Phthalate mediated hydrogelation of a pyrene based system: a novel scaffold for shape-persistent, self-healing luminescent soft material

Two-component super-hydrogelation triggered by the acid-base interaction of a L-histidine appended pyrenyl derivative (PyHis) and phthalic acid (PA) was reported. The use of isomeric isophthalic or terephthalic acid or other comparable acids in place of PA does not lead to salt formation and therefore hydrogelation is not observed. Excimer formation of the pyrenyl unit has not been detected although the PyHis : PA = 1: 1 system undergoes extensive self-assembly in aqueous solution. The synergistic effect of intermolecular H-bonding forces, pi-pi stacking, electrostatic interactions, etc. is found to be responsible for robust hydrogel formation. Development of chiral supramotecular assemblies has been verified through circular dichroism spectroscopy. Morphological investigations involving the PyHis : PA = 1: 1 system show vesicular nano-structures with a definite bilayer width at relatively low concentrations. The latter fuses to construct coiled-coil left-handed helical fibers upon increase in the concentrations of the gelators. The intertwining of the resultant helical fibers eventually results in hydrogel formation. The probable bilayer packing in the self-assembled structures has been probed using X-ray diffraction (XRD) studies and lanthanide sensitization, which suggests that the polar imidazolium hydrogen phthalate unit of the gelator forms the head group and faces the hydrophilic water environment while the hydrophobic pyrenyl units sit inside the hydrophobic core of the bilayer. The hydrogel exhibits multi-stimuli responsiveness including thixotropic behavior. In addition, shape-persistent as well as rapid self-healing behaviour of the hydrogel was established. Furthermore load-bearing characteristics of the hydrogel have also been demonstrated.

Novel architecture for anomalous strengthening of a particulate filled polymer matrix composite

We propose an architecture for dramatically enhancing the stress bearing and energy absorption capacities of a polymer based composite. Different weight fractions of iron oxide nano-particles (NPs) are mixed in a poly(dimethylesiloxane) (PDMS) matrix either uniformly or into several vertically aligned cylindrical pillars. These composites are compressed up to a strain of 60% at a strain rate of 0.01 s(-1) following which they are fully unloaded at the same rate. Load bearing and energy absorption capacities of the composite with uniform distribution of NPs increase by similar to 50% upon addition of 5 wt% of NPs; however, these properties monotonically decrease with further addition of NPs so much so that the load bearing capacity of the composite becomes 1/6th of PDMS upon addition of 20 wt% of NPs. On the contrary, stress at a strain of 60% and energy absorption capacity of the composites with pillar configuration monotonically increase with the weight fraction of NPs in the pillars wherein the load bearing capacity becomes 1.5 times of PDMS when the pillars consisted of 20 wt% of NPs. In situ mechanical testing of composites with pillars reveals outward bending of the pillars wherein the pillars and the PDMS in between two pillars, located along a radius, are significantly compressed. Reasoning based on effects of compressive hydrostatic stress and shape of fillers is developed to explain the observed anomalous strengthening of the composite with pillar architecture.

Twinning induced enhancement of fracture toughness in ultrafine grained Hydroxyapatite-Calcium Titanate composites

Despite being highly bioactive and biocompatible, the limitations of monolithic hydroxyapatite (HA) include extremely low fracture toughness, poor electrical conductivity. While addressing these issues, the present study demonstrates how CaTiO3 (CT) addition to HA can be utilized to obtain a combination of long crack fracture toughness (1.7 MPa m(1/2) SEVNB technique) and flexural strength of 98-155 MPa (3-point bending) and a moderate tensile strength (diametral compression) of 17-36 MPa. The enhancement in fracture resistance in spark plasma sintered HA-CT composites has been explained in reference to the observed twin morphology. TEM reveals the presence of twins in CT grains due to 1800 rotation about 101]. The measured properties along with our earlier reports on biocompatibility and electrical properties make HA-CT suitable for bone tissue engineering applications. When compared with other competing HA-based biocomposites, HA-CT composites are found to have a better combination of properties useful for medium load bearing implant applications. (C) 2015 Elsevier Ltd. All rights reserved.

Wear Studies of Hydroxyapatite Composite Coating Reinforced by Carbon Nanotubes

Multi-walled carbon nanotubes (CNTs) have been successfully introduced into hydroxyapatite (HA) coatings using laser surface alloying. It is evident from transmission electron microscopy (TEM) observations that the CNTs present in the matrix still keep their multi-walled cylinder graphic structure, although they undergo the laser irradiation. Scratching test results indicated that the as-alloyed HA composite coatings exhibit improved wear resistance and lower friction coefficient with increasing the amount of CNTs in the precursor material powders. These composites have potential applications in the field of coating materials for metal implants under high-load-bearing conditions. (c) 2006 Elsevier Ltd. All rights reserved.

Characteristics of the interface of a laser-quenched steel substrate and chromium electroplate

The interface of a laser-discrete-quenched steel substrate and as-deposited chromium electroplate was investigated by ion beam etching, dissolving-substrate-away and using a Vickers microhardness tester, in an attempt to reveal the mechanism that the service life of the chromium-coated parts is increased by the duplex technique of laser pre-quenching plus chromium post-depositing. The laser quenching of the steel substrate can reduce the steep hardness gradient at the substrate/chromium interface and improve the load-bearing capacity of chromium electroplate. Moreover, the laser quenching prior to plating has an extremely great effect on the morphologies and microstructure of the substrate/chromium interface: there is a transient interlayer at the original substrate/chromium interface while there is not at the laser-quenchedzone/chromium interface; the near-substrate surface microstructure and morphologies of the free-standing chromium electrodeposits, whose substrate was dissolved away with nital 30% in volume, inherit the periodically gradient characteristics of the laser-discrete-quenched substrate surface. (c) 2006 Elsevier B.V. All rights reserved.

Critério estatístico para obtenção de valores de NSPT para previsão da capacidade de carga de estacas por métodos semi empíricos.

Uma das tarefas mais desafiadoras do engenheiro na área da Geotecnia é a escolha dos valores de parâmetros geotécnicos obtidos de ensaios de campo ou laboratório e que serão utilizados nos modelos analíticos ou numéricos na fase de projeto de fundações. Diante das incertezas inerentes aos ensaios de SPT e da heterogeneidade de abordagens para a utilização dos valores de NSPT, é proposta neste estudo, a aplicação de um critério estatístico para obtenção de valores de NSPT, a partir da construção de intervalos de confiança de 95% de probabilidade em torno da reta ajustada de regressão linear simples entre a variável aleatória NSPT e a profundidade. Os valores obtidos de NSPT pelo critério aplicado foram utilizados na previsão da capacidade de carga de 19 estacas isoladas a partir da utilização de três métodos semi-empíricos: Aoki-Velloso (1975) com coeficientes alterados por Monteiro (1997), Décourt & Quaresma (1978) alterado pelo método de Décourt (1996) e Método de Alonso (1996). As cargas de ruptura dessas 19 estacas ensaiadas através de Provas de Carga Estática foram obtidas pelos métodos de extrapolação de Van Der Veen (1953) e Décourt (1996) e serviram para comparação e consequente validação do critério estatístico. Adicionalmente, com fulcro no item 6.2.1.2.1 da ABNT NBR 6122:2010 Resistência calculada por método semi-empírico, foram avaliados os fatores de segurança em relação às cargas de projeto, inclusive, também se utilizando da premissa de reconhecimento de regiões representativas, levando em conta o número de ensaios de SPT executados, fato que promove uma diminuição da incerteza dos parâmetros, apontando a um menor fator de segurança. A dissertação enfatiza as vantagens de um adequado tratamento estatístico dos parâmetros geotécnicos, a exemplo da recomendação já existente nas normas internacionais como Eurocódigo e outras. O critério construído permite e encoraja análises e decisões racionais no universo das partes interessadas consumidores, projetistas, fiscais de obras, contratantes e comunidade científica promovendo as discussões de forma mais objetiva e harmoniosa sobre o tema.

Dynamic properties of superconducting magnetic bearings

The potential use of YBa2j as an active component in a magnetic bearing is being investigated. Although the load bearing capacity is high and increases with the square of the magnetic field trapped, the stiffness is low. Both the stiffness and the lévitation height are a function of the loading history of the bearing. At Cambridge we have been investigating the effects of dynamic loading such as single large excursions from steady state loads and cyclically applied loads such as vibrations. Since a superconducting bearing has little inherent damping cyclic loads applied at or near its natural frequency can have catastrophic effects. The information being gathered at Cambridge will be used to enable these effects to be mitigated in the bearing design process. © 1997 IEEE.

Real Time Concrete Damage Visual Assessment for First Responders

First responders are in danger when they perform tasks in damaged buildings after earthquakes. Structural collapse due to the failure of critical load bearing structural members (e.g. columns) during a post-earthquake event such as an aftershock can make first responders victims, considering they are unable to assess the impact of the damage inflicted in load bearing members. The writers here propose a method that can provide first responders with a crude but quick estimate of the damage inflicted in load bearing members. Under the proposed method, critical structural members (reinforced concrete columns in this study) are identified from digital visual data and the damage superimposed on these structural members is detected with the help of Visual Pattern Recognition techniques. The correlation of the two (e.g. the position, orientation and size of a crack on the surface of a column) is used to query a case-based reasoning knowledge base, which contains apriori classified states of columns according to the damage inflicted on them. When query results indicate the column's damage state is severe, the method assumes that a structural collapse is likely and first responders are warned to evacuate.

Machine Vision Enhanced Post-Earthquake Inspection and Rapid Loss Estimation

Manual inspection is required to determine the condition of damaged buildings after an earthquake. The lack of available inspectors, when combined with the large volume of inspection work, makes such inspection subjective and time-consuming. Completing the required inspection takes weeks to complete, which has adverse economic and societal impacts on the affected population. This paper proposes an automated framework for rapid post-earthquake building evaluation. Under the framework, the visible damage (cracks and buckling) inflicted on concrete columns is first detected. The damage properties are then measured in relation to the column's dimensions and orientation, so that the column's load bearing capacity can be approximated as a damage index. The column damage index supplemented with other building information (e.g. structural type and columns arrangement) is then used to query fragility curves of similar buildings, constructed from the analyses of existing and on-going experimental data. The query estimates the probability of the building being in different damage states. The framework is expected to automate the collection of building damage data, to provide a quantitative assessment of the building damage state, and to estimate the vulnerability of the building to collapse in the event of an aftershock. Videos and manual assessments of structures after the 2009 earthquake in Haiti are used to test the parts of the framework.

Fibre optic installation techniques for pile instrumentation

An innovative technique based on optical fibre sensing that allows continuous strain measurement has recently been introduced in structural health monitoring. Known as Brillouin Optical Time-Domain Reflectometry (BOTDR), this distributed optical fibre sensing technique allows measurement of strain along the full length (up to 10km) of a suitably installed optical fibre. Examples of recent implementations of BOTDR fibre optic sensing in piles are described in this paper. Two examples of distributed optical fibre sensing in piles are demonstrated using different installation techniques. In a load bearing pile, optical cables were attached along the reinforcing bars by equally spaced spot gluing to measure the axial response of pile to ground excavation induced heave and construction loading. Measurement of flexural behaviour of piles is demonstrated in the instrumentation of a secant piled wall where optical fibres were embedded in the concrete by simple endpoint clamping. Both methods have been verified via laboratory works. © 2009 IOS Press.

Failure mechanisms in fibrous scaffolds.

Polymeric fibrous scaffolds have been considered as replacements for load-bearing soft tissues, because of their ability to mimic the microstructure of natural tissues. Poor toughness of fibrous materials results in failure, which is an issue of importance to both engineering and medical practice. The toughness of fibrous materials depends on the ability of the microstructure to develop toughening mechanisms. However, such toughening mechanisms are still not well understood, because the detailed evolution at the microscopic level is difficult to visualize. A novel and simple method was developed, namely, a sample-taping technique, to examine the detailed failure mechanisms of fibrous microstructures. This technique was compared with in situ fracture testing by scanning electron microscopy. Examination of three types of fibrous networks showed that two different failure modes occurred in fibrous scaffolds. For brittle cracking in gelatin electrospun scaffolds, the random network morphology around the crack tip remained during crack propagation. For ductile failure in polycaprolactone electrospun scaffolds and nonwoven fabrics, the random network deformed via fiber rearrangement, and a large number of fiber bundles formed across the region in front of the notch tip. These fiber bundles not only accommodated mechanical strain, but also resisted crack propagation and thus toughened the fibrous scaffolds. Such understanding provides insight for the production of fibrous materials with enhanced toughness.

Composite electrospun gelatin fiber-alginate gel scaffolds for mechanically robust tissue engineered cornea.

A severe shortage of good quality donor cornea is now an international crisis in public health. Alternatives for donor tissue need to be urgently developed to meet the increasing demand for corneal transplantation. Hydrogels have been widely used as scaffolds for corneal tissue regeneration due to their large water content, similar to that of native tissue. However, these hydrogel scaffolds lack the fibrous structure that functions as a load-bearing component in the native tissue, resulting in poor mechanical performance. This work shows that mechanical properties of compliant hydrogels can be substantially enhanced with electrospun nanofiber reinforcement. Electrospun gelatin nanofibers were infiltrated with alginate hydrogels, yielding transparent fiber-reinforced hydrogels. Without prior crosslinking, electrospun gelatin nanofibers improved the tensile elastic modulus of the hydrogels from 78±19 kPa to 450±100 kPa. Stiffer hydrogels, with elastic modulus of 820±210 kPa, were obtained by crosslinking the gelatin fibers with carbodiimide hydrochloride in ethanol before the infiltration process, but at the expense of transparency. The developed fiber-reinforced hydrogels show great promise as mechanically robust scaffolds for corneal tissue engineering applications.

Composite electrospun gelatin fiber-alginate gel scaffolds for mechanically robust tissue engineered cornea

A severe shortage of good quality donor cornea is now an international crisis in public health. Alternatives for donor tissue need to be urgently developed to meet the increasing demand for corneal transplantation. Hydrogels have been widely used as scaffolds for corneal tissue regeneration due to their large water content, similar to that of native tissue. However, these hydrogel scaffolds lack the fibrous structure that functions as a load-bearing component in the native tissue, resulting in poor mechanical performance. This work shows that mechanical properties of compliant hydrogels can be substantially enhanced with electrospun nanofiber reinforcement. Electrospun gelatin nanofibers were infiltrated with alginate hydrogels, yielding transparent fiber-reinforced hydrogels. Without prior crosslinking, electrospun gelatin nanofibers improved the tensile elastic modulus of the hydrogels from 78±19. kPa to 450±100. kPa. Stiffer hydrogels, with elastic modulus of 820±210. kPa, were obtained by crosslinking the gelatin fibers with carbodiimide hydrochloride in ethanol before the infiltration process, but at the expense of transparency. The developed fiber-reinforced hydrogels show great promise as mechanically robust scaffolds for corneal tissue engineering applications. © 2013 Elsevier Ltd.

Failure mechanisms in fibrous scaffolds

Polymeric fibrous scaffolds have been considered as replacements for load-bearing soft tissues, because of their ability to mimic the microstructure of natural tissues. Poor toughness of fibrous materials results in failure, which is an issue of importance to both engineering and medical practice. The toughness of fibrous materials depends on the ability of the microstructure to develop toughening mechanisms. However, such toughening mechanisms are still not well understood, because the detailed evolution at the microscopic level is difficult to visualize. A novel and simple method was developed, namely, a sample-taping technique, to examine the detailed failure mechanisms of fibrous microstructures. This technique was compared with in situ fracture testing by scanning electron microscopy. Examination of three types of fibrous networks showed that two different failure modes occurred in fibrous scaffolds. For brittle cracking in gelatin electrospun scaffolds, the random network morphology around the crack tip remained during crack propagation. For ductile failure in polycaprolactone electrospun scaffolds and nonwoven fabrics, the random network deformed via fiber rearrangement, and a large number of fiber bundles formed across the region in front of the notch tip. These fiber bundles not only accommodated mechanical strain, but also resisted crack propagation and thus toughened the fibrous scaffolds. Such understanding provides insight for the production of fibrous materials with enhanced toughness. © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Gelatin nanofiber-reinforced alginate gel scaffolds for corneal tissue engineering.

A severe shortage of donor cornea is now an international crisis in public health. Substitutes for donor tissue need to be developed to meet the increasing demand for corneal transplantation. Current attempts in designing scaffolds for corneal tissue regeneration involve utilization of expensive materials. Yet, these corneal scaffolds still lack the highly-organized fibrous structure that functions as a load-bearing component in the native tissue. This work shows that transparent nanofiber-reinforced hydrogels could be developed from cheap, non-immunogenic and readily available natural polymers to mimic the cornea's microstructure. Electrospinning was employed to produce gelatin nanofibers, which were then infiltrated with alginate hydrogels. Introducing electrospun nanofibers into hydrogels improved their mechanical properties by nearly one order of magnitude, yielding mechanically robust composites. Such nanofiber-reinforced hydrogels could serve as alternatives to donor tissue for corneal transplantation.