Journal of Alloys and Compounds 448 (2008) 257–262

Investigation of wear properties of hydrogenated tin brass heat exchanger

Amjad Saleh El-Amoush ∗
Al-Balqa Applied University, Royal Jordanian Geographic Centre College, Amman 11118, P.O. Box 20214, Jordan
Received 14 July 2006; received in revised form 2 October 2006; accepted 6 October 2006
Available online 9 November 2006

Abstract
The wear properties of hydrogenated tin brass heat exchanger have been investigated using pin on disc wear tests under different cathodic
hydrogen charging conditions. Sliding distance was taken as wear test variable, while applied normal load and sliding velocity were kept constant.
The tests revealed that cathodic hydrogen charging resulted in a reduction of the coefficient of sliding friction of tin brass. The coefficient of sliding
friction was found to decrease with increasing charging time. However, the friction coefficient of hydrogen charged tin brass recovered to its original
value (i.e. before hydrogen charging) after certain sliding distance. Most of the wear debris of the hydrogen charged tin brass heat exchanger had
a particle like shape and exhibited cracking, whereas the wear debris of the uncharged tin brass was indicative of mechanical shearing and plastic
deformation. The amount of wear debris was found to be a uniform function of charging time. A long time of charging produced more wear debris.
Hydrogen cracks across and along the wear tracks of the cathodically charged tin brass heat exchanger were observed. Moreover, the severity of
cracking increased with increasing the cathodic charging time.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Pin-on-disk sliding friction wear; Hydrogen charging; Tin brass heat exchanger

1. Introduction
Heat exchanger tubes in the chemical, petrochemical and oil
refining industries may fail by one or a combination of sev-
eral wear mechanisms, such as corrosion, fatigue and sliding
as well as impact fretting wear. The failure variously manifests
itself as tube thinning, grooving, localized pitting and crack-
ing. The tubular components of heat exchanger are subjected
to pressurized high temperature water flow conditions resulting
in vibrations. Therefore, the mechanical interactions of the two
contacting surfaces, tubes and their guides consist in sliding
with impact at a low contact pressure. Hydrogen can be eas-
ily absorbed into the tubular components from the environment
in which the heat exchanger operates. The combined effect of
absorbed hydrogen and pressurized high temperature water flow
leads to the wear of tubular components of heat exchanger.
Few studies have been reported on the effects of hydrogen
on the wear of metals and alloys. Belyi et al. [1] discussed
hydrogen separation in friction and its effect on wear. It has
been reported that hydrogen evolution during wear can acceler-
∗ Tel.: +962 6 5337856; fax: +962 6 5337846.
E-mail address: el amoush as@yahoo.com.
ate damage of titanium alloys [2]. Armstrong et al. [3] studied
the effects of cathodic charging on the magnetic internal friction
in armco iron and they found that cathodic hydrogen charging
has a pronounced effect on the strain-amplitude-dependent inter-
nal friction in armco iron. The same authors observed that the
hysteresis coefficient decreased at short charging times, and as
charging continued, the hysteresis coefficient recovered and in
fact increased as charging continued. They concluded that the
change in magnetic internal friction is attributed to plastic defor-
mation resulting from hydrogen-induced cracking.
It has been reported that there is the possibility for removal
of most of the hydrogen in steel at room temperature during the
wear process [4] suggesting wear-induced hydrogen effusion
mechanism. Baek et al. [5] studied the effects of wear processes
on enhanced hydrogen evolution from mild steel. In their work,
a wear production system was employed in which a wear test
and a hydrogen extraction measuring process were conducted
sequentially at 19 ◦ C. The authors found that the amount of
hydrogen evolved due to the wear process increased with both
the sliding time and the magnitude of the applied load in the wear
test.
Xiaoxia et al. [6] studied the effect of hydrogen on wear
resistance of titanium alloy in corrosive medium and they found
that the unusual wear losses might be explained by hydrogen

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258 A.S. El-Amoush / Journal of Alloys and Compounds 448 (2008) 257–262

embrittlement of the Ti alloy because of hydrogen evolution on 3. Results and discussion

the specimen surface.
Zhang et al. [7] examined hydrogen-induced embrittlement The coefficients of sliding friction for the uncharged and
wear of a high-strength, low-alloy steel (HSLA) in an acidic hydrogen-charged tin brass specimens at 25 mA cm−2 for 24,
environment and they reported that the increased material 48 and 72 h as a function of the sliding distance at a constant
removal with a negative shift of potential in the cathodically load of 200 g are shown in Fig. 1. The results in this figure
polarized range resulted from the synergistic effect of hydrogen show that the cathodically hydrogen charged tin brass specimens
induced damage and mechanical wear from hydrogen evolution exhibit lower coefficients of sliding friction as compared to that
on the wear surface. of the uncharged tin brass specimen. Moreover, it was found that
In the present work, tin brass heat exchanger specimens were the coefficient of sliding friction decreased with increasing the
cathodically charged with hydrogen for different times in order cathodic charging time applied to tin brass specimens (Fig. 2).
to obtain various concentrations of hydrogen in the material. The However, after certain sliding distances, the friction coefficients
wear properties of heat exchanger under these charging condi- of hydrogen charged specimens recover to that of uncharged
tions were evaluated. specimen as can be seen from Fig. 1. After approximately 45 m
sliding distance, the coefficient of friction for the hydrogen
2. Experimental procedure charged specimen for 24 h begins to increase until a sliding dis-
tance of approximately 58 m (curve b in Fig. 1) and beyond
The wear tests were carried out on round specimens cut from tin brass cylin- this distance, the coefficient of friction showed a value almost
drical rod of 4 cm diameter. The specimens were then machined into pins of
similar to that of the uncharged specimen (curve a in Fig. 1).
0.4 cm thickness. This material was supplied from the Jordan Petroleum Refin-
ery Company and used as heat exchanger in the form of tube. The chemical It is believed that the cathodically charged hydrogen absorbed
composition of this alloy is listed in Table 1. The specimens were annealed for by tin brass specimens resulted in the formation of a hydrogen-
1 h at 300 ◦ C, and then slowly cooled to room temperature in a furnace to relieve segregated layer. The increase in the coefficient of friction of
residual stresses induced from machining.
Before cathodic charging, any oxide or hydroxide layer presented on the
surface, which might act as a barrier to hydrogen uptake was removed by slightly
polishing the samples on 600-grit paper, which was followed by electrolytically
polishing in a solution of 40 vol.% orthophosphoric and 60 vol.% water at 1.5 V
using a stainless steel cathode at room temperature and finally pickling in a
solution of five parts nitric acid, five parts orthophosphoric acid and one part
acetic acid. These steps are very important in order to promote the hydrogen
entrance and for obtaining reliable measurements.
Cathodic hydrogen charging was carried out using graphite anode in an
electrolytic solution of 75% (volume) methanol, 22.4% (volume) distilled water,
2.6% (volume) sulphuric acid and 10 mg per litter of arsenic trioxide to inhibit
hydrogen recombination at the surface. The experiments were performed at room
temperature.
The specimens were cathodically hydrogen charged at a constant current
density of 25 mA cm−2 for 24, 48, 72 h. Immediately after hydrogen charging,
the specimens were tested in the wear machine to minimize possible scatter in
the test results.
A pin-on-disc wear test apparatus was used in this study. Sliding distances Fig. 1. Coefficient of sliding friction μ as a function of sliding distance at a
of 50, 100, 150, 200 m, applied normal load of 200 g and sliding velocity of constant load 200 g (a) uncharged tin brass specimen and hydrogen charged tin
11 cm2 /s were applied to the specimens during the wear test. Weight loss of brass specimens at 25 mA cm−2 for (b) 24 h; (c) 48 h; (d) 72 h.
each specimen due to the wear process was measured to an accuracy of 0.1 mg
with a microbalance.
The microhardness was measured immediately after cathodic hydrogen
charging and after sliding wear. Microhardness measurements also were made
across the thickness of the specimens to examine the depth and the hardness
of different areas through the charged surface layer before and after the sliding
wear. Indentation measurements were carried out with a Vickers indenter of 25 g
load for 20 s. Each measurement was the average of three indentations.
The wear tracks and the morphology of the wear debris were observed by
scanning electron microscopes.

Table 1
Chemical composition of heat exchanger brass (wt%)
Cu 71.72
Zn 26.88
Fe 0.12
Si 0.04
Sn 1.18
Pb 0.06 Fig. 2. Effect of charging time for a constant current density on the coefficient
of sliding friction.
 A.S. El-Amoush / Journal of Alloys and Compounds 448 (2008) 257–262 259

the hydrogen charged specimens resulted from the wear process

that continuously removed the hydrogen-segregated layer thus
approaching to a free hydrogen surface and as a result the coef-
ficient of sliding friction showed an almost similar coefficient
of friction to that of uncharged specimen.
It is believed that the increase in the charging time caused
more hydrogen atoms to diffuse into the specimen, resulting
in an increase in the depth of hydrogen-segregated layer. The
specimens charged for longer times confirm this observation.
The curves c and d in Fig. 1 show the coefficients of friction for
the specimens charged at 25 mA cm−2 for 48 and 72 h, respec-
tively as a function of sliding distance at a constant load of 200 g.
As can be seen, after approximately 80 m sliding distance, the
coefficient of friction for the specimen charged for 48 h begins Fig. 3. Effect of charging time for a constant current density on severity of
to increase until a sliding distance of 87 m (curve c in Fig. 1) microhardness across thickness of tin brass specimens: A, charged; B, near
and beyond this distance, the coefficient of friction was almost charged; C, interior surfaces.
similar to that of the uncharged specimen. While, after approx-
imately 104 m sliding distance, the coefficient of friction for The depth of the hardened region was measured and found to
the specimen charged for 72 h begins to increase until a sliding increase with increasing charging time. The effect of the cathodic
distance of 112 m (curve d in Fig. 1) and beyond this distance, charging time on the depth of hardening across the thickness
the coefficient of friction recovered to its original value, i.e. of the tin brass specimens before sliding wear is shown in
before charging with hydrogen. The above results confirm ear- Fig. 4.
lier observations that by increasing charging time, there is an The microhardness measurements that have been conducted
increase in the depth of the hydrogen-segregated layer which on the surface of uncharged and hydrogen charged tin brass
has been removed by the wear process. specimen after sliding wear revealed that the wear process is
It was observed above that cathodic hydrogen charging also caused hardening on the specimen surface and subsurface.
resulted in a reduction in the friction coefficient of tin brass However, after sliding wear, the microhardness of the hydro-
and after a certain sliding distance, the coefficient of sliding gen charged specimens was found to be higher than that of the
friction of the charged tin brass specimens recovered to its orig- uncharged specimen as shown in Fig. 5. This is due to the harden-
inal value, which it is believed to be due to the different depths ing of tin brass specimens caused by cathodic hydrogen charging
of the hydrogen segregated layer caused by various cathodic as explained above. Furthermore, it is believed that the wear pro-
hydrogen conditions applied to the tin brass specimens. The cess produces a thin layer in a state of heavy plastic deformation,
reduction in the friction coefficient is attributed to the fact that just the same as that of a cold worked specimen resulting in fur-
hydrogen charging caused hardening on the surface and sub- ther hardening of the material. However, the degree of cold work
surface of tin brass before sliding wear. The effect of charged decreased exponentially in the wear process as the depth from
hydrogen could be explained in terms of the dislocation pinning the surface increased [10]. Structural defects generated during
mechanism. Hardening can be attributed to solute hydrogen and wear tests are known to be dislocations [11] and microvoid [4].
dislocation pinning in the surface region. Solute hydrogen atoms The dislocations are the major structural defects in the speci-
act as dislocation pinning sites contributing to work hardening men exposed to the wear test. These dislocations are believed
of the alloy [8]. It is believed that higher cathodic charging time
leads to higher solute hydrogen concentration, in turn leading
to a more effective pinning of the dislocations and, therefore,
decreased dislocation mobility and hence hardening of the mate-
rial [8]. The hardening is considered to be due to the interaction
of hydrogen clusters with the edge component of dislocations
[9].
Therefore microhardness measurements were conducted on
the surface and subsurface of tin brass immediately after hydro-
gen charging and before sliding wear. The results of these mea-
surements revealed a severely hardened region on the charged
and near the charged surfaces and a less severely hardened region
in the interior as compared to the uncharged specimen. The sur-
face charged, near surface charged and the interior surface are
indicated by A, B and C, respectively. Moreover, the severity
of hardening on the above surfaces increased with increasing
charging time (Fig. 3). It can be clearly seen that the spec- Fig. 4. Effect of charging time at a constant current density on the depth of
imens charged for longer times exhibited a higher hardness. hardening of tin brass before the sliding wear.
260 A.S. El-Amoush / Journal of Alloys and Compounds 448 (2008) 257–262
Fig. 5. Hardness increase as a function of sliding distance under a constant
load 200 g for the uncharged (a) and hydrogen charged tin brass specimens at
25 mA cm−2 for (b) 24 h; (c) 48 h; (d) 72 h.
to be the most probable trapping sites for hydrogen and thus
contribute to the hardening of the alloy.
The microhardness measurements conducted on the hydro-
gen charged specimens during wear process showed that after
certain sliding distances, the microhardness values of these spec-
imens decreased to a value of uncharged specimen and then
continue to increase in similar range to that of uncharged spec-
imen. This indicated also that the hydrogen-segregated layer
was removed during sliding wear until approaching to a free
hydrogen surface. However, the sliding distance corresponded
to approaching a free hydrogen surface is depended on the
cathodic hydrogen charging condition applied to the specimens.
The longer charging time applied, the longer sliding distance
required to approach a free hydrogen surface as can be clearly
seen in Fig. 5.
Microscopic observations revealed that the wear debris of the
uncharged specimen was indicative of mechanical shearing and
plastic deformation (Fig. 6(a)), whereas the most of the wear
debris of the hydrogen charged specimens was of a particle like
shape and exhibited surface cracking (Fig. 6(b)). The severity of
cracking was observed to increase with increasing the charging
time (Fig. 6(c)), which might be attributed to the diffusion of
atomic hydrogen into the metal and its accumulation at voids or
Fig. 6. Morphologies of wear debris of (a) uncharged and hydrogen charged tin brass specimens at 25 mA cm−2 for (b) 24 h; (c) 72 h.
Fig. 7. Weight loss as a function of sliding distance under a constant load 200 g
for the uncharged (a) and hydrogen charged tin brass specimens at 25 mA cm−2
for (b) 24 h; (c) 48 h; (d) 72 h.
other internal surface in tin brass during cathodic charging. As
the concentration of hydrogen increases at these microstructural
discontinuities, a high internal pressure is created that enhances
void growth or initiates microcracking. These voids or micro-
cracks are believed to develop into cracking during the sliding
wear process.
The weight loss measurements showed that the hydrogen
charged specimens lost more weight than that of the uncharged
specimen (Fig. 7). This indicates that the sliding wear of hydro-
gen charged tin brass resulted in generation a higher amount
of wear debris. Moreover, the amount of debris was found to
increase with increasing the charging time applied to tin brass
specimens as revealed from the weight loss measurements. The
higher material removal observed in the hydrogen tin brass spec-
imens could be attributed to the fact that hydrogen diffuses into
trapping sites in the stressed area of higher dislocation density
before being removed as wear debris. The diffusible hydrogen
moves and segregates to the dislocation generated by the wear
test and contribute to hardening of the material and during wear
testing the segregated hydrogen is continuously removed testing
in the form of wear debris. Finally, the depths of hardening and
segregated hydrogen layer increased with increasing the charg-
ing time as mentioned previously. All of these factors resulted in
 A.S. El-Amoush / Journal of Alloys and Compounds 448 (2008) 257–262
Fig. 8. SEM micrographs of the wear tracks of (a) uncharged and hydrogen charged tin brass specimens at 25 mA cm−2 for (b) 24 h; (c) 48 h; (d) 72 h.
generation more wear debris during the sliding wear of hydro-
gen charged tin brass specimens. It should be noted here that
weight loss measurements also indicated that after certain slid-
ing distance, the hydrogen charged specimens approached to
free hydrogen surfaces (Fig. 7).
Fig. 8 compared the SEM micrographs of wear tracks of
uncharged and hydrogen charged tin brass specimens after 50 m
sliding distance and under applied load of 200 g. Few cracks
were observed in the wear track of the uncharged specimen
(Fig. 8(a)), which are believed to be as a result of sliding wear
action on microstructural discontinuities presented in the as-
received material from metallurgical processing. While, the wear
tracks of hydrogen charged tin brass specimens exhibited higher
amount of cracking. The severity of cracking depended on the
applied cathodic charging condition. The cracks observed in
the wear track of the specimen charged for 24 h were short
and across the wear track (Fig. 8(b)), while the cracks in the
wear track of the specimen charged for 48 h were longer and
also across the wear track (Fig. 8(c)). Moreover, cracks along
and across the wear tracks were observed in the wear track of
the specimen charged for longer time i.e. 72 h (Fig. 8(d)). It is
believed that the hydrogen around the dislocations could move
with the dislocation by diffusion during the wear process as men-
tioned previously. Moreover, the dislocations with hydrogen are
believed to pile up at the crystal boundary or at strong barriers
where hydrogen is concentrated and result in cracks in the wear
tracks.
261
4. Conclusions
1. Cathodic hydrogen charging resulted in a reduction of the
coefficient of sliding friction of tin brass heat exchanger.
The coefficient of sliding friction decreased with increasing
charging time. After certain sliding distances, the friction
coefficient recovered to its original value, i.e. before hydro-
gen charging. The recovery of friction coefficient depended
on the applied cathodic charging conditions and sliding
distance.
2. Cathodic hydrogen charging caused hardening of tin brass
heat exchanger. The severity of the hardened region increased
with charging time. Further charging increased the depth of
the hardening of tin brass heat exchanger.
3. Most of the wear debris of the hydrogen charged tin brass heat
exchanger had a particle like shape and exhibited cracking.
The amount of wear debris of charged tin brass was found
to be higher than that of uncharged one. Moreover, the wear
debris increased with increasing charging time.
4. Cathodic hydrogen charging resulted in the formation of
cracks across and along the wear track of tin brass heat
exchanger.
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