Structural evolution during inverse vulcanization.

Inverse vulcanization exploits S8 to synthesize polysulfides. However, evolution of products and its mechanism during inverse vulcanization remains elusive. Herein, inverse vulcanization curves are obtained to describe the inverse vulcanization process in terms of three stages: induction, curing and over-cure. The typical curves exhibit a moduli increment before declining or plateauing, reflecting the process of polysulfide network formation and loosing depending on monomers. For aromatic alkenes, in the over-cure, the crosslinked polysulfide evolves significantly into a sparse network with accelerated relaxation, due to the degradation of alkenyl moieties into thiocarbonyls. The inverse vulcanization product of olefins degrades slowly with fluctuated relaxation time and modulus because of the generation of thiophene moieties, while the inverse vulcanization curve of dicyclopentadiene has a plateau following curing stage. Confirmed by calculations, the mechanisms reveal the alkenyl groups react spontaneously into thiocarbonyls or thiophenes via similar sulfur-substituted alkenyl intermediates but with different energy barriers.

Graphene Oxide-Enhanced and Dynamically Crosslinked Bio-Elastomer for Poly(lactic acid) Modification.

Being a bio-sourced and biodegradable polymer, polylactic acid (PLA) has been considered as one of the most promising substitutes for petroleum-based plastics. However, its wide application is greatly limited by its very poor ductility, which has driven PLA-toughening modifications to be a topic of increasing research interest in the past decade. Toughening enhancement is achieved often at the cost of a large sacrifice in strength, with the toughness-strength trade-off having remained as one of the main bottlenecks of PLA modification. In the present study, a bio-elastomeric material of epoxidized soybean oil (ESO) crosslinked with sebacic acid (SA) and enhanced by graphene oxide (GO) nanoparticles (NPs) was employed to toughen PLA with the purpose of simultaneously preserving strength and achieving additional functions. The even dispersion of GO NPs in ESO was aided by ultrasonication and guaranteed during the following ESO-SA crosslinking with GO participating in the carboxyl-epoxy reaction with both ESO and SA, resulting in a nanoparticle-enhanced and dynamically crosslinked elastomer (GESO) via a ß-hydroxy ester. GESO was then melt-blended with PLA, with the interfacial reaction between ESO and PLA offering good compatibility. The blend morphology, and thermal and mechanical properties, etc., were evaluated and GESO was found to significantly toughen PLA while preserving its strength, with the GO loading optimized at ~0.67 wt%, which gave an elongation at break of ~274.5% and impact strength of ~10.2 kJ/m2, being 31 times and 2.5 times higher than pure PLA, respectively. Moreover, thanks to the presence of dynamic crosslinks and GO NPs, the PLA-GESO blends exhibited excellent shape memory effect and antistatic properties.

A Rigid-Flexible and Multi-Siloxane Bridge Strategy for Toughening Epoxy Resin with Promising Flame Retardancy, Mechanical, and Dielectric Properties.

Developing highly efficient and multifunctional epoxy resins (EPs) that overcome the shortcomings of flammability and brittleness is crucial for pursuing sustainable and safe application but remains a huge challenge. In this paper, a novel biomass-containing intumescent flame retardant containing a rigid-flexible and multi-siloxane bridge structure (DPB) was synthesized using siloxane; 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO); and biomass vanillin. DPB could facilitate the formation of a carbon residual with an intumescent structure, which effectively blocked the propagation of heat and oxygen. As a result, the peak heat release rate (pHRR) and total heat release (THR) of DPB/EP-7.5 decreased by 38.8% and 45.0%, respectively. In terms of mechanical properties, the tensile and flexural elongations at break of DPB/EP-7.5 increased by 77.2% and 105.3%, respectively. Impressively, DPB/EP-7.5 had excellent dielectric properties, with a dielectric constant of 2.5-2.9. This was due to the Si-O bonds (multi-siloxane bridges) contained in DPB/EP, which can quench the polarization behavior of the hydroxyl group. This paper provides a facile strategy for the preparation of multifunctional EP, which will pave the way for the promotion and application of EP in the high-end field.

Bio-Inspired Iron-Loaded Polydopamine Functionalized Montmorillonite as an Environmentally Friendly Flame Retardant for Epoxy Resin.

As an important thermosetting material, flame-retardant epoxy resin has various applications in the aerospace, chemical, and electronics industry, and other fields. However, the flame retardancy of epoxy resins is often improved at the expense of mechanical performance. The contradiction between flame retardancy and mechanical properties seriously impedes the practical applications of epoxy resin (EP). Herein, iron-loaded polydopamine functionalized montmorillonite (D-Mt-Fe3+), which was prepared by dopamine, iron chloride and montmorillonite in an aqueous solution, was introduced to prepare iron-loaded polydopamine functionalized montmorillonite/epoxy resin composites (D-Mt-Fe3+/EP). As expected, D-Mt-Fe3+/EP-10 with 10 phr of D-Mt-Fe3+ passed the UL-94 V-0 rating, achieved a limiting oxygen index (LOI) value of 31.0% and reduced the smoke production rate (SPR) and total smoke production (TSP), indicating that the introduction of D-Mt-Fe3+ could endow EP with satisfactory flame retardancy through the radical scavenging function of dopamine in the gas phase and the catalytic charring effect of iron ions, respectively. Encouragingly, the mechanical property was also enhanced with the flexural strength increased by 25.5%. This work provided an attractive strategy for improving both the mechanical properties and fire resistance of EP, which greatly broadened their applications in the chemical industry and electronics field, etc.

Nanofluids of Amphiphilic Kaolinite-Based Janus Nanosheets for Enhanced Oil Recovery: The Importance of Stable Emulsion.

To meet the increasing global demand for energy, better recovery of crude oil from reservoirs must be achieved using methods that are economical and environmentally benign. Here, we have developed a nanofluid of amphiphilic clay-based Janus nanosheets via a facile and scalable method that provides potential to enhance oil recovery. With the aid of dimethyl sulfoxide (DMSO) intercalation and ultrasonication, kaolinite was exfoliated into nanosheets (KaolNS) before being grafted with 3-methacryloxypropyl-triemethoxysilane (KH570) on the Alumina Octahedral Sheet at 40 and 70 °C to form amphiphilic Janus nanosheets (i.e., KaolKH@40 and KaolKH@70). The amphiphilicity and Janus nature of the KaolKH nanosheets have been well demonstrated, with distinct wettability obtained on two sides of the nanosheets, and the KaolKH@70 was more amphiphilic than the KaolKH@40. Upon preparing Pickering emulsion in a hydrophilic glass tube, the KaolKH@40 preferentially stabilized emulsions, while the KaolNS and KaolKH@70 tended to form an observable and high-strength elastic planar interfacial film at the oil-water interface as well as films climbing along the tube's surface, which were supposed to be the result of emulsion instability and the strong adherence of Janus nanosheets towards tube's surface. Subsequently, the KaolKH was grafted with poly(N-Isopropylacrylamide) (PNIPAAm), and the prepared thermo-responsive Janus nanosheets demonstrated a reversible transformation between stable emulsion and the observable interfacial films. Finally, when the samples were subjected to core flooding tests, the nanofluid containing 0.01 wt% KaolKH@40 that formed stable emulsions showed an enhanced oil recovery (EOR) rate of 22.37%, outperforming the other nanofluids that formed observable films (an EOR rate ~13%), showcasing the superiority of Pickering emulsions from interfacial films. This work demonstrates that KH-570-modified amphiphilic clay-based Janus nanosheets have the potential to be used to improve oil recovery, especially when it is able to form stable Pickering emulsions.

Behaviour of polymer-coated composite nanoparticles at bubble-stabilizing interfaces during bubble coarsening and accelerated coalescence: A Cryo-SEM study.

HYPOTHESIS: Dynamics of polymer-coated silica composite nanoparticles (CPs) during bubble coarsening is highly dominated by the behaviour of the polymer layer, while in-situ particle aggregation would lead to accelerated bubble coalescence. EXPERIMENTS: CPs-stabilized foams were prepared in 0.1 M and 0.55 M Na2SO4 solution, referring to the 0.1 M and 0.55 M foam/bubble respectively. The 0.1 M to 0.55 M transition foam was also prepared. High resolution Cryo-SEM was originally used to investigate the CPs behaviour at the bubble-stabilizing interface during bubble coarsening and accelerated coalescence. FINDINGS: The 0.1 M bubble-stabilizing interface buckles in uniaxial compression due to coarsening, with the CPs being observed to desorb from the interface. While the CPs were visualized to rearrange into crumpled particle multi-layers surrounding the shrinking 0.55 M bubbles, due to the adhesion between interpenetrating polymer chains and the unique lubrication effect of the PVP layers. The 0.1 M to 0.55 M transition foaming behaviour was also studied. Cracks and voids were observed at interfaces surrounding the transition bubbles driven by in-situ particle aggregation, resulting in accelerated bubble coalescence during the transition process.

Interfacial behavior of core-shell composite nanoparticles under compression and shear: Influence of polymer shell thickness.

HYPOTHESIS: The mobility of core-shell nanoparticles partitioned at an air-water interface is strongly governed by the compliance of the polymer shell. EXPERIMENTS: The compressional, relaxation and shear responses of two polymer-coated silica nanoparticles (CPs) were studied using a Langmuir trough and needle interfacial shear rheometer, and the corresponding structures of the particle-laden interfaces were visualized using Brewster angle and scanning electron microscopy. FINDINGS: The mobility of CPs partitioned at an air-water interface correlates to the polymer MW. In compression, the CPs40-laden interface (silica nanoparticles coated with 40 kDa PVP) showed distinct gas-liquid-solid phase transitions and when the surface pressure was reduced, the compressed particle-laden interface relaxed to its original state. The compressed-state of the CPs8-laden interface did not relax, and wrinkles in the particle-laden film that had formed in compression remained due to greater adhesion between the compressed particles. The increased mobility of the CPs40-laden interface translated to lower surface shear moduli, with the viscoelastic moduli an order of magnitude or more lower in the CPs40-laden interface than the CPs8-laden interface. Ultimately this contributed to changing the stability of particle-stabilized foams, with less mobile interfaces providing improved foam stability.

Biological compatibility, thermal and in vitro simulated degradation for poly(p-dioxanone)/poly(lactide-co-glycolide)/poly(ethylene succinate-co-glycolide).

Bio-absorbable polymers are widely desired to be applied and used as biomaterials for surgery hemostatic and medical tissue engineering devices. Ring-opening copolymerization reaction was applied to synthesize poly(ethylene succinate-co-glycolide) (PES-b-PGA). Stannous octoate was used as a catalyst whereas poly(ethylene succinate) was used as a macro-initiator to react with glycolide. PES-b-PGA was then used as a compatibilizer to prepare the blend biomaterial of PPDO/PLGA/PES-b-PGA by melt blending poly(p-dioxanone) (PPDO) with poly(lactide-co-glycolide) (PLGA). This would enhance the interactions of the inter-molecular chains and intra-molecular segments thus improving the compatibility. To obtain the biomaterial of PPDO/PLGA/PES-b-PGA with a regulated and controlled degradation and/or hydrolysis period, various ratios of PPDO, PLGA, and PES-b-PGA was blended. Behaviors of the thermal and in vitro simulated degradation, biological compatibility, cytotoxicity and subcutaneous implantation of PPDO/PLGA/PES-b-PGA were investigated. The results show that the in vitro hydrolytic degradation cycle is consistent with the wound healing time and that the biomaterial has slight cytotoxicity and it will do good to the cell proliferation, with 1 grade of cytotoxicity and the relative growth rate being the range from 92.5% to 96.2%. The implantation of the biomaterial into the rabbits' ears will not adversely affect the wound healing and the tissues surrounding the implanted sites. Therefore, the biomaterial has good biocompatibility and potential applications in medical tissue engineering devices.

Interfacial Phenomena in Multi-Micro-/Nanolayered Polymer Coextrusion: A Review of Fundamental and Engineering Aspects.

The multilayer coextrusion process is known to be a reliable technique for the continuous fabrication of high-performance micro-/nanolayered polymeric products. Using laminar flow conditions to combine polymer pairs, one can produce multilayer films and composites with a large number of interfaces at the polymer-polymer boundary. Interfacial phenomena, including interlayer diffusion, interlayer reaction, interfacial instabilities, and interfacial geometrical confinement, are always present during multilayer coextrusion depending on the processed polymers. They are critical in defining the microstructural development and resulting macroscopic properties of multilayered products. This paper, therefore, presents a comprehensive review of these interfacial phenomena and illustrates systematically how these phenomena develop and influence the resulting physicochemical properties. This review will promote the understanding of interfacial evolution in the micro-/nanolayer coextrusion process while enabling the better control of the microstructure and end use properties.

The effect of cationic surfactants on improving natural clinoptilolite for the flotation of cesium.

Flotation using cationic surfactants has been investigated as a rapid separation technique to dewater clinoptilolite ion exchange resins, for the decontamination of radioactive cesium ions (Cs+) from nuclear waste effluent. Initial kinetic and equilibrium adsorption studies of cesium, suggested the large surface area to volume ratio of the fine zeolite contributed to fast adsorption kinetics and high capacities (qc = 158.3 mg/g). Adsorption of ethylhexadecyldimethylammonium bromide (EHDa-Br) and cetylpyridinium chloride (CPC) surfactant collectors onto both clean and 5 ppm Cs+ contaminated clinoptilolite was then measured, where distribution coefficients (Kd) as high as 10,000 mL/g were evident with moderate concentrations CPC. Measurements of particle sizes confirmed that adsorption of surfactant monolayers did not lead to significant aggregation of the clinoptilolite, while < 8% of the 5 ppm contaminated cesium was remobilised. Importantly for flotation, both the recovery efficiency and dewatering ratios were measured across various surfactant concentrations. Optimum conditions were found with 0.5 mM of CPC and addition of 30 µL of MIBC frother, giving a recovery of ∼90% and a water reduction ratio > 4, highlighting the great viability of flotation to separate and concentrate the contaminated powder in the froth phase.

Bio-Inspired Preparation of Clay-Hexacyanoferrate Composite Hydrogels as Super Adsorbents for Cs.

A facile and low-cost fabrication route, inspired by the adhesive proteins secreted by mussels, has been developed to prepare a clay-based composite hydrogel (DHG(Cu)) containing hexacyanoferrate (HCF) nanoparticles for the selective removal of Cs+ from contaminated water. Initially, montmorillonite was exfoliated prior to coating with a thin layer of polydopamine (PDOPA) via the self-polymerization of dopamine. Mixing the composite (D-clay) with the HCF precursor, followed by the addition of copper ions, led to the self-assembly of the polymer-coated exfoliated clay nanosheets into a three-dimensional network and in situ growth of KCuHCF nanoparticles embedded within the gel structure. Analytical characterization verified the fabrication route and KCuHCF immobilization by a copper-ligand complexation. Rheology testing revealed the composite hydrogel to be elastic under low strain and exhibited reversible, self-healing behavior following high strain deformation, providing a good retention of KCuHCF nanoparticles in the membrane. The adsorbent DHG(Cu) showed a superior Cs+ adsorption capacity (∼173 mg/g), with the performance maintained over a wide pH range, and an excellent selectivity for Cs+ when dispersed in seawater at low concentrations of 0.2 ppm. On the basis of its excellent mechanico-chemical properties, the fabricated hydrogel was tested as a membrane in column filtration, showing excellent removal of Cs+ from Milli-Q water and seawater, with the performance only limited by the fluid residence time. For comparison, the study also considered other composite hydrogels, which were fabricated as intermediates of DHG(Cu) or fabricated with Fe3+ as the cross-linker and reactant for HCF nanoparticle synthesis.

The rheology of polyvinylpyrrolidone-coated silica nanoparticles positioned at an air-aqueous interface.

Particle-stabilized emulsions and foams are widely encountered, as such there remains a concerted effort to better understand the relationship between the particle network structure surrounding droplets and bubbles, and the rheology of the particle-stabilized interface. Poly(vinylpyrrolidone)-coated silica nanoparticles were used to stabilize foams. The shear rheology of planar particle-laden interfaces were measured using an interfacial shear rheometer and the rheological properties measured as a function of the sub-phase electrolyte concentration and surface pressure. All particle-laden interfaces exhibited a liquid-like to solid-like transition with increasing surface pressure. The surface pressure-dependent interfacial rheology was then correlated to the formed micron-scale structures of the particle-laden interfaces which were imaged using a Brewster angle microscope. With the baseline knowledge established, foams were prepared using the same composite particles and the particle network structure imaged using cryo-SEM. An attempt has been made to correlate the two structures observed at a planar interface and that surrounding a bubble to elucidate the likely rheology of the bubble stabilizing particle network. Independent of the sub-phase electrolyte concentration, the resulting rheology of the bubble stabilizing particle network was strongly elastic and appeared to be in a compression state at the region of the L-S phase transition.

Foaming Behavior of Polymer-Coated Colloids: The Need for Thick Liquid Films.

The current study examined the foaming behavior of poly(vinylpyrrolidone) (PVP)-silica composite nanoparticles. Individually, the two components, PVP and silica nanoparticles, exhibited very little potential to partition at the air-water interface, and as such, stable foams could not be generated. In contrast, combining the two components to form silica-PVP core-shell nanocomposites led to good "foamability" and long-term foam stability. Addition of an electrolyte (Na2SO4) was shown to have a marked effect on the foam stability. By varying the concentration of electrolyte between 0 and 0.55 M, three regions of foam stability were observed: rapid foam collapse at low electrolyte concentrations, delayed foam collapse at intermediate concentrations, and long-term stability (∼10 days) at the highest electrolyte concentration. The observed transitions in foam stability were better understood by studying the microstructure and physical and mechanical properties of the particle-laden interface. For rapidly collapsing foams the nanocomposite particles were weakly retained at the air-water interface. The interfaces in this case were characterized as being "liquid-like" and the foams collapsed within 100 min. At an intermediate electrolyte concentration (0.1 M), delayed foam collapse over ∼16 h was observed. The particle-laden interface was shown to be pseudo-solid-like as measured under shear and compression. The increased interfacial rigidity was attributed to adhesion between interpenetrating polymer layers. For the most stable foam (prepared in 0.55 M Na2SO4), the ratio of the viscoelastic moduli, G'/G″, was found to be equal to ∼3, confirming a strongly elastic interfacial layer. Using optical microscopy, enhanced foam stability was assessed and attributed to a change in the mechanism of foam collapse. Bubble-bubble coalescence was found to be significantly retarded by the aggregation of nanocomposite particles, with the long-term destabilization being recognized to result from bubble coarsening. For rapidly destabilizing foams, the contribution from bubble-bubble coalescence was shown to be more significant.

Interfacial Particle Dynamics: One and Two Step Yielding in Colloidal Glass.

The yielding behavior of silica nanoparticles partitioned at an air-aqueous interface is reported. Linear viscoelasticity of the particle-laden interface can be retrieved via a time-dependent and electrolyte-dependent superposition, and the applicability of the "soft glassy rheology" (SGR) model is confirmed. With increasing electrolyte concentration (φelect) in the aqueous subphase, a nonergodic state is achieved with particle dynamics arrested first from attraction induced bonding bridges and then from the cage effect of particle jamming, manifesting in a two-step yielding process under large amplitude oscillation strain (LAOS). The Lissajous curves disclose a shear-induced in-cage particle redisplacement within oscillation cycles between the two yielding steps, exhibiting a "strain softening" transitioning to "strain stiffening" as the interparticle attraction increases. By varying φelect and the particle spreading concentration, φSiO2, a variety of phase transitions from fluid- to gel- and glass-like can be unified to construct a state diagram mapping the yielding behaviors from one-step to two-step before finally exhibiting one-step yielding at high φelect and φSiO2.

Correction: Revealing the dynamic heterogeneity of PMMA/PVDF blends: from microscopic dynamics to macroscopic properties.

Correction for 'Revealing the dynamic heterogeneity of PMMA/PVDF blends: from microscopic dynamics to macroscopic properties' by Bo Lu et al., Soft Matter, 2016, DOI: .

Revealing the dynamic heterogeneity of PMMA/PVDF blends: from microscopic dynamics to macroscopic properties.

An effort was made to demonstrate the dynamic heterogeneity of poly(methyl methacrylate) (PMMA)/poly(vinylidene fluoride) (PVDF) blends, where its composition dependence and the role of interphase were probed. Firstly, the composition dependence of thermorheological complexity of PMMA/PVDF blends in the melt was revealed. The molecular entanglement state involving intra- and interchain entanglements was found to govern the scenario of thermorheological complexity. Intriguingly, local heterogeneity was further demonstrated to exist in the melt-state blends with intermediate compositions, and its origin was depicted to be the interphase. The interphase, coupled with unfavourable interchain entanglements in those blends, could explain the reduced viscosity and speed-up relaxations, contributing to the overall thermorheological complexity. Besides, two experimental glass transition temperatures of blends were resolved in view of segment motions in the miscible phase and the crystal-amorphous interphase, and further assessed via the "self-concentration" concept. The presence of a crystal-amorphous interphase, likely leading to three distinct dynamics of segments in blends, was supposed to contribute to the dynamic heterogeneity in segment relaxations for PMMA/PVDF blends in the solid state. Lastly, effects of dynamic heterogeneity on dynamic mechanical properties were also evaluated.