Dopamine-induced functionalization of cellulose nanocrystals with polyethylene glycol towards poly(L-lactic acid) bionanocomposites for green packaging.

Improving the physical properties of biobased polymers using bionanofillers is essential to preserve its biodegradability. This work presents a dopamine-induced functionalization of cellulose nanocrystals (CNCs) with polyethylene glycol (PEG), to enhance the crystallization, mechanical and barrier properties of poly(L-lactic acid) (PLLA) bionanocomposites. The effect of molecular weight of grafted PEG on the properties of PLLA is also studied. PEGylation of CNCs significantly enhance the crystallization of PLLA, especially for CNCs functionalized with PEG of lower molecular weight, which lead to balanced strength and ductility, and 66.4% reduction in the oxygen permeability coefficient at a low content of 0.5 wt %. Moreover, 168% improvement of ductility for PLLA can be obtained by CNCs functionalized with longer PEG chains. The surface functionalization of CNCs proposed here opens up a green avenue towards designing and fabricating fully bio-based, high-barrier and low-cost polymer nanocomposites for packaging applications.

Tailoring Crystalline Morphology by High-Efficiency Nucleating Fiber: Toward High-Performance Poly(l-lactide) Biocomposites.

In this work, a high-melting-point poly(l-lactide) fiber (hPLLA fiber) with high-efficiency nucleation activity was prepared and introduced into PLLA matrix to prepare fully biodegradable PLLA biocomposites. The highly active nucleating surfaces of the hPLLA fiber induced chain ordering and lamellar organization, leading to a preferable formation of well-organized PLLA transcrystallinity at the surface of the hPLLA fiber under quiescent conditions. The construction of such compact transcrystallinity increased the crystallinity and enhanced the interfacial adhesion, which largely promoted heat resistance, tensile strength, and barrier property of PLLA biocomposites at a low content of hPLLA fiber. With the addition of 1 wt % hPLLA fiber, the storage modulus of the PLLA biocomposite was enhanced by 82 times from 4 to 330 MPa at 80 °C and the oxygen permeability coefficient and water permeability coefficient were decreased by 52 and 51% to be 5.9 × 10-15 cm3·cm/cm2·s·Pa and 4.5 × 10-14 g·cm/cm2·s·Pa, respectively, compared with those of pure PLLA. Moreover, the transparency of PLLA was maintained with the incorporation of hPLLA fiber. Thus, this strategy paved a new way to prepare high-performance and fully biodegradable biocomposites.

2D end-to-end carbon nanotube conductive networks in polymer nanocomposites: a conceptual design to dramatically enhance the sensitivities of strain sensors.

New generation wearable devices require mechanically compliant strain sensors with a high sensitivity in a full detecting range. Herein, novel 2D end-to-end contact conductive networks of multi-walled carbon nanotubes (MWCNTs) were designed and realized in an ethylene-α-octene block copolymer (OBC) matrix. The prepared strain sensor showed a high gauge factor (GF) of 248 even at a small strain (5%) and a linear resistance response throughout the whole strain range. The sensors also exhibited very good stretchability up to 300% and high cycling durability. This novel design solved the intrinsic problem of sensors based on carbon nanotube bundles, i.e., a long sliding phase before the disconnection of CNTs in a cost-effective and scalable way. This study rationalizes the 2D end-to-end contact concept to improve the sensitivity of the existing sensors and has great potential to be used in a wide variety of polymer based sensors.

Effect of phase coarsening under melt annealing on the electrical performance of polymer composites with a double percolation structure.

The effect of phase coarsening on the evolution of the carbon black (CB) nanoparticle network under quiescent melt annealing and the electrical performance of polypropylene/polystyrene/carbon black (PP/PS/CB) composites with a double percolation structure was investigated. The results showed that when the CB content is low, the coarsening process of PP/PS/CB blends can be divided into two stages. In the first stage, the coarsening rate is fast before the formation of the CB nanoparticle network, and after annealing for a certain time, the evolution of the co-continuous morphology can drive the CB nanoparticles to self-assemble into a complete nanoparticle network. In the second stage, the coarsening rate is slow after the formation of the CB nanoparticle network. When the CB content is high, the CB nanoparticle network can be maintained throughout the whole annealing process, so that the conductivity and morphology of the PP/PS/CB composites are stable. Moreover, the electrical conductivity of the PP/PS/CB composites greatly increases after annealing for a certain time, and a percolation threshold as low as 0.07 vol% can be obtained. These results reveal the relationship between the evolution of the morphology and the conductivity in the conductive polymer composites with a double percolation structure, and provide a more in-depth and comprehensive understanding of the double percolation structure.

The effect of chain mobility on the coarsening process of co-continuous, immiscible polymer blends under quiescent melt annealing.

Polypropylene (PP) and five kinds of monodisperse polystyrene (PS) with different terminal relaxation times were used to explore the relationship between the mobility of polymer molecular chains and the coarsening process of immiscible polymer blends with a co-continuous morphology under quiescent melt annealing at different temperatures. The terminal relaxation time of all neat PP and PS was determined by a rheological approach to characterize the mobility of molecular chains. A selective dissolution experiment showed that all PP/PS (50/50) blends maintained a co-continuous structure during the whole annealing process. Significant coarsening behaviors were observed for all PP/PS blends under a scanning electron microscope. A linear time dependence of the size of the PS phase was found in all PP/PS blends and the coarsening phenomenon was more obvious with the decrease of the terminal relaxation time of the PS phase because of the increase of the mobility of the polymer molecular chains. A direct relationship between the phase coarsening rate and the terminal relaxation time of the PS phase was found for the first time and it satisfied the equation . According to this equation, the formulae and k ∝ Mw-1 can be derived, which can provide significant information for the control of the phase coarsening process of immiscible polymer blends with a co-continuous morphology.

Induced formation of dominating polar phases of poly(vinylidene fluoride): positive ion-CF2 dipole or negative ion-CH2 dipole interaction.

The "ion-dipole" interaction has been the most widely accepted mechanism for the direct formation of polar phases (ß, γ) of poly(vinylidene fluoride) (PVDF), which have been widely used as transducers, actuators, and sensors. However, the type of charged ions is still controversial. In order to throw light upon this issue, two types of charged small organic molecules that are in different physical states (melt or solid) during the crystallization of PVDF were melt-blended with PVDF resin. Results revealed that only the incorporation of positive charged molecules can lead to the formation of polar phases. Additionally, it is interesting to find that during the crystallization of PVDF, molten positively charged molecules resulted in ß-phase dominating, while solid positively charged molecules exclusively induced γ-phase. These results lead to the understanding that the induced formation of polar phases of PVDF is due to the "positive ion-CF2 dipole" interaction.

Suppression of phase coarsening in immiscible, co-continuous polymer blends under high temperature quiescent annealing.

The properties of polymer blends greatly depend on the morphologies formed during processing, and the thermodynamic non-equilibrium nature of most polymer blends makes it important to maintain the morphology stability to ensure the performance stability of structural materials. Herein, the phase coarsening of co-continuous, immiscible polyamide 6 (PA6)-acrylonitrile-butadiene-styrene (ABS) blends in the melt state was studied and the effect of introduction of nano-silica particles on the stability of the phase morphology was examined. It was found that the PA6-ABS (50/50 w) blend maintained the co-continuous morphology but coarsened severely upon annealing at 230 °C. The coarsening process could be divided into two stages: a fast coarsening process at the initial stage of annealing and a second coarsening process with a relatively slow coarsening rate later. The reduction of the coarsening rate can be explained from the reduction of the global curvature of the interface. With the introduction of nano-silica, the composites also showed two stages of coarsening. However, the coarsening rate was significantly decreased and the phase morphology was stabilized. Rheological measurements indicated that a particle network structure was formed when the concentration of nano-silica particles was beyond 2 wt%. The particle network inhibited the movement of molecular chains and thus suppressed the coarsening process.

Polymorphism of racemic poly(L-lactide)/poly(D-lactide) blend: effect of melt and cold crystallization.

The crystallization and melting behaviors and crystalline structure of melt and cold crystallized poly(L-lactide)/poly(D-lactide) (PLLA/PDLA) blend were investigated by differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD), respectively. The isothermal crystallization kinetics during the melt and cold crystallization process were analyzed using the Avrami equation. The overall crystallization rate constant (k) of cold crystallization is much higher than that of melt crystallization. Moreover, k as a function of crystallization temperature shows different trends in melt and cold crystallization, indicating different crystallization mechanisms in the melt and cold crystallization. The polymorphic crystallization of homocrystallites (the transition crystallization temperature from δ to α form) is not altered by either the equimolar blending of PLLA and PDLA or the type of crystallization procedures, while the crystallization window for exclusive stereocomplex crystallites is widened from 170 °C for melt crystallization to 170-200 °C for cold crystallization. The stereocomplex crystallites are hard to form in both melt and cold crystallization at crystallization temperatures of 90 and 100 °C, and the crystallinity of stereocomplex crystallites for cold crystallization is higher than that of melt crystallization at temperatures above 110 °C. Especially, a pure and significantly higher crystallinity of stereocomplex crystallites can be achieved at 170-200 °C by cold crystallization. The results provide a huge possibility to control stereocomplex crystallization to enlarge its applications.