RESUMEN

The negative temperature gradient under gravity was observed with a vertical air column inside a practically insulated aluminum cylinder filled with sawdust. The temperature drop rate measured between 90 and 10 cm height positions was as much as 2.22 Km-1 when the diameter of the air column was 60 cm. This drop rate is much larger than the mean lapse rate of the earth's troposphere (0.0045-0.0065 Km-1) and the previously reported experimental value (0.07 Km-1) by Graeff for the air column in a relatively small system. We proposed a kinetic model based on classical mechanics to account for this temperature drop, which is significantly larger than the values previously reported. The negative temperature gradient of the air column inside the cylinder showed a tendency to decrease sensitively as the positive temperature gradient of the ambient air outside the cylinder increased, although it was practically insulated. In addition, the temperature drop rate increased as the air column's diameter increased. These results suggest that as the size of the system increases, the external influence that relaxes the negative temperature gradient of the air column is diluted, and thus the negative temperature gradient becomes more pronounced.

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Two types of thermally reduced graphenes (TRGs) having different lateral sizes were non-covalently modified with poly(vinyl alcohol) to endow water-dispersibility. The modified TRGs were examined as Pickering stabilizers for the suspension polymerization of methyl methacrylate (MMA). They were effective graphene-based Pickering stabilizers for the system with almost all of the polymerized composite microparticles having a regular spherical shape. The particle size of the composite microparticles was tunable by the size or the amount of modified TRG used as stabilizer. The almost perfect core-shell structure of the composite microparticles effectively enhanced the thermal stability of the core PMMA. In addition, when the core-shell microparticles were compression molded into a monolith, the obtained composite exhibited an ultra-low percolation threshold of electrical conductivity of around 0.04vol%.

RESUMEN

A graphene was coated with a thin alumina layer to prepare a novel nanosheet which had high thermal conductivity but low electrical conductivity. The nanosheet with minimal aggregation was prepared effectively by first coating it with aluminum tri-sec-butoxide in anhydrous dimethylformamide, followed by rapid calcination in an inert atmosphere after the hydrolysis of the alkoxide. The morphology observed by scanning electron microscopy and elemental mapping by energy-dispersive X-ray spectrometry showed that the alumina layer coated on the graphene surface was uniform and ultra-thin. Thermogravimetry demonstrated that the uniformly coated alumina protective layer substantially improved the thermal stability of the graphene and that the electrically-insulative alumina layer effectively reduced the electrical conductivity of the graphene. The enhanced polar nature of surface as well as the increased surface roughness due to the coated alumina improved the dispersion of the graphene in the polar acrylic rubber matrix and the interaction at the interface. This led to an effective improvement of the thermal conductivity but marginal increase in electrical conductivity by the filler. Tensile modulus increased drastically to as high as 470% for the composite reinforced with the 5 phr (about 2.5 vol%) loading of the alumina-coated graphene.

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The purpose of this study is to develop novel triazole-containing hydrogels (TGs) as drug carrier and to investigate the sustained drug release accomplished by their time-dependent swelling behavior. The synthetic pathway of TGs includes: (1) DCC-coupling on hydroxyethyl methacrylate (HEMA) to prepare HEMA-alkyne (HA), (2) click-coupling to prepare a triazole-ring-containing monomer (TM), and (3) the synthesis of a series of TGs. The aggregation between triazole rings is found to be responsible for drug release controllability. Rhodamine 6G is studied as a model anticancer drug for release experiments. The effects of pH and temperature on the properties of sustained drug release are also studied.

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Shape memory behavior of crystalline shape memory polyurethane (SPU) reinforced with graphene, which utilizes melting temperature as a shape recovery temperature, was examined with various external actuating stimuli such as direct heating, resistive heating, and infrared (IR) heating. Compatibility of graphene with crystalline SPU was adjusted by altering the structure of the hard segment of the SPU, by changing the structure of the graphene, and by changing the preparation method of the graphene/SPU composite. The SPU made of aromatic 4,4'-diphenylmethane diisocyanate (MSPU) exhibited better compatibility with graphene, having an aromatic structure, compared to that made of the aliphatic hexamethylene diisocyanate. The finely dispersed graphene effectively reinforced MSPU, improved shape recovery of MSPU, and served effectively as a filler, triggering shape recovery by resistive or IR heating. Compatibility was enhanced when the graphene was modified with methanol. This improved shape recovery by direct heating, but worsened the conductivity of the composite, and consequently the efficiency of resistive heating for shape recovery also declined. Graphene modified with methanol was more effective than pristine graphene in terms of shape recovery by IR heating.

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A functionalized graphene sheet (FGS), which was prepared by the thermal reduction of graphite oxide, was modified by oxidation with H2O2. Elemental analysis, X-ray photoelectron spectroscopy, and Fourier transform infrared (FTIR) spectroscopy showed that additional oxygen functional groups, either doubly or singly bound to carbon, were created by the oxidation. The size and electrical conductivity of the FGS were reduced by the oxidation. During FGS/Polycaprolactone (PCL) nanocomposite preparation by an in situ polymerization method, PCL was grafted onto a FGS by chain growth from a functional group on FGS such as hydroxyl. Thermogravimetry and FTIR spectra demonstrated that the amount of grafted polycaprolactone (PCL) was decreased by the oxidation of FGS, suggesting that PCL chain growth from the FGS surface was inhibited by the neighboring carboxylic acid group on the FGS. Enhanced compatibility between the oxidized FGS and the PCL matrix was observed by optical microscopy and scanning electron microscopy. The reinforcing effect on tensile properties was also enhanced by the oxidized FGS in the FGS/PCL nanocomposites. This suggests that the surface coverage by the grafted PCL chains on the oxidized FGS is higher than that on a pristine FGS, although the grafted PCL chain length is shorter and the amount grafted is smaller.

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Electrophoretic fluorescence images have been fabricated by deposition of nanoporous polyaniline-fluorescein conducting particles onto a micro-patterned polyaniline film.