Using AMS combined with mineral shape preferred orientation analysis to understand the emplacement fabrics of the Apiai gabbro-norite (Ribeira Belt, SE Brazil)

The Apiai gabbro-norite is a massive fine-grained Neoproterozoic intrusion emplaced in a core of synformal structure that deforms low-grade marine metasedimentary rocks of the Ribeira Belt of south-eastern Brazil. The lack of visible magmatic layering or any internal fabric has been a major limitation in deciding whether the emplacement occurred before or after the regional folding. To assist in the tectonic interpretations, we combine low-field anisotropy of magnetic susceptibility (AMS) and silicate shape preferred orientation (SPO) to reveal the internal structure of the mafic intrusion. Magnetic data indicate a mean susceptibility of about 10(-2) SI and a mean anisotropy degree (P) of about 1.08, essentially yielded by titanomagnetite. The magnetic and silicate foliations for P >= 1.10 are parallel to each other, while the lineations tend to scatter on the foliation plane, in agreement with the dominant oblate symmetry of the AMS and SPO ellipsoids. For lower P values, the magnetic and silicate fabrics vary from coaxial to oblique, and for P <= 1.05, their shapes and orientations can be quite distinct. The crystal size distribution (CSD) of plagioclase for P > 1.05 is log linear, in agreement with a bulk simple crystallisation history. These results combined show that for a strong SPO, corresponding to a magnetic anisotropy above 1.10, AMS is a reliable indicator of the magmatic fabric. They indicate that the Apiai gabbro-norite consists of sill-like body that was inclined gently to the north by the regional folding.

Development of cellulose-based bactericidal nanocomposites containing silver nanoparticles and their use as active food packaging

The use of nanomaterials, including metallic as active fillers in polymeric nanocomposites for food packaging has been extensively investigated. Silver nanoparticles (AgNPs), in particular, have been exploited for technological applications as bactericidal agents. In this paper, AgNPs were incorporated into a hydroxypropyl methylcellulose (HPMC) matrix for applications as food packaging materials. The average sizes of the silver nanoparticles were 41 nm and 100 nm, respectively. Mechanical analyses and water vapor barrier properties of the HPMC/AgNPs nanocomposites were analysed. The best results were observed for films containing smaller (41 nm) AgNPs. The antibacterial properties of HPMC/AgNPs thin films were evaluated based on the diameter of inhibition zone in a disk diffusion test against Escherichia coli (E. coil) and Staphylococcus aureus (S. aureus). The disk diffusion studies revealed a greater bactericidal effectiveness for nanocomposites films containing 41 nm Ag nanoparticles. (C) 2011 Elsevier Ltd. All rights reserved.

Analysis of the color alteration and radiopacity promoted by bismuth oxide in calcium silicate cement

The aim of the study was to determine if the increase in radiopacity provided by bismuth oxide is related to the color alteration of calcium silicate-based cement. Calcium silicate cement (CSC) was mixed with 0%, 15%, 20%, 30% and 50% of bismuth oxide (BO), determined by weight. Mineral trioxide aggregate (MTA) was the control group. The radiopacity test was performed according to ISO 6876/2001. The color was evaluated using the CIE system. The assessments were performed after 24 hours, 7 and 30 days of setting time, using a spectrophotometer to obtain the ΔE, Δa, Δb and ΔL values. The statistical analyses were performed using the Kruskal-Wallis/Dunn and ANOVA/ Tukey tests (p < 0.05). The cements in which bismuth oxide was added showed radiopacity corresponding to the ISO recommendations ( > 3 mm equivalent of Al). The MTA group was statistically similar to the CSC / 30% BO group (p > 0.05). In regard to color, the increase of bismuth oxide resulted in a decrease in the ΔE value of the calcium silicate cement. The CSC group presented statistically higher ΔE values than the CSC / 50% BO group (p < 0.05). The comparison between 24 hours and 7 days showed higher ΔE for the MTA group, with statistical differences for the CSC / 15% BO and CSC / 50% BO groups (p < 0.05). After 30 days, CSC showed statistically higher ΔE values than CSC / 30% BO and CSC / 50% BO (p < 0.05). In conclusion, the increase in radiopacity provided by bismuth oxide has no relation to the color alteration of calcium silicate-based cements.

Numerical combination for nonlinear analysis of structures coupled to layered soils

This paper presents an alternative coupling strategy between the Boundary Element Method (BEM) and the Finite Element Method (FEM) in order to create a computational code for the analysis of geometrical nonlinear 2D frames coupled to layered soils. The soil is modeled via BEM, considering multiple inclusions and internal load lines, through an alternative formulation to eliminate traction variables on subregions interfaces. A total Lagrangean formulation based on positions is adopted for the consideration of the geometric nonlinear behavior of frame structures with exact kinematics. The numerical coupling is performed by an algebraic strategy that extracts and condenses the equivalent soil's stiffness matrix and contact forces to be introduced into the frame structures hessian matrix and internal force vector, respectively. The formulation covers the analysis of shallow foundation structures and piles in any direction. Furthermore, the piles can pass through different layers. Numerical examples are shown in order to illustrate and confirm the accuracy and applicability of the proposed technique.

Clay-containing block copolymer nanocomposites with aligned morphology prepared by extrusion

Clay-containing nanocomposites of polystyrene-b-poly(ethylene-co-butylene)-b-polystyrene (SEBS) copolymers having cylindrical domains were obtained by melt extrusion using a tape die. One type of sample (SEBS-MA) had maleic anhydride attached to the middle block. Two types of organoclays were added, namely Cloisite 20A and Cloisite 30B. Small angle X-ray scattering and transmission electron microscopy (TEM) analyses showed that the addition of 20A clay to SEBS and SEBS-MA resulted in nanocomposites with intercalated and partially exfoliated structures, respectively. The addition of 30B clay to SEBS and SEBS-MA promoted the formation of composites containing relatively large micron-sized and partially exfoliated clay particles, respectively. Our TEM analysis revealed that clay particles embedded in SEBS are preferably in contact with the polystyrene cylindrical domains, while in SEBS-MA they are in contact with the maleated matrix. The extrusion processing promoted alignment of the axes of the polystyrene cylinders along the extrusion direction in all samples, and the basal planes of the clay particles were mostly parallel to the main external surfaces of the extruded tapes. © 2013 Society of Chemical Industry.

Molecular dynamics of poly(Ethylene Glycol) intercalated in clay, studied using 13C solid-state NMR

In this study, Cross-Polarization Magic-angle Spinning CP/MAS, 2D Exchange, Centerband-Only Detection of Exchange (CODEX), and Separated-Local-Field (SLF) NMR experiments were used to study the molecular dynamics of poly(ethylene glycol) (PEG) inside Hectorite/PEG intercalation compounds in both single- and double-layer configurations. The results revealed that the overall amplitude of the motions of the PEG chain in the single-layer configuration is considerably smaller than that observed for the double-layer intercalation compound. This result indicates that the effect of having the polymer chain interacting with both clay platelets is to produce a substantial decrease in the motional amplitudes of those chains. The presence of these dynamically restricted segments might be explained by the presence of anchoring points between the clay platelets and the PEG oxygen atoms, which was induced by the Na+ cations. By comparing the PEG motional amplitudes of the double-layered nanocomposites composed of polymers with different molecular weights, a decrease in the motional amplitude for the smaller PEG chain was observed, which might also be understood using the presence of anchoring points.

Characterization and modeling of the barrier properties in nanostructured systems

The object of the present study is the process of gas transport in nano-sized materials, i.e. systems having structural elements of the order of nanometers. The aim of this work is to advance the understanding of the gas transport mechanism in such materials, for which traditional models are not often suitable, by providing a correct interpretation of the relationship between diffusive phenomena and structural features. This result would allow the development new materials with permeation properties tailored on the specific application, especially in packaging systems. The methods used to achieve this goal were a detailed experimental characterization and different simulation methods. The experimental campaign regarded the determination of oxygen permeability and diffusivity in different sets of organic-inorganic hybrid coatings prepared via sol-gel technique. The polymeric samples coated with these hybrid layers experienced a remarkable enhancement of the barrier properties, which was explained by the strong interconnection at the nano-scale between the organic moiety and silica domains. An analogous characterization was performed on microfibrillated cellulose films, which presented remarkable barrier effect toward oxygen when it is dry, while in the presence of water the performance significantly drops. The very low value of water diffusivity at low activities is also an interesting characteristic which deals with its structural properties. Two different approaches of simulation were then considered: the diffusion of oxygen through polymer-layered silicates was modeled on a continuum scale with a CFD software, while the properties of n-alkanthiolate self assembled monolayers on gold were analyzed from a molecular point of view by means of a molecular dynamics algorithm. Modeling transport properties in layered nanocomposites, resulting from the ordered dispersion of impermeable flakes in a 2-D matrix, allowed the calculation of the enhancement of barrier effect in relation with platelets structural parameters leading to derive a new expression. On this basis, randomly distributed systems were simulated and the results were analyzed to evaluate the different contributions to the overall effect. The study of more realistic three-dimensional geometries revealed a prefect correspondence with the 2-D approximation. A completely different approach was applied to simulate the effect of temperature on the oxygen transport through self assembled monolayers; the structural information obtained from equilibrium MD simulations showed that raising the temperature, makes the monolayer less ordered and consequently less crystalline. This disorder produces a decrease in the barrier free energy and it lowers the overall resistance to oxygen diffusion, making the monolayer more permeable to small molecules.

The Mavuradonha Layered Complex

Der Mavuradonha Layered Complex repräsentiert einen 862 ? 4 Ma alten Komplex, der in einem tiefkrustalen Milieu intrudierte. Eine mehrphasige magmatische Differentiation ist in macro-rhythmischen Einheiten und kleinmaßstäblichen Lagenbau erkennbar, aus denen die Kristallisationssequenzen Pyroxenite, Gabbros/Norite, Leuko-Gabbros oder Ferro-Gabbro und Anorthosite resultieren. ?Nd-Werte zwischen + 0.3 und + 6.6 zeigen krustale Kontamination eines aus dem verarmten Mantel stammenden, tholeiitischen Ursprungsmagma an. ?Nd-Werte (+ 2.4 bis - 3.5) anderer tholeiitischer Gabbros in unmittelbarer Nähe des Komplexes deuten ebenfalls auf Krustenkontamination hin, jedoch in stärkerem Maße.Der Komplex wurde um 554 ? 13 Ma unter granulitfaziellen Bedingungen von 13 ? 2 kbar und 840 ? 30° C überprägt. Die anschließende retrograde, amphibolitfazielle Metamorphose mit Bedingungen von 11 ? 2 kbar und 680 ? 20° C ereignete sich um 546 ? 9 Ma. Abkühlung bis zur Grünschieferfazies erfolgte spätestens um 501 ? 6 Ma.Die vorgestellten Daten zeigen, dass sich der Sambesi-Gürtel im NE Simbabwes als fehlgeschlagenes Rift oder intrakratonisches Becken während einer frühen Pan-Afrikanischen Extensionsphase entwickelte, während die granulitfazielle Metamorphose um 300 Ma später erfolgte. Somit deutet die Intrusion des Mavuradonha Layered Complex rift-bedingten Magmatismus in einer frühen Riftphase an, während das Becken oder Rift während der Pan-Afrikanischen Orogenese geschlossen wurde.

EPR-Spektroskopie zur Untersuchung von Struktur und Dynamik in Polymer-Ton-Nanokompositen

Ziel der vorliegenden Arbeit war die Untersuchung von Struktur und Dynamik in Polymer-Ton-Nanokompositen mittels EPR-Spektroskopie; damit sollten ein Beitrag zur Analyse der Tensidschicht in solchen Systemen geleistet und die Ergebnisse anderer Messmethoden ergänzt werden. Die Tensidschicht in Polymer-Ton-Nanokompositen nimmt großen Einfluss auf das System, denn sie bestimmt die Wechselwirkung zwischen Ton und Polymer: Damit hydrophiler Ton gut mit hydrophobem Polymer (hier Polystyrol) mischbar ist, muss das Schichtsilikat zunächst mit Tensiden organisch-modifiziert werden; dies geschieht durch Kationenaustausch der Natriumionen im Ton gegen Tenside. Um mit Hilfe der EPR einen Einblick in die Tensidschicht zu gewinnen, muss etwa 1% der zur Tonmodifizierung eingesetzten Amphiphile spinmarkiert sein. So gelang es im Rahmen dieser Arbeit, Tenside mit verschiedenen Kopfgruppen, nämlich Trimethylammonium- bzw. Trimethylphosphoniumtenside, zu synthetisieren und sie an verschiedenen Positionen ihrer hydrophoben Alkylkette mit einem Nitroxidradikal zu markieren. Das Nitroxidradikal diente als Spinsonde für die EPR-Experimente. Neben der Synthese verschiedener, spinmarkierter Amphiphile, der anschließenden Darstellung organisch-modifizierten Tons (Kationenaustausch) und verschiedener Polymer-Ton-Nanokomposite (Schmelzinterkalation) wurden alle Proben mittels EPR-Spektroskopie untersucht; dabei wurden sowohl cw- als auch gepulste Messtechniken eingesetzt. Aus cw-Experimenten ging hervor, dass die Dynamik der gesamten Tensidschicht mit der Temperatur zunimmt und die Mobilität der hydrophoben Tensidalkylkette mit wachsendem Abstand zu ihrer Kopfgruppe wächst. Zugabe von Polymer behindert bei steigender Temperatur das Anschwellen des Tons bei Aufschmelzen der Tensidschicht; die Dynamik des Systems ist eingeschränkt. Mit Hilfe gepulster EPR-Messungen (ENDOR und ESEEM), die Informationen über Abstände bzw. Kontakt in den untersuchten Systemen lieferten, ließ sich ein Strukturmodell der Polymer-Ton-Nanokomposite skizzieren, das Vorstellungen anderer, älterer Methoden unterstützt: Hierbei richten sich die Tenside in Multischichten unterschiedlicher Mobilität parallel zur Tonoberfläche aus.

Ex situ X-­Ray absorption study of Li-­rich layered cathode material Li[Li0.2Mn0.56Ni0.16Co0.08]O2

The Li-rich layered transition metal oxides (LLOs) Li2MnO3-LiMO2 (M=Mn, Co, Ni, etc.) have drawn considerable attention as cathode materials for rechargeable lithium batteries. They generate large reversible capacities but the fundamental reaction mechanism and structural perturbations during cycling remain controversial. In the present thesis, ex situ X-ray absorption spectroscopy (XAS) measurements were performed on Li[Li0.2Mn0.56Ni0.16Co0.08]O2 at different stage of charge during electrochemical oxidation/reduction. K-edge spectra of Co, Mn and Ni were recorded through a voltage range of 3.7-4.8V vs. Li/Li+, which consist of X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). Oxidation states during initial charge were discussed based on values from literature as well as XANES analysis. Information about bond distance, coordination number as well as corresponding Debye-Waller factor were extracted from Gnxas analysis of raw data in the EXAFS region. The possibility of oxygen participation in the initial charge was discussed. Co and Ni prove to take part in the oxidation/reduction process while Mn remain in the tetravalent state. The cathode material appears to retain good structural short-range order during charge-discharge. A resemblance of the pristine sample and sample 4 was discovered which was firstly reported for similar compounds.

Multifunctional magnetically loaded polyorganosiloxane nanocomposites for biomedical applications

For the last few decades, the interest in functional nanomaterials is steadily increasing. Especially, in biomedicine the range of possible applications of multifunctional nanoparticles including dye-labeled makers and drug loaded carrier systems is extraordinary large. The incorporation of magnetic nanoparticles allows for an additional magnetic detection and manipulation. One promising system on the way to multifunctional nanomaterials is the polyorganosiloxane system. Via polycondensation of silan monomers in aqueous dispersion polyorganosiloxane nanoparticles with particle diameter between 10 and 150 nm can be synthesized. The versatile silane chemistry allows for the design of multifunctional network structures. In this work, hydrophilic iron oxide nanoparticles could be encapsulated into the polymeric particles in a highly efficient process whereat the superparamagnetic nature of the inorganic particles was restrained. The influence of different sized particles as well as the amount of the incorporated material was investigated. Using a core-shell architecture, controlled core and surface modifications could be achieved. An effective fluorescent labeling was performed via incorporation of dye-labeled monomers. Additionally, a hydrophilic surface modification was carried out via a grafting onto process of poly(ethylene glycol). Individual core and surface functionalization was achieved and the influence of the modification on the efficiency of the magnetic loading was tested. The applicability of the multifunctional particles in biological systems was proved via cellular uptake and toxicity testings. Furthermore, biofunctionalized particles were synthesized by EDC coupling using biotin and insulin.rnrn

Molecular dynamics simulations of silicate and borate glasses and melts : structure, diffusion dynamics and vibrational properties

Molecular dynamics simulations of silicate and borate glasses and melts: Structure, diffusion dynamics and vibrational properties. In this work computer simulations of the model glass formers SiO2 and B2O3 are presented, using the techniques of classical molecular dynamics (MD) simulations and quantum mechanical calculations, based on density functional theory (DFT). The latter limits the system size to about 100−200 atoms. SiO2 and B2O3 are the two most important network formers for industrial applications of oxide glasses. Glass samples are generated by means of a quench from the melt with classical MD simulations and a subsequent structural relaxation with DFT forces. In addition, full ab initio quenches are carried out with a significantly faster cooling rate. In principle, the structural properties are in good agreement with experimental results from neutron and X-ray scattering, in all cases. A special focus is on the study of vibrational properties, as they give access to low-temperature thermodynamic properties. The vibrational spectra are calculated by the so-called ”frozen phonon” method. In all cases, the DFT curves show an acceptable agreement with experimental results of inelastic neutron scattering. In case of the model glass former B2O3, a new classical interaction potential is parametrized, based on the liquid trajectory of an ab initio MD simulation at 2300 K. In this course, a structural fitting routine is used. The inclusion of 3-body angular interactions leads to a significantly improved agreement of the liquid properties of the classical MD and ab initio MD simulations. However, the generated glass structures, in all cases, show a significantly lower fraction of 3-membered planar boroxol rings as predicted by experimental results (f=60%-80%). The largest boroxol ring fraction of f=15±5% is observed in the full ab initio quenches from 2300 K. In case of SiO2, the glass structures after the quantum mechanical relaxation are the basis for calculations of the linear thermal expansion coefficient αL(T), employing the quasi-harmonic approximation. The striking observation is a change change of sign of αL(T) going along with a temperature range of negative αL(T) at low temperatures, which is in good agreement with experimental results.