J of Oral Rehabilitation - 2010 - FERRACANE - Self Adhesive Resin Cements Chemistry Properties and Clinical

Journal of Oral Rehabilitation
Journal of Oral Rehabilitation 2011 38; 295–314
Review Article
Self-adhesive resin cements – chemistry, properties
and clinical considerations
J. L. FERRACANE*, J. W. STANSBURY† & F. J. T. BURKE‡ *Department of Restorative Dentistry,
†
Division of Biomaterials and Biomechanics, Oregon Health & Science University, Portland, OR, Department of Craniofacial Biology, School of
Dental Medicine, University of Colorado Denver, Aurora, CO, USA and ‡Primary Dental Care, University of Birmingham School of Dentistry,
Birmingham, UK
SUMMARY Self-adhesive resin cements were intro- and handling characteristics. The result of this
duced to dentistry within the past decade but have review of self-adhesive resin cements would suggest
gained rapidly in popularity with more than a dozen that these materials may be expected to show
commercial brands now available. This review arti- similar clinical performance as other resin-based
cle explores their chemical composition and its and non-resin based dental cements.
effect on the setting reaction and adhesion to KEYWORDS: dental cement, self-adhesive, self-etch,
various substrates, their physical and biological properties, clinical performance
properties that may help to predict their ultimate
performance and their clinical performance to date Accepted for publication 10 July 2010
glass–ionomer and resin composite. However, dentists

Introduction
may still experience confusion over the specific com-
Self-adhesive resin cements, defined as cements based position and indications for other types of ‘hybrid’
on filled polymers designed to adhere to tooth structure cements, such as resin-modified glass–ionomer and
without the requirement of a separate adhesive or polyacid-modified resin (compomers). Because of their
etchant, were introduced to dentistry within the past relative newness and the comparative lack of availabil-
decade but have gained rapidly in popularity, with ity of scientific evidence, most dentists are likely to be
more than a dozen commercial brands now available. even more confused about the indications and expec-
The major benefit of these materials would appear to be tations for the so-called self-etch or self-adhesive
simplicity of application. While a reasonable body of cements. A recent review article provided an extensive
literature has been generated describing the properties presentation of much of the previous literature on self-
and adhesion of these materials to various substrates, adhesive resin cements (1). This work serves as a useful
the vast majority of the literature has described one base upon which to further investigate these interesting
cement, RelyX Unicem*, which was the first commer- materials from several different perspectives. Specifi-
cial product. Relatively little information exists about cally, this article will explore what is known or can be
the composition and mechanism of adhesion of these inferred about their chemical composition and its effect
materials, and scant independent evaluation of their on the setting reaction and adhesion to various
clinical efficacy has been reported. substrates, their physical and biological properties and
Most dental practitioners are very familiar with the other materials science aspects that may help to predict
qualities and uses of the cements that historically have their ultimate performance, and the important clinical
been used most frequently, such as zinc phosphate, considerations that will determine their indications,
handling and limitations when used by the dental
*3M ESPE, St. Paul, MN, USA. practitioner.
ª 2010 Blackwell Publishing Ltd doi: 10.1111/j.1365-2842.2010.02148.x

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296 J . L . F E R R A C A N E et al.
Compomers are not inherently able to bond directly

Dental cements – evolution of the
to hard tooth tissues (17, 18), and they release
materials
significantly lower levels of fluoride than GICs (19, 20).
Self-adhesive cements are hybrid materials that com- The previous discussion provides the materials con-
bine features of composite restoratives, self-etching text for the introduction of self-adhesive resin cements,
adhesives and, in some cases, dental cements. The of which RelyX Unicem from 3M ESPE* represents the
rational design of dental composites, including the first of this new class of materials. These materials are
development of dimethacrylate monomers specifically most similar in nature to compomers with the primary
for application in resin-based composites, was advanced difference being the acidic monomer concentration.
by Bowen (2–5). When coupled with Buonocore’s acid Also, in most cases, self-adhesive resin cements have a
etching technique (6) to promote adhesion to enamel, somewhat lower filler content compared with compo-
resin composite restorative materials began to emerge mers, and because of the limited luting cement thick-
as viable clinical options. The incorporation of acid- ness in bonding applications, hydrated substrates more
functionalised methacrylate or related monomers is a efficiently facilitate ionisation of the acidic monomers
critical component in self-adhesive resin cements followed by acid–base neutralisation reactions involv-
because effective chemical bonding to tooth requires a ing the tooth and the basic filler. These are important
polyacid matrix structure, whether based on a pre- distinctions because, unlike compomers, the self-
formed polyalkenoate or one that is created in situ adhesive resin cements do offer a reasonable degree of
during a curing process involving acidic monomers. unassisted adhesion to dentin although bonding
Progress in dental cements based on polyacids can be directly with enamel still presents a greater challenge.
traced from polyalkenoate cements, which consist of Beyond the bonding to tooth structure that is possible
zinc polycarboxylate cements (7) and glass–ionomer with these polymer-based acidic matrices, the ability of
cements (GIC) (8), both of which set as the result of an self-adhesive resin cements to deliver fluoride ions
acid–base reaction within an aqueous environment. owing to partial acid dissolution of suitable soluble glass
These were followed by resin-modified glass–ionomer filler also may be considered significant; though, clin-
cements (RMGICs) (9–12) that rely on the formation of ical evidence has yet to be demonstrated. Self-adhesive
a methacrylate-based network to augment the ionic cements that lack the glass–ionomer fluoride leachable
cement structure through either grafting polymerizable filler may, by inclusion of sodium fluoride or related
double bonds onto a polyalkenoate backbone or by the salts as a component of the cement, still provide a
incorporation of free radically polymerizable methac- source for fluoride release.
rylate monomers in the cement composition. Relatively
hydrophilic monomers are used in RMGICs because
Chemical composition – self-adhesive resin cements
these remain water based with the acid–base reaction as
the primary setting mechanism. Like the polyalkeno- There are more than one dozen self-adhesive resin
ates, RMGICs maintain the ability to bond to hard tooth cements on the market at the time of this writing
tissues through the presence of linked acidic functional (Table 1). Specific compositions for commercial mate-
groups capable of chelation with the calcium in rials can be found in the manufacturer’s literature, and
hydroxyapatite (13–15). Soon after RMGICs, compo- have been published in several articles (1, 17, 18) and
mers were introduced with the intent to combine the are summarised in Table 1. In some cases, details about
benefits of composites and glass–ionomers (16). Comp- the composition of the two components for each
omers typically consist of mono-, di- or multi-methac- cement have been provided by the manufacturers,
rylate monomers, polycarboxylates, as well as some and other cases not.
(meth)acrylate monomers bearing pendant carboxylic, The current self-adhesive resin cements are two-part
phosphoric or related acidic functional groups. The filler materials that require either hand mixing, capsule
is similar to the ion-leachable glass present in GICs but trituration or delivery by an auto-mixing dispenser.
may be partially silanised to achieve some covalent One component is comprised of conventional mono-,
attachment with the matrix. There is little or no water di- and ⁄ or multi-methacrylate monomers that are used
included in the compositions, and the primary mode of in a variety of resin-based dental materials: Bis-GMA,
curing is the free radical polymerisation reaction. urethane oligomers of BisGMA, UDMA, HEMA, glycerol
ª 2010 Blackwell Publishing Ltd

SELF-ADHESIVE CEMENTS 297
Table 1. Brands and compositions of self-adhesive resin cements circa 2009
Cement Manufactures Composition
BisCem Bisco* Bis(hydroxyethyl methacrylate) phosphate, tetraethyleneglycoldimethacrylate, glass filler

Breeze Pentron† Not available
Bifix SE Voco‡ Bis-GMA, UDMA, Gly-DMA, phosphate monomers, initiators, stabilisers, glass fillers, aerosol silica
(filler = 70 wt%; 61 vol%; avg. 2 lm)
Clearfil SA Kuraray§ MDP, hydrophobic aromatic dimethacrylate, hydrophobic aliphatic dimethacrylate, colloidal silica,
Cement barium glass (filler = 66 wt%; 45 vol%; avg. 2Æ5 lm)
Embrace Pulpdent¶ Not available
Wet Bond
G-Cem GC** Powder = fluroaluminosilicate glass, initiator, pigment (filler = 71Æ4 wt%, avg. 4 lm)
Liquid = 4-MET, phosphoric acid ester monomer, water, UDMA, dimethacrylate, silica powder,
initiator, stabiliser
iCem Heraeus†† Di-, tri- and multi-functional acrylate monomers, initiators, stabilisers (filler = 41 vol%)
Maxcem Elite Kerr‡‡ Powder = barium aluminosilicate glass, fluoroaluminosilicate glass, nano-ytterbium fluoride,
nanosilica (filler = 67 wt%, avg. 3Æ6 um – orig. Maxcem)
Liquid = GPDM monomer, mono-, di- and multi-methacrylate co-monomers; redox initiator system,
camphorquinone-based photoinitiator
Monocem Shofu§§ Mono-, di- and multi-functional acrylate resins, dual-initiators, fillers (filler = 60 wt%)
Multilink Sprint Ivoclar¶¶ Dimethacrylate monomers, acid monomers, barium glass fillers, ytterbium trifluoride, silicon dioxide
(filler = 57 wt%; avg. 5 lm)
RelyX Unicem 3M ESPE*** Powder = glass, silica, calcium hydroxide, pigment, substituted pyrimidine, peroxy compound,
initiator (filler = 72 wt%; avg. <9Æ5 um)
Liquid = methacrylated phosphoric ester, dimethacrylate (bis-GMA ⁄ TEGDMA), acetate,
stabiliser, initiator
seT SDI††† Not available
Smart Cem 2 Dentsply‡‡‡ UDMA, Di- and Tri-methacrylate resins, phosphoric acid modified acrylate resin, fluroaluminosilicate
glass initiators, accelerators, stabilisers, butylated hydroxyl toluene, titanium dioxide, hydrophobic
silica (filler = 69 wt%; 46 vol%; avg. 3Æ8 lm glass and 16 nm aerosol silica)
Speed Cem Ivoclar¶¶ Dimethacrylates, methacrylated phosphoric esters, copolymers, initiators, catalysts, stabilisers barium
glass, ytterbium trifluoride, high dispersed silica (filler = 40 vol%; size 0Æ1–7 lm)
*Bisco Inc., Schaumburg, IL, USA.

†
Pentron, Wallingford, CT, USA.
‡
Voco, Cuxhaven, Germany.
§
Kuraray America, New York, NY, USA.
¶
Pulpdent, Watertown, MA, USA.
**GC, Alsip, IL, USA.
††
Heraeus, Hanau, Germany.
‡‡
Kerr, Orange, CA, USA.
§§
Shofu, Kyoto, Japan.
¶¶
Ivoclar Vivadent, Schaan, Liechtenstein, Germany.
***3M ESPE, St. Paul, MN, USA.
†††
SDI, Victoria, Australia.
‡‡‡
Dentsply, Konstanz, Germany.
dimethacrylate (GDMA), TEGDMA, trimethyloylpro- phosphoric acid groups (Fig. 3), as with 2-methacryl-
pane trimethacrylate (TMPTMA) and many others oxyethyl phenyl hydrogen phosphate (Phenyl-P),
(Fig. 1). 10-methacryloxydecyl dihydrogen phosphate (MDP),
The acid-functionalised monomers currently utilised bis(2-methacryloxyethyl) acid phosphate (BMP) and
to achieve demineralisation and bonding to the tooth dipentaerythritol pentaacrylate monophosphate (Pen-
surface are still predominantly (meth)acrylate mono- ta-P). There are substantial numbers of new proprietary
mers with either carboxylic acid groups (Fig. 2), as with acidic monomers, primarily those based on phosphates
4-methacryloxyethyl trimellitic anhydride (4-META) and phosphonates that have been developed specifi-
and pyromellitic glycerol dimethacrylate (PMGDM), or cally to perform the surface demineralisation of enamel

O O
O O O O
OH OH
BisGMA
O O
H
O N O
O N O
H
O UDMA O
OH O
O
O O
OH O
O
O HEMA GDMA O
O O
O O
O O O
O O
TEGDMA TMPTMA
O
Fig. 1. Non-acidic methacrylate monomers used in resin adhesive cements.
O O
O O
N N
N N Fig. 2. Examples of hydrolytically
stable, cross-linkable bisacrylamides
for potential use as comonomers in
DEAAP DBAAP
strongly acidic formulations.
and dentin as well as to promote stable salt formation, adaptation to the tooth surface. But the materials
mainly involving calcium. The selection of the acidic become more hydrophobic as the acid functionality is
monomer structure is critically important as exempli- consumed through reaction with calcium on the tooth
fied by the formation of a strong, aqueous insoluble salt and a variety of metal oxides from the ion-leachable
complex between calcium and the relatively hydro- filler. The fillers used are composed of combinations
phobic MDP, whereas 4-Met and Phenyl-P produce a selected from barium fluoroaluminoborosilicate glass,
calcium complex with more limited stability to disso- strontium calcium aluminosilicate glass, quartz, colloi-
lution (15, 21, 22). dal silica, ytterbium fluoride and other glass fillers. The
The concentration of the acidic monomers in these partial surface dissolution of acid-soluble glass serves to
materials must be balanced to be low enough to avoid neutralise the resin acidity and is capable of delivering
excessive hydrophilicity in the final polymer but high sodium, calcium, silicate and fluoride ions that can
enough to achieve an acceptable degree of self-etching either take part in the setting reaction or be released
character and bonding to dentin and enamel. Free locally. The total filler content is typically in the range
radical polymerisation of the acidic monomers to some of 60–75 wt% (23). The necessity for segregation of the
degree replicates the adhesive potential of polyalkeno- materials arises to avoid premature acid–base interac-
ate cements, and it allows the ratio of acidic to non- tions between the acidic monomer and the ion-leach-
acidic comonomers to be fully controlled. Excessive able glass as well as to allow separation of the redox
hydrophilic character can cause swelling that may initiator components that promote the free radical
compromise mechanical strength as well as dimen- chemical curing process. In addition, to provide access
sional stability. As initially mixed, the cements are fairly to a free radical photoinitiated mechanism to be used in
hydrophilic, which facilitates their wetting of and conjunction with the redox curing, a tertiary amine or

O OH
O O
O OH O
CH2 O
10 O
O O O
MAC-10 4-META
O
O O
O
O OH
O OH
4-MET
O
Fig. 3. Carboxylic acid monomers used to promote adhesion in cements.
some other electron-donating compound used as the complications. Because material manufacturers often
photo-reductant must be isolated from the acidic do not fully disclose compositional details, a review of
monomers to prevent deactivation of the photoinitiator current progress involving acidic monomers is included
as well as a gradual spontaneous polymerisation process here although it must be noted that most are these new
that limits the shelf life of monomers in the presence of monomers are likely in development for dental adhesive
acidic and amine functionalities. applications. There are a variety of recently developed
neutral monomers based on bisacrylamide structures,
such as bisacrylamido-N,N¢-diethyl-1,3-propane (DEA-
Current developments of acidic monomers and acid-stable
AP; Fig. 4), as well as a dibenzyl analog (DBAAP)
resin formulations
mentioned in the patent literature, that combine good
Self-adhesive resin cements critically rely on strongly biocompatibility with enhanced hydrolytic stability
acidic monomers that impose formulation stability under aqueous acidic conditions when compared with
OH OH OH
Phosphate s O P OH O P O Phosphona tes P OH
O O O
OH
O O
CH2 P OH
10
O O
MDP
O O
O
OH
O P O
O O HO P
OH MAEPA
O Phenyl-P O
O
H O
O P O N
O O P OH
OH
O O O OH
BMP MAMPA
Fig. 4. Generalised structures of phosphate and phosphonate functional groups and examples of their use in self-etching dental
monomers.

O O
H O
N N P OH N P OH
S O CH2 OH
10 OH
O OH O O O P
OH
AMPS NMADP NPAPBP OH
Fig. 5. An extremely acidic sulfonic acid acrylamide monomer (AMPS) as well as examples of new acrylamide monomers with the
potential to vary the spacer length bridging to the phosphonate group (NMADP) or the length of the N-alkyl substituent as well as the
number of phosphonate groups (NPAPBP).
methacrylates (24, 25). Acrylamide reactive groups are alternate approach is demonstrated with 2,4,6-tri-
preferred because N,N-disubstituted methacrylamides methylphenyl-2-[4-(dihydroxyphosphoryl)-2-oxabutyl]-
are less efficient in homopolymerisations or in copoly- acrylate (MAEPA; Fig. 3) (28). This monomer has the
merisations with methacrylate monomers. There is no benefit of a hydrolytically stable ether linkage rather
clear indication from product labels that these and other than an ester as the connection between the poly-
bisacrylamide monomers are being used currently in merizable vinyl group and the phosphonate function-
any of the adhesive resin cements, but their develop- ality. It also contains a bulky hydrophobic substituent
ment as acid-resistant components for strongly acidic as its ester substituent and thereby can be expected to
formulations appears well suited for this application. provide reasonable overall stability in acidic media. In
It appears that relatively limited use has been made comparison with methacrylate monomers, some
of acidic monomers based on sulfonic acid, such as restriction in reactivity may be encountered for the
2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) more sterically encumbered vinyl group of this type,
(Fig. 5). While the sulfonic acids are extremely strong but overall, their polymerisation behaviour is fairly
acids with pH levels approaching 0, this actually limits similar to and compatible with methacrylate mono-
their practical utility because of potential hydrolytic mers (29).
instability of the attachment between the acidic func- Another method to obtain acid-stable monomers that
tionality and the polymerizable group. This explains the appears to be in development for application in self-
use of the more hydrolytically stable acrylamide group in etching dental resins involves the use of monomers
the AMPS structure rather than reliance on a methac- bearing allyl ether reactive groups (30). This strategy
rylate ester. Further examples of novel monomers may be practical in a two-part formulation where
designed specifically for use in hydrolytically stable, the hydrolytically stable allyl ether linkage, such as
self-etching dental adhesives are 10-(N-methylacrylam- in allyloxyethylphosphate (AOEP: Fig. 6) or 2-(al-
ido)decylphosphonic acid (NMADP) and 3-(N-propyl- lyloxymethyl)-2-ethylpropane-1,3-diyl bis(dihydrogen
acrylamido)propylidenebisphosphonic acid (NPAPBP) phosphate) (AOMEPB), can tolerate an acidic storage
(26, 27). environment but rely on copolymerisation with more
Besides the use of (meth)acrylamides to enhance reactive comonomers from the second neutral mono-
the hydrolytic stabilities of acidic monomers and the mer component to overcome the inherent low free
comonomers with which they are formulated, an radical reactivity of allyl ethers.
O P OH
O OH
O
O P OH O
O
OH
O P OH Fig. 6. Examples of acidic mono-
AOEP AOMEPB
mers with allyl ether polymerizable
OH groups.

approximately two minutes is typical with setting times

Curing chemistry
for self-polymerising systems ranging from about three
A self-curing or redox chemical curing mode of poly- to seven minutes, with some manufacturers specifying
merisation is an essential feature of resin-based dental room temperature and others indicating oral tempera-
cements because the restricted access to adequate light ture (1). Once the material has been placed, the
intensity in most indirect restorations precludes the use restoration seated and excess cement removed from
of photo-initiated polymerisation alone. While some around the restoration, the photocuring process can
materials are designed to employ a self-curing mode then be augmented with a 20- to 40-s exposure to
exclusively, most self-adhesive cements promote the visible light from a conventional dental curing unit to
use of a dual chemical and photochemical cure based significantly increase the rate of the free radical poly-
on the addition of photo-initiators along with the redox merisation process that creates the cross-linked meth-
initiators. The combined access to a chemical cure, acrylate network.
which commences only gradually upon mixing the Unlike the redox systems utilised in self-curing
two-part material components and only after the denture base materials, which employ benzoyl peroxide
inhibitor has been consumed, with photo-initiation, and tertiary amines as the oxidant and reductant,
which provides a rapid, on-demand boost to the setting respectively, the low pH conditions present in the acidic
process, allows improved final conversion and adhesive component of the self-adhesive resin cements compli-
strength properties compared with the self-cure alone. cate or preclude the use of both of these initiating
Several studies have indicated substantial improve- species. In redox polymerisations, benzoyl peroxide is
ments in the methacrylate conversion levels when the susceptible to radical formation in acidic environments
dual light and chemical curing modes are compared and amines form salts that greatly decrease their
with self-curing alone (31, 32). activity with peroxides even more so than in the case
The acid–base reaction between the acidic function- of amines used as photoreductants with a photosensi-
ality on the monomers and the acid-soluble glass or the tiser (33). Instead, an acid-tolerant oxidant, such as
mineralised tooth surface is initiated upon mixing of cumene hydroperoxide (CHP; Fig. 7), is used in the
the two components and placement of the cement on acidic part of the formulation, while various thioureas,
the tooth. The acid–base reaction rate is also control- such as benzoyl thiourea (BTU), are employed as the
lable through physical factors such as water content, reducing agent in the non-acidic part (24). To induce
ion solubility and diffusion constraints. There is some visible light activity so that conventional dental curing
mention in patent literature of encapsulation strategies lights can be used to advance a photocuring comple-
to either isolate certain reactive components or simply ment to the polymerisation reaction, camphorquinone
to retard the onset of the acid–base reaction process. (CQ) and ⁄ or diphenyl-(2,4,6-trimethylbenzoyl) phos-
Similarly, the free radical redox polymerisation pro- phine oxide (TPO) is added to the acidic components,
cess involving the methacrylate monomers could start while a tertiary amine, such as ethyl N,N-dim-
potentially at the time of mixing; however, in practice, ethylaminobenzoate (EDMAB) or N,N-dimethylamino-
the added inhibitor used to extend the shelf life of the benzonitrile, is incorporated with the non-acidic
material also provides a controllable inhibition or components. Redox initiators and, to a lesser extent,
working time that allows a sufficient interval for mixing photoinitiators were found to be sensitive to acidic
and placement of the cement. A working time of monomers, and the acid resistance of both types of
O
S
NH O
OOH N
H2N S
O- Na+ O N O
CHP BTU SBS DPBA
Fig. 7. Cumene hydroperoxide (CHP) is an example of an acid-resistant oxidising agent that can be used with a urea or thiourea, such as
benzoyl thiourea (BTU). Sodium benzene sulfinate (SBS) provides means to recover reactivity in acid sensitive initiating systems. Redox
curing based on barbituric acid derivatives, such as DPBA, has received limited attention as acid-resistant initiators.

initiators was improved by the addition of sodium aryl reported for Maxcem and RelyX Unicem, it appears
sulphates (SBS) and aryl borate salts (33). The likely that the reduced shrinkage noted for the latter
reference to a substituted pyrimidine in the RelyX arises because of expansion effects related to the acid–
Unicem cement product literature may be related to base reaction involving the soluble filler and other basic
barbituric acid derivatives, such as 1,3-dimethyl- components such as calcium hydroxide that partially
5-phenyl barbituric acid (DPBA), that have been used counter the shrinkage derived from the methacrylate
in acidic redox initiating systems in place of conven- polymerisation. However, in the much faster dual-cure
tional amines. mode that preferentially affects the methacrylate curing
The acidic monomers, depending on the type and reaction as opposed to the acid–base reactions, only the
concentration of acid functionality as well as the RelyX Unicem material shows a higher shrinkage value
moisture content, create a pH between ca. 1Æ5 and 3 than that obtained in the self-cure mode.
in the freshly mixed cement, which is certainly acidic
enough to demineralise hard tooth surfaces. As the
Proposed mechanism of adhesion
acid–base reaction proceeds, ionic cross-links that form
between acid groups and calcium or aluminium ions The setting reaction of RelyX Unicem as detailed in the
cause the pH to rise. Some materials include calcium commercial literature emphasises the free radical meth-
hydroxide, which is isolated in the non-acidic part of acrylate polymerisation process as the primary reaction
the formulation, likely to contribute to a more rapid mode. This is activated by chemical and photochemical
neutralisation process rather than simply being present routes to begin the cross-linking polymerisation of
for its antimicrobial action. Also associated with the monomers with and without phosphoric acid function-
neutralisation process, the cement converts from a ality. The acidic groups bind with calcium in the
relatively hydrophilic paste that readily wets moist hydroxylapatite to form a stabilising attachment
dentin and enamel to a fairly hydrophobic state that between the methacrylate network and the tooth. Ions
limits post-cure swelling and material deterioration. released from the acid-soluble filler neutralise the
The reaction kinetics of the setting process of self- remaining acidic groups to create a chelate reinforced
adhesive resin cements has received little attention to three-dimensional methacrylate network. There have
this point. There is manufacturer literature from 3M been at least three studies that have focused on the
ESPE* showing the neutralisation kinetics for RelyX reaction between the acidic monomer components of
Unicem in self-curing mode taking longer than that these cements and calcium in the form of powdered
associated with the dual-cure activation. There is a hydroxylapatite or upon placement on dentin and
rapid initial rise in pH from approximately 2–4 over the enamel surfaces (37–39). There appears to be agree-
first hour of the setting process followed by a long ment that there is very limited interaction with enamel
gradual continued rise in pH that approaches 7 by or dentin in terms of either smear layer demineralisa-
24–48 h. One independent study also reported a neu- tion or tag formation. However, there are indications by
tral pH for this cement at 48-h post-cure (34). Clearly, X-ray photoelectron spectroscopy (XPS) of good chem-
the curing temperature (room or oral) will significantly ical interaction with calcium from hydroxylapatite,
affect the rate of the setting process. One study has which suggests that this latter route provides a means
looked into the use of pre-heated delivery to the to micromechanical retention even though there is no
cement as a means to potentially improve adaptation significant infiltration of more than a micrometre into
with the tooth as well as to raise conversion levels and the dentinal surface (40).
found that working time was less than that needed for
the mixing process at 60 C but not at 37 C (35).
Physical properties of self-adhesive resin
Dynamic dimensional change and shrinkage stress up
cements
to 1 h were monitored for Maxcem, Multilink Sprint
and RelyX Unicem in their self-curing and dual curing
Physical ⁄ mechanical ⁄ wear properties
modes (36). With self-curing, both Maxcem and Mul-
tilink Sprint produced dramatically higher shrinkage There are few studies that have examined the mechan-
strain rates and greater shrinkage than RelyX Unicem. ical properties of self-adhesive resin cements, compar-
With similar 1-h methacrylate conversion levels ing them to other types of cements. Perhaps the most

Flexure Strength vs Cement Type non-self-adhesive resin cement in either self- or dual-
100 P-2003 cure mode.
90 The Behr et al. (42) study also showed the abrasion
K-2004
80
B-2008 wear of the self-adhesive resin cement when self-cured
70
to be substantially greater than that of non-self-adhe-
60
sive resin cement and glass–ionomer, and equivalent to
50
zinc phosphate, though less than resin-modified glass–
40
30
ionomer, which had the highest wear. In contrast, a
20
study of toothbrush abrasion of a zinc phosphate
10 cement placed between ceramic blocks, representing
0 cement in a luting space, showed much higher wear
ZOP GIC RMGIC RC-sc RC-dc SA-sc SA-dc PC
than Unicem when simulating 5 years of wear (about
22 versus 5 micrometre) (43). Whereas these data are
Fig. 8. Flexure Strength versus Type of Cement (data compiled somewhat contradictory, they may be explained by the
from P = Piwowarczyk and Lauer, 2003; K = Kumbuloglu et al.
differences in the test methods, in that the toothbrush-
2004; and B = Behr et al. 2008).
ing test, while clinically relevant, likely presents a much
less aggressive mechanical force than the three body
comprehensive is the study of Piwowarczyk and Lauer
wear test used by Behr et al. (42). Perhaps the most
(41), which compared the flexure and compressive
clinically relevant test of wear has been conducted by
strength of a self-adhesive resin cement, Unicem (3M
placing these cements into a gap between two ceramic
ESPE*), to two zinc phosphates, two glass–ionomers,
surfaces, as would occur clinically (23). Wear tests were
three resin-modified glass–ionomers and four dual-cure
performed by toothbrush abrasion, as well as with the
resin cements. The self-adhesive resin cement tested
ACTA wear machine using an abrasive slurry of millet
either in the self-cure (SA-sc) or dual-cure (SA-dc)
seeds pressed between the material and a rotating steel
mode had nearly equivalent to slightly lower flexure
disk. The authors showed that the eight self-adhesive
and compressive strength than other resin cements
resin cements tested generally had good resistance to
(RC-sc and RC-dc), but both types were much stronger
toothbrush wear but showed more accelerated wear
than zinc phosphate (ZOP), GIC, or RMGIC (Fig. 8).
than non-adhesive resin cements or a flowable com-
The dual-cure cements were slightly stronger than self-
posite when tested in the ACTA machine with higher
cure versions at 1 day, but when retested after storage
abrasion forces. This would suggest that the self-
in water for 150 days, there was no difference between
adhesive resin cements would likely perform well
the two. This was attributed to the fact that the dual-
clinically when exposed to abrasion predominantly
cured Unicem showed a significant reduction in both
created by the toothbrush or food excursions under a
flexure and compressive strength with ageing.
minimal load, but on occlusal surfaces, where forces are
In another study, the flexure strength of the same
higher, material loss at the margins from abrasion
self-adhesive resin cement, Unicem, was lower than
during chewing or grinding may be greater than that
that of a resin cement, while the compressive strength
seen in other resin cements.
showed the opposite relationship (31) (Fig. 8). Both
In a recent study, four self-adhesive resin cements
cements were stronger than polycarboxylate (PC). In a
(G-Cem§; Maxcem, Kerr‡; Smart Cem¶; and Unicem,
more recent study, Behr et al. (42) showed similar
3M ESPE*) were shown to be very susceptible to
flexure strengths for a resin cement, Panavia F† (Fig. 8),
surface erosion when exposed to acetic acid and
and a self-adhesive resin cement, Maxcem‡, but
acetone, with the least affected cement being Unicem
showed the strength of the self-adhesive resin cement
(34). Some surface erosion and loss of particles occurred
to be drastically reduced when mixed with 10% less of
in water as well. Other studies have shown less surface
the catalyst paste, independent of whether it was self-
degradation of dental composites versus glass–ionomers
or dual-cured. This study also showed the hardness of
in acidic solutions (44, 45). The fact that the erosion
the self-adhesive resin cement to be lower than that of a
† §
Kuraray America, New York, NY, USA. GC, Alsip, IL, USA.
‡ ¶
Kerr, Orange, CA, USA. Dentsply, Konstanz, Germany.

seems to be more extensive on the self-adhesive resin Numerous studies have evaluated the bond strength
cements than has generally been shown for dental of self-adhesive resin cements to human dentin and
composite restoratives is likely due to the more hydro- enamel substrates using microtensile (38, 46–51), shear
philic nature of the matrix resin in the self-adhesive (52–56) or tensile (39) testing modes. The bond to root
resin cements. In addition, to allow them to react with canal dentin has also been reported using a micro push
the acidic monomers in the matrix, the surface of the out test (57). The majority of these studies evaluated
basic fillers in these cements is less protected than those RelyX Unicem as the self-adhesive resin cement, and
in restorative composites owing to the absence of a typically in comparison with Panavia F in addition to
hydrophobic resin coating, such as silane. other cements employing self-etch or etch-and-rinse
The overall examination of the strength, hardness adhesives. However, Maxcem, Maxcem Elite, Multilink
and wear of the two brands of resin cements reported in Sprint and iCem were other self-adhesive resin cements
the studies mentioned earlier suggest that their resis- tested at least once. In addition, bovine dentin was used
tance to fracture and wear may be similar to, or perhaps in one study to compare the micro-tensile bond
slightly lower than, that of non-self-adhesive resin strengths of Unicem, Panavia F and Fuji Cem GIC (46).
cements. However, the self-adhesive resin cements Although it is somewhat difficult to draw strong
are in general superior to the non-resin based conclusions from the data because of the limited
cements, such as zinc phosphate, polycarboxylate and number of studies testing under comparable conditions,
the glass–ionomers in this regard. As current clinical i.e. same cements, same substrates, same curing and
studies are only short term, it is not yet possible to storage conditions, etc., the data do suggest that the
determine whether these subtle differences will have a bonding of Panavia F and Variolink II to human dentin
significant clinical effect. and enamel, when used with their associated primers
and ⁄ or etchants, is superior to that of Unicem (Fig. 9).
Analysis of the bond joint after testing shows that, in
Adhesion to different substrates
general, the failure of Unicem to enamel is mostly
Resin cements must bond to a variety of different adhesive, while the failure to dentin is adhesive or a
substrates, including dentin and enamel, porcelain and mixed-mode. Also, when other resin cements were
other ceramics, gold and other metal alloys, and indirect included in the comparison studies using micro-tensile
resin composites. The self-adhesive resin cements were or shear testing, the self-adhesive resin cements
designed specifically to interact with the dentin sub- nearly always showed lower bond strengths than
strate with minimal additional surface preparation.
While historically bonding to enamel through the use
of phosphoric acid etching has been effective, these new 35
cements use alternative acids that may not produce en - uTBS
equivalent mechanical etch patterns for adhesion. Thus, 30 den - uTBS
a result that was taken for granted can no longer be en - shear
25
until verified through appropriate testing. The same can den - shear
be said of the adhesion to the restorative and prosthetic 20
materials used for indirect restorations.
15
Teeth. A number of studies have been conducted on 10

adhesion to dentin and enamel, predominantly on
5
RelyX Unicem, but also for other self-adhesive resin
cements. These studies typically have compared the 0
bond to tooth structure with the cement sandwiched Unicem Panavia
between another substrate representing an indirect
Fig. 9. Bond strength (micro-tensile versus Shear) for enamel and
restorative material, such as ceramic, metal or labora-
dentin comparing Unicem self-adhesive cement to Panavia self-
tory processed dental composite. However, in the etching resin cement (averaged data from Abo-Hamar et al. 2005;
studies, the interface of interest has been that between De Munck et al. 2004; Goracci et al. 2006; Luhrs et al. 2009; Sarr
the cement and the dentin or enamel. et al. 2009; Yang et al. 2006).

non-self-adhesive resin cements (51). The same is true tested shear bond strengths of Unicem and Panavia F as
of the relationship between any of the resin cements well as five other resin cements after 150-day storage in
and the GIC, the latter demonstrating bond strengths to water. They found that when the dual-cured cements
enamel or dentin that are typically one-half to one- were light-cured, as opposed to self-cure only, the bond
third of that of the resin cements (46, 52). strengths were higher for about half of the cements, but
When tested with a pre-etching of enamel by not for Unicem or Panavia. This result is curious as it is
phosphoric acid, Unicem was shown to have higher generally agreed that bonding is enhanced when the
bond strength than when tested without pre-treatment cements are truly dual-cured, because of the enhanced
(35Æ6 versus 19Æ6 MPa), presumably because of the properties of the polymer produced by the higher degree
enhanced microscopic irregularities produced by the of conversion. However, this study only measured
stronger acid compared to that produced by the cement properties after ageing for 150-days in water, and it is
itself (38). But a lower bond strength was shown to possible that the degradation in bond strength occurred
dentin when the phosphoric acid pre-etch was applied for other reasons not related to the cure of the cement
(5Æ9 versus 15Æ9 MPa). This negative effect of pre- itself, thus demonstrating a brand dependent effect.
etching of dentin for self-etch adhesives has been In the laboratory of one of the authors (Ferracane
shown many times in the literature and is likely due to and Hilton, unpublished data), the micro-shear bond
the presence of a thick collageneous matrix created by strength to human dentin and enamel has been tested
phosphoric acid demineralisation that is mostly impen- for a variety of resin cements, including self-adhesive,
etrable to the viscous cement, thus leaving a weak self-etch and glass–ionomer. These results showed
interface (38). When tested without the pre-etch, self- similar bonds to enamel for the resin cements, being
adhesive resin cements have been shown to produce significantly greater than glass–ionomer with or with-
fairly strong bonds to dentin, despite the fact that they out pre-conditioning with polyacrylic acid. However,
do not form a classical hybrid layer and show minimal the data also showed the bond to dentin to be generally
interaction with the dentin substrate when evaluated highest for the self-etch resin cements when compared
microscopically (38, 39, 49, 57). to the self-adhesive resin cements (Fig. 10).
Other interesting findings of note can be gleaned from
some of the different studies of bond testing. Abo-Hamar Ceramics. There are few studies comparing the bond
et al. (52) found that most cements showed a reduction strength of self-adhesive resin cements to ceramics.
in bond strength when subjected to thermal cycling, but Those that exist have used zirconia as the substrate
this was typically only significant when bonding to (58–63). Unicem was the only self-adhesive resin
enamel. In contrast, Piwowarcyzk et al. (53) showed a cement to be tested in these studies, with the exception
reduced bond to dentin for several cements when aged of the latest study by Blatz et al. (63) in which Maxcem
and then thermal cycled as opposed to simply ageing, (though this cement is no longer marketed), BisCem,
but Unicem was not affected by the additional thermal Clearfil SA Cement and G-Cem were also tested. All of
cycling. Walter et al. (46) found similar bond strengths these studies tested the bond of the cements to zirconia
to bovine coronal and root dentin for Unicem, Panavia F with the shear bond test method. While most studies
and glass–ionomer. In contrast, Yang et al. (49) found a used either the cement or another composite (often
reduced bond strength to deep or cervical human dentin pre-cured) as the opposing substrate, one study used
compared to superficial human dentin for Unicem and metal disks and recorded very high strengths (62),
Panavia F, as well as for SuperBond C&B, but all emphasising the importance of the substrates on bond
cements were used in a self-cure mode only in this strength testing.
study. It has been suggested that the high viscosity of the The data generally show that the bond strength of
cement may predispose to poor penetration into the Unicem to air-abraded zirconia is equivalent to that of
dentin surface and that adding pressure during cemen- Panavia F and that the bond of both is enhanced by pre-
tation in the laboratory may better simulate clinical treating the ceramic with the Rocatec process (Fig. 11).
conditions, resulting in higher bond strengths. Goracci This also is generally true for other resin cements.
et al. (48) tested this hypothesis and confirmed it for Recent work in the laboratory of one of the authors
both self-adhesive (Unicem and Maxcem) and a self- (Ferracane and Hilton; unpublished data) testing the
etch resin cement (Panavia F). Piworwarczyk et al. (53) bond strength in micro shear of MaxCem Elite cement

40·00 to various surfaces showed relatively high bonds to cast

Dentin
35·00 Enamel
gold (type III), Ni-Cr alloy (Rexillium), zirconia ceramic
30·00 (LAVA), lithium disilicate ceramic (emax CAD) and
25·00
feldspathic porcelain (Vitablock), suggesting that this
cement would be acceptable for all of these substrates
20·00
(Fig. 12).
15·00
Two other self-adhesive resin cements, G-Cem and
10·00
Clearfil SA, were shown to bond well to air-abraded
5·00 zirconia (22Æ2 and 18Æ4 MPa, respectively), while others
0·00 (Maxcem and BisCem) showed poor bonding (3Æ0 MPa
ite
r
ne
l
f or less). Glass–ionomer, resin-modified glass–ionomer

l
m
m
ua
m
em
el
el
ua
el
El
ce
ce
-s
ce
tio
-s
-s
-d
-d
-c
ji-
ax
ni
di
k
G
ra
X3
ce
k
Fu
X3
on
in
and zinc phosphate were all shown to bond minimally

in
ib
til
ax
N
/c
til
N
al
ul
ul
M
C
M
w
M
to zirconia in comparison, rarely achieving shear bond

m
ce
ji-
Fu
strengths exceeding 6–7 MPa (59, 61, 62) and being

Fig. 10. Micro-shear bond strength of various self-adhesive particularly sensitive to ageing conditions (59, 61). One
cements compared to other resin adhesive cements and a glass– study also showed that extended ageing in water with
ionomer (unpublished data). thermal cycling significantly reduced the bond of
Unicem and Panavia F to air-abraded or silica coated
25 Air-abraded zirconia by 25–45% (62), but several others showed
Rocatec minimal effect of thermal cycling, especially when
20 Rocatec was used to enhance bonding and stability
(59–61). This difference may be related to the numbers
15
of thermal cycles and ageing times used in the studies,
as the study that used the most extreme conditions
(20K cycles and 180 days of ageing in water) showed
10
the most significant effect (62).
Thus, the data for self-adhesive resin cements in
5 terms of bonding to ceramics is confined to zirconia and
demonstrates a brand dependency. The most studied
0 material, Unicem, bonds well to this substrate, espe-
Unicem Panavia F cially when air abraded or silica coated, and in these
Fig. 11. Bond strength of self-adhesive cement (Unicem) and self- cases is equivalent to one of the most popular self-
etch resin cement (Panavia F) to air-abraded and silica-coated etching resin cements (Panavia F) and other resin
(Rocatec) surfaces (Data from Blatz et al. 2007, 2009; Kombuloglu adhesive cements. There is likely some deterioration in
et al. 2006; Piwowarczyk et al. 2005). bond strength during ageing in aqueous fluids, but it is
not possible to predict the effect this will have on
45 clinical retention based on these in vitro studies.
40
Micro shear bond (Mpa)
35 Metals. Little data exist on the adhesion of self-

30
adhesive resin cements to metals used for prosthetics.
25
Wolfart et al. (64) measured the retentive force for
20
noble alloy crowns to titanium abutments and
15
demonstrated that the self-adhesive resin cement,
10
5
Unicem, had retentive strengths as high as poly-
0 carboxylate cement, with both being stronger than
Rexillium eMax CAD Lava ceramic Vitablock Cast gold glass–ionomer, zinc phosphate or zinc oxide eugenol
ceramic ceramic
cements. Studies published in the orthodontic literature
Fig. 12. Micro-shear bond strength of MaxCem elite self-adhesive have examined Unicem for adhering brackets to enamel
cement to various substrates (unpublished data). surfaces and have found that the bond strengths were

poorer than other orthodontic adhesives and the adhesive (Dyract Cem Plus). After thermal and
material could not be supported for this use (65, 66). mechanical cycling, marginal quality (by SEM) and
The analysis of the debonded surface showed that the dye penetration showed equivalent results for Unicem,
amount of cement left on the tooth was less for the self- Variolink II and Panavia F, while poorer marginal
adhesive resin cement than for the typical orthodontic adaptation and greater leakage were observed for
adhesives, suggesting that the bond to the metal bracket the resin-modified glass–ionomer and the compomer
was not the problem and further emphasising that cement.
bonding to unetched and uncut enamel was less More recently, Frankenberger et al. (69) investigated
effective for Unicem. A study in one of the authors’ the marginal integrity of ceramic inlays bonded with
laboratory (unpublished data) showed bond strengths two self-adhesive resin cements (Maxcem and Unicem)
exceeding 20 MPa in microshear (Fig. 12), but the compared with several other resin cements. All speci-
bond to the base metal alloy was significantly higher mens were subjected to thermal cycling and mechanical
than to the gold alloy. This outcome is fairly typical for loading, and marginal analysis by SEM showed a
resin cements bonding to metals of varying nobility, general reduction in gap-free margins after stressing,
based primarily on the presence of the more retentive with Maxcem showing significantly poorer marginal
oxide film on the former. In any case, it seems doubtful adaptation to enamel and dentin than all other
that there should be significant concern over the bond cements. While Unicem was equivalent to the best
to metal alloys used for restorative dentistry, though as performers on dentin, its per cent of gap-free margins to
always, questions linger over the durability of such enamel was poorer than five other resin cements that
bonds. employed a phosphoric acid enamel etch. Thus, this
poorer result to enamel seems consistent with the
minimal ability of these self-adhesive resin cements, as
Marginal adaptation ⁄ microleakage
well as the self-etching resin cements tested in this
Cement adhesion to various substrates is an important study, to etch and subsequently interact with enamel
property, but adequate bonding can be achieved in substrates compared to resin cements used with etch-
cases where there is not a complete seal of the and-rinse adhesives. The contrasting results shown for
tooth ⁄ restorative interface, thus leading to significant the Rosentritt et al. (68) and Frankenberger et al. (69)
clinical problems. Thus, the efficiency by which the studies were suggested by the latter authors to have
self-adhesive resin cements adapt to and seal margins is been attributed to the larger size of the restorations
critical for their success. used in their study.
Bott and Hannig (67) reported that class I porcelain In another study, Behr et al. (70) investigated the
inlays cemented into teeth with a compomer cement marginal adaptation and seal against leakage of luting
(Dyract Cem) used with or without an adhesive primer cements for all-ceramic crowns with dentin margins
(Prime & Bond 2Æ1) showed excellent marginal adap- after in vitro thermal cycling and mechanical loading
tation after in vitro thermal cycling and mechanical and showed the self-adhesive resin cement, Unicem, to
loading. The results were equivalent to those obtained be equal to or better than other resin cements.
with a dual curing resin cement (Dual Cement) and a Furthermore, when used in conjunction with a self-
chemical curing resin cement (Panavia 21). The spec- etch adhesive, Prompt-L-Pop, no further improvement
imens were aged for 4 months in water before being in marginal adaptation or sealing was obtained.
subjected to the thermal and mechanical loading, and Leakage and marginal gaps have also been evaluated
the authors noted that, in part, the excellent marginal for Unicem when used to cement full gold crowns (71)
adaptation could be related to the water uptake and and porcelain veneers (72). In the Piwowarczyk study
subsequent hygroscopic expansion of the compomer (71), the crown margins included areas in both enamel
cement. Rosentritt et al. (68) reported on the marginal and dentin, but the Unicem showed equal or slightly
fit of MOD ceramic inlays cemented with Unicem in better marginal seal to both enamel and dentin
comparison with an etch-and-rinse adhesive cement compared to an etch-and-rinse adhesive cement, a
(Variolink II), a self-etch resin adhesive cement (Pana- self-etching adhesive resin cement, a conventional
via F), a resin-modified glass–ionomer (Fuji Plus), and a glass–ionomer, a resin-modified glass–ionomer and a
self-adhesive compomer cement used with a self-etch zinc phosphate cement exposed to 4 weeks of ageing in

water followed by thermal cycling. All cements showed forces are higher than maximum biting forces measured
less leakage at enamel than dentin margins, including in a large number of men (600 N) and women (400 N)
Unicem. However, marginal gaps were higher for the by Miyaura et al. (75). In another study, Unicem was
Unicem compared to the other cements (except Panavia compared to Panavia F and zinc phosphate for Procera
F). When tested with veneers, Unicem showed compa- alumina crowns which were subjected to 1Æ2 million
rable or better sealing to dentin than other resin fatigue cycles in a chewing simulator before being
cements, but the opposite was true for enamel margins, tested for fracture strength (76). Although all specimens
causing the authors to conclude that Unicem should survived the dynamic loading, Panavia F was shown to
not be used for cementing ceramic veneers, unless a have the highest load to fracture, with Unicem being
separate etch was applied (72). significantly lower and equivalent to the zinc phos-
Thus, collectively these studies suggest that at least phate cement. In any case, the authors pointed out that
one self-adhesive resin cement, Unicem, may show the crowns, independent of cement, exceeded the
nearly equivalent results to other resin cements in expected intraoral forces and would therefore be
terms of marginal sealing and adaptation when bonding expected to survive clinical loading. The study also
inlays or crowns, but that a separate phosphoric acid measured leakage at the margins and showed it to be
etch of the enamel margins is likely to be beneficial, significantly lower for Panavia F then Unicem, with
especially if the cement is used for porcelain inlays. both being lower than the zinc phosphate. In a similar
study, Preuss et al. (77) evaluated the effect of luting
cement on the strength of endodontically treated, post-
Durability ⁄ support – cement and adhesion
restored teeth with ceramic crowns. The study did not
Many of the studies cited previously included some indicate a difference in load bearing capacity of Unicem
aspect of mechanical loading and ⁄ or ageing (water when compared to a zinc phosphate or a GIC.
storage and ⁄ or thermalcycling) before analysing the Thus, the studies examining the fatigue and load
marginal quality or leakage of the cements for various bearing ability of crowns cemented with one self-
restorative applications. Other studies have examined adhesive resin cement, Unicem, suggest that this
the effect of fatigue loading on the failure of teeth material may be at best equivalent to other resin
restored with restorations cemented with self-adhesive cements and likely to be clinically successful in this
resin cements. Ngo Uy et al. (73) compared three resin regard based on a comparison with conventional
cements to a self-adhesive resin (Unicem) and zinc cements, such as glass–ionomer and zinc phosphate,
phosphate in terms of cement failure when subjecting when tested under the same conditions.
gold crowns to fatigue loading. While Unicem only
withstood more fatigue cycles than the zinc phosphate
Biocompatibility
cement before showing signs of failure (though not
significantly more), the number of cycles to failure did There have been very few studies on the biocompati-
not differ significantly for any of the resin cements, bility of self-adhesive resin cements. De Souza Costa
except possibly Calibra. Failures were mainly found at et al. (78) compared the pulpal response to Unicem and
the tooth–cement interface for the resin cements but Variolink II when cementing class V composite inlays in
more frequently at the crown–cement interface for human teeth scheduled for extraction after 7 or
Unicem and zinc phosphate. Based on the historical 60 days. Remaining dentin thickness averaged about
clinical success of zinc phosphate, the results of these 400 lm for the cavities. For both cements, a slight to
studies, taken by themselves, would suggest that any of moderate inflammatory response was seen with tissue
the resin cements would be expected to be as durable as disorganisation, which contrasted with the control
zinc phosphate to mechanical fatigue stresses in the oral teeth containing a calcium hydroxide liner under
cavity. Unicem. The inflammatory response was most severe
Burke et al. (74) evaluated the compressive strength for Variolink II, which showed evidence of resin
of ceramic crown ⁄ tooth assemblies cemented with components deep into the dentin as expected owing
Unicem and another resin cement and showed them to the use of a separate etch with phosphoric acid, and
to be equivalent, with mean compressive fracture the response was inversely related to the remaining
resistance of 890 N and 760 N, respectively. These dentin thickness. The response to Unicem was minimal,

which correlates with its limited penetration into the

The clinical considerations
dentin substrate because of its lack of a pre-etching step
and its relatively high viscosity. In one case for Unicem
Handling ⁄ ease of use of self-adhesive resin cements
where a pulpal exposure occurred, a severe inflamma-
tory response ensued. No reparative dentin was formed, The uptake by practitioners of resin luting cements has
and no bacterial infiltrate was seen for the resin traditionally been slow, with authors identifying this
cements. lack of acceptance more than 15 years ago (81). This
More recently, Ulker and Sengun (79) evaluated the lack of support may well be attributed to the perceived
cytotoxicity of three self-adhesive resin cements (Bis- technique sensitivity of resin-based cements, given the
cem, Maxcem and Unicem) when compared with two large number of clinical stages that are necessary to
other resin cements (Bistite II DC and Panavia F) using achieve a bond to the dentine of the tooth preparation
a 3D pulp cell culture with a 500 lm dentin barrier when using ‘conventional’ resin luting materials, let
between the cements and the cells. Biscem produced alone the meticulous isolation which is needed
the greatest cytotoxic effect, followed by Panavia F, (Table 2).
Unicem and Bistite II DC, with Maxcem being the least Today, increasing numbers of restorative techniques
toxic of the resin cements. This result was in contrast cannot be performed with traditional acid-based luting
with that of De Mendonca et al. (80), in which Unicem materials and without the use of adhesive systems and
was found to be less cytotoxic than calcium hydroxide, resin-based luting materials. In an extensive review of
resin-modified glass–ionomer or adhesive resin cement. luting materials of choice for a variety of ten indirect
The reason for this discrepancy is not readily apparent. clinical techniques including cementation of a cast
The minimal information about the biocompatibility metal or metal-ceramic crown, ceramic inlay and cast
of the self-adhesive resin cements suggests that they post and core (82), of the 30 options available, the
should be well tolerated by the dental pulp, as long as authors chose resin-based systems for a total of 18
there is sufficient underlying dentin to serve as a clinical situations, glass–ionomer luting material for 5,
barrier. However, because of their higher viscosity and phosphate cement and resin-modified glass–ionomer
lack of aggressive etching of the dentin mineral, they both for 3 and polycarboxylate for one. While this
may actually be expected to be better tolerated than ‘straw poll’ may have limited scientific acceptability, it
resin cements that rely on separate etchants and does indicate the increasing diversity of the clinical
bonding agents to secure adhesion. This is borne out techniques to which resin luting materials may be
by the few clinical assessments of one of these cements, considered appropriate.
Unicem, which has shown low levels of pulpal prob- The excellent physical properties and the ability of
lems as explained in the next section. resin luting materials to facilitate ‘adhesive’ luting of
restorations are distinct clinical advantages, because the
Table 2. Comparison of number of stages with conventional and
clinician may not always be able to achieve an ideal
self-adhesive luting materials
taper or crown height. In this respect, Zidan and
Conventional resin Self-adhesive Ferguson (83) compared the retention, in vitro, of
luting materials luting materials complete crowns (with three different tapers) cemented
with four different cements, with the results indicating
Isolate Isolate
Etch preparation with Mix luting material and that the retentive values of the adhesive resins at 24
phosphoric acid apply to restoration degree taper was 20% greater than the conventional
Wash Remove excess cements at 6-degree taper. However, practitioners
Dry Light cure prefer materials that are easy to use, and it has been
Apply bonding agent
considered that ease of use facilitates improved perfor-
Air dry, ensuring that there
are no ‘puddles’ at internal angles mance (84). It could therefore be considered that a
Light cure resin luting material that does not require the etching
Mix luting material and and bonding steps presents distinct advantages to the
apply to restoration clinician when compared with traditional resin luting
Remove excess
materials in terms of ease of use and potential savings in
Light cure
time and chairside costs (Table 2).

Therefore, it may not be surprising to note the product would replace products that they had used
increase in use of resin luting cements by practitioners previously, with 96% of evaluators rating it as excellent
in the United Kingdom since the introduction of this or good and worthy of trial by colleagues (92). The CRA
group of self-adhesive resin cements. The results of a also assessed the clinical performance of RelyX Unicem
2002 survey of 1000 UK dentists indicated that 30% when used by 68 evaluators in the placement of 4820
routinely used zinc phosphate cement for cementation restorations, with follow-up from a few months to
of crowns, with fewer than 10%, stating that they used 1 year (93). The incidence of post-operative sensitivity
resin-based luting materials routinely (85). In contrast, was reported to be ‘very low’, and there was a very low
the results of a similar survey carried out in 2008 incidence of de-bonding (0Æ1%).
indicated that increasing numbers of dentists stated that
they were now using resin cements in the placement of
Clinical evaluation of the performance of self-adhesive resin
metal-ceramic restorations (21Æ3%) and that 9Æ2% were
luting materials
using a self-adhesive variant (unpublished data, Burke,
et al.). There is a paucity of studies that assess the long-term
The assessment of new techniques and materials in performance of self-adhesive luting materials, not
the dental practice plays an important role in their surprising, given the small number of studies which
overall evaluation and acceptance by dentists (86, 87), evaluate the clinical performance of conventional
because ease of use may contribute to good perfor- cements and resin luting materials.
mance. Co-ordinated assessments of new materials by The PREP Panel re-evaluated the restorations
practitioner-based research groups, typically teamed placed using RelyX Unicem after 2 years (94). Ninety
with the research expertise available in academic of the original 144 restorations placed using RelyX
institutions, are becoming more common. Perhaps the Unicem were reviewed, the mean age of the resto-
first such group was the Clinical Research Associates rations being 21 months. Four restorations (4%), all
(CRA), based in the U.S. More recently, other practice- in patients of one operator, were reported to have
based research networks have evolved, including failed at the time of this report. The reasons for these
Practice-based Research in Oral Health (PROH) in the failures were unconnected with the use of the resin
U.S. (88) and the Product Research and Evaluation by cement (root fracture, porcelain fracture and unre-
Practitioners Panel (PREP) based in the U.K. (89–91). lated enamel chipping), and it was concluded that
A UK evaluation by thirteen members of the PREP restorations luted with RelyX Unicem were perform-
Panel used a 21-question questionnaire designed to ing satisfactorily in UK general dental practice after
provide information on the handling and ease of use of 21 months, although it was agreed that a longer
RelyX Unicem and the comparison of this material with evaluation period was needed.
pre-study cementation materials (91). A total of 144 A recent article reported on a 1-year clinical
restorations were placed in the study, and RelyX evaluations of 43 IPS Empress** inlays luted with
Unicem was rated higher by the evaluators for ease of RelyX Unicem and compared with a control group of
use than both the pre-trial resin-based cement and 40 inlays luted with Variolink II with Syntac adhesive
‘conventional’ cements. Ninety-two per cent (n = 12) (Ivoclar Vivadent**) (95). The control group displayed
of the evaluators considered that it was ‘very advanta- significantly better results regarding colour match and
geous’ for the material under evaluation not to require chipping of the inlay margins when compared to
etching and bonding prior to cementation. All the Unicem, but there were no statistical differences
evaluators stated that they would purchase the material between the two groups over a further eight param-
if available at average cost. None of the evaluators eters, and all the inlays were clinically acceptable.
reported any incidence of patients with post-operative The authors concluded that RelyX Unicem showed
sensitivity following placement of restorations with the comparable clinical performance to the conventional
material. resin system.
The results of the PREP Panel study are in broad A prospective clinical trial started in 2003 evaluated
agreement with those reported in the July 2003 CRA the performance of 49 metal-based fixed partial
Newsletter, in which 64% of the 28 evaluators who
assessed the handling of RelyX Unicem stated that this **Ivoclar Vivadent, Schaan, Liechtenstein.

dentures at 3 years, luted with either RelyX Unicem variety of luting materials, including the original type
or zinc phosphate cement (96). The authors con- of RelyX Unicem (Applicap) and a recently intro-
cluded that the self-adhesive resin cemented group duced more easily mixed paste–paste version (Click-
performed comparably with the ‘well-established’ zinc er). They also tested the self-adhesive resin luting
phosphate cement group. The authors, in reviewing materials (which they termed self-adhesive modified
the literature on zinc phosphate cement, commented resin cements) Fuji CEM (GC America), iCEM (He-
that its performance seemed ‘astonishing’, given its reaus Kulzer, Armonk, NY, USA), Bis-Cem (Bisco,
lower compressive strength than resin cements, its Schaumberg, IL, USA) and Maxcem (Kerr‡). They
high solubility and the potential for pulpal irritation made 20-degree standardised preparations on groups
and microleakage. of extracted third molar teeth, placed and removed
The small number of studies examining the clinical provisional restorations to simulate the clinical expe-
performance of RelyX Unicem and other self-adhesive rience and cemented the crowns using gentle finger
luting materials therefore appear to provide promising, pressure. The copings were subjected to dislodgment
albeit early, results. forces along the apico-occlusal axis until failure. The
results indicated that the bond of the newer,
paste ⁄ paste version of RelyX Unicem did not appear
Laboratory studies with clinical relevance
to be as strong to dentine as the original version
The marginal adaptation of all-ceramic crowns luted (Applicap) but that self-adhesive resin luting materials
with RelyX Unicem was assessed after simulation of provided additional retention when this is desired and
5 years of oral stress (70) and compared to crowns luted that all the cements tested retained metal castings as
with a compomer-based luting material (Dyract Cem well as, or better than, zinc phosphate cement.
Plus) used in combination with an adhesive system
(NRC P&B NT, Dentsply**) and a ‘conventional’ resin
Summary
luting material (Variolink II: Ivoclar Vivadent**) used
with the Syntac Classic adhesive system (Ivoclar The result of this review of the chemical and physical
Vivadent**). The results indicated that, without any properties of self-adhesive resin cements would suggest
conditioning or pre-treatment, RelyX Unicem showed that these materials may be expected to show similar
marginal adaptation to dentine which was comparable clinical performance as other resin-based and non-resin
to the established resin luting materials. based dental cements. However, clinical evaluations are
Trajtenberg et al. (97) compared the microleakage of few and short term, so drawing long-term conclusions
all-ceramic crowns (IPS Empress: Ivoclar Vivadent**) about the overall effectiveness of these cements in
luted with RelyX Unicem to two resin cements used dental practice is not yet possible. However, the
with their own self-etching primers, Multilink (Ivoclar handling properties of these materials appear to be
Vivadent**) and Panavia 2.0 (Kuraray America†). The excellent, and their acceptance by the profession is
results indicated that crowns luted with Panavia and increasing.
RelyX Unicem showed the same percentages of micro-
leakage (0Æ76% and 1Æ78%, respectively) on enamel
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Journal of Oral Rehabilitation

Journal of Oral Rehabilitation 2011 38; 295–314

glass–ionomer and resin composite. However, dentists

ª 2010 Blackwell Publishing Ltd doi: 10.1111/j.1365-2842.2010.02148.x

Compomers are not inherently able to bond directly

ª 2010 Blackwell Publishing Ltd

Table 1. Brands and compositions of self-adhesive resin cements circa 2009

Cement Manufactures Composition

BisCem Bisco* Bis(hydroxyethyl methacrylate) phosphate, tetraethyleneglycoldimethacrylate, glass filler

*Bisco Inc., Schaumburg, IL, USA.

ª 2010 Blackwell Publishing Ltd

Fig. 1. Non-acidic methacrylate monomers used in resin adhesive cements.

ª 2010 Blackwell Publishing Ltd

Fig. 3. Carboxylic acid monomers used to promote adhesion in cements.

ª 2010 Blackwell Publishing Ltd

ª 2010 Blackwell Publishing Ltd

approximately two minutes is typical with setting times

ª 2010 Blackwell Publishing Ltd

ª 2010 Blackwell Publishing Ltd

ª 2010 Blackwell Publishing Ltd

Teeth. A number of studies have been conducted on 10

ª 2010 Blackwell Publishing Ltd

ª 2010 Blackwell Publishing Ltd

40·00 to various surfaces showed relatively high bonds to cast

f or less). Glass–ionomer, resin-modified glass–ionomer

and zinc phosphate were all shown to bond minimally

to zirconia in comparison, rarely achieving shear bond

strengths exceeding 6–7 MPa (59, 61, 62) and being

35 Metals. Little data exist on the adhesion of self-

ª 2010 Blackwell Publishing Ltd

ª 2010 Blackwell Publishing Ltd

ª 2010 Blackwell Publishing Ltd

which correlates with its limited penetration into the

ª 2010 Blackwell Publishing Ltd

ª 2010 Blackwell Publishing Ltd

ª 2010 Blackwell Publishing Ltd

ª 2010 Blackwell Publishing Ltd

ª 2010 Blackwell Publishing Ltd

ª 2010 Blackwell Publishing Ltd

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