Bonding of Resin Cements to Post Materials:

Influence of Surface Energy Characteristics

Erik Asmussena/Anne Peutzfeldtb/Alireza Sahafic

Purpose: 1) To determine the surface energy characteristics of three variously treated post materials and two resin
cements, and 2) to investigate if previously measured bond strengths between cements and treated posts could
be related to the surface energy characteristics of the posts and cements.

Materials and Methods: The post materials were those of ParaPost XH, ParaPost Fiber White, and Cerapost, and
the resin cements were ParaPost Cement and Panavia F. The post materials were surface treated by grinding, sand-
blasting, CoJet, or with Alloy Primer. Droplets of four reference liquids were placed on the surfaces and the contact
angles measured. On this basis the dispersive, acid, and base components of the surface free energy of the
materials were calculated. Then the thermodynamic work of adhesion between resin cements and treated post
surfaces was calculated, as well as its dispersive and polar components.

Results: It was found that the surface energy characteristics varied significantly between the investigated surfaces.
The previously measured bond strengths correlated statistically significantly (p < 0.02) to the dispersive compo-
nent of the work of adhesion between posts and cements (r = 0.53), to the dispersive component of the surface
free energy of the posts (r = 0.54), and to the contact angle determined with ethylene glycol as reference liquid
(r = –0.52), but not to other surface energy characteristics.

Conclusion: In spite of the significant correlations, the “explained” part of the variation in bond strength did not
surpass 30%. This means that factors other than surface energy characteristics of adherend and adhesive play a
role in determining the strength of the bond.

Key words: adhesion, contact angle, CoJet, titanium, resin composite, zirconia.

J Adhes Dent 2005; 7: 231–234. Submitted for publication: 27.04.04; accepted for publication: 02.12.04.

hen root canal posts are adhesively bonded to the
W dentin of the root canal by means of a resin cement,
the restored teeth have been found to be stronger
than teeth with posts cemented with zinc phosphate ce-
ment.10 In a recent study of the bonding of resin cements
to prefabricated posts, it was found that the strength of
the bond depended on the post material, the surface
a Professor, Department of Dental Materials, School of Dentistry, University of
Copenhagen, Copenhagen, Denmark.
b Associate Professor, Department of Dental Materials, School of Dentistry,
University of Copenhagen, Copenhagen, Denmark.
c Assistant Professor, Department of Dental Materials, School of Dentistry,
University of Copenhagen, Copenhagen, Denmark.
Reprint requests: Erik Asmussen, Department of Dental Materials, School of
Dentistry, 20 Nörre Alle, DK-2200 Copenhagen N, Denmark. Tel: +45-3532-
6580; Fax: +45-3532-6505. e-mail: ea@odont.ku.dk
treatment of the post, and the resin cement.12 Shear
bond strengths varied between 1 and 37 MPa, but only
qualitative arguments could be offered to explain the
large variation in measured bond strengths.12
The strength of the bond between two materials de-
pends on several factors, among which are the roughness
of the adherend and the ability of the adhesive to wet the
surface of the adherend. The wetting of the adherend by
a liquid may be quantified by measurements of contact
angle of a droplet of the liquid placed on the adherend.
However, the filler content precludes this approach with
resin cements as adhesive. Instead, the thermodynamic
work of adhesion, WA, between adherend and adhesive
may be determined.1-4 It was the purpose of the present
study 1) to determine the dispersive, acid, and base com-
ponents of the surface free energy of root canal posts
and resin cements used in a previous study12 and on this
basis estimate WA as well as the dispersive (WAd) and
polar (WAp) components of WA, and 2) to investigate if pre-

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Asmussen et al
viously measured bond strengths12 could be related to
the surface energy characteristics of posts and cements.
It was hypothesized that such relationships are present.
MATERIALS AND METHODS
The materials studied are described in detail in our previ-
ous study.12 The materials serving as adherends were a
titanium alloy (ParaPost XH, Coltène/Whaledent, Mah-
wah, NJ, USA), a fiber reinforced resin composite (Para-
Post Fiber White, Coltène/Whaledent), and a zirconium
dioxide ceramic (Gebr. Brasseler, Lemgo, Germany). The
three materials were received from the respective manu-
facturers as rectangular plates (titanium alloy and fiber
reinforced composite; 10 mm x 10 mm x 1 mm) or as
disks (zirconium dioxide; diameter = 10 mm, h = 1 mm).
The materials serving as adhesives were two resin ce-
ments (ParaPost Cement, Coltène/Whaledent; and Pana-
via F, Kuraray, Osaka, Japan). The resin cements were
mixed, placed in cylindrical brass molds (diameter =
10 mm; h = 1 mm) covered on both sides with transpar-
ent matrices, and photocured for 40 s by means of a
curing unit (XL3000, 3M ESPE, Seefeld, Germany).
The adherend surfaces were treated with a selected
number of the surface treatments previously described in
detail:12 grinding on carborundum paper #220, grinding
on paper #220 followed by sandblasting with alumina
50 µm, grinding on paper #220 followed by CoJet treat-
ment and application of silane (3M ESPE), and, in the
case of the titanium alloy, grinding on paper #220 fol-
lowed by treatment with Alloy Primer (Kuraray). The sand-
blasting and the CoJet treatment were carried out at 4 bar
for ca 10 s at a distance of about 20 mm. The Alloy
Primer was applied in several coats to ensure complete
coverage of the surface. The surfaces of the adhesive
resin cements were investigated as they appeared after
removal of the matrices without any further surface treat-
ment. This procedure is based on the fact that such a
surface is composed exclusively of resin polymer without
involvement of filler particles.
The contact angles on the surfaces described above of
each of four test liquids with known surface energy
parameters5 were then determined. The four liquids were
water, glycerol, ethylene glycol, and α-bromo naphtalene.
The apparatus used (DAT, Fibro System, Hägersten, Swe-
den) was fitted with a video camera, enabling automatic
measurements of the contact angles. For each liquid, the
equilibrium contact angle was measured at ambient room
temperature on 10 specimens. The surface energy
characteristics of the solids were then determined by use
of the fundamental concepts of wetting6 as follows. In
Young-Dupré’s equation WA = γl · (1 + cosΘ), WA is the
thermodynamic work of adhesion between a solid surface
(subscript s) and a liquid (subscript l), γl is the surface
tension of the liquid, and Θ is the contact angle of a
droplet of the liquid placed on the solid. Alternatively, WA
may be expressed as WA = 2 · (γsd · γld)½ + 2 · (γs+ · γl–)½
+ 2 · (γs– · γl+)½, where γ refers to the surface free energy,
232
and the superscripts d, +, and – refer to the dispersive,
acid, and base components of γ, respectively.13 By deter-
mination of Θ with the four test liquids and by use of the
two expressions of WA, four equations can be set up for
each of the solid surfaces.1 By means of the method of
least squares, (γsd)½, (γs+)½, and (γs–)½ were calculated
from these four equations.
Assuming that (γsd)½, (γs+)½, and (γs–)½ calculated for
the two resin cements in the polymerized state is about
the same as (γld)½, (γl+)½, and (γl–)½ for the monomers of
the uncured cements, an estimate of WA for each combi-
nation of treated post and resin cement was calculated by
means of the formula given above. Further, the dispersive
component of the work of adhesion WAd was calculated
as 2 · (γsd · γld)½, and the polar component of the work
of adhesion, WAp, was calculated as 2 · (γs+ · γl–)½ + 2 ·
(γs– · γl+)½.7,9
Statistical Analysis
Previously obtained bond strength values12 were correlat-
ed to the surface energy characteristics of adherend and
adhesive by means of multidimensional regression analy-
ses.8 The preset level of statistical significance was
α = 0.05.
RESULTS
The results of the contact angle determinations are listed
in Table 1, and the calculated surface energy characteris-
tics of the variously treated surfaces are listed in Table 2.
Table 2 also lists WAd together with the bond strengths
obtained earlier with the respective surfaces and ce-
ments.12 The statistical analyses showed a significant
influence of WAd (p < 0.02; r = 0.53), of (γsd)½ (p < 0.02;
r = 0.54), and of the contact angle measured with ethyl-
ene glycol on the bond strength (p < 0.02; r = –0.52). All
other correlations were not statistically significant.
DISCUSSION
The relationships established in the foregoing were,
although significant, rather weak. Indeed, a coefficient of
correlation of r = 0.54 indicates that only about r2 = 29%
of the total variation can be “explained” by the variable in
question. It was also found that the differences in bond
strength obtained with the two resin cements applied to
the same surface could only be linked to the surface
energy characteristics of the cements in a way that did
not deviate from a description relying solely on the
surface energy characteristics of the adherend surfaces
(WAd vs (γsd)½). There may be several explanations for
these findings.
The thermodynamic work of adhesion, WA, is a mea-
sure of the energy required to separate two materials that
have been brought into intimate contact. On the other
hand, bond strength measurements involve the determi-
nation of the stress necessary to break the bond between
The Journal of Adhesive Dentistry
 Asmussen et al

Table 1 Contact angle (degrees) of droplets of the four reference liquids placed on the investigated surfaces (mean values ± SD; n = 10)

Surface Water Glycerol Ethylene glycol α-Br naphtalene

XH #220 47.3 ± 5.2 33.6 ± 4.4 21.9 ± 3.5 12.7 ± 2.4

XH Al2O3 17.3 ± 1.9 13.9 ± 1.7 13.0 ± 0.7 7.8 ± 0.5
XH CoJet 56.7 ± 3.4 59.8 ± 5.4 13.4 ± 1.1 10.5 ± 0.6
XH AP 58.3 ± 4.1 52.2 ± 6.8 27.2 ± 4.4 15.6 ± 4.7

FW #220 68.3 ± 2.1 53.4 ± 2.7 14.5 ± 1.0 8.5 ± 2.2

FW Al2O3 81.9 ± 4.2 65.5 ± 3.9 20.4 ± 4.5 14.8 ± 0.9
FW CoJet 56.4 ± 8.7 53.4 ± 5.3 15.2 ± 2.0 13.1 ± 1.8

CP #220 70.3 ± 7.7 71.3 ± 5.5 51.8 ± 4.0 27.4 ± 4.4

CP Al2O3 25.5 ± 3.8 26.8 ± 5.0 18.0 ± 5.2 8.5 ± 0.7
CP CoJet 40.3 ± 4.8 41.8 ± 3.0 14.0 ± 0.8 9.0 ± 1.2

PP CEM 73.6 ± 3.7 62.8 ± 1.9 38.7 ± 3.5 12.5 ± 2.0

PAN F 70.2 ± 2.8 67.0 ± 2.1 50.7 ± 4.1 11.8 ± 1.9

The surfaces were titanium alloy (XH), glass fiber composite (FW), and zirconium dioxide (CP), and the resin cements ParaPost Cement (PP CEM) and Panavia F (PAN F). The post materials
were surface treated by grinding (#220), sandblasting (Al2O3), CoJet (CoJet), or application of Alloy Primer (AP).

Table 2 Surface energy characteristics of the surface-treated post materials and of the resin cements (γs in mJ/m2)

Surface (γsd)½ (γs+)½ (γs–)½ WAd (mJ/m2) Bond strength* (MPa)

PP CEM PAN F PP CEM PAN F

XH #220 6.50 1.16 4.88 85.6 85.3 2.2 12.8

XH Al2O3 6.50 1.03 6.97 85.7 85.3 15.7 29.4
XH CoJet 6.77 0.14 4.91 89.3 88.9 36.7 21.8
XH AP 6.53 0.60 4.36 86.0 85.7 20.5 17.4

FW #220 6.66 1.00 2.73 87.7 87.4 14.2 10.8

FW Al2O3 6.65 0.86 1.28 87.6 87.3 26.7 19.3
FW CoJet 6.59 0.47 4.83 86.9 86.6 29.4 15.0

CP #220 6.28 –0.38 4.20 82.9 82.5 1.2 10.9

CP Al2O3 6.52 0.80 6.83 85.9 85.5 6.7 27.2
CP CoJet 6.58 0.58 6.01 86.7 86.4 32.3 27.9

PP CEM 6.59 0.39 2.77

PAN F 6.56 –0.29 3.86

Regarding (γsd)½, (γs+)½, and (γs-)½, see text. WA is the thermodynamic work of adhesion between the resin cements (PP CEM and PAN F) and the post materials titanium alloy (XH), glass
fiber composite (FW), and zirconium dioxide (CP). The post materials were surface treated by grinding (#220), by sandblasting (Al2O3), by CoJet (CoJet), or by application of Alloy Primer
(AP). *The bond strength data are taken from a previous publication.12

the two materials. Thus, the thermodynamic work of
adhesion and bond strength are two distinct expressions
of bonding that are less tightly related than may be the
case with work of adhesion and mechanical (adherence)
energy of bonded surfaces.1,2
In the present work, the calculation of WA, WAd, and
WAp was based on a number of assumptions that may
only be partly valid, one being the very expressions
utilized in the calculations. Another assumption is that
the materials of the plates and disks used in the present

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Asmussen et al
investigation are identical with those of the posts used to
measure bond strengths. A third assumption is that the
polymer of the resin cements has about the same surface
energy characteristics as the monomer from which it is
formed. It is conceivable that as the adhesive is applied
to the solid surface in the liquid state, groups or certain
segments of the monomer with special affinity to the
surface will form part of the boundary zone, while such
groups or segments may preferably be attached to each
other in the absence of the solid. This means that the
polymerized surface of the adhesives on which the
surface energy characteristics were determined may be
different from the polymer that forms the interface
between adherend and polymerized adhesive. The finding
that bond strengths correlated with significance to WAd,
but not to WA or WAp, may support this speculation, be-
cause it may be expected that groups with (Lewis) acid or
base properties will participate in adhesion but also be
likely to interact with each other within the polymer.
Further, when bond strengths are measured, the elas-
tic and plastic properties of the adhesive enter into the
measurements in an unknown manner which may depend
on the level of stress put on the bond. Thus, depending
on the quality of the bond, the two adhesives may behave
differently, as their plasticity may be more or less solicit-
ed during bond strength testing.
Another confounding factor is roughness, since rough-
ness may influence bond strength values.11 The different
surface treatments roughen the surfaces to different but
unknown degrees. Measurements of contact angles in-
corporate the notion of roughness, in that higher rough-
ness gives smaller contact angles,14 but the relation to
bond strength values is not always straightforward.11
The finding that the contact angle obtained with ethyl-
ene glycol was significantly (negatively) correlated with
bond strength may indicate that this liquid has surface
energy characteristics that are similar to those of the two
resin cement monomers. On the other hand, water and
glycerol may be too polar and α-bromo naphtalene not
sufficiently polar to resemble the methacrylate mono-
mers of the resin cements.
CONCLUSION
The hypothesis mentioned in the introduction must be
accepted, although the relationships established were
not particularly strong. This means, as discussed above,
that factors other than surface energy characteristics of
adherend and adhesive are at play and need to be identi-
fied to improve the understanding of the mechanisms
234
involved in bonding of resin cements to root canal posts.
Among such other factors may be the ability of the phos-
phate-containing monomer of Panavia F to associate with
surface oxides of ceramics and metals, and a possible
bonding of resin cements to the organic matrix of fiber
posts.
ACKNOWLEDGMENTS
Thanks are due the following persons for providing material for the investiga-
tion: Ms. Inge Lundgaard, 3M ESPE for the CoJet Sand; Mr. Manuel Oertel,
Gebr. Brasseler for the Cerapost material; and Mr. Jochen Bohnes, Coltène/
Whaledent for the ParaPost XH and ParaPost Fiber White material.
REFERENCES
1. Asmussen E, Attal J-P, Degrange M. Factors affecting the energy of adher-
ence of experimental cements bonded to a nickel-chromium alloy. J Dent
Res 1995;74:715-720.
2. Asmussen E, Attal J-P, Degrange M. Bonding of resin cements to a metal
substrate: influence of pretreatment on the adherence energy. Eur J Oral
Sci 1996;104:595-599.
3. Asmussen E, Peutzfeldt A. The role of maleic anhydride in adhesive resin
cements. Eur J Oral Sci 1998;106:882-886.
4. Attal J-P, Asmussen E, Degrange M. Effect of surface treatment on the free
surface energy of dentin. Dent Mater 1994;10:259-264.
5. Constanzo PM, Giese RF, van OSS CJ. Determination of the acid-base char-
acteristics of clay mineral surfaces by contact angle measurements –
implications for the adsorption of organic solutes from aqueous media. J
Adhesion Sci Technol 1990;4:267-275.
6. Fowkes FM. Quantitative characterisation of the acid-base properties of
solvents, polymers, and inorganic surfaces. J Adhesion Sci Technol 1990;
4:669-691.
7. Good RJ. Contact angle, wetting and adhesion: a critical review. J Adhesion
Sci Technol 1992;6:1269-1301.
8. Hald A. Statistical theory with engineering applications. New York: John
Wiley & Sons, 1952.
9. Lee L-H. Roles of molecular interactions in adhesion, adsorption, contact
angle and wettability. J Adhesion Sci Technol 1993;7:583-634.
10. Mendoza DB, Eakle WS, Kahl EA, Ho R. Root reinforcement with a
resin-bonded preformed post. J Prosthet Dent 1997;78:10-14.
11. Peutzfeldt A, Asmussen E. Silicoating: evaluation of a new method of
bonding composite resin to metal. Scand J Dent Res 1988;96:171-176.
12. Sahafi A, Peutzfeldt A, Asmussen E, Gotfredsen K. Bond strength of resin
cement to dentin and to surface-treated posts of titanium alloy, glass fiber,
and zirconia. J Adhes Dent 2003;5:153-162.
13. Van Oss CJ, Good Rj, Chaudhury MK. The role of Van der Waals forces
and hydrogen bonds in “hydrophobic interactions” between biopolymers
and low energy surfaces. J Coll Interf Sci 1986;111:378-390.
14. Yekta-Fard Y, Ponter AB. Factors affecting the wettability of polymer
surfaces. J Adhesion Sci Technol 1992;6:253-277.
Clinical relevance: A strong bond between post and
resin cement may be obtained in several ways, but a
comprehensive understanding of bonding factors on
a physicochemical basis is still lacking.
The Journal of Adhesive Dentistry