Corrosion–Erosion Of13Cr24Mn0.44 Stainless Steel

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Corrosion–erosion wear behaviors of 13Cr24Mn0.44N stainless steel insaline–sand slurry

Zhou Guanghong, Ding Hongyan , Zhang Yue, Li Nianlian

Faculty of Mechanical Engineering, Huaiyin Institute of Technology, Huaian, Jiangsu 223003, China

a r t i c l e i n f o

Available online 21 December 2009

Keywords:

Stainless steel

Corrosion–erosion wear

Wear mechanism

Synergism

a b s t r a c t

The corrosion–erosion wear behaviors of austenitic stainless steels, 316L and 13Cr24Mn0.44N, were

investigated in water–sand slurry and saline–sand slurry, respectively. The corrosion–erosion wear

mass-loss was measured to evaluate the influence of medium and materials. The worn surface andcorrosion–erosion wear mechanism were analyzed using a scanning electron microscopy and a non-

contact optical profilometer. Results show that the corrosion–erosion wear mass-loss of

13Cr24Mn0.44N is lower than that of 316L in both the slurries. The relative wear resistance increases

with the increasing of the impingement velocity and arrives at maximum of 1.6. The dominant wear

mechanism of 13Cr24Mn0.44N is abrasive wear in the water–sand slurry, whereas it becomes abrasive

wear associated with little corrosive pitting in the saline–sand slurry. As the impingement velocity

increased all the synergism ratios exhibit a tendency of increase, among which the synergism ratio of

13Cr24Mn0.44N is always lower than that of 316L at any given velocity. The results indicate that

13Cr24Mn0.44N possesses a predominant anti-corrosion–erosion wear property.

& 2009 Elsevier Ltd. All rights reserved.

1. Introduction

Austenitic stainless steels are widely used in many compo-

nents where corrosion resistance is crucial, such as slurry

handling in food and chemical industries [1,2]. When used in

such fields, they often undergo tribocorrosion or mechanical

action of hard particles. Generally, the total metal removal is not

simply the sum of the corrosion and the wear measured in

separate experiments. The interaction of erosion with corrosion

could significantly affect entire mass-loss due to the synergism

between mechanical and electrochemical effect. For example, if a

corrosive solution carries the particles, the surface damage due to

corrosion increases as a consequence of synergistic mechanisms

between corrosion and erosion [3–7]. The synergistic effect

between erosion and corrosion has been receiving more and

more attention in recent years. Many studies have showed thatcorrosion is accelerated by wear and the wear may be also

accelerated by corrosion [8–12].

Recently high nitrogen stainless steels have been paid a special

attention due to its good combination of strength, ductility,

toughness, weldability, localized corrosion resistance and tribo-

logical properties [13–16]. Particularly, it has been shown that

nitrogen additions improve the resistance to pitting and crevice

corrosion of stainless steels in solutions containing chloride ions

(Cl) [17]. In addition, high manganese stainless steels have

excellent work hardening effect [18–21]. Mills’ study has shownthat CrMnN steel possesses superior wear corrosion resistance

and good cavitation erosion resistance compared with the 304

stainless steel [18].

In our earlier work, a new type austenitic stainless steel with

high manganese and moderate nitrogen, 13Cr24Mn0.44N, has

been developed [22]. The aim of this work is to study the

corrosion–erosion wear behaviors of 13Cr24Mn0.44N submitted

to liquid impingement accompanied by corrosion–erosion condi-

tion. Reference experiment has also been conducted with com-

mercially used 316L stainless steel under same conditions.

2. Experimental procedures

2.1. Materials and mediums

The 13Cr24Mn0.44N stainless steel used here was developed

by Shanghai Research Institute of Materials. The steel ingot was

firstly austenized at 1050 1C for 1 h, and then oil-quenched, and

lastly annealed at 850 1C for 1 h to relieve internal stresses. The

hardness of 13Cr24Mn0.44N, after annealing treatment, is about

197HV. The rectangular specimens (20mm10mm2mm)

were cut-out using electrical discharge method. It was ground

to an average surface roughness Ra of 1.6mm. Reference experi-

ment was also conducted with commercially used 316L stainless

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Contents lists available at ScienceDirect

journal homepage: www.elsevier.com/locate/triboint

Tribology International

0301-679X/$- see front matter & 2009 Elsevier Ltd. All rights reserved.

doi:10.1016/j.triboint.2009.12.021

Corresponding author. Tel.: +86 517 83559196; fax: +86 517 83559041.

E-mail address: [email protected] (H. Ding).

Tribology International 43 (2010) 891–896

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steel. The chemical compositions of the experimental materials

are listed in Table 1. A strongly saline–sand slurry was used as the

corrosive medium consisting of 5 wt% NaCl solution, 10wt% river–

sand (SiO2 particles, 250–325mm, 2200–2300 HV) and distilled

water. Comparison test was also performed in the slurry only

consisting of 10 wt% river–sand and distilled water, namely

water–sand slurry. All tests were performed at room tempera-

ture and with the medium exposed to air.

2.2. Erosion–corrosion wear test

The wear experiments were performed in a modified solid

particle slurry corrosion–erosion wear apparatus. The impinge-

ment velocity can be well controlled by a motor. The specimens

were mounted in holders at the edge of the impeller, in which the

impingement angle can be adjusted. The impeller was connected

to a rotating spindle by a bar. It is schematically shown in Fig. 1.

For each test, the slurry pot was filled with 1200 ml aqueous

solution, either water–sand slurry or saline–sand slurry.

All the experimental materials were firstly ground by SiC paper

in 240 grit and degreased in acetone. Specimens were then

cleaned by ethanol and air-dried after abraded by SiC paper from

600 to 1000 grit step by step. The experiments were conducted at

three velocities of 100, 500 and 1000r/min for 2 h at room

temperature. After completion of tests, the specimens wereultrasonically cleaned in acetone. Later, their surface character-

istics and mechanical properties were investigated. Note that

three replicate tests were conducted for each specimen.

2.3. Characterization

The microstructure of the 13Cr24Mn0.44N was observed by

optical microscope (OM, Zeiss Axio, Germany) and was deter-

mined by using X-ray diffraction (XRD, D8-Advance Bruker,

Germany). The hardness was measured at 0.98 N for 10 s by a

digital microhardness meter (HXD-1000TMC, China); the mea-

surement was repeated for 5 times and the hardness value in this

paper was the average. The corrosion–erosion wear surface and

its 3D-morphology were observed and analyzed using scanningelectron microscopy (SEM, Hitachi 3000N, Japan) and non-contact

optical profilometer (Micro-XAM ADE, USA). Wear weight-loss

was measured by an electronic balance with sensitivity of 0.1 mg.

The corrosion–erosion wear resistance was evaluated by wear

mass-loss ratio (DM 0), which was calculated from the following

equation:

DM 0 ¼ M 0M

M 0ð1Þ

Where, M 0 is the weight of materials before corrosion–erosion

wear and M stands for the weight of specimen after corrosion–

erosion wear.

Besides, the relative wear resistance (e) was employed to

evaluate the corrosion–erosion wear-ability of 13Cr24Mn0.44N

versus that of 316L, which can be calculated as:

e ¼ W s=W c ð2Þ

Where, W s is the mass-loss of 316L; W c is that of 13Cr24Mn0.44N

under the corresponding condition.

To investigate the synergism ratio (Z) between corrosion–

erosion and wear, the amount of synergy DM cw can be calcu-

lated according to a typical corrosion wear model as following

equation [23]:

DM c -w ¼ M corr M water ð3Þ

Where, M corr is the entire mass-loss after corrosion–erosion in the

saline–sand slurry; M water stands for the mass-loss after abradedin the water–sand slurry. Therefore, the synergism ratio Z, i.e.,

contribution of DM cw to M corr can be calculated as the following

equation:

Z ¼ DM c -w

M corr ¼

M corr M water

M corr ð4Þ

3. Results and discussion

3.1. Microstructure of the 13Cr24Mn0.44N stainless steel

The microstructure of 13Cr24Mn0.44N austenitic stainless

steels is shown in Fig. 2. It presents a typical austenitemicrostructure, which is confirmed further by XRD (Fig. 3). The

peak of the spectrum pattern shows that the structure of

13Cr24Mn0.44N is single austenite phase. In addition, some

twin-crystal structure was also presented in Fig. 2. Previous study

[24] has proved that element Mn in stainless steels is helpful for

the formation of twin-crystal structure.

3.2. Wear resistance of 316L and 13Cr24Mn0.44N in aqueous slurry

The mass-loss ratios of both the austenitic stainless steels,

316L and 13Cr24Mn0.44N, are shown in Fig. 4. It is clear that the

mass-loss ratio of 316L is always larger than that of

13Cr24Mn0.44N whether after corrosion–erosion in saline–sand

slurry or in water–sand slurry.

Table 1

Chemical compositions of the experimental materials (wt%).

Experimental

material

C Mn Si Ni Cr N Mo V Ti

13Cr24Mn0.44N 0.05 24.62 0.57 0.1 13.18 0.44 – – –

316L 0.035 1.32 0.055 10.40 16.60 – 2.20 0.08 0.02

Fig. 1. Schematic diagram of the modified solid particle slurry erosion–corrosionapparatus.

G. Zhou / Tribology International 43 (2010) 891–896 892



ARTICLE IN PRESS

It is of interest that, the more increase of the impingement

velocity, the more is the difference in mass-loss ratio. To

quantitative analyze the difference wear-loss in two slurries

clearly, the relative wear resistance values e are used and

summarized in Table 2. The value of e increased with the

increasing of the impingement velocity; meanwhile, the e was

always higher in saline–sand slurry than that in water–sand

slurry at same impingement velocity. The biggest e was 1.6 at

1000r/min in saline–sand slurry; therefore, we believed that13Cr24Mn0.44N stainless steels can be applied in strongly saline–

sand slurry at higher impingement velocity, compared with 316L.

The result can be interpreted owing to the different chemical

compositions of the two stainless steels. Firstly, it has been

proved that nitrogen element added into austenitic steels can

simultaneously improve fatigue life, strength, wear and localized

corrosion resistance, attributed to the strong hardening effect of

nitrogen in solid solution [18]. In addition, Ref. [25] pointed out

that higher content of manganese in austenite microstructure

would cause rapid work hardening, attribute to the reorientation

of carbon members of C–Mn couples in the cores of dislocations.The hardness results after erosion wear are listed in Table 3. It

can be found that the increment of the impingement velocity can lead

to a higher hardness, indicating a work-hardening effect occurrence.

Compared with 316L, however, the hardness of 13Cr24Mn0.44N

induced by impingement increased by more than 15% attributed to

the strong hardening effect as discussed above. This result agrees with

previous studies [25,26] satisfactorily.

3.3. Synergism ratios between wear and corrosion of 316L and

13Cr24Mn0.44N

From Fig. 4 one can also see that the mass-loss ratio, whether

for 316L or 13Cr24Mn0.44N, is larger in saline–sand slurry than

that in water–sand slurry. This means the corrosive slurry with

Fig. 2. Microstructure of 13Cr24Mn0.44N.

600

400

200

20 30 40 50 60 70 80

2θ/deg

c p s

(111)

(200)(220)

Fig. 3. XRD spectrum pattern of 13Cr24Mn0.44N.

Fig. 4. Mass-loss ratios of 316L and 13Cr24Mn0.44N at various velocities: (a) in water–sand slurry, (b) in saline–sand slurry.

Table 2

Relative wear resistance of 13Cr24Mn0.44N versus 316L in different slurries at

various velocities.

Slurry 100 (r/min) 500(r/min) 1000 (r/min)

Water–sand 1.29 1.39 1.5

Saline–sand 1.42 1.56 1.6




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hard particles accelerates the wear process, which presents a

positive synergism between wear and corrosion. The synergism

ratios calculated from the mass-loss between the two slurries are

summarized in Table 4.

It can be seen that all the synergism ratios exhibit a tendency

of increase as the velocity increased. However, an exciting result

is that the synergism ratios of 13Cr24Mn0.44N are always lower

than those of 316L at any velocity. This indicates that

13Cr24Mn0.44N has a good anti-corrosion–erosion wear abilitycompared with 316L.

3.4. Corrosion–erosion wear mechanism of 316L and

13Cr24Mn0.44N in two slurries

Fig. 5 depicts the SEM images of the worn surface after erosion

wear in both the slurries at the velocity of 1000 r/min. Many

scratch lines along the direction of impingement were observed in

all the cases due to the sharp SiO2 particles. The micro-cut slots of

13Cr24Mn0.44N were relatively narrower and smoother in the

water–sand slurry as shown in Fig. 5(a); in contrast, additional

corrosive pitting and a little of wide deep ditches exhibited in

saline–sand slurry probably caused by impacting hard particles,

as shown in Fig. 5(b). Therefore, the dominant wear mechanism of

13Cr24Mn0.44N is abrasive wear in the water–sand slurry,

whereas it becomes abrasive wear associated with little

corrosive pitting in the saline–sand slurry.As for 316L, the dominant wear mechanism is also abrasive

wear in the water–sand slurry. This can be verified by the SEM

photograph as shown in Fig. 5(c), from which many micro-cut

slots, as well as some impingement pits, were presented. By

Table 4

Synergism ratio (Z) between corrosion and wear of experimental materials at

various velocities.

Materials 100 (r/min) 500 (r/min) 1000 (r/min)

316L 0.21 0.29 0.34

13Cr24Mn0.44N 0.15 0.20 0.28

Fig. 5. SEM image of the surface after erosion in two slurries at high velocity: (a) 13Cr24Mn0.44N, in water–sand slurry, (b) 13Cr24Mn0.44N, in saline–sand slurry,

(c) 316L, in water–sand slurry, (d) 316L, in saline–sand slurry.

Table 3

Hardness (HV) after erosion wear in water–sand slurry at various velocities.

Materials 100 (r/min) 500 (r/min) 1000 (r/min)

316L 378.8 410.8 452.6

13Cr24Mn0.44N 442.8 468.7 592.5

Fig. 6. SEM image of the pitting hole of 316L after erosion in saline–sand slurries

at 1000 r/min.




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contrast, the remarkable pitting corrosion and brittle delamina-

tion took place on the surface when corrosion–erosion wear

conducted in saline–sand slurry, evidenced in Fig. 5(d). Fig. 6

illustrates the higher magnification SEM photograph of the pittinghole after corrosion–erosion in saline–sand slurry. The presence of

plate-like hole in 316L indicated that the corrosive slurry was able

to pass though the surface and locally attack the substrate,

promoting formation of pits and reducing mechanical supporting

ability. The local weak corrosion surface can be continuously

removed by the action of the flow and the presence of solids;

therefore, the brittle delamination may flake from the surface of

the samples.

It is further evidenced by Fig. 7, which shows the 3D-

morphology of the cleaned surface of 316L stainless steel after

corrosion erosion in saline–sand slurry. Obviously the 3D-

morphology (Fig. 7(a), observed from top) was similar to the

SEM image. However, some deep corrosion pittings presented in

another 3D-morphology (Fig. 7(b), observed from side). Thismorphology can also demonstrate that 316L processes a poor

erosion wear resistance in saline–sand slurry, compared with

13Cr24Mn0.44N.

4. Conclusions

The results of the present study on the corrosion–erosion wear

behavior of a new stainless steel 13Cr24Mn0.44N, compared with

the commonly used 316L, in saline–sand slurry and water–sand

slurry, provides a new insight into the synergism between wear

and corrosion. The mass-loss ratio of 316L is always larger than

that of 13Cr24Mn0.44N whether in saline–sand slurry or in

water–sand slurry. The relative wear resistance increases with theincreasing of the impingement velocity and arrives at maximum

of 1.6. Both the stainless steels present a positive synergism

between wear and corrosion. As the impingement velocity

increased all the synergism ratios exhibit a tendency of increase,

among which the synergism ratio of 13Cr24Mn0.44N is always

lower than that of 316L at any given velocity. All above indicates a

predominant anti-corrosion–erosion wear property of high-Mn

austenitic stainless steel. The dominant wear mechanism of

13Cr24Mn0.44N is abrasive wear in the water–sand slurry,

whereas it becomes abrasive wear associated with little corrosive

pitting in the saline–sand slurry. As for 316L, the dominant wear

mechanism is also abrasive wear in the water–sand slurry,

whereas it becomes abrasive wear associated with corrosive

delamination fatigue in the saline–sand slurry.

Acknowledgment

The author would like to acknowledge professor Q.X. Dai for

his help on the preparation of the experimental material.

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Fig. 7. 3D-morphology of the wear scar: (a) plan form, (b) side elevation.




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