 | 0.20 | 0.15 | 0.20 | 0.25 |
B2O3 | 0.12 | 0.05 | 0.15 | 0.15 | 0.15 |
Cr2O3 | 1.85 | 2.52 | 1.23 | 1.65 | 1.20 |
Fe2O3 | 0.08 | 0.09 | 0.07 | 0.08 | 0.07 |
CaO | 0.05 | 0.03 | 0.05 | - | - |
MgO | - | - | - | 0.25 | 0.10 |
TiO2 | 0.05 | 0.06 | 0.07 | 0.03 | 0.10 |
其它杂质 | 余量 | 余量 | 余量 | 余量 | 余量 |
其中:“-”表示含量在0.01%以下。
表2比较例的高纯刚玉砖的原料组成(以氧化物计)wt%
原料 | 比较例1 | 比较例2 | 比较例3 | 比较例4 | 比较例5 |
Al2O3 | 99.33 | 97.86 | 98.50 | 97.34 | 97.05 |
SiO2 | 0.08 | 0.30 | 0.60 | 0.60 | 0.60 |
Na2O | 0.39 | 0.30 | 0.30 | 0.30 | 0.30 |
Li2O | - | 0.10 | 0.08 | - | 0.30 |
P2O5 | - | - | 0.15 | 0.15 | 0.15 |
B2O3 | - | - | 0.15 | 0.15 | 0.15 |
Cr2O3 | - | 1.23 | - | 1.23 | 1.23 |
Fe2O3 | 0.02 | 0.07 | 0.07 | 0.07 | 0.07 |
CaO | 0.13 | 0.10 | 0.05 | 0.05 | 0.05 |
MgO | - | - | - | - | - |
TiO2 | - | - | 0.07 | 0.07 | 0.07 |
其它杂质 | 余量 | 余量 | 余量 | 余量 | 余量 |
其中:“-”表示含量在0.01%以下。
表3和表4分别示出了实施例和比较例的高纯刚玉砖的晶相结构以及性能。
表3实施例的高纯刚玉砖的晶相结构以及性能
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | |
α-Al2O3/β-Al2O3 | 95/5 | 96/4 | 92/8 | 92/8 | 92/8 |
抗折强度(MPa) | 45 | 47 | 45 | 45 | 45 |
抗热震稳定性(次) | 20 | 23 | 27 | 25 | 25 |
耐熔融玻璃侵蚀指数 | 173 | 162 | 203 | 223 | 201 |
表3比较例的高纯刚玉砖的晶相结构以及性能
比较例1 | 比较例2 | 比较例3 | 比较例4 | 比较例5 | |
α-Al2O3/β-Al2O3 | 92/8 | 92/8 | 92/8 | 94/6 | 92/8 |
抗折强度(MPa) | 41 | 45 | 37 | 45 | 45 |
抗热震稳定性(次) | 7 | 13 | 8 | 21 | 23 |
耐熔融玻璃侵蚀指数 | 100 | 82 | 105 | 107 | 117 |
其中:
所述抗热震稳定性次数通过以下方法测量:将尺寸为20cm×10cm×10cm的样品,在加热炉内加热至1500℃保温15min,然后取出后在空气中冷却15min,依次循环直至肉眼观察到出现裂纹时的循环次数,计为抗热震稳定性次数。
所述耐熔融玻璃侵蚀指数通过以下方法测量:规格为φ20mm×100mm的圆柱样品,旋转浸没在内有普通钠钙玻璃浴的容器内,加热到1500℃,并且使得所述圆柱样品绕其中心轴线以6转/分钟的速度旋转,测试时间为24小时,然后测定被侵蚀样品的剩余体积。以比较例1(参比样品)的剩余体积作为比较基准,并且将参比样品的耐熔融玻璃侵蚀指数定义为100,然后采用上述相同的测量被侵蚀样品的剩余体积,以(被侵蚀样品的剩余体积除以参比样品的剩余体积)×100定义为被侵蚀样品的耐熔融玻璃侵蚀指数。
Claims (6)
1.一种高纯刚玉砖,其特征在于:以原料氧化物的重量百分比计含有:0.08~1.0%的SiO2、0.15~0.45%的Na2O、0.05~0.15%的Li2O、0.05~0.25%的P2O5、0.05~0.15%的B2O3、1.2~3.0%的Cr2O3,和余量的Al2O3以及杂质;其中:Na2O/Li2O重量比为3~5,P2O5以BPO4的形式添加;所述杂质的含量小于1.0%,所述杂质中Fe2O3+CaO+MgO+TiO2的总量小于0.4%,其中:Fe2O3的含量小于0.10%,TiO2的含量小于0.10%,CaO的含量小于0.05%;以结晶组成的重量百分比计,所述高纯刚玉砖为电熔α-Al2O3型刚玉砖,并且结晶组成包括92~98%的α-Al2O3和2~8%的β-Al2O3;所述高纯刚玉砖中玻璃相的含量小于2.0%;并且所述高纯刚玉砖的制备方法包括以下步骤:
(1)配料:按照原料氧化物的重量百分比准备Al2O3、SiO2、Na2CO3、Li2CO3、BPO4、B2O3和Cr2O3得到原料粉末;各原料的纯度大于99%;
(2)熔炼:将所述原料粉末加入三相电弧炉中加热熔融,并且通入氧气进行高温熔炼,熔炼温度控制在2100℃以上;
(3)浇铸:将得到的熔液浇铸到石墨铸型中,并放入缓冷槽中用刚玉粉包埋进行保温退火并缓慢冷却至室温;
(4)加工:将保温退火后得到的耐火产品加工成所述高纯刚玉砖。
2.根据权利要求1所述的高纯刚玉砖,其特征在于:所述Al2O3的含量大于95%。
3.根据权利要求1所述的高纯刚玉砖,其特征在于:所述SiO2的含量为0.15~1.0%。
4.根据权利要求1所述的高纯刚玉砖,其特征在于:所述Cr2O3的含量为1.2~2.5%。
5.根据权利要求1所述的高纯刚玉砖,其特征在于:所述Na2O的含量为0.15~0.39%。
6.根据权利要求1所述的高纯刚玉砖,其特征在于:所述P2O5的含量为0.05~0.15%。
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