本文關(guān)鍵詞：激光探針高精度分析方法及其應(yīng)用研究　出處：《華中科技大學(xué)》2016年博士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 激光誘導(dǎo)擊穿光譜 空間約束 磁約束 偏最小二乘回歸 激光探針成分分析儀

【摘要】：激光探針技術(shù),即激光誘導(dǎo)擊穿光譜技術(shù),具有制樣簡單、微損、快速、多元素同時(shí)分析和遠(yuǎn)程檢測等優(yōu)點(diǎn),特別適合實(shí)時(shí)、在線、原位檢測,因而成為眾多領(lǐng)域生產(chǎn)和質(zhì)量檢測極具潛力的分析技術(shù)。然而,由于受光譜干擾、基體效應(yīng)、自吸收效應(yīng)和儀器漂移等因素的影響,激光探針在分析靈敏度、精確度和準(zhǔn)確度上亟待進(jìn)一步提高�；诖�,本文以鋼鐵和鐵礦石為研究對(duì)象,研究了幾種提高激光探針定量分析靈敏度、精確度和準(zhǔn)確度的新方法,并基于自主研發(fā)的激光探針成分分析儀為平臺(tái)解決了儀器分析中建立穩(wěn)健定標(biāo)模型和儀器漂移校準(zhǔn)的兩個(gè)關(guān)鍵問題。具體研究內(nèi)容如下：提出采用可移動(dòng)式空間約束技術(shù)用于激光等離子體光譜增強(qiáng),克服了固定式空間約束技術(shù)的深坑效應(yīng),實(shí)現(xiàn)了對(duì)鋼鐵成分定量分析精密度和準(zhǔn)確度的提高。結(jié)果表明,空間約束光譜增強(qiáng)效果主要受激光波長、激光能量和腔體尺寸的影響,即波長越短增強(qiáng)效果越好,通過優(yōu)化激光能量和腔體尺寸獲得了最大增強(qiáng)因子為5.22。進(jìn)一步研究結(jié)果表明,可移動(dòng)式空間約束技術(shù)可使分析精密度最大提高一倍,使得定量分析準(zhǔn)確度提升1-5%。其原因在于空間約束通過反射沖擊波壓縮等離子體,造成等離子體溫度和電子數(shù)密度的增加,使得等離子體更容易達(dá)到局部熱力學(xué)平衡狀態(tài),從而可改善光譜精密度和定量分析準(zhǔn)確度。首次采用環(huán)形磁鐵約束激光誘導(dǎo)等離子體,實(shí)現(xiàn)了對(duì)等離子體空間約束與磁約束的雙重作用,并將其用于鋼鐵的定量分析。采用最大磁場強(qiáng)度為4090 G的環(huán)形磁鐵,獲得譜線強(qiáng)度的最大增強(qiáng)因子為3.1,信噪比的最大增強(qiáng)因子為2.9,使鋼鐵中V. Mn、Cr、Ti等痕量元素定標(biāo)曲線的決定系數(shù)較無約束時(shí)均提升至0.99以上,檢測極靈敏度提高了2～-4倍。提出一種改進(jìn)的偏最小二乘回歸(PLSR)算法建立了鐵礦石激光探針檢測的多元回歸模型,實(shí)現(xiàn)了對(duì)鐵礦石粉末中8種氧化物、品味和酸堿度的精確定量分析。研究了一種適合于激光探針檢測的粉末壓片制樣的方法,解決了直接壓片難退模、易破碎和開裂的問題。為解決鐵礦石定量分析的基體效應(yīng)、自吸收效應(yīng)和主量元素分析難的問題,只采用10～20 nm一段包含多條元素特征譜線的光譜數(shù)據(jù)建立PLSR多元回歸模型,實(shí)現(xiàn)了鐵礦石粉末中CaO、MgO、Al2O3、SiO2、MnO、TiO2、Na2O、K2O等8種氧化物的精確定量分析,平均相對(duì)誤差在2.9-15.46%之間：鐵礦石品位的預(yù)測均方根誤差(RMSE)和平均相對(duì)誤差(ARE)分別達(dá)到0.5134 wt.%和0.69%(低于1%的行業(yè)允許誤差)：在此基礎(chǔ)上計(jì)算的鐵礦石酸堿度RMSE和ARE分別達(dá)到0.0048和3.65%。采用自主研發(fā)的JGTZ-2型激光探針成分分析儀對(duì)儀器的高精度檢測方法進(jìn)行了研究,主要解決了激光探針儀器分析中建立穩(wěn)健定標(biāo)模型和儀器漂移校準(zhǔn)兩個(gè)關(guān)鍵問題�；诜治鲎V線和內(nèi)標(biāo)線選擇、異常值剔除、分段定標(biāo)、高階多項(xiàng)式擬合等方法建立了JGTZ-2對(duì)低合金鋼9種成分的定標(biāo)曲線,提出采用高低標(biāo)校準(zhǔn)對(duì)儀器漂移進(jìn)行修正的方法,可有效改善JGTZ-2檢測的可重復(fù)性。結(jié)果表明,JGTZ-2對(duì)低合金鋼中Mn、Cr、Ni、Cu、Si、Mo、Ti、V、Al等元素的分析誤差均達(dá)到或優(yōu)于國家標(biāo)準(zhǔn),多次測量值的相對(duì)標(biāo)準(zhǔn)差RSD均小于2%,Mn、Cr、Ni、Cu、Si、Mo和Ti等元素的相對(duì)誤差均小于8%,其檢測準(zhǔn)確度達(dá)到與ARL-4460型火花直讀光譜儀相當(dāng)?shù)乃健?br/>[Abstract]:Laser probe technique, the laser induced breakdown spectroscopy, with sample preparation is simple, rapid, and micro damage analysis and remote detection etc. multiple elements, especially suitable for real-time, on-line, in situ detection, and thus become the analysis technology in many areas of production and quality testing potential. However, due to spectral interference and matrix effect effect of self absorption factors effect and instrument drift, laser probe in the analysis of sensitivity, precision and accuracy should be further improved. Based on this, this paper takes the steel and iron ore as the research object, studied several kinds of improved laser probe quantitative sensitivity analysis, a new method of precision and accuracy, and the laser microprobe analyzer independently based on the development of the platform to solve two key problems to establish robust calibration model and calibration of the instrument drift in instrumental analysis. The specific research contents are as follows: put forward by Mobile space constraint technology for laser plasma spectral enhancement, overcomes the effect of pit fixed space constraint technology, to realize the quantitative analysis of the components of steel to improve the precision and accuracy. The results show that the spectral space constraint enhancement effect mainly by laser wavelength, laser energy and the effect of cavity size, namely, the shorter the wavelength enhancement effect the better, by optimizing the laser energy and the cavity size obtained the maximum enhancement factor of 5.22. further research results show that the mobile space constraint technology can make analysis of the maximum density doubled, making the quantitative analysis accuracy improvement 1-5%. the reason is that the space constraints through the reflection of shock wave compression caused by the increase of plasma, plasma temperature and electron number density that makes the plasma to reach local thermodynamic equilibrium, which can improve the precision and quantitative spectra Accuracy analysis for the first time. The ring magnet constraints of laser induced plasma, the dual role of constraints on the plasma space and magnetic confinement, and used for quantitative analysis of iron and steel. The ring magnet maximum magnetic field strength of 4090 G, obtained the maximum spectral line intensity enhancement factor is 3.1, the signal-to-noise ratio of the maximum enhancement factor 2.9, the V. Mn Cr in iron and steel, and the coefficient of determination Ti trace elements calibration curve with no constraints were increased to more than 0.99, detection sensitivity is increased by 2 ~ -4 times. Proposed a modified partial least squares (PLSR) algorithm to establish the multiple regression model of iron ore laser probe detection and the 8 kinds of iron ore powder oxide, accurate quantitative analysis of taste and pH were studied. A suitable laser probe detection method of powder preparation, solve the difficult direct compression casting, easy Crushing and cracking problems. In order to solve the matrix effect of quantitative analysis of iron ore, the self absorption effect and the main elements of the difficult problem of using only 10 ~ 20 nm a PLSR multiple regression model includes the establishment of a plurality of spectral line spectral data, the iron ore powder in CaO, MgO, Al2O3. SiO2, MnO, TiO2, Na2O, accurate quantitative analysis K2O 8 oxides, the average relative error between 2.9-15.46% in the prediction of iron ore grade of the root mean square error (RMSE) and the average relative error (ARE) reached 0.5134 wt.% and 0.69% respectively (less than 1% of the industry: the calculation of allowable error) on the basis of iron ore pH RMSE and ARE were studied to achieve high precision detection method of JGTZ-2 type laser microprobe analyzer and 0.0048 3.65%. using self-developed instrument, mainly to solve the analysis of laser probe instrument to build robust calibration model And the instrument drift calibration two key problems. The analysis of spectral line and line selection based on abnormal value elimination, subsection calibration, high order polynomial fitting method is established for JGTZ-2 low alloy steel 9 components of the calibration curve, the height calibration correction method for the instrument drift, can effectively improve the JGTZ-2 detection repeatability. The results showed that JGTZ-2 of low alloy steel Mn, Cr, Ni, Cu, Si, Mo, Ti, V, Al and other elements of the error analysis are reached or exceeded national standard, the relative standard deviation of RSD values of repeated measurements were less than 2%, Mn, Cr, Ni, Cu. Si, relative error of Mo and Ti elements were less than 8%, the detection accuracy of ARL-4460 type spark spectrometer equivalent level.

【學(xué)位授予單位】：華中科技大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2016
【分類號(hào)】：TN249

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