KR20040048095A - Standard sample preparation method for x-ray fluorescence analysis of heavy metal in plastic - Google Patents

Standard sample preparation method for x-ray fluorescence analysis of heavy metal in plastic Download PDF

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KR20040048095A
KR20040048095A KR1020020075864A KR20020075864A KR20040048095A KR 20040048095 A KR20040048095 A KR 20040048095A KR 1020020075864 A KR1020020075864 A KR 1020020075864A KR 20020075864 A KR20020075864 A KR 20020075864A KR 20040048095 A KR20040048095 A KR 20040048095A
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heavy metal
standard sample
sample
plastic
ray fluorescence
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KR100507752B1 (en
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권오준
박제명
김종선
최미애
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삼성아토피나주식회사
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/38—Diluting, dispersing or mixing samples
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
    • G01N2001/2866—Grinding or homogeneising
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2223/00—Investigating materials by wave or particle radiation
    • G01N2223/07—Investigating materials by wave or particle radiation secondary emission
    • G01N2223/076—X-ray fluorescence

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
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  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
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  • Analysing Materials By The Use Of Radiation (AREA)
  • Sampling And Sample Adjustment (AREA)

Abstract

PURPOSE: A method of manufacturing a standard sample used for an X-ray fluorescence analysis for analyzing a heavy metal in plastic is provided to make a standard calibration curve having high reproducibility. CONSTITUTION: A heavy metal is grinded such that the size of a particle of the grinded heavy metal is less than 5 micro meter. A standard sample is manufactured by uniformly diluting a master batch with respect to the same plastic. A calibration curve is formed by comparing intensity of a fluorescence X-ray emitted from a sample with intensity of a fluorescence X-ray emitted from a standard sample because the intensity of the fluorescence X-ray emitted from the sample is proportion to density of an element. Intensity of a component to be measured through an X-ray fluorescence analysis varies depending on a type of a plastic including the element.

Description

플라스틱내 중금속 분석을 위한 Ｘ-선 형광분석용 표준시료의 제조방법{STANDARD SAMPLE PREPARATION METHOD FOR X-RAY FLUORESCENCE ANALYSIS OF HEAVY METAL IN PLASTIC}STANDARD SAMPLE PREPARATION METHOD FOR X-RAY FLUORESCENCE ANALYSIS OF HEAVY METAL IN PLASTIC}

본 발명은 플라스틱내 중금속 분석을 위한 X-선 형광분석용 표준시료의 제조방법에 관한 것으로서, 좀더 상세하게는 입자크기가 5㎛ 이하로 되도록 분쇄된 일정량의 중금속 시료를 합성수지에 분산시켜 마스터배치를 제조한 후, 상기 마스터배치를 마스터배치 제조에 사용된 합성수지와 동일한 합성수지에 희석시키므로써 표준시료를 제조하는 것을 특징으로 하는, 플라스틱내 중금속 분석을 위한 X-선 형광분석용 표준시료의 제조방법에 관한 것이다.The present invention relates to a method for preparing a standard sample for X-ray fluorescence analysis for heavy metal analysis in plastic, and more specifically, a master batch by dispersing a predetermined amount of heavy metal samples pulverized to a particle size of 5 μm or less in a synthetic resin. After the preparation, by diluting the master batch in the same synthetic resin used to prepare the master batch, characterized in that to prepare a standard sample, in the manufacturing method of the standard sample for X-ray fluorescence analysis for heavy metal analysis in plastics. It is about.

현재 사용되고 있는 플라스틱은 유기안료를 채용하고 있으나, 유해 중금속계안료(Pb, Cd, Cr 등)의 사용여부를 확인하는 과정은 플라스틱의 안전성을 평가하는 중요한 요소중 하나이다.Currently used plastics adopt organic pigments, but the process of checking the use of harmful heavy metal pigments (Pb, Cd, Cr, etc.) is one of the important factors to evaluate the safety of plastics.

플라스틱내 중금속을 분석하는 방법으로는 습식방법과 기기를 이용하는 방법이 있는데, 기기를 이용하는 방법은 유도결합플라즈마, 원자흡광도법이 널리 사용되고 있다. 이들 방법을 이용한 분석은 높은 재연성과 수㎍/kg 수준의 정밀도를 가지고 있어 매우 일반화 되어 있으나, 시료분석 전에 분석하고자 하는 중금속성분의 추출을 위한 전처리과정이 필수적이고, X-선을 이용한 비파괴 분석법보다 방법이 복잡하다. 따라서 시료준비의 복잡함으로 많은 시료를 일시에 분석할 때에는 어려움이 있고, 또한 시료의 전처리과정 중에 유입될 수 있는 이물 등의 영향을 배제하기 위하여 시료 준비에 많은 주의와 숙련도가 요구된다.As a method of analyzing heavy metals in plastics, there are a wet method and a method using a device. Inductively coupled plasma and atomic absorption method are widely used. The analysis using these methods has high reproducibility and precision of several µg / kg, but it is very generalized, but pretreatment for the extraction of heavy metals to be analyzed before sample analysis is essential, and it is better than non-destructive analysis using X-ray. The method is complicated. Therefore, it is difficult to analyze many samples at once due to the complexity of sample preparation, and much attention and skill are required to prepare a sample in order to exclude the influence of foreign substances which may be introduced during the pretreatment of the sample.

X-선 형광법을 이용한 중금속 분석법은 중금속이 갖는 매트릭스(matrix) 효과로 유리알(Glass Bead)법을 이용하여 중금속을 희석시키는 방법을 이용하고 있으나, 이 방법은 무기계 매트릭스나 중금속 자체의 조성을 분석하는데 주로 사용되고 있으며, 플라스틱내 중금속 분석에는 적합하지 않다.Heavy metal analysis using X-ray fluorescence method uses a method of diluting heavy metal by glass beads method due to the matrix effect of heavy metal, but this method is mainly used to analyze the composition of inorganic matrix or heavy metal itself. It is used and is not suitable for the analysis of heavy metals in plastics.

플라스틱내 무기물 분석을 위한 X-선 형광분석에서의 희석방법은, 난연제와 같은 고분자 복합제 등 수십중량%대의 고농도 무기계 화합물을 분석하는데 사용되고 있으나, 수mg/kg 수준의 중금속을 함유한 시료에는 부적합하다.The dilution method in X-ray fluorescence analysis for analysis of inorganic substances in plastics is used to analyze high concentration inorganic compounds of several ten percent by weight, such as polymer composites such as flame retardants, but is not suitable for samples containing several mg / kg of heavy metals. .

X-선 형광분석을 위해서는 함량을 알고자 하는 중금속 시료의 검량선 작성이 필요하고, 일반적으로 플라스틱내 중금속, 특히 식품용기 등에는 없거나 아주 적은 양의 중금속이 함유되어 있으므로 낮은 농도 범위에서 재연성을 갖는 검량선을 작성하는 기술이 필요하며, 이러한 검량선의 작성은 표준시료 제조 기술과 관련되어 있다.For X-ray fluorescence analysis, it is necessary to prepare calibration curves of heavy metal samples to know the contents.In general, calibration curves having reproducibility in low concentration ranges are included because they contain little or no heavy metals in plastics, especially food containers. There is a need for a technique to prepare the calibration curve, and the preparation of these calibration curves is related to standard sample fabrication techniques.

본 발명의 목적은 시료의 전처리 방법이 간단하고, 높은 재연성을 갖는 표준 검량선을 작성할 수 있게 하는, X-선 형광분석용 표준시료의 제조방법을 제공하는 것이다.It is an object of the present invention to provide a method for preparing a standard sample for X-ray fluorescence, which makes it easy to prepare a standard calibration curve with a high reproducibility.

도 1은 일정량의 중금속 시료를 함유한 마스터배치의 제조와, 마스터 배치를 합성수지에 희석시켜 검량선을 작성하는 순서를 나타낸 것이다.FIG. 1 shows a procedure for preparing a masterbatch containing a certain amount of heavy metal sample and preparing a calibration curve by diluting the masterbatch in a synthetic resin.

도 2는 본 발명의 방법에 의해 제조된 표준시료를 이용하여 작성된 플라스틱내 Hg, Sb, Pb, As의 표준검량선을 나타낸 것이다.Figure 2 shows the standard calibration curve of Hg, Sb, Pb, As in the plastic prepared by using a standard sample prepared by the method of the present invention.

본 발명의 X-선 형광분석용 표준시료의 제조방법은 입자크기가 5㎛ 이하로 되도록 분쇄된 중금속을 중금속별로 100~3,000mg/kg 함량 수준으로 합성수지에 분산시켜 마스터배치를 제조한 후, 상기 마스터배치를 동일한 합성수지에 균일하게 희석시키므로써 표준시료를 제조하는 것을 특징으로 한다.In the method for preparing a standard sample for X-ray fluorescence analysis of the present invention, after dispersing the heavy metal pulverized so that the particle size is 5 μm or less in synthetic resin at a content level of 100 to 3,000 mg / kg for each heavy metal, the master batch is prepared. It is characterized by preparing a standard sample by uniformly diluting the masterbatch in the same synthetic resin.

본 발명에서 제조되는 마스터배치는 X-선 형광분석에 필요한 표준검량선을 작성하기 위하여, 중금속별 시료를 일정량 함유하도록 제조된다. 즉, 상기 마스터배치는 분석하고자 하는 중금속별로 100~3,000mg/kg 함량의 중금속 성분이 포함되도록 중금속 시료를 합성수지에 분산시켜 제조되며, 중금속의 원활한 분산을 위하여 혼합 전에 중금속 시료를 각각의 원소별로 입자크기가 5㎛ 이하로 되도록 분쇄하여 사용한다.In order to prepare a standard calibration curve for X-ray fluorescence analysis, the master batch prepared in the present invention is prepared to contain a certain amount of heavy metal samples. That is, the master batch is prepared by dispersing a heavy metal sample in a synthetic resin so that heavy metal components of 100 ~ 3,000 mg / kg content for each heavy metal to be analyzed, and before the mixing of the heavy metal sample particles for each element for smooth dispersion of heavy metal It is pulverized so that the size becomes 5 micrometers or less.

본 발명의 방법에 의하면, 표준시료는 상기와 같이 마스터배치를 제조한 후 마스터배치에 사용된 합성수지와 동일한, 중금속이 포함되지 않은 합성수지에 마스터배치를 희석하여 중금속별로 중금속 성분의 함량이 5~100mg/kg 수준으로 포함되도록 제조된다.According to the method of the present invention, the standard sample is prepared by the master batch as described above and the same as the synthetic resin used in the master batch, dilute the master batch in a synthetic resin that does not contain heavy metal content of heavy metal components 5 to 100mg for each heavy metal Prepared to include / kg levels.

본 발명의 방법으로 제조된 표준시료를 이용한 검량선의 작성은, 시료로부터 발생된 형광 X-선의 강도가 원소의 농도에 비례하므로 이 값을 본 발명에 따른 표준시료의 값과 비교하므로써 작성된다. 검량선 작성시 공존원소에 의한 흡수 등으로 인하여 발생하는 매트릭스 효과를 배제하기 위하여 흡수영역이 비슷한 금속은 함께 혼입하지 않고 표준시료를 제조한다.The calibration curve using the standard sample prepared by the method of the present invention is prepared by comparing this value with the standard sample according to the present invention because the intensity of the fluorescent X-ray generated from the sample is proportional to the concentration of the element. In order to exclude the matrix effect caused by absorption by coexisting elements when preparing the calibration curve, standard samples are prepared without mixing metals with similar absorption areas.

X-선 형광분석에서는 측정하고자 하는 성분의 강도는 그 원소가 함유된 플라스틱의 종류에 따라 달라진다. 즉, 분석하고자 하는 시료를 함유한 플라스틱의 특성에 따라 같은 원소라도 감도가 달라지는 현상을 발견할 수 있다. 이런 이유로 본 발명에 따른 표준시료를 이용한 중금속 분석을 위한 표준검량선의 작성은 플라스틱 소재별로 검량선을 작성한 경우보다 높은 재연성을 갖는다.In X-ray fluorescence, the strength of the component to be measured depends on the type of plastic it contains. In other words, it is possible to find a phenomenon in which the sensitivity is different even with the same element depending on the characteristics of the plastic containing the sample to be analyzed. For this reason, the preparation of a standard calibration curve for heavy metal analysis using a standard sample according to the present invention has a higher reproducibility than a calibration curve for each plastic material.

일반적으로 검량선은 측정된 농도로 예상한 계산식으로서, 이 검량선의 선형성이 높다는 의미는 계산된 검량선(1차함수를 주로 사용함) 내에 측정결과가 일치한다는 것이다. 즉, 검량선의 선형성이 높다는 것은 검량선에서 예상한 결과와 측정결과가 차이가 없거나 적다는 것으로 실제 적용시 재연성이 높다는 의미이다.In general, the calibration curve is a formula that is expected from the measured concentration, and the linearity of the calibration curve is high, which means that the measurement results coincide within the calculated calibration curve (primarily using a linear function). In other words, the high linearity of the calibration curve means that there is little or no difference between the results expected from the calibration curve and the measured results.

본 발명은 하기의 실시예에 의하여 보다 구체적으로 이해될 수 있으며, 하기의 실시예는 본 발명을 예시하기 위한 예에 지나지 않는 것으로 본 발명의 보호범위를 제한하고자 하는 것은 아니다.The present invention can be understood in more detail by the following examples, the following examples are only examples for illustrating the present invention and are not intended to limit the protection scope of the present invention.

실시예Example

입자크기가 5㎛ 이하로 되도록 분쇄한 Hg, Sb, As 및 Se과 스티렌-아크릴로니트릴 공중합체(SAN : Styrene-Acrylonitrile Copolymer)를 압출기를 이용하여 혼합하여, 각 중금속의 함량이 Hg 1,000mg/kg, Sb 2,000mg/kg, As 400mg/kg, Se 600mg/kg인 마스터배치를 제조하였다.Hg, Sb, As, Se and styrene-acrylonitrile copolymers (SAN: Styrene-Acrylonitrile Copolymer) pulverized to have a particle size of 5 μm or less were mixed using an extruder, and the content of each heavy metal was Hg 1,000 mg / Masterbatch with kg, Sb 2,000mg / kg, As400mg / kg, Se 600mg / kg was prepared.

마스터배치를 제조한 후 검량선을 측정할 수 있도록 상기 마스터배치를 SAN에 각각 2, 5, 10, 15, 20중량%의 농도로 희석하여 농도별 표준시료를 제조하였다.After the master batch was prepared, the master batch was diluted to a concentration of 2, 5, 10, 15, and 20 wt% in the SAN, respectively, so that a calibration curve could be measured, thereby preparing a standard sample for each concentration.

이러한 방법으로 제조된 표준시료를 이용하여 작성된 X-선 형광분석 표준 검량선을 도 2에 나타내었다. 도 2에서 볼 수 있듯이 표준 검량선은 Hg, As, Sb, Se의 중금속 분석에 높은 선형성을 주고 있음을 알 수 있다.2 shows an X-ray fluorescence standard calibration curve prepared using a standard sample prepared in this manner. As can be seen in Figure 2 can be seen that the standard calibration curve gives a high linearity for heavy metal analysis of Hg, As, Sb, Se.

이상에서 볼 수 있는 바와 같이, 본 발명에 의한 X-선 형광 분석용 표준시료의 제조방법은 시료의 전처리방법이 간단하고, 이 방법에 의해 제조된 표준시료를 이용할 경우 재연성이 높은 검량선을 작성할 수 있는 장점을 갖는다.As can be seen from the above, the method for preparing a standard sample for X-ray fluorescence analysis according to the present invention is simple and the method of pretreatment of the sample is easy, and when using the standard sample prepared by this method, a high reproducibility calibration curve can be prepared. That has the advantage.

Claims (1)

입자크기가 5㎛ 이하로 되도록 분쇄된 중금속 시료를 합성수지에 중금속별로 100~3,000mg/kg의 함량 수준이 되도록 분산시켜 마스터배치를 제조한 후, 상기 마스터배치를 동일한 합성수지에 중금속별로 5~100mg/kg의 함량 수준이 되도록 희석시키는 것을 특징으로 하는 중금속 분석을 위한 X-선 형광분석용 표준시료의 제조방법.Dispersing the heavy metal sample pulverized so that the particle size is 5㎛ or less in the synthetic resin to the content level of 100 ~ 3,000mg / kg for each heavy metal to prepare a masterbatch, the masterbatch in the same synthetic resin 5 ~ 100mg / Method for preparing a standard sample for X-ray fluorescence analysis for heavy metal analysis, characterized in that diluted to a content level of kg.
KR10-2002-0075864A 2002-12-02 2002-12-02 Standard sample preparation method for x-ray fluorescence analysis of heavy metal in plastic KR100507752B1 (en)

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Cited By (2)

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CN111474199A (en) * 2020-04-23 2020-07-31 陕西师范大学 Method for measuring molybdenum content in polytetrafluoroethylene plastic
CN114323856A (en) * 2021-12-29 2022-04-12 安徽三义堂生物科技有限公司 Intelligent detection equipment for residual heavy metals in traditional Chinese medicine decoction pieces

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111474199A (en) * 2020-04-23 2020-07-31 陕西师范大学 Method for measuring molybdenum content in polytetrafluoroethylene plastic
CN111474199B (en) * 2020-04-23 2023-05-26 陕西师范大学 Method for measuring molybdenum content in polytetrafluoroethylene plastic
CN114323856A (en) * 2021-12-29 2022-04-12 安徽三义堂生物科技有限公司 Intelligent detection equipment for residual heavy metals in traditional Chinese medicine decoction pieces
CN114323856B (en) * 2021-12-29 2022-09-16 安徽三义堂生物科技有限公司 Intelligent detection equipment for residual heavy metals in traditional Chinese medicine decoction pieces

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