PRACTICE

restorative dentistry

The development of resin-bonding

for amalgam restorations
J. C. Setcos,1 M. Staninec,2 and N. H. F. Wilson,3

The difficulty in bonding to dentine

Adhesive techniques are now used for many dental restorative relates to dentine’s complex histologic
materials, including amalgam. Several generations of dentine structure and variable composition.
bonding agents have been developed, mainly for bonding Whereas enamel is 92% inorganic
composite resins. When bonding is used with amalgam hydroxyapatite by volume, dentine is
(on average) only 45% inorganic. Also,
restorations, the need for retention and resistance form is reduced,
in contrast to the regular arrangement
the seal is improved, and some procedures, such as amalgam of hydroxyapatite crystals in enamel,
sealants, which were not previously possible, can be considered. dentinal hydroxyapatite is randomly
arranged in an organic matrix that con-
sists primarily of collagen, which is per-
At a time of rapid activity in the field, this meated throughout by tubules. These
article gives a timely interim overview of In brief contain vital processes of the pulp odon-
the development of resin-bonding of ● Bonding almagam restorations gives toblasts. Hence, vital dentine is a sensi-
amalgam restorations using adhesive promise for reduced need for tive structure. The high water content
resin bonding agents and chemically-acti- mechanical retention features and provides competition with any adhesive
vated luting agents. Consideration of resistance form which conserves biomaterial for bonding to dentine.
bonding to enamel and dentine is fol- sound tooth tissues. Moreover, when dentine is prepared
● Bonding almagam restorations help
lowed by the development of resin denti- with dental instruments, as in caries
to restore tooth integrity and fracture
nal adhesives over several ‘generations’ of resistance.
removal, the outermost dentine forms
progress to the current multiple-purpose ● Bonding almagam restorations assist
an attached surface smear layer (consist-
bonding systems of conditioners, primers in the improvement of the marginal ing of denatured collagen and debris)4
and adhesives. The specific development seal with potentially less sensitivity. which blocks the tubule openings. To
and adaptation of bonding resins for achieve a strong bond, it is necessary to
metal bonding precedes a brief coverage either strengthen this smear-layer in situ
of some currently popular systems avail- or to remove it entirely. In the latter, it is
able for use in bonding amalgam restora- quent work by Gwinnett and Matsui,2 and imperative to ensure an adequately
tions. Relevant publications are selected Buonocore et al.,3 suggested that the for- adhesive restorative otherwise the open
for their practical clinical value, rather mation of ‘resin tags’ was the primary tubules may allow irritants or bacteria
than furnishing an exhaustive review of attachment mechanism of resin to phos- greater access to the pulp.
all published literature. phoric acid-etched enamel. Acid etching
removes about 10 mm of the enamel sur- Development of resin dentinal adhesives
Bonding to enamel using the face and creates a porous layer ranging Hagger patented a ‘cavity seal’ material in
acid-etch technique from 5 to 50 mm deep. When a low viscos- 1951. This was a glycerophosphoric acid
For more than half a century there have ity resin is applied, it flows into the micro- dimethacrylate and methacrylic acid,
been studies focused on caries and acid porosities and channels of this layer and which was polymerised using a sulfinic
solubility of enamel, including many in polymerises to form a micromechanical acid initiator.5 McLean and Kramer inves-
the 1930s and 1940s. However, it seems bond with the enamel. tigated this in 1952 showing that the agent
that the foundation for the popularisation The most widely used etchant is aque- penetrated the dentine.6
of adhesive restorative and related preven- ous phosphoric acid (usually 30–50%). It Buonocore et al.,7 also reported more
tive dentistry was laid in 1955, when is applied for 15–60 seconds, after which than four decades ago that a resin con-
Buonocore proposed that acids could be the substrate is thoroughly washed and taining glycerophosphoric acid dimeth-
used to alter the surface enamel to ‘render then dried with an oil free air-stream. acrylate could bond to hydrochloric
it more receptive to adhesives’.1 Subse- Prepared (cut) enamel may be etched for acid-etched dentinal surfaces. The bond
less time than unprepared enamel and strengths of this early method of adhesion
1Senior Lecturer, Restorative Dentistry; and still provide a satisfactorily retentive sur- were greatly diminished by immersion in
3Professor of Operative Dentistry and Endodontology,
face for bonding. water. To overcome this problem, Bowen 8
Restorative Dentistry, Turner Dental School,
University of Manchester, Higher Cambridge St, synthesised N-phenylglycine glycidyl
Manchester M15 6FH; 2Clinical Professor, Bonding to dentine methacrylate (NPG-GMA). However,
Restorative Dentistry, University of California, products based on NPG-GMA had very
San Francisco, USA Problems in bonding to dentine poor clinical results when they were used
REFEREED PAPER
Received 14.09.98; accepted 11.01.99 Bonding to dentine has been more diffi- to restore cervical erosion lesions without
© British Dental Journal 1999; 186: 328–332 cult and less predictable than to enamel. mechanical retention.9

328 BRITISH DENTAL JOURNAL, VOLUME 186, NO. 7, APRIL 10 1999

 PRACTICE
restorative dentistry

A second generation of dentinal bond- (Kerr) and Scotchbond MultiPurpose to its original level. The primer also
ing agents was developed for clinical use (3M Dental), among others.5,16 increases the surface energy, and hence
during the early 1980s, but most prod- This ‘fourth generation’ is commonly the wettability, of the dentinal surface.5
ucts are no longer commercially avail- known as the multipurpose bonding sys-
able. Most of these materials were tems because: Dentine adhesives
halophosphorous esters of unfilled resins 1. They can be used in mixed cavities for These are applied by brush or other
such as bisphenol A-glycidyl methacry- both enamel and dentine, and means to cover the treated surface to
late (bis-GMA) or hydroxyethyl 2. Some of their components can also be permit resin wetting and penetration.
methacrylate (HEMA).10,11 Shear bond used for bonding to substrates such as They are unfilled resins that may consist
strengths for these materials were consid- porcelain and alloys (including amal- of hydrophobic monomers alone, such
ered too low to counteract the polymeri- gam). In each case the mechanism of as bis-GMA, or may include adhesion
sation shrinkage of composite resin.12 bonding is micromechanical into promoters to facilitate wetting of the
Also, some evidence indicates that bonds etched or grit-blasted surfaces. dentine. They attach to both the primed
between phosphate-based dental adhe- dentine surface and copolymerise with
sives and dentine were hydrolysed by Components the overlaying composite restoration.
immersion in water.13 The components of the ‘fourth genera- The latest generation of bonding sys-
A major reason that is offered for the tion’ are a set of chemical agents that pro- tems combines either the primers and the
poor performance of second generation ceed in sequence from an initially bonding resins in one bottle, or the condi-
bonding agents is that they were suppos- hydrophilic component (an aqueous, tioner and primer in one bottle. This rep-
edly bonded to the smear layer rather alcohol or acetone solution) through to resents an improvement in convenience,
than to the dentine itself. Hence their gradually more hydrophobic compo- though not necessarily in bond strength.
bond strength was limited by the cohesive nents. Specifically, they comprise the fol- Some examples are: Single Bond (3M),
strength of the smear layer or by the adhe- lowing items: One-Step (Bisco), Prime and Bond
sion of the smear layer to the underlying (Dentsply) and Liner Bond 2 (Kuraray).
dentine.14,15 Conditioners
A third generation of adhesives, unlike These are generally acid solutions such as The ‘hybrid layer’
the second generation, either modify or phosphoric acid (aq) or dilute nitric acid. Unfilled resin, when applied, penetrates
completely remove the smear layer to allow Acid etching removes the smear layer, and the primed dentine, copolymerising with
resin penetration into the underlying den- opens the intertubular and peritubular the primer to form an intermingled layer
tine. Examples include Scotchbond 2 (3M dentine. Removal of hydroxyapatite crys- of collagen and resin, termed the resin-
Dental, St Paul, MN, USA), Gluma tals leaves a collagen meshwork that can reinforced zone, resin-infiltrated zone,
(Bayer/Miles, Leverkusen, Germany), collapse and shrink because of the loss of resin-infiltrated layer, or the hybrid layer.
Tenure (DenMat, Santa Maria, CA, USA), inorganic support, especially if desic- Formation of this hybrid layer, as described
Prisma Universal Bond 3 (Caulk/Dentsply, cated. After placement, the conditioner is by Nakabayashi et al.18 in 1982, is thought
Milford, DE, USA), Syntac (Ivoclar rinsed off. Many bonding agents, particu- to be the primary bonding mechanism of
Vivadent, Schaan, Liechtenstein), and XR larly those containing acetone as a sol- most current adhesive systems.
Bond (Kerr, Romulus, MI, USA).5,11 These vent, work better on dentine that has been
adhesives have been clinically effective left moist after rinsing.17 The development of amalgam
when used beneath composite restorations bonding
and can presumably reinforce tooth struc- Primers
ture that has been weakened by disease, A primer is applied after rinsing of the Early methods of lining preparation walls
trauma or cavity preparation. conditioner. Primer molecules such as for amalgam restorations
HEMA (hydroxy-ethyl-methacrylate), The shortcomings of amalgam restorations,
Current dentinal adhesives biphenyl dimethacrylate (BPDM) and including poor appearance, lack of adhesion
Several major dental manufacturers have 4-methacryloxyethyl trimellitate anhy- to tooth surfaces and microleakage are
introduced new generations of bonding dride (4-META) contain two functional widely recognised. One of the first attempts
systems that use etching of dentine with groups — a hydrophilic group and to improve the retention and seal of amal-
phosphoric acid or other acids. Exam- a hydrophobic group. The hydrophilic gam restorations involved painting the cav-
ples include All-Bond 2 (Bisco Dental, group has an affinity for the dentinal ity walls with a thin coat of zinc phosphate
Itasca, IL USA), Amalgambond (Parkell, surface and the hydrophobic (metha- cement and condensing the amalgam
Farmingdale, CT, USA), Clearfil Liner crylate) group has an affinity for resin. immediately onto this wet surface. This
Bond (Kuraray, Osaka, Japan), ED The primer wets and penetrates the col- technique was described as early as 1897,
Primer/ Panavia 21 (Kuraray), Optibond lagen meshwork, raising it almost back and positive results were reported in terms

BRITISH DENTAL JOURNAL, VOLUME 186, NO. 7, APRIL 10 1999 329

PRACTICE
restorative dentistry

of improving the retention and seal of amal- ing one appointment. The cements were them also have metal bonding capabili-
gam restorations.19 However, it never marketed as Sun Medical’s ‘Superbond’ ties and may be used alone or with addi-
caught on as a standard technique and is (which was based on the 4-META-TBB tional components for amalgam
only infrequently mentioned in some texts adhesive monomer) and Kuraray’s bonding. A few products have been
of operative dentistry.20,21 ‘Panavia’ (based on the MDP monomer). specifically developed for amalgam
A further attempt to improve the inter- bonding. Recently, some dental adhesive
face between amalgam and tooth by bond- Resin cements as amalgam bonding agents resins have shown excellent adhesive
ing was made by Zardiackas in 1976.22 He Soon, researchers in Japan and US began properties to both tooth structures and
developed the so-called ‘selective interfa- testing these resin cements for use as encouraging bonding to amalgam
cial amalgamation’ liner by combining amalgam bonding agents. Varga et al.26 alloys.
components of polycarboxylate cement tested both Superbond and Panavia and Also, in this respect, due to the method
with amalgam alloy particles. This liner found them to bond amalgam to etched of condensing amalgam onto an unset
was tested in tensile adhesion and enamel surfaces and inhibit microleak- adhesive resin liner, there is an intimate
microleakage tests and found to give ten- age. Bond strengths of up to 17.7 MPa mechanical interlocking created. Some
sile bond strengths of around 3.5 MPa, were reported for Superbond. Shimizu et of the main adhesives used in amalgam
with shear punch bond strengths up to 15 al.27 tested various combinations of bonding studies include All-Bond 2
MPa,23 and to inhibit microleakage as Superbond or Panavia in combination (Bisco), Amalgambond Plus with HPA
well.24 For some reason, this process never with fluoride treatment and glass (high performance additive) powder
became popular either, perhaps because ionomer cement for amalgam bonding, (Parkell), Optibond 2 (Kerr), Panavia
the papers were published in journals not and found shear bond strengths up to 10 EX and Panavia 21 (Kuraray).
read by most clinical dentists. MPa on etched enamel and up to 6.4 MPa When All-Bond 2 is used, enamel and
Further development in amalgam bond- on dentine. They also found that Panavia dentine are both etched with 10% phos-
ing came with the development of metal combined with fluoride treatment and phoric acid for 15 seconds. After etching
adhesive resins, originally formulated for glass ionomer reduced microleakage28 and rinsing, the tooth surface is left visi-
bonding fixed partial dentures in the and described the clinical technique.29 bly moist. This is because drying of the
‘Maryland bridge’ technique.25 Staninec30 tested Panavia for bonding dentine can cause collapse of the unsup-
As will be appreciated, the bond amalgam to both enamel and dentine in a ported collagen network, inhibiting
strengths found in vitro have tended to tensile test specifically designed for amal- adequate wetting and penetration by the
increase with successive products. How- gam bonding. Panavia was found to give primer. An unfilled chemically activated
ever, there is still no minimum bond bond strengths of 9.7 ± 1.6 and 3.2 ± 0.4 resin is placed after the primer.
strength that has been definitively shown MPa on etched enamel and dentine, respec- This material is under study in a
to satisfy requirements for retention, frac- tively, whereas the copal varnish control prospective, controlled clinical trial
ture resistance and other properties. Fur- gave a bond strength of 0.0 MPa. Microleak- along with the All-Bond C&B resin lut-
thermore, high bond strengths do not age was also found to be inhibited, particu- ing cement to bond Nordiska Scania
necessarily mean low microleakage values larly on etched enamel margins. 2000 dental amalgam.31 The study
for bonding materials. Since then, many studies have exam- includes bonded amalgam sealants
ined the use of not only resin cements, placed into pits and fissures unprepared,
The development of metal adhesive resin but also a number of dentine bonding apart from prophylaxis with pumice on
cements and their use for amalgam bonding agents, for possible use as adhesive liners a bristle brush and etching with phos-
The early ‘Maryland bridge’ technique for amalgam restorations. Some phoric acid. A minimal extension
involved etching the metal surfaces with a researchers have tested the adhesive liners bonded amalgam restoration and
chemical or electrochemical process, for improving adhesion and retention, anatomic dental pits sealed with bonded
which was inconvenient, because it while others have tested only microleak- amalgam are shown at 3-year recalls in
required sending the bridge back to the age inhibition, expecting the liners to do figures 1 and 2, respectively.
laboratory for etching, after it was conta- no more than improve the seal over the Bonded amalgam sealants have been
minated in the try-in procedure. To sim- previous standard — copal varnish. shown to be as effective as resin sealants in
plify the procedure, two Japanese a clinical study, at least up to 2 years.32
manufacturers developed adhesive resin Current adhesives used to bond However, it is not suggested that bonded
cements, which were formulated with amalgam amalgam sealants are preferable to resin
special resin monomers to enhance bond- Although numerous commercial prod- composite sealants. Rather, it is a demon-
ing to metal surfaces after air abrading or ucts are available for adhesion to enamel stration of another extension to the utility
tin-plating these surfaces. This procedure and dentine, most of these are intended of the bonded amalgam technique. It is
can be easily done in the office, thus sav- for use with resin composites. Some of particularly appropriate in sealing adja-

330 BRITISH DENTAL JOURNAL, VOLUME 186, NO. 7, APRIL 10 1999

 PRACTICE
restorative dentistry

Up to 2 years, three non-bonded restora-

tions were lost due to lack of retention,
with no failures among the bonded
restorations. With this number of failed
restorations, there was no statistically sig-
Fig. 1 Photograph nificant difference between the bonded
from a clinical and non-bonded groups (P = 0.063,
study on bonded Mann-Whitney U test). However, over
amalgam
restorations at the longer evaluation periods, bonded restora-
third year clinical tions may be found to survive better than
review. Note the non-bonded restorations in preparations
bonded amalgam
with no deliberate retention.
minimal distal box
restoration on the
first premolar Conclusion
While the search for suitable tooth-
coloured alternative materials continues,
dental amalgam still remains in extensive
use internationally. This overview has
highlighted the current intense develop-
ment of materials for bonding dental
amalgam restorations that has provided
an opportunity for a re-evaluation of
preparation design here-to-for based on
providing undercuts for mechanical
retention. The promise of reliable bond-
Fig. 2 Additional
third year clinical
ing of dental amalgam restorations
review enables more conservative restoration of
photograph carious destruction ranging from initial
showing premolar lesions, through to complex restorations
anatomic pits and
fissures sealed with cuspal replacement.
with resin-bonded
amalgam Dr Vivian Onu-Nzegbulem, BDS, assisted with the
manuscript preparation.

cent anatomic fissures and pits at the time equal lengths of base and catalyst paste by 1 Buonocore M G. A simple method of
increasing the adhesion of acrylic filling
of bonded amalgam placement. turning an end knob on the dispenser. materials to enamel surfaces. J Dent Res 1955;
Amalgambond is based on a dentinal Mahler et al.34 conducted bond strength 34: 849-853.
bonding system developed in Japan by and microleakage tests on several adhe- 2 Gwinnett A J, Matsui A. A study of enamel
Nakabayashi and co-workers33 more than sives proposed to produce amalgam adhesives. The physical relationship between
enamel and adhesive. Arch Oral Biol 1967; 12:
a decade ago and is very similar to above- bonding, including Panavia EX. They 1615-1620.
mentioned Superbond. Amalgambond reported that ‘of the materials tested, only 3 Buonocore M G, Matsui A, Gwinnett A J.
uses a solution of 10% citric acid and 3% Panavia showed the potential to both Penetration of resin dental materials into
enamel surfaces with reference to bonding.
ferric chloride to remove the smear layer bond amalgam and prevent microleakage’. Arch Oral Biol 1968: 13; 61-70.
and demineralise the dentine surface. A Setcos et al.35 are conducting a ran- 4 Pashley D H. The smear layer; physiological
primer is applied after the dentine is con- domised clinical trial using the Kuraray considerations. Op Dent Suppl 1984; 3: 13-29.
ditioned. Finally, a self-curing methacry- ED Primer with Panavia 21 to bond 5 Albers H F. Tooth-colored restoratives. 8th ed.
Alto Books. California: Santa Rosa.
late resin is applied to impregnate the Dentsply Dispersalloy. This adhesive is an 6 McLean J W, Kramer I R H. A clinical and
primed dentine. The resin contains an autopolymerisable composite cement pathological evaluation of a sulphinic acid-
adhesive monomer called 4-META. based on the phosphate ester MDP. Its activated resin for use in restorative dentistry.
Panavia EX is presented as a powder hardening mechanism is anaerobic in Br Dent J 1952; 93: 255-269, 291-293.
7 Buonocore M, Wileman W, Brudevold F. A
and liquid, whereas Panavia 21 is a paste- nature. This ongoing trial of 113 restora- report on a resin composition capable of
paste system, delivered in a dual syringe tions includes preparations with no delib- bonding to human dentin surfaces. J Dent Res
dispenser that automatically dispenses erate retentive features. 1956: 35; 846-851.

BRITISH DENTAL JOURNAL, VOLUME 186, NO. 7, APRIL 10 1999 331

PRACTICE
restorative dentistry

8 Bowen R L. Adhesive bonding of various 17 Kanca J. 3d. Resin bonding to wet substrate. 1. and adhesive resin cement in various
materials to hard tooth tissues. II. Bonding to Bonding to dentin. Quintessence Int 1992; 23: combinations. Dent Mater J 1986; 5: 225-232.
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comonomer. J Dent Res 1965; 44: 895-902. 18 Nakabayashi N, Kojima K, Masuhara E. The of amalgam restorations with adhesive resin
9 Flynn M. Six-year evaluation of in vivo promotion of adhesion by the infiltration of cement lining, glass ionomer cement base and
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(Abstract no. 322). J Dent Res 1982; 4: 214 Mater Res 1982; 16: 265-273. 29 Shimizu A, Ui T, Kawakami M, Tsuchitani Y.
10 American Dental Association. Council on 19 Baldwin H. Cement and amalgam fillings. Br J Adhesive amalgam restoration with resin cement
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Dentin-polymer bond promoted by Gluma 22 Zardiackas L D, Stoner G E, Smith F K. Dental 31 Mach Z, Ruzickova T, Staninec M, Setcos J C.
and various resins. J Dent Res 1985; 64: 1409- amalgam stabilization by selective interfacial Bonded amalgam restorations: three-year
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13 Eliades G C, Vougiouklakis G J. 31P-NMR 193-203. 1998; 77: 1020.
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14 Tao L, Pashley D H, Boyd L. Effect of different 24 Zardiackas L D, Russin T P. An evaluation of 33 Nakabayashi N, Watanabe A, Gendusa N J.
types of smear layers on dentine and enamel the marginal seal of amalgam using S.I.A. Dentin adhesion of a ‘modified’ 4-META/
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15 Yu X Y, Joynt R B, Wieczkowski G, Davis E L. techniques and long-term results. Quintessence 34 Mahler D B, Engle J H, Adey J D. Bond strength
Scanning electron microscope and energy Int 1993; 24: 701-713. and microleakage of amalgam adhesives (Abst.
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Quintessence Int 1991; 22: 117-123. resin. Dent Mater J 1986; 5: 158-164. evaluation of bonded amalgam restorations
16 Swift E J Jr, Perdigao J, Heymann H O. Enamel 27 Shimizu A, Ui T, Kawakami M. Bond strength over two years (Abs. no. 2589). J Dent Res 1998;
and dentin bonding; a brief history and state of between amalgam and tooth hard tissues with 77: 955.
the art. Quintessence Int 1995; 26: 95-110. application of fluoride, glass ionomer cement

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332 BRITISH DENTAL JOURNAL, VOLUME 186, NO. 7, APRIL 10 1999