Cavitation Erosion Resistance of is liable to cause the erosion of slip bands, plastic deformation,

and localized fatigue failure [7–10].

Sputter-Deposited Cr3Si Film on Recently, a series of surface modification technologies, such as
chemical vapor deposition (CVD) and physical vapor deposition,
Stainless Steel have been developed for improving the cavitation erosion resist-
ance of SS [11–19]. Some positive results have been achieved
through the application of these surface modification treatments,
Shuyun Jiang1 but several problems remain to be solved. For example, although
School of Mechanical Engineering, TiN [11–13] and Cr–N [14,15] are an attractive wear-resistant and
Southeast University, antifriction surface coating material, microcracks and delamina-
Nanjing 211189, China tion of these coatings can frequently form at the tops of micro-
e-mail: [email protected] folds under conditions of cavitation erosion. The a-C coatings
prepared by CVD on steel substrate [16] have also been a focus
Hongqin Ding due to its high elastic modulus and high hardness, but its thin in
thickness (only 2.0–4.5 lm) and the low adhesion strength
School of Mechanical Engineering,
between the coating and the substrate are the main obstacles to
Southeast University, achieve a good surface behavior. Compared with theses coatings,
Nanjing 211189, China plasma nitrided layer not only has advantages in thickness and
low cost but also can increase the incubation period of SS matrix
Jiang Xu [17], which is assigned to the strengthening effect of nitrogen
Department of Material Science and Engineering, [18]. However, it is also worth noting that the addition of nitrogen
Nanjing University of Aeronautics and Astronautics, by plasma nitriding at 500  C decreases the cavitation erosion rate
of the steel [19].
Nanjing 210016, China;
Transition metal silicides, the largest family of intermetallic
School of Mechanical and Electrical Engineering, compounds, have many attractive properties and are regarded as
Wuhan Institute of Technology, promising materials for applications where wear and corrosion re-
693 Xiongchu Avenue, sistance is critical. Among them, Cr3Si has received much atten-
Wuhan 430073, China tion because of its unique combination of high thermal and
chemical stability and high hardness, making it suitable for appli-
cations in extremely harsh working conditions [20–22]. In this
current work, the Cr3Si film was deposited onto 304 SS substrate
In this technical brief, a Cr3Si nanocrystalline film was deposited by a double cathode glow discharge technique. Scratching and
on 304 stainless steel (SS) substrate using a double glow dis- cavitation erosion tests were performed to elucidate the adhesion
charge plasma technique. The film was characterized by X-ray dif- strength and cavitation erosion resistance of the film. SEM studies
fraction, scanning electron microscopy (SEM), transmission on the erosion surface of the samples have been carried out in
electron microscopy, nanohardness tester, and scratch tester. The order to assess the possible erosion mechanisms.
as-deposited film with a thickness of 5 lm consisted of A15 struc-
tured Cr3Si phase with an average grain size of 8 nm. The hard- 2 Experiment Details
ness values of the film were determined to be 26 GPa, which was
ten times greater than 304 SS. A self-designed ultrasonic vibration 2.1 Test Rig. A self-designed ultrasonic vibration cavitation
cavitation erosion apparatus was employed to evaluate the cavita- erosion apparatus was employed to evaluate the cavitation erosion
tion erosion resistance of the Cr3Si film. The results showed that resistance of samples, as shown in Fig. 1(a). The schematic dia-
after cavitation tests of 30 hrs, the erosion mass loss of the film gram of this cavitation erosion experimental apparatus is pre-
was only 60% of that for 304 SS substrate. SEM observation of sented in Figs. 1(b) and 1(c). The vibration horn performs an axial
the erosion surfaces indicated that the surface damage degree of vibration with the frequency of 20 kHz and the amplitude of 6 lm.
the Cr3Si film is significantly less than that of 304 SS. The specimen was mounted on the support table facing the tip of
[DOI: 10.1115/1.4033049] the vibration horn at a distance 500 lm. Tap water was used as the
medium in the beaker. In every 30 mins, the well-handled water in
Keywords: thin films, intermetallic alloys and compounds, the beaker would be replaced by fresh water and the temperature
cavitation erosion, nanomaterials of the water was maintained at 20 6 5  C. During cavitation ero-
sion tests, cavitation bubbles were generated at the tip surface and
1 Introduction directed toward the surface of the specimen. The collapse of bub-
Austenitic SSs have found a wide range of applications ranging bles occurred at near the sample surface, causing cavitation
from marine, urban water, and food processing to chemical areas erosion.
due to their unique combination of corrosion resistance, weldabil-
ity, and slurry erosion resistance. Among them, 304 SS has signifi- 2.2 Test Specimens. A 304 SS with the dimension of
cant potential as a candidate material for manufacturing a water 10 mm  7 mm  5 mm was used as a substrate. The chemical
lubricated bearing or water lubricated seal [1,2], which has been composition of the 304 SS in wt.% was: Cr, 18; Ni, 8.5; C, 0.08;
widely applied in pump, turbine, compressor, machine tool spin- Si < 1.0; Mn < 2.0; P < 0.045; S < 0.035; and the balance, Fe. The
dle, etc. However, cavitation phenomenon is often observed in hy- 304 SS substrates were ground using with SiC abrasives of
draulic machines and components, because the rapid changes in sequentially finer (240–2000) grit, followed by polishing with dia-
pressure lead to the formation of small bubbles or cavities in the mond paste. The Cr3Si film was deposited on the polished 304
liquid [3–6]. In this case, the emission of shock wave or microjet surface using a double cathode glow discharge apparatus. In
induced by the collapse of bubbles near the surface of component double-cathode working mode, one cathode is the source (target)
cathode, fabricated from the desired sputtering materials, and the
other cathode is the substrate material, as described in detail else-
1
where [23]. When the voltage is applied to the cathode, glow-
Corresponding author.
Contributed by the Tribology Division of ASME for publication in the JOURNAL
discharge occurs. The target had the composition with Cr:Si ¼ 3:2
OF TRIBOLOGY. Manuscript received August 24, 2015; final manuscript received in molar ratio. The glow discharge sputtering parameters
January 20, 2016; published online June 23, 2016. Assoc. Editor: Satish V. Kailas. employed in this study are listed in Table 1.

Journal of Tribology Copyright V

C 2017 by ASME JANUARY 2017, Vol. 139 / 014501-1

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 Fig. 1 (a) The ultrasound vibration system—photo, (b) The ultrasound vibration system—
schematic diagram of system, and (c) The ultrasound vibration system—schematic diagram
of specimen placement

Figure 2 shows SEM cross-sectional morphology of the as- The test was carried out by continuous loading with a normal
deposited film formed on 304 SS substrate. Clearly, the films with force from 0 to 100 N and the load was increased using a constant
the thickness of 5 lm are devoid of pores and microcracks, and loading rate of 20 N/min at a scratch speed of 1 mm/min. During
appear compact and quite well adhesive to the 304 SS substrate. scratching, an acoustic emissions (AE) sensor was attached near
Plan-view TEM bright-field image (Fig. 3(a)) reveals that the the diamond indenter to detect the acoustic signal emitted when
microstructure of the film consists of equiaxed grains with an av- the film cracked. The minimum load at which the coating fracture
erage grain size of 8 nm. From HRTEM image (Fig. 3(b)), it is occurred was also called the critical load (LC). Such a load was
clear that the fringe spacings of 0.32 nm correspond to a displac- determined by a sudden increase in the intensity of AE, which
ing of the (110) plane of Cr3Si. was further confirmed by SEM examination. The AE curve is
Figure 4 presents a typical X-ray diffraction pattern of the as- plotted as a function of the normal load in Fig. 5(a) and the corre-
deposited film. The diffraction pattern are characterized by a set sponding scratch track on the as-deposited Cr3Si films is displayed
of broad peak indexed as A15 structured Cr3Si phase (JCPDS in Fig. 5(b). At the early stage of scratching, AE is too weak to be
Card No. 07-0186), indicating that the as-deposited films consist detectable, and AE peaks appear with continuous fluctuation
of a single phase of Cr3Si phase. when the applied normal load is greater than 80 N. Figure 5 shows
The hardness and elastic modulus of the Cr3Si film and 304 SS SEM image of the scratch track on the film. As shown in Fig.
were measured with a nanohardness tester (CSEM Instruments). 5(b), when the scratching load exceeds the critical value that the
The standard analysis procedure proposed by Oliver and Pharr
[24] was used to determine the hardness of the specimens from
the unloading curve. The maximum load applied was 20 mN, with
a loading and unloading rate 10 mN/min. The obtained hardness
and modulus were presented in Table 2.
A commercial scratch tester (WS-97) with a Rockwell-shaped
diamond indenter of 200 lm radius was used to evaluate the criti-
cal load between the as-deposited coating and the SS substrate.

Table 1 Deposition parameters of Cr3Si film

Parameters Cr3Si

Substrate temperature ( C) 800

Treatment time (hr) 3
Target electrode bias voltage (V) 900
Substrate bias voltage (V) 300
Working pressure (Pa) 35
Ar flow rate (sccm) 60
Parallel distance between the 15
source electrode and the substrate (mm) Fig. 2 Cross section SEM morphology of the as-deposited
Cr3Si film

014501-2 / Vol. 139, JANUARY 2017 Transactions of the ASME

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 Table 2 Properties of Cr3Si film and substrate

Properties 304 steel Cr3Si

Film thickness (lm) — 5

Roughness (lm) 0.2 0.2
Hardness (GPa) 2.5 26
Elastic modulus (GPa) 193 300

2.3 Test Procedures. The cavitation tests were performed in

a self-designed ultrasonic vibration cavitation erosion apparatus
with total exposure of 30 hrs. During the first 6 hrs, the specimen
was weighed at each 2 hrs and subsequently, the sample was
weighed at each 3 hrs. Before weighing, the specimens were
cleaned with acetone in an ultrasonic cleaner, and dried in air. The
mass changes of the specimens were measured on an analysis bal-
ance with an accuracy of 0.01 mg. All of the reported results were
verified by repeating erosion tests at least three times, where the
average value and the scatter for repeated erosion tests were
noted. Figure 6 shows optical photograph the specimens of 304
steel and Cr3Si film after 30 hrs of cavitation test.
The mean depth of erosion (MDE) was further defined as
follows:
MDE ðlmÞ ¼ 1000  Dm=ðq  AÞ (1)

where Dm is the mass loss in mg, q is the density of surface layer

of the specimen (304 steel, 7.85 g/cm3, Cr3Si, 6.46 g/cm3), and A

Fig. 3 (a) TEM brighttield micrograph and HRTEM image of the

sputter-deposited nanocrystalline Cr3Si film—TEM brighttield
micrograph and (b) TEM brighttield micrograph and HRTEM
image of the sputter-deposited nanocrystalline Cr3Si film—
HRTEM image

film could support, microcracks initiate and grow perpendicular to

the scratch direction with chipping of the film at the edge of the
scratch track. By correlating AE data with SEM observation, it
suggests that the microcracks initiate coincidentally with a sudden
increase in AE, yielding the critical load (i.e., adhesive strength of
the as-deposited Cr3Si film on 304 SS) of about 80 N.

Fig. 5 (a) The acoustic signal intensity versus load plot and
SEM image of the scratch track on Cr3Si film—the acoustic sig-
nal intensity versus load plot. (b) The acoustic signal intensity
versus load plot and SEM image of the scratch track on Cr3Si
Fig. 4 XRD pattern of the sputter-deposited Cr3Si film film—SEM image of the scratch track on Cr3Si film.

Journal of Tribology JANUARY 2017, Vol. 139 / 014501-3

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 SS and the Cr3Si film after 30 hrs of erosion tests. It is evident
from Fig. 9(a) that, after 30 hrs of erosion test, large pitting pits
and craters are visible on the surface of the 304 SS. For the 304
SS, under cavitation erosion condition, the emission of shock
wave or microjet induced by the collapse of bubbles near the sur-
face of component results in a stress accumulation on the surface
and the occurrence of surface plastic deformation [25]. Fatigue
cracks are generated on the surface of the material and extended
inward, leading to fatigue fracture and abscission. Then the cracks
continue to extend inward, resulting in the further damage. In
addition, some pits agglomerated seriously in the erosion area and
Fig. 6 (a) Specimens after 30 hrs of cavitation test—304 steel these irregular pits are formed from the material removed in the
and (b) specimens after 30 hrs of cavitation test—Cr3Si film erosion time. This phenomenon was also observed in Refs. [26]
and [27]. In contrast, except some fine pitting pits, the surface
is the referenced area of specimen (70 mm2). The surface mor- damage degree of the Cr3Si film is neglected without evidence of
phologies of the specimens were examined by the SEM. cracks. Due to its unique chemical composition and strong bonds
with large covalent component, the Cr3Si film exhibits the higher
hardness and corrosion resistance, which effectively enhance the
3 Results and Discussion
3.1 Mass Loss. Figure 7 shows the mass loss and MDE of the
specimens as a function of test time. As shown in Figs. 7(a) and
7(b), with increasing the test time, the weight loss and MDE of
samples increase. After 30 hrs of cavitation erosion test, the mass
loss of the Cr3Si film was 3.26 mg, which is only 60% of that for
the 304 SS.

3.2 SEM Studies of Cavitation Erosion Surfaces. Figure 8

shows the SEM micrographs of surface morphologies of the 304

Fig. 8 (a) The SEM images of the specimen after 30 hrs test—
Fig. 7 (a) The test curves of Cr3Si film and 304 steel—mass 304 SS and (b) The SEM images of the specimen after 30 hrs
loss and (b) The test curves of Cr3Si film and 304 steel—MDE test—Cr3Si film

014501-4 / Vol. 139, JANUARY 2017 Transactions of the ASME

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 51374130, and 11472078, and the Jiangsu University-Industry
Collaboration Project (Grant No. BY2015070-26).

References
[1] Yoshimoto, S., Oshima, S., Danbara, S., and Shitara, T., 2002, “Stability of
Water-Lubricated, Hydrostatic, Conical Bearings With Spiral Grooves for
High-Speed Spindles,” ASME J. Tribol., 124(2), pp. 398–405.
[2] Yoshimoto, S., Anno, Y., Tamura, M., Kakiuchi, Y., and Kimura, K., 1996,
“Axial Load Capacity of Water-Lubricated Hydrostatic Conical Bearings With
Spiral Grooves (on the Case of Rigid Surface Bearings),” ASME J. Tribol.,
118(4), pp. 893–899.
[3] Abouel-Kasem, A., El-Deen, A. E., Emara, K. M., and Ahmed, S. M., 2009,
“Investigation Into Cavitation Erosion Pits,” ASME J. Tribol., 131(3),
p. 031605.
[4] Abouel-Kasem, A., and Ahmed, S. M., 2008, “Cavitation Erosion Mechanism
Based on Analysis of Erosion Particles,” ASME J. Tribol., 130(3), p. 031601.
[5] Abouel-Kasem, A., and Ahmed, S. M., 2012, “Bubble Structures Between Two
Walls in Ultrasonic Cavitation Erosion,” ASME J. Tribol.,134(2), p. 021702.
[6] Karrab, S. A., Doheim, M. A., Aboraia, M. S., and Ahmed, S. M., 2012, “Study
of Cavitation Erosion Pits on 1045 Carbon Steel Surface in Corrosive Waters,”
ASME J. Tribol., 134(1), p. 011602.
[7] Bregliozzi, G., Di Schinob, A., Ahmeda, S. I.-U., Kennyb, J. M., and Haefke,
H., 2005, “Cavitation Wear Behaviour of Austenitic Stainless Steels With Dif-
ferent Grain Sizes,” Wear, 258(1), pp. 503–510.
[8] Takakuwa, O., and Soyama, H., 2012, “Suppression of Hydrogen-Assisted Fa-
tigue Crack Growth in Austenitic Stainless Steel by Cavitation Peening,” Int. J.
Hydrogen Energy, 37(6), pp. 5268–5276.
[9] Zhang, L., Zhang, Y. K., Lu, J. Z., Dai, F. Z., Feng, A. X., Luo, K. Y., and Qi,
H. L., 2013, “Effects of Laser Shock Processing on Electrochemical Corrosion
Resistance of ANSI 304 Stainless Steel Weldments After Cavitation Erosion,”
Corros. Sci., 66, pp. 5–13.
[10] Haosheng, C., Jiang, L., and Shihan, L., 2009, “Thermal Effect at the Incipient
Fig. 9 (a) Failure behaviors of the Cr3Si film—the pit by brittle Stage of Cavitation Erosion on a Stainless Steel in Ultrasonic Vibration
fracture and (b) failure behaviors of the Cr3Si film—the pit by Cavitation,” ASME J. Fluid Eng., 131(2), p. 024501.
grain spalling [11] Krella, A., and Czyzniewski, A., 2007, “Influence of the Substrate Hardness on
the Cavitation Erosion Resistance of TiN Coating,” Wear, 263(1), pp. 395–401.
resistance to the emission of shock. Therefore, the cavitation ero- [12] Krella, A., and Czyzniewski, A., 2008, “Cavitation Erosion Resistance of
sion resistance of the Cr3Si film is prominently superior to that of Nanocrystalline TiN Coating Deposited on Stainless Steel,” Wear, 265(7),
304 SS. pp. 963–970.
The formation of erosion pits of the Cr3Si film could be attrib- [13] Krella, A., and Czyzniewski, A., 2008, “Investigation Concerning the
Cavitation Resistance of TiN Coatings Deposited on Austenitic Stainless Steel
uted to the inherent brittleness of metal silicides, insufficient adhe- at Various Temperatures,” Wear, 265(1), pp. 72–80.
sion strength of the film/substrate, and macrodroplets formed on [14] Krella, A., and Czyzniewski, A., 2006, “Cavitation Erosion Resistance of Cr–N
the surface of the film. As is well known, the thermal coefficient Coating Deposited on Stainless Steel,” Wear, 260(11), pp. 1324–1332.
of expansion of 304 SS (17  106/K) is higher than that of the [15] Krella, A., and Czyzniewski, A., 2009, “Cavitation Resistance of Cr–N Coat-
ings Deposited on Austenitic Stainless Steel at Various Temperatures,” Wear,
Cr3Si film (9  106/K), leading to a high thermal stresses for 266(7), pp. 800–809.
the Cr3Si film during sputtering deposition, which is harmful to [16] Gerke, L., Stella, J., Schauer, J. C., Pohl, M., and Winter, J., 2010, “Cavitation
adhesion strength of the film/substrate. Moreover, the Cr3Si film Erosion Resistance of a-C:H Coatings Produced by PECVD on Stainless Steel
exhibits low toughness at ambient temperature [28]. Hence, under and NiTi Substrates,” Surf. Coat. Technol., 204(21), pp. 3418–3424.
[17] Garzon, C. M., Thomas, H., dos Santos, J. F., and Tschiptschin, A. P., 2005,
the action of collapsed cavitation bubbles, the brittle fracture may “Cavitation Erosion Resistance of a High Temperature Gas Nitrided Duplex
occur on the Cr3Si film, and the erosion pit can be formed due to Stainless Steel in Substitute Ocean Water,” Wear, 259(1), pp. 145–153.
the partial peeling of the Cr3Si film. Moreover, some macrodrop- [18] Dos Santos, J. F., Garz on, C. M., and Tschiptschin, A. P., 2004, “Improvement
lets formed on the surface of the film are easily flaking away from of the Cavitation Erosion Resistance of an AISI 304L Austenitic Stainless Steel
by High Temperature Gas Nitriding,” Mater. Sci. Eng. A-Struct., 382(1),
the surface of Cr3Si film, which is also responsible for the forma- pp. 378–386.
tion of erosion pits. With the increase of test time, these macro- [19] Allenstein, A. N., Lepienski, C. M., Buschinelli, A. J. A., and Brunatto, S. F.,
droplets are gradually removed, accompanied by a reduction in 2014, “Improvement of the Cavitation Erosion Resistance for Low-
erosion rate of the Cr3Si film. The cavitation erosion mechanisms Temperature Plasma Nitrided Ca-6NM Martensitic Stainless Steel,” Wear,
309(1), pp. 159–165.
of the Cr3Si film and 304 SS are schematically illustrated in [20] Bei, H., George, E. P., Kenik, E. A., and Pharr, G. M., 2003, “Directional Solid-
Fig. 9. ification and Microstructures Of Near-Eutectic Cr–Cr3Si alloys,” Acta Mater.,
51(20), pp. 6241–6252.
[21] Bei, H., George, E. P., and Pharr, G. M., 2004, “Elastic Constants of Single
4 Conclusions Crystal Cr3Si and Cr-Cr3Si Lamellar Eutectic Composites: A Comparison of
Ultrasonic and Nanoindentation Measurements,” Scr. Mater., 51(9),
In this study, the sputter-deposited Cr3Si nanocrystalline film is pp. 875–879.
prepared on 304 SS substrate by double cathode glow discharge. [22] Yuan, L., and Wang, H. M., 2008, “Corrosion Properties of a Cr13Ni5Si2-Based
The results show that the Cr3Si film is comprised of equiaxed Metal Silicide Alloy,” Intermetallics, 16(9), pp. 1149–1155.
Cr3Si grains with a grain size of 8 nm. The hardness values of [23] Xu, J., Sun, J., and Jiang, S., 2009, “Mechanical Properties of Sputter-
Deposited Nanocrystalline Cr3Si Film,” Mater. Lett., 63(12), pp. 1082–1084.
the film were determined to be 26 GPa, which was ten times [24] Oliver, W. C., and Pharr, G. M., 1992, “An Improved Technique for Determin-
greater than 304 SS. The Cr3Si film exhibited higher cavitation ing Hardness and Elastic Modulus Using Load and Displacement Sensing
erosion resistance as compared with the 304 SS. The formation of Indentation Experiments,” J. Mater. Res., 7(06), pp. 1564–1583.
erosion pits of Cr3Si film can be attributed to the inherent brittle- [25] Franc, J., and Michel, J., 2006, Fundamentals of Cavitation, Kluwer Academic,
Dordrecht, The Netherlands.
ness of metal silicides, insufficient adhesion strength of the film/ [26] Cheng, F., and Jiang, S., 2014, “Cavitation Erosion Resistance of Diamond-
substrate, and macrodroplets formed on the surface of the film. Like Carbon Coating on Stainless Steel,” Appl. Surf. Sci., 292, pp. 16–26.
[27] Al-Hashem, A., Caceres, P. G., Abdullah, A., and Shalaby, H. M., “Cavitation
Corrosion of Duplex Stainless Steel in Seawater,” Corrosion, 53(2), pp.
Acknowledgment 103–113.
[28] Wang, H. M., and Duan, G., 2003, “Wear and Corrosion Behavior of Laser
The authors acknowledge the financial support of the National Clad Cr3Si Reinforced Intermetallic Composite Coatings,” Intermetallics,
Natural Science Foundation of China under Grant Nos. 11172065, 11(8), pp. 755–762.

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