黑镍黑铬太阳能选择性吸收涂层的制备与研究
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摘要
随着能源和环境问题的日益严峻,太阳能热利用技术在工业上的应用成为人们关注的焦点。太阳能热利用中的太阳能选择性吸收涂层制备技术是太阳能热利用的关键技术之一。本文分类总结了中高温选择性吸收涂层的基本类型、作用机理和制备方法的同时,介绍了国内外科研工作者的研究工作和最新成果,并设计研制了黑镍、黑铬两种太阳能选择性吸收涂层,并对其选择性吸收机理进行了探讨。
本论文通过分析选择性吸收涂层的基本类型,结合实验室实际制备条件,设计了黑镍、黑铬选择性吸收涂层结构,选择了较为合适的选择性吸收涂层红外反射层(银)。实验过程为采用电镀方法在黄铜基体表面电化学沉积黑镍、黑铬涂层,并分别研究电镀时间、电流密度以及光亮银底层等工艺参数对这两种选择性涂层的吸收率a及发射率ε的影响,最后获得了较为适宜的制备条件。
本论文采用SEM、EDS、XRD以及选择性因子(α/ε)等方法对涂层进行表征,对黑镍、黑铬涂层的表面形貌、表面元素组成以及其相结构进行了分析,并通过涂层截面SEM对涂层厚度以及其对于涂层选择吸收性的影响进行了探索,同时本文就黑镍、黑铬涂层的选择性机理进行了论述。
本论文的创新点在于：(1)采用预镀银作为红外反射层,其具有优良的导热性、耐腐蚀性,且具有优秀的光谱反射性,镀层与基体结合良好,同时镀银工艺还存在工艺简单且稳定易控制、残留镀液易于清理等优点,是本实验的理想选择；(2)获得了工艺稳定的具有实用价值的黑镍太阳能选择性吸收涂层(a=0.90,ε=0.06,α/ε=15)；(3)论证了黑镍、黑铬涂层的选择性吸收机理(干涉型和表面结构型),并提出改善其选择性的可行性方案。
In recent years, Solar thermal utilization in industry application have gain more and more attention as the energy and environmental problems been getting more and more serious, and solar spectrum selective absorbing coatings are the key technology in solar thermal utilization. This thesis summarized the basic types of solar spectrum selective absorbing coatings, their absorption mechanism and preparation methods and introduce the research work and new results of many scientific groups at home and abroad. Furthermore, this thesis studied on black nickel & chrome solar selective absorbing coatings by plating method, and discussed their absorption mechanisms.
According to the five basic absorption mechanisms, combined with the practical preparation conditions, this thesis designed the structure of black nickel & chrome selective coating and chosen the proper material for the selective coating (silver). The brief experimental process is to plate black nickel & chrome on H85 copper alloy, and study the effects of Plating time/Current density/Bright silver bottom-coating's presence or absence on the two coating's solar selectivity and finally a reasonable processing parameters of black nickel selective coating was proposed.
This thesis characterized these selective coatings by surface SEM & EDS, XRD and the solar selectivity (α/ε), studied the effect of thickness on the coating's selectivity through cross-section SEM and meanwhile discussed the difference between the two coating's absorption mechanisms.
The creativity of this thesis lies in:(1) Bright silver was adopted as the reflecting bottom for the solar selective coating, because of its advantage in Heat resistance、Corrosion resistance and excellent spectral reflection, plus the good combination with the substrate, the simple and stable processing parameters and the simplicity of cleaning-up of the residual solution; (2) one reasonable and stable processing parameters of black nickel selective coating was proposed(α=0.90,ε=0.06,α/ε=15); (3) the absorption mechanisms of black chrome selective coating was proved (Interference-structured selective coating & Surface-structured selective coating), and some reasonable schemes to prove the selectivity were proposed.
本论文通过分析选择性吸收涂层的基本类型,结合实验室实际制备条件,设计了黑镍、黑铬选择性吸收涂层结构,选择了较为合适的选择性吸收涂层红外反射层(银)。实验过程为采用电镀方法在黄铜基体表面电化学沉积黑镍、黑铬涂层,并分别研究电镀时间、电流密度以及光亮银底层等工艺参数对这两种选择性涂层的吸收率a及发射率ε的影响,最后获得了较为适宜的制备条件。
本论文采用SEM、EDS、XRD以及选择性因子(α/ε)等方法对涂层进行表征,对黑镍、黑铬涂层的表面形貌、表面元素组成以及其相结构进行了分析,并通过涂层截面SEM对涂层厚度以及其对于涂层选择吸收性的影响进行了探索,同时本文就黑镍、黑铬涂层的选择性机理进行了论述。
本论文的创新点在于：(1)采用预镀银作为红外反射层,其具有优良的导热性、耐腐蚀性,且具有优秀的光谱反射性,镀层与基体结合良好,同时镀银工艺还存在工艺简单且稳定易控制、残留镀液易于清理等优点,是本实验的理想选择；(2)获得了工艺稳定的具有实用价值的黑镍太阳能选择性吸收涂层(a=0.90,ε=0.06,α/ε=15)；(3)论证了黑镍、黑铬涂层的选择性吸收机理(干涉型和表面结构型),并提出改善其选择性的可行性方案。
In recent years, Solar thermal utilization in industry application have gain more and more attention as the energy and environmental problems been getting more and more serious, and solar spectrum selective absorbing coatings are the key technology in solar thermal utilization. This thesis summarized the basic types of solar spectrum selective absorbing coatings, their absorption mechanism and preparation methods and introduce the research work and new results of many scientific groups at home and abroad. Furthermore, this thesis studied on black nickel & chrome solar selective absorbing coatings by plating method, and discussed their absorption mechanisms.
According to the five basic absorption mechanisms, combined with the practical preparation conditions, this thesis designed the structure of black nickel & chrome selective coating and chosen the proper material for the selective coating (silver). The brief experimental process is to plate black nickel & chrome on H85 copper alloy, and study the effects of Plating time/Current density/Bright silver bottom-coating's presence or absence on the two coating's solar selectivity and finally a reasonable processing parameters of black nickel selective coating was proposed.
This thesis characterized these selective coatings by surface SEM & EDS, XRD and the solar selectivity (α/ε), studied the effect of thickness on the coating's selectivity through cross-section SEM and meanwhile discussed the difference between the two coating's absorption mechanisms.
The creativity of this thesis lies in:(1) Bright silver was adopted as the reflecting bottom for the solar selective coating, because of its advantage in Heat resistance、Corrosion resistance and excellent spectral reflection, plus the good combination with the substrate, the simple and stable processing parameters and the simplicity of cleaning-up of the residual solution; (2) one reasonable and stable processing parameters of black nickel selective coating was proposed(α=0.90,ε=0.06,α/ε=15); (3) the absorption mechanisms of black chrome selective coating was proved (Interference-structured selective coating & Surface-structured selective coating), and some reasonable schemes to prove the selectivity were proposed.
引文
[1]张鹤飞主编.太阳能热利用原理与计算机模拟(第二版)西北工业大学出版社.2004：3
[2]胡万里,李长友.太阳能选择性吸收薄膜[J].实用技术,2005(3).
[3]吕坤,王海英,董华.太阳能选择性吸收涂层的现状及发展[J].中国涂料,2003(4)：36-38.Liikun, WANG Hai-ying, DONG Hua. Current status and future development of the solar energy selective absorbing coating[J].China Paint,2003(4):36-38.
[4]葛新石,龚堡,俞善庆.太阳能利用中的光谱选择性涂层.北京：科学技术出版社,1980
[5]殷志强.全玻璃真空太阳集热管.北京：科学出版社,1998
[6]谢光明.中高温太阳选择性吸收表面[J].太阳能,2000(2)：22-023.
[7]谢光明,光谱选择性吸收涂层,太阳能,1998,3：14-15
[8]文明芬,郭忠诚,杨显万,新型太阳选择性吸收涂层研究,太阳能学报,1998,19(2)：217-219
[9]Thornton J A, Lamb J L. Sputter-deposited Pt-A12O3 selective absorber coatings, Thin Solid Films.l981,83(4):377-385
[10]Thornton J A, Lamb J L. Thermal stability studies of sputter-deposited multilayer selective absorber coatings, Thin Solid Films.1982,96(2):175-183
[11]Thornton J A, Penfold A S, Lamb J L. Sputter-deposited A1203/Mo/A1203 selective absorber coatings, Thin Solid Films.1980,72(1):101-109
[12]Ebisawa S, Ihara H, Shinoki F. Solar-selective surface utilizing zirconium carbide film, Journal of the Vacuum Society of Japan,1978,21(4):113-119
[13]Rivory J, Behaghel J M, Berthier S, et al. Optical properties of substoichiometric TiNx, Thin Solid Films,1981,78(2):161-165
[14]Roux L,Hanus J, Francois J C,et al. The optical properties of titanium nitrides and carbides: Spectral selectivity and photothermal conversion of solar energy, Solar Energy Materials,1982, 7(3):299-312
[15]Martin P J, Netterfield R P, Sainty W G. Optical properties of TiNx produced by reactive evaporation and reactive ion-beam sputtering,Vacuum,1982,32(6):359-362
[16]Kothari. N. C. Environmental degradation of solar plate collector surface, Solar World Congress,1983,3:1919-1924
[17]郭信章等.真空镀膜工艺对选择性吸收膜性能的影响.太阳能学报.1995,16(2)：207-209
[18]涂祖文,太阳选择性吸收涂料,太阳能,1984,(1)：18-20
[19]Maeshima M,Saruwatari K,Usuki T,et al. Solar heat absorbing plate.JP99 61490,1997-08-27
[20]Hultmark G. Absorbing layer for solar collectors and a method and aparatus for manufacture it.WO98 11271,1996-09-16
[21]Pethkar S, Takwale M G, Agashe C, et al. Cobalt oxide selective coatings for all glass evacuated collectors[J].Sol. Energy Mater Sol Cells,1993,31(2):109-117
[22]Lee Tai-kyu, Kim Dong-hyung, Auh P Chungmoo. Preparation of new black chrome solar selective coatings[J].Korean J Chem Eng,1995,12(2):207-212
[23]清华大学,溅射太阳能选择性吸收涂层,中国专利,GK85 100142,1985-04-01
[24]中科院上海硅酸盐研究所,光谱选择性吸收黑铝涂层及制造方法,中国专利,GK85100509,1985-04-01
[25]北京市太阳能研究所,光热转换吸收薄膜及制备,中国专利,CN1030101,1991-06-18
[26]北京市太阳能研究所,太阳能选择性吸收膜及制备,中国专利,CN1056159,1991-06-18
[27]战余英,王德荣,刘树博,真空玻璃集热管直流反应溅射不锈钢-碳选择性涂层,太阳能学报,1987,8(1)：6-11
[28]殷志强,徐晟,史月艳,渐变Al-N/Al太阳选择性吸收表面[J].真空科学与技术,1988,8(3)： 141-150
[29]曹搵真,胡行方.太阳选择性吸收薄膜中干涉条件的近似计算[J].太阳能学报,2000,21(3)：279-284
[30]Sun Z Q, Sun D M, Li A X et al. Properties of Ag-MgF2 Cermet Films. vacuum 1999, 52:243-246.
[31]Sun D M, Sun Z Q, Li A x et al. oxidation Behaviour of MgF2 in Ag-MgF2 Cermet, vacuum,1999,55:39-44.
[32]刘晓峰.太阳能光谱选择性吸收涂层新型颜料的合成研究[J].太阳能学报,1994,15(3)：300-304
[33]安茂忠.电镀理论与技术[M].哈尔滨：哈尔滨工业大学出版社,2003,1-5.
[34]ZHANG Qi-chu, MILLS D R. New cermet film structures with much improved selectivity for solar thermal application [J].Appl Phys Lett,1992,60 (5):545-547
[35]杨永刚,王世成,倪沛然,等.粉末法制备太阳能电池Cu2ZnSnS4薄膜吸收层[J].粉末冶金材料科学与工程,2008,13(1)：24-29.
[36]ENRIQUE BARRERA, TOMAS VIVEROS, ASCENCION MONTOYA, et al. Titanium-tin oxide protective films on a black cobalt photothermal absorber [J].Solar Energy Materials and Solar Cells,1999,57:127-140.
[37]VISITSERGNTRAKUL S, THAVARUNGKUL N. Pilot plant production of black chrome in Thailand:From science to technology [J].Solar Energy Materials,1990,21:1-16
[38]ENRIQUE BARRERA, TOMAS VIVEROS,ASENCION MONTOYA, et al. Titanium-tin oxide protective films on a black cobalt photothermal absorber [J].Solar Energy Materials and Solar Cells,1999,57:127-140.
[39]费敬根,周爱梅,王宝珑.太阳能光谱选择性低电流黑铬镀层的研究[J].太阳能学报,1991,12(3)：334-336.
[40]杨晓继,殷志强,史月艳.干涉型太阳选择性吸收涂层的光学性能设计[J]太阳能学 报,1997,18(1)：7-12.
[41]郭贤烙,肖鑫,易翔,等.铜及铜合金化学抛光及钝化的研究[J].表面技术,2001,30(2)：35-39.
[42]Guo Xianluo, Xiao Xin, Yi Xiang, et al. Study on Chemical-polishing and Passivation of Copper and Copper alloy[J]. Surface Technology,2001,30(2):35-39
[43]刘万方,陆崇敦.铜及其合金常温化学抛光[J].电镀与精饰,1996,18(4)：35-36.
[44]张允诚,胡如南,向荣.电镀手册[M].北京：国防工业出版社,2008.
[45]李金花,宋宽秀,王一平等.中高温太阳光谱选择性吸收涂层的研究进展[J].化学工业与工程,2004,21(6)：432-437.
[46]Wackelgard E. Characterization of Black Nickel Solar Absorber Coatings Electroplated in a Nickel Chlorine Aqueous Solution [J].Solar Energy Materials and Solar Cells,1998,56:35-44.
[2]胡万里,李长友.太阳能选择性吸收薄膜[J].实用技术,2005(3).
[3]吕坤,王海英,董华.太阳能选择性吸收涂层的现状及发展[J].中国涂料,2003(4)：36-38.Liikun, WANG Hai-ying, DONG Hua. Current status and future development of the solar energy selective absorbing coating[J].China Paint,2003(4):36-38.
[4]葛新石,龚堡,俞善庆.太阳能利用中的光谱选择性涂层.北京：科学技术出版社,1980
[5]殷志强.全玻璃真空太阳集热管.北京：科学出版社,1998
[6]谢光明.中高温太阳选择性吸收表面[J].太阳能,2000(2)：22-023.
[7]谢光明,光谱选择性吸收涂层,太阳能,1998,3：14-15
[8]文明芬,郭忠诚,杨显万,新型太阳选择性吸收涂层研究,太阳能学报,1998,19(2)：217-219
[9]Thornton J A, Lamb J L. Sputter-deposited Pt-A12O3 selective absorber coatings, Thin Solid Films.l981,83(4):377-385
[10]Thornton J A, Lamb J L. Thermal stability studies of sputter-deposited multilayer selective absorber coatings, Thin Solid Films.1982,96(2):175-183
[11]Thornton J A, Penfold A S, Lamb J L. Sputter-deposited A1203/Mo/A1203 selective absorber coatings, Thin Solid Films.1980,72(1):101-109
[12]Ebisawa S, Ihara H, Shinoki F. Solar-selective surface utilizing zirconium carbide film, Journal of the Vacuum Society of Japan,1978,21(4):113-119
[13]Rivory J, Behaghel J M, Berthier S, et al. Optical properties of substoichiometric TiNx, Thin Solid Films,1981,78(2):161-165
[14]Roux L,Hanus J, Francois J C,et al. The optical properties of titanium nitrides and carbides: Spectral selectivity and photothermal conversion of solar energy, Solar Energy Materials,1982, 7(3):299-312
[15]Martin P J, Netterfield R P, Sainty W G. Optical properties of TiNx produced by reactive evaporation and reactive ion-beam sputtering,Vacuum,1982,32(6):359-362
[16]Kothari. N. C. Environmental degradation of solar plate collector surface, Solar World Congress,1983,3:1919-1924
[17]郭信章等.真空镀膜工艺对选择性吸收膜性能的影响.太阳能学报.1995,16(2)：207-209
[18]涂祖文,太阳选择性吸收涂料,太阳能,1984,(1)：18-20
[19]Maeshima M,Saruwatari K,Usuki T,et al. Solar heat absorbing plate.JP99 61490,1997-08-27
[20]Hultmark G. Absorbing layer for solar collectors and a method and aparatus for manufacture it.WO98 11271,1996-09-16
[21]Pethkar S, Takwale M G, Agashe C, et al. Cobalt oxide selective coatings for all glass evacuated collectors[J].Sol. Energy Mater Sol Cells,1993,31(2):109-117
[22]Lee Tai-kyu, Kim Dong-hyung, Auh P Chungmoo. Preparation of new black chrome solar selective coatings[J].Korean J Chem Eng,1995,12(2):207-212
[23]清华大学,溅射太阳能选择性吸收涂层,中国专利,GK85 100142,1985-04-01
[24]中科院上海硅酸盐研究所,光谱选择性吸收黑铝涂层及制造方法,中国专利,GK85100509,1985-04-01
[25]北京市太阳能研究所,光热转换吸收薄膜及制备,中国专利,CN1030101,1991-06-18
[26]北京市太阳能研究所,太阳能选择性吸收膜及制备,中国专利,CN1056159,1991-06-18
[27]战余英,王德荣,刘树博,真空玻璃集热管直流反应溅射不锈钢-碳选择性涂层,太阳能学报,1987,8(1)：6-11
[28]殷志强,徐晟,史月艳,渐变Al-N/Al太阳选择性吸收表面[J].真空科学与技术,1988,8(3)： 141-150
[29]曹搵真,胡行方.太阳选择性吸收薄膜中干涉条件的近似计算[J].太阳能学报,2000,21(3)：279-284
[30]Sun Z Q, Sun D M, Li A X et al. Properties of Ag-MgF2 Cermet Films. vacuum 1999, 52:243-246.
[31]Sun D M, Sun Z Q, Li A x et al. oxidation Behaviour of MgF2 in Ag-MgF2 Cermet, vacuum,1999,55:39-44.
[32]刘晓峰.太阳能光谱选择性吸收涂层新型颜料的合成研究[J].太阳能学报,1994,15(3)：300-304
[33]安茂忠.电镀理论与技术[M].哈尔滨：哈尔滨工业大学出版社,2003,1-5.
[34]ZHANG Qi-chu, MILLS D R. New cermet film structures with much improved selectivity for solar thermal application [J].Appl Phys Lett,1992,60 (5):545-547
[35]杨永刚,王世成,倪沛然,等.粉末法制备太阳能电池Cu2ZnSnS4薄膜吸收层[J].粉末冶金材料科学与工程,2008,13(1)：24-29.
[36]ENRIQUE BARRERA, TOMAS VIVEROS, ASCENCION MONTOYA, et al. Titanium-tin oxide protective films on a black cobalt photothermal absorber [J].Solar Energy Materials and Solar Cells,1999,57:127-140.
[37]VISITSERGNTRAKUL S, THAVARUNGKUL N. Pilot plant production of black chrome in Thailand:From science to technology [J].Solar Energy Materials,1990,21:1-16
[38]ENRIQUE BARRERA, TOMAS VIVEROS,ASENCION MONTOYA, et al. Titanium-tin oxide protective films on a black cobalt photothermal absorber [J].Solar Energy Materials and Solar Cells,1999,57:127-140.
[39]费敬根,周爱梅,王宝珑.太阳能光谱选择性低电流黑铬镀层的研究[J].太阳能学报,1991,12(3)：334-336.
[40]杨晓继,殷志强,史月艳.干涉型太阳选择性吸收涂层的光学性能设计[J]太阳能学 报,1997,18(1)：7-12.
[41]郭贤烙,肖鑫,易翔,等.铜及铜合金化学抛光及钝化的研究[J].表面技术,2001,30(2)：35-39.
[42]Guo Xianluo, Xiao Xin, Yi Xiang, et al. Study on Chemical-polishing and Passivation of Copper and Copper alloy[J]. Surface Technology,2001,30(2):35-39
[43]刘万方,陆崇敦.铜及其合金常温化学抛光[J].电镀与精饰,1996,18(4)：35-36.
[44]张允诚,胡如南,向荣.电镀手册[M].北京：国防工业出版社,2008.
[45]李金花,宋宽秀,王一平等.中高温太阳光谱选择性吸收涂层的研究进展[J].化学工业与工程,2004,21(6)：432-437.
[46]Wackelgard E. Characterization of Black Nickel Solar Absorber Coatings Electroplated in a Nickel Chlorine Aqueous Solution [J].Solar Energy Materials and Solar Cells,1998,56:35-44.