Materials Letters 61 (2007) 165 167

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Electro-spark deposition of Fe-based amorphous alloy coatings

Dongyan Liu a,b,, Wei Gao a , Zhengwei Li a , Haifeng Zhang b , Zhuangqi Hu b
a
Department of Chemical and Materials Engineering, University of Auckland, New Zealand
b
Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110006, PR China

Received 23 December 2005; accepted 4 April 2006

Available online 11 May 2006

Abstract

A simple and effective surface coating technique, electro-spark deposition (ESD), has been used to produce amorphous alloy coatings. FeCr
MoGdCB amorphous alloy rods produced by copper mould casting were used as electrode to produce coatings onto 304 stainless steel substrate.
Classical X-ray diffraction (XRD), glancing angle XRD (GAXRD), and scanning electron microscopy (SEM) with energy dispersive X-ray (EDX)
analysis indicate that the coatings have an average thickness of 30 m, show an amorphous structure, and are metallurgically bonded to the
substrate. Microhardness tests showed that the coating layer has a high hardness of 1542 kg/mm2, implying a much improved wear resistance on
surface of stainless steels.
2006 Elsevier B.V. All rights reserved.

Keywords: Bulk amorphous alloys; Electro-spark deposition (ESD); Coating; Microhardness; Wear

1. Introduction Among the bulk amorphous alloy systems, Fe-based alloys

Bulk amorphous alloys attract much attention due to the
superior properties over their crystalline counterparts including
mechanical hardness, corrosion resistance, and soft magnetic
properties. A variety of alloy systems, such as MgCuY [1],
ZrAlNiCu [2], FeCo(Zr,Hf,Nb)(Mo,W)B [3], TiNi
CuSn [4], CuZr(Ti,Al) [5,6], and NiCuTiZrAl [7]
bulk amorphous alloys have been synthesized. The size of the
newly developed Fe-, Cu- and Mg-based bulk amorphous alloys
have reached the order of a few centimeters [811]. However,
the further application as engineering materials is restricted by
the still limited size and low toughness in the monolithic
amorphous alloys at room temperature. Therefore, the exploiting
further application of bulk amorphous alloys as coatings is of
great importance since the applications would not be limited by
the size and brittleness of the bulk amorphous alloys.
Furthermore, coatings can save much of the expensive alloy
elements in the bulk amorphous alloys.
Corresponding author. Department of Chemical and Materials Engineering,
University of Auckland, New Zealand. Tel.: +64 9 3737 599 85379; fax: +64 9
3737 463.
E-mail addresses: dliu045@ec.auckland.ac.nz (D. Liu),
w.gao@auckland.ac.nz (W. Gao).
0167-577X/$ - see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2006.04.042
are the promising candidates for coatings as they have high
hardness, excellent wear and corrosion resistance [12,13]. Good
adhesion of the coatings to steels can also be expected since the
coatings and the substrates have similar nature.
Several high energy coating technologies have been used to
produce amorphous alloy coatings, including laser cladding
[14], vacuum plasma spraying [15], magnetron sputtering [16],
high velocity oxygen fuel spraying [17] and electron beam
surface treatment with gas atomized powders [18]. Electro-spark
deposition (ESD) process is a simple and cost-effective low-
energy technique [1922]. This method produces metallurgical
bonding between the coatings and substrates, resulting in a much
better coating adhesion compared to other low-energy coating
processes such as detonation-gun, plasma-spray, and electro-
chemical plating. The short duration of the electrical pulse leads
to an extremely rapid melting and solidification of the electrode
materials to form micro- or nano-structured coatings. In the
present case, the electrode material, FeCrMoGdCB
alloy, has strong glass forming ability [9]. Amorphous alloy
coatings therefore can be expected.
The amorphous alloys, FeCrMoGdCB alloys, were
prepared in our lab by Cu mould casting with low-purity raw
materials. Rods of 8 and 4 mm diameters were cast under va-
cuum and ambient atmosphere, respectively. The present paper
166 D. Liu et al. / Materials Letters 61 (2007) 165167

Fig. 1. Classical X-ray diffraction spectra of: (a) the bulk amorphous alloy rod
with a diameter of 8 mm, (b) amorphous alloy coated 304 stainless steel sample,
and (c) glancing X-ray diffraction spectra of coated sample with incident angle
= 2. Fig. 3. SEM cross-section micrograph of the coated 304 stainless steel sample
( denotes the scanned spot for EDX analysis in Fig. 4 and Table 1).

reports the results of using cast FeCrMoGdCB rods to Beijing. It is a hand-held unit with a rotary electrode that operates
produce amorphous alloy coatings on stainless steel substrate. on a metal substrate. The detailed design of the machine can be
found in previous papers [20,21]. The deposition was conducted for
2. Experimental methods four consecutive passes under ambient atmosphere.

A rectangular 304 stainless steel plate with the size of 20

15 2 mm was used as substrate. Prior to coating, the substrate
was grounded with 600-grit SiC paper and degreased in acetone.
Amorphous alloy Fe48Cr15Mo14Gd2C15B6 (at.%) ingots were
prepared by arc melting a mixture of Fe, Cr, Mo, Gd metals, C
and industrial FeB alloy, which contains 18.9 wt.% B and small
amounts of other elements (total X% of Al, Si, C and P). The
melting was conducted under Ar atmosphere with Ti-getter to
avoid oxidation of the alloy elements. Fe48Cr15Mo14Gd2C15B6
rods with diameters of 4 mm were used as the electrode.
The electro-spark deposition machine was established in our lab
collaborated with Y-D He of University of Science and Technology

Fig. 2. Vickers microhardness measurements from the coating layer to the

substrate (load of 100 g applied for 10 s). Fig. 4. EDX analysis of (a) coating layer and (b) substrate.
 D. Liu et al. / Materials Letters 61 (2007) 165167
Table 1
EDX analysis of the coating layer and substrate
Fe Cr Mo Gd Ni Si
(wt.%) (wt.%) (wt.%) (wt.%) (wt.%) (wt.%)
Coating 55.34 16.26 24.09 4.32
Substrate 72.16 18.62 8.48 0.74
The coated specimens were investigated for their structure and
cross-sectional microstructure by classical X-ray diffraction
(XRD) and glancing angle XRD (GAXRD) using CuK radiation
and SEM/EDX analysis, respectively. Microhardness was mea-
sured on a cross-section surface from the substrate to coating with
a Vickers microhardness tester under the load of 100 g for 10 s.
3. Results and discussion
X-ray diffraction spectra of a coated sample together with
Fe48Cr15Mo14Gd2C15B6 rod with a diameter of 8 mm are shown in
Fig. 1. The spectrum of bulk amorphous alloy rod in Fig. 1(a) exhibits
the typical spectra of the alloy with a broad halo peak, indicative of fully
amorphous structure. The characteristic diffraction peaks of the
substrate (-Fe) are present for the coated sample in Fig. 1(b). The
glancing X-ray diffraction spectrum in Fig. 1(c) shows broad halo peaks
confirming that amorphous coating formed by ESD process.
Fig. 2 illustrates the variation of microhardness across the interface
from the coating to substrate. The microhardness of coating reaches the
value of 1542 kg/mm2, is almost the same as that of the bulk amorphous
alloy, while the stainless steel has a hardness of 240 kg/mm2, much
lower than the coating.
Fig. 3 shows a typical SEM cross-section micrograph of a coated
sample. Different contrasts of the coating and substrate can be observed,
indicating that the coating did not mix with the substrate. Microscopic
hills and valleys resulting from spark melting at various locations were
observed in the cross-section micrograph. However, the uniform and
dense coating with a thickness of about 30 m is seen strongly bonded
to the substrate without observable microcracks or gaps. The apparent
size of microhardness indentation is consistent with the hardness
reading of the coating and substrate. EDX analysis shown in Fig. 4
indicates that both coating and substrate keep their own composition,
indicating that the ESD process does not change the composition of the
substrate and the electrode (Table 1).
Electro-spark deposition operates like a mini-pulsed-arc welding
process using short-duration. Highly concentrated electrical energy
melts and deposits the electrode material onto the metallic substrate. It
was reported that the temperature of the arc generated can reach 5000 K
[23]. In our previous studies, the electrical pulse causes rapid melting
and solidification of the deposited material, resulting in micro- or nano-
structured, uniformly distributed and metallurgically bonded coatings
[2022].
In the present experiment, we use FeCrMoGdCB alloy that
has very strong glass forming ability. The atomic radius and mix
enthalpy play important roles in glass formation. The addition of Gd
introduced atoms with large atomic radius 0.161 nm, facilitating the
packed local structure. Large negative mix heat among the constituent
167
elements enhances the interaction among the components and promotes
the chemical short range ordering in the liquids. It is believed that the
superior glass forming ability comes from the existence of large atomic
size which can destabilize the competing crystalline phase [9]. This can
explain the formation of amorphous structure on the surface of steel
samples during the electro-spark deposition.
4. Conclusions
An amorphous alloy, Fe48Cr15Mo14Gd2C15B6, was success-
fully coated onto 304 stainless steel substrate by electro-spark
deposition technology. The coatings have an amorphous struc-
ture, are fully dense with a typical thickness of 30 m. They are
strongly bonded to the steel substrate, and exhibit high micro-
hardness of 1542 kg/mm2.
Acknowledgement
The authors would like to thank the Dept. of Chemical and
Materials Engineering and the Research Centre for Surface and
Materials Science for various supports.
References
[1] A. Inoue, A. Kato, T. Zhang, S.G. Kim, T. Masumoto, Mater. Trans., JIM
32 (1991) 609.
[2] A. Inoue, T. Zhang, N. Nishiyama, K. Ohba, T. Masumoto, Mater. Trans.,
JIM 34 (1993) 1234.
[3] A. Inoue, T. Zhang, A. Takeuchi, Appl. Phys. Lett. 71 (1997) 464.
[4] T. Zhang, A. Inoue, Mater. Trans., JIM 39 (1998) 1001.
[5] A. Inoue, W. Zhang, T. Zhang, Acta Mater. 49 (2001) 2645.
[6] A. Inoue, W. Zhang, Mater. Trans. 43 (2002) 2921.
[7] D.H. Xu, G. Duan, W.L. Johnson, C. Garland, Acta Mater. 52 (2004) 3493.
[8] Z.P. Lu, C.T. Liu, J.R. Thompson, W.D. Porter, Phys. Rev. Lett. 92 (2004)
245503.
[9] V. Ponnambalam, S.J. Poon, G.J. Shiflet, J. Mater. Res. 19 (2004) 1320.
[10] D.H. Xu, G. Duan, W.L. Johnson, Phys. Rev. Lett. 92 (2004) 245504.
[11] H. Ma, L.L. Shi, J. Xu, Y. Li, E. Ma, Appl. Phys. Lett. 87 (2005) 181915.
[12] A. Inoue, B.L. Shen, Mater. Trans. 43 (2002) 766.
[13] S.J. Pang, T. Zhang, K. Asami, A. Inoue, Acta Mater. 50 (2002) 489.
[14] X. Wu, B. Xu, Y. Hong, Mater. Lett. 56 (2002) 838.
[15] J. Jayaraj, D.J. Sordelet, D.H. Kim, Y.C. Kim, E. Fleury, Corros. Sci. 48
(2006) 950.
[16] P. Sharma, W. Zhang, K. Amiya, H. Kimura, A. Inoue, J. Nanosci.
Nanotechnol. 5 (2005) 416.
[17] H.J. Kim, K.M. Lim, B.G. Seong, C.G. Park, J. Mater. Sci. 36 (2001) 49.
[18] K. Lee, E. Yun, S. Lee, N.J. Kim, Mater. Sci. Eng., A Struct. Mater.: Prop.
Microstruct. Process. 408 (2005) 92.
[19] R.N. Johnson, G.L. Sheldon, J. Vac. Sci. Technol., A 4 (1986) 2740.
[20] Y.D. He, Z. Huang, H.B. Qi, D.R. Wang, Z.W. Li, W. Gao, Mater. Lett. 45
(2000) 79.
[21] W. Gao, Z.W. Li, Y.D. He, Mat. Sci. Forum 369372 (2001) 579.
[22] Y.D. He, H. Pang, H.B. Qi, D.R. Wang, Z.W. Li, W. Gao, Mater. Sci. Eng.,
A Struct. Mater.: Prop. Microstruct. Process. 334 (2002) 179.
[23] A.L. Phillips, Welding Handbook, American Welding Society, Miami,
1968, p. 20.