Designation: E 1508 – 98 (Reapproved 2003)

Standard Guide for

Quantitative Analysis by Energy-Dispersive Spectroscopy1
This standard is issued under the fixed designation E 1508; 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 (e) indicates an editorial change since the last revision or reapproval.

1. Scope 3.2.3 Bremsstrahlung—background X rays produced by

1.1 This guide is intended to assist those using energy- inelastic scattering (loss of energy) of the primary electron
dispersive spectroscopy (EDS) for quantitative analysis of beam in the specimen. It covers a range of energies up to the
materials with a scanning electron microscope (SEM) or energy of the electron beam.
electron probe microanalyzer (EPMA). It is not intended to 3.2.4 critical excitation voltage—the minimum voltage re-
substitute for a formal course of instruction, but rather to quired to ionize an atom by ejecting an electron from a specific
provide a guide to the capabilities and limitations of the electron shell.
technique and to its use. For a more detailed treatment of the 3.2.5 dead time—the time during which the system will not
subject, see Goldstein, et al.2 This guide does not cover EDS process incoming X rays (real time less live time).
with a transmission electron microscope (TEM). 3.2.6 k-ratio—the ratio of background-subtracted X-ray
1.2 This standard does not purport to address all of the intensity in the unknown specimen to that of the standard.
safety concerns, if any, associated with its use. It is the 3.2.7 live time—the time that the system is available to
detect incoming X rays.

--```,,,``,`,,,``,,,,```,,`,``,-`-`,,`,,`,`,,`---
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica- 3.2.8 overvoltage—the ratio of accelerating voltage to the
bility of regulatory limitations prior to use. critical excitation voltage for a particular X-ray line.
3.2.9 shaping time—a measure of the time it takes the
2. Referenced Documents amplifier to integrate the incoming charge; it depends on the
2.1 ASTM Standards: 3 time constant of the circuitry.
E 3 Methods of Preparation of Metallographic Specimens 3.2.10 spectrum—the energy range of electromagnetic ra-
E 7 Terminology Relating to Metallography3 diation produced by the method and, when graphically dis-
E 673 Terminology Relating to Surface Analysis played, is the relationship of X-ray counts detected to X-ray
E 691 Practice for Conducting an Interlaboratory Study to energy.
Determine the Precision of a Test Method
4. Summary of Practice
3. Terminology 4.1 As high-energy electrons produced with an SEM or
3.1 Definitions—For definitions of terms used in this guide, EPMA interact with the atoms within the top few micrometres
see Terminologies E 7 and E 673. of a specimen surface, X rays are generated with an energy
3.2 Definitions of Terms Specific to This Standard: characteristic of the atom that produced them. The intensity of
3.2.1 accelerating voltage—the high voltage between the such X rays is proportional to the mass fraction of that element
cathode and the anode in the electron gun of an electron beam in the specimen. In energy-dispersive spectroscopy, X rays
instrument, such as an SEM or EPMA. from the specimen are detected by a solid-state spectrometer
3.2.2 beam current—the current of the electron beam mea- that converts them to electrical pulses proportional to the
sured with a Faraday cup positioned near the specimen. characteristic X-ray energies. If the X-ray intensity of each
element is compared to that of a standard of known composi-
tion and suitably corrected for the effects of other elements
1
This guide is under the jurisdiction of ASTM Committee E04 on Metallography present, then the mass fraction of each element can be
and is the direct responsibility of Subcommittee E04.11 on X-Ray and Electron calculated.
Metallography.
Current edition approved Nov. 1, 2003. Published December 2003. Originally
approved in 1993. Last previous edition approved in 1998 as E 1508 – 98.
5. Significance and Use
2
Goldstein, J. I., Newbury, D. E., Echlin, P., Joy, D. C., Romig, A. D., Jr., Lyman, 5.1 This guide covers procedures for quantifying the el-
C. D., Fiori, C., and Lifshin, E., Scanning Electron Microscopy and X-ray
Microanalysis, 2nd ed., Plenum Press, New York, 1992.
emental composition of phases in a microstructure. It includes
3
For referenced ASTM standards, visit the ASTM website, www.astm.org, or both methods that use standards as well as standardless
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM methods, and it discusses the precision and accuracy that one
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website.

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 E 1508 – 98 (2003)
can expect from the technique. The guide applies to EDS with the evaporator, is probably thick enough. For the most accurate
a solid-state X-ray detector used on an SEM or EPMA. analysis, standards and unknowns should be coated at the same
5.2 EDS is a suitable technique for routine quantitative time to assure equal coating thicknesses. Specimens mounted
analysis of elements that are 1) heavier than or equal to sodium in a nonconducting medium must make electrical contact with
in atomic weight, 2) present in tenths of a percent or greater by the microscope stage. This is often accomplished by painting a
weight, and 3) occupying a few cubic micrometres, or more, of stripe of carbon or silver paint from the specimen to the
the specimen. Elements of lower atomic number than sodium specimen holder.
can be analyzed with either ultra-thin-window or windowless
spectrometers, generally with less precision than is possible for 8. Spectrum Collection
heavier elements. Trace elements, defined as <1.0 %,2 can be 8.1 Calibration—The analyzer shall be calibrated on two
analyzed but with lower precision compared with analyses of X-ray peaks or other methods implemented by the equipment
elements present in greater concentration. manufacturer in software to set the amplifier gain and offset.
6. Test Specimens Often aluminum and copper are used, and sometimes both the
K and L lines of copper are used. The two elements need not
6.1 Suitable specimens are those that are normally stable be in the same specimen. A spectrum from pure aluminum
under an electron beam and vacuum and are homogeneous could be collected followed by pure copper in the same
throughout the volume of X-ray production. If the specimen is spectrum. Software is usually available to calibrate the EDS
inhomogeneous at the micrometre level, then a truly quantita- system, and one should consult the system manual for the
tive analysis is not possible, and a bulk technique such as X-ray details of operation. To ensure reproducible results, calibration
fluorescence should be used. should be checked periodically.
6.2 The concentration of each element to be analyzed
8.2 Operating Parameters:
should equal or exceed about 0.1 wt %. Lower limits of
8.2.1 The accelerating voltage of the SEM must be chosen
detection are possible with longer counting times, but the
to provide an adequate overvoltage to excite the X-ray lines of
precision of trace element analysis is poorer than when the
interest. An overvoltage that is too low will not sufficiently
element is present at the percent level.
excite X rays; one that is too high yields low spatial resolution
7. Specimen Preparation and causes absorption as X rays escape from deep within the
7.1 Specimens for quantitative EDS analysis should be specimen. An overvoltage of at least 1.5 times the critical
prepared in accordance with standard metallographic or petro- excitation potential of the highest energy X-ray line analyzed is
graphic techniques. Guidelines are given in Methods E 3. The recommended. When analyzing hard and soft X rays in the
specimen must be flat in the region to be analyzed. This same specimen, analyses at two voltages may be necessary. For
requirement does not preclude scratches; however, any materials such as minerals and ceramics, which contain light
scratches in the immediate vicinity of the analyzed region must elements (that is, of low atomic number), 15 kV is usually a
be insignificant with respect to the X-ray volume. The operator good compromise. For many metals containing medium atomic
must also be aware of the possibility of spurious X rays from number elements, 20 to 30 kV is a good choice. Heavy
parts of the chamber, polishing compound elements, or from elements (those of higher atomic number) may be analyzed
adjacent phases or a combination thereof. Note that these using L or M lines, and so higher voltages are not necessary.
requirements for surface preparation preclude the quantitative The actual accelerating voltage of the electron beam does not
analysis of casual samples, such as unpolished surfaces like always correspond with the voltage selected on the instrument.
fracture surfaces. Although data can be generated on these It can be determined by expanding the vertical scale of the EDS
casual surfaces, the results would be of significantly lower spectrum and observing the energy above which continuum X
precision with unpredictable variations. rays do not occur.
7.2 Unetched or lightly etched specimens are preferred. If 8.2.2 Almost all elements can be analyzed using character-
they are etched, the operator must make sure that the compo- istic X-ray lines in the range of 0–10 keV. This range contains
sition in the region to be analyzed has not been altered and that K lines of the first transition series (scandium–zinc (Sc-Zn)), L
the region to be analyzed is flat. lines of the second transition series plus the lanthanides, and M
7.3 Nonconducting specimens should be coated with a lines of the third transition series plus the actinides. Accord-
conductive material to prevent charging. Lowering the accel- ingly, most operators choose a 0–10 keV display at higher
erating voltage may reduce or eliminate the effect of charging display resolution rather than a 0–20 keV display at lower
in some samples, but applying a conductive coating is still the resolution. Tables of X-ray energies can be found in various
most common method. Evaporated carbon is usually the most texts, such as Goldstein, et al2 or Johnson and White.4
suitable coating material. Heavy metals such as gold that are 8.2.3 X-ray spatial resolution degrades with overvoltage,
often used for SEM imaging are less suitable because they because as the electrons penetrate deeper into the specimen, X
heavily absorb X rays; if the coating is thick enough, X-ray rays are generated from a larger volume. An approximation of
lines from those metals will be seen in the spectrum. If one is
analyzing carbon in the specimen, then aluminum makes a
good coating. The coatings are usually applied in thicknesses 4
Johnson, G. G., Jr., and White, E. W., X-Ray Emission Wavelengths and KeV
of several tens of nanometres. Carbon that appears to be tan in Tables for Nondiffractive Analysis, ASTM Data Series DS 46, ASTM, Philadelphia,
color on the specimen surface, or on a piece of filter paper in 1970.

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 E 1508 – 98 (2003)
the diameter of this tear-drop-shaped excitation volume, re-
ferred to as the X-ray range, can be obtained using the
following equation.5
R 5 0.064~Eo1.68 2 Ec1.68!/r (1)

where:
R = the range in µm,
Eo = the accelerating voltage in kV,
Ec = the critical excitation potential in keV, and
r = the density in g/cm3.
More accurate interaction volumes can be computed by
Monte Carlo computer methods to generate random electron
trajectories, but Eq 1 provides a reasonable estimate for most
purposes.
8.2.4 The beam can be placed in the spot mode to form a
probe to analyze the minimum volume, or it can be scanned
over a homogeneous region to lower the electron dose at any
one point. Defocusing the beam or scanning it over an area of FIG. 1 Schematic Diagram of Electron Microscope System
varying composition does not provide an average composition,
because the correction factors applied to the intensity ratio are where:
themselves a function of composition. V = solid angle in steradians,
8.2.5 The current in the electron beam determines the flux of A = active area of the detector crystal; for example, 30
X rays that are generated. It does not affect spatial resolution mm2, and
for X-ray analysis in the same way it detracts from electron r = sample-to-detector distance, mm.
image resolution. Typically it is adjusted to keep the dead time The larger the active area of the detector, the more counts
in the EDS system below 40 %. Dead times of 20 to 30 % will be collected, but at the expense of spectral resolution.
produce good spectra, whereas dead times above 40 % can lead Most detectors have a movable slide and can be brought closer
to spectra containing artifacts, such as those discussed in 8.3.1. to the sample if a higher count rate at a given beam current is
Maximum throughput, that is, the most X rays/real time, is needed. The take-off angle is defined as the angle between the
achieved at about 40 % dead time. Higher count rates can be surface of the sample and a line to the X-ray detector. If the
achieved by lowering the shaping time on the system amplifier sample is not tilted, the take-off angle is defined as follows:
from about 10 µs, but spectral resolution will be lost. For c 5 arctan ~W 2 V!/S (3)
quantitative analysis, a shaping time of about 10 µs or greater
is used. The beam current must remain stable throughout the where:
c = take-off angle,
analysis, because the counts collected are directly proportional
W = working distance,
to the beam current. Thus, a 1 % upward drift in beam current

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V = vertical distance, and
will produce a 1 % increase in all the reported mass fractions, S = spectrometer distance.
resulting in a reported total >100 %. For quantitative analysis Working distance is measured in the microscope; its accu-
using standards, the beam current (not specimen current) must racy depends on the method used to measure it and the
be the same for both the specimen and the standards or one specimen position. Vertical distance is the distance from the
must be normalized to the other. bottom of the pole piece of the final lens to the centerline of the
8.2.6 The geometric configuration of the sample and detec- detector; it usually can be measured within the microscope
tor, shown schematically in Fig. 1, also affects the analysis. The with a ruler. Spectrometer distance is the horizontal distance
number of X-ray photons that reach the detector is a function from the spectrometer to the beam; it is measured using the
of the solid angle and take-off angle, including the effect of scale provided by the manufacturer on the spectrometer slide.
specimen and detector tilt. The count rate incident on an X-ray All distances must be in the same units. The take-off angle
detector is directly proportional to the size of the solid angle should be as high as possible to minimize absorption of X rays
defined as follows for a detector normal to the line of sight to within the specimen and maximize the accuracy of quantitative
the specimen: analysis. If the specimen is tilted such that the beam is not
perpendicular to the specimen surface, an effective take-off
V 5 A/r2 (2)
angle is used. There are several expressions in use by com-
mercial manufacturers to calculate this, and all produce similar
results if the tilt angle is not extreme. When analysis is
5
Andersen, C. A., and Hasler, M. F., X-Ray Optics and Microanalysis, 4th Intl. performed on a tilted specimen, the azimuthal angle between
Cong. on X-Ray Optics and Microanalysis, Hermann, Paris, 1966, p. 310. the line from the analysis point to the EDS detector and the line

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 E 1508 – 98 (2003)
perpendicular to the stage tilt axis must be known. If standards account absorption edges. Some software also allows the
are used, they must be collected under the identical geometrical operator to fit his own background.
conditions as the unknowns. 9.1.2 The other step that must be accomplished before an
8.3 Spectral Artifacts: intensity ratio can be measured is peak deconvolution. EDS
8.3.1 There are a number of artifacts possible with EDS, and detectors do not resolve all peaks. For example, the S Ka, Mo
these are discussed by Fiori, et al.6 Most of them are related to La, and Pb Ma lines are all within about 50 eV of each other
detector electronics and are rarely seen in a properly function- and therefore are severely overlapped. Even though one cannot
ing system. However, two artifacts that are commonly seen are see the individual components of a peak envelope in a
pulse pileup peaks and silicon escape peaks. Pileup peaks spectrum, there are computer methods of deconvolution. Two
occur when several X-ray photons reach the detector at the methods in common use are 1) the method of overlap factors
same time, and the pulse processing electronics erroneously and 2) the method of multiple least squares. Both methods
record the sum of their energies rather than each one individu- work well, and they are usually combined with one of the
ally. Lowering the beam current to lower the count rate usually background subtraction methods in the manufacturer’s soft-
eliminates the problem. Alternatively, the amplifier shaping ware. One should consult the manufacturer’s instructions for
time can be decreased; this action will allow pulses to be their use.
processed faster, but at the expense of degraded spectral 9.1.3 Although in most cases these computer methods
resolution. handle spectra well, the operator should be aware of conditions
8.3.2 A silicon escape peak occurs when an ionized atom of that are difficult. For example, trace element analysis is
silicon in the detector generates an X ray. If that X ray escapes sensitive to background subtraction because the computer is
from the detector, its energy that would ordinarily have been looking for a small peak above the continuum. Accordingly the
--```,,,``,`,,,``,,,,```,,`,``,-`-`,,`,,`,`,,`---

measured is lost. The result is a peak at 1.74 keV (Si Ka) below spectrum must be collected long enough to provide enough
the proper peak. This artifact is greatest at about 2 keV, near the statistics to discern small peaks. In like manner, deconvolution
P Ka or Zr La peaks. The artifact cannot occur at energies routines work well in most cases, but not when the overlapped
below the absorption edge of the Si K line, and it becomes lines arise from elements present in widely different concen-
negligible at higher energies such as the Cu Ka line. trations. For example, if one element constitutes 90 % of the
9. Quantification specimen and the other element 10 %, precision will be greatly
degraded. In this situation use of a different analytical line may
9.1 Background Subtraction and Peak Deconvolution: be possible, or if not, a technique with higher spectral
9.1.1 Before the proportionality between X-ray intensity resolution such as wavelength dispersive spectrometry is
and elemental concentration can be calculated, several steps indicated.
are required to obtain the intensity ratio (k-ratio) between
9.1.4 Once the background is subtracted and the peaks are
unknown and standard. Or, if the standardless technique is
stripped of interferences, one can calculate their ratio to those
used, then a pure net intensity is required. A spectrum of X rays
of similarly background-subtracted, deconvoluted standard
generated by electrons interacting with the specimen contains
spectra. The unknowns and standards must have been collected
a background consisting of continuum X rays, often called
1) under the same geometrical configuration, 2) at the same
Bremsstrahlung. Observing the high-energy cutoff of the con-
accelerating voltage, 3) at the same count rate per current unit,
tinuum, as noted in 8.2.1, gives the most accurate determina-
and 4) with the same processing algorithm.
tion of the beam voltage, and this is the value that should be
used for quantitative analysis. If the voltage measured in this 9.1.5 Even standardless analysis requires background sub-
manner is much lower than the voltage setting, it may be an traction and peak deconvolution, but the intensity is calculated
indication that the specimen is charging. The background in the from pure intensity curves and the ratio of peak integrals in the
spectrum is not linear and simple interpolation is inadequate. unknown spectrum. Standardless analyses always total 100 %,
Two approaches to this problem commonly used in commercial or some other value specified by the analyst. In normalizing the
systems are background modeling and digital filtering. The total concentrations to 100 %, important information is lost. A
background models are based on known physics plus a suitable true mass total, as in analysis against standards, provides
correction for the real world. This method lets the user pass information about the quality of the analysis. It calls attention
judgment on the quality of the model by comparing the model to problems such as elements not specified for analysis or
with the actual spectrum. The digital filter method treats the analysis of more than one phase under the beam. Analyses
background as a low frequency component of the spectrum and totaling exactly 100 % should always be viewed with skepti-
mathematically sets it to zero. This method is not based on any cism, whether they be standardless or normalized standards
model and, therefore, is more general. It is also useful for the analyses. Whichever method is used, all elements present must
light element region of the spectrum where the models were be specified even if some need not be analyzed. This is because
never intended to be used; however, it does not take into a correction is necessary to account for the effect of other
elements (the matrix) present in the specimen.
9.2 Matrix Corrections:
6
Fiori, C. E., Newbury, D. E., and Myklebust, R. L., “Artifacts Observed in 9.2.1 The k-ratio of an element is a starting estimate of that
Energy Dispersive X-ray Spectrometry in Electron Beam Instruments—A Caution-
ary Guide,” NIST Special Publication 604, Proceedings of the Workshop on Energy
element’s concentration. There are, however, effects of atomic
Dispersive Spectrometry, National Institute of Standards and Technology, Gaithers- number, absorption, and fluorescence between the unknowns
burg, Maryland, 1981. and the standards. The atomic number or “Z” factor corrects for

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differences in the number of X rays generated. The absorption 11. Standards
or “A” factor corrects for differences in the number of X rays 11.1 Suitable standards for EDS microanalysis must be 1)
that escape the sample to be detected. The fluorescence or “F” homogeneous at the micrometre level, 2) of known composi-
factor corrects for non-electron generated X rays, that is, those tion as analyzed by an independent method, and 3) stable under
fluoresced by other X rays. If the unknown and standard were the electron beam. For the highest accuracy, standards should
identical, each of these factors would equal one. There are be as similar as possible to the unknowns to minimize matrix
many such “ZAF” computer programs available, each one effects. However, most matrix correction programs are suffi-
using a set of fundamental parameters thought to give the best ciently accurate to permit the use of pure element standards.
results. The differences in the results each produces are usually Nevertheless, metals do not make good standards for nonmet-
much less than the precision of the analysis. als, and vice versa.
9.2.2 There are also many computer programs using the“ 11.2 Standards may be obtained from microscopy suppliers,
phi-rho-z” method. These approach the problem of matrix the National Institute for Standards and Technology, or from
correction using more fundamental physics and sometimes other microscopists. However, one of the best sources of
combine the effects of Z and A into one, but they too require a standards similar to the materials analyzed is one’s own
set of fundamental parameters optimized to each program. facility, if they are checked for homogeneity.
Many phi-rho-z programs claim greater accuracy because they 11.3 Standards can also be used to check the performance of
standardless programs. In many cases, the results are similar,
account for absorption better than the older ZAF programs.
and the standardless method may be used for convenience.

--```,,,``,`,,,``,,,,```,,`,``,-`-`,,`,,`,`,,`---
Consequently, one would expect the most improvement using
a phi-rho-z method in light element analysis. However, in the
TABLE 1 Standardized Operating Parameters for Second Round-
absence of light elements, it is unlikely that the accuracy of Robin Test Program
most EDS analyses is limited by the matrix correction.
Accelerating voltage 20 kV
9.3 Reporting Results: Acquisition time 200 s
Detector dead time '25 %
9.3.1 The analytical conditions are normally reported with Take-off angle '40°
the elemental concentrations determined by EDS. These con-
ditions include the accelerating voltage, take-off angle and tilt,
and the analytical line (KLM) used. The report should also 12. Precision and Bias
specify whether standards or standardless methods were used,
12.1 Interlaboratory Test Program—An interlaboratory
what matrix corrections were applied, and whether any el-
study using two different metallurgical specimens was con-
emental concentrations were calculated by difference or by
ducted to determine the precision of energy-dispersive spec-
stoichiometry. Additional items that may be reported include
troscopy (EDS). Both specimens were analyzed by various
what standards were used, if any, the beam current, and the Z, metal producers, EDS system manufacturers, and one univer-
A, and F factors. It would also be informative to mention the sity. A total of nine laboratories participated in the study. Each
type of window on the EDS detector, if other than a conven- of the specimens was analyzed with a lithium-drifted silicon
tional beryllium window. Concentrations are normally reported detector using a set of standardized operating parameters after
to a tenth of a percent; although many computer programs an initial round-robin wherein parameters were selected by
report more significant figures, they are rarely warranted. each participant. Both sets of data are reported, and the
standardized operating parameters are listed in Table 1.
10. Light Element Analysis 12.1.1 The specimens selected for the round-robin were
10.1 Light elements can be analyzed with an ultra-thin Type 308 stainless steel and INCONEL7 alloy MA 6000. To
window detector that provides better efficiency for the soft X ensure homogeneity, the Type 308 stainless steel specimens
rays that light elements generate. Windowless detectors ap- were homogenized at 1975°F (1079°C) for one hour followed
proach the theoretical highest efficiency of the detecting by a water quench. This produced a 100 % austenitic structure.
crystal, but in the open position contaminants in the sample This material was chosen as a routine analysis for iron,
chromium, and nickel. Some manganese was also present, but
chamber are free to condense on the cold crystal. Additionally,
because its Ka line overlaps the Cr Kb it was not required to
in the windowless mode any light, such as from cathodolumi-
be reported, although some participants did. The alloy MA
nescence, can be picked up by the crystal and will contribute to
6000 specimen was selected because of its inherent homoge-
the overall noise of the system. Quantitative light element
neity and because it presented several analytical problems. The
analysis is less precise than that of heavier elements, because alloy contained both high and low atomic number elements
the count rate of soft X rays is lower. The minimum detect- necessitating the use of K, L, and M lines. There was also a
ability limit of light elements is also degraded because of the severe overlap between the M lines of tantalum and tungsten.
lower peak-to-background ratios found with soft X rays. If the The presence of eight elements also added to the difficulty in
stoichiometry of compounds containing light elements is analyzing this material. The compositions of both alloys, as
known, then calculation by stoichiometry is the most accurate determined by wet chemical analysis, are given in Table 2.
method. For example in silicates, analyzing silicon and multi-
plying by the gravimetric factor for SiO2 (2.14) is more
accurate than analyzing oxygen directly. 7
INCONEL is a registered trademark of Inco Alloys International.

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TABLE 2 Wet Chemical Analysis of Samples of Commercial Type 308 Stainless Steel and INCONEL Alloy MA 6000 Used in ASTM
Round Robin
Chemical Composition—Wt %
Sample
Tantalum Tungsten Chromium Titanium Aluminum Molybdenum Nickel Iron Manganese Y2O3
Commercial Type 308 — — 19.62 — — — 9.50 69.0 1.30 —
Stainless Steel
INCONEL Alloy MA 1.91 3.91 14.76 2.26 4.0 1.91 68.12 1.00 — 0.97
6000

TABLE 4 Precision Statistics of an Interlaboratory Study for

12.1.2 Individual specimens of both materials were sent to Quantitative Analysis by Energy Dispersive Spectroscopy
each of the nine participants, all of whom reported the Quantitative EDS Analysis of MA 6000 with No Set Parameters
specimens to be homogeneous. Each participant was requested Elements x̄ Sr SR r R
to analyze five random areas in each specimen using a standard Iron 0.96 0.09 0.12 0.24 0.32
Tantalum 1.89 0.26 0.37 0.72 1.04
beryllium window EDS detector and their own operating Titanium 2.36 0.26 0.26 0.72 0.72
parameters. The nominal composition of each specimen was Molybdenum 2.43 0.16 0.86 0.45 2.41
also included for reference. A second round-robin test program, Tungsten 3.67 0.30 0.67 0.84 1.87
Aluminum 4.49 0.22 1.31 0.63 3.67
which required the use of a standard accelerating voltage, Chromium 15.33 0.33 0.49 0.92 1.38
detector dead time, take-off angle, and acquisition time, was Nickel 67.78 1.66 2.43 4.64 6.81
also initiated. It was requested that analyses by both standards Quantitative EDS Analysis of Type MA 6000 with Set Parameters

and standardless methods be reported. Elements x̄ Sr SR r R

Iron 1.04 0.05 0.10 0.14 0.29
12.2 Precision: Tantalum 1.81 0.17 0.47 0.49 1.33
12.2.1 The results from the round-robin test program were Molybdenum 2.02 0.07 0.12 0.20 0.34
analyzed in accordance with Practice E 691 to develop repeat- Titanium 2.31 0.16 0.20 0.46 0.56
Tungsten 3.82 0.15 0.38 0.41 1.07
ability and reproducibility standard deviations (see Table 3 and Aluminum 4.78 0.23 0.59 0.63 1.66
Table 4). The inherent precision of the EDS method is Chromium 15.07 0.33 0.46 0.91 1.30
controlled by counting statistics. Clearly, for a given overall Nickel 68.97 0.51 1.25 1.43 3.51
Standardless Quantitative EDS Analysis of MA 6000 with Set Parameters
counting time, the relative precision associated with major
elements is greater than for minor or trace elements, insofar as Elements x̄ Sr SR r R
Iron 0.99 0.08 0.12 0.22 0.32
there are necessarily fewer counts in minor peaks. Practice Molybdenum 1.96 0.11 0.53 0.31 1.49
E 691 is used to analyze the round-robin data for consistency Tantalum 1.98 0.15 1.19 0.42 3.34
and calculates intralaboratory repeatability and interlaboratory Titanium 2.30 0.15 0.18 0.43 0.51

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Tungsten 3.48 0.17 1.39 0.48 3.90
reproducibility statistics. The 95 % repeatability and reproduc- Aluminum 4.56 0.22 2.33 0.63 6.53
ibility, r and R, are defined by E 691 as 2.8 times the standard Chromium 15.31 0.23 0.56 0.64 1.55
deviations, Sr and SR, respectively. When these standard Nickel 64.29 0.43 3.06 1.21 8.56

deviations are divided by the mean concentration for each x̄ = cell average
element, the result is a measure of relative precision within and Sr = repeatability standard deviation
SR = reproducibility standard deviation
between laboratories. r = repeatability limit
R = reproducibility limit

TABLE 3 Precision Statistics of an Interlaboratory Study for

Quantitative Analysis by Energy Dispersive Spectroscopy 12.2.2 In the case of the Type 308 stainless steel, the 95 %
repeatability limit is 7 % of the mean value or better for each
S
Quantitative EDS Analysis of Type 308 Stainless Steel with No Set Parameters
r
Elements x̄ Sr SR r R element x̄ 5 0.64/9.43 5 0.068 for nickel), and about 2 %
Nickel 9.04 0.21 0.35 0.58 0.98
Chromium 20.48 0.27 0.87 0.77 2.43
Iron 70.47 0.68 2.44 1.90 6.84 is possible for iron present at 70 wt %. The 95 % reproduc-
Quantitative EDS Analysis of Type 308 Stainless Steel with Set Parameters
ibility limit ranges from about 14 % to 3 %. Requiring set
Elements x̄ Sr SR r R
Nickel 9.43 0.23 0.49 0.64 1.36
parameters had little effect on the repeatability but improved
Chromium 20.31 0.23 0.47 0.65 1.32 the reproducibility for chromium and iron, but not for nickel.
Iron 69.41 0.38 1.05 1.06 2.95 Standardless methods were about equivalent to those using
Standardless Quantitative EDS Analysis of Type 308 Stainless Steel with Set
Parameters
standards for this specimen. The results obtained from this
specimen represent a typical metallurgical microanalysis with
Elements x̄ Sr SR r R
Nickel 9.23 0.22 0.29 0.60 0.82 no unusual problems. As such, the precision obtained should be
Chromium 20.25 0.15 0.48 0.41 1.34 representative of the technique. The interlaboratory reproduc-
Iron 69.60 0.21 0.78 0.60 2.18 ibility under standard conditions averaged 8.4 %, and the
x̄ = cell average standardless method averaged 6.2 % relative to the mean.
Sr = repeatability standard deviation 12.2.3 In the case of alloy MA 6000, the 95 % repeatability
SR = reproducibility standard deviation
r = repeatability limit values improve with increasing concentration with the excep-
R = reproducibility limit tion of tantalum and tungsten. Those two elements are present

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 E 1508 – 98 (2003)
at the level of a few percent and their lines are overlapped. The resolution. The 200s count specified for the round-robin was
occurrence of these two conditions together resulted in consid- intended to represent typical operating conditions, not the best
erably lower precision than for the other elements. The 95 % achievable precision.
reproducibility limit varied greatly when the parameters were 12.3 Bias:
not specified, but improved with set parameters. It may be that 12.3.1 If the wet chemical analysis of each specimen (Table
differences in background subtraction, peak deconvolution 2) is taken as an accepted reference value, the difference
method, matrix correction, and possibly geometric configura- between it and the concentration measured by EDS can be
tion caused this. It was not possible to specify all of these determined. These values are given in Table 5. The EDS values
conditions because some are inherent to the system used. are the average of five measurements in each of nine labora-
12.2.4 The standardless method produced intralaboratory tories. To the extent that this number of replicate analyses
repeatability results similar to the standards methods but averages out the effects of precision, the remaining error may
considerably less interlaboratory reproducibility, owing to the be attributed to bias. For the Type 308 stainless steel, the
different standardless routines in use by different manufactur- average error was 0.7 % of the amount present—a value close
ers. Although results of the standardless analyses were rather enough to zero to be insignificant. For the alloy MA 6000, the
good on the Type 308 stainless steel, they may be considerably average was 3.12 %. There are many potential sources of bias,
inferior on other types of specimens. On the MA6000 alloy, the but the effect of each is hard to predict. Some sources of bias
reproducibility among laboratories was much less than that of that are under operator control are as follows.
the standards technique (R in Table 4). And even though the

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12.3.1.1 Geometric Configuration—This must be known
average errors compared with the reference composition (Table and reproducible among standards and unknown specimens.
5) are not great, they are probably the result of positive and
12.3.1.2 Standards—The composition of these must be
negative errors among laboratories canceling each other. These
known accurately, and they must be homogeneous at the
errors arise from the different ways various systems generate
micrometre level.
the pure element intensities, rather than from differences in
ZAF or phi-rho-z matrix corrections. Accordingly, before 12.3.1.3 Electron Beam Current—This must be stable
routinely using a standardless method for quantitative analysis, throughout standard collection and unknown analysis or cor-
it is important to validate the method for a particular class of rected for instability through continuous monitoring with an
materials by comparing it against analysis with standards or integrating picoammeter or beam current monitoring before
against a completely different quantitative technique, such as and after analysis if the drift is linear.
X-ray fluorescence or wet chemical analysis if the specimen is 12.3.1.4 Conductive Coating—This must be thick enough to
homogeneous. If the results are comparable, the standardless prevent changing of the specimen, yet thin enough so as not to
method may be used for specimens of composition similar to absorb X rays significantly. It should also be of similar
those on which it was validated. composition and thickness between the standards and the
12.2.5 Precision can usually be improved by acquiring more unknowns.
counts in the spectrum if that is possible. Longer counting 12.3.2 Some sources of bias often not under operator
times and increased beam current produce more counts. There control are as follows.
are practical limits, however, such as beam drift or carbon 12.3.2.1 Method of Background Subtraction and Peak
contamination increasing on the specimen and causing the total Deconvolution—These must use appropriate constants such as
counts to be nonlinear with time. Decreasing the amplifier time detector efficiency for the specific detector being used, back-
constant also increases count rate, but at the expense of ground fitting regions, filter width, and others.

TABLE 5 Comparison Between EDS and Reference Wet Chemical Analysis

Wet Chemistry No Set Parameters (% error) Set Parameters (% error) Standardless (% error)
Type 308 Stainless Steel
Nickel 9.50 9.04 (−4.84) 9.43 (−0.78) 9.23 (−2.84)
Chromium 19.62 20.48 (4.39) 20.31 (3.51) 20.25 (3.23)
Iron 69.00 70.48 (2.14) 69.41 (0.59) 69.60 (0.88)
Average error 0.56 % 1.11 % 0.42 %

Alloy MA 6000
Iron 1.00 0.96 (−4.24) 1.04 (3.67) 0.99 (−1.43)
Tantalum 1.91 1.88 (−1.30) 1.81 (−5.08) 1.96 (2.62)
Titanium 2.26 2.36 (4.30) 2.02 (−10.55) 1.98 (−12.18)
Molybdenum 1.91 2.43 (27.31) 2.31 (20.82) 2.30 (20.19)
Tungsten 3.91 3.67 (−6.02) 3.82 (−2.27) 3.48 (−11.11)
Aluminum 4.00 4.49 (12.16) 4.78 (19.38) 4.56 (13.91)
Chromium 14.76 15.33 (3.87) 15.07 (2.09) 15.31 (3.71)
Nickel 68.12 67.78 (−0.49) 68.97 (1.24) 64.28 (−5.63)
Average error 4.45 % 3.66 % 1.26 %

Average Error for Type 308 0.70 %

Average Error for MA 6000 3.12 %
Overall Average Error 1.91 %

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12.3.2.2 Matrix Correction—This program is dependent on elements, precision is significantly degraded and more X-ray
the accuracy of many constants such as mass absorption counts must be collected. Most sources of bias are either
coefficients, mean ionization potentials, fluorescent yields, and insignificant or under operator control, and the overall accu-
others. racy of the technique is better than 64 % relative to the
12.3.2.3 Standardless Programs—These are dependent on reference composition.
the accuracy of the intensity curves built into them as well as
the sources of bias listed above. 13. Keywords
12.4 Overall, when elements are present in major accounts, 13.1 EDS; elemental analysis; energy-dispersive spectros-
an intralaboratory repeatability of 6 % or better and an inter- copy; light element; matrix correction; microanalysis; phi-
laboratory reproducibility of 14 % or better are possible. With rho-z; quantitative analysis; spectrum; standardless analysis;
trace elements, and especially with peak overlaps among trace standards; X ray; X-ray microanalysis; ZAF

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