Josette Camilleri

Characterization of hydration products of mineral trioxide aggregate.

OBJECTIVE To characterize the hydration products of white mineral trioxide aggregate (MTA). METHODOLOGY Mineral trioxide aggregate, white Portland cement and bismuth oxide were evaluated using X-ray diffraction (XRD) analysis and Rietveld XRD. The cements were tested un-hydrated and after hydration and curing for 30 days at 37 degrees C. Analysis of hydrated cement leachate was performed weekly for five consecutive weeks from mixing using inductively coupled plasma atomic emission spectroscopy after which the cements were viewed under the scanning electron microscope to evaluate the cement microstructure. Quantitative energy dispersive analysis with X-ray was performed and atomic ratios were plotted. RESULTS Both Portland cement and MTA produced calcium silicate hydrate (C-S-H) and calcium hydroxide (CH) on hydration. The tricalcium aluminate levels were low for MTA which resulted in reduced production of ettringite and monosulphate. On hydration the bismuth level in the hydrated MTA decreased; bismuth oxide replaced the silica in the C-S-H and was leached out once the C-S-H decomposed with time. Both MTA and Portland cement released a high amount of calcium ions which decreased in amount over the 5-week period. CONCLUSIONS The hydration mechanism of MTA is different to that of Portland cement. In MTA the bismuth oxide is bound to the C-S-H and is leached out from the cement with time as the C-S-H decomposes. MTA produces a high proportion of calcium ions from CH a by-product of hydration and also by decomposition of C-S-H. The release of calcium ions reduces with time.

Investigation of the hydration and bioactivity of radiopacified tricalcium silicate cement, Biodentine and MTA Angelus

OBJECTIVE Novel root-end filling materials are composed of tricalcium silicate (TCS) and radiopacifier as opposed to the traditional mineral trioxide aggregate (MTA) which is made up of clinker derived from Portland cement and bismuth oxide. The aim of this research was to characterize and investigate the hydration of a tricalcium silicate-based proprietary brand cement (Biodentine™) and a laboratory manufactured cement made with a mixture of tricalcium silicate and zirconium oxide (TCS-20-Z) and compare their properties to MTA Angelus™. METHODS The materials investigated included a cement containing 80% of TCS and 20% zirconium oxide (TCS-20-Z), Biodentine™ and MTA Angelus™. The specific surface area and the particle size distribution of the un-hydrated cements and zirconium oxide were investigated using a gas adsorption method and scanning electron microscopy. Un-hydrated cements and set materials were tested for mineralogy and microstructure, assessment of bioactivity and hydration. Scanning electron microscopy, X-ray energy dispersive analysis, X-ray fluorescence spectroscopy, X-ray diffraction, Rietveld refined X-ray diffraction and calorimetry were employed. The radiopacity of the materials was investigated using ISO 6876 methods. RESULTS The un-hydrated cements were composed of tricalcium silicate and a radiopacifier phase; zirconium oxide for both Biodentine™ and TCS-20-Z whereas bismuth oxide for MTA Angelus™. In addition Biodentine™ contained calcium carbonate particles and MTA Angelus™ exhibited the presence of dicalcium silicate, tricalcium aluminate, calcium, aluminum and silicon oxides. TCS and MTA Angelus™ exhibited similar specific surface area while Biodentine™ had a greater specific surface area. The cements hydrated and produced some hydrates located either as reaction rim around the tricalcium silicate grain or in between the grains at the expense of volume containing the water initially present in the mixture. The rate of reaction of tricalcium calcium silicate was higher for Biodentine™ than for TCS-20-Z owing to its optimized particle size distribution, the presence of CaCO₃ and the use of CaCl₂. Tricalcium calcium silicate in MTA hydrated even more slowly than TCS-20-Z as evident from the size of reaction rim representative of calcium silicate hydrate (C-S-H) around tricalcium silicate grains and the calorimetry measurements. On the other hand, calcium oxide contained in MTA Angelus™ hydrated very fast inducing an intense exothermic reaction. Calcium hydroxide was produced as a by-product of reaction in all hydrated cements but in greater quantities in MTA due to the hydration of calcium oxide. This lead to less dense microstructure than the one observed for both Biodentine™ and TCS-20-Z. All the materials were bioactive and allowed the deposition of hydroxyapatite on the cement surface in the presence of simulated body fluid and the radiopacity was greater than 3mm aluminum thickness. SIGNIFICANCE All the cement pastes tested were composed mainly of tricalcium silicate and a radiopacifier. The laboratory manufactured cement contained no other additives. Biodentine™ included calcium carbonate which together with the additives in the mixing liquid resulted in a material with enhanced chemical properties relative to TCS-20-Z prototype cement. On the other hand MTA Angelus™ displayed the presence of calcium, aluminum and silicon oxides in the un-hydrated powder. These phases are normally associated with the raw materials indicating that the clinker of MTA Angelus™ is incompletely sintered leading to a potential important variability in its mineralogy depending on the sintering conditions. As a consequence, the amount of tricalcium silicate is less than in the two other cements leading to a slower reaction rate and more porous microstructure.

Investigation of the physical properties of tricalcium silicate cement-based root-end filling materials

OBJECTIVE Tricalcium silicate-based cements have been displayed as suitable root-end filling materials. The physical properties of prototype radiopacified tricalcium silicate cement, Bioaggregate and Biodentine were investigated. Intermediate restorative material was used as a control. METHODS The physical properties of a prototype zirconium oxide replaced tricalcium silicate cement and two proprietary cements composed of tricalcium silicate namely Bioaggregate and Biodentine were investigated. Intermediate restorative material (IRM) was used as a control. Radiopacity assessment was undertaken and expressed in thickness of aluminum. In addition the anti-washout resistance was investigated using a novel basket-drop method and the fluid uptake, sorption and solubility were investigated using a gravimetric method. The setting time was assessed using an indentation technique and compressive strength and micro-hardness of the test materials were investigated. All the testing was performed with the test materials immersed in Hanks balanced salt solution. RESULTS All the materials tested had a radiopacity value higher than 3mm thickness of aluminum. IRM exhibited the highest radiopacity. Biodentine demonstrated a high washout, low fluid uptake and sorption values, low setting time and superior mechanical properties. The fluid uptake and setting time was the highest for Bioaggregate. SIGNIFICANCE The addition of admixtures to tricalcium silicate-based cements affects the physical properties of the materials.

Evaluation of the radiopacity of calcium silicate cements containing different radiopacifiers

AIM To identify the suitable ratio of alternative radiopacifiers to impart the necessary radiopacity to calcium silicate cements (CSC) and assess the purity of the radiopacifying agents. METHODOLOGY Alternative radiopacifying materials for incorporation into CSC included barium sulphate, titanium oxide, zinc oxide, gold powder and silver/tin alloy. The chemical composition of the alternative radipacifying materials and bismuth oxide, which is used in mineral trioxide aggregate (MTA), was determined using energy dispersive X-ray analysis. In addition, using an aluminium step-wedge and densitometer, the radiopacity of each material was evaluated as recommended by international standards. The optical density was compared with the relevant thickness of aluminium (Al). A commercial MTA and CSC were used as controls. Statistical analysis comparing the radiodensity of the different cements to MTA was performed using anova with P = 0.05 and post hoc Tukey test. RESULTS All percentage replacements of bismuth oxide, gold and silver-tin alloy powder, and the 25% and 30% replacements with barium sulphate and zinc oxide had radiopacities greater than 3 mm thickness of aluminium (Al) recommended by ISO 6876 (2002). The 25% replacement of cement with gold powder and 20% replacement of cement with silver/tin alloy powder exhibited radiopacity values of 8.04 mm Al and 7.52 mm Al, respectively, similar to MTA (P > 0.05). The cement replaced with 20% bismuth oxide showed a radiopacity of 6.83 mm Al, lower than MTA (P = 0.003). CONCLUSIONS Silver/tin alloy and gold powder imparted the necessary radiopacity to a calcium silicate-based cement. Barium sulphate was also a suitable radiopacifier together with a lower concentration of silver/tin alloy and gold powder that achieved the radiodensity recommended by ISO 6876. Further research is required to investigate the broader properties of the calcium silicate-based cement with the different radiopacifiers.

Evaluation of selected properties of mineral trioxide aggregate sealer cement.

INTRODUCTION The addition of a water-soluble polymer to mineral trioxide aggregate (MTA), which to date has been used primarily to seal lateral root perforations and as a root-end filling material, resulted in material that is suitable for use as an endodontic sealer. METHODS MTA was mixed with water at powder/liquid ratios of 4 and 3.33 and an addition of 2 microL to 20 microL of water-soluble polymer. The materials were tested for flow and film thickness, and the optimal quantity of polymer required to conform to EN ISO 6876 Section 4.3.1, 4.3.4 (2002) was determined. The resultant MTA sealer was tested for radiopacity using methods suggested by ISO 6876 (2002) using pulp canal sealer (PCS) as control. The effect of polymer addition on the hydration characteristics of the MTA and calcium silicate cement was evaluated by assessing paste microstructure under the scanning electron microscope after 30 days and by collecting 50 quantitative analyses of the hydration products and plotting the data as atomic ratios. Plots of Al/Ca versus Si/Ca and S/Ca and Al/Ca were drawn. RESULTS High additions of polymer were required for the flow and film thickness of MTA to conform to ISO 6876 (2002). The resultant cement sealer had a lower radiopacity than PCS but greater than the 3-mm thickness of Al specified by the international standard. The addition of polymer did not modify the hydration mechanism of MTA. CONCLUSIONS The addition of a water-soluble polymer to MTA did not alter the hydration characteristics of the material and resulted in a material with improved properties suitable for use as endodontic sealer cement.

Analyses of Heavy Metals in Mineral Trioxide Aggregate and Portland Cement

INTRODUCTION Portland cement is used in the construction industry as a binder in concrete. It is manufactured from chalk, limestone, and clay, which are clinkered at very high temperatures and ground with gypsum to form Portland cement. The raw materials and the manufacturing process can result in the inclusion of heavy metals in Portland cement. Portland cement with a four to one addition of bismuth oxide is marketed as mineral trioxide aggregate (MTA), which is used mainly as a dental material. Heavy metal inclusion can be of concern because MTA is in contact with hard and soft tissues. METHODS Measurements of arsenic, lead, and chromium in hydrated gray and white Portland cement, ProRoot MTA, and MTA Angelus were conducted with graphite furnace atomic absorption spectrophotometry after acid digestion on the hydrated material. The leaching of the metal ions from the solid material in water and simulated body fluid (SBF) was also determined. RESULTS All cement types showed high relative values of leached chromium compared with arsenic and lead in both the total metal content and leached species. The gray Portland cement showed the highest total amount of metal. The white Portland and both MTAs had lower values for all the leached metal ions. CONCLUSIONS Both MTAs released more arsenic than the amount specified in ISO 9917-1 (2007). Portland cements and MTAs showed evidence of heavy metals in the acid-soluble form as well as leaching in deionized water and SBF. MTA contained levels of arsenic higher than the safe limit specified by the ISO 9917-1 (2007).

Evaluation of the physical properties of an endodontic Portland cement incorporating alternative radiopacifiers used as root‐end filling material

AIM To investigate the physical and chemical properties of Portland cement (PC) loaded with alternative radiopacifying materials for use as root-end filling materials in a mineral trioxide aggregate (MTA)-like system. METHODOLOGY Portland cement loaded with barium sulphate, gold and silver/tin alloy was mixed with water, and the physical and chemical properties of the hydrated cements were evaluated. MTA and intermediate restorative material (IRM) were used as controls. The radiopacity was compared to the equivalent thickness of aluminium, and the setting time of the cements was assessed using an indentation technique. The compressive strength and the stress-strain relationship were determined at 28 days. The stress-strain relationship was determined by monitoring the strain generated when the cement was subjected to compressive load. In addition, the pH was determined in water and simulated body fluid for a period of 28 days. RESULTS The radiopacity of the cements using alternative radiopacifiers was comparable to MTA (P > 0.05). IRM demonstrated a higher radiopacity than all the materials tested (P < 0.05). All the cements with the exception of IRM exhibited an alkaline pH and had an extended setting time when compared to IRM. MTA had a longer setting time than the PC (P < 0.001), and its setting time was similar to the gold-loaded cement (P = 0.159). The addition of a radiopacifier retarded the setting time (P < 0.001) but did not have any effect on the compressive strength as all loaded cements had comparable strength to PC (P > 0.05). IRM was the weakest cement tested (P < 0.001). The cement loaded with gold radiopacifier had comparable strength to MTA (P = 1). The stress-strain relationship was linear for all the cements with IRM generating more strain on loading. CONCLUSIONS Within the parameters set in this study, bismuth oxide in MTA can be replaced by gold or silver/tin alloy. The physical, mechanical and chemical properties of the cement replaced with alternative radiopacifiers were similar and comparable to ProRoot MTA.

Characterization and analyses of acid‐extractable and leached trace elements in dental cements

AIMS Determination of the elemental constitution and investigation of the total and leachable arsenic, chromium and lead in Portland cement, pure tricalcium silicate, Biodentine, Bioaggregate and mineral trioxide aggregate (MTA) Angelus. METHODOLOGY The chemical composition of Portland cement, MTA Angelus, tricalcium silicate cement, Biodentine and Bioaggregate was determined using X-ray fluorescence (XRF). Measurements of arsenic, lead and chromium were taken with inductively coupled plasma-mass spectrometry (ICP-MS), following acid digestion on the hydrated material and on leachates of cements soaked in Hanks balanced salt solution (HBSS). RESULTS All the cements investigated had a similar oxide composition with the main oxide being calcium and silicon oxide. Both the Portland cement and MTA Angelus had an additional aluminium oxide. The dental cements included a radiopacifying material. All the materials tested had higher acid-extractable arsenic content than the level set by ISO 9917-1 (2007) and an acceptable level of lead. Regardless these high levels of trace elements present in the materials, the leaching in HBSS was minimal for all the dental material tested in contrast to the high levels displayed by Portland cement. CONCLUSIONS Dental materials based on tricalcium silicate cement and MTA Angelus release minimal quantities of trace elements when in contact with simulated body fluids. The results of acid extraction could be affected by nonspecific matrix effects by the cement.

Characterization of set Intermediate Restorative Material, Biodentine, Bioaggregate and a prototype calcium silicate cement for use as root-end filling materials

AIM To investigate the composition of materials and leachate of a hydrated prototype cement composed of tricalcium silicate and radiopacifier and compare this to other tricalcium silicate-based cements (Biodentine and Bioaggregate) to assess whether the additives in the proprietary brand cements affect the hydration of the materials, using Intermediate Restorative Material (IRM), a standard root-end filling material as a control. METHODOLOGY The materials investigated included a prototype-radiopacified tricalcium silicate cement, Biodentine, Bioaggregate and Intermediate Restorative Material (IRM). The pH and calcium ion concentration of the leachate were investigated. The hydrated cements were characterized using scanning electron microscopy (SEM) and X-ray energy dispersive analysis (EDX), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). RESULTS All the cements tested were alkaline. The tricalcium silicate-based cements leached calcium in solution. Scanning electron microscopy of the prototype-radiopacified tricalcium silicate cement, Biodentine and Bioaggregate displayed hydrating cement grains, surrounded by a matrix composed of calcium silicate hydrate and calcium hydroxide. The presence of calcium hydroxide was evident from the XRD plots. FT-IR indicated the occurrence of a poorly crystalline calcium silicate hydrate. Biodentine displayed the presence of calcium carbonate. Bioaggregate incorporated a phosphate-containing phase. IRM consisted of zinc oxide interspersed in an organic matrix. CONCLUSIONS The hydration of prototype-radiopacified tricalcium silicate cement, Biodentine and Bioaggregate resulted in the formation of calcium silicate hydrate and calcium hydroxide, which was leached in solution. The hydrated materials were composed of a cementitous phase that was rich in calcium and silicon and a radiopacifying material. Biodentine included calcium carbonate, and Bioaggregate included silica and calcium phosphate in the powders. IRM was composed of zinc oxide interspersed in a matrix of organic material.

Characterization and hydration kinetics of tricalcium silicate cement for use as a dental biomaterial

OBJECTIVES Investigation and characterization of the replacement of the Portland cement component in mineral trioxide aggregate (MTA) with tricalcium silicate cement which is manufactured using the sol-gel method from pure raw materials. METHODS Tricalcium silicate and Portland cement were characterized by viewing under the scanning electron microscope (SEM) and surface imaging and elemental analysis with X-ray energy dispersive analysis (EDX), and by X-ray diffraction analysis with Rietveld refinement. In addition the hydration products of the material after 28 days of curing were evaluated by plotting atomic ratio plots from the EDX data. The cement leachate was evaluated for pH and chemical composition by inductively coupled plasma. RESULTS Portland cement was composed of 68% tricalcium silicate. The tricalcium silicate cement was 99% pure. On hydration both cements produced calcium silicate hydrate and calcium hydroxide. The calcium hydroxide was leached in solution with higher leaching in HBSS. The leaching of calcium hydroxide in solution resulted in an alkaline pH. The reaction of calcium with the phosphorus present in HBSS resulting in the deposition of calcium phosphate on the cement surface. SIGNIFICANCE Tricalcium silicate could prospectively replace the Portland cement component in MTA.