No / As the weakest zone in concrete, the interfacial transition zone (ITZ) between aggregates and cement mortars has important effects on the properties of concrete. This paper aims to investigate the effects and mechanisms of nanofillers on the bond strength and interfacial microstructures between aggregates and cement mortars. A total of 8 representative types of nanofillers (namely nano-SiO2, nano-TiO2, nano-ZrO2, untreated multi-walled carbon nanotubes (MWCNTs), hydroxyl-functionalized MWCNTs, nickel-coated MWCNTs, multi-layer graphenes (MLGs), and nano boron nitride (nano-BN)) were selected to fabricate specimens with scale-up aggregate-cement mortar interface that can be characterized by the three-point bend test. The experimental results indicate that all types of nanofillers can enhance the bond strength between aggregates and cement mortars. The highest relative/absolute increases of 2.1 MPa/35.1%, 2.32 MPa/38.8% and 2.56 MPa/42.8% in interfacial bond strength are achieved by incorporating 2 wt% of nano-ZrO2, 0.3 wt% of nickel-coated MWCNTs, and 0.3 wt% of nano-BN, respectively. Scanning electron microscope observations show the presence of nanofillers can improve hydration products and increase interfacial compactness. Energy dispersive spectrometer results suggest that local content of nanofillers in the ITZ is higher than that in the bulk cement mortars. These findings indicate the nanofillers can transfer with water migration toward aggregates and enrich in ITZ, thus improving the bond strength and interfacial microstructures between aggregates and cement mortars through the nano-core effect. / National Science Foundation of China (51978127 and 51578110), and the Fundamental Research Funds for the Central Universities in China(DUT18GJ203)

Yes / This study investigates the interfacial characteristics between aggregates and cement paste matrix in nanofillers modified concrete. A three-point bend test on the specimens composed of two pieces of aggregates bonded with a thin layer of cement pastes with/without nanofillers was carried out to characterize the interfacial bond strength of the composites. The scanning electron microscope observations and energy dispersive x-ray spectrometry analysis were also performed to characterize the interfacial microstructures and compositions of the composites. The experimental results indicated that the nanocomposites have higher interfacial bond strength and narrower interfacial transition zone thickness as well as more optimized intrinsic compositions and microstructures than that of composites without nanofillers. Specifically, the interfacial bond strength of nanocomposites can reach 7.67 MPa, which is 3.03 MPa/65.3% higher than that of composites without nanofillers. The interfacial transition zone thickness of nanocomposites ranges from 9 μm to 12 μm, while that of composites without nanofillers is about 18 μm. The ratio of CaO to SiO2 in the interface of composites without nanofillers is 0.69, and that of nanocomposites increases to 0.75–1.12. Meanwhile, the nanofiller content in nanocomposite interface is 1.65–1.98 times more than that in the bulk matrix. The interfacial microstructures of nanocomposites are more compact and the content and crystal size of calcium hydroxide were significantly reduced compared with that of composites without nanofillers. / The National Science Foundation of China (51978127 and 51908103), and the China Postdoctoral Science Foundation (2019M651116).

Os objetivos deste estudo foram comparar, através de análise de elementos finitos, a distribuição de tensões em modelos que representam arranjos experimentais nor-malmente utilizados em testes de cisalhamento e micro-cisalhamento, verificar a tendência de variar o local de início e o modo de fratura em função de mudanças nos parâmetros dos ensaios e analisar a influência de dois modos de fixação do substrato sobre a concentração de tensões. Os modelos bidimensionais em estado plano de deformações representaram o compósito (híbrido ou flow) aderido à dentina através de uma camada de adesivo de 50 μm. Duas condições de fixação da dentina foram estabelecidas: na primeira (mais rígida), os deslocamentos foram restritos em todas as direções nos nós das arestas que representam as três superfícies livres de adesão e na segunda, a restrição foi colocada apenas na parte posterior da dentina. Foi aplicado um carregamento pontual a várias distâncias da interface dentina-adesivo, de modo a obter um tensão nominal constante de 4MPa. Foram analisadas as tensões máximas de tração e cisalhamento, a distribuição das tensões ao longo dos nós da interface dentina-adesivo e os vetores de tensão máxima principal, como indicativos do local de início e o provável modo de fratura. A distribuição de tensões ao longo da interface aderida foi sempre não uniforme e apresentou picos muito ele-vados em todos os casos, o que conduz a pensar que os valores de resistência nominal não são representativos da máxima tensão suportada no momento da fratura. A tensão de tração predominou sobre a de cisalhamento. O módulo de elasticidade do compósito aderido, a espessura relativa da camada de adesivo e a distância de aplicação da carga influenciam a concentração de tensões e devem ser padroniza-dos. Para o teste de micro-cisalhamento, a camada de adesivo relativamente mais espessa e o uso do compósito com baixo módulo de elasticidade propiciaram a in-tensificação das tensões. O ensaio de cisalhamento parece mais suscetível que o de micro-cisalhamento para que o início da ruptura ocorra no substrato, pois o ponto de maior concentração de tensões localizou-se na dentina em alguns casos e verifica-se pequena diferença de módulo entre os maiores vetores localizados no adesivo e na dentina de base. O teste de micro-cisalhamento, embora mais favorável a que as fraturas se iniciem no adesivo, concentra muito a tensão, especialmente com a utili-zação de resinas do tipo flow, o que o torna menos representativo da máxima tensão que o espécime realmente resistiu no momento da fratura. / The objectives of this study were to compare the stress distribution in finite element models that represented experimental designs commonly used for shear and micro-shear bond strength testing, to verify the tendency to vary the location and mode of fracture as a consequence of changes in the studied parameters, and to analyze the influence of two substrate restriction conditions on stress concentration. Bi-dimensional plane strain models represented a composite (hybrid or flow) bonded to dentin through a 50 μm adhesive layer. Two dentin restriction conditions were estab-lished: in the first (more rigid), movements were restricted in all directions on the nodes located in the dentin surface edges free of adhesion, and in the second, re-striction was imposed only to the posterior dentin surface. Concentrated loading was applied at several distances from the dentin-adhesive interface so as to obtain con-stant nominal bond strength of 4MPa. Maximum tensile and shear stress values, stress distribution along the dentin-adhesive interfacial nodes and the principal maximum stress vectors as indicative of the most probable location and mode of frac-ture were analyzed. Stress distribution along bonded interfaces was always non-uniform and presented very high stress peaks for all cases. This led to the assump-tion that nominal bond strength values are non-representative of the maximum stress supported at fracture. Tensile stresses were always predominant over shear stresses. The composite elastic modulus, relative adhesive layer thickness and different load application distances influenced stress concentration and should be stan-dardized. For micro-shear tests, the relatively thicker adhesive layer and use of a low modulus composite propitiated stress intensification. The shear test seems to be more susceptible than micro-shear to fracture initiation in the substrate, once the point of highest stress concentration was in some cases located in dentin, and small modulus difference was verified between the greatest stress vectors located both on the adhesive and dentin base. Although more favorable to fracture initiation in the adhesive, the micro-shear test design highly concentrated stresses, especially when flow composite was modeled, hence it might be less representative of the maximum stress the specimen resisted at fracture.

This in vitro study was conducted to evaluate the influence of surface treatments on the bond strength between an yttrium-stabilized tetragonal zirconia polycrystal (Y-TZP) ceramic and resin cement. For this purpose, 120 Y-TZP blocks (IPS e.max® ZirCAD in inLab®) were randomly distributed into 12 experimental groups (n = 10), according to six surface treatment strategies and two storage conditions (24 hours post cementation and after 60 days in water and 10,000 thermocicles): AS (as sintered, no treatment); TBS (tribochemical silica coating followed by silanization); AAP (particle abrasion with 50 μm aluminum oxide followed by application of Monobond®Plus); FS (fusion sputtering); SN (5 nm SiO2 nanofilm deposition and silanization) and FSSN (FS + SN). The Y-TZP blocks were embedded in acrylic resin and cylinders of resin cement (Ø=0.96 mm x 1 mm in height) (RelyX ARC) were built up on the ceramic surface. After the storage, the specimens were submitted to microshear test (μSBS) (1 mm/min) in a universal testing machine. After testing, the surfaces were analyzed with a stereomicroscope and scanning electron microscope (SEM) in order to categorize the failure modes. One additional specimen per surface treatment strategy was analyzed by X-ray diffraction, for phases content, and by SEM for micromorphology observation. Bond strength values were statistically analyzed by Kruskal-Wallis and Mann Whitney tests for surface treatments (p <0.001) and aging factor (p <0.05). In both storage conditions, TBS and AAP provided higher bond strength values, followed by FSSN, FS and SN groups. The aging negatively influenced the results, with one exception for the FS. An increase in the amount of monoclinic phase was observed in the abraded groups. Sandblasting of alumina particles followed by application of a primer with MPA is as effective as the tribochemical treatment combined with silane for pretreatment of the Y-TZP surface, with respect to the bond strength to the composite. / No presente trabalho objetivou-se avaliar, in vitro, o efeito de diferentes tratamentos de superfície na resistência de união de uma cerâmica à base de zircônia policristalina tetragonal estabilizada por ítria (Y-TZP) a um cimento resinoso. Para tanto, 120 blocos de Y-TZP (IPS e.max® ZirCAD for inLab®, Ivoclar-Vivadent, Schaan, Liechtenstein) foram distribuídos randomicamente em 12 grupos experimentais (n=10), conforme 6 estratégias de tratamento de superfície e 2 condições de envelhecimento (24 horas e após o envelhecimento em água e termociclagem): AS (sem tratamento); TBS (jateamento de partículas de alumina revestidas por sílica e silanização); AAP (abrasão com partículas de alumina seguida da aplicação de primer universal); FS (pulverização de micropartículas de zircônia na superfície livre da Y-TZP e após, fusão por sinterização); SN (deposição de nanofilme de sílica com 5 nm) e FSSN (FS seguido de SN). Os blocos de Y-TZP foram embutidos em resina acrílica e microcilindros de cimento resinoso (0,96 mm de diâmetro; 1 mm de altura) (RelyX ARC) foram confeccionados na superfície cerâmica. Após o armazenamento, os testes de microcisalhamento foram conduzidos a uma velocidade de 1 mm/min, em máquina de ensaios universal. Após o teste, as superfícies foram analisadas com estereomicroscópio e microscópio eletrônico de varredura (MEV) para caracterização das falhas. Em um espécime adicional, também foi conduzida análise de fases do material por difração de raios-X e caracterização da micromorfologia de superfície em MEV. Os valores de resistência de união foram submetidos aos testes estatísticos Kruskal-Wallis e Mann Whitney para os tratamentos testados (p<0.001) e para o fator envelhecimento (p<0.05). Em ambas as condições de envelhecimento, TBS e AAP proporcionaram os maiores valores de resistência adesiva, seguidos dos grupos FSSN, FS e SN. O envelhecimento influenciou negativamente os resultados, com única exceção para o FS. A difractometria revelou aumento de conteúdo monoclínico nos grupos jateados. FS não alterou a percentagem de fase monoclínica. O jateamento de partículas de alumina seguido da aplicação de um primer com MPA apresentou-se tão efetivo quanto o tratamento triboquímico aliado ao silano, para o pré-tratamento da superfície da Y-TZP, no que diz respeito à resistência de união ao compósito.

Os objetivos deste estudo foram comparar, através de análise de elementos finitos, a distribuição de tensões em modelos que representam arranjos experimentais nor-malmente utilizados em testes de cisalhamento e micro-cisalhamento, verificar a tendência de variar o local de início e o modo de fratura em função de mudanças nos parâmetros dos ensaios e analisar a influência de dois modos de fixação do substrato sobre a concentração de tensões. Os modelos bidimensionais em estado plano de deformações representaram o compósito (híbrido ou flow) aderido à dentina através de uma camada de adesivo de 50 &#956;m. Duas condições de fixação da dentina foram estabelecidas: na primeira (mais rígida), os deslocamentos foram restritos em todas as direções nos nós das arestas que representam as três superfícies livres de adesão e na segunda, a restrição foi colocada apenas na parte posterior da dentina. Foi aplicado um carregamento pontual a várias distâncias da interface dentina-adesivo, de modo a obter um tensão nominal constante de 4MPa. Foram analisadas as tensões máximas de tração e cisalhamento, a distribuição das tensões ao longo dos nós da interface dentina-adesivo e os vetores de tensão máxima principal, como indicativos do local de início e o provável modo de fratura. A distribuição de tensões ao longo da interface aderida foi sempre não uniforme e apresentou picos muito ele-vados em todos os casos, o que conduz a pensar que os valores de resistência nominal não são representativos da máxima tensão suportada no momento da fratura. A tensão de tração predominou sobre a de cisalhamento. O módulo de elasticidade do compósito aderido, a espessura relativa da camada de adesivo e a distância de aplicação da carga influenciam a concentração de tensões e devem ser padroniza-dos. Para o teste de micro-cisalhamento, a camada de adesivo relativamente mais espessa e o uso do compósito com baixo módulo de elasticidade propiciaram a in-tensificação das tensões. O ensaio de cisalhamento parece mais suscetível que o de micro-cisalhamento para que o início da ruptura ocorra no substrato, pois o ponto de maior concentração de tensões localizou-se na dentina em alguns casos e verifica-se pequena diferença de módulo entre os maiores vetores localizados no adesivo e na dentina de base. O teste de micro-cisalhamento, embora mais favorável a que as fraturas se iniciem no adesivo, concentra muito a tensão, especialmente com a utili-zação de resinas do tipo flow, o que o torna menos representativo da máxima tensão que o espécime realmente resistiu no momento da fratura. / The objectives of this study were to compare the stress distribution in finite element models that represented experimental designs commonly used for shear and micro-shear bond strength testing, to verify the tendency to vary the location and mode of fracture as a consequence of changes in the studied parameters, and to analyze the influence of two substrate restriction conditions on stress concentration. Bi-dimensional plane strain models represented a composite (hybrid or flow) bonded to dentin through a 50 &#956;m adhesive layer. Two dentin restriction conditions were estab-lished: in the first (more rigid), movements were restricted in all directions on the nodes located in the dentin surface edges free of adhesion, and in the second, re-striction was imposed only to the posterior dentin surface. Concentrated loading was applied at several distances from the dentin-adhesive interface so as to obtain con-stant nominal bond strength of 4MPa. Maximum tensile and shear stress values, stress distribution along the dentin-adhesive interfacial nodes and the principal maximum stress vectors as indicative of the most probable location and mode of frac-ture were analyzed. Stress distribution along bonded interfaces was always non-uniform and presented very high stress peaks for all cases. This led to the assump-tion that nominal bond strength values are non-representative of the maximum stress supported at fracture. Tensile stresses were always predominant over shear stresses. The composite elastic modulus, relative adhesive layer thickness and different load application distances influenced stress concentration and should be stan-dardized. For micro-shear tests, the relatively thicker adhesive layer and use of a low modulus composite propitiated stress intensification. The shear test seems to be more susceptible than micro-shear to fracture initiation in the substrate, once the point of highest stress concentration was in some cases located in dentin, and small modulus difference was verified between the greatest stress vectors located both on the adhesive and dentin base. Although more favorable to fracture initiation in the adhesive, the micro-shear test design highly concentrated stresses, especially when flow composite was modeled, hence it might be less representative of the maximum stress the specimen resisted at fracture.

This thesis reports on the research outcome of corrosion mechanism and corrosion rate of mild steel in different environments (saline, alkaline solutions and concrete media) using potentiodynamic polarization technique. The study also included the effect of corrosion on bond strength between reinforcing steel and concrete using pull-out test. Corrosion of mild steel and 316L stainless steel with different surface conditions in 1, 3 and 5% saline (NaCl + Distilled water) was investigated. Specimens ground with 200 and 600 grit silicon carbide grinding paper as well as 1μm surface finish (polished with 1μm diamond paste) were tested. In case of mild steel specimens, reduction in surface roughness caused increase in corrosion rate, while in 316L stainless steel corrosion rate decreased as the surface roughness improved. Metallographic examination of corroded specimens confirmed breakdown of passive region due to pitting corrosion. Corrosion of mild steel was also investigated in alkaline solution (saturated calcium hydroxide, pH =12.5) contaminated with 1, 3 and 5% saline. A series of corrosion experiments were also conducted to examine the efficiency of various concentrations of calcium nitrite (CN) on corrosion behaviour of both as-received and polished mild steel in alkaline solution containing 3% saline after 1 hour and 28 days of exposure. Corrosion rate was higher for the as-received than polished mild steel surface under the same testing conditions in NaCl alkaline solution with and without nitrites due to the effect of surface roughness. Morphology investigation of mild steel specimens in alkaline solution ii containing chlorides and nitrites showed localized pits even at nitrite concentration equal to chloride concentration. Corrosion of steel bars embedded in concrete having compressive strengths of 20, 30 and 46MPa was also investigated. The effect of 2 and 4% CN by weight of cement on corrosion behaviour of steel bar in low and high concrete strengths specimens were also studied. All reinforced concrete specimens were immersed in 3% saline solution for three different periods of 1, 7 and 15 days. In order to accelerate the chemical reactions, an external current of 0.4A was applied. Corrosion rate was measured by retrieving electrochemical information from polarization tests. Pull-out tests of reinforced concrete specimens were then conducted to assess the corroded steel/concrete bond characteristics. Experimental results showed that corrosion rate of steel bars and bond strength were dependent on concrete strength, amount of CN and acceleration corrosion period. As concrete strength increased from 20 to 46MPa, corrosion rate of embedded steel decreased. First day of corrosion acceleration showed a slight increase in steel/concrete bond strength, whereas severe corrosion due to 7 and 15 days corrosion acceleration significantly reduced steel/concrete bond strength. Addition of only 2% CN did not give corrosion protection for steel reinforcement in concrete with 20MPa strength at long time of exposure. However, the combination of good quality concrete and addition of CN appear to be a desirable approach to reduce the effect of chloride induced corrosion of steel reinforcement. At less time of exposure, specimens without CN showed higher bond strength in both concrete mixes than those with CN. After 7 days of corrosion acceleration, the higher concentration of CN gave higher bond strength in both concrete mixes. The same trend was observed at 15 days of corrosion acceleration except for the specimen with 20MPa compressive strength and 2% CN which recorded the highest deterioration in bond strength.

The thermochemistry of several species, and the kinetics of various H atom radical reactions relevant to atmospheric and combustion chemistry were investigated using ab initio theoretical techniques and the flash photolysis / resonance fluorescence technique. Using ab initio quantum mechanical calculations up to the G3 level of theory, the C-H bond strengths of several alkanes were calculated. The bond strengths were calculated using two working reactions. From the results, it is apparent that the bond strengths decrease as methyl groups are added to the central carbon. The results are in good agreement with recent experimental halogenation kinetic studies. Hydrogen bond strengths with sulfur and oxygen were studied via CCSD(T) theory, together with extrapolation to the complete basis set limit. The results for the bond dissociation energies (ground state at 0 K, units: kJ mol-1) are: S-H = 349.9, S-D = 354.7, HS-H = 376.2, DS-D = 383.4, and HO-H = 492.6. These data compare well with experimental literature. The rate constants for the isotopic reactions of H + H2S, D + H2S, H + D2S, and D + D2S are studied at the QCISD(T)/6-311+G(3df,2p) level of theory. The contributions of the exchange reaction versus abstraction are examined through transition state theory. The energy of NS was computed via CCSD(T) theory, together with extrapolation to the complete basis set limit. The results were employed with three working reactions to find ΔfH0(NS) = 277.3 ± 2 kJ mol-1 and ΔfH298(NS) = 278.0 ± 2 kJ mol-1. This thermochemistry is consistent with, but much more precise than, earlier literature values. A kinetic study of the reaction of H + CH2CCl2 was conducted over the temperature range of 298 - 680 K. The reaction was found to be pressure dependent and results of the rate constants and their interpretation via unimolecular rate theory are presented.

Purpose: To compare the in-vitro shear bond strengths of a new paste-paste formulation of resin-modified glass-ionomer cement (Rm-GIC) to an exising powder-liquid formulation. The study will test the hypothesis that the new paste-paste formulation of Rm-GIC (Fuji-Cem ™, GC Corp, Tokyo, Japan) has the same bond strength as an existing popular powder-liquid formulation of Rm-GIC (Rely-X ™ Luting Cement, 3M, St. Paul, MN)Materials and Methods: A total of 33 human molars were sectioned parallel to the occlusal surface to expose mid-coronal dentin and mounted parallel to the bond shearing device on the universal testing machine (Instron). For Group I samples (Rely-X, n=15), the powder and liquid were measured and adjusted to achieve a ratio of 1.6 and mixed for 30 seconds as recommended by the manufacturer. For Group II (Fuji-Cem, n=18), the paste-paste was expressed from the paste-dispenser provided by the manufacturer and mixed for 10 seconds as recommended. After testing, the teeth from group II were bonded on a different site with the same material but mixed for 20 seconds (n=18). To ensure a uniform flow and bond surface area, the mixed cement was syringed into a cylindrical mould (diameter 2.38mm, height 2mm) and allowed to set under constant force. All samples were subjected to fracture by shear loading on a universal testing machine (Instron) at a uniform crosshead speed of .02" per minute and expressed as MPa. Values were analyzed at the pResults: Wilcoxon rank sums test showed significantly higher shear bond strength values for Rely-X compared to Fuji-Cem mixed both at 10 seconds and 20 seconds. Mixing for 20 seconds resulted in stronger bonds for Fuji-Cem compared to 10 seconds, but was still significantly lower than Rely-X.Conclusions: Within the limitations of the study, the Rely-X powder-liquid formula shows a significantly stronger dentin shear bond strength when compared to the new paste-paste formula of resin-modified glass ionomer cement, Fuji-Cem.

The purpose of the current study was to develop a bonding method that can achieve clinically acceptable bond strength values while leaving a minimum amount of adhesive on the tooth surface during the debonding process. One hundred teeth were randomly assigned into groups. Five different enamel surface preparation protocols were tested (N = 20, each): Conventional acid etch, standard SEP, SEP applied with a light brush stroke (altered SEP 1), SEP applied directly to the composite of pre-coated bracket (altered SEP 2), and Primer Only groups. Brackets were debonded using an Instron universal testing machine (Instron, Canton, MA) in shear mode and the mean shear bond strength values were calculated. In addition, enamel surfaces were examined under light microscope to determine the location of failure using ARI. The Primer Only group had significantly lower mean shear strength (0.14 MPa, P0.05). With respect to ARI values, there was a significant difference among these four groups. 85% of samples in the altered SEP 2 group had 10% or less composite resin left on their surfaces. This group had also a mean shear bond strength value of 11.43 MPa, significantly above the minimal strength needed for orthodontic attachment bonding, and the lowest ARI values overall. Therefore, application of SEP directly to the composite resin of the pre-coated brackets may be an ideal bonding method by providing adequate bond strength and leaving a minimum amount of composite resin on the tooth surface during debonding. It should be kept in mind that future in-vivo studies would be needed to confirm the findings obtained from the current in-vitro study.

Statement of problem. Clinicians have used disinfection materials to remove surface contaminants during cavity preparation. It has been postulated that disinfection materials may negatively affect shear bond strength of restorative materials. If so, large numbers of restorations may be predestined for early failure with the use of a disinfection protocol.Purpose. To determine whether there is a difference in the bond strength between dentin and composite resin with a 3-step disinfection technique compared to a conventional bonding technique without the additional disinfection protocol.Material and Methods. Sixty human molar teeth were sectioned parallel to the occlusal surface to expose mid-coronal dentin and mounted parallel to a bond shearing device on a universal testing machine (Instron) and randomly divided into 2 groups. In Group I (n=30), specimens were treated with chlorhexidine, tubulicid red, and sodium hypochlorite before dentin bonding, following the manufacturer's instructions for All Bond 2. In Group II (n=30), specimens were treated only with the bonding protocol of All Bond 2. To ensure a uniform bond surface area, core paste was syringed into a cylindrical mold (diameter 2.38mm, height 2.00mm) that was in contact with the dentin bonding surface of each specimen, and allowed to set under constant force. All specimens were subjected to fracture by shear loading in a universal testing machine (Instron) at a uniform crosshead speed of 0.02 inch per minute and expressed as MPa. Statistical analysis, using nonpaired student's t-test, was performed. Results. A statistically-significant higher shear bond strength was found for the 3-step disinfection group (mean shear bond strength, 25.3; STD, 4.6) compared to the conventional bonding group (mean shear bond strength, 20.5, STD, 3.4) (PConclusions. The 3-step disinfection technique group showed a significantly stronger dentin shear bond strength compared to the conventional bonding technique without disinfection.