激光诱导击穿光谱液态金属成分在线分析仪在线监测熔融铝液中元素成分
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摘要
目前在冶金及压铸行业,产品成分检测属于实验室离线分析,不能实时指导生产过程,而基于激光诱导击穿光谱(LIBS)技术自主研制的液态金属成分在线分析仪,可在线监测冶金工业现场中熔融金属的组分含量,实时指导生产过程,对提高产品质量和降低能源消耗起到重要作用。首先在研究实验室,利用固体LF6铝合金标准样品系列对LIBS液态金属成分在线分析仪进行了测试,验证了仪器的各项性能指标;随后在压铸车间现场,利用在光谱实验室通过火花放电原子发射光谱仪(Spark-OES)定值得到的现场样品的Si、Fe、Cu、Mn、Ti、Mg元素含量值对LIBS液态金属成分在线分析仪进行了标定;最后现场随机选取10个载有熔融铝液的铝包,采用LIBS进行在线分析,同时取样在光谱实验室进行离线对比分析。分析结果表明:10个熔融铝液样品中,Si、Fe、Cu、Mn、Ti在线分析结果的相对标准偏差(RSD)以2%左右居多,Mg的RSD值波动较大,且以10%左右为主;Si的相对偏差绝对值基本都小于2%,Fe、Cu、Mn、Ti的相对偏差绝对值也基本以小于5%为主,但Mg的相对偏差绝对值以大于20%居多。可见,除Mg元素外,LIBS液态金属成分在线分析仪的测量精密度、准确度都能满足工业现场要求,完全可以实现在线监测熔融铝液的成分,在提高生产效率的同时,降低了能源消耗。但Mg元素的精密度和准确度相对较差,有待进一步研究改进。
At present,the composition detection of products in metallurgy and die casting industry usually adopts off-line laboratory analysis,which cannot real-timely guide the production process.The self-developed liquid metal composition on-line analyzer based on laser-induced breakdown spectroscopy(LIBS)can be used for the on-line monitoring of elemental composition in molten metal in the fields of metallurgical industry.The real-time guidance of production process plays an important role to improve the product quality and reduce energy consumption.Firstly,the solid aluminum alloy standard sample of LF6 series were used to test LIBS on-line analyzer for liquid metal composition in laboratory.All performance indexes of instrument were verified.Then,the samples in die casting plants(the contents of Si,Fe,Cu,Mn,Ti and Mg had been calibrated by spark discharge atomic emission spectrometer in spectrographic laboratory)were used to calibrate the LIBS on-line analyzer for liquid metal composition.Finally,ten aluminum ladles containing molten aluminum were randomly selected in the field for on-line analysis by LIBS.Meanwhile,the samples were also off-line analyzed in spectrographic laboratory for comparison.The results showed that the relative standard deviations(RSD)of on-line analysis results were mostly about 2%for Si,Fe,Cu,Mn and Ti.The fluctuation of RSD values for Mg was relatively large,i.e.,about 10%.The absolute values of relative deviations were basically less than 2%for Si,less than 5%for Fe,Cu,Mn and Ti,and more than 20%for Mg.Therefore,except for Mg,the measurement precision and accuracy of LIBS online analyzer for liquid metal composition could meet the field requirements in industry.The chemical composition of molten aluminum could be on-line monitored,which improved the production efficiency and also reduced the energy consumption.However,the determination precision and accuracy were relatively low for Mg,which should be further studied and improved.
At present,the composition detection of products in metallurgy and die casting industry usually adopts off-line laboratory analysis,which cannot real-timely guide the production process.The self-developed liquid metal composition on-line analyzer based on laser-induced breakdown spectroscopy(LIBS)can be used for the on-line monitoring of elemental composition in molten metal in the fields of metallurgical industry.The real-time guidance of production process plays an important role to improve the product quality and reduce energy consumption.Firstly,the solid aluminum alloy standard sample of LF6 series were used to test LIBS on-line analyzer for liquid metal composition in laboratory.All performance indexes of instrument were verified.Then,the samples in die casting plants(the contents of Si,Fe,Cu,Mn,Ti and Mg had been calibrated by spark discharge atomic emission spectrometer in spectrographic laboratory)were used to calibrate the LIBS on-line analyzer for liquid metal composition.Finally,ten aluminum ladles containing molten aluminum were randomly selected in the field for on-line analysis by LIBS.Meanwhile,the samples were also off-line analyzed in spectrographic laboratory for comparison.The results showed that the relative standard deviations(RSD)of on-line analysis results were mostly about 2%for Si,Fe,Cu,Mn and Ti.The fluctuation of RSD values for Mg was relatively large,i.e.,about 10%.The absolute values of relative deviations were basically less than 2%for Si,less than 5%for Fe,Cu,Mn and Ti,and more than 20%for Mg.Therefore,except for Mg,the measurement precision and accuracy of LIBS online analyzer for liquid metal composition could meet the field requirements in industry.The chemical composition of molten aluminum could be on-line monitored,which improved the production efficiency and also reduced the energy consumption.However,the determination precision and accuracy were relatively low for Mg,which should be further studied and improved.
引文
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[14]SUN L X,YU H B,CONG Z B,et al.Applications of laser-induced breakdown spectroscopy in the aluminum electrolysis industry[J].Spectrochimica Acta Part B,2018,142:29-36.
[15]孙兰香,于海斌,丛智博,等.利用LIBS技术在线半定量分析液态钢成分[J].仪器仪表学报,2011,32(11):2602-2608.SUN Lan-xiang,YU Hai-bin,CONG Zhi-bo,et al.Online semi-quantitative analysis of molten steel composition using laser-induced breakdown spectroscopy[J].Chinese Journal of Scientific Instrument,2011,32(11):2602-2608.
[16]孙兰香,于海斌,辛勇,等.基于激光诱导击穿光谱的钢液成分在线监视[J].中国激光,2011,38(9):0915002.SUN Lan-xiang,YU Hai-bin,XIN Yong,et al.On-line monitoring of molten steel compositions by laser-induced breakdown spectroscopy[J].Chinese Journal of Lasers,2011,38(9):0915002.
[2]沈桂花,李华昌,史烨弘.激光诱导击穿光谱发展现状[J].冶金分析,2016,36(5):16-25.SHEN Gui-hua,LI Hua-chang,SHI Ye-hong.Progress in laser induced breakdown spectroscopy[J].Metallurgical Analysis,2016,36(5):16-25.
[3]赵书瑞,王华丽,卢孟柯.内标元素强度筛选法在激光诱导击穿光谱定量分析土壤标样中铁钛锶的应用[J].冶金分析,2018,38(7):33-37.ZHAO Shu-rui,WANG Hua-li,LU Meng-ke.Application of internal standard element intensity-screening in quantitative analysis of iron,titanium and strontium in soil standard sample by laser induced breakdown spectroscopy[J].Metallurgical Analysis,2018,38(7):33-37.
[4]陈林,邓国亮,冯国英,等.基于LIBS及时间分辨特征峰的激光除漆机理研究[J].光谱学与光谱分析,2018,38(2):367-371.CHEN Lin,DENG Guo-liang,FENG Guo-ying,et al.Study on the mechanism of laser paint removal based on LIBS and time resolved characteristic signal[J].Spectroscopy and Spectral Analysis,2018,38(2):367-371.
[5]董美蓉,龙嘉健,陈思如,等.激光诱导分子光谱应用于碳元素形态分析[J].光子学报,2018,47(8):0847001.DONG Mei-rong,LONG Jia-jian,CHEN Si-ru,et al.Laser-induced molecular spectroscopy for carbon with different element speciation[J].Acta Photonica Sinica,2018,47(8):0847001.
[6]DONG F Z,CHEN X L,WANG Q,et al.Recent progress on the application of LIBS for metallurgical online analysis in China[J].Front.Phys.,2012,7(6):679-689.
[7]HUDSON S W,CRAPARO J,SARO R D,et al.Applications of laser-induced breakdown spectroscopy(LIBS)in molten metal processing[J].Metallurgical and Materials Transactions B-Process Metallurgy and Materials Processing Science,2017,48(5):2731-2742.
[8]Gruber J,Heitz J,Strasser H,et al.Rapid in-situ analysis of liquid steel by laser-induced breakdown spectroscopy[J].Spectrochimica Acta Part B:Atomic Spectroscopy,2001,56(6):685-693.
[9]RAI A K,YUEH F Y,SINGH J P.Laser-induced breakdown spectroscopy of molten aluminum alloy[J].Appl.Opt.,2003,42(12):2078-2084.
[10]RAI A K,YUEH F Y,SINGH J P,et al.High temperature fiber optic laser-induced breakdown spectroscopy sensor for analysis of molten alloy constituents[J].Rev.Sci.Instrum.,2002,73(10):3589-3599.
[11]BARIL E,STONGE L,SABSABI M,et al.Novel method for on-line chemical analysis of continuous galvanizing baths,association for iron and steel technology[R].AISTECH,Chicago,IL,United States,2004:1095-1104.
[12]SABSABI M,CIELO P.Quantitative analysis of aluminum alloys by laser-induced breakdown spectroscopy and plasma characterization[J].Appl.Spectrosc.,1995,49(4):499-507.
[13]SUN L X,YU H B,CONG Z B,et al.In situ analysis of steel melt by double-pulse laser-induced breakdown spectroscopy with a Cassegrain telescope[J].Spectrochimica Acta Part B,2015,112:40-48.
[14]SUN L X,YU H B,CONG Z B,et al.Applications of laser-induced breakdown spectroscopy in the aluminum electrolysis industry[J].Spectrochimica Acta Part B,2018,142:29-36.
[15]孙兰香,于海斌,丛智博,等.利用LIBS技术在线半定量分析液态钢成分[J].仪器仪表学报,2011,32(11):2602-2608.SUN Lan-xiang,YU Hai-bin,CONG Zhi-bo,et al.Online semi-quantitative analysis of molten steel composition using laser-induced breakdown spectroscopy[J].Chinese Journal of Scientific Instrument,2011,32(11):2602-2608.
[16]孙兰香,于海斌,辛勇,等.基于激光诱导击穿光谱的钢液成分在线监视[J].中国激光,2011,38(9):0915002.SUN Lan-xiang,YU Hai-bin,XIN Yong,et al.On-line monitoring of molten steel compositions by laser-induced breakdown spectroscopy[J].Chinese Journal of Lasers,2011,38(9):0915002.