Measuring Silicon in Carbon Steel at Ambient

Temperature Using X-ray Fluorescence to

Address Sulfidation Corrosion
Chevron*
Thermo Scientific**
Daniel Chapman*
Brian Wilson** Materials Engineer*
Business Development Manager**
 Objectives

Practical guidance for • Mechanism overview

inspectors, quality, • Common materials
maintenance, reliability, • Equipment selection
corrosion and operations
personnel on how to use • Accuracy checks
handheld XRF analyzers to • Measurement time
quantify the amount of • Sample preparation
silicon present in carbon • Acceptance criteria
steel components/welds
 Sulfidation Corrosion

• Thins pressure boundary

wall of piping,
components and welds
exposed to hydrocarbon
containing sulfur
compounds at elevated
temperatures
• Accelerated corrosion for
carbon steels containing
less than 0.10wt% silicon
 API 939-C Recommended Practice
• One third of high
temperature sulfidation
corrosion failures result
from low silicon content
• API 939-C chart shows
one company’s corrosion
rate vs. silicon content
• 10 mpy vs. 1 mpy makes
a big difference after
decades of service
 A105
Si 0.10-0.35 Common Materials
Flange
Valve
Olet

Piping
A234-WPB A106
Si 0.10 min Si 0.10 min
Elbow ---------
Tee A53
Reducer No min Si %
 PMI Equipment Selection - XRF

• Portable and lightweight

• User interface friendly
• Analytical performance
• Light element capability
• Accurate and repeatable
• Small spot capability
• Technical training
• Silicon in Fe matrix limit
 Limit of Detection (LOD)

• Lowest concentration of an
analyte in a sample that
can be detected, not
necessarily quantified
• Dependant on time, matrix,
statistical confidence
• Calculated as 3 standard
deviations (99.7%)
 Limit of Quantification (LOQ)

• Lowest concentration of Example:

an analyte in a sample
reliably measured to allow If instrument LOD is 300ppm
quantitative readings LOQ = LOD * 3.33
• Assays with acceptable LOQ = 300ppm * 3.33
precision and accuracy
LOQ = 1000ppm or 0.1wt%
• Typically defined as 3.33
x LOD
• LOD comes from
manufacture
Standard Deviation
 Measurement Time

• Multiple tests may be For a silicon LOD = 0.03wt %

desired to ensure reliability
of the measurement
• Limit of detection (LOD)
improves as a function of
measurement time
at 60 seconds
Reducing time from 60s to
15s, LOD will double
Increasing time will reduce
LOD by square root of
increased time
 Reference Standards

• Define the minimum

analytical requirements
• Silicon % above or below
0.10% threshold
• Select standards that
represent critical range
• Typical values are 0.02%
to 0.35%
 Reference Standards

• Good practice to select

0.05%, 0.10%, 0.20%
• Tested for verification of
instrument accuracy and
repeatability
• Periodic checks validate
testing process
 Sample Preparation

• Basic requirement of • Essential to achieving

quantitative x-ray accurate and reliable
fluorescence (XRF) results
• All surface contamination, • Cannot be emphasized
oxidation, scale, rust, enough, more involved
paint must be removed that typical XRF testing
 Sample Preparation
0.10wt% standard
• Prepped w/ 60 grit • Single thumbprint swipe across
• Good agreement • Contaminated & skewed results
 Sample Preparation

• Smallest amount of
contaminants such as
paint, grease or scale will
yield unreliable results
• Example ~0.008” paint
marker dot applied to
prepped sample surface
• Silicon elevated 3x times
Sample Preparation
 Sample Preparation

• Metal alloys will oxidize

when exposed to
atmospheric conditions
• Oxide coating can affect
reliability of the test
• Creating a high, false
positive reading if not
completely removed
 Sample Preparation

• Consider material
composition and grit 60 grit 80 grit 120 grit
when selecting abrasives
• Lower chromium content
likely heavier oxidation
• 60-80 grit for CS/LA
• ZrAlO recommended
• Do not use silicon carbide
 Rapid cleaning Reduced spark
Spark emission Longer prep time

High speed Low speed

~10,000 rpm <2,000 rpm
 Sample Preparation

• 2” grinding discs work

well with quick change
rubber backing wheel
• Ideally suited for exposed
piping and access via
inspection ports
• Flexible backup pad limits
excess metal removal
 Sample Preparation

• Confirm acceptable
testing locations
• Choose an area relatively
free of pitting
• Confirm adequate
material thickness prior to
surface preparation is a
good practice
 Sample Preparation

• Prepare an area approx.

1”x1” for easy positioning
• Requires positive control
to avoid excess removal
• Work the disc near
parallel to the surface to
avoid dishing
• Remove, replace and Example of over-used abrasive disc
discard used discs often
 Window Inspection

• Inspect analyzer window

periodically and replace
as necessary
• Residue and debris can
build on the window
• Window contamination
can result from constant
sample contact
 Program / Acceptance Criteria

• Aim to identify any components on go/no go basis with

a safety factor
• Consider inclusion of welds in program
• Consider existing as well as new incoming material
• Consider how to handle any components identified as
low Si
 Standard Operating Procedure

• Owner-user should
approve the low silicon
testing process including
equipment selection,
inspection methodology,
and surface preparation
techniques.
• Technicians should be
trained and tested
 Questions and Comments
Daniel Chapman
Chevron ETC
510-242-1726 office
daniel.chapman@chevron.com

Brian Wilson
Thermo Scientific
713-380-1287 cell
brian.k.wilson@thermofisher.com