Functional ceramic and nanocomposite fibers, cellular articles and microspheres via radiation curable colloidal dispersions

We present here new cellular ceramics, fibers and microspheres produced by novel and general microshaping techniques employing colloidal dispersions in solvent free radiation curable monomer mixtures. High loading, low viscosity dispersions of functional nanoparticles such as TiO₂ and α-Fe₂O₃ and colloidal Fe(C₂O₄)·2H₂O metal salt are achieved with comb-polyelectrolyte surfactants and/or mildly polar resins. TiO₂ dispersions are spun and solidified “on the fly” by UV radiation into continuous ceramic/polymer nanocomposite fibers with dimensions below 10 μm. Fe(C₂O₄)·2H₂O dispersions provide a UV curable alternative to α-Fe₂O₃ dispersions which can only be thermally cured. The Fe(C₂O₄)·2H₂O nanocomposites transform to α-Fe₂O₃ below 550 °C. Novel cellular Al₂O₃, TiO₂ and α-Fe₂O₃ articles with porosity >80% and precise replication of the pore-forming agents have also been produced from such dispersions. Al₂O₃ nanocomposite microspheres are produced by emulsification of the dispersions in an appropriate medium and UV curing.     

Fabrication and characterisation of cellular alumina articles produced via radiation curable dispersions

A general and versatile method for the production of cellular materials from radiation curable solvent-free colloidal ceramic dispersions containing pore formers has been developed. By this technique cellular ceramic articles with a precisely controlled porosity, cell size and shape are obtained for compositions containing solid pore formers. Monolithic bulk samples are obtained by thermal curing, whereas thin films and multi-layered articles are advantageously produced by UV curing. In this work the influence of three different spherical pore former types, PE, PS and PMMA, on the processing and final properties of the porous materials using alumina as model material is studied. The effect of pore former type and concentration on rheology, curing behaviour, debinding and sintering steps as well as thermal conductivity and mechanical strength of the sintered cellular materials is presented. It is also shown that the choice of pore former type modifies the sintering behaviour and resulting properties.     

Proteomic analysis of cerebrospinal fluid in a fulminant case of multiple sclerosis

Multiple Sclerosis (MS) is a chronic disease, but in rare fulminant cases rapid progression may lead to death shortly after diagnosis. Currently there is no diagnostic test to predict disease course. The aim of this study was to identify potential biomarkers/proteins related to rapid progression. We present the case history of a 15-year-old male MS patient. Cerebrospinal fluid (CSF) was taken at diagnosis and at the time of rapid progression leading to the patient's death. Using isobaric tag labeling and nanoflow liquid chromatography in conjunction with matrix assisted laser desorption/ionization time of flight tandem mass spectrometry we quantitatively analyzed the protein content of two CSF samples from the patient with fulminant MS as well as one relapsing-remitting (RR) MS patient and one control headache patient, whose CSF analysis was normal. Seventy-eight proteins were identified and seven proteins were found to be more abundant in both fulminant MS samples but not in the RR MS sample compared to the control. These proteins are involved in the immune response, blood coagulation, cell proliferation and cell adhesion. In conclusion, in this pilot study we were able to show differences in the CSF proteome of a rapidly progressing MS patient compared to a more typical clinical form of MS and a control subject.     

Preterm Intraventricular Hemorrhage-Induced Inflammatory Response in Human Choroid Plexus Epithelial Cells

Following an intraventricular hemorrhage (IVH), red blood cell lysis and hemoglobin (Hb) oxidation with the release of heme can cause sterile neuroinflammation. In this study, we measured Hb derivates and cellular adhesion molecules ICAM-1 and VCAM-1 with cell-free miRNAs in cerebrospinal fluid (CSF) samples obtained from Grade-III and Grade-IV preterm IVH infants (IVH-III and IVH-IV, respectively) at multiple time points between days 0–60 after the onset of IVH. Furthermore, human choroid plexus epithelial cells (HCPEpiCs) were incubated with IVH and non-IVH CSF (10 v/v %) for 24 h in vitro to investigate the IVH-induced inflammatory response that was investigated via: (i) HMOX1, IL8, VCAM1, and ICAM1 mRNAs as well as miR-155, miR-223, and miR-181b levels by RT-qPCR; (ii) nuclear translocation of the NF-κB p65 subunit by fluorescence microscopy; and (iii) reactive oxygen species (ROS) measurement. We found a time-dependent alteration of heme, IL-8, and adhesion molecules which revealed a prolonged elevation in IVH-IV vs. IVH-III with higher miR-155 and miR-181b expression at days 41–60. Exposure of HCPEpiCs to IVH CSF samples induced HMOX1, IL8, and ICAM1 mRNA levels along with increased ROS production via the NF-κB pathway activation but without cell death, as confirmed by the cell viability assay. Additionally, the enhanced intracellular miR-155 level was accompanied by lower miR-223 and miR-181b expression in HCPEpiCs after CSF treatment. Overall, choroid plexus epithelial cells exhibit an abnormal cell phenotype after interaction with pro-inflammatory CSF of IVH origin which may contribute to the development of later clinical complications in preterm IVH.     

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Role of Cinnabar in Luster Production

Ancient documentation referring to the use of cinnabar in the production of luster decorations has recently been corroborated by archaeological findings. However, luster decorations do not show any trace of the use of cinnabar in their composition because the temperatures involved in luster firing (500°–600°C) result in the complete decomposition and volatilization of cinnabar. An in situ x-ray diffraction experiment was designed to clarify the role of cinnabar in the production of luster decorations. The high-energy, high-flux radiation ID15B beamline at the European Synchrotron Radiation Facility was necessary to ensure good time/temperature resolution, penetration, and high-quality data. Results show that cinnabar acts as a reducing agent for copper because it provides the formation of copper (Cu⁺) and silver (Ag⁺) sulfur-containing phases, and it inhibits the crystallization of metallic silver in the temperature range of interest in luster production. The addition of elemental sulfur also produces these phases, but at temperatures <500°C, which are not adequate for the production of copper-containing lusters.     

Blends of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) with polystyrene-based thermoplastic rubbers: A comparative study

This work presents the first part of our study on the modification of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) with styrenic thermoplastic rubbers. Polystyrene-b-polyisobutylene-b-polystyrene (SIBS), polystyrene-b-polybutadiene-b-polystyrene (SBS) and polystyrene-b-poly(ethylene/butylene)-b-polystyrene (SEBS) triblock copolymers were melt blended with PPO and the blends were characterized. Differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA) and transmission electron microscopic (TEM) studies revealed that PPO/SEBS blends displayed the most pronounced phase-separated morphology with largest rubbery domains. SBS showed the most miscibility, and the least detrimental effect on dynamic mechanical properties and tensile strength. The results of this comparative study guided us to develop optimum conditions for the impact modification of PPO by SIBS thermoplastic rubbers.     

Effect of sample thickness on the mechanical properties of injection-molded polyamide-6 and polyamide-6 clay nanocomposites

The effect of the thickness on the mechanical properties of injection-molded specimens of pure polyamide-6 (PA6) and polyamide-6 clay nanocomposites (PA6-NC) with 5 wt% of layered silicates was investigated. Plates of 0.5, 0.75, 1 and 2 mm thickness were characterized in the injection direction using Dynamic Mechanical Analysis under torsion and tension respectively, and tensile tests. The fracture surfaces were analyzed by Scanning Electron Microscopy. In contrast with PA6, PA6-NC showed thickness effect and clear differences in the mechanical and thermomechanical properties between skin and core, especially in the 2 mm thick samples. Increasing thickness in PA6-NC led to a reduction of tensile modulus and yield stress. In the fracture surface of the thicker tensile specimens the formation of a sheet-like structure was observed. Multiple voiding in the core causing initial failure in this region and a stiffer skin with a better orientation of the layered silicates in the injection direction are two important elements of a micromechanical model proposed in this paper to explain the fracture mechanism in PA6-NC.     

Asymptotic and numerical analysis of a simple model for blade coating

Motivated by the industrial process of blade coating, the two-dimensional flow of a thin film of Newtonian fluid on a horizontal substrate moving parallel to itself with constant speed under a fixed blade of finite length in which the flows upstream and downstream of the blade are coupled via the flow under the blade is analysed. A combination of asymptotic and numerical methods is used to investigate the number and nature of the steady solutions that exist. Specifically, it is found that in the presence of gravity there is always at least one, and (depending on the parameter values) possibly as many as three, steady solutions, and that when multiple solutions occur they are identical under and downstream of the blade, but differ upstream of it. The stability of these solutions is investigated, and their asymptotic behaviour in the limits of large and small flux and weak and strong gravity effects, respectively, determined.