CN116123741A - 一种用于槽式热发电高温真空集热管的太阳光谱选择性吸收涂层及其制备方法 - Google Patents

一种用于槽式热发电高温真空集热管的太阳光谱选择性吸收涂层及其制备方法 Download PDF

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CN116123741A
CN116123741A CN202310094199.8A CN202310094199A CN116123741A CN 116123741 A CN116123741 A CN 116123741A CN 202310094199 A CN202310094199 A CN 202310094199A CN 116123741 A CN116123741 A CN 116123741A
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王聪
孙丙辉
孙莹
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Abstract

太阳光谱选择性吸收涂层能够将太阳能高效转化为热能，可用于各种光热转换的集热器。而耐高温的太阳光谱选择性吸收涂层主要用于高温真空集热管，是槽式聚光太阳能热发电***中的关键材料之一，耐高温是其重要技术参数。本发明涉及一种高温太阳光谱选择性吸收涂层。涂层具有三层膜系结构，从底层至顶层依次分别为红外反射层、吸收层和减反层。吸收层的成分由Mo、Al、Si与其氮化物的混合物组成；减反层由两个具有不同折射率和厚度的亚层构成，两个减反射亚层之间可产生干涉相消效应，从而增强对太阳光的吸收作用。涂层制备采用磁控溅射镀膜技术，整个涂层仅涉及Mo靶、Al靶和Si靶三种材料作为溅射源，材料廉价丰富；以Ar气和N2分别作为溅射气体和反应气体，通过反应共溅射的方式制备。在对涂层不同膜层进行制备时，基本采用直流磁控溅射方法既可完成，仅需改变反应气体的流量、选择三个溅射靶材的不同组合以及不同溅射功率进行共溅，其工艺简单，操作方便；涂层具有较高的沉积速率以及良好的实验重复性，可缩短生产周期，降低生产成本。所制备的涂层具有优异的太阳光谱选择性(太阳光波段高吸收、红外光波段低发射)以及良好的高温稳定性(可耐温800℃)。适用于在较高温度(600℃～800℃)工作的真空太阳能集热管。

Description

一种用于槽式热发电高温真空集热管的太阳光谱选择性吸收涂层及其制备方法
技术领域：
本发明涉及太阳能槽式聚光热发电利用技术领域，具体涉及一种可用于高温真空集热管的太阳光谱选择性吸收涂层。
背景技术：
槽式聚光太阳能热发电***通过真空太阳能集热管将收集到的太阳光转换为热能，来推动涡轮机发电。而真空太阳能集热管之所以能够将太阳光高效转换为热能，所依赖的是沉积在其内管表面的太阳光谱选择性吸收涂层。太阳光谱选择性吸收涂层是一种在太阳光波段(0.3μm～2.5μm)具有高吸收率，而在中红外波段(2.5μm～20μm)具有低发射率的光学薄膜。因此，太阳光谱选择性吸收涂层能够将入射的太阳光高效转换为热能，并减少真空太阳能集热管以热辐射损耗的能量。根据热机原理，提高涡轮机高温温度，可有效提高热机效率，进而降低槽式聚光太阳能热发电***的发电成本。而涡轮机的工作温度主要受限于太阳光谱选择性吸收涂层的高温稳定性，因而有必要研发出能够在高温下(≥550℃)光学性能保持稳定的太阳光谱选择性吸收涂层，以满足真空太阳能集热管在更高温度下稳定服役的需求，并提高集热管的工作寿命。这是国内外在太阳能聚光热发电技术领域的重要研究课题之一。
目前对太阳光谱选择性吸收涂层已经开展了大量的研究，旨在提高太阳光谱选择性吸收涂层的光谱选择性(即光热转换效率)、高温稳定性与服役寿命。在中低温太阳能热利用领域普遍采用的Al-AlN基太阳光谱选择性吸收涂层具有光学性能优良、制备工艺简单、成本低等优点，但该涂层在聚焦热发电所要求的高温下具有较差的热稳定性，不能满足高温槽式光热电站的应用需求。而金属陶瓷基太阳光谱选择性吸收涂层，如W-Al2O3、Mo-Al2O3、Mo-SiO2、WNi-Al2O3和W-Ti-Al2O3基太阳光谱选择性吸收涂层表现出较高的吸收率、较低的红外发射率以及良好的耐温性，但由于氧化物为绝缘体，这些涂层在实际生产当中都需要通过磁控溅射中的大功率射频技术制备大面积薄膜，沉积速率慢，大功率射频电源受到限制，设备昂贵，极大增加了工业化生产的成本。
由此可知，目前高温槽式聚光太阳能热发电电站的低成本商业化运行，需要光学性能良好(吸收率高、发射率低)、耐高温，并且制备工艺简单、成本低的太阳光谱选择性吸收涂层及其相应的制备技术。本技术中，以过渡金属氮化物作为主吸收层的太阳光谱选择性吸收涂层，不仅具有较高的吸收率和较低的红外发射率，并且还能够在高温下表现出良好的热稳定性，尤其是涂层的制备可采用直流磁控溅射技术，成本低、工艺简单。因此，以过渡金属氮化物作为主吸收层的太阳光谱选择性吸收涂层具有广阔的应用前景。
发明内容
本发明的目的是提供一种太阳光谱选择性吸收涂层，适用于高温(工作温度为600℃～800℃)槽式聚光太阳能热发电***中应用的真空集热管，目前在高达800℃的高温下稳定工作的太阳光谱选择性吸收涂层很少，而需求紧迫。该涂层不但具有较高的吸收率和较低的红外发射率，而且能够在高温下(达到800℃)保持光学性能稳定。另外，涂层制备工艺简单、生产周期短、材料原料丰富廉价。
本发明开发了一种耐高温的太阳光谱选择性吸收涂层，该涂层可被沉积于吸热体基材表面，从底部至顶部由三层薄膜构成，各单层的功能、组成与制备方法如下：
第1层为红外反射层，由金属(如W、Mo、Ag、Cu等)薄膜构成；在制备红外反射层时，以金属靶材和Ar气分别作为溅射源和溅射气体，通过直流溅射的方法进行制备。该层在红外波段具有较高的反射率和较低的发射率，能够降低整体涂层的红外发射率。
第2层为吸收层，成分上由Mo、Al和Si与其氮化物的混合物构成。吸收层采用Mo靶、Al靶和Si靶作为溅射源，通过反应共溅射的方法制备，溅射气体和反应气体分别为Ar气和N2，通过改变Mo靶和Al靶的溅射功率以及N2的流量，能够得到具有不同材料成分的吸收层。该吸收层具备本征吸收特性，自身能够对太阳光进行吸收，并且该层还能够与其它层之间产生干涉相消，从而进一步增强对入射太阳光的吸收作用。
第3层为减反层，由陶瓷膜构成，如AlN、Al2O3、Si3N4、SiO2等，该层具有两个亚层，位于底部的亚层中不能含有氧元素，并且底部亚层的折射率高于顶部的亚层。减反层采用反应溅射方法制备，通过改变溅射靶材的种类(如Al靶、Si靶)以及反应气体的类型(如N2、O2)，能够调控减反层亚层的材料成分和光学折射率。这两个减反射亚层具有增透、减反、耐磨的作用，并且两个亚层之间的干涉相消还能够提高涂层的光吸收率，此外，位于第二层的减反射亚层还能够抑制高温下涂层内部层与层之前的氧元素扩散。
本发明所提供的太阳光谱选择性吸收涂层由金属红外反射层、Mo、Al、Si与其氮化物的混合物组成的吸收层和双干涉减反层构成，该涂层在太阳光波段具有高吸收率，而在中红外波段具有低发射率。此外，由于涂层具有特殊的膜系结构，并且吸收层中含有难熔金属Mo及其氮化物，因此涂层在高温下具有良好的热稳定性，尤其在真空环境中可以耐温到800℃的高温。在该涂层的制备过程中，固定各个靶材，只需调节反应气体的流量或靶材的溅射功率，工艺简单、操作方便；该涂层具有较快的沉积速率，生产周期短，工艺成本低，并且该涂层的实验重复性好。能够满足高温真空太阳能集热管的使用需求。
附图说明：
图1为该种太阳光谱选择性吸收涂层的剖面示意图。
具体实施方式：
以下实施例为本发明的具体实施方式，仅用于说明本发明，而非用于限制本发明。
结合附图所示的太阳光谱选择性吸收涂层剖面示意图，涂层的制备工艺流程为：(1)选用纯度为99.95％的Mo靶，涂层的基底材料可使用石英玻璃或不锈钢1。溅射前将真空腔体内预抽至本底真空(≤6×10-4Pa)，通入惰性气体Ar气作为溅射气体，通过摸索制备工艺，调节靶基距，溅射气压与溅射功率到合适的值。通过直流溅射的方式在基底上制备厚度为200nm的Mo膜2；(2)选用纯度分别为99.95％和99.999％的Al靶和Si靶，同时通入Ar和N2气混合气，以N2作为反应气体，调节Ar:N2气体流量比、溅射气压、溅射功率等薄膜制备参数，通过反应共溅射的方式在Mo膜上沉积一层厚度为66nm的、由Mo、Al、Si与其氮化物的混合物组成的薄膜3；(3)调节Ar:N2气体流量比、溅射气压、溅射功率等薄膜制备参数，通过射频反应溅射的方式在薄膜3上沉积一层厚度为64nm的Si3N4膜，即膜4-1；(4)同时通入Ar气和O2混合气，以O2作为反应气体，调节Ar：N2气体流量比、溅射气压、溅射功率等薄膜制备参数，通过射频反应溅射的方式在Si3N4膜上沉积一层厚度为75nm的SiO2膜，即膜4-2。
本实施例制备的太阳光谱选择性吸收涂层的性能如下：在大气质量因子AM1.5条件下，涂层吸收率为93.2％，法向发射率为4.7％。在0.02Pa的真空度下进行真空热处理，涂层经600℃真空热时效处理200小时后，涂层吸收率为92.8％，法向发射率为3.4％；涂层经700℃真空热时效处理200小时后，涂层吸收率为92.2％，法向发射率为3.6％；涂层经800℃真空热时效处理200小时后，涂层吸收率为90.3％，法向发射率为3.0％，说明该成分与膜层结构组成的多层膜涂层在真空环境、800℃温度下是稳定的，该发明保护的涂层体系可用于高温真空集热管在600℃-800℃的工作环境下长期服役。

Claims (6)

1.一种光谱选择性吸收涂层，其特征在于，由三层薄膜结构组成，最底层为金属红外反射膜，中间层是以Mo、Al、Si与其氮化物的混合物为组成成分的吸收层，表面层是以两层陶瓷膜组成的双干涉减反射层。
2.如权利要求1所述的太阳光谱选择性吸收涂层，其特征在于，所述最底层金属红外反射膜，采用金属靶直流磁控溅射、以Ar气作为溅射气体制备。
3.如权利要求1所述的太阳光谱选择性吸收涂层，其特征在于，所述中间层由Mo、Al、Si与其氮化物的混合物组成，沉积时以Ar气为溅射气体，以N2为反应气体，采用Mo、Al和Si靶同时反应溅射制备。
4.如权利要求1所述的太阳光谱选择性吸收涂层，其特征在于，所述表面层为两层陶瓷减反射层，沉积时以Ar气作为溅射气体，采用陶瓷靶射频溅射、陶瓷靶射频反应溅射或金属靶反应溅射制备。
5.如权利要求1所述的太阳光谱选择性吸收涂层，其特征在于，所述表面层为可形成干涉减反射效应的双亚层结构，由厚度和折射率不同的两个亚层构成，不同的折射率通过调整溅射时溅射靶材或反应气体的类型获得。
6.一种制备太阳光谱选择性吸收涂层的方法，包括下述三个步骤：
(1)采用金属靶，在基体表面直流溅射沉积金属红外反射膜；
(2)采用Mo、Al和Si靶，在金属红外反射膜表面反应溅射沉积吸收层；
(3)在吸收层表面沉积具有干涉减反射效应的、双亚层结构的减反射膜。
CN202310094199.8A 2023-02-10 2023-02-10 一种用于槽式热发电高温真空集热管的太阳光谱选择性吸收涂层及其制备方法 Pending CN116123741A (zh)

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Publication number Priority date Publication date Assignee Title
CN116705887A (zh) * 2023-05-29 2023-09-05 中航凯迈(上海)红外科技有限公司 一种红外探测器用吸收膜及其制备方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116705887A (zh) * 2023-05-29 2023-09-05 中航凯迈(上海)红外科技有限公司 一种红外探测器用吸收膜及其制备方法
CN116705887B (zh) * 2023-05-29 2024-03-12 中航凯迈(上海)红外科技有限公司 一种红外探测器用吸收膜及其制备方法

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