Extensional Flow-Induced Concentration Gradient in Entangled Polymer Solutions with Chemically Identical Species.

Entangled polymer solutions show different rheological behavior from melts in fast extensional flow. This discrepancy is not expected according to the classic tube model and is an urgent issue to be solved in polymer physics. While in the tube model the polymer concentration is considered to be homogeneous, we show that extensional flow-induced concentration gradient may happen in polymer solutions even with chemically identical solutes and solvents. Through labeling an aggregation-induced emission (AIE) probe on oligomeric solvents, the flow-induced concentration gradient is visualized by combining extensional rheology and ex situ fluorescence microscopy. Microdomains of oligomeric solvents with a length scale of tens of micrometers are observed, and their influence on rheological behavior cannot be ignored.

Functional characterization of MaEXPA11 and its roles in response to biotic and abiotic stresses in mulberry.

Mulberry is a traditional economic tree with various values in sericulture, ecology, food industry and medicine. Expansins (EXPs) are known as cell wall expansion related proteins and have been characterized to involve in plant development and responses to diverse stresses. In present study, twenty EXP and expansin-like (EXL) genes were identified in mulberry. RNA-seq results indicated that three EXP and EXL genes showed up-regulated expression level under sclerotiniose pathogen infection in three independent RNA-seq datasets. The most significant upregulated EXPA11 was selected as key EXP involving in response to sclerotiniose pathogen infection in mulberry. Furthermore, a comprehensive functional analysis was performed to reveal subcellular location, tissue expression profile of MaEXPA11 in mulberry. Down-regulation of MaEXPA11 using virus induced gene silence (VIGS) was performed to explore the function of MaEXPA11 in Morus alba. Results showed that MaEXPA11 can positively regulate mulberry resistance to Ciboria shiraiana infection and negatively regulate mulberry resistance to cold or drought stress.

Fully biodegradable polylactide foams with ultrahigh expansion ratio and heat resistance for green packaging.

Long chain branching (LCB) structures are efficiently introduced into polylactide (PLA) by employing sustainable soybean oil (SO) under the initiation of trace amount of cyclic peroxide, which displays robust foamability and heat resistance. It is discovered that with the introduction of 0.6 wt% SO, the expansion ratio and Vicat softening temperature of LCB PLA are sharply raised to 75.2-fold and 155.8 °C, respectively, which is about 17.9 and 2.6 times those of linear PLA. This is because that the amounts of LCB structures are significantly increased in LCB PLA by the addition of SO with low reactivity of internal CC bonds, which can avoid the oligomerization reaction, resulting in more dramatically improved melting strength and crystallization performance of LCB PLA. Moreover, the hydrolytic degradation of LCB PLA is largely expedited as compared to linear PLA, owing to the more rapid water permeation caused by the loose packing of LCB structures. Finally, the PLA foam tray with light weight and good heat resistance is successfully developed by using LCB PLA with 0.6 wt% SO through extrusion foaming with supercritical carbon oxide and thermoforming techniques. Hence, this research offers a green route to produce eco-friendly light-weight and high-heat-resistance LCB-PLA foam with full biodegradability, which is an ideal alternative to the non-degradable oil-based plastics in the field of disposable packaging products.

Vorticity-Aligned Droplet Bands in Sheared Immiscible Polymer Blends Induced by Solid Particles.

The spatiotemporal organization of complex fluids under flow can be strongly affected by incorporating solid particles. Here, we report that a monolayer of interfacially active microspheres preferentially wetted by the matrix phase can bridge droplets into vorticity-aligned bands in immiscible polymer blends at intermediate particle concentrations and low shear rates. Strong particle bridging ability and the formation of rigid anisotropic droplet bands with a negligible inertia effect in the Newtonian matrix are suggested to be responsible for the vorticity orientation of droplet bands during slow shear flow, which could be understood based on Jeffery orbit theory in the framework of fluid mechanics and strong confinement effect acted by shear walls and adjacent bands. However, increasing the aspect ratio of particles could restrain the formation of anisotropic bands because of reduced particle coverage and promoted droplet coalescence induced by sharp particle corners, increased and uneven distribution of particle aggregates in the matrix phase, and weakened particle bridging ability.

Synthesis of poly(ionic liquid) for trifunctional epoxy resin with simultaneously enhancing the toughness, thermal and dielectric performances.

Poly(ionic liquid) (PIL), integrating the characteristics of both polymers and ionic liquid, is synthesized and employed to modify diglycidyl-4,5-epoxy-cyclohexane-1,2-dicarboxylate (TDE-85). With the addition of PIL, the fracture toughness, and thermal and dielectric performances of TDE-85 were discovered to be simultaneously improved, meanwhile the tensile modulus and strength is increased. Upon an optimal loading of 3 wt% PIL, the critical stress intensity factor (K IC), tensile modulus and strength are raised by 92.9%, 13.3% and 10.7%, respectively. Multi-toughening mechanisms due to spherical domains of PIL formed in TDE-85 during curing are responsible for the improved toughness. Moreover, the dielectric and thermal properties of TDE-85 are also enhanced by adding PIL. With the optimal addition of 5 wt% PIL, the dielectric constant of the composites is enhanced by 62.5%, the glass transition temperature is increased by 16.58 °C and the residual weight of carbon is increased by 59%.

Exfoliated Graphene Leads to Exceptional Mechanical Properties of Polymer Composite Films.

Polymers with superior mechanical properties are desirable in many applications. In this work, polyethylene (PE) films reinforced with exfoliated thermally reduced graphene oxide (TrGO) fabricated using a roll-to-roll hot-drawing process are shown to have outstanding mechanical properties. The specific ultimate tensile strength and Young's modulus of PE/TrGO films increased monotonically with the drawing ratio and TrGO filler fraction, reaching up to 3.2 ± 0.5 and 109.3 ± 12.7 GPa, respectively, with a drawing ratio of 60× and a very low TrGO weight fraction of 1%. These values represent by far the highest reported to date for a polymer/graphene composite. Experimental characterizations indicate that as the polymer films are drawn, TrGO fillers are exfoliated, which is further confirmed by molecular dynamics (MD) simulations. Exfoliation increases the specific area of the TrGO fillers in contact with the PE matrix molecules. Molecular dynamics simulations show that the PE-TrGO interaction is stronger than the PE-PE intermolecular van der Waals interaction, which enhances load transfer from PE to TrGO and leverages the ultrahigh mechanical properties of TrGO.

Toward simultaneous toughening and reinforcing of trifunctional epoxies by low loading flexible reactive triblock copolymers.

Flexible reactive poly(glycidyl methacrylate)-b-poly(propylene glycol)-b-poly(glycidyl methacrylate) (GPG) and nonreactive poly(ethylene glycol)-b-poly(propylene glycol)-b-poly(ethylene glycol) (EPE80) were utilized to toughen a trifunctional epoxy (diglycidyl 4, 5-epoxycyclohexane-1, 2-dicarboxylate, TDE-85). In comparison with the nonreactive EPE80 and reactive GPG92 with long reactive blocks (L reactive), the incorporation of reactive GPG83 with short L reactive improved the comprehensive mechanical properties of the epoxy. Upon an optimal GPG83 loading of 2.5 wt%, the tensile strength, elongation at break and critical strain energy release rate (G 1c) increased by ca. 31%, 45.9% and 130.8%, respectively, without sacrificing the modulus and thermal stability. Morphology characterization evidenced that micro-scale domains and nanosized vesical micelles coexisted in the nonreactive EPE80 toughened systems. However, homogeneous morphologies were formed in reactive GPG83 and GPG92 toughened systems. Fracture morphology analysis suggested that GPG can toughen epoxy thermosets by incorporating flexible PPG blocks into the epoxy network, thereby enabling an energy dissipation mechanism. The good balance between the mobility of flexible PPG and degree of cross-link density leads to the simultaneous toughening and reinforcing effect of GPG83 toward the trifunctional epoxy.

Morphology Mapping of Nanoparticle-Filled Immiscible Polymer Blends in Flow: The Existence of a Critical Ratio between Nanoparticle Concentration and Droplet Concentration.

The delicate flow-induced morphology of immiscible polypropylene/polystyrene blends in the presence of silica nanoparticles (NPs) is investigated in a multiparameter space. The morphology map constructed based on in situ morphology observation reveals that a critical ratio of NP concentration to droplet concentration, which strongly depends on the NP surface chemistries and the ratio of the NP concentration to the droplet concentration, exists. Below or above the critical ratio, the NPs display diverse effects on the morphology (promote or suppress droplet coalescence). These results can be interpreted by the competition between the bridging mechanism (acceleratory effect) and the enhanced viscoelasticity (inhibitory effect) exerted by the NPs.

Controlling the Orientation of Droplets in Ellipsoid-Filled Polymeric Emulsions with Particle Parameters and Flow Conditions.

The effect of particle parameters [aspect ratio (AR) and concentration] and flow conditions (gap spacing and shear rate) on droplet orientation deformation behavior in polystyrene (PS) particle-filled binary polymeric emulsions is investigated by using a rheo-optical technique and confocal microscopy. Interesting vorticity orientation behavior is achieved by tailoring experimental conditions to yield rigid anisotropic droplets during slow confined shear flow. PS ellipsoids with a high AR are found to reside both at the fluid interface in a monolayer side-on state and inside droplets, leading to the formation of rigid anisotropic droplets because of the interfacial/bulk jamming effect at appropriate particle concentrations. In unconfined bulk samples, droplets with a vorticity orientation can also be observed under the wall migration effect and confinement effect arising from nearby droplets. However, the overly strong wall confinement effect remarkably facilitates the coalescence of vorticity-aligned droplets during slow shear, eventually leading to the formation of a long stringlike phase aligning along the flow direction. High shear rates generate refined droplets with lower particle coverage and weak rigidity, which restrain the formation of anisotropic droplets and thus suppress the droplet vorticity orientation.

Morphology Evolution of Polymer Blends under Intense Shear During High Speed Thin-Wall Injection Molding.

The morphology evolution under shear during different processing is indeed an important issue regarding the phase morphology control as well as final physical properties of immiscible polymer blends. High-speed thin wall injection molding (HSTWIM) has recently been demonstrated as an effective method to prepare alternating multilayered structure. To understand the formation mechanism better and explore possible phase morphology for different blends under HSTWIM, the relationship between the morphology evolution of polymer blends based on polypropylene (PP) under HSTWIM and some intrinsic properties of polymer blends, including viscosity ratio, interfacial tension, and melt elasticity, is systematically investigated in this study. Blends based on PP containing polyethylene (PE), ethylene vinyl alcohol copolymer (EVOH), and polylactic acid (PLA) are used as examples. Compatibilizer has also been added into respective blends to alter their interfacial interaction. It is demonstrated that dispersed phase can be deformed into a layered-like structure if interfacial tension, viscosity ratio, and melt elasticity are relatively small. While some of these values are relatively large, these dispersed droplets are not easily deformed under HSTWIM, forming ellipsoidal or fiber-like structure. The addition of a moderate amount of compatibilizer into these blends is shown to be able to reduce interfacial tension and the size of dispersed phase, thus, allowing more deformation on the dispersed phase. Such a study could provide some guidelines on phase morphology control of immiscible polymer blends under shear during various processing methods.

Functionalized Graphene Enables Highly Efficient Solar Thermal Steam Generation.

The ability to efficiently utilize solar thermal energy to enable liquid-to-vapor phase transition has great technological implications for a wide variety of applications, such as water treatment and chemical fractionation. Here, we demonstrate that functionalizing graphene using hydrophilic groups can greatly enhance the solar thermal steam generation efficiency. Our results show that specially functionalized graphene can improve the overall solar-to-vapor efficiency from 38% to 48% at one sun conditions compared to chemically reduced graphene oxide. Our experiments show that such an improvement is a surface effect mainly attributed to the more hydrophilic feature of functionalized graphene, which influences the water meniscus profile at the vapor-liquid interface due to capillary effect. This will lead to thinner water films close to the three-phase contact line, where the water surface temperature is higher since the resistance of thinner water film is smaller, leading to more efficient evaporation. This strategy of functionalizing graphene to make it more hydrophilic can be potentially integrated with the existing macroscopic heat isolation strategies to further improve the overall solar-to-vapor conversion efficiency.

Sequence control of phase separation and dewetting in PS/PVME blend thin films by changing molecular weight of PS.

The morphology evolution mechanism of polystyrene (PS)/poly (vinyl methyl ether) (PVME) blend thin films with different PS molecular weights (Mw) was studied. It was found that the morphology evolution was closely related to the molecular weight asymmetry between PS and PVME. In the film where Mw(PS) ≈ Mw(PVME), dewetting happened at the interface between the bottom layer and substrate after SD phase separation. While in the film where Mw(PS) >> Mw(PVME), dewetting happened at the interface between the middle PS/PVME blend layer and bottom PVME layer near the substrate prior to phase separation. The different sequences of phase separation and dewetting and different interface for dewetting occurrence were studied by regarding the competitive effects of viscoelasticity contrast between polymer components and preferential wetting between PVME and the substrate. The viscoelastic nature of the PS component played a crucial role in the sequence of phase separation and dewetting.

Thermal oxidative and ozone oxidative stabilization effect of hybridized functional graphene oxide in a silica-filled solution styrene butadiene elastomer.

Hybridization of modified functional graphene oxide (fGO) in silica-filled solution styrene butadiene rubber (SSBR) endows preferable tensile and dynamic properties before and after thermal oxidative aging, and similar mechanical hysteresis performance compared with the composites without fGO. The preventing mechanism of fGO is attributed to its intrinsic peroxy radical scavenging and gas barrier abilities, which significantly reduces the peroxy radical concentration and oxygen permeability of nanocomposites and then prolongs oxidative induction time (OIT), characterized by differential scanning calorimetry (DSC). The ozone resisting effect of different loadings of fGO on nanocomposites have also been investigated by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM) after ozonization under 50 ppm ozone concentration. As a result, incorporation of fGO apparently suppresses both the formation of oxygenic groups of the olefinic elastomer and crack morphology extension upon ozonization. We propose that fGO protects the SSBR elastomer from ozone attack through the conjugated delocalized π-bonds of the fGO instead of the C[double bond, length as m-dash]C bonds of the elastomer matrix being attacked, and the compared experiments, characterized by X-ray photoelectron spectroscopy (XPS), confirm that this presumption is perhaps reasonable. Moreover, more than 3 phr incorporation of fGO in nanocomposites deteriorates the chemical and mechanical properties of the elastomer during the thermal oxidation and ozonization because of the cleavage influence of oxygenic groups on peroxy radicals.

Droplet coalescence and clustering behavior in microsphere-filled polymeric emulsions under shear flow: the key role of asymmetric interfacial affinities.

The flow-induced spatial organization of the droplet phase in ternary polymeric emulsions consisting of two Newtonian fluids, namely polyisobutylene (PIB) and polydimethylsiloxane (PDMS), in the presence of a small amount of solid polystyrene (PS) microspheres are explored by direct flow visualization. The results suggest that the asymmetric affinities of interfacially located PS microspheres to two fluid components lead to diverse flow-induced morphologies in PIB/PDMS blends with different compositions. In 10/90 blends where microspheres are preferentially wetted by the PIB droplets, significantly promoted coalescence of PIB droplets is observed. Increasing the loading of microspheres or changing the shear rate will alter the size and spatial distribution of PIB droplets. In contrast, in the inverse 90/10 blends where microspheres are wetted by the continuous PIB phase, bridging of PDMS droplets is found, leading to the generation of string-like or grape-like clusters. These results indicate that the flow-induced morphology of PIB/PDMS blends in the presence of PS microspheres is not only determined by the experimental conditions such as shear rate but also to a large extent by the asymmetric interfacial affinities of microspheres for fluid components.

Suppression of wetting-induced percolation-to-droplet transition in near-critical polymer blend films by nanoparticles.

A new kind of percolation-to-droplet transition (PDT) caused by selective wetting was identified in near-critical polymer blend films. Nanoscale particles proved to possess superior ability in suppressing this morphological transition.

Vorticity Deformation in Polymeric Emulsions Induced by Anisotropic Ellipsoids.

We study the influence of particle shape on shear-induced droplet deformation in polymeric emulsions. During shearing, droplets become elongated and rotate periodically about their major axes while aligning along the vorticity direction in ellipsoid-filled emulsions, while similar behavior is not observed in the pristine, microsphere-filled or ellipsoid-filled inverse systems. Based on the Jeffery orbit theory, the formation of anisotropic droplets with extremely small Reynolds number due to arrested coalescence in Newtonian matrix and strong confinement effect are suggested to be responsible for the vorticity alignment of droplets during slow shearing.