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Vacuum 86 (2012) 648e651

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Vacuum
journal homepage: www.elsevier.com/locate/vacuum

Analysis of inclusions in spring steel using scanning electron microscopy


and Auger spectroscopy
Arsim Bytyqi a, b, *, Monika Jenko a, b, Matja
z Godec a, b
a
Institute of Metals and Technology, Lepi pot 11, 1000 Ljubljana, Slovenia
b 
Store Steel Company d.o.o., Zelezarska cesta 3, Slovenia

a b s t r a c t
Keywords: Different electron beam based techniques such us SEM/EDS and AES are very similar with regard to their
SEM/EDS imaging capabilities, but there are significant differences in the compositional information they can
AES
provide about the sample. In order to determine the usefulness of a technique for the identification of
Inclusions
Spring steel
inclusions in spring steel the SEM/AES analysis techniques were used and are shown to be well suited for
characterizing of these inclusions. From the results it was possible to evaluate the nature of inclusions,
their location, size and chemical composition. It is evident from this study that applications of different
techniques in inclusion determination are more representative and reflect inclusion size distribution in
sample more objectively.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction The effects of inclusions in mechanical properties of materials


often depend on local values rather than mean values such as
There are many analytical methods using focused electron, ion volume fraction, particle size, and particle spacing. Thus to
or photon beams for the analysis of a sample. In modern nano- completely characterize inclusion distributions for correlation with
technology analysis methods are needed which are able to inves- mechanical properties, it is necessary to measure their spatial
tigate extremely small volumes, thus surface sensitive techniques distribution, in addition to their size distribution and volume
with a high spatial and depth resolution are required. The high fraction [3]. The development of steel-making methods has, over
surface sensitivity of AES classifies it as a surface analysis technique, the years, decreased the undesirable elements in steel. Normally
while EDS, due to its large analysis volume, is considered a bulk these undesirable elements are oxygen, sulfur, phosphorus, and
analysis technique. This difference in analysis depth has conse- hydrogen. The oxygen content of steel should be as low as possible
quences for the application of these techniques for the analysis of because low oxygen content decreases the probability of large
inclusions. oxide inclusions [4]. The objective of the present study is to further
Inclusions are mostly considered as impurities and are present investigate the characterization of inclusions in spring steel based
as small particles in most materials. Since solid steel cannot on a detailed microscope investigation of specimens prepared in
completely dissolve these elements, inclusions will probably the laboratory.
always be present in commercial steel products. The presence of
micro inclusions influences a number of material properties.
2. Experimental
Magnesium and aluminum oxide type inclusions reduce the fatigue
strength of steel [1]. The mechanical behavior of steel is controlled
The base material used for examination was spring steel 51CrV4.
to a large degree by the volume fraction, size distribution,
The chemical composition of the investigated steel is given in
composition and morphology of inclusions and precipitates, which
Table 1. In order to evaluate each method carefully a standard set of
act as stress raisers. The inclusion size distribution is particularly
samples was prepared and analyzed. A metallographic cross-
important, because large macro-inclusions are the most harmful to
section of the samples was prepared using metallographic proce-
mechanical properties [2].
dures. Samples were cut into 8  8  3 mm plates and were
mechanically polished by diamond paste (1 mm) to produce
* Corresponding author. Institute of Metals and Technology, Lepi pot 11, 1000
a smoother surface. They were then washed several times with tap
Ljubljana, Slovenia. water and dried and their metallurgical structures were developed.
E-mail address: arsim.bytyqi@imt.si (A. Bytyqi). The adsorbed impurities on the surface of the sample were

0042-207X/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.vacuum.2011.09.015
A. Bytyqi et al. / Vacuum 86 (2012) 648e651 649

Table 1 of O and Al with significant amount of other elements such as Mg,


Chemical composition of the spring steel 51CrV4 (wt %). S, Mn, C, and Ca. SEM/EDS microanalysis show that sulphide
Sample C Si Mn Cr V S Al (MnS), calcium-alumo-silicate, and other complex, mainly oxide
A 0.52 0.35 0.96 0.93 0.12 0.007 0.010 inclusions are present in spring steel. These defects can also
contribute to a larger scatter and lower fatigue strength of the
spring steel [5].
removed by cleaning by argon sputtering in a UHV chamber at It was demonstrated that apart from chemical composition
3 keV ion energy. The 10 keV electron beam energy was used for the size of inclusions is crucial for steel properties. However for
HRAES and SEM analysis. The high resolution Auger electron large inclusions, SEM/EDS and AES are truly complementary
spectroscopy VG Scientific Microlab 310-F spectrometer was used techniques [6].
in this study, equipped with a spherical-sector analyzer and field
emission electron gun that can produce a beam 10 nm in diameter 3.1. Observation by auger electron spectroscopy
at an electric current of 1 nA. Measurements were then carried out
with a high-resolution Scanning Electron Microscope JEOL JSM- Assignment of inclusions was performed by Auger electron
6500F and AES. spectroscopy. Auger spectra of inclusion and related material are
shown in Fig. 2. Studies of inclusion characterization in spring steel
3. Results and discussion were carried out first using scanning electron microscopy; however
this technique, due to its large analysis volume, is considered a bulk
The overall composition of the inclusion was initially deter- analysis technique. AES on the other hand can give information on
mined using SEM/EDS analysis. While EDS is the easiest and fastest the chemical composition of the outermost layer between 5 Å and
way to analyze the overall composition of the defect Auger electron 20 Å depth.
microscopy was used to provide additional insight into the makeup The concentrations of the elements in the inclusion were
of the defect. Fig. 1 shows an SEM image of the spring steel (51CrV4) determined by peak-to-peak intensity ratio measurements of
with a complex inclusion. The results are shown in Table 2. differentiated Auger spectra for the non-metallic inclusion. Analysis
Detail analysis show that the concentration of Mn in the first two shows that the average inclusion size is approximately 1.0 mm. An
spectra is (44.35%, 53.38%) and S is (23.00%, 33.63%) therefore this AES survey spectra acquired at two different locations (point1, and
part consists mainly on manganese sulfide inclusion (MnS). The 3) on the inclusion showed the increased amount of Mn and S with
result indicates significant amounts of other elements such us Ca, significant amount of other elements such as O and Al. The
Mg. EDS measurements acquired at four different locations measured concentrations of the elements in the inclusion are given
(spectrum 3,4,5,6) on the inclusion showed the increased amount in Table 3.

Fig. 1. Scanning electron microscope image of a complex, non-metallic inclusion taken by secondary electrons.

Table 2
Semi-quantitative chemical analysis of inclusion in studied spring steel 51CrV4 (At %).

Elements C O Mg Al Si S K Ca Cr Mn Fe Cu Br Total
Spectrum 1 1.43 e 0.46 e e 23.00 e 1.28 0.58 44.35 27.79 1.11 e 100.0
Spectrum 2 2.61 e 0.70 e e 33.63 e 1.64 e 53.38 6.55 e 1.50 100.0
Spectrum 3 1.22 46.85 12.60 33.64 e e e e e 0.50 5.19 e e 100.0
Spectrum 4 1.62 37.01 6.55 29.02 e 8.01 e 0.48 e 11.45 5.86 e e 100.0
Spectrum 5 e 46.44 12.29 34.77 e e 0.23 e e 0.65 5.63 e e 100.0
Spectrum 6 8.37 42.47 3.97 24.22 e 5.17 0.67 0.40 0.38 6.91 7.45 e e 100.0
Spectrum 7 2.24 e e e 0.51 e e e 1.46 1.27 94.53 e e 100.0
650 A. Bytyqi et al. / Vacuum 86 (2012) 648e651

Fig. 2. (a) SAM image of an inclusion in spring steel 51CrV4; (b) AES spectra at positions P1eP3.

AES spectra at positions 2 indicate aluminum and oxygen


Table 3 enrichment in the inclusion. A detailed analysis of the whole
Concentration of elements (At %) calculated from the Auger Spectra measured at inclusion supported this finding and further showed that the
positions (P1, P2, P3) labeled in Fig. 2. inclusion is complex consisting of two different chemical compo-
S O Mn Al Fe Mg sitions. The same sort of inclusions are frequently present in spring
P1 44.1 21.8 17.1 17 e e steel and are less deleterious than those in single phase alumina
P2 10.1 39.1 5.5 29.2 9.3 6.8 since the presence of a more deformable inclusion phase such us
P3 45.7 15.2 21.9 17.2 e MnS modifies the dangerous properties of the hard oxides.
Fig. 3 shows the SEM image and Auger spectrum of an inclu-
sion in the spring steel (51CrV4) surface. Despite the small size of

Fig. 3. (a) SEM image of an inclusion in spring steel 50CrV4; (b) AES spectra at positions P1eP2.
A. Bytyqi et al. / Vacuum 86 (2012) 648e651 651

the defect, a strong Auger signal of the inclusion can be obtained. sulfur and manganese enrichment in the non-metallic inclusions.
Auger point analysis done prior to mapping indicates that the The majority of the inclusions found in spring steel contain
inclusion consist of manganese sulfide (MnS). AES spectra at manganese sulphide (MnS), and aluminum oxide (Al2O3) or
positions P1eP2 indicate the sulfur and manganese enrichment a mixture of these. According to the results there is no single ideal
in the inclusion composition. The two points have different method to measure steel purity, so it is best to couple several
concentrations of Mn and S but both contain Fe. A better picture methods together to give a more accurate evaluation.
of the qualitative elemental distribution in the outermost layer of
the inclusion is given by Auger maps in Fig. 3. Elongated inclu- References
sions are potentially harmful to ductility owing to their anisot-
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ropy behavior and their orientation relative to the working
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[2] Zhang Lifeng, Thomas Brian G. Inclusions in continuous casting of steel. Mech
Eng Build; 2003:138e83.
4. Conclusions
[3] Shehata MT, Boyd JD. Measurement of spatial distribution of inclusions. In:
Inclusions and Their Influence in Material Behavior, 1998, pp. 123e131.
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 starsis Borivoj, Borkovi
[5] Su c Predrag, Echlseder Wifried, Gerstmayr Gerhard,
carefully designed experiments using scanning electron micros- Javidi Ataollah. Bojan Sencic New Tre Fat Fra 2011;27:34.
copy and Auger spectroscopy. AES and SEM/EDS spectra indicate [6] Scherer Juergen, Schnabel Patrick, Childs Kenton. SEMATECH 2001;3:4.