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286 Analyst, February, 1983, Vol. 108, $9. 286-292

Application of Optical Emission Source

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Developments in Metallurgical Analysis

Hugh Hughes
Consultant, 7 Rowan Avenue, Guisborough, Cleveland, TS14 8DR

Recent developments in metallurgical analysis, which have potential for use in

industry, are described. The paper concentrates on three techniques : firstly
the use of pulse distribution analysis in spark-source optical emission spectro-
scopy to determine soluble aluminium in steel separately from the aluminium
that is present as inclusions in the steel matrix; secondly, glow discharge
spectroiiietry for the determination of alloying elements in steel, a technique
which has potential for both bulk and surface analysis of steel, and lastly,
inductively coupled plasma spectrometry. Data are presented, together with
reproducibility measurements, which give the optimum conditions for
niultielenient analysis of stccl using this technique.

Keywords : Pulse distvihution analysis ; spark-source optical emission spectro-

scopy ; glow dischavge lamp ; inductively coupled plasma spectroiizetry ;
metallurgical analysis

Ohls, in his paper on new aspects of atomic-spectroscopy presented a t this Symposium, made
it clear that tlie application of optical emission spectroscopy in the metallurgical industry has
been given new impetus in recent years by new developments in sources and their application.
This paper is intended to expand on this, in certain areas, concentrating specifically on three
subjects : the use of pulse distribution analysis in spark-source optical emission spectroscopy;
the use of tlie glow discharge lamp for both bulk and surface analysis of steel ; and tlie potential
of inductively coupled plasma spectrometry in the metallurgical industry.
Pulse Distribution Analysis
This technique has been developed by the Japanese, mainly to determine soluble aluminium
in steel separately from the aluminium that is present as inclusions in the steel matrix,
referred to as insoluble aluminium. In the past only the total aluminium content could be
determined by optical emission. However, a rapid determination of the soluble aluminium
content is essential during production in order to adjust the content to the levels required
by the specification being produced. Onodera ct a1.l first described the development at Nippon

Discharge spot
Including Excluding
insol. A1 insol. Al

Insol. Al

Discharge spots

Fig. 1 . Principle of pulse height analysis inethod.

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HUGHES 287
Steel and Figs. 1 and 2, taken from their work, describe the principle of the method. Briefly,
the sizes of the individual light pulses from individual sparks vary depending on whether
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inclusions in the steel (insoluble aluminium) contribute light intensity to particular sparks
(Fig. 1 ) . As illustrated in Fig. 2, the analysis of the pulse-height distribution of the light

I sol. AI Insoi. AI I

r,h-4 Light intensity

Soluble Al chemical Insoluble Al chemical

Pig. 2. Principle of pulsc height analysis method. I m ,Distribution mcdian; N ,total number of pulses.
intensity from individual sparks separates the contribution of insoluble and soluble aluminium
and allows the conversion of the data into their respective contents. There was much
interest in the British steel industry when the method was first described and samples were
submitted for analysis. killings from the same samples were at tlie same time chemically
analysed by several laboratories. Fig. 3 illustrates the comparison of chemical and spectro-

0.14 1 ’ /
5000

*s
.-c
L
0.12
v)
.-
4-

5 4000

0.10 2
3000
2 0.08
+
.-
a,

-2 0.06 .-c
2000

2 0.04
v)
C,
a

<
-
0
0.02
E
-
1000

cn
0 0.02 0.040.060.080.100.120.1~ 0 5.0 10.0 15.0 20.0 25.0
Soluble Al (chemical), O/O Co ba It concentration , O/O
Fig. 3 ilnalysis of U K steels using 1;ig. 4 . Glow discharge for cobalt
J , ~ p ~ n e i vcalibration (pulse height (345.3 n m ) , I3inary steel calibration with
analyis method). corrccted intensities.

metric soluble aluminium contents. The agreement i\ riot ,atisfactory, particularly at tlie
higher contents. Furthcr investigation showed that the particle size of the inclusions in the
British samples \\as much coarser than that in the calibration samples. This u.ould seem to
indicate tliat the sanipling, in particular the cooling rate of samples for anal>vsis, must be
matched very closely to that of the calibration samples as this was thc only difference between
the t\vo 5ets of samples. The Institut de Recherches de la Siderurgie Franqaise in Metz 1s at
present investigating the topic further as part of the European Coal and Steel Community
(ECSC) research programme and this should clarify the position prior to its more general
introduction in European steelworks.
Glow Discharge Spectrometry
The glow discharge lanip wa\ first developed by Grinsm2 and the principle of its operation
has been described b c f o r ~ . ~I.t~has potential for both bulk5 and surface analysis.6 In the
case of bulk analysis, Kutterworth7 illustrated the simplicity of the technique for alloy steel
analyiis compared with .park-iource optical einiiiion when glow discharge conditions are
properly selected. Fig. 4 illustrates a basic calibration graph for cobalt based on binary
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288 HUGHES: APPLICATION OF OPTICAL EMISSION SOURCE AnaZyst, VoZ. 108

TABLE
I
GLOWDISCHARGE
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DETERMINATION OF COBALT I N HIGH-SPEED STEELS

Certificate Glow discharge 95% Confidence

Sample value, % value, % limit, 20
SS 481 .. *. .. 0.21 0.20 0.01
SS 482 .. .. .. 0.24 0.25 0.01
ss 483 .. .. .. 1.94 2.00 0.06
SS 484 .. .. .. 10.20 10.30 0.14
ss 485 .. .. .. 5.06 5.10 0.09
SS 486 .. .. .. 0.13 0.11 0.01

standards and Table I shows the results obtained for the determination of cobalt in high-
speed steels using this calibration graph. Compared with spark-source optical emission
where complex procedures are used to correct for interference effects, a simple procedure is
used. This is based on correcting the light intensities in the steels to be analysed by the
factors with which the iron line intensities are enhanced or reduced in the steels compared
with the line intensities for the same iron contents in the binary calibration standards. Apart
from the application by Radmacher and de S ~ a r d thowever,
,~ it still remains for the lamp
to be widely introduced into the steel industry for routine bulk analysis production control.
This probably reflects a degree of conservation on the part of the steelwork’s chemist. A
parallel can be drawn from the relatively slow introduction of X-ray fluorescence into the
industry because of the entrenched position of spark-source optical emission, X-ray
fluorescence is now, however, fully established and integrated into the analytical scheme.
Much more interest has latterly been shown in the application of the glow discharge lamp
to surface analysis. The work of Berneron and Charbonnier6 and Le Roy8 typifies application
to steel surface problems, particularly Le Roy’s work on the contamination of strip steel
surfaces. Work by Jowitt and Hughes a t the Teesside Laboratories of the Hritish Steel
Corporation (BSC) has confirmed the potential of the glow discharge lamp for application in
another area, namely the problem of de-carburisation of some sheet and round steel products
during their production. I t is important to be able to measure this to ensure that product
performance is not affected by excessive de-carburisation. At present, de-carburisation is
determined by a metallographic method that is labour intensive and highly subjective in
the operator’s judgement. In this work, samples were examined using an RSV glow dis-
charge lamp. The operating conditions selected, lOOOV and 140mA, gave a surface
removal rate of 4 p m min-l. Fig. 5 shows the profile of the crater formed. This is satis-

Fig. 5. Profile of glow discharge crater.

0 5 10 15
Depth of penetrationlym
Fig. 6. Carbon profile of standard steel.

factorily uniform with some build-up of debris around the edges. Fig. 6 shows a continuous
profile of the carbon content of a standard steel which is not de-carburised and Fig. 7
illustrates the profile obtained in the case of a production sample of sheet steel. This shows
a de-carburised layer extending approximately 15 p m into the steel. Fig. 8 illustrates a
calibration graph for carbon using BCS standards. This is satisfactory even though the
193.1 nm line, which is used because of spectrometer limitations, is not the best carbon line
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February, 1983 DEVELOPMENTS I N METALLURGICAL ANALYSIS 289

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I I

0 0.2 0.4 0.6 0.8 1.0 1.2

Depth of penetrationlym Carbon, O/O
Fig. 7. Carbon profile of de-car- Fig. 8. Glow discharge calibration for
burised steel. carbon in low-alloy steel.

for glow discharge analysis owing to its high background, The profile of the de-carburisa-
tion can therefore be quantified as well as the depth. The glow discharge lamp based on
the RSV design is now available from instrument manufacturers such as Philips and ARI,.
I t now remains for it to become established and accepted as a tool in metallurgical analysis,
both for the surface analysis application just described and in bulk analysis for production
control.
Inductively Coupled Plasma Spectrometry
With the general availability of commercial instruments, the metallurgical industry has
shown much interest in plasma sources. The steel industry in fact illustrated this interest
by the funding by the European Coal and Steel Community of a major project to investigate
the potential of the inductively coupled plasma. German, French, Belgian and British
laboratories participated in this joint project. My former laboratory a t Teesside was
responsible for investigating the performance of a high power plasma using a Kontron
system capable of an output of up to 10 kW at the induction coil. One of the objectives was
to optimise operating conditions to allow simultaneous analysis using an E 1000 dual
grating direct-reading spectrometer .
Table I1 summarises the variations in operating parameters which were used, these being

TABLE
I1
VARIATION
OF PLASMA OPERATING PARAMETERS

Power .. .. .. .. .. Fixed, 10 k W
Coolant gas (N,) . . .. .. .. Varied, 19.5-33 1min-l
Plasma gas (Ar) . . .. .. .. Varied, 10.5-17 1 min-l
Sample uptake rate (carrier gas, Ar) .. Varied, 1.9-4 nil min-l
2.4-4.5 1 min-'
Observation height .. .. .. Varied, 2-26 mm (above the coil)

varied systematically but independently. Fig. 9 illustrates a set of data obtained with fixed
coolant gas and uptake rate (24 1 min-l and 2.8 ml min-l, respectively). Line to back-
ground ratios are plotted against observation height for four plasma gas flow-rates. Fig. 10
is a similar figure with variable coolant gas rate for fixed plasma gas and uptake rate
(17 1 min-l and 3.6 ml min-1). These data, together with reproducibility measurements,
gave the optimum conditions for multi-element analysis. These were as follows: coolant gas
flow-rate, 33 1 min-l; plasma gas flow-rate, 15 1 min-1; sample uptake rate, 3.5 ml min-l;
and observation height, 12 mm above the coil.
A compromise observation height has to be used in simultaneous multi-element determina-
tion but Table I11 shows that such a compromise does not seriously reduce performance, this
being on average over 90% of best performance. Using these conditions multi-element
solutions were used to determine the linear ranges of calibration graphs, the usable ranges of
calibration graphs allowing some curvature within the limits of detection. Table I V illustrates
a selection of the results obtained and Fig. 11 the calibration graph obtained for aluminium.
 View Article Online

290 HUGHES : APPLICATION OF OPTICAL EMISSION SOURCE A~zaZyst,VoZ. 108

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I I I I I
5 20 16 12 8 4 20 16 12 8 4

20 16 12 8 4 20 16 12 8 4
Height/mm above coil

Fig. 9. Characteristicsof plasma with variable plasma gas flow-rate: (a)

10.5; (b) 12.5; (c) 15.0; and (d) 17.0 1 min-l. Coolant gas, 24 1 min-'; uptake
rate, 2.8 ml min-l.

TABLE
I11
LINETO BACKGROUND RATIOS AT COMPROMISE HEIGHT (12 mm) AS A
PERCENTAGE OF THE VALUE AT OPTIMUM HEIGHT

Optimum
Element heightlmm AH %
A1 .. .. 12 0 100
As .. .. 12 0 100
Ce .. .. 20 8 83
Mo .. .. 14 2 99
V .. .. 10 -2 97
Zn .. .. 10 -2 55
 View Article Online

February , 1983 DEVELOPMENTS I N METALLURGICAL ANALYSIS 291

TABLE
IV
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TYPICAL
DETECTION LIMITS AND LINEAR AND USABLE DYNAMIC RANGES

Detection limit/ Linear dynamic Usable dynamic

Element pg ml-l rangelpg ml-1 range/ pg ml-l
A1 .. .. 0.2 2 x 103 > 6 x lo3
Cd .. .. 0.02 5 x 103 105
Fe .. .. 0.01 104 4 x 105
Mn .. .. 0.002 2 x 104 >2 x 106
Ni .. .. 0.1 104 5 x 104
V .. .. 0.05 > 104 > 104

3500 F
:. 3000 }

-
J
2 2500 -
F
2000 -
e
*=

-E 5 1500 -
50, 20 16 12 8 4 .-w
20 16 12 8 4
P 1000 -
+.
- 500 -
I I

0 2000 4000
Concentration/Fg m I- '
Fig. 11. Aluminium cali-
bration graph.

I I I

20 16 12 8 4 20 16 12 8 4
Height/mm above coil

Fig. 10. Characteristics of plasma with variable

coolant gas flow-rate: (a) 19.5; (b) 24.0; (c) 28.5; and
(d) 33.0 1 min-'. Plasma gas, 17 1 min-l; uptake rate,
3.6 ml min-l.

These illustrate a capability to determine from micrograms per millilitre to percentage

contents.
Limits of detection for elements of interest in steel are listed in Table V and have been
supplemented by values obtained using a Philips P V 8210 and data reported by Wagner
and Petins using an ARL 34000. The results are not directly comparable, the first two are
for dilute acid or water solutions but the data of Wagner and Petin are for solutions con-
taining 1 g of steel per 100 ml. If 1 0 times the limit of detection is taken as the lowest
quantitative determinable concentration (LQDC) and a dissolution procedure based on 1 g
of steel in 100 ml is used, the LQDC, in percentage steel content, is one tenth of the numerical
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292 HUGHES

TABLE
V
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LIMITSOF DETECTION FOR ELEMENTS I N STEEL

E 1ooo* PV82 1O* 340007

7 7- 7 7-
- - i 7
-T-+---7
Limit of detection/ Limit of detection/ Limit of detection/
Element h/nm pg ml-l h/nm pg ml-l A/nm pg ml-l
A1 .. .. 308.2 0.2 308.2 0.04 396.1 0.013
As .. . . 193.7 0.3 193.7 0.007 197.3 0.15
co .. . . 228.6 0.1 228.6 0.003 345.3 0.02
Cr .. . . 267.7 0.02 267.7 0.002 267.7 0.019
cu .. . . 327.4 0.1 324.7 0.002 327.4 0.004
Mn .. .. 257.6 0.002 257.6 0.0005 257.6 0.006
Mo .. . . 287.1 0.1 202.0 0.005 281.6 0.016
Ni .. . . 231.6 0.1 341.4 0.015 341.4 0.01
P .. .. 178.2 1.5 214.9 0.04 178.2 0.12
Si .. . . 251.6 0.09 251.6 0.01 288.1 0.13
V .. .. 311.0 0.05 290.8 0.003 311.0 0.015

Dilute solutions.
t 1 g steel per 100 ml solutions.

value of the limit of detection listed. With the first two sets o f data some allowance must be
made for the effect of iron in solution on the limits of detection but for most purposes the
technique can cover steel analysis requirements. The same characteristics, namely good
limits of detection and wide dynamic ranges, make the technique suitable for a wide range
of other applications in the metallurgical industry such as oxide and non-ferrous alloy analysis.

References
1. Onodera, M., Mishizaka, M., Saeki, M., Salrata, T., hrippon Steel Tech. Rep. Ovrvsras, 1!)77, No. 9,
73-77.
2. Grimni, W., Spectvochim. Acta, Pavt €3, 1968, 23, 443.
3. Boumans, 1’. W. J. M., A n a l . Chern., 1972, 44, 1219.
4. Hughes, H., “Proceedings of the 29th Chemists conference, Scarborough,” HISPA, Lo~ldoa,1976,
pp. 30-38.
5. Radmacher, H. W., and de Swardt, M. C., Spectvochim. Acta, Pavt H, 1975, 30, 353.
6. Berneron, Ii., and Charbonnier, J . C., A n a l . Proc., 1980, 17, 488.
7. Butterworth, A., ESC Open Report T/CS/552/3/78/C.
8. Le Roy, V., “Proceedings of the 34th Chemists Conference, Scarborough,” BSC Teesside Laboratories,
Grangetown, Middlesbrough, 1983.
9. Wagner, A., and Petin, J., “Proceedings of CETAS conference, Salzburg,” ClIM, Liege, Belgium,
1979.

Received August 26th, 1982

Accepted October 27th, 1982