CN113295666B - Quantitative Analysis Method of As Element in Pyrite Using Mineral Raman Parameters - Google Patents
Quantitative Analysis Method of As Element in Pyrite Using Mineral Raman Parameters Download PDFInfo
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- 229910052683 pyrite Inorganic materials 0.000 title claims abstract description 62
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000011028 pyrite Substances 0.000 title claims abstract description 62
- 238000001069 Raman spectroscopy Methods 0.000 title claims abstract description 39
- 229910052500 inorganic mineral Inorganic materials 0.000 title claims abstract description 27
- 239000011707 mineral Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000004445 quantitative analysis Methods 0.000 title claims abstract description 19
- 239000000523 sample Substances 0.000 claims abstract description 52
- 238000010586 diagram Methods 0.000 claims abstract description 24
- 238000003384 imaging method Methods 0.000 claims abstract description 23
- 238000006073 displacement reaction Methods 0.000 claims abstract description 20
- 238000003332 Raman imaging Methods 0.000 claims abstract description 15
- 238000012360 testing method Methods 0.000 claims abstract description 12
- 238000001237 Raman spectrum Methods 0.000 claims abstract 3
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 230000003595 spectral effect Effects 0.000 claims description 4
- 238000001344 confocal Raman microscopy Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000002083 X-ray spectrum Methods 0.000 claims 1
- 230000003872 anastomosis Effects 0.000 abstract 1
- 229910052785 arsenic Inorganic materials 0.000 description 10
- 229910052737 gold Inorganic materials 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000001530 Raman microscopy Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000000918 plasma mass spectrometry Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence
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Abstract
Description
技术领域technical field
本发明涉及一种利用矿物拉曼参数对黄铁矿中As含量的定量分析方法。The invention relates to a quantitative analysis method for As content in pyrite by using mineral Raman parameters.
背景技术Background technique
黄铁矿是铁的常见硫化物，因其浅黄铜色和明亮的金属光泽，常被误认为是黄金。黄铁矿是金矿床中重要的载金矿物，通过对黄铁矿中As含量的测定可以提供大量金矿成因和找矿信息，所以对于快速测定黄铁矿中As的含量有着十分重要的实际应用价值。Pyrite, a common sulfide of iron, is often mistaken for gold because of its light brassy color and bright metallic luster. Pyrite is an important gold-bearing mineral in gold deposits. The determination of As content in pyrite can provide a large amount of gold ore genesis and prospecting information, so it is very important for the rapid determination of As content in pyrite. Value.
对于黄铁矿中的As元素含量测试，目前主要是根据电子探针或者激光剥蚀等离子质谱分析，具有准备工作繁琐，仪器操作复杂，损坏样品等缺点。因此需要一种可以快速定性，结果可靠的新型技术方式。For the determination of As element content in pyrite, at present, it is mainly based on electron probe or laser ablation plasma mass spectrometry analysis, which has the disadvantages of cumbersome preparation work, complicated instrument operation, and damage to samples. Therefore, there is a need for a new technical method that can be characterized quickly and with reliable results.
发明内容Contents of the invention
本发明的目的在于克服现有技术的不足，提供一种利用矿物拉曼参数对对黄铁矿中As含量的含量进行定量分析，其操作简单，且样品准备时间较少，测试速度快；拉曼光谱特征信号较强，信噪比高，特异性强，能够提高识别准确率的利用矿物拉曼参数对黄铁矿中As含量的定量分析方法。The purpose of the present invention is to overcome the deficiencies in the prior art, provide a kind of utilization mineral Raman parameter to carry out quantitative analysis to the content of As content in pyrite, its operation is simple, and sample preparation time is less, and testing speed is fast; The characteristic signal of Mann spectrum is strong, the signal-to-noise ratio is high, and the specificity is strong, which can improve the identification accuracy. It is a quantitative analysis method of As content in pyrite using mineral Raman parameters.
本发明的目的是通过以下技术方案来实现的：利用矿物拉曼参数对黄铁矿中As含量的定量分析方法，包括以下步骤：The object of the present invention is achieved by the following technical solutions: utilize mineral Raman parameter to the quantitative analysis method of As content in pyrite, comprises the following steps:
S1、进行黄铁矿拉曼光谱成像扫描：采用556nm波长的入射光源对待测黄铁矿样品进行面扫，获得待测黄铁矿样品的拉曼图像；S1. Carry out pyrite Raman spectral imaging scanning: use an incident light source with a wavelength of 556nm to scan the surface of the pyrite sample to be tested, and obtain a Raman image of the pyrite sample to be tested;
S2、对拉曼图像进行分峰拟合，拟合出图像上每个点的Ag拉曼位移值，做出该样品关于Ag拉曼位移值的精确成像分布图；S2. Perform peak fitting on the Raman image, fit the Ag Raman shift value of each point on the image, and make an accurate imaging distribution map of the sample about the Ag Raman shift value;
S3、对待测黄铁矿样品进行电子探针扫面测试，测出该样品同一区域的As含量的拉曼成像图；S3. Carry out electron probe scanning test on the pyrite sample to be tested, and measure the Raman imaging diagram of the As content in the same area of the sample;
S4、进行图像处理以及数据的转化：首先将关于Ag拉曼位移值的精确成像分布图和As含量拉曼成像图进行Photoshop的校对吻合，之后利用origin数据处理软件将两张图像转换为数据图；S4. Carry out image processing and data conversion: firstly, the precise imaging distribution map of Ag Raman shift value and the As content Raman imaging map are checked and matched by Photoshop, and then the two images are converted into data maps using origin data processing software ;
S5、通过电子探针和拉曼成像的数据图做出笛卡尔坐标系的散点图，来分析Ag拉曼位移与黄铁矿中的As含量的量化关系，并拟合出方程。S5. Make a scatter diagram of the Cartesian coordinate system through the data diagram of the electron probe and Raman imaging to analyze the quantitative relationship between the Ag Raman shift and the As content in the pyrite, and fit the equation.
进一步地，所述步骤S1中，采用法国HORIBA JOBIN YVON公司生产的LabRAM HREvolution激光共聚焦显微拉曼光谱仪对待测矿物样品进行扫描，光谱分辨率为0.65cm-1，光谱仪焦长800mm，采用556nm的Ar+激光，10倍Leica物镜，扫描范围为300～400-1cm。Further, in the step S1, the mineral sample to be tested is scanned with the LabRAM HREvolution laser confocal micro-Raman spectrometer produced by the French HORIBA JOBIN YVON company, the spectral resolution is 0.65cm -1 , the focal length of the spectrometer is 800mm, and the Ar + laser, 10 times Leica objective lens, scanning range is 300 ~ 400 -1 cm.
进一步地，所述待测黄铁矿样品需满足以下三个黄铁矿识别的特征波峰段：在343cm-1位移上的Fe-[S2]2-变形振动，简称Eg；在379cm-1位移上的Fe-[S2]2-伸缩振动，简称Ag；在430cm-1位移上的S—S伸缩振动，简称Tg；并且岩相学和显微镜观察未出现任何相变过程以及氧化。Further, the pyrite sample to be tested needs to meet the following three characteristic peak sections for pyrite identification: Fe-[S 2 ] 2- deformation vibration at a displacement of 343cm -1 , referred to as Eg ; Fe-[S 2 ] 2- stretching vibration at displacement, referred to as Ag; S—S stretching vibration at 430cm -1 displacement, referred to as Tg; petrographic and microscope observations did not show any phase transition process and oxidation.
进一步地，所述步骤S1中，矿物拉曼面扫区域x、y轴点数步长分别为7.4μm、6.8μm，其长宽分别为806.5μm、472.38μm。Further, in the step S1, the step lengths of points on the x and y axes of the mineral Raman surface scan area are 7.4 μm and 6.8 μm, respectively, and the length and width are 806.5 μm and 472.38 μm, respectively.
进一步地，所述步骤S2中，分峰拟合确定每个点的Ag位移值所采用的软件为法国HORIBA JOBIN YVON公司的labspec6中的夹峰法。Further, in the step S2, the software used to determine the Ag displacement value of each point by peak fitting is the peak clamping method in labspec6 of HORIBA JOBIN YVON company in France.
进一步地，所述步骤S3中，采用日本电子公司生产的JEOL-JXA-8230微区X射线光谱分析仪，采用10倍物镜，在20KV、20nA的条件下进行电子探针进行面扫，扫面区域x、y轴点数步长分别为2.5μm、2.5μm。Further, in the step S3, the JEOL-JXA-8230 micro-area X-ray spectrometer produced by Japan Electronics Co., Ltd. is used, and the electron probe is used for surface scanning under the conditions of 20KV and 20nA with a 10 times objective lens. The step size of the area x and y axis points is 2.5 μm and 2.5 μm, respectively.
进一步地，所述步骤S4中，两张成像图像的尺寸相同，两张成像图所转化出的数据点个数相同。两张成像图根据灰度图像以像素点黑白亮度大小转换为数据点，根据各自原图的图例转换为真实数据。Further, in the step S4, the size of the two imaging images is the same, and the number of data points converted from the two imaging images is the same. The two imaging images are converted into data points according to the grayscale image with the black and white brightness of pixels, and converted into real data according to the legends of the respective original images.
本发明的有益效果是：本发明利用矿物拉曼参数对对黄铁矿中As含量的含量进行定量分析，只需要找准样品所测区域即可，其操作简单；数据丰富，且样品准备时间较少，测试速度快；拉曼光谱特征信号较强，信噪比高，特异性强，能够提高识别准确率，减少误识别。The beneficial effects of the present invention are: the present invention uses mineral Raman parameters to quantitatively analyze the content of As in pyrite, only needs to find out the measured area of the sample, and its operation is simple; the data is abundant, and the sample preparation time Fewer, fast test speed; Raman spectral characteristic signal is strong, signal-to-noise ratio is high, and specificity is strong, which can improve the recognition accuracy and reduce false recognition.
附图说明Description of drawings
图1为利用矿物拉曼参数对黄铁矿中As含量的定量分析方法的流程图；Fig. 1 is the flowchart of the method for quantitative analysis of As content in pyrite by using mineral Raman parameters;
图2为为本实施例中利用拉曼位移定量分析黄铁矿中As含量效果图；Fig. 2 is the effect diagram of using Raman shift quantitative analysis of As content in pyrite in the present embodiment;
图3为As和Ag位移关于像素值取中位数进行划分，并进行拟合的曲线图。Fig. 3 is a curve diagram of dividing As and Ag displacements with respect to the median of pixel values and performing fitting.
具体实施方式Detailed ways
下面结合附图进一步说明本发明的技术方案。The technical solution of the present invention will be further described below in conjunction with the accompanying drawings.
如图1所示，本发明所述的利用矿物拉曼参数对黄铁矿中As含量的定量分析方法，包括以下步骤：As shown in Figure 1, the quantitative analysis method utilizing mineral Raman parameter of the present invention to As content in pyrite comprises the following steps:
S1、进行黄铁矿拉曼光谱成像扫描：采用556nm波长的入射光源对待测黄铁矿样品进行面扫，获得待测黄铁矿样品的拉曼图像；本步骤中，采用法国HORIBA JOBIN YVON公司生产的LabRAM HR Evolution激光共聚焦显微拉曼光谱仪对待测矿物样品进行扫描，光谱分辨率为0.65cm-1，光谱仪焦长800mm，采用556nm的Ar+激光，10倍Leica物镜，扫描范围为300～400-1cm。S1. Carry out pyrite Raman spectral imaging scanning: use the incident light source of 556nm wavelength to scan the surface of the pyrite sample to be tested, and obtain the Raman image of the pyrite sample to be tested; in this step, the French HORIBA JOBIN YVON company is used The produced LabRAM HR Evolution laser confocal micro-Raman spectrometer scans the mineral sample to be tested, the spectral resolution is 0.65cm -1 , the focal length of the spectrometer is 800mm, the Ar + laser is used at 556nm, the 10x Leica objective lens, and the scanning range is 300 ~400 -1 cm.
所述待测黄铁矿样品需满足以下三个黄铁矿识别的特征波峰段：在343cm-1位移上的Fe-[S2]2-变形振动，简称Eg；在379cm-1位移上的Fe-[S2]2-伸缩振动，简称Ag；在430cm-1位移上的S—S伸缩振动，简称Tg；并且岩相学和显微镜观察未出现任何相变过程以及氧化。The pyrite sample to be tested needs to meet the following three characteristic peak sections of pyrite identification: Fe-[S 2 ] 2- deformation vibration at a displacement of 343cm -1 , referred to as Eg; Fe-[S 2 ] 2- stretching vibration, referred to as Ag; S—S stretching vibration at 430cm -1 displacement, referred to as Tg; petrographic and microscope observations did not show any phase transition process and oxidation.
矿物拉曼面扫区域x、y轴点数步长分别为7.4μm、6.8μm，其长宽分别为806.5μm、472.38μm，，共计7800个点(含无用背景区域)。Mineral Raman surface scan area x, y-axis point step size is 7.4μm, 6.8μm, its length and width are 806.5μm, 472.38μm, a total of 7800 points (including useless background area).
S2、对拉曼图像进行分峰拟合，拟合出图像上每个点的Ag拉曼位移值，做出该样品关于Ag拉曼位移值的精确成像分布图；S2. Perform peak fitting on the Raman image, fit the Ag Raman shift value of each point on the image, and make an accurate imaging distribution map of the sample about the Ag Raman shift value;
本步骤中，分峰拟合确定每个点的Ag位移值所采用的软件为法国HORIBA JOBINYVON公司的labspec6中的夹峰法，同时得出的成像图应为为马赛克灰度图，且马赛克点为2μm*2μm。In this step, the software used to determine the Ag displacement value of each point by peak fitting is the peak clipping method in labspec6 of French HORIBA JOBINYVON company, and the image obtained at the same time should be a mosaic grayscale image, and the mosaic points It is 2μm*2μm.
S3、对待测黄铁矿样品进行电子探针扫面测试，测出该样品同一区域的As含量的拉曼成像图；S3. Carry out electron probe scanning test on the pyrite sample to be tested, and measure the Raman imaging diagram of the As content in the same area of the sample;
本步骤中，采用日本电子公司生产的JEOL-JXA-8230微区X射线光谱分析仪，采用10倍物镜，在20KV、20nA的条件下进行电子探针进行面扫，扫面区域x、y轴点数步长分别为2.5μm、2.5μm，扫面点数为201930个(含无用背景区域)。In this step, the JEOL-JXA-8230 micro-area X-ray spectrometer produced by Japan Electronics Co., Ltd. is used, and the 10x objective lens is used to scan the surface of the electronic probe under the conditions of 20KV and 20nA. The x and y axes of the scanning area The step size of points is 2.5 μm and 2.5 μm respectively, and the number of scanning points is 201930 (including useless background area).
本发明所述的As含量包括Co、Ni、Au、As等黄铁矿中常见As含量，且测试结果中样品需有且仅有一种As含量占主要影响如，Co，Ni或As，其他As含量应含量较低或无。The As content described in the present invention includes common As content in pyrite such as Co, Ni, Au, As, and in the test result, the sample needs to have and only one As content accounts for the main influence, such as, Co, Ni or As, other As The content should be low or none.
S4、进行图像处理以及数据的转化：首先将关于Ag拉曼位移值的精确成像分布图和As含量拉曼成像图进行Photoshop的校对吻合，之后利用origin数据处理软件将两张图像转换为数据图；S4. Carry out image processing and data conversion: firstly, the precise imaging distribution map of Ag Raman shift value and the As content Raman imaging map are checked and matched by Photoshop, and then the two images are converted into data maps using origin data processing software ;
本步骤中，首先将两张图像中的无用背景区域删除，然后将两张图像的尺寸调至相同，两张成像图所转化出的数据点个数也保持相同(可将两张图中位置无法对应的扫描点删除)。两张成像图根据灰度图像以像素点黑白亮度大小转换为数据点，根据各自原图的图例转换为真实数据。In this step, first delete the useless background area in the two images, then adjust the size of the two images to be the same, and the number of data points converted from the two imaging images also remains the same (the positions in the two images cannot be corresponding scan point deletion). The two imaging images are converted into data points according to the grayscale image with the black and white brightness of the pixels, and converted into real data according to the legends of the respective original images.
S5、通过电子探针和拉曼成像的数据图做出笛卡尔坐标系的散点图，来分析Ag拉曼位移与黄铁矿中的As含量的量化关系，并拟合出方程。S5. Make a scatter diagram of the Cartesian coordinate system through the data diagram of the electron probe and Raman imaging to analyze the quantitative relationship between the Ag Raman shift and the As content in the pyrite, and fit the equation.
下面通过实验进一步验证本发明的识别效果。The recognition effect of the present invention is further verified through experiments below.
对照组：采用电子探针对黄铁矿样品中As进行元素分析测试。对照组和实验组的样品来源均为同一个样品的同一区域。Control group: Elemental analysis of As in pyrite samples was carried out by electron probe. The sample sources of the control group and the experimental group are both from the same area of the same sample.
根据电子探针成像数据分析，该样品选择测试的As含量应、为Co，Ni，Au，As等黄铁矿中常见As含量，且测试结果中样品需有且仅有一种As含量占主要影响如，Co，Ni或As，其他As含量应、含量较低或无。According to the analysis of electron probe imaging data, the As content of the sample selected for testing should be the common As content in pyrite such as Co, Ni, Au, As, etc., and the sample must have and only one As content should be the main influence in the test results For example, Co, Ni or As, other As content should be low or none.
实验组：选用556nm的激光光源，物镜采用10倍数焦距镜头，找到目标视野后，对同一样品同一区域进行拉曼面扫。Experimental group: A 556nm laser light source is selected, and the objective lens adopts a 10 times focal length lens. After finding the target field of view, a Raman surface scan is performed on the same area of the same sample.
将已经测试过电子探针的黄铁矿样品薄片将其置于载物台的物镜视野下，同一区域进行测试。Place the thin piece of pyrite sample that has been tested by the electron probe under the field of view of the objective lens of the stage, and test in the same area.
测定该区域的拉曼成像图，拉曼位移扫描范围在300～400cm-1进行扫描。The Raman imaging map of this area is measured, and the Raman shift scanning range is 300-400 cm -1 for scanning.
测试完成之后，利用HORIBA JOBIN YVON公司的labspec6中的夹峰法处理数据，得出的马赛克灰度Ag位移成像图，夹峰范围在378cm-1～380cm-1。After the test was completed, the data was processed using the clamping peak method in labspec6 of HORIBA JOBIN YVON Company, and the mosaic gray scale Ag displacement imaging map was obtained, and the clamping peak ranged from 378cm -1 to 380cm -1 .
利用Photoshop，origin等软件进行图像处理以及数据的转化，首先将同区域两张成像图首先进行Photoshop的校对吻合，之后利用origin数据处理软件对两张成像图进行图像转数据的操作。Use Photoshop, origin and other software for image processing and data conversion. Firstly, the two imaging images in the same area are checked and matched by Photoshop, and then the two imaging images are converted to data using origin data processing software.
通过矿物样品的电子探针和拉曼成像图面扫数据做出笛卡尔坐标系的散点图来分析拉曼Ag峰位移对于指示黄铁矿中的As含量的定量分析。The scatter plot of the Cartesian coordinate system is made through the electron probe and Raman imaging scan data of the mineral samples to analyze the quantitative analysis of the Raman Ag peak shift indicating the As content in the pyrite.
上述检测在300～4000-1cm区域中黄铁矿Fe—S伸缩振动379cm-1(Ag)拉曼位移可以指示着黄铁矿中As含量的大小变化。黄铁矿中，As含量的变化，往往会引起矿物结构的变化，例如键长，键能的改变。The above detection in the region of 300 ~ 4000-1cm pyrite Fe—S stretching vibration 379cm-1 (Ag) Raman shift can indicate the size change of As content in pyrite. In pyrite, the change of As content often causes the change of mineral structure, such as the change of bond length and bond energy.
当As以类质同像形式进入黄铁矿晶格形成富砷黄铁矿及富砷环带。砷取代硫在晶格中的位置在晶格中和硫结合时为[S—As]3-，其键[S—S]2-所在的振动频率会向低频偏移，对于双原子分子，拉曼位移有(c为光速，k为键力常数，μ为折合质量)，当As和S逐渐结合形成[S—As]3-与之前[S—S]2-相比，电负性增大，共价键向离子键过渡，使得键力常数k值变小，另一方面，由于As相对原子质量远大于S，导致其折合质量μ增大,致使振动频率减小，从而振动频率向低频移动。When As enters the pyrite lattice in isomorphic form, arsenic-rich pyrite and arsenic-rich rings are formed. The position of arsenic replacing sulfur in the crystal lattice is [S—As] 3- when it is combined with sulfur in the lattice, and the vibration frequency of its bond [S—S] 2- will shift to low frequency. For diatomic molecules, Raman shift has (c is the speed of light, k is the bond force constant, μ is the reduced mass), when As and S are gradually combined to form [S—As] 3- , compared with the previous [S—S] 2- , the electronegativity increases, and the total The transition from valence bond to ionic bond makes the value of the bond force constant k smaller. On the other hand, because the relative atomic mass of As is much larger than that of S, its equivalent mass μ increases, resulting in a decrease in vibration frequency, and thus the vibration frequency moves to a lower frequency.
所以当Ag拉曼位移增大时，说明该点位或区域黄铁矿中的As含量变大。Therefore, when the Ag Raman shift increases, it means that the As content in the pyrite at this point or region becomes larger.
因此本发明可以通过分析拉曼位移和电子探针成像的大数据拟合，找出拉曼位移与As含量的量化关系，进而来指示着As含量的变化情况。Therefore, the present invention can find out the quantitative relationship between Raman shift and As content by analyzing the large data fitting of Raman shift and electron probe imaging, and then indicate the change of As content.
图2为As和Ag位移关于像素值得散点图，由于数据量巨大，因此需要将数据进行更一步的统筹，取中位数进行划分(图3)，进行一元多次方程的拟合，拟合出拉曼位移相对于As含量的定量方程负相关关系。由此可以看出黄铁矿的拉曼位移(x轴)和由电子探针探针所测黄铁矿中As含量(y轴)整体呈现出明显的反比关系，这暗示着拉曼位移对于As含量的指示效果和电子探针大致吻合。Figure 2 is a scatter diagram of As and Ag displacements with respect to pixel values. Due to the huge amount of data, it is necessary to carry out further overall planning of the data, take the median for division (Figure 3), and carry out the fitting of a multivariate equation. The negative correlation relationship of Raman shift relative to the quantitative equation of As content is obtained. It can be seen that the Raman shift (x-axis) of pyrite and the As content (y-axis) in the pyrite measured by the electron probe probe present an obvious inverse proportional relationship as a whole, which implies that the Raman shift has a great influence on The indicating effect of As content is roughly consistent with that of electron probe.
那么我们就可以通过拉曼Ag位移进行对As含量的估算，首先测试出黄铁矿某一点上的拉曼Ag位移值，将得出的Ag位移值转化为像素值带入图3的方程式，得出As关于含量的像素值大小。然后利用公式对像素值进行转换，最终估算出黄铁矿该位置的As含量大小。因此，表明本发明的利用矿物拉曼参数对黄铁矿中As含量的定量分析结果可靠。Then we can estimate the As content through the Raman Ag shift, first test the Raman Ag shift value at a certain point of the pyrite, convert the obtained Ag shift value into a pixel value and bring it into the equation in Figure 3, Get the pixel value of As with respect to content. Then use the formula to convert the pixel value, and finally estimate the As content of the pyrite at this position. Therefore, it shows that the quantitative analysis results of As content in pyrite by using mineral Raman parameters in the present invention are reliable.
本领域的普通技术人员将会意识到，这里所述的实施例是为了帮助读者理解本发明的原理，应被理解为本发明的保护范围并不局限于这样的特别陈述和实施例。本领域的普通技术人员可以根据本发明公开的这些技术启示做出各种不脱离本发明实质的其它各种具体变形和组合，这些变形和组合仍然在本发明的保护范围内。Those skilled in the art will appreciate that the embodiments described here are to help readers understand the principles of the present invention, and it should be understood that the protection scope of the present invention is not limited to such specific statements and embodiments. Those skilled in the art can make various other specific modifications and combinations based on the technical revelations disclosed in the present invention without departing from the essence of the present invention, and these modifications and combinations are still within the protection scope of the present invention.
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