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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
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
XRF Theory
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Atomic Representation
K
L
M
Elements Detected by HHXRF
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Mg through Pu detection
The Alloy Process Cycle Traditional Applications for HHXRF
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Alloy users
Recyclers Producers and fabricators
• Petrochemical plants • Power utilities • OEMs • Chemical process Plants
• Stainless • Nickel • Copper • Titanium • Aluminum • Low alloy
• Foundries • Forging operations • Machining operations • Fabrication/assembly • Powder metallurgy
HHXRF Application Studies
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Application Focus: High Temperature Hydrogen Attack (HTHA) § Tesoro Explosion: U.S. CHEMICAL SAFETY AND HAZARD INVESTIGATION BOARD
INVESTIGATION REPORT
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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
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§ 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
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
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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
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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
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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
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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
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New Developments in HHXRF — Hardware
§ Outer envelope redesign Ø Environmental resistance Ø Reliable electronics
– Both aspects enable increased functionality and reliability in harsh environments
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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
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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
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New Developments in HHXRF — Olympus Axon™ Technology
X-Ray Tube
X-Ray Detector
X-Ray Pulse Processor
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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
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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
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§ Detector resolution improved Ø Resolution decrease enables more precise allocation of X-ray counts and
spectral analysis
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
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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
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Incoming Count Rate O
utgo
ing
Cou
nt R
ate
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
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2-second live test for each unit
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
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2-second live test for each unit
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
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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
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Connectivity Features
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Wi-Fi enabled
Bluetooth® enabled
Cloud enabled
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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
§ For additional product information, please visit:
http://www.olympus-ims.com/en/innovx-xrf-xrd/
§ Presenter information: Alex Thurston, Alloy Applications Scientist Email: [email protected]
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