Wide-angle X-ray scattering study of structural parameters in non-crystalline polymers

The paper presents an analysis of WAXS (wide-angle X-ray scattering) data which aids an understanding of the structure of non-crystalline polymers. Experimental results are compared with calculations of scattering from possible models. Evidence is presented which supports the view that the chains in molten PE do not lie parallel but have a conformation in accord with the predictions of energy calculations. However, the evidence indicates that in “molten” PTFE the chains lie parallel over distances well in excess of their diameters. WAXS-based proposals are made for the conformations of a-PMMA and a-PS.

A wide-angle X-ray study of the development of molecular orientation in crosslinked natural rubber

Molecular orientation parameters have been measured for the non-crystalline component of crosslinked natural rubber samples deformed in uniaxial tension as a function of the extension ratio and of temperature. The orientation parapeters 〈P2(cosα)〉 and 〈P4(cosα)〉 were obtained by an analysis of the anisotropy of the wide-angle X-ray scattering functions. For the measurements made at high temperatures the level of crystallinity detected was negligible and the orientation-strain behaviour could be compared directly with the predictions of molecular models of rubber elasticity. The molecular orientation behaviour with strain was found to be at variance with the estimates of the affine model particularly at low and moderate strains. Extension of the crosslinked rubber at room temperature led to strain-crystallization and measurements of both the molecular orientation of the non-crystalline chains and the degree of crystallinity during extension and relaxation enabled the role of the crystallites in the deformation process to be considered in detail. The intrinsic birefringence of the non-crystalline component was estimated, through the use of the 〈P2(cosα)〉 values obtained from X-ray scattering measurements, to be 0.20±0.02.

Wide-angle X-ray scattering for swollen and glassy poly(2-hydroxyethyl methacrylate)

The wide angle X-ray scattering from glassy poly(2-hydroxyethyl methacrylate) (1) is presented together with that obtained from oriented and swollen samples. The scattering is compared with that previously reported for poly(methyl methacrylate) (PMMA) and the structure discussed in relation to this polymer. The chain conformation is similar to that of PMMA, although some measure of molecular interlocking appears to reduce the main interchain peak while correlated regions of inaccessible free volume between the substantial side groups are held responsible for the main peak at s = 1,25 Å−1.

Application of cylindrical distribution functions to wide-angle X-ray scattering from oriented polymers

A systematic approach is presented for obtaining cylindrical distribution functions (CDF's) of noncrystalline polymers which have been oriented by extension. The scattering patterns and CDF's are also sharpened by the method proposed by Deas and by Ruland. Data from atactic poly(methyl methacrylate) and polystyrene are analysed by these techniques. The methods could also be usefully applied to liquid crystals.

Conformational analysis of oriented non-crystalline polymers using wide angle X-ray scattering

A procedure is presented for obtaining conformational parameters from oriented but non-crystalline polymers. This is achieved by comparison of the experimental wide angle X-ray scattering with that calculated from models but in such a way that foreknowledge of the orientation distribution function is not required. X-ray scattering intensity values for glassy isotactic poly(methylmethacrylate) are analysed by these techniques. The method could be usefully applied to other oriented molecular systems such as liquid crystalline materials.

Wide-angle, high-concentration photovoltaics to compete with flat plate systems

A novel photovoltaic concentrator enables highly uniform irradiance on a small number of efficient solar cells. The maximum electrical power of a photovoltaic (PV) energy installation depends on three factors: the available irradiance, the size of the systems collecting sunlight, and the rate at which the device transforms light into electricity (the conversion efficiency). Developers can maximize the irradiance by carefully selecting the site and orientation of the solar facility. But they can only expand their sunlight collection systems for standard flat plate PV devices by increasing the number of solar cells, at greater cost. Here, we consider the advantages of an alternative PV system that produces more energy without increasing the number of cells used (actually, reducing it), by improving the conversion rates.We also present a new device that may enhance the commercial viability of such technologies.

New Building - Interior - Composing Room - Wide Angle (Best Picture) - 8 x 11 Negative [Detroit News]

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Bioactive glass sol-gel foam scaffolds:evolution of nanoporosity during processing and in situ monitoring of apatite layer formation using small- and wide-angle X-ray scattering

Recent work has highlighted the potential of sol-gel-derived calcium silicate glasses for the regeneration or replacement of damaged bone tissue. The work presented herein provides new insight into the processing of bioactive calcia-silica sol-gel foams, and the reaction mechanisms associated with them when immersed in vitro in a simulated body fluid (SBF). Small-angle X-ray scattering and wide-angle X-ray scattering (diffraction) have been used to study the stabilization of these foams via heat treatment, with analogous in situ time-resolved data being gathered for a foam immersed in SBF. During thermal processing, pore sizes have been identified in the range of 16.5-62.0 nm and are only present once foams have been heated to 400 degrees C and above. Calcium nitrate crystallites were present until foams were heated to 600 degrees C; the crystallite size varied from 75 to 145 nm and increased in size with heat treatment up to 300 degrees C, then decreased in size down to 95 rim at 400 degrees C. The in situ time-resolved data show that the average pore diameter decreases as a function of immersion time in SBF, as calcium phosphates grow on the glass surfaces. Over the same time, Bragg peaks indicative of tricalcium phosphate were evident after only 1-h immersion time, and later, hydroxycarbonate apatite was also seen. The hydroxycarbonate apatite appears to have preferred orientation in the (h,k,0) direction.

Insights into the influence of solvent polarity on the crystallization of poly(ethylene oxide) spin-coated thin films via in situ grazing incidence wide-angle X-ray scattering

Controlling polymer thin-film morphology and crystallinity is crucial for a wide range of applications, particularly in thin-film organic electronic devices. In this work, the crystallization behavior of a model polymer, poly(ethylene oxide) (PEO), during spin-coating is studied. PEO films were spun-cast from solvents possessing different polarities (chloroform, THF, and methanol) and probed via in situ grazing incidence wide-angle X-ray scattering. The crystallization behavior was found to follow the solvent polarity order (where chloroform < THF < methanol) rather than the solubility order (where THF > chloroform > methanol). When spun-cast from nonpolar chloroform, crystallization largely followed Avrami kinetics, resulting in the formation of morphologies comprising large spherulites. PEO solutions cast from more polar solvents (THF and methanol) do not form well-defined highly crystalline morphologies and are largely amorphous with the presence of small crystalline regions. The difference in morphological development of PEO spun-cast from polar solvents is attributed to clustering phenomena that inhibit polymer crystallization. This work highlights the importance of considering individual components of polymer solubility, rather than simple total solubility, when designing processing routes for the generation of morphologies with optimum crystallinities or morphologies.

Accelerating wide-angle converging waves in the near field

We show that a wide-angle converging wave may be transformed into a shape-preserving accelerating beam having a beam-width near the diffraction limit. For that purpose, we followed a strategy that is particularly conceived for the acceleration of nonparaxial laser beams, in contrast to the well-known method by Siviloglou et al (2007 Phys. Rev. Lett. 99 213901). The concept of optical near-field shaping is applied to the design of non-flat ultra-narrow diffractive optical elements. The engineered curvilinear caustic can be set up by the beam emerging from a dynamic assembly of elementary gratings, the latter enabling to modify the effective refractive index of the metamaterial as it is arranged in controlled orientations. This light shaping process, besides being of theoretical interest, is expected to open up a wide range of broadband application possibilities.

Deep structure of the Santos basin-São Paulo plateau system, SE Brazil

The structure and nature of the crust underlying the Santos Basin-São Paulo Plateau System (SSPS), in the SE Brazilian margin, are discussed based on five wide-angle seismic profiles acquired during the Santos Basin (SanBa) experiment in 2011. Velocity models allow us to precisely divide the SSPS in six domains from unthinned continental crust (Domain CC) to normal oceanic crust (Domain OC). A seventh domain (Domain D), a triangular shape region in the SE of the SSPS, is discussed by Klingelhoefer et al. (2014). Beneath the continental shelf, a similar to 100km wide necking zone (Domain N) is imaged where the continental crust thins abruptly from similar to 40km to less than 15km. Toward the ocean, most of the SSPS (Domains A and C) shows velocity ranges, velocity gradients, and a Moho interface characteristic of the thinned continental crust. The central domain (Domain B) has, however, a very heterogeneous structure. While its southwestern part still exhibits extremely thinned (7km) continental crust, its northeastern part depicts a 2-4km thick upper layer (6.0-6.5km/s) overlying an anomalous velocity layer (7.0-7.8km/s) and no evidence of a Moho interface. This structure is interpreted as atypical oceanic crust, exhumed lower crust, or upper continental crust intruded by mafic material, overlying either altered mantle in the first two cases or intruded lower continental crust in the last case. The deep structure and v-shaped segmentation of the SSPS confirm that an initial episode of rifting occurred there obliquely to the general opening direction of the South Atlantic Central Segment.

Major and rare earth element concentrations of basalts beneath ODP Hole 118-735B (Table 3)

A wide-angle seismic experiment at the Atlantis II Fracture Zone, Southwest Indian Ridge, together with geochemical analyses of dredged basalt glass samples from a site conjugate to Ocean Drilling Program hole 735B has allowed determination of the thickness and the most likely lithological composition of the crust beneath hole 735B. The measured Na, composition of 3.3 +/- 0.1 corresponds to a melt thickness of 3 +/- 1 km, a result consistent with rare earth element inversions which indicate a melt thickness of between 1.5 and 4.5 km. The seismic crustal thickness to the north and south of the Atlantis Platform (on which hole 735B is located) is 4 +/- 1 km, and probably consists largely of magmatic material since the seismic and inferred melt thicknesses agree within experimental uncertainty. Beneath hole 735B itself. the Moho is at a depth of 5 +/- 1 km beneath the seafloor. The seismic model suggests that, on average. about 1 km of upper crust has been unroofed on the Atlantis Platform. However, allowing for the inferred local unroofing of 2 km of upper crust at 735B, the base of the magmatic crust beneath this location is probably about 2 km beneath the seafloor, and is underlain by a 2-3 km thick layer of serpentinised mantle peridotite. The P-wave velocity of 6.9 km/s for the serpentinised peridotite layer corresponds to a 35 +/- 10 vol% serpentine content. The Moho beneath hole 735B probably represents a serpentinisation front.

The TOMO-ETNA experiment: an imaging active campaign at Mt. Etna volcano. Context, main objectives, working-plans and involved research projects

The TOMO-ETNA experiment was devised to image of the crust underlying the volcanic edifice and, possibly, its plumbing system by using passive and active refraction/reflection seismic methods. This experiment included activities both on-land and offshore with the main objective of obtaining a new high-resolution seismic tomography to improve the knowledge of the crustal structures existing beneath the Etna volcano and northeast Sicily up to Aeolian Islands. The TOMO ETNA experiment was divided in two phases. The first phase started on June 15, 2014 and finalized on July 24, 2014, with the withdrawal of two removable seismic networks (a Short Period Network and a Broadband network composed by 80 and 20 stations respectively) deployed at Etna volcano and surrounding areas. During this first phase the oceanographic research vessel “Sarmiento de Gamboa” and the hydro-oceanographic vessel “Galatea” performed the offshore activities, which includes the deployment of ocean bottom seismometers (OBS), air-gun shooting for Wide Angle Seismic refraction (WAS), Multi-Channel Seismic (MCS) reflection surveys, magnetic surveys and ROV (Remotely Operated Vehicle) dives. This phase finished with the recovery of the short period seismic network. In the second phase the Broadband seismic network remained operative until October 28, 2014, and the R/V “Aegaeo” performed additional MCS surveys during November 19-27, 2014. Overall, the information deriving from TOMO-ETNA experiment could provide the answer to many uncertainties that have arisen while exploiting the large amount of data provided by the cutting-edge monitoring systems of Etna volcano and seismogenic area of eastern Sicily.

From unthinned continent to ocean: The deep structure of the West Iberia passive continental margin at 38 degrees N

The crustal and lithospheric mantle structure at the south segment of the west Iberian margin was investigated along a 370 km long seismic transect. The transect goes from unthinned continental crust onshore to oceanic crust, crossing the ocean-continent transition (OCT) zone. The wide-angle data set includes recordings from 6 OBSs and 2 inland seismic stations. Kinematic and dynamic modeling provided a 2D velocity model that proved to be consistent with the modeled free-air anomaly data. The interpretation of coincident multi-channel near-vertical and wide-angle reflection data sets allowed the identification of four main crustal domains: (i) continental (east of 9.4 degrees W); (ii) continental thinning (9.4 degrees W-9.7 degrees W): (iii) transitional (9.7 degrees W-similar to 10.5 degrees W); and (iv) oceanic (west of similar to 10.5 degrees W). In the continental domain the complete crustal section of slightly thinned continental crust is present. The upper (UCC, 5.1-6.0 km/s) and the lower continental crust (LCC, 6.9-7.2 km/s) are seismically reflective and have intermediate to low P-wave velocity gradients. The middle continental crust (MCC, 6.35-6.45 km/s) is generally unreflective with low velocity gradient. The main thinning of the continental crust occurs in the thinning domain by attenuation of the UCC and the LCC. Major thinning of the MCC starts to the west of the LCC pinchout point, where it rests directly upon the mantle. In the thinning domain the Moho slope is at least 13 degrees and the continental crust thickness decreases seaward from 22 to 11 km over a similar to 35 km distance, stretched by a factor of 1.5 to 3. In the oceanic domain a two-layer high-gradient igneous crust (5.3-6.0 km/s; 6.5-7.4 km/s) was modeled. The intra-crustal interface correlates with prominent mid-basement, 10-15 km long reflections in the multi-channel seismic profile. Strong secondary reflected PmP phases require a first order discontinuity at the Moho. The sedimentary cover can be as thick as 5 km and the igneous crustal thickness varies from 4 to 11 km in the west, where the profile reaches the Madeira-Tore Rise. In the transitional domain the crust has a complex structure that varies both horizontally and vertically. Beneath the continental slope it includes exhumed continental crust (6.15-6.45 km/s). Strong diffractions were modeled to originate at the lower interface of this layer. The western segment of this transitional domain is highly reflective at all levels, probably due to dykes and sills, according to the high apparent susceptibility and density modeled at this location. Sub-Moho mantle velocity is found to be 8.0 km/s, but velocities smaller than 8.0 km/s confined to short segments are not excluded by the data. Strong P-wave wide-angle reflections are modeled to originate at depth of 20 km within the lithospheric mantle, under the eastern segment of the oceanic domain, or even deeper at the transitional domain, suggesting a layered structure for the lithospheric mantle. Both interface depths and velocities of the continental section are in good agreement to the conjugate Newfoundland margin. A similar to 40 km wide OCT having a geophysical signature distinct from the OCT to the north favors a two pulse continental breakup.

Structural modifications in stretch-induced crystallization in PVDF films as measured by small-angle X-ray scattering

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)