Dental Materials (2005) 21, 272–277

www.intl.elsevierhealth.com/journals/dema

The surface free energy of dental

gold-based materials
Shawn D. Knorra, Edward C. Combea,*, Larry F. Wolffb, James S. Hodgesc

a
Minnesota Dental Research Center for Biomaterials and Biomechanics, University of Minnesota,
School of Dentistry, 16-212 Moos Tower, 515 Delaware Street SE, Minneapolis, MN 55455, USA
b
Department of Preventive Sciences, University of Minnesota School of Dentistry, Minneapolis, MN, USA
c
University of Minnesota Division of Biostatistics and School of Dentistry, Minneapolis, MN, USA

KEYWORDS Summary Objective: A gold composite material (Capteke) has been developed which
Surface free energy; Gold is claimed to resist plaque deposition. This study’s aim was to compare the surface
free energy (SFE) of this composite material with that of a type III casting gold.
Methods: Contact angle measurements, using the Wilhelmy technique, were made
on four bar-shaped samples of each material, using five test liquids (diiodomethane,
ethylene glycol, formamide, glycerol and water) and four measurements per sample
per liquid. For each material, the dispersive, Lewis acid and Lewis base components of
S ; gS ; respectively) were estimated by least squares analysis and also by a
SFE (gDS , gþ 2

Bayesian method.
Results: The gold composite material and the type III casting gold did not differ
significantly in their gDS values (95% confidence interval for gold composite minus type
III gold, 25.0 to þ 2.7). Both materials had low gþ S values in common with most solids.
The gold composite had a significantly lower Lewis base component of SFE than the
type III gold-8.4 mN/m for the former material compared to 19.1 mN/m for the latter
(95% confidence interval for gold composite minus type III gold, 2 16.4 to 24.9). The
difference between materials could be related to the lack of non-precious metals and
the structure of the gold composite material.
Conclusions: It is hypothesized that difference in g2S components of SFE may be an
important parameter in predicting bacterial adhesion and plaque resistance. Methods
that only determine SFE as a single parameter may be unable to differentiate
adequately between dental restorative materials.
Q 2004 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Introduction identified bacteria, only a limited number have

The adhesion of bacteria to enamel and tooth
restorative materials can be responsible for caries,
gingivitis, and periodontal disease. Upwards of 400
different bacterial species are now considered
indigenous to the human oral cavity [1]. Of these
*Corresponding author. Tel.: þ1-612-624-0190; fax: þ 1-612-
626-1484.
E-mail address: combe001@umn.edu
been associated with dental caries or periodontal
diseases. It is essential to reduce the pathogenic
bacterial flora to prevent caries and periodontal
disease. One way to achieve this is to use dental
restorations resistant to bacterial accumulation. To
develop these restorations, it is essential to under-
stand both the bacterial ecology of the mouth and
the factors contributing to bacterial adhesion.
Various factors have been identified as contri-
buting toward bacterial adhesion. Essentially, each

0109-5641/$ - see front matter Q 2004 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.dental.2004.06.002
Surface free energy of dental gold
component of the adhesion process is related to the
surface characteristics of the interacting substra-
tum and bacteria. Consequently, the physicochem-
ical surface characteristics of both bacteria and
dental surfaces have been described and correlated
with bacterial adhesion. Physicochemical surface
components found to be involved with bacterial
adhesion are surface charge (zeta potential), [2,3],
hydrophobicity/hydrophilicity, [4,5], surface free
energy (SFE) [6] and surface roughness [7,8].
Physicochemical surface components interact
with the substratum and bacteria through a variety
of forces. Models of the bacterial adhesion process
divide this interaction into three phases. These are
bacterial transport to a surface, initial reversible
adhesion, and irreversible adhesion. As bacteria
first approach a surface, van der Waals forces and
electrostatic forces bring the bacterium and sur-
face in close contact. Short-range forces such as
hydrogen bonding and ion pair formation then come
into play, adhering the bacterium irreversibly.
Important in short-range interactions are
specific receptor interactions between bacteria
and the acquired salivary pellicle. Bacterial recep-
tors are species specific and even strain specific
[9]. These bacterial receptors, called adhesins, are
extracellular proteinaceous (lectin-like) com-
ponents that bind to saccharide and proteinaceous
receptors of the pellicle-covered tooth [10]. The
salivary pellicle, on the other hand, provides the
saccharide or proteinaceous receptors. Within
seconds to minutes after exposure to saliva,
teeth and dental restoratives are covered by the
salivary pellicle, an amorphous protein-rich
organic film with no discernable, organized pattern
[11]. After 2 h, equilibrium between adsorption
and desorption of salivary components occurs [12]
and the pellicle stabilizes at a thickness of around
0.5 – 0.73 mm [13].
Salivary pellicle is also thought to be involved in
the protection of oral tissues [13]. Studies have
found bacterial adhesion decreases after pellicle
deposition on both oral tissues and restoratives,
[14,15] while preferentially allowing the adherence
of harmless bacterial species as opposed to virulent
ones such as S. mutans [14,16] Also, only certain
species of bacteria, through specific and lectin-like
interactions, can effectively adhere to and pro-
liferate on the pellicle and oral tissues. Species
known to be initial colonizers are overwhelmingly
streptococci, which constitute 47 – 85% of the
cultivable cells found during the first 4 h after
tooth cleaning [17]. In particular, Streptococcus
sanguis, Streptococcus mitis biovar 1, and
Streptococcus oralis have been found to be initial
colonizers [18]. Actinomyces vicosus also attaches
273
to and colonizes tooth surfaces by absorbing
pellicle proline rich proteins (PRPs) and statherin
[9]. Subsequent attachment by other bacterial
species, such as S. mutans, P. gingivalis and
A. actinomycetemcomitans, occurs through coag-
gregation reactions. Thus, considering the protec-
tive qualities of the salivary pellicle as well as its
diverse composition, manipulating pellicle charac-
teristics and composition on tooth and restorative
surfaces is of significant importance in reducing
virulent bacteria and preventing initial attachment.
Because the salivary pellicle is so important in
adhesion, it has been questioned whether the
physicochemical properties of the underlying den-
tal substrata still influence bacterial adhesion. This
brings the importance of the dental substratum into
further doubt; various studies found that the SFE
and zeta potential of a dental surface are altered
with pellicle formation [3,19– 21]. Despite these
findings, various authors have reported a sustaining
influence of the underlying substratum on bacterial
adherence [3,14,15,21,22]. Support comes from
findings that the protein composition of pellicles
varies from surface to surface, depending on the
underlying substratum’s chemical properties and
SFE [23,24]. Furthermore, in shear force tests
observing levels of bacterial adhesion, detachment
of bacteria was linked to cohesive failures in the
pellicle, which is substratum surface-dependent
[8]. Also, numerous in vivo and in vitro studies have
found that teeth and dental restoratives, both
coated and uncoated with pellicle, are subject to
differences in bacterial adherence and accumu-
lation. Consequently, pellicle formation and bac-
terial adherence are highly dependent upon the
reactivity of the surface, which leaves the necessity
for precise measurements of the physicochemical
characteristics of dental surfaces.
One parameter for describing the reactivity of a
surface is SFE. This is defined as the work required
to increase the area of a substance by 1 cm2 [25].
The concept of SFE is sometimes misunderstood. It
must be emphasized that the SFE of a solid is not a
measure of its reaction with any one liquid. It is a
unique, solid-defined parameter, measured through
its interactions with multiple liquids.
It is now possible to measure SFE in terms of its
component parts, namely the dispersive, Lewis acid
and Lewis base components (gDS ; gþ S ; gS ; respect-
2
ively), by the LWAB (Lifschitz Van der Waals –Acid
Base) method [26,27]. This work was undertaken
with the particular aim of measuring the SFE, and
its component factors, of a gold composite material
(Capteke) which is claimed to be plaque resistant,
and to compare it with a typical type III casting gold
274 S.D. Knorr et al.

† Estimation of the SFE and its component parts by

Table 1 cos u values for gold composite and Type III gold
alloys. least squares analysis and by Bayesian methods.

Test liquid cos u for gold cos u for type III

composite* gold*
Results
Water 0.260 (0.036) 0.403 (0.073)
Glycerol 0.337 (0.082) 0.328 (0.078) The average cos u values for both gold systems are
Formamide 0.690 (0.027) 0.628 (0.066) shown in Table 1. For the gold composite material
Diiodomethane 0.544 (0.049) 0.604 (0.093) the cos u values ranged from 0.260 (SD ¼ 0.036) for
Ethylene glycol 0.779 (0.055) 0.690 (0.049)
water to 0.779 (SD ¼ 0.055) for ethylene glycol.
*Standard deviations in parentheses. The cos u values for the type III alloy ranged from
0.403 (SD ¼ 0.073) for water to 0.690 (SD ¼ 0.049)
alloy which is traditionally used in restorative for ethylene glycol.
materials. The LWAB data for the gold composite and type
III gold samples, based on the Bayesian method, are
given in Table 2. The dispersive (gDS ) and Lewis base
(g 2
S ) components of the gold composite samples are
Materials and methods less than that of the type III gold samples, while the
total polar (gPS ) and Lewis acid (gþ
S ) components for
Materials the four composite samples are greater than those
of the type III gold samples. Differences between
Four polished bar shaped specimens of each of two the two materials were tested by computing 95%
dental gold systems, a composite gold system confidence intervals for the difference; if zero was
(Capteke) and conventional type III gold alloy, excluded from the 95% confidence interval, the
were supplied by Precious Chemical Ltd., Longwood materials differed significantly ðp , 0:05Þ:
FL, USA. LWAB data for both gold systems, based on least
squares analysis, are given in Table 3. Similar to the
Bayesian method, the gold composite samples had
Methods lower dispersive (gDS ) and Lewis base (g2 S ) com-
ponents, but had larger total polar (gPS ) and Lewis
SFE and its component parts (gDS ; gþ 2
S , gS ) were acid (gþ S ) components compared to the type III gold
measured following a previously described protocol alloy. Total SFEs for the composite samples and
[28] using the LWAB method This involved: type III gold samples were 37.31 and 36.52 mN/m,
respectively. Using a simple permutation test
† Measuring specimen width and thickness. comparing the average of the two groups (n ¼ 4
† Cleaning the specimens rigorously using an samples per group), the Lewis acid ðp ¼ 0:029Þ and
ultrasonic regime. Lewis base ðp ¼ 0:029Þ components were found to
† Measuring advancing contact angles (u) by the be significantly different for the two materials.
Wilhelmy method using a Cahn Dynamic Contact
Analyzer (DCA 322; Thermo Cahn, Madison, WI)
with five test liquids (diiodomethane, ethylene Discussion
glycol, formamide, glycerol and water). The
contact angle of each specimen was measured Justification for analyzing the two gold-based
four times in each of the five liquids. materials is based on a recent clinical study carried

Table 2 Lifshitz-van der Waals acid base (LWAB) data, based on the Bayesian method.

SFE component Gold composite material Type III gold

Estimate 95% confidence Estimate 95% confidence

(mN/m) interval (mN/m) (mN/m) interval (mN/m)

gDS (dispersive) 31.8 29.3– 35.1 33.1 30.7–36.0

gPS (polar) 6.3* 5.0– 7.6 3.4* 1.4–5.4
gþS (Lewis acid) 1.2 0.66– 1.9 0.16 0.024–0.44
g2S (Lewis base) 8.4* 5.5– 12.0 19.1* 14.6–24.0

*Significantly different ðp , 0:05Þ based on the Bayesian method.

Surface free energy of dental gold
Table 3 Lifshitz-van der Waals acid base (LWAB) data from least squares analysis.
SFE component Gold composite estimate (mN/m)
gDS (dispersive) 31.3 (1.43)
gPS (polar) 6.02 (0.68)
gþS (Lewis acid) 1.18 (0.21)*
g2S (Lewis base) 7.77 (1.08)*
gTOT
S (total) 37.3 (1.65)
*For a permutation test with two groups of four samples each, this is the smallest possible p-value and the only one less than 0.05.
out by Goodson et al. [29]. This study found that the
gold composite material reduced total bacterial
numbers by 71% when compared to the normal
tooth dentition. However, they did not compare
this material to other dental gold systems or to any
other dental restorative material. Therefore, the
significance of such a finding by these investigators
was limited in scope.
The LWAB calculations found similarities in the
dispersive components for both materials. These
results were to be expected due to their high gold
content. The total polar component of SFE was
found to be different by the Bayesian method and
almost different by the least squares method. The
Lewis base components were found to be signifi-
cantly different ðp , 0:05Þ using both the Bayesian
and least squares methods. Lewis acid components
were found to be statistically significant ðp ¼ 0:029Þ
after applying the permutation test to the least
squares data, but were not found to be significantly
different by the Bayesian method. Because the
acidic components of the surfaces tested were so
small compared to their base components, the
margin of error in calculating the Lewis acid
component was considered to be rather high.
Differences in the Lewis base component of the
SFEs may be related to a lack of non-precious
metals and to the structure of the gold composite
samples. To attain the composite, two materials
are involved in casting, namely Captek P and Captek
G. Captek P and G are 0.3 mm elastic sheets that
are manually modeled to form crown copings over
refractory dies. Captek P is not similar to a
traditional alloy, but is composed of particles of
noble metals (39% Au, 29% Pt, 30% Pd, and 3% Ag). It
is first processed in a porcelain furnace at 1076 8C
for 4 min. After baking, Captek P is characterized
by a capillary network. Then, Captek G (composed
of 98% Au and 2% Ag) is manually molded over the
capillary network of Captek P and fired as men-
tioned previously. After processing, a composite
precious metal structure remains, with Captek G
infiltrating and surrounding a distinct capillary
network of Captek P. When compared to conven-
tional gold alloy, the composite nature of Capteke
275
Type III gold estimate (mN/m) p value
33.5 (4.02) 0.54
3.01 (2.08) 0.23
0.168 (0.117)* 0.029*
19.3 (3.47)* 0.029*
36.5 (2.70) 0.11
provides increased strength, while at the same time
retaining the softer element of Captek G. In
addition, electrochemical corrosion resistance
tests indicate that the composite behaves
similarly to pure gold; thus, it is less vulnerable to
corrosion [30].
Conventional gold alloys used for crowns and
bridges are type III golds. These alloys are not
composite in nature and have consistent compo-
sition from surface to center, being composed of
approximately 62 – 78% Au, 8 –26% Ag, 8 –11% Cu,
0 – 3% Pt, 2 – 4% Pd, and 1% Zn [31]. Despite having a
high gold concentration, type III gold alloys are
composed of a relatively high percentage of silver
and copper at their surface compared to the
precious metal composite material.
The LWAB approach, in contrast to other
approaches for measuring SFE, gives values for the
acid and base components of a solid, which provides
more detailed information on surface reactivity. It
is noteworthy that the LWAB approach found a
statistical difference between the two materials
that would not have been found using other
methods. Considering the different chemical com-
positions of the two gold systems, a difference in
SFEs would be expected. The LWAB method was
found to be sensitive to this difference.
Currently, little work has been reported using
the LWAB method. In particular, studies have not
correlated bacterial adherence with either the
Lewis acid or base components of the SFE of a
solid. Considering that solids tend to have low Lewis
acid components and are more basic on their
surfaces [32], it could be hypothesized that the
Lewis base component of a solid plays an important
role in the ability of bacteria to adhere to the
solid’s surface. Moreover, because polar inter-
actions tend to create stronger bonds and most
solids have relatively low Lewis acid components, a
solid with a high Lewis base component, such as
type III gold alloy, may attract bacteria more than a
solid with a low Lewis base component, such as the
composite gold material.
Studies have supported the observation that
bacteria adhere more readily to a higher energy
276
substrate. In an in vivo study observing bacterial
adherence to four dental restoratives with different
SFEs, Quirynen et al. [6]. found that on surfaces
with low SFE, significantly less plaque accumulation
was observed. The reasons cited by the investi-
gators were a lower binding force between bacteria
and surfaces of lower SFE, and the nature of the
pellicle adsorbed by the dental material.
Presumably, lower energy pellicle constituents
would adhere preferably to lower energy substrata.
Bacteria, particularly colonizers such as S. sanguis,
S. mitis biovar 1, S. oralis, and A. vicosus,
selectively adhere to the pellicle through specific
receptors and colonize a dental surface. Altering
the amount and type of receptors as well as the
overall energy of the substratum influences the
amount and species of bacteria that can adhere to
it. Therefore, future in vitro or in vivo studies on
bacterial adherence to a solid should assess the
composition of an absorbed pellicle and its SFE.
Also, the success of bacterial colonizers associated
with dental disease, such as S. mutans and
P. gingivalis, should be further explored in regards
to their relationship with various restorative
materials that differ in SFE.
Conclusions
Using the LWAB method, additional information
relevant to surface reactivity is provided that other
approaches cannot provide. In particular, the LWAB
method was able to determine that the composite
gold had a significantly lower Lewis base component
than a type III gold alloy, while other components of
their SFEs were similar. Due to solids being over-
whelmingly basic on their surfaces, it is hypoth-
esized that the Lewis base component is critical in
predicting bacterial adherence. It was also con-
cluded that methods for the determination of SFE as
a single parameter may fail to detect important
differences between materials.
Acknowledgements
The authors are grateful to the Captek Division of
Precious Chemicals Ltd, FL, for support of this
research, including the preparation and supply of
the specimens. This research was supported by
NIDCR grant P30 DE09737 (Dr Hodges) and by the
Minnesota Dental Research Center for Biomaterials
and Biomechanics.
S.D. Knorr et al.
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