Method for determining cerium content in nickel-based alloy based on ICP-AES method

文档序号:1377279 发布日期:2020-08-14 浏览:10次 中文

阅读说明:本技术 一种基于icp-aes法测定镍基合金中铈含量的方法 (Method for determining cerium content in nickel-based alloy based on ICP-AES method ) 是由 张亮亮 吴锐红 张方 于 2020-06-01 设计创作,主要内容包括:本发明公开了一种基于ICP-AES法测定镍基合金中铈含量的方法,具体为:设置测定设备的参数;预选铈元素的6条分析线,分别对物理干扰行为和光谱干扰行为进行分析,将分析线404.076nm、413.765nm和456.236nm作为测定镍基合金中铈的分析线;确定各共存元素的等效浓度;采用干扰系数法对在三条分析线处共存元素所产生干扰进行校正;最后在干扰系数法建立的校正模型下,实现镍基合金样品中铈的准确测定。本发明测定结果的正确度和精密度满足实验要求,运算简便、易于操作,能很好的满足日常生产检测需求。(The invention discloses a method for determining cerium content in a nickel-based alloy based on an ICP-AES method, which comprises the following steps: setting parameters of the measuring equipment; preselecting 6 analysis lines of cerium, analyzing physical interference behaviors and spectral interference behaviors respectively, and taking the analysis lines of 404.076nm, 413.765nm and 456.236nm as analysis lines for determining cerium in the nickel-based alloy; determining the equivalent concentration of each coexisting element; correcting the interference generated by the coexisting elements at the three analysis lines by adopting an interference coefficient method; and finally, under a correction model established by an interference coefficient method, the accurate determination of cerium in the nickel-based alloy sample is realized. The accuracy and precision of the measurement result of the invention meet the experimental requirements, the operation is simple and convenient, the operation is easy, and the daily production detection requirements can be well met.)

1. A method for measuring cerium content in a nickel-based alloy based on an ICP-AES method is characterized by comprising the following steps:

step 1, taking a plasma atomic emission spectrometer as a measuring device and setting parameters of the measuring device; the analytical line for the preselected cerium element is: 380.152nm, 401.239nm, 404.076nm, 413.765nm, 456.236nm and 535.353 nm;

step 2, analyzing physical interference behaviors of 6 preselected spectral lines; measuring the cerium standard series solution by using measuring equipment, establishing a working curve of the standard series solution at each analysis line, measuring various acids to obtain structural interference with larger spectral intensity at the center position of 380.152nm of a spectral line, and removing the spectral line;

step 3, analyzing the spectral interference behaviors of the 5 preselected spectral lines; absorbing the cerium standard series solution in a measuring device to establish a working curve of the standard series solution at each analysis line, and then sequentially measuring the single element standard solutions of Fe, Cr, Ni, Co, Al, Ti, Mo, W, V, Nb, Cu, Mn, Si, B, Zr, Sn, As and P by using the measuring device to determine the interference form and the interference degree of each coexisting element; and analyzing lines 404.076nm, 413.765nm and 456.236nm as analyzing lines for determining cerium in the nickel-based alloy;

step 4, absorbing the cerium standard series solution in a measuring device to establish a working curve of the standard series solution at each analysis line, sequentially measuring the single element standard solutions with the concentrations of Fe, Co, Ti, Mo, W, V, Nb, Mn and Zr of 100 mu g/mL, and determining the equivalent concentration of each coexisting element;

step 5, correcting the interference generated by the coexisting elements at the three analysis lines by adopting an interference coefficient method;

and 6, accurately measuring cerium in the nickel-based alloy sample under the correction model established by the interference coefficient method.

2. The ICP-AES method-based method for determining cerium content in nickel-based alloy according to claim 1, wherein in the step 1, the parameters of the determination equipment are set to comprise RF emission power 1125W, integration time: short wave 15s, long wave 5s, pump speed 50r/min, auxiliary gas flow 0.5L/min, cooling gas flow 13L/min, atomizer gas flow 0.95L/min, vertical observation height 13mm, sample lifting rate 1.5mL/min, and spectrum peak calculation mode: surface integral; the instrument carrier gas was liquid argon.

3. The ICP-AES method-based method for determining cerium content in nickel-based alloy according to claim 1, wherein in the step 2, the acid is hydrochloric acid with a volume concentration of 1%, hydrochloric acid with a volume concentration of 5%, nitric acid with a volume concentration of 1%, nitric acid with a volume concentration of 5%, citric acid with a mass concentration of 10g/mL, and tartaric acid with a mass concentration of 10 g/mL.

4. The ICP-AES method-based method for determining cerium content in nickel-based alloy according to claim 1, wherein in the step 3, the concentrations of the single element standard solutions of Fe, Cr, Ni, Co, Al, Ti, Mo, W, V, Nb, Cu, Mn, B, Zr, As and P are all 1000 μ g/mL, and the concentration of the single element standard solution of Si and Sn is 500 μ g/mL.

5. The ICP-AES method-based method for determining cerium content in nickel-based alloy according to claim 1, wherein in the step 5, the correction factor is the ratio of the equivalent concentration of the interference element for correcting the cerium spectrum line to the true concentration of the interference element in the single-element standard solution, and the specific implementation can be calculated according to the following formula:

in the formula (1), ICTo correct the equivalent concentration of cerium element, IATo determine the apparent concentration, CI iAs content of interfering elements (wt.%), k1 iFor the calibration factor, k is the slope of the curve of the cerium standard solution, and i is the interfering element.

6. The ICP-AES method-based method for determining cerium content in nickel-based alloy according to claim 1, wherein the step 6 is implemented by the following steps:

step 6.1, weighing 0.100g of nickel-based alloy to be detected in a beaker, adding 5-10 mL of high-grade pure hydrochloric acid and 1mL of high-grade pure nitric acid into the beaker, and heating the beaker in a low-temperature furnace until the nickel-based alloy to be detected is completely dissolved to obtain a nickel-based alloy dissolving solution;

step 6.2, adding 40mL of deionized water into the nickel-based alloy dissolving solution to dissolve salt, then continuously adding 10mL of citric acid or tartaric acid with the mass concentration of 0.10g/mL into the bottle, finally fixing the volume to 100mL, shaking up, and filtering with medium-speed qualitative filter paper to remove insoluble precipitates such as carbide, tungsten and tantalum in the solution; after the sample solution is prepared, the instrument is preheated for 30 minutes, then analysis is performed according to optimized instrument parameter conditions, acid blank is deducted during analysis, the cerium content in the nickel-based alloy is finally obtained, and the measurement of the cerium content in the nickel-based alloy is completed based on an ICP-AES method.

Technical Field

The invention belongs to the technical field of analysis and detection, and particularly relates to a method for determining cerium content in a nickel-based alloy based on an ICP-AES method.

Background

The addition of rare earth elements to the alloy can improve the oxidation resistance and hot workability of the alloy, and can effectively inhibit the brittle fracture caused by the segregation of harmful elements and brittle phases in steel through strong purification, modification and trace alloying. Cerium is the most abundant rare earth element, not only is a good deoxidizing and desulfurizing agent for steel, but also can change the form and distribution of inclusions in the steel, thereby optimizing the quality of the steel and improving the performance of the steel. At present, the analysis method for measuring cerium in steel and alloy mainly comprises plasma atomic emission spectrometry (ICP-AES), spectrophotometry, atomic absorption spectrometry, mass spectrometry and the like. ICP-AES is one of the main means of component analysis in alloy materials due to its advantages of high sensitivity, low detection limit, wide linear range, capability of simultaneously measuring a plurality of elements and the like.

The spectral lines 413.380nm and 418.660nm have high relative intensity and less interference and are often used as analysis lines for measuring cerium by ICP-AES (inductively coupled plasma-atomic emission spectrometry), but the two spectral lines cannot be found or analyzed in various instruments, so that the particularity of the two spectral lines, namely the reference property is poor, a plurality of available analysis lines are necessarily found from a cerium characteristic spectral line sequence, and meanwhile, in order to correct or eliminate the spectral interference of coexisting elements in a sample on cerium, common correction methods comprise a matrix matching method, an internal standard method, a Multivariate Spectral Fitting (MSF) and an interference coefficient method. Experiments show that the method for correcting the spectral interference by adopting the interference coefficient method is the simplest and most effective, and the correction is implemented by acquiring a correction factor between an interference element and a target element.

Disclosure of Invention

The invention aims to provide a method for determining cerium content in a nickel-based alloy based on an ICP-AES method, which can effectively eliminate spectral interference at a cerium spectral line and improve the accuracy of cerium determination.

The technical scheme adopted by the invention is that the method for determining the cerium content in the nickel-based alloy based on the ICP-AES method is implemented according to the following steps:

step 1, taking a plasma atomic emission spectrometer as a measuring device and setting parameters of the measuring device; the analytical line for the preselected cerium element is: 380.152nm, 401.239nm, 404.076nm, 413.765nm, 456.236nm and 535.353 nm;

step 2, analyzing physical interference behaviors of 6 preselected spectral lines; measuring the cerium standard series solution by using measuring equipment, establishing a working curve of the standard series solution at each analysis line, measuring various acids to obtain structural interference with larger spectral intensity at the center position of 380.152nm of a spectral line, and removing the spectral line;

step 3, analyzing the spectral interference behaviors of the 5 preselected spectral lines; absorbing the cerium standard series solution in a measuring device to establish a working curve of the standard series solution at each analysis line, and then sequentially measuring the single element standard solutions of Fe, Cr, Ni, Co, Al, Ti, Mo, W, V, Nb, Cu, Mn, Si, B, Zr, Sn, As and P by using the measuring device to determine the interference form and the interference degree of each coexisting element; and analyzing lines 404.076nm, 413.765nm and 456.236nm as analyzing lines for determining cerium in the nickel-based alloy;

step 4, absorbing the cerium standard series solution in a measuring device to establish a working curve of the standard series solution at each analysis line, sequentially measuring the single element standard solutions with the concentrations of Fe, Co, Ti, Mo, W, V, Nb, Mn and Zr of 100 mu g/mL, and determining the equivalent concentration of each coexisting element;

step 5, correcting the interference generated by the coexisting elements at the three analysis lines by adopting an interference coefficient method;

and 6, accurately measuring cerium in the nickel-based alloy sample under the correction model established by the interference coefficient method.

The present invention is also characterized in that,

in step 1, parameters of the measurement apparatus were set to include RF transmission power 1125W, integration time: short wave 15s, long wave 5s, pump speed 50r/min, auxiliary gas flow 0.5L/min, cooling gas flow 13L/min, atomizer gas flow 0.95L/min, vertical observation height 13mm, sample lifting rate 1.5mL/min, and spectrum peak calculation mode: surface integral; the instrument carrier gas was liquid argon.

In step 2, the acid is hydrochloric acid with a volume concentration of 1%, hydrochloric acid with a volume concentration of 5%, nitric acid with a volume concentration of 1%, nitric acid with a volume concentration of 5%, citric acid with a mass concentration of 10g/mL, and tartaric acid with a mass concentration of 10g/mL, respectively.

In the step 3, the concentrations of the single element standard solutions of Fe, Cr, Ni, Co, Al, Ti, Mo, W, V, Nb, Cu, Mn, B, Zr, As and P are all 1000 mug/mL, and the concentration of the single element standard solution of Si and Sn is 500 mug/mL.

In step 5, the correction factor is the ratio of the equivalent concentration of the interference element in the cerium spectrum line for correction to the true concentration of the interference element in the single element standard solution, and the specific implementation can be calculated according to the following formula:

in the formula (1), ICTo correct the equivalent concentration of cerium element, IATo determine the apparent concentration, CI iAs content of interfering elements (wt.%), k1 iFor the calibration factor, k is the slope of the curve of the cerium standard solution, and i is the interfering element.

Step 6 is implemented according to the following steps:

step 6.1, weighing 0.100g of nickel-based alloy to be detected in a beaker, adding 5-10 mL of high-grade pure hydrochloric acid and 1mL of high-grade pure nitric acid into the beaker, and heating the beaker in a low-temperature furnace until the nickel-based alloy to be detected is completely dissolved to obtain a nickel-based alloy dissolving solution;

step 6.2, adding 40mL of deionized water into the nickel-based alloy dissolving solution to dissolve salt, then continuously adding 10mL of citric acid or tartaric acid with the mass concentration of 0.10g/mL into the bottle, finally fixing the volume to 100mL, shaking up, and filtering with medium-speed qualitative filter paper to remove insoluble precipitates such as carbide, tungsten and tantalum in the solution; after the sample solution is prepared, the instrument is preheated for 30 minutes, then analysis is performed according to optimized instrument parameter conditions, acid blank is deducted during analysis, the cerium content in the nickel-based alloy is finally obtained, and the measurement of the cerium content in the nickel-based alloy is completed based on an ICP-AES method.

The invention has the beneficial effects that:

1. three characteristic analysis lines of the cerium screened by the experiment provide method reference for analyzing and determining the cerium content in the nickel-based alloy;

2. the method defines how to optimally select an analysis line when determining cerium in the nickel-based alloy with different chemical compositions;

3. the interference form and the interference degree of the coexisting elements under different cerium analysis lines and an interference correction model under three available analysis lines are given, and the mathematical operation method of the model has universal applicability in the interference correction.

Drawings

FIG. 1 is a graph of the working curve of cerium before and after correction for cobalt interference at 404.076nm of the analytical line in example 1;

FIG. 2 is a graph of the work of cerium before and after the correction of titanium and cobalt interferences at 456.236nm of the analytical line in example 2;

FIG. 3 is a graph of the operating curves of cerium before and after the calibration of the interference of tungsten and niobium at the analytical line 413.765nm in example 3.

Detailed Description

The following detailed description is to be read in connection with the detailed description and the drawings.

The invention relates to a method for measuring cerium content in a nickel-based alloy based on an ICP-AES method, which is implemented according to the following steps:

step 1, taking an iCAP 7400 Radial plasma atomic emission spectrometer as a measuring device and setting parameters of the measuring device, wherein the parameters of the measuring device comprise RF emission power 1125W and integration time: short wave 15s, long wave 5s, pump speed 50r/min, auxiliary gas flow 0.5L/min, cooling gas flow 13L/min, atomizer gas flow 0.95L/min, vertical observation height 13mm, sample lifting rate 1.5mL/min, and spectrum peak calculation mode: surface integral; the pre-selected analysis line is: 380.152nm, 401.239nm, 404.076nm, 413.765nm, 456.236nm and 535.353 nm; the instrument carrier gas was liquid argon.

And 2, analyzing and researching physical interference behaviors of 6 spectral lines 380.152nm, 401.239nm, 404.076nm, 413.765nm, 456.236nm and 535.353nm of the cerium element. Selecting the 6 spectral lines as cerium analysis lines, sucking the cerium standard series solution under the optimized instrument parameter condition to establish a working curve of the standard series solution at each analysis line, and then measuring hydrochloric acid with the volume concentration of 1%, hydrochloric acid with the volume concentration of 5%, nitric acid with the volume concentration of 1%, nitric acid with the volume concentration of 5%, citric acid with the mass concentration of 10g/mL and tartaric acid with the mass concentration of 10 g/mL.

Table 1 physical interference wt% of acid

The experimental results show that: at the analysis lines of 404.076nm, 413.765nm and 456.236nm, the different types of acids have no interference basically; however, at 380.152nm, 401.239nm and 535.353nm, interference of organic acids is different, especially at 380.152nm, which is serious because of structural interference with large spectral intensity at the center of the spectral line, so that the spectral line is excluded from 380.152 nm;

and 3, analyzing and researching the spectral interference behaviors of the remaining 5 spectral lines of cerium element at 401.239nm, 404.076nm, 413.765nm, 456.236nm and 535.353 nm. Selecting the 5 spectral lines As cerium analysis lines, sucking cerium standard series solutions under the optimized instrument parameter condition to establish a working curve of the standard series solutions at each analysis line, and sequentially measuring the single element standard solutions of Fe, Cr, Ni, Co, Al, Ti, Mo, W, V, Nb, Cu, Mn, Si, B, Zr, Sn, As and P by using an analysis instrument, wherein the concentrations of the single element standard solutions of Fe, Cr, Ni, Co, Al, Ti, Mo, W, V, Nb, Cu, Mn, B, Zr, As and P are all 1000 mug/mL, and the concentrations of the single element standard solutions of Si and Sn are 500 mug/mL. And checking the measured spectrograms of the coexisting elements, selecting proper background points and deducting the background, and then determining the interference forms and the interference degrees of the coexisting elements.

TABLE 2 interference of pure solutions of the single elements at the cerium analysis line

The experimental results show that: (1) if the contribution concentration of the single element pure solution is less than 0.001 percent, no interference exists; if the content is between 0.001 and 0.010 percent, interference exists; if the content is between 0.010 and 0.050 percent, the interference is serious; if the interference is more than 0.050%, the interference is extremely serious; (2) al, Cu, Si, B, Sn, As and P do not interfere with 6 spectral lines of cerium, and the interference situations of other elements on a cerium analysis line are different; (3) in 6 analysis lines of cerium, interference at 535.353nm of a spectral line is the most complex and the most serious, especially the interference by Co is the most serious, the contribution concentration is as high as 2.25%, and the spectral line is not available; lines 380.152nm and 401.239nm are most seriously interfered by Ti, the contribution concentration of the lines is higher than 10%, but the Ti is usually a main element in the nickel-based alloy, so the peak of the Ti can completely cover the peak of the Ce, and the lines cannot be used; the interference conditions at 404.076nm, 413.765nm and 456.236nm of the analysis line are relatively simple and are less interfered. The 3 spectral lines can be used as analytical lines for determining cerium in the nickel-based alloy in combination with the analytical results of Table 1.

And 4, accurately quantifying the interference degree of the coexisting elements generating interference at the analysis lines of 404.076nm, 413.765nm and 456.236 nm. Spectral lines 404.076nm, 413.765nm and 456.236nm are selected as cerium analysis lines, cerium standard series solutions are sucked under the optimized instrument parameter condition to establish working curves of the standard series solutions at each analysis line, and then the analytical instrument is adopted to sequentially measure the single element standard solutions with the concentrations of Fe, Co, Ti, Mo, W, V, Nb, Mn and Zr of 100 mu g/mL. And checking the measured spectrograms of the coexisting elements, selecting proper background points and deducting the background, and then determining the equivalent concentration of the coexisting elements.

TABLE 3 equivalent concentration in wt% of pure solution of single element at cerium analysis line

As can be seen from Table 3, the line 404.076nm is mainly disturbed by Co and is less disturbed by V and Mn; the spectral line 413.765nm is seriously interfered by W and Nb, and is slightly interfered by Co, Ti and V; the spectral line 456.236nm is seriously interfered by Ti, Zr and Nb are secondarily interfered, and the interference by Co and Mn is smaller.

And 5, correcting the interference generated by the coexisting elements at the analysis lines of 404.076nm, 413.765nm and 456.236nm by adopting an interference coefficient method. The interference coefficient method is to perform correction by acquiring a correction factor between an interference element and a target element. In the experiment, the correction factor is the ratio of the equivalent concentration of the interference element in the cerium spectrum line for correction to the true concentration of the interference element in the single element standard solution, and the specific implementation can be calculated according to the following formula:

in the formula (1), ICTo correct the equivalent concentration of cerium element, IATo determine the apparent concentration, CI iAs content of interfering elements (wt.%), k1 iFor the correction factor, k is the slope of the curve of the cerium standard solution (different values of k for different analysis lines), and i is an interference element.

When interference correction is performed by adopting an interference coefficient method, the correction factor k is1The results can be obtained from the calculations in Table 3 and are shown in Table 4. When performing interference analysis, k is always reserved1≥10-5While the nickel-based alloys generally have only Ni, Cr, Fe and Co contents higher than 10%, the other elements only retain k in order to perform effective interference correction and simplify the calculation1≥10-4

TABLE 4 interference factor k of pure solutions of single elements at cerium analysis line1Value of

And 6, accurately measuring cerium in the nickel-based alloy sample under the correction model established by the interference coefficient method. Weighing a certain amount of nickel-based alloy to be tested, dissolving the nickel-based alloy to be tested by using superior pure hydrochloric acid and superior pure nitric acid to prepare a solution to be tested of the nickel-based alloy to be tested, and analyzing by using an analyzer. Before interference correction is carried out, the chemical components of the nickel-based alloy to be tested are determined, if not, the main elements are determined, and the main elements mainly comprise the contents of Co, Ti, W, V, Nb, Mn and Zr; then, corresponding interference elements are judged according to the selected cerium analysis line and chemical components in the nickel-based alloy, and then a reasonable interference correction model is established based on the table 4 to correct the intensity of experimental data; and finally, directly reading the cerium content corresponding to the corrected intensity value by using the fitted curve.

Step 6 is implemented according to the following steps:

step 6.1, weighing 0.100g (accurate to 0.0001g) of nickel-based alloy to be detected in a beaker, adding 5-10 mL of high-grade pure hydrochloric acid and 1mL of high-grade pure nitric acid into the beaker, and heating the beaker in a low-temperature furnace until the nickel-based alloy to be detected is completely dissolved to obtain a nickel-based alloy solution;

step 6.2, adding 40mL of deionized water into the nickel-based alloy dissolving solution to dissolve salt, then continuously adding 10mL of citric acid or tartaric acid with the mass concentration of 0.10g/mL into the bottle, finally fixing the volume to 100mL, shaking up, and filtering with medium-speed qualitative filter paper to remove insoluble precipitates such as carbide, tungsten and tantalum in the solution; after the sample solution is prepared, the instrument is preheated for 30 minutes, then analysis is performed according to optimized instrument parameter conditions, acid blank is deducted during analysis, the cerium content in the nickel-based alloy is finally obtained, and the measurement of the cerium content in the nickel-based alloy is completed based on an ICP-AES method.

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