Outset of the Morphology of Nanostructured Silica Particles during Nucleation Followed by Ultrasmall-Angle X-ray Scattering.

Nucleation and growth of SBA-15 silica nanostructured particles with well-defined morphologies has been followed with time by small-angle X-ray scattering (SAXS) and ultrasmall-angle X-ray scattering (USAXS), using synchrotron radiation. Three different morphologies have been compared: platelets, toroids, and rods. SEM observations of the particles confirm that two key physical parameters control the morphology: the temperature and the stirring of the solution. USAXS curves demonstrate that primary particles with a defined shape are present very early in the reaction mixture, immediately after a very fast nucleation step. This nucleation step is detected at 10 min (56 °C) or 15 min (50 °C) after the addition of the silica precursor. The main finding is that the USAXS signal is different for each type of morphology, and we demonstrate that the difference is related to the shape of the particles, showing characteristic form factors for the different morphologies (platelet, toroid, and rod). Moreover, the size of the mesocrystal domains is correlated directly with the particle dimensions and shape. When stirred, aggregation between primary particles is detected even after 12 min (56 °C). The platelet morphology is promoted by constant stirring of the solution, through an oriented aggregation step between primary particles. In contrast, toroids and rods are only stabilized under static conditions. However, for toroids, aggregation is detected almost immediately after nucleation.

Interplay between polymer chain conformation and nanoparticle assembly in model industrial silica/rubber nanocomposites.

The question of the influence of nanoparticles (NPs) on chain dimensions in polymer nanocomposites (PNCs) has been treated mainly through the fundamental way using theoretical or simulation tools and experiments on well-defined model PNCs. Here we present the first experimental study on the influence of NPs on the polymer chain conformation for PNCs designed to be as close as possible to industrial systems employed in the tire industry. PNCs are silica nanoparticles dispersed in a styrene-butadiene-rubber (SBR) matrix whose NP dispersion can be managed by NP loading with interfacial coatings or coupling additives usually employed in the manufacturing mixing process. We associated specific chain (d) labeling, and the so-called zero average contrast (ZAC) method, with SANS, in situ SANS and SAXS/TEM experiments to extract the polymer chain scattering signal at rest for non-cross linked and under stretching for cross-linked PNCs. NP loading, individual clusters or connected networks, as well as the influence of the type, the quantity of interfacial agent and the influence of the elongation rate have been evaluated on the chain conformation and on its related deformation. We clearly distinguish the situations where the silica is perfectly matched from those with unperfected matching by direct comparison of SANS and SAXS structure factors. Whatever the silica matching situation, the additive type and quantity and the filler content, there is no significant change in the polymer dimension for NP loading up to 15% v/v within a range of 5%. One can see an extra scattering contribution at low Q, as often encountered, enhanced for non-perfect silica matching but also visible for perfect filler matching. This contribution can be qualitatively attributed to specific h or d chain adsorption on the NP surface inside the NP cluster that modifies the average scattering neutron contrast of the silica cluster. Under elongation, NPs act as additional cross-linking junctions preventing chain relaxation and giving a deformation of the chain with the NP closer to a theoretical phantom network prediction than a pure matrix.

Photon statistics and speckle visibility spectroscopy with partially coherent X-rays.

A new approach is proposed for measuring structural dynamics in materials from multi-speckle scattering patterns obtained with partially coherent X-rays. Coherent X-ray scattering is already widely used at high-brightness synchrotron lightsources to measure dynamics using X-ray photon correlation spectroscopy, but in many situations this experimental approach based on recording long series of images (i.e. movies) is either not adequate or not practical. Following the development of visible-light speckle visibility spectroscopy, the dynamic information is obtained instead by analyzing the photon statistics and calculating the speckle contrast in single scattering patterns. This quantity, also referred to as the speckle visibility, is determined by the properties of the partially coherent beam and other experimental parameters, as well as the internal motions in the sample (dynamics). As a case study, Brownian dynamics in a low-density colloidal suspension is measured and an excellent agreement is found between correlation functions measured by X-ray photon correlation spectroscopy and the decay in speckle visibility with integration time obtained from the analysis presented here.

Anomalous dynamics at the hard-sphere glass transition.

We use X-ray photon correlation spectroscopy to study the dynamics of hard sphere suspensions and report the emergence of ergodicity restoring anomalous intermittent relaxation modes in the highest concentration suspension that is estimated to be above the glass transition concentration. We associate these phenomena with non-thermal stress induced relaxations and support our interpretation by a direct comparison of the results with predictions of the mode coupling theory.

Highly ordered and highly aligned two-dimensional binary superlattice of a SWNT/cylindrical-micellar system.

We report a highly ordered intercalated hexagonal binary superlattice of hydrophilically functionalized single-walled carbon nanotubes (p-SWNTs) and surfactant (C12 E5 ) cylindrical micelles. When p-SWNTs (with a diameter slightly larger than that of the C12 E5 cylinders) were added to the hexagonally packed C12 E5 cylindrical-micellar system, p-SWNTs positioned themselves in such a way that the free-volume entropies for both p-SWNTs and C12 E5 cylinders were maximized, thus resulting in the intercalated hexagonal binary superlattice. In this binary superlattice, a hexagonal array of p-SWNTs is embedded in a honeycomb lattice of C12 E5 cylinders. The intercalated hexagonal binary superlattice can be highly aligned in one direction by an oscillatory shear field and remains aligned after the shear is removed.

Research on Alloying Elements' Influence on CuETP-Grade Copper's Mechanical and Electrical Properties.

The continuous industrial development that occurs worldwide generates the need to develop new materials with increasingly higher functional properties. This need also applies to the basic material for electricity purposes, which is copper. In this article, we carry out studies on the influence of various alloying elements such as Mg, In, Si, Nb, Hf, Sb, Ni, Al, Fe, Zr, Cr, Zn, P, Ag, Sc, Pb, Sn, Co, Ti, Mn, Te and Bi on the electrical and mechanical properties of ETP-grade copper. The research involves producing copper alloys using the gravity die casting method with alloy additions of 0.1 wt.%, 0.3 wt.% and 0.5 wt.%. All resulting materials are cold-worked to produce wires, which are subsequently homogenized and annealed. The materials produced in this manner undergo testing to determine their specific electrical conductivity, tensile strength, yield strength, elongation and Vickers hardness (HV10 scale).

Microstructure, Mechanical and Corrosion Properties of Copper-Nickel 90/10 Alloy Produced by CMT-WAAM Method.

In the case of copper and its alloys, Wire Arc Additive Manufacturing (WAAM) 3D printing technology is mainly used to produce elements for the maritime industry and research has focused on the use of Cu-Al alloys. There is little information devoted to the use of Cu-Ni alloys in this technology, which are also widely used in the maritime industry. In this work, tests were carried out on the microstructure, mechanical properties, and corrosion properties in a 1M NaCl solution of Cu-Ni 90/10 alloy 3D walls printed using the WAAM method. The obtained objects are characterized by a microstructure with elongated column grains and particles of the Ni-Ti phase, hardness in the range of 138-160 HV10, ultimate tensile strength of 495-520 MPa, yield strength of 342-358 MPa, elongation of 16.6-17.9%, and a low average corrosion rate of 7.4 × 10-5 mm/year. The work shows that it is possible to obtain higher mechanical properties of Cu-Ni 90/10 alloy 3D objects produced using the WAAM method compared to cast materials, which opens up the possibility of using this alloy to produce objects with more complex shapes and for use in corrosive working conditions.

New Graphene Composites for Power Engineering.

Intensive research is underway worldwide to develop new conductive materials for applications in the power industry. Such tests aim to increase the electrical conductivity of materials for conductors and cables, thus increasing the current carrying capacity of the line and reducing the loss of electricity transmission. The scientific discovery of recent years, graphene, one of the allotropic types of carbon with very high electrical and thermal conductivity and mechanical strength, creates great opportunities for designing and producing new materials with above-standard operational properties. This project concentrates on developing technology for manufacturing aluminum-graphene and copper-graphene composites intended to be used to produce a new generation of power engineering conductors. In particular, we present the results of the research on the mechanical synthesis of aluminum-graphene and copper -graphene composites, as well as the results of the electric, mechanical, and structural properties of rods obtained after the extrusion process and wires after the drawing process.

External Surface Quality of the Graphite Crystallizer as a Factor Influencing the Temperature of the Continuous Casting Process of ETP Grade Copper.

Today's world is a place where lack of electrical energy would be unimaginable for most of society. All the conductors in the world, both aluminum and copper, have their origin in various types of casting lines where the liquid metal after crystallization is being processed into the form of wires and microwires. However, the efficiency of the continuous casting processes of metals and the final quality of the manufactured product strictly depend on the design of the used crystallizers, the materials used during its production and its quality. Research conducted in this paper focuses on the latter, i.e., external surface quality of the graphite crystallizer at the place of contact with the primary cooling system. In order to quantify its influence on the continuous casting process numerical analyses using the finite element method has been conducted, which results have been further confirmed during empirical tests in laboratory conditions. It has been proven with all of the proposed methods that the temperature of the obtained cast rod is closely linked to the aforementioned surface quality, as when its roughness coefficient surpasses a certain value the temperature of the obtained product increases almost twofold from approx. 150-170 °C to 300-320 °C. These values might influence the quality and final properties of the cast rod, the susceptibility to wire drawing process and possible formation of wire drawing defects and therefore be of much importance to the casting and processing industry.

A microvolume shear cell for combined rheology and x-ray scattering experiments.

An experimental setup is presented for x-ray scattering studies of soft matter under shear flow that employs a low-background coaxial capillary cell coupled to a high-resolution commercial rheometer. The rotor of the Searle type cell is attached to the rheometer shaft, which allows the application of either steady or oscillatory shear of controlled stress or rate on the sample confined in the annular space between the stator and the rotor. The shearing device facilitates ultrasmall-angle x-ray scattering and ultrasmall-angle x-ray photon correlation spectroscopy measurements with relatively low scattering backgrounds. This enables the elucidation of weak structural features otherwise submerged in the background and probes the underlying dynamics. The performance of the setup is demonstrated by means of a variety of colloidal systems subjected to different rheological protocols. Examples include shear deformation of a short-range attractive colloidal gel, dynamics of dilute colloids in shear flow, distortion of the structure factor of a dense repulsive colloidal suspension, shear induced ordering of colloidal crystals, and alignment of multilamellar microtubes formed by a surfactant-polysaccharide mixture. Finally, the new possibilities offered by this setup for investigating soft matter subjected to shear flow by x-ray scattering are discussed.

Implementation of in situ SAXS/WAXS characterization into silicon/glass microreactors.

A successful implementation of in situ X-ray scattering analysis of synthetized particle materials in silicon/glass microreactors is reported. Calcium carbonate (CaCO3) as a model material was precipitated inside the microchannels through the counter-injection of two aqueous solutions, containing carbonate ions and calcium ions, respectively. The synthesized calcite particles were analyzed in situ in aqueous media by combining Small Angle X-ray Scattering (SAXS) and Wide Angle X-ray Scattering (WAXS) techniques at the ESRF ID02 beam line. At high wavevector transfer, WAXS patterns clearly exhibit different scattering features: broad scattering signals originating from the solvent and the glass lid of the chip, and narrow diffraction peaks coming from CaCO3 particles precipitated rapidly inside the microchannel. At low wavevector transfer, SAXS reveals the rhombohedral morphology of the calcite particles together with their micrometer size without any strong background, neither from the chip nor from the water. This study demonstrates that silicon/glass chips are potentially powerful tools for in situ SAXS/WAXS analysis and are promising for studying the structure and morphology of materials in non-conventional conditions like geological materials under high pressure and high temperature.

Sequential Single Shot X-ray Photon Correlation Spectroscopy at the SACLA Free Electron Laser.

Hard X-ray free electron lasers allow for the first time to access dynamics of condensed matter samples ranging from femtoseconds to several hundred seconds. In particular, the exceptional large transverse coherence of the X-ray pulses and the high time-averaged flux promises to reach time and length scales that have not been accessible up to now with storage ring based sources. However, due to the fluctuations originating from the stochastic nature of the self-amplified spontaneous emission (SASE) process the application of well established techniques such as X-ray photon correlation spectroscopy (XPCS) is challenging. Here we demonstrate a single-shot based sequential XPCS study on a colloidal suspension with a relaxation time comparable to the SACLA free-electron laser pulse repetition rate. High quality correlation functions could be extracted without any indications for sample damage. This opens the way for systematic sequential XPCS experiments at FEL sources.