A study on mitigating the effect of sulphates in lime stabilised Cochin marine clays

Soft clays known for their high compressibility, low stiffness and low shear strength are always associated with large settlement. In place soil treatment using calcium-based stabilizers like lime and cement is a feasible solution to readdress strength deficiencies and problematic shrink/swell behaviour of unstable subgrade soils. Out of these, lime has been proved unambiguously as the most effective and economical stabilising agent for marine clays. Lime stabilisation creates long-term chemical changes in unstable clay soils to create strong, but flexible, permanent structural layers in foundations and other pavement systems. Even though calcium-based stabilizers can improve engineering properties of soft clays, problems can arise when they are used in soils rich in sulphates. It is possible for marine clays to be enriched with sulphates, either by nature or due to the discharge of nearby industrial wastes containing sulphates. The presence of sulphates is reported to adversely affect the cation exchange and pozzolanic reactions of cement and lime treated soil systems. The anions of sulphates may combine with the available calcium and alumina, and form insoluble ettringite in the soil system. Literature on sulphate attack in lime treated marine clays reports that formation of ettringite in lime-sodium sulphate-clay system is capable of adversely affecting the engineering behavior of marine clays. Only very few studies have been conducted on soft marine clays found along the coastal belt of Kerala and that too, is limited to Cochin marine clays. The studies conducted also have the limitation that the strength behaviour of lime stabilised clay was investigated only for one year. Practically no data pertaining to long term adverse effects likely to be brought about by sulphates on the strength and compressibility characteristics of Cochin marine clays is available. The overriding goal of this investigation was thus to examine the effectiveness of lime stabilisation in Cochin marine clays under varying sulphate contents. The study aims to reveal the changes brought about by varying sulphate contents on both physical and engineering properties of these clays stabilised by lime and the results for various curing periods up to two years is presented in this thesis. Quite often the load causing an unacceptable settlement may be less than the load required to cause shear failure and therefore attempt has been made in this research to highlight sulphate induced changes in both the compressibility and strength characteristics of lime treated Cochin marine clays. The study also aimed at comparing the available IS methods for sulphate quantification and has attempted to determine the threshold level of sulphate likely make these clays vulnerable by lime stabilisation. Clays used in this study were obtained from two different sites in Kochi and contained sulphate in two different concentrations viz., 0.5% and 0.1%. Two different lime percentages were tried out, 3% and 6%. Sulphate content was varied from 1% to 4% by addition of reagent grade sodium sulphate. The long term influence of naturally present sulphate is also investigated. X-ray diffraction studies and SEM studies have been undertaken to understand how the soil-lime reactions are affected in the presence of sodium sulphate. Natural sulphate content of 0.1% did not seem to have influenced normal soil lime reactions but 0.5% sulphate could induce significant changes adversely in both compressibility and strength behaviour of lime treated clays after long duration. Compressibility is seen to increase drastically with increasing sulphate content suggesting formation of ettringite on curing for longer periods. Increase in compression index and decrease in bond strength with curing period underlined the adverse effects induced in lime treated marine clays by the presence of sulphates. Presence of sulphate in concentrations ranging from 0.5 % to 4% is capable of adversely affecting the strength of lime treated marine clays. Considerable decrease is observed with increasing concentrations of sulphate. Ettringite formation due to domination of sodium ions in the system was confirmed in mineralogical studies made. Barium chloride and barium hydroxide is capable of bringing about beneficial changes both in compressibility and strength characteristics of lime treated Cochin marine clays in the presence of varying concentrations of sulphate and is strongly influenced by curing time. Clay containing sodium sulphate has increased strength values when either of barium compounds was used with lime ascompared with specimens treated with lime only. Barium hydroxide is observed to remarkably increase the strength as compared to barium chloride,when used in conjunction with lime to counteract the effect of sulphate.

Density functional energy decomposition into one- and two-atom contributions

The present work provides a generalization of Mayer's energy decomposition for the density-functional theory (DFT) case. It is shown that one- and two-atom Hartree-Fock energy components in Mayer's approach can be represented as an action of a one-atom potential VA on a one-atom density ρ A or ρ B. To treat the exchange-correlation term in the DFT energy expression in a similar way, the exchange-correlation energy density per electron is expanded into a linear combination of basis functions. Calculations carried out for a number of density functionals demonstrate that the DFT and Hartree-Fock two-atom energies agree to a reasonable extent with each other. The two-atom energies for strong covalent bonds are within the range of typical bond dissociation energies and are therefore a convenient computational tool for assessment of individual bond strength in polyatomic molecules. For nonspecific nonbonding interactions, the two-atom energies are low. They can be either repulsive or slightly attractive, but the DFT results more frequently yield small attractive values compared to the Hartree-Fock case. The hydrogen bond in the water dimer is calculated to be between the strong covalent and nonbonding interactions on the energy scale

Bond durability in erbium:yttrium-aluminum-garnet laser-irradiated enamel

This study sought to evaluate the influence of thermocycling and water storage on the microtensile bond strength of composite resin bonded to erbium:yttrium-aluminum-garnet (Er:YAG)-irradiated and bur-prepared enamel. Eighty bovine incisors were selected and sectioned. Specimens were ground to produce a flat enamel surface. Samples were randomly assigned according to cavity preparation device: (I) Er:YAG laser and (II) high-speed turbine, and were subsequently restored with composite resin. They were subdivided according to the duration of water storage (WS)/number of thermocycles (TCs): 24 h WS/no TCs; 7 days WS/500 TCs; 1 month WS/2,000 TCs; 6 months WS/12,000 TCs. The teeth were sectioned into 1.0 mm(2)-thick slabs and subjected to tensile stress in a universal testing machine. Data were submitted to two-way analysis of variance (ANOVA) and Tukey`s test at a 0.05 significance level. The different periods of water storage and thermocycling did not influence the microtensile bond strength (A mu TBS) values in the Er:YAG laser-prepared groups. In bur-prepared enamel, the group submitted to 12,000 TCs/6 months` WS (IID) showed a significant decrease in bond strength values when compared to the group stored in water for 24 h and not submitted to thermocycling (IIA), but values were statistically similar to those obtained in all Er:YAG laser groups and in the bur- prepared groups degraded with 500 TCs/1 week WS (IIB) or 2,000 TCs/1 month WS (IIC). It may be concluded that adhesion of an etch-and-rinse adhesive to Er:YAG laser-irradiated enamel was not affected by the methods used to simulate degradation of the adhesive interface and was similar to adhesion in the bur-prepared groups in all periods of water storage and thermocycling.

Supramolecular Approach to Gold Nanoparticle/Triruthenium Cluster Hybrid Materials and Interfaces

A systematic and comprehensive study of the interaction of citrate-stabilized gold nanoparticles with triruthenium cluster complexes of general formula [Ru(3)(CH(3)COO)(6)(L)](+) [L = 4-cyanopyridine (4-CNpy), 4,4`-bipyridine (4,4`-bpy) or 4,4`-bis(pyridyl)ethylene (bpe)] has been carried out. The cluster-nanoparticle interaction in solution and the construction of thin films of the hybrid materials were investigated in detail by electronic and surface plasmon resonance (SPR) spectroscopy, Raman scattering spectroscopy and scanning electron microscopy (SEM). Citrate-stabilized gold nanoparticles readily interacted with [Ru(3)O(CH(3)COO)(6)(L)(3)](+) complexes to generate functionalized nanoparticles that tend to aggregate according to rates and extents that depend on the bond strength defined by the characteristics of the cluster L ligands following the sequence bpe > 4,4`-bpy >> 4-CNpy. The formation of compact thin films of hybrid AuNP/[Ru(3)O(CH(3)COO)(6)(L)(3)](+) derivatives with L = bpe and 4,4`-bpy indicated that the stability/lability of AuNP-cluster bonds as well as their solubility are important parameters that influence the film contruction process. Fluorine-doped tin oxide electrodes modified with thin films of these nanomaterials exhibited similar electrocatalytic activity but much higher sensitivity than a conventional gold electrode in the oxidation of nitrite ion to nitrate depending on the bridging cluster complex, demonstrating the high potential for the development of amperometric sensors.

Pt monolayer electrocatalysts for O-2 reduction: PdCo/C substrate-induced activity in alkaline media

We measured the activity of electrocatalysts, comprising Pt monolayers deposited on PdCo/C substrates with several Pd/Co atomic ratios, in the oxygen reduction reaction in alkaline solutions. The PdCo/C substrates have a core-shell structure wherein the Pd atoms are segregated at the particle`s surface. The electrochemical measurements were carried out using an ultrathin film rotating disk-ring electrode. Electrocatalytic activity for the O-2 reduction evaluated from the Tafel plots or mass activities was higher for Pt monolayers on PdCo/C compared to Pt/C for all atomic Pd/Co ratios we used. We ascribed the enhanced activity of these Pt monolayers to a lowering of the bond strength of oxygenated intermediates on Pt atoms facilitated by changes in the 5d-band reactivity of Pt. Density functional theory calculations also revealed a decline in the strength of PtOH adsorption due to electronic interaction between the Pt and Pd atoms. We demonstrated that very active O-2 reduction electrocatalysts can be devised containing only a monolayer Pt and a very small amount of Pd alloyed with Co in the substrate.

Analysis of the effects of irradiation in osseointegrated dental implants

Objective: The purpose of the present study was to evaluate the influence of radiation in osseointegrated dental implants installed in tibiae of rats.Material and methods: Screw-shaped implants (2.5 mm diameter by 3.5 mm length) were custom made from commercially pure titanium bars. Titanium implants were blasted and sterilized before implantation. Animals were divided into two groups of 12 animals each and the rats were not paired after the groups' formation. The experimental group (group 1) received external irradiation 4 weeks after surgery while in the control group (group 2) animals were kept free of radiation. The shear strength required to detach the implant from bone was measured by push-out testing and osseointegration was histologically evaluated.Results: Results showed that the compressive strength of irradiated implants (33.49 MPa) was significantly lower than the compressive strength of non-irradiated implants (48.05 MPa).Conclusions: We concluded that the mechanical strength bonding between implants and host tissues decreased after irradiation.

Bonding strength between a hard chairside reline resin and a denture base material as influenced by surface treatment

Direct relining of dentures made with hard chairside reline resins is faster than laboratory-processed reline systems and the patient is not without the prosthesis for the time necessary to perform the laboratory procedures. However, a weak bond between the autopolymerizing acrylic reline resins and the denture base material has been observed. This study evaluated the effect of six different surface treatments on the bond strength between a hard chairside reline acrylic resin and ia heat-cured acrylic resin. Specimens of the heat-cured acrylic resin were divided into seven groups. one of these groups remained intact. In the other groups, a 10-mm square section was removed from the centre of each specimen. The bonding surfaces were then treated with (i) methyl methacrylate monomer, (ii) isobutyl methacrylate monomer, (iii) chloroform, (iv) acetone, (v) experimental adhesive and (vi) no surface treatment-control group. Kooliner acrylic resin was packed,into the square sections and polymerized. The bonding strength was evaluated by a three-point loading test. The results were submitted to one-way analysis of variance (ANOVA) followed by a Tukey multiple range test at a 5% level of significance. No significant difference was found between the surface treatment with Lucitone 550 monomer or chloroform, but both were stronger than the majority of the other groups. The bond strength provided by all the surface treatments was lower than that of the intact heat-cured resin.

THE EFFECT of IMMEDIATE DENTIN SEALING on THE MARGINAL ADAPTATION and BOND STRENGTHS of TOTAL-ETCH and SELF-ETCH ADHESIVES

Statement of problem. Sealing ability and bond strengths of total-etch and self-etch dentin adhesives used for immediate dentin sealing have not been assessed and established.Purpose. The purpose of this study was to determine the effectiveness of immediate dentin sealing (IDS) using total-etch or self-etch dentin adhesives on microleakage and microtensile bond strength.Material and methods. Twenty recently extracted molars were selected, and standard MOD inlay preparations were made with the gingival margins located below the cemento-enamel unction. The teeth were assigned to 4 experimental groups (n=5) according to the indirect composite restoration cementation technique used: (1) immediate dentin sealing with Adper Single Bond (TEBI); (2) conventional adhesive cementation technique using Adper Single Bond (TEAI); (3) immediate dentin sealing using Adper Prompt L-Pop (SEBI); or (4) conventional adhesive cementation technique using Adper Prompt L-Pop (SEAI). The restored teeth were thermal cycled 1,000 times between 5 degrees and 55 degrees C and then immersed in 50% ammoniacal silver nitrate. Three specimens per restoration were evaluated for microleakage, according to predefined scores, and submitted to Friedman's test (alpha-.05). The specimens were then sectioned to obtain 0.8 +/- 0.2-mm-thick sticks (with n ranging from 32 to 57 specimens) and submitted to microtensile bond strength (mu TBS) testing. The obtained data were submitted to 2-way ANOVA test (alpha=.05).Results. None of the experimental groups demonstrated complete elimination of marginal microleakage. There were significant differences in microleakage of the tested adhesives (P>.001). IDS microleakage scores were similar to those obtained using the conventional cementation technique (CCT) for both adhesives. The highest mean bond strengths were obtained with TEBI (51.1 MPa), whereas SEAI showed the lowest mean bond strengths (1.7 MPa). IDS resulted in significantly higher bond strengths than CCT (P<.001).Conclusions. Total-etch and self-etch adhesives have a significant effect on IDS. IDS resulted in high bond strengths for both adhesives; however, the microleakage was similar to that obtained with CCT (J Prosthet Dent 2009;102:1-9)

Effect of Airborne-Particle Abrasion and Mechanico-Thermal Cycling on the Flexural Strength of Glass Ceramic Fused to Gold or Cobalt-Chromium Alloy

Purpose: To evaluate the effect of airborne-particle abrasion and mechanico-thermal cycling on the flexural strength of a ceramic fused to cobalt-chromium alloy or gold alloy.Materials and Methods: Metallic bars (n = 120) were made (25 mm x 3 mm x 0.5 mm): 60 with gold alloy and 60 with Co-Cr. At the central area of the bars (8 mm x 3 mm), a layer of opaque ceramic and then two layers of glass ceramic (Vita VM13, Vita Zahnfabrick) were fired onto it (thickness: 1 mm). Ten specimens from each alloy group were randomly allocated to a surface treatment [(tungsten bur or air-particle abrasion (APA) with Al(2)O(3) at 10 mm or 20 mm away)] and mechanico-thermal cycling (no cycling or mechanically loaded 20,000 cycles; 10 N distilled water at 37 degrees C and then thermocycled 3000 cycles; 5 degrees C to 55 degrees C, dwell time 30 seconds) combination. Those specimens that did not undergo mechanico-thermal cyclingwere stored inwater (37 degrees C) for 24 hours. Bond strength was measured using a three-point bend test, according to ISO 9693. After the flexural strength test, failure types were noted. The data were analyzed using three factor-ANOVA and Tukey's test (alpha = 0.05).Results: There were no significant differences between the flexural bond strength of gold and Co-Cr groups (42.64 +/- 8.25 and 43.39 +/- 10.89 MPa, respectively). APA 10 and 20 mm away surface treatment (45.86 +/- 9.31 and 46.38 +/- 8.89 MPa, respectively) had similar mean flexural strength values, and both had significantly higher bond strength than tungsten bur treatment (36.81 +/- 7.60 MPa). Mechanico-thermal cycling decreased the mean flexural strength values significantly for all six alloy-surface treatment combinations tested when compared to the control groups. The failure type was adhesive in the metal/ceramic interface for specimens surface treated only with the tungsten bur, and mixed for specimens surface treated with APA 10 and 20 mm.Conclusions: Considering the levels adopted in this study, the alloy did not affect the bond strength; APA with Al(2)O(3) at 10 and 20 mm improved the flexural bond strength between ceramics and alloys used, and the mechanico-thermal cycling of metal-ceramic specimens resulted in a decrease of bond strength.

Does Adhesive Resin Application Contribute to Resin Bond Durability on Etched and Silanized Feldspathic Ceramic?

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Durability of Microtensile Bond to Nonetched and Etched Feldspar Ceramic: Self-adhesive Resin Cements vs Conventional Resin

Purpose: The objective of this study was to evaluate the effect of thermocycling (TC), self-adhesive resin cements and surface conditioning on the microtensile bond strength (mu TBS) between feldspathic ceramic blocks and resin cements.Materials and Methods: Fifty-six feldspathic ceramic blocks (10 x 7 x 5 mm) (Vita Mark II) were divided into groups according to the factors "resin cement" (3 cements) and "surface conditioning" (no conditioning or conditioning [10% hydrofluoric acid etching for 5 min + silanization]) (n = 8): group 1: conditioning+Variolink II (control group); group 2: no conditioning+Biscem; group 3: no conditioning+RelyX U100; group 4: no conditioning+Maxcem Elite; group 5: conditioning+Biscem; group 6: conditioning+RelyX U100; group 7: conditioning+Maxcem Elite. The ceramic-cement blocks were sectioned to produce non-trimmed bar specimens (adhered cross-sectional area: 1 +/- 0.1 mm(2)), which were divided into two storage conditions: dry, mu TBS immediately after cutting; TC (12,000x, 5 degrees C/55 degrees C). Statistical significance was deterimined using two-way ANOVA (7 strategies and 2 storage conditions) and the post-hoc Tukey test (p<0.05).Results: Resin cement and thermocycling affected the mu TBS significantly (p = 0.001). In the dry condition, group 5 (18 +/- 6.5 MPa) presented the lowest values of mu TBS when compared to the other groups. TC decreased the mean mu TBS values significantly (p<0.05) for all resin cements tested (9.7 +/- 2.3 to 22.1 +/- 6.3 MPa), except for the resin cement RelyX U100 (22.1 +/- 6.3 MPa). In groups 3 and 4, it was not possible to measure mu TBS, since these groups had 100% pre-test failures during sectioning. Moreover, the same occurred in group 2 after TC, where 100% failure was observed during thermocycling (spontaneous failures).Conclusion: Hydrofluoric acid etching and silanization of the feldspathic ceramic surface are essential for bonding self-adhesive resin cement to a feldspathic ceramic, regardless of the resin cement used. Non-etched ceramic is not recommended.

Opaque Layer Firing Temperature and Aging Effect on the Flexural Strength of Ceramic Fused to Cobalt-Chromium Alloy

Purpose: To evaluate the effect of the opaque layer firing temperature and mechanical and thermal cycling on the flexural strength of a ceramic fused to commercial cobalt-chromium alloy (Co-Cr). The hypotheses were that higher opaque layer temperatures increase the metal/ceramic bond strength and that aging reduces the bond strength.Materials and Methods: Metallic frameworks (25 x 3 x 0.5 mm(3); ISO 9693) (N = 60) were cast in Co-Cr and airborne-particle abraded (Al(2)O(3): 150 mu m) at the central area of the frameworks (8 x 3 mm(2)) and divided into three groups (N = 20), according to the opaque layer firing temperature: Gr1 (control)-900 degrees C; Gr2-950 degrees C; Gr3-1000 degrees C. The opaque ceramic (Opaque, Vita Zahnfabrick, Bad Sackingen, Germany) was applied, and the glass ceramic (Vita Omega 900, Vita Zahnfabrick) was fired onto it (thickness: 1 mm). While half the specimens from each group were randomly tested without aging (water storage: 37 degrees C/24 hours), the other half were mechanically loaded (20,000 cycles; 50 N load; distilled water at 37 degrees C) and thermocycled (3000 cycles; 5 degrees C to 55 degrees C, dwell time: 30 seconds). After the flexural strength test, failure types were noted. The data were analyzed using 2-way ANOVA and Tukey's test (alpha = 0.05).Results: Gr2 (19.41 +/- 5.5 N) and Gr3 (20.6 +/- 5 N) presented higher values than Gr1 (13.3 +/- 1.6 N) (p = 0.001). Mechanical and thermal cycling did not significantly influence the mean flexural strength values (p > 0.05). Increasing the opaque layer firing temperature improved the flexural bond strength values (p < 0.05). The hypotheses were partially accepted.Conclusion: Increasing of the opaque layer firing temperature improved the flexural bond strength between ceramic fused to Co-Cr alloy.

Microtensile bond strengths and scanning electron microscopic evaluation of self-adhesive and self-etch resin cements to intact and etched enamel

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Effects of Resinous Monomers Used in Restorative Dental Modeling on the Cohesive Strength of Composite Resin

Purpose: The purpose of this study was to evaluate the cohesive strength of the composite using different resinous monomers to lubricate instruments used in the Restorative Dental Modeling Insertion Technique (RDMIT).Materials and Methods: The composite specimens were made by using a prefabricated Teflon device. Different resinous monomers were used at the interface to lubricate the instruments, for a total of 72 specimens divided into 6 groups: 1. control group, no resinous monomer was used; 2. Composite Wetting Resin; 3. C & B Liquid; 4. Scotchbond Multi-Purpose Adhesive; 4. Adper Single Bond Adhesive; 6. Prime & Bond NT. Specimens were submitted to the circular area tensile test to evaluate the cohesive strength at the composite interfaces. Data were analyzed using ANOVA and Tukey's test (alpha = 0.05).Results: ANOVA showed a value of p < 0.0001, which indicated that there were significant differences among the groups. The means (SD) for the different groups were: Adper Single Bond Adhesive: 26 (12) a; control group: 28 (3) ab; Prime & Bond NT: 32 (12) ab; Composite Wetting Resin: 36 (9) abc; C&B Liquid: 38 (7) bc; Scotchbond Multi-Purpose Adhesive: 46 (10) c. Groups denoted with the same letters were not significantly different. Only Scotchbond Multi-Purpose Adhesive, used for direct restorations, had a statistically significantly higher bond strength than the control group, Adper Single Bond Adhesive, and Prime & Bond NT. Adper Single Bond with Adhesive showed a statistically significantly lower mean value than C & B Liquid.Conclusion: The results of this study indicate that the resinous monomers used for lubricating the instruments in the RDMIT did not alter the mechanical properties of the composite, and therefore did not reduce the cohesive bond strength at the composite interfaces.

Effect of silica coating combined to a MDP-based primer on the resin bond to Y-TZP ceramic

The aim of this study was to evaluate the influence of silica coating and 10-methacryloyloxydecyl dihydrogen phosphate (MDP)-based primer applications upon the bonding durability of a MDP-based resin cement to a yttrium stabilized tetragonal zirconia (Y-TZP) ceramic. Ninety-six Y-TZP tabs were embedded in an acrylic resin (free surface for adhesion: 5 x 5 mm(2)), ground finished and randomly divided into four groups (N = 24) according to the ceramic surface conditioning: (1) cleaning with isopropanol (ALC); (2) ALC + phosphoric acid etching + MDP-based primer application (MDP-primer); (3) silica coating + 3-methacryloyloxypropyl trimethoxysilane (MPS)-based coupling agent application (SiO(2) + MPS-Sil); and (4) SiO(2) + MDP-primer. The MDP-based resin cement was applied on the treated surface using a cylindrical mold (diameter=3 mm). Half of the specimens from each surface conditioning were stored in distilled water (37 C, 24 h) before testing. Another half of the specimens were stored (90 days) and thermo-cycled (12,000x) during this period (90d/TC) before testing. A shear bond strength (SBS) test was performed at a crosshead speed of 0.5 mm/min. Two factors composed the experimental design: ceramic conditioning strategy (in four levels) and storage condition (in two levels), totaling eight groups. After 90d/TC (Tukey; p < 0.05), SiO(2) + MDP-primer (24.40 MPa) promoted the highest SBS. The ALC and MDP-primer groups debonded spontaneously during 90d/TC. Bonding values were higher and more stable in the SiO2 groups. The use of MDP-primer after silica coating increased the bond strength. (C) 2010 Wiley Periodicals, Inc. J Biomed Mater Res Part 8: Appl Biomater 95B: 69-74, 2010.