CHARACTERIZATION OF THERMAL AND MECHANICAL PROPERTIES OF POLYPROPYLENE–BASED COMPOSITES FOR FUEL CELL BIPOLAR PLATES AND DEVELOPMENT OF EDUCATIONAL TOOLS IN HYDROGEN AND FUEL CELL TECHNOLOGIES

In this project we developed conductive thermoplastic resins by adding varying amounts of three different carbon fillers: carbon black (CB), synthetic graphite (SG) and multi–walled carbon nanotubes (CNT) to a polypropylene matrix for application as fuel cell bipolar plates. This component of fuel cells provides mechanical support to the stack, circulates the gases that participate in the electrochemical reaction within the fuel cell and allows for removal of the excess heat from the system. The materials fabricated in this work were tested to determine their mechanical and thermal properties. These materials were produced by adding varying amounts of single carbon fillers to a polypropylene matrix (2.5 to 15 wt.% Ketjenblack EC-600 JD carbon black, 10 to 80 wt.% Asbury Carbons’ Thermocarb TC-300 synthetic graphite, and 2.5 to 15 wt.% of Hyperion Catalysis International’s FIBRILTM multi-walled carbon nanotubes) In addition, composite materials containing combinations of these three fillers were produced. The thermal conductivity results showed an increase in both through–plane and in–plane thermal conductivities, with the largest increase observed for synthetic graphite. The Department of Energy (DOE) had previously set a thermal conductivity goal of 20 W/m·K, which was surpassed by formulations containing 75 wt.% and 80 wt.% SG, yielding in–plane thermal conductivity values of 24.4 W/m·K and 33.6 W/m·K, respectively. In addition, composites containing 2.5 wt.% CB, 65 wt.% SG, and 6 wt.% CNT in PP had an in–plane thermal conductivity of 37 W/m·K. Flexural and tensile tests were conducted. All composite formulations exceeded the flexural strength target of 25 MPa set by DOE. The tensile and flexural modulus of the composites increased with higher concentration of carbon fillers. Carbon black and synthetic graphite caused a decrease in the tensile and flexural strengths of the composites. However, carbon nanotubes increased the composite tensile and flexural strengths. Mathematical models were applied to estimate through–plane and in–plane thermal conductivities of single and multiple filler formulations, and tensile modulus of single–filler formulations. For thermal conductivity, Nielsen’s model yielded accurate thermal conductivity values when compared to experimental results obtained through the Flash method. For prediction of tensile modulus Nielsen’s model yielded the smallest error between the predicted and experimental values. The second part of this project consisted of the development of a curriculum in Fuel Cell and Hydrogen Technologies to address different educational barriers identified by the Department of Energy. By the creation of new courses and enterprise programs in the areas of fuel cells and the use of hydrogen as an energy carrier, we introduced engineering students to the new technologies, policies and challenges present with this alternative energy. Feedback provided by students participating in these courses and enterprise programs indicate positive acceptance of the different educational tools. Results obtained from a survey applied to students after participating in these courses showed an increase in the knowledge and awareness of energy fundamentals, which indicates the modules developed in this project are effective in introducing students to alternative energy sources.

Risk assessment of liquid hydrogen tanks for heavy duty vehicles

The advent of the hydrogen economy has already been predicted but it does not represent a tangible reality yet. However, decarbonizing the global economy and particularly the energy sector is vital to limit global warming and reduce the incumbent environmental problems. Hydrogen is a promising zero-emission fuel that could replace traditional fossil fuels, playing a key role in the transition towards a more sustainable economy. At present, hydrogen-powered cars are already spread worldwide and the deployment of hydrogen buses seems to be the next goal in the decarbonization process of the transportation sector. In contrast with the undeniable benefits introduced by the use of this alternative fuel, given its hazardous properties, safety is a topic of high concern. The present study concerns the evaluation of the risks linked to the on board storage of hydrogen on hydrogen-powered buses in case of road accident. Currently, hydrogen can be stored on board as a high-pressure gas, as a cryogenic liquid or in cryo-compressed form. Those solutions are compared from a safety point of view. First, the final accidental scenarios that could follow the release of the fuel in case of a road crash are pointed out. Secondly, threshold values for the hazardous effects of each scenario are fixed and the corresponding damage distances are calculated thanks to the use of the software PHAST 8.4. Finally, indicators are quantified to compare the different options. Results are discussed to find out the safer solution and to evaluate whether the replacement of fossil fuels with hydrogen introduces new safety issues.

Experimental and numerical characterization of flame instability in hydrogen-containing flames

In the framework of the energy transition, the acquisition of proper knowledge of fundamental aspects characterizing the use of alternative fuels is paramount as well as the development of optimized know-how and technologies. In this sense, the use of hydrogen has been indicated as a promising route for decarbonization at the end-users stage in the energy supply chain. However, the elevated reactivity and the low-density at atmospheric conditions of hydrogen pose new challenges. Among the others, the dilution of hydrogen with carbon dioxide from carbon capture and storage systems represents a possible route. However, the interactions between these species have been poorly studied so far. For these reasons, this thesis, in collaboration between the University of Bologna and Technische Universität Bergakademie of Freiberg in Saxony (Germany), investigates the laminar flame of hydrogen-based premixed gas with the dilution of carbon dioxide. An experimental system, called a heat flux burner, was adopted ad different operating conditions. The presence of the cellularity phenomenon, forming the so-called cellular flame, was observed and analysed. Theoretical and visual methods have allowed for the characterization of the investigated flames, opening new alternatives for sustainable energy production via hydrogen transformation.

The Effect Of Poly(methyl Methacrylate) Surface Treatments On The Adhesion Of Silicone-based Resilient Denture Liners.

Different surface treatment protocols of poly(methyl methacrylate) have been proposed to improve the adhesion of silicone-based resilient denture liners to poly(methyl methacrylate) surfaces. The purpose of this study was to evaluate the effect of different poly(methyl methacrylate) surface treatments on the adhesion of silicone-based resilient denture liners. Poly(methyl methacrylate) specimens were prepared and divided into 4 treatment groups: no treatment (control), methyl methacrylate for 180 seconds, acetone for 30 seconds, and ethyl acetate for 60 seconds. Poly(methyl methacrylate) disks (30.0 × 5.0 mm; n = 10) were evaluated regarding surface roughness and surface free energy. To evaluate tensile bond strength, the resilient material was applied between 2 treated poly(methyl methacrylate) bars (60.0 × 5.0 × 5.0 mm; n = 20 for each group) to form a 2-mm-thick layer. Data were analyzed by 1-way ANOVA and the Tukey honestly significant difference tests (α = .05). A Pearson correlation test verified the influence of surface properties on tensile bond strength. Failure type was assessed, and the poly(methyl methacrylate) surface treatment modifications were visualized with scanning electron microscopy. The surface roughness was increased (P < .05) by methyl methacrylate treatment. For the acetone and ethyl acetate groups, the surface free energy decreased (P < .05). The tensile bond strength was higher for the methyl methacrylate and ethyl acetate groups (P < .05). No correlation was found regarding surface properties and tensile bond strength. Specimens treated with acetone and methyl methacrylate presented a cleaner surface, whereas the ethyl acetate treatment produced a porous topography. The methyl methacrylate and ethyl acetate surface treatment protocols improved the adhesion of a silicone-based resilient denture liner to poly(methyl methacrylate).

Effects of Low-Level Laser Therapy and Orthodontic Tooth Movement on Dental Pulps in Rats

Objectives: To describe the microscopic pulpal reactions resulting from orthodontically induced tooth movement associated with low-level laser therapy (LLLT) in rats. Materials and Methods: Forty-five young male Wistar rats were randomly assigned to three groups. In group I (n = 20), the maxillary right first molars were submitted to orthodontic movement with placement of a coil spring. In group II (n = 20), the teeth were submitted to orthodontic movement plus LLLT at 4 seconds per point (buccal, palatal, and mesial) with a GaAlAs diode laser source (830 nm, 100 mW, 18 J/cm(2)). Group III (n = 5) served as a control (no orthodontic movement or LLLT). Groups I and 11 were divided into four subgroups according to the time elapsed between the start of tooth movement and sacrifice (12 hours, 24 hours, 3 days, and 7 days). Results: Up until the 3-day period, the specimens in group I presented a thicker odontoblastic layer, no cell-free zone of Weil, pulp core with differentiated mesenchymal and defense cells, and a high concentration of blood vessels. In group II, at the 12- and 24-hour time points, the odontoblastic layer was disorganized and the cell-free zone of Weil was absent, presenting undifferentiated cells, intensive vascularization with congested capillaries, and scarce defense cells in the cell-rich zone. In groups I and II, pulpal responses to the stimuli were more intense in the area underneath the region of application of the force or force/laser. Conclusions: The orthodontic-induced tooth movement and LLLT association showed reversible hyperemia as a tissue response to the stimulus. LLLT leads to a faster repair of the pulpal tissue due to orthodontic movement. (Angle Orthod. 2010;80:116-122.)

Confronting dark energy models using galaxy cluster number counts

The mass function of cluster-size halos and their redshift distribution are computed for 12 distinct accelerating cosmological scenarios and confronted to the predictions of the conventional flat Lambda CDM model. The comparison with Lambda CDM is performed by a two-step process. First, we determine the free parameters of all models through a joint analysis involving the latest cosmological data, using supernovae type Ia, the cosmic microwave background shift parameter, and baryon acoustic oscillations. Apart from a braneworld inspired cosmology, it is found that the derived Hubble relation of the remaining models reproduces the Lambda CDM results approximately with the same degree of statistical confidence. Second, in order to attempt to distinguish the different dark energy models from the expectations of Lambda CDM, we analyze the predicted cluster-size halo redshift distribution on the basis of two future cluster surveys: (i) an X-ray survey based on the eROSITA satellite, and (ii) a Sunayev-Zeldovich survey based on the South Pole Telescope. As a result, we find that the predictions of 8 out of 12 dark energy models can be clearly distinguished from the Lambda CDM cosmology, while the predictions of 4 models are statistically equivalent to those of the Lambda CDM model, as far as the expected cluster mass function and redshift distribution are concerned. The present analysis suggests that such a technique appears to be very competitive to independent tests probing the late time evolution of the Universe and the associated dark energy effects.

Thermodynamic origin of cooperativity in actomyosin interactions: The coupling of short-range interactions with actin bending stiffness in an Ising-like model

We present Monte Carlo simulations for a molecular motor system found in virtually all eukaryotic cells, the acto-myosin motor system, composed of a group of organic macromolecules. Cell motors were mapped to an Ising-like model, where the interaction field is transmitted through a tropomyosin polymer chain. The presence of Ca(2+) induces tropomyosin to block or unblock binding sites of the myosin motor leading to its activation or deactivation. We used the Metropolis algorithm to find the transient and the equilibrium states of the acto-myosin system composed of solvent, actin, tropomyosin, troponin, Ca(2+), and myosin-S1 at a given temperature, including the spatial configuration of tropomyosin on the actin filament surface. Our model describes the short- and long-range cooperativity during actin-myosin binding which emerges from the bending stiffness of the tropomyosin complex. We found all transition rates between the states only using the interaction energy of the constituents. The agreement between our model and experimental data also supports the recent theory of flexible tropomyosin.

Power-law creep behavior of a semiflexible chain

Rheological properties of adherent cells are essential for their physiological functions, and microrheological measurements on living cells have shown that their viscoelastic responses follow a weak power law over a wide range of time scales. This power law is also influenced by mechanical prestress borne by the cytoskeleton, suggesting that cytoskeletal prestress determines the cell's viscoelasticity, but the biophysical origins of this behavior are largely unknown. We have recently developed a stochastic two-dimensional model of an elastically joined chain that links the power-law rheology to the prestress. Here we use a similar approach to study the creep response of a prestressed three-dimensional elastically jointed chain as a viscoelastic model of semiflexible polymers that comprise the prestressed cytoskeletal lattice. Using a Monte Carlo based algorithm, we show that numerical simulations of the chain's creep behavior closely correspond to the behavior observed experimentally in living cells. The power-law creep behavior results from a finite-speed propagation of free energy from the chain's end points toward the center of the chain in response to an externally applied stretching force. The property that links the power law to the prestress is the chain's stiffening with increasing prestress, which originates from entropic and enthalpic contributions. These results indicate that the essential features of cellular rheology can be explained by the viscoelastic behaviors of individual semiflexible polymers of the cytoskeleton.

Structure of (46)Ti at low excitation energy

The nucleus (46)Ti has been studied with the reaction (42)Ca((7)Li,p2n)(46)Ti at a bombarding energy of 31 MeV. Thin target foils backed with a thick Au layer were used. Five new levels of negative parity were observed. Several lifetimes have been determined with the Doppler shift attenuation method. Low-lying experimental negative-parity levels are assigned to three bands with K(pi) = 3, 0, and 4, which are interpreted in terms of the large-scale shell model, considering particle-hole excitations from d(3/2) and s(1/2) orbitals. Shell model calculations were performed using a few effective interactions. However, good agreement was not achieved in the description of either negative- or positive-parity low-lying levels.

Accurate band gaps of AlGaN, InGaN, and AlInN alloys calculations based on LDA-1/2 approach

We present parameter-free calculations of electronic properties of InGaN, InAlN, and AlGaN alloys. The calculations are based on a generalized quasichemical approach, to account for disorder and composition effects, and first-principles calculations within the density functional theory with the LDA-1/2 approach, to accurately determine the band gaps. We provide precise results for AlGaN, InGaN, and AlInN band gaps for the entire range of compositions, and their respective bowing parameters. (C) 2011 American Institute of Physics. [doi:10.1063/1.3576570]

Dissipation as a mechanism of energy gain

Some properties of the annular billiard under the presence of weak dissipation are studied. We show, in a dissipative system, that the average energy of a particle acquires higher values than its average energy of the conservative case. The creation of attractors, associated with a chaotic dynamics in the conservative regime, both in appropriated regions of the phase space, constitute a generic mechanism to increase the average energy of dynamical systems.

Free-fall in a uniform gravitational field in noncommutative quantum mechanics

We study the free-fall of a quantum particle in the context of noncommutative quantum mechanics (NCQM). Assuming noncommutativity of the canonical type between the coordinates of a two-dimensional configuration space, we consider a neutral particle trapped in a gravitational well and exactly solve the energy eigenvalue problem. By resorting to experimental data from the GRANIT experiment, in which the first energy levels of freely falling quantum ultracold neutrons were determined, we impose an upper-bound on the noncommutativity parameter. We also investigate the time of flight of a quantum particle moving in a uniform gravitational field in NCQM. This is related to the weak equivalence principle. As we consider stationary, energy eigenstates, i.e., delocalized states, the time of flight must be measured by a quantum clock, suitably coupled to the particle. By considering the clock as a small perturbation, we solve the (stationary) scattering problem associated and show that the time of flight is equal to the classical result, when the measurement is made far from the turning point. This result is interpreted as an extension of the equivalence principle to the realm of NCQM. (C) 2010 American Institute of Physics. [doi:10.1063/1.3466812]

Temperature effects on the oscillatory electro-oxidation of methanol on platinum

We report in this paper the effect of temperature on the oscillatory electro-oxidation of methanol on polycrystalline platinum in aqueous sulfuric acid media. Potential oscillations were studied under galvanostatic control and at four temperatures ranging from 5 to 35 degrees C. For a given temperature, the departure from thermodynamic equilibrium does not affect the oscillation period and results in a slight increase of the oscillation amplitude. Apparent activation energies were also evaluated in voltammetric and chronoamperometric experiments and were compared to those obtained under oscillatory conditions. In any case, the apparent activation energies values fell into the region between 50 and 70 kJ mol(-1). Specifically under oscillatory conditions an apparent activation energy of 60 +/- 3 kJ mol(-1) and a temperature coefficient q(10) of about 2.3 were observed. The present findings extend our recently published report (J. Phys. Chem. A, 2008, 112, 4617) on the temperature effect on the oscillatory electro-oxidation of formic acid. We found that, despite the fact that both studies were carried out under similar conditions, unlike the case of formic acid, only conventional, Arrhenius, dynamics was observed for methanol.

Enzymatic Resolution of Racemic Sulcatol by Lipase from Candida Antarctica in a Large Scale

Large scale enzymatic resolution of racemic sulcatol 2 has been useful for stereoselective biocatalysis. This reaction was fast and selective, using vinyl acetate as donor of acyl group and lipase from Candida antarctica (CALB) as catalyst. The large scale reaction (5.0 g, 39 mmol) afforded high optical purities for S-(+)-sulcatol 2 and R-(+)-sulcatyl acetate 3, i.e., ee > 99 per cent and good yields (45 per cent) within a short time (40 min). Thermodynamic parameters for the chemoesterification of sulcatol 2 by vinyl acetate were evaluated. The enthalpy and Gibbs free energy values of this reaction were negative, indicating that this process is exothermic and spontaneous which is in agreement with the reaction obtained enzymatically.

Solution Polymerization of N-vinylcaprolactam in 1,4-dioxane. Kinetic Dependence on Temperature, Monomer, and Initiator Concentrations

The kinetics of the solution free radical polymerization of N-vinylcaprolactam, in 1,4-dioxane and under various polymerization conditions was studied. Azobisisobutyronitrile and 3-mercaptopropionic acid were used as initiator and as chain transfer agent (CTA), respectively. The influence of monomer and initiator concentrations and polymerization temperature on the rate of polymerizations (R(p)) was investigated. In general, high conversions were obtained. The order with respect to initiator was consistent with the classical kinetic rate equation, while the order with respect to the monomer was greater than unity. The overall activation energy of 53.6 kJ mol(-1) was obtained in the temperature range 60-80 degrees C. The decreasing of the absolute molecular weights when increasing the CIA concentration was confirmed by GPC/SEC/LALS analyses. It was confirmed by UV-visible analyses the effect of molecular weights on the lower critical solution temperature of the polymers. It was also verified that the addition of the CTA influenced the kinetic of the polymerizations. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 118: 229-240, 2010