Journal of Dentistry xxx (xxxx) xxx–xxx

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Journal of Dentistry
journal homepage: www.elsevier.com/locate/jdent

Effects of smear layer removal agents on the physical properties and

microstructure of mineral trioxide aggregate cement
⁎
Nidambur Vasudev Ballala, Mrunali Sonab, Franklin R. Tayc,
a
Department of Conservative Dentistry & Endodontics, Manipal College of Dental Sciences Manipal University, Manipal, Karnataka, India
b
Department of Metallurgical & Materials Engineering, National Institute of Technology, Surathkal, Srinivasnagar, Mangalore, Karnataka, India
c
Department of Endodontics, The Dental College of Georgia, Augusta University, Augusta, GA 30912-1129, USA

A R T I C L E I N F O A B S T R A C T

Keywords: Objective: To compare the effect of QMix (Dentsply Sirona), 7% maleic acid (MA), and 17% ethylenediamine-
Ethylenediaminetetraacetic acid tetraacetic acid (EDTA) on the microhardness, flexural strength and microstructure of mineral trioxide aggregate
Flexural strength (MTA; ProRoot MTA, Dentsply Sirona).
Mineral trioxide aggregate Methods: Forty MTA specimens were divided into four groups: [I] QMix [II] 7% MA [III] 17% EDTA and [IV]
Microhardness
distilled water (control). After treatment with 5 mL of the respective solution for 1 min, the specimens were
Maleic acid
tested for microhardness using a Knoop hardness tester. Forty additional specimens were similarly treated and
QMix
Smear layer evaluated for the flexural strength using a universal testing machine. For microstructure evaluation, MTA spe-
cimens were treated in a similar manner and examined by X-ray diffractometry and scanning electron micro-
scopy (SEM).
Results: For microhardness, there were no differences between distilled water, QMix and EDTA groups.
However, MTA exposed to distilled water had higher microhardness than MA. When compared with QMix and
EDTA, MA had lower microhardness; there was no difference between EDTA and QMix. For flexural strength,
distilled water group had higher flexural strength than the other agents. There were no differences between
EDTA vs MA and EDTA vs QMix. Specimens treated with QMix had higher flexural strength than MA. X-ray
diffraction indicated that EDTA inhibited hydration of MTA. For SEM, all the tested agents altered the micro-
structure of MTA when compared to distilled water.
Conclusion: MA had more detrimental effect on the physical properties of MTA and EDTA was more detrimental
to the hydration of MTA.
Clinical significance: The present study highlights the effect of newer chelating agents on the physical properties
and microstructure of MTA. Preventing the deterioration of MTA is important for its long term success in en-
dodontic procedures.

1. Introduction
Mineral trioxide aggregate (MTA) is a biocompatible tricalcium si-
licate hydraulic cement with numerous applications in endodontics
[1,2]. Its clinical applications include repair of resorption, pulp cap-
ping, perforation repair, root end filling, apexification, regenerative
endodontics and as a root canal sealer [1,2].When mixed with an
aqueous solution, ProRoot (white) MTA (Dentsply Sirona, Tulsa Divi-
sion, Tulsa, OK, USA) sets in approximately 3–4 h to form a hard ce-
ment composing mainly of calcium oxide, silicon oxide and bismuth
oxide [3]. It has been reported that MTA must be allowed to set in the
presence of moisture to optimise the material’s physical and chemical
properties [4,5]. Factors such as particle size, powder-to-liquid ratio,
environmental temperature and presence of air in the mixture may all
affect the physical properties of MTA [4,6]. Torabinejad et al. reported
that MTA remains soft when it is used in the vicinity of an acidic en-
vironment, such as that present in severe inflammation [1]. Nilfor-
oushan et al. reported that the setting behaviour of MTA is adversely
affected by the presence of alkaline-earth metal chlorides, including
sodium chloride [7]. Lee et al. reported that hydration of MTA is ad-
versely affected by an acidic environment, which results in weakening
of the material’s microstructure [5].
Ideally, MTA should possess adequate strength especially when used
as a furcation perforation repair material, where it will be subjected to
forces by occlusal loading. The strength of a brittle material such as
MTA may be evaluated by measuring its compressive or flexural

⁎
Corresponding author.
E-mail address: ftay@augusta.edu (F.R. Tay).

http://dx.doi.org/10.1016/j.jdent.2017.08.018
Received 7 July 2017; Received in revised form 12 August 2017; Accepted 30 August 2017
0300-5712/ Published by Elsevier Ltd.

Please cite this article as: Ballal, N.V., Journal of Dentistry (2017), http://dx.doi.org/10.1016/j.jdent.2017.08.018
N.V. Ballal et al.
strength. Flexural strength testing provides a collective measure of both
compressive stress on the upper surface and tensile stress on the lower
surface of a specimen. It closely simulates the clinical situation because
fatigue failure via continuous flexion is the principal contributor to the
failure of tooth restorations [8,9]. Microhardness testing of MTA ex-
posed to various root canal irrigants may be used as an indicator of its
setting process and its overall strength or resistance to deformation
under various setting conditions [10].
The goal of root canal treatment is to completely disinfect the root
canal system [11]. This may be achieved by mechanical instrumenta-
tion, irrigation with disinfecting solutions and the use of inter-ap-
pointment intracanal medicaments. Mechanical instrumentation of the
root canal produces a smear layer which covers the dentinal tubules in
the canal wall [12]. Removal of the smear layer in bacteria-infected
root canals enables more efficient penetration of intracanal medications
and irrigants into the dentinal tubules [13,14]. Various agents have
been used for the removal of smear layer. Ethylenediaminetetraacetic
acid (EDTA) is a commonly used chelating agent for removing canal
wall smear layers [15,16]. When EDTA is used as a final irrigant after
the placement of MTA, the chelating agent may adversely affect the
physical and chemical properties of the set tricalcium silicate cement.
17% EDTA interferes with the hydration of MTA, resulting in a set
cement with decreased microhardness, flexural strength and reduced
biocompatibility [17,18].
QMix® 2in1 (QMix; Dentsply Sirona, Tulsa Division) is a root canal
irrigant which contains EDTA, chlorhexidine, a detergent and water. It
has been reported that QMix removes canal wall smear layers as ef-
fectively as 17% EDTA [19]. Seven percent maleic acid (MA) is a root
canal irrigant that possesses better smear layer removal capability than
17% EDTA or QMix [20,21]. It is also less cytotoxic compared to17%
EDTA [22]. To date, no information is available on the effect of QMix or
7% MA on the microstructure and physical properties of MTA. Ac-
cordingly, the objectives of the present in-vitro study were to compare
the effect of QMix, 7% MA and 17% EDTA on the microhardness,
flexural strength and microcrystalline structure of MTA cement. The
null hypotheses tested were: (1) there are no differences in the potential
of QMix, 7% MA and 17% EDTA in reducing the microhardness and
flexural strength of set MTA cement; and (2) there is no difference in
the microstructure of set MTA cement after it is treated with QMix, 7%
MA or 17% EDTA.
2. Materials and methods
2.1. Microhardness
Forty ProRoot MTA cylindrical shaped specimens (6 mm high, 4 mm
diameter) were prepared using a split mould. The MTA cement was
mixed according to the manufacturer’s instructions and packed into the
mould using MTA carrier (Dentsply Sirona, Tulsa Division). The spe-
cimens were stored in a 100% relative humidity chamber at room
temperature for 24 h. After the specimens were completely set, they
were separated from the mould and were grounded flat using a pol-
ishing machine with a series of ascending grades of silicon carbide
abrasive papers (500, 800, 1000, 1200 grit) under distilled water. Final
polishing was achieved with 0.1 μm alumina suspension (Ultra-Sol R,
Eminess Technologies. Scottsdale, Arizona, USA) on a rotary felt disk.
The polished specimens were randomly divided into four groups
(n = 10) based on the irrigant used: [I] QMix:5 mL of QMix (pH 8.0)
for 1 min; [II] MA: 5 mL of 7% MA solution (pH 1.3; MilliporeSigma, St.
Louis, MO, USA) for 1 min; [III] EDTA: 5 mL of 17% EDTA solution (pH
8.5; Vista Dental Products, Racine, WI, USA) for 1 min; and [IV] con-
trol: 5 mL of distilled water for 1 min. For all groups, the specimens
were immersed in a beaker containing the respective irrigant. A mag-
netic stirrer was placed inside the beaker to ensure complete wetting of
the specimens with the irrigating solutions. After 1 min of treatment, all
the specimens were rinsed with distilled water and air-dried.
2
Journal of Dentistry xxx (xxxx) xxx–xxx
Microhardness was determined using a Knoop hardness tester
(Matsuzawa Seiki Co. Ltd, Tokyo, Japan). Indentations were made with
a Knoop diamond indenter on each specimen using 100 g force and 15 s
dwell time. The diamond-shaped indentations were examined with an
optical microscope equipped with an image analysis software, to enable
accurate measurement of their diagonals. The average length of the two
diagonals recorded for each indentation was used to calculate the mi-
crohardness value. Three measurements were made on the surface of
each specimen, and the mean value was taken as the hardness of that
particular specimen.
2.2. Flexural strength
Forty ProRoot MTA beams (25 mm long and 2 mm thick) were
prepared using a split mould. The MTA was mixed and placed in the
mould in the manner previously described. The set specimens were
randomly divided into four groups(n = 10) and treated with the test
irrigants in the manner described for microhardness testing. All the
specimens were subjected to three-point bending to analyze the flexural
strength. The testing procedure consisted of placing the MTA beams on
two cylindrical rods mounted parallel to each other at a 20 mm dis-
tance. The MTA beams were then loaded at the centre with the in-
denter. Testing was performed using a universal testing machine
(Model 3366, Instron Corp., Norwood, MA, USA). Flexural strength was
determined using the equation S = 3PL/2bh2, where P = maximum
load (N), L = support span (mm), b = width of the specimen (mm),
and h = height of the specimen (mm). Data was expressed in
megaPascals (MPa).
2.3. Microstructure
2.3.1. X-ray diffraction
The crystalline phases of MTA after treatment with the test irrigants
was determined by X-ray diffraction (XRD). Twelve rectangular-shaped
ProRoot MTA specimens (5 mm long, 3 mm wide, 2 mm thick) were
prepared and randomly divided into four groups (n = 3). The speci-
mens were prepared and treated with the test solutions in the same
manner described for microhardness testing. After treatment with the
respective solution, the specimens were examined with an X-ray dif-
fractometer (JDX-8P-XRD, JEOL, Tokyo, Japan) using Ni filter and Cu
Kα radiation; the latter was generated at 30 kV and 20 mA. The spe-
cimens were scanned from 10° to 60° 2θ and the data was collected in a
continuous scan mode at a scanning rate of 4°/min. Crystalline changes
was identified by a computer-automated system and compared with
Joint Committee on Powder Diffraction Standards (JCPDS) files.
2.3.2. Scanning electron microscopy
Twelve cylindrical-shaped ProRoot MTA specimens (6 mm high,
4 mm diameter) were prepared using a split mould. The specimens were
randomly divided into four groups (n = 3) and treated with the test
irrigants in the same manner described for microhardness testing. The
specimens were rinsed and dehydrated subsequently using ascending
grades of ethanol (25%, 50%, 75% and 100%) for 15 min each,
mounted on metal stubs, coated with gold using an ion-sputtering
machine and examined with a scanning electron microscope (SEM;
JSM-6010, JEOL). Images were taken to identify the surface char-
acteristics of the MTA specimens at 3500× magnification and 10 kV.
2.4. Statistical analysis
Because the microhardness and flexural strength data appeared to
have violated the normality and equal variance assumptions, the data
were analyzed separately using Kruskal-Wallis analysis of variance and
Dunn’s multiple comparison procedures. For all analyses, the sig-
nificance level was pre-set at α = 0.05.
N.V. Ballal et al.
Table 1
Microhardness of the MTA specimens after treatment with different smear layer
removing agents.
Groups (n = 10) Microhardness*
Distilled water (control) 147.90 ± 19.84a
Ethylenediaminetetraacetic acid 144.40 ± 26.11a
QMix 142.60 ± 12.42a
Maleic acid 67.10 ± 15.36b
* Values are means ± standard deviations. Groups labelled with the same letter
superscripts are not significantly different (p > 0.05).
3. Results
3.1. Microhardness
Microhardness of the four groups are summarised in Table 1. There
was a significance difference in microhardness among the 4 groups
(p < 0.05). The MA group had significantly lower microhardness than
the distilled water (control) group (p < 0.001), the QMix group
(p < 0.001) and the EDTA group (p < 0.001). There was no sig-
nificance difference between the microhardness of the control and
QMix, the control and EDTA, and between EDTA and QMix (p > 0.05
for all pairwise comparisons).
3.2. Flexural strength
Flexural strength of the four groups are summarised in Table 2.
There was a significant difference in flexural strength among the 4
groups (p < 0.05). The flexural strength in the distilled water control
group was significantly higher than the other 3 experimental groups
(p < 0.001). Flexural strengths of the three experimental groups were
in the order: QMix = EDTA > EDTA = MA (p < 0.05).
3.3. X-ray diffraction
Representative XRD patterns of MTA specimens treated with dif-
ferent irrigants are shown in Fig. 1. The four groups all demonstrated
distinct peaks of tricalcium silicate [20]. The intensities of the tri-
calcium silicate peaks were similar for the QMix, MA and distilled water
groups, which were considerably lower than the tricalcium silicate
peaks obtained for the EDTA group. Additional peaks of dicalcium si-
licate and tricalcium aluminate were also detected. These peaks cor-
responded to similar unreacted mineral phases in the XRD spectrum of
non-hydrated MTA powder (not shown). Additional peaks corre-
sponding to portlandite (crystalline calcium hydroxide) and small et-
tringite (hydrated calcium sulphoaluminate) peaks were seen in the set
hydrated specimens that were exposed to distilled water (control). The
portlandite and ettringite peaks were not apparent in the MTA speci-
mens after exposure to EDTA, MA or QMix.
3.4. Scanning electron microscopy
Representative SEM images of MTA treated with different
Table 2
Flexural strength of the MTA beams after treatment with different smear layer re-
moving agents.
Groups (n = 10) Flexural strength*
Distilled water (control) 15.74 ± 0.60a
Ethylenediaminetetraacetic acid 5.13 ± 0.78b,c
QMix 5.72 ± 0.42b
Maleic acid 4.52 ± 0.38c
* Values are means ± standard deviations. Groups labelled with the same letter
superscripts are not significantly different (p > 0.05).
3
Journal of Dentistry xxx (xxxx) xxx–xxx
Fig. 1. X-ray diffraction spectra of hydrated, set mineral trioxide aggregate specimens
after treatment with distilled water (control), ethylenediaminetetraacetic acid (EDTA),
QMix and maleic acid (MA). A: peaks corresponding to tricalcium silicate; B: dicalcium
silicate; C: tricalcium aluminate; P: portlandite; E: ettringite.
experimental solutions are shown in Fig. 2. The microstructure of MTA
treated with distilled water (control) had needle-shaped crystals
(Fig. 2A). In the EDTA-treated (Fig. 2B) and the MA-treated MTA spe-
cimens (Fig. 2C), there were more amorphous materials among the
exposed crystals. In the QMix treated group, the MTA surface had more
cuboidal-shaped crystals (Fig. 2D).
4. Discussion
The present study evaluated the effect of various smear layer re-
moval root canal irrigants on the microhardness, flexural strength and
microstructure of white MTA cement. Because treatment with7% MA
resulted in significantly lower microhardness and flexural strength of
the set MTA cement specimens, the first null hypothesis that “there are
no differences in the potential of QMix, 7% MA and 17% EDTA in re-
ducing the microhardness and flexural strength of set MTA cement” has
to be rejected.
The adverse effect of 7% MA on the physical and quasistatic me-
chanical properties of set MTA may be attributed to acidity of this ir-
rigant (pH = 1.3). This finding is similar to the results achieved with
exposure of set MTA to other types of acidic solutions [5,24–27], in that
an acidic environment is detrimental to the physical properties and
hydration behaviour of MTA. Deterioration of the mechanical proper-
ties (compressive strength) of different tricalcium silicate cements in
the presence of an acidic environment has also been reported [28]. As a
hydraulic cement, MTA solidifies into a hard structure upon hydration
of the dry cement powder [6]; dissolution of the non-hydrated mineral
phases is followed by crystallisation of the hydrates into an interlocking
mass [29]. When an acidic root canal irrigant comes in contact with the
set MTA, it causes dissolution of the poorly-crystallised calcium silicate
hydrate (C-S-H) binding phase and reduces the cohesiveness of the
crystalline structure of the set cement [30]. This probably accounts for
the reduction in microhardness and flexural strength. Acid-induced
dissolution of the CSH phase in set tricalcium silicate cements has po-
tential undesirable consequences when these cements are used in en-
dodontics as a sealer for filling material. These undesirable con-
sequences may include reduction in margin sealing quality [31,32] as
well as reduction in dislocation resistance [33,34]. In contrast, reduc-
tions of the microhardness and flexural strength of MTA after treatment
with EDTA or QMix were minimal. This may be attributed to the neutral
or alkaline pH of these two irrigants, which is less corrosive on the C-S-
H binding phase in the irrigant-treated cement [35]. Similar to the re-
sults of the present study, the solubility of different tricalcium silicate-
N.V. Ballal et al.
based cements has been reported to be in the order: pH 4.4 > pH
7.4 > pH 10.4 [36].
Changes in the physical and mechanical properties of MTA in the
presence of different root canal irrigants are reflected by alterations in
the microstructure of the specimen surfaces. Hence, the second null
hypothesis that “there is no difference in the microstructure of set MTA
cement after it is treated with QMix, 7% MA or 17% EDTA” has to be
rejected. The presence of needle-like crystals on the set MTA cement
surface of the control specimens (i.e. after treatment with distilled
water) is similar to the observation reported by Lee et al. [17]. These
needle-shaped crystals probably represent ettringite, the hydration re-
action product of calcium aluminate with water, in the presence of
gypsum (CaSO4). Nevertheless, hydration of tricalcium silicate cements
produces predominantly C-S-H and portlandite [23,37,38]. The process
proceeds in two stages: dissolution of the tricalcium complex in water,
and precipitation and crystallisation of the hydrated compounds
[39,40]. In contrast with MTA specimens that had been exposed to
distilled water, surfaces of MTA specimens treated with EDTA and MA
appeared less crystalline and more porous, probably due to the dis-
solution of the ettringite and portlandite interlocking crystalline com-
ponents. These crystalline phases are important in interlocking the
entire mass of the set, hydrated material [27]. Their disappearance may
cause the material hardness to decrease as seen in the present study.
Cuboidal crystals were observed on the surface of MTA specimens
treated with QMix; these crystals were not identified from the other
three groups. They probably represent crystallisation of a component
(EDTA, chlorhexidine or detergent) derived from the QMix irrigant that
leached out from the internal porosities of the set MTA cement. Al-
though the specimens were rinsed prior to ethanol dehydration, liquids
that occupied the internal pores of the set cement were unlikely to be
completely removed. Dehydration would have caused these materials to
diffuse out of the internal porosities and crystallise on the material’s
surface.
In MTA specimens that were treated with EDTA, MA or QMix, no
portlandite peak could be observed from the XRD spectra. This finding
suggested that the crystalline calcium hydroxide reaction phase on the
surface of the MTA specimens were dissolved by the acidic irrigant
(MA) or chelating agents (EDTA and QMix). However, in the EDTA
4
Journal of Dentistry xxx (xxxx) xxx–xxx
Fig. 2. Scanning electron microscopy images of hy-
drated, set mineral trioxide aggregate specimens
after exposure to [A] distilled water (control), [B]
17% EDTA, [C] 7% maleic acid and [D] QMix for
1 min.
group, the intensity of the tricalcium silicate peaks were considerably
stronger than similar peaks present in the spectra derived from the
other groups. The tricalcium silicate peaks in the hydrated MTA spe-
cimens represent unreacted cement particles that are surrounded by the
reaction phases after the hydration reaction. The presence of much
stronger tricalcium silicate peaks in the EDTA group suggests disruption
of continuing hydration of MTA by EDTA. When compared to MA and
QMix, EDTA may have chelated more Ca2+ ions from the MTA to form
Ca-EDTA complexes. This probably leads to the reduction of reaction
phases such as amorphous C-S-H and crystalline calcium hydroxide
(portlandite) due to lack of free calcium ions. It has also been reported
that EDTA decreased the apical sealing ability of MTA when used as a
root end filling material [41,42]. This may be attributed to the removal
of inorganic content of the smear layer by EDTA [43] and also its effect
on MTA hydration.
5. Conclusion
The present study demonstrated that exposing a set mineral trioxide
aggregate cement to maleic acid is more detrimental on its physical
properties, when compared to exposing similar specimens to EDTA or
QMix. In addition, EDTA is more detrimental to the hydration of mi-
neral trioxide aggregate cement than the other tested agents.
Acknowledgement
The authors thank Mrs. Marie Churchville for administrative sup-
port.
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