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Article history:
Received 14 May 2008
Received in revised form 14 November 2008
Accepted 20 December 2008
Available online 10 January 2009
Keywords:
Metal release
Martensitic stainless steel
Acetic acid
Surface nish
a b s t r a c t
Martensitic stainless steel grade AISI 420 intended for cutlery knives and scissor blades has been investigated in an attempt to correlate microstructure and surface nish (polishing procedure) to metal release
rates of the main alloy constituents, iron and chromium. Metallographic investigations proved the knife
steel and, in particular the scissor steel to have very inhomogeneous microstructures. The knife steel contained bands of ferrite in the martensitic structure while the scissor steel revealed large amounts of tempered martensite and inclusions of manganese sulphides and silicon oxides. Samples of different surface
nish were immersed in 3 vol% acetic acid at 40 C from 1 to 10 days for metal release testing, simulating
food contact. The largely inhomogeneous microstructure of the scissor steel results in high and greatly
varying metal release rates, despite a fairly high chromium content of the surface oxide. Areas of inclusions seem to act as initiation points for accelerated metal release and the forming of a surface oxide
depleted in chromium, but rich in copper. The generation of high surface temperatures during polishing
was found benecial from a metal release perspective as a result of the formation of a surface oxide of
improved passivating properties.
2008 Elsevier Ltd. All rights reserved.
1. Introduction
This paper is the second in a series of two papers so far investigating metal release and material characteristics of stainless
steels in contact with food simulating media. The rst paper
(Herting et al., 2008) investigated release rates from the ferritic
stainless steel grade 430 and the impact of different test parameters. This second paper will address martensitic stainless steel
with different surface nishes and alloy content. As generally
known, stainless steels have a wide range of applications ranging
from skyscrapers to medical implants to food related applications.
The most prominent feature rewarding stainless steel its high
reputation is the well developed corrosion resistance in a wide
variety of environments (Wrangln, 1967). General information
on stainless steel presented in Herting et al. (2008). Martensitic
stainless steels provide the possibility for sharp edges on knife
and scissor blades as they have a high carbon content varying between 0.1 and 0.4 wt% enabling hardening and tempering. With a
chromium content in the range of 10.515 wt% and 06 wt% nickel (Council of Europe, 2001) the corrosion resistance can some-
* Corresponding author.
E-mail addresses: herting@kth.se (G. Herting), davidb01@kth.se (D. Lindstrm),
ingero@kth.se (I.O. Wallinder), chrisl@kth.se (C. Leygraf).
0260-8774/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2008.12.019
24
2. Experimental
2.1. Material and surface nish
Stainless steel grade AISI 420 from two suppliers, from here on
entitled knife steel and scissor steel, respectively, was investigated
within this study. The nominal bulk composition of each steel,
measured using X-ray uorescence spectroscopy, are shown in
Table 1. The knife steel is used to produce knife blades in cutlery,
and the scissor steel to manufacture scissor blades. The aim of
the higher carbon content of the scissor steel compared with the
knife steel, is to enable the generation of sharp cutting edges on
the scissor blades. Compared with the knife steel, the scissor steel
shows generally a higher alloying content of primarily copper,
nickel, phosphorous and sulphur. Both grades have relatively low
chromium bulk content, close to the lower limit of specication
of the AISI 420 stainless steel.
Metal release studies in acetic acid were performed for each
grade of company polished surface conditions, i.e., real product
surfaces. No details were obtained by the suppliers on the company polishing procedure. In addition, in order to investigate if differences in polishing procedure (deliberate modication of the
surface nish) could have a signicant inuence the metal release
process, unpolished knife and scissor blades (raw surfaces after
heat treatment) were polished manually by a professional at
Schmidts Polermedel AB, Ljungby, Sweden, following the stateof-the-art procedure to obtain a similar surface roughness as the
company polished surfaces (based on visual observations). The
professional was also asked to polish the raw material of each
grade as poorly as possible from a professional perspective obtaining high surface temperatures as a result of high applied pressures
and lack of polishing agents, still in the end obtaining a, by appearance, similar surface nish as the company polished surfaces. The
polishing procedure for both surfaces followed a stepwise process
using aluminium oxide on the polishing wheel (sisal bre) as the
polishing agent; (i) grinding without polishing agent, (ii) pre-polishing (430 lm), and (iii) polishing (<4 lm). The main difference
between the modied surfaces was the applied pressure against
the polishing wheel, the excess of, or shortage of, polishing agent
and the frequency of changes in contact points between the polished surface and the polishing wheel, aiming to achieve, or avoid
too high surface temperatures. In both cases, the polishing direction was changed repeatedly to avoid the enhancement of polishing scratches from the previous step.
2.2. Immersion experiments
Triplicate samples, sized approximately 35 cm2 of each grade
and surface nish were cut from the knife and the scissor blades.
Due to the fact that samples were cut from real products, the sample size varied somewhat between the samples. All cutting edges
were wet ground to 1200 SiP to remove any burrs present. Prior
to exposure, all samples were ultrasonically cleaned in acetone
and isopropyl alcohol for 3 min, respectively, rinsed in isopropyl
alcohol and dried with nitrogen gas.
Immersion experiments were performed according to the Italian law text D.M. 21-03-1973. The test solution (3 vol% acetic acid)
Table 1
Bulk alloy composition, wt%, of the two grades of AISI 420 stainless steel measured by
means of X-ray uorescence spectroscopy. Iron in balance.
Grade
Cr
Ni
Mn
Mo
Si
Cu
Knife steel
Scissor steel
13.6
12.6
0.09
0.19
0.51
0.30
0.01
0.03
0.14
0.23
0.46
0.38
0.02
0.03
0.002
0.017
0.03
0.12
was obtained by mixing analytic grade acetic acid (100 vol%), and
ultra pure water (<18 MX cm). All vessels used in the immersion
experiments were acid cleaned in 10% HNO3 for at least 24 h and
carefully rinsed with ultra pure water before use.
Ten day-immersion studies were performed at 40 1 C in dark
conditions with a surface area to solution volume ratio of 1 cm 1
for all samples. To obtain kinetic information, triplicate samples
of each grade were immersed for 1, 2, 4, 6, 8 and 10 days, in total.
Reference samples of acetic acid without stainless steel immersed
were exposed in parallel for background correction. After immersion, the samples were removed from the solution and carefully
rinsed in ultra pure water prior to the surface analyses. All immersion solutions were kept for chemical analyses of released metals.
The total metal concentrations of released iron, chromium and
nickel were measured with atomic absorption spectroscopy (PerkinElmer AAnalyst 800). The limits of detection were 1, 1 and
15 lg L 1 for chromium, nickel and iron, respectively. A calibration
with four standard solutions was performed for each element and
control samples of a known concentration were analysed every 10
samples for quality assurance.
In cases with discoloured test solutions (due to very high released metal concentrations) the total metal concentration of released iron, chromium, nickel and copper were analysed with
ICP-AES (Spectro CirosCCD, Smart Analyzer Vision, SPECTRO A. I.)
at the Environmental Research Laboratory, Swedish University of
Agricultural Sciences, Ume, Sweden.
2.3. Surface analysis
The composition of the outermost surface lm was examined by
means of XPS, X-ray photoelectron spectroscopy (Kratos AXIS HS).
Wide and detailed scans (pass energy of 80 eV) of Cr 2p, Ni 2p, Fe
2p, Mo 3d, Cu 2p, C 1s, O 1s were obtained at two different areas
(each approximately 0.4 mm2) using a monochromatic Al Ka Xray source (1486.6 eV) operated at 300 W (15 kV/20 mA). Sensitivity factors (Cr 2p 2.3 and Fe 2p 3.0) were used to estimate the
relative proportion of chromium and iron in the outermost surface
lm. No distinction was made between metals in their oxidised or
metallic state.
EIS, electrochemical impedance spectroscopy, was applied to
evaluate and compare the electrochemically active surface area
(0.5 vol% acetic acid) of each grade and surface nish before and
after immersion in 3 vol% acetic acid. The method is described in
detail elsewhere (Herting et al., 2006).
FEG-SEM, eld emission gun scanning electron microscopy
studies (Leo 1530 with an In-Lens column) was performed for
microstructural investigations. To enable detailed studies, the samples were embedded in Bakelite mould, grinded consecutively
using 240, 500, 800 and 1200 SiC paper, and polished in sequence
with 6, 3, 1 and 0.25 lm diamond paste. The surfaces were then
etched in a solution containing 10 mL HNO3, 100 mL HCl and
100 mL H2O at 65 2 C (Vogels etching solution, V2A) for 10
15 s. EDS, energy dispersive spectroscopy (model INCA-energy
from LINK), was performed to acquire bulk compositional information on identied microstructural features using an acceleration
voltage of 15 kV.
The possibility to discern relative differences in surface nobility
(Volta potential) between the sample matrix and different features
in the microstructure was investigated for selected samples using
SKPFM, scanning Kelvin probe force microscopy (Veeco Nanoscope
IV Multimode AFM at the Nano-Fab Lab at the Royal Institute of
Technology). SKPFM is a method of analysis based on the AFM
technique that enables both topography and variations in Volta potential for a localised area to be visualised (Davoodi et al., 2008).
The probe was made of antimony doped with Si. To minimise
any inuence of surface topography, which falsely could inuence
25
Fig. 1. Secondary electron image of polished (0.25 lm) and etched surfaces (Vogels
solution) of stainless steel grade AISI 420 knife steel illustrating (a) zones of ferritic
grains in a martensitic matrix, (b) the martensitic matrix with randomly spread
ferritic grains, and (c) a chromium carbide randomly located in the matrix.
26
Fig. 2. (a) 20 20 lm topography image using AFM, and (b) Volta potential image of the same area, 20 20 lm using SKPFM, of a diamond-polished the ferriticmartensitic
AISI 420 knife steel, and (c) Volta potential line prole along the martensite matrix and two separate ferrite areas. Dark colours of the images represent low relative height and
low relative nobility, respectively.
experimental. The results are illustrated in Fig. 2. Since the polishing scratches visible in the AFM topography image (Fig. 2a),
are barely seen in the Volta potential image (Fig. 2b), it indicates
that observed differences in surface nobility are not an artefact.
Both images display areas which in size and geometry are very
similar to the presence of the ferritic grains in the martensitic
matrix observed with SEM (Fig. 1). These ferritic grains show a
lower nobility (darker appearance in the image) compared with
the surrounding martensitic matrix. The difference in nobility,
approximately 200 mV, between the different areas is illustrated
in Fig. 2c. Areas of lower Volta potential are believed to be associated to the ferritic phase, and areas of higher potential to the
martensitic matrix. The large difference in surface nobility suggests a preferential corrosion and dissolution rate of the less noble ferritic phase compared with the nobler martensitic phase.
Similar ndings have previously been observed for duplex stainless steels showing a preferential dissolution of the ferritic phase
compared with the austenitic phase (Femenia et al., 2003). Volta
potential differences are expected in areas with chromium carbides, however, no such measurements were performed due to
their low numbers present in the matrix. The ferrite within the
tempered martensite could not be distinguished as the ferrite
areas were individually too small to be differentiated from the
tempered martensite with certainty.
The measured bulk composition of the scissor steel (Table 1),
correlated fairly well with the denition of an AISI 420 stainless
steel (Wrangln, 1967). However, a detailed metallographic investigation revealed an inhomogeneous microstructure, illustrated in
Fig. 3, consisting of a martensitic matrix containing tempered martensite, primarily at the grain boundaries but also within the
grains, elongated domains of particles primarily composed of silicon and oxygen, chromium carbides, and sub-micron sized inclusions rich in mainly manganese, sulphur and to some extent also
aluminium (pinholes).
Compositional analysis with EDS of the martensitic phase
showed a chromium to iron ratio of 0.13 (Cr/(Cr + Fe)), i.e., similar
to the bulk compositional ratio determined with XRF Table 1. The
tempered martensite phase constitutes a large volume of the bulk
material. This phase, consisting of ferrite and cementite (white
akes) precipitates, can be transformed from martensite through
a solid phase diffusional process at temperatures between 250
and 650 C (Callister, 1994). The reason for its appearance in the
bulk material is unknown, however, it can be speculated that the
cooling process during production is too slow, or that the phase
may form during the polishing procedure.
Non-metallic inclusions are well known to act as initiation
points for corrosion and metal release, and as a result be detrimental for the corrosion resistance of a material (Marcus et al., 1984). A
highly inhomogeneous material was also obvious from surface
hardness measurements showing large variations, from 644 to
689 HV (200 g), signicantly different from the recommended values of 560580 HV for scissor steel.
27
Fig. 4. Total and individual metal release rates of Fe and Cr from the knife steel and
the scissor steel after 10 days of immersion in 3 vol% acetic acid at 40 C. No release
rates of copper were measured.
Fig. 3. SEM images of polished (0.25 lm) and etched (Vogels solution) surfaces of
AISI 420 scissor steel with a highly inhomogeneous microstructure consisting of a
martensitic matrix and tempered martensite, inclusions and bands of silicon-rich
particles.
time-dependent metal release rates were evaluated for the company polished surface nish.
As seen in Fig. 4, fairly small differences in total release rates
were observed for the knife steel. For comparison, AISI 430 stainless steel of different surface nish, exposed to identical exposure
conditions, revealed total release rates varying from 0.4 to
6 lg cm 2 week 1 (Herting et al., 2008). Released concentrations
of chromium from the knife steel were close to the stipulated
threshold value of 0.1 mg L 1, given by recommendations on metal
release from stainless steels in food contact (D.M. 21-03-1973).
Immersion in acetic acid results in an increasing relative chromium content in the surface oxide of the knife steel from 0.11
0.12 to 0.52 (Cr/(Cr + Fe)). An increasing chromium content of the
surface oxide has previously been illustrated in numerous studies
(Herting et al., 2006, 2008) to enhance the passivating properties
of the surface oxide and to restrain metal release. The chromium
is enriched in the surface oxide during immersion due to preferential release of iron causing depletion of iron and hence an increase
in chromium in the surface oxide. The proportion of released metals in relation to the bulk composition, and surface oxide composition, is illustrated in Fig. 5. From the results it is evident, that the
released fraction of chromium is signicantly less than, and not
correlated to, the bulk composition or to the surface oxide composition. Similar to previous ndings, the presence of a chromiumrich surface oxide reduces the degree of metal release from
stainless steel (Herting et al., 2006, 2008). The results imply that
repeated food contact generally may improve the corrosion resistance, at least for the knife steel in this investigation.
Large variations in total release rates were observed for the scissor steel both between samples originating from the same scissor
blade, and between samples from different blades. Comparison of
the electrochemically active surface area by means of electrochemical impedance spectroscopy, EIS, shows that the active surface
areas were similar in size. No distinction could be made between
samples showing high release rates and samples with low release
rates.
Two samples out of six remained shiny without visible corrosion products after 10 days of immersion, whereas the remaining
four samples displayed blackish corrosion products on the surface,
from here on denoted corroded surfaces. Still shiny surfaces, denoted uncorroded surfaces, after immersion resulted in an enrichment of the chromium content in the surface oxide, increasing
from 0.120.13 to 0.49 (Cr/(Cr + Fe)), whereas the corroded surfaces formed were primarily enriched in copper and sulphur (as
sulphide) and depleted in chromium, hence reducing the passivating properties signicantly. High concentrations of released metals, signicantly exceeding the threshold value for chromium
release, strongly discoloured the acetic acid solution at rates several orders of magnitude higher compared with the shiny surfaces.
28
Fig. 5. Released fraction of chromium (Cr/(Cr + Fe)) from the AISI 420 knife steel
compared to its bulk alloy composition determined with XRF and its surface oxide
composition by using XPS, prior to, and after 10 days of immersion in 3 vol% acetic
acid at 40 C.
Higher release rates from the scissor steel compared with the
knife steel are not very surprising in view of the low and varying
chromium content of the surface oxide and the highly inhomogeneous material in terms of microstructure and surface nobility.
However, the extreme metal release rates observed from the
majority of samples of the scissor steel was not expected, and
had to be further investigated (see paragraphs below).
In view of the fact that both steels revealed high, or extremely
high or accelerated released metal concentrations, close to or signicantly exceeding the stipulated threshold value for chromium
release from stainless steels in food contact, further studies were
necessary. One hypothesis to be investigated was the importance
of surface nish in addition to the inhomogeneous microstructure.
3.2. Inuence of surface nish on the metal release process
The surface nish, combined with other surface properties
such as oxide composition and thickness, has previously shown
to largely inuence the metal release process for stainless steels
(Herting et al., 2006; Wallinder et al., 2003). The process to acquire a specic surface nish can vary signicantly between different producers, depending on factors such as if the surface
treatment is hand-operated or automatically produced, differences in applied grinding/polishing pressure, surface temperatures, grinding agents.
Raw surfaces of the knife and the scissor steel were manually
polished by a professional according to a state-of-the-art polishing
procedure (excess of polishing agent and a low applied pressure
between the polishing wheel and the surface, minimising the surface temperature, see experimental). The different polishing procedures were investigated in order deduce if the way of polishing
(various surface nishes) could have a signicant inuence on
the metal release process.
EIS measurements of the different surfaces of the knife and scissor steel presented: (i) knife steel active surface area > scissor steel
active surface area, (ii) state-of-the-art polished surfaces had more
inhomogeneous surfaces than poorly polished surfaces, (iii) poorly
polished knife steel had smaller active surface area than state-ofthe-art polished knife steel, whereas scissor steel had similar surface areas for the two polishing procedures.
Identical immersion experiments, as for the company polished
surfaces, were performed on the knife and the scissor steel (18
samples of each grade) with this modied surface nish. For both
steels, the passivating properties of the modied surface nish
were not improved compared to the company polished surfaces,
in particular pronounced for the scissor steel. One sample out of
18 samples investigated in total of the knife steel, and ve samples
of the scissor steel, displayed an accelerated metal release process
forming blackish surfaces and discolouration of the acetic acid. Released metal concentrations and relative surface composition closely resemble the company polished scissor steel samples
showing the same behaviour.
Uncorroded surfaces after immersion of the knife steel revealed
similar or slightly higher release rates of both chromium and iron
compared with the company polished surface nish (Fig. 6). However, the modied surface nish of the scissor steel, proven to have
a highly inhomogeneous microstructure, displayed large differences in metal release rates compared with the company polished
surfaces. The results imply that inhomogeneities in the matrix are
of greater importance for the degree of metal release in relation to
the corresponding effect of surface oxide ageing.
The discrepancy in results between the company polished surfaces and the modied surfaces is most likely related to an air-aged
surface oxide of improved passivating properties compared to
freshly polished surfaces.
As state-of-the-art polishing did not improve the passivating
properties, interpreted as the degree of metal release, the surface
nish was modied further. Raw surfaces of the knife and the scissor steels were polished with a high applied pressure and a deciency of polishing agents, aiming to obtain a high surface
temperature during the polishing process, i.e., diametrically opposed to the state-of-the-art procedure described above.
These modied surfaces proved to possess improved passivating properties from a metal release perspective both for the knife
steel, and in particular for the highly inhomogeneous scissor steel,
Fig. 6. Metal release rates of iron and chromium from company polished knife and scissor steels of grade AISI 420 immersed in 3 vol% acetic acid at 40 C for 10 days
compared to the same materials with modied surface nishes, polished to achieve a minimal increase in surface temperature during treatment, exposed to identical
conditions.
29
Fig. 7. Metal release rates of iron and chromium from company polished knife and scissor steels of grade AISI 420 immersed in 3 vol% acetic acid at 40 C for 10 days
compared to the same materials with modied surface nishes, polished to achieve a maximal increase in surface temperature during treatment, exposed to identical
conditions.
Fig. 8. Changes in average release rates (a) and calculated momentary release rates
of chromium (b) for the scissor steel (grade AISI 420) with the modied surface
nish, polished to achieve a maximal increase in surface temperature during
treatment, immersed for 10 days in 3 vol% acetic acid at 40 C. The scatter reects
variations between triplicate samples.
30
Bardal, E., 2004. Corrosion and Protection. Springer-Verlag, London Limited, ISBN
1-85233-758-3.
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