An examination of the calcium and strontium site distribution in bioactive glasses through isomorphic neutron diffraction, X-ray diffraction, EXAFS and multinuclear solid state NMR.

Strontium has been substituted for calcium in the glass series (SiO2)49.46(Na2O)26.38(P2O5)1.07(CaO)23.08x(SrO)x (where x = 0, 11.54, 23.08) to elucidate their underlying atomic-scale structural characteristics as a basis for understanding features related to the bioactivity. These bioactive glasses have been investigated using isomorphic neutron and X-ray diffraction, Sr K-edge EXAFS and solid state 17O, 23Na, 29Si, 31P and 43Ca magic-angle-spinning (MAS) NMR. An effective isomorphic substitution first-order difference function has been applied to the neutron diffraction data, confirming that Ca and Sr behave in a similar manner within the glass network, with residual differences attributed to solely the variation in ionic radius between the two species. The diffraction data provides the first direct experimental evidence of split Ca–O nearest-neighbour correlations in these melt quench bioactive glasses, together with an analogous splitting of the Sr–O correlations; the correlations are attributed to the metal ions correlated either to bridging or to non-bridging oxygen atoms. Triple quantum (3Q) 43Ca MAS NMR corroborates the split Ca–O correlations. Successful simplification of the 2 < r (A) < 3 region via the difference method has also revealed two distinct Na environments. These environments are attributed to sodium correlated either to bridging or to nonbridging oxygen atoms. Complementary multinuclear MAS NMR, Sr K-edge EXAFS and X-ray diffraction data supports the structural model presented. The structural sites present will be intimately related to their release properties in physiological fluids such as plasma and saliva, and hence the bioactivity of the material. Detailed structural knowledge is therefore a prerequisite for optimising material design.

Morphology modification of polyethylene/clay nanocomposite samples under convergent flow

The morphology of PE/CL nanocomposite samples subjected to convergent flows is studied. Elongational flow – the typical flow involved in spinning and film-blowing processing operations – significantly increases with the reduction of the capillary diameter. The values of the convergent extensional stress (calculated by Cogswell's formula) for the PE/CL systems, for all the adopted capillary geometries, are greater than the calculated values for pure polyethylene. The applied convergent flow, at the entrance of the capillary, is able to change the clay morphology and consequently the final material properties on the PE/CL system with limited affinity between the matrix and organo-modified clay particles.

Activated polarization pulling and de-correlation of signal and pump states of polarization in fiber Raman amplifier

We report on a theoretical study of activated polarization pulling and de-correlation of signal and pump states of polarization based on an advanced vector model of a fiber Raman amplifier accounting for random birefringence and two-scale fiber spinning. As a result, we have found that it is possible to provide de-correlation and simultaneously suppress PDG and PMD to 1.2 dB and 0.035 ps/km1/2 respectively.

Effect of calcium source on structure and properties of sol-gel derived bioactive glasses

The aim was to determine the most effective calcium precursor for synthesis of sol-gel hybrids and for improving homogeneity of sol-gel bioactive glasses. Sol-gel derived bioactive calcium silicate glasses are one of the most promising materials for bone regeneration. Inorganic/organic hybrid materials, which are synthesized by incorporating a polymer into the sol-gel process, have also recently been produced to improve toughness. Calcium nitrate is conventionally used as the calcium source, but it has several disadvantages. Calcium nitrate causes inhomogeneity by forming calcium-rich regions, and it requires high temperature treatment (>400 C) for calcium to be incorporated into the silicate network. Nitrates are also toxic and need to be burnt off. Calcium nitrate therefore cannot be used in the synthesis of hybrids as the highest temperature used in the process is typically 40-60 C. Therefore, a different precursor is needed that can incorporate calcium into the silica network and enhance the homogeneity of the glasses at low (room) temperature. In this work, calcium methoxyethoxide (CME) was used to synthesize sol-gel bioactive glasses with a range of final processing temperatures from 60 to 800 C. Comparison is made between the use of CME and calcium chloride and calcium nitrate. Using advanced probe techniques, the temperature at which Ca is incorporated into the network was identified for 70S30C (70 mol % SiO, 30 mol % CaO) for each of the calcium precursors. When CaCl was used, the Ca did not seem to enter the network at any of the temperatures used. In contrast, Ca from CME entered the silica network at room temperature, as confirmed by X-ray diffraction, Si magic angle spinning nuclear magnetic resonance spectroscopy, and dissolution studies. CME should be used in preference to calcium salts for hybrid synthesis and may improve homogeneity of sol-gel glasses.

Structural characterization of titanium-doped Bioglass using isotopic substitution neutron diffraction

Melt quenched silicate glasses containing calcium, phosphorus and alkali metals have the ability to promote bone regeneration and to fuse to living bone. Of these glasses 45S5 Bioglass® is the most widely used being sold in over 35 countries as a bone graft product for medical and dental applications; particulate 45S5 is also incorporated into toothpastes to help remineralize the surface of teeth. Recently it has been suggested that adding titanium dioxide can increase the bioactivity of these materials. This work investigates the structural consequences of incorporating 4 mol% TiO2 into Bioglass® using isotopic substitution (of the Ti) applied to neutron diffraction and X-ray Absorption Near Edge Structure (XANES). We present the first isotopic substitution data applied to melt quench derived Bioglass or its derivatives. Results show that titanium is on average surrounded by 5.2(1) nearest neighbor oxygen atoms. This implies an upper limit of 40% four-fold coordinated titanium and shows that the network connectivity is reduced from 2.11 to 1.97 for small quantities of titanium. Titanium XANES micro-fluorescence confirms the titanium environment is homogenous on the micron length scale within these glasses. Solid state magic angle spinning (MAS) NMR confirms the network connectivity model proposed. Furthermore, the results show the intermediate range order containing Na-O, Ca-O, O-P-O and O-Si-O correlations are unaffected by the addition of small quantities of TiO2 into these systems.

Gravity spun polycaprolactone fibres for soft tissue engineering:interaction with fibroblasts and myoblasts in cell culture

Poly(ε-caprolactone) (PCL) fibres were produced by wet spinning from solutions in acetone under low shear (gravity flow) conditions. As-spun PCL fibres exhibited a mean strength and stiffness of 7.9 MPa and 0.1 GPa, respectively and a rough, porous surface morphology. Cold drawing to an extension of 500% resulted in increases in fibre strength (43 MPa) and stiffness (0.3 GPa) and development of an oriented, fibrillar surface texture. The proliferation rate of Swiss 3T3 mouse fibroblasts and C2C12 mouse myoblasts on as-spun, 500% cold-drawn and gelatin-modified PCL fibres was determined in cell culture to provide a basic measure of the biocompatibility of the fibres. Proliferation of both cell types was consistently higher on gelatin-coated fibres relative to as-spun fibres at time points below 7 days. Fibroblast growth rates on cold-drawn PCL fibres exceeded those on as-spun fibres but myoblast proliferation was similar on both substrates. After 1 day in culture, both cell types had spread and coalesced on the fibres to form a cell layer, which conformed closely to the underlying topography. The high fibre compliance combined with a potential for modifying the fibre surface chemistry with cell adhesion molecules and the surface architecture by cold drawing to enhance proliferation of fibroblasts and myoblasts, recommends further investigation of gravity-spun PCL fibres for 3-D scaffold production in soft tissue engineering. © 2005 Elsevier Ltd. All rights reserved.

Fiber Raman amplification in a two-scale spun fiber

We report on a theoretical study of activated de-correlation of pump and signal states of polarization in a fiber Raman amplifier based on 10 km of fiber with two-scale fiber spinning profile. As a result of the decorrelation, polarization dependent gain can be suppressed to 0.11 dB, PMD to 0.037 ps/km1/2 and gain can be increased to 15 dB. © 2012 Optical Society of America.

Fiber Raman depolarizer

We report on a theoretical study of activated de-correlation of signal and pump states of polarization based on an advanced vector model of a fiber Raman amplifier accounting for random birefringence and periodic fiber spinning. © 2012 OSA.

Activated escape from polarization pulling in fibre Raman amplifiers

Fluctuation-induced escape (FIE) from a metastable state with probability controlled by external force is a process inherent in many physical phenomena such as diffusion in crystals, protein folding, activated chemical reactions etc. [1-3]. In this work we present a novel example of FIE problem, considering a very practical nonlinear system recently emerged in the area of fibre telecommunications. Unlike the standard FIE problems where noise is time-dependent, in fibre Raman amplifier (FRA) the role of noise is played by frozen fluctuations of parameters (random birefringence) along the fibre span which result from the breaking of cylindrical symmetry during the fibre drawing [4-6]. The role of periodic forcing in this problem is played by the periodic fibre spinning, leading to key model that is formally similar to the time-domain equations for periodically forced escape [1-3]. © 2011 IEEE.

Bioactive sol-gel glasses at the atomic scale:the complementary use of advanced probe and computer modeling methods

Sol-gel-synthesized bioactive glasses may be formed via a hydrolysis condensation reaction, silica being introduced in the form of tetraethyl orthosilicate (TEOS), and calcium is typically added in the form of calcium nitrate. The synthesis reaction proceeds in an aqueous environment; the resultant gel is dried, before stabilization by heat treatment. These materials, being amorphous, are complex at the level of their atomic-scale structure, but their bulk properties may only be properly understood on the basis of that structural insight. Thus, a full understanding of their structure-property relationship may only be achieved through the application of a coherent suite of leading-edge experimental probes, coupled with the cogent use of advanced computer simulation methods. Using as an exemplar a calcia-silica sol-gel glass of the kind developed by Larry Hench, in the memory of whom this paper is dedicated, we illustrate the successful use of high-energy X-ray and neutron scattering (diffraction) methods, magic-angle spinning solid-state NMR, and molecular dynamics simulation as components to a powerful methodology for the study of amorphous materials.

Optimizing storage and memory systems for energy and performance

Electrical energy is an essential resource for the modern world. Unfortunately, its price has almost doubled in the last decade. Furthermore, energy production is also currently one of the primary sources of pollution. These concerns are becoming more important in data-centers. As more computational power is required to serve hundreds of millions of users, bigger data-centers are becoming necessary. This results in higher electrical energy consumption. Of all the energy used in data-centers, including power distribution units, lights, and cooling, computer hardware consumes as much as 80%. Consequently, there is opportunity to make data-centers more energy efficient by designing systems with lower energy footprint. Consuming less energy is critical not only in data-centers. It is also important in mobile devices where battery-based energy is a scarce resource. Reducing the energy consumption of these devices will allow them to last longer and re-charge less frequently. Saving energy in computer systems is a challenging problem. Improving a system's energy efficiency usually comes at the cost of compromises in other areas such as performance or reliability. In the case of secondary storage, for example, spinning-down the disks to save energy can incur high latencies if they are accessed while in this state. The challenge is to be able to increase the energy efficiency while keeping the system as reliable and responsive as before. This thesis tackles the problem of improving energy efficiency in existing systems while reducing the impact on performance. First, we propose a new technique to achieve fine grained energy proportionality in multi-disk systems; Second, we design and implement an energy-efficient cache system using flash memory that increases disk idleness to save energy; Finally, we identify and explore solutions for the page fetch-before-update problem in caching systems that can: (a) control better I/O traffic to secondary storage and (b) provide critical performance improvement for energy efficient systems.

Chemical characterization of dissolved organic nitrogen in an oligotrophic subtropical coastal ecosystem

Water samples were collected from rivers and estuarine environments within the Florida Coastal Everglades (FCE) ecosystem, USA, and ultrafiltered dissolved organic matter (UDOM; 1 kDa) was isolated for characterization of its source, bioavailability and diagenetic state. A combination of techniques, including 15N cross-polarization magic angle spinning nuclear magnetic resonance (15N CPMAS NMR) and X-ray photoelectron spectroscopy (XPS), were used to analyze the N components of UDOM. The concentrations and compositions of total hydrolysable amino acids (HAAs) were analyzed to estimate UDOM bioavailability and diagenetic state. Optical properties (UV–visible and fluorescence) and the stable isotope ratios of C and N were measured to assess the source and dynamics of UDOM. Spectroscopic analyses consistently showed that the major N species of UDOM are in amide form, but significant contributions of aromatic-N were also observed. XPS showed a very high pyridinic-N concentration in the FCE–UDOM (21.7 ± 2.7%) compared with those in other environments. The sources of this aromatic-N are unclear, but could include soot and charred materials from wild fires. Relatively high total HAA concentrations (4 ± 2% UDOC or 27 ± 4% UDON) are indicative of bioavailable components, and HAA compositions suggest FCE–UDOM has not undergone extensive diagenetic processing. These observations can be attributed to the low microbial activity and a continuous supply of fresh UDOM in this oligotrophic ecosystem. Marsh plants appear to be the dominant source of UDOM in freshwater regions of the FCE, whereas seagrasses and algae are the dominant sources of UDOM in Florida Bay. This study demonstrates the utility of a multi-technique and multi-proxy approach to advance our understanding of DON biogeochemistry.

Quantitative and Qualitative Aspects of Dissolved Organic Carbon Leached from Senescent Plants in an Oligotrophic Wetland

We conducted a series of experiments whereby dissolved organic matter (DOM) was leached from various wetland and estuarine plants, namely sawgrass (Cladium jamaicense), spikerush (Eleocharis cellulosa), red mangrove (Rhizophora mangle), cattail (Typha domingensis), periphyton (dry and wet mat), and a seagrass (turtle grass; Thalassia testudinum). All are abundant in the Florida Coastal Everglades (FCE) except for cattail, but this species has a potential to proliferate in this environment. Senescent plant samples were immersed into ultrapure water with and without addition of 0.1% NaN3 (w/ and w/o NaN3, respectively) for 36 days. We replaced the water every 3 days. The amount of dissolved organic carbon (DOC), sugars, and phenols in the leachates were analyzed. The contribution of plant leachates to the ultrafiltered high molecular weight fraction of DOM (>1 kDa; UDOM) in natural waters in the FCE was also investigated. UDOM in plant leachates was obtained by tangential flow ultrafiltration and its carbon and phenolic compound compositions were analyzed using solid state 13C cross-polarization magic angle spinning nuclear magnetic resonance (13C CPMAS NMR) spectroscopy and thermochemolysis in the presence of tetramethylammonium hydroxide (TMAH thermochemolysis), respectively. The maximum yield of DOC leached from plants over the 36-day incubations ranged from 13.0 to 55.2 g C kg−1 dry weight. This amount was lower in w/o NaN3 treatments (more DOC was consumed by microbes than produced) except for periphyton. During the first 2 weeks of the 5 week incubation period, 60–85% of the total amount of DOC was leached, and exponential decay models fit the leaching rates except for periphyton w/o NaN3. Leached DOC (w/ NaN3) contained different concentrations of sugars and phenols depending on the plant types (1.09–7.22 and 0.38–12.4 g C kg−1 dry weight, respectively), and those biomolecules comprised 8–34% and 4–28% of the total DOC, respectively. This result shows that polyphenols that readily leach from senescent plants can be an important source of chromophoric DOM (CDOM) in wetland environments. The O-alkyl C was found to be the major C form (55±9%) of UDOM in plant leachates as determined by 13C CPMAS NMR. The relative abundance of alkyl C and carbonyl C was consistently lower in plant-leached UDOM than that in natural water UDOM in the FCE, which suggests that these constituents increase in relative abundance during diagenetic processing. TMAH thermochemolysis analysis revealed that the phenolic composition was different among the UDOM leached from different plants, and was expected to serve as a source indicator of UDOM in natural water. Polyphenols are, however, very reactive and photosensitive in aquatic environments, and thus may loose their plant-specific molecular characteristics shortly. Our study suggests that variations in vegetative cover across a wetland landscape will affect the quantity and quality of DOM leached into the water, and such differences in DOM characteristics may affect other biogeochemical processes.

Hybrid Power System Intelligent Operation and Protection Involving Plug-in Electric Vehicles

Two key solutions to reduce the greenhouse gas emissions and increase the overall energy efficiency are to maximize the utilization of renewable energy resources (RERs) to generate energy for load consumption and to shift to low or zero emission plug-in electric vehicles (PEVs) for transportation. The present U.S. aging and overburdened power grid infrastructure is under a tremendous pressure to handle the issues involved in penetration of RERS and PEVs. The future power grid should be designed with for the effective utilization of distributed RERs and distributed generations to intelligently respond to varying customer demand including PEVs with high level of security, stability and reliability. This dissertation develops and verifies such a hybrid AC-DC power system. The system will operate in a distributed manner incorporating multiple components in both AC and DC styles and work in both grid-connected and islanding modes. The verification was performed on a laboratory-based hybrid AC-DC power system testbed as hardware/software platform. In this system, RERs emulators together with their maximum power point tracking technology and power electronics converters were designed to test different energy harvesting algorithms. The Energy storage devices including lithium-ion batteries and ultra-capacitors were used to optimize the performance of the hybrid power system. A lithium-ion battery smart energy management system with thermal and state of charge self-balancing was proposed to protect the energy storage system. A grid connected DC PEVs parking garage emulator, with five lithium-ion batteries was also designed with the smart charging functions that can emulate the future vehicle-to-grid (V2G), vehicle-to-vehicle (V2V) and vehicle-to-house (V2H) services. This includes grid voltage and frequency regulations, spinning reserves, micro grid islanding detection and energy resource support. The results show successful integration of the developed techniques for control and energy management of future hybrid AC-DC power systems with high penetration of RERs and PEVs.

Avaliação das propriedades das fibras de algodões coloridos naturalmente e ecologicamente corretas cultivados nos assentamentos do município de Guamaré/RN

In this work evaluate the technical characteristics of the fibers grown in settlements Guamaré, colored cotton seeds were donated existing in the Germplasm Bank of Embrapa Cotton. We sought through the breeding program, raising the resistance, fineness, length and uniformity of cotton fibers, as well as stabilize the staining of fibers in the BRS Topaz, BRS Brown and BRS Green shades and raise their productivity in the field. First, the individual selections to test progeny seeds, and thereafter the hybridization method followed by family selection to obtain variations in the color tones were performed. The BRS Topaz, BRS Brown and BRS Green varieties were produced, analyzed and compared with existing cottons in the region which is the White cotton. The properties amount of impurities and neps, length, length uniformity, short fiber content, fineness and tensile strength of the fibers were sized in Classifiber, NATI, Pressley and Micronaire devices. 10 trials each with 10 tests for all four fiber types were carried out. The White and Topaz fibers showed greater length (32-34mm) and greater resistance (7.94 lb/mg and 7.97 lb/mg respectively) and showed finesse with lower micronaire index 3,71μg/inch and 3, 73μg/inch and a low rate of short fibers. The results were very promising for the use of genetically improved cotton in the manufacturing of fabric and yarn in the textile industry. The fibers were brown colored cotton used in the manufacture of a composite fiber with thermoplastic resin