“HOT TOPICS”
Issue #11, 2005
Spectrometers in Iron Foundries
In today’s ductile iron foundries, the lab is
faced with a large burden of samples. Raw
Material samples, Base iron, post treatment
iron and actual castings are being evaluated
around the clock. Specifications, Standard
Operating Procedures and SPC guide us to
maintain control of the process most of the
time.
The reality is that we are relying on many
factors in the process i.e.: Raw material
supplier is supposed to send you material that
is within specifications, the melt charge
operator remembered to add all the elements,
all the treatment and additives got added to
the treatment vessel and of course the
inoculant actually made it into the metal
stream.
We use a number of tools on the shop floor
and in the lab to help us guide our way and
verify that everything is working properly.
Thermal analysis, chill wedges, nodularity
coupons, micro analysis, combustion analysis
all help but none are as fast as a spectrometer
to provide an indication that the chemical
process is in control.
The spectrometer is one of the most utilized
instruments in the lab yet it is probably the
least understood. To many, this is just a black
box where a sample goes in, push a button
and numbers come out. In order to obtain
reliable numbers that are repeatable, one must
consider many issues in operating a
spectrometer:
Sample taking
Compared to other analytical methods (wet
analysis or combustion methods), an optical
arc-spark spectrometer samples a small area
on the surface of the sample. The spark
excitation source vaporizes a few micrograms
of material to produce an energy release
resulting in an emission of photons. It is
important that this small sample be
representative of the iron that is being
sampled.
Apart from being a defect free sample (no
voids/shrink, slag, sand etc) a Ductile iron
sample must be homogeneous. This means
that the sample must be fully chilled and that
no elements especially Carbon have had a
chance to segregate or form nodules. The
sample has to be thick enough to handle and
grind a surface flat but also be thin enough to
ensure adequate chill in the sample. Many
foundries use copper molds to chill the
samples and some resort to air or water
cooling of the mold to ensure a proper chill. A
micrographic examination will help in
evaluating the suitability of the sample.
Sample type
Base iron, treated iron and post
inoculated iron sample types are easily
obtained in the foundry process using spoon
and copper block assemblies. Some foundries
try to analyze actual pieces of casting with
mixed success. Depending on the
solidification rate and casting section
thickness some elements can be measured but
not to a reliable level. Some foundries will re-
melt the sample in a special induction furnace
or re-heater and pour a sample into a copper
chill block to obtain a good chilled sample.
This significantly improves the reliability of
the results. Note that some Carbon may be
lost in this process .
Many foundries will also use their
spectrometers to analyze their incoming scrap
steel deliveries. Depending on the material
condition (moisture, oily, rusty, flatness etc..)
the success can be mixed. Again, many
foundries will melt the sample down and pour
it into a standard chill block for accurate
results.
Sample preparation
A Flat 60 grit Al2O3 or ZrO2 grinding disk
will normally do a sufficient job of grinding
the sample. Avoid water cooling as moisture
could contaminate the sample while at the
same time avoiding overheating and burning
the sample.
Argon Quality
White or “Milky” burns are an indication that
the area around the sample during the burn
has been contaminated (assuming that the
sample has been ground flat and the test stand
is not worn causing leakage) . Leaks in the
system or impure Argon gas allow
contaminants such as moisture, oxygen or
hydrocarbons enter the exposure area.
Recommendations for good operating
practices include:
- specify ultra high purity Argon gas
from the supplier (99.996% +
pure)
- use liquid argon with an
evaporator (450 lb cylinder)
- never use the last 50-100 lbs of
the cylinder as ice forms in the
bottom will send O2 to the
spectrometer once it thaws out
- have supplier of the gas flush
the cylinder out prior to filling to
remove any built up Oxygen and
moisture.
- use refrigeration grade copper
tubing
- install an electric catalyst gas
purifier
- have a spare Argon bottle (liquid
or gaseous) available to switch to
if there is a problem and verify gas
contamination
Electrical power
- it is recommended that a good
quality isolated electrical feed be
used to supply the instrument
- An isolation transformer with tap
settings to bring the line voltage to
within spectrometer
manufacturer’s specification is
also recommended
Many foundrymen have been enticed to
locate the spectrometer close to the melting
furnaces. It only makes sense to have the
machine close to the action but many have
found that this can lead to disaster:
- vibration
- keeping constant temperature in
the room is difficult. Changing
temperatures lead to expansion
and contraction of the primary
optical tank and subsequently
constant drift requiring
standardization and profiling.
- voltage, frequency fluctuations
- harmonics, stray magnetic fields
from melt furnaces
- Dirt entering instrument
Environmental Control
The optical “tank” that contains the Roland
Circle or Arc is a precise assembly that was
built in the factory and adjusted during field
commissioning to ensure that each diffracted
light beam is aligned with the coordinated
photomultiplier tube (or Solid State Detector).
If the spectrometer lab is subject to large
temperature swings, many have noticed that
the spectrometer will need frequent
standardization (drift correction) or even
Profiling to bring the set-up standards within
allowable limits.
Spectrometer Photomultiplier
housing tubes
Vacuum frame
Slit
region
Excitation
spark
source
stan
Ar flushed
Grating Primary slit
entranced
optics
The cause of this phenomenon is thermal
expansion/contraction of the tank. When there
are temperature swings in the lab, the metal
tank expands or contracts and the optics
become miss-aligned providing poor results.
It is recommended that a spectrometer lab
have a dedicated HVAC system capable of
controlling the temperature (and humidity) to
the manufacturer’s specification during all
ambient and foundry climate conditions.
Some spectrometer manufacturer’s have
resorted to wrapping the optical tank with a
thermostatically controlled heating blanket to
maintain constant temperature.
Spectrometer configuration
Many spectrometer manufacturers supply
equipment that have the capability of
configuring the Pre-burn, Burn and Exposure
times for a category of metal types defined in
the software. For some iron grades where the
matrix is not very homogeneous, these
parameters can be modified to actually micro-
melt a larger sample size and obtain more
accurate results especially for some trace
elements. Modifications to these settings
should be made after extensive testing has
been conducted.
When analyzing elements that have
wavelengths close together, one must
consider the interference factor from
neighboring diffracted light beams. This
typically will happen when the focal length of
the spectrometer is short (0.5 or 0.75 meters
as apposed to a full length machine of 1.0
meters) and/or there are many elements that
are being analyzed and the photomultiplier
tubes are very close together. In most cases,
selecting an alternative wavelength line for a
troublesome element would be resolve this
issue. In most cases the spectrometer supplier
will recommend the optimum line choice for
each element to minimize the interference.
All Spectrometer manufacturers provide an
initial set of calibration curves developed
using their library of acquired CRM standards
(Certified Reference Material). For most
foundries producing normal grades of ductile
iron these calibration curves are adequate. In
recent years, the requirements have changed
for the foundries for a number of reasons:
1) Detrimental tramp elements in
small quantities have surfaces in
many raw material sources
2) Master Alloys and inoculants that
have been introduced contain
small quantities of exotic elements
3) Foundries are producing new alloy
grades of ductile iron for special
applications
Foundries are finding that they must add more
elemental channels to their spectrometers,
find CRMs or RMs (reference materials) or
even home made standards to produce new
calibration curves in the correct operating
range. Special care must be given not to
create interference issues, not extrapolating
above or below the extent of the existing
curves and ensuring that there are enough
points on the line to generate a good curve.
Overall Recommendations for the Foundry:
1) Training – take advantage of the
supplier’s training courses in-
house and at their facility
2) Regular cleaning and maintenance
of the equipment
 3) Participate in round robin testing need for correction
with related foundries, outside labs (standardization)
and Foundry Associations where 7) Perform Gauge R&R testing to
members produce similar grades understand where variation is
of iron coming from on a regular
4) Provide adequate environmental schedule.
controls for the lab as well as
proper voltage regulator and Sources
electrical isolation
5) Specify high purity Argon and Carl Slickers, Automatic Atomic-Emission
train the supplier on how to flush Spectroscopy, Second Edition 1993
and fill the bottles (liquid or ASTM – Optical Emission Spectro-chemical
gaseous) and use a gas purifier. Analysis training Course notes
6) Use control charts to track drift in ARL
the machine over time and identify Spectro Analytical

Tony Thoma, Wescast Industries Inc. Brantford