高能量激光诱导等离子体的谱线品质研究
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摘要
激光诱导等离子体的过程是一个相当复杂的过程，它与许多因素密切相关。本文采用高能量钕玻璃激光器，研究了激光器工作电压、功率密度、等离子体的观测高度、样品位置、环境气体及气压对等离子体的谱线强度及谱线质量的影响，获得了最佳的实验条件，并测量了金属分析样品中某些元素的含量。结果表明：等离子体的谱线强度随激光器工作电压、功率密度的增大而增大。(1)对于光谱标钢准样品，当激光器工作电压为1600V、氩气压力为600乇时，谱线强度达到最大，并且在相同压强下，氩气中的等离子体与空气中的等离子体相比，其辐射强度明显增强；氩气压力为320乇时的谱线信背比约为600乇条件下的5倍，而等离子体温度却下降了近1000K，即等离子体温度随环境气压的增大而增大；当激光束的焦斑在样品表面上下移动时，激光诱导量、等离子体的激发温度、谱线强度都呈不对称性分布，其最大值对应的焦斑位置都位于样品表面之下0.4mm左右。(2)对于标准铝样品，在激光器工作电压为1600V、等离子体观测高度为2mm、氩气压力为660乇时，其谱线强度最强；以Al Ⅰ 308.22nm、Al Ⅰ 309.27nm两条谱线为分析线，发现随着环境气压的增大，谱线自吸效应明显增强，当环境气压达到600-700乇时，谱线几乎产生自蚀。
作为激光诱导等离子体技术的应用，对于光谱标钢样品6-3中的Mn、Ni、Ti元素进行定量分析，其分析精密度(RSD)分别为：5.949％、4.779％、5.214％，元素含量相对误差在10.7％范围内；对715号标样铝中Zn元素的分析结果为：RSD为3.749％，元素含量相对误差位于8.2％范围内。结果表明元素含量与谱线强度之间有良好的线性关系。
Laser induced -plasma is a very complex process. It strongly depends on many factors. In this experiment , a neodymium glass laser is used to study the effects of the operating voltage, power density, the height from the observed location of the plasma to the surface of the sample, the location of the sample, the gas composition and the pressure on the intensity and quality of the spectrum. The optimized experimental conditions are determined and the densities of some elements in the mental alloy standard samples are measured .The experimental results shows that the spectral intensity of the plasma enhances significantly with the increase of the operating voltage and the power density.(1) To the steel ally sample, the emission intensities of the spectra reach to the maximum values when the laser operating voltage is 1600V and the argon pressure is 600 torr. Under the same pressure, the spectral intensity of the plasma in the argon atmosphere is stronger than that in the air. When the argon pressure is 320 to
rr, the signal-noise ration is about 5 times than that which the argon pressure is 700 torr, but the temperature of plasma is less about 1000k. That is to say, the temperature increase with the increase of the atmospheric pressure. If the focal point of the len shifts around the surface of the sample, the mass ablation, the temperature of the plasma and the spectral intensity appear asymmetric and their maximum occur at the location which is about 0.4mm under the surface of the sample. (2) To the plasma of the aluminum alloy sample, when the operating voltage is 1600V,the height from the observed location of the plasma to the surface of the sample is 2mm and the argon pressure is 660 torr, the spectral intensity have the maximum values. The self-absorption ability of the Al(I)308.22nm and A(I)309.27nmlines is strengthen with the increase of increase of the pressure, and even appear self-reversal when the pressure is 600-700 torr.
As the use of the laser induced-plasma , we determine the densities of the Mn, Ni, Ti elements in the 6-3 steel alloy standard sample and the Zn element in the 715 aluminum alloy, The Relative Standard Deviation(RSD) are respectively 5.949%,4.779%,5.214%,3.749%.and the relative errors are lower than 10.7%. This
shows there is a good linear relation between the spectral intensity and the elemental density.
作为激光诱导等离子体技术的应用，对于光谱标钢样品6-3中的Mn、Ni、Ti元素进行定量分析，其分析精密度(RSD)分别为：5.949％、4.779％、5.214％，元素含量相对误差在10.7％范围内；对715号标样铝中Zn元素的分析结果为：RSD为3.749％，元素含量相对误差位于8.2％范围内。结果表明元素含量与谱线强度之间有良好的线性关系。
Laser induced -plasma is a very complex process. It strongly depends on many factors. In this experiment , a neodymium glass laser is used to study the effects of the operating voltage, power density, the height from the observed location of the plasma to the surface of the sample, the location of the sample, the gas composition and the pressure on the intensity and quality of the spectrum. The optimized experimental conditions are determined and the densities of some elements in the mental alloy standard samples are measured .The experimental results shows that the spectral intensity of the plasma enhances significantly with the increase of the operating voltage and the power density.(1) To the steel ally sample, the emission intensities of the spectra reach to the maximum values when the laser operating voltage is 1600V and the argon pressure is 600 torr. Under the same pressure, the spectral intensity of the plasma in the argon atmosphere is stronger than that in the air. When the argon pressure is 320 to
rr, the signal-noise ration is about 5 times than that which the argon pressure is 700 torr, but the temperature of plasma is less about 1000k. That is to say, the temperature increase with the increase of the atmospheric pressure. If the focal point of the len shifts around the surface of the sample, the mass ablation, the temperature of the plasma and the spectral intensity appear asymmetric and their maximum occur at the location which is about 0.4mm under the surface of the sample. (2) To the plasma of the aluminum alloy sample, when the operating voltage is 1600V,the height from the observed location of the plasma to the surface of the sample is 2mm and the argon pressure is 660 torr, the spectral intensity have the maximum values. The self-absorption ability of the Al(I)308.22nm and A(I)309.27nmlines is strengthen with the increase of increase of the pressure, and even appear self-reversal when the pressure is 600-700 torr.
As the use of the laser induced-plasma , we determine the densities of the Mn, Ni, Ti elements in the 6-3 steel alloy standard sample and the Zn element in the 715 aluminum alloy, The Relative Standard Deviation(RSD) are respectively 5.949%,4.779%,5.214%,3.749%.and the relative errors are lower than 10.7%. This
shows there is a good linear relation between the spectral intensity and the elemental density.
引文
1．《发射光谱分析》冶金工业出版社
2．《原子发射光谱分析原理》陈新坤 天津科学技术出版社
3．《近代原子光谱分析》马成龙 王忠厚等 辽宁大学出版社
4. Y Iida, Appli. Spectrosc. 1989 43(2),229
5. S S Harilal, C V Bindhu, V P Nampoori, and C P G Vallabhan Appli. Phys. Lett. 1998 72(2), 167
6. Yong_Ill Lee and J Sneddon Spectrosc. Lett. 1996 29(6), 1157
7. M Owens and V Majidi Appli. Spectrosc. 1991 45, 1463
8. M Kuzuya, H Matsumoto, H Takechi, et al. Appli. Spectrosc. 1993 47, 1659.
9. W S Budi, W T Baskoro, M Pardede, H Kurniawan, M on Tjia, and K Kagawa Appli. Spectrosc. 1999 53(11), 1347
10. R Q Aucelio, B C Castle, B W Smith, and J D Winefordner Appli. Spectrosc. 2000 54(6), 832
11. A K Knight, N L Scherbarth, D Cremers, and M J Ferris Appli. Spectrosc. 2000 54(3), 331
12. J Hermann, C Boulmer—Leborgne, and D Hong Appli. Phys. 1998 83(2), 691
13. MAN Bao-yuan, WANG Gong-tang, LIU Ai-hua, WANG Xiang-tai (满宝元 王公堂 刘爱华 王象泰) Spectroscopy and Spectral Analysis (光谱学与光谱分析)1998 18(4), 411
14. SONG Yi-zhong, LI Zun-ying, ZHU Rui-fu, WANG Jian-hua(宋一中 李尊营 朱瑞富 王建华) Sprctroscopy and Spectral Analysis (光谱学与光
谱分析) 2001 21(3), 290
15. AN Cheng-wu, WANG You-qing, SONG Wen-dong(安承武 王又青 宋文栋)Chinese Journal of Lasers (中国激光)1996 A23(8), 192
16. M Caetano, X Mao, R E Russo Spectrochim. Acta Part B 1996 51, 1473
17. M Caetano, Xianglei Mao, R E Russo Spectrochim. Acta Bart B 1996 51, 1473
18. K J Grant and G L Paul, Appli. Spoctrosc. 1990 44, 1349
19. HUANG Qing-ju, FANG Er-ti (黄庆举 方尔梯) Laser & Infrared (激光与红外) 1999 29(4), 205
20. HUANG Qing-ju, FANG Er-ti 黄庆举 方尔梯 Laser & Infrared (激光与红外) 1999 29(5), 286
21. SONG Yi-zhong, LI Liang (宋一中 李亮) Laser % Infrared (激光与红外) 2000 30(3), 148
22. SONG Yi-zhong, LI Zun-ying, ZHU Rui-fu, WANG Jian-hua(宋一中 李尊营 朱瑞富 王建华) Spectroscopy and Spectral Analysis (光谱学与光谱分析) 2002 22(2), 192
23. J. Hermann, C. Boulmer—Leborgne, I. N. Mihailescu. J. Appli. Phys. 1993 74, 3071
24. ZHANG Shu-dong, ZHANG Wei-jun(张树东 张为俊) Acta Physica Sinica(物理学报) 2001 50(8), 1512
25. L Balazs Anal. Chem. 1991 63,314
26. A Vertes, L Balazs and R Gijbels The 1990 winter conference on plasma Spectrochemistry, st. Petersburg, FL. USA, 1990 8(13)
27. K J Grant, G L Paul, and J A Oneill Appli. Spectrosc. 1991 45(4), 701
28. V Pakhomov, W Nichols and J Borysow Appli. Spectrosc. 1996 50 (7), 880
29. D A Cremers, J E Barefield Ⅱ, and A C Koskelo Appli. Spectrosc. 1995 49(6), 857
30. W E Ernst, D F Farson, and D J Sames Appli. Spectrosc. 1996 50(3), 306
31. K Y Yamamoto, D A Cremers, M J Ferris, and L E Foster Appli. Spectrosc. 1996 50(2), 222
32. M Tran, B W Smith, D W Hahn and J D Winefordner Appli. Spectrosc. 2001 55(11), 1455
33. Jong-Il Yun, T Bundschuh, V Neck, and Jaeee-Il Kim Appli. Spectrosc. 2001. 55(3), 273
34. C Aragon, J A Aguilera, and F Penalba Appli. Spectrosc. 1999 53 (10), 1259
35. P Lucerna, J M Vadddillo, and J J Leserna Appli. Spectrosc. 2001 55(3), 267
36. J A Bolger Appli. Spectrosc. 2000 54(2), 181
37. D N Straits, K L Eland, and S M Angel. Appli. Spectrosc. 2000 54(9), 1270
38. E Kim, K J Yoo, H K Park, K J Oh, and D W Kim Appli. Spectrosc. 1997 51(1), 22
39. M Tran, Q Sun, B W Smith, and J D Winefordner Applisc. Spectro. 2001 55(11), 1455
40. M Martin and Meng_Dawn Cheng Appli. Spectrosc. 2000 54 (9), 1279
41. H. Kurniawan, K. Kagawa, M. Okamoto, M. Ueda, T. Kobayashi, and S. Nakajima Appli. Spectrosc. 1996 50(3), 299
42. M Pardede, H Kurniawn, M O Tjia, K Ikezawa, T Maruyama, and K Kagawa Appli. Spectrosc. 2001 55(9), 1229
43. H Kurniawan, K Laban, T J Lie, K Kagawa, and M O Tjla Appli. Spectrosc. 2001 55(1), 92
44. H Kurniawan, S Nakajima, J E.Batubara, M Marpaung , M Okamoto, and K Kagawa Appli. 1995 49(8), 1067
45. Jae_Min Lim, Jae_Kuk Kim, Chang_Soon Lee, Gern_Ho gack, and Yong_Ill Lee Appli. Spectrosc. 2000 54(9), 1253
46. YU Jian-qiao, LI Wei-hua(郁建桥 李维华)Sprctroscopy and Spectral Analysis (光谱学与光谱分析)1995 15(5)47
47. ZHENG Cun-jiang, WU Chao, CHEN Yan-ling, LIN Song-lin(郑存江 吴超 陈艳玲 林宋麟) Sprctroscopy and Spectral Analysis (光谱学与光谱分析) 1995 15 (6) 47
48. S Shuttleworth and D T Kremser J. Anal. Atom. Spectrom. 1998 13, 697
49. M Bi, Antonio Ruiz M., B W Smith, and J D Winefordner Appli. Spectrosc. 2000 54(5), 639
50. O V Borisov, C J Bannochie, and R E Russo Appli. Spectrosc. 2001 55 (10), 1304
51. B C Castle, A K Knight, K Visser, B W Smith and J D Winefordner J. Anal. Atom. Spectrom. 1998 13, 589
52. Pei Liang, Yongchao Qin, Bin Hu, Tianyou Peng, Zucheng Jiang Analytica Chimica Acta 2001 440, 207
53. H Y Kim, H B Lim Analytica Chimica Acte 2001 429, 145
54. P Goodall, S G Johnson, E Wood Spectrochim. Acta B 1995 50, 1823
55. J Ubbering, J Burst, W Sdorra, F Leis and K Niemax Appli. Spectrosc. 1991, 1419
56. K Kagawa, T Manda, M Ueda and Z Z Li J. Spectrosc. Soc. Jpn. 1991, 40, 150
57. H Kurniawan, N Ikeda, T Kobayshi and K Kagawa J. Spectrosc. Soc. Jpn. 1992, 41, 21
58. H Kurniawan, T Kobayshi and K Kagawa Rov. Laser Eng. 1992, 20, 31
59. H Kurniawan, T Kobayshi and K Kagawa Appli. Spoctrosc. 1992, 46, 581
60. Yeung E S. The X X V Colloquium Spectroscopicum International. Toronto, Canada, June 21st-26th, 1987
61. G Y Chen, E S Yeung Anal. Chem. 1988, 60,864
62．《激光光谱技术原理及应用》陆同兴 路轶群 中国科技大学出版社
63．《原子光谱分析》寿曼立 姜桂兰 普通高等教育地质矿产类规划教材
64．《光谱分析法》郭德济 孙洪飞 胡皆汉 重庆大学出版社
65．郑国经 原子发射光谱仪的新进展 现代科学仪器 2000，2
66. S S Harilal, C V Bindhu, V P N Nmapoori, and C P G Vallabhan Appli. Phys. Lett 1998, 72(2), 167
67. R A Multari, L E Foster, D A Cremers, and M J Ferris Appli. Spectrosc 1996, 50(12), 1483
2．《原子发射光谱分析原理》陈新坤 天津科学技术出版社
3．《近代原子光谱分析》马成龙 王忠厚等 辽宁大学出版社
4. Y Iida, Appli. Spectrosc. 1989 43(2),229
5. S S Harilal, C V Bindhu, V P Nampoori, and C P G Vallabhan Appli. Phys. Lett. 1998 72(2), 167
6. Yong_Ill Lee and J Sneddon Spectrosc. Lett. 1996 29(6), 1157
7. M Owens and V Majidi Appli. Spectrosc. 1991 45, 1463
8. M Kuzuya, H Matsumoto, H Takechi, et al. Appli. Spectrosc. 1993 47, 1659.
9. W S Budi, W T Baskoro, M Pardede, H Kurniawan, M on Tjia, and K Kagawa Appli. Spectrosc. 1999 53(11), 1347
10. R Q Aucelio, B C Castle, B W Smith, and J D Winefordner Appli. Spectrosc. 2000 54(6), 832
11. A K Knight, N L Scherbarth, D Cremers, and M J Ferris Appli. Spectrosc. 2000 54(3), 331
12. J Hermann, C Boulmer—Leborgne, and D Hong Appli. Phys. 1998 83(2), 691
13. MAN Bao-yuan, WANG Gong-tang, LIU Ai-hua, WANG Xiang-tai (满宝元 王公堂 刘爱华 王象泰) Spectroscopy and Spectral Analysis (光谱学与光谱分析)1998 18(4), 411
14. SONG Yi-zhong, LI Zun-ying, ZHU Rui-fu, WANG Jian-hua(宋一中 李尊营 朱瑞富 王建华) Sprctroscopy and Spectral Analysis (光谱学与光
谱分析) 2001 21(3), 290
15. AN Cheng-wu, WANG You-qing, SONG Wen-dong(安承武 王又青 宋文栋)Chinese Journal of Lasers (中国激光)1996 A23(8), 192
16. M Caetano, X Mao, R E Russo Spectrochim. Acta Part B 1996 51, 1473
17. M Caetano, Xianglei Mao, R E Russo Spectrochim. Acta Bart B 1996 51, 1473
18. K J Grant and G L Paul, Appli. Spoctrosc. 1990 44, 1349
19. HUANG Qing-ju, FANG Er-ti (黄庆举 方尔梯) Laser & Infrared (激光与红外) 1999 29(4), 205
20. HUANG Qing-ju, FANG Er-ti 黄庆举 方尔梯 Laser & Infrared (激光与红外) 1999 29(5), 286
21. SONG Yi-zhong, LI Liang (宋一中 李亮) Laser % Infrared (激光与红外) 2000 30(3), 148
22. SONG Yi-zhong, LI Zun-ying, ZHU Rui-fu, WANG Jian-hua(宋一中 李尊营 朱瑞富 王建华) Spectroscopy and Spectral Analysis (光谱学与光谱分析) 2002 22(2), 192
23. J. Hermann, C. Boulmer—Leborgne, I. N. Mihailescu. J. Appli. Phys. 1993 74, 3071
24. ZHANG Shu-dong, ZHANG Wei-jun(张树东 张为俊) Acta Physica Sinica(物理学报) 2001 50(8), 1512
25. L Balazs Anal. Chem. 1991 63,314
26. A Vertes, L Balazs and R Gijbels The 1990 winter conference on plasma Spectrochemistry, st. Petersburg, FL. USA, 1990 8(13)
27. K J Grant, G L Paul, and J A Oneill Appli. Spectrosc. 1991 45(4), 701
28. V Pakhomov, W Nichols and J Borysow Appli. Spectrosc. 1996 50 (7), 880
29. D A Cremers, J E Barefield Ⅱ, and A C Koskelo Appli. Spectrosc. 1995 49(6), 857
30. W E Ernst, D F Farson, and D J Sames Appli. Spectrosc. 1996 50(3), 306
31. K Y Yamamoto, D A Cremers, M J Ferris, and L E Foster Appli. Spectrosc. 1996 50(2), 222
32. M Tran, B W Smith, D W Hahn and J D Winefordner Appli. Spectrosc. 2001 55(11), 1455
33. Jong-Il Yun, T Bundschuh, V Neck, and Jaeee-Il Kim Appli. Spectrosc. 2001. 55(3), 273
34. C Aragon, J A Aguilera, and F Penalba Appli. Spectrosc. 1999 53 (10), 1259
35. P Lucerna, J M Vadddillo, and J J Leserna Appli. Spectrosc. 2001 55(3), 267
36. J A Bolger Appli. Spectrosc. 2000 54(2), 181
37. D N Straits, K L Eland, and S M Angel. Appli. Spectrosc. 2000 54(9), 1270
38. E Kim, K J Yoo, H K Park, K J Oh, and D W Kim Appli. Spectrosc. 1997 51(1), 22
39. M Tran, Q Sun, B W Smith, and J D Winefordner Applisc. Spectro. 2001 55(11), 1455
40. M Martin and Meng_Dawn Cheng Appli. Spectrosc. 2000 54 (9), 1279
41. H. Kurniawan, K. Kagawa, M. Okamoto, M. Ueda, T. Kobayashi, and S. Nakajima Appli. Spectrosc. 1996 50(3), 299
42. M Pardede, H Kurniawn, M O Tjia, K Ikezawa, T Maruyama, and K Kagawa Appli. Spectrosc. 2001 55(9), 1229
43. H Kurniawan, K Laban, T J Lie, K Kagawa, and M O Tjla Appli. Spectrosc. 2001 55(1), 92
44. H Kurniawan, S Nakajima, J E.Batubara, M Marpaung , M Okamoto, and K Kagawa Appli. 1995 49(8), 1067
45. Jae_Min Lim, Jae_Kuk Kim, Chang_Soon Lee, Gern_Ho gack, and Yong_Ill Lee Appli. Spectrosc. 2000 54(9), 1253
46. YU Jian-qiao, LI Wei-hua(郁建桥 李维华)Sprctroscopy and Spectral Analysis (光谱学与光谱分析)1995 15(5)47
47. ZHENG Cun-jiang, WU Chao, CHEN Yan-ling, LIN Song-lin(郑存江 吴超 陈艳玲 林宋麟) Sprctroscopy and Spectral Analysis (光谱学与光谱分析) 1995 15 (6) 47
48. S Shuttleworth and D T Kremser J. Anal. Atom. Spectrom. 1998 13, 697
49. M Bi, Antonio Ruiz M., B W Smith, and J D Winefordner Appli. Spectrosc. 2000 54(5), 639
50. O V Borisov, C J Bannochie, and R E Russo Appli. Spectrosc. 2001 55 (10), 1304
51. B C Castle, A K Knight, K Visser, B W Smith and J D Winefordner J. Anal. Atom. Spectrom. 1998 13, 589
52. Pei Liang, Yongchao Qin, Bin Hu, Tianyou Peng, Zucheng Jiang Analytica Chimica Acta 2001 440, 207
53. H Y Kim, H B Lim Analytica Chimica Acte 2001 429, 145
54. P Goodall, S G Johnson, E Wood Spectrochim. Acta B 1995 50, 1823
55. J Ubbering, J Burst, W Sdorra, F Leis and K Niemax Appli. Spectrosc. 1991, 1419
56. K Kagawa, T Manda, M Ueda and Z Z Li J. Spectrosc. Soc. Jpn. 1991, 40, 150
57. H Kurniawan, N Ikeda, T Kobayshi and K Kagawa J. Spectrosc. Soc. Jpn. 1992, 41, 21
58. H Kurniawan, T Kobayshi and K Kagawa Rov. Laser Eng. 1992, 20, 31
59. H Kurniawan, T Kobayshi and K Kagawa Appli. Spoctrosc. 1992, 46, 581
60. Yeung E S. The X X V Colloquium Spectroscopicum International. Toronto, Canada, June 21st-26th, 1987
61. G Y Chen, E S Yeung Anal. Chem. 1988, 60,864
62．《激光光谱技术原理及应用》陆同兴 路轶群 中国科技大学出版社
63．《原子光谱分析》寿曼立 姜桂兰 普通高等教育地质矿产类规划教材
64．《光谱分析法》郭德济 孙洪飞 胡皆汉 重庆大学出版社
65．郑国经 原子发射光谱仪的新进展 现代科学仪器 2000，2
66. S S Harilal, C V Bindhu, V P N Nmapoori, and C P G Vallabhan Appli. Phys. Lett 1998, 72(2), 167
67. R A Multari, L E Foster, D A Cremers, and M J Ferris Appli. Spectrosc 1996, 50(12), 1483