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Bone substitutes are widely employed for applications in orthopedic surgery for the replacement of injured bone. Among the diverse methods that are used to design 3D bioceramic matrices, Freeze Foaming has gained attention, since it provides the ability to tune the shape of the created structures. One of the major problems related to these constructs is the lack of porosity at the outwards sides (holder) of the scaffold, thus reducing the cellular affinity and creating a rejection of the implant. In this research, we aimed to develop a bone scaffold with enhanced surface properties and improved cellular affinity. The main aim was to alter the biocompatibility characteristics of the 3D bioceramic constructs. We have produced three-dimensional, complex-shaped hollow shell structures, manufactured by Additive Manufacturing processes and as a second step, filled with a ceramic suspension by the Freeze-Foaming process. 3D constructs from HAP-derived TCP and TCP/ZrO2 were synthesized by freezefoaming method and subsequently irradiated with a fs-laser (λ = 800 nm) spanning a range of parameters for achievement of optimal surface processing conditions. The designed scaffolds demonstrated enhanced topographical properties with improved porosity examined by SEM, EDX, and 3D profilometry after laser treatment. Wettability and computer tomography (CT) evaluation was also performed. The results from X-ray diffraction (XRD) and micro-Raman analysis did not show photochemical and surface or volume defects and changes after laser processing of the ceramic samples. Preliminary results from MG-63 osteoblast-like cell tests showed good cell affinity on the processed surfaces and no cytotoxic effect on the cells. [ABSTRACT FROM AUTHOR]

A pilot study using a non-destructive imaging technique to detect the presence of microparticles of lead shot in earthworms Lumbricus terrestris was carried out. Earthworms play a crucial role as inhabitants of soil communities, constituting a substantial portion of their biomass. They are regarded as valuable indicators providing insights into the functional status of soils and the deposition of heavy metals. The differentiation of lead-shot microparticles from other metallic or organic particles was achieved using high-resolution X-ray computed microtomography. Applying this method allowed the reconstruction of the internal structure of the samples without compromising their integrity. [ABSTRACT FROM AUTHOR]

Biomacromolecules control mineral formation during the biomineralization process, but the effects of the organic components' functionality on the type of mineral phase is still unclear. The biomimetic precipitation of calcium phosphates in a physiological medium containing either polycarboxybetaine (PCB) or polysulfobetaine (PSB) was investigated in this study. Amorphous calcium phosphate (ACP) or a mixture of octacalcium phosphate (OCP) and dicalcium phosphate dihydrate (DCPD) in different ratios were identified depending on the sequence of initial solution mixing and on the type of the negative functional group of the polymer used. The more acidic character of the sulfo group in PSB than the carboxy one in PCB determines the dominance of the acidic solid phases, namely, an acidic amorphous phase or DCPD. In the presence of PCB, the formation of ACP with acicular particles arranged in bundles with the same orientation was observed. A preliminary study on the remineralization potential of the hybrid material with the participation of PSB and a mixture of OCP and DCPD did not show an increase in enamel density, contrary to the materials based on PCB and ACP. Moreover, the latter showed the creation of a newly formed crystal layer similar to that of the underlying enamel. This defines PCB/ACP as a promising material for enamel remineralization. [ABSTRACT FROM AUTHOR]

Dielectric glass-ceramic materials find various applications as parts of sensors, electronic components and even in biomedicine. The present work reports on the synthesis of glass-ceramic materials in the complex oxide system (23.1-z)Na2O/17.1BaO/6SrO/23TiO2/17.4SiO2/7.6B2O3/5.8Fe2O3/zAl2O3, z = 0 and 3 mol %. The melts show spontaneous crystallization during quenching. The phase composition is studied using X-ray diffraction and reveals crystallization of Ba1-xSrxTiO3 solid solutions with varying Ba/Sr ratio. The valence states and the local environments of the Ba, Ti and Fe ions of the prepared materials are investigated by utilizing X-ray photoelectron spectroscopy. It is shown that all the elements in the composition are present in their oxidized states and the formation of barium titanate based compounds is possible. The microstructure of the obtained samples is imaged by scanning electron microscopy and shows bright polygon-like crystalline structures embedded in a dark amorphous matrix. The further evaluation of the microstructure as average crystal size and volume fraction of the precipitated crystals is done by using microcomputed tomography. Thus, a relatively high crystalline volume fraction is observed for the samples without alumina. The samples with alumina possess comparable as size and volume fraction crystals. [ABSTRACT FROM AUTHOR]

In this study two hybrid organic–inorganic ureasilicate monomers with different length of polymer segments were chosen for preparation of sol–gel material that includes two moieties blended on the molecular scale. The first monomer was obtained by crosslinking a double terminated polyoxyalkyleneamine with an isocyanate modified silicone ethoxide and the second one – by crosslinking between the isocyanate modified silicone ethoxide with an amino modified silicone ethoxide. Sol–gel route was applied for transformation of the liquid monomer blends in transparent materials with varying degree of rigidity. The prepared samples were characterized by small‐angle X‐ray scattering, Fourier‐transform infrared spectroscopy, positron annihilation lifetime spectroscopy, and swelling experiments. The results demonstrate that the structure of the obtained materials could be tuned by a simple variation of molar fraction ratio between these two monomers. This makes it possible to obtain nanostructured materials with predictable properties. [ABSTRACT FROM AUTHOR]

Herein we report on a detailed investigation of the irreversible capacity in the first cycle of pyrolytic graphite electrodes in aluminum batteries employing 1-ethyl-3-methylimidazolium chloride:aluminum trichloride (EMIMCl:AlCl3) as electrolyte. The reaction mechanism, involving the intercalation of AlCl4− in graphite, has been fully characterized by correlating the micro/nanostructural modification to the electrochemical performance. To achieve this aim a combination of X-ray diffraction (XRD), small angle X-ray scattering (SAXS) and computed tomography (CT) has been used. The reported results evidence that the irreversibility is caused by a very large decrease in the porosity, which consequently leads to microstructural changes resulting in the trapping of ions in the graphite. A powerful characterization methodology is established, which can also be applied more generally to carbon-based energy-related materials. [ABSTRACT FROM AUTHOR]

ABSTRACT Observations of the interaction of poly(dimethylsiloxane) (PDMS) sheet (210 μm thick) with KrF excimer laser irradiation (λ = 248 nm), with low energy of 50 mJ/pulse are presented. The negative ablation or swelling of the material caused by low frequency pulse irradiation is characterized by optical microscopy, μ-Raman spectrometry and X-ray micro-tomography. The appearance of defected areas in the form of cones inside the sheet and changes of material chemistry are discussed. These phenomena are considered as a precursor of the ablation occurring after passing a threshold of absorbed laser irradiation energy. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44541. [ABSTRACT FROM AUTHOR]

The present work reports the structural analysis of magnetic nanocrystals of Fe- and Mn-containing phases formed during annealing of the glass 13.6Na2O-62.9SiO2-8.5MnO-15.0Fe2O3− x (mol%) at 823 K for different periods of time. X-ray diffraction investigation shows the formation of a mixture of MnFe2O4 and Fe3O4 phases. Furthermore, small-angle X-ray scattering and anomalous small-angle X-ray scattering (ASAXS) experiments were used to extract quantitative information about the structure of the formed nano-sized crystals, as well as their phase compositions, volume fractions and size distributions. ASAXS analysis reveals the formation of spherical core-shell particles with the size of the particles between 10 and 50 nm. The concentrations of iron atoms in the core are higher than those in the shell and in the remaining matrix. With increasing annealing time, the ratio of Mn to Fe increases in the nanoparticles and the crystalline phase moves toward the pure jacobsite phase. Evaluated compositions reveal the presence of SiO2 in the shell. This shell acts as a diffusion barrier for the nanocrystal-forming ions, and the growth of the particles is kinetically constrained. [ABSTRACT FROM AUTHOR]

In this investigation, glasses from the system NaO/MnO/SiO/FeO are prepared using a conventional glass-melting technique. During annealing the glass, a nanocrystalline (Fe, Mn)-based spinel phase is precipitated. The phase composition and microstructure of the formed glass-ceramics are studied using X-ray diffraction and electron microscopy. Anomalous small-angle X-ray scattering experiment is used to gather information on the size, composition and element distribution for the precipitated (Fe, Mn)-based nanocrystals. The sizes of the formed spinel crystals, as determined by scanning electron microscopy and anomalous X-ray scattering, are in the range from 12 to 50 nm for annealing temperatures in the range from 550 to 700 °C. Annealing for a longer period of time at temperatures ≥600 °C results in the formation of a second crystalline phase, NaFe(SiO) (aegirine). The ASAXS data show the formation of core-shell structure for the (Fe, Mn)-based crystals with core consisting mostly of iron oxide and a shell, depleted of Fe and Mn. The growth of the spinel crystals is assumed to be kinetically self-constrained. [ABSTRACT FROM AUTHOR]

The morphology of sol–gel derived dip-coated yttria-doped zirconia films containing variable amounts of yttria has been studied using in situgrazing-incidence small-angle X-ray scattering (GISAXS) whilst heated incrementally to 1000 °C.A procedure to analyse in situGISAXS data has been devised which allows a quantitative analysis of time-dependent GISAXS data tracing processes such as chemical reactions or manufacturing procedures. To achieve this, the relative positions of the Yoneda peak and the through beam are used to fix the vertical qscale when the sample thickness is subject to fluctuations due to chemical reactions or deposition processes.A version of Beaucage's unified model with a structure factor from Hosemann's model for paracrystals describes the yttria-zirconia film data best. It is interpreted in terms of particles forming from a polymeric gel network and subsequently agglomerating into larger units subject to Ostwald ripening as both size and average separation distance of the scattering objects increase. The sample with the highest yttria content shows progressive surface roughening from 850 °C which may indicate the onset of chemical segregation. [ABSTRACT FROM AUTHOR]

The two-phase approximation in small-angle scattering is well known and is still the dominant approach to data analysis. The intensity scattered at small angles is proportional to the second power of the difference between the scattering densities of the two phases. Nevertheless, scattering contrast variation techniques are widely used, and they are obviously suitable for multiphase systems or systems with gradually varying scattering density, since if no parasitic scattering contributions are present the scattering contrast variation would only change a proportionality coefficient. It is shown here that the scattered intensity at small angles of a multiphase system can be represented as a sum of the scattering of two-phase systems and terms describing interference between all pairs of phases. Extracting two-phase scattering patterns from multiphase samples by contrast variation is possible. These two-phase patterns can be treated with the usual small-angle scattering formalism. The case of gradually varying scattering density is also discussed. [ABSTRACT FROM AUTHOR]

The theory of small-angle scattering is reviewed with special attention paid to the anomalous scattering and multiphase systems. A general equation is derived that describes the scattering of a multiphase system as a sum of scattering functions of each of the phases, as if it scattered alone in a two-phase system, and interphase interference scattering functions. These scattering functions depend only on the spatial distribution of the phase boundaries, but not on the scattering density. Contrast variation techniques are most rewarding when the scattering density of only one phase can be varied. For anomalous small-angle X-ray scattering (ASAXS), this means the most favourable is the case in which resonant atoms are contained in one phase only. The general equation involves n(p - 1) unknown partial atomic number density differences, where p is the number of phases and n the number of the different atom types in the sample. These partial atomic number density differences can be found if a suitable structure model is applied to calculate the phase scattering functions. Then, the phase compositions and densities can be calculated by solving a system of linear equations incorporating the atom number conservation law. The partial structure factors formalism is also reviewed. Corresponding equations for a system of n types of atoms and p phases are derived. The number of independent partial structure factors is p(p - 1)/2 and depends on the number of phases, but not on the number of the types of the atoms in the sample, as in the case of wide-angle scattering. [ABSTRACT FROM AUTHOR]

Several aspects of the application of the maximum-entropy method (MEM) to the determination of particle size distributions by small-angle scattering (SAS) are discussed. The 'historic' version of the MEM produces completely satisfying results. Limiting the data error from below (i.e. imposing a minimal relative error) is proposed as a solution of some convergence problems. The MEM is tested against the Fourier transform technique. The size distribution of Pb particles in an Al-Pb alloy is determined by the MEM and the Fourier transform technique. The size distributions obtained by transmission electron microscopy (TEM) and SAXS show partial agreement. [ABSTRACT FROM AUTHOR]

The extension of the small-angle scattering technique with polarized neutrons invokes the necessity of new tools for data analysis. Up to five scattering curves can be derived from a single experiment. It is shown that for the case of a dilute system of particles in a matrix, the maximum-entropy method can be modified to analyse any combination of these curves in order to find the underlying particle size distribution. An additional step of simplex or simulated-annealing optimization is introduced in order to determine the particle form-factor parameters. Computer simulations demonstrate the functionality of this method. [ABSTRACT FROM AUTHOR]

The use of laser processing for the creation of diverse morphological patterns onto the surface of polymer scaffolds represents a method for overcoming bacterial biofilm formation and inducing enhanced cellular dynamics. We have investigated the influence of ultra-short laser parameters on 3D-printed poly-ε-caprolactone (PCL) and poly-ε-caprolactone/hydroxyapatite (PCL/HA) scaffolds with the aim of creating submicron geometrical features to improve the matrix biocompatibility properties. Specifically, the present research was focused on monitoring the effect of the laser fluence (F) and the number of applied pulses (N) on the morphological, chemical and mechanical properties of the scaffolds. SEM analysis revealed that the femtosecond laser treatment of the scaffolds led to the formation of two distinct surface geometrical patterns, microchannels and single microprotrusions, without triggering collateral damage to the surrounding zones. We found that the microchannel structures favor the hydrophilicity properties. As demonstrated by the computer tomography results, surface roughness of the modified zones increases compared to the non-modified surface, without influencing the mechanical stability of the 3D matrices. The X-ray diffraction analysis confirmed that the laser structuring of the matrices did not lead to a change in the semi-crystalline phase of the PCL. The combinations of two types of geometrical designs—wood pile and snowflake—with laser-induced morphologies in the form of channels and columns are considered for optimizing the conditions for establishing an ideal scaffold, namely, precise dimensional form, mechanical stability, improved cytocompatibility and antibacterial behavior. [ABSTRACT FROM AUTHOR]

We report on a new approach toward a laser-assisted modification of biocompatible polydimethylsiloxane (PDMS) elastomers relevant to the fabrication of stretchable multielectrode arrays (MEAs) devices for neural interfacing technologies. These applications require high-density electrode packaging to provide a high-resolution integrating system for neural stimulation and/or recording. Medical grade PDMS elastomers are highly flexible with low Young's modulus < 1 MPa, which are similar to soft tissue (nerve, brain, muscles) among the other known biopolymers, and can easily adjust to the soft tissue curvatures. This property ensures tight contact between the electrodes and tissue and promotes intensive development of PDMS-based MEAs interfacing devices in the basic neuroscience, neural prosthetics, and hybrid bionic systems, connecting the human nervous system with electronic or robotic prostheses for restoring and treating neurological diseases. By using the UV harmonics 266 and 355 nm of Nd:YAG laser medical grade PDMS elastomer is modified by ns-laser ablation in water. A new approach of processing is proposed to (i) activate the surface and to obtain tracks with (ii) symmetric U-shaped profiles and (iii) homogeneous microstructure This technology provides miniaturization of the device and successful functionalization by electroless metallization of the tracks with platinum (Pt) without preliminary sensitization by tin (Sn) and chemical activation by palladium (Pd). As a result, platinum black layers with a cauliflower-like structure with low values of sheet resistance between 1 and 8 Ω/sq are obtained. [ABSTRACT FROM AUTHOR]

A comparison between the resonant scattering curve obtained by anomalous small-angle X-ray scattering at the X-ray absorption edge of Ni and the complementary small-angle neutron scattering curve from an Al89Ni6La5 alloy sample is reported. The sample does not comply with the two-phase approximation. The two resulting scattering curves are approximately proportional to each other in this particular case. The anomalous small-angle X-ray scattering resonant curve at the Ni absorption edge equals the Ni-Ni partial structure factor and, owing to the favourable neutron scattering lengths of Ni, La and Al, the neutron scattering curve is also proportional to that partial structure factor. [ABSTRACT FROM AUTHOR]