journal of dentistry 38 (2010) 698–706

available at www.sciencedirect.com

journal homepage: www.intl.elsevierhealth.com/journals/jden

Dentin wetting by three adhesive systems: Influence of

etching time, temperature and relative humidity

P. Farge a,b,*, L. Alderete a,b, S.M.M. Ramos b

a
Faculté d’Odontologie, Université Lyon 1, Villeurbanne, Université de Lyon, F-69622, Lyon, France
b
Laboratoire PMCN – CNRS UMR 5586, Université Lyon 1, Villeurbanne, Université de Lyon, F-69622, Lyon, France

article info abstract

Article history: Objectives: The purpose of this study was to investigate the wetting properties of three
Received 15 December 2009 adhesives systems on etched dentin surfaces submitted to a brief air-drying procedure, as in
Received in revised form clinical conditions. The influence of two clinical parameters (surface temperature and
19 March 2010 surrounding hygrometry) on wetting was investigated.
Accepted 22 March 2010 Methods: Two total-etch adhesives (ExciteTM Vivapen and AdperTM Scothbond 1XT) and one
self-etching adhesive (GC-G BondTM) were used. Superficial and deep dentin slice were
obtained from six caries-free extracted third molars. Before the adhesive deposition, the
Keywords: dentin samples were etched with 37% phosphoric acid for different time durations. The
Contact angle surface topography was characterised by atomic force microscopy (AFM) observations and
Wetting the wetting properties of dentin were studied by contact angle measurements.
Dentin surfaces Results: Unlike clinical expectations, the contact angles increased with the acid exposure
Etching time, and consequently with both surface roughness and the organic–mineral ratio of the
Total-etch adhesives dentin components. The wetting properties were clearly more sensitive to the surrounding
Solvent relative humidity than the temperature. The contact angles values were reduced by about
50% when the relative humidity increased from 37% to 80% and by about 15% when the
PACS: temperature was raised from 25 8C to 37 8C.
68.08 Bc Conclusion: Acid-etched dentin exposed to a brief air-drying appears as the key parameter to
61.30 Hc control the wetting properties of total-etch adhesive–dentin systems. The experimental
68.35 Ct results seem to be well described by the Cassie–Baxter approach, and suggest that dentinal
87.85 jf tubules through an adhesive repellent contribution should account for the observed wet-
tability decreases.
# 2010 Elsevier Ltd. All rights reserved.

1. Introduction morphological variations. The physical characteristics of the

As opposed to the high predictability of bonding to enamel,
dentin bonding remains a challenging procedure. Several
works1–5 devoted to this subject have outlined the structural
complexity of dentin, its heterogeneous structure both organic
and mineral that can be modified by acid preconditioning, and
its variable porosity through the dentinal tubule density and
dentin surface can be constantly modified by fluid movements
through both intra-dentinal and trans-dentinal permeabili-
ty.6–8
Pre-treatment of dentin by mild acid etching is a routine
clinical procedure designed to enhance the adhesion of
polymeric resins.9–11 In addition to the modification of surface
roughness, the etching procedure is assumed to favour the

* Corresponding author at: Laboratoire PMCN – CNRS UMR 5586, Université Lyon 1, Université de Lyon, F-69622, Villeurbanne, France.
Tel.: +33 4 78 77 70 38/72 43 10 25; fax: +33 4 72 43 15 92.
E-mail address: pierre.farge@univ-lyon1.fr (P. Farge).
0300-5712/$ – see front matter # 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jdent.2010.03.013
 journal of dentistry 38 (2010) 698–706
infiltration of the exposed collagen network by the hydrophobic
dentin–adhesive molecules, in the demineralised dentin.12–15
To evaluate the effect of etching on the adhesive properties of
dentin, a good understanding of the wetting properties is
required. Although contact angle measurements appear as the
most adequate technique to provide such information, some
cautions are required in the experimental procedure. As is well
known, the value of the contact angle is usually strongly
affected by surface roughness, chemical heterogeneities on the
solid surface and by the surface hydration state.
A general consensus exists that the presence of a certain
amount of water in the demineralised dentin is critical to
prevent the collapse of the collagen network, leading to
several bonding formulations designed specifically according
to the amount of water content on the surface. Hence, the
optimal amount of surface wetness varies among the adhesive
systems, leading to different concepts from dry to wet bonding
depending on the control of moisture.14–24
Therefore the wetting behaviour is influenced by at least
two parameters: the physical–chemical characteristics of the
adhesive blend – namely the type of solvent and the
hydrophilic/hydrophobic ratio of the monomers – and
environmental conditions, i.e., the drying procedure, the
surrounding hygrometry and temperature.
Indeed, most of published studies of adhesive dentin
wetting deal essentially with completely hydrated surfaces,
i.e., with an aqueous surface layer of variable thick-
ness.5,10,25,26 Experimental investigations, taking into account
slightly dry dentin, are still limited.23,25 It is likely that such
studies were compromised by difficulty in obtaining consis-
tent drying processes, and consequently fail to reproduce
surfaces with similar characteristics. However, the drying
process of dentinal surfaces is a key step in adhesive dentistry
and accounts for the failure or success of the clinical
procedure.1,19–22 On the other hand, despite their importance
to the clinical situation, few investigations have been devoted
to the effects of temperature and humidity on adhesive
wetting. A complete study taking into account the influence of
these two parameters simultaneously on the adhesives
behaviour and on the dentin surface is lacking.
The aim of this work was threefold: (i) to investigate the
wetting properties of three adhesives systems on etched dentin
surfaces, submitted to a brief drying procedure, similar to that
used in clinical conditions. The influence of the surface
characteristics (topography and organic–mineral ratio of dentin
constituents) and the resin constituents (solvents and mono-
mers) on the wetting behaviour of adhesives was evaluated. (ii)
To determine the influence of temperature and surrounding
humidity on the adhesives wetting process. (iii) To identify the
mechanisms governing the wetting process. For this purpose
experimental data were confronted to theoretical predictions
that describe wetting behaviour on a heterogeneous surface.
2. Material and methods
2.1. Sample preparation
Caries-free extracted third molars were used in this study.
Following removal they were kept in a 0.5%-chloramine
699
solution at 4 8C temperature until further processing. After
cleaning and removal of superficial debris from the surface,
occlusal enamel was removed. Two sections parallel to the
occlusal surface were cut to obtain two dentin slices per tooth.
We used a saw equipped with a diamond disc operating with
slow speed and under constant irrigation (Isomed, Buehler Ltd,
Lake Bluff, IL, USA). The superficial dentin section was cut
2 mm beneath the dentin–enamel junction and the deep
dentin section 2 mm below the first one, above the roof of the
pulp chamber. The distance between the sections was
1.5 mm. The obtained dentin slices were then prepared
according to the following two-steps procedure: first, the
surfaces were mechanically polished as previously de-
scribed.27 Briefly the surfaces were mechanically polished
using an initial sequence of 120-400-800 grit waterproof
abrasive papers of silicon carbide. An additional and final
polishing was performed with 6 mm, 3 mm and 1 mm diamond
abrasive paper to maximise the removal of the smear layer. At
the end of the polishing process, all the specimens were
ultrasonically cleaned for 8 min in water, rinsed thoroughly in
ultra pure water, and finally kept in de-ionised water at 4 8C
temperature. Although this preparation may be does not
warrant complete elimination of the smear layer, this provides
flat and highly polished surface that constitute a reference for
roughness and contact angle measurements. According to
previous investigations9,10 the opening or partial occlusion of
dentin tubules can be considered as a good indicator of the
removal process of the smear layer.
Second, the dentin samples were etched with 37%
phosphoric acid with a dental etching gel (Total EtchTM Ivoclar
Vivadent, Lichenstein) for different durations (e.g., 3 s, 5 s,
10 s, 15 s, and 30 s) in order to modify the surface roughness in
a controlled way. Following the etching, the samples were
rinsed again in de-ionised water and then air-dried. In order to
match the clinical procedure used in adhesive dentistry, the
drying step was performed by flushing the samples with a light
dry nitrogen gas flux for 10 s maximum at 5 L/min volume
flow, just before the contact angle measurements. In order to
avoid the collapse of the collagen fibrils, or the dentin
desiccation, the gas flux was applied at a grazing incidence
(<108), onto the dentin surfaces. Note that this brief drying
procedure was aimed at only removing the excess liquid from
the dentin surfaces. This procedure left some residual water
on the dentin. To avoid any kind of surface modification
(contamination, dehydration, . . .) this last step in the dentin
preparation was always performed immediately before
experimental measurements.
2.2. Adhesives systems
The following three adhesives systems were studied on two
different dentin matrices (superficial and deep): AdperTM
Scothbond 1XT (3M ESPE), ExciteTM Vivapen (Ivoclar Vivadent)
and GC-G BondTM (GC Fuji). These systems, which belong to
different families of chemical adhesives and composite resins,
were chosen on the basis of the nature of the solvent and the
presence of hydrophobic (e.g., Bis-GMA) or hydrophilic
components (e.g., HEMA) in their composition. Their chemical
characteristics are briefly summarised in Table 1. The
conditioner effect on the dentin roughness and dentin wetting
700 journal of dentistry 38 (2010) 698–706

Table 1 – Composition of the three adhesives used.

Adhesive system Chemical characteristics Manufacturer
TM
Adper Scotchbond 1XT Dimethacrylates, HEMA, olyalkenoic adic, silanized particles with 3M ESPE, St Paul, MN, USA
colloidal silicium. Solvent: ethanol and water
ExciteTM Vivapen Phosphonic acid acrylate, HEMA, Bis-GMA dimethacrylate, highly Ivoclar Vivadent, Schaan, Lichenstein
dispersed silica, catalysts and stabilisers. Solvent: ethanol
GC-G BondTM 4-META, phosphoric ester monomer, UDMA, TEGDMA. Solvent: GC Fuji, Tokyo, Japan
acetone and water
HEMA: 2-hydroxyethyl methacrylate; Bis-GMA: bisphenol A glycidyl methacrylate; 4-META: 4-methacryloyloxyethyl trimellitate anhydride;
UDMA: urethane dimethacrylate; and TEGDMA: triethylene glycol dimethacrylate.

by these polymeric resins was analysed. For this purpose two
complementary techniques were used: atomic force micros-
copy (AFM) and sessile drop. The modifications of the wetting
properties of these adhesives by the oral environment
conditions (temperature, hygrometry) were also investigated
in this paper.
2.3. Characterisation methods
The dentin surfaces were probed under ambient conditions
(temperature: 25  1 8C; relative humidity (RH) at 37  3%)
using a Nanoscope III Digital Instruments atomic force
microscope (AFM) operating in tapping mode and using silicon
tips of a nominal radius curvature of 10 nm. Each sample was
probed at four different locations and the images were
flattened to eliminate the experimentally obtained bowing
effects. Prior to characterising the topographic modifications
induced on the etched surfaces, the pristine superficial and
deep dentins were examined by AFM. These flat surfaces were
uses as reference our investigations of the wetting properties.
The characterisation of dentin topography was completed by
rms-roughness measurements on a scanned zone of two
different sizes: 625 mm2 and 25 mm2. These zones respectively
correspond to the dentin matrix as a whole and to the
intertubular region.
In order to investigate the wettability properties of the
investigated surfaces, contact angle measurements were
performed using the sessile drop method. For such experiments
the samples were introduced in a glass chamber, with
controlled temperature and humidity, and the liquid drop
was put onto the substrate, through a micro syringe. Droplets of
liquid adhesives, in a volume of 1.0 mL, were used to measure
the static contact angle u*. The angle values were obtained from
at least five drops placed at different locations on the surface.
For each drop, a set of six images was recorded, at 15-s intervals.
This procedure allows taking into account a possible non-
uniformity of the surface, as probed by the contact angle. The
measurements were done optically with an accuracy of 28.
The experiments were carried out at two controlled relative
humidities (RHs) at 37  3% and 80  5% and controlled
temperatures at 25  1 8C and 37  1 8C, respectively. The
values of temperatures and humidity were chosen in order to
simulate the oral environment in the clinical situation of teeth
isolated by a rubber dam or in a closed mouth. The constant
hygrometry during the contact angle measurements was
assured by introduction into the glass chamber of a saturated
solution with potassium chloride salt.28 This chamber was
obviously preserved closed during the experiments.
3. Results
3.1. Surface characteristics
In order to analyse the influence of the surface morphology in
the adhesive behaviour on dentin substrates, we characterised
separately the surface of both superficial and the deep dentins.
Fig. 1 shows top and 3D views of AFM micrographs recorded
on the deep dentin, respectively, before and after etching in
acid solution for 30 s. It appears that the surface morphology
consists of a distribution of quasi-circular holes corresponding
to the dentinal tubules on the dentin matrix separated by an
pffiffiffiffi
average distance l, given by l ¼ 1= N where N is the number
of tubules per surface unit N (that is the tubule density). The
two following values were measured from AFM analysis:
l = 6.9 mm and l = 5.1 mm for superficial and deep dentin,
respectively, It corresponds to the following tubule density
Ns = 2.1  106 tubules cm2 for superficial dentin and
Nd = 3.8  106 tubules cm2 for deep dentin. These values
clearly show that N increases markedly with dentin depth.
These results are in good agreement with those obtained
previously by Pashley.1 According to this referred work N
varies from 1.9  106 tubules cm2 at the enamel junction to
4.5  106 tubules cm2 at the pulp chamber (deep dentin) and
the tubule diameter increases, from superficial to deep dentin.
The geometric characteristics of dentin tubules were
extracted from profile line scans performed over exposed areas
(as in Fig. 1-d) where more than 40 objects per sample were
analysed. The values of tubules diameter on bare and etched
samples are summarised in Table 2 for both superficial and
depth dentin. From these data the following features are
evidenced: (i) the tubule diameters are systematically higher in
the deep than in the superficial dentin; each tubule can be seen
as an inverted cone with smaller diameter at superficial dentin–
enamel interface, increasing to a maximal value near the pulp;
(ii) the tubules diameter strongly increases with the acid
etching-time increasing thus the contact area between dentinal
tubules and adhesive. However we note that it is not enough to
ensure alone, the monomer penetration into dentin surfaces.
The characterisation of the dentin surfaces (before and
after etching) was completed by rms-roughness measure-
ments on a scanned zone of 625 mm2. The data reported in
Table 2 clearly show that the general roughness increases as a
function of the acid etching duration. These results are based
on the loss of the mineral content that induces a more porous
structure, an irregular intertubular dentin and opened dentin
tubules. Dentin depth also influenced roughness and deep
dentin is about 30–40% rougher than superficial dentin. The
 journal of dentistry 38 (2010) 698–706 701
[(Fig._1)TD$IG]

Fig. 1 – Top view recorded on deep dentin surfaces. Bare sample (a); sample etched for 30 s (b). 3D view of two tubules
recorded on etched surface (c). Surface profiles recorded on (d) surface. The dashed lines illustrate the border between the
tubule lumen and the surrounding intertubular matrix.

reason can be found on the highest tubule density observed on
the deep dentin. Our results are consistent with those
previously reported by different authors.5,9,25
Finally, it must be noticed that when the rms-roughness
evaluation is limited to a scanned zone of 25 mm2, correspond-
ing to the intertubular zone, the roughness values (e.g., for
bare dentins, rms (DD) = 28 nm and rms (SD) = 24 nm) of deep
and superficial dentins differ by 10%, that is within the
accuracy interval of our measurements. These low roughness
values indicate that only a thin thickness of the smear layer
should persist on the dentin surface, thus validating our
experimental procedure. This also means that each dentin
surface presents, at least, a dual roughness scale, composed of
micro and nano-features. As we have pointed out in a previous
study27 it is well known that the surface wetting properties can
be strongly modified, when faced with dual or multiple
roughness scales.29–33 To date, the influence of such a feature
on the wetting behaviour of dentin is not yet well established.

Table 2 – Etching time t, rms-roughness value measured on scanned zones of 625 mm2 for superficial (SD) and deep (DD)
dentins. Tubules diameter DAFM measured on bare and etched dentins. Fraction F of intertubular dentin in contact with
the liquid adhesive determined from AFM images.
t (s) Rms-roughness of dentin ma- DAFM (mm) F = 1  (NpD2/4)
trix (nm)

SD DD SD DD SD DD

0 42  7 63  7 0.8  0.2 1.2  0.2 0.99 0.96

5 69  6 78  8 1.2  0.2 1.9  0.3 0.98 0.89
15 107  9 144  11 2.0  0.4 2.9  0.4 0.93 0.75
30 173  11 230  10 2.2  0.3 3.2  0.4 0.92 0.70
702 journal of dentistry 38 (2010) 698–706

3.2. Wetting properties
The contact angle values measured on bare and etched
surfaces for the three adhesives at two different temperatures
are reported in Table 3. The AdperTM Scothbond 1XT clearly
presents the highest contact angle values whereas ExciteTM
Vivapen and GC-G BondTM and show similar values. GC-G
BondTM is however a self-etching adhesive and consequently,
by reasons that will be explained below, it is not directly
comparable to AdperTM Scothbond 1XT and ExciteTM Vivapen
which both require a previous acid treatment. These two
adhesives differ for example first by their solvent content that
for ExciteTM Vivapen is the ethanol, and for AdperTM
Scothbond 1XT which is an ethanol–water solution. Knowing
that the liquid surface tension g plays a fundamental role in
the wetting behaviour and bearing in mind the surface tension
of water and ethanol (gwater = 72 mN/m; gethanol = 22.4 mN/m)
we can consider that gscothbond > gvivapen. Although this
difference can satisfactorily explain the best wetting proper-
ties of ExciteTM Vivapen, other factors dealing with the
physical–chemical characteristics of both substrates (e.g.,
surface energy, . . .) and the adhesives chemical composition
could also account for these results. However, differently to
reports by Pazinatto and Atta in the literature,8 the presence of
hydrophobic monomers, like Bis-GMA in the ExciteTM Vivapen
composition, does not appear to bring any significant
contribution to the contact angles that are systematically
lower than those measured with AdperTM Scothbond 1XT.
This can be ascribed to the ethanol presence in the solvent
composition that according to recent investigations16,18,34,35
provides a better infiltration of Bis-GMA monomers into the
demineralised dentin.
As shown in Table 3, the contact angles measured with
ExciteTM Vivapen and AdperTM Scothbond 1XT adhesives
increase linearly with the etching time and consequently with
both tubules diameter and surface roughness. These results
are opposed to both ‘‘clinical practice expectative’’ and other
reports in the literature,5,9,25 where the dentin wettability
systematically increases with the surface roughness. The
explanation for such a discrepancy lies in the dentin
preparation. In the referred works only the excess of water
was removed from the surfaces, through blotting. In these
conditions, a liquid film usually persists on the surface, and its
progression on the roughness features implies the develop-
ment of a liquid-vapour interface, that induces an increase of
wettability by capillarity. In our investigations, just before the
contact angles measurements, the samples were briefly air-
dried (<10 s). In this case, the collagen network remains
standing following demineralisation thus letting the polymer
resin permeate the network. This procedure is only aimed at
removing the liquid from the upper demineralised part of the
tubule and the dentin surfaces.
In addition, data in Table 3 shows that for these two
adhesives the contact angles are slight lower in the deep
dentin than in the superficial dentin. Such a deviation is
however small and close to the accuracy (28) of our
measurements. It is surprising if we consider that the tubules
density in superficial dentin is about two times lower than in
the deep dentin (Nd  2Ns) and that the relative amount of
organic matter (mainly collagen having a low surface energy)
is expected to be higher at superficial than at deep dentin.
Meanwhile, in recent investigations dealing with air-drying
effects on dentin wetting by water we have clearly shown that
the dentin wetting is driven by the dentinal tubules which
bring a hydrophobic contribution to the wetting phenome-
non.27 Thus, in deep dentin the smaller amount of collagen is
compensated by a higher tubules concentration.
Another point analysed in this study concerns the influ-
ence of the temperature on the adhesive wetting properties.
From Table 3 it appears that, independently of the dentin
depth, the contact angle values are reduced of about 15% when
the temperature evolves from 258 to 378 consequently and as
expected, the adhesive wetting on the dentin surfaces
increases with the temperature. Such an effect is consistent

Table 3 – Etching time t, contact angle u* measured on bare and etched dentin surfaces at controlled humidity rate 37 W 3%
and controlled temperatures of 25 8C and 37 8C.
t (s) u (8) – ExciteTM Vivapen u (8) – AdperTM Scotchbond 1XT u (8) – GC-G. BONDTM

Ethanola Ethanol and watera Acetone and watera

DD SD DD SD DD SD

T: 25 8C – H: 37%
0 19 23 34 36 21 22
3 23 – 29 – – –
5 27 27 35 39 – –
10 30 – 37 – – –
15 30 29 37 40 – –
30 32 35 40 42 – –
T: 37 8C – H: 37%
0 16 18 29 31 18 19
3 20 – 32 – – –
5 25 28 32 33 – –
10 29 – 34 – – –
15 29 28 35 35 – –
30 30 32 36 38 – –

a
Ethanol, ethanol and water, and acetone and water are the solvents.
 journal of dentistry 38 (2010) 698–706 703
[(Fig._2)TD$IG]
with a decrease in the viscosity of the resin when the
temperature increases, is in good agreement with previous
investigations.36,37
The spreading time of the solvated co monomer blends
deposited on bare superficial dentin as a function of
temperature is displayed in Fig. 2 at two different tempera-
tures. ExciteTM Vivapen is clearly the resin that spreads more
quickly. At 25 8C, the spreading process is completely
stabilised after about 120 s (first arrow Fig. 2). For the AdperTM
Scotchbond 1XT and GC-G BondTM the total resin spread
requires about 180 s (second arrow Fig. 2) indicating that the
water-based resins thus need a longer time to achieve the
stabilisation of the drop spreading. The interpretation of the
adhesive spreading time is however relatively intricate. In fact,
two phenomena result in the contact angle evolution of a
deposited liquid on a heterogeneous porous substrate such as
dentin: the liquid spreading on the surface and the liquid
infiltration into the substrate. In the case of adhesive resins
other aspects must be also considered: (i) the evaporation of
the solvent. In the present case, the three investigated
adhesives are constituted of three different solvent with
consequently different vapour pressures and different evapo-
ration rates. In particular, a phase separation of water from the
comonomer blend may occur with the evaporation of the
solvent and thus account for an increased viscosity.38,39 This
phenomenon is mostly enhanced when acetone is present in
the adhesive formulation as in G-Bond. (ii) For a self-etching
adhesive (like GC-G BondTM) a competition between the
spreading process and surface etching occurs. In this case,
the wetting of dentin is different due to the substrate changes
during the adhesive spreading. Once the self-etching adhesive
begins to spread onto the dentin surface, the demineralisation
is initiated and the surface characteristics vary. According to
previous investigations9,22 dentin demineralisation induced
by self-etching primers provides similar chemical and
morphological characteristics to phosphoric acid etching.
However, the self-etching process also implies a resin
infiltration into the dentin. This effect that involves loss of
free volume at the surface should limit the adhesive
spreading. However, such a limitation does not occur in the Fig. 2 – Spreading kinetics of three different adhesives on
case of GC-G BondTM spreading that behaves similarly to bare deep dentin at two temperatures (a) 25 8C and (b)
AdperTM Scotchbond 1XT a total-etching adhesive. 37 8C.
At 37 8C, the spreading kinetics is clearly accelerated for all
adhesives and the time required to reach the stabilisation is
shortened of about 30 s. The result is a more homogeneous
film and consequently an improvement in the adhesive intertubular dentin as well as inside the opened tubules
properties can thus be expected. facilitating the adhesive spreading. This could explain the low
In order to simulate the oral cavity conditions we also obtained contact angle values. (ii) Temperature and relative
investigated the influence of the relative humidity on the humidity do not modify the etching effect on the dentin
wetting properties of the adhesives. The results obtained for wetting properties. In all cases, the contact angle values
deep dentin with AdperTM Scothbond 1XT S adhesive are increase on etched samples submitted to an air-drying
reported in Fig. 3 together with data extracted from Table 3, procedure regardless of temperature and relative humidity.
dealing with a temperature effect. These results lead to the
following conclusions: (i) the wetting properties are strongly
influenced by the relative humidity. A decrease of about 50% in 4. Discussion
the contact angle value is evidenced at RH = 80%. Although not
shown here, this strong reduction on the u values was also It is well known that successful resin bonding on a dentin
observed for ExciteTM Vivapen adhesive. This behaviour can be surface depends on two main factors: the adhesive wetting
explained by the formation of molecular film of water on the and the adhesive impregnation into the dentin substrates. In
dentin surface. Thus the global water content increases in the this work, we focused our investigations on the wetting
704 journal of dentistry 38 (2010) 698–706
[(Fig._3)TD$IG]
hydroxyapatite and the collagen, that constitute the inter-
tubular region, and the dentinal tubules, with a peritubular
region enriched in the collagen fibbers.3 In this way, we
initially calculated the fraction of intertubular zone on the
dentin matrix by using the following relation:

NpD2
F¼1 (1)
4

where N is the number of tubules per surface unit given above

and D is the dentinal tubule diameter. The values obtained are
reported in Table 2. Then, we assumed that the Cassie–Bax-
ter’s approach40 can be extended to a heterogeneous surface
constituted of the three chemically different domains. In this
case, the apparent contact angle u* of a liquid on such a surface
can be written in terms of the respective surface fractions f1, f2
and f3 by the following relations:
Fig. 3 – Measured contact angle u* on deep dentin as cos u ¼ f 1 cos u1 þ f 2 cos u2 þ f 3 cos u3 (2)
function of the etching time.
with f 1 þ f 2 ¼ F and f 3 ¼ 1  F:

phenomenon with the purpose of a quantitative analysis of where f1, f2 and f3 denote the fractions of the surface, occupied
the influence of acid etching coupled to a brief drying by the hydroxyapatite, the collagen and the dentinal tubules,
procedure. respectively. The contact angles u1, u2 and u3 correspond to
The effect of acid etching on the dentin surfaces is twofold: these phases, respectively.
first, a modification of the surface topography occurs Noting that Eq. (2) can be re-written as:
inducing an increase of both the tubules diameters and the
surfaces roughness. Secondly, an evolution of the surface cos u ¼ Fðcos u1  cos u3 Þ þ f 2 ðcos u2  cos u1 Þ þ cos u3 (3)
energy after etching: due to the loss of the mineral compo-
nent, the collagen fibbers are more exposed, the organic/ Fig. 4 shows plots of the cosine of measured apparent
mineral ratio component increases, and consequently the contact angles on deep dentin as a function of F for the two
surface energy decreases. Up to now this last contribution is adhesives. Clearly, cos u* decreases linearly with F and then u*
still the subject of controversies. On the basis of this factor values increases with the fraction of dentinal tubules (1  F)
Attal et al.2 suggested that acid etching does not promote on the dentin. The obtained linear dependence indicates that
wettability, because demineralisation leads to a more our results should be consistent with the Cassie–Baxter theory
hydrophobic surface. On the other hand Rosales et al.5 and consequently the increase of the surface roughness does
showed that the tubules area increases with the etching time; not necessarily promote the dentin wettability as assumed by
consequently the tubules being normally filled with liquid many investigators. It clearly appears that the tubules
(their samples are not dried after etching) the wettability contribute to an average decrease of the dentin wettability.
increases by a capillary effect. In a recent paper,27 we showed
[(Fig._4)TD$IG]
that acid etching can drastically reduce the dentin wettability
in samples prepared in a similar manner as described above.
This effect should result from a hydrophobic contribution of
dentinal tubules.
The experimental data presented in this paper (Tables 2
and 3) show that the contact angles with both AdperTM
Scotchbond 1XT and ExciteTM Vivapen increase with the
surface roughness (but also with tubules diameter); the
evolution of the organic–mineral ratio seems to play an
important role in this behaviour. In order to complete the
analysis of our results we compared them with the theoretical
prediction for wetting on heterogeneous surfaces proposed by
Cassie and Baxter.40 In such an approach, it is assumed that
the liquid drop sits on a heterogeneous surface, with different
chemistries, each characterised by its own contact angle ui. For
this purpose, as in our previous study, the dentin matrix was
considered as a heterogeneous medium containing a distri-
bution of micrometric holes. We assumed that the liquid drop Fig. 4 – Measured cos u* on deep dentin, as a function of the
sits on a composite surface containing three phases: the intertubular fraction F in contact with the liquid interface.
 journal of dentistry 38 (2010) 698–706
This may be ascribed to two contributions: (i) an increase in
the surface energy of the inner wall of the tubules induced by
the acid etching, where it should reduce their local wettability.
(ii) The presence of small air pockets in the dentinal tubules
probably trapped during the drying procedure. As reported
previously,29–33 a local formation of a composite solid–air–
liquid interface in the tubules wall should improve the
apparent contact angle increase on the dentin surfaces. This
effect, usually evoked to describe surfaces that are strong
repellents to water, should explain the fact that AdperTM
Scotchbond 1XT adhesive presents higher contact angle
values than ExciteTM Vivapen. The dentinal tubules would
bring a hydrophobic contribution to the dentin surface and
thus account for the decrease of the wettability observed on
the etched surfaces.
Obviously, complementary experiments are required to
quantify the organic–mineral ratio on the etched surfaces;
they will enable unambiguous conclusions about the physical
origin of the wetting behaviour of adhesives on etched dentin.
However, independently of a more quantitative analysis
leading to a more satisfactory theoretical description of our
results, the present study clearly reveals the fundamental role
played by the routine clinical procedure of brief drying of acid-
etched dentin surfaces, in the control of dentin wetting
properties.
5. Conclusion
In this study we investigated the behaviour of adhesive
droplets deposited on the acid-etched dentin surfaces sub-
mitted to a standardised brief air-drying procedure.
For this purpose, three different adhesive systems were
used. By focusing our initial investigations on the evolution of
contact angles on the etched surfaces, we have shown that the
contact angle values increases with three factors: the surface
roughness, the fraction occupied by the dentinal tubules on
dentin and the organic–mineral ration of dentin constituents.
We propose to describe our results by the Cassie–Baxter theory
extended to a heterogeneous system constituted of three
different chemistries. An adhesive repellency effect on
dentinal tubules was inferred, to account for the decrease of
wettability of increasingly etched surfaces. The influences of
surface temperature and relative humidity on the adhesives
wetting were also investigated. Although both variables
enhanced dentin wettability, the contact angle values are
clearly more sensitive to humidity than temperature. Howev-
er, it does not modify the etching effect on the dentin wetting
properties. In all cases, the contact angle values increase on
etched samples submitted to an air-drying procedure evidenc-
ing so, the strong influence of the drying step in adhesive
dentistry.
Finally, the results open at least two main directions
for further work. On one hand, investigations about the
effect of the etching time on the organic–mineral ratio,
which are now underway and will contribute to a better
understanding of the physical origin of wetting on the
dentinal surfaces. On the other hand, the apparent capture
of air pockets inside the dentinal requires complementary
experimental investigations.
705
references
1. Pashley DH. Clinical correlations of dentin structure and
function. Journal of Prosthetic Dentistry 1991;66:777–81.
2. Attal JP, Asmussen E, Degrange M. Effects of surface
treatment on the free surface energy of dentin. Dental
Materials 1994;10:259–64.
3. Kinney JH, Balooch M, Haupt DL, Marshal SJ, Marshall GW.
Mineral distribution and dimensional changes in human
dentin during demineralization. Journal of Dental Research
1995;74:1179–84.
4. Perdigão J, Lambrechts P, Van Meerbeek B, Tome AR,
Vanherle G, Lopes AB. Morphological field emission-SEM
study of the effect of six phosphoric acids etching agents on
human dentin. Dental Materials 1996;12:262–71.
5. Rosales JI, Marshall GW, Marshall SJ, Watanabe LG,
Toledano M, Cabrerizo MA, et al. Acid-etching and hydration
influence on dentin roughness and wettability. Journal of
Dental Research 1999;78:1554–9.
6. Pashley DH, Pashley EL, Carvalho RM, Tay FR. The effects of
dentin permeability on restorative dentistry. Dental Clinics of
North America 2002;46:211–45. v–vi.
7. Pashley DH, Carvalho RM. Dentine permeability and dentine
adhesion. Journal of Dentistry 1997;25:355–72.
8. Pazinatto FB, Atta MT. Influence of differently oriented
dentin surfaces and the regional variation of specimens on
adhesive layer thickness and bond strength. Journal of
Esthetic and Restorative Dentistry 2008;20:119–28.
9. Aguilar-Mendoza JA, Rosales-Leal JI, Rodrı́guez-Valverde
MA, Cabrerizo-Vı́lchez MA. Effect of acid etching on dentin
wettability and roughness: self-etching primers versus
phosphoric acid. Journal of Biomedical Materials Research-B
Applied Biomaterials 2008;84:277–85.
10. Aguilar-Mendoza JA, Rosales-Leal JI, Rodrı́guez-Valverde
MA, González-López S, Cabrerizo-Vı́lchez MA. Wettability
and bonding of self-etching dental adhesives. Influence of
the smear layer. Dental Materials 2008;24:994–1000.
11. De Munck J, Van Landuyt K, Peumans M, Poitevin A,
Lambrechts P, Braem M, et al. A critical review of the
durability of adhesion to tooth tissue: methods and results.
Journal of Dental Research 2005;84:118–32.
12. Kanca III J. Improving bond strength through acid etching of
dentin and bonding to wet dentin surfaces. The Journal of the
American Dental Association 1992;123:35–43.
13. Van Meerbeek B, Dhem A, Goret-Nicaise M, Braem M,
Lambrechts P, Vanherle G. Comparative SEM and TEM
examination of the ultrastructure of the resin–dentin
interdiffusion zone. Journal of Dental Research 1993;42:
495–501.
14. Rosales-Leal JI, Osorio R, Holgado-Terriza JA, Cobrerizo-
Vilchez MA, Toledano M. Dentin wetting by four adhesive
systems. Dental Materials 2001;17:526–32.
15. Osorio R, Aguillera FS, Otero PR, Romero M, Osorio E, Garcia-
Godoy F, et al. Primary dentin etching time, bond strength
and ultra-structure characterization of dentin surfaces.
Journal of Dentistry 2010;38:222–31.
16. Manso AP, Marquezini Jr L, Silva SM, Pashley DH, Tay FR,
Carvalho RM. Stability of wet versus dry bonding with
different solvent-based adhesives. Dental Materials
2008;24:476–82.
17. Reis A, Loguercio AD, Azevedo CL, de Carvalho RM, da Julio
Singer M, Grande RH. Moisture spectrum of demineralized
dentin for adhesive systems with different solvent bases.
The Journal of Adhesive Dentistry 2003;5:183–92.
18. Pashley DH, Tay FR, Carvalho RM, Rueggeberg FA, Agee KA,
Carrilho M, et al. From dry bonding to water-wet bonding to
ethanol-wet bonding. A review of the interactions between
706 journal of dentistry 38 (2010) 698–706
dentin matrix and solvated resins using a macromodel of
the hybrid layer. The American Journal of Dentistry 2007;
20:7–20.
19. Spencer P, Wang Y. Adhesive phase separation at the dentin
interface under wet bonding conditions. Journal of Biomedical
Materials Research 2002;62:447–56.
20. Asmussen E, Peutzfeldt A. The influence of relative
humidity on the effect of dentin bonding systems. The
Journal of Adhesive Dentistry 2001;3:123–7.
21. Hashimoto M, Ohno H, Kaga M, Sano H, Endo K, Oguchi H.
Fractured surface characterization: wet versus dry bonding.
Dental Materials 2002;18:95–102.
22. Schulze KA, Oliveira SA, Wilson RS, Gansky SA, Marshall
GW, Malshall SJ. Effect of hydration variability on hybrid
layer properties of a self-etching versus an acid-etching
system. Biomaterials 2005;26:1011–8.
23. Ikeda T, De Munck J, Shirai K, Hikita K, Inoue S, Sano H, et al.
Effect of air-drying and solvent evaporation on the strength
of HEMA-rich versus HEMA-free one-step adhesives. Dental
Materials 2008;24:1316–23.
24. Hitmi L, Bouter D, Degrange M. Influence of drying and
HEMA treatment on dentin wettability. Dental Materials
2002;18:503–11.
25. Wege HA, Aguilar JA, Rodrı́guez-Valverde MA, Toledano M,
Osorio R, Cabrerizo-Vilchez MA. Dynamic contact angle and
spreading rate measurements for the characterisation of
the effect of dentin surface treatments. Journal of Colloid and
Interface Science 2003;263:162–9.
26. Wege HA, Holgado-Terriza JA, Rosales-Leal JI. Contact angle
hysteresis on dentin surfaces measured with ADSA on
drops and bubbles. Colloids and Surfaces A 2002;206:469–83.
27. Ramos SMM, Alderete A, Farge A. Dentinal tubules driven
wetting dentin: Cassie–Baxter modelling. The European
Physical Journal E 2009;30:187–95.
28. Restagno F. Interaction entre contacts solides et cinétique
de la condensation capillaire. Aspects macroscopiques et
microscopiques. PhD Thesis, Ecole Normale Superieure of
Lyon (2000) in D. Quéré, Rough ideas on wetting Physica A
2002;313:32–46.
29. Quéré D. Rough ideas on wetting. Physica A 2002;313:32–46.
30. Krupenkin TN, Taylor JA, Schneider TM, Yang S. From rolling
ball to complete wetting: the dynamic tuning of liquids on
nanostructured surfaces. Langmuir 2006;22:3824–7.
31. Toledano M, Osorio R, Moreira MAG, Cabrizio-Vilchez MA,
Gea P, Tay FR, et al. Effects of the hydratation status of the
smear layer on the wettability bond strength of a self
etching primer to dentin. The American Journal of Dentistry
2004;17:310–4.
32. Cao L, Price TP, Weiss M, Gao D. SuperWater and oil-
repellent surfaces on intrinsically hydrophilic and
oleophilic porous silicon films. Langmuir 2008;24:1640–3.
33. Ramos SMM, Canut B, Benyagoub A. Nanodesign of
superhydrophobic surfaces. Journal of Applied Physics
2009;106. 024305-1024305-7.
34. Hosaka K, Nishitani Y, Tagami J, Yoshiyama M, Brackett
WW, Agee KA, et al. Durability of resin–dentin bonds to
water- vs. ethanol-saturated dentin. Journal of Dental
Research 2009;88:146–51.
35. Shin TP, Yao X, Huenergardt R, Walker MP, Wang Y.
Morphological and chemical characterization of bonding
hydrophobic adhesive to dentin using ethanol wet bonding
technique. Dental Materials 2009;25:1050–7.
36. Pazinatto FP, Marquezini L, Atta MT. Influence of
temperature on spreading velocity of simplified-step
Adhesive Systems. Journal of Esthetic and Restorative Dentistry
2006;18:38–45.
37. Garcia FC, Almeida JC, Osorio R, Carvalho RM, Toledano M.
Influence of drying time and temperature on bond strength
of contemporary adhesives to dentine. Journal of Dentistry
2009;37:315–20.
38. Van Landuyt KL, De Munck J, Snauwert J, Coutinho E,
Yoshida Y, Inoue S, et al. Monomer–solvent phase
separation in one-step self-etch adhesives. Journal of Dental
Research 2005;84:183–8.
39. Van Landuyt KL, Snauwert J, De Munck J, Coutinho E,
Poitevin A, Yoshida Y, et al. Origin of interfacial droplets
with one-step adhesives. Journal of Dental Research
2007;86:739–43.
40. Cassie ABD, Baxter S. Wettability of porous surfaces.
Transactions of the Faraday Society 1944;40:546–51.