A novel and fluorescence retention inverse opal has been achieved from organosilane-polymerized carbon dots (SiCDs), which is prepared via infiltrating SiCD solution into the interstice of photonic crystal (PC) template, low temperature treatment, heating polymerization and removing the colloidal template. The as-prepared SiCD inverse opals demonstrate close-cell structure, which is completely different from conventional open-cell structure. Then the fluorescence signal of as-prepared sample keeps almost unchanged in CuCl suspension while the fluorescence of SiCD solution can be quenched by CuCl suspension through an effective electron transfer process. This phenomenon can be attributed to the combined effect of high hydrostatic pressure in the pore structure, stable crosslinking network and fluorescence enhancement by PC structure. The SiCD inverse opals have advantages of unique close-cell structure, easy preparation and good repeatability that give an important insight into the design and manufacture of novel and advanced optical devices.

4D printing has attracted great interest since the concept was introduced in 2012. The past 5 years have witnessed rapid advances in both 4D printing processes and materials. Unlike 3D printing, 4D printing allows the printed part to change its shape and function with time in response to change in external conditions such as temperature, light, electricity, and water. In this review, we first overview the history of 4D printing and discuss its definition. We then summarize recent technological advances in 4D printing with focuses on methods, materials, and their intrinsic links. Finally, we discuss potential applications and offer perspectives for this exciting new field.

Despite the fact that numerous infection-resistant surfaces have been developed to prevent bacterial colonization and biofilm formation, developing a stable, highly antibacterial and easily produced surface remains a technical challenge. As a crucial structural component of biofilm, extracellular DNA (eDNA) can facilitate initial bacterial adhesion, subsequent development, and final maturation. Inspired by the mechanistic pathways of natural enzymes (deoxyribonuclease), here we report a novel antibacterial surface by employing cerium (Ce(Ⅳ)) ion to mimic the DNA-cleavage ability of natural enzymes. In this process, the coordination chemistry of plant polyphenols and metal ions was exploited to create an in situ metal-phenolic film on substrate surfaces. Tannic acid (TA) works as an essential scaffold and Ce(Ⅳ) ion acts as both a cross-linker and a destructor of eDNA. The Ce(Ⅳ)-TA modified surface exhibited highly enhanced bacteria repellency and biofilm inhibition when compared with those of pristine or Fe(Ⅲ)-TA modified samples. Moreover, the easily produced coatings showed high stability under physiological conditions and had nontoxicity to cells for prolonged periods of time. This as-prepared DNA-cleavage surface presents versatile and promising performances to combat biomaterial-associated infections.

A self-healing supramolecular polymer composite (HSP-GO) was designed and prepared via incorporation of modified graphene oxide to hyperbranched polymer by hydrogen-bonding interactions. The polymer matrix based on amino-terminated hyperbranched polymer (HSP-NH₂) was synthesized by carboxylation, Curtius rearrangement, and amination of hydroxyl-terminated hyperbranched polyester (HP-OH), while the modified graphene oxide was prepared by transformation of hydroxyl to isocyanate and further to carbamate ester. Spectroscopic methods were utilized to characterize the obtained polymer composites. Stress-strain test was selected to carefully study the self-healing property of HSP-GO. It is found that a small amount of modified graphene oxide (up to 2 wt%) improves the glass transition temperature (T_g), tensile strength, Young's modulus, and self-healing efficiency of the polymer composites. After healed at room temperature for 10 min, the addition of modified graphene oxide improves the self-healing efficiency to 37% of its original tensile strength. The experiment result shows that the self-healing efficiency is related to the density of hydrogen bonding site and the molecular movement.

Styrene emulsion polymerization using an alkyl-9-BBN, synthesized by reacting 9-BBN (9-borabicyclo-[3.3.1]-nonane) and styrene, in an aqueous sodium dodecyl sulfate (SDS) solution was studied. Ultra-high-molecular-weight > 1.0×10⁷) polystyrene was synthesized using a radical initiator formed through the aerobic oxidation of this alkyl-9-BBN in a high yield > 80%). The kinetics of this emulsion polymerization of styrene with the alkyl-9-BBN was investigated. We confirmed that in the initial stage of the polymerization, the initial reaction rate followed first-order kinetics. The activation energy for this emulsion polymerization of styrene was approximately 56.2 kJ/mol.

Poly(vinylidene fluoride) (PVDF) exhibits pronounced polymorphs. Its γ phase is attractive due to the electroactive properties. The γ-PVDF is however difficult to obtain under normal crystallization condition. In a previous work, we reported a simple melt-recrystallization approach for producing γ-phase rich PVDF thin films through selective melting and subsequent recrystallization. We reported here another approach for promoting the αγ' phase transition to prepare γ-phase rich PVDF thin films. To this end, a stepwise crystallization and subsequent annealing process was used. The idea is based on a quick generation of a large amount of α-PVDF crystals with some of their γ-PVDF counterparts at suitable crystallization temperature and then annealing at a temperature above the crystallization temperature for enhancing the molecular chain mobility to overcome the energy barrier of phase transition. It was found that crystallizing the PVDF melt first at 152℃ for 4 h, then quenching to room temperature and finally annealing the sample at 160℃ for 100 h was the most efficient to produce γ-PVDF rich films. This is related to the melting and recrystallization of the α-PVDF crystals produced during quenching in the annealing process at 160℃, which favors the formation of γ-PVDF crystals for triggering the αγ' phase transition.

Poly(vinyl chloride) (PVC) is one of the mostly produced plastics in the world and is widely used in single-use medical devices. However, the additives that are often necessary for PVC arouse concerns of its safety, thus quests the modifications of PVC itself. In this study, poly(ethylene glycol) (PEG) and polydimethylsiloxane (PDMS) segments were grafted onto PVC backbone in similar ways, and the chemical structures of the modified PVCs were characterized by Fourier transform infrared spectra, X-ray photoelectron spectra, thermogravimetric analysis and differential scanning calorimetry. Moreover, the water contact angle, protein adsorption, platelet adhesion, cell attachment and proliferation on different material surfaces were studied and compared. It was found that both PEG and PDMS grafting yielded improvement on biocompatibility compared with bare PVC, while hydrophobic PDMS grafted PVC showed more effective on cell attachment and proliferation than that of hydrophilic PEG grafted PVC.

Cu(OH)₂ nanowires were prepared and incorporated into poly(vinylidene fluoride) (PVDF) to fabricate Cu(OH)₂-PVDF ultrafiltration (UF) membrane via immersion precipitation phase inversion process. The effect of Cu(OH)₂ nanowires on the morphology of membranes was investigated by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectroscopy, atomic force microscopy (AFM), scanning electron microscopy (SEM) and X-ray diffraction (XRD) measurements. The results showed that all the Cu(OH)₂-PVDF membranes had wider fingerlike pore structure and better hydrophilicity, smoother surface than pristine PVDF membrane due to the incorporation of Cu(OH)₂ nanowires. In addition, water flux and bovine serum albumin (BSA) rejection were also measured to investigate the filtration performance of membranes. The results indicated that all the Cu(OH)₂-PVDF membranes had high water flux, outstanding BSA rejection and excellent antifouling properties. It is worth mentioning that the optimized performance could be obtained when the Cu(OH)₂ nanowires content reached 1.2 wt%. Furthermore, the membrane with 1.2 wt% Cu(OH)₂ nanowires showed outstanding oil-water emulsion separation capability.

The main aim of this research was to investigate the synergistic influence of additives and poly(butylene succinate) (PBS) in improving both the mechanical and flame retardant properties of polylactide (PLA) blends. Tricresyl phosphate (TCP) and montmorillonite (MMT) were the additives used to improve the mechanical characteristics and fire resistance of PLA. Differential scanning calorimetry (DSC) thermograms revealed that the addition of TCP and MMT significantly affected their thermal behaviors. The results of the mechanical and morphological characterizations were in agreement with the changes in thermal behavior. The impact strength and limiting oxygen index (LOI) value of PLA significantly increased with the presence of PBS. The failure mode of the blends as evidenced by scanning electron microscopy (SEM) changed from brittle to ductile. The addition of TCP and MMT produced excellent anti-dripping and self-extinguishing behaviors of the blends, achieving Ⅴ-0 rating. For the PLA/PBS blends, the synergistic combination of PBS and additives led to an acceleration of cold crystallization, a significant increment of flexibility and impact toughness, and an improvement of flame retardancy.

The physical and mechanical properties of blends composed of two kinds of epoxy resins of different numbers of functional groups and chemical structure were studied. One of the resins was a bifunctional epoxy resin based on diglycidyl ether of bisphenol A and the other resin was a multifunctional epoxy novolac resin. Attempt was made to establish a correlation between the structure and the final properties of cured epoxy samples. The blend samples containing high fraction of multifunctional epoxy resin showed higher solvent resistance and lower flexural modulus compared with the blends containing high fraction of bifunctional epoxy resin. The epoxy blends showed significantly higher ductility under bending test than the neat epoxy samples. The compressive modulus and strength increased with increasing of multifunctional epoxy in the samples, probably due to enhanced cross-link density and molecular weight. Morphological analysis revealed the presence of inhomogeneous sub-micrometer structures in all samples. The epoxy blends exhibited significantly higher fracture toughness (by 23% at most) compared with the neat samples. The improvement of the fracture toughness was attributed to the stick-slip mechanism for crack growth and activation of shear yielding and plastic deformation around the crack growth trajectories for samples with higher content of bifunctional epoxy resin as evidenced by fractography study.

In order to extend the application of epoxy vitrimer, 1, 4-cyclohexanedicarboxylic acid (CHDA) was used as a co-curing agent and structure modifier for sebacic acid (SA) cured diglycidyl ether of bisphenol A (DGEBA) epoxy vitrimer to tailor the mechanical properties of epoxy vitrimers with 1, 5, 7-triazabicylo[4.4.0]dec-5-ene (TBD) as a transesterification catalyst. The glass transition temperature (T_g) of vitrimer increased gradually with the increase in CHDA content. Vitrimers behaved from elastomer to tough and hard plastics were successfully achieved by varying the feed ratio of CHDA to SA. Both the Young's modulus and storage modulus increased apparently with the increase in CHDA content. Stress relaxation measurement indicated that more prominent stress relaxation occurred at elevated temperatures and the stress relaxation decreased with the increase of CHDA content due to the reduced mobility of the vitrimer backbone. The vitrimers showed excellent recyclability as evidenced by the unchanged gel fraction and mechanical properties after compression molded for several times. With tunable mechanical properties, the epoxy vitrimers may find extensive potential applications.

In this work, low-temperature vulcanized, transparent silane modified epoxy resins for LED filament bulb package were prepared. Firstly, transparent silane modified epoxy resins were produced through a controllable sol-gel method using γ-(2, 3-epoxypropoxy)propytrimethoxysilane and dimethyldiethoxylsilane. The features of the reaction were investigated and the products were characterized in detail. Subsequently, various curing agents were explored to prepare transparent silane modified epoxy resins. The silane modified epoxy resins cured by PEA-230 at a fairly low temperature (40℃/2 h then 60℃/1 h) exhibited excellent thermal stability with a thermal degradation temperature as high as 316.5℃ and adjustable hardness between 40-60 shore A. The application tests showed the materials obtained were good candidates for LED filament bulb package.

A phosphorus-nitrogen containing flame retardant additive of poly(phosphoric acid piperazine), defined as PPAP, was synthesized by the salt-forming reaction between anhydrous piperazine and phosphoric acid, and the dehydration polymerization under heating in nitrogen atmosphere. Its chemical structure was well characterized by Fourier transform infrared (FTIR) spectroscopy, ¹³C and ³¹P solid-state nuclear magnetic resonance measurements. The synthesized PPAP and curing agent m-phenylenediamine were blended into epoxy resin (EP) to prepare flame retardant EP thermosets. The effects of PPAP on the fire retardancy and thermal degradation behavior of cured EP/PPAP composites were investigated by limiting oxygen index (LOI), vertical burning (UL-94), thermogravimetric analysis/infrared spectrometry (TG-IR) and cone calorimeter tests. The morphologies and chemical compositions of char residues for cured epoxy resin were investigated by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), respectively. The results demonstrated that the flame retardant EP thermosets successfully passed UL-94 Ⅴ-0 flammability rating and the LOI value was as high as 30.8% when incorporating 5wt% PPAP into the EP thermosets. The TGA results indicated that the synthesized PPAP flame retardant additive possessed high thermal stability and excellent charring capability. Meanwhile, the incorporation of PPAP stimulated the epoxy resin matrix to decompose and charring ahead of time due to its catalytic decomposition effect, which led to a higher char yield at high temperature. The morphological structures and the analysis results of XPS for char residues of EP thermosets revealed that the introduction of PPAP benefited the formation of a sufficient, more compact and homogeneous char layer containing phosphorus-nitrogen flame retardant elements on the material surface during combustion. The formed char layer with high quality effectively prevented the heat transmission and diffusion, limited the production of combustible gases, and inhibited the emission of smoke, leading to the reduction of heat and smoke release.

Dielectric relaxation spectroscopy (DRS) of poly(ε-caprolactone) with different draw ratios showed that the mobility of polymer chains in the amorphous part decreases as the draw ratio increases. The activation energy of the α process, which corresponds to the dynamic glass transition, increases upon drawing. The enlarged gap between the activation energies of the α process and the β process results in a change of continuity at the crossover between the high temperature a process and the α and β processes. At low drawing ratios the a process connects with the β process, while at the highest drawing ratio in our measurements, the a process is continuous with the α process. This is consistent with X-ray diffraction results that indicate that upon drawing the polymer chains in the amorphous part align and densify upon drawing. As the draw ratio increases, the α relaxation broadens and decreases its intensity, indicating an increasing heterogeneity. We observed slope changes in the α traces, when the temperature decreases below that at which τ_α ≈ 1 s. This may indicate the glass transition from the 'rubbery' state to the non-equilibrium glassy state.

The conventional low-temperature method of solution polycondensation was developed to realize the reaction of p-phenylenediamin and terephthaloyl chloride for the preparation of poly(p-phenylene terephthalamide) (PPTA). Some main factors influencing this process were investigated to determine the optimum condition for high molecular weight. Experiment showed significant slowing of the reaction and gradual deviation of second-order reaction kinetics due to diffusion control. These phenomena were studied theoretically via dynamic Monte Carlo simulation. A concise expression, $ {\bar X_{\rm{n}}} \sim c_0^{ - 0.88} \cdot {t^{0.37}} $, was proposed to describe the diffusion-controlled polycondensation process as a function of the monomer concentration and reaction time. The theoretical results provided a good description of diffusion-effected kinetics for the polycondensation process of PPTA, and demonstrated good agreement with the experimental data. Some differences of scaling relations between model and experiment results were also discussed.