Adhesive Dental Materials-A Review: John W. Nicholson
Adhesive Dental Materials-A Review: John W. Nicholson
Adhesive Dental Materials-A Review: John W. Nicholson
Abstract
The use of adhesive substances in dentistry, particularly in the restoration of decayed teeth, is growing. Adhesive materials are also
used for securing brackets to the teeth in orthodontic treatment and for luting the form of artificial teeth known as jacket crowns in
place. In recent years, there has been considerable growth in the use of adhesive systems to repair teeth damaged by caries. In this
application, adhesive materials show two important advantages over traditional materials, such as silver amalgam, namely: (i) that
marginal leakage is prevented, thereby eliminating the development of secondary caries; and (ii) that adhesive materials are more
clinically conservative, since they allow the dentist to repair the tooth without removing excessive amounts of healthy tissue. Teeth
repaired in this way are stronger and more likely to last that those treated with silver amalgam fillings. Adhesive dental materials
include the glass—ionomer and zinc polycarboxylate cements, and also the dentine bonding agents used to bond composite resin
restorations to the dentine of the tooth. This article reviews these materials and their clinical applications and discusses likely future
developments in the light of the changes occurring in oral health and age distribution of the population. ( 1998 Elsevier Science Ltd.
All rights reserved.
Keywords: adhesive dentistry; bonding agents; glass—ionomer; zinc polycarboxylate; composite resin; dentine and enamel
0143-7496/98/$—see front matter ( 1998 Elsevier Science Ltd. All rights reserved.
PII: S0143-7496(98)00027-4
230 JW. Nicholson / International Journal of Adhesion & Adhesives 18 (1998) 229—236
to spread across the surface and penetrate the micro- ployed for attaching crowns to posts and for the adhesion
porosity [19], thus forming a strong attachment. of orthodontic brackets [1].
The first truly adhesive dental restorative material was The development of the glass—ionomer cement arose
the zinc polycarboxylate cement, introduced by Smith in from previous fundamental studies on dental silicate ce-
the late 1960s [20]. This material is prepared from deac- ments, materials which were formed from special basic
tivated zinc oxide, admixed with a minor amount (10%) glasses and aqueous phosphoric acid [27]. It was assisted
of magnesium oxide. Deactivation of the zinc oxide is by work on the zinc polycarboxylate cement [20] in
achieved by heating, and leads to the development of pale which Smith showed that dental cements exhibiting the
yellow colouration, due to the loss of a small amount of property of adhesion could be prepared from poly(acrylic
the oxygen to generate the non-stoichiometric form of acid). Glass—ionomers have therefore been described as
the oxide ZnO where x is less than or equal to hybrids of dental silicates and zinc polycarboxylates.
(-~x)
70 ppm [21]. This basic powder is then reacted with However, although this view seems attractive, it is not
aqueous poly(acrylic acid) to form the cement. The re- actually correct [28]. A practical cement cannot be pre-
sulting cement is a reasonably brittle material, though it pared from these two components alone, because the
shows some moderate plasticity for some time after dental silicate glass is not sufficiently basic to react with
formation [22]. Typical properties are shown in Table 2. aqueous poly(acrylic acid). In fact, to make a glass—
The set cement comprises zinc poly(acrylate) as the ionomer cement required new glasses of altered basicity
matrix, with unreacted zinc oxide/magnesium oxide pow- and it was only later, when the discovery of the effect of
der embedded in it. The powdered base thus acts jointly the additive (#)-tartaric acid was made [29], that glass-
as a reactant and filler. es similar in composition to the old dental silicate glasses
Zinc polycarboxylate cements have been shown to could be used.
behave somewhat like thermoplastic composites The initial problem was to enhance the reactivity of the
with very weak crosslinks between the polyacrylate glass towards the polymer. Early cements set sluggishly,
chains [23]. One consequence of this is that there being unworkable relatively quickly but taking a con-
is a relatively large plastic zone at the fracture tip, siderable time to harden. They also remained sensitive to
which in turn makes the material senstitive to the thick- moisture loss and water ingress for extended periods of
ness at which it is used [24]. The plastic zone size for time after setting. The glass that first approximated to an
an experimental zinc polycarboxylate was found to acceptably reactive component, so-called G200, was high
vary with the molecular weight of the poly(acrylic acid) in fluoride, and itself highly opaque. It thus gave cements
from 40 lm at a molecular weight of 11 500 to 290.0 lm whose translucency was very low and hence which were
at a molecular weight of 383 000 [24]. A subse- unacceptable aesthetically.
quent study confirmed this effect of an optimum adhesive The early difficulties began to be solved following the
layer thickness for a commercial zinc polycarboxylate in discovery of the effect of (#)-tartaric acid. This material,
clinical use, showing it to have an optimum layer added in small amounts, improved the manipulation of
at 205 lm, which was assumed also to be the approxim- the cement paste by modifying the setting rate, extending
ate size of the plastic zone at the crack tip as the bond the working time and sharpening the set. The resulting
failed [25]. material thus has significantly enhanced handling prop-
Zinc polycarboxylate cements are used a variety of erties [30]. However, despite the fact that more than
clinical procedures, all of which rely on the inherently 20 years have passed since this discovery of its effect, the
good adhesion of the material to a number of substrates precise mode of action of (#)-tartaric acid remains un-
[26]. For example, they are used to line cavities prior to clear.
placement of the main restorative material, they are em- Clinically, the use of glass—ionomer cements was de-
veloped to exploit the adhesion of the cement to natural
tooth material. An early suggestion was the use in sealing
Table 2 deep fissures in the surface of molars, in which bacterial
Properties of zinc polycarboxylate cement
plaque otherwise accumulates [31]. This application also
Property Typical components/values exploited the fluoride-releasing capability of the material.
Other suggestions to emerge early in the development of
Liquid 40—45% polyacid these materials included their use as restoratives for so-
Powder:liquid ratio 2.5—3.0:1 called Class V erosion lesions (i.e. cavities along the gum
Setting time/min 2—4
line thought to be caused by heavy brushing), as liners or
Compressive strength/MPa 80—100
bases beneath composite resins and in minimal cavity
232 JW. Nicholson / International Journal of Adhesion & Adhesives 18 (1998) 229—236
restorations [32—34]. This latter idea was extended to a clear, ion enriched layer due to interpenetration of the
develop the so-called tunnel preparation [35], in which vital tooth tissue with the porous cement surface. This
caries is removed from within the tooth while preserving layer is stronger than the bulk of the cement, and conse-
the maximum amount of surface enamel. This is followed quently resists failure in shear bonding experiments.
by injecting glass—ionomer cement, which sets and acts as Glass—ionomer cements are relatively brittle materials
the core which binds the enamel shell together. Most of and, as mentioned, they suffer the important disadvan-
these have become more or less routine procedures in tage of sensitivity to early moisture damage. In an at-
clinical dentistry. tempt to overcome these problems, resin-modified
Modern glass—ionomers undergo a sharp set to yield glass—ionomers have been devloped in the last ten years
a brittle material approximately four minutes from the or so.
start of mixing. This is the time at which the metal matrix Resin-modified glass—ionomers are a group of dental
band, used as a former for the surface of the restoration, restorative materials that consist substantially of
can be removed and the placement examined for defects. glass—ionomer components, i.e. water-soluble polymeric
The material is still, though, slightly susceptible to water acid, ion-leachable glass and water, but also include
uptake and/or loss, which inhibits the setting reaction organic, photopolymerizable monomers and their asso-
and results in an inferior material. To overcome this ciated initiation system [40]. The first of these materials
problem, a newly placed cement is usually painted with was described in a patent application, since abandoned,
a waterproof sealant as the matrix band is removed [36]. and comprised simply a mixture of ingredients, including
Manufacturers typically supply a special varnish sealant, 2-hydroxyethylmethacrylate, HEMA (I), to act as cosol-
but this does not necessarily provide a sufficiently imper- vent for the organic and aqueous components [41].
meable finish, at least as just a single coat. An alternative Shortly afterwards, the development of a cement-forming
procedure adopted by some clinicians is to employ a low system based on graft copolymers of poly(acrylic acid)
viscosity light-cured unfilled resin system. As the matrix was announced. In these materials, a minor proportion of
band is removed, a generous amount of such resin is the carboxylic acid functional groups were replaced with
allowed to flow over the cement restoration. When the crosslinkable branches that were terminated in vinyl
contour is completed, further resin can be added if neces- groups [42]. For these materials, too, HEMA was re-
sary, and the whole protective coating cured by irradia- quired in order to retain all of the components in a single
tion with light. The resinous layer can be removed after phase.
24 h, at which time the cement can be finished by polish-
ing under air/water spray. This technique gives optimum
translucency and physical properties.
Glass—ionomers continue to harden slowly after the
initial setting is complete, developing a compressive
strength of 180—220 MPa at 24 h [37]. Measuring adhes- (I) Hydroxyethylmethacrylate, HEMA
ive bond strength is somewhat problematical. Many The resin-modified glass—ionomers, whatever the de-
studies have been carried out, and treated the results as tail of their composition, have been shown to adhere to
though they are a measure of the interfacial adhesion enamel and dentine [43], though bond strengths seem
between the glass—ionomer and the substrate, usually less than for the self-hardening glass—ionomers [44]. This
dentine or enamel. However, glass—ionomers typically had led some manufacturers to specify that dentine bond-
fail cohesively within the cement itself, and most of the ing agents of the type used for composite resins should be
reported values of bond strength, which are low used with these materials. Resin-modified glass—
(3—6 MPa) are actually measures of the shear strength of ionomers have also been shown to release clinically use-
the cement. ful amounts of fluoride [45, 46]. On the other hand, they
Rather than rely on apparent shear bond strengths, have been found to swell in aqueous media [47], a pro-
other evidence has to be considered that indicates the cess which seems to be driven by the chemical potential
bond between the cement and enamel is very strong. of the solvent system, and is therefore greater in pure
Retention rates for glass—ionomers placed in Class V cav- water than in, for example, 0.9% sodium chloride solu-
ities, where inherent adhesion is essential, show them to tion, or than would be expected in saliva [48].
be excellent. For example, one commercial glass— Despite these disadvantages, overall the combination
ionomer cement, Ketac-Fil (ex. ESPE, Seefeld, Germany) of bonding to the tooth, fluoride release, and control of
showed a retention of at least 86% after 4 years [38,39]. setting has made resin-modified glass—ionomers attract-
These retention rates are superior to bonded composite ive to clinicians. At least one has predicted that these
resins, even though in vitro measurements showed them materials are likely to make obsolete the use of silver
to have much higher shear bond strengths, of the order of amalgam within the foreseeable future, at least in chil-
15 MPa. Glass—ionomers show good compatibility with dren’s dentistry [49], where long term durability is not
the tooth surface, and this can develop with time into required.
JW. Nicholson / International Journal of Adhesion & Adhesives 18 (1998) 229—236 233
(II) Bis-GMA monomer of liquid bonding agent into tubules with widened open-
ings [58]. The formation of such a hybrid layer has
been shown to be more important than tag formation
in creating a clinically durable bond between the com-
posite resin and the tooth. Results have shown that
bonding agents which do not flow into the tubules, and
hence cannot form tags, can promote good adhesion
(III) Diethylene diemethacrylate diluent solely through the development of the hybrid zone
For clinical use, composite resins are usually supplied [59, 60].
as one-paste systems that are cured by exposure to visible A number of organic compounds have been con-
light, typically blue light at 470 nm. Initiation in such sidered for use as bonding agents. One interest-
formulations is effected by an a-diketone, such as cam- ing example was the organophosphorus compound used
phorquinone, with an amine reducing agent. Exposure of as the very first dentine bonding agent of all, de-
this initiator system to light yields the free radicals re- veloped by Hagger in the early 1950s. This was based
quired to effect polymerisation of the monomer molecules on glycerophosphoric acid dimethacrylate (IV) [61]
[53]. and sold under the name of Sevriton Cavity Seal.
Composite resins are aesthetically attractive mater- Like many molecules employed in dentine bonding
ials, having the translucency and colour to match a agents, glycerophosphoric acid dimethacrylate has
variety of shades of natural teeth. They also show a non-polar tail and a strongly polar head. It was
good durability in the oral environment, both in terms thought to bond to the calcium of the dentine via
of resistance to erosion and wear, and in terms of the phosphate groups [62], though this was never dem-
colour stability. However, their major disadvantage is onstrated conclusively. Whatever its method of action,
their lack of adhesion to dentine. Bond failure in these it did not prove very effective, since it was hydro-
systems stems from lack of wetting of the tooth surface lytically unstable and bond failures occured during cli-
due to their hydrophobic character and is made nical testing [63].
234 JW. Nicholson / International Journal of Adhesion & Adhesives 18 (1998) 229—236
a neutralisation, but only by polymerisation, and also evidence [74], is nonetheless influencing clinical practice.
they lack the ion-exchange bonding mechanism that All of these trends place adhesion in dentistry at the
gives true glass—ionomers their inherent adhesion to den- forefront of dental research. The development of new
tine and enamel [36]. The multifunctional monomer, materials is continuing rapidly, and most if not all of the
known as TCB resin (VI) is used in Dyract, and is newer restorative materials are being expected to show at
illustrated below: least some adhesion to enamel and dentine. Yet the
mouth is an inhospitable place for materials, subjecting
them to high humidities and large shearing and compres-
sive forces. Given these constraints, progress to date in
finding materials capable of developing reliable and dur-
able adhesive bonds under these conditions has been
remarkable.
[38] Reich E, Volkl H. J. Dent. Res. (Special Issue), 1994, 73, Abstract [56] Nakabayashi N, Kojima K, Masuhara ET. J. Biomed. Mater. Res.
1394. 1982;16:265.
[39] Tyas MJ, Beech DR. Aust. Dent. J. 1985;30:260. [57] Pashley DH. Trans. Acad. Dent. Mater. 1990;3:55.
[40] McLean JW, Nicholson JW, Wilson AD. Quintessence Interna- [58] Walshaw PR, McComb DM. J. Dent. 1995;23:281.
tional 1994;25:587. [59] Nakabayashi N, Ashizawa M, Nakamura M. Quintessence Inter-
[41] Antonucci JM, McKinney JE, Stansbury RW. US Pat Appl. national 1992;23:135.
160 856, 1988. [60] Wang T, Nakabayashi N. J. Dent. Res. 1991;70:59.
[42] Mitra SB. Eur Pat Appl., 0 323 120 A2, 1989. [61] Hagger O. Swiss patent 278 946, 1951.
[43] Mitra SB. J. Dent. Res. 1991;70:72. [62] Kramer IRH, McLean JW. Brit. Dent. J. 1952;93:291.
[44] Cortes O, Garci-Godoy F, Boj JR. Am. J. Dent. 1993;6:299. [63] Buonocore MG, Wileman W, Brudevold F. J. Dent. Res.
[45] Mitra SB. J. Dent. Res. 1991;70:75. 1956;35:849.
[46] Forss H. J. Dent. Res. 1993;72:1257. [64] Nicholson JW, Singh GS. Biomaterials 1997;17:2023.
[47] Nicholson JW, Anstice HM, McLean JW. Brit. Dent. J. [65] Fusayama T, Nakamura M, Kurosaki N, Iwaku M. J. Dent. Res.
1992;173:98. 1979;58:1364.
[48] Anstice HM, Nicholson JW. J. Mater. Sci.; Mater. in Med. [66] Nakabayashi N. Int. Dent. J. 1985;35:145.
1992;3:447. [67] Stanford JW, Sabri Z, Jose S. Int. Dent. J. 1985;35:139.
[49] Croll TP. Dental Clin. N. Am. 1995;39:737. [68] Asmussen E, Munksgaard EC. Int. Dent. J. 1988;38:97.
[50] Smith BGN, Wright PS, Brown D. Clinical Handling of Mater- [69] DeTrey Dentsply Company, Technical brochure for Dyract,
ials, 2nd edition, Butterworth-Heinemann, Oxford, 1994. 1993.
[51] McCabe JF. Applied Dental Materials, 7th edition, Blackwells, [70] Ivoclar Company, Technical brochure for Compoglass, 1995.
Oxford, 1992. [71] Millar BJ, Abiden F, Nicholson JW. J. Dent. 1998; 26:133.
[52] McCabe JF. Brit. Dent. J. 1984;157:440. [72] Pospiech P, Rammelsberg P, Tichy H, Gernet W. Journal of
[53] Anstice HM. Chem. & Ind., 1994, 899. Dental Research, 1995, 74, 475, Abstract 600.
[54] Davidson CL, de Gee AJ, Feilzer AJ. J. Dent. Res. 1984;63:1396. [73] Preston AJ and Mair LH. Journal of Dental Research, 1996, 75,
[55] Legler LR, Retief DH, Bradley EL, Denys FR, Sadowsky PL. 1177, Abstract 368.
Amer. J. Orthodont. & Dentofacial Orthopedics 1989;96:485. [74] Jones DW. Brit. Dent. J. 1994;177:159.