D ie T ydskrif van die T.V.S.A.

THE PRINCIPLES OF ADHESION

D. H. Retief*
Denial Research Unit of the University of the Witwatersrand and the South African Medical
Research Council

A MAJOR part of dental practice is the

treatment of localised lesions in
where the filling material has been blamed
for the pulp pathology, it has been shown
conclusively that it is not so; it is the gross
teeth and the replacement of lost tissue
with' restorative materials. As stated by leakage around the filling that docs the
Skinner and Phillips (1967), the lack of damage (Phillips, 1961). This leakage
adhesion of most of them to the structure could be eliminated by a restorative ma­
of the prepared tooth presents a serious terial or film capable of forming a strong
problem; it causes seepage of deleterious adhesive bond with enamel and dentine
agents along the interface between the that would survive under oral conditions
restoration and the tooth (Nelscn et al, (Buonocore, 1963). Fig. 2.
1952). Fig. 1. Research programmes aimed at the de­
Micro-leakage of saliva, acid and bac­ velopment of such a material are under
teria has been demonstrated by various way. If successful, it will replace many of
techniques: radioactive tracers, (Going et those in use today and will change the
al, 1960; Petersen et al, 1966), dye pene­ method of cavity preparation. It could
tration (Holliger, 1967; McLcaji and also be used to bond orthodontic attach­
Kramer. 1952), and penetration of bac­ ments directly to enamel surfaces (Retief
teria (Rose et al. 1961; Kraus and Kraus, and Dreycr, 1967; Mizrahi and Smith,
1951). 1969) or to coat the entire tooth surface
It leads to the breakdown of the mar­ thus forming an impermeable barrier to
ginal areas of the filling with resultant the caries process (Gwinnett and Buono­
secondary caries along the interface be­ core, 1965; Roydhousc, 1968).
tween the restoration and the tooth struc­ The stage has not yet been reached
ture. It is likely that certain phenomena where an adhesive can readily be synthe­
such as post-operative sensitivity and pulp sised for a particular purpose because, in
pathology are associated with the leakage spite of advanced technology, many of
pattern (Phillips, 1967). In many instances the principles underlying the mechanism
of adhesion remain unknown.
•Elida-Gibbs Fellow 1970.

F ig. 2: Elimination of microlcakagc by

Fig. 1: Marginal leakage at the restora- adhesive film or adhesive restorative
tion/tooth interface. material.

September 1970 285

 Tin: J ou rnal of t i i l D.A.S.A.
X X
T hf N ature o f A d iifsio n
Adhesion is defined as the molecular NaCI Na* u* M W
attraction exerted between the surfaces X X

of bodies in contact or the attraction be­ in Sodium atom Chlorine Sodium Chloride
ide One electron atom ion ton
tween molecules at an interface. This
force is called adhesion when unlike m in t electrons
in outer tirhit
molecules arc attracted and cohesion
when molecules of the same kind are The force of attraction is given by:
attracted. The material added to pro­ 9+ • 9-
duce the adhesion is known as the ad­ I-- = ----------------------

hesive and that to which it is applied is r

called the adherend. The interface is the where 9 *• and 9“ are the charges of the
zone between the interacting substances. ions.
The molecular forces involved in ad­ r = the distance between the ions.
hesion may be divided into chemical and Although the typical ionic bond only
physical attractive forces. The former in­ appears in ion-crystals, similar forces ap­
clude eleclrovalcnt, covalent and metallic pear in any system containing ions.
bonds and constitute the primary bonds:
the latter arise from van dcr Waal's forces (2) Covalent Bond.
and hydrogen bonding and constitute the This is formed by the sharing of elec­
secondary bonds. trons of the valency orbits, and a shared
i. Eleclrovalcnt or ionic bond pair of electrons constitute a covalent
Chemical or 2. Covalent bond: a. nonpolar bond.
primary forces b. polar A purely covalent or noil-polar
. .
1 Metallic bond. bond is formed by the equal sharing of
1. van dcr Waal’s forces. electron pairs by similar atoms, for ex­
Physical or a. Kecsom forces—orienta­
ample C l . (Parker and Taylor, 1966).
secondary tion effect.
forces b. Debye forces—induction
cITcct. X x x /CA xx
c. London forces—disper­ X Cl © Cl'
sion cllcct. XX XX
2. Hydrogen bond.
Such a bond has no ionic character.
The Chemical Forces. If the electron pairs are shared by dis­
These arc intramolecular attractive similar atoms, that is. those which have
forces. clilTerent degrees of electro-negativity,
lliey will be displaced closer towards the
(I) Electrovalent or Ionic Bond. more electro-negative atom. The bond
The bond is formed by the electron or bonds between the atoms will have a
transfer from the valency orbit of one partly ionic character: and they will have
atom to the valency orbit of another a polar characteristic due to the unequal
atom. This transfer results in the forma­ sharing of the electron pairs.
tion of positively- and negatively-charged
ions, and the attractive forces arise from C ( C l] - > -C * + 4 xC l
the electrostatic attraction between these 4 • xx
ions.
This type of bond is found in sodium ? c i;
chloride. The outer valency electron of <
S>
the sodium atom is transferred to the XX + X X
chlorine atom which already has seven
outer valency electrons, and positively- - » * xc xi ©
u
+ c + © c i;
**
charged sodium ions and negatively-
charged chloride ions are formed. In a <3)
sodium chloride crystal the ions arc held
together by electrostatic attraction.

286 Sli’TI.mdlk, 1970

 Du; T y d s k r if van d ii ; T.V.S.A.

The shared pairs of electrons. -X, are ( I) Van tier Waal's forces.
displaced towards the more electro-nega­ According to Elcy (1961), these forces
tive chlorine atoms which thus are given of molecular attraction are due to three
a negative charge and the carbon atom main factors: the Keesom, Debye and
a positive charge. London forces.
The ionic character of polar covalent
bonds varies as it is dependent on the (a) The Keesom forces—orientation
electro-negativity of the atoms between effect.
which the bonds are formed. The esti­
mated ionic character of some single These result from the interaction of
bonds is ; permanent dipoles in neighbouring mole­
Bond Approximate ionic cules of polar compounds. If in a bimolc-
character cular reaction the two dipoles arc free to
C-C 0 rotate they will take up a hcad-to-tail or
C- H 4 lowest energy configuration as here
C -C I 10 shown ;
C-F 44
Covalent bonds are commonly found in
organic compounds.
A dipole results whenever a covalent A typical molecule in a liquid will have
10 - 12 molecules in its immediate vicinity,
bond is formed by the unequal sharing all interacting with one another. Except
of the electron pairs that go to make up for molecules of very low polarity, the
the bonds. The shared electron pair is rotation of the dipoles will certainly not
displaced towards the most electro-nega­ be free and the problem of the relative
tive atom and the degree of electron dis­ orientation of dipoles in a liquid is a very
placement is reflected by the dipole mo­ difficult one (Good 1967).
ment.
The electric dipole moment (b) Debye forces— induction effect.
a = q/
where q = the magnitude of the charges These arise from the induction ched
separated. that hikes into account the influence of
/ = the distance separating the the dipole moment in a molecule which
charges. induces tin additional dipole moment in a
neighbouring molecule; that is to say.
Permanent dipoles are found in polar they result from the interaction of a per­
organic compounds and are of consider­ manent dipole with a bond system capable
able importance in adhesion. of being polarized. A dipole in a mole­
(3) Metallic Bond. cule may provide the electrical field to
The free valence electrons of metals polarize a neighbouring symmetrical
can move about the metal space lattice molecule. Once a dipole moment has been
to form an electron cloud. The movement induced, the two molecules attract each
of these electrons is responsible for some other.
of the properties of metals such as the
conduction of electricity; and the move­
ment of the free valence electrons leads to
a regular array of positive ion cores being
found in the crystal. The electron clouds
and the positive ion cores provide the
forces of attraction which bond the metal
atoms together. The surface of metals
will have some free electron deficient
sites available for bonding.
The Physical Forces. The Keesom and Debye forces both
These tire intermolecular attractive depend on the existence of permanent
forces. dipole moments in molecules and there-
Srm:M:iiit 1470 287
 Tim Journal o r Tin; D.A.S.A.

fore play no part in a medium consisting

of non-polar molecules.
(c) London forces—dispersion effect.
These arc not dependent on the exist­
ence of permanent dipoles. Slight displace­
ment of the electrons or nuclei in an
atom or molecule is constantly occurring:
it is instantaneous and at random, and
results in the formation of a dipole which
at any one instant induces another dipole
in a neighbouring molecule.
The Kccsom and London forces are
[h 2 o ] 3
by far the most important in adhesion.
Fill. 3: Hydrogen bonding in Ihc associa­
(2) Hydrogen Bond. ted water molecule.
This can be regarded as a special type to the negative oxygen portions of neigh­
of dipole—dipole interaction. According bouring molecules and two hydrogen
to Good (1967) it calls for two condi­ bonds, which are inter-molecular attrac­
tions : tive forces, arc established. Fig. 3.
(a) A highly electro-negative atom The physical forces of attraction result
such as F, O or Cl, or strongly electro­
negative groups like -CN with a hydrogen in the physical adsorption of the adhesive
atom attached. on the adherend; the adsorption is a
rapid and reversible process and requires
(b) Another highly electro-negative no activation energy as the molecules re­
atom which may or may not be in a main chemically intact on the surface. In
molecule of the same species as the first all three types of physical interaction,
atom or group, to be in the vicinity. For Kccsom, Debye and London, there is the
example the water molecule, FLO, does same marked dependence on separation
not exist as such but as (FLO).-, where the between the interacting molecules—a de­
three associated molecules arc held to­ pendence on the inverse sixth power of
gether by hydrogen bonds. the distance. The London or dispersion
The primary intramolecular bonds be­ clfcct is universal and operates whenever
tween the hydrogen and the oxygen two molecules, atoms or ions arc in close
wuhin the water molecule is of the cova­ contact. The London forces are sufficiently
lent type: the bonds arc formed by elec­ strong so that good adhesive performance
tron sharing. should be observed no matter what the
chemical nature of the two phases in con­
xx xx tact, provided that enough intimate inter-
H20-^ ? H ' + xQx -> H H molecular contact is achieved at the inter­
ONE
S/x
lace.
ELECTRON
electrons Chemisorption is preceded by physical
IN O R B IT INOUTER SHARED PAIRS
adsorption. In the former the interaction
QR&IT OF ELECTRONS
with the surface is much more specific
As the two shared pairs of electrons than is the case of the latter. The ad­
will be orientated much closer to the sorbed molecules arc held to the surface
strongly clcclro-ncgativc oxygen atom, by bonds which may be covalent, ionic
the electron density around the oxygen or metallic. The rate of chemisorption
nucleus will be much greater than around may be slow because an activation energy
the hydrogen one (proton). Consequently is required before the adsorption process
the hydrogen portions of the water mole­ can lake place. The nature of the ad­
cule arc positive in relation to the oxygen herend will have a profound effect on the
portion. When a single water molecule rate of the reaction. Chemisorption gives
intermingles with other water molecules, rise to very strong attractive forces and
its positive hydrogen parts arc attracted once established is not easily reversed.

288 S i:i*ti ;MIii:r , 1970

 D ie T ydskrif van die T.V.S.A.

Surface P henomena ing close contact with them. The mole­

(1) Surface Contact. cular forces of attraction between the
solid surfaces operating at the tip of the
Adhesion, depending essentially on the asperities will be supplemented by those
forces of molecular attraction at the inter­ between the adhesive and the adherend
face, exists only at short distances of se­ at the interfaces. Fig. 4(c). It is not only
paration, in the order of one or two necessary to obtain molecular closeness
Angstrom units. If solid surfaces are natu­ but also to maintain it. For this reason a
rally smooth on an atomic scale they liquid adhesive that solidifies is used:
will adhere spontaneously when brought one with a volatile component which sets
together without an intermediate layer of when it evaporates, or one whose mole­
adhesive. Fig. 4(a). An example of the cules can be made to polymerise or cross­
adhesive force uniting atomically smooth link with each other by means of heat,
surfaces is the bond between mica sheets. catalysts or reactive hardeners.
The strength of this adhesion is about
14,000 lbs/sq. inch, as strong as the mica (2) Wetting.
itself (Buonocore 1963). A film of oxide
or organic contamination only one mole­ To produce adequate adhesion the
cule thick will greatly decrease the ad­ liquid adhesive must flow, easily over the
hesion of solids. entire surface, thereby ensuring the wet­
ting of the adherend surface. The funda­
mental requirement for good adhesive
A to m ic a lly sm o o th s u r fa c e s
performance is intimate interfacial con­
tact between the adhesive and its sub­
strate or adherend. When the attractive
forces between the molecules of the ad­
herend and the molecules of the adhesive
Rough s u r fo c e s are stronger than the attractive forces be­
o o o tween the molecules of the adhesive, wet­
ting will occur.
Huntsbcrger (1967) uses the term wet­
R o u g h s u r fo c e s w it h o d h e s iv e
ting in reference to a process, and a state.
The wetting process is described as the
establishment of interfacial contact. The
F ig. 4: (a) Adhesion between atomically
wetting state is defined as the number of
smooth surfaces. interfacial contacts between the phases at
(b) Adhesion between rough sur­ the interface in relation to the maximum
faces. number possible for the system when wet­
(c) Adhesion with adhesive be­ ting is complete.
tween rough surfaces.
The extent to which an adhesive will
In practice it is impossible to obtain wet a surface depends on its viscosity and
such atomically smooth surfaces; those on the shape of the irregularities on the
to be bonded arc very rough at an atomic surface of the adherend (Dc Bruyne,
level. If such rough surfaces are brought 1962). If the depressions are of the ink-
into contact the molecular forces of attrac­ bottle type with increasing distance be­
tion will operate only where the tips of tween the lateral walls, the adhesive can
the asperities on the surfaces meet. Fig. hardly penetrate. Fig. 5(a). If the pit is
4(b). These widely spaced attractive forces
are so small that poor adhesion will re­ A d h e s iv e •*

sult. The actual area of contact is gene­

rally a small fraction of the apparent one. A d h e re n d '*

In practice the small separation neces­

sary for adhesion is almost always ob­
b
tained by introducing a liquid adhesive
between solid surfaces; its function is to Ink bottle pit Flower pot pit
adapt itself to the irregularities of the F ig. 5: Types of depressions on adherend
surfaces to be bonded thereby establish­ surfaces.

September 1970 289

 I in; J ournal of Tin; D.A.S.A.

shaped like a Ilowcr-pot, ils penetration WETTING ADHESION CONTACT

is facilitated: and it will cease only when ANGLE
the force of the surface tension pulling
the adhesive into the depression is ba­
lanced by the pressure of the entrapped
air. Fig. 5(b). The process of filling the
depression will be slowed down by an
increase in viscosity of the adhesive.
(3) Contact Angle.
The contact angle, 0, is the one formed
between the surface of the adhesive drop
and the surface of the adherend upon
which it is resting. Fig. 6 gives a diagram­
matic scheme for the drop of liquid in
equilibrium with the solid surface and the
surrounding atmosphere saturated with the
liquid vapour.
F i g . 7 : I lie e llc c l o f llic contact angle
on wetting and adhesion.

from both sides (Fig. 8). The attractive

forces always include the London disper­
sion forces but additional attractive forces
such as dipole interactions or ionic inter­
actions will operate in polar or ionic
0 = CONTACT ANGIE
liquids respectively. A molecule in the sur­
F ig. 6: Contact angle. face of a liquid is attracted from below
and from the sides but not from above.
The degree of wetting depends on the As a result molecules in the surface arc
contact angle at which the adhesive meets in a one-sided field force pulling them
the surface of the adherend. It increases as downward in the bulk of the liquid
the angle decreases. The contact angle is (Fowkes, 1907). The surface tension re­
small if the attraction between the mole­ sults from this one sided field force
cules of the adhesive and that of the exerted on surface layers. The stronger
adherend is greater than the altraclivc this force the greater the surface tension.
forces between the molecules of the ad­ Since the range of these forces is short,
hesive. If this angle is small the adhesive most of the tension is in the outer layer
will wet the adherend surfaces, and the of the liquid.
molecular forces of attraction will ope­ The surface of the liquid may be re-
rate along the entire interface and strong
adhesion will result. If it is large the
adhesion will be poor. Fig. 7 gives a vapour
diagrammatic presentation of the cfTccl O (9 (D Q ® -< ® > -O 9 ®
of the contact angle on wetting and ad­ AA A 'a
hesion. O O O O o O O O

(4) Surface Tension. yj

o o o o o o o -( 0 > 0
The surface tension of the adhesive a''a
and the adherend play an important role o o o o o o o
in adhesion. liquid
In liquids and solids there is a tension
in the surface region. A molecule in the Surface tension
bulk of a liquid is surrounded by neigh­ F ig. S: Molecular forces of attraction in a
bouring molecules and is attracted equally liquid.

243 St I’l l.M ill It. 1970

 Din T ydskrif van dif T.V.S.A.

garded as the seal of a special force which )’st. F v ' /'sv' •• • • (I)
acts perpendicular to the surface; and if .v
the section of the surface involved is 1.0 Cos 0 ----- where 0 — con-
cm long it is called the surface tension v° tact angle
and is expressed in dynes/cm. .’. .V }’i v" COS 0
Substitute .v in (1)
)’sl r 5’i.v cos 0 - )’sv'
(5) Thermodynamic Considerations. or ysv" - ysu >'i.v° cos 0 .. (2)
In 1805 Thomas Young enunciated that /s v ° - )'sl
the three surface tensions, ysv', )’sl mid and cos 0 ------------ .. (3)
o
yi,v° existing at the phase boundaries of a }'l. v
drop of liquid at rest on a solid surface The cosine of the contact angle formed
must form a system in static equilibrium between a liquid drop and the plane sur­
Fig. 9 (a). face of a solid on which the drop is rest­
ing has, at equilibrium, a definite rela­
tionship to the surface tensions of the
T lv ' liquid and the solid in contact with the
saturated vapour.
\ The free surface energy expressed in
vapour
ergs/cm2 is dimensionally the same as
"lTouicT the surface tension expressed in dynes/
T sl r"sv° cm. Sumner (1937), using a thermodyna­
,~t __ -*rr mic approach, substituted the specific
free energies in the system for the surface
SOLID tensions and showed that the Young
A equation (2) could be written;
)’sv° - '/si. =- )’i.v° cos 0 .. (4)
Where ySv" r= the free surface energy of
the solid in equilibrium
with the vapour.
)’SL — the free surface energy at
the solid/liquid interface,
/i.v" the free surface energy of
the liquid in equilibrium
with the vapour.
Dupre (1869) showed that WA, the re­
Fici. 9: (a) The surface tensions at the versible work of adhesion per unit area
phase boundaries of a liquid of a liquid with a solid (or another liquid),
at rest on a solid surface. is related to the decrease in free energy
(b) Resolution of forces at the when the two surfaces come together to
point where the phases meet. form an interface.
Wa ys" •! /i.v" -■ /si.. . (5)
Where ysv° - the surface tension of the Where ys" the free surface energy of
solid in equilibrium with the solid in a vacuum.
the vapour. It was realized, however, that the solid
yLV“ - the surface tension of the surface will be covered by adsorbed vapour
liquid in equilibrium with of the liquid and consequently a new
the vapour. quantity W a * was defined (Zisman, 1963).
W a * is the reversible work of adhesion to
ySL the surface tension at the
interlace between the pull the liquid oil' the surface leaving the
solid anc! the liquid. eq ui1ibr ium-a bsorbed ftIm.
Wa* ysv" : yi.v" ysi. (6)
If we resolve the forces acting along the Where ysv" the free surface energy of
line of the solid to liquid interface (Fig. the solid in equilibrium
9b) we obtain the following expression : with the vapour.

S i i’ l l m iii r 1670 291

 T he Journal of the D.A.S.A.

By eliminating y sL from equations (4) (6) The Critical Surface Tension of Wetting
and (6) -y e .
Wa * = )-l v ° (1 -f cos 0) . . (7) Zisman and his co-workers (Glantz
and 0 can readily be determined
yLV ° 1969), in their studies of the contact angles
experimentally and Wa* calculated. between various liquids and different solid
The specific reversible work of cohesion surfaces, revealed a rectilinear relationship
(We) of the liquid is calculated by applying between the cosine of the contact angle and
equation (7) to a liquid—liquid interface the surface tension, yL V °, for each homolo­
made up of two layers of the same liquid. gous series of organic liquids. The inter­
We = 2yLV° (0 = 0"; cos 0 = 1) .. (8) cept of the extrapolated straight line plot
In equations (5) and (6) ys° and ysv° of cos 0 vs. yLV” with the horizontal line
refer respectively to the free surface energy cos 0 = 1 occurs at ye (Fig. 10). ye is
of the solid in a vacuum and the free sur­
face energy of the solid immersed in the
saturated vapour of the liquid. Thus
ys° — ysv° is the decrease in the surface
energy of the solid obtained on immersing
it in the saturated vapour of the liquid. The
free energy change is presented by /sv° and
/sv° = ys" — ysv°.. .. (9)
/sv° is referred to as the equilibrium­
spreading coefficient.
From equations (5) and (6) it can be
calculated that: F ig .10: The critical surface tension of
W a - Wa * = ys° - ysv ° wetting.
= J sv°........................ (10) called the critical surface tension of wetting
It has been shown (Zisman 1963) that of a solid surface for each homologous
/sv° will always have a positive value and series of organic liquids. For a liquid to
hence W a > Wa*. wet a surface completely, the surface ten­
Cooper and Nuttal (1915) laid down the sion of the liquid must be lower than ye,
conditions for the spreading of a liquid the critical surface tension of wetting of the
substance on a solid surface. adherend.
For spreading to occur S > 0 Even when cos 0 is plotted against the
For non-sprcadinc S< 0 surface tension for noil-homologous
Where S = ys° - (y L V ° + y sL ) ..(11) liquids, the points on the graph lie close to
For an organic liquid spreading on an a straight line or form a narrow rectilinear
organic solid surface it can be assumed that band; and although the intercept is less
y sL is negligibly small in comparison with precisely defined than is the ease with a
yL V °, therefore: homologous series of liquids, it is an even
For spreading to occur ys° > yLV° (12) more useful parameter because it is
Thus in systems where the specific sur­ characteristic of the solid only, y e has been
face free energy of the liquid is less than used to study the wettability of a variety of
that of the solid, spreading should occur. low-energy surfaces.
From equation (7) it is clear that for any The surface constitution of solids affects
system having 0 — 0°, i.c. cos 0 = 1 , the value of y e . Zisman (1961) has ob­
WA*^2yLV° .........................(13) served a parallel and regular increase in y e
This value is much greater than the ten­ with progressive replacement of fluorine by
sile strength of common adhesives. When hydrogen atoms in the surfaces of bulk
the adhesive wets the adherend surface polymers.
properly (0 — 0°) the tensile strength of
the adhesive joint will be considerably O ther F actors A ffecting Bond
more than that of the adhesive. Therefore Strength
if the joint fails it will break within the bulk The manner in which some of the physi­
of the adhesive rather than at the adhesive/ cal and chemical properties of the adhe­
adherent interface. sive and the adherend affect the bond

292 S eptember, 1970

 D ie T ydskrif van die T.V.S.A.

strength has been described. In addition and counteract the molecular forces
the external influencing factors have to be of attraction between the adherend
considered. These are prevalent when the and adhesive at the interface.
bond is processed and subsequently when The effect of the thickness of the ad­
it is subjected to use. hesive on the bond strength is presented
During processing of the bond the way graphically in Fig. 11. Up to an optimum
the adhesive is applied is important. It point, .v, the thinner the adhesive layer
should be at a temperature at which its the stronger is the joint strength. Beyond
viscosity provides for adequate spreading this, insufficient material is available to
on the adherend surface. The setting con­ cover the whole joint and the bond will
ditions, pressure and temperature, must fail as a result of joint starvation.
be correct for the selected material. In Several factors will affect the bond
the setting or curing of the adhesive there strength during use: the type of stress
is shrinkage, which causes residual strain to which the joint is exposed; the rate and
in the bond. speed at which the stresses are applied;
Another significant factor affecting the the temperature changes to which the
bond strength is the nature of the adhesive joint is exposed; and the chemical stresses
layer: thick ones give weaker joints than to which the bond may be subjected
thin ones. A number of reasons have been (Patrick. 1961).
postulated for this observation. The effect of certain of these factors
1. In a thin layer there is less chance can be lessened by the addition of fillers.
of flaws occurring which may cause These are inert inorganic particles which
stress concentrations when the joint are added to the adhesive to improve
is subjected to a load (Buonocorc, some of its physical properties. The im­
1963). provement in adhesive performance may
2. A thick layer is more likely to be­ be obtained by reducing the shrinkage
come deformed and thus will frac­ during cure, approximating the coefficient
ture sooner. of thermal expansion of the adhesive to
3. There is less shrinkage in a thin that of the adherend. and improving the
layer during polymerization. Fur­ bulk strength of the adhesive.
ther, the swelling of the adhesive A biiesives
due to the absorption of fluid Abhesives are coatings applied to a
during use, or the effect of a signi­ solid to greatly decrease or prevent the
ficant difference in the thermal ex­ adhesion to another solid in intimate con­
pansion of the adhesive and the tact with it. They are commonly employed
adherend are reduced. De Bruync in moulding or coating operations. Mate­
and Houwink (1951) suggest that rials employed for this purpose include
these factors produce tangential vec­ high molecular weight fatty acids, poly-
tors of force which are proportional dimcthylsiloxanc and Teflon. A mono­
to the thickness of the adhesive layer layer of the abhesive agent suffices to
cause the optimum parting effect. The
abhesive coating converts the high-energy
solid surface to a low-energy one. This
results in the critical surface tension of
wetting, )’C. being markedly reduced.
The equilibrium contact angle of any
liquid in contact with an abhesive coating
will be large; and the greater the differ­
ence between the surface tension of the
liquid and the critical surface tension of
wetting of the abhesive coating the larger
it will be. When it becomes large enough
the resultant adhesion is so poor that a
F ig. 11 : The effect of adhesive thickness modest external stress suffices for effec­
on the joint strength. tive mould release.

S l il’T EM U E R 1970 293

 Tin- Journal of the D.A.S.A.

Summary 15. Abhesives are materials which are

1. Adhesion, depending essentially on applied as coatings to solid surfaces
the forces of molecular attraction be­ to decrease or prevent the adhesion
tween surfaces, exists only at short of another solid in intimate contact
distances of separation. with it.
2. In practice the small separation ne­ REFERENCES
cessary for adhesion is almost always Buonocore, M. G. 1963. Principles of adhesive
obtained by introducing a liquid ad­ retention and adhesive restorative mate­
hesive between solid surfaces. rials. J.A.D.A.. 67:382-391.
3. To produce molecular closeness the Cooper. W. A. and N uital. W. H. 1915. 7.
liquid adhesive must wet the acllic- A eric. Sci.. 7:219. Cited by /.isman,
1961, 1963.
rend surfaces. De Bruyne. N. A. 1962. The action of ad­
4. The degree of wetting depends on hesives. Scientific American, 206:114-
the contact angle at which the boun­ 126.
dary of the liquid adhesive meets the Du Bruyne. N. A. and H ouwink . R. 1951.
Adhesion and Adhesives. Oxford Univer­
surface of the adherend. It increases sity Press.
as the contact angle decreases. D upre , A. 1869. Thcoric mcchaniquc de la
5. Surface tension results from the one­ chalcnr. Cauthicr-Villars, Paris, p. 369.
sided field force exerted on surface Cited by Zisman, 1961. 1963.
E l e y , D. D. 1961. Adhesion. Oxford University
layers of metals and liquids. Press, p. 21.
6. The contact angle formed between Powkcs. F. M. 1967. In: Treatise on adhesion
a liquid drop and the plane surface and adhesives. Vol. 1. Theory. Ed. R. L.
of a solid on which the drop is rest­ Patrick, Edward Arnold Publishers, Lon­
don. p. 327.
ing has, at equilibrium, a definite G lantz, P er-O loe. 1969. On wettability and
relationship to the surface tension of adhesiveness. Odont. Revy., 20 (Suppl.
the liquid and solid. 17): 1-132.
7. The surface tension is dimensionally G oing. R„ Massier. M. and D uel. 11. I960.
Marginal penetration of dental restora­
the same as the surface-free energy. tions by different radioactive isotopes.
8. The force of adhesion or the revers­ J. dent. Res., 39:273-284.
ible work necessary to separate a G ood, R. J. 1967. In: Treatise on adhesion
liquid from a solid must be the same and adhesives. Ed. R. L. Patrick. Edward
Arnold Publishers, London pp. 27, 28.
as the free energy changes of the G winnett, A. J. and Buonocore. M. G. 1965.
system. Adhesives and caries prevention. A pre­
9. The force of adhesion can be calcu­ liminary report. H.D.J., 119:77-80.
lated from experimentally-determined H olliger, H. H. 1967. Penetration of restorative
margins. A fluorescent dye study. Dent.
values of cos 0 and the surface Rad. Phot. 40:9-14.
tension of the liquid, ySv"- U unt.nhi rger. J. R. 1967. In: Treatise on
10. For spreading to occur the free sur­ adhesion and adhesives. Vol. I. Theory.
face energy of the liquid must be Ed. R. L. Patrick, Edward Arnold Pub­
lishers, London, p. 127.
less than that of the adherend: K raus. E. E. and K raus L. L. 1951. Evaluation
)’sv }’lv of the auto polymer direct plastic filling
11. When the adhesive has wetted the materials. 7. dent. Res., 30:498 Abstr.
Mc Lean, J. W. and K ramer, I. R. H. 1952.
adherend completely, the joint must A clinical and pathological evaluation
break by cohesive failure—that is, in of a sulphinic activated resin for use in
the bulk of the adhesive rather than restorative dentistry. B.D.J., 93:255-269.
at the adhesive/adherend interface. M izrahi. E. and S mith , D. C. 1969. Direct
cementation of orthodontic brackets to
12. A liquid will wet a surface com­ denial enamel. B.DJ.. 127:371-375.
pletely if the surface tension of the N i.lsen, R. J., Wolcott, R. B. and Paffen-
liquid is lower than the critical sur­ harger. G. C. 1952. Fluid exchange at
face tension of wetting yc) of the the margins of dental restorations.
J.A.D.A.. 44:288-295.
solid. Parker. R. S. R. and T aylor, P. 1966. Adhe­
13. The thinner the adhesive thickness, sion and adhesives. Pergamon Press, Ox­
the stronger the joint. ford. p. 10.
14. The critical surface tension of wet­ P atrick, R. I.. 1961. In: Workshop proceed­
ings, adhesive restorative dental mate­
ting varies with the constitution of rials. Owen Lilho Service, Indiana, pp.
the solid surface. 137-152.

294 S eptum her. 1970

 Din T ydskrie van die T.V.S.A.

P eterson, E. A., P hillips , R. W. and S wartz, Owen Litho Service, Indiana, pp. 164-
M. L. 1966. A comparison of the physi­ 170.
cal properties of four restorative resins. R oydiiouse, R. H. 1968. Prevention of occlusal
J.A.D.A., 73:1324-1336. fissure caries by use of a sealant. A pilot
P hillips , R. W. 1961. In: Workshop proceed­ study. J. dent. Cliil., XXXV: 253-262.
ings, adhesive restorative dental mate­ S kinner, E. W. and P hillips , R. W. 1967. The
rials. Owen Litho Service, Indiana, p. Science of Dental Materials. W. 13.
170. Saunders Co., Philadelphia and London.
P hillips , R. W. 1967. Advances in adhesive S umner, C. G. 1937. Symposium on Deter­
restorative dental materials. J. dent. Res., gency. Chem. Publ. Co., New York. p.
47:1662-1667. 15. Cited by Zisman, 1961, 1963.
Y oung, T. 1805. Phil. Trans. Roy. Soc. (Lon­
R etief , D. H. and D rp.yer, C. J. 1967. Epoxy don) 95:65. Cited by Zisman, 1963.
resins for bonding orthodontic atta c h ­ Z isman, W. A. 1961. Constitutional effects on
ments to teeth. J. dent. Ass. S. Afr., 22: adhesion and abhesion. In: Workshop
338-346. proceedings, adhesive restorative dental
R ose, E. E., Lal, J., W illiams, N. B. and materials. Owen Litho Service, Indiana,
F alcetti, J. P. 1961. The screening of pp. 106-136.
materials for adhesion to human tooth Z isman, W. A. 1963. Influence of constitution
structure. In: Workshop proceedings, on adhesion. Ind. E rif;. Chem., 55:19-
adhesive restorative dental materials. 38.

September 1970 295