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Solubility of root-canal sealers in water and artificial saliva

Article  in  International Endodontic Journal · October 2003

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 Solubility of root-canal sealers in water and
artificial saliva
E. Scha«fer & T. Zandbiglari
Department of Operative Dentistry, University of Mu«nster, Mu«nster, Germany
Abstract
Scha«fer E, Zandbiglari T. Solubility of root-canal sealers in
water and artificial saliva. International Endodontic Journal, 36,
660^669, 2003.
Aim To compare the weight loss of eight di¡erent root-
canal sealers in water and in arti¢cial saliva with di¡er-
ent pH values.
Methodology For standardized samples (n ˆ 12 per
group), ring moulds were ¢lled with epoxy resin (AH
26, AH Plus)-, silicone (RSA RoekoSeal)-, calcium hydro-
xide (Apexit, Sealapex)-, zinc oxide^eugenol (Aptal-
Harz)-, glass-ionomer (Ketac Endo)- and polyketone
(Diaket)-based sealers. These samples were immersed
in double-distilled water or arti¢cial saliva with di¡erent
pH values (7.0, 5.7 and 4.5) for 30 s, 1 min, 2 min, 5 min,
10 min, 20 min, 1 h, 2 h, 10 h, 24 h, 48 h, 72 h, 14 days
and 28 days. Mean loss of weight was determined and
analysed statistically using a one-way ANOVA and Stu-
dent^Newman^Keuls test for all pairwise comparisons.
Introduction
The purpose of a root ¢lling is to entomb residual micro-
organisms and prevent ingress of microorganisms from
the oral environment and their passage to the periapical
tissues (Nguyen1994, Scha«fer 2000). The physical prop-
erties necessary for materials meeting this function
include insolubility or at least low solubility (Grossman
1982, Òrstavik 1983). This property is of utmost impor-
tance for a root-canal sealer, as the long-lasting bac-
teria-tight seal of the root canal, which is necessary for
successful results of endodontic therapy depends mostly
Correspondence: Prof Dr Edgar Scha«fer, Department of Opera-
tive Dentistry, Waldeyerstr. 30, D-48149 Mu«nster, Germany
(Tel.: ‡49 251 834 70 40; fax: ‡49 251 834 70 37; e-mail:
eschaef@uni-muenster.de).
660 International Endodontic Journal, 36, 660^669, 2003
Results Most sealers were of low solubility, although
Sealapex, Aptal-Harz and Ketac Endo showed a
marked weight loss in all liquids. Even after 28 days
of storage in water, AH 26, AH Plus, RSA RoekoSeal, and
Diaket showed less than 3% weight loss. At exposure
times greater than 14 days, Sealapex showed the
signi¢cantly greatest weight loss of all sealers tested
(P < 0.05). Aptal-Harz and Ketac Endo were sig-
ni¢cantly more soluble in saliva (pH 4.5) than in water
(P < 0.05).
Conclusions Under the conditions of the present
study, AH Plus showed the least weight loss of all sealers
tested, independent of the solubility medium used. Sea-
lapex, Aptal-Harz and Ketac Endo had a marked weight
loss in all liquids.
Keywords: degradation, disintegration, endodontic
sealers, physical properties, weight loss.
Received 2 January 2003; accepted19 May 2003
on the integrity of the sealer component (Nguyen
1994). Degradation of the sealer may result in gaps and
voids along the sealer/dentine or the sealer/gutta-percha
interface (Kazemi et al. 1993, Geurtsen & Leyhausen
1997, Òrstavik et al. 2001). These spaces may provide an
environment for bacterial colonization and passage of
microorganisms and their products into the periapical
tissues (Nguyen 1994). Therefore, insolubility of root-
canal sealers may have a major impact on the success
rate of root-canal treatment. Moreover, sealers should
be of low solubility because components leaching from
the root-canal ¢lling may have undesirable biological
e¡ects on the surrounding tissues (Òrstavik 1983,
Geurtsen & Leyhausen 1997).
Surprisingly, few studies have been carried out on the
solubility of root-canal sealers. Zinc oxide^eugenol-
based sealers are generally associated with a certain
degree of weight loss after storage in water, ranging from
ß 2003 Blackwell Publishing Ltd
 Scha«fer & Zandbiglari Solubility of root-canal sealers

approximately 7% to less than 1% (Higginbotham 1967,

phosphate 3%, zinc stearate 3%; component B: trimethylhexandiol disalicylate 25%, bismuth carbonate 18%, bismuth oxide 18%,
McComb & Smith 1976, Òrstavik 1983, Kazemi et al.
1993). The calcium hydroxide-containing sealer Seala-
pex is also believed to be soluble over time (Tronstad
et al. 1988), but little experimental work is available to

Component A: Ca(OH)2 25%, ZnO 7%; component B: polymethylene salicylate resin 33%, BaSO4 19%,TiO2 5%

Powder: ZnO 97% bismuth phosphate 3%; liquid: propionylacetophenone 76%, copolymers of vinyl acetate,
con¢rm this (Wrbas et al. 1998). On the contrary, it has

Component A: Bisphenol-A-diglycidylether, Calcium tungstate, ZrO2; component B: adamantane amine,

been demonstrated that silicone- (Kazemi et al. 1993),

Component A: Ca(OH)2 32%, hydrogenated colophonium 32%, SiO2 8%, CaO 6%, ZnO 6%, tricalcium
960814/9606010Powder: Bi2O3 60%, methenamine 25%, silver 10%,TiO2 5%; liquid: bisphenol-A-diglycidylether 100%

Powder: ZnO 61%, colophonium 26%, silver 10%, SiO2 3%; liquid: eugenol 45%, balsam of Peru 30%,
polyketone- (Higginbotham 1967, McComb & Smith

vinyl chloride, and vinyl isobutyl ether 23%, 2.20 -dihydroxy-5,50 -dichlorodiphenylmethane 0.5%,
1976, Grossman 1978, Òrstavik 1983) and epoxy resin-
based sealers (Grossman 1978, Òrstavik 1983, Kazemi
et al. 1993) have a relatively low solubility in water.

SiO2 15%, 1,3-butanediol disalicylate 11%, tricalcium phosphate 5%, zinc stearate 2%
Evaluation of the solubility of root-canal sealers has,
in general, been based on studies in which the weight
loss of set sealers in distilled water has been determined.
Higginbotham (1967) used 0.001 M acetic acid bu¡ered
to pH 4 and Grossman (1978) used awater-broth solution
in order to approximate the viscosity of periapical exu-
date to study the solubility of di¡erent sealers. To date,
no other solubility media have been used in order to
mimic in£ammatory exudate, tissue £uids or saliva.
Low solubility of root-canal sealers has been intro-
duced as a requirement in the International Standard
6876 (2001) for root-canal sealing materials. According
to this standard, the solubility of the set sealer shall not
Table 1 Sealers tested (according to Geurtsen & Leyhausen1997, Scha«fer 2000, Òrstavik et al. 2001)

exceed 3% mass fraction after immersion in water for

Polymaleinate glass-ionomer
24 h.

colophonium 10%, oil 15%

Therefore, the aim of this in vitro study was to apply the
Addition type silicone

triethanolamine 0.2%
diamines, silicon oil

method proposed in the ISO standard to compare the

solubility of eight di¡erent paste-type root-canal sealers
Ingredients

in water and arti¢cial saliva over a period of 28 days.

Materials and methods

FW 0064632
Dentsply Maillefer, Konstanz,0005001130

Eight commercially available sealers, representing six

Roeko, Langenau, Germany 2906758

B 06053

063/033
9^1083

di¡erent chemical classes of materials were included in

Batch

0227

this study (Table 1). Solubility was determined in double-

distilled water and arti¢cial saliva, which was prepared
Zinc oxide^eugenolAptal-Harz Speiko, Mu«nster, Germany
Sealapex Kerr, Karlsruhe, Germany

from analytical grade components at the pharmacy

Ketac EndoEspe, Seefeld, Germany
Espe, Seefeld, Germany

of the College of Medicine (Mu«nster, Germany). The

Konstanz, Germany
Dentsply Maillefer,

Vivadent, Schaan,

ingredients of the arti¢cial saliva solutions are listed

Manufacturer

Liechtenstein

in Table 2: Three di¡erent arti¢cial saliva solutions

Germany

were prepared, adjusted with 1 M HCl to pH 7.0, 5.7

or 4.5.
The solubility tests recorded weight loss of the test spe-
RoekoSeal
AH Plus

cimens and to a great extent followed the methodology

AH 26

Calcium hydroxide Apexit

Diaket
Sealer

RSA

of the International Standard 6876 (2001). Stainless

steel ring moulds having an internal diameter (i.d.)
20.0  0.1 mm and a height of 1.6  0.1 mm were used
Glass-ionomer
Type of sealer

Epoxy resins

Polyketone

for sample preparation. All moulds were cleaned with

Silicone

acetone in an ultrasound bath for 15 min. Thereafter, a

copper wire was ¢xed at each mould in order to hang

ß 2003 Blackwell Publishing Ltd International Endodontic Journal, 36, 660^669, 2003 661
 Solubility of root-canal sealers Scha«fer & Zandbiglari
Table 2 Ingredients of the arti¢cial saliva solutions (¢lled up
with distilled water to1 kg)
Ingredient
Carboxymethyl cellulose
Xylitol solution (70%)
KCl
NaCl
MgF2
CaCl2
K2PO4
KSCN
Methyl-4-hydroxybenzoate
the specimens in a glass dish in such way that the sur-
faces did not touch and the sealers remained undis-
turbed in the dish. All moulds were weighed thrice
prior to use (accuracy: 0.0001 g).
The moulds were placed on a glass plate and ¢lled to
slight excess with the mixed sealer using a 2-mL syringe
(Almo, Bad Arolsen, Germany) avoiding air entrapment.
All sealers were mixed in accordance with manufac-
turers instructions. As it is well known that both Apexit
and Sealapex require moisture for setting (Tagger et al.
1988), these sealers were mixed with a spatula moistened
with tap water. All samples were left to set on a grating
in a cabinet at 37 8C for 24 h and 95% relative humidity.
Excess material was then trimmed level to the surface
of the mould using silicone carbide paper (600 grit). From
each sealer, 672 samples were prepared which were
divided into four groups of 12, for immersion in the four
di¡erent liquids for 30 s, 1 min, 2 min, 5 min, 10 min,
20 min, 1 h, 2 h, 10 h, 24 h, 48 h, 72 h, 14 days and
28 days. Thus, a total of 5376 samples were prepared
for this study.
Prior to the immersion of the samples, all sealers in
their moulds were weighed (Sartorius type 1801 MPS,
Go«ttingen, Germany) thrice and the average reading
was recorded. All weight measurements were in grams,
recorded to four decimal places.
Six samples of each sealer in its mould were immersed
in a fresh 160 mL aliquot of liquid at 37  1 8C a time
for 1 day and subsequently in fresh 160 mL aliquots at
weekly intervals. The specimens were placed in an air-
tight dish (7 cm  10.5 cm  8 cm) with 95^100% rela-
tive humidity such that both surfaces of each sample
were freely accessible to the liquid. There was no agita-
tion of the dish. As controls, 24 empty sample moulds
together with the copper wire were immersed in the four
di¡erent liquids for 28 days, and any changes in weight
were recorded.
Samples of sealers were removed from the dish after
the speci¢ed immersion period using a pair of tweezers,
662 International Endodontic Journal, 36, 660^669, 2003
touching only the metal mould. Samples were washed
with 3 mL of double-distilled water and allowed to dry
Content for 24 h at 37 8C in an oven. The specimens were placed
10 g on a grating in such a way that only the metal moulds
43 g touched the grating. Thereafter, the samples were
1g weighed thrice and the mass of the sealer was deter-
1g
mined to the nearest 0.0001 g. The amount of sealer
50 mg
150 mg
removed from the specimen was recorded as the di¡er-
400 mg ence between the original weight of sealer and its ¢nal
100 mg weight to the nearest 0.0001 g. This di¡erence in mass
1g was calculated as a percentage of the original weight of
the sealer, recorded to the nearest 0.001%.
The di¡erences in solubility of each sealer in the di¡er-
ent liquids was assessed by analysis of variance (ANOVA;
P <0.05). Di¡erences between the eight sealers with
respect to their solubility in each liquid were analysed
using a one-way ANOVA and Student^Newman^Keuls test
for all pairwise comparisons (P < 0.05).
Results
There was no change inthe weight of empty moulds after
immersion in either of the four liquids after 28 days.
The results for all sealers are shown in Fig. 1.
The epoxy-based materials AH 26 and AH Plus were of
low solubility. The weight loss of AH 26 after 28 days'
immersion in the four di¡erent liquids ranged from
2.79% to 4.32% whereas the weight loss of AH Plus
was in the range of 0.11^0.19% (Fig. 1a). Thus, AH Plus
was virtually insoluble in all liquids tested. At an expo-
sure time of 28 days AH Plus was less soluble inall liquids
than the other sealers (P < 0.05). There were no signi¢-
cant di¡erences between the weight loss of AH Plus after
immersion in either of the four liquids at all exposure
times (P > 0.05). At exposure times greater than 10 h
AH 26 was signi¢cantly more soluble in all liquids than
AH Plus (P < 0.05). AH 26 was signi¢cantly more soluble
in arti¢cial saliva pH 7.0 than in the three other liquids
at exposure times greater than 14 days (P < 0.05).
The silicone-based sealer RSA RoekoSeal showed a
low solubility in all liquids ranging from 0.85 to 1.01%
after 28 days (Fig. 1b). At exposure times greater than
72 h there were no signi¢cant di¡erences in the solubi-
lity of RSA RoekoSeal in either of the four liquids
(P > 0.05).
Out of the two calcium hydroxide-based sealers,
Apexit showed a low solubility of 1.1% after 2 min
(Fig. 1c) with a slight but consistent continuous increase
in solubility over the next days. The weight loss of Apexit
after 28 days immersion in the four di¡erent liquids ran-
ged from 1.68 to 2.74%. At an exposure time of 28 days,
ß 2003 Blackwell Publishing Ltd
 Scha«fer & Zandbiglari Solubility of root-canal sealers

Figure 1 Mean weight loss of sealers over time (notice the di¡erent scaling of the y-axis). (a) Epoxy resins, (b) silicone-based
sealers, (c) calcium hydroxide-based sealers, (d) zinc oxide^eugenol-based sealers, (e) glass-ionomer-based sealers and
(f) polyketone-based sealers.

ß 2003 Blackwell Publishing Ltd International Endodontic Journal, 36, 660^669, 2003 663
 Solubility of root-canal sealers Scha«fer & Zandbiglari
Figure 1 continued
Apexit was signi¢cantly more soluble in water than in
saliva (P < 0.05). Sealapex displayed a low solubility of
some 1.1% after 1 h, followed by a pronounced increase
in solubility to over 10% after 28 days. The weight loss
of Sealapex after 28 days immersion in the four di¡erent
664 International Endodontic Journal, 36, 660^669, 2003
liquids ranged from 5.55 to 10.14%. At exposure times
greater than10 h, Sealapex was signi¢cantly more solu-
ble in water than in saliva (P < 0.05). At exposure times
greater than 14 days, Sealapex was signi¢cantly more
soluble in water than all other seven sealers (P < 0.05).
ß 2003 Blackwell Publishing Ltd
 Scha«fer & Zandbiglari Solubility of root-canal sealers

Figure 1 continued

The zinc oxide^eugenol-based sealer, Aptal-Harz, Aptal-Harz was signi¢cantly more soluble in saliva
showed a consistent, continuous and marked weight loss pH 4.5 than in the other three liquids (P < 0.05).
in all liquids over the 28-day period ranging from 5.74 Ketac Endo (Espe, Seefeld, Germany), the glass-
to 9.27% (Fig. 1d). At exposure times greater than 72 h, ionomer-based material, displayed a marked weight loss

ß 2003 Blackwell Publishing Ltd International Endodontic Journal, 36, 660^669, 2003 665
 Solubility of root-canal sealers Scha«fer & Zandbiglari
Figure 2 Mean weight loss and standard deviation of sealers after 24-h immersion in water, as required in the International
Standard 6876 (2001). The bold horizontal line represents the requirement for compliance with the standard.
after 30 s of storage in the range of 3.27^7.49%, with an
apparent but slight continuous weight loss over the next
28 days (Fig. 1e). At all exposure times, Ketac Endo was
more soluble in saliva pH 4.5 and 5.7 than in the other
liquids (P < 0.05). This sealer was signi¢cantly more
soluble in saliva pH 4.5 and 5.7 than all other sealers,
with the exception of Aptal-Harz at an exposure time of
28 days (P < 0.05).
Diaket showed a low solubility in all liquids ranging
from 1.45 to 2.64% after 28 days (Fig. 1f). At exposure
times less than 28 days, Diaket was signi¢cantly more
soluble in water than in saliva (P < 0.05).
The results for all sealers after 24 h storage in water
are shown in Fig. 2.
Discussion
Experimental set-up
The procedure to determine the solubility of set sealer in
water is described in the International Standard ISO
6876 (2001).The solubility tests performed in the present
study followed to a great extent the methodology of this
International Standard. However, whilst weight loss of
the test specimens was recorded by determining the
decline in mass of the sealers samples after storage in
666 International Endodontic Journal, 36, 660^669, 2003
the di¡erent liquids, as already described by some
authors (McComb & Smith 1976, Òrstavik 1983, Kazemi
et al. 1993, Ono & Matsumoto 1998), the International
Standard suggests that the increase in weight of the
dish in which the samples have been placed (residue
method) should be ascertained as the amount of mate-
rial removed from the specimens (Higginbotham 1967,
Kaplan et al. 1997, International Organization for
Standardization 2001). The specimens were weighed in
order to avoid an underestimation of the material going
into solution. For instance, it is well known that when
the residue method is applied to zinc oxide^eugenol
cements, eugenol, the major constituent of the eluate,
is lost by volatilization during the course of evaporation
and hence is not estimated (Wilson 1976). Moreover, it
has been shown that the best indication of the extent
of the disintegration can be obtained by weighing the
specimens before and after the test (Wilson 1976). In
order to enhance the accuracy of the measurements,
one sample was used for just one immersion period,
thus undesirable weight loss of the sealer because of
repeated drying and immersion was excluded. After
the immersion period, all samples were washed with
double-distilled water in order to remove loose debris of
decomposition (Wilson 1976). The standard deviation
obtained was low for all sealers and ranged from 0 to
ß 2003 Blackwell Publishing Ltd

1.66%, and was lower than those described by Òrstavik
(1983) under nearly identical experimental conditions.
Moreover, sealers di¡ering by less than 0.5% in solubility
could be separated with statistical signi¢cance. Based
on these ¢ndings, the experimental method seemed
appropriate.
It has to be kept in mind that with regard to the strict
de¢nition of the physicochemical term solubility, the test
used in the present study measured the elution of
water-soluble material, but not the solubility (Wilson
1976). Solubility of a solid is the situation, where a pure
chemical compound is in thermodynamic equilibrium
with its solution (Wilson 1976). Moreover, it has to be
taken into account, that measuring weight di¡erences
of the sealer specimens may also record disintegra-
tion processes that may not be the result of dissolution
(Wilson1976, Òrstavik1983). For instance, ¢ller particles
of the material may fall out from the sealer structure
during storage in the liquids (Wilson 1976, Òrstavik
1983). Furthermore, water uptake may compensate
for dissolved material (Òrstavik 1983, Caicedo & von
Fraunhofer 1988, Kazemi et al. 1993, Wrbas et al. 1998).
This aspect might have an e¡ect on the changes in
weight of zinc oxide^eugenol- and glass-ionomer-based
sealers, according to the ¢ndings reported byWrbas et al.
(1998); and ¢nally, the drying process of the specimens
after immersion in the di¡erent liquids may lead to eva-
poration of volatile components in the sealer (Wilson
1976, Òrstavik 1983).
In the present study, all sealers were allowed to set for
24 h prior to immersion. Glass-ionomer-based sealer
set in two stages: ¢rst, a reaction between the polyalke-
noic acid and the calcium occurs that is followed by a
curing for about 24 h when there is a reaction between
the acid and the aluminium. That is why the samples
were immersed only after 24 h following preparation.
This method did not reproduce in vivo conditions, when
the sealer comes in contact with periapical or oral £uids
immediately. However, the sealer is not completely
immersed under clinical conditions.
It has been suggested that dilute acids (Higginbotham
1967, Wilson 1976) or culture medium (Grossman
1978) should be used for solubility tests rather than dis-
tilled water in order to mimic tissue £uids (Òrstavik
1983). In the present study, distilled water as well as arti-
¢cial saliva solutions adjusted to three di¡erent pH
values (7.0, 5.7 and 4.5) were used. Saliva was included
in the study in order to investigate the solubility of
root-canal sealers in the case of coronal leakage under
acid conditions developed in stagnation areas. This
might be of clinical signi¢cance (Wilson 1976) because
ß 2003 Blackwell Publishing Ltd
Scha«fer & Zandbiglari Solubility of root-canal sealers
acid conditions can occur orally either by ingestion of
acidic food or by the degradation of polysaccharides
to acids because of the action of various streptococci
and bacilli. However, the similarity between arbitrarily
chosen formulas of arti¢cial saliva and oral condi-
tions is questionable (Òrstavik 1983). Distilled water was
used as solubility medium in order to provide a baseline
for solubility studies, and, as suggested by Òrstavik
(1983), these results may be taken to represent a mini-
mum solubility.
Weight loss of sealers
Under the conditions of the present study, AH Plus
showed the least weight loss of all sealers tested, inde-
pendent of the solubility medium used (Fig. 1). This is a
new ¢nding and no data on the solubility of AH Plus
has been reported. AH Plus was less soluble than RSA
RoekoSeal and Diaket. On average, these sealers showed
less than 3% weight loss after 28 days, independent of
the storage medium (Fig. 1). The latter ¢ndings are in
good agreement with previously published results (Hig-
ginbotham 1967, McComb & Smith 1976, Grossman
1978, Òrstavik 1983, Kazemi et al. 1993, Wrbas et al.
1998). The rates of solubility of AH 26 were low for
immersion times up to 48 h (less than 1% weight loss
in all liquids; Fig. 1a), which is coincident with previous
¢ndings (Òrstavik 1983, Kazemi et al. 1993, Kaplan et al.
1997). This may be explained by the relative insolubility
in water of its additives (Òrstavik 1983, Wrbas et al.
1998). At 28 days, however, some solubility was noted
in AH 26 (weight loss ranging from 2.79 to 4.32%). This
observation corroborates the results of McComb & Smith
(1976) and Kazemi et al. (1993), in that in the latter study
some disintegration was noted in AH 26 at the 180 day
observation period. According to the authors, this may
be a result of polymer degradation of unreacted hexam-
ethylenetetramine and its break down to ammonia and
formaldehyde (Kazemi et al.1993).This polymer degrada-
tion of unreacted hexamethylenetetramine may also be
an explanation for the higher solubility of AH 26 in com-
parison to AH Plus (Fig. 1a). In the present study, AH 26
was signi¢cantly more soluble in arti¢cial saliva pH 7.0
than in the other three liquids at exposure times
greater than 14 days (P < 0.05). An explanation for this
phenomenon cannot be given based on the present
results.
As regards the present data on the solubility of AH 26,
it has to be taken into account that all sealers were
exposed to di¡erent media after 24 h. But according to
a study of Allan et al. (2001), AH 26 was completely set
International Endodontic Journal, 36, 660^669, 2003 667
 Solubility of root-canal sealers Scha«fer & Zandbiglari
not before 1 week. Although, in the present study, we
could not detect any evidence that AH 26 was only
partially set or even unset after 24 h, this fact might have
in£uenced the results to a certain extent.
The calcium hydroxide-containing sealer Sealapex
was signi¢cantly more soluble in water than all other
sealers tested at exposure times greater than 14 days.
These data are in accordance with the results of previous
reports (Tagger et al. 1988,Tronstad et al. 1988). Surpris-
ingly, Apexit, the other Ca(OH)2-based sealer, showed
less solubility than Sealapex (Fig. 1c). The reason for that
might be related to the content of zinc stearate in Apexit,
which is known to be highly hydrophobic, thus prevent-
ing an ingress of water. On the contrary, it has been
shownthat set Sealapex has a poorly formed matrix (Cai-
cedo & von Fraunhofer 1988) and demonstrated a very
high water sorption (Caicedo & von Fraunhofer 1988,
Wrbas et al.1998). It was assumed that this porous mate-
rial permits marked ingress of water over time that pro-
motes continued reaction between powder and binder
(Caicedo & von Fraunhofer1988).This could be the cause
of the high solubility of Sealapex.
The zinc oxide^eugenol-based sealerexhibited marked
weight loss after 28 days (Fig. 1d), which correlates with
the results of other authors (McComb & Smith 1976,
Òrstavik 1983, Kazemi et al. 1993). This high degree of
solubility is probablya result of the leaching out of excess
and nonreacted eugenol as well as the hydrolysis reaction
of hardened zinc eugenolate (Òrstavik1983, Kazemi et al.
1993,Wrbas et al. 1998). At exposure times greater than
72 h, this material was signi¢cantly more soluble in
saliva pH 4.5 than in the three other liquids (P < 0.05).
Zinc oxide^eugenol-based materials are hydrolyti-
cally decomposed according to the following equation:
Zn(C10H11O2)2 ‡2H2O ˆ Zn(OH)2 ‡ 2C10H12O2 (Wilson
1976). The cause of the higher solubility of Aptal-Harz
in acidic saliva is probably related to the fact that one
product of the hydrolytical degradation of zinc oxide
eugenol, zinc hydroxide, is almost insoluble in neutral
but highly soluble inacidic solutions (Wilson1976).Thus,
in neutral solutions this water-insoluble zinc hydroxide
will adhere to the sealer and will not be transferred to
the solution and measured.
Ketac Endo, the glass-ionomer-based material, dis-
played a marked weight loss even after 30 s with an
apparent but small continuous weight loss over the next
28 days (Fig. 1e), which is coincident with other reports
(Kaplan et al. 1997, Wrbas et al. 1998). This early weight
loss of glass-ionomer cements can be attributed to three
causes (Crisp et al. 1980, Causton 1981). First, they con-
tain sodium which forms water-soluble salts with the
668 International Endodontic Journal, 36, 660^669, 2003
matrix-forming anions. Secondly, aluminium ions react
rather slowly with the matrix-forming anions, thus they
are vulnerable to early water-leaching. Thirdly, the
weight loss can be attributed to a loss of water bound
in the matrix because of the drying of the specimens
for 24 h at 378C after storage. In the present study, at
all exposure times, Ketac Endo was more soluble in saliva
pH 4.5 and 5.7 than in saliva pH 7.0 or in water
(P < 0.05). The reason for this ¢nding is probably related
to the two-phase structure of the set glass-ionomer
cement (Fukazawa et al.1987). Unreacted glass particles
are embedded in the matrix gel which contains polycar-
boxylate and £uoride complexes. Even after curing for
24 h, a considerable amount of unreacted ^COOH
groups still remain in the matrix. Fukazawa et al. (1987)
suggested that the density of cross-linking between
^COOH groups of polyacids by bonding with Ca2‡ or
Al3‡ ions is rather low. Further, it was considered
that H‡ ions di¡use from the solubility medium into
the cement and exchanges with Ca2‡ or Al3‡ ions in
the matrix. These free metal cations di¡use through the
cement outward and can be leached out (Fukazawa
et al. 1987). Thus, the cause of Ketac Endo solubility in
acidic saliva seemed to be in£uenced by the structure
of the glass-ionomer matrix and the [H‡] at the sealer
surface.
The requirement for compliance with the Interna-
tional Standard (2001) has been set at a weight loss of
not more than 3% after storage in distilled water for
24 h.Whilst three sealers clearly exceeded the proposed
maximum weight loss (Fig. 2), the majority of materials
tested met the standard. Even after 28 days of storage
in water, these ¢ve sealers showed less than 3% weight
loss. These ¢ndings coincide with data from clinical stu-
dies, in which the latter sealers have been proved to pos-
sess good sealing capabilities (Nguyen 1994, Scha«fer
2000).
Conclusions
Within the limitations of this laboratory study, most sea-
lers were of low solubility. Sealapex, Aptal-Harz and
Ketac Endo had a marked weight loss in all liquids. The
use of distilled water proved to be an essential screening
test for the solubility of sealers. Nevertheless, some sea-
lers, especially Ketac Endo and Aptal-Harz, were signi¢-
cantly more soluble in acidic saliva than in water. Thus,
the method proposed by the ISO should be supplemented
by the use of acidic test media if a more valid assessment
is to be achieved. As all sealers showed a consistent
continuous increase in solubility over the 28-days
ß 2003 Blackwell Publishing Ltd

immersion time, the period of the speci¢cation test,24 h,
is not su¤cient.
References
Allan NA,Walton RE, Scha¡er M (2001) Setting times for endo-
dontic sealers under clinical usage and in vitro conditions.
Journal of Endodontics 27, 421^3.
Caicedo R, von Fraunhofer JA (1988) The properties of endodon-
tic sealer cements. Journal of Endodontics 14, 527^34.
Causton BE (1981) The physico-mechanical consequences of
exposing glass ionomer cements to water during setting. Bio-
materials 2, 112^5.
Crisp S, Lewis BG,Wilson AD (1980) Characterization of glass-
ionomercements. Part 6. A studyof erosionand water absorp-
tion in both neutral and acidic media. Journal of Dentistry 8,
68^74.
Fukazawa M, Matsuya S,Yamane M (1987) Mechanism for ero-
sion of glass-ionomer cements in an acidic bu¡er solution.
Journal of Dental Research 66, 1770^4.
GeurtsenW, Leyhausen G (1997) Biological aspects of root canal
¢lling materials ^ histocompatibility, cytotoxicity, and muta-
genicity. Clinical Oral Investigations 1, 5^11.
Grossman LI (1978) Solubility of root canal cements. Journal of
Dental Research 57, 927.
Grossman LI (1982) Endodontic Practice,10th edn. Philadelphia:
Lea & Febiger. p. 297.
Higginbotham TL (1967) A comparative study of the physical
properties of ¢ve commonly used root canal sealers. Oral Sur-
gery 24, 89^101.
International Organization for Standardization (2001)
International Standard ISO 6876: 2001: dental root canal
sealing materials. Genf: International Organization for
Standardization.
ß 2003 Blackwell Publishing Ltd
View publication stats
Scha«fer & Zandbiglari Solubility of root-canal sealers
Kaplan AE, Goldberg F, Artaza LP, De Silvio A, Macchi RL (1997)
Disintegration of endodontic cements in water. Journal of
Endodontics 23, 439^41.
Kazemi RB, Safavi KE, SpÔngberg LSW (1993) Dimensional
changes of endodontic sealers. Oral Surgery 76,766^71.
McComb D, Smith DC (1976) Comparison of physical properties
of polycarboxylate-based and conventional root canal sea-
lers. Journal of Endodontics 2, 228^35.
Nguyen TN (1994) Obturation of the root canal system. In:
Cohen S, Burns RC, eds. Pathways of the Pulp,6th edn. St.Louis:
Mosby, pp. 219^71.
Ono K, Matsumoto K (1998) Physical properties of CH61, a newly
developed root canal sealer. Journal of Endodontics 24,
244^7.
Òrstavik D (1983) Weight loss of endodontic sealers, cements and
pastes in water. Scandinavian Journal of Dental Research 91,
316^9.
Òrstavik D, Nordahl I,Tibbals JE (2001) Dimensional change fol-
lowing setting of root canal sealer materials. Dental Materials
17, 512^9.
Scha«fer E (2000) Root ¢lling materials. Deutsche Zahna«rztliche
Zeitschrift 55, 15^25.
Tagger M,Tagger E, K¢r A (1988) Release of calcium and hydro-
xyl ions from set endodontic sealers containing calcium
hydroxide. Journal of Endodontics 14, 588^91.
Tronstad L, Barnett F, Flax M (1988) Solubility and biocompat-
ibility of calcium hydroxide-containing root canal sealers.
Endodontics and Dental Traumatology 4, 152^9.
Wilson AD (1976) Speci¢cation test for the solubility and disin-
tegration of dental cements: a critical evaluation of its mean-
ing. Journal of Dental Research 55,721^9.
Wrbas KT, Kielbassa AM, Hellwig E (1998) Hydration and dehy-
dration behaviour of di¡erent root canal sealers. Deutsche
Zahna«rztliche Zeitschrift 53, 146^51.
International Endodontic Journal, 36, 660^669, 2003 669