Wear 267 (2009) 1634–1641

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Tribological behavior of PTFE sliding against steel in sea water

Jianzhang Wang a,b , Fengyuan Yan a,∗ , Qunji Xue a
a
State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, No. 18, Tianshui Middle Road, Lanzhou 730000, PR China
b
Graduate School of the Chinese Academy of Sciences, Beijing 100049, PR China

a r t i c l e i n f o a b s t r a c t

Article history: In this paper the tribological behaviors of PTFE against GCr15 steel in air, distilled water, sea water and
Received 27 March 2008 3.5 wt.% NaCl solution were comparatively investigated. The influence of sea water composition on the
Received in revised form 28 March 2009 tribological behavior of PTFE was also studied. Results show that the friction process in sea water was
Accepted 8 June 2009
relatively stable, the friction coefficient and the wear rate of PTFE were slightly lower and a little larger
Available online 16 June 2009
than those in distilled water, respectively, but both were much lower than those in air and NaCl solution.
In aqueous environment, medium affected the tribological behavior of PTFE mainly by corrosion to the
Keywords:
counterface, the wear rate of PTFE depended on the corrosion extent of the counterface, and this wear
PTFE
Sea water
model can be called indirect corrosive wear. In salt solution, green rusts were formed on the counterface
Tribological behavior and had some lubricating effect. In addition, the results show Mg2+ and Ca2+ were the key factors for the
Indirect corrosive wear relatively low friction coefficient and wear rate of PTFE in sea water, because the corrosion of counterface
Green rust was reduced and the lubricating effect of green rusts was enhanced as a result of the deposition of Mg(OH)2
Deposition of Mg(OH)2 and CaCO3 and CaCO3 on the counterface.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction water and excellent corrosion-resistant property as well. Conse-

Ocean, which covers 71% of the earth’s surface, contains abun-
dant resources and is the treasure house of resources that ensures
the further development of human society. At present, human
society is facing three large crises such as population explosion,
resource shortage and environment deterioration, and one of the
main ways to solve the crises is to exploit and protect ocean. A blue
revolution marked with exploiting ocean is springing up all over
the world [1].
Presently many equipments for ocean exploitation are operated
by using sealed oil hydraulic drive system which has many disad-
vantages such as serious waste of resources, environment pollution
caused by leakage of oil, inflammable and explosive hazard, large
bulk and complex structure, poor flexibility and maneuverability.
In many cases, especially in deep sea water, the system cannot be
used even. However, the open hydraulic drive system directly using
sea water as working fluids economize resources, and is with envi-
ronmental compatibility, safe and flexible, and can work highly
efficiently in large depth occasion. With outstanding superiority,
the sea water hydraulic drive is considered as a key technology in
ocean exploitation in future [1,2]. However, the sea water hydraulic
drive system has rigorous requirements for friction pair materials
which are required to possess excellent tribological property in sea
∗ Corresponding author. Fax: +86 931 827 7088.
E-mail address: wangjianz@sohu.com (F. Yan).
quently, corrosion and wear are the two key technical problems
faced by the sea water hydraulic elements [1].
Compared with metals and ceramics, polymers and polymer-
based composites have good corrosion-resistant property and the
ability of burying foreign matters such as wear particles or sand
particles, and often have excellent tribological property [3]. So poly-
mers and their composites, e.g. nylon and rubber, have been widely
used to produce water-lubricated bearings and gears. Investigations
on tribological behaviors of polymers in aqueous environments
have also been reported by many researchers. From previous
reports, aqueous medium affects the tribological behavior of poly-
mer mainly by the following two ways: (1) direct way: plasticization
of polymer. Absorption of water can lead to the plasticization of
polymer, which results in the reduction of hardness and strength of
polymer [4–7]. Evans [4] and Srinath [5] reported that the introduc-
tion of water into a polymer–metal sliding combination generally
reduced the coefficient of friction, but may increase the wear rate
of the polymer as a result of the decreased hardness of polymer
due to plasticization. (2) Indirect way: corrosion to counterface.
Lancaster [8] found that the wear rate of carbon fibre-reinforced
polymer was significantly lower during sliding against S80 stainless
steel or mild steel in sea water than in pure water, this attributed
to the increased corrosiveness of sea water towards ferrous sur-
faces which are beneficial to polish the counterface and reduce the
roughness of counterface.
Presently many polymers have been used as friction materials
in aqueous environments, however, they have many disadvan-

0043-1648/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.wear.2009.06.015
 J. Wang et al. / Wear 267 (2009) 1634–1641 1635

Table 1 Table 2
Chemical composition of salt solutions. Properties of salt solutions.

Part Compound Concentration (g/l) Medium [Cl− ] (mol/l) Salinity (‰) pH

Sea water Solution 1 Solution 2 Solution 3 3.5 wt.% NaCl
Sea water 0.56 35 8.2
I NaCl 24.53 25.62 31.18 32.01 36.10 Solution 1 0.57 35 8.2
Solution 2 0.55 35 8.2
II Na2 SO4 4.09 4.09 4.09 4.09 –
Solution 3 0.55 35 8.2
III MgCl2 5.20 5.20 3.5 wt.% NaCl 0.62 35 8.2
CaCl2 1.16 1.16 – – –
SrCl2 0.025 0.025 – – –
KCl 0.695 – 0.695 – –
In the above three solutions, the concentrations of compounds
IV NaHCO3 0.201 – 0.201 – – except NaCl are the same as those in sea water (Table 1). For all
KBr 0.101 – 0.101 – –
salt solutions, by adjusting the content of NaCl the salinities were
H3 BO3 0.027 – 0.027 – –
NaF 0.003 – 0.003 – –
adjusted to 35‰ which was the average salinity of the natural sea
water, by using 0.1 mol/l NaOH or HCl the pH values were adjusted
to 8.2 which was the average pH value of the natural sea water,
tages, e.g. poor running performance under dry and boundary and the concentration of Cl− was largest in 3.5 wt.% NaCl solution
lubrication, accuracy decrease as a result of swelling caused by (Tables 1 and 2).
water adsorption [3]. Polytetrafluoroethylene (PTFE), which is an
excellent self-lubricating matrix material, has very low friction 2.2. Test apparatus and experimental procedures
coefficient and water absorption, excellent chemical stability in
various corrosive environments. So it is considered as a potential The PTFE samples in this paper were made of PTFE powder
friction material used in sea water and other aqueous environ- by compression molding and then sintering, the dimension was
ment. During the past years, the investigations of the tribological 19 mm × 12 mm × 12 mm, the density was 2.2 g/cm3 , and the shore
behavior of PTFE are mainly in the field of dry friction, several hardness was 58. The contact angles of PTFE samples for aqueous
researchers have also studied the friction and wear behavior of PTFE mediums were measured using a contact angle instrument. The
under distilled water lubrication. Unfortunately there are hardly water absorption of PTFE samples in a certain aqueous medium
any investigations on tribological behavior of PTFE in sea water. In was examined by immersing dry samples in the medium for 24 h at
this paper, the tribological behavior of PTFE sliding against steel in room temperature, then the increase in the mass of the samples due
sea water was investigated in detail and the corresponding wear to water absorption was quantified using an electronic weighing
mechanism was also discussed. balance with an accuracy of 0.1 mg, and the percentage increase in
the weight was the water absorption in the medium. The hardness
2. Experimental details of PTFE samples was measured before and after 24 h immersion. An
average of three measurement results was reported.
2.1. Medium The friction and wear behavior of PTFE was evaluated on an
MRH-03 model ring-on-block test rig. The contact schematic dia-
In this paper, the friction and wear tests included: (1) com- gram of the frictional couple is shown in Fig. 1. The blocks were PTFE
parative investigation of the tribological behaviors of PTFE in air, samples. The ring of ˚49.22 mm × 13.06 mm was made of GCr15
distilled water, sea water and 3.5 wt.% NaCl solution; (2) investiga- steel (AISI52100, the composition seen in Table 3), the microhard-
tion of the influence of sea water composition on the tribological ness of the steel was approximately HV726.
behavior of PTFE. Normally, 3.5 wt.% NaCl solution is widely used The friction and wear tests were carried out at a linear velocity
by researchers as a substitute of sea water. However, besides NaCl, of 0.5 m/s, load of 100 N, and duration of 40 min. Before each test,
sea water contains many other components. In this study sea water the steel ring was polished with abrasive papers to reach a surface
was prepared according to the standard ASTM 1141-98 as shown in roughness of about 0.15 ␮m. Then the ring and blocks were ultra-
Table 1. As shown in Table 1, the composition of sea water can be
divided into four parts:

I. Main component: NaCl.

II. Sodium sulphate: Na2 SO4 .
III. Divalent metal salts: MgCl2 + CaCl2 + SrCl2 .
IV. Other trace components: KCl + NaHCO3 + KBr + H3 BO3 + NaF.

According to the four parts, another three solutions were

prepared and used to investigate the influence of sea water com-
position on the tribological behavior of PTFE. The three solutions
were
Solution 1: I + II + III

NaCl + Na2 SO4 + MgCl2 + CaCl2 + SrCl2

Solution 2: I + II + IV

NaCl + Na2 SO4 + KCl + NaHCO3 + KBr + H3 BO3 + NaF

Solution 3: I + II

NaCl + Na2 SO4 Fig. 1. Contact schematic diagram for the frictional couple (unit: mm).
1636 J. Wang et al. / Wear 267 (2009) 1634–1641

Table 3
Chemical composition of the GCr15 steel (wt.%).

C Mn Si Cr P S Fe

0.950–1.050 0.200–0.400 0.150–0.350 1.300–1.650 <0.027 <0.020 Remainder

Table 4
Properties of PTFE in different mediums.

Medium Contact angle (◦ ) Water absorption (%) Hardness (Shore S)

Before immersion After immersion

Distilled water 103 0.002 58 57

Sea water 104 0.002 58 57
3.5 wt.% NaCl 104 0.003 58 56

sonically cleaned with acetone. The aqueous medium lubrication 0.002–0.003%, and the decreases in hardness are only 1–2 (2–3%).
between the sliding surfaces was realized by continuously dropping However, comparatively the water absorption of Polymide 6 (PA6)
of the medium onto the sliding surface at a rate of 100–105 drops [5] and Polyimide (PI) [10] are 1.425% and 0.93%, respectively. Due
per minute (300–315 ml/h). The width of the wear track was mea- to plasticization the hardness decrease of PA6 can reach to 25% after
sured with a digital-reading microscope to an accuracy of 0.01 mm. 24 h immersion [5]. This suggests that PTFE has high hydrophobic
In order to make clear the influence of creep deformation of PTFE on property and ultra low water absorption, so the plasticization of
the wear volume of PTFE, some specimens were loaded statically PTFE is slight and thus cannot be the main factor that affects the
with a 100 N normal force in the test rig for about 40 min, which tribological behavior of PTFE in aqueous environment.
was similar to that described by Jacobs et al. [9]. The penetration
of steel ring into the specimen due to creep deformation was esti- 3.2. Friction and wear
mated to be less than 1 ␮m using a microXAM three-dimensional
surface profiler. So the creep deformation was negligible in compar- Figs. 2 and 3 show the friction coefficients and wear rates of
ison to the wear of the material, which was not further considered PTFE in seven mediums: air, distilled water, sea water, 3.5 wt.% NaCl
in the wear volume calculation of PTFE. Then the wear vol- solution, solution 1, solution 2 and solution 3. It can be obviously
ume loss V of the specimen was calculated from the following observed that the results can be divided into the following five
relationship: groups:
  
2 b b b2
V = B R arcsin − R2 − (1) (a) In distilled water: friction is relatively stable and the friction
2R 2 4
coefficient is very low (about 0.04). Moreover, the wear rate of
PTFE is the lowest (2.9 × 10−5 mm3 /Nm) in seven mediums.
where V is the wear volume loss (mm3 ), B is the width of the sample
(b) In sea water and solution 1: frictions are relatively stable and the
(mm), R is the semi-diameter of the steel ring (mm) and b is the
friction coefficients are nearly equal to those in distilled water,
width of the wear trace (mm). The specific wear rate K (mm3 /Nm)
even slightly lower in sea water than in distilled water, but the
was calculated from the volume loss using the following equation:
wear rates of PTFE are slightly larger, which is nearly twice as
V large as those in distilled water.
K= (2)
Ld (c) In air: friction is very stable and the friction coefficient is about
4 times as large as that in distilled water, also the wear rate of
where d is the sliding distance (m), L is the load (N). The average
PTFE is about 13 times as large as that in distilled water.
of the three replicate test results was reported. The morphologies
of worn surfaces were examined on a JEM-5600LV scanning elec-
tron microscope (SEM). In order to increase the resolution for the
SEM observation, the tested PTFE samples were plated with gold
coating to render them electrical conductivity. The chemical states
of the elements on the worn surface were determined using X-ray
photoelectron spectroscopy (XPS) and Raman spectroscopy.

3. Results

3.1. Properties of PTFE in aqueous mediums

In aqueous environments, polymer plasticization often occurs,

which is highly related to the tribological behavior of polymer [4,5].
And some polymers in different aqueous environments have dif-
ferent water absorptions, as a result, the plasticization extents are
also different, thus the tribological behaviors of polymers are varied
with the surrounding mediums [7]. The contact angles of PTFE, the
increases in weight of PTFE after 24 h immersion and the hardness
of PTFE in three aqueous mediums before and after immersion are
shown in Table 4. It can be seen that relatively slight differences
Fig. 2. Variations in the friction coefficients with sliding time in different mediums,
in above properties of PTFE are observed in different mediums, the Distilled: distilled water; Sea: sea water; NaCl: 3.5 wt.% NaCl solution; S1: solution
contact angles of PTFE are 103–104◦ , the increases in weight are only 1; S2: solution 2; S3: solution 3.
 J. Wang et al. / Wear 267 (2009) 1634–1641
Fig. 3. Specific wear rates of PTFE in different mediums, Distilled: distilled water;
Sea: sea water; NaCl: 3.5 wt.% NaCl solution; S1: solution 1; S2: solution 2; S3:
solution 3.
(d) In solution 2 and solution 3: the friction coefficients increase
with sliding time from 0.09 to 0.17, and the wear rates of PTFE
are about 15 times as large as those in distilled water.
(e) In 3.5 wt.% NaCl solution: the friction coefficients increase with
sliding time from 0.10 to 0.21, and such increase is faster than
that in solution 2 and solution 3. In addition, the wear rate
of PTFE is largest, which is about 17 times as large as that in
distilled water.
It is clearly seen that the tribological behaviors of PTFE in 3.5 wt.%
NaCl solution (I), solution 3 (I + II) and solution 2 (I + II + IV) are
highly different from those in sea water (I + II + III + IV). However,
the friction and wear behavior of PTFE in solution 1 (I + II + III) is
nearly the same as that in sea water. It is thus concluded that the
components III, mainly Mg2+ and Ca2+ , are the key factors that result
in the relatively low friction coefficient and wear rate of PTFE in sea
water.
3.3. Morphological analysis of worn surface
Fig. 4(A), (B), (C), and (D) shows SEM micrographs of the worn
surfaces of PTFE in air, distilled water, sea water, and 3.5 wt.% NaCl
solution, respectively. Under dry friction, the worn surface of PTFE
is characterized by adherence and slight scratches (Fig. 4(A)). In
distilled water, the worn surface of PTFE is smooth, and exhibits
fine furrows and slight plastic deformation (Fig. 4(B)). In sea water,
the furrows and plastic deformation on the worn surface of PTFE are
more obvious (Fig. 4(C)). While in 3.5 wt.% NaCl solution, the surface
of PTFE is destroyed by severe plowing effect which leads to deep
and wide furrows and serious plastic deformation (Fig. 4(D)). It can
be concluded that the main wear mechanism of PTFE is adhesive
wear under dry friction, while abrasive wear characterized with
plowing effect is the main wear mechanism in aqueous medium.
Fig. 4(a), (b), (c), and (d) shows SEM micrographs of worn sur-
faces of steel in air, distilled water, sea water, 3.5 wt.% NaCl solution,
respectively. It can be seen that some discontinuous transfer films
of PTFE are formed on the surface of steel (Fig. 4(a)). However,
there are any transfer films on the counterface in liquid mediums
(Fig. 4(b)–(d)), because liquids can effectively hinder the forma-
tion of transfer film [2,5,8,11,12]. In distilled water, the worn surface
of steel is smooth and clean, and the steel is almost not corroded
(Fig. 4(b)). In sea water, the counterface is covered with a thin and
smooth layer of corrosion products, on which some slight micro-
crack like patterns on the turtle shell are observed owing to stress
1637
effect (Fig. 4(c)). In 3.5 wt.% NaCl solution, the steel suffers extensive
uniform corrosion together with scattered pitting, which is similar
to the report from U.S. Naval Research Laboratory [13], and the layer
of corrosion products on the steel counterface is thick and rough
(Fig. 4(d)).
As shown in above SEM results, the wear loss of PTFE in aque-
ous medium is mainly caused by plowing effect of the counterface,
so the wear of PTFE is highly related with the surface roughness of
the counterface. Fig. 5 shows the variations in the surface rough-
ness of steel in air and six aqueous mediums before and after
tests. In distilled water the surface roughness of steel exhibits very
slight increase from 0.15 ␮m to 0.16 ␮m. Because of the medium
corrosion, however, the surface roughness of steel increases from
0.15 ␮m to about 0.5 ␮m in sea water and solution 1, sharply
increases to about 1.0 ␮m in solution 2 and solution 3, and to
1.18 ␮m in 3.5 wt.% NaCl solution. As a result, the plowing effects
of the counterface on PTFE increase in the order of distilled water,
sea water and solution 1, solution 2 and solution 3, 3.5 wt.% NaCl
solution, and consequently the wear rates of PTFE increase in the
same order. Under dry friction, it should be pointed that the surface
roughness slightly decreases from 0.15 ␮m to 0.13 ␮m, which may
be caused by the filling of PTFE wear debris in the grooves of the
steel counterface.
3.4. Chemical analysis of the corrosion products
As shown in Fig. 4, the layer of corrosion products is formed
on the surface of steel. Moreover, the steel is also corroded in
solution 1, solution 2 and solution 3. It can be observed in exper-
iments that a layer of blue-green matters like slurry was formed
on the counterface in salt solutions. The matters were unstable,
and could be oxidized and ultimately changed from blue-green to
red-brown. The color transformation took place only several min-
utes in 3.5 wt.% NaCl solution and much longer time in solution
2 and solution 3, while needed the longest time and the blue-
green matter could be preserved well during friction in sea water
and solution 1. The blue-green intermediate corrosion products are
named green rusts (GRs), which are iron (II–III) hydroxysalts that
belong to a class of divalent–trivalent ionic minerals which are
characterized by a crystal structure that consists of the stacking
of Fe(OH)2 brucite-like layers carrying a positive charge as due to
the presence of Fe(III) and interlayers constituted anions and water
molecules [14], Fig. 6 shows the crystal structure of GR(SO4 2− ) [15].
The green rusts formed in 3.5 wt.% NaCl solution are GR(Cl− ), while
in other salt solution and sea water which contain SO4 2− GR(SO4 2− )
are formed even though the molar ratio of Cl− /SO4 2− is about 20,
because the affinity of the GR layered structure for divalent anions is
stronger than for monovalent anions [14,16]. The chemical formula
of GR(SO4 2− ) is Fe4 II Fe2 III (OH)12 SO4 ·8H2 O [14]. Fig. 7 shows Raman
spectrums of the ultimate corrosion products of the steel ring in
different aqueous mediums. In the Raman spectrum, the peaks
at about 250 cm−1 and 690 cm−1 are attributed to lepidocrocite
␥-FeOOH and magnetite Fe3 O4 , respectively [14,16]. The band at
480 cm−1 is an artifact originated from the apparatus itself when
long acquisition times are required, as it is the case for this spec-
trum. It is demonstrated that in distilled water the surface of steel is
slightly corroded and small amounts of ␥-FeOOH are formed, while
in sea water and 3.5 wt.% solution the ultimate corrosive products
are mainly ␥-FeOOH with a little Fe3 O4 . The chemical reactions
occurred on the steel surface in sea water are as follows [14]:
Fe → Fe2+ + 2e (3)
H2 O + 1/2O2 + 2e → 2OH−
Fe2+ + 2OH− → Fe(OH)2
1638 J. Wang et al. / Wear 267 (2009) 1634–1641

Fig. 4. SEM micrographs of the worn surfaces (A)–(D) PTFE; (a)–(d) steel; (A) and (a) in air; (B) and (b) in distilled water; (C) and (c) in sea water; (D) and (d) in 3.5 wt.% NaCl
solution.

bonate CaCO3 are deposited on the surface of the steel in sea water.
5Fe(OH)2 + Fe2+ + SO4 2− + 1/2O2 + H2 O → Fe4 II Fe2 III (OH)12 SO4 (4) The chemical reactions are as follows:
Mg2+ + 2H2 O → Mg(OH)2 + 2H+ (6)
− 2− +
HCO3 → CO3 +H (7)
Fe4 II Fe2 III (OH)12 SO4 + 3/4O2 → 5␥-FeOOH + Fe2+ + SO4 2−

+ 7/2H2 O (5) Ca2+ + CO3 2− → CaCO3

As analyzed above, the divalent metal ions, mainly Mg2+ and

Ca2+ , are the key factors to result in the relatively low friction coef-
ficient and wear rate of PTFE in sea water. XPS spectrums of Mg
and Ca on the worn surface of the steel counterface in sea water are
given in Fig. 8. The main peak of Mg2s around 88 eV is assigned to
Mg(OH)2 , and the peaks of Ca2p at 347 eV and 351 eV are assigned
to CaCO3 , which suggests that brucite Mg(OH)2 and calcium car-
4. Discussion
4.1. Mixed lubricating effect
In salt solution, GRs are formed on the surface of steel. With a
layered structure like that of hydrotalcite [17], GRs may have some
 J. Wang et al. / Wear 267 (2009) 1634–1641 1639

Fig. 5. Variations in the surface roughness of steel counterface before and after fric-
tion in different mediums, Distilled: distilled water; Sea: sea water; NaCl: 3.5 wt.%
NaCl solution.

lubricating effect. So the lubricating effect between PTFE and steel

not only attributes to aqueous medium but also attributes to GRs,
which is a mixed lubricating effect. So the tribological behavior of
PTFE in different aqueous mediums can be understood on the basis
of a competition between the following two antagonistic mecha-
nisms. On the one hand, once the surface of steel is corroded, the
surface roughness of steel will increase (Fig. 5). As a result the for-
mation of liquid films becomes difficult and the lubricating effect of
liquid medium decreases [8]. Meanwhile, the direct contact of PTFE
with steel increases and then the plowing effect of steel to PTFE also
increases. Consequently the friction coefficient of PTFE increases
Fig. 6. Crystal structure of GR(SO4 2− ) [13].
with the surface roughness increase of steel counterface. On the
other hand, corrosion products with lubricating effect are formed
on the steel surface, and this is beneficial to reduce the friction
coefficient. In solution 1 and sea water, the increase in the surface
roughness of steel is relatively smaller (Fig. 5), and the lubricating
effect of GRs is enhanced by Mg(OH)2 (This will be discussed later).
As a result the lubricating effect of corrosion products can counter-

Fig. 7. Raman analysis of the corrosion products on the surface of steel counterface: (a) in air, (b) in sea water, and (c) in 3.5 wt.% NaCl solution.
1640 J. Wang et al. / Wear 267 (2009) 1634–1641
Fig. 8. XPS analysis on the worn surface of steel counterface in sea water: (a) Mg2s and (b)Ca2p.
Fig. 9. Indirect corrosive wear model of PTFE, ↑ denotes increase, ↓ denotes decrease.
act the increase of the friction coefficient caused by the decrease
in the lubricating effect of aqueous medium and the increase in
the plowing effect of steel to PTFE. So it is reasonable that the fric-
tion coefficient is stable and slightly changed both in sea water and
solution 1, and nearly equal to those in distilled water, in sea water
even slightly less. However, in 3.5 wt.% NaCl solution, solution 2 and
solution 3, the increase in surface roughness of steel is quite obvious
(Fig. 5), the lubricating effect of liquid medium decreases sharply
while the plowing effect increases dramatically. As a result, the fric-
tion increases too rapidly to be overcome by the lubricating effect
of GRs, so with the increase of sliding time, the corrosion extent and
the surface roughness of counterface increase, and accordingly the
friction coefficient also increases.
4.2. Indirect corrosive wear
Lancaster [8] had reported that the most important factor affect-
ing the wear rate of carbon fiber-reinforced polymers during sliding
in water and other aqueous solutions was the topography of the
counterface. In this paper, the wear of PTFE in aqueous medium
belongs to the similar case. PTFE has ultra low water absorption
and the plasticization of PTFE in aqueous medium is quite slight.
As shown in Table 4, the mechanical and physical properties of
PTFE only have little differences in different mediums; however,
the wear behaviors of PTFE in different aqueous mediums exhibit
significant differences. This can be attributed to the modification of
the counterface by medium, which is realized mainly by the corro-
sion during the wear process. As discussed in the above section,
the corrosion of counterface in aqueous medium would signifi-
cantly worsen the lubricating effect of aqueous medium and greatly
increase the plowing breakage to PTFE, consequently the wear rate
of PTFE increases too much. It can be concluded that the wear extent
of PTFE depends on the corrosion extent of steel counterface and
such wear model can be called indirect corrosive wear as shown in
Fig. 9.
So according to the different corrosion extents of steel in dif-
ferent mediums, friction and wear test demonstrates different
results, which also reflect the corrosion extent of the steel. The
wear rates of PTFE in six aqueous mediums increase in the fol-
lowing order: distilled water < sea water and solution 1 < solution 2
and solution 3 < 3.5 wt.% NaCl solution. Therefore, it can be inferred
that the corrosion extents and the surface roughness increases of
steel counterface in six mediums increase in the same order: dis-
tilled water < sea water and solution 1 < solution 2 and solution
3 < 3.5 wt.% NaCl solution. The SEM morphological analysis and the
surface roughness measurement on the steel exactly verify the
above trend (Figs. 4 and 5).
4.3. The influence of sea water composition on the tribological
behavior of PTFE
The tribological behavior of PTFE depends on the corrosion
extent of steel counterface, so the influence of sea water compo-
sition on the tribological behavior of PTFE is achieved indirectly by
influencing the corrosion extent of the counterface.
4.3.1. The effect of Cl− and SO4 2−
Sea water contains larger amount of Cl− which can greatly accel-
erate the corrosion of steel counterface. Due to its high electric
polarization, Cl− can adsorb easily on the steel surfaces, which
can cause strong electric field and consequently make iron easily
dissolve as Fe2+ ions [18]. Moreover, Cl− may react with metal to
form complex compounds, thus accelerate the dissolution of metal
[19]. Therefore, with increasing Cl− concentration in solution, the
corrosion of steel is easy to occur and be accelerated.
As mentioned above, when SO4 2− exists in the solution, more
stable GR(SO4 2− ) will be formed on the steel ring surface. Increasing
the stability of the intermediate corrosive products will delay the
transformation of corrosive products and reduce the corrosion rate,
thus alleviate the steel corrosion.
 J. Wang et al. / Wear 267 (2009) 1634–1641
The Cl− concentrations in solution 2 and solution 3 are lower
than that in 3.5 wt.% NaCl solution (Table 3), and GR(SO4 2− ) are
formed in the former two solutions, so the corrosion extents of steel
in the two solutions are lower, the increases in surface roughness
are also lower, thus the friction coefficients and wear rates of PTFE
in solution 2 or solution 3 are lower than those in 3.5 wt.% NaCl
solution.
4.3.2. The effect of Mg2+ and Ca2+
The friction coefficients of PTFE/GCr15 in sea water and solu-
tion 1 are relatively low, and the wear rates of PTFE in above two
solutions are less than those in 3.5% NaCl solution, solution 2 and
solution 3. For the better tribological performance of PTFE in sea
water and solution 1, besides the reasons of the low Cl− concen-
tration and the formation of GR(SO4 2− ), the most important reason
is that the sea water and solution 1 contain Mg2+ and Ca2+ . The
XPS analysis shows that Mg(OH)2 and CaCO3 are deposited on the
steel surface in sea water. The deposition of Mg(OH)2 and CaCO3
would play an important role in the friction and wear of PTFE in sea
water and solution 1. Firstly, the deposited layer of Mg(OH)2 and
CaCO3 has high resistance, and can isolate the steel surface with
corrosive medium and prevent Cl− and O2 from diffusing onto the
surface of the steel, thus reduces the corrosion of steel. Secondly,
brucite Mg(OH)2 has a layered crystal structure which is similar to
the structure of green rusts, can stabilize the structure of GR(SO4 2− )
[20], so the transformation rate of GRs to ␥-FeOOH is reduced and
the lubricating effect of GRs is enhanced as well. Finally when Mg2+
and Ca2+ exist in the aqueous medium, the system friction is very
low and the wear rate of PTFE greatly decreases.
5. Conclusion
1. The friction of PTFE/GCr15 in sea water is relatively stable, the
friction coefficient and the wear rate of PTFE are slightly lower
and a little larger than those in distilled water, while both are
much lower than those in air and 3.5 wt.% NaCl solution. The
main wear mechanism of PTFE is adhesive wear under dry fric-
tion, while abrasive wear characterized with plowing effect in
aqueous medium.
2. In aqueous environment, due to the ultra low water absorption of
PTFE, the plasticization of PTFE is slight and nearly has no influ-
ence on the tribological behavior of PTFE. The aqueous mediums
affect the tribological behavior of PTFE mainly by corrosion to
the counterface.
3. In salt solution, green rusts are formed on the counterface and
have some lubricating effect, so the lubricating effect between
PTFE and steel is a mixed lubricating effect attributed to aqueous
medium and corrosion products.
4. Corrosion to counterface can cause the increase in surface rough-
ness of the counterface. The wear rate of PTFE in aqueous
medium depends on the corrosion extent of the counterface,
such wear model can be called indirect corrosive wear.
5. Because of the deposition of Mg(OH)2 and CaCO3 on the coun-
terface, the corrosion of the counterface is reduced and the
1641
lubricating effect of corrosion products is enhanced, so the fric-
tion coefficient and wear rate of PTFE are relatively low in sea
water.
Acknowledgements
The research is financially supported by National High Technol-
ogy Research and Development Program of China (“863” Program)
(Grant No. 2007AA03Z358) and National Science Foundation of
China (Grant No. 50772115).
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