Application

Note: 41220
Analysis of Iron and Steel by Optical Emission
ARL 4460 Metals Analyzer

Introduction 2. High alloy steels

Key Words Significant progress has been made in the analysis of iron High alloy steels contain, in addition to iron and carbon,
and steel. Sample analysis time, sensitivity, precision and notable quantities of one or more of the following
• ARL 4460
accuracy have all been substantially improved with the elements: Ni, Cr, Mn, Si, Co, W, Mo and V.
• Optical Emission Thermo Scientific ARL 4460 Metals Analyzer. This category covers steels which are intended for a
Our long experience in metals analysis comes from an wide variety of uses such as:
• Metals Analyzer
installed base of over 10’000 spectrometers worldwide. • Stainless steels
• Iron & Steel The ARL 4460 is the answer to your metallurgical • Tool steels
analysis needs; whether they be incoming material control
• High manganese steels
or metal QC and production analysis. Working 24 hours
a day and 7 days a week, the • High speed steels
ARL 4460 delivers dependable • Special high alloys steels, such as Ni-hard, Ni-resist, etc.
performance year after year.
The ARL 4460 Metals Analyzer Current Controlled Source (CCS)
can determine up to 60 elements The Thermo Scientific Current Controlled Source presents
simultaneously in about 50 seconds. significant advantages in comparison to any other spark
Specific performance is detailed in generator currently used for OES. It is the only servo-
this application summary. controlled “digital source” on the market.
The current waveform is computer controlled and can
Cast irons be selected for each type of metal. The high degree of
From a metallurgical point of view, a distinction can be flexibility in selection of peak current (250 A max.),
made between white cast iron and grey cast iron which frequency (1000 Hz max.) and current waveforms enables
contains free graphite. In alloyed cast irons, alloying the optimization of all analytical figures.
elements such as Ni, Cr, Mn, Cu, etc. are added to The very compact design close to the spark stand, in a
improve hardness, corrosion resistance or engineering Faraday cage, suppresses RF leakage and improves general
properties (Ni-hard, Ni-resist, etc.). stability (less current lost in connecting cables).

Steels Current [A]

Typically steels are divided in two main qualities: Peak (30-250 A)

1. Low alloy steels (≥ 94 % iron)

2. High alloy steels (with notable quantities of Cr, Ni,
Mn, Mo, Co, W, etc.) Plateau (any form: 256 points)

1. Low alloy steels

The total content of the alloying elements is generally less
than 5-7%. The main elements are C (≤ 1.5 %), Si
(≤ 3 %), Mn (≤ 2 %), Cr (≤ 3 %), Mo (≤ 1.5 %), Cu Time [µs]
(≤ 1 %), Ni (≤ 5 %), and V (≤ 1 %). The so-called “free-
cutting steels” with a concentration of 0.2 - 0.3 % S or Pb,
need a special calibration and a specific source condition.
Time Resolved Spectroscopy (TRS) • Global Iron "Small Samples” (including all qualities
In TRS mode, the acquisition takes place during a well- except for free cutting steel)
defined time window (“TRS window”) of each individual • Low Alloy Steel and Free Cutting Steel Small Samples
spark. The optimization of the start and the duration of The global calibration offers more than a sorting
the window make it possible to maximize the signal to program in terms of accuracy and number of analyzed
noise ratio (e.g. in avoiding acquisition during the initial elements. It can be considered as the cheapest solution to
peak current causing high background), which results in analyze all types of samples.
lower detection limits and better precision. They also The use of a global calibration is recommended when
make it possible in certain cases to reduce interferences the program choice function is used.
between atomic/low potential lines and ionic/high The global calibration for small samples can also be
potential lines, improving thus accuracy. used for massive samples with some performance
limitations.
Current [A]

Factory calibration (CARL)

Window#1 The Thermo Scientific optical emission spectrometers can
be factory calibrated for iron and steel utilizing CARL, a
Window#2 very sophisticated multi-variable regression tool that
corrects for matrix effects as well as spectral interferences.
CARL can provide an immediate “turnkey” system which
gives the user the highest accuracy possible. The
calibrations are available for the different qualities given
Time [µs] above. For each quality Thermo Fisher uses certified
reference material (CRM) as standard samples and setting-
Sample preparation up samples (SUS) are delivered with the instrument to
The sample is generally prepared by using a grinding maintain the accuracy of the calibration.
machine. Milling machines are also recommended.
Accuracy
Sample analysis time Precision is only a small part of providing accurate
The analysis time is taken between the start of the analysis analyses. The most important factor is the accuracy and
and the display of its result. quality of the calibration standards. Next is the
development of the calibration curve relative to a specific
MATERIAL CONVENTIONAL ARL 4460 analytical task. Matrix matching and high energy pre-
EXCITATION EXCITATION
burns reduce or eliminate matrix effects and spectral
Steels (except free cutting steels) 27 s 22 s
interferences are significantly reduced by applying
High- and low-alloyed cast irons 31 s 22 s
appropriate corrections.
(except grey cast irons)
The example shown below illustrates the significant
Free cutting steels 68 s 57 s
improvement in the calibration curve thanks to the
Grey cast irons 50-120 s 50-95 s
TRS feature.

5 to 11 seconds can be saved in an environment where

the analysis time is critical.

Calibration summary SEE SEE

Numerous qualities are available for specific types of

alloys, including:
• Low Alloy Steel
• Free Cutting Steel (with S and Pb ≤ 0.3 %)
• Chrome Steel (ferritic stainless steel)
• Chrome-Nickel Steel (austenitic stainless steel)
• Manganese Steel (Mn ≤ 20 %)
• High Speed Steel (Co ≤ 10 %) Element: Cu without TRS Element: Cu with TRS
• Cast Iron (including nodular iron and Ni-hard -
Ni ≤ 7 %)
• High Alloy Cast Iron (Cr ≤ 32 % and Ni ≤ 16 %)
• Nickel Resist (Ni ≤ 35 %)
• Global Iron (including all qualities except for free
cutting steel)
ARL 4460 - Typical detection limits (3 sigma) and precision values (1 sigma) for IRON base
ELEMENT Al As B Bi C Ca Ce Co Cr Cu La Mg Mn Mo N Nb*
TYPICAL DL [ppm] 0.4 0.7 0.2 1 2 0.2 2 0.6 1.3 0.2 0.1 0.3 0.7 1.4 2.7 0.7
GUARANTEED DL [ppm] <1 <1.5 <0.4 <2 <5 <0.3 <4 <1 <2 <0.4 <0.3 <0.5 <1.2 <2 <4.5 <1.5
Level [%] SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD
0.001 0.00003 0.00005 0.00001 0.00005 0.00007 0.00004 0.00015 0.00003 0.00005 0.00002 0.00002 0.00002 0.00005 0.00006 0.00008 0.00002
0.002 0.00004 0.00006 0.00002 0.0001 0.00008 0.00007 0.00015 0.00003 0.00005 0.00002 0.0001 0.00005 0.00007 0.00007 0.00009 0.00002
0.005 0.00006 0.00008 0.00003 0.0001 0.00015 0.00017 0.00015 0.00004 0.00008 0.00004 0.0003 0.00015 0.0001 0.0001 0.00016 0.00004
0.01 0.0001 0.0001 0.00005 0.00015 0.0002 0.0003 0.0003 0.00005 0.0001 0.00006 0.0006 0.00025 0.00012 0.00015 0.00025 0.0001
0.02 0.0002 0.00016 0.0001 0.0003 0.0003 0.0005 0.0005 0.0001 0.00015 0.0001 0.0012 0.0004 0.00015 0.0002 0.0003 0.0002
0.05 0.00045 0.0003 0.00055 0.0012 0.0002 0.00025 0.00025 0.0011 0.0003 0.0004 0.00055 0.0003
0.1 0.0009 0.00045 0.00075 0.00035 0.0004 0.0005 0.002 0.0005 0.0006 0.001 0.0005
0.2 0.002 0.003 0.001 0.0007 0.0007 0.001 0.004 0.0008 0.001 0.002 0.001
0.3 0.0025 0.007 0.0015 0.001 0.0009 0.0015 0.001 0.0015 0.003 0.0015
0.5 0.004 0.013 0.002 0.0016 0.0015 0.0025 0.002 0.002 0.006 0.0025
1 0.008 0.004 0.0035 0.0025 0.005 0.003 0.004 0.005
2 0.008 0.0065 0.004 0.01 0.006 0.006 0.01
3 0.013 0.01 0.005 0.015 0.008 0.008 0.012
4 0.016 0.013 0.0065 0.02 0.01 0.01
5 0.016 0.008 0.025 0.013 0.012
10 0.03 0.015 0.025 0.02
20 0.02
30 0.03
40 0.04

ELEMENT Ni O P Pb S Sb Se Si Sn Ta* Te Ti V W Zn Zr
TYPICAL DL [ppm] 1 20 0.3 0.5 0.7 2 1.5 3 1.5 5 1.5 0.3 0.7 5 0.6 0.6
GUARANTEED DL [ppm] <1.7 <30 <0.8 <1 <1 <3.5 <3 <5 <3 <10 <3.5 <0.6 <1.5 <10 <1.2 <1
Level [%] SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD SD
0.001 0.00008 0.00003 0.00003 0.00003 0.00008 0.00007 0.00006 0.00005 0.0002 0.00006 0.00003 0.00004 0.0003 0.00003 0.0001
0.002 0.00008 0.00003 0.00004 0.00006 0.0001 0.0001 0.00006 0.00006 0.0002 0.00008 0.00003 0.00004 0.0003 0.00003 0.0001
0.005 0.00008 0.0005 0.00006 0.00008 0.00014 0.00012 0.0002 0.00008 0.00008 0.00025 0.00015 0.00005 0.00006 0.0003 0.00004 0.00015
0.01 0.0001 0.0006 0.0001 0.0002 0.00025 0.00015 0.00025 0.0001 0.0001 0.0003 0.00025 0.0001 0.0001 0.0003 0.00007 0.0003
0.02 0.0001 0.001 0.0002 0.0005 0.0005 0.0002 0.0003 0.00015 0.00015 0.0004 0.0002 0.00015 0.0003 0.00012 0.0006
0.05 0.0002 0.002 0.0005 0.0015 0.001 0.0004 0.0005 0.0003 0.0003 0.0008 0.0005 0.0004 0.0004 0.00022 0.0015
0.1 0.0003 0.0009 0.003 0.0025 0.0007 0.0007 0.0005 0.0005 0.0022 0.001 0.0007 0.0006 0.0004 0.0025
0.2 0.0005 0.0015 0.008 0.006 0.001 0.001 0.002 0.0014 0.001 0.004
0.3 0.0007 0.002 0.012 0.01 0.0014 0.003 0.002 0.0015 0.006
0.5 0.0015 0.0035 0.0022 0.005 0.003 0.0025 0.009
1 0.0025 0.006 0.004 0.01 0.005 0.005
2 0.005 0.008 0.02 0.009 0.01
3 0.008 0.012 0.012 0.014
4 0.01 0.015 0.015 0.017
5 0.015 0.02 0.02
10 0.025 0.1 0.035
20 0.045 0.08
30 0.075 0.15
40 0.1

Remarks: This data applies when homogeneous samples are prepared by recommended sample preparation methods.
The precison values given are typical. The guaranteed precision values are 1.5 times higher.
For multibase instruments, some analytical performance may vary based on the analytical line and grating selected.
Guaranteed DLs are calculated at 95 % confidence limit.
Performance for C, N and O can be improved with the so-called CNO option (see dedicated application note).
*DL of Nb if Ti > 0.2 % : 2.4 ppm typical and 3.7 ppm guaranteed.
*DL of Ta if not for low alloy steel analysis: 12 ppm typical and 18 ppm guaranteed.

Performance guarantee The precision is calculated from the formula:

Our company guarantees the precision shown in the above where:
tables using homogeneous samples and recommended i=n
X i the individual readings
2
sample preparation. The list will be updated as Σ(X i -X) X the arithmetic mean of
SD(1σ)= ± i=1 the individual readings
improvements are announced. Please contact your nearest n–1
Thermo Fisher Scientific office for the most recent values. n the number of
determinations
The DL (Detection Limit)) is defined as three times the
standard deviation of the background expressed in
concentration units. The lower limits of quantification (LLQ)
are alloy dependent and are defined in the calibration menus.
 Moving Average Chart: Mn[%]
Options
0.2200 UCL
1. PIM 2
In addition to these
The PIM 2 method permits the determination of soluble/
offices, Thermo Fisher
insoluble aluminum and boron in low alloy steel. It does 0.2100 LSL LCL
Scientific maintains
not need special skills from the operator and replaces a
a network of represen-
costly wet chemistry procedure. 28-12-99
22:46:0
04-01-99
19:07:0
09-01-99
15:20:0
14-11-99
01:08:0
18-01-99
12:51:0
23-01-99
03:50:0
tative organizations
Moving Average Chart: Si[%]
2. Small samples analysis throughout the world.
UCL
This option permits the quantitative determination of 0.0230

wires and small samples with diameters down to 3 mm.,

0.0220
thanks to a special excitation condition developed for this
purpose. Small samples are normally analyzed with more LCL
0.0210
labor intensive and costly methods (ICP, wet chemistry…). 28-12-99 04-01-99 09-01-99 14-11-99 18-01-99 23-01-99
22:46:0 19:07:0 15:20:0 01:08:0 12:51:0 03:50:0 Africa-Other
+27 11 570 1840
3. CNO option
Australia
The CNO option permits the determination of C, N and Conclusion +61 3 9757 4300
O at ultra-low levels, as well as improves the analysis of The ARL 4460 provides not only state-of-the-art technology, Austria
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these elements at low levels, so that no alternative
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fastest method to obtain information related to the ARL SMS-2000 and ARL SMS-3000 Germany
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simultaneously with the steel composition. Spark-DAT can All these features allow you to optimize your
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