ASTM E2465-23

Standard Test Method for Analysis of Ni-Base Alloys by Wavelength Dispersive X-Ray Fluorescence Spectrometry

SIGNIFICANCE AND USE
5.1 This procedure is suitable for manufacturing control and for verifying that the product meets specifications. It provides rapid, multi-element determinations with sufficient accuracy to assure product quality. The analytical performance data included may be used as a benchmark to determine if similar X-ray spectrometers provide equivalent precision and accuracy, or if the performance of a particular spectrometer has changed.
SCOPE
1.1 This test method covers the analysis of nickel and cobalt based alloys by wavelength dispersive X-ray fluorescence spectrometry for determination of the following elements:    
Element  
Composition Range  
Aluminum  
0.0X to X.XX  
Chromium  
0.XX to XX.XX  
Copper  
0.0X to XX.XX  
Cobalt  
0.XX to XX.XX  
Hafnium  
0.0X to 0.XX  
Iron  
0.XX to XX.XX  
Manganese  
0.XX to X.XX  
Molybdenum  
0.0X to XX.XX  
Nickel  
XX.XX to XX.XX  
Niobium  
0.XX to X.XX  
Phosphorus  
0.00X to 0.0XX  
Silicon  
0.0X to 0.XX  
Tantalum  
0.00X to X.XX  
Titanium  
0.XX to X.XX  
Tungsten  
0.XX to X.XX  
Vanadium  
0.00X to 0.XX  
1.2 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.  
1.3 This method has been interlaboratory tested for the elements and quantification ranges specified in 1.1. The ranges in 1.1 indicate intervals within which results have been demonstrated to be quantitative by the interlaboratory study. It may be possible to extend this method to other elements or different composition ranges provided that a method validation study as described in Guide E2857 is performed and that the results of this study show that the method extension is meeting laboratory data quality objectives.  
1.4 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.  
1.5 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

• Status: Published
• Publication Date: 31-Oct-2023
• ICS: 77.040.20 - Non-destructive testing of metals
• ICS: 77.120.50 - Titanium and titanium alloys
• Technical Committee: E01 - Analytical Chemistry for Metals, Ores, and Related Materials
• Drafting Committee: E01.08 - Ni and Co and High Temperature Alloys

Relations

• Replaces: ASTM E2465-19 - Standard Test Method for Analysis of Ni-Base Alloys by Wavelength Dispersive X-Ray Fluorescence Spectrometry
• Effective Date: 01-Nov-2023
• Referred By: ASTM F2063-18 - Standard Specification for Wrought Nickel-Titanium Shape Memory Alloys for Medical Devices and Surgical Implants
• Effective Date: 01-Nov-2023
• Referred By: ASTM E1473-22 - Standard Test Methods for Chemical Analysis of Nickel, Cobalt, and High-Temperature Alloys
• Effective Date: 01-Nov-2023
• Referred By: ASTM F3049-14(2021) - Standard Guide for Characterizing Properties of Metal Powders Used for Additive Manufacturing Processes
• Effective Date: 01-Nov-2023
• Referred By: ASTM B994/B994M-22 - Standard Specification for Nickel-Cobalt Alloy Coating
• Effective Date: 01-Nov-2023

Overview

ASTM E2465-23 is the standard test method established by ASTM International for the analysis of nickel-base (Ni-base) and cobalt-base alloys using wavelength dispersive X-ray fluorescence (WDXRF) spectrometry. This widely-recognized method enables rapid, reliable, and multi-element analysis, ensuring product quality and verification against specifications in industrial settings. By following the procedures outlined in ASTM E2465-23, users can assess the composition of alloys with sufficient accuracy for manufacturing control, quality assurance, and ongoing equipment performance monitoring.

Key Topics

• Scope of Elements: The method covers the quantitative determination of multiple elements commonly found in Ni-base and Co-base alloys. These include aluminum, chromium, copper, cobalt, hafnium, iron, manganese, molybdenum, nickel, niobium, phosphorus, silicon, tantalum, titanium, tungsten, and vanadium.
• Analytical Range: Each element’s composition range is defined, supporting multi-element analysis across a variety of high-temperature superalloys.
• Method Validation: The procedure has been thoroughly tested in interlaboratory studies to confirm its accuracy and reproducibility within specified element ranges. Extension to additional elements or ranges can be validated as described in ASTM guides.
• Instrument Requirements: The procedure relies on wavelength dispersive X-ray fluorescence spectrometers designed for metals analysis. It emphasizes calibration using certified reference materials, and addresses correction for matrix and spectral line overlaps using mathematical models.
• Precision and Benchmarking: The included analytical performance data serve as a benchmark to compare other X-ray spectrometers and to identify calibration drift or equipment performance changes over time.
• Safety Considerations: To ensure safe operation, the standard highlights adherence to radiation safety regulations and equipment manufacturer guidelines.

Applications

ASTM E2465-23 is essential for:

• Manufacturing and Quality Control: Fast, accurate alloy composition analysis during production to verify that products meet strict material specifications.
• Product Certification: Ensuring compliance with industry and customer requirements for alloy content.
• Process Monitoring: Ongoing performance tracking of alloys during processing and over the lifetime of equipment.
• Laboratory Benchmarking: Establishing data reliability across different labs and instruments, supporting ISO/IEC 17025 accreditation.
• Material Research and Development: Facilitating alloy development and process optimization by providing precise elemental analysis.

Typical industries benefiting from ASTM E2465-23 include aerospace, power generation, automotive, chemical processing, and other sectors utilizing nickel-based superalloys and other high-performance materials.

Related Standards

To ensure comprehensive and consistent analysis, ASTM E2465-23 references and aligns with several other key ASTM and international standards:

• ASTM E29: Practice for using significant digits in test data
• ASTM E1172: Practice for describing and specifying WDXRF spectrometers
• ASTM E1361 and E1621: Guides for correcting interelement effects and elemental analysis by WDXRF
• ASTM E2857: Guide for validating analytical methods
• ASTM E2972: Guide for in-house reference materials in metals analysis
• ISO/IEC 17025: General requirements for the competence of testing and calibration laboratories

These related documents provide further guidance on calibration, validation, terminology, and performance evaluation to support accurate and reliable WDXRF analysis in line with industry best practices.

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Keywords: ASTM E2465-23, Ni-base alloy analysis, cobalt-base alloys, wavelength dispersive X-ray fluorescence, WDXRF spectrometry, elemental analysis, manufacturing control, alloy certification, ASTM standards, quality assurance, XRF.

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: E2465 − 23
Standard Test Method for
Analysis of Ni-Base Alloys by Wavelength Dispersive X-Ray
Fluorescence Spectrometry
This standard is issued under the fixed designation E2465; 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 1.5 This international standard was developed in accor-
dance with internationally recognized principles on standard-
1.1 This test method covers the analysis of nickel and cobalt
ization established in the Decision on Principles for the
based alloys by wavelength dispersive X-ray fluorescence
Development of International Standards, Guides and Recom-
spectrometry for determination of the following elements:
mendations issued by the World Trade Organization Technical
Element Composition Range
Barriers to Trade (TBT) Committee.
Aluminum 0.0X to X.XX
Chromium 0.XX to XX.XX
2. Referenced Documents
Copper 0.0X to XX.XX
Cobalt 0.XX to XX.XX
2.1 ASTM Standards:
Hafnium 0.0X to 0.XX
E29 Practice for Using Significant Digits in Test Data to
Iron 0.XX to XX.XX
Manganese 0.XX to X.XX
Determine Conformance with Specifications
Molybdenum 0.0X to XX.XX
E135 Terminology Relating to Analytical Chemistry for
Nickel XX.XX to XX.XX
Niobium 0.XX to X.XX Metals, Ores, and Related Materials
Phosphorus 0.00X to 0.0XX
E1172 Practice for Describing and Specifying a Wavelength
Silicon 0.0X to 0.XX
Dispersive X-Ray Spectrometer
Tantalum 0.00X to X.XX
E1361 Guide for Correction of Interelement Effects in
Titanium 0.XX to X.XX
Tungsten 0.XX to X.XX
X-Ray Spectrometric Analysis
Vanadium 0.00X to 0.XX
E1601 Practice for Conducting an Interlaboratory Study to
1.2 The values stated in SI units are to be regarded as
Evaluate the Performance of an Analytical Method
standard. No other units of measurement are included in this
E1621 Guide for Elemental Analysis by Wavelength Disper-
standard.
sive X-Ray Fluorescence Spectrometry
E2857 Guide for Validating Analytical Methods
1.3 This method has been interlaboratory tested for the
E2972 Guide for Production, Testing, and Value Assignment
elements and quantification ranges specified in 1.1. The ranges
of In-House Reference Materials for Metals, Ores, and
in 1.1 indicate intervals within which results have been
Other Related Materials
demonstrated to be quantitative by the interlaboratory study. It
2.2 Other Documents:
may be possible to extend this method to other elements or
ISO/IEC 17025 General requirements for the competence of
different composition ranges provided that a method validation
testing and calibration laboratories
study as described in Guide E2857 is performed and that the
2.3 U.S. Government Standards:
results of this study show that the method extension is meeting
10 CFR Part 19 Notices, Instructions and Reports to Work-
laboratory data quality objectives.
ers: Inspection and Investigations
1.4 This standard does not purport to address all of the
10 CFR Part 20 Standards for Protection Against Radiation
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro-
3. Terminology
priate safety, health, and environmental practices and deter-
3.1 Definitions—For definitions of terms used in this test
mine the applicability of regulatory limitations prior to use.
method, refer to Terminology E135.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
This test method is under the jurisdiction of ASTM Committee E01 on contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
Analytical Chemistry for Metals, Ores, and Related Materials and is the direct Standards volume information, refer to the standard’s Document Summary page on
responsibility of Subcommittee E01.08 on Ni and Co and High Temperature Alloys. the ASTM website.
Current edition approved Nov. 1, 2023. Published February 2024. Originally Available from the U.S. Nuclear Regulatory Commission, Public Document
approved in 2006. Last previous edition approved in 2019 as E2465 – 19. DOI: Room, One White Flint North, 11555 Rockville Pike, Rockville, MD 20852-2738,
10.1520/E2465-23. http://www.nrc.gov.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
E2465 − 23
4. Summary of Test Method 7.2 Wavelength Dispersive X-ray Spectrometer, designed for
X-ray fluorescence analysis. Refer to Practice E1172 for a
4.1 Specimens and calibration reference materials are fin-
detailed discussion on the spectrometer components necessary
ished to a clean, uniform surface. These are irradiated by
for analysis.
highenergy X-ray photons in a spectrometer designed for this
function. Secondary X-rays are fluoresced from the materials.
8. Reagents and Materials
Using analyzing crystals, this radiation is diffracted and di-
rected toward a detector that measures the count rates at
8.1 Detector Gases—Only gas-flow proportional counters
specified wavelengths. The output(s) of the detector(s) is
require a detector gas. Use the gas and purity of gas specified
integrated or counted for a fixed time or until the counts reach
by the instrument manufacturer. Typical gases specified include
a certain fixed number. Either a fixed-channel (simultaneous)
P-10 or P-5. P-10 consists of a mixture of 90 % argon and 10 %
spectrometer or a goniometer (sequential) spectrometer, or an
methane, and P-5 consists of a mixture of 95 % argon and 5 %
instrument combining both one or more fixed-channels and one
methane. Other gases may be specified as well.
or more goniometers shall be used.
4.2 Calibrations for each element to be determined are
9. Reference Materials
prepared using reference material measurement responses and
9.1 Certified Reference Materials—These are produced and
assigned mass fractions. Mass fractions of the elements in the
sold by national metrology institutes, international research
specimens are determined by relating the measured responses
institutes, and commercial sources. It is preferred that calibra-
for the specimens to the calibrations.
tions be characterized using certified reference materials.
5. Significance and Use
9.2 Reference Materials—It is recognized that certified
5.1 This procedure is suitable for manufacturing control and
reference materials may not be available to fully cover the
for verifying that the product meets specifications. It provides
calibration ranges required for analysis of the variety of nickel
rapid, multi-element determinations with sufficient accuracy to
and cobalt alloy systems produced. For this reason, it is
assure product quality. The analytical performance data in-
acceptable to augment calibrations with non-certified reference
cluded may be used as a benchmark to determine if similar
materials such as in-house reference materials. Reference
X-ray spectrometers provide equivalent precision and
materials developed using the guidance of Guide E2972 may
accuracy, or if the performance of a particular spectrometer has
be suitable for this purpose.
changed.
6. Interferences
10. Hazards
6.1 Line overlaps, interelement, and matrix effects or some
10.1 All governing federal, state, and local regulations shall
combination of these exist for some of the scope elements.
be observed during installation and operation of X-ray fluores-
Table 1 lists some of the common line overlaps encountered in
cence spectrometers in the United States. The user should
nickel and cobalt alloys. Modern X-ray spectrometers provide
follow the guidelines for safe operation given in equipment
software for generation of mathematical corrections to model
manufacturer operating manuals. U.S. Nuclear Regulatory
the effects of line overlaps, interelement, and matrix interfer-
standards for ionizing radiation as found in the Code of Federal
ences. The user of this method may choose to use these
Regulations, 10 CFR Part 19 and 10 CFR Part 20 provide
mathematical corrections for analysis. Guide E1621 provides
recommendations on the safe use of X-ray producing equip-
an extensive overview of mathematical interference correction
ment.
methods which may be available in the spectrometer software.
10.2 Exposure to excessive quantities of high energy radia-
7. Apparatus
tion such as those produced by X-ray spectrometers is injurious
7.1 Specimen Preparation Equipment:
to health. The operator should take appropriate actions to avoid
7.1.1 Surface Grinder, with abrasive belts or disks capable
exposing any part of their body, not only to primary X-rays, but
of providing a flat, uniform surface on the reference materials
also to secondary or scattered radiation that might be present.
and test specimens. Aluminum oxide, Silicon carbide, and
The X-ray spectrometer should be operated in accordance with
Zirconium oxide belts and discs with a grit size user between
the regulations governing the use of ionizing radiation. Manu-
60 and 180 have been found suitable.
facturers of X-ray fluorescence spectrometers generally build
7.1.1.1 The laboratory should consider the potential for
appropriate shielding/safety interlocks into X-ray equipment
surface contamination of the specimens by any media chosen
during manufacturing that minimize the risk of excessive
for grinding. For example, the use of an aluminum oxide belt
radiation exposure to operators. Operators should not attempt
or disk may significantly contaminate the surface of “soft”
to bypass or defeat these safety devices. Only authorized
alloys with aluminum. A surface preparation precision study
personnel should service X-ray spectrometers.
could help evaluate the media chosen.
10.3 Monitoring Devices, either film badges or dosimeters
7.1.2 Lathe or milling machine, as an alternative to abrasive
may be worn by all operating and maintenance personnel.
surfacing of test specimens. A lathe or milling machine may be
Safety regulations shall conform to applicable local, state, and
used to produce a uniform surface. Carbide type inserts have
been found acceptable tooling for this purpose. federal regulations.
E2465 − 23
11. Preparation of Reference Materials and Test 12.2 Measurement Conditions:
Specimens
12.2.1 Tube Power Supply—The power supply conditions
(kV/mA) should be optimized for the elements being deter-
11.1 The user must choose a measurement area or diameter
mined.
from the options built into the spectrometer. All test specimens
and reference materials must have a flat surface of greater
12.2.1.1 In general, excitation of lighter mass elements is
diameter than the chosen viewed area.
favored by higher current, lower voltage settings and excitation
of heavier mass elements is favored by lower current, higher
11.2 Prepare the reference materials and test specimens to
provide a clean, flat uniform surface to be exposed to the X-ray voltage settings. It is desirable, but not mandatory, that the
beam. One surface of a reference material may be designated power be held constant for all elements determined via a single
by the producer as the certified surface. The same preparation
program.
medium shall be used for all reference materials and test
12.2.1.2 Once established the optimized current and voltage
specimens.
settings shall be used for generation of calibration curves and
11.3 Refinish the surface of the reference materials and test for all subsequent specimen measurements.
specimens as needed to eliminate oxidation.
12.2.2 Detection System—The detection systems will con-
sist of masks, collimators, diffraction crystals, and detectors.
12. Preparation of Apparatus
The crystals, X-ray lines, and detectors specified in Table 1
12.1 Prepare and operate the spectrometer in accordance
have been found to provide acceptable performance for analy-
with the instrument manufacturer’s guidance.
sis of nickel and cobalt alloys. Set up the instrument to analyze
NOTE 1—It is not within the scope of this test method to prescribe
using the available detection systems. Manufacturers are now
minute details relative to the preparation of the apparatus. For detailed
offering synthetic multi-layer structures which may provide
operating protocols pertaining to a specific spectrometer, refer to the
equivalent performance to natural crystals. Alternatives to the
manufacturer’s operating manual and published application notes.
detection system configurations described in Table 1 may be
12.1.1 Start-up—Turn on the power supply and electronic
used if performance is acceptable.
circuits and allow sufficient time for instrument stabilization
prior to taking measurements.
TABLE 1 Suggested Detection Parameters
A B
Element Line Designation Wavelength (nm) Crystal Detector Potential Line Overlaps
Aluminum Kα 0.8340 PET, EDDT Sc,FP
Chromium Kα 0.2291 L1 SP,Sc,FP V
Cobalt Kα 0.1790 L1,L2 SP,Sc,FP
Copper Kα 0.1542 L1,L2 SP,Sc,FP Ta
Hafnium Lα 0.1570 L1,L2 SP,Sc
Iron Kα 0.1937 L1,L2 SP,Sc
Manganese Kα 0.2103 L1, SP,Sc,FP Cr
Molybdenum Kα 0.0711 L1,L2 Sc
Nickel Kα 0.1659 L1,L2 SP,Sc,FP
Niobium Kα 0.0748 L1,L2 Sc
Phosphorus Kα 0.06158 Ge FP,SP Mo
Silicon Kα 0.7126 PET,InSb FP,SP
Tantalum Lα 0.1522 L1,L2 SP,Sc
Titanium Kα 0.2750 L1, SP,Sc,FP
Tungsten Lα 0.1476 L1,L2 SP,Sc
Vanadium Kα 0.2505 L1, SP,Sc,FP Ti
Zirconium Kα 0.0787 L1,L2 Sc
L1 = LiF200 SP = Sealed Proportional
L2 = LiF220 Sc = Scintillation
FP = Flow Proportional
A
Line designations listed in this method are based on the Siegbahn system, which has been superseded by the IUPAC Nomenclature System for X-Ray Spectrometry,
Jenkins,R., Manne, R., Robin, R., and Senemaud, C., Pure& Appl. Chem., 63(5), 1991, pp. 735-746.
B nd
Wavelengths listed in this method are taken from X-ray and Absorption Wavelengths and Two-Theta Tables, 2 Edition; E.W. White and G. G. Johnson, Jr; ASTM Data
Series DS 37A; American Society of Testing and Materials; May 1970, pp. inserted wavelength table.
12.2.3 Counting Time—Collect a sufficient number of measured intensity (counts per second) and the minimum
counts so that the precision of the analysis will not be number of required counts (that is, 10 000 or 40 000).
significantly affected by the variation in the number of counts Alternatively, measurement times of 10 s for each of the
collected. A minimum of 10 000 counts is required for 1 % elements are a good starting point.
relative standard uncertainty of X-ray counting and 40 000 for 12.2.4 Additional spectrometer considerations:
0.5 % relative standard uncertainty. If fixed time measurements 12.2.4.1 Measuring conditions must be selected so that the
are used, the measurement times can be derived from the manufacturer-specified, detector count rate maximum is not
E2465 − 23
exceeded when materials with mass fractions at the calibration 13.1.3 Given the complex nature of nickel and cobalt alloys,
maximum are analyzed. Verify this before analyzing calibra- it is highly recommended that matrix and line overlap correc-
tion reference materials. Some manufacturers may recommend
tions be calculated and applied to the calibration data using the
the use of attenuators to reduce radiation reaching the detector.
instrument software.
Use them if necessary.
13.1.3.1 Instrument software typically provides a math-
12.2.4.2 Some manufacturers may recommend the use of
ematical expression describing the quality of the curve fit.
filters, for example, primary beam filters or finer detector
Examples of expressions commonly used are the root mean
collimators, to reduce tube radiation reaching the detector. Use
square difference between known and calculated mass
them if necessary.
fractions, a chi-square parameter, or correlation coefficient.
12.2.4.3 When a gas-flow proportional counter is used,
The root mean square calculation could be augmented to yield
adjust the flow of the gas in accordance with the equipment
a weighted residual error. Refer to the instrument manufactur-
manufacturer’s recommendations.
er’s operating guide or other references on statistical math-
12.2.4.4 Simultaneous instruments will have a fixed crystal
ematics for an in-depth discussion of these calculations.
and detector assembly for each element being detected. A
13.1.3.2 If a significant number of calibration materials are
sequential instrument will have a goniometer that allows
available for an element, it may be possible to calculate the
crystal and detector combinations to be configured by the
matrix corrections empirically.
laboratory. Some instruments may employ a combination of
fixed detector(s) and goniometer(s) to achieve required wave- 13.1.3.3 If the number of calibration materials is minimal, it
may be preferable to use matrix corrections calculated using an
length coverage. These three instrument designs are allowed by
this method. algorithm based on the fundamental parameters of X-ray
12.2.4.5 Once the measurement conditions are established, fluorescence.
the laboratory shall verify the calibration of the 2-theta angle
13.1.3.4 Both approaches to generation of calibration curve
and the pulse height distribution for each element established
corrections are allowed by this method.
in the analytical program.
13.1.3.5 For detailed information on correction of interele-
12.2.4.6 Most sequential spectrometer software allows for
ment effects in X-ray Spectrometric Analysis refer to Guide
the correction of effects of background radiation on the analyte
E1361. Information on correction of spectral line overlap in
peak intensity. Use of background correction is allowed by this
wavelength dispersive X-ray spectrometry can be found in
method. If used, one or more “background points” are selected
Guide E1621.
in the region of the analyte peak and counted for a software
defined period of time. Care must be taken in the selection of 13.2 Drift Correction (Standardization)—Generally a drift
these points, as it is desirable that these points represent the correction protocol is established to allow the use of the
background affecting the analyte intensity. Avoid setting back-
calibration over an extended period. With a properly designed
ground points on obviously structured regions of the back- protocol it may be possible to use a calibration curve set for
ground. The software calculates and applies the correction to
numerous years. If used, establish the instrument drift correc-
the analyte raw intensity.
tion (standardization) protocol at the time of calibration, using
12.2.5 Ancillary Parameters:
the software function designed for this purpose. Some manu-
12.2.5.1 Most instruments allow the option of spinning the
facturers software allows the use of a previously established
sample cup. Spin the sample if this option is allowed. If the
drift control protocol with new developed measurement meth-
sample is not rotated during measurement, effects resulting
ods. In this case, it is acceptable to use the established drift
from the interaction of the X-rays with specimen crystal phases
correction (standardization) protocol.
or grinding striations or both may significantly bias analytical
13.2.1 For drift control, materials are measured and the
results. Crystal phases can cause diffraction features that may
responses are used by the software to calculate mathematical
interfere with analyte peaks or background. Differences in
adjustments, either to the slope or both to the slope and
orientation of grinding striations can significantly affect mea-
intercept of a calibration curve. A correction is typically
sured count rates.
calculated and applied for each element being determined.
13. Calibration and Drift Correction (Standardization)
13.2.2 To monitor the calibration slope for changes, select
materials which contain a significant amount of the elements
13.1 Calibration:
being monitored. These materials should generate a count rate
13.1.1 Using the conditions given in Section 12, measure a
on the order of the count rate observed for of the higher mass
series of reference materials covering the required mass
fraction reference materials used for calibration. The analysis
fraction range for each element to be quantified. A minimum of
response for these materials is used to calculate the calibration
three reference materials shall be used for each element. A
slope adjustment. To monitor the calibration intercept, the lab
greater number of reference materials will be required if the
may select materials with low amount of the elements being
user chooses to perform mathematical corrections for interele-
monitored. The analytical response of these materials will be
ment effects.
used to calculate a calibration intercept adjustment. The count
13.1.2 Prepare a calibration curve for each element being
determined. Refer to Guide E1621. The instrument software rates for th
...

This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: E2465 − 19 E2465 − 23
Standard Test Method for
Analysis of Ni-Base Alloys by Wavelength Dispersive X-Ray
Fluorescence Spectrometry
This standard is issued under the fixed designation E2465; 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
1.1 This test method covers the analysis of Ni-base nickel and cobalt based alloys by wavelength dispersive X-ray Fluorescence
Spectrometry for the fluorescence spectrometry for determination of the following elements:
Element Composition Range
Manganese 0.06 % to 1.6 %
Phosphorus 0.008 % to 0.015 %
Silicon 0.08 % to 0.6 %
Chromium 1.6 % to 22 %
Nickel 23 % to 77 %
Aluminum 0.20 % to 1.3 %
Molybdenum 0.03 % to 10 %
Copper 0.007 % to 2.5 %
Titanium 0.11 % to 3.0 %
Niobium 0.55 % to 5.3 %
Iron 0.17 % to 46 %
Tungsten 0.06 % to 0.50 %
Cobalt 0.04 % to 0.35 %
Element Composition Range
Aluminum 0.0X to X.XX
Chromium 0.XX to XX.XX
Copper 0.0X to XX.XX
Cobalt 0.XX to XX.XX
Hafnium 0.0X to 0.XX
Iron 0.XX to XX.XX
Manganese 0.XX to X.XX
Molybdenum 0.0X to XX.XX
Nickel XX.XX to XX.XX
Niobium 0.XX to X.XX
Phosphorus 0.00X to 0.0XX
Silicon 0.0X to 0.XX
Tantalum 0.00X to X.XX
Titanium 0.XX to X.XX
Tungsten 0.XX to X.XX
Vanadium 0.00X to 0.XX
NOTE 1—Unless exceptions are noted, ranges can be extended by the use of suitable reference materials. Once these element ranges are extended they
must be verified by some experimental means. This could include but not limited to Gage Repeatability and Reproducibility studies, Interlaboratory
Round Robin studies, or both. Once these studies are completed, they will satisfy the ISO/IEC 17025 requirements for capability.
This test method is under the jurisdiction of ASTM Committee E01 on Analytical Chemistry for Metals, Ores, and Related Materials and is the direct responsibility of
Subcommittee E01.08 on Ni and Co and High Temperature Alloys.
Current edition approved Oct. 1, 2019Nov. 1, 2023. Published November 2019February 2024. Originally approved in 2006. Last previous edition approved in 20132019
as E2465E2465 – 19.–13. DOI: 10.1520/E2465-19.10.1520/E2465-23.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
E2465 − 23
1.2 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.3 This method has been interlaboratory tested for the elements and quantification ranges specified in 1.1. The ranges in 1.1
indicate intervals within which results have been demonstrated to be quantitative by the interlaboratory study. It may be possible
to extend this method to other elements or different composition ranges provided that a method validation study as described in
Guide E2857 is performed and that the results of this study show that the method extension is meeting laboratory data quality
objectives.
1.4 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.
1.5 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.
2. Referenced Documents
2.1 ASTM Standards:
E29 Practice for Using Significant Digits in Test Data to Determine Conformance with Specifications
E135 Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
E1172 Practice for Describing and Specifying a Wavelength Dispersive X-Ray Spectrometer
E1361 Guide for Correction of Interelement Effects in X-Ray Spectrometric Analysis
E1601 Practice for Conducting an Interlaboratory Study to Evaluate the Performance of an Analytical Method
E1621 Guide for Elemental Analysis by Wavelength Dispersive X-Ray Fluorescence Spectrometry
E2857 Guide for Validating Analytical Methods
E2972 Guide for Production, Testing, and Value Assignment of In-House Reference Materials for Metals, Ores, and Other
Related Materials
2.2 Other Documents:
ISO/IEC 17025 General requirements for the competence of testing and calibration laboratories
2.3 U.S. Government Standards:
10 CFR Part 19 Notices, Instructions and Reports to Workers: Inspection and Investigations
10 CFR Part 20 Standards for Protection Against Radiation
3. Terminology
3.1 Definitions—For definitions of terms used in this test method, refer to Terminology E135.
4. Summary of Test Method
4.1 The test specimen is finished to a clean, uniform surface, then irradiated with an X-ray beam of high energy. The secondary
X-rays produced are dispersed by means of crystals and the intensities are measured by suitable detectors at selected wavelengths.
The outputs of the detectors in voltage pulses are counted. Radiation measurements are made based on the time required to reach
a fixed number of counts, or on the total counts obtained for a fixed time (generally expressed in counts or kilocounts per unit time).
4.1 Mass fractions of the elements are determined by relating the measured radiation of unknown specimens to analytical
calibrations prepared with suitable reference materials. Specimens and calibration reference materials are finished to a clean,
uniform surface. These are irradiated by highenergy X-ray photons in a spectrometer designed for this function. Secondary X-rays
are fluoresced from the materials. Using analyzing crystals, this radiation is diffracted and directed toward a detector that measures
the count rates at specified wavelengths. The output(s) of the detector(s) is integrated or counted for a fixed time or until the counts
reach a certain fixed number. Either a fixed-channel (simultaneous) spectrometer or a sequential goniometer (sequential)
spectrometer, or an instrument combining both one or more fixed-channels and one or more goniometers shall be used.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
Available from the U.S. Nuclear Regulatory Commission, Public Document Room, One White Flint North, 11555 Rockville Pike, Rockville, MD 20852-2738,
http://www.nrc.gov.
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4.2 Calibrations for each element to be determined are prepared using reference material measurement responses and assigned
mass fractions. Mass fractions of the elements in the specimens are determined by relating the measured responses for the
specimens to the calibrations.
5. Significance and Use
5.1 This procedure is suitable for manufacturing control and for verifying that the product meets specifications. It provides rapid,
multi-element determinations with sufficient accuracy to assure product quality. The analytical performance data included may be
used as a benchmark to determine if similar X-ray spectrometers provide equivalent precision and accuracy, or if the performance
of a particular spectrometer has changed.
6. Interferences
6.1 Interelement or matrix effects Line overlaps, interelement, and matrix effects or some combination of these exist for some of
the elements listed. Mathematicalscope elements. Table 1 correction may be used to solve for these effects. Various mathematical
correction procedures are commonly utilized (see lists some of the common line overlaps encountered in nickel and cobalt alloys.
Modern X-ray spectrometers provide software for generation of mathematical corrections to model the effects of line overlaps,
interelement, and matrix interferences. The user of this method may choose to use these mathematical corrections for analysis.
Guide E1361E1621). Any of these procedures that achieves analytical accuracy equivalent to that provided by this test method is
acceptable. provides an extensive overview of mathematical interference correction methods which may be available in the
spectrometer software.
7. Apparatus
7.1 Specimen Preparation Equipment:
7.1.1 Surface Grinder or Sander With Abrasive Belts or Disks, or Lathe, Grinder, with abrasive belts or disks capable of providing
a flat, uniform surface on the reference materials and test specimens. Aluminum oxide and zirconiumoxide, Silicon carbide, and
Zirconium oxide belts and discs with a grit size ofuser between 60 and 180 have been found suitable.
7.1.1.1 The laboratory should consider the potential for surface contamination of the specimens by any media chosen for grinding.
For example, the use of an aluminum oxide belt or disk may significantly contaminate the surface of “soft” alloys with aluminum.
A surface preparation precision study could help evaluate the media chosen.
7.1.2 Lathe or milling machine, as an alternative to abrasive surfacing of test specimens. A lathe or milling machine may be used
to produce a uniform surface. Carbide type inserts have been found acceptable tooling for this purpose.
7.2 Excitation Source:
7.2.1 Tube Power Supply, providing a constant potential or rectified power of sufficient energy to produce secondary radiation of
the specimen for the elements specified. The generator may be equipped with a line voltage regulator and current stabilizer.
7.2.2 X-ray Tubes, with targets of various high-purity elements that are capable of continuous operation at required potentials and
currents and that will excite the elements to be determined.
7.2 Wavelength Dispersive X-ray Spectrometer, designed for X-ray fluorescence analysis and equipped with specimenanalysis.
Refer to Practice E1172 holders and a specimen chamber. The chamber shall contain a specimen spinner, and must be equipped
for vacuum or helium-flushed operation for the determination of elements of atomic number 20 (calcium) or lower.for a detailed
discussion on the spectrometer components necessary for analysis.
7.3.1 Analyzing Crystals, flat or curved crystals with optimized capability for the diffraction of the wavelengths of interest. The
use of synthetic multilayer structures can also be found in some state-of-the-art equipment.
7.3.2 Collimators or Slits, for controlling the divergence of the characteristic X-rays. Use in accordance with the equipment
manufacturer’s recommendations.
7.3.3 Detectors, sealed-gas, gas-flow, and scintillation counters, or equivalent.
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7.3.4 Vacuum System, providing for the determination of elements whose radiation is absorbed by air (for example, silicon,
phosphorus, and sulfur). The system shall consist of a vacuum pump, gage, and electrical controls to evacuate the optical path, and
maintain a controlled pressure, usually 13 Pa (100 mm Hg) or less, controlled to 63 Pa (20 mm Hg). A helium-flushed system
is an alternative to a vacuum system.
7.4 Measuring System, consisting of electronic circuits capable of amplifying and integrating pulses received from the detectors.
For some measurements, a pulse height selector in conjunction with the detectors may be used to remove high order lines and
background. The system shall be equipped with an appropriate device.
8. Reagents and Materials
8.1 Detector Gases—Only gas-flow proportional counters require a detector gas. Use the gas and purity of gas specified by the
instrument manufacturer. Typical gases specified include P-10 or P-5. P-10 consists of a mixture of 90 % argon and 10 % methane
90 % argon and 10 % methane, and P-5 consists of a mixture of 95 % 95 % argon and 5 % 5 % methane. Other gases may be
specified as well.
9. Reference Materials
9.1 Certified Reference Materials Materials—are available from These are produced and sold by national metrology institutes,
international research institutes, and commercial sources. It is preferred that calibrations be characterized using certified reference
materials.
9.2 Reference Materials with matrices similar to that of the test specimens and containing varying amounts of the elements in the
scope of this test method may be used provided they have been analyzed using validated standard methods of test. These reference
materials shall be homogeneous and free of voids and porosity.
9.2 Reference Materials—The reference materials shall cover the mass fraction ranges of the elements being sought. A minimum
of three reference materials shall be used for each element. A greater number of reference materials may be required if the analyst
chooses to performIt is recognized that certified reference materials may not be available to fully cover the calibration ranges
required for analysis of the variety of nickel and cobalt alloy systems produced. For this reason, it is acceptable to augment
calibrations with non-certified reference materials such as in-house reference materials. Reference materials developed using the
guidance of Guide E2972 mathematical corrections for interelement effects (see Guide may be suitable for this purpose.E1361).
10. Hazards
10.1 All governing federal, state, and local regulations shall be observed during installation and operation of X-ray fluorescence
spectrometers in the United States. The user should follow the guidelines for safe operation given in equipment manufacturer
operating manuals. U.S. Nuclear Regulatory standards for ionizing radiation as found in the Code of Federal Regulations, 10 CFR
Part 19 and 10 CFR Part 20 shall be observed at all X-ray emission spectrometer installations in the United States. It is also
recommended that operating and maintenance personnel follow the guidelines of safe operating procedures given in similar
handbooks on radiation safety.provide recommendations on the safe use of X-ray producing equipment.
10.2 Exposure to excessive quantities of high energy radiation such as those produced by X-ray spectrometers is injurious to
health. The operator should take appropriate actions to avoid exposing any part of their body, not only to primary X-rays, but also
to secondary or scattered radiation that might be present. The X-ray spectrometer should be operated in accordance with the
regulations governing the use of ionizing radiation. Manufacturers of X-ray fluorescence spectrometers generally build appropriate
shielding/safety interlocks into X-ray equipment during manufacturing that minimize the risk of excessive radiation exposure to
operators. Operators should not attempt to bypass or defeat these safety devices. Only authorized personnel should service X-ray
spectrometers.
10.3 Monitoring Devices, either film badges or dosimeters may be worn by all operating and maintenance personnel. Safety
regulations shall conform to applicable local, state, and federal regulations.
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11. Preparation of Reference Materials and Test Specimens
11.1 The analystuser must choose a measurement area or diameter from the options built into the spectrometer. All test specimens
and reference materials must have a flat surface of greater diameter than the chosen viewed area.
11.2 Prepare the reference materials and test specimens to provide a clean, flat uniform surface to be exposed to the X-ray beam.
One surface of a reference material may be designated by the producer as the certified surface. The same preparation medium shall
be used for all reference materials and test specimens.
11.3 Refinish the surface of the reference materials and test specimens as needed to eliminate oxidation.
12. Preparation of Apparatus
12.1 Prepare and operate the spectrometer in accordance with the instrument manufacturer’s instructions.guidance.
NOTE 1—It is not within the scope of this test method to prescribe minute details relative to the preparation of the apparatus. For a description and specific
details concerning the operation of a particulardetailed operating protocols pertaining to a specific spectrometer, refer to the manufacturer’s
manual.operating manual and published application notes.
12.1.1 Start-up—Turn on the power supply and electronic circuits and allow sufficient time for instrument warm-upstabilization
prior to taking measurements.
12.2 Tube Power Supply—The power supply conditions should be set in accordance with the manufacturer’s recommendations.
12.2.1 The voltage and current established as optimum for the X-ray tube power supply in an individual laboratory shall be
reproduced for subsequent measurements.
12.3 Proportional Counter Gas Flow—When a gas-flow proportional counter is used, adjust the flow of the P-10 gas in accordance
with the equipment manufacturer’s instructions. When changing P-10 cylinders, the detectors should be adequately flushed with
detector gas before the instrument is used. After changing P-10 cylinders, check the pulse height selector in accordance with the
manufacturer’s instructions.
12.2 Measurement Conditions—Conditions: The K-L (Kα) lines for each element are used, except for tungsten. For tungsten,
2,3
the L -M (Lα) line is used. When using a sequential spectrometer, measurement angles shall be calibrated in accordance with the
3 5
manufacturer’s guidelines.
12.2.1 Tube Power Supply—The power supply conditions (kV/mA) should be optimized for the elements being determined.
12.2.1.1 In general, excitation of lighter mass elements is favored by higher current, lower voltage settings and excitation of
heavier mass elements is favored by lower current, higher voltage settings. It is desirable, but not mandatory, that the power be
held constant for all elements determined via a single program.
12.2.1.2 Once established the optimized current and voltage settings shall be used for generation of calibration curves and for all
subsequent specimen measurements.
12.2.2 Crystals and Detectors—Detection System—The following crystals and detectors are suggesteddetection systems will
consist of masks, collimators, diffraction crystals, and detectors. The crystals, X-ray lines, and detectors specified in Table 1for the
elements indicated: have been found to provide acceptable performance for analysis of nickel and cobalt alloys. Set up the
instrument to
Element Crystal Detector
Chromium L1,L2 SP,Sc,FP
Cobalt L1,L2 SP,Sc,FP
Copper L1,L2 SP,Sc,FP
Manganese L1,L2 SP,Sc,FP
Molybdenum L1,L2 Sc
Nickel L1,L2 SP,Sc,FP
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Element Crystal Detector
Niobium L1,L2 Sc
Phosphorus Ge FP,SP
Silicon PET,InSb FP,SP
Titanium L1,L2 SP,Sc,FP
Aluminum PET Sc,FP
Iron L1,L2 SP,Sc
Tungsten L1,L2 SP,Sc
L1 = LiF200 SP = Sealed Proportional
L2 = LiF220 Sc = Scintillation
FP = Flow Proportional
analyze using the available detection systems. Manufacturers are now offering synthetic multi-layer structures which may
provide equivalent performance to natural crystals. Alternatives to the detection system configurations described in Table 1
may be used if performance is acceptable.
TABLE 1 Suggested Detection Parameters
A B
Element Line Designation Wavelength (nm) Crystal Detector Potential Line Overlaps
Aluminum Kα 0.8340 PET, EDDT Sc,FP
Chromium Kα 0.2291 L1 SP,Sc,FP V
Cobalt Kα 0.1790 L1,L2 SP,Sc,FP
Copper Kα 0.1542 L1,L2 SP,Sc,FP Ta
Hafnium Lα 0.1570 L1,L2 SP,Sc
Iron Kα 0.1937 L1,L2 SP,Sc
Manganese Kα 0.2103 L1, SP,Sc,FP Cr
Molybdenum Kα 0.0711 L1,L2 Sc
Nickel Kα 0.1659 L1,L2 SP,Sc,FP
Niobium Kα 0.0748 L1,L2 Sc
Phosphorus Kα 0.06158 Ge FP,SP Mo
Silicon Kα 0.7126 PET,InSb FP,SP
Tantalum Lα 0.1522 L1,L2 SP,Sc
Titanium Kα 0.2750 L1, SP,Sc,FP
Tungsten Lα 0.1476 L1,L2 SP,Sc
Vanadium Kα 0.2505 L1, SP,Sc,FP Ti
Zirconium Kα 0.0787 L1,L2 Sc
L1 = LiF200 SP = Sealed Proportional
L2 = LiF220 Sc = Scintillation
FP = Flow Proportional
A
Line designations listed in this method are based on the Siegbahn system, which has been superseded by the IUPAC Nomenclature System for X-Ray Spectrometry,
Jenkins,R., Manne, R., Robin, R., and Senemaud, C., Pure& Appl. Chem., 63(5), 1991, pp. 735-746.
B nd
Wavelengths listed in this method are taken from X-ray and Absorption Wavelengths and Two-Theta Tables, 2 Edition; E.W. White and G. G. Johnson, Jr; ASTM Data
Series DS 37A; American Society of Testing and Materials; May 1970, pp. inserted wavelength table.
12.2.3 Counting Time—Collect a sufficient number of counts so that the precision of the analysis will not be significantly affected
by the variation in the counting statistics. number of counts collected. A minimum of 10,00010 000 counts is required for one
percent relative precision of the counting statistics and 40,000 for one-half percent relative. 1 % relative standard uncertainty of
X-ray counting and 40 000 for 0.5 % relative standard uncertainty. If fixed time measurements are used, the measurement times
can be derived from the measured intensity (counts per second) and the minimum number of required counts (that is, 10,000 or
40,000).10 000 or 40 000). Alternatively, measurement times of 10 s 10 s for each of the elements are a good starting point.
12.2.4 Additional spectrometer considerations:
12.2.4.1 Measuring conditions must be selected so that the manufacturer-specified, detector count rate maximum is not exceeded
when materials with mass fractions at the calibration maximum are analyzed. Verify this before analyzing calibration reference
materials. Some manufacturers may recommend the use of attenuators to reduce radiation reaching the detector. Use them if
necessary.
12.2.4.2 Some manufacturers may recommend the use of filters, for example, primary beam filters or finer detector collimators,
to reduce tube radiation reaching the detector. Use them if necessary.
12.2.4.3 When a gas-flow proportional counter is used, adjust the flow of the gas in accordance with the equipment manufacturer’s
recommendations.
12.2.4.4 Simultaneous instruments will have a fixed crystal and detector assembly for each element being detected. A sequential
instrument will have a goniometer that allows crystal and detector combinations to be configured by the laboratory. Some
instruments may employ a combination of fixed detector(s) and goniometer(s) to achieve required wavelength coverage. These
three instrument designs are allowed by this method.
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12.2.4.5 Once the measurement conditions are established, the laboratory shall verify the calibration of the 2-theta angle and the
pulse height distribution for each element established in the analytical program.
12.2.4.6 Most sequential spectrometer software allows for the correction of effects of background radiation on the analyte peak
intensity. Use of background correction is allowed by this method. If used, one or more “background points” are selected in the
region of the analyte peak and counted for a software defined period of time. Care must be taken in the selection of these points,
as it is desirable that these points represent the background affecting the analyte intensity. Avoid setting background points on
obviously structured regions of the background. The software calculates and applies the correction to the analyte raw intensity.
12.2.5 Ancillary Parameters:
12.2.5.1 Most instruments allow the option of spinning the sample cup. Spin the sample if this option is allowed. If the sample
is not rotated during measurement, effects resulting from the interaction of the X-rays with specimen crystal phases or grinding
striations or both may significantly bias analytical results. Crystal phases can cause diffraction features that may interfere with
analyte peaks or background. Differences in orientation of grinding striations can significantly affect measured count rates.
13. Calibration and Drift Correction (Standardization)
13.1 Calibration—Calibration: Using the conditions given in Section 12, measure a series of reference materials that cover the
required mass fraction ranges. Use at least three reference materials for each element. Prepare an analytical calibration for each
element being determined (refer to Guide E1621). For information on correction of interelement effects in X-ray Spectrometric
Analysis refer to Guide E1361. Information on correction of spectral line overlap in wavelength dispersive X-ray spectrometry can
be found in Guide E1621.
13.1.1 Using the conditions given in Section 12, measure a series of reference materials covering the required mass fraction range
for each element to be quantified. A minimum of three reference materials shall be used for each element. A greater number of
reference materials will be required if the user chooses to perform mathematical corrections for interelement effects.
13.1.2 Prepare a calibration curve for each element being determined. Refer to Guide E1621. The instrument software will provide
the calibration models used to calculate the calibration curve.
13.1.3 Given the complex nature of nickel and cobalt alloys, it is h
...