Application

Note: 52108

XPS Analysis of Stainless Steel Surfaces

Tim Nunney, Thermo Fisher Scientific, East Grinstead, West Sussex, UK

Key Words
Passivation

The Thermo Scientific K-Alpha XPS was used to analyze

the surface and layer composition of stainless steel surfaces
to identify the successfulness of the passivation process.

Stainless Steel

Introduction

Surface Analysis

The surface chemistry of stainless steel is strongly influenced

by the chemical or mechanical processing of that surface.
Preventing corrosion is a major ambition of any steel
manufacturing process and this is often achieved through
passivation. This typically involves the formation of a
chromium-rich passive layer on the top surface (Figure 1)
and there is a number of different methods employed to
encourage the growth of such a layer. The key metrics which
can be used to identify properly passivated steel are the
total Cr/Fe atomic ratio, the Cr oxide/Fe oxide ratio, and
the total oxide thickness.

XPS

Experimental and Results

Figure 1: Passivated stainless steel samples and schematic of layer composition

Passivated Sample

Unpassivated Sample

Passivated and unpassivated steel samples were analyzed

using Thermo Scientific K-Alpha XPS. The iron chemistry of
surfaces was investigated using high energy resolution XPS.
Metallic and oxide states were observed in both cases, with
significantly reduced oxidation on the passivated sample.
Figure 2 shows the chemistry of the top 5 nm of the surface.
Peak fitting of the two spectra allows us to quantify the
different chemical states. The broader oxide peak shape
of the passivated sample is due to a mixture of iron (III)
and iron (II) states. These two oxide states are present in
almost equal quantities. In contrast, the unpassivated
sample only has iron (III).
Passivation significantly changes the ratio of iron oxide
and metallic states. Chromium data from the unpassivated
and passivated samples, in contrast, showed only a minor
difference in the oxide-to-metal ratio between the two
samples (Table 1). Combining the iron and chromium
datasets, we can derive the useful parameters which are
then used to assess the quality of the passivation (Figure 3).
The goal of passivation is to maximize the chromiumcontaining layer on the surface.
Non-destructive Surface Measurement

CrTotal/FeTotal
Figure 2: High resolution Fe spectra from passivated and unpassivated
stainless steel surfaces

Passivated

Unpassivated

1.56

0.77

Cr-O/Fe-O

2.85

0.76

Fe-O/Femetal

0.77

4.26

Cr-O/Crmetal

5.33

5.38

Oxide Thickness

1.2 nm

3 nm

Table 1: Useful steel parameters measured non-destructively with K-Alpha

In addition to these

Passivated

Passivated

offices, Thermo Fisher

Scientific maintains
a network of representative organizations
throughout the world.

Unpassivated

Unpassivated

Passivated

Unpassivated

Figure 3: Comparison of Cr and Fe chemical states of passivated and

unpassivated steel surfaces

Figure 4: Sputter depth profiles of unpassivated and passivated steel surfaces

These parameters describe the elemental and chemical

properties of the steel between 0 and 5 nanometers. When
the results of these measurements indicate a deviation from
required passivation standards, a sputter profile experiment
can be used to gain a better understanding of the problems
involved. Profiles of the passivated and unpassivated samples
(Figure 4) confirm the significant reduction in oxide thickness
on the steel. The passivation prevents much of the iron
oxidation observed on the unpassivated sample. However,
the chromium oxide thickness is also reduced on the
passivated sample. This reduction in total oxide thickness
means that more of the iron-rich metallic substrate is seen
by the surface XPS measurement.

Summary
K-Alpha analysis indicated significant reduction in iron
oxidation as a result of passivation. Quantification of
elemental and chemical states using XPS showed that the
passivation quality fell short of requirements. Sputter depth
profiling revealed the cause of the passivation problem to be
a significant reduction in the level of iron oxidation at the
surface. Quantitative measurement of a number of useful
parameters, however, demonstrated that the passivation
method had not produced a protective layer of the required
quality. Sputter profiling of the surface revealed that the
passivating chromium oxide layer was too thin.

Acknowledgements
Thermo Fisher Scientific would like to acknowledge
Brian Strohmeier and RJ Lee Group for all of their
help with this work.

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