Graphene constitutes a two dimensional sp2 hybridized carbon material with outstanding electrical and mechanical properties. To date, novel methods for producing large quantities of graphene and its derivatives (doped or functionalized graphenes, nanoribbons and nanoplatelets) are emerging, and research dedicated to the fabrication of polymer nanocomposites using graphenes has started. In this Research News, we summarize the synthesis and properties of graphene and its derivatives, and provide an overview of the latest research dedicated to the fabrication of polymer composites for different applications, including mechanical, electrical, optical and thermal. Some of the recently fabricated composites exhibit outstanding properties, however, it is vital to understand the chemistry and physics of the interphases established between the polymer and the graphene surfaces. The challenges in the fabrication of super robust and highly conducting composites using graphenes are also discussed. It is believed that graphene-based polymer composites will result in commercial products if their interphases and reactivity are carefully controlled.
Blends of poly(vinyl acetate) (PVAc) and poly(cyclohexyl methacrylate) (PCHMA) labeled by copolymerization with 4-methacryloylamine-4′-nitrostilbene (Sb), with (1-pyrenylmethyl)methacrylate (Py) or with 3-(methacryloylamine)propyl-N-carbazole (Cbz), were prepared by casting dilute solutions in tetrahydrofurane (THF) or chloroform onto silanized glass plates. The resulting films were studied by epifluorescence microscopy, microfluorescence spectroscopy, DSC and optical microscopy. Epifluorescence micrography probes the chemical composition of the different regions in phase separated blends, with black areas corresponding to PVAc rich regions and colored areas corresponding to labeled PCHMA rich regions. The technique also visualizes primary and secondary morphologies, which depend on the composition of the polymer blend and on the casting solvent. Mixtures containing 80 wt % PCHMA show, in general, a bicontinuous primary morphology suggesting a spinodal demixing mechanism. Solvent effects are particularly relevant for 50% and 20% PCHMA samples showing morphologies composed of PCHMA rich domains, in a matrix of solvent-dependent compositions. Samples cast from chloroform are more homogeneous and the matrix is always highly fluorescent. In contrast, the domains of samples cast from THF are heterogeneous in size and shape and the matrix is non-fluorescent, being thus formed by nearly pure PVAc. Small voids are formed in the polymer-air interface. They are submicrometric for THF cast films and disappear with annealing at 122°C. For chloroform cast samples they are much less frequent and appear well ordered, forming a mostly hexatic two dimensional network. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1284–1290, 2003
A new thermoset material based on DGEBA with polyaminosiloxane curing agents is presented. The system shows reaction-induced compatibilization which prevents coalescence of polysiloxane and DGEBA rich domains, leading to gradient structured morphologies. The influence of curing temperature and/or chemical nature of the siloxane on the morphology and surface microhardness were examined. When siloxane is pre-reacted with epoxypropylphenylether (EPPE), a more homogeneous material is obtained. Microhardness profiles on the material are strongly influenced by the extension of the compositional gradients.
The compression modulus of poly(N-vinylimidazole) (PVI) hydrogels synthesized by cross-linking polymerization in aqueous solution, was measured at room temperature in several related systems: i) just after polymerization, ii) swollen at equilibrium in deionized water, iii) swollen in HCl (aq) (pH=2.5), iv) swollen in HCl (pH=2.5) and 1 M NaCl (aq) solution and v) swollen in H2SO4 (pH=2.5) (aq) solution. Samples of the first and second groups are neutral whereas hydrogels of the other three groups are ionic because of protonation of basic imidazole groups. The experimental results were fitted with the Erman-Monnerie theory, applied to compression measurements for the first time, to determine the phantom modulus, [fph*], and the parameter κG which measures the constraining role of entanglements on the fluctuations of chains between knots.
Curing of epoxy resins with aliphatic diamines at low temperatures deviates from the 4EQ mechanism (catalytic and non-catalytic dual path) at relatively low conversions, far from vitrification. Although the Horie mechanism relies on a third order reaction it is possible a more realistic approach to epoxy curing kinetics if a detailed analysis of auto-acceleration is made. A single parameter dependent only on the nature of the amine is proposed.
Water absorption of an epoxy resin was studied by steady-state fluorescence spectroscopy and gravimetry. It was found that the intrinsic emission of the epoxy resin could be modified selecting an adequate excitation wavelength. The epoxy component of the resin was labelled with a trans-4-nitro-4′-aminostilbene fluorescent probe. Using an excitation wavelength of 340 nm it was possible to induce energy transfer to the suitable acceptor trans-4-nitro-4′-dialkylaminostilbene (NDAS). The relative fluorescence intensity I433/I596 was used as a convenient means to follow the quenching effect of water on the emission of NDAS when excited via energy transfer. It was found that both the relative intensity and the water content increase linearly with the square root of diffusion time in the early stages of the process. The apparent Stern–Volmer constants for the quenching of the fluorophore, when excited directly in a fluid THF solution or in the polymer matrix, were very similar but lower than when the fluorophore was excited via energy transfer. It was concluded that, at least in the early stages of the water diffusion process, the interchromophoric distance should increase.
© 2002 Society of Chemical Industry
The morphology of the diglycidyl ether of bisphenol-A/poly(3-aminopropylmethylsiloxane) (DGEBA/PAMS) reactive blends was studied by fluorescence techniques as a function of the initial composition. Some fluorescence results were compared with those from optical and electron microscopy investigations. Several morphological aspects were studied including the distribution of PAMS in the blend. The microsegregation of PAMS was discussed in terms of diffusion restriction of DGEBA through the PAMS dispersed phase.
The use of the fluorescence technique for monitoring the UV-curing of two polyurethane-based adhesives containing acrylic monomers is described in this paper. The increase of the fluorescence intensity as well as the maximum wavelength shift on emission was measured in real time during the photopolymerisation process. The established relationship between fluorescence and conversion allowed monitoring of the course of the process beyond vitrification. In that sense, all the fluorescent probes studied were sensitive to the formulation curing and in some cases, the range of conversions in which they were useful was limited by their size and probably, by the free volume fraction in the polymeric matrix. Moreover, polymerisation rates were obtained from fluorescent kinetic profiles and used to carry out a comparative study of the different photosensitive formulations. The real time FTIR (RTIR) results show the highest photoinitiation efficiency of the photoinitiator 2-benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)-1-butanone (Irgacure 369) compared to that of 2,2-dimethoxy-2-phenylacetophenone (Irgacure 651). The limitation of RTIR method for monitoring slow post-reactions was overcome by the use of the fluorescence-based method. Thus, a fluorescence intensity increase and a blue-shift of the emission band were measured after the limiting conversion was attained. Dynamic mechanical analysis showed that the glass transition temperature of the polymer increases during prolonged exposure to irradiation confirming the increase of the system rigidity.
