Showing papers in "Frontiers in Materials in 2015"

Fatigue Performance of Laser Additive Manufactured Ti–6Al–4V in Very High Cycle Fatigue Regime up to 109 Cycles

Abstract: Additive manufacturing technologies are in the process of establishing themselves as an alternative production technology to conventional manufacturing such as casting or milling. Especially laser additive manufacturing (LAM) enables the production of metallic parts with mechanical properties comparable to conventionally manufactured components. Due to the high geometrical freedom in LAM the technology enables the production of ultra-light weight designs and therefore gains increasing importance in aircraft and space industry. The high quality standards of these industries demand predictability of material properties for static and dynamic load cases. However, fatigue properties especially in the very high cycle fatigue regime until 109 cycles have not been sufficiently determined yet. Therefore this paper presents an analysis of fatigue properties of laser additive manufactured Ti-6Al-4V under cyclic tension-tension until 107 cycles and tension-compression load until 109 cycles. For the analysis of laser additive manufactured titanium alloy Ti-6Al-4V Woehler fatigue tests under tension-tension and tension-compression were carried out in the high cycle and very high cycle fatigue regime. Specimens in stress-relieved as well as hot-isostatic-pressed conditions were analyzed regarding crack initiation site, mean stress sensitivity and overall fatigue performance. The determined fatigue properties show values in the range of conventionally manufactured Ti-6Al-4V with particularly good performance for hot-isostatic-pressed additive-manufactured material. For all conditions the results show no conventional fatigue limit but a constant increase in fatigue life with decreasing loads. No effects of test frequency on life span could be determined. However, independently of testing principle, a shift of crack initiation from surface to internal initiation could be observed with increasing cycles to failure.

Sporopollenin, The Least Known Yet Toughest Natural Biopolymer

Abstract: Sporopollenin is highly cross-linked polymer composed of carbon, hydrogen and oxygen that is extraordinarily stable and has been found chemically intact in sedimentary rocks some 500 million year old. It is the outer shell (exine) of plant spores and pollen and when extracted it is in the form of an empty exine or microcapsule. The exines resemble the spores and pollen from which they are extracted, in size and morphology. Also, from any one plant such characteristics are incredible uniform. The exines can be used is microcapsules or simply as micron-sized particles due to the variety of functional groups on their surfaces. The loading of the exine microcapsules into their cavities is via multi-directional nano-diameter sized channels. The exines can be filled with a variety of polar and non-polar materials. Such as enzymes can be encapsulated within the shells and still remain active. In vivo studies in humans have shown that an encapsulated active substance can have a substantially increased bioavailability than if it is taken alone. The sporopollenin exine surface possesses phenolic, alkane, alkene, ketone, lactone and carboxylic acid groups. Therefore it can be derivatised in a number of ways, which has given rise to its having been used for, such as, solid supported for peptide synthesis, catalysis and ion-exchange chromatography. Also, the presence of the phenolic groups on sporopollenin endows it with antioxidant activity.

Group IV direct band gap photonics: Methods, Challenges and Opportunities

Abstract: The concept of direct band gap group IV materials offers a paradigm change for Si-photonics concerning the monolithic implementation of light emitters: The idea is to integrate fully compatible group IV materials with equally favorable optical properties as the chemically incompatible group III-V-based systems The concept involves either mechanically applied strain on Ge or alloying of Ge with Sn and permits to drastically improve the insufficient radiative efficiency of Ge The favorable optical properties result from a modified band structure transformed from an indirect to a direct one The first demonstration of such a direct band gap laser, accomplished in GeSn, exemplifies the capability of this new concept These systems may permit a qualitative as well as a quantitative expansion of Si-photonics into traditional but also new areas of applications, provided they can be operated energy efficiently, under ambient conditions and integrated with current Si technologies This review aims to discuss the challenges along this path in terms of fabrication, characterization and fundamental understanding, and will elaborate on evoking opportunities of this new class of group IV-based laser materials

Recent progress in the growth and applications of graphene as a smart material: a review

Abstract: Innovative breakthroughs in fundamental research and industrial applications of graphene material have made its mass and low-cost production a necessary step toward its real world applications. This one-atom thick crystal of carbon, gathers a set of unique physico-chemical properties, ranging from its extreme mechanical behavior to its exceptional electrical and thermal conductivities, which are making graphene as a serious alternative to replace many conventional materials for various applications. In this review paper, we highlight the most important experimental results on the synthesis of graphene material, its emerging properties with reference to its smart applications. We discuss the possibility to successfully integrating graphene directly into device, enabling thereby the realization of a wide range of applications, including actuation, photovoltaic, thermoelectricity, shape memory, self-healing, electrorheology and space missions. The future outlook of graphene is also considered and discussed.

Intrinsic Nano-Ductility of Glasses: The Critical Role of Composition

Abstract: Understanding, predicting and eventually improving the resistance to fracture for silicate materials is of primary importance to design tougher new glasses suitable for advanced applications. However, the fracture mechanism at the atomic level in amorphous silicate materials is still a topic of debate. In particular, there are some controversies about the existence of ductility at the nanoscale during crack propagation. Here, we present simulations of fracture of three archetypical silicate glasses, using molecular dynamics. The simulations clearly show that, depending on their composition, silicate glasses can exhibit different degrees of ductility at the nanoscale. Additionally, we show that the methodology used in the present work can provide realistic predictions of fracture energy and toughness.

Dodecylamine-Loaded Halloysite Nanocontainers for Active Anticorrosion Coatings

Abstract: Currently the most promising approach in the corrosion protection by smart coatings is the use of nanoreservoirs loaded with corrosion inhibitors. Nanocontainers are filled with anti-corrosive agents and embedded into a primer coating. Future prospective containers are halloysite nanotubes due to their low price, availability, durability, with high mechanical strength and biocompatibility. The aim of this work is to study the use of halloysite nanotubes as nanocontainers for encapsulated dodecylamine for active corrosion protection of carbon steel. Halloysite clay was characterized by XRD and TGA- thermogravimetric analysis techniques. Halloysite nanotubes were loaded with dodecylamine and embedded into an alkyd primer with a weight ratio of 10 wt.% . The anticorrosive performance of the alkyd primer doped with 10 wt.% of entrapped-dodecylamine halloysite was tested on coated carbon steel by direct exposure of the coated samples with a provoked defect into 0.01 mol/L NaCl corrosive media using electrochemical impedance spectroscopy (EIS) and scanning vibrating electrode technique (SVET). EIS and SVET measurements showed the self-healing properties of the doped alkyd coating. Coated samples were also evaluated in a salt spray chamber and the self-healing effect was unequivocally noticed.

Mechanical behavior of osteoporotic bone at sub-lamellar length scales

Abstract: Osteoporosis is a disease known to promote bone fragility but the effect on the mechanical properties of bone material, which is independent of geometric effects, is particularly unclear. To address this problem, micro-beams of osteoporotic bone were prepared using focused ion beam (FIB) microscopy and mechanically tested in compression using an atomic force microscope (AFM) while observing using in situ electron microscopy. This experimental approach was shown to be effective at measuring the subtle changes in the mechanical properties of bone material required to evaluate the effects of osteoporosis. Osteoporotic bone material was found to have lower elastic modulus and increased strain to failure when compared to healthy bone material, while the strength of osteoporotic and healthy bone was similar. A mechanism is suggested based on these results and previous literature that indicates degradation of the organic material in osteoporosis bone is responsible for resultant mechanical properties.

The interfacial Transition Zone in alkali-activated slag Mortars

Abstract: The interfacial transition zone (ITZ) is known to strongly influence the mechanical and transport properties of mortars and concretes. This paper studies the ITZ between siliceous (quartz) aggregates and alkali activated slag binders in the context of mortar specimens. Backscattered electron images (BSE) generated in an environmental scanning electron microscope (ESEM) are used to identify unreacted binder components, reaction products and porosity in the zone surrounding aggregate particles, by composition and density contrast. X-ray mapping is used to exclude the regions corresponding to the aggregates from the BSE image of the ITZ, thus enabling analysis of only the binder phases, which are segmented into binary images by grey level discrimination. A distinct yet dense ITZ region is present in the alkali-activated slag mortars, containing a reduced content of unreacted slag particles compared to the bulk binder. The elemental analysis of this region shows that it contains a (C,N)-A-S-H gel which seems to have a higher content of Na (potentially deposited through desiccation of the pore solution) and a lower content of Ca than the bulk inner and outer products forming in the main binding region. These differences are potentially important in terms of long-term concrete performance, as the absence of a highly porous interfacial transition zone region is expected to provide a positive influence on the mechanical and transport properties of alkali-activated slag concretes.

Switchable Surfactant-Assisted Carbon Nanotube Coatings: Innovation through pH Shift

Abstract: The inner surface of fused silica capillaries has been coated with a dense/homogeneous coating of commercial multi-wall carbon nanotubes (MWCNTs) using a stable ink as deposit precursor. Solubilization of the MWCNTs was achieved in water/ethanol/dimethylformamide by the action of a surfactant which can switch between a neutral or an ionic form depending on the pH of the medium, which thus becomes the driving force for the entire deposition process. Careful control of the experimental conditions have allowed us to selectively deposit CNTs on the inner surface of insulating silica capillaries by a simple, reproducible, and easily adaptable method.

Nanostructured Colloidal Particles by Confined Self-Assembly of Block Copolymers in Evaporative Droplets

Abstract: Block copolymers (BCPs) can create various morphology by self-assembly in bulk or film. Recently, using BCPs in confined geometries such as thin film (one-dimension), cylindrical template (two-dimension), or emulsion droplet (three-dimension), nanostructured BCP particles have been prepared, in which unique nanostructures of the BCP are formed via solvent annealing process and can be controlled depending on molecular weight ratio and interaction parameter of the BCPs, and droplet size. Moreover, by tuning interfacial property of the BCP particles, anisotropic particles with unique nanostructures have been prepared. Furthermore, for practical application such as drug delivery system, sensor, self-healing, metamaterial, and optoelectronic device, functional nanoparticles can be incorporated inside BCP particles. In this article, we summarize recent progress on the production of structured BCP particles and composite particles with metallic nanoparticles.

High-Throughput Multiple Dies-to-Wafer Bonding Technology and III/V-on-Si Hybrid Lasers for Heterogeneous Integration of Optoelectronic Integrated Circuits

Abstract: Integrated optical light source on silicon is one of the key building blocks for optical interconnect technology. Great research efforts have been devoting worldwide to explore various approaches to integrate optical light source onto the silicon substrate. The achievements so far include the successful demonstration of III/V-on-Si hybrid lasers through III/V-gain material to silicon wafer bonding technology. However, for potential large-scale integration, leveraging on mature silicon complementary metal oxide semiconductor (CMOS) fabrication technology and infrastructure, more effective bonding scheme with high bonding yield is in great demand considering manufacturing needs. In this paper, we propose and demonstrate a high-throughput multiple dies-to-wafer (D2W) bonding technology which is then applied for the demonstration of hybrid silicon lasers. By temporarily bonding III/V dies to a handle silicon wafer for simultaneous batch processing, it is expected to bond unlimited III/V dies to silicon device wafer with high yield. As proof-of-concept, more than 100 III/V dies bonding to 200 mm silicon wafer is demonstrated. The high performance of the bonding interface is examined with various characterization techniques. Repeatable demonstrations of 16-III/V-die bonding to pre-patterned 200 mm silicon wafers have been performed for various hybrid silicon lasers, in which device library including Fabry-Perot (FP) laser, lateral-coupled distributed feedback (LC-DFB) laser with side wall grating, and mode-locked laser (MLL). From these results, the presented multiple D2W bonding technology can be a key enabler towards the large-scale heterogeneous integration of optoelectronic integrated circuits (H-OEIC).

Sensing the Difference: The Influence of Anisotropic Cues on Cell Behavior

Abstract: From tissue morphogenesis to homeostasis, cells continuously experience and respond to physical, chemical and biological cues commonly presented in gradients. In this article we focus our discussion on the importance of nano/micro topographic cues on cell activity, and the role of anisotropic milieus play on cell behavior, mostly adhesion and migration. We present the need to study physiological gradients in vitro. To do this, we review different cell migration mechanisms and how adherent cells react to the presence of complex tissue-like environments and cell-surface stimulation in 2D and 3D (e.g. ventral/dorsal anisotropy).

Electrically conductive polyaniline-coated electrospun poly(vinylidene fluoride) mats

Abstract: Electrically conductive polyaniline (PANI)-coated electrospun poly(vinylidene fluoride) (PVDF) mats were fabricated through aniline (ANI) oxidative polymerization on electrospun PVDF mats. The effect of polymerization condition on structure and property of PVDF/PANI mats was investigated. The electrical conductivity and PANI content enhanced significantly with increasing ANI concentration due to the formation of a conducting polymer layer that completely coated the PVDF fibers surface. The PANI deposition on the PVDF fibers surface increased the Young Modulus and the elongation at break reduced significantly. Attenuated Total Reflectance-Fourier Transform Infrared spectroscopy (ATR-FTIR) revealed that the electrospun PVDF and PVDF/PANI mats display a polymorph crystalline structure, with absorption bands associated to the β, α and γ phases.

Cork - a renewable raw material: forecast of industrial potential and development priorities

Abstract: This article aims to report the main applications of cork material from ancient times until nowadays, describing its industrial potential for other applications under study. It is also described the cork origin, the extraction process and the relationship between composition and cellular structure with properties.

Quantum Dot-Doped Glasses and Fibers: Fabrication and Optical Properties

Abstract: Quantum dot-doped glasses have been the hotspot for their excellent electronic and optical properties. Owing to its tunable and broadband near-infrared (NIR) emission by controlling the size and distribution of QDs, QD-doped glasses and fibers are potentially applied in photoelectric devices. In this review, we mainly introduce the preparation, tunable emission, and multi-wavelength optical amplification of QD-doped glasses. Due to their excellent optical performances, the fabrication of QD-doped glass fibers is also presented, containing the successful fabrication of QD-doped glass fibers with tunable NIR emission. Furthermore, the achievements and existing problems about QD-doped glasses and fibers are also proposed with several prospects. These QD-doped glasses and fibers show promising applications as the gain medium of NIR broadband fiber amplifiers and tunable fiber lasers.

Ultrasonic Assisted Consolidation of Commingled Thermoplastic/Glass Fiber Rovings

Abstract: Thermoplastic matrix composites are finding new applications in different industrial area thanks to their intrinsic advantages related to environmental compatibility and processability. The approach presented in this work consists in the development of a technology for the simultaneous deposition and consolidation of commingled thermoplastic rovings through to the application of high energy ultrasound. An experimental equipment, integrating both fiber impregnation and ply consolidation in a single process, has been designed and tested. It is made of an ultrasonic welder, whose titanium sonotrode is integrated on a filament winding machine. During winding, the commingled roving is at the same time in contact with the mandrel and the horn. The intermolecular friction generated by ultrasound is able to melt the thermoplastic matrix and impregnate the reinforcement fibers. The heat transfer phenomena occurring during the in situ consolidation were simulated solving by finite element (FE) analysis an energy balance accounting for the heat generated by ultrasonic waves and the melting characteristics of the matrix. To this aim, a calorimetric characterization of the thermoplastic matrix has been carried out to obtain the input parameters for the model. The FE analysis has enabled to predict the temperature distribution in the composite during heating and cooling The simulation results have been validated by the measurement of the temperature evolution during ultrasonic consolidation. The reliability of the developed consolidation equipment was proved by producing hoop wound cylinder prototypes using commingled continuous E-glass rovings and Polypropylene (PP) filaments. The consolidated composite cylinders are characterized by high mechanical properties, with values comparable with the theoretical ones predicted by the micromechanical analysis.

Shape Memory Polymer Nanofibers and Their Composites: Electrospinning, Structure, Performance, and Applications

Abstract: Shape memory polymers (SMPs) have been defined as a kind of smart materials under great investigation from academic research to industry applications. Research on SMPs and their composites, now incorporates a growing focus on nanofibers which offers new structures in microscopic level and the potential of enhanced performance of SMPs. This paper presents a comprehensive review of the development of shape memory polymer nanofibers and their composites, including the introduction of electrospinning technology, the morphology and structures of nanofibers (non-woven fibers, oriented fibers, core/shell fibers and functional particles added in the fibers), shape memory performance (thermal and mechanical properties, stimulus responsive behavior, multiple and two-way shape changing performance), as well as their potential applications in the fields of biomedical and tissue engineering.

Cork: sustainability and new applications

Abstract: Cork is a strategic material used in multiple applications and its use has accompanied mankind since the days of Ancient Egypt. The cork oak forests are extremely well adapted to the semi-arid regions of south- ern Europe and northern Africa (west- ern Mediterranean). These forests help to prevent the advance of desertification, improve water penetration into the soil and hydrological regulation, promote soil conservation, and being the perfect habi- tat for many animal and vegetables species. Consequently, these forests promote biodi- versity (Pereira, 2007; Gil, 2011, 2014). the extraction. During the tree lifetime in operation, an average cork oak produces about four times more cork bark than the cork tree would produce if it were not sub- ject to stripping. The sum of the various layers of cork produced and harvested is greater than the single layer of cork pro- duced if there was no extraction during the life of a tree (Gil, 1998, 2011). Related to environmental aspects of the transformation of the cork raw mater- ial, it can be mentioned the production of expanded cork agglomerate. The man- ufacture of this cork product only uses superheated steam, using generators fueled with cork waste, not introducing any other products not exclusively cork, and giving up agglomeration based on resins of the cork itself. So, this is a completely nat- ural and ecological product. In addition, in the processing of this and other cork products an important residue is produced, cork powder. This powder is commonly burned to produce steam and/or power used in the factories themselves, given the high energy content of this material. Also, all other industrial cork wastes are reused or valorized in another way (Gil, 1998). So, there is really no wasted cork.

Hydrogels with micellar hydrophobic (nano)domains

Abstract: Hydrogels containing hydrophobic domains or nanodomains, especially of the micellar type, are reviewed. Examples of the reasons for introducing hydrophobic domains into hydrophilic gels are given; typology of these materials is introduced. Synthesis routes are exemplified and properties of a variety of such hydrogels in relation with their intended applications are described. Future research needs are identified briefly.

Silicon-nitride-based Integrated Optofluidic Biochemical Sensors Using a Coupled-resonator Optical Waveguide

Abstract: Silicon nitride (SiN) is a promising material platform for integrating photonic components and microfluidic channels on a chip for label-free, optical biochemical sensing applications in the visible to near-infrared wavelengths. The chip-scale SiN-based optofluidic sensors can be compact due to a relatively high refractive index contrast between SiN and the fluidic medium, and low-cost due to the complementary metal-oxide-semiconductor (CMOS)-compatible fabrication process. Here, we demonstrate SiN-based integrated optofluidic biochemical sensors using a coupled-resonator optical waveguide (CROW) in the visible wavelengths. The working principle is based on imaging in the far field the out-of-plane elastic-light-scattering patterns of the CROW sensor at a fixed probe wavelength. We correlate the imaged pattern with reference patterns at the CROW eigenstates. Our sensing algorithm maps the correlation coefficients of the imaged pattern with a library of calibrated correlation coefficients to extract a minute change in the cladding refractive index. Given a calibrated CROW, our sensing mechanism in the spatial domain only requires a fixed-wavelength laser in the visible wavelengths as a light source, with the probe wavelength located within the CROW transmission band, and a silicon digital charge-coupled device (CCD) / CMOS camera for recording the light scattering patterns. This is in sharp contrast with the conventional optical microcavity-based sensing methods that impose a strict requirement of spectral alignment with a high-quality cavity resonance using a wavelength-tunable laser. Our experimental results using a SiN CROW sensor with eight coupled microrings in the 680nm wavelength reveal a cladding refractive index change of ~1.3 × 10^-4 refractive index unit (RIU), with an average sensitivity of ~281 ± 271 RIU-1 and a noise-equivalent detection limit (NEDL) of 1.8 ×10^-8 RIU ~ 1.0 ×10^-4 RIU across the CROW bandwidth of ~1 nm.

Whispering Gallery Mode Resonances from Ge Micro-Disks on Suspended Beams

Abstract: Ge is considered to be one of the most promising materials for realizing full monolithic integration of a light source on a silicon (Si) photonic chip. Tensile-strain is required to convert Ge into an optical gain material and to reduce the pumping required for population inversion. Several methods of strain application to Ge are proposed in literature, of which the use of free-standing beams fabricated by micro-electro-mechanical systems (MEMS) processes are capable of delivering very high strain values. However, it is challenging to make an optical cavity within free-standing Ge beams, and here, we demonstrate the fabrication of a simple cavity while imposing tensile strain by suspension using Ge-On-Insulator (GOI) wafers. Ge micro-disks are made on top of suspended SiO$_{2}$ beams by partially removing the supporting Si substrate. According to Raman spectroscopy, a slight tensile strain was applied to the Ge disks through the bending of the SiO2 beams. Whispering-Gallery-Mode (WGM) resonances were observed from a disk with a diameter of 3um, consistent with the finite-domain time-difference simulations. The quality (Q) factor was 192, and upon increasing the pumping power, the Q-factor was degraded due to the red-shift of Ge direct-gap absorption edge caused by heating.

A Hierarchical Lattice Spring Model to Simulate the Mechanics of 2-D Materials-Based Composites

Abstract: In the field of engineering materials, strength and toughness are typically two mutually exclusive properties. Structural biological materials such as bone, tendon or dentin have resolved this conflict and show unprecedented damage tolerance, toughness and strength levels. The common feature of these materials is their hierarchical heterogeneous structure, which contributes to increased energy dissipation before failure occurring at different scale levels. These structural properties are the key to exceptional bioinspired material mechanical properties, in particular for nanocomposites. Here, we develop a numerical model in order to simulate the mechanisms involved in damage progression and energy dissipation at different size scales in nano- and macro-composites, which depend both on the heterogeneity of the material and on the type of hierarchical structure. Both these aspects have been incorporated into a 2-dimensional model based on a Lattice Spring Model, accounting for geometrical nonlinearities and including statistically-based fracture phenomena. The model has been validated by comparing numerical results to continuum and fracture mechanics results as well as finite elements simulations, and then employed to study how structural aspects impact on hierarchical composite material properties. Results obtained with the numerical code highlight the dependence of stress distributions on matrix properties and reinforcement dispersion, geometry and properties, and how failure of sacrificial elements is directly involved in the damage tolerance of the material. Thanks to the rapidly developing field of nanocomposite manufacture, it is already possible to artificially create materials with multi-scale hierarchical reinforcements. The developed code could be a valuable support in the design and optimization of these advanced materials, drawing inspiration and going beyond biological materials with exceptional mechanical properties.

Hydrogen storage in rippled graphene: perspectives from multi-scale simulations

Abstract: Exploring new perspectives for green technologies is one of the challenges of the third millennium, in which the need for non-polluting and renewable powering has become primary. In this context, the use of hydrogen as a fuel is promising, since the energy released in its oxidation per unit mass (~142 MJ/kg) is three times that released, on average, by hydrocarbons, and the combustion product is water (Ramage, 1983). Being hydrogen a vector of chemical energy, efficient conservation, and non-dispersive transportation are the main goals. Three issues must be considered to this respect: (i) storage capacity, (ii) storage stability, and (iii) kinetics of loading/release. Commercial technologies are currently based on cryo-compression or liquefaction of H2 in tanks. These ensure quite a high gravimetric density [GD, point (i)], namely 8–13% in weight of stored hydrogen, and a relatively low cost (Zuttel, 2003). However, concerning points (ii) and (iii), these technologies pose problems of safety, mainly due to explosive flammability of hydrogen, and consequent unpractical conditions for transportation and use (Mori and Hirose, 2009). Therefore, research efforts are directed toward solidstate based storage systems (energy.gov, Bonaccorso et al., 2015). Interactions of hydrogen with materials are classified as physisorption, occurring with H2 by means of van der Waals (vdW) forces, or chemisorption, i.e., chemical binding of H leading to the formation of hydrides (Mori and Hirose, 2009), requiring dissociative(associative) chemi(de)sorption of H2. Intermediate nature interactions, sometimes called “phenisorption,” can also occur between hydrogen electrons and the electrons of external orbital of metals. Indeed, stable and robust (light) metal hydrides (Sakintuna et al., 2007; Harder et al., 2011) are currently considered an alternative to tanks. Their main drawback is their high chemisorption and chemidesorption barrier, both many times the typical thermal energy, implying slow operational kinetics, which becomes acceptable only at very high temperature. Physisorption, conversely, generally results in barrierless and weak binding. It was considered as a storage mechanism in layered (Zhirko et al., 2007) or porous (Sastre, 2010) materials, and shown to be effective at low temperatures and/or high pressure. Therefore, it generally seems that if storage stability (ii) is improved then the loading/release kinetics (iii) is worsened. Graphene shows good potential to be an efficient hydrogen-storage medium (Tozzini and Pellegrini, 2013): carbon is among the lightest elements forming layered and porous structures, and graphene is probably the material with the largest surface to mass ratio. These two conditions are in principle optimal to produce high GD [point (i)]. In addition, the chemical versatility of carbon allows it to interact with hydrogen both by physisorption (in sp2 hybridization) and chemisorption (Goler et al., 2013a) (in sp3 hybridization). [“Phenisorption is also obtained in graphene by functionalization with metals (Mashoff et al., 2013)]. On the other hand, concerning points (ii) and (iii), pure graphene does not perform dramatically better than other materials. H2 easily physisorbs onto graphene layers or within multilayers, but it was theoretically shown (Patchkovskiim et al., 2005) that large GD (6–8%) are reached within multi-layered graphene at cryogenic temperatures, while the room temperature value is at best ~2–3%. This was confirmed by measurements (Klechikov et al., private communication), which also indicate that graphene does not perform better than other carbon based bulk materials, such as nanoporous carbon or carbon nanotubes. In all cases, a key parameter determining GD is the specific surface to volume ratio. Theoretical works also show that stability can be improved (and GD optimized) at specific interlayer spacing (~7–8 A), due to a cooperative effect of vdW forces (Patchkovskiim et al., 2005). A similar effect is responsible for the accumulation of physisorbed hydrogen within graphene troughs at low temperatures (~100 K) observed in simulations (Tozzini and Pellegrini, 2011). On the other hand, hydrogen chemisorption on graphene produces graphane (Sofo et al., 2007), its completely hydrated alkane counterpart, stable at room temperature [point (ii)] and with 8.2% GD [point (i)]. Graphane, however, shares with other hydrides high chemi(de)sorption barrier (~1.5 eV/atom). As in other materials, physisorption has good kinetics (iii), and

A bottom-up approach for the synthesis of highly ordered fullerene-intercalated graphene hybrids

Abstract: Much of the research effort on graphene focuses on its use as a building block for the development of new hybrid nanostructures with well-defined dimensions and properties suitable for applications such as gas storage, heterogeneous catalysis, gas/liquid separations, nanosensing and biomedicine. Towards this aim, here we describe a new bottom-up approach, which combines self-assembly with the Langmuir Schaefer deposition technique to synthesize graphene-based layered hybrid materials hosting fullerene molecules within the interlayer space. Our film preparation consists in a bottom-up layer-by-layer process that proceeds via the formation of a hybrid organo-graphene oxide Langmuir film. The structure and composition of these hybrid fullerene-containing thin multilayers deposited on hydrophobic substrates were characterized by a combination of X-ray diffraction, Raman and X-ray photoelectron spectroscopies, atomic force microscopy and conductivity measurements. The latter revealed that the presence of C60 within the interlayer spacing leads to an increase in electrical conductivity of the hybrid material as compared to the organo-graphene matrix alone.

Automated, Miniaturized, and Integrated Quality Control-on-Chip (QC-on-a-Chip) for Cell-Based Cancer Therapy Applications

Abstract: The combination of microfabrication-based technologies with cell biology has laid the foundation for the development of advanced in vitro diagnostic systems capable of evaluating cell cultures under defined, reproducible and standardizable measurement conditions. In the present review we describe recent lab-on-a-chip developments for cell analysis and how these methodologies could improve standard quality control in the field of manufacturing cell-based vaccines for clinical purposes. We highlight in particular the regulatory requirements for advanced cell therapy applications using as an example dendritic cell-based cancer vaccines to describe the tangible advantages of microfluidic devices that overcome most of the challenges associated with automation, miniaturization and integration of cell-based assays. As its main advantage lab-on-a-chip technology allows for precise regulation of culturing conditions, while simultaneously monitoring cell relevant parameters using embedded sensory systems. State-of-the-art lab-on-a-chip platforms for in vitro assessment of cell cultures and their potential future applications for cell therapies and cancer immunotherapy are discussed in the present review.

Therapeutic Ion-Releasing Bioactive Glass Ionomer Cements with Improved Mechanical Strength and Radiopacity

Abstract: Bioactive glasses (BG) are used to regenerate bone, as they degrade and release therapeutic ions. Glass ionomer cements (GIC) are used in dentistry, can be delivered by injection and set in situ by a reaction between an acid-degradable glass and a polymeric acid. Our aim was to combine the advantages of BG and GIC, and we investigated the use of alkali-free BG (SiO2-CaO-CaF2-MgO) with 0 to 50% of calcium replaced by strontium, as the beneficial effects of strontium on bone formation are well documented. When mixing BG and poly(vinyl phosphonic-co-acrylic acid), ions were released fast (up to 90% within 15 minutes at pH 1), which resulted in GIC setting, as followed by infrared spectroscopy. GIC mixed well and set to hard cements (compressive strength up to 35 MPa), staying hard when in contact with aqueous solution. This is in contrast to GIC prepared with poly(acrylic acid), which were shown previously to become soft in contact with water. Strontium release from GIC increased linearly with strontium for calcium substitution, allowing for tailoring of strontium release depending on clinical requirements. Furthermore, strontium substitution increased GIC radiopacity. GIC passed ISO10993 cytotoxicity test, making them promising candidates for use as injectable bone cements.

Polyhydroxyester Films Obtained by Non-Catalyzed Melt-Polycondensation of Natural Occurring Fatty Polyhydroxyacids

Abstract: Free-standing polyesters films from mono and polyhydroxylated fatty acids (C16 and C18) have been obtained by non-catalyzed melt-condensation polymerization in air at 150°C. Chemical characterization by Fourier Transform Infrared Spectroscopy (FTIR) and 13C Magic Angle Spinning Nuclear Magnetic Resonance (13C MAS-NMR) has confirmed the formation of the corresponding esters and the occurrence of hydroxyl partial oxidation which extent depends on the type of hydroxylation of the monomer (primary or secondary). Generally, polyester films obtained are hydrophobic, insoluble in common solvents, amorphous and infusible as revealed by X-ray Diffraction (XRD) and Differential Scanning Calorimetry (DSC). In -polyhydroxy acids, esterification reaction with primary hydroxyls is preferential and, therefore, the structure can be defined as linear with variable branching depending on the amount of esterified secondary hydroxyls. The occurrence side oxidative reactions like the diol cleavage are responsible for chain cross-linking. Films are thermally stable up to 200-250°C though this limit can be extended up to 300°C in the absence of ester bonds involving secondary hydroxyls. By analogy with natural occurring fatty polyesters (i.e. cutin in higher plants) these polymers are proposed as biodegradable and non-toxic barrier films or coatings to be used, for instance, in food packing

Smart Synthesis of High-Performance Thermosets Based on ortho-Amide–Imide Functional Benzoxazines

Abstract: High performance thermosets via amide-imide functional benzoxazine resins as precursors have been synthesized. The structures of synthesized monomers have been confirmed by 1H NMR and FT-IR. Among these two benzoxazine monomers, the ortho-amide-imide functional benzoxazine resin shows powerful features both in the synthesis of benzoxazine monomers and the properties of the corresponding thermosets. For the cross-linked poly(amide-co-imide) based on ortho-amide-imide functional benzoxazine, a smart route is adopted to develop a more thermally stable cross-linked poly(benzoxazole-co-imide). Besides, the poly(benzoxazole-co-imide) can also undergo a further thermal treatment to form polybenzoxazole. Furthermore, a main-chain type ortho-functional polybenzoxazine with amide-co-imide and benzoxazine groups as repeating units has also been prepared. Both the ortho-amide-imide functional benzoxazine and main-chain type polybenzoxazine resins show the possibility to form high performance thermosets with low cost and easy processability .

Strain Localization and Shear Band Propagation in Ductile Materials

Abstract: A model of a shear band as a zero-thickness nonlinear interface is proposed and tested using finite element simulations An imperfection approach is used in this model where a shear band, that is assumed to lie in a ductile matrix material (obeying von Mises plasticity with linear hardening), is present from the beginning of loading and is considered to be a zone in which yielding occurs before the rest of the matrix This approach is contrasted with a perturbative approach, developed for a J2-deformation theory material, in which the shear band is modelled to emerge at a certain stage of a uniform deformation Both approaches concur in showing that the shear bands (differently from cracks) propagate rectilinearly under shear loading and that a strong stress concentration should be expected to be present at the tip of the shear band, two key features in the understanding of failure mechanisms of ductile materials

Computational Amphiphilic Materials for Drug Delivery

Abstract: Amphiphilic materials can assemble into a wide variety of morphologies and have emerged as a novel class of candidates for drug delivery. Along with a large number of experiments reported, computational studies have been also conducted in this field. At an atomistic/molecular level, computations can facilitate quantitative understanding of experimental observations and secure fundamental interpretation of underlying phenomena. This review summarizes the recent computational efforts on amphiphilic copolymers and peptides for drug delivery. Atom-resolution and time-resolved insights are provided from bottom-up to microscopically elucidate the mechanisms of drug loading/release, which are indispensable in the rational screening and design of new amphiphiles for high-efficacy drug delivery.