UNIVERSIDADE ESTADUAL PAULISTA
“JÚLIO DE MESQUITA FILHO”
Instituto de Ciência e Tecnologia
Campus de São José dos Campos
ORIGINAL ARTICLE DOI: https://doi.org/10.4322/bds.2025.e4277
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Braz Dent Sci 2025 Jan/Mar;28 (1): e4277
This is an Open Access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in
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Physicochemical properties analysis of experimental retrograde
filling materials
Análise das propriedades físico-químicas de cimentos retrobturadores experimentais
Pedro Cesar Gomes TITATO1 , Hebertt Gonzaga dos Santos CHAVES2 , Bruno Carvalho de VASCONCELOS3 ,
Murilo Priori ALCADE1 , Rodrigo Ricci VIVAN1 , Marco Antônio Hungaro DUARTE1
1 - Universade de São Paulo, Departamento de Dentística, Endodontia e Materiais Dentários. Bauru, SP, Brazil
2 - Universidade Federal de Minas Gerais, Faculdade de Odontologia, Departamento de Dentísitca Restauradora. Belo Horizonte, MG, Brazil
3 - Universidade Federal do Ceará, Departamento de Dentística. Fortaleza, CE, Brazil
How to cite: Titato PCG, Chaves HGS, Vasconcelos BC, Alcade MP, Vivan RR, Duarte MAH. Physicochemical properties analysis of
experimental retrograde lling materials. Braz Dent Sci. 2025;28(1):e4277. https://doi.org/10.4322/bds.2025.e4277
ABSTRACT
Objetive: To evaluate radiopacity, setting time, owability, pH, ions release and volumetric change of four
experimental endodontic repair cements, MTA white and MTA Repair HP Angelus. The experimental tricalcium
cement groups were composed of zirconia oxide or calcium tungstate as a radiopacier associated to calcium
phosphate, the vehicle tested composed by 80% distilled water and 20% arnica extract. Also, the other two
experimental consisted of an association of polydimethylsiloxane to tricalcium silicate and same radiopaciers.
Material and Methods: Radiopacity, ow, and setting time tests were done according to ISO 6876 and ASTM
C266/2008 specications. pH was determined with a calibrated pH meter. The ions calcium release was carried
out by an atomic absorption spectrophotometer. Volumetric change was assessed by micro-computed tomographic
imaging before and after 28 days of immersion in ultrapure water. One-way ANOVA followed by Tukey’s test
(α=0.05) was performed for pH, setting time and ow rate. Kruskal-Wallis test, followed by Dunn’s test (α=0.05),
were performed for radiopacity, ions release and volumetric change. Results: All experimental cements presented
radiopacity above 3 mm/Al (p < 0.05). Polydimethylsiloxane experimentals showed a higher ow rate (p < 0.05)
and better dimensional stability (p < 0.05). Calcium silicate cements resulted in more favorable properties such
as alkalinization, longer working time and higher ions release (p < 0.05), though more signicant volumetric
loss. Conclusion: polydimethylsiloxane experimental cements presented greater ow and dimensional stability,
the addition of tricalcium silicate was not able to enhance calcium release nor perform a favorable pH.
KEYWORDS
Dental cements; Endodontics; Root repair; Tricalcium silicate; X-ray microtomography.
RESUMO
Objetivo: Avaliar características de quatro cimentos retrobturadores experimentais, MTA branco e MTA
Repair HP Angelus, incluindo radiopacidade, tempo de presa, escoamento, pH, liberação de íons e alteração
volumétrica. Os cimentos tricálcio experimentais foram compostos por óxido de zircônia ou tungstato de cálcio
como radiopacicador, associados a fosfato de cálcio, com veículo contendo 80% de água destilada e 20% de
extrato de arnica. Os outros experimentais envolveram polidimetilsiloxano com silicato tricálcio e os mesmos
radiopacicadores. Material e Métodos: Os testes de radiopacidade, escoamento e tempo de presa seguiram
especicações ISO 6876 e ASTM C266/2008. O pH foi medido com pHmetro. Liberação de íons cálcio foi
analisada com espectrofotômetro de absorção atômica. Alteração volumétrica foi avaliada por microtomograa
computadorizada antes e após 28 dias de imersão em água ultrapura. ANOVA e teste de Tukey (α=0,05) foram
usados para pH, tempo de presa e escoamento. O teste de Kruskal-Wallis e teste de Dunn (α=0,05) foram aplicados
para radiopacidade, liberação de íons e alteração volumétrica. Resultados: Todos os cimentos experimentais
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Titato PCG et al.
Physicochemical properties analysis of experimental retrograde filling materials
Titato PCG et al. Physicochemical properties analysis of experimental
retrograde filling materials
INTRODUCTION
Clinicians in the field of endodontics
require reliable retrograde filling materials
that ensure proper handling, exhibit stable
dimensional properties, are biocompatible, and
possess adequate radiopacity to enable effective
treatment. These materials are frequently
employed to address procedural complications,
such as perforations during pulp chamber access,
and as lling material for the root-end cavities,
with their physicochemical and biological
properties playing a crucial role in the healing
of periapical tissues [1].
A wide range of materials has been
developed for root apex sealing [2], including
mineral trioxide aggregate (MTA), intermediate
restorative material (IRM), super ethoxy benzoic
acid (Super-EBA), glass ionomer cement,
amalgam, resin, calcium hydroxide, calcium
silicate, and silicone-based materials. However,
no single root-end lling material encompasses
all desirable attributes. Consequently, the search
for the ideal root-end lling material remains
ongoing [3].
Mineral trioxide aggregate (MTA) and
Portland cement share similar compositions,
including tricalcium silicate, dicalcium silicate,
tricalcium aluminate, tretacalcium aluminoferrite,
and dihydrated calcium sulfate [4]. The low
radiopacity of Portland cement can be addressed
by incorporating alternative radiopacifying
agents, such as zirconium oxide (ZrO2) and
calcium tungstate (CaWO4) [5].
These alternative radiopaciers have been
investigated as substitutes for bismuth oxide
(Bi2O3). Although less radiopaque than Bi2O3,
they are less likely to stain tooth structure and do
not interfere with MTA hydration [6]. Notably,
the inclusion of ZrO2 and CaWO4 into Portland
cement yields materials with radiopacity levels
exceeding those recommended by ANSI/ADA
Specication 57 [5,7].
MTA has emerged as a dynamic root repair
material. This cement interacts with dentin,
providing superior sealing, bioactivity and
setting capabilities even in the presence of blood.
Its chemical bond to dentin and regenerative
potential occurs through a hydration reaction
that forms calcium hydroxide [3]. However, its
handling limitations, extended setting time, and
susceptibility to washout can impact its clinical
use [8]. Furthermore, bismuth oxide (Bi2O3),
the radiopacier in its composition, can cause
discoloration of dental structures [9].
MTA Repair HP (Angelus; Londrina, PR,
Brazil) is a derivative of the traditional MTA
composition, incorporating calcium tungstate
for radiopacity and a mixing liquid containing
a plasticizing agent. Its intended applications
include root-end lling, pulp capping, pulpotomy,
apexogenesis, apexication, and repairing root
canal perforations. According to the manufacturer
guidelines, this novel formulation retains the
chemical characteristics of the traditional MTA
while enhancing its handling and manipulation
properties [10].
The incorporation of propylene glycol to
improve ow characteristics has been proposed
as a means of enhancing the overall properties of
MTA. Furthermore, enhancing the antimicrobial
properties of MTA is particularly advantageous
in the critical apical regions. Plant extracts
with inherent antimicrobial properties, when
combined with MTA, offer potential alternatives.
The augmentation or reinforcement of MTA’s
antibacterial efcacy through the substitution of
distilled water or its combination with antiseptic
solutions is already demonstrated [11].
Previous research has shown that the
ethanolic extract of
Lychnophora trichocarpha
mostraram radiopacidade acima de 3 mm/Al (p < 0,05). Experimentais de polidimetilsiloxano exibiram maior
escoamento (p < 0,05) e estabilidade dimensional (p < 0,05). Cimentos de silicato de tricálcio demonstraram
propriedades vantajosas como alcalinização, tempo de trabalho prolongado e maior liberação de íons (p < 0,05),
apesar da perda volumétrica. Conclusão: Cimentos de polidimetilsiloxano apresentaram melhor escoamento
e estabilidade dimensional, no entanto, a adição de silicato tricálcio não melhorou a liberação de cálcio nem
favoreceu o pH.
PALAVRAS-CHAVE
Cimentos dentários; Endodontia; Materiais de reparo; Silicato tricálcico; Microtomograa de raios X.
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Titato PCG et al.
Physicochemical properties analysis of experimental retrograde filling materials
Titato PCG et al. Physicochemical properties analysis of experimental
retrograde filling materials
possesses anti-inammatory, antinociceptive, and
xanthine oxidase inhibitory properties. Regarding
the control of cellular response and the creation
of inflammatory mediators, the mechanism
underlying the anti-inflammatory effect of
the ethanol extract and its active components
has not yet been established [12, 13]. These
properties justify the incorporation of this extract
into experimental cements intended for direct
application to areas of critical inammation.
Silicon-based cements, such as Roeko
Seal (Roeko, Langenau, Germany) have
demonstrated great dimensional stability and seal
capabilities, in addition to low cytotoxicity [14].
Polydimethylsiloxane, a biocompatible material,
has shown promising results in previous studies
involving silicon-based cements. However,
while these materials are suitable for clinical
applications, they lack components that actively
stimulate tissue repair [15].
Based on the foregoing, the objective of
this study was to evaluate the physic chemical
properties of experimental sealers containing
varying proportions of calcium silicate, arnica
glycolic extract and alternative radiopaciers; as
well as experimental sealers containing silicone,
calcium silicate and alternative radiopaciers
agents. The goal for calcium silicate-based
cements was to enhance their properties, such
as owability and handling, by adding arnica
glycolic extract and evaluating its interaction with
zirconium oxide and calcium tungstate in terms
of radiopacity. For the silicone-based cements, it
was hypothesized that the addition of tricalcium
silicate would promote alkalinization and calcium
ions release, and improved dimensional stability.
MATERIALS AND METHODS
Sample preparation
The cements evaluated are shown in Table I.
Two commercially available MTA based
cements MTA white (G1) and MTA HP (G2)
(Angelus; Londrina, PR, Brazil) were handled
as suggested by manufacturers. An electronic
analytical balance (Gehaka AND-GR-202, Tokyo,
Japan) was employed to prepare the experimental
cements, following the 1 gram of powder ratio
to 0.3 mL of liquid for the experimental cements
G3 (CSZO) and G4 (CSCT). For experimental
G5 (CSSilZO) and G6 (CSSilCT), powder portions
were placed in the base paste, the exact length
of base and catalyst paste were employed in the
handling.
Radiopacity
Metallic rings with an internal diameter
of 10 mm and a thickness of 1 mm were used
according to ISO 6876 [16], with three cement-
filled specimens per group. Freshly mixed
cements were inserted into the rings, supported
by a glass plate, and kept in an oven at 37 °C
until fully setting. The thickness of the samples
was measured using a digital caliper (Mitutoyo
Corp, Tokyo, Japan).
Cement specimens and an aluminum step
wedge (graduated from 2 to 16 mm of Al) were
placed on occlusal lm (Kodak Comp, Rochester,
New York, USA). Radiographs were taken using
a radiographic unit (Gnatus XR 6010; Gnatus,
Ribeirão Preto, SP, Brazil) set at 60 kV and 10 mA,
with an exposure time of 0.3 seconds. The focus-
Table I - Composition of each cement used in the study
Cements Composition
G1 – MTA White (MTAW) (Angelus)
Powder: silicon dioxide, potassium oxide, aluminium oxide, sodium oxide, ferric oxide, sulfur
trioxide, calcium oxide, calcium tungstate, magnesium oxide. (Batch number: 42605)
Liquid: distilled water;
G2 - MTA HP (MTAHP) (Angelus)
Powder: tricalcium silicate, calcium silicate, tricalcium aluminate, calcium oxide, calcium
tungstate. (Batch number: 41296)
Liquid: water and plasticizer;
G3 - Experimental 1 (CSZO) Powder: 60% calcium silicate, 10% calcium phosphate, 30% zirconium oxide. Liquid: 80% water
and 20% arnica glycolic extract;
G4 - Experimental 2 (CSCT) Powder: 60% calcium silicate, 10% calcium phosphate, 30% calcium tungstate
Liquid: 80% water and 20% arnica glycolic extract;
G5 - Experimental 3 (CSSilZO) 50% polydimethylsiloxane + silicone oil + paraffin + 20% (by weight) tricalcium silicate + 30% (by
weight) zirconium oxide;
G6 - Experimental 4 (CSSilCT) 50% polydimethylsiloxane + silicone oil + paraffin + 20% (by weight) tricalcium silicate + 30% (by
weight) calcium tungstate.
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Physicochemical properties analysis of experimental retrograde filling materials
Titato PCG et al. Physicochemical properties analysis of experimental
retrograde filling materials
film distance was 30 cm. After processing,
the radiographs were digitized using a digital
scanner and imported into the Adobe Photoshop
CS6 13.0.
The area corresponding to each specimen was
selected in the radiographic image to determine
the thickness of the aluminum step wedge
that corresponded to the radiographic density
of the specimen. This assessment quantified
the radiopacity of the specimen in millimeters
of aluminum using a conversion equation, as
proposed in previous studies [5].
Setting time
ISO 6876 [16] normative was also followed to
obtain the samples, and the ASTM C266/08 [17]
to determine the setting time of the cements.
Freshly mixed cements were immediately poured
into metal rings with internal diameter of 10 mm
and a thickness if 2 mm. Three specimens per
cement group were prepared and stored in an
oven at 37 °C with 95% throughout the test.
After 180 seconds from the start of the
spatulation, the specimens were subjected
to vertical pressure using Gilmore needles
(113.4 g and 453.6 g). The setting time, measured
in minutes, was recorded as the time elapsed from
the beginning of the spatulation until no visible
indentation was observed on the surface of the
samples, representing the initial and nal setting
time of the cements.
Flow rate
A total volume of 0.5 ± 0.05 mL of cement
was mixed and placed at the center of a 40 mm
x 40 mm glass plate with a thickness of 5 mm
using a graduated disposable 1 mL syringe. After
3 minutes from the start of mixing, a second glass
plate weighing 20 ± 2 g was carefully positioned
centrally on top of the cement, followed by
an additional weight of approximately 100 g,
resulting in a total applied load of 120 g.
Ten minutes after mixing, the weight was
removed. The values of maximum and minimum
diameters of the compressed discs cements were
measured using a digital caliper (Mitutoyo MTI
Corporation, Tokyo, Japan). The mean of the
two diameters was recorded as the cement ow.
Three measurements were taken for each cement
group (n = 3), and the results were expressed
in millimeters. This test also was conducted
following ISO 6876 [16].
Volumetric change
Volumetric change was assessed using
computerized microtomography (micro-CT),
based on a previous study [18,19]. Sixty acrylic
teeth (n = 10) with standardized root-end
cavities created using a #1012 diamond burr (KG
Sorensen, São Paulo, SP, Brazil) were lled with
the tested cements using an MTA carried device.
The specimens were then individually scanned
using a micro-CT (SkyScan 1174v2; SkyScan,
Kontich, Belgium) at 50 kV and 800 μA.
The images were captured with a voxel size
of 14.1 μm, using 360º rotation scan. Each scan
produced images with a resolution of 1024 x
1304 pixels. For volumetric analysis, the data
were reconstructed using NReconv software
(version 1.6.4.8, SkyScan) and CTan software
(version 1.11.10.0, SkyScan). In CTan software,
each sample was analyzed individually, and
the region of interest (ROI) was delineated for
subsequent scans.
A quantitative analysis of the material
volume was performed using three-dimensional
reconstruction, and the total volume (mm3) was
automatically calculated. After the initial scan,
the samples were immersed in individual asks
containing 15 mL of deionized water and stored
in an oven at 37ºC for 28 days. At the end of this
period, the samples were removed, dried on lter
paper, and re-scanned using the same parameters
as the initial scan. The solubility of the cements
was determined by calculating the volume lost
during immersion, and the results were expressed
as percentages [18,19].
pH and calcium release
Sixty acrylic teeth (n = 10) with standardized
root-end cavities created using a #1012 diamond
burr (KG Sorensen) were filled with the
tested cements using an MTA carried device.
The specimens were then individually immersed
in asks containing 10 mL of ultrapure water
(Purelab Option Q, Elga, Brazil) with an initial
pH of 6.61.
The asks were sealed and placed in an oven
at 37 °C for the duration of the experimental
period. Evaluations were conducted after 3, 7, and
15 days of immersion, as described in previous
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retrograde filling materials
studies [18,20]. At each time point, the specimens
were transferred to new asks containing 10 mL
of ultrapure water. pH measurements were
performed using a calibrated pH meter (Orion
Star Plus pH meter; Thermo Scientic Electron
Corporation, San Jose, CA) with control solutions
at known pH values of 4, 7, and 14.
After specimen removal, the liquid in each
container was agitated in a shaker (Farmen, São
Paulo, SP, Brazil) for 5 seconds, poured into
a Becker, and measured using the pH meter
electrode. The calibration was conducted at a
controlled temperature of 25 °C.
Calcium ion release was assessed in the
same periods using an atomic absorption
spectrophotometer (Thermo Fisher, São Paulo,
SP, Brazil) equipped with a calcium-specific
hollow cathode lamp. To prevent possible alkali
metal interferences, a lanthanum solution was
used.
A standard calcium solution was prepared
at concentrations of 20 mg/L, 10 mg/L, 5 mg/L,
2.5 mg/L, and 1.25 mg/L. A blank sample was
prepared by mixing 6 mL of ultrapure water
with 2 mL of lanthanum chloride solution.
The standards, blank, and the samples solutions
were analyzed using an atomic absorption
spectrophotometer [18,20].
Statistical analysis
Data distribution was assessed using the
Kolmogorov-Smirnov normality test. After
normality evaluation, pH, setting time and ow
rate data followed a parametric distribution, while
radiopacity, ions release, and volumetric change
data followed a non-parametric distribution.
One-way ANOVA followed by Tukey’s test
was performed for pH, setting time and flow
rate. The Kruskal-Walli’s test, followed by Dunn’s
test, was used for radiopacity, ions release and
volumetric change. A signicance level of 5%
(α = 0.05) was adopted for all statistical tests.
RESULTS
Table II presents the data of radiopacity,
setting time, volumetric change and owability
of the cements tested.
All experimental cements exhibited
radiopacity values above 3 mm/Al, the minimum
recommended by ISO 6876. Statistically
significant differences were observed when
compared to MTA (2.12 mm/Al) (p < 0.05).
The highest radiopacity value was recorded
in Group 3 (6.14 mm/Al), which contained
zirconium oxide as a radiopacier.
Regarding the initial setting time, statistically
significant differences were found among all
groups (p < 0.05), except between MTA white and
Group 4 - Experimental cement 2 (CSCT), as well
as between the silicon-based experimental groups
(G5 and G6) (p > 0.05). MTA White exhibited
the longest nal setting time (129 minutes) while
the silicon-based experimental cements had the
shortest setting times (44 – 47 minutes), with
statistically significant differences among the
studied groups (p < 0.05).
Despite the addition of tricalcium silicate, the
silicone-based experimental groups demonstrated
similar ow rates (14.27 mm – 14.84 mm) and
significantly higher values (p < 0.05) when
compared to the other cements.
Volumetric change analysis showed that
G6 – Experimental cement 4 (CSSilCT) (Figure 1)
exhibited a statistically lower volumetric loss
rate compared to the other groups (p < 0.05),
except for CSSilZO (p > 0.05). Meanwhile, the
experimental groups CSZO (Figure 2) and CSCT
Table II - Mean (X) and standard deviation (SD) values of radiopacity, setting time, and flowability of both commercial MTA cements and
experimental cements. The median (med) and the range of minimum and maximum (min–max) values are provided for volumetric change after
28 days of immersion in ultrapure water.
Radiopacity
(mm Al) X
± SD
Setting Time (min) X ± SD Volumetric change
(%) Med (Min-Max)
Flow rate
(mm) X ± SD
Initial Final
G1 – MTA 2.39 ± 0.23 A,C 41.00 ± 5.5 A129.7 ± 4.5 A14.36 (7.6 – 17.62) A,C 7.39 ± 0.48 A
G2 – MTA HP 2.12 ± 0.44 A14.67 ± 2.5 B110.0 ± 8.0 B15.94 (7.99 – 21.84) A,C 7.92 ± 0.15 A
G3 –Experimental cement 1 (CSZO) 5.98 ± 0.41 B,C 59.33 ± 3.0 C99.33 ± 3.05 B15.44 (6.2 – 30.44) A,C 8.66 ± 0.33 A
G4 – Experimental cement 2 (CSCT) 5.81 ± 0.54 B,C 45.00 ± 2.0 D,A 84.33 ± 6.02 C16.59 (10.19 – 37.49) A8.51 ± 0.41 A
G5 –Experimental cement 3 (CSSilZO) 6.14 ± 2.12 B,C 25.00 ± 3.6 E44.33 ± 3.51 D9.62 (4.81 – 13.61) B,C 14.27 ± 1.52 B
G6 – Experimental cement 4 (CSSilCT) 5.33 ± 2.53 C29.00 ± 3.6 E47.67 ± 2.51 D5.49 (3.0 – 10.75) B14.84 ± 0.12 B
Different Capital letters represent statistically significant differences among groups (p<0.05).
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Titato PCG et al.
Physicochemical properties analysis of experimental retrograde filling materials
Titato PCG et al. Physicochemical properties analysis of experimental
retrograde filling materials
presented higher solubility (15.44% and 16.59%,
respectively), although these values were not
signicantly different from those of MTA white
and MTA HP (p > 0.05).
Table III presents the averages and standard
deviations of the pH and calcium release of the
analyzed materials in the analyzed periods.
After 3 days, the silicon-based experimental
groups showed a slight decrease in pH compared to
the initial value. On day 7, MTA white and MTA HP
differed statistically from all experimental groups,
with a slight increase in alkalinity. After 15 days,
only MTA HP remained statistically different from
all experimental groups, maintaining a stable pH
of 7.64. When analyzed within the same group,
MTA HP, G3 – Experimental 1 (CSZO) and
G6 – Experimental 4 (CSSilCT) showed stable
pH values (p > 0.05).
Regarding calcium ion release, after 3 days,
MTA White stood out with the highest release
values, with a statistically signicant difference
compared to the others (p < 0.05). Group
4 (CSSilCT) showed the lowest calcium ion
release and differed significantly from MTA
White and MTA HP at both the 3-day and
7-day time points (p < 0.05). After 15 days,
Figure 1 - Representative micro-computed tomography (micro-CT) 3D image showing the volumetric change of the silicon-based experimental
cement. The initial volume (gray) is superimposed with the final volume (red) after immersion in ultrapure water.
Figure 2 - Representative micro-computed tomography (micro-CT) 3D image showing the volumetric change of the silicate-based experimental
cement. The initial volume (gray) is superimposed with the final volume (red) after immersion in ultrapure water.
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Physicochemical properties analysis of experimental retrograde filling materials
Titato PCG et al. Physicochemical properties analysis of experimental
retrograde filling materials
MTA White continued to exhibit the highest
calcium release, while G5 –Experimental 3
(CSSilZO) and G6 – Experimental 4 (CSSilCT)
with the lowest values (p < 0.05). Within-group
comparisons revealed that only MTA White
and G5 –Experimental 3 (CSSilZO) exhibited a
slight decrease in calcium release over time, with
statistically signicant differences between the
3-day and 7-day periods (p < 0.05).
DISCUSSION
Radiopacity plays a crucial role in the
radiographic visualization of the materials
used for root-end llings or perforation repair.
This study reported that the MTA and MTA HP
presented radiopacity below the ISO standard,
suggesting that both material presents the
similar and same quantities radiopacifier
agent. The experimental cements demonstrated
higher radiopacity compared to the commercial
MTA cements tested, with values ranging
from 5.33 to 6.14 mm Al. These differences
may be attributed to the higher proportion
of radiopaciers in the experimental cements
(30% by weighted) compared to the commercial
materials, which contain approximately 15%.
Increased radiopacity facilitates the distinction
between dentin and adjacent anatomical
structures [5].
In cases of root resorptions, perforations,
apexication and retrograde llings, cements
with prolonged setting times may be more
susceptible to dissolution, potentially
compromising clinical success [10]. The silicon-
based experimental cements exhibited the
shortest setting times compared to the calcium
silicate-based group, which may be associated
with the hydration time [18] and the composition
of polydimethylsiloxane itself [21].
The initial setting time of MTA HP in
this study (14 minutes) was similar to the
manufacturer’s reported value of 15 minutes.
The nal setting time was 25 minutes, which
was longer than reported in previous study [22].
This difference may be related to variations in the
powder-to-liquid ratio during mixing. MTA White
demonstrated an initial setting time of 41 minutes
and a final setting time of 129 minutes, in
accordance with other study [23].
Concerning the experimental cements
containing calcium silicate and Arnica’s propylene
glycol, their initial setting times were longer
than those of MTA and MTA HP. This could be
attributed to the presence of 20% propylene
glycol extract, in agreement with previous
studies that incorporated pure propylene glycol
or other extracts [11]. A shorter setting time may
contribute to reduced material solubility, which
is benecial for clinical application.
Flowability is a critical property that
enables cements to fill retro-end cavities and
penetrate dentinal tubules, improving their
sealing capacity [8]. In this study, the silicone-
based experimental groups exhibited greater
owability, likely due to the intrinsic plasticity
of the material [21]. The experimental cements
containing propylene glycol extracts also
demonstrated higher ow rates than MTA and
MTA HP. This is attributed to propylene glycol’s
ability to improve material wettability, allowing
Table III - Mean (X) and standard deviation (SD) values for pH (A) and calcium ions release (B) of the cements in different studied periods.
3 days X ± SD 7 days X ± SD 15 days X ± SD
(A) pH of soaking
water
G1 – MTA 7.45 ± 0.93 A,a,b 8.11 ± 1.03 A,a 6.70 ± 0.22 A,b
G2 – MTA HP Angelus 7.73 ± 0.86 A,a 7.66 ± 0.84 A,a 7.64 ± 1.0 B.a
G3 – Experimental 1 (CSZO) 7.01 ± 0.70 A,C,a 6.53 ± 0.80 B,a 6.42 ± 0.48 A,a
G4 –Experimental 2 (CSCT) 7.03 ± 0.61 A,a 6.49 ± 1.20 B,a,b 5.93 ± 0.78 A,b
G5 –Experimental 3 (CSSilZO) 6.20 ± 0.36 B,C,a 5.47 ± 0.29 B,b 5.84 ± 0.68 A,a,b
G6 – Experimental 4 (CSSilCT) 6.20 ± 0.45 B,C,a 5.88 ± 0.61B, a 6.28 ± 0.69 A,a
(B) Calcium release
G1 – MTA 238.6 (215.8 – 270.6) A,a 213.8 (204.7 – 224.2) A,b 206.5 (199.1 – 215.4) A,b
G2 – MTA HP Angelus 5.4 (1.54 – 14.18) B,a 7.01 (3.16 – 14.7) A,B,a 6.82 (0.60 – 9.37) A,B,a
G3 – Experimental 1 (CSZO) 3.37 (0.28 – 37.82) B,a 1.43 (0.10 – 12.14) B,C,a 2.22 (0.67 – 30.2) B,a
G4 –Experimental 2 (CSCT) 2.9 (0.14 – 6.61) B,a 2.48 (1.49 – 6.4) B,C,a 4.28 (0.12 – 10.69) B,a
G5 –Experimental 3 (CSSilZO) 2.8 (2.13 – 4.76) B,a 1.97 (1.32 – 3.02) B,C,a,b 0.63 (0.06 – 5.24) B,b
G6 – Experimental 4 (CSSilCT) 0.35 (0.02 – 7.91) C,a 0.7 (0.22 – 5.71) C,a 0.7 (0.11 – 8.78) B,a
Different capital letters represent statistically significance differences (p < 0.05) in the same line, whilst different small letters represent
differences in the same colum
8
Braz Dent Sci 2025 Jan/Mar;28 (1): e4277
Titato PCG et al.
Physicochemical properties analysis of experimental retrograde filling materials
Titato PCG et al. Physicochemical properties analysis of experimental
retrograde filling materials
better adaptation to irregularities in the tooth
structure or cavity. Additionally, propylene
glycol lowers surface tension compared to water,
leading to smoother and more homogeneous
ow [10,11].
Volumetric change is another relevant
physical property considering that root repair
cements remain in direct contact with adjacent
tissues for extended periods [1]. Materials with
high solubility tend to create voids, compromising
the sealing ability and increasing the risk of
bacterial inltration, which can lead to treatment
failure [18]. Micro-CT analysis has been widely
used to assess volumetric loss in previous
studies [18,19]. In the present study, the lowest
solubility values were observed in the silicone-
based groups (9.62% and 5.49%). The calcium
silicate-based cements exhibited greater mass
loss (15.44%–16.59%), indicating that silicon
contributes to lower volumetric loss, even when
calcium silicate powder and radiopacifiers
are present. MTA White and MTA HP showed
no significant discrepancies, with volumetric
losses of 14.36% and 15.94%, respectively.
Lower solubility prevents the formation of voids
that may allow uid inltration and bacterial
colonization [18,22].
The pH of calcium silicate cements has been
widely investigated [18,21-23], as mineralized
tissue repair is thought to depend on alkalinity
and calcium ions release [24]. Previous studies
have reported pH values for MTA ranging
from 8 to 12 [23,25,26]. In the present study,
MTA White, MTA HP, and the calcium silicate-
based experimental cements exhibited slight
alkalinization in the initial period, whereas the
silicone-based cements maintained a lower pH,
likely due to their reduced solubility.
MTA White showed an increase in pH
over the first 7 days, followed by a decrease
at 15 days. In contrast, MTA HP maintained a
stable pH throughout the experimental periods.
The experimental cements containing
Arnica
extract had the highest alkalinity only at the
3-day mark, with no signicant alkalinization
at 7 or 15 days. This may be explained by the
fact that these materials contain only calcium
silicate and not Portland cement. Consequently,
the hydration reaction and Portlandite formation
occur entirely within the rst 3 days, with no
further pH increase thereafter.
A recent study [26] reported an alkaline pH
of 8.5 in the 2 days, followed by a decrease to
8.1 at 7 days and 7.8 at 28 days for MTA White.
These differences may be attributed to variations
in methodology or the initial pH of the immersion
water. Although the present study reported lower
pH values, it aligned with the previous study at
the 7-day mark. Notably, pH levels above 7.8 may
inhibit broblast migration and interfere with the
repair process [27].
Regarding calcium ion release, MTA White
exhibited the highest release levels in the
present study, likely due to increased Portlandite
formation and the presence of calcium tungstate.
Among the experimental cements, the calcium
silicate-based groups demonstrated the highest
release levels at 3 days, suggesting that the setting
reaction facilitates ion diffusion.
Conversely, the silicone-based experimental
groups exhibited the lowest calcium ion release
across all time points, which can be attributed to
their lower calcium silicate content. While MTA
White and MTA HP contain approximately 85%
Portland cement, the experimental cements contain
only 60% calcium silicate. The bioactivity of calcium
silicate materials is largely dependent on the release
of calcium and hydroxyl (OH−) ions [28].
Despite the limitations of this in vitro study,
the experimental cements demonstrated higher
radiopacity than the commercial materials,
regardless of the radiopacier used. This property
may assist clinicians in differentiating dentin
from other structures. The addition of 30% by
weight of zirconium oxide or calcium tungstate
was found to improve the radiopacity of the
experimental cements.
An alkaline pH and calcium ion release
are desirable properties in repair cements.
The calcium silicate and calcium phosphate-
based experimental cements exhibited these
characteristics, whereas the silicone-based
materials demonstrated lower solubility and
greater owability. These properties may facilitate
their handling and placement in perforations
within the root canal while providing dimensional
stability, thereby reducing the risk of void
formation and bacterial inltration. The longer
setting time observed in calcium silicate-based
cements may also enhance handling properties,
making them suitable for endodontic applications.
9
Braz Dent Sci 2025 Jan/Mar;28 (1): e4277
Titato PCG et al.
Physicochemical properties analysis of experimental retrograde filling materials
Titato PCG et al. Physicochemical properties analysis of experimental
retrograde filling materials
CONCLUSION
Although the polydimethylsiloxane-
based experimental cements exhibited greater
owability and dimensional stability, the addition
of tricalcium silicate did not enhance calcium ion
release or achieve a favorable pH. Further studies
are necessary to evaluate the long-term behavior
and biocompatibility of these new experimental
materials.
Acknowledgements
We are grateful to the São Paulo Research
Foundation for supporting this work.
Author’s Contributions
PCGT: Writing – Original Draft Preparation,
Review & Editing, Visualization, Supervision,
Conceptualization, Methodology, Validation,
Formal Analysis, Investigation, Data Curation.
HGSC: Writing – Review & Editing, Formal
Analysis, Investigation, Data Curation. BCV:
Writing – Review & Editing, Formal Analysis,
Investigation, Data Curation.
MPA: Writing – Review & Editing,
Visualization, Supervision, Project Administration,
Conceptualization, Methodology, Validation.
RRV: Writing – Review & Editing,
Visualization, Supervision, Project Administration
and Funding Acquisition, Conceptualization,
Methodology, Validation, Resources. MAHD:
Writing – Original Draft Preparation, Review
& Editing, Visualization, Supervision, Project
Administration and Funding Acquisition,
Conceptualization, Methodology, Validation,
Formal Analysis, Investigation, Resources, Data
Curation.
Conict of Interest
The authors declare no conict of interest.
Funding
This research was nanced by the São Paulo
Research Foundation (FAPESP 2017/06545-0).
Regulatory Statement
Not applicable.
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Pedro Cesar Gomes Titato
(Corresponding address)
University of São Paulo, Department of Dentistry, Endodontics and Dental
Materials, Bauru, SP, Brazil.
E-mail: pedro.titato@usp.br
Date submitted: 2024 Feb 21
Accept submission: 2025 Mar 10
