Tribology International 44 (2011) 956–962

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Tribology International
journal homepage: www.elsevier.com/locate/triboint

Influence of ionic strength on the tribological properties of

pre-adsorbed salivary films
Lubica Macakova a,b,n,1, Gleb E. Yakubov a, Mark A. Plunkett b, Jason R. Stokes a,c,n,2
a
Unilever Discover, Colworth Science Park, Sharnbrook, Bedford, MK44 1LQ, United Kingdom
b
Institute for Surface Chemistry, Drottning Kristinas vag 45, Stockholm, Sweden
c
School of Chemical Engineering, University of Queensland, Brisbane, QLD, Australia

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

Article history: We have studied tribological properties of pre-adsorbed salivary films formed in vitro on compliant
Received 3 May 2010 hydrophobic surfaces. The adsorbed salivary film significantly decreases boundary friction under
Received in revised form physiological ionic strength, which is related to a hydrophilic character of the adsorbed film and its
8 December 2010
structure. Decrease in the ionic strength below physiological conditions affects film’s structure, but it
Accepted 19 December 2010
does not significantly affect boundary lubrication at low loads. Applications of high loads led to a
Available online 4 January 2011
gradual loss of lubrication due to shear-induced wear of the films. The wear became more extensive as
Keywords: the ionic strength of the solvent was lowered below physiological conditions.
Saliva & 2011 Published by Elsevier Ltd.
Boundary lubrication
Ionic strength
Wear

1. Introduction response of a pre-adsorbed salivary film following exposure to a

Water-based lubrication is present in many biological systems,
including tribological contacts within human and animal synovial
joints, between the eye and eyelid, as well as in oral and throat
environment to facilitate tongue movements and oral food
processing [1]. Oral lubrication is provided by saliva, which is a
solution containing a multitude of various proteins [2] that gives
rise to saliva’s specific bulk and interfacial properties, including
its highly viscoelastic rheology [3–5]. An extended and highly
hydrated proteinaceous film is rapidly adsorbed on surfaces
exposed to saliva [6,7], and it is this film that is likely to play a
significant role in providing a low boundary friction between
these rubbing surfaces [8–11]. Good lubrication is important for
maintaining oral health and therefore it is one of the factors
evaluated when developing salivary substitutes intended for
patients suffering from dry mouth syndrome (xerostomia) [11].
Oral friction is also considered to play a role in the perception of
the food texture during eating [12] and in the mouthfeel of
beverages [4,13]. In this paper, we focus on the tribological
n
Corresponding authors.
E-mail addresses: lubica.macakova@yki.se (L. Macakova),
Jason.Stokes@uq.edu.au (J.R. Stokes).
1
Institute for Surface Chemistry, Drottning Kristinas vag 45, SE-114 86
Stockholm, Sweden. Tel: +46 10 516 6092.
2
School of Chemical Engineering, The University of Queensland, Brisbane, Qld,
4072 Australia. Tel.: + 61 7 336 54361.
decrease in the ionic strength from physiological values of
70 mM, in order to develop a more fundamental understanding
on how saliva functions as a lubricant when interacting with
beverages. Saliva ionic strength, being lower than that of blood
plasma ( 150 mM), varies due to individual differences and
various other factors; 70 mM is chosen because it is around the
upper limit of saliva’s natural variation [14].
While mucins are believed to be the main functional compo-
nents of the salivary pellicles [6,15], and purified mucin-like
glycoproteins were shown to form highly lubricious layers
[1,16–19], we found that the structural response of adsorbed
salivary films is notably different to that observed for model
layers comprising only purified mucins [15,20]. This arises
because of the interactions between the multiple components
within the salivary film [7]. Considering the high number of
components within saliva, we have taken a top-down approach
by using films adsorbed from ex vivo saliva to mimic the oral
surface chemistry in its complexity.
It has been previously observed that solvent properties have a
significant effect on the structure of absorbed polymeric films as
well as its lubrication properties; in particular, environments that
promote pre-adsorbed polymeric layers to become more
extended and hydrated were observed to enhance the boundary
lubrication between surfaces carrying such layers [21,22]. In our
recent publication [7], we reported that structural changes also
occur for salivary films that were pre-adsorbed on hydrophobic
surfaces following exposure to ionic strengths lower than that of

0301-679X/$ - see front matter & 2011 Published by Elsevier Ltd.

doi:10.1016/j.triboint.2010.12.006
 L. Macakova et al. / Tribology International 44 (2011) 956–962
saliva. We found that a decrease in the ionic strength down to
1 mM leads to an increase in the film thickness of the pre-
adsorbed film due to an increase in hydration. In addition, the
viscoelasticity of the adsorbed saliva film also became more
viscous and less elastic in response to high frequency deforma-
tions. However, the heterogeneous salivary film collapse when
exposed to deionised water due to intralayer electrostatic attrac-
tion and the film became thin and rigid [7]. In this study, we
investigate how these changes in the preadsorbed salivary layer
influence the lubrication properties in a soft-tribological contact.
2. Material and methods
2.1. Saliva
Mechanically stimulated saliva was obtained from a single
volunteer with good oral health. Salivary flow was stimulated by
chewing a piece of silicon tubing, and the collected saliva was
immediately centrifuged for 10 min at 7200g at room tempera-
ture. The saliva collection protocol is detailed elsewhere [7]. The
centrifugation has been shown not to significantly affect the
boundary lubricating properties of the expectorated saliva, even
though centrifugation nearly completely removes shear thinning
and elastic nature of the bulk salivary liquid [9].
2.2. Solvents of different ionic strengths
All solutions were prepared in deionised and filtered water
(filters pore size 0.22 mm) with a resistivity of 18 MO cm provided
by a Barnstead NanoPure Diamond water purification unit
(Triple Reds). Sodium chloride salt of analytical grade was used
to adjust the ionic strength. Solvents of four different ionic
strengths were used: 70, 10, 1 mM NaCl and deionised water.
All solvents were adjusted to pH of 7.3 70.2 by addition of
NaOH shortly before measurements in order to achieve the pH
measured for the collected saliva.
2.3. Friction measurements
Friction measurements were performed with a Mini Traction
Machine (MTM, PCS Instruments Ltd., UK). The schematic of the
experimental set up is shown in Fig. 1. The temperature was set to
37 1C. The tribopairs consisted of elastomeric polydimethylsilox-
ane (PDMS) substrates in order to mimic the intrinsically hydro-
phobic and soft nature of the oral surfaces of interest, tongue and
Fig. 1. The schematic of the experimental set-up. Rotating elastomeric sphere and
disk, both with pre-adsorbed salivary films, are brought into contact while
immersed in solvent with adjusted ionic strength. The load is varied while friction
force between disk and sphere is monitored.
957
palate [23]. PDMS was obtained from Dow Corning under a trade
name Sylgards184, and the elastomers were prepared according
to manufacturers recommendation; the base and curing agent
were mixed in a weight ratio of 10:1, deaerated under vacuum
and cured overnight in an oven set to 70 1C. The rubbing contact
consisted of PDMS ball with a radius of 0.95 cm and a disk with
radius of 23 mm and thickness of 4 mm. Young’s modulus of the
used PDMS elastomer was 2.4 MPa. The ball and disk were
prepared according to a procedure described in previous articles
by our group [9,24]. The root-mean-square roughness of the
resulting balls and disks were 26 nm and 9 nm, respectively, as
determined from 80  80 mm2 AFM height image [24]. The effect
of surface wettability and surface roughness on the tribological
behavior of PDMS tribopairs in our experimental set up was
measured and discussed by Bongaerts et al. [24].
The details of the instrumental set-up are presented elsewhere
[25,26] and therefore we will summarize only the main features
here. A normal load, FN, is applied by pressing the ball against the
disk and it is continuously monitored by a gage force sensor.
The lateral friction force Ff is measured by a force transducer. The
sphere and the disk can rotate at different speeds maintained by
high precision motors, which results in a relative motion between
the surfaces of the ball and the disk. By adjusting these speeds, it
is possible to achieve different slide-to-roll ratios defined as
SRR¼(Vball–Vdisk)/U, where U is entrainment speed defined as
U¼(Vball + Vdisk)/2, Vball is the surface velocity of the ball and Vdisk
is the surface velocity of the disk at the contact point. Throughout
measurements reported in this paper, SRR was kept equal to 50%,
the value chosen to mimic a friction between tongue and soft
palate in oral cavity, which has both sliding and rolling compo-
nents. For the hydrophobic PDMS tribopair, denoted HB-PDMS,
the highest applied load of 5 N results in an elastic contact radius
of 2 mm and hence a pressure of 0.4 MPa.
PDMS tribopairs with hydrophilic surface, HL-PDMS, were
prepared by exposure of the clean hydrophobic surfaces to air
plasma for 99 s (Cressington, 0.2 mBarr, 15 mA). HB-PDMS tribo-
pairs with adsorbed salivary films, HWS-HB-PDMS, were pre-
pared by application of 500 ml of saliva in front of the
hydrophobic ball–disk contact during rotation. Salivary film was
allowed to adsorb on both the disk and the sphere at the contact
areas, which were wetted by saliva, for half an hour. The bulk
salivary liquid was then replaced by protein-free solvent of
similar ionic strength. To this end, the chamber was filled with
50 ml of 70 mM NaCl solution, and then it was emptied and filled
with another 50 ml dose of 70 mM NaCl to ensure a complete
exchange. Then the pre-adsorbed saliva film was left to equili-
brate in the new solvent for half an hour. Analogously, when a
change in the ionic strength of the solvent was desired, the
measurement chamber was emptied, re-filled with 50 ml of a
new solution, then emptied and re-filled by another 50 ml dose of
the new solution to ensure full exchange of solvents and then left
to equilibrate with the film for half an hour. During this process
(salivary film adsorption and exposure to different solutions), the
ball and disk were kept close to each other but not in contact, by
setting the load to  0.15 N, in order to avoid possible wear of the
adsorbed film prior to data collection.
3. Results
3.1. The effect of adsorbed salivary film on the friction between
PDMS tribopairs
A basic insight into a tribological behavior of HWS-HB-PDMS
tribopairs (hydrophobic PDMS modified by the adsorbed salivary
film) can be obtained by its comparison with the behavior of two
958 L. Macakova et al. / Tribology International 44 (2011) 956–962

tribopairs with a distinctive and well-defined surface chemistry; a
hydrophobic tribopair (HB-PDMS); a hydrophilic tribopair (HL-
PDMS). For these three tribopairs we recorded Stribeck curves
(Fig. 2a) showing a dependence of the friction coefficient on an
entrainment speed. The curves were recorded at a constant load
of 1 N, while the entrainment speed was first stepwise decreased
from 750 to 1 mm/s and then stepwise increased back from 1 to
750 mm/s.
For HB-PDMS tribopair, the Stribeck curve shows an increase
in the friction coefficient with decrease in the entrainment speed
for speeds between 750 and 20 mm/s. This part of the Stribeck
curve corresponds to a mixed lubrication regime, when surfaces
are only partially lubricated by the solvent residing in the contact.
The solvent is gradually removed from the contact area as the
entrainment speed decreases, until the friction is dominated by
the interaction between the asperities of the hydrophobic PDMS
substrates in a boundary lubrication regime indicated by the
plateau below 20 mm/s with a friction coefficient of about 2.0.
For HL-PDMS tribopair, the friction coefficients are signifi-
cantly lower than those measured for the HB-PDMS tribopair at
all entrainment speeds. A plateau in the friction coefficient is not
observed at low entrainment speeds, which would otherwise
indicate an onset of the boundary regime; this lack of a true
boundary regime arises because the HL-PDMS hydrophilic and
negatively charged surfaces make it more difficult to remove a
solvent layer from space between them [24,27]. The friction
coefficients continue to increase with decrease in speed all the
way down to the minimum sampled speed of 1 mm/s, a behavior
indicative of the mixed lubrication regime. At the highest speeds,
a slight increase in the friction coefficient with entrainment speed

Fig. 2. The effect of surface modification on a tribological behavior of PDMS tribopairs in 70 mM NaCl at 37 1C. (a) Stribeck friction curves at a load of 1 N for different
tribopairs: hydrophobic (HB-PDMS), hydrophilic (HL-PDMS) and saliva-coated hydrophobic (HWS-HB-PDMS) polydimethylsiloxane surfaces. The entrainment speed was
first step-wise decreased from 750 to 1 mm/s (filled symbols), and then increased in a step-wise manner back to 750 mm/s (empty symbols). The error bars correspond to
a standard deviation between five data points, which were collected at each speed during one experimental run. (b) Friction coefficient as a function of applied load at an
entrainment speed of 5 mm/s for each tribopair. An additional point (gray diamond) corresponds to a friction coefficient for HWS-HB-PDMS at 1 N obtained following the
measurement at loads increasing up to 5 N; this indicates that the film has undergone an irreversible alteration. The error bars correspond to standard deviation between
at least three independent experiments. (Fit of the HB PDMS data using a model (explained in the text) that accounts for adhesion contribution to the total load, i.e.
FN_total ¼FN_applied +Fadhesion. The best fit was obtained with Fadhesion equal to 0.5 N and mintrinsic equal to 1.2.)
 L. Macakova et al. / Tribology International 44 (2011) 956–962 959

is observed, indicative of the system entering the elastohydrody-
namic lubrication regime where the surfaces are separated by a
full liquid film and friction is determined by the gap between
shearing surfaces and lubricant viscosity. The measured Stribeck
curves for both the HL-PDMS and HB-PDMS tribopairs, lubricated
by 70 mM NaCl, are essentially the same as those previously
found for the same surfaces lubricated by ion-free deionised
water [24]. This indicates that the presence of Na + and Cl  ions
in the aqueous lubricant has a negligible effect on the friction
between these tribopairs.
The presence of the adsorbed salivary films on surfaces of HB-
PDMS renders surfaces hydrophilic; this was possible to observe
by eye as water droplets visibly spread over the saliva coated
substrates. The Stribeck curve for HWS-HB-PDMS tribopair
resembles that of the HL-PDMS for all sampled entrainment
speeds, while the friction coefficients are significantly lower in
comparison to those measured for unmodified HB-PDMS. How-
ever, in difference to HL-PDMS, the Stribeck curve for HWS-HB-
PDMS shows a distinctive plateau at the entrainment speeds
lower than 20 mm/s that we consider to correspond to the
boundary regime with a friction coefficient arising from the
adsorbed salivary film of  0.06. The adsorbed film is irregular
[6] and has a mean thickness of about 20 nm [7], which is greater
than the surface roughness of the underlying disk (rms roughness
of 9 nm) [24]. Another distinctive feature of the Stribeck curve for
HWS-HB-PDMS is a hysteresis, which is observed upon an
increase in the entrainment speed back to high values; this may
be caused by a wear of the adsorbed film following a rubbing in
the boundary contact at low speeds.
A dependence of the effective friction coefficients on the
applied load for the three different tribopairs is shown in
Fig. 2b. The load was gradually increased from 0 to 5 N, while
the entrainment speed was kept constant at 5 mm/s, which
corresponds to the boundary lubrication regime for the HB-PDMS
and HWS-HB-PDMS substrates at a load of 1 N. The friction
coefficient for HB-PDMS decreases with the applied load, whilst
for HL-PDMS surfaces in accordance with Amonton’s law friction
coefficient stays practically constant at  0.03. From these data
we infer that the decrease in Ffriction/FN_applied values with an
increase in applied load observed for HB-PDMS surfaces is a
resulting effect from adhesive forces between hydrophobic PDMS
surfaces. We further suggest that the adhesion force additively
contributes to the effective load [28], so that
FN_total ¼ FN_applied þ Fadhesion
As a result, the effective (measured) friction coefficient, meff,
which is calculated as a ratio between detected friction force and
load applied by the instrument, can be written as
Ffriction ðFN_applied þ Fadhesion Þ  mintrinsic
meff ¼ ¼
FN_applied FN_applied

a HWS
d HWS-70-10
1.0 1.0
Friction coefficient

Friction coefficient

0.8 0.8
0.6 0.6
0.4 0.4
0.2 0.2
0.0 0.0
0 1 2 3 4 5 0 1 2 3 4 5
Load (N) Load (N)

b HWS-70 e HWS-70-1
1.0 1.0
Friction coefficient

Friction coefficient

0.8 0.8
0.6 0.6
0.4 0.4
0.2 0.2
0.0 0.0
0 1 2 3 4 5 0 1 2 3 4 5
Load (N) Load (N)

c HWS-70-70-70 f HWS-70-DIW
1.0 1.0
Friction coefficient
Friction coefficient

0.8 0.8
0.6 0.6
0.4 0.4
0.2 0.2
0.0 0.0
0 1 2 3 4 5 0 1 2 3 4 5
Load (N) Load (N)

Fig. 3. Friction coefficients as a function of an applied load for HB-PDMS tribopairs with the adsorbed salivary film. The error bars correspond to standard deviations
between at least three independent experiments using different tribopairs and saliva collected on different occasions. Data were collected by MTM at an entrainment
speed of 5 mm/s for adsorbed salivary film in contact with bulk saliva (a), after a single rinse with 70 mM NaCl (b), after repetitive rinses with 70 mM NaCl (c) and after a
single rinse with 70 mM NaCl followed by a decrease in the ionic strength to (a) 10 mM NaCl, (e) 1 mM NaCl, (f) deionised water.
960 L. Macakova et al. / Tribology International 44 (2011) 956–962

Thus, for adhesive contacts, the effective friction coefficient

will decrease with the applied load and also, the effective friction
coefficient will asymptotically approach the intrinsic (and load
independent) friction coefficient at high loads. The best fit to the
data using the above model is presented in Fig. 2b), with resulting
values of fitting parameters being mintrinsic ¼1.2 and Fadhesion ¼0.5 N.
The friction between HWS-HB-PDMS surfaces shows an inter-
mediate behavior; the friction coefficient is constant within the
experimental error and equal to about 0.02 for loads below 2 N,
while for loads above 2 N it increases with an increase in load. We
assign this load-related increase in the boundary friction between
HWS-HB-PDMS surfaces to a wear of the adsorbed salivary layers,
since the friction coefficient measured after decreasing the load
back to 1 N is higher than the friction coefficient measured for the
same HWS-HB-PDMS tribopair at the load 1 N before the high
loads were applied.

3.2. A dependence of the wear of pre-adsorbed salivary films on

ionic strength
Fig. 2 shows the boundary friction coefficients for HWS-HB-
PDMS tribopairs exposed to solvents of different ionic strengths.
The friction coefficient of the film exposed to additional saliva is
very low and it does not alter with increase in applied loads,
which indicates essentially no wear of the adsorbed film (Fig. 3a).
This shows that saliva is a highly effective lubricant on its own.
When the bulk volume of saliva is exchanged with 70 mM NaCl,
which has a similar ionic strength to the saliva, the friction
coefficient from the adsorbed salivary film does not alter at low
loads but gradually increases for loads higher than 2 N (Fig. 3b).
While the exchange of saliva to the salt solution removes
adsorbents (salivary proteins) from the bulk lubricant, we have
previously shown that the mass of the adsorbed salivary film is
only weakly affected by the rinse [7]. We therefore suspect that
increase in friction coefficient at the high loads is primarily
associated with a wear of the adsorbed film rather than arising
from desorption. This view is supported by the fact that a
prolonged exposure to 70 mM NaCl does not significantly affect
the film’s lubricious properties in comparison to the case of a
shorter exposure (90 min versus 30 min; Fig. 3c versus 3b). When
the pre-adsorbed salivary film is exposed to solvents of a lower
ionic strength following an initial rinse with 70 mM NaCl, the
adsorbed film is still highly lubricious at loads below 1 N. On the
other hand, at higher loads there is a greater increase in friction
coefficient with load as the ionic strength is lowered (Fig. 3d and
e). In de-ionized water (Fig. 3f), the friction between HWS-HB-
PDMS tribopair rapidly increases already from very little loads
(about 0.3 N), and the friction coefficient levels off at a value of
approximately 0.9 at the load of about 2 N.
After the gradual increase in a load from 0 to 5 N, we
decreased the load back to 1 N. Fig. 4 shows that the re-measured
friction coefficients at a load of 1 N were considerably higher than
those measured originally at the same load. Also, the values re-
measured at 1 N are higher than the values measured at the
highest applied load of 5 N, which strongly suggests that the
difference in the two values measured at 1 N is rather caused by a
removal of the adsorbed layer than by some structural changes in
the layer that might be induced by a high compression of the film
at high loads. The wear of the layer is clearly more extensive for
the layers that are exposed to lubricants with low ionic strengths.
The data collected for the adsorbed films that were left in contact
with bulk saliva indicated no wear of the film (Fig. 3a); we
suspect that the salivary proteins could rapidly re-adsorb from
the bulk reservoir and heal eventual worn patches even if some
wear of the film eventually occurs Fig. 5.
Fig. 4. Wear of the salivary film exposed to solutions with different ionic
strengths. The values of friction coefficients at load 1 N obtained during the
stepwise increase in load (black columns), at 5 N (gray columns) and after
decrease in the load back to 1 N (transparent columns). The entrainment speed
was 5 mm/s. The error bars correspond to standard deviations between at least
three independent experiments.
Fig. 5. Tentative schematic picture of the adsorbed salivary film according to
observations reported in Refs. [6] and [7]. The heterogeneous film consists of an
anchoring sublayer and a lubricious outer layer. The anchoring sublayer contains
small salivary proteins and non-glycosylated parts of large salivary glycoproteins
(different colors represent the whole host of different globular salivary proteins
forming this sub-layer). The lubricious outer layer consists of glycosylated
hydrated chains of the glycoproteins (some of the glycosylated groups are drown
in blue color to illustrate that some of them carry a negative charge originating
chiefly the sialic acid residues [28]). (For interpretation of the references to color
in this figure, the reader is referred to the web version of this article.)
4. Discussion
4.1. Boundary lubrication by adsorbed salivary films
We consider here the boundary lubricating properties of saliva in
the context of our companion study that focused on the adsorption
of saliva under similar conditions and characterized the adsorbed
mass, hydration and film viscoelasticity [7]. Our previous study
highlighted that saliva adsorbs to hydrophobic surfaces in the form
of a film that is highly hydrated and viscoelastic [7], and we
anticipate that the nature of this film is promoting good boundary
lubrication between these surfaces at low loads. An adsorbed
salivary film has a heterogeneous structure consisting of an anchor-
ing sublayer, which contains small salivary proteins and non-
glycosylated parts (hydrophobic ‘naked’ polypeptide region) of
glycoproteins, and a lubricious outer layer consisting of glycosylated
hydrated chains (hydrophilic region) of the glycoproteins [6].
A schematic picture of the heterogeneous salivary film is presented
in Fig. 4 from our previous study [7]. The glycoproteins incorporated
in the adsorbed salivary films are most likely mucins, which are
amphiphilic molecules with partly negatively charged glycosylated
chains [29]. The observed low friction provided by the presence of
 L. Macakova et al. / Tribology International 44 (2011) 956–962
Table 1
Properties of the pre-adsorbed salivary films exposed to solvents of different ionic
strengths.
Solvent Film thicknessa Solvent content Debye length in
(nm) in filma (%) the solvent (nm)
70 mM NaCl 20.1 83.3 1 of these potential mechanisms in the following discussion.
10 mM NaCl 27.7 88.6 3
1 mM NaCl 34.3 90.9 9.5
Deionised 44.4 92.9 300
water
a
From Ref. [7].
extended salivary films at the surfaces can be understood in the
context of boundary lubrication provided by other polyelectrolyte
structures in good solvents. The good boundary lubrication proper-
ties of the extended and hydrated polymers and polymer brushes
arise from a strong anchoring of the polymers onto the tribopair
surfaces [16] and from their ability to support applied loads [30–32].
The friction appears mainly due to viscous loses during movement
of the molecules residing in the contact zone between the sliding
surfaces. In the presence of an adsorbed polymer brush, a compres-
sion due to an applied load causes an increase in the osmotic
pressure within the interpenetration zone of the adsorbed polymer
chains and this pressure acts opposite to the compression [30]. This
leads to a decrease in an effective load and to lower friction
coefficients defined as a ratio between friction force and the applied
load. Beside the grafting density of the extended polymer chains,
another important parameter affecting the lubricious properties of
an adsorbed film is its hydration (solvent content) [21]. Highly
hydrated polymer chains can easily slide along each other within
the interpenetration zone, which contains a low monomer concen-
tration due to extensive presence of the solvent and therefore, the
viscous energy dissipation and related friction coefficient remains
low even in the boundary regime.
The ionic strength of the solvent has a large impact on the
conformation and on the strength of the polymers–substrate
interaction and thus, on the ability of the adsorbed polymers to
reduce the friction as well as resist film and surface wear. It was
previously reported that increasing hydration of the adsorbed/
grafted polymer brush layers [21,22] and polyelectrolyte layers
[33,34] leads to lower boundary friction coefficients. However, for
our system the film thickness and hydration of the adsorbed
salivary films increase with decrease in ionic strength down to
1 mM (Table 1) [7] but the boundary friction coefficient at low
loads ( o0.5 N) stays relatively constant despite these structural
changes. In deionised water, we also observed a similarly low
friction coefficient at these low loads, while the adsorption
studies showed an initial increase in film thickness and hydration
with time before collapse of the film at 10 min after solvent
exchange.
At high loads, the lubrication behavior is dominated by the
adsorbed films’ susceptibility to wear that increases with
decrease in ionic strength. This directly leads to deterioration of
boundary lubrication with decrease in ionic strength, which is
opposite to what may be anticipated based on the film thickness
and hydration measured under load-free conditions; however,
such measurements assist in providing an explanation for this
increase in friction as discussed in the next section.
4.2. The origin of the increased susceptibility to wear in the solvents
of low ionic strengths
There may be several reasons why we observe an increase in
the shear-induced removal of the adsorbed salivary films as we
961
lower the ionic strength from physiological conditions. These
include: (a) increasing adhesion between the saliva coated sur-
faces; (b) a decrease in viscoelasticity and cohesiveness of the
adsorbed films related to a decrease in the Na + counter ions in
solution; (c) a partial desorption of the extended lubricious
components of the heterogeneous salivary film. We consider each
Our favoured mechanism is that adhesion between adsorbed
polymers on opposing surfaces may arise due to a change in a
conformation of the polymers at low ionic strength. Our adsorp-
tion study showed that decrease in ionic strength led to an
expanded, more open structure, and we consider that this
structure will be more susceptible to entanglements and/or
attractive electrostatic interactions. This was reflected in the
average thickness of the adsorbed layer that swelled from 20.1
to 34.3 nm when the ionic strength decreased from 70 to 1 mM
NaCl [7]. This has the potential to lead to a thicker interpenetra-
tion zone between the adsorbed brushes upon compressive load
and thus to more entanglements. Bridging between the polymers
on opposing tribopair surfaces is expected due to attractive
electrostatic interactions between negatively charged glycosy-
lated chains within the lubricious layer on one surface and
oppositely charged proteins within the anchoring layer on the
other surface. As the ionic strength is decreased from physiolo-
gical conditions, there is a corresponding increase in the range of
the electrostatic forces. The screening Debye lengths are equal to
1, 3 and 9.5 nm in 70, 10 and 1 mM NaCl, respectively, and as
large as 300 nm in deionised water at pH 7.3 (Table 1). In order to
experience sufficiently strong attractive forces, the oppositely
charged species need to be separated by a distance comparable
to or less than the Debye length. Such condition was demon-
strated by Pasche et al.[35] for the attraction between proteins
and oppositely charged surfaces, which were coated with an
adsorbed layer of highly hydrated polyethylene glycol brushes,
across which the proteins and the surfaces interacted. The
necessity of the critical approach would also explain the fact that
the wear was not observed at higher ionic strengths unless high
compressive loads were applied.
An alternative explanation to polymer bridging induced wear
arises from our observation of a change in viscoelasticity of the
adsorbed film with decrease in ionic strength [7]. This decrease in
viscoelasticity and cohesiveness of the adsorbed film may result from
a loss of salt ion mediated cross-linking between the adsorbed
protein chains, and we suspect that this weakening of the net-
work structure makes the film less adhered to the surface and
more susceptible to removal from wear. Cross-linking of adsorbed
films increase its elasticity and cohesiveness, and several studies
show that this generally improves wear resistance; for example,
Kampf et al. [36] for adsorbed chitosan layers and by Bongaerts
et al. [37] for multilayers of chitosan and hyaluronic acid. Cross-
linking of extended glycosylated chains of salivary films by a
monovalent counterions might be expected to be rather weak.
However, such a weak cross-linking by Na + ions was previously
suggested as a mechanism of wear-protection by Raviv et al. [38]
for grafted poly(ethylene glycol) layers, which were more wear
resistant in 0.1 mM NaCl than in deionised water.
A partial desorption with a preferential removal of the lubricious
part of the salivary film is another possible explanation of the
increased susceptibility of the layers to a shear-induced wear at
low ionic strengths. Such a selective removal may still be
consistent with our observation of only limited desorption of
the film in low ionic strengths, which has been shown to amount
to less than 10% in terms of a mass of adsorbed salivary
proteins [7]. If this corresponds to desorption of the most
lubricious molecules that are present in the outer extended and
hydrated sublayer of heterogeneous salivary film, it would lead
962 L. Macakova et al. / Tribology International 44 (2011) 956–962
to a significant and irreversible deterioration of the boundary
lubrication.
5. Conclusions
The presence of the adsorbed salivary film on the surface of
hydrophobic polydimethylsiloxane (PDMS) tribopair renders
these surfaces hydrophilic and significantly reduces boundary
friction coefficient between these surfaces in aqueous media.
When bulk saliva is replaced by a protein-free salt solution, the
pre-adsorbed proteinaceous salivary film becomes susceptible to
a shear-induced wear at high loads when the ionic strength is
reduced from that corresponding to oral physiological conditions.
We have previously shown that the adsorbed salivary films
become progressively more extended and hydrated upon
decrease in ionic strength [7]. At low loads (o0.5 N), these
structural changes did not lead to any enhancement of boundary
lubrication. However, at high loads, the lubricious properties were
dominated by the films’ susceptibility to wear, which increased
with decrease in ionic strength. We discussed several mechan-
isms that may be responsible for this wear that includes bridging
of proteins adhered to opposing tribopairs, a loss of network
structure of the adsorbed film or desorption of the lubricious
components from the adsorbed films. This study highlights the
fact that while Surface Plasmon Resonance and Quartz Crystal
Microbalance studies performed under friction-free conditions
can provide us with relevant information on the structure of the
adsorbed film in terms of its thickness and hydration, they do not
necessarily directly reflect the lubricious properties of the film
and we are not at the stage where we could use such studies to
predict a tribological response.
Acknowledgment
The authors thank Ann-Marie Williamson, Jeroen Bongaerts,
Damiano Rossetti (Unilever) and Adam Feiler, Ulla Eloffsson, Mark
Rutland (Institute for Surface Chemistry) for their input into
project planning and for useful discussions. Authors acknowledge
the EU TOK Marie Curie Program for the financial support of the
project ‘Oral Biolubrication and Bioadsorption from Multiphased
Complex Fluids’ MTKD-CT-2006-042779.
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