耐候性太阳选择性吸收涂层的研究
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摘要
随着能源和环境问题的日益严峻,太阳能热利用技术中的太阳选择性吸收涂层的研制及其在工业上的应用成为人们关注的焦点。太阳能建筑一体化中的光热转换涂层是太阳能建筑一体化发展的关键技术,不仅要求具有较好的选择性,而且要求直接与外界环境接触、具有较好的耐候性。本文在较全面了解选择吸收涂层的基本类型、作用机理、制备方法以及国内外选择性吸收涂层的研究工作和最新成果的基础上,利用设备简单、操作方便、成本低廉、污染小的水溶液化学法对耐候性吸收涂层的制备进行研究。
首先,本文利用薄膜光学理论,选择两种多孔涂层计算模型:Maxwell-Garnet理论和Bruggeman理论修正的单层均匀膜模型以及非均匀膜模型。对两种计算模型进行比较,发现修正的单层均匀膜模型与实际的多孔膜差别较大;而按非均匀模型计算的结果更为接近。利用非均匀模型计算了多孔PbS/Al、PbS/Cu和PbS/Ni涂层的反射曲线,发现PbS/Cu涂层具有与PbS/Al涂层相似的优良光学性能,具有比PbS/Ni涂层更低的发射率。利用均匀膜模型计算了具有致密结构的钼黑涂层的吸收率与涂层厚度的关系。利用非均匀模型考察了多孔CuO涂层中杂质Cu2O对吸收率的影响,发现纯CuO涂层具有更高的吸收率。
其次,采用水溶液化学法,在碱性条件下用乙酸铅和硫脲直接在铜锌合金和纯铜片上制备了PbS涂层;用多钼酸铵和氯化铵在铝(和铝合金)片上制备了钼黑涂层;用次氯酸钠作为氧化剂,在铜锌合金和纯铜片制备了高纯度的CuO涂层。论文探讨了反应温度、反应时间、反应溶液的pH值、反应物配比以及基片前处理方式等操作条件对三种太阳光谱选择性涂层的吸收率的影响,获得了它们的适宜制备条件。通过XPS、SEM、紫外可见近红外分光光度计和傅立叶变换红外光谱仪等对以上三种涂层进行了表征。比较了一定厚度下PbS涂层、钼黑涂层和CuO涂层的吸收率计算值与实测值,结果吻合较好。
最后,在PbS、钼黑和CuO涂层上加涂TiO2膜制备了复合涂层,并对比了原涂层与复合涂层的吸收率、耐温性、耐腐蚀性、耐磨性、隔热保温性和自清洁等性能,结果表明,复合涂层的吸收率满足应用的要求,其耐温性、耐腐蚀性和耐磨性等性能均优于原涂层;由于TiO2具有光催化功能,复合涂层具有较强的自清洁功能;复合涂层的总体使用性能得到提高,使用寿命得到延长。
In recent years, the research and application in the industry of solar spectrum selective absorbing coatings have been given more and more attention. This thesis summarized their basic types, absorption mechanisms,preparation methods,introduced the research work and new results at home and abroad.Then perdurable coatings were prepared using solution growth technique,which is simple ,cheap and less pollution.
Firstly, model was selected to calculate the porous coatings by comparing the modified uniformity monolayer with heterogeneous film.Even modified with Maxwell-Garnet theory and Bruggeman theory ,the uniformity monolayer was not suit to the actual porous coating .While the model of heterogeneous film fit the the actual porous coating well.Using the the later model ,the optical performance of PbS/Al,PbS/Cu and PbS/Ni coatings were calculated .The PbS/Cu and PbS/Al coatings were better than PbS/Ni coating.Then the optical performance of molybdenum black coating was calculated with uniformity film model for its compact fabric. The optical performance of CuO/Cu was calculated consider the effect of Cu2O ,and pure CuO coating was better than the impure coating.
Secondly, three kinds of coatings were prepared using solution growth technique.The coating of lead sulphide was prepared by dissociating thiourea in an alkaline solution containing lead acetate on the base material of copper . The molybdenum black coating was prepared by deoxidizing (NH4)6Mo7O24 in the solution containing NH4Cl on the base material of aluminium and aluminium alloy .And the pure coating of cuprum oxide by oxidating copper with hypochlorous sodium in the alkaline solution. The optimized condition was studied considering reaction temperature , reaction time , pH of the solution , concentration of reactant and pretreatment of the base material. The coatings were analyzed by XPS, SEM, UV-visible-near infrared light spectrophotometer and Fourier transform infrared light spectrograph. The difference in solar absorptivity between the calculated and measured values of these coatings was small.
Finally, an additional TiO2 film was deposited on three coatings ,and the performance,such as absorptivity, temperature-fast acid-resistant, abrasion resistance,heat insulation and self-cleanness , were compared between the original coatings and the compound coatings.The results showed that compound coatings basicly reached our criterion and was superior to the original coatings.
首先,本文利用薄膜光学理论,选择两种多孔涂层计算模型:Maxwell-Garnet理论和Bruggeman理论修正的单层均匀膜模型以及非均匀膜模型。对两种计算模型进行比较,发现修正的单层均匀膜模型与实际的多孔膜差别较大;而按非均匀模型计算的结果更为接近。利用非均匀模型计算了多孔PbS/Al、PbS/Cu和PbS/Ni涂层的反射曲线,发现PbS/Cu涂层具有与PbS/Al涂层相似的优良光学性能,具有比PbS/Ni涂层更低的发射率。利用均匀膜模型计算了具有致密结构的钼黑涂层的吸收率与涂层厚度的关系。利用非均匀模型考察了多孔CuO涂层中杂质Cu2O对吸收率的影响,发现纯CuO涂层具有更高的吸收率。
其次,采用水溶液化学法,在碱性条件下用乙酸铅和硫脲直接在铜锌合金和纯铜片上制备了PbS涂层;用多钼酸铵和氯化铵在铝(和铝合金)片上制备了钼黑涂层;用次氯酸钠作为氧化剂,在铜锌合金和纯铜片制备了高纯度的CuO涂层。论文探讨了反应温度、反应时间、反应溶液的pH值、反应物配比以及基片前处理方式等操作条件对三种太阳光谱选择性涂层的吸收率的影响,获得了它们的适宜制备条件。通过XPS、SEM、紫外可见近红外分光光度计和傅立叶变换红外光谱仪等对以上三种涂层进行了表征。比较了一定厚度下PbS涂层、钼黑涂层和CuO涂层的吸收率计算值与实测值,结果吻合较好。
最后,在PbS、钼黑和CuO涂层上加涂TiO2膜制备了复合涂层,并对比了原涂层与复合涂层的吸收率、耐温性、耐腐蚀性、耐磨性、隔热保温性和自清洁等性能,结果表明,复合涂层的吸收率满足应用的要求,其耐温性、耐腐蚀性和耐磨性等性能均优于原涂层;由于TiO2具有光催化功能,复合涂层具有较强的自清洁功能;复合涂层的总体使用性能得到提高,使用寿命得到延长。
In recent years, the research and application in the industry of solar spectrum selective absorbing coatings have been given more and more attention. This thesis summarized their basic types, absorption mechanisms,preparation methods,introduced the research work and new results at home and abroad.Then perdurable coatings were prepared using solution growth technique,which is simple ,cheap and less pollution.
Firstly, model was selected to calculate the porous coatings by comparing the modified uniformity monolayer with heterogeneous film.Even modified with Maxwell-Garnet theory and Bruggeman theory ,the uniformity monolayer was not suit to the actual porous coating .While the model of heterogeneous film fit the the actual porous coating well.Using the the later model ,the optical performance of PbS/Al,PbS/Cu and PbS/Ni coatings were calculated .The PbS/Cu and PbS/Al coatings were better than PbS/Ni coating.Then the optical performance of molybdenum black coating was calculated with uniformity film model for its compact fabric. The optical performance of CuO/Cu was calculated consider the effect of Cu2O ,and pure CuO coating was better than the impure coating.
Secondly, three kinds of coatings were prepared using solution growth technique.The coating of lead sulphide was prepared by dissociating thiourea in an alkaline solution containing lead acetate on the base material of copper . The molybdenum black coating was prepared by deoxidizing (NH4)6Mo7O24 in the solution containing NH4Cl on the base material of aluminium and aluminium alloy .And the pure coating of cuprum oxide by oxidating copper with hypochlorous sodium in the alkaline solution. The optimized condition was studied considering reaction temperature , reaction time , pH of the solution , concentration of reactant and pretreatment of the base material. The coatings were analyzed by XPS, SEM, UV-visible-near infrared light spectrophotometer and Fourier transform infrared light spectrograph. The difference in solar absorptivity between the calculated and measured values of these coatings was small.
Finally, an additional TiO2 film was deposited on three coatings ,and the performance,such as absorptivity, temperature-fast acid-resistant, abrasion resistance,heat insulation and self-cleanness , were compared between the original coatings and the compound coatings.The results showed that compound coatings basicly reached our criterion and was superior to the original coatings.
引文
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