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Metal Release of Stainless Steel
Metal Release of Stainless Steel
Metal release of stainless steel
particles in artificial lung fluid:
complexation and synergistic effects
Yi Liu
Master Thesis
Examiner: Inger Odnevall Wallinder
Supervisors: Yolanda Hedberg;
Inger Odnevall Wallinder
Stockholm, 2010
Division of Surface and Corrosion Science
School of Chemical Science and Engineering
Royal Institute of Technology, KTH
Stockholm, Sweden
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Contents
Summary ................................................................................................................. 1
1. Basics and background ........................................................................................... 2
1.1 Basics of stainless steels and passive films .................................................. 2
1.2 Corrosion and metal release ........................................................................ 3
1.3 Metal release in aqueous solutions ............................................................. 4
1.4 Redox and metal release .............................................................................. 5
1.5 Complexation assisted metal release ........................................................... 7
1.6 Selective dissolution ..................................................................................... 8
1.7 Background of this project ........................................................................... 8
2. Experimental ......................................................................................................... 11
2.1 Materials and characterization .................................................................. 11
2.2 Exposure experimental plan ....................................................................... 11
2.3 Atomic Absorption Spectroscopy (AAS) ..................................................... 14
2.4 Polarography .............................................................................................. 14
2.5 X‐ray photoelectron spectroscopy (XPS) .................................................... 14
2.6 Raman ......................................................................................................... 15
3. Results and discussions ........................................................................................ 16
3.1 Characterization of stainless steel particles ............................................... 16
3.2 Total metal release ..................................................................................... 17
3.3 Iron and chromium release ........................................................................ 19
3.4 Nickel and manganese release ................................................................... 24
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3.5 Synergistic effects ....................................................................................... 26
3.6 Complexing agents and metal release rate ................................................ 27
4. Conclusions and future works .............................................................................. 33
5. Acknowledgement ................................................................................................ 35
6. References ............................................................................................................ 36
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Summary
Numerous metal release data have been published by the Div. Surface and Corrosion
Science and the AISI 316L stainless steel particles’ behavior in artificial lysosomal
fluid (ALF). This study aims to evaluate the effect of chemical components in ALF on
metal release from stainless steel particles with a bottom‐up methodology. Two
sizes of 316L stainless steel particles were used to assess the particle size influence
on the metal release in detail.
The results show that organic complexing agents e.g. lactate, tartrate and citrate are
responsible for the high metal release rate in ALF. Correlations between the metal
release rate and the number of carboxyl groups of the organic ligand were observed.
Moreover, metal release data in this study indicates no synergistic effects in ALF
solution, and continued research is on‐going to study the synergistic effects further.
No quantitative rules of iron, chromium and nickel release from the same stainless
particles could be found which may indicate that these metals are released through
different pathways e.g. diffusion or chemical dissolution. In different solutions with
different chemical components, one or more metal release mechanisms dominate
over others and make the metal release rate unpredictable.
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1. Basics and background
1.1 Basics of stainless steels and passive films
Stainless steels are iron alloys containing a minimum of 11 wt% chromium. They can
be named in various ways and AISI 316L stainless steels are named according to the
American Iron and Steel Institute (AISI) numbering system. 316L stainless steels are
widely used in chemical, petroleum and power industries as well as permanent
implants in vivo, because of its excellent corrosion resistance. The excellent
corrosion‐resistance comes from its low carbon content (<0.03 wt%, resist to crevice
corrosion) and the stable chromium‐rich passive film (resist to generalized corrosion
and pitting).
There are three crystallographic structures of stainless steels: austenitic
(face‐centered cubic), ferritic (body‐centered cubic) and martensitic (body‐centered
tetragonal or cubic). Duplex stainless steels have both austenitic and ferritic
structures with roughly equal amounts. Alloy elements in stainless steels could be
either austenite stabilizers (e.g. Ni) or ferrite stabilizers (e.g. Cr). Austenitic stainless
steels appear to have significantly greater potential for aqueous corrosion resistance
than their ferritic counterparts (Sedriks 1996). This conclusion is perhaps also true
from a metal release point of view as suggested by the previous work published in
(Herting, Odnevall Wallinder et al. 2007).
Generally, the passive film is a thin oxide (thickness in the range of a few
nanometers) with a compositional enrichment in Fe and Cr oxides, hydroxides
and/or oxyhydroxides. The structure of the passive film could be described as double
layers. For pure iron, it has been known that the outer layer is γ‐Fe2O3 and the inner
layer is Fe3O4. The chemical composition of the passive film of stainless steels is
more complicated because the alloy elements will participate in the passive film
formation directly and/or indirectly. Under mild temperature and sufficient oxygen
supply, the passive film is enriched in iron‐, and chromiumoxides. Alloy elements (i.e.
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nickel and manganese) may also exist in the passive layers, usually in an alloy surface
layer beneath the outermost surface oxide. (Landolt 1995)
1.2 Corrosion and metal release
Corrosion and metal release are two different but related processes, which are often
not distinguished in literature. They both are descriptions of the degradation of
metallic materials but from different point of views. Corrosion is an electrochemical
process while metal release describes an overall outcome which could be caused
by electrochemical, chemical or mechanical processes (degradation of the metal and
metal oxide).
One example illustrating how metal release and corrosion are different is the alloy
element effects. Mn is believed to be beneficial to improve corrosion resistance. But
Schwertmann et al. (Schwertmann 1991) observed that when alloying with Mn, the
release rate increased in contrast to the corrosion rate which decreased.
Moreover, corrosion inhibitors don’t necessarily mean metal release inhibitors.
Corrosion rates are determined through electrochemical measurements of current
densities while metal release rates are determined using the total released metal
species in solution divided by time and surface areas with unit such as μg/cm2/hour.
Carboxylic acids such as oxalate and tartrate anions are believed to be corrosion
inhibitors because when these anions are added, the critical current density
decreases and hence also the corrosion rate (Badea and Badea 2005). However,
carboxylic acids are generally believed to be metal release accelerators, an effect
also observed in our experiments. The possible reason for the decrease of the critical
current density with oxalate and tartrate additives may be the selective dissolution
of Fe while Cr is enriched in the passive layer. The selective dissolution of Fe has
been respectively observed during exposures in various solutions both in our lab and
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in other publications (Hedberg, Midander et al. 2010; Hultquist, Leygraf et al. 1984;
He, Knudsen et al. 2009; Midander, Frutos et al. 2010)
1.3 Metal release in aqueous solutions
A general review of key issues occuring on the surfaces when a particle is exposed in
an aqueous solution is shown in figure 1. Film formation happens simultaneously
with surface oxide dissolution.
Figure 1 Reactions during the exposures in solutions; (1) corrosion and metal release when no complexing
agents are involved, the metal ions are released by diffusion and chemical dissolution of metal oxides; (2) film
formation controlled by oxygen diffusivity; (3) redox reactions controlled by electrons transfer; (4) metal
release process when complexing agents are present
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On the surface, metal oxide dissolution processes can take place through three
pathways: protonation, reduction and complexation as shown as equations as
follows (Schwertmann 1991)
The rate law of protonation assisted metal release could be described as follows
(Blesa, Weisz et al. 2000)
The rate law is only suitable for highly unsaturated media. The rate constant kexp
depends on the surface/volume ratio, on ionic strength, and on the history of the
sample. According to the rate law, protonation assisted metal release is a function of
pH. pH is well controlled at 4.5±0.1 in this study to eliminate the influence of pH
effects.
1.4 Redox and metal release
Reductive dissolution of metal oxides has been intensively studied and is believed to
be an important mechanism to accelerate metal release. In Fe(III) oxide dissolution,
H+ attack is generally less important than the attack by reductants (Afonso, Morando
et al. 1990). Two broad classes of reductants are effective: reducing metal ions
especially in the form of complexes, and other non‐metallic reductants. In principle,
all organic matter is thermodynamically apt to reduce Fe(Ⅲ). Some examples of
non‐metallic reductants in literature are ascorbic acids (Afonso, Morando et al. 1990)
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and cysteine (Amirbahman, Sigg et al. 1997). Take ascorbic acid as an example, the
reaction is as follows (Afonso, Morando et al. 1990)
(5)
A2‐ represents ascorbate and A‐ is an ascorbate radical. The radicals could regenerate
themselves and autocatalize the reactions.
Ligand‐promoted reductive dissolution is more important in ALF solutions. The
mechanism could briefly explain as follows, take EDTA as an example (Ananthan,
Venkateswaran et al. 2003):
(6)
Fe2+ itself is a reductant too, but its reductivity is increased when complexed with
EDTA. The complexes diffuse and adsorb on the metal oxide surface to reduce Fe(Ⅲ)
on the surface. The electron exchange between adsorbed Fe (III) and surface Fe (II)
weakens Fe‐O bonds and generates surface Fe (III) that is readily labile. After adding
extra Fe2+ ions, the dissolution rate could reach its maximum value (Ballesteros,
Rueda et al. 1998). This mechanism could also apply to Cr release by complexing
with Cr (III) and reducing Cr (VI).
It is apparent that there is a synergistic effect between the complexing agents and
reductants. Reductants like ascorbic acids could help to produce extra Fe2+ as
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showed above. A formulation citric acid‐ascorbic acid‐EDTA is designed to dissolve
Fe2O3 particles (Ananthan, Venkateswaran et al. 2003).
1.5 Complexation assisted metal release
The complexation assisted metal release is believed to take place through the
following series of steps (Carbonaro, Gray et al. 2008): (i) diffusion of ligand from
bulk solution to the mineral surface; (ii) formation of an initial adsorbed species or
complex; (iii) conversion to an adsorbed species capable of detaching surface‐bound
metal atoms; (iv) detachment of the metal ion‐chelating agent complex from the
surface; and (v) diffusion of this complex into bulk solution.
The stability constant logK value is used to quantify the complexation ability of a
ligand. According to the constants, the complexation ability of chloride is negligible
(Martell 1977) . But chloride ions could still be part of the process by weakening Fe‐O
bonds (Cornell, Posner et al. 1976).
It is reasonable to assume that the stronger complexation ability, the higher is the
metal release rate. Milosev et al. (Milosev and Strehblow 2000; Milosev 2002;
Milosev and Kosec 2007) believed there is a correlation between the metal release
rate and the stability constants. However, the dissolution of synthetic iron oxide
particles with citrate and oxalate were compared by Zhang and colleagues (Zhang,
Kallay et al. 1985) . Although citrate forms stronger complexes with Fe than oxalate,
much less Fe was dissolved by citrate. In this paper, the author also observed a linear
relationship between log R and log Γ, where R is the metal release rate in μmol/g and
Γ stands for the carboxylic acid adsorbed amount in mole/m2. So they concluded that
the adsorption of complexing agents plays a dominate role on the metal release rate.
In the results and discussion parts, we also discuss the mechanisms which may
influence the metal release rate results in more detail.
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In general, complexing agents could increase the metal release rate by assisting
reductive dissolution indirectly or by complexing with metal ions directly. However, a
complexing agent could also decrease the metal release rate sometimes by blocking
the adsorption sites and hinder for example the protonation process.
1.6 Selective dissolution
Simultaneous dissolution is defined as the dissolution of the alloy elements at a rate
proportional to their atomic concentration in the alloy, while selective dissolution is
defined as the dissolution of the alloy elements at a rate higher than their
concentration in the alloy and thus cause the enrichment of other elements
(Keddam 1995). A selective dissolution factor SMe could be employed to represent
the dissolution selectivity of a specific element (Castle and Qiu 1989).
%
; % ⁄∑ (7)
%
SMe is the selectivity factor for a metal element Me, and Me wt% is the content of
the metal in weight percentage. Me is selectively dissolved if SMe > 1. Uniform or
simultaneous dissolution occurs when SMe = 1, while the element is enriched in the
oxide layer if SMe < 1.
1.7 Background of this study
The purpose of this project is to explain some very interesting results in previous
work within the KTH research team, as shown in figure 2 (from Hedberg, Gustafsson
et al. 2010). The release rate of Fe is the total released amount of Fe normalized to
the surface area and time. Since the coarse and fine particles are both gas‐atomized
316L stainless steel, it is reasonable to expect similar Fe release rates. However, the
results showed a five‐time difference in artificial lysosomal fluid (ALF) while not in
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other pH‐neutral physiological fluids. It was also noticed that ALF is very aggressive
in terms of metal release rate regarding the low pH effect, especially for the fine
particles. The coarse and fine particles are also studied and denoted as 45μm and
ultrafine (UF) particles in this thesis. Chemical compositions and further information
related to the four physiological fluids are given in the doctoral thesis of Klara
Midander (Midander 2009).
In addition, a high complexation ability of ALF with polarography was also observed
(Hedberg, Gustafsson et al. 2010; Midander et al. 2010). It was unclear if some
synergistic effects occur in the ALF fluid. A synergistic effect means different entities
corporate in favor of a final outcome. In this case, it means two or more chemicals
contribute to the overall metal release rate that is higher than the sum of the metal
release rates generated by each of the chemicals individually. This master thesis
project is therefore designed based on a bottom‐up methodology using each
component of ALF in each solution. The aim is to assess the contribution of each
chemical individually and combined to enable comparisons between the summed
metal release rate and the real metal release rate in the ALF solution.
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Figure 2 Fe metal release rate of coarse and fine 316L stainless steel particles in different physiological fluids
( Hedberg, Gustafsson et al. 2010). Coarse and fine particles are denoted as 45μm and ultrafine (UF) particles in
the framework of this thesis, respectively. ALF=artificial lysosomal fluid; ASW=artificial sweat; GMB=Gamble’s
solution; ATF=artificial tear fluid.
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2. Experimental
2.1 Materials and characterization
The 45μm and UF powders were provided by Arcam AB, Sweden, and Sandvik
Osprey Limited, respectively, and used as‐received. According to the manufacturer,
87 wt% of the 45μm sized particles had a diameter less than 45μm. For the ultrafine
(UF) particles, 93 wt% had a diameter less than 4μm.
Prior to exposure experiments, the surface topography, specific surface area and
particle size distribution of both powders were characterized by scanning electron
microscopy (SEM, Hitachi TM‐1000), Brunnauer‐Emmet‐Teller (BET) method and
laser diffraction technique (Malvern® Mastersizer 2000), respectively. Details of the
instruments are given in the master thesis of Yolanda Ullmann (Ullmann 2009) and in
(Hedberg, Gustafsson et al. 2010).
2.2 Exposure experimental plan
In the framework of this thesis, we performed 15 groups of exposure tests. The
controlled experimental conditions set for each exposure and the 8 exposures in
each group are schematically illustrated in figure 3.
Figure 3. Scheme of the exposure experimental design; (a) Controlled experimental parameters for all
exposures; (b) 8 exposures in one group
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15 different solutions were used for each group of exposure, respectively, including
12 solutions with only one chemical in artificial lysosomal fluids (ALF) each, and
adjusted to pH 4.5±0.1 with HNO3 or NaOH; 2 controlled groups with ultra pure MQ
water (18.2 MΩ/cm) only and MQ water adjusted to pH 4.5±0.1 with HNO3; and one
group with full‐spectra ALF solution. The chemical composition of ALF is shown in
table 1 with 12 chemicals. All solutions were adjusted to pH 4.5±0.1 with appropriate
amounts of nitric acid or NaOH.
Table 1. The chemical composition of artificial lysosomal fluid (ALF) (Moss 1979)
For each exposure, first 100±1mg stainless steel particles were weighed in a 50mL
PMP Nalgene® jar and then 50mL of solution was added into the jar with glass
pipettes. The jar was placed into the incubator (Platform Rocker S180) which had
been preheated to 37°C and the linear agitation was started at a speed of 25 cycles
per minute. The starting time was recorded. After 24h, the jar was taken out and
40mL of the upper clear liquid was poured into a 50mL HDPE centrifuge tube and the
left liquid and particles was poured into a 15mL HDPE centrifuge tube. To accelerate
particles to settle down, both the 50mL and 15mL centrifuge tubes were centrifuged
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at 3000 r.p.m. (704 r.c.f.) for 10min. After centrifugation, the upper clear solution
(supernatant) in the 50mL centrifuge tube was poured in a polypropylene 25mL
storage flask. After waiting until the solutions cooled down to room temperature,
the solutions were frozen. Extreme care was taken to avoid any particles to be
included when transferring the solutions into the 25ml flasks. The pH after exposure
was recorded with the rest of solutions in the 50mL centrifuge tubes.
Stainless steel particles after exposure were separated from the liquid by sucking out
the solutions in the 15mL centrifuge tubes. One or two samples in every 3 replicates
were washed by refilling the centrifuge tubes with MQ water and then shaking
manually. They were re‐centrifuged at 3000 r.p.m. for 10min and the liquid was
sucked out . A strong magnet was used to help the separation of UF particles from
solutions. The washed and unwashed particles were air‐dried in desiccators under
room temperature. It took days to air‐dry the particles and after drying, the particles
after exposure were also stored in the freezer to avoid transformations.
All containers and pipettes used in the exposure experiments were cleaned following
a strict acid‐cleaning procedure. First, the equipment was cleaned with warm water,
detergents and brush. Then they were immersed in 10% HNO3 for at least 24h. The
equipment was then rinsed with MQ water 4 times and air‐dried before using.
2.3 Atomic Absorption Spectroscopy (AAS)
The total metal release of Fe, Cr, Ni and Mn was measured with Atomic Absorption
Spectroscopy (Perking‐Elmer AAnalyst 800), with the graphite furnace for low
concentration (μg/L) and flame for high concentration (mg/L). All samples were
acidified with 65% HNO3 before the measurement. Detailed information in (Ullmann
2009). The limits of detection (based on 3 times the standard deviation of blank
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samples) were 1μg/L, 0.5μg/L, and 0.5μg/L for Fe, Cr, and Ni, respectively. (Hedberg,
Midander et al. 2010)
2.4 Polarography
Polarography is a subclass of voltammetry where the working electrode is a dropping
mercury electrode (DME) or a static mercury drop electrode (SMDE). The dropping
mercury electrode was used in this study. 10mL of the sample solution was mixed
with 2.5mL supporting electrolyte and adjusted to a pH of 6.2 ± 0.1 with 30% NaOH.
In a sample solution without complexation ability, the peak height is expected to
increase linearly with the amount of Cr6+ added. But with complexation ability, the
peak height does not change initially or increases only slowly until a certain point.
After this point, the peak height increases with added Cr6+ amount again. A curve is
drawn with peak height as Y‐axis and added Cr6+ amount as X‐axis. Complexation
ability of the sample solution is described using the slope of the peak height‐added
Cr6+ amount curve or the point where it starts to increase linearly. More information
in (Midander et al. 2010).
2.5 Xray photoelectron spectroscopy (XPS)
X‐ray photoelectron spectroscopy (XPS) is a quantitative and qualitative
spectroscopic technique that measures the elemental composition, empirical
formula, chemical state and electronic state of the elements that exist within a
material (Wikipedia 2010). It could access the depth from 1 to 10nm and detect all
elements with atomic number 3 (lithium) and above. The binding energy (BE) used
and mass concentration are summarized in results and discussion parts. XPS analysis
was conducted using UltraDLD spectrometer from Kratos Analytical. Wide spectra
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were run to detect elements present in the outermost surface oxide layer
(information depth of a few nanometers) at different locations.
2.6 Raman
Raman spectroscopy is a spectroscopic technique used to study vibration, rotation,
and other low‐frequency modes in a system. When light impinges on the sample,
molecules are excited from the ground state to higher energy state. The molecules
then return to a new energy state. The difference in energy between the original
state and this new state leads to a shift in the emitted photon frequency away from
the excitation wavelength. The shift of the wavelength is characteristic according to
the vibration and/or rotation modes. Measurements were run at 5 different spots
per sample were measured and the average results reported to represent the overall
composition of the samples.
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3. Results and discussions
3.1 Characterization of stainless steel particles
The measured specific surface areas of 45μm and UF powders were 0.069 and 0.7
m2/g, respectively. Particle size distribution information is described elsewhere
(Ullmann 2009; Hedberg, Gustafsson et al. 2010). The shape and morphology of the
two powders were characterized by means of SEM as shown in figure 4. The stainless
particles had nearly spherical shapes with smooth surfaces with local dents.
Figure 4 SEM images of the morphology of 316L powders of varying size prior to exposure; (a) 45μm; (b) UF
Raman results of the unexposed particles are presented in figure 5. Clear peaks were
observed for α‐Fe2O3 at about 225cm‐1, 295cm‐1, 400cm‐1, and 1320cm‐1, respectively.
The most intense peak observed in the Raman spectra was observed at
approximately 680cm‐1. From wavenumber 300cm‐1 to about 600cm‐1, peaks were
severely overlapped. Fe(OH)2 could also exist with characteristic wavenumbers at
460cm‐1 and 550cm‐1 (Gui and Devine 1994) but could not be clearly identified from
the spectra. No peaks attributed to chromium oxides were observed in the Raman
results, despite the fact that Cr was present in the passive film, as evidenced by
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previous XPS findings (Midander et al. 2007; Hedberg, Gustafsson et al. 2010;
Hedberg et al. manuscript).
Figure 5 Raman results of unexposed 316L particles of varying size.
3.2 Total metal release
The total amount of iron, chromium, nickel and manganese release normalized to
the amount of particles loaded is shown in figure 6 and indicates the percentage of
particles dissolved. After 24h of exposure, up to about 0.05% and 1.6% of loaded
45μm and ultrafine particles were dissolved, respectively. In ALF, citric acid and
other solutions with organic ligands, primarily iron and manganese were released,
whereas chromium and nickel were only released to a very small portion. However,
in other solutions without organic ligands, no such preference was observed. The
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different proportions of released iron, chromium, nickel, and manganese in the
different solutions may suggest dissolution through different pathways.
Figure 6 Total amount of iron, chromium, nickel and manganese release per amount of 316L particles loaded
(45 µm‐top; UF‐bottom)
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3.3 Iron and chromium release
Metal release rates of iron and chromium of 45μm and UF particles are presented in
figure 7. Iron and chromium exist in the passive layer mainly in the form of oxides.
The release of iron from the UF powder was about five times higher in ALF and citric
acid solutions compared with the 45μm sized powder. These results are consistent
with previous findings illustrated in figure 2 (Hedberg, Gustafsson et al. 2010).
Within the current project, it was concluded that the presence of citric acid was
responsible for high release of iron in ALF. In ALF, citric acid is the main component
to an amount of 20.86g. Citric acid is also a well‐known complexing agent. With the
exception of citric acid and ALF, the release rate of iron was lower for UF particles
compared with 45μm particles in all other solutions. Chromium revealed a similar
behavior as iron, however released to a significantly lower extent in citric acid and
ALF. The release of chromium from UF particles was higher in ALF and citric acid
solution compared with the 45 µm sized particles but less in all the other solutions.
XPS data of 45μm and UF particles before and after exposures in citric acid and ALF
solutions are presented in figure 8. We noticed that iron was selectively dissolved
from the outer layer and this selective dissolution effect in ALF is largely due to citric
acid.
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Figure 7 Iron and chromium release rates in two control groups, 12 single solutions and ALF fluid with full
spectra of all the 12 chemical components. The bars indicate average values of 2 or 3 samples and error bars
indicated the standard deviations between or among samples; <blank=iron concentration in solution after
exposure is less than the concentration in control groups without particles; (2) =mean values of 2 exposures,
one sample is eliminated in CaCl2 45μm, CaCl2 UF and pyruvate UF groups, respectively, because of
contamination
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45μm UF
Before
citric
acid
ALF
Figure 8 Relative presence of iron and chromium in the outermost surface layer determined by means of XPS
(mass‐%) of 45μm and ultrafine particles before and after exposures in citric acid and ALF solutions
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The chromium release rate could be influenced by pH change. We observed Cr2O3 on
some particle samples after exposure as shown in figure 9. Four Raman spectra are
selected to illustrate that the characteristic peak of Cr2O3 at approximately 580cm‐1
appears only when the solution pH after exposure exceeds 6, while it is not in
relation to particle size or solution type.
For chromium release rates as shown in figure 7, UF particles released more Fe and
Cr in citric acid and ALF solutions compared to 45μm particles, while it was the
opposite situation in all the other solutions. This pattern might be explained by
chromium readsorption. pH of solutions after exposures changed less for 45μm
particles compared with UF particles. After exposure, solutions with the 45μm
powder increased slightly above 4.5. However, exposures with the UF powder
resulted in an increased pH up to 5‐6 depending on the total amount of metal
release and the buffering ability of the solution. Because of the high pH, dissolved
Cr(III) can re‐adsorb on the particle surface. Iron oxide on the particle surface is
believed to be preferential adsorption sites for chromium. Overall, UF particles
released less metals in all solutions except in ALF and citric acid as a result of
re‐adsorption of dissolved chromium forming Cr2O3 on the surface.
However, the solution pH did not change in citric acid and ALF after exposure
because of their strong buffering abilities. In these cases, chromium was not
re‐adsorbed and the UF particles showed as a consequence higher chromium release
rate than observed for the 45μm sized powder. These observations are supported by
results presented in figure 10 (Richard and Bourg 1991).
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Figure 9 Raman results of 316L particles after exposure, selected results with two powders (Ultrafine‐UF and
45 µm sized particles‐45 µm) exposed in NaCl and citric acid solutions. The dashed line shows the position of
the characteristic peak of Cr2O3 at about 580cm‐1
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Figure 10 Chromium (III) adsorption as a function of pH and of solution composition at 25°C (Richard and Bourg
1991). Initial chromium concentration 1.5 x 10‐3 mol/l; 2 g kaolinite/l; the curve labelled "blank" represents a
Cr(NO3)3 solution without kaolinite
3.4 Nickel and manganese release
Nickel and manganese release rates are presented in figure 11. After exposures in
citric acid and ALF solutions, UF particles released more Ni and Mn than 45μm
particles in both cases. However, in all the other groups, nickel and manganese
release showed different patterns. Nickel was released to a higher extent for the UF
powder while manganese was released to a higher extent from the 45μm powders.
A large difference between manganese release rates in citric acid and ALF solutions
was observed. We previously believed that metal release in ALF solution was largely
due to citric acid both because of its high concentration and its high corrosion ability.
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Observed release rates of iron, chromium, nickel, and manganese release rates
results support this belief.
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Figure 11 Nickel and manganese release rates in two control groups, 12 single solutions and ALF fluid with full
spectra of the all 12 chemical components. The bars indicate average value of 2 or 3 samples and error bars
indicate the standard deviations between or among samples; (2) =mean values of 2 exposures, one sample is
eliminated in CaCl2 45μm, CaCl2 UF and pyruvate UF groups respectively due to contamination
3.5 Synergistic effects
In this study, the ALF solution was “separated” into 12 single solutions with one
component in each solution to study if there are any synergistic effects which make
the ALF solution so aggressive for metal release beside the effect of its low pH. The
metal release rate of the sum of each solution (summation ALF) was calculated
according to equation 8 by adding metal release rates in all 12 single solutions and
subtracting 11 metal release rates in MQ pH4.5 to eliminate duplicate pH effects.
Comparisons between metal release rates in the summation ALF and real ALF
solution are shown in figure 12. The results suggest that there is no significant
difference between the summation ALF and the real ALF solution, which implies that
no synergistic effects appeared to exist in the ALF solution. However, it could also be
that the synergistic effect is very weak and hidden by other inhibitive effects or
systemic errors. Some continued studies were performed with different
combinations of chemicals to further verify or falsify synergistic effects in ALF
solutions.
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Figure 12 Comparison between metal release rate in summation ALF and real ALF, p=0.926>0.05 indicating no
significant differences between the metal release rate in summation ALF and real ALF; summation ALF is
calculated according to equation 8 to eliminate duplicated pH effects
3.6 Complexing agents and metal release rate
Chemical structures of six organic ligands are shown in figure 13 with one amino acid,
two mono‐carboxylic ligands, one di‐carboxylic ligand and one tri‐carboxylic ligand.
Citrate is the salt form of citric acid.
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Figure 13 Chemical structures of organic components in ALF; citrate is the salt form of citric acid.
For iron, chromium, nickel and manganese, a correlation between the metal release
rate and the number of carboxyl groups was observed as shown in figure 14. It
seems that metal release increased with the number of carboxyl groups for iron,
chromium and nickel. The underlying mechanisms of this correlation could be their
adsorption ability and/or complexation ability. We did not investigate the adsorption
isotherms of the organic ligands in this project, something that may be investigated
in the near future.
The complexation ability of the organic ligand was investigated by means of
polarography and the results are shown in figure 15. The sequence of complexation
ability from strong to weak is pyruvate>lactate≈tartrate≈citrate>glycine. This
sequence does not fit to the metal release observations. Another parameter used to
quantify the complexation ability was the stability contant, log K. The stability
constant is defined according to equation 9.
log K M · L ⁄ M · L for reaction M L M · L (9)
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Stability constants can be found in the NTIS database (Martell 1977). However, not
enough data for iron and chromium was found, why only data for nickel is used to
compare with the nickel release rate normalized to molar chemical as shown in table
2. No correlations were found between metal release rates per mol chemical and
stability constants log K.
29
30
Figure 14 Iron, chromium, nickel, and manganese release rates normalized to molar concentration of chemicals
added, showing relations between release rate per mol chemical and functional groups of the chemical
Figure 15 Complexation abilities of glycine, pyruvate, lactate, tartrate and citrate characterized by
polarography. The complexation ability, from strong to weak, was pyruvate>lactate≈tartrate≈citrate>glycine
31
Table 2 Comparison of stability constants log K of nickel and metal release rates normalized to molar chemicals
32
4. Conclusions and future work
The aims of this project were to address and answer two main questions: (1) why the
ALF solution is very aggressive in terms of metal release beside its pH effect; (2) why
UF particles release five times more metals per surface area and time unit?
This master thesis project was able to partially answer the two questions and left a
number of new questions to be answered. The following main conclusions were
drawn:
Citric acid contributes most to metal release in ALF solution due to its high
concentration and complexation ability. We have confirmed that the high metal
release ability of ALF is due to its high complexation ability and we also observed a
correlation between metal release rate per molar organic ligand and the chemical
structures of the ligand. A higher number of carboxyl groups of the chemical
structure resulted in a higher metal release rate per molar chemicals. The underlying
reasons could be adsorption abilities and/or complexation abilities of the carboxyl
groups. However, at this stage the exact underlying mechanisms could not be
determined. Furthermore, no synergistic effect appeared as investigated through a
bottom‐up methodology.
The different behaviors of the UF and 45μm powders became even more evident
after the project. Iron, chromium and nickel release rates were quite different for
the different powders in the different solutions. For iron, chromium, and manganese,
UF particles released more in ALF and citric acid solutions but less in all the other
solutions. For nickel, UF particles released the most in all solutions. These results
may suggest that iron and chromium, nickel, and manganese are released through
different pathways, probably in correlation to their position on the surface. For
example, iron is located in the outer surface which may be released through iron
oxide dissolution assisted by organic complexing agents. Further efforts are required
to analyze the microstructures of the two particles.
33
Some continued studies are performed in the Div. Surface and Corrosion Science. For
example, the relationship between metal release rate and concentration of citric
acid and metal release rate caused by different combination of chemicals on
synergistic effects has been available. We observed a strange Raman peak at
860cm‐1 on particles after exposure in citric acid which could be Cr (VI) but more
evidence is needed.
We also have some quite interesting findings on alloy elements i.e. nickel and
manganese. In our powders, manganese exists in the outermost surface oxide prior
to exposures, which was not the case for nickel. However, after 24h exposure in ALF
and citric acid solutions, manganese disappeared, while nickel became present in the
outermost surface oxide according to XPS.
The results of this study and some further studies will be published in a scientific
peer‐reviewed paper (Hedberg, Hedberg et al. manuscript in preparatino), where
also further detailed information can be found.
34
5. Acknowledgement
I wish to express my sincere gratitude to Professor Inger Odnevall Wallinder and
Yolanda Hedberg for providing the great opportunity to work in the Div. Surface and
Corrosion Science and the original genius design of the whole project which makes
the process smooth and a lot of fun.
I feel very indebted and also thankful to my supervisor Yolanda Hedberg because of
her unremitting encouragement and strong backup. I also want to thank all the
predecessors working on metal release for their excellent work which lay a solid
ground for this project and among them, Klara Midander and Yolanda Hedberg must
be mentioned by names. I’m also grateful to Gunilla Herting for her spirit inspiration
and support, who gave me a great lesson on how to facing failures.
I owe a lot of debt to Jonas Hedberg for his efforts on Raman analysis and Raman
data interpretations without returns. All the members in stainless steel particle
group (SSPG) are all experts and I learn a lot of them through the inspiring
discussions. And I feel lucky that I can work in the Surface and Corrosion Division.
35
6. References
Afonso, M. D., Morando, P. J., Blesa, M. A., Banwart, S., Stumm, W. (1990). THE
REDUCTIVE DISSOLUTION OF IRON‐OXIDES BY ASCORBATE ‐ THE ROLE OF
CARBOXYLATE ANIONS IN ACCELERATING REDUCTIVE DISSOLUTION. Journal
of Colloid and Interface Science, 138(1), 74‐82.
Amirbahman, A., Sigg, L., vonGunten, U. (1997). Reductive dissolution of Fe(III)
(hydr)oxides by cysteine: Kinetics and mechanism. Journal of Colloid and
Interface Science, 194(1), 194‐206.
Ananthan, P., Venkateswaran, G., Manjanna, J. (2003). Enhanced dissolution of
hematite in reductive‐complexing formulation under regenerative mode.
Chemical Engineering Science, 58(22), 5103‐5109.
Badea, G. E., Badea, T. (2005). Corrosion and passivation behaviour of 18Cr‐10Ni
stainless steel in in H2SO4 solutions in the presence of oxalate and tartrate
anions. Revue Roumaine De Chimie 50(7‐8): 689‐694.
Ballesteros, M. C., Rueda, E. H., Blesa, M. A. (1998). The influence of iron (II) and (III)
on the kinetics of goethite dissolution by EDTA. Journal of Colloid and
Interface Science, 201(1), 13‐19.
Blesa, M. A., Weisz, A. D., Morando, P. J., Salfity, J. A., Magaz, G. E., Regazzoni, A. E.
(2000). The interaction of metal oxide surfaces with complexing agents
dissolved in water. Coordination Chemistry Reviews, 196, 31‐63.
Carbonaro, R. F., Gray, B. N., Whitehead, C. F., Stone, A. T. (2008).
Carboxylate‐containing chelating agent interactions with amorphous
chromium hydroxide: Adsorption and dissolution. Geochimica Et
Cosmochimica Acta, 72(13), 3241‐3257.
Castle J. E., Qiu, (1989). A COORDINATED STUDY OF THE PASSIVATION OF
ALLOY‐STEELS BY PLASMA SOURCE‐MASS SPECTROMETRY AND X‐RAY
PHOTOELECTRON‐SPECTROSCOPY .1. CHARACTERIZATION OF THE PASSIVE
FILM. Corrosion Science 29(5): 591‐603.
Cornell, R. M., Posner, (1976). KINETICS AND MECHANISMS OF ACID DISSOLUTION
OF GOETHITE ALPHA‐FEOOH). Journal of Inorganic & Nuclear Chemistry 38(3):
563‐567.
Gui, J., Devine, T. M. (1994). The influence of sulfate‐ions on the surface‐enhanced
Raman‐spectra of passive films formed on irons. Corrosion Science, 36(3),
441‐462.
He, W., Knudsen, O. O., Diplas, S. (2009). Corrosion of stainless steel 316L in
simulated formation water environment with CO2‐H2S‐Cl. Corrosion Science,
51(12), 2811‐2819.
Hedberg, Y., Midander, K., Odnevall Wallinder, I. (2010). Particles, sweat, and tears:
A comparative study on bioaccessibility of ferrochromium alloy and stainless
steel particles, the pure metals and their metal oxides, in simulated skin and
36
eye contact. Integrated Environmental Assessment and Management 6, (3),
456‐468.
Hedberg, Y., Gustafsson, J., Möller, L., Karlsson, H.L., Odnevall Wallinder, I. (2010).
Bioaccessibility, bioavailability and toxicity of commercially relevant iron‐ and
chromium‐based particles: in vitro studies with an inhalation perspective.
Particle and Fibre Toxicology 7:23.
Hedberg, Y., Hedberg, J., Liu, Y., Odnevall Wallinder, I. (2011) Complexation‐ and
ligand‐induced metal release from 316L particles – dependence on particle
size and crystallographic structure. manuscript.
Herting, G., Odnevall Wallinder, I., Leygraf, C. (2007). Metal release from various
grades of stainless steel exposed to synthetic body fluids. Corrosion Science
Progress in Corrosion Research in Commemoration of Centenary of Birth of
Professor Go Okamoto, International Symposium on "Progress in Corrosion
Research", 49(1), 103‐111.
Hultquist, G., Leygrof, C., Brune, D. (1984). Quantitative Measurements of Passive
Dissolution of Chromium, Iron, and Molybdenum from a Stainless Steel.
Journal of The Electrochemical Society, 131(8), 1773‐1776.
Keddam, M., Ed. (1995). Anodic Dissolution. Corrosion Mechanisms in Theory and
Practice. New York, Marcel Dekker, Inc.
Landolt, D., Ed. (1995). Introduction to Surface Reactions: Electrochemical Basics of
Corrosion. Corrosion Mechanisms in Theory and Practice. New York, Marcel
Dekker, Inc.
Martell, A. E. (1977). Critical stability constants. New York, Plenum, Cop.
Midander, K., Pan, J., Odnevall Wallinder, I., Leygraf, C. (2007). Metal release from
stainless steel particles in vitro ‐ influence of particle size. Journal of
Environmental Monitoring, 9(1), 74‐81.
Midander, K. (2009). Metal Particles – Hazard or Risk? Elaboration and
Implementation of a Research Strategy from a Surface and Corrosion
Perspective: xiv, 69, Doctoral thesis, KTH.
Midander, K., de Frutos, A., Hedberg, Y., Darrie, G., Odnevall Wallinder, I. (2010).
Bioaccessibility studies of ferro‐chromium alloy particles for a simulated
inhalation scenario. A comparative study with the pure metals and stainless
steel. Integrated Environmental Assessment and Management 6, (3),
441‐455.
Milosev, I. (2002). Effect of complexing agents on the electrochemical behaviour of
orthopaedic stainless steel in physiological solution. Journal of Applied
Electrochemistry 32(3): 311‐320.
Milosev, I. and Kosec, T. (2007). Metal ion release and surface composition of the
Cu‐18Ni‐20Zn nickel‐silver during 30 days immersion in artificial sweat.
Applied Surface Science 254(2): 644‐652.
Milosev, I. and Strehblow, H. H. (2000). The behavior of stainless steels in
physiological solution containing complexing agent studied by X‐ray
37
photoelectron spectroscopy. Journal of Biomedical Materials Research 52(2):
404‐412.
Moss, O. R. (1979). SIMULANTS OF LUNG INTERSTITIAL FLUID. Health Physics 36(3):
447‐448.
Richard, F. C. and Bourg, A. C. M. (1991). AQUEOUS GEOCHEMISTRY OF CHROMIUM
‐ A REVIEW. Water Research 25(7): 807‐816.
Schwertmann, U. (1991). SOLUBILITY AND DISSOLUTION OF IRON‐OXIDES. Plant and
Soil 130(1‐2): 1‐25.
Sedriks, A. J. (1996). Corrosion of stainless steels. New York, John Wiley & Sons, Inc.
Ullmann, Y. (2009). Fe‐ and Cr‐based metal particles. Bioaccessibility studies from
human health and environment perspective. Division of Surface and
Corrosion Science. Stockholm, KTH.
Wikipedia. (2010). X‐ray photoelectron spectroscopy. Retrieved 1 June, 2010, from
http://en.wikipedia.org/wiki/X‐ray_photoelectron_spectroscopy.
Zhang, Y., Kallay, N., et al. (1985). INTERACTIONS OF METAL HYDROUS OXIDES WITH
CHELATING‐AGENTS .7. HEMATITE‐OXALIC ACID AND HEMATITE‐CITRIC ACID
SYSTEMS. Langmuir 1(2): 201‐206.
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