LIBS法定量分析钛合金中的合金元素
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摘要
采用波长1064 nm Nd:YAG固态激光器对钛合金样品进行激发,中阶梯光栅光谱仪作为分光系统,时间分辨增强型(ICCD)检测器检测光信号,激光诱导击穿光谱(LIBS)分析方法对钛合金中合金元素的含量进行测定。实验优化了延时时间参数以提高方法分析性能,并最终确定最佳延时时间为2μs。在优化的实验参数下对TC11钛合金系列标准样品中的5种元素Al,Mo,Zr,Fe,Si绘制标准曲线,并对TC11样品中合金元素的含量进行定量分析。结果表明,Al,Mo,Zr,Fe,Si各元素的方法检出限分别为8.98×10~(-4),8.43×10~(-4),4.99×10~(-4),1.73×10~(-4),4.03×10~(-4)。TC11样品中Al,Mo,Zr,Fe,Si含量(质量分数)分别为6.84%,3.24%,1.55%,0.11%,0.26%。采用t检验法将LIBS测定结果与国标方法 GB/T 4698的结果进行对比,验证方法的准确度,Al,Mo,Zr,Fe,Si元素的t值分别为1.37,1.63,0.82,0.61,1.83,均小于95%显著性水平下的临界值t0.05,6=2.45。说明对钛合金样品成分进行定量分析,激光诱导击穿光谱是一项快速、有效的分析技术,分析结果具有可靠性。
Titanium alloy samples were induced by solid state Nd: YAG laser,of which the output wavelength was 1064 nm,echelle spectrograph was used to disperse compound light,intensified charge-coupled device(ICCD) was used to detect optical signal,and the contents of alloying elements in titanium alloy were determined by laser-induced breakdown spectroscopy(LIBS). For a better analysis capability of LIBS,the parameters of delay time were optimized and the best delay time was determined as 2 μs finally. Under the optimized conditions,the calibration curves were made by a series of certified TC11 titanium alloy samples for five elements,Al,Mo,Zr,Fe,and Si,and the contents of alloying elements in TC11 sample were quantified. The results indicated that the detection limit of LIBS were 8. 98 × 10~(-4)(Al),8. 43 × 10~(-4)(Mo),4. 99 × 10~(-4)(Zr),1. 73 × 10~(-4)(Fe) and 4. 03 × 10~(-4)(Si),respectively. The contents(mass fraction) of Al,Mo,Zr,Fe and Si were 6. 84%,3. 24%,1. 55%,0. 11%,and 0. 26%. T-test method was used to compare the results of LIBS with national standard method GB/T 4698. 2-4698. 3 and to test the accuracy of the method. The t values of Al,Mo,Zr,Fe and Si were 1. 37,1. 63,0. 82,0. 61,1. 83 respectively,which were all less than the critical value of 95% confidence probability(t0. 05,6= 2. 45). The results showed that LIBS was a fast and effective for quantitative analysis of titanium alloy samples.
Titanium alloy samples were induced by solid state Nd: YAG laser,of which the output wavelength was 1064 nm,echelle spectrograph was used to disperse compound light,intensified charge-coupled device(ICCD) was used to detect optical signal,and the contents of alloying elements in titanium alloy were determined by laser-induced breakdown spectroscopy(LIBS). For a better analysis capability of LIBS,the parameters of delay time were optimized and the best delay time was determined as 2 μs finally. Under the optimized conditions,the calibration curves were made by a series of certified TC11 titanium alloy samples for five elements,Al,Mo,Zr,Fe,and Si,and the contents of alloying elements in TC11 sample were quantified. The results indicated that the detection limit of LIBS were 8. 98 × 10~(-4)(Al),8. 43 × 10~(-4)(Mo),4. 99 × 10~(-4)(Zr),1. 73 × 10~(-4)(Fe) and 4. 03 × 10~(-4)(Si),respectively. The contents(mass fraction) of Al,Mo,Zr,Fe and Si were 6. 84%,3. 24%,1. 55%,0. 11%,and 0. 26%. T-test method was used to compare the results of LIBS with national standard method GB/T 4698. 2-4698. 3 and to test the accuracy of the method. The t values of Al,Mo,Zr,Fe and Si were 1. 37,1. 63,0. 82,0. 61,1. 83 respectively,which were all less than the critical value of 95% confidence probability(t0. 05,6= 2. 45). The results showed that LIBS was a fast and effective for quantitative analysis of titanium alloy samples.
引文
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[2]Andrzej W Miziolek,Vincenzo Palleschi,Israel Schechter.Laser-Induced Breakdown Spectroscopy(LIBS):Fundamentals and Applications[M].Cambridge University,2006.15.
[3]Lee W B,Wu J Y,Lee Y I.Recent applications of laser-induced breakdown spectrometry:a review of material approaches[J].Applied Spectroscopy Reviews,2004,39(1):27.
[4]Eseller K E,Tripathi M M,Yueh F Y.Elemental analysis of slurry samples with laser induced breakdown spectroscopy[J].Applied Optics,2010,49(13):C21.
[5]Brech F,Cross L.Optical micro-emission stimulated by a ruby laser[J].Applied Spectroscopy,1962,16(2):59.
[6]Chen K,Lu J D,Li J Y.Real-time,quantitative analysis of multi-elements in liquid steel by LIBS[J].Spectroscopy and Spectral Analysis,2011,31(3):823.(陈凯,陆继东,李俊彦.钢液中多元素的LIBS实时定量分析[J].光谱学与光谱分析,2011,31(3):823.)
[7]Gong G M,Yang J.Quantitative analysis of Cr in milk powder by laser induced breakdown spectroscopy[J].Journal of Anhui Agricultural Sciences,2015,43(22):219.(龚刚猛,杨珺.激光诱导击穿光谱快速检测奶粉中重金属Cr的定量分析研究[J].安徽农业科学,2015,43(22):219.)
[8]Wang J,Tan J,Wu J,Wu J Q.Application progress of laser induced breakdown spectroscopy in the field of environment[J].Environmental Monitoring in China,2015,31(3):124.(王卿,谭娟,吴健,吴建强.激光诱导击穿光谱技术在环境领域中的应用动态[J].中国环境监测,2015,31(3):124.)
[9]Ferreira E C,Anzano J M,Milori D M B P.Multiple response optimization of laser-induced breakdown spectroscopy parameters for multi-element analysis of soil samples[J].Applied Spectroscopy,2009,63(9):1081.
[10]Liu X Y,Wang Z Y,Hao L Q,Zhao W W,Huang M Q,Long B,Zhang W J.Application of laser induced breakdown spectroscopy technology in biomedicine field[J].Laser Technology,2008,32(2):135.(刘宪云,王振亚,郝立庆,赵文武,黄明强,龙波,张为俊.激光诱导击穿光谱在生物医学中的应用[J].激光技术,2008,32(2):135.)
[11]Knight A K,Scherbarth N L,Cremers D A.Characterization of laser-induced breakdown spectroscopy(LIBS)for application to space exploration[J].Applied Spectroscopy,2000,54(3):331.
[12]De Lucia F C,Gottfried J L,Miziolet A W.Evaluation of femtosecond laser-induced breakdown spectroscopy for explosive residue detection[J].Optics Express,2009,17(2):419.
[13]Colao F,Fantoni R,Lazic V.LIBS as a diagnostic tool during the laser cleaning of copper based alloys:experimental results[J].J.Anal.At.Spectrom.,2004,19(4):502.
[14]Sun L X,Yu H B,Xin Y,Cong Z B.Quantitative analysis of Mn and Si of alloy steels by laser-induced breakdown spectroscopy[J].Spectroscopy and Spectral Analysis,2010,30(12):3186.(孙兰香,于海斌,辛勇,丛智博.采用激光诱导击穿光谱技术测定合金钢中锰和硅的含量[J].光谱学与光谱分析,2010,30(12):3186.)
[15]Sun D X,Su M G,Dong C Z,Wang X L,Zhang D C,Ma X W.Quantitative analysis of element concentration in Al alloy by using laser-induced breakdown spectroscopy[J].Acta Physica Sinica,2010,59(7):4571.(孙对兄,苏茂根,董晨钟,王向丽,张大成,马新文.基于激光诱导击穿光谱技术的铝合金成分定量分析[J].物理学报,2010,59(7):4571.)
[16]Yang C,Jia Y H,Chen J W,Li D L,Liu J,Zhang Y.Characterization of inclusion type in steel by laser-induced breakdown spectroscopy[J].Chinese Journal of Analytical Chemistry,2014,42(11):1623.(杨春,贾云海,陈吉文,李冬玲,刘佳,张勇.激光诱导击穿光谱法对钢中夹杂物类型的表征[J].分析化学,2014,42(11):1623.)
[17]GB/T 4698.2-2011.Methods for chemical analysis of titanium sponge,titanium and titanium alloys-Determination of iron content[S].2011.(GB/T 4698.2-2011.海绵钛、钛及钛合金化学分析方法铁量的测定[S].2011.)
[18]GB/T 4698.3-1996.Sponge titanium,titanium and titanium alloys-Determination of silicon content-Molybdenum blue spectrophotometric method[S].1996.(GB/T 4698.3-1996.海绵钛、钛及钛合金化学分析方法钼蓝分光光度法测定硅量[S].1996.)
[19]GB/T 4698.21-1996.Sponge titanium,titanium and titanium alloys-Determination of manganese,chromium,nickel,aluminum,molybdenum,tin,vanadium,yttrium,copper,zirconium content-Emission spectrographic method[S].1996.(GB/T 4698.21-1996.海绵钛、钛及钛合金化学分析方法发射光谱法测定锰、铬、镍、铝、钼、锡、钒、钇、铜、锆量[S].1996.)
[20]Wallis F J,Chadwick B L,Morrison R J S.Analysis of lignite using laser-induced breakdown spectroscopy[J].Applied Spectroscopy,2000,54(8):1231.
[2]Andrzej W Miziolek,Vincenzo Palleschi,Israel Schechter.Laser-Induced Breakdown Spectroscopy(LIBS):Fundamentals and Applications[M].Cambridge University,2006.15.
[3]Lee W B,Wu J Y,Lee Y I.Recent applications of laser-induced breakdown spectrometry:a review of material approaches[J].Applied Spectroscopy Reviews,2004,39(1):27.
[4]Eseller K E,Tripathi M M,Yueh F Y.Elemental analysis of slurry samples with laser induced breakdown spectroscopy[J].Applied Optics,2010,49(13):C21.
[5]Brech F,Cross L.Optical micro-emission stimulated by a ruby laser[J].Applied Spectroscopy,1962,16(2):59.
[6]Chen K,Lu J D,Li J Y.Real-time,quantitative analysis of multi-elements in liquid steel by LIBS[J].Spectroscopy and Spectral Analysis,2011,31(3):823.(陈凯,陆继东,李俊彦.钢液中多元素的LIBS实时定量分析[J].光谱学与光谱分析,2011,31(3):823.)
[7]Gong G M,Yang J.Quantitative analysis of Cr in milk powder by laser induced breakdown spectroscopy[J].Journal of Anhui Agricultural Sciences,2015,43(22):219.(龚刚猛,杨珺.激光诱导击穿光谱快速检测奶粉中重金属Cr的定量分析研究[J].安徽农业科学,2015,43(22):219.)
[8]Wang J,Tan J,Wu J,Wu J Q.Application progress of laser induced breakdown spectroscopy in the field of environment[J].Environmental Monitoring in China,2015,31(3):124.(王卿,谭娟,吴健,吴建强.激光诱导击穿光谱技术在环境领域中的应用动态[J].中国环境监测,2015,31(3):124.)
[9]Ferreira E C,Anzano J M,Milori D M B P.Multiple response optimization of laser-induced breakdown spectroscopy parameters for multi-element analysis of soil samples[J].Applied Spectroscopy,2009,63(9):1081.
[10]Liu X Y,Wang Z Y,Hao L Q,Zhao W W,Huang M Q,Long B,Zhang W J.Application of laser induced breakdown spectroscopy technology in biomedicine field[J].Laser Technology,2008,32(2):135.(刘宪云,王振亚,郝立庆,赵文武,黄明强,龙波,张为俊.激光诱导击穿光谱在生物医学中的应用[J].激光技术,2008,32(2):135.)
[11]Knight A K,Scherbarth N L,Cremers D A.Characterization of laser-induced breakdown spectroscopy(LIBS)for application to space exploration[J].Applied Spectroscopy,2000,54(3):331.
[12]De Lucia F C,Gottfried J L,Miziolet A W.Evaluation of femtosecond laser-induced breakdown spectroscopy for explosive residue detection[J].Optics Express,2009,17(2):419.
[13]Colao F,Fantoni R,Lazic V.LIBS as a diagnostic tool during the laser cleaning of copper based alloys:experimental results[J].J.Anal.At.Spectrom.,2004,19(4):502.
[14]Sun L X,Yu H B,Xin Y,Cong Z B.Quantitative analysis of Mn and Si of alloy steels by laser-induced breakdown spectroscopy[J].Spectroscopy and Spectral Analysis,2010,30(12):3186.(孙兰香,于海斌,辛勇,丛智博.采用激光诱导击穿光谱技术测定合金钢中锰和硅的含量[J].光谱学与光谱分析,2010,30(12):3186.)
[15]Sun D X,Su M G,Dong C Z,Wang X L,Zhang D C,Ma X W.Quantitative analysis of element concentration in Al alloy by using laser-induced breakdown spectroscopy[J].Acta Physica Sinica,2010,59(7):4571.(孙对兄,苏茂根,董晨钟,王向丽,张大成,马新文.基于激光诱导击穿光谱技术的铝合金成分定量分析[J].物理学报,2010,59(7):4571.)
[16]Yang C,Jia Y H,Chen J W,Li D L,Liu J,Zhang Y.Characterization of inclusion type in steel by laser-induced breakdown spectroscopy[J].Chinese Journal of Analytical Chemistry,2014,42(11):1623.(杨春,贾云海,陈吉文,李冬玲,刘佳,张勇.激光诱导击穿光谱法对钢中夹杂物类型的表征[J].分析化学,2014,42(11):1623.)
[17]GB/T 4698.2-2011.Methods for chemical analysis of titanium sponge,titanium and titanium alloys-Determination of iron content[S].2011.(GB/T 4698.2-2011.海绵钛、钛及钛合金化学分析方法铁量的测定[S].2011.)
[18]GB/T 4698.3-1996.Sponge titanium,titanium and titanium alloys-Determination of silicon content-Molybdenum blue spectrophotometric method[S].1996.(GB/T 4698.3-1996.海绵钛、钛及钛合金化学分析方法钼蓝分光光度法测定硅量[S].1996.)
[19]GB/T 4698.21-1996.Sponge titanium,titanium and titanium alloys-Determination of manganese,chromium,nickel,aluminum,molybdenum,tin,vanadium,yttrium,copper,zirconium content-Emission spectrographic method[S].1996.(GB/T 4698.21-1996.海绵钛、钛及钛合金化学分析方法发射光谱法测定锰、铬、镍、铝、钼、锡、钒、钇、铜、锆量[S].1996.)
[20]Wallis F J,Chadwick B L,Morrison R J S.Analysis of lignite using laser-induced breakdown spectroscopy[J].Applied Spectroscopy,2000,54(8):1231.