Confined hydration in nanometer-graded plasma polymer films: Insights from surface-enhanced infrared absorption spectroscopy

To shed light on recently explored long-range surface forces generated by subsurface-confined water, the structural characteristics of water molecules penetrating into nanoporous homogeneous and nanograded siloxane plasma polymer films (PPFs) over the time scale of 24 hours are studied by surface-enhanced IR spectroscopy (SEIRAS). Chemically graded PPFs, with embedded hydrophobic-to-hydrophilic gradient, are found to significantly change the average interfacial water orientation due to a unique nanoporous morphology and silanol group coordination. Diffusion of water through the hydrophobic SiO:CH matrix creates an evolution of the coordination of matrix silanol groups, which are eventually deprotonated as soon as the hydration network connects to the aqueous environment. This occurs after -6 hours of water immersion and coincides with the change of average interfacial water orientation. Both effects are present on hydrophobic samples, but are significantly amplified by the presence of the subsurface vertical amphiphilic gradient (Vgrad), whereas enhanced water uptake in oxygen-plasma modified graded PPFs is covering such effects

Improving flame retardancy of in-situ silica-epoxy nanocomposites cured with aliphatic hardener: Combined effect of DOPO-based flame-retardant and melamine

Silica-epoxy nanocomposites were prepared via an “in-situ ”sol-gel synthesis process and a phosphorus (P) flame-retardant i.e. 6H-dibenz[c,e][1,2]oxaphosphorin,6-[(1-oxido-2,6,7-trioxa-1-phosphabicyclo[2.2.2]oct- 4-yl)methoxy]-, 6-oxide (DP) and melamine (Mel) were further added to the matrix to improve its fire perfor- mance. The main components of epoxy resin were bisphenol A diglycidyl ether (DGEBA) and isophorone diamine (IPDA) hardener. The addition of DP as well as silica alone into the epoxy system stopped the melt dripping phe- nomena in the vertical fire test (UL 94), however, the addition of melamine was crucial for achieving the highest fire classification (UL 94-V0 rating). The presence of DP and Mel in the silica-epoxy nanocomposite promoted a large reduction (ranging from 53% up to 80%) in the heat release rate (HRR) and a delay (up to 31%) in the igni- tion time in the cone calorimetry experiments. Improved fire performance of the epoxy system was attributed to i) a condensed phase activity of silica, DP and melamine to form a protective thermal barrier during combustion and ii) a minor gas phase flame inhibition activity of DOPO component of DP. The mechanical characterization of the epoxy nanocomposites through tensile tests showed that the addition of DP increases the stiffness of the epoxy resin, resulting in a strong increase of Young modulus (up to 32%) and in a slight decrease of fracture strength, elongation at break and toughness. An increased glass transition temperature (up to 8%) of the epoxy system possibly due to hydrogen bonds and polar interactions of DP with the matrix was also observed

Detailed thermal, fire, and mechanical study of silicon-modified epoxy resin containing humic acid and other additives

Following a waste-to-wealth approach, humic acid (HA) was exploited as a flame retardant additive. The effect of its addition alone and in combination with urea (UR) and ammonium polyphosphate (APP) on the thermal, fire, and mechanical performances of a bisphenol A diglycidyl ether (DGEBA)-based epoxy resin modified with (3-aminopropyl)-triethoxysilane (AP) and cured with aliphatic isophoronediamine (IDA) has been investigated. Unlike in previous studies, a UL 94-V-0 classification was achieved for epoxy resin containing HA at 6 wt % and APP at only 1 wt % phosphorus (P) loading. The presence of silicon-modified epoxy chains ameliorated the distribution of the biowaste within the resin, and the addition of HA alone avoided melt dripping. Besides, APP and UR promoted a remarkable reduction (up to 52%) of the peak heat release rate (pHRR) values and a significant delay (up to 21%) of the time to ignition in cone calorimetry tests, and hence an increase (up to 1.8 min) of the time to flashover, without any detrimental effect on the overall mechanical behavior. The evolved gas, thermal, and fire analysis was used to propose the combined mode of action of HA, UR, APP, and silicon in the fire performance improvement of the hybrid epoxy system

Fire and mechanical properties of DGEBA-based epoxy resin cured with a cycloaliphatic hardener: combined action of silica, melamine and DOPO-derivative

The effect of the addition of additives such as melamine (Mel), silica nanoparticles and a phosphorus-based compound, i.e. 3-(6-oxidodibenzo[c,e][1,2]oxaphosphinin-6-yl)propenamide (DA), on the fire and mechanical performance of a bisphenol A diglycidyl ether (DGEBA)-based epoxy resin cured with isophoronediamine has been investigated. A UL 94-V0 classification was achieved for epoxy resin containing DA at 2 wt% of phosphorus loading. However, addition of silica nano particleswas necessary to avoid melt dripping. The incorporation of DA and Mel to the epoxy resin promoted a remarkable reduction (48% to 70%) in the heat release rate (HRR) values, a significant delay (up to 47%) in the ignition time in cone calorimetry experiments, and thus an increase (~75%) in the time to flashover. Evolved gas, thermal and fire analysiswas used to propose the combined mode of action of DA, Mel and silica in the fire performance improvement of the epoxy system. Tensile and three-point bending flexural tests showed that the addition of DA increases the rigidity of the resin, resulting in a strong increase in the Young's modulus (up to 34%) and in a slight reduction in fracture strength, elongation break and toughness which is typical for non-reactive additives

The 1430s: a cold period of extraordinary internal climate variability during the early Spörer Minimum with social and economic impacts in north-western and central Europe

Changes in climate affected human societies throughout the last millennium. While European cold periods in the 17th and 18th century have been assessed in detail, earlier cold periods received much less attention due to sparse information available. New evidence from proxy archives, historical documentary sources and climate model simulations permit us to provide an interdisciplinary, systematic assessment of an exceptionally cold period in the 15th century. Our assessment includes the role of internal, unforced climate variability and external forcing in shaping extreme climatic conditions and the impacts on and responses of the medieval society in north-western and central Europe. Climate reconstructions from a multitude of natural and anthropogenic archives indicate that the 1430s were the coldest decade in north-western and central Europe in the 15th century. This decade is characterised by cold winters and average to warm summers resulting in a strong seasonal cycle in temperature. Results from comprehensive climate models indicate consistently that these conditions occurred by chance due to the partly chaotic internal variability within the climate system. External forcing like volcanic eruptions tends to reduce simulated temperature seasonality and cannot explain the reconstructions. The strong seasonal cycle in temperature reduced food production and led to increasing food prices, a subsistence crisis and a famine in parts of Europe. Societies were not prepared to cope with failing markets and interrupted trade routes. In response to the crisis, authorities implemented numerous measures of supply policy and adaptation such as the installation of grain storage capacities to be prepared for future food production shortfalls

Production of He-4 and (4) in Pb-Pb collisions at root(NN)-N-S=2.76 TeV at the LHC

Results on the production of He-4 and (4) nuclei in Pb-Pb collisions at root(NN)-N-S = 2.76 TeV in the rapidity range vertical bar y vertical bar <1, using the ALICE detector, are presented in this paper. The rapidity densities corresponding to 0-10% central events are found to be dN/dy4(He) = (0.8 +/- 0.4 (stat) +/- 0.3 (syst)) x 10(-6) and dN/dy4 = (1.1 +/- 0.4 (stat) +/- 0.2 (syst)) x 10(-6), respectively. This is in agreement with the statistical thermal model expectation assuming the same chemical freeze-out temperature (T-chem = 156 MeV) as for light hadrons. The measured ratio of (4)/He-4 is 1.4 +/- 0.8 (stat) +/- 0.5 (syst). (C) 2018 Published by Elsevier B.V.Peer reviewe

Synthesis of polar polynorbornenes with high dielectric relaxation strength as candidate materials for dielectric applications

Materials with high dielectric permittivity and dielectric relaxation strength are sought for thermal and pressure sensors and electrical energy generators. However, most polymers have either too low dielectric permittivity or are so polar that their glass transition temperature (T-g) is too high and thus decomposition and side reactions occur before an electric field can polarize the polar groups. Here, we use the power and versatility of ring-opening metathesis polymerization (ROMP) to synthesize polar polymers with high dielectric relaxation strength and T-g significantly below the decomposition temperature. We first synthesized six polar norbornene monomers by conventional esterification, which were then polymerized by ROMP using Grubbs first- and third-generation catalysts. The structure of the polynorbornenes obtained were verified by multinuclear NMR spectroscopy, molecular weights determined by gel permeation chromatography (GPC), and thermal properties evaluated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Additionally, their dielectric permittivity, conductivity, and dielectric losses were measured at different temperatures and frequencies ranging between 0.1 and 10(6) Hz.UPNUE

Insight into the Synthesis and Characterization of Organophosphorus-Based Bridged Triazine Compounds

In this article, we report the synthesis of 2,4,6-substituted s-triazine-based organophosphorus compounds via a two-step process, which enables their production in high yields, and with a high purity as solids. In the first step, a Michaelis&ndash;Arbuzov rearrangement of cyanuric chloride with triethyl phosphite afforded 2,4,6-trisdiethoxyphosphinyl-1,3,5-triazine (HEPT). Subsequently, the nucleophilic substitution reaction on the triazine carbon was achieved, owing to the electron-withdrawing ability of the phosphonate groups. This characteristic of HEPT facilitated its derivatization with bi-functional amines, producing novel P&ndash;C containing bridged triazine organophosphorus compounds. The molecular structures of all of the compounds were confirmed by NMR spectroscopy, CHN elemental analysis, and single crystal X-ray analysis. In the thermogravimetric analysis in an N2 environment, &gt;33% char formation was observed for the bridged compounds. The chemical composition analysis of the char obtained under the oxidative thermal decomposition of the bridged compounds confirmed the presence of phosphorus- and nitrogen-enriched species, which indicate their function in the condensed phase. Comparatively, the detection of HPO and H&ndash;C&equiv;P in the gas phase during the pyrolysis of the bridged compounds can act as a source for PO&bull;, which is known for its gas phase flame inhibition reactions. The synergy of significant char formation and the generation of intermediates leading to PO&bull; during pyrolysis makes these molecules promising flame-retardant additives