Low-dimensional nanoparticles have a strong ability to induce the crystallization of polymer matrices. One-dimensional carbon nanotubes (CNTs) and two-dimensional graphene nanosheets (GNSs), both of which are both carbon-based nanoparticles, provide a good opportunity to investigate the effects of differently dimensional nanoparticles on the crystallization behavior of a polymer. For this purpose, respective nanocomposites of CNTs and GNSs with poly(l-lactide) (PLLA) as matrix were prepared by solution coagulation. Time-resolved Fourier-transform infrared spectroscopy (FTIR) and synchrotron wide-angle X-ray diffraction (WAXD) were performed to probe chain conformational changes and to determine the crystallization kinetics during the isothermal crystallization of the PLLA nanocomposites and neat PLLA, especially in the early stages. Both CNTs and GNSs could serve as nucleating agents in accelerating the crystallization kinetics of PLLA; however, the ability of CNTs to induce crystallization was stronger than that of GNSs. On increasing the content of CNTs from 0.05 to 0.1 wt %, the induction period was shortened and the crystallization rate was enhanced, but the reverse situation was found for GNSs nanocomposites. In the case of neat PLLA, −CH3 interchain interactions preceded −(COC + CH3) interchain interactions during the crystallization. Conversely, in the CNTs and GNSs nanocomposites, the conformational ordering began with −(COC + CH3) interchain interactions, which resulted directly in a reduced induction period. Interchain interactions of this type could be explained in terms of surface-induced conformational order (SICO). Finally, the effect of the dimensionality of the nanoparticles on the crystallization behavior of PLLA is discussed.
One-dimensional (1D) semiconducting nanoscale materials have attracted considerable attention because of their importance in understanding the fundamental properties of low dimensionality in materials as well as in nanodevice applications. Many methods, including vapor-liquid-solid (VLS), [1] vapor-solid (VS), [2] and solution-based, have been developed to synthesize 1D semiconducting nanoscale materials such as nanoscale wires, [3][4][5][6][7][8][9][10][11] belts, [12][13][14][15][16] rods, [17,18] tubes, [19][20][21][22] and needles. [23,24] Usually, these methods require templates/catalysts and tedious operational procedures.Here, we demonstrate a new strategy for the growth of aligned ultralong ZnO nanobelts, yielding an average length of 3.3 mm and widths up to 6 lm, on metal substrates in a one-step process via molten-salt-assisted template-free thermal evaporation. These ultralong nanobelts show enhanced field emission. The electric field for an emission current density of 1 mA cm -2 is 2.9 V lm -1 , the lowest value ever reported for pure 1D ZnO nanostructures grown on flat surfaces, corresponding to a field-enhancement factor of about 1.4 × 10 4 . This approach is simple, efficient, and inexpensive, which significantly facilitates device fabrication.By combining a general molten-salt process, [25] which is usually used to prepare micrometer-scale ceramic powders (although it was also used for the synthesis of ZnO nanorods [26] in a thermal evaporation process [16] ), we have designed a new approach, molten-salt-assisted thermal evaporation, and we demonstrate that this approach can produce aligned ultralong ZnO nanobelts over a large area. The key point of this new approach is the evaporation of Zn metal powder in a liquid environment of molten sodium chloride (NaCl) salt.
In our previous work [Macromolecules 2010, 43, 1191–1194], we synthesized dynamic covalent cross-linked polymer gels through condensation of acylhydrazines at the chain ends of poly(ethylene oxide) (A2) and aldehyde groups in tris[(4-formylphenoxy)methy]ethane (B3) and reported reversible sol–gel transition and self-healing properties of the gels. For those dynamic gels, this paper examines the gelation kinetics and rheological behavior in pre- and postgelation stages and discusses the molecular mechanism underlying the mechanical and self-healing properties. The results showed that the condensation reaction before the critical gelation point can be treated as the pseudo-second-order reaction. The scaling exponent n (=0.75) for the frequency dependence of the complex moduli at the critical gel point, the exponent γ (=1.5) for the concentration dependence of the viscosity in the pregel regime, and the exponent z (=2.5) for the concentration dependence of the equilibrium modulus in the postgel regime were found to not exactly obey the relationship for covalent gels, n = z/(z + γ), possibly because of the dynamic nature of the gels. The terminal relaxation of the dynamic gels at high temperature (125 °C) accorded with the Maxwellian model, as often observed for transient associating networks. In contrast, at low temperature (25 °C) where this transient network reorganization was essentially quenched in a time scale of experiments (∼50 s), the uniaxial stress–strain behavior of the gel was well described by the classical model of rubber elasticity σeng = G(λ – 1/λ2) up to 300% stretch (as similar to the behavior of usual gels chemically cross-linked in a swollen state). Ultimately, the gel cut into two pieces was found to exhibit self-healing under ambient conditions in 8 and 24 h, respectively, when the edges of those pieces were coated and not coated with acid (catalyst for dynamic covalent bond formation).
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