Principles of

adhesive retention and

adhesive restorative materials

M ichael G. B uonocore,* D .M .S ., R ochester, N .Y .

Dental applications for adhesives include the sealing of pits and fissures for caries
prevention, the prevention of marginal leakage in restorations and cavity lining. An
ideal dental adhesive should provide a lasting bond with both enam el and dentin;
polym erize rapidly near body tem perature, with little or no shrinkage; be sufficiently
cross linked to minimize expansion on water absorption; have sufficient strength to
resist masticatory fo rces; have the same coefficient of thermal expansion as tooth
structure; have mechanical properties close to those of tooth structure; be innocuous
to the pulp and oral tissues, and resist degradation in the oral environm ent.

T h e term “ adaptation” is defined for den­ NATURE OF ADHESION

tistry in Dorland’s Illustrated M ed ical
D ictionary1 as “ T he proxim ity o f a filling Adhesion is defined as the m olecular at­
material to a cavity wall.” T h e adaptation traction exerted between the surfaces of
o f restorative materials to cavity walls has
been the subject of numerous investiga­ J
tions. T h e fact that the adaptation o f
existing materials is not sufficient to pre­
vent leakage o f dyes between the restora­ m Steel
tive material and cavity wall has been
dem onstrated;2' 10 m oreover, it has been \
shown by Nelsen and co-workers11 that
the size o f this leakage space varies as the
result o f thermal changes. These authors
stated, “ it would not be unreasonable to
assume that a channel 10 m icrons in d i­
ameter could develop at the junction o f
the resin filling and the tooth.” This space
is many times larger than most m icro­
organisms and would allow a virtual
pouring in o f enzymes and acid molecules. Fig . I • N ature of co n tact between surfaces
T h e elimination o f this leakage space under pressure, a : Polished steel su rfaces. Rough­
ness prevents com plete co n tact, with bonds
could be achieved by a restorative m ate­
form ed at tips of asp erities which are under high
rial or liner capable o f form ing a strong ela stic stress. O n rem oving pressure, release of
adhesive bond with tooth structure that ela stic stresses may break junctions, b : Lead on
steel under pressure. So fter lead flows and con­
would survive under oral conditions. In form s to irre g u larities of steel su rface. Because
view o f the potential im portance o f ad­ of flow, elastic stress does not build up ap p re ­
hesion in dentistry, a discussion o f some c ia b ly, and adhesion m ay not be broken on re­
moval of pressure, c : Lead on steel. W h en moved
o f the principles involved should be d e­ over steel, lead surface is sheared at points of
sirable. co n tact, leaving p iece of lead adhering to steel

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bodies in contact or the attraction be­
tween molecules at an interface. Im plied
in this definition are a variety o f therm o­
dynam ic considerations which have been
defined by com plex mathematics. T h e
m ore interested reader is referred to a
num ber o f g ood references on the sub­
je c t ;12'20 however, an attempt will be
m ade to present in simple form pertinent
aspects o f the theory o f adhesive action,
obtained from the aforem entioned ther­
m odynam ic considerations.
T h e m olecular attractive forces in ­
volved in adhesion may be divided into
two classes, physical and chemical.
Physical forcés, including V an der W aal’ s
forces, are related to the existence o f
dipoles, induced dipoles and the nonpolar
dispersion effect which results from inter­
action between the random motions o f
internal electrons o f molecules, atoms or
ions. A m on g the physical forces m ay also
be included hydrogen bonding, which
may be considered a special kind o f a
dipole-dipole interaction. Chem ical forces
are those resulting from the form ation o f
covalent, ionic and metallic bonds and so
forth and are considerably stronger than
physical bonds. Chem ical bonds are dis­
tinguished from physical bonds in that, in
the form er, there may be a sharing o f
electrons such as that which occurs be­
tween two atoms o f hydrogen to form a
m olecule, or there may be actual transfer
o f electrons from one atom to another as
in the reaction o f sodium with chlorine
in which sodium, by giving an electron
to the chlorine, becomes a positive sodium
ion and chlorine, by receiving the elec­
tron, becom es a negative chloride ion. O f
special interest is the chemical bond
form ed when a glass surface is made
hydrophobic by reaction with dimethyl-
dichlorosilane. T h e organic methyl groups
o f the silane are bonded to the glass sur­
face through a covalent silicon-oxygen-
silicon attachment.
Adhesion, depending essentially on the
forces o f m olecular attraction between
surfaces, exists only at short distances of
separation; these are o f the order o f no
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BUONOCORE . . . VOLUME 67, SEPTEMBER 1963 • 73/383
Contact Angle = 0
Clean Surface
Contact Angle =8°
I liiliiiiiM T ffl
Slightly Contaminated Surface
Contact Angle = 80°
Mono Layer of Fatty Acid
Contact Angle = 105°
Teflon or Polyethylene
F ig . 2 • W e tta b ility o f different types o f sur­
fa c e s. a : Z e ro con tact angle on clean su rface,
b : Sm all co n tact angle on slig htly contam inated
su rface, c : Larg er co n tact angle on layer of
fa tty acid contam inating su rface, d : Large con­
ta c t angle, in d icative of poor w etting o f p o ly(tet-
rafluoroethylene) or polyethylene surface
m ore than 1 or 2 ten thousandths o f a
m icron ( angstrom u n its). Little or no
adhesion can be realized with separations
greater than these values. This implies
that surfaces which are flat at an atom ic
level, if brought into contact, will adhere
spontaneously to each other with a strong
bon d without the need o f an intermediate
layer o f adhesive. An example o f the ad­
hesive forces uniting atomically smooth
surfaces is demonstrated by the bond be­
tween m ica sheets. T h e strength o f this
adhesion is about 14,000 lb. per square
inch, as strong as the m ica itself.18 A dh e­
sion can be weakened or destroyed by
water penetrating between adhering sur­
faces. It has been calculated that a layer
o f water molecules penetrating between
two unit layers o f clay exerts a force o f
2,000 atmospheres in separating the lay­
ers.21 This figure gives an idea o f the
tremendous forces with which the inter­
faces o f the clay can attract water to
bring about their separation. W ith adap­
tation o f a restorative material to a cavity
wall o f the order o f no more than 1 or 2
angstrom units o f separation, other fa c­
tors being conducive, strong adhesion
w ould also exist. T h e key to lasting ad­
hesion, however, lies not only in getting
surfaces in molecular nearness, but also
in maintaining this proximity.
 74/384 • THE JO URN AL OF THE AM ERICAN DENTAL ASSOCIATION
FACTORS IN OBTAINING AND
MAINTAINING ADHESION
Surface C ontact • In the examples cited,
I referred to solid substances having
atom ically smooth surfaces between which
strong adhesive forces exist. Although
considerable adhesive forces are obtained,
the examples are only o f theoretical and
laboratory interest. T h e best surfaces that
scientists have been able to produce are
smooth to only a millionth o f an inch,
which is about 250 times less smooth than
is required for m olecular attraction. In
actual practice, it is often necessary to
bond surfaces which may be as m uch as
a million times less smooth. Dental cutting
instruments leave surface im perfections
o f this oi'der.
Although surfaces may appear smooth,
they are rough on an atom ic scale. W hen
brought together under pressure, contact
occurs only around the tips o f the asperi­
ties; however, the adhesive forces pro­
duced at these contact points may be
appreciable. W ith hard metals, these con ­
tact points are under considerable stress
and, when the contact pressure is re­
m oved, the release o f the stress because
o f the elastic recovery o f the material at
these junctions m ay be sufficient to break
them. W ith softer metals such as lead or
indium, flow occurs under contact pres­
sure (Fig. 1, b ) , and stress is m inim ized;
hence, on release o f pressure, the ju n c­
tions may not be broken. W hen junctions
a Fig . 3 • Effe ct of shape of
asp e rity on adhesive pene­
tra tio n . a : Ink bottle typ e
o f p it shows lim ited pen­
etration o f adhesive, b :
Flow er pot ty p e o f pit
shows b e tter penetration of
' M z m adhesive
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are not broken on release o f contact pres­
sure, slight sliding motions ( shear forces)
may break the contact, with rupture most
likely not at the contact points but within
the materials themselves (Fig. 1, c ) . This
indicates that the bond is stronger than
the metal.
In all the examples o f surfaces in co n ­
tact in Figure 1, there are voids which
represent absence o f complete contact be­
tween the surfaces and failure to obtain
m axim um adhesion. In the presence o f
fluids, such voids could serve as seepage
channels if they were interconnecting.
For m axim um adhesion, these should be
eliminated, and an important way o f d o ­
ing this is to use liquid adhesives in jo in ­
ing surfaces. Because atomically smooth
surfaces cannot be obtained at a practical
level, the problem is circum vented by
using fluid adhesives which will flow into
the irregularities o f the surfaces.
W etting and C ontact Angles • In order
to establish adhesion, a liquid adhesive
must “ wet” (give molecular nearness to)
the surface o f the material. W etting is a
manifestation o f the attractive forces b e ­
tween molecules o f adhesive and ad-
herend. W hen the attractive forces be­
tween the molecules o f the adhesive and
those o f the adherend are strong, wetting
will occur. T h e phenom enon o f wetting
is associated with the existence o f a small
or zero contact angle as shown in Figure
2, a. T h e stronger the attraction, the
smaller will be the wetting angle.
A zero contact angle w ould indicate
that the molecules o f the adhesive are
attracted to the solid adherend molecules
as m uch as, or more than, they are to
themselves. W ith mercury, as with certain
other liquids, the mutual attraction o f its
ow n molecules is so strong that it does
not even wet such polar substances as
glass and tooth structure.
M ercury is described as having high
surface tension. Bonds form ed involving
zero contact angles are extremely strong;
fo r example, it has been calculated that,
fo r a nonpolar liquid having a relatively
low surface tension o f 30 ergs per centi-
 BUONOCORE . . .VO LUM E 67, SEPTEMBER 1963 • 75/385

meter squared and attached solely by a

physical forces to a solid with w hich it
form s a zero contact angle, it w ould re­
quire theoretically a force o f 24,000 lb.
per square inch to remove the liquid and
w ould leave the surface covered with a
layer o f absorbed material.22 T his calcu­
lation is based on the premise that a vapor
film o f the liquid will remain on the sur­
face o f the solid; therefore, rupture in the
liquid has been produced, and the force
o f 24,000 lb. per square inch is essentially Fig . 4 • a : Discontinuity o f ad hesive la ye r caused
by co n tact between projections on both surfaces
a measure o f cohesive forces holding
results in weak jo in t. Regions o f d iscon tinu ity may
molecules o f the liquid together. T h e a c t as initiation points fo r propag ation o f fr a c ­
force necessary to remove com pletely the ture under stress, b : Stron g er adhesive jo in t with
continuous, th icker la yer o f adhesive
liquid from the surface may be as m uch
as tw ice this value. In practice, however,
strengths o f these orders are never o b ­
o f entrapped air. W ith fluid adhesives,
tained. Fracture o f the adhesive or the
filling o f pits is a m ore rapid process than
adherend usually occurs at m uch lower
with viscous adhesives. Unless sufficient
forces. Figure 2, b, c and d show, re­
time is allowed fo r flow into the voids,
spectively, contact angles achieved by sur­
not only will the area o f contact be re­
faces o f decreasing ability to be wet by a
duced, but potential and actual areas o f
given liquid. C ontact angles as shown in
stress concentrations may develop, both
Figure 2, d are obtained on surfaces such
o f which will contribute to early failure
as poly(tetrafluoroethylene), which has a
under load. In addition, rough surfaces
low level o f surface energy. T his accounts
require a thicker adhesive layer between
for the fact that few materials will w et
them to form a continuous film than
this substance suitably. Again from prac­
smooth ones. This is diagrammatically
tical experience, the form ation o f droplets
illustrated in Figure 4, a, b. Breaks in ad­
o f water on a newly waxed autom obile
hesive continuity that result from contact­
h ood is because o f a large contact angle
ing surface projections, seen in Figure
which indicates that the w ax coating is
4, a, produce a weak joint. These breaks
wetted poorly by water.
or cracks may be considered initiation
points from which larger, disastrous frac­
Physical Characteristics o f A dherend Sur­ tures through the adhesive may be propa­
fa ce • T h e smaller the contact angle gated under relatively light loads as a
(g ood w ettin g), the better an adhesive result o f stress concentration. Figure 4, b,
is able to fill in irregularities in the sur­ shows a stronger joint with a continuous
face o f a solid. T h e extent to w hich voids adhesive layer.
or depressions in a surface are filled also
depends on their shape and viscosity o f
Thickness of Adhesive L ayer and Strength
the adhesive. In Figure 3, a and b, the
o f Adhesion • Before relating these prin­
effect o f the shape o f pits on penetration ciples o f adhesive action to the dental
is shown. Figure 3, a shows an ink bottle situation, the problem o f thick versus thin
type, wherein the increasing distance be­ layers o f adhesive should be considered.
tween the lateral walls contributes to Generally, the adhesive industry recog­
making the situation unfavorable fo r pen­ nizes that thick adhesive layers give
etration. In the flower pot type o f pit, weaker joints than thin ones. A number
penetration is facilitated and will cease o f reasons have been postulated fo r this,
only when the pressures driving the liquid one o f w hich is the probability o f a
are counterbalanced by the compression greater num ber o f im perfections, such as

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 76/386 • THE JOURNAL OF THE AM ERICAN DENTAL ASSOCIATION
Fig . 5 • a : C y lin d rica l rod of d uctile m aterial in
tension, with shear type of break a t point o f re ­
d uced d iam e te r, b : Same c y lin d e r cross-sectioned
with one segm ent placed under same tension as
in a ; g re a te r resistance to rupture can be a t­
trib u ted to a b ility of thin la ye r to resist late ral
deform ation b etter than th ick one does
voids and cracks, in thicker layers. These
may cause stress concentrations under
load, with the likelihood o f early failure
related to the num ber and size o f these
imperfections. Another reason postulated
for the weakness o f thick adhesive layers
is that they are more likely to becom e de­
form ed than thin ones and thus will frac­
ture sooner; for example, w hen a cylin­
drical rod o f ductile material is drawn
out under tension (Fig. 5, a ) , failure o c ­
curs in the area o f reduced diameter. O n
the other hand, a thin layer, which may
be considered as a thin cross section of
a cylinder, is constrained from deform ing
laterally. W hen rupture occurs, it will
take place in a cross section almost equal
to the original. O nce good adhesion is
achieved, the adhesive bon d is not likely
to break; instead, the adhesive o r ad-
herend will rupture. T h e resistance o f
the adhesive or adherend is the limiting
factor in bond strength. T h e practical
loads under which materials will break in
tension are far below calculated theoreti­
cal values, w hich are o f the order o f m il­
lions o f pounds per square inch. In prac­
tice, the strengths o f polym eric materials
are far from theoretical values because
they are not oriented or crystallized ide­
ally and contain imperfections. U nder
load, the m echanical stresses are not dis­
tributed evenly, which results in stress
concentrations that initiate early failure.
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Another reason postulated fo r prefer­
ring thin adhesive layers is important
from the dental aspect and has to d o with
shrinkage. M ost adhesives undergo shrink­
age on hardening or polymerization
w hich induces internal stresses in the
material, acting tangentially to the ad-
hesive-adherend interface. I f one consid­
ers a thick layer as m ade up o f many thin
layers, the sum o f stresses caused by
shrinkage, acting at the adherend-adhe-
sive interface, will increase with the thick­
ness o f the adhesive layer. These shrink­
age forces tend to pull the adhesive from
the adherend and, consequently, to en­
danger adhesion. I f adhesion is not actu­
ally disrupted during shrinkage, it may
becom e so weakened that only a small
additional external force will break it.
Swelling o f the adhesive because o f ab­
sorption o f fluids can endanger adhesion
also. In addition, excessive shrinkage and
swelling m ay cause spontaneous fractures
in the body o f the adhesive. W ith adhe­
sives having a high elastic modulus, in­
ternal stresses at the adhesive interface,
caused by polymerization shrinkage and
other factors, are likely to be greater than
with adhesives having a low elastic m odu­
lus. Polymerization shrinkage during the
viscous state is o f little consequence when
com pared with that occurring after the
adhesive has hardened. A material o f low
elastic m odulus and high yield value, al­
though not suitable fo r bulk use, could
be used as a thin layer.
ADHESION IN DENTISTRY
T h e problems associated with obtaining
adhesion to tooth structure are com plex,
centering largely around the fact that one
must deal with an aqueous environment.
M ost adhesive chemists agree that the
presence o f water is detrimental before
and after bonding. F or dental applica­
tions, however, there is no alternative; a
dental adhesive must be capable o f b on d ­
ing to tooth surfaces which may not toler­
ate adequate drying and, m ore important,
the adhesive must maintain its adhesion
in continuous contact with water.

Bonding to tooth structure involves a
consideration o f two separate tissues: en­
amel and dentin. Enamel is essentially
inorganic but contains a relatively small
inert organic com ponent which may be
im portant in securing adhesion. Dentin is
com posed o f about 75 per cent inorganic
material that is em bedded in or sur­
rounded by a protein matrix. Obviously,
the surfaces presented fo r adhesion by
these tissues are different. Enamel, be­
cause o f its external location on the tooth,
can be subjected to m ore drying than
dentin and, in this respect, provides a p o ­
tentially more desirable adherend surface;
however, dentin, which cannot be dried
rigorously without endangering the pulp,
may be less suitable in this respect. N ever­
theless, its larger amount o f organic m at­
ter may offer a greater potential fo r bon d­
ing through chem ical reaction with the
adhesive. T h at these tissues do not behave
similarly to the same adhesive is shown
by the rather strong adhesion o f methyl-
methacrylate filling resin obtained by
Buonocore and others23 on acid etched
enamel surfaces and the complete absence
o f adhesion to similarly treated dentin
surfaces. Another demonstration o f the
divergent behavior o f these tissues is af­
forded by the finding that a polym er­
izable, phosphate-containing material will
bond to dentin but not to enamel.24
A D H E S IV E S FO R CARIES P R E V E N T IO N
Adhesives in Fissure Sealing • A n im por­
tant application for adhesives in dentistry
is the sealing o f pits and fissures for caries
prevention. T h e fissures are the most vul­
nerable spots and usually decay" rapidly
soon after eruption in advance o f inter-
proxim al decay. Sealing the fissure areas
o f molars and bicuspids soon after tooth
eruption could result in the saving o f
large numbers o f teeth while providing
a pleasant introductory experience for
young patients.
This possibility has been under investi­
gation at the Eastman Dental Dispensary.
Attempts to obtain lasting adhesion o f
existing restorative materials to uncut
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BUONOCORE . . . VOLUME 67, SEPTEMBER 1963 • 77/387
fissure areas have failed consistently. A l­
though good initial adhesion to enamel
may be obtained with various acrylic
resins, it is lost after a short time in the
mouth. From laboratory tests, it has been
found that this loss results from the effect
o f moisture. Strong adhesion o f methyl-
methacrylate resins to teeth occurs when
teeth have been air dried fo r a long time.
As long as these teeth are kept dry, the
acrylic resin adheres firmly, but adhesion
is lost rapidly when teeth are placed in
water.
This parallels the experience o f den­
tists w ho have seen how well acrylic resin
adheres to dappen dishes and glass mixing
slabs. Although this bon d is so strong
when dry that attempts to dislodge the
resin often result in tearing out pieces o f
the glass, the bond can be broken readily
by immersion o f the slab o r dappen dish
in water. In fact, after a short immersion
time, the acrylic resin virtually floats off
the glass. Loss o f adhesion occurs because
water has greater affinity fo r the enamel
or glass surface than the adhesive, and it
displaces the adhesive from the surface.
T he failure o f adhesion in the mouth also
can be attributed to the developm ent o f
internal stress from the substantial poly­
merization shrinkage and the irregular
contour o f the fissure in w hich the resin
is placed. Conceivably, the total stresses
so induced could weaken the adhesion
so that, on subsequent contact with oral
fluids, expansion forces caused by water
absorption by the resin, the enamel or
both set up sufficient additional stresses
at the adhesive boundary to destroy what­
ever residual adhesion existed. Failure o f
unmodified Eastman 910 m onom er to
adhere to enamel fissures fo r appreciable
times may be related to these facts. U nder
polarized light, one can see the evidence
o f stresses in this adhesive as alternating
light regions and dark bands in the body
o f the material (Fig. 6 ) ; a void is present
also.
T h e addition o f fillers has been sug­
gested as a means o f reducing stresses
caused by contraction o f an adhesive in
bulk. Supposedly, the filler acts by m e­
 78/388 • TH E JO U R N A LO FT H E AM ERICAN DENTAL ASSOCIATION
chanical means to equalize the distribu­
tion o f stress and to prevent the form ation
o f cracks. In our ow n laboratories, we
have been able to produ ce long-lasting,
water-resistant adhesion to enamel sur­
faces by the incorporation o f fillers in
Eastman 910 m onom er. Clinical trials
also indicate that adhesion o f this co m ­
position to enamel fissures survives under
oral conditions.
Enam el Surface in Adhesion • T h e ad­
hesive is only half o f the possible cause;
the other half rests in the enamel itself.
O n e o f the first considerations in securing
adhesion is the cleanliness o f the tooth
surface. Ordinarily, cut tooth surfaces are
covered with loosely attached enamel and
dentin dust from the cutting procedure.
T h e usual washing does a p oor jo b of
rem oving this debris but, unless it is re­
m oved, it is apparent that adhesion fail­
ure m ay exist even before the adhesive
is put to oral use. A protein or fatty layer
on the surface could be responsible for
p oor adhesion by preventing contact o f
the adhesive with enamel. A n adhesive
might adhere to such an extraneous layer,
and the degree o f adhesion w ould be de­
termined by the strength o f the attach­
ment o f the layer to enamel. Even if such
interposing layers can be rem oved to pro-
Fig . 6 • Eastm an 910 m onomer polym erized in
uncut enam el fissure. S : Strain reg ion. V : V oid .
F : Base of fissure is unfilled because monomer did
not penetrate
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duce a clean enamel surface, the presence
o f absorbed water still poses a problem
and will affect wetting characteristics o f
the adhesive.
In view o f the energy with which water
is attached to hydroxyapatite, which
makes up m ore than 95 per cent o f the
enamel, the usual clinical drying proce­
dures fo r enamel are wholly ineffective.
A t the National Bureau o f Standards,
R . L . Bowen has been investigating sub­
stances that will displace water from
tooth surfaces with the idea that they
m ight be used as pretreatments fo r the
enamel or dentin or be incorporated into
the adhesive.25 A lon g similar lines, I have
tried to im prove the adhesion o f acrylic
resins to enamel by surface treatments
before application o f the resins. As a re­
sult, it was fou n d that etching enamel
surfaces with phosphoric acid increases
the duration o f adhesion under water.
A lthough the increased adhesion may be
primarily the result o f m echanical reten­
tion from an increase in surface rough­
ness, the possibility must be considered
that the treatment changed the surface
chemically, m aking it m ore reactive to
the adhesive. T his chem ical change may
have involved placing groups on the sur­
face which attract the adhesive more
strongly than water so that when in con ­
tact with oral fluids, the resin will not be
displaced by water. Zettlem oyer26 has in­
dicated that this m ight be accomplished
by nitro groups, w hich can com pete with
water.
ADHESIVES AS
RESTORATIVE MATERIALS
Preventing M arginal Leakage • Another
application fo r adhesives is in the prob­
lem o f marginal leakage. T h e importance
o f this leakage in recurrent caries and
pulp irritation has never been assessed
adequately, but it is reasonable that it cre­
ates a potentially dangerous situation.
Obtaining adhesion to cavity walls, pref­
erably through chem ical reaction with
tooth structure, w ou ld eliminate gross
leakage through the interface. Presently
 BUONOCORE . . . VOLUME 67, SEPTEMBER 1963 • 79/389

available materials d o not bond to tooth

structure, and it has been shown that
penetration o f dyes, bacteria and acids
occurs th rou gh , the space between the
restoration and cavity wall. Further, one
has to consider that two different kinds
o f surfaces are involved in a cavity. An
adhesive may bond to one and not the
other. Theoretically, if it would bond only
to the enamel margins, it would be suffi­
cient to seal the cavity. T here m ay be
some doubt whether present cavity design
offers sufficient contact surface to m ain­
tain the adhesive seal under occlusal Fig . 7 • a : M odification o f enam el ca v ity w all to
forces. Cavity preparation, however, in crease co n tact area fo r adhesive bo nd ing, b :
could readily be modified by substantial Leakag e (arro w ) through enam el-adhesive in te r­
fa c e in absence of adhesion. Adhesion between
flaring o f enamel walls, to increase the adhesive and dentin prevents leakage along d en ­
contact area. W ith strong adhesives, this tin in te rface but does not prevent it from passing
along dentoenam el junction into dentin
might be sufficient to maintain the ad­
hesive seal. Such a preparation is shown
in Figure 7, a and represents only one as­
in a viscous state, it m ight n ot contact
pect o f cavity design m odification.
the entire cavity surface and thus w ould
Adhesion to dentin alone w ould be less
leave voids about which stress could origi­
desirable than just to the enamel, since
nate (Fig. 8, a ) . Because o f shrinkage,
it w ould n ot eliminate the leakage space
during and after hardening, em bedded
between the enamel margin and the res­
surface projections, which are exagger­
toration. O u r studies show that enamel
ated in Figure 8, b, may be sheared from
margin leakage passes along the dento-
the cavity wall, or pieces o f the resin
enamel junction and penetrates the den­
may be broken; this is simply a question
tin beyond the boundary o f the cavity.
o f w hich material is the weaker. T herm al
W e fou n d that, although experimental
expansion and contraction and expansion
dentin adhesives virtually eliminated leak­
because o f water absorption could con ­
age between dentin and adhesive, they
tribute to this. Also, occlusal forces caus­
did not eliminate entirely leakage via the
ing elastic deform ation o f the adhesive
dentoenamel junction through the dentin
m ay result in the shearing o f surface p ro­
to the pulp (Fig. 7, b ) .
jections, which would contribute to the
form ation o f channels between the resin
Shrinkage of A dhesive Restorations • and cavity wall. By use o f the resin ad­
T h e problems associated with obtaining hesive in a m ore fluid form , one might
and maintaining adhesion to enamel fis­ minimize voids, although this w ould not
sures also apply to filling materials. In eliminate the detrimental effects o f the
fact, because there would be a larger other factors.
bulk o f adhesive, the problems arising
from polymerization shrinkage are m agni­
ADHESIVES AS LINING MATERIALS
fied because greater total stress m ay be
involved. Figure 8 shows diagrammati- T o circum vent some o f the difficulties
cally w hat m ight occu r when a resin ad­ associated with bulk adhesives, one can
hesive is allowed to polymerize in a cavity, take advantage o f the fact that adhesives
the walls o f w hich can be expected to be seem to give optimal strength when used
rough.27’ 28 Arrows indicate polymeriza­ in thin layers. This leads logically to use
tion shrinkage forces in the adhesive. o f an adhesive cavity liner. W ith cavity
Since the resin adhesive usually is applied liners, a certain amount o f shrinkage on

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 90/390 • THE JOURNAL OF THE AM ERICAN DENTAL ASSOCIATION
Fig . 8 • There are
void spaces ( A )
tween ca v ity wall and
resin adhesive because
adhesive did not pen­
etrate asp e ritie s. Shrink­
age, expansion on w ater
a b s o r p t io n , o c c lu s a l
stress or all three cause
movem ent of restoration
which results in sheared
dentin frag m ents
em bedded in body of
resin
polymerization or hardening cou ld be
tolerated better, since the stresses acting
at the bond interface w ould be consider­
ably less than in bulk; m oreover, a liner
w ould have to bond only to the cavity
wall and not necessarily to the restoration.
H ence, induced stresses, both from poly­
merization and differences in coefficients
o f thermal expansion, would be smaller
when the adhesive was attached to only
one material rather than when it bridged
a fixed gap between two. A thin layer
o f adhesive containing fewer voids and
im perfections than bulk material w ould
be easier to obtain. In addition, thin lin­
ers could serve the conventional purpose
o f protecting the teeth from harm ful in­
gredients o f restorative materials. It
should be pointed out that most materials
usable in bulk could be adapted fo r use
as liners, but the reverse w ould not be
true. For example, lining materials could
be deposited from solution, with the thin
layers permitting rapid evaporation o f
solvent, the retention o f which, occurring
in bulk, might impair the properties o f
the liner. Liner materials could be elas­
tomers yet serve adequately, although this
property w ould not be desirable in resto­
rations. Because a thin film between two
surfaces is, in effect, a load absorbing and
distributing medium , an elastomer might
be m ore desirable than a brittle, friable
substance; moreover, thin layers allow the
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quick dissipation o f heat from high exo­
thermic materials, and potential heat
damage to the tooth w ould be minimized.
Also, this would broaden the scope o f
be­ materials that could be em ployed as ad­
hesives.
TOXICITY
W hatever type o f adhesive material is
used, the question o f primary concern is
(B ) their toxicity to the pulp and oral tissues.
M ost o f the catalysts used to polymerize
resins probably would be toxic to the
pu lp ; it is fortunate that most d o not re­
main after they are m ixed with resin
monomers. T h e problem then is a matter
o f the potency o f the catalyst and the
amount and time necessary to produce
harm. T h e use o f thin layers w ould mini­
mize the amount o f toxic material in­
volved. M igration or leaching o f unre­
acted toxic agents from the adhesive to
the pulp and oral tissues is potentially
harmful, as is the use o f chem ical pre­
treatments o f tooth structure. W ith en­
amel, the potential harm is slight, but
with dentin, the danger is greater and
means the reagents used to effect better
adhesion must be considered carefully.
T h e evaluation o f adhesives should stress
long-term studies, since pulpal effects may
not be evident over short periods.
REQUIREMENTS FOR ADHESIVE
DENTAL MATERIAL
A num ber o f properties would contribute
to making an ideal dental adhesive mate­
rial. T h e adhesive should produ ce a last­
ing bond with both enamel and dentin;
polymerize rapidly near b od y tempera­
ture, with little or no shrinkage; be suffi­
ciently cross linked to minimize expansion
on water absorption; have sufficient
strength to resist masticatory forces; have
the same coefficient o f thermal expansion
as tooth structure; have m echanical prop­
erties close to those o f tooth structure; be
innocuous to the pulp and oral tissues,
and be resistant to degradation in the oral
environment.

P R O S P E C T S F O R D E N T A L A D H E S IO N
Although one can be optimistic about the
possibility o f eventually obtaining a satis­
factory dental adhesive, there are difficul­
ties to overcom e. A t the present level o f
knowledge o f adhesives and synthetic res­
ins, the attainment o f optim al strength
and water resistance generally requires
either considerable setting time or the ap­
plication o f heat above that w hich would
be practical for oral use. Although such
resins as the furans and the epoxy have
little or n o polymerization shrinkage, they
require relatively long periods fo r curing
at room temperature and do n ot develop
m axim um desirable properties until fully
cured. T h e problem o f m atching thermal
coefficients o f expansion o f the filling m a­
terial and the tooth is a m ajor obstacle.
T h e im portance o f this problem depends
on the magnitude o f the difference in
coefficients and on the nature o f the ad­
hesive. Perhaps adhesives derived from
polar substances are best suited to match
*Research coordinator, Eastman Dental Dispensary,
Rochester, N.Y.
1. Dorland's lllustrate.d Medical Dictionary, ed. 23.
Philadelphia and London, W. B. ’Saunders Company,
1957, p . 33.
2. Going, R.; Massler, M., and Dute, H. Marginal
penetration of dental restorations by different radio­
active isotopes. J . D. Res. 39:273 March-April I960.
3. Hirsh, L., and Weinreb, M. Marginal fit of direct
acrylic restorations. J.A .D .A . 56:13 Jan. 1958.
4. Fiasconaro, J . E., and Sherman, H. Sealing prop­
erties of acrylics. New York D. J . 18:189 May 1952.
5. Massler, M., and Ostrovsky, A . Sealing qualities
of various filling materials. J . Den. Children 21:228 4th
quart. 1954.
6. Phillips, R. W .; Gilmore, H . W . ; Swartz, M. L., and
Schenker, S. I. Adaptations of restorations in vivo as
assessed by Ca45. J.A .D .A . 62:9 Jan. 1961.
7. Swartz, M., and Phillips, R. W . In vitro studies on
the marginal leakage of restorative materials. J.A .D .A .
62:141 Feb. 1961.
9. Armstrong, W . D., and Simon, W . J . Penetration
of radiocalcium at margins of filling materials: a pre­
liminary report. 43:684 Dec. 1951.
9. Sausen, R. E .; Armstrong, W . D., and Simon, W . J .
Penetration of radiocalcium at margins of acrylic resto­
rations made by compression and noncompression tech­
nics. J.A .D .A . 47:636 Dec. 1953.
10. Gi(lings, B.; Buonocore, M., and Sarda, O. In
vitro evaluation of cavity liners. D. Progress 1:57 Oct.
I960.
11. Nelsen, R. J . ; Wolcott, R. B., and Paffenbarger,
G . C . Fluid exchange at margins of dental restorations.
J.A .D A . 44:288 March 1952.
12. Eley, D. D. (ed.) Adhesion. London, Oxford Uni­
versity Press, 1961.
13. Delmonte, J . Technology of adhesives. New York,
Reinhold Publishing Corporation, 1947.
Pedro Augusto Senem - senem.pedroaugusto@gmail.com - CPF: 115.478.529-76
BUONOCORE . . . VOLUME 67, SEPTEMBER 1963 • 81/391
the m echanical properties o f strong m ate­
rials such as enamel and dentin. T h e
polar groups not only provide for inter­
nal bonding am ong polym er chains (p ro ­
ducing a strong material) but also
contribute to better adhesion to polar
adherends; however, the pressure o f polar
groups, although beneficial in these re­
spects, may be detrimental since water
absorption is favored and would result in
swelling, softening and weakening o f the
adhesion. Although the question o f
degradation by oral bacteria must be
considered, the bacterial resistance o f
available resins is good.
Finally, it should be emphasized that
the search fo r a dental adhesive is a p i­
oneer effort. T h e properties o f a successful
adhesive may be novel and different from
materials presently used; therefore, we
may need to espouse not only new con ­
cepts in cavity design and a réévaluation
o f requirements relating to physical p rop ­
erties o f materials but also a reorientation
o f approach to dental treatment.
14. de Bruyne, N. A ., and Howwink, R. (ed.) Adhe­
sion and adhesives. London, Elsevier, 1951.
15. Herring, C . Structure and properties of solid
surfaces. Chicago, University of Chicago Press, 1953.
16. Bowden, F. P., and Tabor, D. Friction and lubri­
cation of solids. Oxford, Clarendon Press, 1954.
17. Timoshenko, S. Theory of elasticity. New York,
McGraw-Hill Book- Company, 1934.
18. de Bruyne, N. A . Action of adhesives. Scient. Am.
206:1 J4 April 1962.
19. Harkins, W. D. Physical chemistry of surface films.
New York, Reinhold Publishing Corporation, 1952.
20. Green, H. Industrial rheology and rheological
structures. New York, John Wiley & Sons, Inc., 1949.
21. Van Olphen, H. In Adhesive restorative dental
materials, Phillips, R. W ., and Ryge, G . (ed .). Spencer,
Ind., Owen Litho Service, 1961, p. 103.
22. Tabor, D. In Adhesion, Eley, D. D. (ed .). London,
Oxford University Press, 1961, p. 9.
23. Buonocore, M. G. Simple method of Increasing
the adhesion of acrylic filling materials to enamel sur­
face. J . D. Res. 34:849 Dec. 1955.
24. Buonocore, M. G .; Wileman, W ., and Brudevold,
F. Report of a resin composition capable of bonding to
human dentin surfaces. J . D. Res. 35:846 Dec. 1956.
25. Bowen, R. L. Investigations of the surface of hard
tooth tissues by a surface activity test. In Adhesive
restorative dental materials, Phillips, R. W ., and Ryge,
G . (ed .). Spencer, Ind., Owen Litho Service, 1961, p.
177.
26. Zettlemoyer, A . C. In Adhesive restorative dental
materials, Phillips, R. W., and Ryge, G . (ed .). Spencer,
Ind., Owen Litho Service, 1961, p. 88.
27. Peyton, F. A ., and Mortel, J . F., Jr . Surface ap­
pearance of tooth cavity walls when shaped with various
instruments. J . D. Res. 35:509 Aug. 1956.
28. Street, E. V. Effects of various instruments on
enamel walls. J.A .D .A . 46:274 March 1953.