CN110423131A - 一种太阳能吸热复合材料的制备方法 - Google Patents
一种太阳能吸热复合材料的制备方法 Download PDFInfo
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Abstract
本发明涉及一种太阳能吸热复合材料的制备方法,属于太阳能技术领域。本发明通过添加红柱石、碳化硅和氮化硅,制备一种太阳能吸热复合材料,红柱石是一种铝硅酸盐矿物,红柱石在常压下加热至1350℃以后,开始转化成与原晶体平行的针状莫来石,莫来石化后的红柱石耐骤冷骤热,机械强度大,抗热冲击力强,抗渣性强,荷重转化点高,并具有极高的化学稳定性和极强的抗化学腐蚀性,碳化硅结合氮化硅具有良好的抗氧化性,材料中碳化硅本身除了耐磨性好外,热传导率较高,热膨胀系数低,使氮化硅结合碳化硅具有优良的抗热震性能,对外来侵蚀介质渗透起着阻碍和延缓作用,从而使太阳能吸热复合材料具有良好的化学稳定性。
Description
技术领域
本发明涉及一种太阳能吸热复合材料的制备方法,属于太阳能技术领域。
背景技术
石油、煤炭、天然气等传统化石能源正日益枯竭,而人类的发展对能源需求的不断增加,能源紧缺问题迫在眉睫。世界各国采取了可再生能源替代传统化石能源的一系列措施,太阳能热发电技术正是在此背景发展的一种有效解决能源短缺问题的方法。而事实证明,利用太阳能替代一部分化石能源是一种切实可行的方法,人们开发出了多种太阳能利用技术,如太阳能热水器、太阳能釆暖、太阳能干燥、太阳能热发电等。如前所述,化石能源的有限性和使用过程中导致环境日益恶化使得发展可再生能源已经成为不可逆转的趋势,太阳能以其分布广、储量丰富、清洁环保等优点受到了广泛关注。自1878年人类建立历史上第一个太阳能热交互式蒸汽机以来,经过多年经验和技术的积累,太阳能热利用技术应用越来越广泛。如今,美许多国家都将太阳能热利用技术作为能源战略的重点。从本世纪开始,可再生能源的发展将进入兴盛期,但在相当长的一段时间,太阳能热利用技术大规模应用的成本依旧难以下降,经济成本上仍无法与传统的化石能源相比。再加上太阳能的不连续性、不稳定性、光能转化效率低等缺点同样是制约其发展的重要难题。
太阳能利用技术种类很多,其中以太阳能发电技术最受重视。目前,又以太阳能光伏发电和热发电技术较为成熟,许多国已经推广家庭式太阳能光伏发电系统多年,同时这些国家还非常重视太阳能热发电技术的开发,取得了大量科研成果,建立了多座太阳能热发电站,现正有蓬勃发展之势。
塔式太阳能热发电系统由聚光集热子系统、吸热与传热子系统、蓄热子系统、蒸汽发生器子系统和发电子系统组成。太阳能热发电的工作原理是:太阳光由集热子系统聚焦并反射到吸热子系统;高热流密度的太阳能经吸热器的HTF(传热介质)吸收后转化成热能;高温HTF流过地面的蒸汽发生器,产生蒸汽或气体进入汽轮机发电机组或燃气轮机发电机组产生电能。作为太阳能热发电吸热体材料,需要承受1000℃以上的高温以及恶劣的工作环境。因此对吸热体材料最基本的要求是其必须具有良好的高温性能,如高温弯曲强度、热膨胀系数、抗热震性、抗高温氧化性等。在高温环境下使用的吸热体材料,需要经受传热介质的侵蚀、冲刷,环境介质的氧化作用以及温度急剧变化所带来的热冲击力。因此,材质选择和性能设计时不但要考虑材料的温度水平,更要考虑材料的抗侵蚀、抗氧化及抗热震性能。
发明内容
本发明所要解决的技术问题:针对普通吸热材料不能满足太阳能吸热体耐氧化的问题,提供了一种太阳能吸热复合材料的制备方法。
为解决上述技术问题,本发明是通过以下技术方案实现的:
(1)将改性碳纤维浆料、氧化镁粉末、氯化钙粉末加入混合浆料中,置于搅拌机内,常温下以600~800r/min转速搅拌1~2h,得复合浆料;
(2)将复合浆料倒入模具中,置于微波烧结炉中,从常温升至1300~1500℃,保温煅烧2~4h,随炉冷却至室温,脱模,得太阳能吸热复合材料。
所述的混合浆料、改性碳纤维浆料、氧化镁粉末、氯化钙粉末的重量份为80~100份混合浆料、20~25份改性碳纤维浆料、4~5份氧化镁粉末、8~10份氯化钙粉末。
步骤(2)所述的模具的规格为80cm×60cm×60cm,升温速率为50℃/min。
步骤(1)所述的混合浆料的具体制备步骤为:
(1)将碳化硅粉末、氮化硅粉末、氧化锆粉末、红柱石粉末、刚玉粉末置于高速搅拌机中,常温下以1000~1200r/min转速搅拌20~30min,得混合粉末;
(2)将羧甲基纤维素、聚乙烯醇加入去离子水中,在40~50℃的水浴条件下以240~280r/min的转速搅拌20~30min,得聚合物溶液;
(3)将混合粉末加入聚合物溶液中,置于球磨机内,常温下以200~250r/min转速球磨6~8h,过筛,得混合浆料。
所述的碳化硅粉末、氮化硅粉末、氧化锆粉末、红柱石粉末、刚玉粉末、羧甲基纤维素、聚乙烯醇、去离子水的重量份为40~50份碳化硅粉末、40~50份氮化硅粉末、16~20份氧化锆粉末、12~15份红柱石粉末、8~10份刚玉粉末、4~5份羧甲基纤维素、8~10份聚乙烯醇、120~150份去离子水。
步骤(3)所述的筛目规格为80~100。
步骤(1)所述的改性碳纤维浆料的具体制备步骤为:
(1)将碳纤维置于剪切机中剪切5~10min,得短碳纤维;
(2)将短碳纤维置于马弗炉中,在500~550℃的条件下保温煅烧2~3h,随炉冷却至室温,得预氧化短碳纤维;
(3)将硝酸加入丙酮中,常温下以160~180r/min转速搅拌10~15min,得改性液;
(4)将预氧化短碳纤维加入改性液中,置于40~50℃的水浴条件下以180~200r/min转速搅拌10~12h,过滤,取滤饼,用去离子水洗涤至中性,置于80~90℃的烘箱中干燥1~2h,得改性短碳纤维;
(5)将改性短碳纤维、羧甲基纤维素加入去离子水中,置于超声波分散机内,在50~60℃的条件下超声处理2~4h,常温冷却,得改性碳纤维浆料;
所述的碳纤维、硝酸、丙酮、羧甲基纤维素、去离子水的重量份为20~30份碳纤维、20~30份质量分数10%的硝酸、20~30份丙酮、12~18份羧甲基纤维素、60~90份去离子水。
步骤(1)所述的短碳纤维的平均长度为2~4mm。
步骤(5)所述的超声处理的功率本发明与其他技术相比,有益效果在于:
本发明通过添加红柱石、碳化硅和氮化硅,制备一种太阳能吸热复合材料,红柱石是一种铝硅酸盐矿物,它是耐火材料和瓷器的原料,红柱石在常压下加热至1350℃以后,开始转化成与原晶体平行的针状莫来石,莫来石晶体是铝硅酸盐在高温作用下唯一稳定的形式,红柱石在加热转化成莫来石的过程中,可以形成良好的莫来石网络,体积稍微膨胀,这是一种不可逆的晶体转化,一经转化,则具有更高的耐火性能,耐火度可达1800℃以上,且红柱石的莫来石化通常由颗粒边沿或颗粒裂隙部位逐步向颗粒的中心部位扩展,玻璃相处于颗粒之间基质中呈针状晶体莫来石,交织成网状,强化了基质与骨料颗粒的结合程度红柱石的莫来石化程度受锻烧温度的影响,温度愈高,莫来石的生成量愈高,转化愈完全,红柱石的莫来石化结晶具有方向性,平行于原红柱石晶面,仍保留原红柱石颗粒轮廓形状,柱状莫来石作为主晶相交错分布形成了特殊的网络结构,构成骨架,为连续相,而玻璃相则处于颗粒之间,莫来石化后的红柱石耐骤冷骤热,机械强度大,抗热冲击力强,抗渣性强,荷重转化点高,并具有极高的化学稳定性和极强的抗化学腐蚀性,碳化硅是一种力学性能好、化学性能稳定、导热系数高、热膨胀系数小、耐磨性能好的材料,碳化硅的抗氧化性能很好,同时,还具有热膨胀系数小及抗热震性能良好的性能,氮化硅与碳化硅的性能接近,具有较高的热稳定性和化学稳定性,是材料的理想结合相,碳化硅与氮化硅均为强共价键化合物,并且都具有高的导热系数,同时,氮化硅结合碳化硅材料具有优良的抗折强度、耐高温性、断裂韧性和抗热震性,且表面氧化后可形成致密氧化物保护膜,阻止氧化的进一步进行,具有较好的抗氧化性,很适合作高温材料,氮化硅结合碳化硅陶瓷材料的烧结属于固相反应烧结,液相量很少,这种显微结构赋予该材料较高的高温强度,碳化硅结合氮化硅具有良好的抗氧化性,这是因为高温氧化时,陶瓷表面形成的二氧化硅玻璃相封闭了气孔,有效地防止了内部材料免受氧化而保持强度不会快速下降,材料中碳化硅本身除了耐磨性好外,热传导率较高,热膨胀系数低,使氮化硅结合碳化硅具有优良的抗热震性能,该材料紧密交织的结合形式使碳化硅颗粒表面得到良好保护,对外来侵蚀介质渗透起着阻碍和延缓作用,从而使太阳能吸热复合材料具有良好的化学稳定性。
具体实施方式
按重量份数计,分别称量20~30份碳纤维、20~30份质量分数10%的硝酸、20~30份丙酮、12~18份羧甲基纤维素、60~90份去离子水,将碳纤维置于剪切机中剪切5~10min,得平均长度2~4mm的短碳纤维,将短碳纤维置于马弗炉中,在500~550℃的条件下保温煅烧2~3h,随炉冷却至室温,得预氧化短碳纤维,将硝酸加入丙酮中,常温下以160~180r/min转速搅拌10~15min,得改性液,将预氧化短碳纤维加入改性液中,置于40~50℃的水浴条件下以180~200r/min转速搅拌10~12h,过滤,取滤饼,用去离子水洗涤至中性,置于80~90℃的烘箱中干燥1~2h,得改性短碳纤维,将改性短碳纤维、羧甲基纤维素加入去离子水中,置于超声波分散机内,在50~60℃的条件下以500~600W的功率超声处理2~4h,常温冷却,得改性碳纤维浆料;再按重量份数计,分别称量40~50份碳化硅粉末、40~50份氮化硅粉末、16~20份氧化锆粉末、12~15份红柱石粉末、8~10份刚玉粉末、4~5份羧甲基纤维素、8~10份聚乙烯醇、120~150份去离子水,将碳化硅粉末、氮化硅粉末、氧化锆粉末、红柱石粉末、刚玉粉末置于高速搅拌机中,常温下以1000~1200r/min转速搅拌20~30min,得混合粉末,将羧甲基纤维素、聚乙烯醇加入去离子水中,在40~50℃的水浴条件下以240~280r/min的转速搅拌20~30min,得聚合物溶液,将混合粉末加入聚合物溶液中,置于球磨机内,常温下以200~250r/min转速球磨6~8h,得混合浆料;再按重量份数计,分别称量80~100份混合浆料、20~25份改性碳纤维浆料、4~5份氧化镁粉末、8~10份氯化钙粉末,将改性碳纤维浆料、氧化镁粉末、氯化钙粉末加入混合浆料中,置于搅拌机内,常温下以600~800r/min转速搅拌1~2h,得复合浆料,将复合浆料倒入规格为80cm×60cm×60cm的模具中,置于微波烧结炉中,以50℃/min的升温速率从常温升至1300~1500℃,保温煅烧2~4h,随炉冷却至室温,脱模,得太阳能吸热复合材料。
实施例1
按重量份数计,分别称量20份碳纤维、20份质量分数10%的硝酸、20份丙酮、12份羧甲基纤维素、60份去离子水,将碳纤维置于剪切机中剪切5min,得平均长度2mm的短碳纤维,将短碳纤维置于马弗炉中,在500℃的条件下保温煅烧2h,随炉冷却至室温,得预氧化短碳纤维,将硝酸加入丙酮中,常温下以160r/min转速搅拌10min,得改性液,将预氧化短碳纤维加入改性液中,置于40℃的水浴条件下以180r/min转速搅拌10h,过滤,取滤饼,用去离子水洗涤至中性,置于80℃的烘箱中干燥1h,得改性短碳纤维,将改性短碳纤维、羧甲基纤维素加入去离子水中,置于超声波分散机内,在50℃的条件下以500W的功率超声处理2h,常温冷却,得改性碳纤维浆料;再按重量份数计,分别称量40~50份碳化硅粉末、40份氮化硅粉末、16份氧化锆粉末、12份红柱石粉末、8份刚玉粉末、4份羧甲基纤维素、8份聚乙烯醇、120份去离子水,将碳化硅粉末、氮化硅粉末、氧化锆粉末、红柱石粉末、刚玉粉末置于高速搅拌机中,常温下以1000r/min转速搅拌20min,得混合粉末,将羧甲基纤维素、聚乙烯醇加入去离子水中,在40℃的水浴条件下以240r/min的转速搅拌20min,得聚合物溶液,将混合粉末加入聚合物溶液中,置于球磨机内,常温下以200r/min转速球磨6h,得混合浆料;再按重量份数计,分别称量80份混合浆料、20份改性碳纤维浆料、4份氧化镁粉末、8份氯化钙粉末,将改性碳纤维浆料、氧化镁粉末、氯化钙粉末加入混合浆料中,置于搅拌机内,常温下以600r/min转速搅拌1h,得复合浆料,将复合浆料倒入规格为80cm×60cm×60cm的模具中,置于微波烧结炉中,以50℃/min的升温速率从常温升至1300℃,保温煅烧2h,随炉冷却至室温,脱模,得太阳能吸热复合材料。
实施例2
按重量份数计,分别称量25份碳纤维、25份质量分数10%的硝酸、25份丙酮、15份羧甲基纤维素、75份去离子水,将碳纤维置于剪切机中剪切8min,得平均长度3mm的短碳纤维,将短碳纤维置于马弗炉中,在525℃的条件下保温煅烧2.5h,随炉冷却至室温,得预氧化短碳纤维,将硝酸加入丙酮中,常温下以170r/min转速搅拌13min,得改性液,将预氧化短碳纤维加入改性液中,置于45℃的水浴条件下以190r/min转速搅拌11h,过滤,取滤饼,用去离子水洗涤至中性,置于85℃的烘箱中干燥1.5h,得改性短碳纤维,将改性短碳纤维、羧甲基纤维素加入去离子水中,置于超声波分散机内,在55℃的条件下以550W的功率超声处理3h,常温冷却,得改性碳纤维浆料;再按重量份数计,分别称量45份碳化硅粉末、45氮化硅粉末、18份氧化锆粉末、14份红柱石粉末、9份刚玉粉末、4.5份羧甲基纤维素、9份聚乙烯醇、135份去离子水,将碳化硅粉末、氮化硅粉末、氧化锆粉末、红柱石粉末、刚玉粉末置于高速搅拌机中,常温下以1100r/min转速搅拌25min,得混合粉末,将羧甲基纤维素、聚乙烯醇加入去离子水中,在45℃的水浴条件下以260r/min的转速搅拌25min,得聚合物溶液,将混合粉末加入聚合物溶液中,置于球磨机内,常温下以225r/min转速球磨7h,得混合浆料;再按重量份数计,分别称量90份混合浆料、23份改性碳纤维浆料、4.5份氧化镁粉末、9份氯化钙粉末,将改性碳纤维浆料、氧化镁粉末、氯化钙粉末加入混合浆料中,置于搅拌机内,常温下以700r/min转速搅拌1.5h,得复合浆料,将复合浆料倒入规格为80cm×60cm×60cm的模具中,置于微波烧结炉中,以50℃/min的升温速率从常温升至1400℃,保温煅烧3h,随炉冷却至室温,脱模,得太阳能吸热复合材料。
实施例3
按重量份数计,分别称量30份碳纤维、30份质量分数10%的硝酸、30份丙酮、18份羧甲基纤维素、90份去离子水,将碳纤维置于剪切机中剪切10min,得平均长度4mm的短碳纤维,将短碳纤维置于马弗炉中,在550℃的条件下保温煅烧3h,随炉冷却至室温,得预氧化短碳纤维,将硝酸加入丙酮中,常温下以180r/min转速搅拌15min,得改性液,将预氧化短碳纤维加入改性液中,置于50℃的水浴条件下以200r/min转速搅拌12h,过滤,取滤饼,用去离子水洗涤至中性,置于90℃的烘箱中干燥2h,得改性短碳纤维,将改性短碳纤维、羧甲基纤维素加入去离子水中,置于超声波分散机内,在60℃的条件下以600W的功率超声处理4h,常温冷却,得改性碳纤维浆料;再按重量份数计,分别称量50份碳化硅粉末、50份氮化硅粉末、20份氧化锆粉末、15份红柱石粉末、10份刚玉粉末、5份羧甲基纤维素、10份聚乙烯醇、150份去离子水,将碳化硅粉末、氮化硅粉末、氧化锆粉末、红柱石粉末、刚玉粉末置于高速搅拌机中,常温下以1200r/min转速搅拌30min,得混合粉末,将羧甲基纤维素、聚乙烯醇加入去离子水中,在50℃的水浴条件下以280r/min的转速搅拌30min,得聚合物溶液,将混合粉末加入聚合物溶液中,置于球磨机内,常温下以250r/min转速球磨8h,得混合浆料;再按重量份数计,分别称量100份混合浆料、25份改性碳纤维浆料、5份氧化镁粉末、10份氯化钙粉末,将改性碳纤维浆料、氧化镁粉末、氯化钙粉末加入混合浆料中,置于搅拌机内,常温下以800r/min转速搅拌2h,得复合浆料,将复合浆料倒入规格为80cm×60cm×60cm的模具中,置于微波烧结炉中,以50℃/min的升温速率从常温升至1500℃,保温煅烧4h,随炉冷却至室温,脱模,得太阳能吸热复合材料。
将本发明制备的太阳能吸热复合材料进行性能检测,具体检测结果如下表表1。
性能测试:
抗氧化性能:将实施例1-3制备的太阳能吸热复合材料切取一小块,放入空气流动状况良好的箱式硅钼棒电阻炉中进行氧化,测试条件为:时间10h,温度1100℃。测得其氧化增重数据。
表1太阳能吸热复合材料性能表征
检测项目 | 实施例1 | 实施例2 | 实施例3 |
m<sub>0</sub>/g | 6.0773 | 5.8927 | 6.1675 |
m/g(10h) | 6.2785 | 6.1293 | 6.3036 |
△m/mg·cm<sup>-2</sup> | 10.1578 | 12.2007 | 7.0968 |
由表1可知,本发明制备的太阳能吸热复合材料具有良好的抗氧化性。
Claims (10)
1.一种太阳能吸热复合材料的制备方法,其特征在于,具体制备步骤为:
(1)将改性碳纤维浆料、氧化镁粉末、氯化钙粉末加入混合浆料中,置于搅拌机内,常温下以600~800r/min转速搅拌1~2h,得复合浆料;
(2)将复合浆料倒入模具中,置于微波烧结炉中,从常温升至1300~1500℃,保温煅烧2~4h,随炉冷却至室温,脱模,得太阳能吸热复合材料。
2.根据权利要求1所述的一种太阳能吸热复合材料的制备方法,其特征在于,所述的混合浆料、改性碳纤维浆料、氧化镁粉末、氯化钙粉末的重量份为80~100份混合浆料、20~25份改性碳纤维浆料、4~5份氧化镁粉末、8~10份氯化钙粉末。
3.根据权利要求1所述的一种太阳能吸热复合材料的制备方法,其特征在于,步骤(2)所述的模具的规格为80cm×60cm×60cm,升温速率为50℃/min。
4.根据权利要求1所述的一种太阳能吸热复合材料的制备方法,其特征在于,步骤(1)所述的混合浆料的具体制备步骤为:
(1)将碳化硅粉末、氮化硅粉末、氧化锆粉末、红柱石粉末、刚玉粉末置于高速搅拌机中,常温下以1000~1200r/min转速搅拌20~30min,得混合粉末;
(2)将羧甲基纤维素、聚乙烯醇加入去离子水中,在40~50℃的水浴条件下以240~280r/min的转速搅拌20~30min,得聚合物溶液;
(3)将混合粉末加入聚合物溶液中,置于球磨机内,常温下以200~250r/min转速球磨6~8h,过筛,得混合浆料。
5.根据权利要求4所述的一种太阳能吸热复合材料的制备方法,其特征在于,所述的碳化硅粉末、氮化硅粉末、氧化锆粉末、红柱石粉末、刚玉粉末、羧甲基纤维素、聚乙烯醇、去离子水的重量份为40~50份碳化硅粉末、40~50份氮化硅粉末、16~20份氧化锆粉末、12~15份红柱石粉末、8~10份刚玉粉末、4~5份羧甲基纤维素、8~10份聚乙烯醇、120~150份去离子水。
6.根据权利要求4所述的一种太阳能吸热复合材料的制备方法,其特征在于,步骤(3)所述的筛目规格为80~100。
7.根据权利要求1所述的一种太阳能吸热复合材料的制备方法,其特征在于,步骤(1)所述的改性碳纤维浆料的具体制备步骤为:
(1)将碳纤维置于剪切机中剪切5~10min,得短碳纤维;
(2)将短碳纤维置于马弗炉中,在500~550℃的条件下保温煅烧2~3h,随炉冷却至室温,得预氧化短碳纤维;
(3)将硝酸加入丙酮中,常温下以160~180r/min转速搅拌10~15min,得改性液;
(4)将预氧化短碳纤维加入改性液中,置于40~50℃的水浴条件下以180~200r/min转速搅拌10~12h,过滤,取滤饼,用去离子水洗涤至中性,置于80~90℃的烘箱中干燥1~2h,得改性短碳纤维;
(5)将改性短碳纤维、羧甲基纤维素加入去离子水中,置于超声波分散机内,在50~60℃的条件下超声处理2~4h,常温冷却,得改性碳纤维浆料。
8.根据权利要求7所述的一种太阳能吸热复合材料的制备方法,其特征在于,所述的碳纤维、硝酸、丙酮、羧甲基纤维素、去离子水的重量份为20~30份碳纤维、20~30份质量分数10%的硝酸、20~30份丙酮、12~18份羧甲基纤维素、60~90份去离子水。
9.根据权利要求7所述的一种太阳能吸热复合材料的制备方法,其特征在于,步骤(1)所述的短碳纤维的平均长度为2~4mm。
10.根据权利要求7所述的一种太阳能吸热复合材料的制备方法,其特征在于,步骤(5)所述的超声处理的功率为500~600W。
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CN110835135A (zh) * | 2019-11-14 | 2020-02-25 | 中国科学院宁波材料技术与工程研究所 | 一种海水蒸发淡化材料的制备方法及其产品和应用 |
CN111253158A (zh) * | 2020-01-21 | 2020-06-09 | 武汉理工大学 | 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 |
CN111269015A (zh) * | 2020-03-25 | 2020-06-12 | 武汉理工大学 | 一种致密化的莫来石-刚玉-SiC太阳能热发电用复相储热陶瓷材料及其制备方法 |
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CN110835135A (zh) * | 2019-11-14 | 2020-02-25 | 中国科学院宁波材料技术与工程研究所 | 一种海水蒸发淡化材料的制备方法及其产品和应用 |
CN110835135B (zh) * | 2019-11-14 | 2021-11-30 | 中国科学院宁波材料技术与工程研究所 | 一种海水蒸发淡化材料的制备方法及其产品和应用 |
CN111253158A (zh) * | 2020-01-21 | 2020-06-09 | 武汉理工大学 | 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 |
CN111253158B (zh) * | 2020-01-21 | 2022-02-01 | 武汉理工大学 | 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 |
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