【作者】 王斌；

【导师】 杨中民； 宋武元；

【作者基本信息】 华南理工大学 ， 电子与信息（专业学位）， 2023， 博士

【摘要】 元素分析方法在矿产品、聚合物等非金属材料中的应用是元素分析领域的一个重要研究方向。快速、准确、有效的对材料中目标元素进行定性定量分析,获得准确可靠的分析结果,对进出口产品质量的甄别和控制有着非常重要的意义。本论文在研究矿产品中元素分析方法时,是以铜精矿中稀土元素为研究对象,应用电感耦合等离子体质谱（ICP-MS）和有效的混酸消解体系,建立了铜精矿中稀土元素含量分析方法;聚合物标准样品/标准物质（RM）的研制是按照聚合物材料的生产工艺,以塑料、皮革、纺织品、油漆涂层等材料中的有毒有害元素为研究对象,应用ICP-MS、电感耦合等离子体发射光谱（ICP-OES）、能量色散X射线荧光光谱（EDXRF）进行目标元素分析,研制出了用于产品质量控制的聚合物RM。具体研究内容和取得的研究成果如下:（1）基于铜精矿成分特征和强酸的作用机理,对8个国家的近200份铜精矿样品的混酸消解体系进行了研究。研究发现:合理的混酸配比和添加顺序,对铜精矿的消解起到了促进作用。实验获得了3 m L氢氟酸（H）-1 m L高氯酸（P）-3 m L勒福特王水（L）的最佳混合强酸消解体系。使用ICP-MS,比较了开启和关闭高基体样品进样系统（HMIs）前后,铜精矿中目标元素稀土的信号响应和干扰情况。研究发现:开启HMIs,等离子体的耐受性和稳定性会大大提高,基体抑制效应会减少。实验获得了15种稀土元素的线性回归方程的相关系数都在0.9993以上,方法的回收率在98.3%～107.7%,精密度均优于3.1%,检出限均在0.00404μg·L^-1～0.03623μg·L^-1。（2）根据不同聚合物材料的合成原理和工艺流程,制备了含有目标元素铅（Pb）、铬（Cr）、镉（Cd）、汞（Hg）、溴（Br）的塑料RM、皮革RM、纺织品RM、油漆涂层RM。采用F检验法（F-test）、t检验法（T-test）等统计方法对其均匀性、稳定性进行了评估。研究发现:依照聚合物的生产和加工流程,将目标元素化合物与相匹配的添加剂共同添加,能够得到目标元素含量均匀稳定的聚合物RM。实验获得了满足ISO Guide 35和GB/T 15000.3要求的,具有良好均匀性、稳定性的一系列聚合物材料RM,在技术层面对文字标准进行有效的补充和支撑。基于RM的研究和检测技术,完成了1项国家实物标准的研制和2项行业标准的制定工作。（3）使用聚丙烯（PP）RM,通过对取样点个数、每个取样点测定次数、脉冲能量、延迟时间的研究,建立了激光诱导击穿光谱（LIBS）技术应用于塑料中目标元素（Pb、Cr）含量的定量分析方法。研究发现:LIBS的探测器可有效收集到PP被激光激发后产生的等离子体中目标元素的特征信号。实验获得了Pb和Cr的标准工作曲线的线性相关系数为0.9992和0.9989,Pb和Cr元素定量分析方法的检出限分别为35 mg·kg^-1和28 mg·kg^-1,此研究方法使得基于LIBS技术的目标元素定量分析成为可能。（4）使用EDXRF,进行了皮革RM中元素分析方法研究。研究发现:皮革RM的应用可以达到基体匹配作用,建立了快速、准确的皮革中元素定量分析方法,起草了行业标准SN/T 5231-2019。实验获得了对10家定值机构的定值结果数据良好的验证效果。使用ICP-MS,进行了功能性纺织品中15种目标元素稀土含量分析方法的研究。研究发现:所建立的分析方法可行,起草了行业标准SN/T 5288-2022。实验获得了方法的精密度均小于3.63%,重复性标准差S_r均小于0.00386,再现性标准差S_R均小于0.00463,准确度在±0.007 mg·kg^-1以内。（5）使用油漆涂层RM和自制的萃取装置,建立了涂层与软胶溶剂分离方法。研究发现:乙酸乙酯是软胶与其表面涂层萃取分离的最佳溶剂。基于目标元素铅的分析,实验获得了有效的分离效果。基于不同的添加剂和加入量,进行了甘油的高温耐黄变研究。研究发现:添加剂的最小用量为1.0%时,甘油在保持自身性能的同时具有了高温耐黄变能力,实验获得了高温耐黄变甘油的制备方法。更多还原

【Abstract】 The application of elemental analysis method in non-metallic materials such as mineral products and polymers is an important research direction of element analysis.It is of great significance to identify and control the quality of import and export products by using the accurate and reliable analysis of the target elements in the material quickly,accurately and effectively.In this paper,the elemental analysis method in the mineral products was studied,and the analysis method of rare earth elements in copper concentrate was established by using the Inducted Coupled Plasma Mass Spectrometry（ICP-MS）and effective mixed acid dissolving system.Based on the production process of polymer reference materials（RM）,the products of plastic,leather,textile,paint coating are studied by the application of ICP-MS,Inductance Coupled Plasma Optical Emission Spectrometer（ICP-OES）,Energy Dispersion X-Ray Fluorescence spectrometer（EDXRF）,which is used to analyze the target elements,and developed the polymer RM that is used for the quality control of the product.The results of the research are as follows:（1）Based on the characteristics of copper concentrate composition and the action mechanism of different acids,the mixed acid digestion system of nearly 200 copper concentrate samples from different mining areas in 8 countries was studied.It was found that the rational mixing ratio and adding order of acid had a positive effect on the digestion of copper concentrate.The optimum digestion system of 3 m L Hydrofluoric acid（H）-1 m L Perchloric acid（P）-3 m L Lefort aqua regia（L）was obtained.The signal response and interference of target elements such as rare earth elements in copper concentrate before and after opening the High Matrix sample Injection system（HMIs）were compared by ICP-MS.It was found that when HMIs was turned on,the tolerance stability of plasma was greatly improved and the matrix effect was reduced.Experiment obtained 15 rare earth elements,such as the correlation coefficient were above 0.9993,the recoveries were 98.3%～107.7%,the precision was less than 2.9%,and the detection limits were 0.00404μg·L^-1～0.03623μg·L^-1.（2）According to the synthesis principle and process flow of different polymer materials,plastic RM,leather RM,textile RM and paint coating RM containing target elements such as Lead（Pb）,Chromium（Cr）,Cadmium（Cd）,Mercury（Hg）and Bromine（Br）were developed.The homogeneity and stability were evaluated by F-test,T-test and other statistical methods.It was found that according to the production and processing process of polymer,the polymer RM with uniform and stable content of target element could be obtained by adding the target element compound and matching additives together.One case study was performed with ISO Guide 35 and GB/T 15000.3,a series of polymer RM with good homogeneity and stability,can effectively supplement and support the written standards at the technical level.Based on the research and testing technology of RM,we have completed the formulation of 1 national physical standard and 2 industry standards.（3）Using polypropylene（PP）RM,through the study of the number of sampling points,measurement times of each sampling point,pulse energy and delay time,a quantitative analysis method of Laser Induced Breakdown Spectroscopy（LIBS）technology applied to the content of target elements（Pb,Cr）in plastic was established.It is found that the detector of LIBS can effectively collect the characteristic signals of the target elements in the plasma generated by PP after laser excitation.The linear correlation coefficients of Pb and Cr were0.9992 and 0.9989,and the detection limits of Pb and Cr quantitative analysis methods were35 mg·kg^-1and 28 mg·kg^-1,respectively.This research method made the quantitative analysis of target elements based on LIBS technology possible.（4）Using EDXRF,the method of element analysis in leather RM was studied.It is found that the application of leather RM could achieve the function of matrix matching,and a rapid,accurate quantitative analysis method was established,and an industry standard SN/T5231-2019 was drafted.The experiments have obtained a good verification effect on the data of 10 setting mechanisms.The analysis method of 15 rare earth elements in functional textiles was studied by ICP-MS.It is found that the established analytical method was feasible,and the industry standard SN/T 5288-2022 was drafted.The experimental results show that the precision of the method is less than 3.63%,the repeatability S_ris less than 0.00386,the reproducibility S_Ris less than 0.00463,and the accuracy is within±0.007 mg·kg^-1.（5）Using paint coating RM and self-made extraction device,the separation method of coating and soft glue solvent was established.It was found that dichloromethane,ethyl acetate is the best solvent for the separation of soft rubber and its surface coating.Based on the Analysis of target element lead,an effective separation effect was obtained in the experiment.The high temperature yellowing resistance of glycerol was studied based on different additives and amounts.It was found that when the minimum dosage of additive is 1.0%,glycerol had the ability of high temperature yellowing resistance while maintaining its own performance.The preparation method of high temperature yellowing resistant glycerol was obtained.更多还原