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Reversible solid-state hydrogen storage is one of the key technologies toward pollutant-free and sustainable energy conversion. The composite system LiBH4-MgH2 can reversibly store hydrogen with a gravimetric capacity of 13 wt%. However, its dehydrogenation/hydrogenation kinetics is extremely sluggish (~40 h) which hinders its usage for commercial applications. In this work, the kinetics of this composite system is significantly enhanced (~96%) by adding a small amount of NbF5. The catalytic effect of NbF5 on the dehydrogenation/hydrogenation process of LiBH4-MgH2 is systematically investigated using a broad range of experimental techniques such as in situ synchrotron radiation X-ray powder diffraction (in situ SR-XPD), X-ray absorption spectroscopy (XAS), anomalous small angle X-ray scattering (ASAXS), and ultra/small-angle neutron scattering (USANS/SANS). The obtained results are utilized to develop a model that explains the catalytic function of NbF5 in hydrogen release and uptake in the LiBH4-MgH2 composite system., The authors thank the great support from the BT5-Instrument staff at NIST center for Neutron Research. In particular, the authors are thankful to Dr David Mildner and Dr Steve Kline for the fruitful discussions and help for the USANS data evaluation and interpretation. The authors thank also CONICET (Consejo Nacional de Invetigaciones Científicas y Técnicas), ANPCyT – (Agencia Nacional de Promoción Científica y Tecnológica), for financial support to carry out this work. We would also like to thank the Metals Physics Division at Helmoltz-Zentrum Hereon for providing the TEM devices. The research leading to these results has received funding from Alexander von Humboldt Foundation, Fellowship number: ARG-1187279-GF-P. This project has received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No 712949 (TECNIOspring PLUS) and the Government of Catalonia's Agency for Business Competitiveness (ACCIÓ).

Vimentin intermediate filaments constitute a distinct filament system in mesenchymal cells that is instrumental for cellular mechanics and migration. In vitro, the rod-like monomers assemble in a multi-step, salt-dependent manner into micrometer long biopolymers. To disclose the underlying mechanisms further, we employed small angle X-ray scattering on two recombinant vimentin variants, whose assembly departs at strategic points from the normal assembly route: (i) vimentin with a tyrosine to leucine change at position 117; (ii) vimentin missing the non-α-helical carboxyl-terminal domain. Y117L vimentin assembles into unit-length filaments (ULFs) only, whereas ΔT vimentin assembles into filaments containing a higher number of tetramers per cross section than normal vimentin filaments. We show that the shape and inner structure of these mutant filaments is significantly altered. ULFs assembled from Y117L vimentin contain more, less tightly bundled vimentin tetramers, and ΔT vimentin filaments preserve the number density despite the higher number of tetramers per filament cross-section. peerReviewed

The long term stability of air processed inkjet infiltrated carbon based perovskite solar cells (CPSCs) is investigated under intense ultra-violet light soaking equivalent to 1.5 Sun UV light illumination. Two batches of the fabricated CPSCs were exposed systematically i.e. first without implementing any protective coating and then epoxying the CPSCs through a low cost commonly available epoxy which was applied to serve as a barrier against moisture and humidity intrusions. The CPSCs with no protective layer against moisture and humidity first exhibited impressive preliminary stability for hundreds of hours during their exposition by intense UV light and provided great motivation to test the CPSCs further with more optimization. As a result, the CPSCs having commonly available epoxy as a protective barrier exhibited remarkable durability and showed no performance degradation for a period of 1002 hours under intense and continuous 1.5 Sun equivalent UV light illumination proving that the technology is clearly not inherently instable and that future developments might lead to market breakthrough.

Conducting polymers (CP) as an active material in electrochemical actuators are often likened to “artificial muscles”. To transfer the isotropic change of volume in the CP component into an anisotropic actuation as in a natural muscle, different design approaches, mostly bilayer or triple layer bending devices, have been studied. Herein, we report a novel actuator design with an almost linear strain response, consisting of nanostructured aligned multi-walled carbon nanotube arrays in which each MWCNT is individually coated with a thin layer of polypyrrole.

Lithium reactive hydride composite 2LiBH4 + MgH2 (Li-RHC) has been lately investigated owing to its potential as hydrogen storage medium for mobile applications. However, the main problem associated with this material is its sluggish kinetic behavior. Thus, aiming to improve the kinetic properties, in the present work the effect of the addition of Fe to Li-RHC is investigated. The addition of Fe lowers the starting decomposition temperature of Li-RHC about 30 °C and leads to a considerably faster isothermal dehydrogenation rate during the first hydrogen sorption cycle. Upon hydrogenation, MgH2 and LiBH4 are formed whereas Fe appears not to take part in any reaction. Upon the first dehydrogenation, the formation of nanocrystalline, well distributed FeB reduces the overall hydrogen storage capacity of the system. Throughout cycling, the agglomeration of FeB particles causes a kinetic deterioration. An analysis of the hydrogen kinetic mechanism during cycling shows that the hydrogenation and dehydrogenation behavior is influenced by the activity of FeB as heterogeneous nucleation center for MgB2 and its non-homogenous distribution in the Li-RHC matrix. Fil: Puszkiel, Julián Atilio. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Helmholtz-zentrum Geesthacht - Zentrum Für Material- Und Küstenforschung Gmbh; Fil: Gennari, Fabiana Cristina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Centro Atómico Bariloche; Argentina Fil: Arneodo Larochette, Pierre Paul. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Centro Atómico Bariloche; Argentina Fil: Ramallo Lopez, Jose Martin. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina Fil: Vainio, U.. Helmholtz-zentrum Geesthacht - Zentrum Für Material- Und Küstenforschung Gmbh; . Deutsches Elektronen-Synchrotron; Alemania Fil: Karimi, F.. Helmholtz-zentrum Geesthacht - Zentrum Für Material- Und Küstenforschung Gmbh; Fil: Pranzas, P. K.. Helmholtz-zentrum Geesthacht - Zentrum Für Material- Und Küstenforschung Gmbh; Fil: Troiani, Horacio Esteban. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Centro Atómico Bariloche; Argentina Fil: Pistidda, C.. Helmholtz-zentrum Geesthacht - Zentrum Für Material- Und Küstenforschung Gmbh; Fil: Jepsen, J.. Helmholtz-zentrum Geesthacht - Zentrum Für Material- Und Küstenforschung Gmbh; Fil: Tolkiehn, M.. Deutsches Elektronen-Synchrotron; Alemania Fil: Welter, E.. Deutsches Elektronen-Synchrotron; Alemania Fil: Klassen, T.. Helmholtz-zentrum Geesthacht - Zentrum Für Material- Und Küstenforschung Gmbh; Fil: Bellosta Von Colbe, J.. Helmholtz-zentrum Geesthacht - Zentrum Für Material- Und Küstenforschung Gmbh; Fil: Dornheim, M.. Helmholtz-zentrum Geesthacht - Zentrum Für Material- Und Küstenforschung Gmbh

A preparation strategy is developed for monolithic samples of nanoporous gold with a hierarchical structure comprising two nested networks of solid "ligaments" on distinctly different structural length scales. The electrochemical dealloying protocol achieves a large retention of less noble element in a first corrosion step, thereby allowing an extra corrosion step which forms a separate structural hierarchy level. The beneficial impact of adding Pt to the Ag-Au master alloys that are more conventionally used in dealloying approaches to nanoporous gold is demonstrated. At approximate to 6 nm, the lower hierarchy level ligament size emerges extremely small. Furthermore, Pt favors the retention of Ag during the first dealloying step even when the master alloy has a high Au content. The high Au content reduces the corrosion-induced shrinkage, mitigating crack formation during preparation and favoring the formation of high-quality macroscopic (mm-sized) samples. The corrosion effectively carves out the nanoscale hierarchical ligament structure from the parent crystals tens of micrometers in size. This is revealed by X-ray as well as electron backscatter diffraction, which shows that the porous crystallites inherit the highly ordered, macroscopic crystal lattice structure of the master alloy.

Isoporous asymmetric polystyrene- block -poly(4-vinylpyridine) (PS- b -P4VP) hollow fiber membranes were successfully made by a dry-jet wet spinning process. Well-defined nanometer-scale pores around 20–40 nm in diameter were tailored on the top surface of the fiber above a non-ordered macroporous layer by combining block copolymer self-assembly and non-solvent induced phase separation (SNIPS). Uniformity of the surface-assembled pores and fiber cross-section morphology was improved by adjusting the solution concentration, solvent composition as well as some important spinning parameters such as bore fluid flow rate, polymer solution flow rate and air gap distance between the spinneret and the precipitation bath. The formation of the well-organized self-assembled pores is a result of the interplay of fast relaxation of the shear-induced oriented block copolymer chains, the rapid evaporation of the solvent mixture on the outer surface and solvent extraction into the bore liquid on the lumen side, and gravity force during spinning. Structural features of the block copolymer solutions were investigated by small-angle X-ray scattering (SAXS) and rheological properties of the solutions were examined as well. The scattering patterns of the optimal solutions for membrane formation indicate a disordered phase which is very close to the disorder-order transition. The nanostructured surface and cross-section morphology of the membranes were characterized by scanning electron microscopy (SEM). The water flux of the membranes was measured and gas permeation was examined to test the pressure stability of the hollow fibers.

Carbon nanotube “forests” show great promise in a variety of applications, from supercapacitors to fuel cells, but the realization of such materials for functional devices relies on a better control over processing routes such that targeted structures and associated properties can be reproducibly obtained. The orientation distribution of the nanotubes is a critical structural property affecting both electrical and mechanical response, yet it remains a challenging characteristic to quantify. Small-angle X-ray scattering (SAXS) is a technique well suited to investigate the vertical alignment of nanotubes. Here we show that the orientation distribution obtained from SAXS is not satisfactorily represented by the normal distribution or the Lorentzian, which have been used until now. Instead, an excellent agreement between model and data is found with the generalized normal distribution (GND). Such quantification of the carbon nanotube alignment can be used as direct input in simulations for optimizing structur...

Time-resolved grazing-incidence small-angle X-ray scattering (GISAXS) and cryo-microscopy were used for the first time to understand the pore evolution by copolymer assembly, leading to the formation of isoporous membranes with exceptional porosity and regularity. The formation of copolymer micelle strings in solution (in DMF/DOX/THF and DMF/DOX) was confirmed by cryo field emission scanning electron microscopy (cryo-FESEM) with a distance of 72 nm between centers of micelles placed in different strings. SAXS measurement of block copolymer solutions in DMF/DOX indicated hexagonal assembly with micelle-to-micelle distance of 84–87 nm for 14–20 wt% copolymer solutions. GISAXS in-plane peaks were detected, revealing order close to hexagonal. The d -spacing corresponding to the first peak in this case was 100–130 nm (lattice constant 115–150 nm) for 17 wt% copolymer solutions evaporating up to 100 s. Time-resolved cryo-FESEM showed the formation of incipient pores on the film surface after 4 s copolymer solution casting with distances between void centers of 125 nm.

Owing to a theoretical hydrogen storage capacity of 10.5 wt% H2, Ca(BH4)2+MgH2, the so-called calcium reactive hydride composite (Ca-RHC), has a great potential as a hydrogen storage material. However, its dehydrogenation temperature (∼623 K) is too high for any mobile applications. By addition of 10 mol% of NbF5into Ca(BH4)2+MgH2, a decrease of the dehydrogenation onset temperature by ∼120 K is observed. In order to understand the reasons behind this desorption temperature decrement two sets of samples [Ca(BH4)2+MgH2and Ca(BH4)2+MgH2+0.1NbF5] in different hydrogenation states, were prepared. The structural investigation of the above mentioned sets of samples by means of volumetric measurements, anomalous small-angle X-ray scattering (ASAXS) and X-ray absorption spectroscopy (XAS) is reported here. The XAS results show that after the milling procedure NbB2is formed and remains stable upon further de/rehydrogenation cycling. The results of Nb ASAXS point to nanometric spherical NbB2particles distributed in the hydride matrix, with a mean diameter of ∼10 nm. Results from Ca ASAXS indicate Ca-containing nanostructures in the Ca-RHC+0.1NbF5samples to be ∼50% finer compared to those without additive. Thus, a higher reaction surface area and shorter diffusion paths for the constituents are concluded to be important contributions to the catalytic effect of an NbF5additive on the hydrogen sorption kinetics of the Ca(BH4)2+MgH2composite system.

The assembly kinetics of intermediate filament (IF) proteins from tetrameric complexes to single filaments and networks depends on the protein concentration, temperature and the ionic composition of their environment. We systematically investigate how changes in the concentration of monovalent potassium and divalent magnesium ions affect the internal organization of the resulting filaments. Small angle X-ray scattering (SAXS) is very sensitive to changes in the filament cross-section such as diameter or compactness. Our measurements reveal that filaments formed in the presence of magnesium chloride differ distinctly from filaments formed in the presence of potassium chloride. The principle multi-step assembly mechanism from tetramers via unit-length filaments (ULF) to elongated filaments is not changed by the valency of ions. However, the observed differences indicate that the magnesium ions free the head domains of tetramers from unproductive interactions to allow assembly but at the same time mediate strong inter-tetrameric interactions that impede longitudinal annealing of unit-length filaments considerably, thus slowing down filament growth.

Metal nanoparticles have attracted much attention due to their unique properties. Size control provides an effective key to an accurate adjustment of colloidal properties. The common approach to size control is testing different sets of parameters via trial and error. The actual particle growth mechanisms, and in particular the influences of synthesis parameters on the growth process, remain a black box. As a result, precise size control is rarely achieved for most metal nanoparticles. This contribution presents an approach to size control that is based on mechanistic knowledge. It is exemplified for a common silver nanoparticle synthesis, namely, the reduction of AgClO4 with NaBH4. Conducting this approach allowed a well-directed modification of this synthesis that enables, for the first time, the size-controlled production of silver nanoparticles 4–8 nm in radius without addition of any stabilization agent.

Catalysis, energy storage, and light harvesting require functional materials with tailored porosity and nanostructure. However, common synthesis methods that employ polymer micelles as structure-directing agents fail for zinc oxide, for cobalt oxide, and for metal carbonates in general. We report the synthesis of the oxides and carbonates of zinc, cobalt, and aluminum with micelle-templated structure. The synthesis relies on poly(ethylene oxide)-block-poly(butadiene)-block-poly(ethylene oxide) triblock copolymers and a new type of precursor formed by chemical complexation of a metal nitrate with citric acid. A general synthesis mechanism is deduced. Mechanistic insights allow for the prediction of optimal processing conditions for different oxides and carbonates based on simple thermogravimetric analysis. Employing this synthesis, films of ZnO and Co3O4 with micelle-controlled mesoporosity become accessible for the first time. It is the only soft-templating method reported so far that also yields mesoporo...

Nanoscale 5, 3969-3975 (2013). doi:10.1039/c3nr33282a, The mesostructure of ordered arrays of anisotropic nanoparticles is controlled by a combination of packing constraints and interparticle interactions, two factors that are strongly dependent on the particle morphology. We have investigated how the degree of truncation of iron oxide nanocubes controls the mesostructure and particle orientation in drop cast mesocrystal arrays. The combination of grazing incidence small-angle X-ray scattering and scanning electron microscopy shows that mesocrystals of highly truncated cubic nanoparticles assemble in an fcc-type mesostructure, similar to arrays formed by iron oxide nanospheres, but with a significantly reduced packing density and displaying two different growth orientations. Strong satellite reflections in the GISAXS pattern indicate a commensurate mesoscopic superstructure that is related to stacking faults in mesocrystals of the anisotropic nanocubes. Our results show how subtle variation in shape anisotropy can induce oriented arrangements of nanoparticles of different structures and also create mesoscopic superstructures of larger periodicity., Published by RSC Publ., Cambridge

International audience; In the present paper, we demonstrate a versatile approach for the one-pot synthesis of metal oxide yolk@shell nanostructures filled with bimetallic nanocores. This novel approach is based on the principles of hydrophobic nanoreactor soft-templating and is exemplified for the synthesis of various AgAu NP @tin-rich ITO (AgAu@ITO TR) yolk@shell nanomateri-als. Hydrophobic nanoreactor soft-templating thereby takes advantage of polystyrene-block-poly(4-vinylpiridine) inverse micelles as two-compartment nanoreactor template, in which the core and the shell of the micelles serve as metal and metal oxide precursor reservoir, respectively. The composition, size and number of AuAg bimetallic nanoparticles incorporated within the ITO TR yolk@shell can easily be tuned. The conductivity of the ITO TR shell and the bimetallic composition of the AuAg nanoparticles, the as-synthesized AuAg NP @ ITO TR yolk@shell materials could be used as efficient electrocatalysts for electrochemical glucose oxidation with improved onset potential when compared to their gold counterpart.

Small-angle X-ray scattering (SAXS) analysis of the diblock copolymer poly(styrene-b-(4-vinyl)pyridine) in a ternary solvent system of 1,4-dioxane, tetrahydrofuran, and N,N-dimethylformamide, and the triblock terpolymer poly(isoprene-b-styrene-b-(4-vinyl)pyridine) in a binary solvent system of 1,4-dioxane and tetrahydrofuran, reveals a concentration-dependent onset of ordered structure formation. Asymmetric membranes fabricated from casting solutions with polymer concentrations at or slightly below this ordering concentration possess selective layers with the desired nanostructure. In addition to rapidly screening possible polymer solution concentrations, solution SAXS analysis also predicts hexagonal and square pore lattices of the final membrane surface structure. These results suggest solution SAXS as a powerful tool for screening casting solution concentrations and predicting surface structure in the fabrication of asymmetric ultrafiltration membranes from self-assembled block copolymers.

Small-angle scattering was measured from activated carbon monoliths prepared from three different wood species (European beech, Pedunculate oak and Norwegian spruce). Substantial differences were found in the scattering images of axial and tangential slices, attributed to their characteristic phytogenic structures. The decrease in anisotropy in the nanostructured carbon matrix due to the activation process is also different among the three investigated types of wood. For quantitative characterization of the anisotropy and its decrease, the degree of alignment was calculated from the azimuthal scattering curves. A simple numeric model was constructed on the basis of direct information obtained by atomic force microscopy. Scattering patterns calculated from the model were compared with the experimental ones to explain the possible structural changes in the carbon skeleton.

The influence of Gd addition on phase separation of rapidly quenched Cu46Zr47−xAl7Gdx metallic glasses (x = 2,5,7) was studied. For low Gd content (x = 2), a homogeneous glass is obtained for the as-quenched state. Annealing leads to cluster formation by nucleation and growth prior to crystallization. For the Gd contents x = 5 and 7, early stages of spinodal decomposition are observed in the as-quenched glasses. Further annealing increases the amplitude of the compositional fluctuations prior to crystallization. Atom probe tomography gives evidence of the presence of Gd-enriched clusters of 2–5 nm size for the Cu46Zr42Al7Gd5 glass. The structure formation as a function of the Gd content is essentially determined by the composition dependence of the miscibility gap of the metastable undercooled melt. Early stages of spinodal decomposition or almost homogeneous glassy states are obtained if the critical temperature of liquid–liquid phase separation is close or below to the glass transition temperature.

A process is described to manufacture monodisperse asymmetric pH-responsive nanochannels with very high densities (pore density2 × 10(14) pores per m(2)), reproducible in m(2) scale. Cylindric pores with diameters in the sub-10 nm range and lengths in the 400 nm range were formed by self-assembly of metal-block copolymer complexes and nonsolvent-induced phase separation. The film morphology was tailored by taking into account the stability constants for a series of metal-polymer complexes and confirmed by AFM. The distribution of metal-copolymer micelles was imaged by transmission electron microscopy tomography. The pH response of the polymer nanochannels is the strongest reported with synthetic pores in the nm range (reversible flux increase of more than 2 orders of magnitude when switching the pH from 2 to 8) and could be demonstrated by cryo-field emission scanning electron microscopy, SAXS, and ultra/nanofiltration experiments.

Complex hydrides are very promising candidates for future light-weight solid state hydrogen storage materials. The present work illustrates detailed characterization of such novel hydride materials on different size scales by the use of synchrotron radiation and neutrons. The comprehensive analysis of such data leads to a deep understanding of the ongoing processes and mechanisms. The reaction pathways during hydrogen desorption and absorption are identified by in situ X-ray diffraction (XRD). Function and size of additive phases are estimated using X-ray absorption spectroscopy (XAS) and anomalous small-angle X-ray scattering (ASAXS). The structure of the metal hydride matrix is characterized using (ultra) small-angle neutron scattering (SANS/USANS). The hydrogen distribution in tanks filled with metal hydride material is studied with neutron computerized tomography (NCT). The results obtained by the different analysis methods are summarized in a final structural model. The complementary information obtained by these different methods is essential for the understanding of the various sorption processes in light metal hydrides and hydrogen storage tanks.

Films with high pore density and regularity that are easy to manufacture by conventional large-scale technology are key components aimed for fabrication of new generations of magnetic arrays for storage media, medical scaffolds, and artificial membranes. However, potential manufacture strategies like the self-assembly of block copolymers, which lead to amazing regular patterns, could be hardly reproduced up to now using commercially feasible methods. Here we report a unique production method of nanoporous films based on the self-assembly of copper(II) ion−polystyrene-b-poly(4-vinylpyridine) complexes and nonsolvent induced phase separation. Extremely high pore densities and uniformity were achieved. Water fluxes of 890 L m−2 h−1 bar−1 were obtained, which are at least 1 order of magnitude higher than those of commercially available membranes with comparable pore size. The pores are also stimuli (pH)-responsive.

A recent report on the “room temperature superplasticity” in the Zr64.13Cu15.75Ni10.12Al10 bulk metallic glass [Y.H. Liu et al., Science315, 1385 (2007)] was ascribed to the distinctive micrometer-sized structural heterogeneity. To verify the microstructure in this alloy, transmission electron microscopy (TEM) and anomalous small-angle x-ray scattering experiments were conducted. The results show that no micrometer-sized or nanometer-sized structural heterogeneities can be found. The micrometer-sized dark and bright regions that were previously reported as the reason for the plasticity are artifacts caused by TEM specimen preparation, rather than the intrinsic structure feature of this alloy. This finding is important for further studying the unique properties of this alloy.

Unique magnetic properties of superparamagnetic iron oxide (hematite) nanoparticles prepared by nanocasting in a periodic nanoporous silica (PNS) matrix are described in this work. The nanoparticles were prepared via a novel approach, when the external surface of PNS was modified to become more hydrophobic. The prepared composite sample was characterized by the synchrotron related techniques small-angle X-ray scattering (SAXS), wide-angle X-ray scattering (WAXS), and X-ray absorption near edge spectra (XANES) measurements, by nitrogen adsorption/desorption, and by high resolution transmission electron microscopy (HRTEM). The investigation of the magnetic properties by superconducting quantum interference device (SQUID) magnetometry at the temperatures 2−300 K shows the superparamagnetic relaxation of the particles with a blocking temperature of TB ∼32 K. Below TB, the ferromagnetic interactions are present as suggested by coercivity HC ∼1900 Oe. The value of magnetic moment mP = 296 μB of the hematite par...

Polymeric matrices with stabilized metallic nanoparticles constitute an important class of nanostructured materials, because polymer technology allows fabrication of components with various electronic, magnetic and mechanical properties. The porous cellulose matrix has been shown to be a useful support material for platinum, palladium, silver, copper and nickel nanoparticles. In the present study, nanosized cobalt particles with enhanced magnetic properties were made by chemical reduction within a microcrystalline cellulose (MCC) matrix. Two different chemical reducers, NaBH4 and NaH2PO2, were used, and the so-formed nanoparticles were characterized with X-ray absorption spectroscopy, X-ray diffraction, scanning electron microscopy and transmission electron microscopy. These experimental techniques were used to gain insight into the effect of different synthesis routes on structural properties of the nanoparticles. Magnetic properties of the nanoparticles were studied using a vibrating sample magnetometer. Particles made via the NaBH4 reduction were amorphous Co-B or Co oxide composites with diminished ferromagnetic behaviour and particles made via the NaH2PO2 reduction were well-ordered ferromagnetic hcp cobalt nanocrystals.

Lignosulfonate is a colloidal polyelectrolyte widely used as a dispersant in various industrial applications and produced during chemical pulping of wood chips. Here we present a systematic small-angle X-ray scattering (SAXS) and rheological study of fractionated lignosulfonate (mass weighted molar mass M w 18 000 g/mol) dissolved in water and 0.2 M NaCl. The concentration range varied from semidilute to concentrated regime. SAXS intensity of all solutions followed the Porod law at all concentrations, which is a clear indication of a compact shape of the lignosulfonate particle. In water, below 10 mass % lignosulfonate, the average interparticle distance obtained from SAXS patterns relates to concentration via a power law with exponent -0.28. Deviation of the power law exponent from ideal -0.33 and a linear decrease in volume fraction normalized Porod constant as a function of concentration are taken as indications of self-association of lignosulfonate. In saline solutions at high lignosulfonate mass fractions the average distance between lignosulfonate particles was longer and the average particle size was larger than those in aqueous solutions. The intrinsic viscosity in saline solution also was larger than that in aqueous solution. Lignosulfonate solutions showed Newtonian viscosity, except at very high concentrations. The variation of the relative zero-shear viscosity eta(0),r) with concentration was interpreted with the Krieger-Dougherty equation. An oblate spheroid shape with an axial ratio of 3.5 describes the average shape of the lignosulfonate particles in saline solutions based on SAXS intensities, the size distribution obtained using gel permeation chromatography, and rheological characterization. The largest dimension of the particles was about 8 nm. SAXS and rheology studies as a function of temperature reveal indications of temperature-dependent self-association.

The microfibril angle (MFA) distribution and the size of cellulose crystallites in isolated double cell walls of Norway spruce (Picea abies [L.] Karst.) tracheids were determined by synchrotron X-ray microdiffraction using the reflections 200 and 004. Samples were 25 μm thick longitudinal sections of earlywood from annual rings 6–18 of several stems. The asymmetric MFA distributions extended from −20° to 90°. The mean MFA of tangential cell walls decreased from an average of 24° into 19° from the pith to the bark. The mode of the MFA distribution was about 10° smaller than the mean MFA. The standard deviation of the MFA distribution varied between 18° and 25°. The mean MFA and the mode of the MFA distribution were larger in radial than in tangential cell walls. MFA distributions of mature wood samples exhibited a separate small peak at around 90°. The average width and length of cellulose crystallites varied between 28.9–30.9 A and 192–284 A, respectively. Both increased slightly as a function of annual ring number from the pith up to the 15th annual ring. An irrigation–fertilisation treatment of some of the stems resulted in longer cellulose crystallites compared to the untreated stems.

Copper and nickel nanoparticles were synthesized in the insoluble microcrystalline cellulose support by reduction of metal ions with several reducers in various media resulting in cellulose-metal nanocomposites. Wide-angle X-ray scattering results showed that supramolecular structure of cellulose did not change. Crystalline Cu 2 O and Cu← 1 0 nanoparticles were prepared with reducers NaBH 4 and N 2 H 4 .H 2 SO 4 , CuO nanoparticles - with cellulose itself as a reducer. Crystalline Ni 0 nanoparticles were synthesized with N 2 H 4 .2HCl and NaBH 4 ; Ni 0 nanoparticles in amorphous form were prepared with KH 2 PO 2 . H 2 O, SEM revealed large agglomerates of metal particles on the fibre surface. ASAXS and TEM have shown the nanoparticles to be in the range 5-55 nm.

Ethylene/1,7-octadiene copolymer was polymerised with metallocene catalyst and hydrosilylated to form silane functionalised polyethylenes (PE-co-SiX, X=Cl, OEt, Ph). The functionalised species were tested as modifiers in composites of rubber toughened polypropylene (heterophasic PP, hPP) and microsilica filler (μSi). A metallocene-based functionalised PE (PE-co-SiF) produced earlier in our laboratory and three commercial grades of functionalised polyolefins (one PE- and two PP-based) were used as reference modifiers. Major differences were seen in the toughness of the composites both above and below the glass transition temperature (Tg) of PP. In addition to increasing the stiffness, the microsilica filler enhanced the toughness of the heterophasic polypropylene by over 200% at ambient temperature. Below the Tg of PP (at −20 °C), the influence of μSi was the opposite and the impact strength of the hPP/μSi composite was below that of unfilled hPP. With the addition of just 2 wt% of functionalised polyethylene, the poor cold toughness of hPP/μSi composite was improved by nearly 100%. With the same addition, the toughness of the composites at ambient temperature was improved by 50 to 100% compared with the unfilled hPP. This behaviour was explained by significant changes in the fracture mechanism. Addition of functionalised PE increased the concentration of microsilica in the rubbery phase, allowing the crack to enter that phase. The rubbery phase was also able to absorb a large amount of impact energy below the glass transition temperature of PP.

Nickel nanoparticles were synthesized by adding aqueous nickel salt into a microcrystalline cellulose matrix. The NiII ions were reduced with either sodium borohydride, NaBH_4, or potassium hypophosphite, KH_2PO_2, in water or aqueous NH_3 medium. The mass fraction of Ni in the samples was between 3.7 and 8.9%. X-ray absorption spectra at the Ni K-edge showed that Ni was partially oxidized only in a sample reduced with NaBH_4. Wide-angle X-ray scattering results showed that nickel was in nanocrystalline or amorphous form in the samples. Upon heating fcc Ni, hcp Ni, NiO, Ni_3P and other Ni–P phases formed depending on the reduction parameters. Using anomalous small-angle X-ray scattering the nanometre-scale particle size distributions of the Ni particles were determined. A large fraction of particles less than 15 nm in size were observed in the samples reduced in aqueous ammonium compared with the samples reduced in water. Particles reduced in aqueous ammonium had a large ferromagnetic component.

Previously we demonstrated hierarchical self- assembly and mesoporosity in electrospun fibers using selected polystyrene- block- poly(4- vinylpyridine) (PS- b- P4VP) diblock copolymers with hydrogen- bonded 3- n- pentadecylphenol (PDP), which rendered distorted spherical P4VP(PDP)(1.0) domains within the PS matrix, internal lamellar order within the P4VP(PDP)(1.0) domains, and allowed distorted spherical pores by removing PDP (Adv. Mater. 2005, 17, 1048). Here we study whether the internal structure of electrospun fibers can be systematically tailored by varying the compositions of PS- b- P4VP(PDP)(1.0). We expect these complexes to be feasible choices to combine electrospinning and self- assembly, as relatively high molecular weight block copolymers are useful for electrospinning, and enhanced structure formation due to plasticization by the amphiphilic PDP was expected. Not surprisingly, the self- assembled structures of the as- prepared fibers were less perfect than those in the corresponding well- annealed bulk materials. Compositions that show spherical self- assembly of P4VP(PDP)(1.0) within the PS matrix in bulk lead to distinct and elongated worm- like P4VP(PDP)(1.0) domains within the PS matrix in electrospun fibers. More symmetric compositions, which showed lamellar self- assembly in bulk, lead to structures where both PS and P4VP(PDP)(1.0) domains were worm- like and elongated in a relatively symmetric manner. Finally, compositions which in bulk showed self- assembly of PS spheres within the P4VP(PDP)(1.0) matrix, lead to separate distorted PS domains in the P4VP(PDP)(1.0) matrix. Additionally, SAXS measurements suggest a lamellar structure within the P4VP(PDP)(1.0) domains. As electrospinning is a facile method to prepare mesoscale fibers, and it is known that the amphiphiles can be removed from the hierarchical assemblies, the present method offers the potential to tune the internal porosity of the fibers for e. g. release and absorption purposes.

Designing safe, compact and high capacity hydrogen storage systems is the key step towards introducing a pollutant free hydrogen technology into a broad field of applications. Due to the chemical bonds of hydrogen-metal atoms, metal hydrides provide high energy density in safe hydrogen storage media. Reactive hydride composites (RHCs) are a promising class of high capacity solid state hydrogen storage systems. Ca(BH4)2 + MgH2 with a hydrogen content of 8.4 wt% is one of the most promising members of the RHCs. However, its relatively high desorption temperature of ∼350 °C is a major drawback to meeting the requirements for practical application. In this work, by using NbF5 as an additive, the dehydrogenation temperature of this RHC was significantly decreased. To elucidate the role of NbF5 in enhancing the desorption properties of the Ca(BH4)2 + MgH2 (Ca-RHC), a comprehensive investigation was carried out via manometric measurements, mass spectrometry, Differential Scanning Calorimetry (DSC), in situ Synchrotron Radiation-Powder X-ray Diffraction (SR-PXD), X-ray Absorption Spectroscopy (XAS), Anomalous Small-Angle X-ray Scattering (ASAXS), Scanning and Transmission Electron Microscopy (SEM, TEM) and Nuclear Magnetic Resonance (NMR) techniques. Fil: Karimi, Fahim. Helmholtz-zentrum Geesthacht; Alemania Fil: Klaus Pranzas, P.. Helmholtz-zentrum Geesthacht; Alemania Fil: Pistidda, Claudio. Helmholtz-zentrum Geesthacht; Alemania Fil: Puszkiel, Julián Atilio. Helmholtz-zentrum Geesthacht; Alemania. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina Fil: Milanese, Chiara. Universita Degli Studi Di Pavia; Italia Fil: Vainio, Ulla. Helmholtz-zentrum Geesthacht; Alemania Fil: Paskevicius, Mark. Curtin University; Australia Fil: Emmler, Thomas. Helmholtz-zentrum Geesthacht; Alemania Fil: Santoru, Antonio. Helmholtz-zentrum Geesthacht; Alemania Fil: Utke, Rapee. Helmholtz-zentrum Geesthacht; Alemania. Suranaree University of Technology; Tailandia Fil: Tolkiehn, Martin. No especifíca; Fil: Minella, Christian B.. Helmholtz-zentrum Geesthacht; Alemania Fil: Chaudhary, Anna Lisa. Helmholtz-zentrum Geesthacht; Alemania Fil: Boerries, Stefan. Helmholtz-zentrum Geesthacht; Alemania Fil: Buckley, Craig E.. Curtin University; Australia Fil: Enzo, Stefano. University of Sassari; Italia Fil: Schreyer, Andreas. Helmholtz-zentrum Geesthacht; Alemania Fil: Klassen, Thomas. Helmholtz-zentrum Geesthacht; Alemania Fil: Dornheim, Martin. Helmholtz-zentrum Geesthacht; Alemania

A matrix of microcrystalline cellulose was used as a nanoreactor for the reduction of Ni(II) ions with hydrazine dihydrochloride.

Wood is a complex material, from which different structural factors are extensively studied. Despite decades of work, the question on how cellulose chains are oriented in a mature wood cell wall is not yet fully answered. The orientation is defined as the angle between the chains and the cell axis (microfibril angle, MFA). In this work tracheids of Norway spruce (Picea abies [L.] Karst.) were studied with a micrometer-size beam of synchrotron radiation to probe the single cell walls through bordered pits. The obtained MFA distributions are asymmetric and contain mostly either left- or right-handed helices. The asymmetry most likely arises from the structure of the S2-layer of the secondary wall. The mean values and the positions of the maxima of the distributions obtained by X-ray diffraction were compared to values of MFA obtained by polarisation microscopy from the same parts of the cell walls. The results by polarisation microscopy were different; possible reasons for this are discussed.

The properties of polypropylene composites can be tailored through the use of nanoclay fillers. The effectiveness of a metallocene-catalyzed hydroxyl-functional polypropylene in the compatibilization of polypropylene layered nanosilicate composites was studied, and the results were compared with those for a commercial maleic anhydride functionalized polypropylene. Polypropylene/organoclay nanocomposites were prepared by melt blending, and two polypropylene/compatibilizer/organoclay ratios, 90/5/5 and 70/20/10, were characterized. The organomodification of the clay was carried out with octadecylamine and N-methylundecenylamine. The structure of the layered silicate was studied by transmission electron microscopy, wide-angle X-ray scattering, and small-angle X-ray scattering. The fracture surfaces of the composites and thus the efficiency of the compatibilizers to penetrate the galleries of the organoclays were characterized by scanning electron microscopy, and the melt viscosity was studied by stress-controlled rotational rheometry. The nanostructure was observed with both alkyl amines used for intercalation. The fillers facilitated the processability of all the composites, consisting of equal amounts of compatibilizer and organoclay filler and, in some of the composites, containing twice as much compatibilizer as organoclay filler.

We present investigations of the self-organized structure, overall uniaxial alignment, and larger-scale interface morphology in thin films of low-molecular-weight hairy-rodlike,pi-conjugated poly(9,9-bis(ethylhexyl)-fluorene2-7-diyl), (LMW-PF2/6) (M-n = 7600 g/mol) and a comparison of high-molecular-weight PF2/6 (HMW-PF2/ 6) (M-n = 150 000 g/mol). Photoabsorption, grazing-incidence X-ray diffraction, small/wide-angle X-ray scattering. and X-ray reflectivity methods have been used. The experiments have been supported by molecular mechanics-calculated molecular structure and recursively simulated reflectivity curves and discussed in terms of the semiquantitative theoretical analysis of the self-organization of hairy-rodlike polymers. As with HMW-PF2/6. LMW-PF2/6 is found to be a thermotropic liquid crystal consisting of rodlike 5/2 helices. Blue photoluminescence with an absolute photoluminescence quantum yield of 32% in the solid films is observed. After thermotropic alignment on rubbed substrates, considerably higher dichroic ratios in absorption, >10, are found, indicating a far higher degree of axial alignment compared to the similarly processed HMW-PF2/ 6. The degree of spatial order has been found to be high along the rubbing direction, the z axis but, in contrast to HMW-PF2/6, the structure perpendicular to the z axis on the (ab0) plane is observed to be less ordered, and no multiple orientation (Knaapila, M.; Lyons, B. P.; Kisko, K.; Foreman, J. P.; Vainio, U.; Mihaylova, M.; Seeck, O. H.; Palsson, L.-O.; Serimaa, R.; Torkkeli, M.; Monkman, A. P. J. PhYs. Chem. B 2003, 107, 12425-12430) is seen. Both in bulk and in thin aligned films, LMW-PF2/6 is suggested to approach a nematic instead of a well-defined hexagonal structure. These findings are in agreement with the presented theoretical arguments. LMW-PF2/6 is also shown to form well-developed larger-scale morphology and surface roughness below 2 nm in films over the thickness range from 20 to 200 nm. There is also a difference in macroscopic texture in polarized micrographs between these materials, but the influence of the molecular weight cannot be rigorously established at present.

International audience; This contribution provides a comprehensive mechanistic picture of the gold nanoparticle synthesis by citrate reduction of HAuCl4, known as Turkevich method, by addressing five key questions. The synthesis leads to monodisperse final particles as a result of a seed-mediated growth mechanism. In the initial phase of the synthesis, seed particles are formed onto which the residual gold is distributed during the course of reaction. It is shown that this mechanism is a fortunate coincidence created by a favorable interplay of several chemical and physicochemical processes which initiate but also terminate the formation of seed particles and prevent the formation of further particles at later stages of reaction. Since no further particles are formed after seed particle formation, the number of seeds defines the final total particle number and therefore the final size. The gained understanding allows illustrating the influence of reaction conditions on the growth process and thus the final size distribution

International audience; Due to their unique morphology-related properties, yolk@shell materials are promising materials for catalysis, drug delivery, energy conversion, and storage. Despite their proven potential, large-scale applications are however limited due to demanding synthesis protocols. Overcoming these limitations, a simple softtemplated approach for the one-pot synthesis of yolk@shell nanocomposites and in particular of multicore metal nanoparticle@metal oxide nanostructures (M NP @MO x ) is introduced. The approach here, as demonstrated for Au NP @ITO TR (ITO TR standing for tin-rich ITO), relies on polystyrene- block -poly(4- vinylpyridine) (PS- b -P4VP) inverse micelles as two compartment nanoreactor templates. While the hydrophilic P4VP core incorporates the hydrophilic metal precursor, the hydrophobic PS corona takes up the hydrophobic metal oxide precursor. As a result, interfacial reactions between the precursors can take place, leading to the formation of yolk@shell structures in solution. Once calcined these micelles yield Au NP @ITO TR nanostructures, composed of multiple 6 nm sized Au NPs strongly anchored onto the inner surface of porous 35 nm sized ITO TR hollow spheres. Although of multicore nature, only limited sintering of the metal nanoparticles is observed at high temperatures (700 °C). In addition, the as-synthesized yolk@shell structures exhibit high and stable activity toward CO electrooxidation, thus demonstrating the applicability of our approach for the design of functional yolk@shell nanocatalysts.

In this study, the rheological properties of polystyrene-block-polyisoprene (PS-b-PI) diblock copolymer melts with different types of morphology are analysed. Using the technique of anionic polymerization three different PS-b-PI diblock copolymers with a spherical, cylindrical and lamellar morphology, respectively, were synthesised. The objective of our study was to determine the viscous and elastic properties of these PS-b-PI diblock copolymers and to investigate the influence of morphology on the viscoelastic properties at short and long times. The analysis of our experiments reveals that morphological changes take place in the melt which lead to changes of the dynamic moduli. Furthermore, all three diblock copolymers of this study reveal a non-terminal behaviour in oscillatory shear flow in the microphase-separated state. Our creep recovery experiments indicate that microphase-separated diblock copolymers are characterised by a pronounced recoverable deformation.

Hypothesis Zirconia microparticles produced by sol–gel synthesis have great potential for photonic applications. To this end, identifying synthetic methods that yield reproducible control over size uniformity is important. Phase transformations during thermal cycling can disintegrate the particles. Therefore, understanding the parameters driving these transformations is essential for enabling high-temperature applications. Particle morphology is expected to influence particle processability and stability. Yttria-doping should improve the thermal stability of the particles, as it does in bulk zirconia. Experiments Zirconia and YSZ particles were synthesized by improved sol–gel approaches using fatty acid stabilizers. The particles were heated to 1500 °C, and structural and morphological changes were monitored by SEM, ex situ XRD and high-energy in situ XRD. Findings Zirconia particles (0.4–4.3 μm in diameter, 5–10% standard deviation) synthesized according to the modified sol–gel approaches yielded significantly improved monodispersities. As-synthesized amorphous particles transformed to the tetragonal phase at ∼450 °C with a volume decrease of up to ∼75% and then to monoclinic after heating from ∼650 to 850 °C. Submicron particles disintegrated at ∼850 °C and microparticles at ∼1200 °C due to grain growth. In situ XRD revealed that the transition from the amorphous to tetragonal phase was accompanied by relief in microstrain and the transition from tetragonal to monoclinic was correlated with the tetragonal grain size. Early crystallization and smaller initial grain sizes, which depend on the precursors used for particle synthesis, coincided with higher stability. Yttria-doping reduced grain growth, stabilized the tetragonal phase, and significantly improved the thermal stability of the particles.

Parallel and concentric alignment of microscopic building blocks into several orders of magnitude larger structures is commonly observed in nature. However, if similarly aligned structures are artificially produced their thickness is generally limited to just about one or two orders of magnitude more than the dimensions of the smallest element. We show that sedimentation provides a promising approach to manufacture solid materials consisting of well-aligned platelet-shaped particles while being more than 30 000 times thicker than the individual particle. Such sediments contain up to 28 vol% of particles without any further treatment and can be densified to 67 vol% particle fraction by subsequent unidirectional pressing. The degree of orientation of the platelet-shaped particles within the sediments was tracked by high-energy X-ray diffraction measurements. The Hermans orientation parameter, a statistical measure of the quality of alignment, was determined to be 0.63 ± 0.03 already for as-sedimented samples while the standard deviation of the orientation distribution of particles, another measure of average misalignment, was found to be (21.5 ± 1.4)°. After pressing, these values further improved to (0.81 ± 0.01) and (14.6 ± 0.4)°, respectively. Such quality of alignment competes with, if not even exceeds, values reported in the literature.

The formation of azo dyestuff aggregates in dilute aqueous solution induced by the addition of Mg2+, Ca2+, Sr2+, or Ba2+ ions is followed by time-resolved static light scattering (SLS) and time-res...

Cobalt nanoparticles play an important role as catalysts for the Fischer–Tropsch synthesis, which is an attractive route for production of synthetic fuels. It is of particular interest to understand the varying conversion rate during the first hours after introducing synthesis gas (H2 and CO) to the system. To this end, several in situ characterization studies have previously been done on both idealized model systems and commercially relevant catalyst nanoparticles, using bulk techniques, such as X-ray powder diffraction and X-ray absorption spectroscopy. Since catalysis takes place at the surface of the cobalt particles, it is important to develop methods to gain surface-specific structural information under realistic processing conditions. We addressed this challenge using small-angle X-ray scattering (SAXS), a technique exploiting the penetrating nature of X-rays to provide information about particle morphology during in situ experiments. Simultaneous wide-angle X-ray scattering was used for monitoring the reduction from oxide to catalytically active metal cobalt, and anomalous SAXS was used for distinguishing the cobalt particles from the other phases present. After introducing the synthesis gas, we found that the slope of the scattered intensity in the Porod region increased significantly, while the scattering invariant remained essentially constant, indicating a change in the shape or surface structure of the particles. Shape- and surface change models are discussed in light of the experimental results, leading to an improved understanding of catalytic nanoparticles.

International audience; The controlled incorporation of single metal nanoparticles within the pores of mesostructured conducting metal oxide ultrathin films is demonstrated, taking advantage of the controlled metal precursor loading capacities of PS-b-P4VP inverse micellar templates. The presented one-pot approach denoted as Evaporation-Induced Hydrophobic Nanoreactor Templating (EIHNT) unusually involves the nanostructuration of the metal oxide via the hydrophobic shell of the micellar template, while the concomitant nanostructuration of the metal is achieved via its confinement in the hydrophilic micellar core. This approach is applied to tin-rich ITO and gold, to yield unique mesoporous tin-rich ITO ultrathin film electrodes remarkably loaded with one size-controlled gold nanoparticle per pore. Interestingly, the resulting tin-rich ITO-supported gold nanoparticles exhibit improved catalytic activity and durability in electrocatalytic CO oxidation compared to similarly sized gold nanoparticles supported on conventional ITO coatings.

We fabricated block copolymer hollow fiber membranes with self-assembled, shell-side, uniform pore structures. The fibers in these membranes combined pores able to respond to pH and acting as chemical gates that opened above pH 4, and catalytic activity, achieved by the incorporation of gold nanoparticles. We used a dry/wet spinning process to produce the asymmetric hollow fibers and determined the conditions under which the hollow fibers were optimized to create the desired pore morphology and the necessary mechanical stability. To induce ordered micelle assembly in the doped solution, we identified an ideal solvent mixture as confirmed by small-angle X-ray scattering. We then reduced p-nitrophenol with a gold-loaded fiber to confirm the catalytic performance of the membranes.

Polymer 54(15), 3860 - 3873 (2013). doi:10.1016/j.polymer.2013.05.025, Published by Elsevier Science, Oxford