Influence of gallium on the surface properties of zinc based glass polyalkenoate cements

This study investigates the effect of gallium (Ga) additions, substituting for zinc (Zn), on the physio-chemical surface properties of aluminium-free glass polyalkenoate cements (GPCs). Substituting Zn with Ga resulted in a significant increase in hydrophilicity and thusly wettability, as shown by a decrease in water contact angle. Increasing Ga resulted in increased Zn release, irrespective of decreasing Zn content of the starting glass. This resulted in increased antibacterial efficiency, against Escherichia coli, but not Staphylococcus epidermidis. Ga was shown to have no effect on antibacterial efficiency.     

The effect of glass synthesis route on mechanical and physical properties of resultant glass ionomer cements

Glass ionomer cements (GICs) have potential orthopaedic applications. Solgel processing is reported as having advantages over the traditional melt-quench route for synthesizing the glass phase of GICs, including far lower processing temperatures and higher levels of glass purity and homogeneity. This work investigates a novel glass formulation, BT 101 (0.48 SiO₂–0.36 ZnO–0.12 CaO–0.04 SrO) produced by both the melt-quench and the solgel route. The glass phase was characterised by X-ray diffraction (XRD) to determine whether the material was amorphous and differential thermal analysis (DTA) to measure the glass transition temperature (T _g). Particle size analysis (PSA) was used to determine the mean particle size and X-ray photoelectron spectroscopy (XPS) was used to investigate the structure and composition of the glass. Both glasses, the melt-quench BT 101 and the solgel BT 101, were mixed with 50 wt% polyacrylic acid (M _w, 80,800) and water to form a GIC and the working time (T _w) and the setting time (T _s) of the resultant cements were then determined. The cement based on the solgel glass had a longer T _w (78 s) as compared to the cement based on the melt derived glass (19 s). T _s was also much longer for the cement based on the solgel (1,644 s) glass than for the cement based on the melt-derived glass (25 s). The cements based on the melt derived glass produced higher strengths in both compression (σ_c) and biaxial flexure (σ_f), where the highest strength was found to be 63 MPa in compression, at both 1 and 7 days. The differences in setting and mechanical properties can be associated to structural differences within the glass as determined by XPS which revealed the absence of Ca in the solgel system and a much greater concentration of bridging oxygens (BO) as compared to the melt-derived system.     

Effects of glass ionomer cements on bone tissue

In vivo biocompatibility of glass ionomer cements (GICs) was evaluated for use in orthopaedic surgery using a rat model and compared with conventional bone cement, Polymethyl methacrylate, PMMA. The unset GICs and PMMA were inserted into the marrow cavities of rat femora and retained in situ for various periods of time. The PMMA bone cement showed complete biocompatibility with no interference with reparative bone. The conventional GIC with smaller glass particles and lower powder/liquid ratio showed an initial minor toxic effect on rat bone tissue with later disturbance of adjacent bone formation. The conventional GIC with larger-size glass particles and higher powder/liquid ratio and resin-modified GIC showed more severe toxic effect on rat tissue with the resin-modified GIC affecting the rat bone tissue later. The causes of toxicity associated with the conventional GIC with larger glass particles and higher powder/liquid ration and the resin-modified GIC are thought to be related with the unreacted acid component of both materials and longer ongoing metallic ion release.     

Influence of 0.05% sodium fluoride solutions on microhardness of resin-modified glass ionomer cements

This study aimed to evaluate the influence of fluoride-containing mouthrinse solutions (Fluorgard and Oral B) on the superficial microhardness of two resin-modified glass ionomer cements (Vitremer and Fuji II LC). Fifteen discs-shaped specimens of each glass ionomer cement (Ø10 mm; 2 mm thick) were prepared, thereby forming two groups. After 24-hour storage in artificial saliva, the microhardness was measure and the data were recorded. Next, each group was divided into three subgroups (n = 5), according to the solution to be immersed in. Control specimens were kept in artificial saliva along the whole experiment. The test specimens were kept in mouthrinse solution for 30 days. Vickers surface microhardness was analyzed at predetermined evaluation periods: 24 h, 48 h, 7, 14, 21 and 30 days after specimens’ preparation. Data were subjected to three-way ANOVA and to Tukey test (p<0.05). A better behavior of Fuji II LC was observed and Fluorgard affected most the characteristics of the tested materials. It may be concluded that fluoride-containing solutions influenced the tested characteristics of materials, mainly of Vitremer.     

The processing,mechanical properties and bioactivity of zinc based glass ionomer cements

The suitability of Glass Ionomer Cements (GICs) for use in orthopaedics is retarded by the presence in the glass phase of aluminium, a neurotoxin. Unfortunately, the aluminium ion plays an integral role in the setting process of a GIC and its absence is likely to hinder cement formation. However, zinc oxide, a bacteriocide, can act both as a network modifying oxide and an intermediate oxide in a similar fashion to alumina and so ternary systems based on zinc silicates often have extensive regions of glass formation. The purpose of this research was to produce novel GICs based on calcium zinc silicate glasses and to evaluate their rheological, mechanical and biocompatible properties with the ultimate objective of developing a new range of cements for skeletal applications. The work reported shows that GICs based on two different glasses, A and B (0.05CaO ⋅ 0.53ZnO ⋅ 0.42SiO₂ and 0.14CaO ⋅ 0.29ZnO ⋅ 0.57SiO₂, respectively), exhibited handling properties and flexural strengths comparable to conventional GICs. Upon immersion in simulated body fluid of a GIC based on glass B, an amorphous calcium phosphate layer nucleated on the surface of the cement indicating that these cements are bioactive in nature.     

Bond strength of experimental cyanoacrylate-modified dental glass ionomer cements

Glass ionomer cement (GIC) has been successfully used in dental field for more than 40 years. Despite numerous advantages of GIC, low bond strength and slow setting rate limited conventional GICs for use only at low stress-bearing areas. To improve bond strength to tooth, two kinds of cyanoacrylates such as ethyl 2-cyanoacrylate (EC) and allyl 2-cyanoacrylate (AC) were added in a commercial GIC. Changes in setting time of cyanoacrylate-modified GICs (CMGICs) according to the concentration of cyanoacrylates and/or p-toluene sulfonic acid (TSA) was investigated using a rheometer. Shear bond strength to human dentin was measured. Biocompatibility was determined by the viability of fibroblasts. Optimal concentrations for EC and TSA were 5–10% of the GIC powder and 30% of the GIC liquid, respectively. EC-based CMGIC showed twofold increase of initial bond strength compared with conventional GIC. Also, AC-based CMGIC showed three times higher bond strength and similar biocompatibility compared with the GIC. Therefore, CMGIC materials can be widely applied in dental adhesive restoration field because they showed improved bond strength and proper setting time.     

Influence of poly(acrylic acid) molar mass on the fracture properties of glass polyalkenoate cements

The failure behaviour of glass polyalkenoate cements was investigated using a linear elastic fracture mechanics (LEFM) approach. Cements were based on four model glasses with varying reactivity and four poly(acrylic acid)s (PAA)s with number average molar masses (Mn) ranging from 3.25 × 104 to 1.08 × 105. Cement properties were studied at time intervals of one, seven and twenty eight days. Compressive strengths (c) of the cements increased with increasing fluorine content of the glass, with increased molar mass of the PAA and with ageing time. The Young's moduli increased with time, but were lower for cements based on the fluorine free glass. Moduli values were independant of PAA molar mass. The un-notched fracture strength (f) of the cement increased with the molar mass of the PAA and with ageing time. Glass composition did not appreciably influence the un-notched fracture strength. The fracture toughness (KIC) increased with the molar mass of the PAA and with ageing time, but reduced with increasing fluorine content of the glass. The toughness (GIC) was dependant on molar mass. The influence of molar mass was not as great as predicted by the reptation chain pull-out model for fracture. The molar mass dependence of toughness was greatest with the lower fluorine content glasses. The plastic zone size at the crack tip increased with the molar mass of the PAA. However the plastic zone size decreased with ageing time for all the cements studied and was smaller for the more reactive higher fluorine content glasses.     

The effect of ultrasound on the uptake of fluoride by glass ionomer cements

Ultrasound has been shown to improve the set of glass ionomer cements (GICs) and also other cement properties. In particular, the release of fluoride is enhanced. These cements also can take up fluoride ion from liquids. The aim of this study is to investigate the effect of ultrasound on this cement property. Two commercial dental restorative GICs were used together with a modified commercial material and an experimental material based on a F-free glass. All three commercial materials came in capsules which were mixed as makers directed, the experimental material was mixed as in previous papers. Mixed cement was placed polyethylene moulds to create 3 × 2 mm thick discs. These were either allowed to standard set for 6 min or set with ultrasound for 55 s. 18 samples were made for each material/set. Three samples were placed in 4 ml of 0.2% NaF solution for 24 h at 37°C. The cylinders were removed and the F concentration of the solutions measured by ISE using TISAB decomplexant. F uptake was determined by difference from the original NaF concentration. The two conventional GICs showed reductions of 17.4 and 8.5% for ultrasound compared to standard set whereas the modified material increased by 32.3% and the experimental one by 20.6%. It is suggested that the effect of ultrasound may increase the surface area of the residual glass particles in the GIC which would increase F uptake. In GICs where considerable F ion is released into the cement matrix by the enhanced reaction caused by ultrasound this may be sufficient to reverse the former effect producing the reduced uptake observed.     

Post-irradiation hardness of resin-modified glass ionomer cements and a polyacid-modified composite resin

This study examined the post-irradiation hardness of resin-modified glass ionomer cements and a polyacid-modified composite resin using a digital microhardness tester. Change in hardness of these materials over a period of 6 months was compared to that of conventional glass ionomer cements and a composite resin. With the exception of the composite resin, all materials showed a significant increase in hardness over 24 h after their initial set. Dual-cure resin-modified glass ionomer cements showed decreased hardness with increased storage time in saline at 37°C. Results suggest that the addition of resins to glass ionomer cements does not improve initial hardness and does not negate the acid-base reaction of conventional cements. Resin addition may, however, lead to increased water sorption and decreased hardness.     

The role of aluminium and silicon in the setting chemistry of glass ionomer cements

A model of the setting chemistry of glass-ionomer cements (GICs) is proposed based on ²⁷Al and ²⁹Si solid state nuclear magnetic resonance spectroscopy data on three GICs. All the precursor glasses are found to contain three aluminium species viz.: four, five and six-coordinate aluminium environments as well as four-bridging silicate tetrahedra. Upon cement formation, Al³⁺ ions in the glass are leached out from the surface layer of the glass. On entering the cement matrix, these ions adopt six-coordination and crosslink the polymer chains as part of the setting reaction. The remaining four-coordinate aluminium is distributed between two species: one in the inert core of the glass particles; and a second, less concentrated, in the surface layer of the glass particles, modified by the curing reactions. There is some evidence for residual five and six coordinate aluminium species in the final cement in some of the systems. In the case of the silicate tetrahedra, the curing reactions result in a decrease in the number of aluminium atoms in the second coordination sphere, with a subsequent recondensation of silicate network of the glass.     

Antibacterial activity of four glass ionomer cements used in atraumatic restorative treatment

The in vitro antibacterial activity of four glass ionomer cements (Fuji IX, Ketac Molar, Vidrion R and Vitromolar) indicated for Atraumatic Restorative Treatment (ART) was studied against strains of bacteria involved in the development of oral diseases, Streptococcus mutans, Streptococcus sobrinus, Lactobacillus acidophilus and Actinomyces viscosus. The agar plate diffusion test was used for the cultures, which included chlorhexidine as a positive control. The results demonstrated that all the cements evaluated presented antibacterial activity. Based on the results of this study, it can be concluded that Fuji IX and Ketac Molar presented the most effective antibacterial activity considering the ART approach.     

Qualitative assessment of microstructure and Hertzian indentation failure in biocompatible glass ionomer cements

Discs of biocompatible glass ionomer cements were prepared for Hertzian indentation and subsequent fracture analyses. Specifically, 2 × 10 mm samples for reproducing bottom-initiated radial fracture, complemented by 0.2 × 1 mm samples for optimal resolution with X-ray micro tomography (μCT), maintaining dimensional ratio. The latter allowed for accurate determination of volumetric-porosity of the fully cured material, fracture-branching through three Cartesian axes and incomplete bottom-initiated cracking. Nanocomputed tomography analyses supported the reliability of the μCT results. Complementary 2-dimensional fractographic investigation was carried out by optical and scanning electron microscopies on the larger samples, identifying fracture characteristics. The combined 3-D qualitative assessment of microstructure and fractures, complemented by 2-D methods, provided an increased understanding of the mechanism of mechanical failure in these cements. Specifically, cracks grew to link pores while propagating along glass-matrix interfaces. The methodological development herein is exploitable on related biomaterials and represents a new tool for the rational characterisation, optimisation and design of novel materials for clinical service.     

Genotoxicity and cytotoxicity of glass ionomer cements on Chinese hamster ovary (CHO) cells

Glass ionomer cements are widely used in dentistry as restorative materials and adhesives for composite restorations. However, the results of genotoxicity studies using these materials are inconclusive in literature. The goal of this study was to examine the genotoxic and cytotoxic potential of three different glass ionomer cements available commercially (Ketac Cem, Ketac Molar and Vitrebond) by the single cell gel (comet) assay and trypan blue exclusion test, respectively. For this, such materials were exposed to Chinese hamster ovary (CHO) cells in vitro for 1 h at 37^∘C. Data were assessed by Kruskall-Wallis nonparametric test. The results showed that the powder from Ketac Molar displayed genotoxicity only in the maximum concentration evaluated (100 μg/mL). In the same way, the liquid from Vitrebond at 0.1% dilution caused an increase of DNA injury. Significant differences (P < 0.05) in cytotoxicity provoked by all powders tested of glass ionomer cements were observed for exposure at 1000 μg/mL concentration. With respect to liquids of glass ionomer cements evaluated, the major toxic effect on cell viability was produced at 10%, beginning at the dilution of 0.5% for Vitrebond. Taken together, we conclude that some components of glass ionomer cements show both genotoxic and cytotoxic effects.     

The role of glass composition in the behaviour of glass acetic acid and glass lactic acid cements

Cements have recently been described, made from glass ionomer glass reacted with acetic and lactic acid instead of polymeric carboxylic acid. From their behaviour a theory relating to a possible secondary setting mechanism of glass ionomer has been adduced. However, only one glass (G338) was used throughout. In this study a much simpler glass ionomer glass (MP4) was compared with G338. This produced very different results. With acetic acid G338 formed cement which became resistant to water over a period of hours, as previously reported, MP4 formed cement which was never stable to water. With lactic acid G338 behaved similarly to G338 with acetic acid, again as reported, but MP4 produced a cement which was completely resistant to water at early exposure and unusually became slightly less resistant if exposure was delayed for 6 h or more. These findings indicate that the theories relating to secondary setting in glass ionomer maturation may need revision.     

Influence of poly(acrylic acid) molar mass on the fracture properties of glass polyalkenoate cements based on waste gasifier slags

The failure behaviour of glass polyalkenoate cements was investigated using a linear elastic fracture mechanics (LEFM) approach. Cements were based on Drayton gasifier slag and four poly(acrylic acid)s with number average molar masses ranging from 3.03 × 10³ to 6.44 × 10⁴. Cement properties were studied at time intervals of one, seven and twenty eight days. Compressive and flexural strengths of the cements increased with increasing molar mass of the poly(acrylic acid)s and time. The Young's modulii increased with time and were independent of poly(acrylic acid) molar mass. Fracture toughness increased with increasing molar mass of the poly(acrylic acid)s. Fracture toughness increases over an ageing time of one week and subsequently decreased over one month. Toughness increased with poly(acrylic acid) molar mass, these increases being most pronounced at higher molar mass. The toughness values decreased with time for the higher molar mass cements, which is consistent with increased crosslinking of the poly(acrylic acid) chains and reducing molecular flow at the crack tip. Plastic zone size increased with poly(acrylic acid) molar mass and decreased with time for lower molar mass cements, remained constant for intermediate molar mass cements and increased with high molar mass cements.     

Influence of poly(acrylic acid) content on the fracture behaviour of glass polyalkenoate cements

A linear elastic fracture mechanics approach (LEFM) was used to study glass polyalkenoate cements as a function of the poly(acrylic acid) content. Cement specimens were tested at three time intervals after mixing; one, seven and twenty eight days. Two series of cements were investigated one with a glass volume fraction of 0.4 and the other with a glass volume fraction of 0.5. The fracture toughness, toughness, Young's modulus and un-notched fracture strength increased significantly with the percentage polyacid content. The Young's modulus increased with time for all the cement samples studied. In many cases the moduli values at twenty eight days were twice the values at one day. This is consistent with increased ionic crosslinking of the polyacrylate matrix. The toughness increased with the polyacid content as predicted by the chain pull-out model for fracture and did not change significantly on increasing the glass volume fraction from 0.4 to 0.5. Fracture toughness and Young's modulus increased significantly with glass volume fraction consistent with the residual glass particles acting as a reinforcing filler.