CN107151123A - 一种高效水泥基热电材料及其制备方法 - Google Patents
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Abstract
本发明属于热电材料领域,具体涉及一种高效水泥基热(三氧化二铁复合水泥基)电材料及其制备方法。高效水泥基热电材料为水泥中添加纳米三氧化二铁粉体作为热电组分;其中,热电组分添加量占水泥质量的1%‑5%。本发明中高效水泥基热电材料养护28d后热电系数在1000μv/℃以上。该高效水泥基热电材料热电性能高,制备方法简便,成本低,便于应用推广。
Description
技术领域
本发明属于热电材料领域,具体涉及一种高效水泥基热(三氧化二铁复合水泥基)电材料及其制备方法。
背景技术
能源是人类活动的物质基础,人类社会的发展离不开优质能源的出现和先进能源技术的使用。考虑到化石能源的日益枯竭及其使用产生的环境问题,对于获取可持续、清洁能源的兴趣日益浓厚。热电材料可利用材料两端的温差直接将热能转化为电能,这一过程是通过热能激发材料内部载流子的定向运动实现的。用热电材料制作的元件具有绿色环保,运行时无噪音、免维护和安全可靠等优点,在利用太阳能及工业余热等一些低品位热源领域具有广泛的应用前景。
水泥基复合材料是目前应用最为广泛的建筑材料,在城市建筑、道路、桥梁、水利等工程中占据着重要地位。这些水泥基复合材料的结构在使用过程中由于受到太阳光照射,会在其内外两侧产生温差。同时,作为城市建筑墙壁的主体材料,夏季和冬季墙体两侧产生的温差由于室内制冷或制热作用会超过20℃,因此水泥基复合材料结构中温差发电的利用将具有非常大的发展潜力。但是普通热电材料一般价格昂贵,与混凝土结构相容性不佳,受到荷载作用容易损坏,难以在混凝土结构中广泛使用。
发明内容
本发明目的在于提供一种高效水泥基(三氧化二铁复合水泥基)热电材料及其制备方法。
为解决上述技术问题,本发明采用的技术方案为:
一种高效水泥基热电材料,高效水泥基热电材料为水泥中添加纳米三氧化二铁粉体作为热电组分;其中,热电组分添加量占水泥质量的1%-5%。
所述纳米三氧化二铁粉体为采用化学沉淀法制得,粒径范围为1-100nm。
所述纳米三氧化二铁颗粒为将氯化铁溶液与尿素按摩尔比为1:2-1:4的比例混合在90-100℃下加热反应3-5h,反应后的粉末在500-550℃的马弗炉中煅烧3-5h,即得到目标产物纳米三氧化二铁。
所述高效水泥基热电材料由水泥、水、超细硅质矿物外加剂、热电组分和高效减水剂;其中,水、超细硅质矿物外加剂、热电组分和高效减水剂的添加量分别占水泥质量的35%-45%、5%-15%、1%-5%、0.5%-2.5%。
所述水泥为硅酸盐水泥或普通硅酸盐水泥,强度等级为42.5或52.5;所述高效减水剂为减水率20%-30%的聚羧酸系高效减水剂;所述的超细硅质矿物外加剂为超细硅灰,比表面积不小于15000m2/kg,SiO2含量不低于90%。
一种高效水泥基热电材料的制备方法,将作为热电组分的纳米三氧化二铁粉体制成悬浮液加入至水泥中搅拌均匀后成型,再经标准养护即可。
将作为热电组分的纳米三氧化二铁粉体加入到水中进行超声分散形成悬浮液,而后按照上述比例依次加入减水剂、水泥和硅灰,用水泥净浆搅拌机进行梯度搅拌使其搅拌均匀后成型,再经过标准养护即可。
所述热电组分为化学沉淀法制备的纳米三氧化二铁,粒径范围为1-100nm。具体方法为将氯化铁溶液与尿素按摩尔比为1:2-1:4的比例混合在90-100℃下加热反应3-5小时,反应后的粉末在500-550℃的马弗炉中煅烧3-5h,即得到目标产物纳米三氧化二铁。
所述梯度搅拌为首先以60-65转/分的速度慢速搅拌3-4分钟,而后再以125-135转/分的速度快速搅拌2-3分钟。
所述标准养护为20℃,95%相对湿度养护28天。
所述的水泥为硅酸盐水泥或普通硅酸盐水泥,强度等级为42.5或52.5。
所述的高效减水剂为减水率20%的同树牌聚羧酸高效减水剂。
按上述方案:所述的超细硅质矿物外加剂为超细硅灰,比表面积不小于15000m2/kg,SiO2含量不低于90%。
原理:对于本发明的水泥基热电材料而言,通过在其制备过程中添加纳米热电组分,使得水泥基复合材料的热电性能显著提高。水泥基复合材料中加入纳米尺度热电组分后引起量子约束效应,提高载流子在费米面附近的能量梯度,降低晶格热导率,最终提高材料的热电效率。
本发明的有益效果:
本发明的高效水泥基热电材料热电性能高,制备成本低,便于应用推广。与传统的水泥基热电材料相比,本发明该高效水泥基热电材料养护28d后热电系数达到1000μv/℃以上(而以往的碳纤维复合水泥基材料、钢纤维复合水泥基材料以及钢渣复合水泥基材料的热电系数一般不超过100μv/℃)。
附图说明
图1为水泥基热电材料热电效应测试示意图。
图2为本发明实施例提供的水泥基热电材料电压随温差变化关系图。
图3为本发明制备的纳米三氧化二铁扫描XRD图,X-射线粉末衍射的特征峰与标准卡片PDF 89-0597相同,说明为纯净的α-Fe2O3。
图4为本发明制备的纳米三氧化二铁扫描电镜图。
具体实施方式
下面结合以下实施例对本发明的发明内容作详细说明。
实施例
将普通硅酸盐水泥、水、硅灰、减水剂以及纳米三氧化二铁粉末按照表1配比取料(以各组分与水泥的质量百分比计)后,先将纳米三氧化二铁粉末加入到水中超声分散15分钟,再将同树牌聚羧酸减水剂、普通硅酸盐水泥和硅灰加入悬浮液中用水泥净浆搅拌机以60转/分钟的慢速下搅拌3分钟、再以130转/分钟的快速下搅拌2分钟,搅拌均匀后在20℃,95%相对湿度养护28天。
上述纳米三氧化二铁粉末的制备为:具体方法为将氯化铁溶液与尿素按摩尔比为1:3的比例混合在95℃下加热反应4h,反应后的粉末在520℃的马弗炉中煅烧4h,即得到目标产物纳米三氧化二铁(目标产物测试表征参见图3和4)。
由图3和4可见制备出的产物为纯净的α-Fe2O3,粒径在100nm以内,略有团聚。
所用水泥为山东山水水泥厂生产的42.5普通硅酸盐水泥。
硅灰为Elken公司提供的超细硅灰,平均粒径0.15-0.20μm,比表面积约18000m2/kg。
对照例1:
将普通硅酸盐水泥、水、硅灰、减水剂按照表1对照例1中配比取料(以各组分与水泥的质量百分比计)后,将同树牌聚羧酸减水剂、普通硅酸盐水泥和硅灰依次加入水中用水泥净浆搅拌机以60转/分钟的慢速下搅拌3分钟、再以130转/分钟的快速下搅拌2分钟,搅拌均匀后在20℃,95%相对湿度养护28天。
表1各实施例中水泥基热电材料的配合比设计
编号 | 水泥 | 水 | 硅灰 | 减水剂 | 三氧化二铁 |
实施例1 | 100% | 42% | 10% | 1.0% | 1.0% |
实施例2 | 100% | 42% | 10% | 1.5% | 2.0% |
实施例3 | 100% | 42% | 15% | 1.0% | 3.0% |
实施例4 | 100% | 40% | 15% | 1.5% | 4.0% |
实施例5 | 100% | 40% | 5% | 0.5% | 5.0% |
对照例1 | 100% | 42% | 10% | 1.0% | 0 |
将以上各实施例制得的水泥基热电材料按照图1所示的方式进行热电性能测试:材料的两端分别与铜片相连,材料的一端用平板式电阻丝加热器以0.05℃/min的速率加热,另一端用水冷降温。试件两端的温差通过K型热电偶监测,产生的电压通过Fluke B15型万用表监测,电压与温差变化的关系如图2所示。根据电压随温差的变化(二者的比值),可以计算出当三氧化二铁的掺量为1.0%时,其热电系数就已经超过1000μv/℃,且掺量越高,其热电系数越高,由此可见通过在其制备过程中添加纳米热电组分,使得水泥基复合材料的热电性能显著提高。水泥基复合材料中加入纳米尺度热电组分后引起量子约束效应,提高载流子在费米面附近的能量梯度,降低晶格热导率,最终提高材料的热电效率。
Claims (9)
1.一种高效水泥基热电材料,其特征在于:高效水泥基热电材料为水泥中添加纳米三氧化二铁粉体作为热电组分;其中,热电组分添加量占水泥质量的1%-5%。
2.按权利要求1所述高效水泥基热电材料,其特征在于:所述纳米三氧化二铁粉体为采用化学沉淀法制得,粒径范围为1-100nm。
3.按权利要求1或2所述高效水泥基热电材料,其特征在于:所述纳米三氧化二铁颗粒为将氯化铁溶液与尿素按摩尔比为1:2-1:4的比例混合在90-100℃下加热反应3-5h,反应后的粉末在500-550℃的马弗炉中煅烧3-5h,即得到目标产物纳米三氧化二铁。
4.按权利要求1所述高效水泥基热电材料,其特征在于:高效水泥基热电材料由水泥、水、超细硅质矿物外加剂、热电组分和高效减水剂;其中,水、超细硅质矿物外加剂、热电组分和高效减水剂的添加量分别占水泥质量的35%-45%、5%-15%、1%-5%、0.5%-2.5%。
5.按权利要求4所述高效水泥基热电材料,其特征在于:所述水泥为硅酸盐水泥或普通硅酸盐水泥,强度等级为42.5或52.5;所述高效减水剂为减水率20%-30%的聚羧酸系高效减水剂;所述的超细硅质矿物外加剂为超细硅灰,比表面积不小于15000m2/kg,SiO2含量不低于90%。
6.一种权利要求1所述的高效水泥基热电材料的制备方法,其特征在于:将作为热电组分的纳米三氧化二铁粉体制成悬浮液加入至水泥中搅拌均匀后成型,再经标准养护即可。
7.按权利要求6所述的的高效水泥基热电材料的制备方法,其特征在于:将作为热电组分的纳米三氧化二铁粉体加入到水中进行超声分散形成悬浮液,而后按照上述比例依次加入减水剂、水泥和硅灰,用水泥净浆搅拌机进行梯度搅拌使其搅拌均匀后成型,再经过标准养护即可。
8.按权利要求7所述的的高效水泥基热电材料的制备方法,其特征在于:所述梯度搅拌为首先以60-65转/分的速度慢速搅拌3-4分钟,而后再以125-135转/分的速度快速搅拌2-3分钟。
9.按权利要求6和7所述的的高效水泥基热电材料的制备方法,其特征在于:所述标准养护为20℃,95%相对湿度养护28天。
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