Self-assembled lignin-based flame retardant hybrids carrying Cu2+ for poly(lactic acid) composites with improved fire safety and mechanical properties.

To enhance the flame retardancy and mechanical performance of PLA, a polyelectrolyte complex predicated on lignin was obtained by electrostatic mutual adsorption of ammonium polyphosphate (APP), polyethyleneimine (PEI), and copper ions as raw materials. The FT-IR spectra and EDX analysis confirmed the successful synthesis of a lignin-based flame retardant hybrid (APL-Cu2+) containing copper, phosphorus, and nitrogen elements. The combustion test results showed that the peak heat release rate and total heat release of the PLA composite containing 12 wt% APL-Cu2+ were decreased by 15.1 % and 18.2 %, respectively, as compared to those of pure PLA. The char residue morphology observation revealed that the addition of APL-Cu2+ could promote the formation of a highly dense and stable graphitized char layer, while TG-MS detected the emission of refractory gases such as ammonia gas, carbon dioxide, and water during combustion. The strong hydrogen bonding between APL-Cu2+ and the PLA matrix kept the composite maintaining good strength and toughness. The tensile strength and impact strength of PLA/6APL-Cu2+ increased by 4.73 % and 65.71 %, respectively, due to its high crystallinity and good interfacial compatibility. This work provides a feasible method to develop biobased flame retardant hybrids for PLA composites with better fire safety and improved mechanical properties.

Oxidization and Chain-Branching Reaction for Recycling HDPE and Mixed HDPE/PP with In-situ Compatibilization by Ozone-Induced Reactive Extrusion.

High-density polyethylene (HDPE) and isotactic polypropylene (iPP) are widely used in industrial and residential applications due to their low cost and chemical stability, thus their recycling process can contribute to a circular economy. However, both polymers are non-polar materials, and the incompatibility with most other materials leads to substantially inferior properties of blends. In this work, we propose a flexible compatibilization strategy to improve the compatibility of HDPE/iPP blends. Ozone is adopted to induce reactive extrusion for rapid oxidation of HDPE and chain-branching reactions for both HDPE and HDPE/iPP blends. During extrusion process, ozone oxidizes HDPE effectively in a short time and introduces oxygen-containing groups such as carbonyl and ester groups, which improves the hydrophilicity. The addition of trimethylolpropane triacrylate (TMPTA) could promote branching reaction and facilitate the formation of HDPE-g-iPP copolymers, which improved the compatibility for HDPE/iPP. As a result, the impact strength of ozone-modified HDPE and HDPE/iPP blends increased by 22 % and 82 %, respectively, and the tensile strength also increased. This strategy would have potential applications in the field of sorting-free and solvent-free recycling of waste polyolefin plastics.

Construction of highly ductile, UV-shielding polylactide/poly(butylene adipate-co-terephthalate) biocomposites with hyperbranched polysiloxane functionalized lignin as a biocompatibilizer.

Biodegradable polylactide/poly(butylene adipate-co-terephthalate) (PLA/PBAT) blends have been widely utilized as packaging materials. However, it is urgent to develop a biocompatibilizer to improve the interfacial interaction of the biodegradable immiscible polymer blends in practice. In this paper, a novel type of hyperbranched polysiloxane (HBPSi) with terminal methoxy groups was synthesized and then utilized to functionalize lignin through a hydrosilation reaction. The HBPSi modified lignin (lignin@HBPSi) was incorporated into immiscible PLA/PBAT blends to serve as a biocompatibilizer. The lignin@HBPSi was uniformly dispersed in the PLA/PBAT matrix with improved interfacial compatibility. Dynamic rheological results revealed that the addition of lignin@HBPSi reduced the complex viscosity, improving the processing ability of the PLA/PBAT composite. The PLA/PBAT composite containing 5 wt% lignin@HBPSi had a superior toughness with an elongation at break of 300.2 % and a slight enhancement in tensile stress (34.47 MPa). In addition, the presence of lignin@HBPSi contributed to blocking ultraviolet rays in the full ultraviolet band. This work provides a feasible way to develop highly ductile PLA/PBAT/lignin composites with good UV-shielding properties for the packaging applications.

Self-assembled biobased chitosan hybrid carrying N/P/B elements for polylactide with enhanced fire safety and mechanical properties.

The inherent shortcomings such as flammability, brittleness, and low crystallinity limit the broad applications of poly(lactic acid) (PLA). To improve the fire resistance and mechanical properties of PLA, a chitosan-based core-shell flame retardant additive (APBA@PA@CS) was prepared for PLA via the self-assembly of interionic interactions among chitosan (CS), phytic acid (PA), and 3-aminophenyl boronic acid (APBA). The peak heat release rate (pHRR) and total heat release rate (THR) of PLA composite containing 3 wt% APBA@PA@CS decreased from 460.1 kW/m2 and 75.8 MJ/m2 to 419.0 kW/m2 and 53.1 MJ/m2, respectively. The presence of APBA@PA@CS contributed to the formation of a high-quality char layer rich in phosphorus and boron in the condensed phase and released non-flammable gases in the gas phase to hinder the exchange of heat and O2, thereby having a synergistic flame retardant effect. Meanwhile, the tensile strength, elongation at break, impact strength, and crystallinity of PLA/APBA@PA@CS were increased by 3.7 %, 17.4 %, 5.3 %, and 55.2 %, respectively. This study provides a feasible route to construct a chitosan-based N/B/P tri-element hybrid to improve the fire safety performance and mechanical properties of PLA biocomposites.

Self-Assembled Serpentine Ni3Si2O5(OH)4 Hybrid Sheets with Ammonium Polyphosphate for Fire Safety Enhancement of Polylactide Composites.

Biodegradable polylactide (PLA) has been widely utilized in people's daily lives. In order to improve the fire safety of PLA, ammonium polyphosphate (APP) was self-assembled onto the surface of serpentine Ni3Si2O5(OH)4 through the electrostatic method, followed by mixing with PLA by melt compounding. The APP-modified serpentine (serpentine@APP) dispersed uniformly in the PLA matrix. Compared with pure PLA, the PLA composite with 2 wt% serpentine@APP reduced the peak heat release rate (pHRR) and total heat release (THR) by 43.9% and 16.3%, respectively. The combination of APP and serpentine exhibited suitable synergistic flame-retardant effects on the fire safety enhancement of PLA. In addition, the dynamical rheological tests revealed that the presence of APP and serpentine could reduce the viscosity of PLA composites. The plasticizing effects of APP and serpentine benefited the processing of PLA. The mechanical properties of PLA/serpentine@APP maintained suitable performance as pure PLA. This study provided a feasible way to enhance the fire safety of PLA without sacrificing its mechanical properties.

Nanohybrid of Co3O4 Nanoparticles and Polyphosphazene-Decorated Ultra-Thin Boron Nitride Nanosheets for Simultaneous Enhancement in Fire Safety and Smoke Suppression of Thermoplastic Polyurethane.

Thermoplastic polyurethane (TPU) is widely used in daily life due to its characteristics of light weight, high impact strength, and compression resistance. However, TPU products are extremely flammable and will generate toxic fumes under fire attack, threatening human life and safety. In this article, a nanohybrid flame retardant was designed for the fire safety of TPU. Herein, Co3O4 was anchored on the surface of exfoliated ultra-thin boron nitride nanosheets (BNNO@Co3O4) via coprecipitation and subsequent calcination. Then, a polyphosphazene (PPZ) layer was coated onto BNNO@Co3O4 by high temperature polymerization to generate a nanohybrid flame retardant named BNNO@Co3O4@PPZ. The cone calorimeter results exhibited that the heat release and smoke production during TPU combustion were remarkably restrained after the incorporation of the nanohybrid flame retardant. Compared with pure TPU, the peak heat release rate (PHRR) decreased by 44.1%, the peak smoke production rate (PSPR) decreased by 51.2%, and the peak CO production rate (PCOPR) decreased by 72.5%. Based on the analysis of carbon residues after combustion, the significant improvement in fire resistance of TPU by BNNO@Co3O4@PPZ was attributed to the combination of quenching effect, catalytic carbonization effect, and barrier effect. In addition, the intrinsic mechanical properties of TPU were well maintained due to the existence of the PPZ organic layer.

Photo-irradiation tunes highly active sites over ß-Ni(OH)2 nanosheets for the electrocatalytic oxygen evolution reaction.

A facile photo-irradiation method is developed to tune active sites over ß-Ni(OH)2 nanosheets. Photo-irradiated ß-Ni(OH)2 nanosheets possess disordered surface atoms and preferred growth of highly active crystal facets, which exhibit enhanced performance for the electrocatalytic oxygen evolution reaction.

Biodegradable and renewable UV-shielding polylactide composites containing hierarchical structured POSS functionalized lignin.

The demand for biodegradable and renewable UV-shielding materials is ever increasing due to the rising concern for the environment. In this paper, biobased lignin was functionalized by polyhedral oligomeric silsesquioxane (POSS) with an epoxy substituent. Then the POSS decorated lignin (lignin-POSS) was mixed with polylactide (PLA) to act as UV-shielding filler by melt compounding. The SEM observation revealed that the presence of POSS contributed to improving the homogeneous dispersion of lignin-POSS in the PLA matrix with good compatibility when the content of lignin-POSS was lower than 5 wt%. The synergistic effects of lignin and POSS endowed PLA composite films with a good balance of UV-shielding ability and transparency in the visible light region. With the addition of 5 wt% lignin-POSS, the PLA composite film absorbed almost all UV irradiation across the entire UV spectrum. In addition, the presence of lignin-POSS could serve as a nucleating agent to increase the degree of crystallinity of PLA. The dynamical rheological tests revealed that the lignin-POSSS reduced the complex viscosity and storage modulus of PLA composites, improving the flowability of PLA composites. This work presents a viable pathway to prepare biodegradable and renewable UV-shielding materials for potential packaging applications.

Fabrication of Self-Lubricating Porous UHMWPE with Excellent Mechanical Properties and Friction Performance via Rotary Sintering.

Porous ultra-high-molecular-weight polyethylene (UHMWPE) self-lubricating materials were designed and fabricated by a rotary sintering method, and the microstructure and properties were evaluated. Results showed that the rotary molding could not only significantly improve the molding efficiency but also formed uniform internal microstructures with high porosity, excellent mechanical properties, and low friction coefficient. Under oil lubricating conditions, the friction curve of samples quickly reached a steady state, the friction coefficient was reduced by 50%, and the repeat utilization was up to 99%. The following optimum sintering conditions were shown: Sintering temperature of 180 °C or 190 °C, sintering time determined as 10 min, and loading capacity of between 3.6 g and 3.8 g. Therefore, it is expected that this work will open a convenient and compatible strategy for fabricating porous materials with good self-lubricating performance.

Facile Synthesis of Phosphorus and Cobalt Co-Doped Graphitic Carbon Nitride for Fire and Smoke Suppressions of Polylactide Composite.

Due to the unique two-dimensional structure and features of graphitic carbon nitride (g-C3N4), such as high thermal stability and superior catalytic property, it is considered to be a promising flame retardant nano-additive for polymers. Here, we reported a facile strategy to prepare cobalt/phosphorus co-doped graphitic carbon nitride (Co/P-C3N4) by a simple and scalable thermal decomposition method. The structure of Co/P-C3N4 was confirmed by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The carbon atoms in g-C3N4 were most likely substituted by phosphorous atoms. The thermal stability of polylactide (PLA) composites was increased continuously with increasing the content of Co/P-C3N4. In contrast to the g-C3N4, the Polylactide (PLA) composites containing Co/P-C3N4 exhibited better flame retardant efficiency and smoke suppression. With the addition of 10 wt % Co/P-C3N4, the peak heat release rate (PHRR), carbon dioxide (CO2) production (PCO2P) and carbon oxide (CO) production (PCOP) values of PLA composites decreased by 22.4%, 16.2%, and 38.5%, respectively, compared to those of pure PLA, although the tensile strength of PLA composites had a slightly decrease. The char residues of Co/P-C3N4 composites had a more compact and continuous structure with few cracks. These improvements are ascribed to the physical barrier effect, as well as catalytic effects of Co/P-C3N4, which inhibit the rapid release of combustible gaseous products and suppression of toxic gases, i.e., CO.

Ecofriendly UV-protective films based on poly(propylene carbonate) biocomposites filled with TiO2 decorated lignin.

It is highly desirable to develop biodegradable UV-shielding materials from the renewable resources as the ever-increasing demand for the sustainable environment. In this work, TiO2 decorated lignin particles (TiO2@lignin) were synthesized successfully by hydrothermal method in aqueous solution to improve the UV shielding performance of lignin particles. The poly(propylene carbonate) (PPC) composite films (thickness of ~23 µm) with different contents of TiO2@lignin were prepared via a blade-casting method. Morphological analysis showed that the TiO2@lignin dispersed uniformly in the PPC matrix with a good miscibility. UV-vis transmission spectra results revealed that the PPC composite film containing 5 wt% TiO2@lignin could absorb about 90% of UV light in the full UV band (200-400 nm), indicating the TiO2@lignin had a good UV-shielding property. Moreover, the presence of TiO2@lignin could significantly improve the thermal stability of the PPC/TiO2@lignin composite films. The DMA results showed that the introduction of TiO2@lignin could enhance the storage modulus and glass transition temperature simultaneously.

Rhelogical and antibacterial performance of sodium alginate/zinc oxide composite coating for cellulosic paper.

Coating of antibacterial layer on the surface of cellulosic paper has numerous potential applications. In the present work, sodium alginate (SA) served as a binder to disperse Zn2+ and the prepared zinc oxide (ZnO) particles were used as antibacterial agents. The rheology test revealed that there were cross-linking between Zn2+ and SA molecular chains in the aqueous solution, resulting in the viscosity of ZnO/SA composite coating increased in the low shear rate region and decreased in the high shear rate region as compared with pure SA. SEM and EDS mapping images showed that the ZnO particles were prepared successfully at 120 °C and dispersed homogeneously on the surface of cellulose fibers and the pores of cellulosic papers. The thermal stabilities of the coated papers decreased as compared to the original blank cellulosic paper, which was ascribed to the low thermal stability of SA and the catalytic effect of ZnO on SA. The tensile stress and Young's modulus of ZnO/SA composite coated paper increased up 39.5% and 30.7%, respectively, as compared with those of blank cellulosic paper. The antibacterial activity tests indicated that the ZnO/SA composite coating endowed the cellulosic paper with effectively growth inhibition of both Gram-negative bacteria E. coli and Gram-positive bacteria S. aureu.

Clinical device-related article evaluation of morphology and functions of a foldable capsular vitreous body in the rabbit eye.

We previously proposed a new strategy to replace a vitreous body with a novel foldable capsular vitreous body (FCVB). In this study, the FCVB was designed to mimic natural vitreous morphology, and evaluate its physiological functions compared with traditional silicone oil substitutes, in an established rabbit model of proliferative vitreoretinopathy. We found that FCVB was a very good replacement for closely mimicking the morphology and restoring the physiological functions, such as the support, refraction, and cellular barriers, of the rabbit vitreous body. The study has provided us with a novel research and therapy strategy that could effectively mimic the morphology and physiological function of the rabbit vitreous body.

Technical standards of a foldable capsular vitreous body in terms of mechanical, optical, and biocompatible properties.

We previously proposed a new strategy to fabricate a novel foldable capsular vitreous body (FCVB) as a vitreous substitute and found that the FCVB was a very good replacement for closely mimicking the morphology and restoring the physiologic function of the rabbit vitreous body. The aim of this article was to assess the mechanical, optical, and biocompatible properties of a FCVB made from liquid silicone rubber. The mechanical properties show that the shore hardness is 37.80 degrees, the tear strength is 47.14 N/mm, the tensile strength is more than 7.28 MPa, and the elongation ratio is more than 1200%; in addition, the FCVB has 300 nm mili apertures in the capsule. The optical properties reveal that transmittances are 92%, hazes are 5.74%, and spectral transmittance is 97%. The transmittance mission is 2.3% and can sustain a 1500 mW, 0.2 s, 532 nm green laser. The biocompatible properties are shown in the stable extracts experiment, no significant fever, good genetic safety, and no structural abnormality or apoptosis in the cornea, ciliary body, and retina over a 6-month observation period. These results indicate that the FCVB has good mechanical, optical, and biocompatible properties, and the assessment results can be recommended as the FCVB technical standards for industrial manufacturing and inspection.