This document summarizes recent advances in handheld x-ray fluorescence technology for alloy and material testing. It discusses improvements to hardware including more powerful x-ray tubes, improved silicon drift detectors, and advanced pulse processing that enable higher count rates and better resolution. These upgrades allow for faster and more precise material composition analysis. The document also provides examples of how handheld XRF is used for process monitoring and inspection to prevent corrosion and ensure alloy specification compliance in industries like oil and gas production.
Recent Advances in Handheld X-Ray Fluorescence-Based Alloy PMI/Material Testing
1. Recent Advances in Handheld X-Ray Fluorescence-
Based Alloy PMI/Material Testing
Olympus | Alex Thurston
ASNT – Long Beach, CA – October 27, 2016
THE AMERICAN SOCIETY FOR
NONDESTRUCTIVE TESTING
2. Overview
§ XRF Theory and Traditional Applications
§ XRF for PMI and Material Testing
– API Recommended Practices
– Corrosion prediction and prevention examples
§ Recent Innovations in Handheld X-ray Fluorescence (HHXRF)
– Hardware improvements
– X-ray tube, silicon drift detector, pulse processor
– Advancements in spectral processing
– Streamlined user interface and experience
7. OLYMPUS Scientific Solutions
Application Focus: High Temperature Hydrogen Attack (HTHA)
§ Tesoro Explosion: U.S. CHEMICAL SAFETY AND HAZARD INVESTIGATION BOARD
INVESTIGATION REPORT
OLYMPUS Scientific Solutions
8. OLYMPUS Scientific Solutions
Application Focus: HTHA
§ Tesoro Explosion: Recommendations from API
– 2010-08-I-WA-10
– Recommendations per API RP 941: Steels for Hydrogen Service at Elevated
Temperatures and Pressures in Petroleum Refineries and Petrochemical Plants
– Require the use of inherently safer materials to the greatest extent
feasible
– Require verification of actual operating conditions to confirm that
material of construction selection prevents HTHA equipment failure
– Prohibit the use of carbon steel in processes that operate above 400 ºF
and greater than 50 psi hydrogen partial pressure.
– 2010-08-I-WA-11
– Recommendations per API RP 581: Risk-Based Inspection Technology
– Prohibit the use of carbon steel in processes that operate above 400 ºF
and greater than 50 psia hydrogen partial pressure
9. OLYMPUS Scientific Solutions
§ XRF can be used for prevention, NDT and IE technologies can be used for detection
§ https://inspectioneering.com/tag/high+temperature+hydrogen+attack
– “Typically HTHA can be avoided by choosing the proper steel to resist the
combination of hydrogen partial pressure and temperature, or by adjusting the
operating conditions to stay below the Nelson Curve limit for the existing materials of
construction. However, there have been several cases where HTHA was found even
though operating conditions were below the Nelson Curve.”
§ http://www.twi-global.com/technical-knowledge/faqs/material-faqs/what-is-high-
temperature-hydrogen-attack-htha-hot-hydrogen-attack/
– “… the composition of the steel influences the resistance to HTHA; in particular,
elements that tie-up carbon stable precipitates such as Cr, Mo, and V are very
important. Increasing content of such elements increases the resistance to HTHA, so
that chromium steels with more than 5% Cr, and austenitic stainless steels, are not
susceptible to HTHA.”
Application Focus: HTHA
10. API Recommended Practice 578
- Material Verification Program for New and Existing Alloy Piping Systems
§ For users with this practice in place, HHXRF is indispensable
§ Piping alloy grade identification is performed in less than 10 seconds, in
most cases, less than 3 seconds
§ Allows for weld material + parent material analysis before, during, and after
joining
OLYMPUS Scientific Solutions
11. API Recommended Practice 939-C
- Guidelines for Avoiding Sulfidic Corrosion Failures in Oil Refineries
§ Process streams with hydrogen-free, sulfurous material may exhibit
corrosion in carbon steel piping with less than 0.1% Si (McConomy
Curves)
– Increasing Cr content of the alloy can provide increasing resistance to this
form of corrosion
§ Streams with a combination of hydrogen and sulfur-containing materials at
elevated temperature can corrode steels with Cr levels below 12% (i.e. non-
stainless alloys, Couper-Gorman curves)
– Recommended to use 18Cr-8Ni stainless steel to avoid corrosion issues
OLYMPUS Scientific Solutions
12. Flow Accelerated Corrosion (FAC)
§ In carbon steel piping, lines with a high flow rate can affect and remove
native oxide layers present on the alloy surface
– Magnetite or hematite layer compromised
§ Phenomenon occurs as flow direction is impinged, at elbows, tees, and
reducer couplings
§ Ducreaux model specifies that carbon steels with less than 0.04% Cr levels
can be subject to FAC
OLYMPUS Scientific Solutions
13. Residual Alloying Elements
§ HF Alkylation Plants — carbon steel piping with total residual element
content above 0.2% of Cr + Ni + Cu
– Can exhibit advanced corrosion issues when in HF service
OLYMPUS Scientific Solutions
14. HHXRF Future PMI Applications
§ As detection limits decrease, better resolution on critical elemental ranges
helps give user increased confidence
§ Supplier quality tool — used as a tool to aid receiving departments in
identifying material quality issues at the first point of a user’s process
§ Process control and QA/QC — XRF can provide 100% process screening
control
OLYMPUS Scientific Solutions
15. New Developments in HHXRF — Hardware
§ Outer envelope redesign
Ø Environmental resistance
Ø Reliable electronics
– Both aspects enable increased functionality and reliability in harsh
environments
OLYMPUS Scientific Solutions
16. Environmental Resistance —
Envelope Redesign
§ HHXRF can now withstand an IP65
environment
Ø Dust ingress eliminated — “6”
Ø Protected against jets of water,
limited ingress — “5”
Ø Sprays, drips, and mists are no
longer a problem for HHXRF
Ø Vanta™ M series analyzers are IP64
rated
OLYMPUS Scientific Solutions
17. Electronic Reliability — Envelope Redesign
§ HHXRF survives MIL-STD-810G drop testing method
– 4-foot drop (approximates user hand height to ground level)
– Instrument retains user interface and analytical functionality after drop test
OLYMPUS Scientific Solutions
18. New Developments in HHXRF — Olympus Axon™ Technology
X-Ray Tube
X-Ray Detector
X-Ray Pulse Processor
OLYMPUS Scientific Solutions
19. Signal Hardware — Miniature X-Ray Tube
§ X-ray tube optimized to operate near full power
Ø Develops a much higher number of resultant X-rays generated from the
sample
Ø Incoming count rate of X-rays now up to 3x higher than previous
technologies
OLYMPUS Scientific Solutions
20. Signal Hardware — Silicon Drift X-Ray Detector
§ Detector now enables greater throughput of the X-ray signal
Ø Reduction of signal dead-time in detector
Ø More useable counts per test, less rejected signal overall
OLYMPUS Scientific Solutions
§ Detector resolution improved
Ø Resolution decrease enables more precise allocation of X-ray counts and
spectral analysis
21. Signal Hardware — X-Ray Pulse Processor
§ Advances in processor technology enable increased count rates (up to 3x
over previous generation)
§ Extremely low noise floor electronics
§ Less rejected counts from the detector from signal complexities leads to
increased speed in signal processing
§ Improved fundamental parameter calculation engine characteristics
OLYMPUS Scientific Solutions
22. X-Ray Count Rates
Higher count rates
§ Better limit of detection
§ Better precision
§ Faster test
§ Enhanced productivity
§ For a given detector, increasing the OCR requires decreasing the
spectrometer’s peaking time, which increases resolution
§ New DPP algorithms and better resolution enable much shorter peaking
times to be implemented and higher throughput
OLYMPUS Scientific Solutions
Incoming Count RateOutgoingCountRate
23. Improved Precision of Results
§ Precision of the instrument is a function of the count rate
§ With earlier technology, count rates were limited by the throughput of the
detector and pulse processor, requiring the tube to be run below maximum
power
§ New streamlined electronics enable the tube to operate at a higher power
setting
§ Tube operation power is proportional to the amount of X-rays generated
OLYMPUS Scientific Solutions
2-second live
test for each unit
24. Improved Precision of Results
§ Increase in overall count rate across the generated spectrum
§ Increase in precision for each elemental region
§ Better compositional accuracy from resolution gains
§ Testing time needed to achieve accurate and precise results is decreased
due to the higher count rate
OLYMPUS Scientific Solutions
2-second live
test for each unit
25. Improved Resolution
§ Previous technology had a resolution of approx. 150–180eV
§ Theoretical resolution limit of a silicon drift detector is 110–120eV
§ Resolution improvement of nearly 40% towards the theoretical limit
achieved over previous technologies
OLYMPUS Scientific Solutions
26. Improved Resolution Benefits
§ Spectral quantification accuracy improved
– Lower resolution enables counts at specific energies to be better
categorized
§ Elemental X-ray energy overlaps or interferences reduced
– Better resolution of close proximity elements
– Fe-Co-Ni
– Cu-Zn
– Mg-Al-Si
§ Elemental region assignment becomes more focused
– Avoids false positive aspects of other analyte elements in sample
OLYMPUS Scientific Solutions
28. OLYMPUS Scientific Solutions
END USER BENEFITS OF HHXRF ADVANCES
– Sample testing in seconds
– Reliable light element results down to Mg in < 10 seconds
– Most test results in 1–2 seconds
– Improved statistical accuracy of results to confirm composition
– Increased throughput, increased confidence of results
– Near-lab-based equipment results in an ergonomic, portable, and
rugged envelope