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Revista odontológica mexicana

Print version ISSN 1870-199X

Rev. Odont. Mex vol.19 n.3 Ciudad de México Jul./Sep. 2015 

Original research

Physicochemical analysis of MTA Angelus ® and Biodentine ® conducted with X ray difraction, dispersive energy spectrometry, X ray fluorescence, scanning electron microscope and infra red spectroscopy

Alejandra Citlalli Rodríguez Rochaa 

Genoveva Hernández Padrónd 

Margarita V García Garduñoc 

Raúl Luis García Arandab  * 

a Graduate of Endodontics Specialty, National School of Dentistry, National University of Mexico (UNAM).

b Professor, Endodontics Specialty, Graduate and Research School, National School of Dentistry, National University of Mexico (UNAM).

c PhD researcher, Dental Materials Laboratory, Graduate and Research School, National School of Dentistry, National University of Mexico (UNAM).

d PhD, Academic Technician, Nanotechnology Department, Center of Applied Physics and Advanced Technology, UNAM, Juriquilla Campus.


The aim of the present study was to characterize components of commercial cements used in dentistry MTA Angelus® White (Angelus Lodrina, Parana Brazil) and Biodentine TM (Septodont, Saint-Maurdes Fosses, France). Techniques used for said characterization were Scanning Electron Microscope, X-Ray Diffraction, X Ray Fluorescence, Electron Dispersion Spectrometry, and Infrared Spectroscopy. Both cements were mixed according to manufactures instructions. A study of surface texture was conducted with Scanning Electron Microscope (SEM), and X Ray Diffraction (XRD) analysis, and X Ray fluorescence analysis (XRF), an analysis of Dispersive Energy Spectrometry (DES), as well as an Infra Red Spectroscopy (IRS) in order to determine functional groups.


In XRD analysis, a difference was found: Biodentine exhibited Na2O and ZrO2. These elements were absent in MTA. MTA presented Cr2O3 and BiO2 which in turn were absent in Biodentine. EDS analysis revealed that differences were found in the radio-opacifying agent, and that Biodentine presented CaCl2 differing in this from MTA. Statistical analysis conducted revealed statistically signifi cant percentages in contents, even though components were found to be practically the same. SEM analysis revealed marked differences: MTA presented irregular and porous surface whereas Biodentine exhibited irregular and filament form.


There is a great similarity in the chemical components of MTA Angelus and Biodentine, with the exception of chemical components providing radio-opacity, the size and form of the grain, and, in Biodentine presence of calcium chloride.

Keywords MTA Angelus®; Biodentine TM; DES; SEM; XRD; XRF; IRS


El propósito de este estudio fue caracterizar los componentes de los cementos comerciales para uso en odontología MTA Angelus ® Blanco (Angelus, Lodrina, Paraná Brasil) y de Biodentine TM (Septodont, Saint-Maur-des Fosses, Francia) mediante Microscopia Electrónica de Barrido, difracción de rayos X, fluorescencia de rayos X, espectrometría de dispersión de electrones y espectroscopia infrarroja. Los dos cementos se mezclaron según las indicaciones del fabricante. Se les practicó un estudio de textura de superficie mediante el microscopio electrónico de barrido (MEB), un análisis de difracción de rayos X (DRX), un análisis de fluorescencia de rayos X (FRX), un análisis de espectrometría de energía dispersiva (EDS) y un análisis de espectroscopia infrarroja (IR), para determinar los grupos funcionales.


Se presentó una diferencia en el análisis XRD entre Biodentine presentó Na2O y ZrO2 mientras que están ausentes en el MTA. El MTA presentó Cr2O3 y BiO2 ausentes en el Biodentine. En el análisis de EDS las diferencias fueron en el agente radiopacador y que el Biodentine presentó Cl a diferencia del MTA y en el análisis estadístico realizado, a pesar de que prácticamente se presentaron los mismos componentes, los porcentajes en los contenidos de éstos fueron estadísticamente signifi cativos. En el análisis de MEB hay una gran diferencia, el MTA presenta una superfi cie porosa e irregular, el Biodentine una forma fi brilar e irregular.


Existe una gran similitud en los componentes químicos entre el MTA Angelus y Biodentine con excepción de los componentes químicos para proporcionarles radiopacidad, el tamaño y la forma del grano y en el caso del Biodentine el cloruro de calcio.

Palabras clave MTA Angelus®; Biodentine TM; EDS; MEB; DRX; FRX; IR


Dental materials have been evolving alongside dentistry due to technological advances, which have assisted these materials to possess better physical, chemical and biological properties.

Retro-filling materials are commonly used in endodontic surgical procedures. An ideal endodontic reparation material should be radio-opaque, biocompatible, with anti-bacterial effect, dimensionally stable, easy to manipulate and not be contaminated or affected by blood. Other desirable characteristics for the selected material would include for it to be osteo-inductor, provide suitable sealing against bacteria and fluids as well as being able to avoid filtrations when placed in humid environment and possessing sufficient resistance to compression and hardness.1

Many materials have been used to perform retrograde filling. Among them we can count amalgam, zinc oxide-eugenol, polycarboxylate cements, glass ionomer cements, composite resin, epoxy-resin, guttapercha and mineral trioxide aggregate (MTA) type cements based on Portland cement.

Main disadvantages of the aforementioned materials include micro-leakage, varied degrees of toxicity, as well as sensitivity to presence of humidity.2,3 Among these MTA has been recognized as a bioactive material,4 hard tissue conductor5 hard tissue inductor as well as biocompatible.6

MTA is a material commonly used for retrograde filling procedures, apex formation and perforation repairs, nevertheless its handling is less than ideal due to its long setting time and difficulties in preserving mix consistency.7

Calcium silicate cements, especially those derived from Portland cement, such as mineral trioxide aggregate (MTA) and others have been designed and are used in clinical dental applications.

Self-adjusting properties of calcium silicate cements are due to the progressive hydration reaction of orthosilicate ions (SiO4).

When calcium silicate particles react to water a hydrated calcium silicate nanoporous amorphous gel is formed (HCS gel) in the cement particles, while calcium hydroxide ( Ca(OH)2) (portlandite) forms nuclei and grows in available gaps and spaces of the pores. With time, HCS gel polymerizes and hardens, forming thus a solid net which is associated to greater mechanical resistance. HCS gel is soluble in Ca(OH)2 ,released by the cement surface and increases alkalinity of surrounding environment.8

The purpose of the present study was to explore the components of MTA Angelus® White cement (Angelus, Lodrina, Paraná Brazil) and Biodentine TM (Septodont, Saint-Maur-des Fosses, France) by means of X-ray diffraction and electron dispersion spectrometry, X -ray fluorescence, as well as observing the surface with scanning electron microscope and infra red spectroscopy.


Both cements used for the present project were divided into two groups:

  • Group 1 MTA Angelus® White (Angelus, Lodrina, Parana, Brazil).

  • Group 2: Biodentine TM (Septodent, Saint-Maur-des-Fosses, France).

One gram of the powder provided by the manufacturer was used for XRD and XRF analyses. For DES, SEM and IRS analyses all products were mixed using powder and liquid provided by the manufacturer. Manufacturer's instructions were strictly followed. One 8 mm diameter x 4 mm thickness sample was manufactured for each group. Five points were randomly taken for the analysis.

X ray diffraction analysis was conducted with a diffractometer Phillips Mod 1130/96 (generator) and pw1050/24 (goniometer) using CuKα at angular intervals ranging from 4o to 70o.

X ray fluorescence analysis (XRF): An X ray fluorescence quantitative chemical analysis was conducted with a Siemens SRS 3000 spectrometer, gauged with Geochemical Reference materials. This analysis was conducted with the sample in dry base, and loss by calcination (LBC) was determined by calcinating 1 g of the sample at 950 oC during one hour.

Dispersive energy spectrometry (DES) and scanning electron microscopy (SEM): Once hardened, the samples were placed on the sample holder with a carbon film to which they adhered. Observations were made with Scanning Electron Microscope (leol model 5900 LV, Tokio, Japan). Used magnifications were 500X, 1000X and 2000X.

For the dispersive energy spectrometry analysis (DES) an elemental chemical analysis was conducted with an Oxford device, ISIS model, with 133 eV resolution, with carbon to uranium element detection.

For the present study amplifications of 500X, 1000X and 2000X were used in all samples at four predetermined points.

Infrared spectroscopy (IRS): Samples were analyzed with attenuated total reflectance technique (ATR) in a Bruker Brand spectrometer, model Vector 33 with 32 scanning and resolution of 4 cm-1. Samples to be analyzed were directly placed on the diamond crystal for analysis, since this technique did not require previous preparation.


XRD results of MTA and Biodentine were the following:

  • In both cements presence of calcite and larnite was detected.

  • In MTA there was presence of bismite, vesuvianite, and bassanite. These materials were absent in Biodentine.

  • In Biodentine there was presence of hatrurite and baddeleyite. These materials were absent in MTA.

In XRF analysis, the following were identified in both cements: SiO2 Al203, Fe2O3t, MgO, CaO, K2O, P2O5 TiO2. MTA exhibited Cr2O3 and BiO2, these materials were not detected in Biodentine. Biodentine exhibited Na2O and ZrO2. which were absent in MTA Angelus ( Table I).

SEM analysis of samples revealed Biodentine structure with fibrillar and irregular shape, with crystal appearance ( Figure 1) whereas MTA samples exhibited irregular and porous structure, loose granules were observed and identified as Bismuth ( Figure 2).

DES results revealed presence of Bi in Group 1 (MTA Angelus). Bi wasn't present in any other group. In Group 2 (Biodentine) CI presence was observed, which was absent in Group 1.

C, O, Al, Si, Ca were regularly detected in both groups ( Tables II and III).

T Student test was used for statistical analysis. Results revealed that points from where samples were taken were homogeneous, and there were statistically significant differences in the percentages of the varied detected components in both cements with DES tests ( Tables IV and V).

Figure 1. Biodentine Scanning electron micrographs at magnifications of 500X, 1000X and 2000X where irregular and filiform shaped crystals can be observed. 

Figure 2. MTA Angelus scanning electron micrographs at magnifications of 500X, 1000X, and 2000X where irregular and porous structure can be observed. Bismuth can be observed in the shape of loose granules. 

Table I.  Percentages and components found in Group 1 (MTA Angelus) and Group 2 (Biodentine) through ray diffraction procedures. 

Cement SiO2% Al2O3% Fe2O3t % MnO % MgO % CaO % Na2O % Cr2O3% BiO2% K2O % P2O5% ZrO2% TiO2% LBC % Sum %
Biodentine 20.65 0.247 0.062 0.004 0.072 64.839 0.434 ND ND 0.036 0.015 6.50 0.009 6.72 99.60
MTA Angelus 21.07 3.47 0.36 ND 0.67 52.49 ND 0.96 16.50 0.021 0.11 ND 0.18 8.56 95.83

ND = Not detected; LBC = Loss by calcination.

Table II. Percentages of elements found in the five samples of each cement. 

Element MTA1% MTA2% MTA3% MTA4% MTA5% Biode 1% Biode 2% Biode 3% Biode 4% Biode 5%
C 16.77 14 13.38 14.54 12.92 7.16 9.14 7.65 7.97 9.05
O 38.39 39.69 41.30 39.57 40.24 33.02 32.20 32.33 31.39 30.73
Al 2.15 2.33 2.49 2.26 2.50 0.28 0.32 0.61 0.06 -0.02
Cl ND ND ND ND ND 18.52 16.77 16.99 18.49 18.69
Ca 32.50 33.85 32.73 33.63 33.54 41.02 41.56 42.24 41.98 41.46
Si 5.64 6.08 5.59 5.88 5.76 0 0 0.19 0.10 0.10

Table III.  Percentages of elements found in the five samples of each cement. 

Element MTA1% MTA2% MTA3% MTA4% MTA5% Biode 1% Biode 2% Biode 3% Biode 4% Biode 5%
C 28.44 24.22 23.09 25.03 22.65 14.14 17.72 15.09 15.79 17.77
O 48.88 51.54 53.50 51.15 52.96 48.95 46.86 47.89 46.71 45.32
Al 1.62 1.79 1.91 1.73 1.95 0.25 0.28 0.53 0.05 -0.02
Cl ND ND ND ND ND 12.39 11.01 11.36 12.42 12.44
Ca 16.52 17.55 16.93 17.35 17.62 24.27 24.14 24.97 24.94 24.40
Si 4.09 4.50 4.13 4.33 4.32 0 0 0.16 0.09 0.08
Bi 0.44 0.40 0.45 0.41 0.51 ND ND ND ND ND


Results obtained from MTA sample ( Figure 3) revealed calcium carbonate characteristic groups in the absorption bands in 1410,869 and 660 cm-1 in the C-O group. The band 952cm-1 corresponded to calcium chloride (CaCl2).

Figure 4 shows the Biodentine sample spectrum. It can be observed that bands at 3567 7 3426 cm-1 correspond to groups N-H. The band at 2925 cm-1 corresponds to methylene groups (CH2) The band at 1739 cm-1 is assigned to C=O of a carboxylic acid, this is corroborated with bands at 1558 and 1419 cm-1 with the group COO- of carboxylic acids. The band at 1620 cancorrespond to an aromaticring or a secondary amine. The aromatic ring can be corroborated in the region of 1410 to 1500 cm-1 and the amine group at the 795 cm-1 band. The 1168 cm-1 band corresponds to the CN group. Bands between 702 and 676 cm-1 correspond to monosubstituted groups (in the aromatic ring) C-CH2 and C-H respectively.


Hydroxyapatite as such and other materials which contain Ca exhibit excellent biocompatibility, which is expressed in minimal tissue toxicity and reaction to foreign body, osteoconductivity and osteogenicity (LeGeros, 1991).9

Table IV.  Statistical analysis conducted with Student t-test. 

Element Cemento Average Standard deviation T Student p
Carbon MTA 14.32 1.499 7.898 0.001
Biodentine 8.19 0.8722
Oxygen MTA 39.83 2.059 12.78 0.001
Biodentine 31.93 0.887
Aluminum MTA 2.346 0.1504 16.65 0.001
Biodentine 0.258 0.237
Calcium MTA 33.25 0.596 24.67 0.001
Biodentine 41.65 0.473
Silicon MTA 5.79 0.197 59.99 0.0001

Table V.  Statistical analysis conducted with Student t-test. 

Element Cemento Average Standard deviation T Student p
Carbon MTA 24.68 2.798 6.84 0.001
Biodentine 16.10 1.61
Oxygen MTA 51.60 1.80 4.408 0.002
Biodentine 47.146 1.36
Aluminum MTA 1.80 0.134 14.329 0.001
Biodentine 0.226 0.2057
Calcium MTA 17.19 0.4627 27.26 0.001
Biodentine 24.54 0.386
Silicon MTA 4.276 0.164 52.95 0.0001
Biodentine 0.066 0.0676

Figure 3. Infra-red spectroscopy of MTA simple. 

Figure 4. Infrared spectroscopy of Biodentine sample. 

The composition of Biodentine powder is tricalcium silicate, calcium carbonate and zirconium oxide (Koubi et al, 2011).10

Calcium chloride is one of the most efficient accelerators for Portland cement hydration and configuration (Camilleri et al, 2006).11

Calcite (CaCO3), which was observed in both cements, has two different functions: 1. as active agent involved in the hydration process and 2. as filling which improves the cement's mechanical properties. (Garrault et al 2006).12

Hydration of tricalcium silicate (3CaO.SiO2) leads to the formation of a hydrated calcium, gel silicate hydroxide (gel CSH) and calcium hydroxide (Ca(OH)2) (Taylor 1997).13

Biodentine surface examined with SEM reveals crystals of varied sizes in the shape of hexagonal plates of Ca(OH) 2 (Taylor 1997)13 which differs from the present study which observed crystals of filament shape.

Asgary14 reported in his XRD analysis of white MTA the presence of CaO, SiO2 Bi2O3Al2O3, MgO, SO3 Cl, FeO, P2O5, TiO2. In the present study, no Cl was found in MTA and contrary to Asgarty's reports presence of Cr2O3, K2O was observed.

White MTA is composed of a variety of oxides typically of SiO2 CaO and Al2O3 Among oxides, aluminum (Al), a neurotoxin, is harmful to human health due to its ability to alter cellular calcium homeostasis, and promote cellular oxidation (Zatta 2002).15

Gandolfi16 reported that in his DES analysis of MTA he obtained the following elements: Ca, Si, Cl, Bi, and O. No Cl was found in the analysis we conducted, and C and Al were found in addition to results reported by Gandolfi.

Song17 in an DES analysis of MTA reported presence of Ca, Si, C, O, Mg, Al, S and Bi. Our analysis differed from Song's inasmuch as S and Mg were not present.

MTA has a proportion of 4:1 of bismuth, radio-opacity oxide (Camilleri 2007 18, Torabinejad 1995 19) In the present study proportion of bismuth oxide was 16.5% as shown in Table I .

Asgary S et al 20 reported in DES analysis the highest peaks of calcium, silica and bismuth contents. Nevertheless, aluminum, magnesium and especially iron peaks were significantly lower in white MTA, this could explain color differences. We concur with results obtained in our study.


Chemical components of MTA Angelus and Biodentine are very similar, the exception would be inthechemical components which provide opacity, size and shape of grain, and in the case of Biodentine, calcium chloride.


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**This article can be read in its full version in the following page:

Received: October 15, 2014; Accepted: April 15, 2015

* Mailing address: Raúl Luis García Aranda, E-mail:

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