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Introduction
Carbon steels are by far the most frequently used steels. More than 85% of the steel produced in the
US is carbon steel. These steels are classified by their carbon content. Table 1 shows the
classification of carbon steels and some typical uses.

Type Carbon Content Typical Uses

Low < 0.30% Auto body panels, Wire products
Medium 0.30 -0.60% Axles, Gears, Crankshafts
High 0.60 - 1.00% Springs, Dies, High-Strength Wires
Ultra High 1,25 - 2.0% Metal Cutting tools, Truck Springs
Table 1. Carbon Steel Classification
Variations in the carbon content have a great effect on the mechanical properties of steel. Higher
carbon content leads to increasing hardness and strength. Though carbon is the most cost effective
alloying material for iron, other alloying elements are used. For example, Manganese and vanadium
are added to increase hardness of carbon steels.

This application note will demonstrate the ability of the Teledyne Leeman Labs Prodigy High
Dispersion ICP to determine alloying elements in High Carbon Steel.
Instrumentation
A Prodigy High Dispersion Inductively Coupled Plasma (ICP) Spectrometer
equipped with a radial view torch and an 88-position autosampler was used
to generate the data for this application note.

The Prodigy is a compact bench-top simultaneous ICP-OES system
featuring an 800 mm focal length Echelle optical system coupled with a
mega-pixel Large Format Programmable Array Detector (L-PAD). At 28 x 28
mm, the active area of the L-PAD is significantly larger than any other solid-
state detector currently used for ICP-OES. This combination allows Prodigy
to achieve significantly higher optical resolution than other solid-state
detector based ICP systems. The detector also provides continuous
wavelength coverage from 165 to 1100 nm permitting measurement over the
entire ICP spectrum in a single reading without sacrificing wavelength range
or resolution. This detector design is inherently anti-blooming and is capable
of random access, nondestructive readout that results in a dynamic range of
more than 6 orders of magnitude. For applications that require the measurement of chlorine,
bromine or iodine, an optional halogen detection system is available.

Determination of Alloying Elements in High Carbon Steel
by Radially Viewed Inductively Coupled Plasma Spectrometry
Prodigy ICP Application Note: # 1045

2

The Prodigy uses a 40.68 MHz free running, water-cooled oscillator, allowing it to handle the most
difficult sample matrices. A high sensitivity sample introduction system ensures that sufficient and
steady emission signals are transmitted to the spectrometer. The torch and sample introduction system
are uniquely integrated into the optical system through Prodigys innovative Image Stabilization system,
which treats the torch as an optical component by rigidly attaching it to the spectrometer.

The sample introduction system consists of a four-channel peristaltic pump, cyclonic spray chamber with
a knockout tube, single piece quartz torch and a high solids concentric nebulizer. Operating Parameters
are shown in Table 2 below.


Parameter Setting
Part Number
RF 1.2 kW

Coolant Flow 16 l/m

Auxiliary Flow 0 l/m

Plasma View Radial

Nebulizer Pressure 50 psi

Torch Demountable
120-00479-1
Injector Alumina
318-00071
Sample Uptake Rate 1.0 l/m

Nebulizer Hildebrand Grid
120-3028-1
Spray Chamber HF Resistant Ryton

Scott 120-00341-1
Optical Purge Flow Low

Integration Time 30 sec

Table 2. Instrument Operating Parameters

The analytical viewing zone was set by using a 10 ppm Mn standard. The optimum viewing position is
automatically selected by the Prodigys software.

Method

Sample Preparation

A High Carbon Steel (0.87% C)reference material, SRM 364 (NIST), was used in this study.
Approximately 1 gram of the material was then placed in a Teflon

beaker, covered with a minimum of

deionized water (DIW) and placed on a hot plate. The samples were dissolved using 5 ml of nitric acid
(HNO
3
) and 1 ml hydrofluoric acid (HF) while gently heating. Once the dissolution was complete, the
samples were diluted to 100ml with DIW.

Calibration Standards

Calibration standards were made from single element Teledyne Leeman Labs Plasma Pure

ICP
standards. In addition, the standards were matrix-matched to the Fe concentration of the reference
material by using Plasma Pure

Fe concentrate. The final acid concentration in the standards was 5%

HNO
3
/1% HF. The concentrations in the calibration standards are listed in Table 3.

3

Element std1 std2 std3
As, B, Ca, Co, Cr, Cu, Mg,
Mo, Pb, Sb, Si, Sn, Ta, W,
Zn
0 5 10

Mn, Ti 0 20 40

Nb, Ni, V 0 10 20
Table 3. Calibration Concentrations, ppm

Wavelength Parameters

For each wavelength, the Prodigy uses a 3 x 15 pixel subarray, which is centered on the wavelength of
interest. Background correction points and the analytical peak have both position and width values
within the subarray. In the Table 3 below, the position value is designated by x in the column header,
while w indicates the width. The default position for the analytical peak is 7 with a width of 3 pixels.
Where possible, two wavelengths were used for each element. All data in the subarrays are collected
simultaneously. In addition, all pixel data are saved, permitting recalculation of results at a later time.


Left
Background
Position
Left
Background
Position
Peak
Position Peak Width
Right
Background
Position
Right
Background
Width
LBX LBW Peak X Peak W RBG X LBG W
Mn 257.610 r 1 1 7 3 13 2
Mn 259.372 r 2 2 7 3 13 2
Si 251.611 r 2 1 7 3 12 2
Si 288.158 r 3 2 7 3 12 2
Cu 324.754 r 1 1 7 3 12 2
Cu 327.396 r 5 1 7 3 12 1
Ni 231.604 r 2 1 7 3 13 1
Ni 221.648 r 2 2 7 3 14 2
Cr 267.716 r 2 2 7 3 12 2
Cr 205.552 r 4 0 7 3 11 2
V 309.311 r 2 1 7 3 14 1
V 310.230 r 4 1 7 3 12 1
Mo 202.030 r 2 2 7 3 12 2
W 207.911 r 4 2 7 3 15 1
W 224.875 r 6 1 7 3 10 1
Co 228.615 r 3 2 7 3 12 2
Co 345.351 r 4 1 7 3 11 2
Ti 337.280 r 3 2 7 3 12 2
Ti 334.941 r 1 1 7 3 12 2

4
As 189.042 r 3 1 7 3 12 1
As 197.262 r 5 1 7 3 11 1
Sn 189.991 r 3 2 7 3 12 1
Nb 313.079 r 3 1 7 3 13 1
Ta 263.558 r 3 1 7 3 15 1
Ta 226.230 r 4 1 7 3 0 1
B 182.641 r 1 1 7 3 13 2
Pb 220.353 r 4 0 7 1 13 1
Zr 343.823 r 2 1 7 3 13 1
Zr 339.198 r 3 1 7 3 10 1
Sb 206.833 r 6 0 7 3 11 1
Table 1. Wavelength Parameters

As an example, illustrates the elements parameters for the Sn 189.991 nm line. In Figure 1, the left and
right background regions begin at pixel positions 3 and 12, respectively, with widths of 2 pixels. The
analytical region of interest, where the Pb peak is found, begins at pixel position 7 and has a width of 3
pixels. The thin line running under the peak shows the calculated background correction based on the
two correction regions.

Figure 1. Sn 189.991 nm Element Parameter Example

Figure 2 illustrates a calibration curve showing typical precision and linearity for the concentration range
used.

Figure 2. Typical Calibration Curve

5
Results

After igniting the plasma and allowing a 15 minute warm-up period, the Prodigy was calibrate using the
88-position autosampler. Once the calibration was complete, a 1 ppm QC Standard was analyzed with
an acceptance criteria of 10%. Upon successful completion of the QC Standard analysis, the reference
samples were analyzed. After the sample analysis, the QC Standard was re-analyzed. (The Prodigys
software allows the entire sequence to be run unattended. Should a QC Standard be out of
specification, the Prodigy will automatically recalibrate and rerun the QC Standard and any samples that
were analyzed since the last successful QC Standard was run.)

The analysis results are shown in Table 5. All concentrations are in %. The values measured by the
Prodigy are contained in the column labeled Found % while the certified values are in the column
labeled Certified %. (The certified value listed is not expected to deviate from the true value by more
than 1 in the last significant figure reported; for a subscript figure, the deviation is not expected to be
more than 5). The agreement between the measured and certified values is quite good.

Found, %
Certified
%
Mn 257.610 r 0.255
Mn 259.372 r 0.251
0.25
Si 251.611 r 0.069
Si 288.158 r 0.065
0.06
5

Cu 324.754 r 0.247
Cu 327.396 r 0.244
0.24
9

Ni 231.604 r 0.142
Ni 221.648 r 0.143
0.14
4

Cr 267.716 r 0.066
Cr 205.552 r 0.062
0.06
3

V 309.311 r 0.109
V 310.230 r 0.106
0.10
5

Mo 202.030 r 0.473 0.49
W 207.911 r 0.096
W 224.875 r 0.099
0.1
Co 228.615 r 0.145
Co 345.351 r 0.146
0.15
Ti 337.280 r 0.257
Ti 334.941 r 0.241
0.24
As 189.042 r 0.045
As 197.262 r 0.044
0.05
2

Sn 189.991 r 0.007 0.008
Nb 313.079 r 0.151 0.15
7

Ta 263.558 r 0.093
Ta 226.230 r 0.103
0.11
B 182.641 r 0.012 0.0106
Pb 220.353 r 0.022 .023
Zr 343.823 r 0.072
Zr 339.198 r 0.072
0.068
Sb 206.833 r 0.033 0.034
Table 5. 364 High Carbon Steel Results, %

6
Discussion

The determination of the alloying elements in the 364 high carbon steel reference material was
straightforward. Of all the elements determined, the most challenging was that of Pb.

During line selection, a number of Pb lines were examined. All were found to have significant
interferences. The most promising line was the primary Pb line at 220.353 nm. A scan of a 10 ppm Pb
standard and the 364 reference sample is displayed in Figure 3, where the interference is clearly seen.


Figure 3. 220.353 nm Pb line

The Prodigy software is sufficiently flexible in that it provides a couple of solutions to deal with this type
on interference. First, the analytical region of interest (ROI) can be reduced thereby avoiding the
contribution from the interfering peak. This method has the advantage is that it is not necessary to
determine the identity of the interfering peak.

An example of this is shown in Figure 4. Without reducing the ROI interval, the Pb concentration was
reported as 0.451%. The single pixel width reported the accurate value of 0.022%, as shown in Table 6.


Figure 4. Example of a Single Pixel ROI

7
The second method is to perform an Interfering Element Correction (IEC). In order to perform this
correction, the element responsible for the interfering peak must be determined. The Prodigy software
also provides tools to identify unknown peaks.

The first step to identifying an unknown peak is to take a Full Frame Image of the sample. The Full
Frame image takes a complete spectrum from 165 to 1100nm without any gaps. A Full Frame Image of
the 364 reference sample is shown in Figure 5.


Figure 5. 364 High Carbon Steel Full Frame Image

The next step is to zoom in to the wavelength in question (see Figure 6) and use the IDENTIFER
button.


Figure 6. Full Frame Image Zoomed to 220.353 nm Pb Subarray

8
By clicking on the IDENTIFIER button and then inside the PB subarray (as indicated by the red arrow
in Figure 6, the wavelength line library will be searched for possible elements. The result of the search
is displayed in Figure 7.


Figure 7. Search Results

The search results suggest the interfering peak is due to niobium (Nb). A scan of a Nb standard added
to the scans in Figure 4 confirms the identification (See Figure 8). Once the interfering element has
been identified, the IEC factor and be determined by analyzing the Nb standard to obtain the correction
ratio.


Figure 8. Confirmation of Nb As Interferent

9
Conclusion

The analysis of alloying elements in high carbon steel has been carried out for 18 element using a
radially viewed Teledyne Leeman Labs, Prodigy High Dispersion ICP. Accurate results were obtained
by carefully matrix matching the base iron concentration of the samples to the calibration standards.

The HF sample introduction system performed without any clogging of the torch or nebulizer and did not
require the use of an argon humidifier. The Hildebrand Grid nebulizer with its platinum screens is an
ideal nebulizer for use with HF containing samples, as well as sample containing high levels if dissolved
solids.

The image stabilized plasma and the simultaneous data collection of both peak and background data
combine to provide exceptionally precise and stable results.