The promotion of adhesion by the infiltration of

monomers into tooth substrates

Nobuo Nakabayashi, Katsunori Kojima, and Eiichi Masuhara

Institute for Medical and Dcntal Engineering, Tokyo Medical and Dental University, Kanda
Surugadai, Chiyoda-ku, Tokyo 101, japan

The effectiveness of 4-methacryloxyethyl trated monomers polymerized in situ and

trimellitate anhydride (4-META) on the
adhesion of an acrylic rod with etched den-
tine and enamel was studied. Etching of
tooth substrates with a 10% citric acid-3%
ferric chloride solution prior to the adhesion
proved effective. Monomers with both
hydrophobic and hydrophilic groups like
4-META promoted the infiltration of
monomers into the hard tissue. The infil-
good adhesion with the tooth substrates took
place. The tensile adhesive strength was 18
MPa on the etched dentine. Scanning
electron microscopic studies suggested that
the monomers possess affinity with the hard
tissue. The good adhesion was not pro-
vided by the interlocking at the tubules as
had been considered previously.

INTRODUCTION
Several adhesives that bond with etched enamel through an interlocking
mechanism and two types of adhesives that bond to dentine have been suc-
cessful. Of the dentine adhesives, the first is the tri-n-butyl borane (TBB)-
initiated graft polymerization of methyl methacrylate (MMA) onto dentine
collagen.* The other is methacryloxyethyl phenyl phosphoric acid (phenyl-P)
which may penetrate and bond to dentine on the molecular level.2 The 4-
methacryloxyethyl trimellitate anhydride (4-META) monomer has also been
shown to promote adhesion with tooth substrate^.^ We have previously
suggested that monomers containing both hydrophobic and hydrophilic
groups promote adhesion when polymerized to hard tissue or tooth sub-
strates.2.3
The effectiveness of cleansers and mordants in providing adhesion has been
suggested, but their use with surface active monomers4 does not produce
maximum adhesive strength with dentine. The application of an etchant such
as phosphoric acid is surely important in the case of adhesion to enamel and
it has been recommended for bonding to dentine.5
Nordenvall and Brannstrom have described the resin impregnation of

Journal of Biomedical Materials Research, Vol. 16,265-273 (1982)

0 1982 John Wiley & Sons, Inc. CCC 0021-9304/ 82/030265-09$01.90
266 NAKABAYASHI, KOJIMA, AND MASUHARA

dentine tubules and have suggested several new ideas or concepts regarding
the promotion of the impregnation.6 The presence of resin tags in dentine
tubules6t7have been shown. In these cases, however, a space or void is present
between the resin tag and the wall of the tubule. To date, convincing evidence
of monomer infiltration into intra- and intertubular dentine has not been
presented. Adhesion with dentine due to interlocking by the resin tags in
tubules may be weaker than adhesion with the dentine itself due to poly-
merized monomers which have infiltrated the dentine. During our study,
the importance of monomer penetration into the tooth substrate was recog-
nized to clarify the adhesion mechanisms of the HNPM,8 phenyl-P,2 and 4-
META3 monomers to hard tissue.

EXPERIMENTAL

Preparation of 4-META (ref. 3)

4-META was prepared by the condensation of 2-hydroxyethyl methacrylate

and trimellitic anhydride chloride in the presence of pyridine to remove hy-
drogen chloride. The yield was 52% after recrystallization from dry benzene,
mp 95.0 "C-95.8 "C.

Adhesion

Fresh bovine and human dentine and enamel specimens were ground with
emery papers up to #800 to create a consistent adhesive surface. The dentine
or enamel specimen was covered with a tape having a round hole of 5.0 mm
diam to create a constant area of adhesion and then etched with an aqueous
mixture of 1%citric acid-1% ferric chloride ( 1 : l ) or 10% citric acid-3% ferric
chloride (10:3) for 30 s and washed with water. Monomers (0.1g), MMA alone
(I), or 5% 4-META in MMA (11), and partially oxidized TBB8 (TBB-0, 0.005 g)
were well stirred and then mixed with 0.1 g of poly(methy1 methacrylate)
(PMMA) powder to prepare the cement. An acrylic rod 5.0 mm in diam at its
lower end was fixed perpendicularly to the etched dentine or enamel surface,
with the cement paste. The joined specimens were allowed to stand for 30
min at room temperature, immersed in water at 37 "C for one day, and then
positioned in a tensile testing machine.* The tensile adhesive strength was
measured at a crosshead speed of 2.0 mm / min.
The joined specimens were alternately immersed in two water baths, one
maintained at 4 "C f 1 " C and the other at 60 "C f 2 "C for a percolation test
to check the adhesive stability. Joined specimens were alternately immersed
in each bath for 60 s, and the cycling between baths was repeated 60 times.
* Autograph DDS-500, Shimazu Mfg. Co., Kyoto, Japan.
INFILTRATION OF MONOMERS INTO TOOTH SUBSTRATES 267

RESULTS

Tensile adhesive strength

Tensile adhesive strength between human or bovine dentine and PMMA
with I or I1 is summarized in Tables I and 11.

Scanning electron microscopic observation

A ground human dentine surface etched with an aqueous solution of 1:l
or of 10:3 was observed by a SEMt (Figs. 1 and 2, respectively). Specimens for
SEM were prepared in the usual manner. A fracture surface parallel to the
tubules of human dentine which has been ground vertically to the tubules and
etched with 10:3, a perpendicularly fractured surface of the joint between I1
and the etched human dentine, and a tensile fracture surface of the joint on
the dentine side are shown in Figures 3,4, and 5, respectively. Resin tags of
I1 cured in the dentine tubules were exposed by decalcification of the human
dentine with 6N HC1 for 48 h and are shown in Figure 6. Partially deminer-
alized fracture surfaces and parallel to the tubules of the etched human dentine,
are shown in Figures 7 and 8, respectively. The specimen in Figure 7 had

TABLE I
Tensile Adhesive Strength between Human and Bovine Dentine and PMMA with I or I1
Adhesive Strength to Dentine (MPa)
Human Bovine
Monomer Etchanta 1:l 10:3 1:l 10:3
~ ~ ~

MMA +
10.9 4.3b +
10.7 1.7 +
12.1 4.4
(ref. 7)c (ref. 5) (ref. 3)
5%4-META +
13.4 2.2 +
17.5 5.3 +
16.3 0.2 +
18.1 3.2
in MMA (ref. 6) (ref. 5) (ref. 3) (ref. 4)
5%4-META +
13.9 4.4 +
15.1 5.3
in MMA (ref. 3) (ref. 5)
(after percolation)
a 4, standard deviation.
Etchant: 1:1, 1%citric acid-1% ferric chloride; 10:3; 10%citric acid-3% ferric chloride.
The numbers of specimens measured are in parentheses.

TABLE I1
Adhesive Bond Strength between PMMA and Pretreated Brushed or Ground Bovine
Enamel (MPa)
Etching solution for pretreatment
(conc, %) Enamel
Citric acid Ferric chloride Brushed Ground
1 1 8.8 f 1.Y (ref. 4)b 7.1 f 2.6 (ref. 5)
10 3 14.0 f 2.4 (ref. 5) 16.1 f 6.7c (ref. 4)
a f , standard deviation.
Numbers of specimens measured are in parentheses.
Fractured at dentine-enamel junction.
t Comtec CMS-501, Comtec, Tokyo, Japan
268 NAKABAYASHI, KOJIMA, AND MASUHARA

Figure 1. SEM picture of a ground human dentine surface etched with 1%

citric acid-1% ferric chloride (X2000).

adhesive applied to the etched surface, while the specimen in Figure 8 did
not.

DISCUSSION

The effectiveness of TBB-0 and 4-META on the adhesion between the

PMMA rod and the tooth substrates is shown in Tables I and 11. Considering
adhesion with the enamel, the solution of 1:l was not as effective in etching
the enamel surfaces as the 10:3 solution (Table 11). In the case of the brushed
enamel, the tensile strength was 1.6 times greater for the 10:3 solution. With
ground enamel, the tensile strength was 2.2 times greater when comparing
the two different etchants. Clinically, it is inconvenient to use two different
etchants for dentine and enamel, respectively, in the pretreatment prior to
cavity filling with an adhesive resin. Fortunately, the 10:3 solution is appli-
cable to both enamel and dentine while the 1:l solution provides adequate
cleaning only for dentine. Methyl methacrylate polymerized by benzoyl

Figure 2. SEM picture of a ground human dentine surface etched with 10%
citric acid-3% ferric chloride (X2000).
INFILTRATION O F MONOMERS INTO TOOTH SUBSTRATES 269

Figure 3. A surface fractured parallel to the tubules of human dentine

(X4000).

peroxide with N,N-dimethyl p-toluidine at room temperature does not usually

adhere to the etched dentine. On the other hand, the TBB-0-initiated graft
polymerization of methacrylates onto dentine collagen1 occurs easily at room
temperature. The stability of the adhesion after the previously described
temperature cycling and percolation was also superior.
In an effort to gain insight into the adhesion mechanism, we undertook a
scanning electron microscopic study to determine the efficiency of the various
etching solutions and the role of monomer penetration on the adhesion be-
tween PMMA and tooth substrates. Figure 1 shows ground human dentine
etched with the 1:1 solution. The surface became cleaner than the ground
surface of human dentine by the etching, but debris is still present in the
dentine tubules. Experiments have shown that this debris may not produce
an adverse effect on the adhesive strength. On the other hand, cleaning of
the debris has been very important to get good adhesion.*r6 A ground human
dentine surface etched with 10:3is shown in Figure 2. Extensive cleaning of
the dentine surface (Fig. 2) is not necessary for good adhesion as the data in

Figure 4. SEM picture of a fracture surface orthogonal to the joint surface

(X4000). The joint surface is at the top of the photograph (arrow),
270 NAKABAYASHI, KOJIMA, AND MASUHARA

Figure 5. SEM picture of a tensile fracture surface of the joint on the dentine
side (X2000).

Table I shows no large difference in the adhesive strengths of the surfaces

etched by either solution.
A fracture surface perpendicular to the tubules of human dentine which
has been ground vertically to the tubules and etched with 10:3 is shown in
Figure 3. Empty tubules and intra- and inter-tubula dentine are clearly ob-
served. The orifices of the tubules have been slightly enlarged by the etching.
Figure 4 shows a surface fractured parallel to the tubules of human dentine
which have been treated as described above and then adhered with I1 cement.
Cracks are not identified at the adhesive interface and, more importantly, no
spaces or voids are present between the resin tags and the tubular walls as have
been observed with other dental filling materials.6 Mushroom-shaped cracks
are seen on the tops of tubules and they are presumably formed by shrinkage
during the resin polymerization in the tubule. This type of crack suggests
that the monomer has a strong affinity for the tubular wall and that the tooth
substrate compatibility with monomers is stronger than the cohesive energy
of the resulting monomer-polymer mixture. Similar mushroom-shaped

Figure 6. SEM picture of cured 4-META resin in tubules after removal of

human dentine by decalcification (X2000).
INFILTRATION OF MONOMERS INTO TOOTH SUBSTRATES 271

Figure 7. A partially demineralized fracture surface orthogonal to the joint

surface (XlOOO). The joint surface is at the middle of the photomicrograph
(arrow) and the white bar shows the depth of the demineralization-resistant
zone.

nodules, presumably due to tensile stress at the nodules, are also seen on the
tops of the tubules in the tensile fracture surface on the dentine side (Fig. 5).
It is necessary to point out that the adhesive strength decreased to 3.0 MPa in
the case of these mushroom-shaped fractures. Cohesive failure of the cement
was observed at the tensile fracture surfaces of the specimens having high
adhesive strengths (18 MPa). Adhesive failure, however, did not occur at the
interface when we polymerized I1 on dentine etched with either of the two
solutions. The polymerized adhesive impregnated in tubules after removal
of dentine from the adhered specimen by decalcification with 6N HC1 for two
days is seen in Fig. 6. The geometry of the impregnated resin tags is similar
to that of the geometry of tubules as seen in Figure 3.
Studies of the adhesion between PMMA initiated with the benzoyl perox-
ide-amine system and the dentine etched with 10:3 showed that the adhesive
tensile strength did not exceed 5 MPa. This system provides adhesion only
through a tubular impregnation and interlocking mechanism which is similar

Figure 8. A partially demineralized fracture surface of the dentine

(X2000).
272 NAKABAYASHI, KOJIMA, AND MASUHARA

to that seen in Figure 6. The large difference between the value of 18 MPa
for the 4-META cement cured with TBB-0 and that of 5 MPa for the MMA
cement cured with benzoyl peroxide-amine is the result of the infiltration of
monomers into the irltra- and intertubular dentine prior to polymerization.
This is suggested by the cohesive failure of the cement that occurred during
the tensile strength measurement. We did not observe adhesive failure in
these cases.
The fracture surface of the adhered specimen shown in Figure 4 changed
remarkably with the partial demineralization of dentine with 6 N HC1 for 30
s (Fig. 7). There is a thin band just under the adhesive interface which resists
the hydrochloric acid demineralization. This resistant band is the zone of
dentine infiltrated by the monomers. Porous strings of cement impregnated
in the tubules were exposed by the demineralization. Figure 8 shows the
partially demineralized fracture surface of dentine. This specimen is com-
parable to the specimen in Figure 3 which is not demineralized.
Infiltration of monomers, which may have compatibility or affinity with
hard tissue, into tooth substrates takes place just after the application of the
adhesive paste on the etched dentine, and the polymerization is initiated in
situ by TBB-0. The infiltrated and polymerized layer in the subsurface dentine
zone is observed in Figure 7. It appears that homogeneous mixing between
the tooth substrate dentine and the polymer has occurred, following the
penetration of the monomers into intra- and intertubular dentine. In other
words, tooth substrates may be reinforced by biocompatible monomers which
penetrate the substrates and then polymerize.
In conclusion, the preparation of monomers having both hydrophobic and
hydrophilic groups which promote adhesion with tooth substrates by pene-
tration and in filtration is a new concept in biocompatible materials for dental
use. The penetration of monomers into tissue, followed by polymerization,
represents a mechanism by which stress concentration, as a failure mode, can
be avoided. This is especially true for hard tissue-material interfaces. We
have presented one such application in this article and we are continuing these
studies and expanding our efforts to use this concept in providing biocom-
patible and mechanically stable soft tissue-material interfaces.

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Received August 19,1981
Accepted November 28,1981