3-Pentadecylphenol (PDP) as a Novel Compatibilizer for Simultaneous Toughened and Reinforced PA10,12 Composites.

The utilization of polyamide 10,12 (PA10,12) composites in various industries has been limited constrained by their inherent low toughness, making it a challenge to achieve a balance between toughness and structural integrity through conventional elastomer addition strategies. Herein, we introduce a straightforward method for the concurrent toughening and reinforcement of PA10,12 composites. This is accomplished by blending polyolefin elastomer (POE) and 3-pentadecylphenol (PDP) with the PA10,12 matrix. The incorporation of 5 wt% PDP effectively blurred the PA10,12/POE interface due to PDP's role as a compatibilizer. This phenomenon is attributed to the formation of intermolecular hydrogen bonds, as evidenced by Fourier Transform Infrared Spectroscopy (FTIR) analysis. Further investigation, using differential scanning calorimetry (DSC), elucidated the crystallization thermodynamics and kinetics of the resulting binary PA10,12/POE and ternary PA10,12/POE/PDP composites. Notably, the crystallization temperature (Tc) was observed to decrease from 163.1 °C in the binary composite to 161.5 °C upon the addition of PDP. Increasing the PDP content to 10% led to a further reduction in Tc to 159.5 °C due to PDP's capacity to slow down crystallization. Consequently, the ternary composite of PA10,12/POE/PDP (92/3/5 wt%) demonstrated a synergistic improvement in mechanical properties, with an elongation at break of 579% and a notch impact strength of 61.54 kJ/m2. This represents an approximately eightfold increase over the impact strength of unmodified PA10,12. Therefore, our work provides the potential of PDP as a compatibilizer to develop nylon composites with enhanced stiffness and toughness.

Molecular dynamics simulation of the 3-15alkyphenol compatibilizer in highly toughened and robust polyamide 10,12/MWCNT composites.

Highly toughened and stiff polyamide 10,12 (PA10,12) composites present a promising alternative to metal products for high-impact environments. However, it is challenging to toughen PA10,12 composites without compromising their robustness. Herein, we report a facile and scalable route to simultaneously develop reinforced and toughened PA10,12 composites via compounding PA10,12, carbon nanotubes (CNTs) and 3-15alkyphenol (PDP). The PDP acted as a compatibilizer to well-disperse MWCNTs since they tended to be adsorbed onto the CNT surface, which was revealed by molecular dynamics simulation. According to the simulation statistics, the vertical PDP conformations (to the CNT surface) were predominant in the ternary composites with ∼78.7% probability. Moreover, the hydrogen bonds (H-bonds) between the PDP and the PA matrix were confirmed using FTIR. A crystallization kinetics study also revealed that the crystallization temperature increased from 166.7 °C for the neat PA10,12 to 168.7 °C for the ternary PA/PDP/CNT composites containing 1.5 wt% CNTs, while the crystallization half-time increased from 0.58 s for the neat PA10,12 to 1.2 s for the ternary composites. It was also found that the notched impact strength of the ternary composites reached 75.2 kJ m-2, which was 970% higher than that of the neat PA10,12 without compromising their tensile strength of 50.5 MPa much. This work provides a new insight into PDP as a compatibilizer to develop simultaneously stiff and toughened nylon composites.

Ratiometric detection of I- using a dysprosium-based metal-organic framework with a single emission center.

In this study, a dysprosium-based metal-organic framework (MOF) sensor (Dy-MOF) was developed for the ratiometric detection of I- in aqueous medium. Upon excitation at 230 nm, Dy-MOF shows two dominant emission bands at 464 nm and 574 nm assigned to (4F, 4D)5/2 → 6H9/2 + 6F11/2 and 4F9/2 → 6H13/2 transition of Dy3+, respectively, which have different sensitivities toward iodide ions. The introduction of I- slightly weakened the blue emission at 464 nm and significantly quenched the yellow emission at 574 nm. Thus, ratiometric sensing for iodide was realized using the yellow-to-blue intensity ratio of Dy3+. Dy-MOF exhibits superior sensing behavior towards I- with high selectivity, sensitivity and low detection limit (24 nM). This study also provides a strategy for the construction of a ratiometric sensor with dual-emission bands originating from only one emission center.

Polybutadiene Dielectric Elastomers with High Dielectric Constant and Ultralow Dielectric Loss via Tuning Grafted Polar Groups.

This work describes an easy and effective process for preparing a homogeneous polybutadiene (PB) dielectric elastomer with improved actuated strain by utilizing a photochemical thiol-ene click reaction. The carboxyl groups and various ester groups are used for grafting on the PB. Since the length of the alkyl chains of the ester groups will significantly influence the polarities of the carbonyl groups and hydrogen bonding effect, the influence of polarity and hydrogen bonding effect on the dielectric properties and mechanical properties of the modified polybutadienes is carefully discussed. Very interestingly, it is found that the increment of dielectric constant of PB modified by carboxyl groups is the lowest one compared to other modified PBs with the ester groups. Meanwhile, the modified PBs with the ester groups could achieve pretty low dielectric loss factor, and finally, a high dielectric constant (3.6), low dielectric loss factor (0.0005), and large actuated strain (≈25%) of the modified polybutadienes could be achieved by the modified PBs with butyl acrylate groups. This work provides a simple and effective method for the designing and synthesizing of a homogeneous high electromechanical performance dielectric elastomer with high dielectric constant and low dielectric loss.

A ratiometric luminescence sensing platform based on lanthanide-based silica nanoparticles for selective and sensitive detection of Fe3+ and Cu2+ ions.

Detection of Fe(III) and Cu(II) in water is highly desirable because their abnormal levels can cause serious harm to human health and environmental safety. In this work, a ratiometric luminescence sensing platform based on lanthanide-based silica nanoparticles was constructed for the detection of Fe3+ and Cu2+ ions. The terbium-silica nanoparticles (named SiO2@Tb) with dual-emission signals were successfully prepared by grafting Tb3+ ions onto trimellitic anhydride (TMA) functionalized silica nanospheres. It can serve as a ratiometric fluorescent probe for the detection of Fe3+ and Cu2+ ions in water with the green emission of Tb3+ ions as a response signal and the blue emission of silica nanospheres as the reference signal. Significantly, an easy-to-differentiate color change for visual detection was also realized. SiO2@Tb shows high sensitivity even in very low concentration regions towards the sensing of Fe3+ and Cu2+ with low detection limits of 0.75 µM and 0.91 µM, respectively. Moreover, the mechanism for the luminescence quenching of SiO2@Tb was systematically investigated, and was attributed to the synergetic effect of the absorption competition quenching (ACQ) mechanism and cation exchange. This study demonstrates that SiO2@Tb can be employed as a promising fluorescent probe for the detection of Fe3+ and Cu2+ ions, and the combination of lanthanide ions with silica nanoparticles is an effective strategy to construct a ratiometric fluorescent sensing platform for the determination of analytes in environmental detection.

Janus Hydrogel to Mimic the Structure and Property of Articular Cartilage.

Designing hydrogels with adequate strength, remarkable swelling resistance, low friction coefficient, excellent biocompatibility, and osseointegration potential is essential for replacing articular cartilage. However, it remains challenging to integrate all these properties into one material. In this work, a Janus hydrogel was prepared from polyvinyl alcohol, chitosan, and sodium hyaluronate, followed by a one-sided dipping in situ precipitation mineralization to form a layer of hybridized hydroxyapatite (HAp), wherein the two surfaces had distinct compositions and functions. Because of the negative carboxyl groups from sodium hyaluronate, the top surface possessed a friction coefficient as low as 0.024. On account of the HAp mineralized layer, the bottom side had osteogenesis potential. Owing to the synergy of physical linkages, the hydrogel displayed compressive strength as high as 78 MPa. Furthermore, it demonstrated remarkable swelling resistance with strength retention near 100% even after soaking in PBS solution at 37 °C for 7 days. The absence of toxic chemicals maintained the merits of starting polymers and resulted in excellent biocompatibility (cell viability ≈ 100%), making it an ideal substitute for articular cartilage.

Confined Crystallization and Melting Behaviors of 3-Pentadecylphenol in Anodic Alumina Oxide Nanopores.

To explore the effects of end groups on the confined crystallization of an alkyl chain, 3-pentadecylphenol (PDP) was infiltrated into the anodic aluminum oxide template (AAO) to investigate the melting and crystallization behaviors of PDP in a nanoconfined environment. Wide-angle X-ray diffraction (WAXD) found that the solid-solid phase transition of PDP occurred under confined conditions, and the absence of the (00L) reflections indicated that the stacking of the end groups of the alkyl chain layered structure was seriously disturbed. Thermal analysis (TG) showed that the thermal stability of the confined samples decreased due to the confinement effect, and the introduction of end groups made the confinement effect more obvious. Differential scanning calorimeter (DSC) results well reflected the space-time equivalence in the PDP crystallization processes, i.e., the solid-solid phase transition can be achieved by reducing the cooling rate or confining PDP in the nanometer space. Compared with C15, the introduction of the end groups with a phenol ring led to the disappearance of the solid-solid phase transition of an alkyl chain at high cooling rates. In the confined environment, the introduction of the end groups with a phenol ring caused the melting double peaks of the alkyl chain to become a single melting peak, and it also caused the disappearance of the surface freezing monolayer for alkyl chains. Through the analysis of crystallinity, it was found that AAO-PDP was more sensitive to AAO pore size changes than AAO-C15, the X c of AAO-PDP had a good linear relationship with the pore size d, but the X c of the AAO-C15 had a nonlinear relationship with the pore size d. Attenuated total reflection (ATR)-IR proved that in the confined environment, the order of the alkyl chain decreased and the degree of chain distortion increased.

A review on nanocellulose as a lightweight filler of polyolefin composites.

Nanocellulose (NC) possesses low density, high aspect ratio, impressive mechanical properties, nanoscale dimensions, which shows huge potential applications as a reinforced filler. Polyolefin (PO), represented by polyethylene (PE) and polypropylene (PP), has been widely used in industries. Recently nanocellulose/polyolefin nanocomposites (NC/PO nanocomposites) have caught more attention from the application of automotive components, aerospace, furniture, building, home appliances, and sport. In this review, the surface modifications of nanocellulose and polyolefin are summarized respectively, such as surface adsorption modification, small molecule modification, and graft copolymerization modification. The common preparations of NC/PO nanocomposites are discussed, including the melting compounding, the solvent casting, and the in-situ polymerization. The lightweight, mechanical properties, and aging-resistant properties of NC/PO nanocomposites are highlighted. Finally, the potentials and challenges for industrial production development of NC/PO nanocomposites are discussed.

Graphene Oxide-Supported Catalyst with Thermoresponsive Smart Surface for Selective Hydrogenation of Cinnamaldehyde.

In this study, a graphene oxide (GO)-based thermoresponsive smart catalytic material with a phase-transition temperature of approximately 37 °C was developed by growing poly( N-isopropylacrylamide) (PNIPAM) on GO sheets (i.e., GO-PNIPAM). The composite was characterized by Fourier transform infrared spectroscopy, N2 adsorption, thermogravimetric analysis, organic elemental analysis, differential scanning calorimetry, and X-ray photoelectron spectroscopy. GO-PNIPAM-supported Ru catalysts (i.e., Ru/GO-PNIPAM) were then prepared for cinnamaldehyde (CAL) hydrogenation. The influence of thermosensitive smart surface on the reaction was investigated. Results indicated that GO-PNIPAM exhibited the hydrophilic surface at 25 °C, which resulted in highly dispersed Ru nanoparticles on the composite. Afterward, the surface wettability of Ru catalyst was spontaneously changed to hydrophobicity at 70 °C that greatly improved CAL sorption on the catalyst in the reaction. The synergistic effect between Ru and GO-PNIPAM as well as the great adsorption ability to reactants on Ru/GO-PNIPAM jointly resulted in the enhancement of catalytic activity over it in comparison to that over GO-supported Ru catalyst (Ru/GO). Meanwhile, the hydrophobic surface of Ru/GO-PNIPAM at a high-temperature preferred C═O adsorption mode, yielding a higher cinnamyl alcohol selectivity than Ru/GO did.

Lamellae Assembly in Dendritic Spherulites of Poly(l-lactic Acid) Crystallized with Poly(p-Vinyl Phenol).

Lamellar assembly with fractal-patterned growth into dendritic and ringed spherulites of crystallized poly(l-lactic acid) (PLLA), of two molecular weight (MW) grades and crystallized at (temperature of crystallization) Tc = 120 and 130 °C, respectively, are evaluated using optical and atomic-force microscopies. The results of surface-relief patterns in correlation with interior microscopy analyses in this work strongly indicate that the observed birefringence changes in PLLA polymer dendritic or ringed spherulites (from blue to orange, or to optical extinction) need not be definitely associated with the continuous helix twisting of lamellae; they can be caused by sudden and discontinuous lamellae branching at intersected angles with respect to the original main lamellae, as proven in the case of dendritic and zig-zag rough-ringed spherulites. Intersection angles between the main stalks and branches tend to be governed by polymer crystal lattices; for PLLA, the orthorhombic lattice (α-form) usually gives a 60° angle of branching and hexagonal growth. The branching lamellae then further bend to convex or concave shapes and finally make a 60⁻90° angle with respect to the main stalks. Such mechanisms are proven to exist in the straight dendritic/striped high-molecular weight (HMW)-PLLA spherulites (Tc = 120 °C); similar mechanisms also work in circularly ringed (Tc = 130 °C) HMW-PLLA spherulites.

Miscibility, Morphology and Crystallization Behavior of Poly(Butylene Succinate-co-Butylene Adipate)/Poly(Vinyl Phenol)/Poly(l-Lactic Acid) Blends.

Amorphous poly(vinyl phenol) (PVPh) is introduced into poly(butylene succinate-co-butylene adipate)/poly(l-lactic acid) (PBSA/PLLA) blends via solution casting. Fourier transform infrared spectroscopy (FTIR) analysis verifies that intermolecular hydrogen bonding formed in PBSA/PVPh/PLLA blends. The miscibility between PBSA and PLLA is improved with PVPh incorporation as evidenced by approaching Tgs of the two components. When PVPh content reaches up to 50 wt %, the blend sample exhibits only one Tg, meaning complete miscibility between PBSA and PLLA. The improved miscibility of PBSA/PLLA blends is further confirmed by scanning electron microscope (SEM). Typical "see-island" phase separation structure for PBSA/PLLA blend transforms into homogenous phase structure for blend samples with 5 wt % PVPh and above. Non-isothermal crystallization analysis shows that the crystallization temperature and crystallization enthalpy of PBSA decrease with PVPh addition, and those of PLLA also show a decreasing trend. Isothermal crystallization rate of PBSA in blend samples distinctly decreases with PVPh incorporation, whereas that of PLLA in blend samples increases slightly with PVPh addition. Wide angle X-ray diffraction (WAXD) analysis indicated that PLLA in blend samples remained partly crystallized, while PBSA turned into amorphous state with increasing PVPh contents.

Solid-solid phase transition of n-alkanes in multiple nanoscale confinement.

The crystallization behavior of n-C(19)H(40)/SiO(2) nanosphere composites was investigated by a combination of differential scanning calorimetry (DSC) and temperature-dependent X-ray diffraction (XRD). Three kinds of confined alkanes with different solid-solid phase transition supercoolings and a surface (or interface) freezing monolayer of n-C(19)H(40) at the bulk liquid/SiO(2) interface were found in the composites at high SiO(2) loading. The surface freezing monolayer induces the chain packing of bulk alkanes by forming a 2D close-packed arrangement without long-range positional ordering in 3D space. A homogeneous nucleation and growth mechanism is found for the solid-solid transition in confined geometry, in which the supercooling of the transition is sensitive to the confined size.