太阳能选择性吸收涂层光谱发射率测量技术研究
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摘要
随着能源危机和环境污染问题的凸显，新能源利用技术受到世界各国的重视，尤以太阳能热发电技术倍受青睐。在太阳能热发电领域，太阳能集热管是太阳能-热能转换的核心部件，集热管涂层的光谱发射率是决定太阳能吸收效率的基础技术指标，是决定太阳能热发电系统效率的关键因素。光谱发射率测量技术对优化涂层结构设计和提高涂层制备工艺具有重要的科学价值，对推动太阳能热发电技术发展、解决能源危机和环境污染具有深远的社会意义。
针对发射率假设模型在集热管涂层原位多光谱发射率测量中存在的问题，解决多层膜系涂层的发射率模型问题，实现涂层发射率多光谱原位测量是发射率测量领域亟待解决的重要问题之一。针对尚无统一参考反射标准的现状，解决反射法测量对参考反射标准的依赖问题，实现无参考反射标准的光谱发射率量值传递具有重要的理论意义，是本文研究的另一重要问题。模拟涂层的高真空工作环境，解决积分球反射计在红外光谱测量领域的应用难题，研制高真空、宽光谱的太阳能选择性吸收涂层光谱发射率测量系统是本文要解决的关键技术问题。针对上述问题，开展本文的研究工作，主要研究内容如下：
（1）集热管涂层发射率的原位多光谱测量方法研究。针对集热管涂层的多层膜结构，分析金属的电磁波穿透深度及反射特性，研究吸收膜光学常数与金属掺杂体积数的依赖关系、吸收膜厚度对复合膜系反射率的影响规律，建立基于膜结构参数的金属-陶瓷涂层发射率模型。建立光谱辐射亮度测量值与发射率模型计算值之间的约束方程，推导基于自适应模拟退火算法的发射率模型参数求解方法，实现涂层发射率的原位测量。基于傅里叶光谱仪的光谱辐射亮度测量值，与现有的两种发射率假设模型相比，基于膜系结构参数模型的涂层多光谱发射率测量值与能量法测量值的一致性更好。
（2）积分球反射法的发射率量值传递方法研究。针对涂层试样常温发射率的测量难题，解决积分球反射法对参考反射标准的依赖问题，分析有限立体角的辐射功率分布规律，推导探测器表面与试样的入射辐照面所张立体角的函数关系，以探测器表面所张立体角内辐射功率的测量电压值对试样入射功率进行标定。推导截面积与探测器表面积相等的积分球球冠的球面度函数，建立试样反射辐射功率的推导方法。标定测量电压值与光谱发射率量值之间的传递系数，建立光谱发射率的量值传递模型。
（3）研制太阳能选择性吸收涂层光谱发射率测量系统。建立10-3Pa的高真空测量环境，解决高温发射率测量的涂层氧化问题；研制玻璃-镀铝的红外光谱高反射积分球，解决积分球反射计在红外宽光谱发射率测量的应用难题；研究多级重叠谱线的消除方法，解决谱线重叠对发射率测量的干扰问题；研究动态赋值的加热方法，解决高真空环境下加热超调温度的控制难题。建立300-900K、0.4-10μm的高真空、宽光谱发射率测量系统。
（4）利用太阳能选择性吸收涂层光谱发射率测量系统，标定了积分球反射法发射率量值传递模型的传递系数。高、低发射率材料的发射率测量实验表明，发射率的量值传递值与文献值具有一致性；选择性吸收涂层试样的发射率测量实验表明，Mo-SiO2涂层试样的光谱发射率测量曲线与文献数据曲线一致。分析测量系统的不确定度，估计了发射率测量结果的不确定度为0.029。
The solar thermal power technology has been paid more attention by countriesall over the world with the energy crisis and environmental pollution. In the solarpower generation, selective absorbing coatings are the key components of thesolar-thermal energy conversion. Spectral radiance characteristic of the coatings isthe underlying technology indicator to determine the absorption efficiency and keyfator influencing on the efficiency of the solar thermal power generation system.Emissivity measurements have an important scientific value for coatings to enhancethe absorption of solar energy and reduce its thermal radiation losses at hightemperature by improving the design and preparation of coatings, and a far-reachingsignificance for solving the problem of energy crisis and environmental pollution bypromoting the development of solar thermal power generation technology.
The multi-spectral emissivity measurement method based on the assumingmodel has its limitations for in-situ measurement. It is important to solve theproblem of emissivity model for multilayer materials in order to achieve in-situemissivity measurement of collector coatings. Without the uniform referencestandard, emissivity measurement technology based on integrating spherereflectometer is impossible to solve problems arised from the emssivity quantitytransmission. It has an important theoretical significance to achieve the emissivityquantity transmission without the utilization of reference standard. For the oxidationof remarkable selectivity coatings and significant change of its spectral emissivity, itis the key technology problem solved in this paper to develop the spectral emissivitymeasurement system for solar selective absorbing coating. According to theproblems above, the main research contents are as follows:
An in-situ multi-spectral emissivity measurement method of collector tubecoatings is proposed. For the multi-layer structure of coatings, electromagnetic wavepenetration depth and reflective characteristics of metal films are analysised. Therelations between optical constants of absorbing film and metal-doped volumenumber, and the influence of the absorption film thickness on the reflectivity of thecomposite membrane are studied. The emissivity model of metal-ceramic coatingfilm structure parameters is established. The method to achieve emissivity modelparameters in adaptive simulated annealing is proposed with the constraint equationsbetween measurement values of spectral radiance and calculated values withemissivity model. Using the spectral radiance values measured by the fouriertransform infrared spectrometer, the consistency of values measured by multi-spectral emissivity measurement method based on the structural parametersmodel of coatings and values measured by energy method is better than two existingassume models.
A new quantity transmission method of spectral emissivity measurement basedon integrating sphere reflectometer is proposed. Based on the radiation powercalibration, the incident radiation power of the sample is derived by a function of themeasured voltage of detector and solid angle relationship formula between theprojection area of the sample and the sensitive area of detector. The reflectedradiation power of the sample is derived by a function of the measured outputvoltage of integrating sphere and steradian formula of its output hole. Thetransimissin model of spectral emissivity is established by determining the transfercoefficient between measured voltages and spectral emissivities.
A spectral emissivity measurement system for the solar selective absorbingcoating is developed. The high vacuum equipment with10-3Pa is developed to avoidthe oxidation of coatings being measured at high temperature. A silica glassintegrating sphere vacuum-plated with Al on its internal surface is developed tosolve the spectral emissivity measurement problems in the infared region. Thedifficult problem of temperature overshooting control in the heating process underhigh vacuum is solved with dynamic heating algorithm of target temperature value.The emissivity measurement system in the range0.4-10μm and in the temperaturefrom300K to over900K is built.
Based on the emissivity measurement system for the solar selective absorbingcoating, the transfer coefficient between measured voltages and spectral emissivitiesis calibrated. Measurement experiments of the high and low emissivity materialshow that the transfered values of emssivity is consistent with literature values. Theemissivity of the Mo-SiO2coating sample is measured, its measurement curve isconsistent with literature data. The uncertainty is analyzed and estimated emissivitymeasurement standard uncertainty is0.029.
针对发射率假设模型在集热管涂层原位多光谱发射率测量中存在的问题，解决多层膜系涂层的发射率模型问题，实现涂层发射率多光谱原位测量是发射率测量领域亟待解决的重要问题之一。针对尚无统一参考反射标准的现状，解决反射法测量对参考反射标准的依赖问题，实现无参考反射标准的光谱发射率量值传递具有重要的理论意义，是本文研究的另一重要问题。模拟涂层的高真空工作环境，解决积分球反射计在红外光谱测量领域的应用难题，研制高真空、宽光谱的太阳能选择性吸收涂层光谱发射率测量系统是本文要解决的关键技术问题。针对上述问题，开展本文的研究工作，主要研究内容如下：
（1）集热管涂层发射率的原位多光谱测量方法研究。针对集热管涂层的多层膜结构，分析金属的电磁波穿透深度及反射特性，研究吸收膜光学常数与金属掺杂体积数的依赖关系、吸收膜厚度对复合膜系反射率的影响规律，建立基于膜结构参数的金属-陶瓷涂层发射率模型。建立光谱辐射亮度测量值与发射率模型计算值之间的约束方程，推导基于自适应模拟退火算法的发射率模型参数求解方法，实现涂层发射率的原位测量。基于傅里叶光谱仪的光谱辐射亮度测量值，与现有的两种发射率假设模型相比，基于膜系结构参数模型的涂层多光谱发射率测量值与能量法测量值的一致性更好。
（2）积分球反射法的发射率量值传递方法研究。针对涂层试样常温发射率的测量难题，解决积分球反射法对参考反射标准的依赖问题，分析有限立体角的辐射功率分布规律，推导探测器表面与试样的入射辐照面所张立体角的函数关系，以探测器表面所张立体角内辐射功率的测量电压值对试样入射功率进行标定。推导截面积与探测器表面积相等的积分球球冠的球面度函数，建立试样反射辐射功率的推导方法。标定测量电压值与光谱发射率量值之间的传递系数，建立光谱发射率的量值传递模型。
（3）研制太阳能选择性吸收涂层光谱发射率测量系统。建立10-3Pa的高真空测量环境，解决高温发射率测量的涂层氧化问题；研制玻璃-镀铝的红外光谱高反射积分球，解决积分球反射计在红外宽光谱发射率测量的应用难题；研究多级重叠谱线的消除方法，解决谱线重叠对发射率测量的干扰问题；研究动态赋值的加热方法，解决高真空环境下加热超调温度的控制难题。建立300-900K、0.4-10μm的高真空、宽光谱发射率测量系统。
（4）利用太阳能选择性吸收涂层光谱发射率测量系统，标定了积分球反射法发射率量值传递模型的传递系数。高、低发射率材料的发射率测量实验表明，发射率的量值传递值与文献值具有一致性；选择性吸收涂层试样的发射率测量实验表明，Mo-SiO2涂层试样的光谱发射率测量曲线与文献数据曲线一致。分析测量系统的不确定度，估计了发射率测量结果的不确定度为0.029。
The solar thermal power technology has been paid more attention by countriesall over the world with the energy crisis and environmental pollution. In the solarpower generation, selective absorbing coatings are the key components of thesolar-thermal energy conversion. Spectral radiance characteristic of the coatings isthe underlying technology indicator to determine the absorption efficiency and keyfator influencing on the efficiency of the solar thermal power generation system.Emissivity measurements have an important scientific value for coatings to enhancethe absorption of solar energy and reduce its thermal radiation losses at hightemperature by improving the design and preparation of coatings, and a far-reachingsignificance for solving the problem of energy crisis and environmental pollution bypromoting the development of solar thermal power generation technology.
The multi-spectral emissivity measurement method based on the assumingmodel has its limitations for in-situ measurement. It is important to solve theproblem of emissivity model for multilayer materials in order to achieve in-situemissivity measurement of collector coatings. Without the uniform referencestandard, emissivity measurement technology based on integrating spherereflectometer is impossible to solve problems arised from the emssivity quantitytransmission. It has an important theoretical significance to achieve the emissivityquantity transmission without the utilization of reference standard. For the oxidationof remarkable selectivity coatings and significant change of its spectral emissivity, itis the key technology problem solved in this paper to develop the spectral emissivitymeasurement system for solar selective absorbing coating. According to theproblems above, the main research contents are as follows:
An in-situ multi-spectral emissivity measurement method of collector tubecoatings is proposed. For the multi-layer structure of coatings, electromagnetic wavepenetration depth and reflective characteristics of metal films are analysised. Therelations between optical constants of absorbing film and metal-doped volumenumber, and the influence of the absorption film thickness on the reflectivity of thecomposite membrane are studied. The emissivity model of metal-ceramic coatingfilm structure parameters is established. The method to achieve emissivity modelparameters in adaptive simulated annealing is proposed with the constraint equationsbetween measurement values of spectral radiance and calculated values withemissivity model. Using the spectral radiance values measured by the fouriertransform infrared spectrometer, the consistency of values measured by multi-spectral emissivity measurement method based on the structural parametersmodel of coatings and values measured by energy method is better than two existingassume models.
A new quantity transmission method of spectral emissivity measurement basedon integrating sphere reflectometer is proposed. Based on the radiation powercalibration, the incident radiation power of the sample is derived by a function of themeasured voltage of detector and solid angle relationship formula between theprojection area of the sample and the sensitive area of detector. The reflectedradiation power of the sample is derived by a function of the measured outputvoltage of integrating sphere and steradian formula of its output hole. Thetransimissin model of spectral emissivity is established by determining the transfercoefficient between measured voltages and spectral emissivities.
A spectral emissivity measurement system for the solar selective absorbingcoating is developed. The high vacuum equipment with10-3Pa is developed to avoidthe oxidation of coatings being measured at high temperature. A silica glassintegrating sphere vacuum-plated with Al on its internal surface is developed tosolve the spectral emissivity measurement problems in the infared region. Thedifficult problem of temperature overshooting control in the heating process underhigh vacuum is solved with dynamic heating algorithm of target temperature value.The emissivity measurement system in the range0.4-10μm and in the temperaturefrom300K to over900K is built.
Based on the emissivity measurement system for the solar selective absorbingcoating, the transfer coefficient between measured voltages and spectral emissivitiesis calibrated. Measurement experiments of the high and low emissivity materialshow that the transfered values of emssivity is consistent with literature values. Theemissivity of the Mo-SiO2coating sample is measured, its measurement curve isconsistent with literature data. The uncertainty is analyzed and estimated emissivitymeasurement standard uncertainty is0.029.
引文
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