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The role of chromium content in the long-term atmospheric

corrosion process
1 1,2 ✉ 1,2 ✉
Baozhuang Sun , Xiaomei Zuo1, Xuequn Cheng and Xiaogang Li

The corrosion of alloy steels with different amounts of Cr was studied using electrochemical tests, wet–dry cycle corrosion, X-ray
diffraction, and Kelvin probe force microscopy. The results show that the content of Cr is positively correlated with the corrosion
resistance of bare steel, but the corrosion resistance of atmospheric corrosion does not show the same pattern. The atmospheric
corrosion resistance of Cr-containing steel exhibits three different stages with the change of Cr element content. When the Cr
content is in the range of 1–4%, the corrosion rate is high and does not change within the Cr content. As the Cr content was further
increased from 4 to 7%, the corrosion rate exhibited a linear decrease and then drops rapidly when the Cr content reaches 8%.
These three different corrosion rate stages are related to the influence of Cr content on Fe3O4 content in the rust layer.
npj Materials Degradation (2020)4:37 ; https://doi.org/10.1038/s41529-020-00142-5
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INTRODUCTION existence of Cr element can replace the nano-sized goethite

It is well known that the corrosion resistance of materials can be particles to create a denser protective rust layer in the inner rust
improved by adding corrosion-resistant alloying elements1–3. In layer. Although all the existing studies so far used several alloying
recent years, a method to improve the corrosion resistance of elements together28,29, it is not difficult to see from these studies
materials is to form a dense and stable rust layer. One of the that the Cr content and the corrosion resistance have a close
typical examples is weathering steel. By adding certain amounts of correlation. However, the study of the influence of chromium on
corrosion-resistant elements, a dense rust layer is formed on the the initial stages of the atmospheric corrosion of weathering steels
steel surface, which can impede further corrosion process of the by Kamimura and Stratmann21 found that the positive effect of
substrate to achieve improvement of the steel corrosion chromium is not only not apparent in saline environments but
resistance4–8. The recent researches have suggested that addition also seems to be even harmful by accelerating weathering steels
of Cr, Cu, or P alloying elements can significantly improve the rust corrosion in coastal environments. Other researchers30–32 also
layer structure stability of the weathering steel, thereby improving pointed out that the presence of 0.60–1.30 wt% Cr was sometimes
its applicability in severe industrial and marine environments9–15. slightly detrimental, especially in industrial atmospheres. There-
Several studies have focused on the effect of alloying elements fore, the effect of the Cr content on the formation of the weather-
on the corrosion resistance. A study by Ma et al.16 on the resistant rust layer in steel, as well as the relationship between the
atmospheric corrosion behavior of weathering steel in the tropical Cr content and the density of the rust layer, has not yet reached a
marine environment found that the weathering resistance of consentient understanding.
weathering steel is related to the deposition of chloride ions and In this work, the steel samples with eight different Cr contents
the enrichment of Cr in the rust layer and that the latter can were studied to identify the relationship between the Cr content
significantly improve the corrosion resistance of weathering steels and the atmospheric corrosion resistance. A dry–wet cyclic
in environments with low chloride ion deposition. Several corrosion test was used to study the effect of the Cr content on
studies17–21 found that Cu can enhance the stability of the rust the corrosion resistance of the corrosion layer during the
layer when used together with Cr, thus improving the corrosion atmospheric corrosion process. The purpose of this study is to
resistance of weathering steel. However, a minimum of 0.10 wt% provide an insight into the influence of the Cr content on
Cu is required in order to significantly improve the corrosion atmospheric corrosion resistance. In addition, this study may
resistance of the steel22. The rust layer of corrosion-resistant steel provide useful data for the development of micro-alloyed
after long-term exposure to the atmosphere has a two-layer corrosion-resistant materials.
construction, and a significant difference Cr content presents in
the inner and outer layers, respectively23. A Cr-enriched inner layer
mainly consists of α-(Fe1−x,Crx)OOH, a Cr substituted FeOOH, RESULTS
which acts as a final stable protective layer. Other studies also Microstructure
found that a pseudo-passivation film formed on some Cr- The metallographic structure of the eight experimental materials
containing steels in the CO2 corrosion environment, and this film is shown in Fig. 1. It can be seen from the figure that Cr changes
is consisted of Cr(OH)324,25. After analyzing the rust layer structure the microstructure of the matrix. The Cr content primarily affects
of Cr-containing steel, Jiang et al.26 found that Cr is mainly in the the proportion of bainite in the steel. The W1 structure is
forms of Cr(OH)3, CrOOH, or FeCr2O4 in the rust layer, that is, Cr essentially ferrite with a very small amount of lath bainite. W2, W3,
mainly exists in the form of Cr3+ among the participants during and W4 are both granular bainite and ferrite. As the Cr content
the iron oxide process. Yamashita et al.27 believed that the increases, the proportion of granular bainite increases gradually.

1
Corrosion and Protection Centre, University of Science and Technology Beijing, 100083 Beijing, China. 2Key Laboratory for Corrosion and Protection (MOE), 100083 Beijing, China.
✉email: [email protected]; [email protected]

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This occurs because the addition of Cr to a steel can delay the Wet–dry cycles corrosion results
pearlite transformation and promote the bainite transformation, To study the atmospheric corrosion behavior of the steels with
making it easier to form the bainite structure at a slow cooling rate different Cr contents, dry and wet cycle experiments were carried
after austenitizing. When the Cr content reaches ≥5%, the out on the eight steel samples. Figure 2 shows that, as the
structure is all bainite, and the size of bainite becomes finer with corrosion cycles increased, the corrosion rate gradually stabilizes.
the increase of Cr content; the W8 has the smallest grain size. At the initial stage of the experiment, the main reaction is the

(a) (b) (c) (d)

50μm 50μm 50μm 50μm

(e) (f) (g) (h)

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50μm 50μm 50μm 50μm

Fig. 1 Metallographic structure of samples with various Cr content. a–h correspond to W1–W8 samples, respectively, and as the Cr content
increases, the proportion of granular bainite increases gradually.

(a) (b)

(c) (d)

Fig. 2 Corrosion rate of eight experimental steels during alternating wet–dry test in 0.5% NaCl (pH = 3) solution. a 24 h, b 72 h, c 120 h,
d 168 h. The dotted line corrosion rate in b is 3.8 mm y−1, the dotted line in c for 3.7 mm y−1, and the dotted lines in d for 5 and 2.5 mm y−1,
respectively. Based on corrosion rate variation, there are two corrosion stages in b, c and three in d.

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corrosion of the steel substrate. Therefore, the corrosion rate section are shown in Fig. 4, and energy-dispersive spectroscopic
gradually decreases with the increase of Cr content. The Cr (EDS) line scan analysis was performed on the marked areas in
content showed a certain positive effect on the corrosion Fig. 4. It can be seen from the cross-sectional topography that
resistance in the early stage of corrosion. However, after the 72- there is no obvious delamination in the rust layer. For W1–W4, the
h dry–wet cycle accelerated experiment, the corrosion rate change number of the pitting pits increases gradually as the Cr content
started to show two different trends for the samples with different increases, the rust layer cross-section is uneven, and there are
Cr contents. The effect of Cr on corrosion rate of the samples with many microscopic cracks and holes. Samples W5–W7 exhibit
low Cr contents (W1–W4) decreased gradually and trended to be significant local corrosion, the bonding between the rust layer and
the same, while the effect of Cr on corrosion resistance in those the substrate is weak, and large cracks exist in the rust layer. The
with high Cr content (W5–W8) still showed a positive correlation rust layer of W8 is the thinnest, with a thickness only ~20 μm. The
with the Cr content. This is mainly due to the gradual formation of rust layer structure is very dense and exhibits good bonding with
the rust layer on the steel surface during the prolonged the matrix. It can be seen from the EDS line scan that the rust layer
experiment time, where the main factor that affects the corrosion near the substrate is enriched in Cr. Cl− exists in the entire rust
resistance has shifted from the corrosion resistance of the steel layer and is slightly higher in the inner layer than that in the outer
substrate to the density of the rust layer. The results after 120-h rust layer. This indicates that the rust layer is an ion conduction
experiment show no more significant difference in the corrosion layer, and Cl− can penetrate through the rust layer to the metal
rate when the Cr content is the steel is <4%. The result from long- interface, causing corrosion reaction therewith; this gradually
period cycling corrosion test indicated that 4% Cr content increases the density of the rust layer. Cracks and holes also
appeared to be a threshold for its role in affecting the corrosion appear in the cross-section of the rust layer. This is because the
rate. After the 168-h dry and wet cycle corrosion experiment rust layer contains various corrosion products, and the densities of
(Fig. 2d), a stable rust layer structure has been formed on the different corrosion products are different and smaller than that of
surface of the material, and the corrosion rate at this time can be the matrix. During the continuous accumulation of corrosion
divided into 3 groups: (1) The corrosion rates of W1–W4 are products on the surface of the steel substrate, stress is generated
basically the same, at ~5.5 mm y−1. (2) The corrosion resistance of at the interface between the rust layer and the substrate, and
W4–W7 gradually increases, and the corrosion rate decreases corrosion products themselves have poor ductility, resulting in
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linearly from 5.5 to 2.7 mm y−1; (3) The corrosion rate of W8 is only cracks and holes.
0.3 mm y−1, which is merely one-eighteenth of W1. The X-ray diffraction (XRD) analysis on the rust layers of the
The macroscopic morphology (Supplementary Fig. 1) of the samples after the wet–dry cycles corrosion test was performed,
eight experimental materials after wet–dry cycles corrosion test and the results are shown in Fig. 5. It can be seen from figure that,
shows that, at 24 h, the surface of the experimental steel features a for all the samples analyzed, the rust layers contain α-FeOOH, γ-
thin layer of corrosion products, which is relatively flat and does FeOOH, and Fe3O4. However, the content of each substance is
not bubble. The surface rust layers of W1–W6 are predominantly significantly different in the different samples. Therefore, the K
dark brown, with some yellow-brown rust spots; W7 has a small value method was used in order to semi-quantitatively analyze the
amount of brick red rust on the surface, and W8 exhibits only a rust layers to calculate the proportion of different phases in the
very slight corrosion and the substrate is visible. At 72 h, the rust layers. The results are shown in Table 1.
presence of corrosion products is clearly more noticeable It can be seen from the table that, during the initial 24 h of
compared with 24-h samples but still not dense. There is obvious corrosion, the rust layers of W1–W6 contain a large amount of
surface bubbling for W1–W4. The surface rust layers for W5–W7 Fe3O4, while those of W7 and W8 only contain α-FeOOH. At 72 and
are relatively flat. W8 is evenly covered with yellowish brown rust 120 h, surface corrosion of the samples became more extensive,
and is very dense. After 120 h, bubbling was observed for W5–W7, and the proportion of Fe3O4 is detectably higher, which is
and there was no change in the surface appearance for W8. After consistent with the increase in the black rust amount, as
168 h, the degree of corrosion had obviously increased, the rust evidenced by the macroscopic morphology results (Supplemen-
layer morphology for W1–W4 exhibited no difference, the tary Fig. 1). After 168 h, the proportion of Fe3O4 becomes relatively
corrosion extent for W5–W7 gradually reduced, and for W8 small. Most of the corrosion products for W1–W7 are Fe3O4, while
the surface was still covered in the yellow-brown rust layer, and most of the corrosion products for W8 are α-FeOOH and γ-FeOOH
the corrosion was trivial. Furthermore, the microscopic morphol- with almost no Fe3O4. The proportion of α-FeOOH increases with
ogy of corrosion products after 168 h (Supplementary Fig. 2) show the increase of number of corrosion cycles.
that the surfaces of W1–W7 feature more corrosion products, The XRD results show that increasing the Cr content has little
significant surface bubbling, and many cracks. The surface of W8, effect on the γ-FeOOH content in the rust layer, which remains at a
however, is covered by fine and uniform corrosion products, low level. Therefore, for each experimental steel we analyzed the
which is very dense with no cracks, thus protecting the substrate. relationship between the corrosion rate and the ratio of Fe3O4 in
Figure 3 shows the microscopic morphologies of the experi- the rust layer for different corrosion cycles (Fig. 6). For each
mental steels after the removal of the rust. The surfaces of W1–W4 corrosion cycle, the ratio of Fe3O4 in the corrosion product of W8
exhibit many pitting pits and severe uniform corrosion morphol- is consistent with its corrosion rate. After 168 h, it can be seen
ogy. W5–W7 present many localized corrosion features. There are clearly that the Fe3O4 ratio can be categorized into three groups
virtually no obvious corrosion marks on the surface of W8, but a based on the Cr content. For W1–W4, the ratio of Fe3O4 remains
small number of small pits. These results show that, in the Cr stable at ~92%. For W4–W7, the ratio of Fe3O4 decreases linearly
content range from 1 to 4%, the uniform corrosion decreases and from 92 to 73%, while the rust layer of W8 contains only 0.9%
the local corrosion increases as the Cr content increases. In the Cr Fe3O4. This change of Fe3O4 content in the rust layer is consistent
content range from 5 to 7%, the depth and the number of pitting with the results from the corrosion rate change curve.
pits decrease with increasing Cr content. When the Cr content
reaches 8%, the corrosion behavior of the surface changes
suddenly, resulting in improved corrosion resistance and less DISCUSSION
surface corrosion. These results are consistent with the other The polarization curves (Supplementary Fig. 3) of the eight
studies, which had a conclusion that the local corrosion of steel experimental materials in the 3.5% NaCl solution shown that the
becomes more obvious, and the interface of the base rust layer corrosion resistance of the steel matrix improves as the Cr content
becomes uneven after adding Cr to steel33. The scanning electron increases. This is consistent with the traditional understanding of
microscopic (SEM) observation results of the rust layer cross- the role of Cr element but not with the results observed in the

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(a) (b)
General
corrosion

500μm 500μm

(c) (d)

Deep
pitting General
corrosion

500μm 500μm

(e) (f)
Deep
pitting

Deep
pitting

500μm 500μm

(g) (h)

500μm 500μm

Fig. 3 Micro morphologies of eight experimental steels (rust removal) after 168 h alternating wet–dry cycles. a–h correspond to
W1–W8 samples, respectively. The area marked with the red line is general corrosion area and marked by the yellow line is the severe pitting
corrosion area. The surface corrosion form changes with Cr content. Localized corrosion of steel becomes more obvious from W2 to
W7 samples.

atmospheric corrosion process. In order to further investigate this of two phases of ferrite and bainite. When the Cr content was
difference, the microscopic structure change of the substrate increased to 8%, the grain size further improved the corrosion
caused by Cr was studied to further clarify the reason for resistance. Therefore, it is considered that the difference of the
improving the corrosion resistance of the substrate. Many corrosion resistance in the experiment might be mainly con-
studies34–36 investigated the possibility that the steel structure tributed by the structural changes caused by the addition of
affects the corrosion resistance, and the addition of alloying different amount of Cr. To validate the hypothesis, W3 sample was
elements changes the microstructure of the steel matrix, which in selected for Kelvin probe force microscopy (KPFM) analysis.
turn can affect its corrosion resistance. Our work showed that, (Supplementary Fig. 4 and Fig. 7).
when Cr was added as an alloying element to low-carbon steel, it Supplementary Fig. 4 shows the metallographic structure of the
delayed the pearlite transformation and promoted the bainite W3 steel containing 3% Cr. The structure is composed of ferrite
transformation, allowing the bainite structure to form more easily and granular bainite. The locus marked in the figure was where
after austenitization. It can also be seen from Fig. 1 that the the KPFM testing performed. The KPFM result is shown in Fig. 7.
addition of Cr does changes the original phase structure of the Figure 7a–d are the height map, the potential map, the three-
material. When the Cr content is <4%, the material was composed dimensional map of the potential, and the potential change curve

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 B. Sun et al.
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(a) Rust layer Epoxy (b) Rust layer Epoxy (c) Rust layer Epoxy (d) Rust layer Epoxy

Cl Cl
Cl Cl

Cr Cr
Cr Cr
100μm 100μm 100μm 100μm

(e) Rust layer Epoxy (f) Rust layer Epoxy (g) Rust layer Epoxy (h) Rust layer Epoxy

Cl
Cl Cl
Cl

Cr
Cr Cr
Cr
100μm 100μm 100μm 10μm

Fig. 4 Micro morphologies and Cl and Cr element line scan of the rust layers for eight experimental steels after wet–dry cycle corrosion
for 168 h. a–h correspond to W1–W8 samples, respectively; the yellow line represents the EDS line scan position, the green curve for the Cl
content variation, the blue curve for Cr content variation, the orange line marks the position of Cr enrichment.

(a) (b) (c) (d)

(e) (f) (g) (h)

Fig. 5 X-ray diffraction diagrams of rust phases for eight experimental steels after wet–dry cycle corrosion for 24, 72, 120, and 168 h. a–h
correspond to W1–W8 samples, respectively. The black, red, blue, and green lines represent for wet–dry cycle corrosion for 24, 72, 120, and
168 h, severally.

of the section, respectively. It can be seen from Fig. 7d that the the rust layer. Therefore, a detailed analysis of the changes in the
potential of the granular bainite is much higher than the potential structure of the rust layer is also required.
of the matrix ferrite, and the difference between the two is The rust layer structure plays an important role in the corrosion
~≥80 mV. The existence of this potential difference may have two resistance of materials40,41. In atmospheric corrosion, the main
effects. (1) The corrosion resistance of the steel matrix improves process on the material surface is the oxidation of Fe and the
with more phase content that has better corrosion resistance, as transformation of the rust layer. In Evans model42, it is considered
shown in Fig. 2a and Supplementary Fig. 3 that display an early that a carbon steel undergoes strong cathodic depolarization in
corrosion rate decrease. The corrosion resistance of the steel the rust layer at the beginning of corrosion and then an anodic
matrix continues to improve with the addition of more Cr reaction in the rust layer. This process occurs at the metal/Fe3O4
content29,37–39. (2) The galvanic difference between the two interface:
phases caused the variations of the morphology and structure Fe ! Fe2þ þ 2e (1)
during the atmospheric corrosion process. Due to the difference of
the potential between the two phases, the corrosion process is The cathodic reaction occurs at the Fe3O4/FeOOH interface:
promoted and the corrosion morphology changes from uniform
Fe2þ þ 8FeOOH þ 2e ! 3Fe3 O4 þ 4H2 O (2)
corrosion to local pitting, as shown in Fig. 3. At the later stage after
a long-period dry–wet alternate corrosion process, the major
factor that influence the corrosion rate became the structure of 3Fe3 O4 þ 3=4O2 þ 9=2H2 O ! 9FeOOH (3)

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 B. Sun et al.
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increase the passivation tendency of the material’s surface,
Table 1. Semi-quantitative analysis of rust layer XRD results.
thereby suppressing the reaction process. In summary, Cr addition
Number period Fe3O4 (wt.%) α-FeOOH (wt.%) γ-FeOOH (wt.%) affects the passivation and rust layer structure of steels, thereby
suppressing the corrosion process.
W1 24 h 84.57157 15.42843 0 In the present work, the effect of Cr addition on the corrosion
72 h 94.97698 2.433409 2.589607 resistance of low-corrosion-resistance steels was investigated
120 h 94.46285 0 5.537148 using KPFM and dry–wet cycle corrosion testing. The following
168 h 92.74633 2.08922 5.164446 conclusions were drawn from the present study:
W2 24 h 90.46199 6.302565 3.235448 ● The corrosion resistance for the long-period atmospheric
72 h 97.693 0 2.307004 corrosion can be significantly improved when the Cr content
120 h 95.57277 0 4.427234 is >4%. For the low-carbon steel with 1–8% Cr content, the
effect of Cr content on the atmospheric corrosion rate can be
168 h 92.2527 3.897821 3.849475
divided into three ranges: almost no effect <4%, a negative
W3 24 h 89.17726 10.82274 0 correlation at 4–7%, and a step point at 8% content.
72 h 96.78247 0 3.217528 ● When the Cr content is <4%, it has almost no effect on the
120 h 96.3087 0 3.691301 Fe3O4 content in the atmospheric corrosion rust layer. When
168 h 90.77812 4.26159 4.960292 the Cr content is >4%, the Cr content can promote the
conversion of Fe3O4 to FeOOH in the rust layer, and this
W4 24 h 87.33965 6.457475 6.202879
conversion and Cr content present positive correlation.
72 h 91.09919 2.112929‘ 6.787885
120 h 96.28258 0 3.717421
168 h 94.20305 2.495278 3.301669 METHODS
W5 24 h 77.43117 22.56883 0 Materials preparation
72 h 95.23767 0 4.762329 Eight groups of experimental steel samples with different Cr contents
120 h 95.84923 0 4.150765 marked as W1, W2, W3, W4, W5, W6, W7, and W8 were prepared. The
compositions of these samples are shown in Table 2. They were prepared
168 h 83.20685 5.125722 11.66742
by vacuum melting and then casting into round ingots, followed by 1-h
W6 24 h 76.53408 16.6905 6.775412 homogenization at 1200 °C. The steel ingots were rolled into 6-mm-thick
72 h 94.01022 0 5.989777 strips with a final rolling temperature of approximately 900 °C, followed by
120 h 93.85057 0 6.149432 water quenching to 520–540 °C and then air cooled to room temperature.
In order to eliminate internal stress from the rolling process, the samples
168 h 76.78732 14.32297 8.889715 were normalized at 850 °C for 0.5 h. The detailed process is described in
W7 24 h 0 100 0 Supplementary Fig. 5. The final samples were cut into 10 mm × 10 mm ×
72 h 73.21516 15.47285 11.31199 3 mm. All the samples were sanded to 2000#, polished, and etched with
4% nitric acid alcohol solution to observe the microstructure.
120 h 92.93271 0 7.067288
168 h 73.77694 14.75088 11.47218
Wet–dry cyclic corrosion test
W8 24 h 0 100 0
The dry–wet cycle experiment is generally considered as one of the more
72 h 0 43.52924 56.47076 efficient methods for simulating atmospheric corrosion because of its
120 h 0 88.43245 11.56755 similarity with the actual outdoor corrosion45,46. Each cycle of the wet/dry
168 h 0.881889 91.302 7.816115 corrosion test is 1 h, which consists of two stages: (1) immersing the
specimens in a 0.5% NaCl solution with pH = 3.0 at 40 °C for 45 min and (2)
drying the specimens with four heating lamps for 15 min. The relative
humidity inside the testing container was maintained at 70% (±5%) during
It is considered that α-FeOOH is an insulating inactive the experiment. The samples have a size of 50 mm × 25 mm × 3 mm, and
substance, which is the most stable hydroxy iron oxide and a each experimental group was made of three samples. Prior to the
main constituent of the protective rust layer. Tanaka et al.43 experiments, all of the samples were processed as follows: sanding (to
identified that Fe3O4 plays an important role in reducing the 1500#) → pure water cleaning → acetone degreasing → anhydrous ethanol
dehydration → 24-h drying. The experimental periods were 24, 72, 120,
corrosion resistance of rust layers, while α-FeOOH and γ-FeOOH
and 168 h. For each sample, the initial weight was recorded as W0 (accurate
promote the formation of Fe3O4. Fe3O4 serves as a conductor in
to 0.0001 g), and the sample size was measured using a Vernier caliper.
the rust layer. Its conductivity is similar to that of pure metal. The After the experiment, all the samples were placed in an ultrasonic cleaner
electrons in the metal can be transferred by Fe3O4 as carriers. with a solution of 500 mL HCl + 500 mL H2O + 3.5 g hexamethylenete-
Therefore, when the rust layer contains a large amount of Fe3O4, it tramine at 25 °C for about 15 min to remove the corrosion product47. Then
does not provide a protective effect. Instead, Fe3O4 acts as an the samples were rinsed using deionized water, followed by anhydrous
active point on the surface and provides carriers for the alcohol and dried in cold air. The final masses Wt were recorded (accurate
electrochemical process, thus promoting the corrosion process to 0.0001 g). Meanwhile, an untreated sample also went through the same
of metals. Addition of Cr can have two effects on the alteration of processes for each steel to calibrate the mass loss produced during the
low-carbon steel rust layer. On the one hand, Cr often exists in the process of removing corrosion products. The corrosion rates (R, mm y−1)
form of Cr3+, which replaces Fe3+ ions in FeOOH44. This breaks the were calculated as follows:
balance process in Eq. (3) above, thus accelerating the conversion
of Fe3O4 into FeOOH and promoting the formation of FeOOH W0  Wt
R ¼ 8:76 ´ 104 ; (4)
(Fig. 5 and Table 1). To validate this, the content of the rust layers Sρt
of the samples after 168 h of the wet–dry cycles corrosion is
plotted in Fig. 8 along with their Cr content. The figure shows that, where (W0 − Wt) represents the weight loss of the sample after the
as Cr content increases, the content of Fe3O4 decreases dry–wet cyclic corrosion test, measured in grams; S represents the exposed
continuously, while FeOOH increases. On the other hand, as a area of the sample and is in cm2; ρ represents the sample’s density and
general passivation element, the addition of Cr will inevitably was taken as 7.8 g cm−3; and t is the test time in years.

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Fig. 6 Variation tendency of Fe3O4 content in corrosion products and corrosion rate for eight experimental steels during various wet–dry
corrosion cycles. a 24 h, b 72 h, c 120 h, d 168 h. The orange lines in a–d all represent the change curve of corrosion rate, and the black line
represents the change of Fe3O4 content of corrosion products.

(a) (b)

(c) (d)

Fig. 7 The KPFM of different structure in 3% Cr content experimental steel. a Height map, b Potential map, c 3D map of potential,
d potential change curve of the red section line in b.

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to the tip to induce harmonic oscillation of the cantilever. Afterwards, a
voltage of the same magnitude is applied to the tip to stop the oscillation
and reduce the potential difference. Using this method, the work function
of the sample can be derived. Some studies have shown that the work
function is closely related to the corrosion potential. The lower the work
function of a material, the lower the corrosion potential and the easier the
corrosion48,49.

DATA AVAILABILITY
The data of this study are available from the corresponding authors upon reasonable
request.

Received: 15 June 2020; Accepted: 19 October 2020;

Fig. 8 The content of constituents in rust layer as a function of Cr

content after 168 h alternating wet–dry cycles. The black, red, and
green lines correspond to the variation of Fe3O4, α-FeOOH, and REFERENCES
γ-FeOOH versus Cr content. 1. Cui, Z. et al. Passivation behavior and surface chemistry of 2507 super duplex
stainless steel in artificial seawater: influence of dissolved oxygen and pH. Corros.
Sci. 150, 218–234 (2019).
2. Yao, J., Macdonald, D. D. & Dong, C. Passive film on 2205 duplex stainless steel
Table 2. Chemical composition of the experiment materials. studied by photo-electrochemistry and ARXPS methods. Corros. Sci. 146, 221–232
(2019).
Materials Element compositions (wt.%)
3. Liu, M., Cheng, X., Li, X., Pan, Y. & Li, J. Effect of Cr on the passive film formation
C Si Mn P S Cr mechanism of steel rebar in saturated calcium hydroxide solution. Appl. Surf. Sci.
389, 1182–1191 (2016).
W1 0.037 0.035 1.06 0.008 0.0072 1.02 4. Tewary, N. K., Kundu, A., Nandi, R., Saha, J. & Ghosh, S. Microstructural char-
acterisation and corrosion performance of old railway girder bridge steel and
W2 0.035 0.045 1.12 0.009 0.0080 1.94
modern weathering structural steel. Corros. Sci. 113, 57–63 (2016).
W3 0.037 0.058 1.22 0.008 0.0080 3.06 5. Hao, L., Zhang, S., Dong, J. & Ke, W. Atmospheric corrosion resistance of MnCuP
W4 0.043 0.042 1.12 0.008 0.0075 3.98 weathering steel in simulated environments. Corros. Sci. 53, 4187–4192 (2011).
6. Cheng, X., Jin, Z., Liu, M. & Li, X. Optimizing the nickel content in weathering
W5 0.052 0.044 1.15 0.008 0.0075 5.09
steels to enhance their corrosion resistance in acidic atmospheres. Corros. Sci.
W6 0.054 0.057 1.13 0.009 0.0070 6.09 115, 135–142 (2017).
W7 0.054 0.053 1.14 0.008 0.0083 7.07 7. Thee, C. et al. Atmospheric corrosion monitoring of a weathering steel under an
electrolyte film in cyclic wet-dry condition. Corros. Sci. 78, 130–137 (2014).
W8 0.058 0.045 1.09 0.008 0.0082 7.78
8. Morcillo, M., Chico, B., Díaz, I., Cano, H. & De la Fuente, D. Atmospheric corrosion
data of weathering steels. A review. Corros. Sci. 77, 6–24 (2013).
Corrosion morphology and rust analysis 9. Li, X. et al. Share corrosion data. Nature 527, 441–442 (2015).
10. Fu, G., Zhu, M. & Gao, X. Rust layer formed on low carbon weathering steels with
Surface and cross-sectional morphologies of the samples were observed different Mn, Ni contents in environment containing chloride ions. Mater. Sci. 22,
using a KEYENCE VX-200 stereomicroscope and a FEI Quanta250 SEM. Their 501–505 (2016).
rust layers were analyzed with an EDS. The phases in the corrosion 11. Zhou, Y., Chen, J., Xu, Y. & Liu, Z. Effects of Cr, Ni and Cu on the corrosion behavior
products were determined by XRD on a Rigaku analyzer over a 10–90° of low carbon microalloying steel in a CF-containing environment. J. Mater. Sci.
range with a scanning rate of 4 ° min−1. The parameters of the generator Technol. 29, 168–174 (2013).
were set to 40 kV and 40 mA. 12. Cheng, X., Tian, Y., Li, X. & Zhou, C. Corrosion behavior of nickel‐containing
weathering steel in simulated marine atmospheric environment. Mater. Corros.
Electrochemical test 65, 1033–1037 (2014).
13. Wu, W., Cheng, X., Hou, H., Liu, B. & Li, X. Insight into the product film formed on
Electrochemical tests were performed using a M2273 electrochemical Ni-advanced weathering steel in a tropical marine atmosphere. Appl. Surf. Sci.
workstation and a three-electrode system, where the samples were used as 436, 80–89 (2018).
the working electrodes, a Pt plate as the counter electrode, and a saturated 14. Morcillo, M., Díaz, I., Cano, H., Chico, B. & De, lF. D. Atmospheric corrosion of
calomel electrode (SCE) as the reference electrode. The test solution was weathering steels. Overview for engineers. Part I: Basic concepts. Constr. Build.
0.5% NaCl (pH = 3). The samples were cut to 10 mm × 10 mm × 3 mm in Mater. 213, 723–737 (2019).
size and were then covered with epoxy resin with a 1.0-cm2 exposed area. 15. Cano, H. et al. Characterization of corrosion products formed on Ni 2.4wt%-Cu
Prior to each test, the open circuit potential (OCP) was monitored for at 0.5wt%-Cr 0.5wt% weathering steel exposed in marine atmospheres. Corros. Sci.
least 20 min until it reached a stable state. Potentiodynamic polarization 87, 438–451 (2014).
tests ranged from −0.25 V (versus OCP) to −0.3 VSCE, and the scanning rate 16. Ma, Y., Li, Y. & Wang, F. Weatherability of 09CuPCrNi steel in a tropical marine
was 0.5 mV s−1. All of the measurements were performed at room environment. Corros. Sci. 51, 1725–1732 (2009).
temperature (∼25 °C) and were repeated three times to ensure 17. Song, L., Chen, Z. & Hou, B. The role of the photovoltaic effect of γ-FeOOH and
reproducibility. β-FeOOH on the corrosion of 09CuPCrNi weathering steel under visible light.
Corros. Sci. 93, 191–200 (2015).
18. Yamashita, M., Miyuki, H., Matsuda, Y., Nagano, H. & Misawa, T. The long term
KPFM test growth of the protective rust layer formed on weathering steel by atmospheric
Atomic force microscope (Multimode 8, Bruker) is used in the KPFM corrosion during a quarter of a century. Corros. Sci. 36, 283–299 (1994).
measurements. The equipment was located in a clean room at a constant 19. Díaz, I. et al. Five-year atmospheric corrosion of Cu, Cr and Ni weathering steels in
temperature of 25 °C and an ambient relative humidity of approximately a wide range of environments. Corros. Sci. 141, 146–157 (2018).
20%. The probes used in the KPFM measurements were PFQNE-AL with a 20. Kamimura, T., Hara, S., Miyuki, H., Yamashita, M. & Uchida, H. Composition and
force constant of 1.5 N m−1 and a resonant frequency of 300 kHz. The protective ability of rust layer formed on weathering steel exposed to various
dual-scan mode was used to record the second signal in addition to the environments. Corros. Sci. 48, 2799–2812 (2006).
surface topographic signal. In a KPFM measurement, when a potential 21. Kamimura, T. & Stratmann, M. The influence of chromium on the atmospheric
difference exists between the tip and the sample, an AC voltage is applied corrosion of steel. Corros. Sci. 43, 429–447 (2001).

npj Materials Degradation (2020) 37 Published in partnership with CSCP and USTB
 B. Sun et al.
9
22. Larrabee, C.P. & Coburn, S. k. The atmospheric corrosion of steels as influenced by 45. Lyon, S. B., Thompson, G. E. & Johnson, J. B. Accelerated atmospheric corrosion
changes in chemical composition, Proc. 1st International Congress on Metallic testing using a cyclic wet/dry exposure test: aluminum, galvanized steel, and
Corrosion, London, 279–285 (1961). steel. Corrosion 43, 719–726 (1987).
23. Nishimura, T., Katayama, H., Noda, K. & Kodama, T. Effect of Co and Ni on the 46. Zhu, F., Persson, D. & Thierry, D. Formation of corrosion products on open and
corrosion behavior of low alloy steels in wet/dry environments. Corros. Sci. 42, confined metal surfaces exposed to periodic wet/dry conditions-a comparison
1611–1621 (2000). between zinc and electrogalvanized steel. Corrosion 57, 582–590 (2001).
24. Wang, B., Xu, L., Zhu, J., Xiao, H. & Lu, M. Observation and analysis of pseudo- 47. British Standards Institute Staff. ISO 8407. Corrosion of Metals and Alloys.
passive film on 6.5%Cr steel in CO2 corrosion environment. Corros. Sci. 111, Removal of Corrosion Products from Corrosion Test Specimens (B S I Standards,
711–719 (2016). 2009).
25. Zhu, J. et al. Essential criterion for evaluating the corrosion resistance of 3Cr steel 48. Lacroix, L., Laurence, R., Christine, B. & Georges, M. Combination of AFM, SKPFM,
in CO2 environments: prepassivation. Corros. Sci. 93, 336–340 (2015). and SIMS to study the corrosion behavior of S-phase particles in AA2024-T351. J.
26. Jiang, S., Chai, F., Su, H. & Yang, C. Influence of chromium on the flow-accelerated Electrochem. Soc. 155, C131 (2008).
corrosion behavior of low alloy steels in 3.5% NaCl solution. Corros. Sci. 123, 49. Li, M., Guo, L. Q., Qiao, L. J. & Bai, Y. The mechanism of hydrogen-induced pitting
217–227 (2017). corrosion in duplex stainless steel studied by SKPFM. Corros. Sci. 60, 76–81 (2012).
27. Yamashita, M., Shimizu, T., Konishi, H., Mizuki, J. & Uchida, H. Structure and
protective performance of atmospheric corrosion product of Fe-Cr alloy film
analyzed by Mssbauer spectroscopy and with synchrotron radiation X-rays. ACKNOWLEDGEMENTS
Corros. Sci. 45, 381–394 (2003). The authors acknowledge the support of the National Natural Science Foundation of
28. Qian, Y., Ma, C., Niu, D., Xu, J. & Li, M. Influence of alloyed chromium on the China (No. 51671028) and the National Key Research and Development Program of
atmospheric corrosion resistance of weathering steels. Corros. Sci. 74, 424–429 China (No. 2016YFB0300604)
(2013).
29. Qian, Y., Niu, D., Xu, J. & Li, M. The influence of chromium content on the
electrochemical behavior of weathering steels. Corros. Sci. 71, 72–77 (2013).
AUTHOR CONTRIBUTIONS
30. Guo, S., Xu, L., Zhang, L., Chang, W. & Lu, M. Corrosion of alloy steels containing
2% chromium in CO2 environments. Corros. Sci. 63, 246–258 (2012). X.C. and X.Z. conceived the project and designed the experiments. B.S. and X.Z.
31. Morcillo, M., Diaz, I., Chico, B., Cano, H. & Fuente, D. D. L. Weathering steels: from performed the experiments and analyses. B.S. wrote the paper. X.L. and X.C. revised
empirical development to scientific design. A review. Corros. Sci. 83, 6–31 (2014). the paper. All the authors contributed to the interpretation of the experimental data
32. Xu, L., Wang, B., Zhu, J., Li, W. & Zheng, Z. Effect of Cr content on the corrosion and discussed the results.
performance of low-Cr alloy steel in a CO2 environment. Appl. Surf. Sci. 379,
39–46 (2016).
33. Tahara, A. & Shinohara, T. Influence of the alloy element on corrosion morphol- COMPETING INTERESTS
ogy of the low alloy steels exposed to the atmospheric environments. Corros. Sci. The authors declare no competing interests.
47, 2589–2598 (2005).
34. Wang, C., Wang, T., Cao, L. & Zhang, G. The effect of phase structure on the
corrosion behavior of Al100-xMox alloy thin films. J. Alloy. Compd. 790, 563–571 ADDITIONAL INFORMATION
(2019). Supplementary information is available for this paper at https://doi.org/10.1038/
35. Cano, H. Atmospheric corrosion of weathering steels. Overview for engineers. s41529-020-00142-5.
Part II: Testing, inspection, maintenance. Constr. Build. Mater. 222, 750–765
(2019). Correspondence and requests for materials should be addressed to X.C. or X.L.
36. Gong, W. et al. Effects of ausforming temperature on bainite transformation,
microstructure and variant selection in nanobainite steel. Acta Mater. 61, Reprints and permission information is available at http://www.nature.com/
4142–4154 (2013). reprints
37. Uhlig, H. H. & King, C. Corrosion and corrosion control. J. Electrochem. Soc. 119,
327C (1972). Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims
38. Ha, H. Y., Lee, T. H., Lee, C. G. & Yoon, H. Understanding the relation between in published maps and institutional affiliations.
pitting corrosion resistance and phase fraction of S32101 duplex stainless steel.
Corros. Sci. 149, 226–235 (2019).
39. Zhang, Y., Huang, F., Hu, Q., Peng, Z. & Liu, J. Effect of micro-phase electro-
chemical activity on the initial corrosion dynamics of weathering steel. Mater.
Chem. Phys. 241, 122045 (2020). Open Access This article is licensed under a Creative Commons
40. Tamura, H. The role of rusts in corrosion and corrosion protection of iron and Attribution 4.0 International License, which permits use, sharing,
steel. Corros. Sci. 50, 1872–1883 (2008). adaptation, distribution and reproduction in any medium or format, as long as you give
41. Rocca, E., Faiz, H., Dillmann, P., Neff, D. & Mirambet, F. Electrochemical behavior of appropriate credit to the original author(s) and the source, provide a link to the Creative
thick rust layers on steel artefact: mechanism of corrosion inhibition. Electrochim. Commons license, and indicate if changes were made. The images or other third party
Acta 316, 219–227 (2019). material in this article are included in the article’s Creative Commons license, unless
42. Evans, U. R. & Taylor, C. A. J. Mechanism of atmospheric rusting. Corros. Sci. 12, indicated otherwise in a credit line to the material. If material is not included in the
227–246 (1972). article’s Creative Commons license and your intended use is not permitted by statutory
43. Tanaka, H., Mishima, R., Hatanaka, N., Ishikawa, T. & Nakayama, T. Formation of regulation or exceeds the permitted use, you will need to obtain permission directly
magnetite rust particles by reacting iron powder with artificial α-, β- and γ- from the copyright holder. To view a copy of this license, visit http://creativecommons.
FeOOH in aqueous media. Corros. Sci. 78, 384–387 (2014). org/licenses/by/4.0/.
44. Mancio, M., Kusinski, G., Monteiro, P. J. M. & Devine, T. M. Electrochemical and in-
situ SERS study of passive film characteristics and corrosion performance of 9%Cr
microcomposite steel in highly alkaline environments. J. ASTM Int. 6, 1–10 (2009). © The Author(s) 2020

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