positive metal identification - xrf by alan logan
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PMI in the Petrochemical
Plant and RefineryPlant and Refinery
2009: Niton XL3t GOLDD 7th Generation
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3
Operation of HHXRF
Excitation Source
Atomic Level Process of Fluorescence Production
4
The Complete System
Pulses
From
Detector
Alloy
Sample
Excitation
Source
DSPDetector
Primary X-
Ray Beam
0
0.5
1
1.5
2
2.5
3
3.5
4
Spectra to µP
5
Microprocessor (µP) Display
Data Storage
Fluorescent
X-Rays
10 10.5 11 11.5 12 12.5 13 13.5 14 14.5 15
How it works – 1
� Each individual element produces its own set of characteristic x-rays; the basis for qualitative analysis
� By counting the number of characteristic x-rays of a given element we can determine its concentration; the basis for quantitative analysis
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for quantitative analysis
Results display
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Measured with portable XRF
Not possible with portable XRF, use OES
May require GOLDD technology
Ideal for routine HHXRF
Element Range for Alloy Measurement
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HHXRF Selected Alloying Element Channels
25/30 elements analyzed in alloysNote: Analytical capability is not limited to the elements shown; the full analytical range extends from Mg to U
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427 alloys in grade library
PMI Overview
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PMI Overview
• AutomatedSample
Data entry
• SimplePoint &
•Fast IDWith FPAnalysis
•Small size•Light weight
PowerPowerPlantsPlants
RefineriesRefineries
PMI is Mission Critical for Verification
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• Test tightCorners &
& fillet welds
Point &Shoot
Operation
• Test 800 ° FVibrating
Pipes
•Light weight•Ergonomic
•Design
AerospaceAerospace
ProducersProducersFabricatorsFabricators
Consequences of Using IncorrectMaterials Can Range From
ToToToToToToToTo
12
Why do PMI?
13
Source: Marsh and McLennen (property protection and risk consultants)
PMI can Prevent the Largest Losses
“41% of the 170 largest losses in the
hydrocarbon process industry
resulted from failures of piping
14
resulted from failures of piping
systems…”
Second International Symposium on the Mechanical Integrity of Process Piping
January 1996, Houston, TX, USA
PMI Cycle Overview
15
PMI in Petrochem Industry analytically speaking…
5 0
6 0
7 0
8 0
9 0
1 0 0
Pe
rce
nt
co
nc
en
tra
tio
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We are facing a We are facing a
seemingly seemingly
impossible task:impossible task:
analyzing with analyzing with
sufficient sufficient
accuracy and accuracy and
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NIC
KE
L 2
00
Mo
nel
500
Inco
625
Inco
750
Inco
825
Hay
nes
230
RA
333
Has
tell
oy
B-2
Has
tell
oy
C-2
76
Has
tell
oy
X
Ste
llit
e 6B
Ste
llit
e 18
8
N iC r
F eM o
M nC u
WC o
N bT i
A l
0
1 0
2 0
3 0
4 0
Pe
rce
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nc
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precision to be precision to be
able to able to
distinguish one distinguish one
alloy from many alloy from many
thousands of thousands of
others others
(estmates are up to (estmates are up to 50,000 alloys grades 50,000 alloys grades in use today)in use today)
Fortunately, Petrochem Alloys Are Few
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PMI in Petrochem Industry analytically speaking…con’t
We are facing a second We are facing a second seemingly impossible seemingly impossible task:task:
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Correcting for an Correcting for an awesome variety of awesome variety of samples forms, sizes samples forms, sizes and shapesand shapes
FP with Normalization
� Automatically normalizes for size,
shape, curvature and distance (up
to ~6 mm)
• Mathematical iteration continues until all measured elements add to ~100%
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PMI Tool in Petrochem Industry
•• Automatically corrects Automatically corrects for an intimidating set of for an intimidating set of environmental and environmental and sampling conditionssampling conditions
•• Ambient heatAmbient heat
•• Ambient coldAmbient cold
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� Temp up to 850oF / 440oC
• extension handle keeps hand well away from heat
• “volcano suit” protects plastic case
• Velcro flip cover for ease of viewing
•• Ambient coldAmbient cold
•• RainRain
•• Hot samplesHot samples
•• Vibrating samplesVibrating samples
•• High noiseHigh noise
•• Small samplesSmall samples
Hotfoot Adapter
Remote Display Option
� Wireless data
transfer up to 300 ft
� Remote control of
analyzer
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PMI Testing of Welds with WeldSpotTM and CamShotTM
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Thermo Scientific Niton XL3t XRF Analyzer Analyzer with GOLDD Technology
Geometrically Optimized Large Area Drift
Detector
GOLDD Technology
�Thermo Scientific presents
the Niton XL3t XRF
Analyzer with GOLDDTechnology
�This new analyzer delivers
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• Light element detection (Mg, Al, Si, P, S) without helium or vacuum purging
• The lowest limits of detection and the fastest analysis available
• True lab-quality performance in a handheld instrument
GOLDD – SDD (Silicon Drift Detector)
� Similar to Si PIN, but unique electrode array that guides electrons
to very low capacitance anode
� This means that the detector
• Has a short rise time, achieving high count rates with minimal pile up
• Provides better resolution
• Has lower noise
25
GOLDD with external Field Effect Transistor (FET)• Shorter processing, lower cost
• No partial charge collection under FET
• No effects on FET from SDD
• Up to 450,000 counts per second input
GND C1C2
UBACK Homogeneous thin entrance window
-V
drift–field Anode
GOLDD: Quantum Advancements with XL3 Analyzers
� 2 W, 50 kV X-ray tube, SDD GOLDD
• Improved sensitivity, speed, accuracy, precision, stability and confidence
• New ability to analyze residual elements
• New ability to determine light elements
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Significantly lower LOD’s for critical elements
Optimized Excitation
� To take advantage of a detector with a higher count rate, more fluorescent x-rays should be produced by the sample
� That is achieved using a higher voltage x-ray tube
• Niton XL3t: 50kV
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• Niton XL3t: 50kV
• Typical older technology: 40 or 45kV
• Excitation intensity is 2x more sensitive to increase in high voltage compared to other factors (current, Z of anode material). Increasing the excitation voltage by 25% has a 50% greater effect than increasing the tube current by a similar amount
Optimized Geometry
� To take advantage of a detector with a higher count rate, you want to collect more of the fluorescent x-rays from the sample
� For the same size detector, the
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� For the same size detector, the closer it is to the sample, the more fluorescent x-rays it will detect
� The Niton XL3t was designed with this optimized geometry
Large Area Drift Detector
� A large detector will collect more fluorescent x-rays than a small detector
� The Niton XL3t employs a unique 25 mm2 detector, instead of an off-the-shelf 10 mm2 detector
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off-the-shelf 10 mm detector
� Therefore, the Niton XL3t collects 2.5 times more signal
The GOLDD Advantage
� This all adds up to the GOLDDAdvantage
� 10X better than conventional Si PIN detectors
� 2.5X better than analyzers with
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� 2.5X better than analyzers with off-the-shelf SDD detectors
Twin Alloys and SolutionsGuideline to PMI Alloys that Mix (or May Mix) with XRF based on UNS Spec Ranges
ALLOY/ ELEMENT Ti V Cr Mn Fe Ni Cu Cb Mo Other
9Cr(F9) - 8 - 10 1.0* Bal 0.9 - 1.1
9Cr+V(F91) 0.2 - 0.5 8 - 10 1.0* Bal 0.9 - 1.1
Long test times on XL3p (30-40s). XL3t with low filter will pick up low V content in seconds
M405( R) - 2.0* 2.5* 63 - 70 Bal -
M500(K) 0.3 -0.8 1.5* 2.0* 63 - 70 Bal Al 2.3 - 3.15
Long test times on XL3p (30-40s). XLt3 with low filter will separate R/K Monel in seconds. Al determination requires GOLDD Unit
SS304 18 - 20 2.0* Bal 8 - 10.5 ~0.5* C 0.08*
SS304L 18 - 20 2.0* 8 - 12 C 0.03*
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SS304L 18 - 20 2.0* 8 - 12 C 0.03*
SS321 0.15-0.45 17 - 19 2.0* Bal 9 - 12
304/304L C (OES) / Long test times on XL3p (30-40s). XL3t 304/321 Ti with low filter in seconds / Remove 301 from alloy grade library
15-5 14 - 15.5 3.5-5.5 2.5-4.5 0.15-0.45
17-4 15.5 - 17.5 3 - 5 3 - 5 0.15-0.45
Usually unseparable unless Cr, Ni, Cu values at nominal composition
F11 1 - 1.5 0.3 - 0.6 Bal 0.44 - 0.65 Si 0.5 -1.0
F12 0.8 - 1.1 0.3 - 0.6 Bal 0.44 - 0.65 Si 0.1 0.6
Long Mtime for Cr / Si determination requires GOLDD Unit
4130 0.8 - 1.1 0.4 - 0.6 Bal 0.15-0.25 C 0.28-0.33
4140 0.8 - 1.1 0.75-1.0 Bal 0.15-0.25 C 0.38-0.43
Not possible with XL3p / Use XL3t with 20s measuring time, or GOLDDD Unit with 5s test time* Indicates maximum (Mo not specified in 304 but most always present)
Thermo Scientific NITON Analyzer Turnkey PMI Kit
Extension
Pole
Hotfoot
Button Reader
CMB Buttons
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PMI-15
Certest
Wireless
Printer
Wireless
Bar Code
Reader
GPSEPI
Manual
Button
mounted
On plate
�Computerized Monitoring Buttons ( CMB )-API 570 3rd
Edition , Page 30
�PMI data are traceable to the point of installation
�XRF Analyzer data file can tie Report Documentation to
the field PI&D drawings
CMB Buttons: Traceability to Field Components
33
PMI of Hot Pipes and Difficult to Access Areas
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Extension Pole /Tri-Pod
• Variable pole length
• Dual Electronic Triggers
• Clip on Tri-Pod adapter for
hands-free analysis of
samples on ground or table
XL3t/p without heat shield: 315o C
XL3t with heat shield : 450o C
XL3p with heat shield : 540o C
API 578Material Verification Program for New
and Existing Alloy Piping Systems
May 1999
API RP-578 (section 1)
� 1. Scope• Guidelines for material
QC of ferrous and non-
ferrous alloys
36
• C steel not included
• Covers owners /users,
and indirectly vendors,
fabricators, contractors
• Owner must define
roles and responsibilities
of each above
API Recommended Practice 578 (section 2 and 3)
� 2. References
• API 570 Piping Inspection Code, Publ. 581 RBI, ASME Boiler
and Pressure Vessel Code, B31.3 Process Piping, PFI ES22
Color Coding
37
� 3. Definitions
• See full report for glossary of definitions
� 4. Extent of Verification
• Owner must establish written program for PMI
including up to 100% PMI for higher risk systems
• Must provide for review of:
API Recommended Practice 578 (section 4)
38
• Must provide for review of:
� Third party testing
� Fabrication assembly testing
• Cannot substitute mill test report for PMI
� Examples of components covered
• Pipes lengths
• Pipe fittings
• Flanges
• Forgings
• Process valves
API Recommended Practice 578 (section 4 cont)
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• Process valves
• Pressure containing welds
• Instruments
• Weld overlays or cladding
• Bolting
• Expansion joints and bellows
� PMI of welding consumables
• PMI one electrode per lot
• Compare markings on balance
• PMI of weld metal or button is alternative
� PMI of longitudinal pipe and weld fittings
API Recommended Practice 578 (section 4 cont)
40
� PMI of longitudinal pipe and weld fittings
• Verify base metal and weld metal
� PMI of autogenous welds
• PMI on base metal only
� PMI of components from distributor
• Higher degree of testing due to handling mix-up potential
� Existing piping systems
• In service but procedures were not in accord with above
• PMI limited to pressure containing components and
attachments
API Recommended Practice 578 (section 4 cont)
41
attachments
• Owner determines if retro PMI appropriate and for
prioritizing testing
• Prioritizing considerations
• Likelihood of mix based on past verification program
• Consequences of failure
• Reason for alloy spec (corrosion, etc)
• Historical data on past issues with the process unit or plant
• See API 581 (RBI) for more detailed discussion
� Carbon steel substitutions in LA systems
• Greatest number of mixes have been C-steel in place of Cr-Mo steels
• SS, Monels, and non-ferrous mix is easier to spot (appearance, weldability)
� Other Factors
• Site specific experience
• Past construction and maintenance practices
API Recommended Practice 578 (section 4 cont)
42
• Past construction and maintenance practices
• Past PMI procedures - lax vs rigorous
• Reason for material specified – how critical?
• May not be mission critical (SS used for oil purity)
� Component prioritization factors
• Some systems have higher likelihood of mix*
• Pump and check valve warm-up and bypass lines
• Small dia. piping & welds (less than 2”)
• Valves and removable devices (discs, spacers, gaskets, etc)
API Recommended Practice 578 (section 4 cont)
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• Thermowells
• Bolting
• Piping as part of packaged system
• Components without ASTM stamp
* Note: especially in older plants (author’s anecdotal experience -- data not extracted from API 578)
� Factors in determining extent of PMI
• Historical inspection PMI records
• Number of plant modifications
• Material control at time of construction or modification
• Material PMI program quality during construction and
fabrication
• Likelihood of corrosion/degradation
API Recommended Practice 578 (section 4 cont)
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• Likelihood of corrosion/degradation
• Consequence of release
� Material Verification Program as element of
maintenance systems
• Owner must establish written procedures program for repair
maintenance activities as well as for receiving and suppliers
� 5. Material Verification Program Test Methods
• Intended to ID the alloy, not to establish conformance
• Existing visual stamps and markings not a substitute for PMI
� Methods
• P-XRF
• Principle
API Recommended Practice 578 (section 5)
45
• Principle
• Interpretation of results
� Spectral match or composition percentage
� Not possible to detect all elements (S, C)
• P-OES
• Principle
• Interpretation of results
� Spectral match or composition percentage
� May be able to detect S, C
� Chem lab
• Owner approved lab using XRF, OES or wet chemical methods
• Accuracy higher than needed for PMI
• May be destructive to sample
• May be costly and slow
� Chemical spot tests
• Produces colors to indicate presence of specific elements
API Recommended Practice 578 (section 5 cont)
46
• Produces colors to indicate presence of specific elements
• Slow and subjective
� Resistivity testing
• Thermoelectric principle, comparative test only
• Not capable of consistently sorting LA and austenitic SS’s
� Other
• Eddy current, EM, etc., qualitative only; not specific
� Equipment calibration
• Accuracy verification: follow mfg ‘s recommendations; or
owner must provide procedure
� Precision
• Repeatability: must be consistent with test objectives;
owner must establish acceptance criteria
� Personnel qualifications
• Operator must be knowledgeable in all aspects of test
API Recommended Practice 578 (section 5 cont)
47
• Operator must be knowledgeable in all aspects of test
method and operation
• Operator qualifications must be approved by owner
� Safety issues
• PMI method: must include review of any mechanical prep
and it’s effect on sample (integrity)
• Arcing equipment: will require Hot Work permit (OES)
• Chemical tests: take appropriate cautions in use of
chemicals
� 6. Evaluation of PMI Test Results
• Methods for material acceptance
• Confirm alloying elements against relevant spec (ASTM, ASME, etc)
• Classify by qualitative sort (ID only)
• Material out of spec can be accepted if owner (knowledgeable person) evaluates damage
mechanisms and confirms performance is OK
API Recommended Practice 578 (section 6)
48
mechanisms and confirms performance is OK
• If material is rejected based on portable or qualitative
method a more accurate method can allow acceptance*
• Dissimilar metal welds must take into account dilution
effect
• If representative sample of a lot is rejected, extend
testing to rest of lot
* Modern P-XRF analyzers rival lab methods
� 7. Marking and record keeping
• Material ID process
• Materials should be ID’ed by alloy designation (grade) or composition
� Acceptable methods
• Color coding
• Low stress stamp
• Document PMI result and location (drawing)
API Recommended Practice 578 (section 7)
49
• Document PMI result and location (drawing)
• Color Coding/Marking
• Record according to PFI ES22
• Marking components
• Specify
� Life of marking legibility
� If for temporary use, can be semi-permanent paint
� Material certifications (mill reports, CoC’s)
• Not substitute for PMI
� Shop and field test documentation
• Individuals performing PMI testing must follow owner approved test
procedures
� New and existing piping system documentation
• Must keep PMI records as long as piping exists in original location
API Recommended Practice 578 (section 7 cont)
50
� PMI test record information
• PMI procedure used
• Date
Instrument ID or serial number
• Name and company of test person
• Result of tests
• Basis and action for resolution
• Documentation of criteria for prioritizing piping systems for PMI testing
� PMI test procedures
• Must include
• Techniques
• Equipment calibration
• Qualification requirements for PMI test personnel
• Test methodology
API Recommended Practice 578 (section 7 cont)
51
• Test methodology
• Documentation requirements
� Traceability to field components
• All test record info must be traceable to point of
installation
Why PMI is So Critical to Process Safety Management
� It is too Easy to Mix up Alloys with Serious Consequences
� Without PMI Serious Accidents Will Happen
� The OHSA (Occupational Health and Safety Administration) SafetyRecord for Key Industries Handling Highly Hazardous Chemicals is telling:
• The Refinery Safety Record is Three Times Worse than the combined Record of the Next Three Vulnerable Industries over the same time period
52
the Next Three Vulnerable Industries over the same time period
• Many of the Serious Incidents have involved Improper or Lack of PMI of Critical Refinery Alloy Components
• Injuries, Deaths, and Financial Costs have been substantial since 1992:
• Injuries ─ 250
• Deaths ─ 52
• Financial Losses ─ Many Tens of Million of Dollars
� Not Only the PetroChemical Industry, but Many Others are Dependent on Good PMI—Utility, DOD, Aerospace, BioTech, Critical System and Subsystem Manufacturing
Why do PMI?
� Explains How OSHA Instruction-CLP 03-00-004 Nation Emphasis Program (NEP)
Applies to The Refining Industry
53
�
Source: Marsh and McLennen (property protection and risk consultants)
PMI Can Prevent The Largest Losses
� Process Safety Management (PSM) 29CFR1910.119 With Proper Material Verification
Program and Training
“41% of the 170 largest losses in
the hydrocarbon process industry
resulted from failures of piping
systems…”Second International Symposium on the Mechanical Integrity of Process Piping
54
� Understand & Apply API Recommended Practice 578
Positive Material Identification (PMI) Guidelines
Second International Symposium on the Mechanical Integrity of Process Piping
January 1996, Houston, TX, USA
�According to OSHA’s Data Base:
• Since May 1992 (36) Fatality/Catastrophe (36) Fatality/Catastrophe (FAT/CAT) incidents related to HHC have Occurred
• Incidents include 52 Employee Deaths 52 Employee Deaths and 250 Employee Injuries, 98 of which required Hospitalization
Reasons Why
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Injuries, 98 of which required Hospitalization
• The number of “Refinery” Incidents SurpassesSurpasses the Combined Total of the Next 3 Highest Industries Next 3 Highest Industries over the same period, and many are due to Lack of or Faulty PMI
� Chemical Manufacturing-12 FAT/CAT
� Industrial Organic Chemical Manufaturing-12 FAT/CAT
� Explosives Manufacturing-11 FAT/CAT
�Standard API-570-Piping Inspection Code
�Standard API-510-Pressure Vessel Inspection Code
�Standard API-653-Storage Tank Inspection Code
�Recommended Practice API-RP-578-Material
American Petroleum InstituteAPI
56
�Recommended Practice API-RP-578-Material
Verification Program-MVP/PMI
�Recommended Practice –API 571-HF ALKY
�Recommended Practice—API 939-C-Sulfidation
RAGAGEP
� Priority for API 578 2nd Edition:
� Residual Elements in Carbon Steels in Hydrofluoric Acid Alkylation Units: Note: Carbon Steels in HF Acid service have been reported to suffer increased corrosion rates based on the Residual Elements (RE) in steels. In general, it has been reported that steels with a high RE content are likely to suffer enhanced corrosion attack. Operators should review the potential impact of this in HF service. A guideline is that for base metal of C> 0.18% wt% and Cu + Ni + Cr,
Inspection Program for HF ALKYAll Refineries
57
guideline is that for base metal of C> 0.18% wt% and Cu + Ni + Cr, 0.15% wt % is optimum. These values are critical as the type and concentrations to be measured will directly affect the analytical methods operations need to adopt.
� API RP 571—Pages 12,38
� Priority for API PR-578—2nd Edition
� Process Units Susceptible to Sulfidation: Note: Carbon Steels with low silicon (0.10%) content can corrode at an accelerated rate when exposed to hydrogen-free sulfidation conditions. There phenomena are discussed more extensively in API 571 and API RP 939-C. Operators with assets at risk from this type of degradation should consider the risks and the requirements to apply PMI control in order to determine Silicon
Inspection Program for Low SiAll Refineries
58
and the requirements to apply PMI control in order to determine Silicon levels and the extent to which the material may corrode.
High Temperature Sulfidic Corrosion-API RP-939-C
59
Low SiLow Si--33%,PMI33%,PMI--18%,Specification Break18%,Specification Break--17%17%
GOLDD Alloy PMI
� Stainless Steels for PMI of low Z elements, e.g.,
• Si in Zecor alloy at ~6%
• Al in 13-8Mo at 1%,
• 17-7 and 301 separation by 1% Al,
• 303/304 and 410/416 separation by ~0.3% S
� HF Alkylation units guideline for base metal of C> 0.18% wt% and Cu + Ni + Cr = 0.15% or less as optimum for minimizing flow accelerated
60
+ Ni + Cr = 0.15% or less as optimum for minimizing flow accelerated corrosion
• LOD for sum is 600 ppm (0.06%) at 10 sec per filter
� Process Units Susceptible to Sulfidation: Carbon Steels with low silicon (0.10%) content can corrode at an accelerated rate when exposed to hydrogen-free sulfidation conditions.
• Si LOD is 400 ppm (0.04%) in C steels at 15s per filter using He purge
GOLDD HF Alkylation, cont.
Al Oxide disc used with a right angle grinder (<10 sec)
approx. 0.004” removed
Cu Ni Cr RE Sum
0.050 0.078 0.084 0.212
61
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