Thin Solid Films 376 Ž2000.

159᎐163

Microstructures and properties of PVD aluminum bronze

coatings

Wang LiangU , Xu Xiaolei, Xu Jiujun, Hei Zukun

Institute of Metals and Technology, Dalian Maritime Uni¨ ersity, Dalian, 116024, PR China

Received 21 October 1999; received in revised form 10 June 2000; accepted 20 June 2000

Abstract

Aluminium bronze coatings were deposited by the hollow cathode discharge ŽHCD. ion plating technique. The thickness of
coatings were over 20 ␮m with excellent adhesion to the substrate. The structures of the coatings deposited on QAL10-4-4
aluminum bronze were studied by cross-sectional transmission electron microscopy ŽX-TEM. and X-ray diffraction ŽXRD.. The
results show that coating consists of different morphology zones. There are more ␥ 2ŽCu 9 Al 4 .and ␤ŽNiAl. phase in the coating
than in the bulk material. The wear test and practical application showed that after deposit the wear resistance evidently
improved. 䊚 2000 Elsevier Science S.A. All rights reserved.

Keywords: Aluminum bronze coatings; Ion plating; X-TEM; Wear resistance

1. Introduction
Because of its excellent comprehensive mechanical
anti-wear and anti-corrosion properties, aluminum
bronze has been widely used in air industry. Many
precise parts of airplane are made of aluminum bronze.
In order to repair and strengthen these precise parts,
we used physical vapor deposition ŽPVD. to deposit
coating on them. Few papers report on PVD aluminum
bronze coatings w1x. In this paper we take a particular
interest in the microstructures and properties of such
coatings deposited on aluminum bronze. Compared
U ness is approximately 5 ␮m for each single layer and
Corresponding author. Tel.: q86-411-4729611; fax: q86-411-
4671395.
E-mail address: coldmc@mail.dlptt.ln.cn ŽW. Liang..
with the bulk materials, the coatings have much better
wear-resistance, which have been used to repair and
modify the precise part surfaces such as the fuel needle
of airplane motors.
The coating prepared by evaporating aluminum
bronze alloy was not homogeneous because nickel and
iron have relatively low evaporation rates compared
with those of copper and aluminum.
In order to produce multi-layer and thicker coatings,
it is necessary to feed the coating materials into the
plumbago crucible consecutively during deposition. In
this work, aluminum bronze slugs could be fed one-by-
one into the plumbago crucible using a slug feeder
developed and designed for this purpose. So the thick-
the total thickness could reach above 20 ␮m. However,
this method inevitably causes concentration variations

0040-6090r00r$ - see front matter 䊚 2000 Elsevier Science S.A. All rights reserved.
PII: S 0 0 4 0 - 6 0 9 0 Ž 0 0 . 0 1 2 1 3 - X
160 W. Liang et al. r Thin Solid Films 376 (2000) 159᎐163
Fig. 1. Cross-section micrograph of the aluminum coating.
in the coatings. Compared to the original substrate
materials, the hardness and wear resistance could in-
crease by more than two times.
2. Experimental details
The deposition of aluminum bronze coatings was
carried out in a HCD ion plating apparatus.
Fig. 2. XRD patterns obtained from the bulk material and coating.
Both substrates and coating materials were QAL10-
4-4 Ž10 wt.% Al, 4 wt.% Ni, 4 wt.% Fe, balance Cu..
The coating material was evaporated from a plumbago
crucible. Before deposition, the specimens were sputter
cleaned at a negative voltage of y1500 V in an argon
atmosphere for 15 min. During deposition, the operat-
ing argon pressure was kept at 0.26 Pa. The power of
the electron gun was kept at approximately 10 kW. A
bias voltage of approximately y40 V was applied to the
substrates. The current density of the substrate was 2
mA. The substrate temperature was maintained at
300⬚C. The number of feeding slugs and the total
deposition time were determined according to the
thickness required of deposited coating. Structure anal-
ysis was done using X-ray diffraction ŽXRD. and cross-
section transmission electron microscopy ŽXTEM..
XRD was performed in a ␪᎐2␪ geometry using Cu K ␣
radiation. For the X-TEM experiments, H-800 electron
microscope was used operating at 175 kV acceleration
voltage. XTEM specimens were prepared by mechani-
cal polishing and ion milling using Ar ions at 5 kV and
an incident angle of 7⬚ with the cross-sectional surface.
 W. Liang et al. r Thin Solid Films 376 (2000) 159᎐163
Fig. 3. Glancing-angle XRD patterns obtained at different incidence
angles for a coated sample.
The wear test was carried out using a MM-200 wear
tester with lubricating oil. The load was 150 N and
sliding speed was 0.84 mrs. During testing, the coated
and uncoated specimens were rotating against a statio-
nary slider of 0.45% C steel.
3. Results and discussion
Fig. 1 shows the cross-section structure of an ion-
plated aluminum bronze substrate. The film thickness
observed was 20 ␮m. It had a layered structure, each
sublayer being approximately 3᎐4 ␮m, as can be seen
in Fig. 1. It can also be seen that the coating is very
dense and that the number of layers in the coating is
exactly the same as the number of slugs feeded.
Fig. 2 shows the X-ray diffraction patterns of the
coating material before evaporation and of the coat-
ings. The diffraction angles of various phases have
Fig. 4. Cross-sectional transmission micrographs and SAD patterns from aluminum bronze coatings deposited on aluminum bronze substrate. Ža.
Cross-sectional overview transmission electron micrograph of the coating. Žb. Selected electron diffraction pattern from the ‘a’ region near the
interface between coating and substrate. Žc. High magnification cross-sectional transmission electron micrograph from the ‘b’ region.
161
been marked in the graph. Both materials have similar
structures, and consist of phases ␣ , ␥ 2 , ŽCu 9 Al 4 . and ␤
ŽNiAl.. Compared with the bulk materials, there are
more ␥ 2 ŽCu 9 Al 4 . and ŽNiAl. phases in the coating.
One sample was investigated by grazing-incidence
diffraction in which the incident angle was fixed at
various values from 0.5 to 8⬚ to detect different depths
into the surface Žin Fig. 3.. ␥ 2 or ␤ is evident for
␣ s 0.5 and 1⬚ indicating that it is most abundant in the
surface region. Traces of ␣-Cu was detected for ␣ s 0.5
and 1⬚. With the incident angle increasing, the ␣-Cu
peaks become more visible.
A cross-sectional electron micrograph of the
aluminum bronze coating is shown in Fig. 4. It consists
of several different zones, in which the micrograph is
different. The grains are equiaxial and randomly ori-
ented near the interface. Looking further into the
aluminum bronze coating, it was observed that the
average grain size is increasing gradually from the
interface to the coating surface. The microstructure of
the coating is different from the growth of the coating,
i.e. from being equiaxial near the interface to columnar
for a longer deposition. As is clear from this micro-
graph, for the initially deposited aluminum bronze,
because of the intense ionicratomic bombardment, the
surface mobility of the atoms is relatively high. There-
fore, the metal atoms deposited ŽCu, Fe, Al, Ni. could
fill in the low atomic density areas, thus suppressing
columnar growth w2᎐5x. After a short time of deposi-
tion, the coating structure became fine columnar with
column of diameter 15᎐20 nm. Selected-area diffrac-
tion pattern obtained from the coating region close to
the coatingrsubstrate interface showed reflections cor-
responding to ␣-Cu indicating that in this region the
alloying elements ŽAl, Fe, Ni. especially Fe and Ni have
a lower concentration than in the bulk material. The
contents of the alloying elements were measured by
electron probe microanalysis ŽEPMA. Žsee Table 1.. It
can be seen from Table 1 that on the surface of the
coating Ni, Fe and Al contents are gradually increasing
162 W. Liang et al. r Thin Solid Films 376 (2000) 159᎐163

Table 1
The contents of alloying elements in coating as a function of distance
from the coatingrsubstrate interface

Distance from Al Fe Ni Cu
interface Ž␮m.
2 3.4 1.5 0.2 94.9
5 3.9 1.4 0.3 94.4
8 4.4 1.8 0.5 93.3
14 7.2 2.5 1.4 88.9
20 12.4 4.8 3.5 79.3
24 14.4 7.2 6.8 71.6
Fig. 6. Electron diffraction pattern of Cu, NiAl, Cu 9 Al 4 and index-
ing.

of these elements, as compared to Cu. Following the

Fig. 5. Cross-section microstructure of the two sublayers.
with the distance increase from the interface between
coating and substrate due to the lower evaporation rate
fine columnar region the grains of coating became
large rapidly forming the main area of the coating. Fig.
5 is a typical micrograph of the film structure in the
center region of the coating, the thickness of which is
approximately 20 ␮m. In this region the growth direc-
tion of the columnar crystal is vertical to the substrate
surface and has Cu twin microstructure. For the copper
alloy with lower stacking fault energy, at the higher
growth rate the probability of twin appearance is large.
In the region near the surface of the coating there are
NiAl and ␥ 2 ŽCu 9 Al 4 . phases formed in the ␣-Cu ma-
trix. The corresponding electron diffraction pattern and
indexing are shown in Fig. 6. The orientation relation-
ships of them with ␣-Cu are Ž111.NiAlrrŽ011. ␣ ,
w 1 1 0 x N iA lr r w 1 1 1 x ␣ , Ž 5 1 1 . C u 9 A l 4 r r Ž 0 1 1 . ␣ ,
w150xrrw111x␣. Because the coating consists of six sub-
layers, the interface condition of each sublayer is im-
portant for the all coating. The cross-section mi-
crostructure of local coating including two sublayer
interfaces is shown in Fig. 5. Distinct interfaces appear
between the sequential thin layers marked by the arrow
in Fig. 6. It is evident from this micrograph that the
microstructure of the Cu grains is not disturbed obvi-
ously because on the interface the epitaxial process is
visible.
The microhardness of the bulk aluminum bronze is

Fig. 7. Scanning electron micrographs of worn surface of coated and uncoated specimens.
 W. Liang et al. r Thin Solid Films 376 (2000) 159᎐163
Hv0.1 350. After coating the microhardness reaches ap-
proximately 640.
The typical morphologies of the wear tracks are
shown in Fig. 7, from which it can be seen that deep
ploughing and severe adhesive trace result in wire-like
debris for uncoated specimens. On the contrary, for the
coated specimens there are very fine and shallow traces
left on the surface with fine power debris created.
Under the same conditions the weight loss is 10 and 30
mg for coated and uncoated specimens, respectively.
4. Conclusion
Successful aluminum bronze multi-layer coatings can
be prepared by an HCD ion plating process with a slug
feeding mechanism, the thickness of the coating being
approximately 20 ␮m. From the XTEM micrographs it
can be seen that the interface between the coating and
163
substrate, sublayer and sublayer is obscure so the adhe-
sion between the coating and substrate is excellent.
The compositions of the alloys are not homogeneous
creating a gradient of the concentration especially for
Fe and Ni. Compared with the original materials the
specimens with coatings have a better wear resistance.
References
w1x H.A. Sundquist, A. Matthews, D.G. Teer, Thin Solid Films 73
Ž1980. 309.
w2x C.C. Cheng, A. Erdemir, G.R. Fenske, Surf. Coat. Technol.
39r40 Ž1989. 365.
w3x U. Helmersson, J.-E. Sundgren, J.E. Greene, J. Vac. Sci. Tech-
nol. A 4 Ž1986. 500.
w4x A. Erdemir, C.C. Cheng, J. Vac. Sci. Technol. A 9 Ž1991. 439.
w5x G. Hakansson, L. Hultman, J.-E. Sundgren, J.E. Greene, W.-D.
Munz, Surf. Coat. Technol. 48 Ž1991. 51.