Self-assembled healable materials through a combination of pi-pi stacking and hydrogen bonding

The discovery of polymers with stimuli responsive physical properties is a rapidly expanding area of research. At the forefront of the field are self-healing polymers, which, when fractured can regain the mechanical properties of the material either autonomically, or in response to a stimulus. It has long been known that it is possible to promote healing in conventional thermoplastics by heating the fracture zone above the Tg of the polymer under pressure. This process requires reptation and subsequent re-entanglement of macromolecules across the fracture void, which serves to bridge, and ‘heal’ the crack. The timescale for this mechanism is highly dependent on the molecular weight of the polymer being studied. This process is in contrast to that required to affect healing in supramolecular polymers such as the plasticised, hydrogen bonded elastomer reported by Leibler et al. The disparity in bond energies between the non-covalent and covalent bonds within supramolecular polymers results in fractures propagating through scission of the comparatively weak supramolecular interactions, rather than through breaking the stronger, covalent bonds. Thus, during the healing process the macromolecules surrounding the fracture site only need sufficient energy to re-engage their supramolecular interactions in order to regenerate the strength of the pristine material. Herein we describe the design, synthesis and optimization of a new class of supramolecular polymer blends that harness the reversible nature of pi-pi stacking and hydrogen bonding interactions to produce self-supporting films with facile healable characteristics.

HIGH STRENGTH CONCRETE: THE REINFORCED CONCRETE OF THE CENTURY 21(ST)

This work is about the 21st century reinforced concrete analysis under the point of view of its constituent materials. First of all it is described the theoretical approach of the bending elements calculated based on the Norms BAEL 91 standarts. After that, numerical load-displacement are presented from reinforced concrete beams and plates validated by experimental data. The numerical modellings has been carried on in the program CASTEM 2000. In this program a elastoplastic model of Drucker-Prager defines the rupture surface of the concrete in non associative plasticity. The crack is smeared on the Gauss points of the finite elements with formation criterion starting from the definition of the rupture surface in the branch traction-traction of the Rankine model. The reinforcements were modeled in a discrete approach with perfect bond. Finally, a comparative analysis is made between the numerical results and calculated criteria showing the future of high performance reinforced concrete in this beginning of 21st century.

Effect of disinfection by microwave irradiation on the strength of intact and relined denture bases and the water sorption and solubility of denture base and reline materials

This study evaluated the influence of microwave disinfection on the strength of intact and relined denture bases. Water sorption and solubility were also evaluated. A heat-polymerized acrylic resin (Lucitone 550) was used to construct 4-mm-thick (n = 40) and 2-mm-thick (n = 160) denture bases. Denture bases (2mm) were relined with an autopolymerizing resin (Tokuso Rebase Fast, Ufi Gel Hard, Kooliner, or New Truliner). Specimens were divided into four groups (n = 10): without treatment, one or seven cycles of microwave disinfection (650 W for 6 min), and water storage at 37 degrees C for 7 days. Specimens were vertically loaded (5 mm/min) until failure. Disc-shaped specimens (50 min x 0.5 mm) were fabricated (n = 10) to evaluate water sorption and solubility. Data on maximum fracture load (N), deflection (%), and solubility (%) were analyzed by two-way analysis of variance and Student-Newman-Keuls tests (alpha = 0.05). One cycle of microwave disinfection decreased the deflection at fracture and fracture energy of Tokuso Rebase Fast and New Truliner specimens. The strength of denture bases microwaved daily for 7 days was similar to the strength of those immersed in water for 7 days. Microwave disinfection increased the water sorption of all materials and affected the solubility of the reline materials. (C) 2007 Wiley Periodicals, Inc.

Evaluation of the Cohesive Strength Between Resin Composite and Light-curing Characterizing Materials

Purpose: To evaluate the cohesive strength between composite and different light-curing characterizing materials (LCCM), which were prepared using the intrinsic technique.Materials and Methods: One hundred composite specimens were made by using a prefabricated Teflon device, and a layer of LCCM was applied at the interface. The specimens were divided into 5 groups (n = 20): group 1 (control), no LCCM was used; group 2: application of White Kolor Plus Pigment (Kerr) LCCM; group 3: White Tetric Color Pigment (Ivoclar/Vivadent) LCCM; group 4: Brown Kolor Plus Pigment (Kerr) LCCM; group 5: Black Tetric Color Pigment (Ivoclar/Vivadent) LCCM. All materials were used according to the manufacturers' instructions. Specimens were submitted to a tensile test in a universal testing machine (EMIC DL-200MF) to evaluate the cohesive strength at the composite interface. Data were subjected to one-way ANOVA and Tukey's test (alpha = 5%).Results: ANOVA showed a p-value = 0.0001, indicating that there were significant differences among the groups. The mean values in MPa (+/- standard deviation) obtained for the groups were: G1: 28.5 (+/-2.74)a; G2: 23.5 (+/-2.47)b; G3: 20.3 (+/-2.49)b; G4: 10.5 (+/-2.40)c; G5: 9.66 (+/-3.06)c. The groups with the same letters presented no significant differences. The control group presented statistically significantly higher cohesive strengths when compared to the other groups. The groups in which Brown Kolor Plus Pigment and Black Tetric Color Pigment LCCM were used showed significantly lower cohesive strengths when compared to the groups in which White Kolor Plus Pigment and White Tetric Color Pigment LCMM were used.Conclusion: The use of LCCM produced with the intrinsic technique reduced the cohesive strength of composite.

The effect of adhesive systems on the pullout strength of a fiberglass-reinforced composite post system in bovine teeth

Purpose: To evaluate the pullout strength of a glass fiber-reinforced composite post (glass FRC) cemented with three different adhesive systems and one resin cement. The null hypothesis was that pullout strengths yielded by the adhesive systems are similar. Materials and Methods: Thirty bovine teeth were selected. The size of the specimens was standardized at 16 mm by sectioning off the coronal portion and part of the root. The specimens were divided into three groups, according to the adhesive system, which were applied following the manufacturers' instructions: G1, ScotchBond Multi-Purpose Plus; G2, Single Bond; G3, Tyrian SPE/One-Step Plus. The glass FRCs (Reforpost) were etched with 37% H3PO4 for 1 min and silanized (Porcelain Primer). Thereafter, they were cemented with the dual resin cement En-Force. The specimens were stored for 24 h, attached to an adapted device, and submitted to the pullout test in a universal testing machine (1 mm/min). The data were submitted to the one-way ANOVA and Tukey's test (α = 0.05). Results: G1 (30.2 ± 5.8 Kgf) displayed the highest pullout strength (p < 0.001) when compared to G2 (18.6 ± 5.8 Kgf) and G3 (14.3 ± 5.8 Kgf), which were statistically similar. Analysis of the specimens revealed that all failures occurred between the adhesive system and the root dentin (pullout of the post cement), regardless of group. Conclusion: The multiple-bottle, total-etch adhesive system provided higher pullout strength of the glass FRC when compared to the single-bottle, total-etch, and single-step self-etching adhesive systems. The null hypothesis was rejected (p < 0.001).

Alkali activated materials based on fluid catalytic cracking catalyst residue (FCC): Influence of SiO2/Na2O and H 2O/FCC ratio on mechanical strength and microstructure

Reuse of industrial and agricultural wastes as supplementary cementitious materials (SCMs) in concrete and mortar productions contribute to sustainable development. In this context, fluid catalytic cracking catalyst residue (spent FCC), a byproduct from the petroleum industry and petrol refineries, have been studied as SCM in blended Portland cement in the last years. Nevertheless, another environmental friendly alternative has been conducted in order to produce alternative binders with low CO2 emissions. The use of aluminosilicate materials in the production of alkali-activated materials (AAMs) is an ongoing research topic which can present low CO2 emissions associated. Hence, this paper studies some variables that can influence the production of AAM based on spent FCC. Specifically, the influence of SiO 2/Na2O molar ratio and the H2O/spent FCC mass ratio on the mechanical strength and microstructure are assessed. Some instrumental techniques, such as SEM, XRD, pH and electrical conductivity measurements, and MIP are performed in order to assess the microstructure of formed alkali-activated binder. Alkali activated mortars with compressive strength up to 80 MPa can be formed after curing for 3 days at 65°C. The research demonstrates the potential of spent FCC to produce alkali-activated cements and the importance of SiO2/Na2O molar ratio and the H2O/spent FCC mass ratio in optimising properties and microstructure. © 2013 Elsevier Ltd. All rights reserved.

Compressive strength of esthetic restorative materials polymerized with quartz-tungsten-halogen light and blue LED

Este estudo comparou a resistência à compressão de uma resina composta e de um compômero, fotoativados com luz halógena convencional de quarto-tungstênio (QTH) (XL 300, 3M/SPE) e LED azul (SmartLite PS; Dentsply/De Trey). Foram confeccionados 40 espécimes em forma de disco usando uma matriz bipartida de politetrafluoretileno (4,0 mm de diâmetro x 8,0 mm de altura) em que o material foi inserido incrementalmente. O tempo de polimerização de cada incremento foi de 40 s para a luz halógena convencional e de 10 s para o LED. Os espécimes foram aleatoriamente alocados em 4 grupos (n=10), de acordo com a fonte de luz e com o material restaurador. Depois de armazenadas em água destilada a 37°C ± 2°C por 24 h, a resistência à compressão dos espécimes foi testada em uma máquina universal de ensaios com célula de carga de 500 kgf a uma velocidade de carregamento de 0,5 mm/min. Os dados (em MPa) foram analisados estatisticamente por ANOVA e teste de Student-Newman-Keuls (p<0,05). Para a resina composta, a fotopolimerização com luz halógena não produziu diferença estatisticamente significante (p>0,05) em sua resistência à compressão quando comparada à fotopolimerização com LED. Contudo, a fotopolimerização do compômero com a luz halógena resultou em uma resistência à compressão significativamente maior que a feita o LED (p>0,05). A resina composta apresentou resistência à compressão significativamente maior que a do compômero, independente da fonte de luz. Concluiu-se que a resistência à compressão dos materiais fotopolimerizados com luz halógena e LED foi influenciada pela densidade de energia empregada e pela composição química dos materiais restauradores estéticos.

Modeling and simulations of some anisotropic soft-matter systems: from biaxial to chiral materials

We have modeled various soft-matter systems with molecular dynamics (MD) simulations. The first topic concerns liquid crystal (LC) biaxial nematic (Nb) phases, that can be possibly used in fast displays. We have investigated the phase organization of biaxial Gay-Berne (GB) mesogens, considering the effects of the orientation, strength and position of a molecular dipole. We have observed that for systems with a central dipole, nematic biaxial phases disappear when increasing dipole strength, while for systems characterized by an offset dipole, the Nb phase is stabilized at very low temperatures. In a second project, in view of their increasing importance as nanomaterials in LC phases, we are developing a DNA coarse-grained (CG) model, in which sugar and phosphate groups are represented with Lennard-Jones spheres, while bases with GB ellipsoids. We have obtained shape, position and orientation parameters for each bead, to best reproduce the atomistic structure of a B-DNA helix. Starting from atomistic simulations results, we have completed a first parametrization of the force field terms, accounting for bonded (bonds, angles and dihedrals) and non-bonded interactions (H-bond and stacking). We are currently validating the model, by investigating stability and melting temperature of various sequences. Finally, in a third project, we aim to explain the mechanism of enantiomeric discrimination due to the presence of a chiral helix of poly(gamma-benzyl L-glutamate) (PBLG), in solution of dimethylformamide (DMF), interacting with chiral or pro-chiral molecules (in our case heptyl butyrate, HEP), after tuning properly an atomistic force field (AMBER). We have observed that DMF and HEP molecules solvate uniformly the PBLG helix, but the pro-chiral solute is on average found closer to the helix with respect to the DMF. The solvent presents a faster isotropic diffusion, twice as HEP, also indicating a stronger interaction of the solute with the helix.

The Role of Hydrogen Bond in Designing Molecular Optical Materials

In this perspective article, we revise some of the empirical and semi-empirical strategies for predicting how hydrogen bonding affects molecular and atomic polarizabilities in aggregates. We use p-nitroaniline and hydrated oxalic acid as working examples to illustrate the enhancement of donor and acceptor functional-group polarizabilities and their anisotropy. This is significant for the evaluation of electrical susceptibilities in crystals; and the properties derived from them like the refractive indices.

Multi-criteria selection of structural adhesives to bond ABS parts obtained by rapid prototyping

One of the most used methods in rapidprototyping is Fused Deposition Modeling (FDM), which provides components with a reasonable strength in plastic materials such as ABS and has a low environmental impact. However, the FDM process exhibits low levels of surface finishing, difficulty in getting complex and/or small geometries and low consistency in “slim” elements of the parts. Furthermore, “cantilever” elements need large material structures to be supported. The solution of these deficiencies requires a comprehensive review of the three-dimensional part design to enhance advantages and performances of FDM and reduce their constraints. As a key feature of this redesign a novel method of construction by assembling parts with structuraladhesive joints is proposed. These adhesive joints should be designed specifically to fit the plastic substrate and the FDM manufacturing technology. To achieve this, the most suitable structuraladhesiveselection is firstly required. Therefore, the present work analyzes five different families of adhesives (cyanoacrylate, polyurethane, epoxy, acrylic and silicone), and, by means of the application of technical multi-criteria decision analysis based on the analytic hierarchy process (AHP), to select the structuraladhesive that better conjugates mechanical benefits and adaptation to the FDM manufacturing process