CN113321494A - 一种抗氧化、长寿命吸储热一体的刚玉-莫来石陶瓷及其制备方法 - Google Patents
一种抗氧化、长寿命吸储热一体的刚玉-莫来石陶瓷及其制备方法 Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 15
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Abstract
一种抗氧化、长寿命吸储热一体的刚玉‑莫来石陶瓷及其制备方法,制备所述陶瓷的原料及改性剂的质量百分比为:氧化铝65~75wt%、苏州土15~20wt%、氧化钛3~5wt%、氧化钼3~6wt%、氧化铁5~7%、氧化镍2~3wt%。本发明所制备的陶瓷具备优良的储热能力和优良的储热和吸热能力,抗高温氧化能力、抗折强度高,具有良好的机械性能和抗热震循环稳定性,且该材料更长的使用寿命。
Description
技术领域
本发明涉及一种太阳能热发电等所使用的陶瓷技术领域,尤其涉及一种抗氧化、长寿命吸储热一体的刚玉-莫来石陶瓷及其制备方法。
背景技术
传统的太阳能热发电系统中吸热材料和储热材料是分开的两个系统,即吸热材料吸热后,加热空气或熔盐等传热介质,再由传热介质加热储热材料。而新一代的太阳能热发电系统越来越强调吸热储热一体化,即将吸热与储热材料合为一体,从而减少热交换过程中的能量损失,提高热发电效率。如中国发明专利《集吸热、储热及蒸汽发生于一体的太阳能热发电多功能设备》(CN200810029316.8)采用铝合金作为吸/储热一体材料。中国发明专利《一种太阳能吸热储热塔及太阳能光热发电系统》(CN201911126096.5)采用熔盐作为吸/储热一体材料。中国实用新型专利《基于太阳能高温热化学颗粒的吸热储热系统》(CN201921475614.X)采用热化学颗粒作为吸/储热一体材料。
吸/储热一体材料要求同时具备高太阳辐射吸收率,又需具备高储热密度、优良抗热震性、热稳定性等优异性能。陶瓷材料由于具有优良的高温稳定性和严苛热循环条件下的稳定服役能力,是一类有前景的吸/储热一体材料。中国发明专利《太阳能热发电吸/储热一体化刚玉/SiC陶瓷材料及其制备方法》(CN202010072667.8)制备了一种刚玉/SiC材质的吸/储热一体材料,同时关注了其吸热和储热性能,其强度为76-85MPa,抗高温氧化性能有待提高,高温氧化导致长期使用后其吸/储热性能的降低,使用寿命不高。
发明内容
为解决上述问题,本发明提出抗氧化、长寿命吸储热一体的刚玉-莫来石陶瓷,具体技术方案为:
一种抗氧化、长寿命吸储热一体的刚玉-莫来石陶瓷,制备所述陶瓷的原料及改性剂的质量百分比为:氧化铝65~75wt%、苏州土15~20wt%、氧化钛3~5wt%、氧化钼3~6wt%、氧化铁5~7%、氧化镍2~3wt%。
一种制备如权利要求1所述的陶瓷的方法,包括以下步骤:
(1)原料处理:将氧化铝粉、苏州土过250目筛,制备粉料备用;
(2)原料配比与混合:原料中加入改性剂,各原料和改性剂按一定质量百分数配比后,用球磨机球磨1~3h混合均匀,得到混合料,其中,料球质量比为1:2;
(3)造粒和陈腐:采用喷雾干燥法往混合料中加入质量为3~5%的水,造粒后陈腐48h以上得到坯料;
(4)半干压成型:采用液压机将陈腐好的坯料压制成型后得到圆柱状太阳能储热陶瓷生坯,其中,生坯尺寸为800mm,高度为100mm;成型压力为90~120kN;
(5)干燥:将成型好的生坯置于干燥箱中在95~120℃下干燥24~48h,得到坯体;
(6)烧成:将干燥好坯体放入电炉中在一定温度下烧成,得到太阳能储热陶瓷。
进一步地,步骤(2)中,所述改性剂为纯度为98%以上的氧化钛、氧化钼、氧化铁和氧化镍,其粒度为5~10μm。
进一步地,步骤(2)中,各原料及改性剂的所占质量百分数为:氧化铝65~75wt%、苏州土15~20wt%、氧化钛3~5wt%、氧化钼3~6wt%、氧化铁5~7%、氧化镍2~3wt%。
进一步地,步骤(6)中,烧成的温度控制为:电炉中的温度<1000℃时,升温速率7~10℃/min,每整百温度点保温30min;温度≥1000℃时,升温速率3~5℃/min,每整百温度点保温1h,最高温度点保温120min,再随炉冷却。
进一步地,步骤(6)中,所述烧成的最高温度为1500~1600℃。
本发明的有益效果:
(1)本发明所制备的陶瓷具备优良的储热能力,其比热容为1.02~1.15kJ/kg·℃,200~1000℃储热密度可达3000~3300kJ/kg,这得益于添加改性剂氧化钛促进了烧成的致密化;另外,其太阳光吸收率最高可达90~95%,这是由于氧化铁和氧化镍的添加,极大地提高了该材料对太阳光的吸热能力。因此本发明制备的陶瓷材料兼具优良的储热和吸热能力。
(2)本发明所制备的陶瓷具有优良的抗高温氧化能力,其抗折强度可达280~350MPa,经受室温~1000℃热震循环50次不开裂,具有良好的机械性能和抗热震循环稳定性。这得益于添加剂氧化钼,促进了体系中莫来石晶须的生长,且调控了显微结构生长为柱状莫来石结合刚玉晶粒的高强韧结构,赋予了该材料更长的使用寿命。
附图说明
图1为本发明制备的陶瓷材料的典型微观结构。
具体实施方式
下面结合具体实施例及附图对本发明做进一步描述:
一种抗氧化、长寿命吸储热一体的刚玉-莫来石陶瓷,制备所述陶瓷的原料及改性剂的质量百分比为:氧化铝65~75wt%、苏州土15~20wt%、氧化钛3~5wt%、氧化钼3~6wt%、氧化铁5~7%、氧化镍2~3wt%。
下面通过具体的实施例来阐述制备该陶瓷材料的方法:
实施例1:
本实施例制备所述陶瓷,包括以下步骤:
(1)原料处理:将氧化铝粉、苏州土过250目筛制备粉料备用;
(2)原料配比与混合:原料中加入改性剂,各原料和改性剂按一定质量百分数配比后,用球磨机球磨1h混合均匀,得到混合料,其中,料球质量比为1:2;
(3)造粒和陈腐:采用喷雾干燥法往混合料中加入质量为3%的水,造粒后陈腐48h得到坯料;
(4)半干压成型:采用液压机将陈腐好的坯料压制成型后得到圆柱状太阳能储热陶瓷生坯,其中,生坯尺寸为800mm,高度为100mm;成型压力为90kN;
(5)干燥:将成型好的生坯置于干燥箱中在95℃下干燥24h,得到坯体;
(6)烧成:将干燥好坯体放入电炉中在一定温度下烧成,得到太阳能储热陶瓷。
其中,步骤2所述改性剂为纯度为98%的氧化钛、氧化钼、氧化铁、氧化镍,粒度为10μm。
步骤2各原料及改性剂的所占质量百分数为:氧化铝65wt%,苏州土20wt%、氧化钛5wt%、氧化钼3wt%、氧化铁5%、氧化镍2wt%。
步骤6中的烧成的温度控制为:电炉中的温度<1000℃时,升温速率7℃/min,每整百温度点保温30min;温度≥1000℃时,升温速率3℃/min,每整百温度点保温1h,最高温度点保温120min,再随炉冷却。
步骤6所述烧成的最高温度为1500℃。
本实施例制备的刚玉-莫来石质吸/储热一体陶瓷具备优良的储热能力,其比热容为1.02kJ/kg·℃,200~1000℃储热密度可达3100kJ/kg;另外,其太阳光吸收率最高可达90%。刚玉-莫来石吸/储热一体材料的抗折强度可达280MPa,经受室温~1000℃热震循环50次不开裂;经1000℃高温氧化实验后样品外观与质量均无变化。
实施例2:
本实施例制备所述陶瓷,包括以下步骤:
(1)原料处理:将氧化铝粉、苏州土过250目筛制备粉料备用;
(2)原料配比与混合:原料中加入改性剂,各原料和改性剂按一定质量百分数配比后,用球磨机球磨3h混合均匀,得到混合料,其中,料球质量比为1:2;
(3)造粒和陈腐:采用喷雾干燥法往混合料中加入质量为5%的水,造粒后陈腐48h以上得到坯料;
(4)半干压成型:采用液压机将陈腐好的坯料压制成型后得到圆柱状太阳能储热陶瓷生坯,其中,生坯尺寸为800mm,高度为100mm;成型压力为120kN;
(5)干燥:将成型好的生坯置于干燥箱中在120℃下干燥48h,得到坯体;
(6)烧成:将干燥好坯体放入电炉中在一定温度下烧成,得到太阳能储热陶瓷。
进一步地,步骤2所述改性剂为纯度为98%的氧化钛、氧化钼、氧化铁、氧化镍,粒度为10μm。
进一步地,步骤2各原料及改性剂的所占质量百分数为:氧化铝70wt%,苏州土15wt%、氧化钛3wt%、氧化钼3wt%、氧化铁7%、氧化镍2wt%。
进一步地,步骤6中的烧成的温度控制为:电炉中的温度<1000℃时,升温速率10℃/min,每整百温度点保温30min;温度≥1000℃时,升温速率5℃/min,每整百温度点保温1h,最高温度点保温120min,再随炉冷却。
进一步地,步骤6所述烧成的最高温度为1600℃。
本实施例制造的刚玉-莫来石质吸/储热一体陶瓷具备优良的储热能力,其比热容为1.15kJ/kg·℃,200~1000℃储热密度可达3300kJ/kg;另外,其太阳光吸收率可达95%。刚玉-莫来石吸/储热一体材料的抗折强度可达350MPa,经受室温~1000℃热震循环50次不开裂;经1000℃高温氧化实验后样品外观与质量均无变化。
实施例3:
本实施例制备所述陶瓷,包括以下步骤:
(1)原料处理:将氧化铝粉、苏州土过250目筛制备粉料备用;
(2)原料配比与混合:原料中加入改性剂,各原料和改性剂按一定质量百分数配比后,用球磨机球磨2h混合均匀,得到混合料,其中,料球质量比为1:2;
(3)造粒和陈腐:采用喷雾干燥法往混合料中加入质量为4%的水,造粒后陈腐48h以上得到坯料;
(4)半干压成型:采用液压机将陈腐好的坯料压制成型后得到圆柱状太阳能储热陶瓷生坯,其中,生坯尺寸为800mm,高度为100mm;成型压力为105kN;
(5)干燥:将成型好的生坯置于干燥箱中在110℃下干燥36h,得到坯体;
(6)烧成:将干燥好坯体放入电炉中在一定温度下烧成,得到太阳能储热陶瓷。
进一步地,步骤2所述改性剂为纯度为98%的氧化钛、氧化钼、氧化铁、氧化镍,粒度为7.5μm。
进一步地,步骤2各原料及改性剂的所占质量百分数为:氧化铝72wt%,苏州土15wt%、氧化钛3wt%、氧化钼3wt%、氧化铁5%、氧化镍2wt%。
进一步地,步骤6中的烧成的温度控制为:电炉中的温度<1000℃时,升温速率8℃/min,每整百温度点保温30min;温度≥1000℃时,升温速率4℃/min,每整百温度点保温1h,最高温度点保温120min,再随炉冷却。
进一步地,步骤6所述烧成的最高温度为1550℃。
本实施例制造的刚玉-莫来石质吸/储热一体陶瓷具备优良的储热能力,其比热容为1.08kJ/kg·℃,200~1000℃储热密度可达3210kJ/kg;另外,其太阳光吸收率可达92%。刚玉-莫来石吸/储热一体材料的抗折强度可达322MPa,经受室温~1000℃热震循环50次不开裂;经1000℃高温氧化实验后样品外观与质量均无变化。
经测试,实施例1至3所制备的刚玉-莫来石陶瓷的性能数据如下:
综上,本发明的刚玉-莫来石质吸/储热一体陶瓷具备优良的吸热-储热一体化能力,且具有优秀的抗高温氧化能力、良好的机械性能和抗热震循环稳定性;如图1所示为本发明所制备的陶瓷材料的典型微观结构,添加剂的加入,调控了显微结构生长为柱状莫来石结合刚玉晶粒的高强韧结构,赋予了该材料更长的使用寿命。
Claims (6)
1.一种抗氧化、长寿命吸储热一体的刚玉-莫来石陶瓷,其特征在于,制备所述陶瓷的原料及改性剂的质量百分比为:氧化铝65~75wt%、苏州土15~20wt%、氧化钛3~5wt%、氧化钼3~6wt%、氧化铁5~7%、氧化镍2~3wt%。
2.一种制备如权利要求1所述的陶瓷的方法,其特征在于,包括以下步骤:
(1)原料处理:将氧化铝粉、苏州土过250目筛,制备粉料备用;
(2)原料配比与混合:原料中加入改性剂,各原料和改性剂按一定质量百分数配比后,用球磨机球磨1~3h混合均匀,得到混合料,其中,料球质量比为1:2;
(3)造粒和陈腐:采用喷雾干燥法往混合料中加入质量为3~5%的水,造粒后陈腐48h以上得到坯料;
(4)半干压成型:采用液压机将陈腐好的坯料压制成型后得到圆柱状太阳能储热陶瓷生坯,其中,生坯尺寸为800mm,高度为100mm;成型压力为90~120kN;
(5)干燥:将成型好的生坯置于干燥箱中在95~120℃下干燥24~48h,得到坯体;
(6)烧成:将干燥好坯体放入电炉中在一定温度下烧成,得到太阳能储热陶瓷。
3.根据权利要求2所述的方法,其特征在于,步骤(2)中,所述改性剂为纯度为98%以上的氧化钛、氧化钼、氧化铁和氧化镍,其粒度为5~10μm。
4.根据权利要求3所述的方法,其特征在于,步骤(2)中,各原料及改性剂的所占质量百分数为:氧化铝65~75wt%、苏州土15~20wt%、氧化钛3~5wt%、氧化钼3~6wt%、氧化铁5~7%、氧化镍2~3wt%。
5.根据权利要求2所述的方法,其特征在于,步骤(6)中,烧成的温度控制为:电炉中的温度<1000℃时,升温速率7~10℃/min,每整百温度点保温30min;温度≥1000℃时,升温速率3~5℃/min,每整百温度点保温1h,最高温度点保温120min,再随炉冷却。
6.根据权利要求5所述的方法,其特征在于,步骤(6)中,所述烧成的最高温度为1500~1600℃。
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