Nanomechanical Mapping, Hierarchical Polymer Dynamics, and Miscibility in the Presence of Chain-End Grafted Nanoparticles

To improve the spatial distribution of nano particles in a polymeric host and to enhance the interfacial interaction with the host, the use of chain-end grafted nanoparticle has gained popularity in the field of polymeric nanocomposites. Besides changing the material properties of the host, these grafted nanoparticles strongly alter the dynamics of the polymer chain at both local and cooperative length scales (relaxations) by manipulating the enthalpic and entropic interactions. It is difficult to map the distribution of these chain-end grafted nanoparticles in the blend by conventional techniques, and herein, we attempted to characterize it by unique technique(s) like peak force quantitative nanomechanical mapping (PFQNM) through AFM (atomic force microscopy) imaging and dielectric relaxation spectroscopy (DRS). Such techniques, besides shedding light on the spatial distribution of the nanoparticles, also give critical information on the changing elasticity at smaller length scales and hierarchical polymer chain dynamics in the vicinity of the nanoparticles. The effect of one-dimensional rodlike multiwall carbon nanotubes (MWNTs), with the characteristic dimension of the order of the radius of gyration of the polymeric chain, on the phase miscibility and chain dynamics in a classical LCST mixture of polystyrene/ poly(vinyl methyl ether) (PS/PVME) was examined in detail using the above techniques. In order to tune the localization of the nanotubes, different molecular weights of PS (13, 31, and 46 kDa), synthesized using RAFT (reversible addition fragmentation chain transfer) polymerization, was grafted onto MWNTs in situ. The thermodynamic miscibility in the blends was assessed by low-amplitude isochronal temperature sweeps, the spatial distribution of MWNTs in the blends was evaluated by PFQNM, and the hierarchical polymer chain dynamics was studied by DRS. It was observed that the miscibility, concentration fluctuation, and cooperative relaxations of the PS/PVME blends are strongly governed by the spatial distribution of MWNTs in the blends. These findings should help guide theories and simulations of hierarchical chain dynamics in LCST mixtures containing rodlike nanoparticles.

Strength reliability and in vitro degradation of three-dimensional powder printed strontium-substituted magnesium phosphate scaffolds

Strontium ions (Sr2+) are known to prevent osteoporosis and also encourage bone formation. Such twin requirements have motivated researchers to develop Sr-substituted biomaterials for orthopaedic applications. The present study demonstrates a new concept of developing Sr-substituted Mg-3(PO4)(2) - based biodegradable scaffolds. In particular, this work reports the fabrication, mechanical properties with an emphasis on strength reliability as well as in vitro degradation of highly biodegradable strontium-incorporated magnesium phosphate cements. These implantable scaffolds were fabricated using three-dimensional powder printing, followed by high temperature sintering and/or chemical conversion, a technique adaptable to develop patient-specific implants. A moderate combination of strength properties of 36.7 MPa (compression), 242 MPa (bending) and 10.7 MPa (tension) were measured. A reasonably modest Weibull modulus of up to 8.8 was recorded after uniaxial compression or diametral tensile tests on 3D printed scaffolds. A comparison among scaffolds with varying compositions or among sintered or chemically hardened scaffolds reveals that the strength reliability is not compromised in Sr-substituted scaffolds compared to baseline Mg-3(PO4)(2). The micro-computed tomography analysis reveals the presence of highly interconnected porous architecture in three-dimension with lognormal pore size distribution having median in the range of 17.74-26.29 mu m for the investigated scaffolds. The results of extensive in vitro ion release study revealed passive degradation with a reduced Mg2+ release and slow but sustained release of Sr2+ from strontium-substituted magnesium phosphate scaffolds. Taken together, the present study unequivocally illustrates that the newly designed Sr-substituted magnesium phosphate scaffolds with good strength reliability could be used for biomedical applications requiring consistent Sr2+-release, while the scaffold degrades in physiological medium. Statement of significance The study investigates the additive manufacturing of scaffolds based on different strontium-substituted magnesium phosphate bone cements by means of three-dimensional powder printing technique (3DPP). Magnesium phosphates were chosen due to their higher biodegradability compared to calcium phosphates, which is due to both a higher solubility as well as the absence of phase changes (to low soluble hydroxyapatite) in vivo. Since strontium ions are known to promote bone formation by stimulating osteoblast growth, we aimed to establish such a highly degradable magnesium phosphate ceramic with an enhanced bioactivity for new bone ingrowth. After post-processing, mechanical strengths of up to 36.7 MPa (compression), 24.2 MPa (bending) and 10.7 MPa (tension) could be achieved. Simultaneously, the failure reliability of those bioceramic implant materials, measured by Weibull modulus calculations, were in the range of 4.3-8.8. Passive dissolution studies in vitro proved an ion release of Mg2+ and PO43- as well as Sr2+, which is fundamental for in vivo degradation and a bone growth promoting effect. In our opinion, this work broadens the range of bioceramic bone replacement materials suitable for additive manufacturing processing. The high biodegradability of MPC ceramics together with the anticipated promoting effect on osseointegration opens up the way for a patient-specific treatment with the prospect of a fast and complete healing of bone fractures. (C) 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Prussian blue as a single precursor for synthesis of Fe/Fe3C encapsulated N-doped graphitic nanostructures as bi-functional catalysts

We report a unique, single source precursor Prussian blue (iron(III) ferrocyanide (Fe-4(III)Fe-II(CN)(6)](3))) for the synthesis of Fe/Fe3C nanoparticle encapsulated N-doped graphitic layers and bamboo-like graphitic nanotubes. Hollow N-doped graphite (N-HG) nanostructures are obtained when the encapsulated nanostructures are treated with an acid. Both the encapsulated nanostructures and N-HG are shown to be applicable as bi-functional electrocatalysts for oxygen reduction (ORR) and oxygen evolution reactions (OER). The ORR activity is shown to be improved for N-HG and is comparable to commercial Pt/C. On the other hand, encapsulated nanostructures exhibit OER activity with long-term stability comparable to commercial RuO2.

High Loading of Pd Nanoparticles by Interior Functionalization of MOFs for Heterogeneous Catalysis

In this report, the issue related to nanoparticle (NP) agglomeration upon increasing their loading amount into metal-organic frameworks (MOFs) has been addressed by functionalization of MOFs with alkyne groups. The alkynophilicity of the Pd2+ (or other noble metals) ions has been utilized successfully for significant loading of Pd NPs into alkyne functionalized MOFs. It has been shown here that the size and loading amount of Pd NPs are highly dependent on the surface area and pore width of the MOFs. The loading amount of Pd NPs was increased monotonically without altering their size distribution on a particular MOF. Importantly, the distinct role of alkyne groups for Pe(2+) stabilization has also been demonstrated by performing a control experiment considering a MOF without an alkyne moiety. The preparation of NPs involved two distinct steps viz. adsorption of metal ions inside MOFs and reduction of metal ions. Both of these steps were monitored by microscopic techniques. This report also demonstrates the applicability of Pd@MOF NPs as extremely efficient heterogeneous catalysts for Heck-coupling and hydrogenation reactions of aryl bromides or iodides and alkenes, respectively.

Deformation pathways and breakup modes in acoustically levitated bicomponent droplets under external heating

Controlled breakup of droplets using heat or acoustics is pivotal in applications such as pharmaceutics, nanoparticle production, and combustion. In the current work we have identified distinct thermal acoustics-induced deformation regimes (ligaments and bubbles) and breakup dynamics in externally heated acoustically levitated bicomponent (benzene-dodecane) droplets with a wide variation in volatility of the two components (benzene is significantly more volatile than dodecane). We showcase the physical mechanism and universal behavior of droplet surface caving in leading to the inception and growth of ligaments. The caving of the top surface is governed by a balance between the acoustic pressure field and the restrictive surface tension of the droplet. The universal collapse of caving profiles for different benzene concentration (<70% by volume) is shown by using an appropriate time scale obtained from force balance. Continuous caving leads to the formation of a liquid membrane-type structure which undergoes radial extension due to inertia gained during the precursor phase. The membrane subsequently closes at the rim and the kinetic energy leads to ligament formation and growth. Subsequent ligament breakup is primarily Rayleigh-Plateau type. The breakup mode shifts to diffusional entrapment-induced boiling with an increase in concentration of the volatile component (benzene >70% by volume). The findings are portable to any similar bicomponent systems with differential volatility.

Observation of Size-Dependent Electron-Phonon Scattering and Temperature-Dependent Photoluminescence Quenching in Triangular-Shaped Silver Nanoparticles

Research studies on plasmonic properties of triangular-shaped silver nanoparticles might lead to several interesting applications. However, in this work, triangular-shaped silver nanoparticles have been synthesized by simple solvothermal technique and reported the effect of size on the electron-phonon scattering in the synthesized materials by analyzing their temperature-dependent photoluminescence (PL) emission characteristics. It has been observed that total integrated PL emission intensity is quenched by 33 % with the increase in temperature from 278 to 323 K. The observed decrease in PL emission intensity has been ascribed to the increase of electron-phonon scattering rate with the increase in temperature. The values of electron-phonon coupling strength (S) for synthesized samples have been evaluated by theoretical fitting of the experimentally obtained PL emission data. Smaller sized triangular nanoparticle has been found to exhibit stronger temperature dependence in PL emission, which strongly suggests that smaller sized triangular silver nanostructures have better electron-phonon coupling.

The effect of carbon encapsulation on the magnetic properties of Ni nanoparticles produced by arc discharge in de-ionized water

Despite intensive research on optimizing the methods for depositing carbon encapsulated ferromagnetic nanoparticles, the effect of the carbon cages remains unclear. In the present work, the effect of the graphitic cages on the magnetization of the ferromagnetic core has been studied by comparing the magnetic properties of pure and carbon encapsulated Ni particles of the same size. The carbon encapsulated Ni particles were formed using an electric arc discharge in de-ionized water between a solid graphite cathode and an anode consisting of Ni and C in a mass ratio of Ni:C = 7:3. This method is shown to have potential for low cost production of carbon encapsulated Ni nanoparticle samples with narrow particle size distributions. X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM) analysis were used to study the crystallography, morphology, and size distribution of the encapsulated and pure Ni nanoparticle samples. The availability of encapsulated particles with various sizes allowed us to elucidate the role of carbon cages in size-dependent properties. Our data suggest that even though encapsulation is beneficial for protection against hostile chemical environments and for avoiding low proximity phenomena, it suppresses the saturation magnetization of the Ni cores.

Efecto del revestimiento de la semilla con fertilizante fosfórico sobre el crecimiento y rendimiento de tres variedades de sorgo granífero (Sorghum bicolor (L) Moench)

El presente experimento fue llevado a cabo del 15 de junio al 4 de octubre del 2002 en la Finca Experimental La Compañía, ubicada en el municipio de San Marcos, departamento de Carazo. El propósito de esta investigación fue probar las ventajas de revestir la semilla con fósforo sobre las primeras etapas de crecimiento y rendimiento, de tres variedades de sorgo granífero. Se realizó un diseño bifactorial propiamente dicho con distribución de bloques completos al azar, donde el factor A: consistió en tres variedades de sorgo (tortillero precoz, INTA trinidad y pinolero 1) y el factor B: dos dosis de fósforo (16-00-13 y 16-40-13) revistiendo o no la semilla de sorg o. Los tratamientos se replicaron cuatro veces (3*4*4) para un total de 48 parcelas experimentales. La semilla de sorgo fue revestida por la empresa KEMIRA (Finlandia) con un 2 % de fósforo (KH 2 PO 4 ). El revestimiento consistió en la aplicación de fósforo en polvo y un agente adherente (KT- 60018) como emulsión, el cual contiene un aceite biodegradable elaborado por las empresas KEMIRA y FORTUM. Las variables estudiadas se analizaron como un diseño BCA (bloques completos al azar) y las medias fueron comparadas utilizando la prueba de rangos múltiples de Tukey al 5 % de margen de error y para ello se utilizó el sistema de análisis estadístico (SAS). Los resultados obt enidos indican que la semilla revestida con fósforo tuvo mayor efecto en la variedad pinolero 1 en las variables (altura de planta y número de hojas). El efecto del revestimiento de la semilla de sorgo en el mayor contenido de biomasa seca se refleja en la variedad tortillero precoz tanto a los 21 dds como la floración y la variedad pinolero 1 solo en la etapa de floración. En cuanto al rendimiento los mayores resultados se obtuvieron con semilla revestida para la variedad pinolero 1 con 4522.26 kg/ha y sin revestir para las variedades Tortillero Precoz e INTA Trinidad con 3685 y 2453 kg/ha respectivamente de acuerdo con a los resultados obtenidos al concluir este estudio se recomienda seguir el experimento con el uso de semilla revestida con fósforo en la variedad pinolero 1 ya que fue la que respondió mejor al uso de esta tecnología.

Tailoring The Mechanical Performance Of Epoxy Resin By Various Nanoparticles

Flexible organic elastomeric nanoparticles (ENP) and two kinds of rigid inorganic silica nanoparticles were dispersed respectively into a bisphenol-A epoxy resin in order to tailor and compare the performance of mechanical properties. It was found that the well-dispersed flexible ENP greatly enhanced the toughness of the epoxy with the cost of modulus and strength. Comparatively, the rigid silica nanoparticles improved Young's modulus, tensile strength and fracture toughness simultaneously. Both fumed and sol-gel-formed nanosilica particles conducted similar results in reinforcing the epoxy resin, although the latter exhibited almost perfect nanoparticle dispersion in matrix. The toughening mechanisms of nanocomposites were further discussed based on fractographic analysis.

Design,optimization and in vivo evaluation of non-viral vectors for gene therapy. Applications in ocular disorders

227 págs.

Degradación de alcanos mediante Alcanivorax venutensis inmovilizada en hidrogeles adhesivos y biodegradables

188 p.

Wire array photovoltaics

Over the past five years, the cost of solar panels has dropped drastically and, in concert, the number of installed modules has risen exponentially. However, solar electricity is still more than twice as expensive as electricity from a natural gas plant. Fortunately, wire array solar cells have emerged as a promising technology for further lowering the cost of solar.

Si wire array solar cells are formed with a unique, low cost growth method and use 100 times less material than conventional Si cells. The wires can be embedded in a transparent, flexible polymer to create a free-standing array that can be rolled up for easy installation in a variety of form factors. Furthermore, by incorporating multijunctions into the wire morphology, higher efficiencies can be achieved while taking advantage of the unique defect relaxation pathways afforded by the 3D wire geometry.

The work in this thesis shepherded Si wires from undoped arrays to flexible, functional large area devices and laid the groundwork for multijunction wire array cells. Fabrication techniques were developed to turn intrinsic Si wires into full p-n junctions and the wires were passivated with a-Si:H and a-SiNx:H. Single wire devices yielded open circuit voltages of 600 mV and efficiencies of 9%. The arrays were then embedded in a polymer and contacted with a transparent, flexible, Ni nanoparticle and Ag nanowire top contact. The contact connected >99% of the wires in parallel and yielded flexible, substrate free solar cells featuring hundreds of thousands of wires.

Building on the success of the Si wire arrays, GaP was epitaxially grown on the material to create heterostructures for photoelectrochemistry. These cells were limited by low absorption in the GaP due to its indirect bandgap, and poor current collection due to a diffusion length of only 80 nm. However, GaAsP on SiGe offers a superior combination of materials, and wire architectures based on these semiconductors were investigated for multijunction arrays. These devices offer potential efficiencies of 34%, as demonstrated through an analytical model and optoelectronic simulations. SiGe and Ge wires were fabricated via chemical-vapor deposition and reactive ion etching. GaAs was then grown on these substrates at the National Renewable Energy Lab and yielded ns lifetime components, as required for achieving high efficiency devices.

Estudio del vertedero de RSU de acuerdo con la nueva normativa comunitaria en relación con el vertido de materia orgánica

[ES]Mediante este documento se pretende analizar el estado de la gestión de la fracción biodegradable de los residuos urbanos atendiendo a la normativa vigente. Ese estudio se complementa con el desarrollo teórico de los tratamientos a los que se puede destinar así como ciertas aplicaciones numéricas. De esta manera, se busca establecer unas bases que posibiliten en un futuro profundizar en la temática y obtener diseños aplicables en el ámbito real.

Polilaktida oinarri duten 3D zelula-euskarri (scaffold) polimeriko biodegradagarrien diseinu, fabrikazio eta propietateak

[EU]Hiru dimentsioko inprimaketa etorkizun handiko teknologia bezala azaltzen zaigu gaur egun. Esate baterako, biomedikuntza arloan aukera berritzaileak ekar ditzake, baina baita hezkuntza, heziketa eta ikerketa munduetan ere. Teknologia berri honen abantailarik nagusiena prototipatze azkarrean datza, eta honi esker, mikro- eta makro- egitura definituak dituzten objektuak diseinatu eta fabrikatu daitezke modu lehiakorrean. Lan honen helburua 3D inprimagailu baten bitartez inprimaturiko polimero biobateragarri eta biodegradagarrietan oinarrituriko ereduen garapen eta fabrikazioan datza. Hala ere, lehenik eta behin, lehengaiak bai fisikoki eta bai termikoki karakterizatu behar dira, ondoren, 3D inprimagailuaren parametroen arteko erlazioa ezarri, eta azkenik, produktu finalaren egitura propietateak eta kalitatea aztertu. Aipaturiko lana aurrera eramateko erabili den materiala polilaktida (PLA) izan da, zeinen erabilera oso zabaldua dagoen medikuntza arloan inplante (torloju, iltze, plaka eta abar) moduan eta ehun ingeniaritzaren munduan.

Polilaktida oinarri duten inplante polimeriko biodegradagarrien diseinu, fabrikazio eta propietateak

[EU]3D inprimaketa gaur egun, biomedikuntzaren garapenerako aukera ezberdinak ematen dituen teknologia iraultzaile gisa aurkezten da; bai medikuntza arloan formazio eta ikerkuntzarako erreminta gisa, baita dispositibo berrien diseinu eta fabrikaziorako. Bere abantailarik aipagarriena prototipaketa azkarra da. Gainera, teknologia honek barne egitura eta forma ezberdineko objektuak fabrikatzea ahalbidetzen du koste lehiakor batean. Lan honen helburua 3D inprimagailuen bidezko prototipoen fabrikazioan zentratzen da, horretarako lehengai bezala polimero biodegradagarri eta biobateragarria erabiliz. Horrez gain, metodo tradizionalarekin konparatuz teknologia honek izan ditzakeen abantailak ere aztertu nahi dira, ez bakarrik alde ekonomikoari edo denborari begira, baita fabrikatutako objektuen propietateei begira ere. Dena dela, horrekin hasi aurretik ezaugarritze fisiko eta termikoa burutu beharko zaie lehengaiei, 3D inprimagailuaren parametroen aukeraketa egokia egiteko eta parametro horien eta amaierako produktuaren kalitate, egitura eta propietateen artean erlazio egokia ezartzeko. Lan hau aurrera eramateko poli(L-laktida)-rekin (PLLA) egingo da lan, bai ehun ingeniaritzan baita hezurren apurketen finkapenerako dispositiboetan oso erabilia izan den polimeroa.