Adhesive Bonding of Various Materials to Hard Tooth

Tissues. I. Method of Determining Bond Strength

R. L. BOWEN
American Dental Association, National Bureau of Standards, Washington, D.C.

A test method has been devised to measure

the strength of bonds between materials and
hard tooth tissues.' The method may also
be used to test the adhesion of certain interfacial compounds and other materials to
substrates that cannot readily be formed,
molded, or machined. For example, adhesion may be tested between a self-curing
resin and the surface of a single crystal of
fluorapatite, a mineral having a composition
closely resembling that of the inorganic
portion of teeth and bones. The test method
is not designed for mass-production testing
of large numbers of objects but rather for
testing a limited number of specimens of
small size. This paper describes the apparatus, procedure, and calculations. Part II will
give data on the effects of certain interfacial
compounds, particularly a surface-active
comonomer,6 upon the adhesion between a
direct filling resin and dentin surfaces. Part
III will give further data showing how the
bonding to dentin is affected by treatments
of the dentin surfaces. Subsequent parts
will deal with comparisons between different
kinds of surfaces as well as different treatments of these surfaces.

position) and the polymer powder contained

0.5-0.75 per cent benzoyl peroxide initiator.
It was mixed and used according to the
manufacturer's directions. Except where
otherwise noted, this resin was used throughout the tests reported here.
The substrate surfaces, against which the
adhesive joints were made, consisted of prepared tooth specimens, fluorapatite crystals,
or other substrate materials. Dentin for
example, is the substrate illustrated in
Figures 1 and 2. The adhesive joint consisted of the interface between the substrate
surface, with or without an interfacial compound, and the hardened resin. The complementary steel plunger, to which the resin is
affixed, will not be referred to as a substrate
in this series.
To obtain the specimens for testing, noncarious teeth, after being extracted, were
stored in water at about 50 C. with no
chemical preservatives. The enamel was
removed, when dentin was to be tested, with
rotating abrasive instruments under running
water. Holes were cut into the roots, and
the soft tissues of the pulp were removed.
The teeth were at no time allowed to become dry.
Dentin and enamel are not isomorphous
materials, and the influence of orientation
relative to the plane of the test surface is
not known. This test method requires that
the dentinal tubules or enamel rods be predominately perpendicular to the test surface.

Materials and Methods

At present, most organic formulations
used for the direct filling of dental cavities
are based on methacrylate esters and their
polymers. The material selected for this
investigation was one in which the methyl
methacrylate monomer contained about 0.5
per cent N,AT-dimethyl-p-toluidine reducing ADHESION TESTS
agent (accelerator for the peroxide decomApparatus.-Six replicate stainless steel
assemblies were used to test adhesion; one
This investigation was supported in part by USPHS Research Grant D-589 (C4Rl), Adhesion and Related Properties of these is shown in Figures 1, 2, and 3.
of Dental Materials, from the National Institute of Dental
The substrate specimens were imbedded in
Research, National Institutes of Health, Bethesda, Md., to the
American Dental Association, and is part of the dental research
gypsum (dental stone) in the cupped ends
of
in
Bureau
National
at
the
Standards,
conducted
program
co-operation with the American Dental Association; the Army of one of the cylinders (Figs. 1 and 2).
Dental Corps; Dental Services Division of the USAF School of
Another one of the complementary cylinders
Aerospace Medicine; and the Veterans Administration.
in each assembly had a smaller cylindrical
Received for publication January 29, 1964.
690

"%saw

N"W

1F1(. 1. --\ molar specimen is Shoxn mountlel inl white (detal stone with (denltiTn surface exposed (left);
opposing plunger and (Iiap)hragm p)arts are shown ( ight) The hole in the diaphragm limited the bonded area
to a 6-n-lllimeter diameter.

Fwa;, 2. -The (diapihragm (cc,

i
Jloeg;rouund) was placed] flat against the test surface (right) before freshly
mixed resin, on the plunger (Iuaf),
was lbroutht into contact with it. The tube (in back ground) surrounded
these parts uimth ma king, string, and breaking of the test specimens.

692 BOll EN

plunger,

6
mini. in diameter, on one end
(Fig. 1), to which was attached the resin
that was laLter pullled from. the substrate

J. dent. Res. Jldv OAugust 1965

tained; then the appearance of the resin

layer after 1ond rupture suggested that
stress contcentrations due to these retention
surf ace.
holes in the end of the plunger might have
Preliminary indicaLtions were that the initiated the fracture. Fortunately, this oc1)0nd1 between the resin anIdC stainless steel currec] only in cases where the bond Was
plunger would always be stronger than that already significantly higher than that of the
between the resin and test surface. Occa- comparison group. Si\Leans are l)ei ng st died
to prevent such localization of stresses. To
limit the area, of the joint, a diaphragm
(Figs. 1 and 2) was used which had an
opening 6 mm. in diameter where it contracted the specimen. The clearance between the plunger and the diaphragm111 WaLS
about 25 g. The opening in the diaphragm
tapered so that excess resin Wclas squeezed tip
around the plunger rather than being spread
on the substrate surface. A film of silicone
compound on the (liaphragnl prevented the
resin from adhering to it.
As illustrated in Figure 3, the cylinders
and diaphragm fit ted with close tolerances
into a stainless steel tube which held the
assembly in alignment throughout. the making, soaking, and testing of the bonded assembly. This sliding fit gave mechanical constraint to the assemblies. All parts of each
assembly were numbered and marked so
that in all of the tests they were oriented in
the same way during surfacing, bonding,
and loading.
The surfaces of the imbedded specimens
and the opposing plungers were prepared on.
the device shown in Figure 4. Trhe abrasive
cloth strip* was 1 inch wide. TFhe circular
areas tested were concentric with and perpendicular to the long axes of the cylinders.
A dial gauge with an accuracy better than
13 y (0.0005 inch), mounted rigidly above a
steel table, was used to determine resin
thickness and the thickness of the material
Fie.. 3.-The alignment marks are visible in this removed by the abrasive s-trip. The differclosed assembly. The upper and lower chambers
ence between the measurements of the asverc filled with distilled xatcr 15 minutes after the
start of the resin mix. The masking tape (right) was sembly (a) after the surfaces of the substrate
usel to retain the water.
and the plunger had been prepared, and (b)
after the resin had hardened, was taken as
sionally, however, the resin pulled loose the thickness of the resin between the plungfromt the plunger when adhesion between er and the specimen surfaces.
In the intervals between testing and reresin and the specimen was sufficient. In
order to att-ach the resin more firmly to the surfacing, the imbedded specimens were
pltnger, six small undercut holes were stored in a humidor with air ;atmosphere at
drilled into the end of the plunger (Fig. 1). 100 per cent relative humidity at room
This appeared to be an adequate solution temperature.
to the problem until bond strengths apPreparat io n of test assemblies. -Th e m e th * Grit 320, Behr-Manning Company, Troy, N.Y.
proaching 140 kg/cm2 (2,000 psi) were at-

Vovl. -1. 1,

A DIJESION TO HA RD TOOT1 TISSUTES. I. TEST I!ETIHOD 693

od of preparation of the test assemblies was

standardized and used throtughout (the few
exceptions are indicated). The substrate and
the opposing stainless steel plunger were
resurfaced by two strokes (one forward and
one back), each against unused sections of
the abrasive cloth strip (Fig. 4). This resurfacing removed approximately 25 p of
material from the specimen and a very small
amount of steel front the plunder part. The
rough and unpolished specimen surface was
chosen for the first series of tests, since more
elaborate polishing or "cleaning" procedures
would not only complicate interpretation of
results but also depart further from conditions of the surface likely to be found after
clinical cavity preparation. The interfacial
compounds to he tested were applied to the
specimen surface. The direct-filling resin was
mixed and applied to the steel plunger. The
steel tube was put over the cylinder containincg the specimen, the silicone-coated

weight of the cylinder containing the plunger; this gave about 0.6 kg cmnw2 (9 psi) of
pressure on the area during the time that
hardening of the resin occurred. Distilled
water was then injected through holes in
the outer steel tubes,filling) the chunbers
above the resin and around the periphery
of the adhesive joint. Masking tape (Fig. 3)
was used to retain the water in the chmtbers.

Ftc. 4. -l)evice employing an abrasive cloth

strip) to clean anid resurface the steel plungersand the
substrate surfaces. Tlnhe carriage and tracks served as
a guide in producing surfaces perpenmlicular to the
long axis of the cylinders.

FlcG. 5.---The assembly is shown on the loading

machine. Tl8he forks with the removable pings at top
and bottom are clamped into grips on the testing
machine. T'he peg in the front of the louier cylinder
prevente(I the outer tube from sliding down.

diaphragm was inserted and pressed down

flat against the substrate surface, and then
the plunger with the soft plastic mix was
brought into contact with the specimen
surface through the opening in the diaphra-gm. A weight was placed on top of the
vertical assembly for 15 seconds so that a
pressure of 10.5 kg 'cn2 (150 psi) was exerted on the test airea to spread the plastic
on the surface. The plastic was then allowed
to harden for 15 minutes under only the

Storage of the assemblies. -The closed assemblies, containing water arotind the resin
and periphery of the bonded area, were
stored vertically in. the humidor at room
temperature. Exposure of the bonds to
water for 24 + 4 hrs was recorded as 1 day's
immersion of the specimen; 4 hours were
adequate for the testing and remaking of
the adhesive joints for the following day's
testing.
Loading and breaking of the bonds. As
illustrated in Figure 5, the cylinders con-

694 BOWEN

training the specimens and plungers had

concentric, threaded holes in their ends, into
which bolts were gently screwed just before
loading. The bolts each had a flattened end
with a hole through which a pin was fitted
in such a manner as to give the effect of a
universal joint. The pins also went through
holes in plates clamped in grips of the testing machine. To apply the tensile load, the
grips of the testing machine were drawn
apart at a constant rate of 0.0125 cm/
minute. This was equivalent to a loading
rate of about 35 kg/cm2/minute (500 psi/
minute).
After the bond had broken, the machine
was run back until the resin and substrate
surfaces were again in contact. Loading was
again applied and a loading correction was
obtained. This correction accounted for the
friction of the sliding parts of the assembly
and the weight of the parts of the assembly
not accounted for in the zero setting of the
machine. This correction was subtracted
from the apparent load to break the bond.
The difference was considered to be the real
load supported by the bond just before it
failed.
The load to break the bond in each assembly was multiplied by the appropriate
factor to give the bond strength in kg/cm2 or
in psi; the bond areas averaged about 0.285
cm.2

The six numbered replicate assemblies

treated and tested in series. The resurfacing was assumed to remove enough
of the surface in depth so that penetration
of bonding materials used in one test would
not affect subsequent tests. This assumption
would be invalid if these materials were
capable of penetrating more than about 25
g. Consequently, the chronological sequence
must be considered during the evaluation
and interpretation of the results.
The entire procedure was carried out at a
constant temperature of 23 + 20 C. (73.4 +
3.60 F.).
METHOD OF CALCULATING RESULTS
Since a single set of specimens was being
retreated and retested, one would expect a
particular specimen and its assembly to
give higher or lower test values than others,
due to constant but unknown systematic
differences. These differences, due to sampling and equipment, were not of interest in
were

J. dent. Res. July-August 1965

the comparison of treatments and resulting

adhesion values.
Two-way tables used for the analysis of
variance.--Several readings for each treatment were needed. If the same treatment
were applied to several different specimens,
the scatter in the results would not only
depend on the test error but also include
whatever differences there were between
specimens. The problem was to establish
the experimental error of the tests, eliminating the variation between specimens. By
applying the method of analysis of variance7
it is possible to segregate the effect of the
differences between teeth from that of experimental error and thus obtain a valid determination of the differences among treatments.
The adhesion-test data were arranged in
tables, with each entry characterized by two
indexes, one determining the rows (treatment or interfacial compound) and the
other the columns (the specimens with their
particular assemblies). From the differences
between the grand average and the border
averages, a value was calculated for each
cell of the tables and this was then compared with the observed value. The difference between the calculated and the observed values represented the "unpredictable variation"; the sum of the squares of
these differences divided by the number of
degrees of freedom gave the variance of the
data in each table.
The error, as established by the analysis
of the data, proved to be sufficiently small
to make the apparatus described above
suitable for discriminating between treatments. In this evaluation of the test procedure, the standard deviation of individual
values (about the grand average for all data
in the table) was 8.4 kg/cm2 (120 psi).
The standard deviation of averages of
six values (about the grand average) was
3.5 kg cm2 (50 psi).
Missing data.---Occasionally, accidents
resulted in the loss of data in some of the
cells of the tables. The predicted values,
based on treatment (row) and tooth (column) averages, were inserted in their places
as has been suggested.7' 8 This inserted value
had zero deviation from the expected, but
the deduction of one degree of freedom for
each missing datum made the estimate of error unbiased.

Vol. 44, No. 4

ADHESION TO HARD TOOTH TISSUES. I. TEST METHOD 695

Discussion
The present adhesion equipment and test
method permitted close control of interfacial
area,

measurement of the thickness of the

resin, exposure of the periphery of the adhesive joint to water at any desired time,
and measurement of the amount of substrate removed between tests.
Some of the disadvantages of this test
method follow. A limited number of tests
could be made where prolonged exposures
of the bonds to moisture were desired as the
assemblies were intact during the soaking
time. Small subassemblies, such as were
used by Swartz and Phillips,' would be more
economical for prolonged immersion of numerous adhesive joints. The bonding or attachment between the resin and the stain
less-steel plunger was a limiting factor in the
range of 140 kg 'cm2 (2,000 psi) bond
strengths. A better means of connecting the
resin with the upper (load applying) part of
the assembly which would not project stress
concentrations to the resin-substrate interface would be desirable. Perhaps a replaceable part of porous metal (prepared by
powder metallurgy) or of an organic polymer would serve this purpose.
Close control of the thickness of the resin
was not obtained; the thickness appeared to
vary in a random manner. However, a trend
of decreased strength with increased resin
thickness was not observed. This is in harmony with the visual observation that, with
the exception of the few cases in which the
resin pulled loose from the steel plunger, the
failure of the adhesive joint occurred at (or
very near to) the substrate surface.
While useful by its expediency, the repeated, sequential testing on a resurfaced
substrate such as dentin carried with it the
possibility that some reagents may penetrate deeply into the substrate and thereby
affect the values obtained on subsequent

tests. There was no apparent tendency,

however, for the bonds to become progressively weaker (or stronger) with successive
use of the same specimens when the substrates were resurfaced between tests.

Summary
A tensile adhesion test was developed to
compare the degrees of bonding of materials
and interfacial compounds to hard tooth
tissues, such as dentin and enamel, and
other substrates.
The analysis of variance by means of twoway tables eliminated from the error the
systematic differences between specimens.
The experimental error proved to be sufficiently small to make the apparatus suitable
for discriminating between treatments to be
described in subsequent parts of this series.
The author gratefully acknowledges the helpful
suggestions made by Dr. W. J. Youden.

References
l. SWAARTZ, M. L., and PHILLIPS, R. W. A Method of
Measuring the Adhesive Characteristics of Dental
Cement, J. Amer. dent. Ass., 50:172-77, 1955.
2. SWARTZ, M. L., PHILLIPS, R. W., DAY, R., and JOHNSTON, J. F. A Laboratory and Clinical Investigation of
Certain Resin Restorative and Cementing Materials,
J. pros/h. Dent., 5:698- 704, 1955.
3. ROSE, E. E., LAL, J., WILLIAMS, N. B., and FALcETTI,
J. P. The Screening of Materials for Adhesion to Human Tooth Structure, J. dent. Res., 34:577-88, 1955.
4. SCHOnBOE, P. J., PAFFENBARGER, G. C., and SWEENEY,
W. T. Resin Cements and Posterior-Type DirectFilling Resins, J. Amer. dent. Ass., 52:584-600, 1956.
5. BuoNOCORE, M., WILEMAN, W., and BRUDEVOLD, F. A.
A Report on a Resin Composition Capable of Bonding
to Human Dentin Surfaces, J. dent. Res., 35:846-S51,
1956.
6. BOWEN, R. L. Investigation of the Surfaces of Hard
Tooth Tissues by a Surface Activity Test. Adhesive
Restorative Dental Materials. Spencer, Ind.: Owen
Litho Service. (Proceedings of a workshop held at
Indiana University Medical Center, Indianapolis,
Indiana, Sept. 28 and 29, 1961.)
7. SNEDECOR, G. W. Statistical Methods, pp. 253 and 269.
Ames, Iowa: Collegiate Press, Inc., 1946.
8. HEALY, -M., and WESTMACOTT, M. Missing Values in
Experiments Analyzed on Automatic Computers,
Applied Statistics, 5:203-6, 1956.