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Valuable emissive properties of organic fluorophores have become indispensable analytical tools in biophotonics, but frequently suffer from low solubilities and radiationless deactivation in aqueous media, that is, in biological ambience as well. In this report, nanoscaled dyeclay hybrids based on laponite, Na0.7{(Li0.3Mg5.5)[Si8O20(OH)4]}, are taken advantage of to solubilize neutral dyes, which are natively not encountered in water. Previously reported efficiency and solubility bottlenecks of such hybrids can to a large extent be overcome by comparably simple chemical measures, as demonstrated here for two prominent examples, the fluorescent dyes Nile Red and Coumarin 153. On controlled co-adsorption of small bifunctional quaternary ammonium ions (Me3N+C2H5OH and Me3N+C2H5NH2) we observed an outright efficiency boost by an order of magnitude, and a 30-fold brightness gain. Even at higher concentrations, transparency and stability of the hybrid dispersions are retained, rendering them useful for employment as optically functional nanoparticles in bioassays and beyond.
The influence of different organobentonites on the decomposition and the combustion behaviour of an epoxy resin were examined. The epoxy resin is a cationically polymerised cycloaliphatic epoxy resin flexibilised with poly(tetrahydrofuran) (PTHF), with hydroxyl endgroups. The bentonite was modified with either an ammonium or a phosphonium salt. The thermal decomposition of the PTHF induced by the initiator, used for the cationic polymerisation, did neither take place for the nanocomposite based on the ammonium bentonite nor for that based on the phosphonium bentonite. This improved decomposition characteristic lead to a larger time to ignition for both kinds of nanocomposites compared to the not modified polymer, which is not the case for other polymer/clay nanocomposites described in the literature. The fire behaviour was investigated using limiting oxygen index (LOI), a horizontal burner test and a cone calorimeter. The forced flaming conditions in the cone calorimeter were varied using different external heat fluxes between 30 and 70 kW · m-2. The fire behaviour of the nanocomposites was improved in comparison to the polymer, and phosphonium bentonite was superior to ammonium bentonite. The main mechanism is a barrier formation resulting in a reduction of the fire growth rate, which was more pronounced in the case of high external heat fluxes.
A low melting organic-inorganic glass and its effect on flame retardancy of clay/epoxy composites
(2011)
A low-melting organic-inorganic glass with a high molecular weight soluble in solvents was synthesized by hydrolytic polycondensation of phenyltriethoxysilane followed by a subsequent heat treatment. Softening point and thermostability were strongly increased after heat treatment. The composites of glass/epoxy and glass/clay/epoxy were studied with respect to their thermal properties, fire behavior and mechanical properties. Heat release rate as measured by cone calorimetry was remarkably reduced in the presence of glass, relative to neat epoxy resin and polymer/clay composites. The combination of glass and clay is a promising approach. It showed mainly superposition and even synergistic effects in some fire properties for higher filler concentrations due to the formation of an enhanced barrier. The structure of residue was investigated by transmission electron microscopy (TEM).
New low-melting organic–inorganic glassy polymers containing phosphorus and silicon are synthesized by the reaction between phenylphosphonic acid and methyltrichlorosilane or methyltriethoxysilane. They possess both low-softening points and high onset decomposition temperatures, which are favorable for preparing flame retardant composites. Although the glass by itself is sensitive to water, the composites are not significantly affected in that way. For glass/clay/epoxy composites glass transition temperature (Tg) as well as storage modulus increase with the glass amount. The glasses improve flame retardancy significantly due to flame inhibition and the formation of fire residue working as protection layer during burning. The total heat evolved is reduced by 23–28% for using 5–15 wt.% glass and the maximum HRR even by 5848%. The latter effect decreases with increasing glass amount due to an adulterate residue deformation. The combination of glass and clay is proposed as a possible route to enhance flame retardancy.
Due to optimised processing of epoxy based composite materials containing a low-melting organic–inorganic glass together with an organo clay, the size of the glass particles could be successfully reduced. Thus truly nano-dispersed composites were obtained, with glass particles in the range of 10 nm to 200 nm. The small particle size allowed efficient interaction of glass particles and organo clay layers. The flame retardancy as well as the thermo-mechanical properties were tested, and the results showed that the low-melting glass led to a remarkable reduction of peak heat release rate by forming an enhanced barrier layer. Nevertheless no further improvement could be achieved by lowering the particle size to the nanometre region. For good flame retardancy a microdispersion of the low-melting glass was already sufficient.