ASTM F2617-15(2023)
(Test Method)Standard Test Method for Identification and Quantification of Chromium, Bromine, Cadmium, Mercury, and Lead in Polymeric Material Using Energy Dispersive X-ray Spectrometry
Standard Test Method for Identification and Quantification of Chromium, Bromine, Cadmium, Mercury, and Lead in Polymeric Material Using Energy Dispersive X-ray Spectrometry
SIGNIFICANCE AND USE
5.1 This test method is intended for the determination of chromium, bromine, cadmium, mercury, and lead, in homogeneous polymeric materials. The test method may be used to ascertain the conformance of the product under test to manufacturing specifications. Typical time for a measurement is 5 to 10 min per specimen, depending on the specimen matrix and the capabilities of the EDXRF spectrometer.
SCOPE
1.1 This test method describes an energy dispersive X-ray fluorescence (EDXRF) spectrometric procedure for identification and quantification of chromium, bromine, cadmium, mercury, and lead in polymeric materials.
1.2 This test method is not applicable to determine total concentrations of polybrominated biphenyls (PBB), polybrominated diphenyl ethers (PBDE) or hexavalent chromium. This test method cannot be used to determine the valence states of atoms or ions.
1.3 This test method is applicable for a range from 20 mg/kg to approximately 1 wt % for chromium, bromine, cadmium, mercury, and lead in polymeric materials.
1.4 This test method is applicable for homogeneous polymeric material.
1.5 The values stated in SI units are to be regarded as the standard. Values given in parentheses are for information only.
1.6 This test method is not applicable to quantitative determinations for specimens with one or more surface coatings present on the analyzed surface; however, qualitative information may be obtained. In addition, specimens less than infinitely thick for the measured X rays, must not be coated on the reverse side or mounted on a substrate.
1.7 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety, health, and environmental practices and determine the applicability of regulatory limitations prior to use.
1.8 This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
General Information
Relations
Standards Content (Sample)
This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: F2617 − 15 (Reapproved 2023)
Standard Test Method for
Identification and Quantification of Chromium, Bromine,
Cadmium, Mercury, and Lead in Polymeric Material Using
Energy Dispersive X-ray Spectrometry
This standard is issued under the fixed designation F2617; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope mendations issued by the World Trade Organization Technical
Barriers to Trade (TBT) Committee.
1.1 This test method describes an energy dispersive X-ray
fluorescence (EDXRF) spectrometric procedure for identifica-
2. Referenced Documents
tion and quantification of chromium, bromine, cadmium,
2.1 ASTM Standards:
mercury, and lead in polymeric materials.
D883 Terminology Relating to Plastics
1.2 This test method is not applicable to determine total
D3641 Practice for Injection Molding Test Specimens of
concentrations of polybrominated biphenyls (PBB), polybro-
Thermoplastic Molding and Extrusion Materials
minated diphenyl ethers (PBDE) or hexavalent chromium. This
D4703 Practice for Compression Molding Thermoplastic
test method cannot be used to determine the valence states of
Materials into Test Specimens, Plaques, or Sheets
atoms or ions.
D6299 Practice for Applying Statistical Quality Assurance
and Control Charting Techniques to Evaluate Analytical
1.3 This test method is applicable for a range from 20 mg/kg
Measurement System Performance
to approximately 1 wt % for chromium, bromine, cadmium,
E29 Practice for Using Significant Digits in Test Data to
mercury, and lead in polymeric materials.
Determine Conformance with Specifications
1.4 This test method is applicable for homogeneous poly-
E135 Terminology Relating to Analytical Chemistry for
meric material.
Metals, Ores, and Related Materials
1.5 The values stated in SI units are to be regarded as the
E177 Practice for Use of the Terms Precision and Bias in
standard. Values given in parentheses are for information only.
ASTM Test Methods
E691 Practice for Conducting an Interlaboratory Study to
1.6 This test method is not applicable to quantitative deter-
Determine the Precision of a Test Method
minations for specimens with one or more surface coatings
E1361 Guide for Correction of Interelement Effects in
present on the analyzed surface; however, qualitative informa-
X-Ray Spectrometric Analysis
tion may be obtained. In addition, specimens less than infi-
F2576 Terminology Relating to Declarable Substances in
nitely thick for the measured X rays, must not be coated on the
Materials
reverse side or mounted on a substrate.
1.7 This standard does not purport to address all of the
3. Terminology
safety concerns, if any, associated with its use. It is the
3.1 Definitions:
responsibility of the user of this standard to establish appro-
3.1.1 Definitions of terms applying to XRF, plastics and
priate safety, health, and environmental practices and deter-
declarable substances appear in Terminology E135, Terminol-
mine the applicability of regulatory limitations prior to use.
ogy D883 and Terminology F2576, respectively.
1.8 This international standard was developed in accor-
3.1.2 Compton scatter—the inelastic scattering of an X-ray
dance with internationally recognized principles on standard-
photon through its interaction with the bound electrons of an
ization established in the Decision on Principles for the
atom; this process is also referred to as incoherent scatter.
Development of International Standards, Guides and Recom-
3.1.3 Rayleigh scatter—the elastic scattering of an X-ray
photon through its interaction with the bound electrons of an
atom; this process is also referred to as coherent scatter.
This test method is under the jurisdiction of ASTM Committee F40 on
Declarable Substances in Materials and is the direct responsibility of Subcommittee
F40.01 on Test Methods. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved Oct. 1, 2023. Published November 2023. Originally contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
approved in 2008. Last previous edition approved in 2015 as F2617 – 15. DOI: Standards volume information, refer to the standard’s Document Summary page on
10.1520/F2617-15R23. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
F2617 − 15 (2023)
3.1.3.1 Discussion—The measured count rate of Compton ascertain the conformance of the product under test to manu-
and Rayleigh scattered radiation varies depending upon speci- facturing specifications. Typical time for a measurement is 5 to
men composition and may thus be used to compensate for 10 min per specimen, depending on the specimen matrix and
matrix effects. One option is to use the measured count rate of the capabilities of the EDXRF spectrometer.
the Compton scatter in the same manner as the measured count
rate of an internal standard element. Alternatively, the mea- 6. Interferences
sured count rate of the Compton scatter or the Compton/
6.1 Spectral Interferences—Spectral interferences result
Rayleigh scatter ratio may be used indirectly for estimating the
from the behavior of the detector subsystem of the spectrom-
effective mass absorption coefficient of the specimen, which is
eter and from scattering of X rays by the specimen, by a
used to compensate for matrix effects. The concept of correc-
secondary target or by a monochromator, if the spectrometer is
tions based on the Compton scatter effect is discussed as an
so equipped. Overlaps among the X-ray lines from elements in
optional part of several calibration choices in this standard.
the specimen are caused by the limited resolution of the
3.1.4 fundamental parameters (FP) model—a model for
detection subsystem. Depending upon the resolution of the
calibration of X-ray fluorescence response, including the cor-
detector system, the peaks from Zn, Br, Hg and Pb may overlap
rection of matrix effects, based on the theory describing the
with one another. Peaks from Cd may overlap with peaks from
physical processes of the interactions of X rays with matter.
Ca, Sn, or other elements. Interactions of photons and electrons
3.1.5 homogeneous polymeric material—polymeric mate- inside the detector give rise to additional peaks in a spectrum
rial is considered homogeneous for XRF when the elemental known as escape peaks and sum peaks. Fundamental Param-
composition is independent with respect to the measured eters equations require that the measured net count rates be free
location on the specimen and among separate specimens from line overlap effects. Some empirical approaches incorpo-
prepared from the same polymeric material. rate line overlap corrections in their equations. Manufacturers’
software may provide tools to compensate for overlapped
3.1.6 infinite thickness (or critical thickness)— the thickness
peaks, escape peaks, and sum peaks in spectra. The degree of
of specimen which, if increased, yields no increase in intensity
line overlap and the best method to account or correct for it
of secondary X rays, due to absorption by the polymer matrix.
must be ascertained on an individual basis and must be
3.1.6.1 Discussion—This thickness varies with secondary
considered when calibrating the instrument.
X-ray energy, or wavelength.
6.2 Interelement Effects—Interelement effects, also called
3.2 Abbreviations:
matrix effects, exist among all elements as the result of
3.2.1 EDXRF—energy dispersive X-ray fluorescence
absorption of fluorescent X rays (secondary X rays) by atoms
3.2.2 FP—fundamental parameters
in the specimen. Absorption reduces the apparent sensitivity
3.2.3 PBB—polybrominated biphenyl
for the element. In contrast, the atom that absorbs the X rays
3.2.4 PBDE—polybrominated diphenyl ether
may in turn emit a fluorescent X ray, increasing the apparent
sensitivity for the second element. Mathematical methods may
4. Summary of Test Method
be used to compensate for matrix effects. A number of
4.1 The optimum test sample is a smooth plaque or disk
mathematical correction procedures are commonly utilized
large enough to cover the viewed area of the spectrometer.
including full FP treatments and mathematical models based on
Suitable specimens may be die-cut from extruded sheets, or
influence coefficient algorithms. The influence coefficients may
molded from resin pellets, from powders or from granules.
be calculated either from first principles or from the empirical
data, or some combination of the two approaches. See Guide
4.2 The specimen is placed in the X-ray beam, and the
E1361 for examples of these approaches. Also, consult the
appropriate region of its spectrum is measured to give the count
software manual for the spectrometer for information on the
rates or fluorescent intensities of lead, mercury, cadmium,
approaches provided with the spectrometer. Any of these that
chromium and bromine.
will achieve the necessary analytical accuracy is acceptable.
4.3 The EDXRF spectrometer is calibrated by one of several
Examples of common interelement effects are listed in Table 1.
approaches including fundamental parameters and empirical,
classical curve construction, with either empirical or theoreti-
7. Apparatus
cal influence coefficients, from measured polymer reference
materials. The calibration may be performed by the manufac- 7.1 EDXRF Spectrometer—Designed for X-ray fluorescence
analysis with energy dispersive selection of radiation. The
turer or by the user.
spectrometer is equipped with specimen holders and a speci-
4.4 Choices of appropriate characteristic X-ray lines and
men chamber. Any EDXRF spectrometer may be used if its
spectrometer test conditions may vary according to each
design incorporates the following features.
element and with factors such as detector response, concentra-
7.1.1 Source of X-ray Excitation , capable of exciting the
tion range and other elements present in the polymer matrix.
recommended lines listed in Table 2, typically an X-ray tube.
5. Significance and Use
7.1.2 X-ray Detector, with sufficient energy resolution to
5.1 This test method is intended for the determination of resolve the recommended lines listed in Table 2. An energy
chromium, bromine, cadmium, mercury, and lead, in homoge- resolution of better than 250 eV at Mn K-L (Kα) has been
2,3
neous polymeric materials. The test method may be used to found suitable.
F2617 − 15 (2023)
TABLE 1 Common Interelement Effects in Formulated Plastics mens containing the relevant elements (Cr, Br, Cd, Hg, and Pb) or
elements that have fluorescence with the same energies as the elements of
Cause Effect
interest.
Absorption by Cl in PVC Reduced sensitivity for all analytes as
compared to when they are occurring
at the same concentration level in 8. Reagents and Materials
polyolefins
8.1 Purity of Reagents —Reagent grade chemicals shall be
Polymers of similar composition but Differences in C/H among calibrants
used in all tests. Unless otherwise indicated, it is intended that
differences in the relative and samples may result in biases of a
all reagents conform to the specifications of the Committee on
concentrations of H and C few percent (relative).
Analytical Reagents of the American Chemical Society (ACS)
Unmeasured elements B, N, O, and F If concentrations differ from the
where such specifications are available. Other grades may be
present in the matrix of the polymer, calibrants, substantial concentrations
used provided it is first ascertained that the reagent is of
for example, amide, fluorinated, and of these elements may cause
sufficiently high purity to permit its use without lessening the
terephthalate compounds. significant changes in both apparent
sensitivity and background count rates.
accuracy of the determination. Reagents used include all
materials used for the preparation of reference materials and
Absorption by elements present in Reduction of apparent sensitivity for
for cleaning of specimens.
flame-retardant compounds such as most analytes
PBBs, PBDEs, and Sb O
2 3
8.2 Reagents:
Absorption by Na, P, S, Ca, Ti, Zn, Reduction of apparent sensitivity for
8.2.1 Isopropanol or ethanol.
Mo, Sn, Ba, and other elements most analytes
8.2.2 Nitric acid (HNO ).
included in a formulation as fillers or
8.2.3 Hexane.
performance additives
8.2.4 Deionized water (H O).
8.3 Gloves—Disposable cotton gloves are recommended for
TABLE 2 Recommended X-ray Lines for Individual Analytes
handling reference materials and other specimens to minimize
NOTE 1—Other choices may provide adequate performance. contamination.
Analyte Preferred Line Secondary Line
8.4 Appropriate personal protective equipment for the han-
Chromium, Cr K-L (Kα )
2,3 1,2
dling of reagents.
Bromine, Br K-L (Kα ) K-M (Kβ )
2,3 1,2 2,3 1,3
Cadmium, Cd K-L (Kα ) K-M (Kβ )
2,3 1,2 2,3 1,3 8.5 Reference Materials:
Mercury, Hg L -M (Lα )
3 4,5 1,2
8.5.1 Polymer reference materials are available from both
Lead, Pb L -M (Lβ ) L -M (Lα )
2 4 1 3 4,5 1,2
metrology institutes and commercial sources. Some are pro-
vided in disk form, and some are available as granules or
extruded pellets.
8.5.2 Reference materials may be prepared by adding
7.1.3 Signal Conditioning and Data Handling Electronics
that include the functions of X-ray counting and peak process- known amounts of pure compounds or additives (or both), to
an appropriate polymeric base material. It is recommended to
ing.
make reference materials using the same base polymer as the
7.2 The following spectrometer features and accessories are
unknown samples.
optional:
8.5.2.1 Thorough mixing of ingredients is required for
7.2.1 Beam Filters—Used to make the excitation more
optimum homogeneity. Options may include grinding, melt-
selective and reduce background count rates.
blending, repeated extrusion, and solvent dissolution.
7.2.2 Secondary Targets—Used to produce semi-
8.5.2.2 Elemental concentrations may be calculated from
monochromatic radiation enhancing sensitivity for selected
the concentrations and molecular formulae of the compounds
X-ray lines and to reduce spectral background for improved
and additives used.
detection limits. The use of monochromatic radiation also
8.5.2.3 The elemental compositions of user-prepared refer-
allows the simplification of FP calculations.
ence materials must be confirmed by one o
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