Basic ResearchTechnology
Tricalcium Silicate Cements with Resins
and Alternative Radiopacifiers
Josette Camilleri, BChD, MPhil, PhD, FADM, FIMMM
Abstract
Objective: The objectives of this study were the inves-
tigation of the setting mechanisms and characterization
of radiopacified tricalcium silicatebased materials
mixed with different liquid vehicles. Methods: Trical-
cium silicate cement replaced with 20% of either zirco-
nium oxide or barium zirconate radiopacifier was
investigated. The cements were mixed with water, an
epoxy resin, or a light-cured Bis-GMAbased resin.
The setting mechanism and characterization of set ma-
terials after immersion in Hanks balanced salt solution
(HBSS) for 28 days were investigated by scanning elec-
tron microscopy of polished specimens and x-ray diffrac-
tion analysis. The bioactivity and surface microstructure
of cements immersed in HBSS or water were also as-
sessed by similar techniques together with leaching in
solution investigated by inductively coupled plasma
emission spectroscopy. Results: The formation of cal-
cium hydroxide as a by-product of cement reaction
was affected by the type of radiopacifier and also by
the resin vehicle used. Barium zirconate enhanced the
formation of calcium hydroxide as indicated by both
scanning electron microscopy and x-ray diffraction anal-
ysis. The use of resins as vehicles reduced the formation
of calcium hydroxide, with the Bis-GMAbased resin be-
ing mostly affected. Calcium hydroxide was deposited
on the material surface regardless of the type of vehicle
used. Formation of beta calcium phosphate was
observed on materials containing barium zirconate ra-
diopacifier immersed in HBSS. Inductively coupled
plasma emission spectroscopy analysis showed high
levels of calcium leached from materials by using water
and light-curable resin as mixing vehicles. Barium was
leached in solution, with the highest amount from the
water-based mixtures. Zirconium leaching was negli-
gible in materials containing zirconium oxide as radiopa-
cifier, but leaching of zirconium was measurable in
materials by using barium zirconate with tricalcium sili-
cate. Conclusions: The resin type and composition of
the radiopacifier affect the calcium releasing ability
and bioactivity of tricalcium silicate cements. Barium
was leached in solution with barium zirconate radiopa-
From the Department of Restorative Dentistry, Faculty of Dental Surgery, University of Malta, Malta.
Address requests for reprints to Prof Josette Camilleri, Department of Restorative Dentistry, Faculty of Dental Surgery, University of Malta, Medical School, Mater Dei
Hospital, Msida MSD 2090, Malta. E-mail address: josette.camilleri@um.edu.mt
0099-2399/$ - see front matter
Copyright 2014 American Association of Endodontists.
http://dx.doi.org/10.1016/j.joen.2014.08.016
JOE Volume -, Number -, - 2014
cified variants. Light-cured Bis-GMAbased resins did not exhibit cement hydration;
however, they encouraged leaching of calcium ions in solution and promoted surface
deposition of calcium phosphate. (J Endod 2014;-:16)
Key Words
Epoxy resin, hydration, light cure resin, radiopacifier, tricalcium silicate
T ricalcium silicate cements have been reported as suitable for use as root-end filling
and repair materials, for pulp capping, and more recently as sealer cements. The
bioactivity is an important parameter for repair materials (1, 2) and sealer cements
used in gutta-percha obturations (3, 4), whereas the ability to elicit dentin bridge
formation (5, 6) is mandatory for pulp-capping materials. Light-curable tricalcium sil-
icatebased materials are indicated for use as liner under composite restorations aim-
ing to achieve a bond between the layers of materials, thus reducing microleakage. The
classic mineral trioxide aggregate (MTA) mixed with water creates a problem when
layering with composite because calcium silicatebased materials have been shown
to be adversely affected by acid etching, which is a necessary step in composite place-
ment. Acid etching affected the compressive strength and surface microhardness of Pro-
Root MTA (7). This indicates that it may be better to postpone restorative procedures
for at least 96 hours after mixing MTA (7). Biodentine exhibited microleakage and sur-
face erosion when etched with 37% phosphoric acid used under composite resin res-
torations (8). Postponement of acid etching will not reduce the acid susceptibility.
Etching of materials based on tricalcium silicate should be avoided.
The use of a resin vehicle with tricalcium silicate cement may prospectively
improve the material properties. The main light-curing dental resin systems are
Bis-GMA and a biocompatible resin (9, 10), 2-hydroxyethyl methacrylate (HEMA),
tetraethylene glycol dimethacrylate (TEGDMA), camphorquinone, and ethyl-4-
(dimethylamino)benzoate with and without polyacrylic co-maleic acid (11, 12), Bis-
GMA, TEGDMA (13) and Bis-GMA, pyromellitic acid diethylmethacrylate, and HEMA
(14). A light-curable tricalcium silicatebased material would make an ideal pulp-
capping material because it will allow command cure, and also improved bonding of
overlying resin composites can be anticipated. The light-curing systems proposed so
far have exhibited alkaline pH, calcium ion release, formation of apatite (11, 13),
and functional groups able to chelate calcium ions (11). Furthermore, therapeutic re-
mineralization of dentin was observed (12, 14, 15). Experimental light-cured MTA
formed mineralized tissue close to the materials in alveolar tissue of rats (10). It pre-
sented a moderate chronic inflammatory response at 30 days that decreased at 60 days
but was more intense than with Angelus MTA and without dystrophic calcifications.
Light-cured MTA was similar to MTA at 60 days, but it did not stimulate mineralization
(9). Hydration did not occur by the resin-modified MTA. Reaction rims around the
cement particles were absent, and the formation and leaching of calcium hydroxide
were shown to be negligible (13).
Tricalcium Silicate Cements with Resins, Alternative Radiopacifiers 1
Basic ResearchTechnology
Addition of epoxy resins to MTA increases the material flow and
improves handling characteristics (4). A range of sealers to be used
with gutta-percha for root canal obturations similarly to AH Plus have
thus been developed. One formulation marketed by Angelus (Londrina,
Brazil) as MTA Fillapex is composed of MTA, methyl salicylate, butylene
glycol colophony, and other additives. Other experimental resin systems
based on epoxy resin have also been reported in use with MTA as a
sealer cement (16).
Tricalcium silicatebased materials include radiopacifiers to be
detected radiographically. MTA has bismuth oxide, whereas alternative
radiopacifiers are in use by other systems. The main role of radiopacifer
is for enhancement of material detection on a radiograph. However,
there are few reports on the effect of radiopacifier on material proper-
ties and hydration. The aim of this research was to investigate the hydra-
tion reaction and characterize pure tricalcium silicate to which different
radiopapacifiers and liquid vehicles were added.
Materials and Methods
The materials used in this study included pure tricalcium silicate
cement (Mineral Research Processing, Meyzieu, France) with 20%
zirconium oxide (ZrO2; Sigma-Aldrich, Buchs, Germany); TCS-Zr and
tricalcium silicate cement with 20% barium zirconate (TCS-BaZr;
Mineral Research Processing) were both developed at the University
of Malta. The powders were mixed with different vehicles: (1) water
(water/powder ratio 0.35); (2) epoxy resin based on bisphenol A-(epi-
chlorhydrin), oxirane, and mono[(C12-14-alkyloxy)methyl] deriva-
tives (resin/powder ratio 0.35); and (3) Bis-GMA and TEGDMA
(resin/powder ratio 0.35).
The epoxy resin was based on bisphenol A-(epichlorhydrin),
oxirane, and mono[(C12-14-alkyloxy)methyl] derivatives resin and
hardener components were pre-mixed in 3:2 proportion by volume.
The epoxy resin was then added to the powder in a resin/powder ratio
of 0.35. The Bis-GMAbased resin was light-cured with an LED light-
curing unit for 20 seconds per 1-mm increment. After preparation
the materials were immersed in Hanks balanced salt solution
(HBSS) (H6648; Sigma-Aldrich, St Louis, MO) for 28 days at 37 C
unless otherwise indicated.
Characterization of Materials and Material Surfaces
The set materials were characterized by scanning electron micro-
scopy (SEM), energy-dispersive spectroscopy (EDS), and x-ray diffrac-
tion (XRD) analysis.
Microscopy and Elemental Analysis. Cylindrical specimens
10 mm in diameter and 2 mm in height were prepared and stored
in HBSS for 28 days. For microscopy and elemental analysis of pol-
ished specimens, the materials were vacuum desiccated and
embedded in resin (Epoxyfix; Struers GmbH, Ballerup, Denmark)
and were then ground by using progressively finer diamond disks
and pastes by using an automatic polishing machine (Tegramin 20;
Struers GmbH). The polished specimens were attached to aluminum
stubs, carbon coated, and viewed under the SEM (Zeiss MERLIN Field
Emission SEM; Carl Zeiss NTS GmbH, Oberkochen, Germany). Scan-
ning electron micrographs of the different material microstructural
components at different magnifications in back-scatter electron
mode were captured, and EDS was carried out. Calcium-to-silicon
ratio plots of different zones were drawn from the back-scattered
electron images of the polished specimens. Area 1 indicated the cal-
cium/silicon ratio in cement particle center, Area 2 in the reaction
rim, and Area 3 in the cement matrix.
Another 2 sets of specimens were prepared for surface character-
ization. One set was placed in water and another set in HBSS at 37 C for
2 Camilleri
28 days. For surface characterization, the cement disks were dried in
vacuum desiccator and were then mounted on aluminum stubs, carbon
coated, and viewed under SEM in secondary electron mode for surface
characterization.
X-ray Diffraction Analysis. Specimens measuring 15 mm in
diameter and 2 mm high of each material type were prepared and
immersed in HBSS at 37 C for 28 days. At the end of the curing
period the specimens were dried in vacuum desiccator and
powdered. Powder diffractometry of the specimens was performed
by using a Rigaku Ultima IV (Rigaku, Tokyo, Japan) with a CuKa
source set at 40 mA and 45 kV, and the detector was set to rotate
between 15 and 45 , with a sampling width of 0.05 and scan
speed of 1 /min at 15 revs/min.
Another 2 sets of samples of similar dimensions were prepared.
Half were immersed in water and the other half in HBSS at 37 C for
28 days. The surface analysis was performed by using the same
diffractometer in grazing incidence asymmetric Bragg mode with
an incidence angle of 3 . The diffractometer was operated at 40
mA and 45 kV from 15 to 45 2q range, with a sampling width
of 0.05 and a scan speed of 1 /min. The diffractometer slit system
has divergent slits at 1 mm, divergent height slits of 10 mm, a scin-
tillator slit of 8 mm, and a receiver slit of 13 mm. Phase identifica-
tion of the powder diffractograms and glancing angle XRDs was
accomplished by using a search-match software indexing the peaks
against Power Diffraction Files data provided by International Centre
for Diffraction Data (ICDD; Newtown Square, PA).
Assessment of Leaching
Cylindrical specimens 10 mm in diameter and 2 mm in height were
prepared, weighed, and stored in 5 mL water or HBSS at 37 C for 28
days. The storage solution was tested for calcium, silicon, zirconium,
and barium by using inductively coupled plasma-emission spectroscopy
(ICP-ES). Ion release was calculated, taking into consideration the
sample size and volume of solution used. A blank water and HBSS
solution served as controls. The values for the elements present in
the soaking liquids were reduced from the analyses.
Results
Characterization of Materials and Material Surfaces
The back-scattered scanning electron micrographs of polished
material surfaces are shown in Figure 1. The prototype cements were
composed of cement particles around which was interspersed the
radiopacifier, which appeared whiter on the micrograph. The cements
mixed with water and epoxy resin exhibited a darker reaction rim
(labeled on micrographs) around the cement particle, indicating
cement hydration. The cements that were mixed with Bis-GMA and
TEGDMA did not have any reaction rims around the cement particle
and no hydration product in the cement matrix.
The calcium/silicon ratio plots for the 6 experimental materials
are shown in Supplemental Figure S1 (available online at www.
jendodon.com). The materials mixed with water or epoxy resin showed
lower calcium-to-silicon ratios moving from the center of the cement
particle toward the reaction rim and material matrix. Thus, calcium
ions were released into the matrix as calcium hydroxide, a well-
known mechanism of tricalcium silicate cement setting. The cements
mixed with the light-curable Bis-GMA/TEGDMA resin did not have a
calcium-to-silicon gradient, indicating the lack of formation of calcium
hydroxide.
The secondary electron micrographs of the materials immersed
in water and HBSS for 28 days are shown in Supplemental Figures S2
and S3 (available online at www.jendodon.com). The surface of the
JOE Volume -, Number -, - 2014

Figure 1. Back-scatter scanning electron micrographs of set materials stored in HBSS for 28 days at 37 C showing microstructural features.
materials immersed in water was characterized by the presence of
calcium silicate hydrate, which has a honeycomb appearance visible
in the cements mixed with water and epoxy resin. The calcium sili-
cate hydrate is a reaction by-product of cement hydration. The ma-
terials using Bis-GMA/TEGDMA resin as a vehicle contained calcium
silicate hydrate but to a lesser extent (Supplemental Fig. S2 is avail-
able online at www.jendodon.com). All the materials immersed in
HBSS exhibited the presence of globular deposits. The tricalcium sil-
icatebased materials mixed with water exhibited a very dense depo-
sit of hexagonal particles, which were rich in calcium and oxygen on
the material surface (Supplemental Fig. S4 is available online at www.
jendodon.com).
The XRD analysis of the set materials is shown in Figure 2A. All
the materials exhibited peaks for tricalcium silicate phase (ICDD: 04-
009-5560) present at 29.5 and a bifid peak at 32.1 and 32.4 and at
34.2 and 41.1 2q. Furthermore, a calcium hydroxide (Portlandite
ICDD: 01-075-9147) peak was also shown at 18.0 2q and at
34.1 2q. The radiopacifiers were visible at 28.1 and 31.4 2q for
the zirconium oxide phase (ICDD: 04-007-9268) and at 30.1 and
43.1 2q for the cements containing barium zirconate (ICDD: 04-
014-0273). The cements mixed with water exhibited the highest
calcium hydroxide peak present at 18.0 2q accompanied by trical-
cium silicate peaks of lower intensity at 32.1 and 32.5 2q than
JOE Volume -, Number -, - 2014
Basic ResearchTechnology
the cements mixed with resins. The calcium hydroxide peak at
34.1 2q was less evident because the calcium hydroxide peak is
superimposed with the tricalcium silicate peak at 34.2 2q. For the
cement mixed with Bis-GMA/TEGDMA, the tricalcium silicate peaks
at 32.1 and 32.5 2q were stronger than for the cements mixed
with epoxy resin and water. Furthermore, the hump-shaped baseline
in the diffractogram for the cement mixed with water indicates an
amorphous phase (calcium silicate hydrate). The cements with
barium zirconate radiopacifier exhibited a calcium hydroxide peak
of double the intensity compared with the cements mixed with zirco-
nium oxide radiopacifier.
Surface x-ray diffractometry (Fig. 2B) of tricalcium silicatebased
materials mixed with zirconium oxide radiopacifier exhibited peaks
characteristic of material phases that were mostly of low intensity except
for the Bis-GMA/TEGDMA resinbased material immersed in HBSS
where calcium hydroxide peaks were visible on the material surface.
The materials where barium zirconate was used as radiopacifier ex-
hibited calcium hydroxide peaks of high intensity on the material sur-
face, whereas the barium zirconatecontaining cements immersed in
HBSS showed the formation of both calcium hydroxide and calcium
phosphate on the material surface. The calcium hydroxide peaks
were of lower intensity than those present in the materials immersed
in water.
Tricalcium Silicate Cements with Resins, Alternative Radiopacifiers 3
Basic ResearchTechnology

Figure 2. (A) X-ray diffractograms of tricalcium silicatebased prototype materials mixed with different radiopacifiers and vehicles. (B) Surface x-ray diffracto-
grams of tricalcium silicatebased prototype materials mixed with different radiopacifiers and vehicles immersed in either water or HBSS.

Assessment of Leaching
The results for leaching in solution are shown in Tables 1 and 2 for
water and HBSS, respectively. Leaching of all elements was higher in
HBSS than in water. Calcium ion leaching was high when using water
and Bis GMA/TEGDMA resin as mixing vehicle. An epoxy resin base
did not allow the leaching of calcium ions in solution. High levels of
barium were leached from the samples composed of cement, barium
zirconate mixed with water, and stored in either water or HBSS. The
zirconium was not leached from the samples with zirconium oxide
but was present in the samples that contained barium zirconate and
stored in either water or HBSS.
Discussion
The cement hydration was assessed by evaluating the deposition of
hydration product around cement particles in polished sections viewed
under the scanning electron microscope. This technique has been used
to assess hydration kinetics of MTA (17) and tricalcium silicate cement
(18). This was coupled by powder diffraction and glancing angle XRD.

4 Camilleri JOE Volume -, Number -, - 2014


TABLE 1. Leaching of Calcium, Silicon, Barium, and Zirconium in Water after
28 Days
Elements leached (mg/g)
Material tested Ca Si Ba Zr
TCS-Zr water 13,426.8 159.6
TCS-Zr epoxy 2594.1 302.6
TCS-Zr Bis-GMA/TEGDMA 13,921.1 71.7
TCS BaZ water 12,729.7 10.2 2443.1 9.8
TCS BaZ epoxy 4092.5 213.5 143.2 0.4
TCS BaZ Bis-GMA/TEGDMA 26,924.0 13.5 744.4 2.6
Crystalline phases were detected on the powder diffractograms,
whereas surface layers could be assessed by using the glancing angle
XRD. The glancing angle XRD is useful to assess the crystalline deposits
over a material surface. The same technique has been used to assess
Theracal and Biodentine in a recent study (19).
Tricalcium silicate cement was chosen as the main cementitious
phase because the material is composed of 99.9% pure tricalcium sil-
icate (18), thus avoiding any side reactions occurring. In this way the
changes in the hydration pattern caused by changing the radiopacifier
and resin vehicle could be assessed. The first-generation materials that
are based on tricalcium silicate used Portland cement as the main con-
stituent material as in all brands of MTA and Theracal. The newer ma-
terials like Biodentine, Bioaggregate, and Endosequence BC sealer use
pure tricalcium silicate to avoid the aluminate phase and also any heavy
metal inclusions that are synonymous with the use of Portland cement.
The tricalcium silicate cement reacted with water, producing calcium
silicate hydrate and calcium hydroxide. This is in agreement with pre-
vious studies investigating the hydration reaction of tricalcium silicate by
using water as a vehicle (18). Using resin vehicles was observed to
reduce the cement hydration because no reaction rims were visible
around the cement particles and no calcium hydroxide was detected
by XRD analysis. Furthermore, the tricalcium silicate peaks were stable
and did not show any reduction in peak intensity. Reaction of tricalcium
silicate, which is crystalline, results in reduction in peak intensity
because less of the phase is present after reaction and the calcium sil-
icate hydrate formed is amorphous and thus cannot be seen on the x-ray
diffractogram. The calcium/silicon ratio plots did not show a reduction
of calcium-to-silicon ratio around the reaction rim and in the material
matrix for the light-curable resin. These results are in accordance with
previous reports (13). Although there was no evidence of hydration in
the light-curable resins, calcium hydroxide was leached in solution as
demonstrated by ICP analysis. This is in agreement with literature that
used resin where calcium ion leaching and dentin remineralization
were reported (11, 12, 14, 15). Thus although the light-curable ce-
ments did not exhibit evidence of reaction, calcium hydroxide that re-
acted with simulated tissue fluid to produce a calcium phosphate phase
was released on the material surface and in solution.
TABLE 2. Leaching of Calcium, Silicon, Barium, and Zirconium in HBSS after
28 Days
Elements leached (mg/g)
Basic ResearchTechnology
The surface analysis of the materials exhibited reacting
cement particles with the formation of calcium silicate hydrate,
which has a honeycomb appearance. The reaction was more
obvious in the materials mixed with water or epoxy resin for either
radiopacifier. Immersion in the physiological solution formed acic-
ular deposits rich in phosphorus. The surface of the materials
mixed with water contained a phosphate-rich phase and hexagonal
crystals composed of calcium and oxygen attributed to calcium hy-
droxide.
The formation of hydroxyapatite when light-curable resin modified
tricalcium silicatebased materials are in contact with physiological so-
lution has already been reported (11, 12). The resin vehicle used was
HEMA-TEGDMA, and calcium ion leaching was measured together with
the identification of hydroxyapatite by using micro-Raman (11). Dentin
remineralization has been demonstrated with other light-curable resins
by using tricalcium silicate as filler (15). A Portland cementbased sys-
tem containing Bis-GMA, pyromellitic acid diethylmethacrylate, and
HEMA also promoted dentin remineralization (14). However, the
cement hydration was not assessed in any of these studies. The lack
of cement hydration with Bis-GMA/TEGDMA systems has already been
reported (13).
The use of barium zirconate as radiopacifier further intensified
the release of calcium hydroxide because a stronger peak was visible
at 18 2q with these mixtures compared with those using zirconium
oxide. Calcium phosphate was also deposited on the material surface
in the light-curable resin modified materials when barium zirconate
was used as radiopacifier. ICP analysis also showed a higher calcium
ion release when using barium zirconate as radiopacifier in the light-
curable material. This was not evident with the use of zirconium
oxide. The high calcium ion release is beneficial for pulp-capping
materials. The radiopacifer also modified the calcium ion release
as shown in an earlier study where the addition of bismuth oxide
to Portland cement increased the leaching of calcium hydroxide in
solution (20). The materials that used barium zirconate as radiopa-
cifier exhibited leaching of barium in solution, particularly the water-
based materials. The leaching of barium has been reported with
barium containing fillers in resin-based composites (21, 22). The
leaching was lower in artificial saliva than in distilled water,
indicating that the storage medium is an important parameter and
affects the results (21). This was also verified in the current study
where the leaching in HBSS was different than in water. Ingestion
of high levels of barium has been reported to cause cardiac arrhyth-
mias. This has also been reported when using barium for enemas
(23). The clinical implications of barium leaching from dental mate-
rials need to be investigated further.
Conclusions
The resin type and composition of the radiopacifier affect the
calcium-releasing ability and bioactivity of tricalcium silicate cements.
Barium was leached in solution with barium zirconate radiopacified
variants. Light-cured Bis-GMAbased resins did not exhibit cement hy-
dration; however, they encouraged leaching of calcium ions in solution
and promoted surface deposition of calcium phosphate.

Material tested Ca Si Ba Zr Acknowledgments

TCS-Zr water 16,877.9 103.3
TCS-Zr epoxy 5481.6 571.7 0.6
The author acknowledges Dr Francois Sorrentino of Mineral
TCS-Zr Bis-GMA/TEGDMA 15,141.7 121.0 Research Processing for the materials; The University of Malta
TCS BaZ water 18,748.1 66.5 2641.1 4.5 Research Grant committee for funding; Ing. James Camilleri of
TCS BaZ epoxy 5807.4 469.4 321.3 125.5 the Department of Metallurgy and Materials Engineering, Faculty
TCS BaZ Bis-GMA/ 20,231.7 71.4 496.8 15.6 of Engineering, University of Malta for his technical expertise;
TEGDMA
and ERDF (Malta) for the financing of the testing equipment

JOE Volume -, Number -, - 2014 Tricalcium Silicate Cements with Resins, Alternative Radiopacifiers 5
Basic ResearchTechnology
through the project Developing an Interdisciplinary Material
Testing and Rapid Prototyping R&D Facility (Ref. no. 012).
The author denies any conflicts of interest related to this study.
Supplementary Material
Supplementary material associated with this article can be
found in the online version at www.jendodon.com (http://dx.doi.
org/10.1016/j.joen.2014.08.016).
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