In this work, an alternative flame-retardant filler based on phosphate- and urea-grafted bamboo charcoal (BC-m) at 10–30 wt % addition was aimed at improving the flame retardancy of polylactic acid (PLA) composites. The filler caused only a small reduction in strength properties but a slight increase in the modulus of elasticity of PLA composites. BC-m significantly improved the flame-retardant performance compared with pure BC. The limiting oxygen index (LOI) was 28.0 vol % when 10 wt % of BC-m was added, and 32.1 vol % for 30 wt % addition, which was much greater than the value of 22.5 vol % for 30 wt % pure BC. Unlike pure BC, adding BC-m at 20 wt % or more gave a UL-94 vertical flame test rating of V-0 with significantly reduced melt dripping. The peak heat release rate (pHRR) and total heat release (THR) of BC-m/PLA composites decreased by more than 50% compared with pure PLA, and the values for 20% BC-m were significantly less than that for 25% BC addition. The grafted biochar-based system provides an effective flame retardancy effect by a condensed-phase protective barrier through the rapid formation of a dense, honeycomb-like cross-linked carbonized char layer. The results suggest a promising route to enhancing the flame-retardant properties of biodegradable polymer composites using nontoxic, more environmentally friendly grafted biochar.

In this study, bamboo charcoal (BC) was used as a substitute filler for bamboo powder (BP) in a lignocellulose-plastic composite made from polylactic acid (PLA), with aluminum hypophosphite (AHP) added as a fire retardant. A set of BC/PLA/AHP composites were successfully prepared and tested for flame-retardancy properties. Objectives were to (a) assess compatibility and dispersibility of BC and AHP fillers in PLA matrix, and (b) improve flame-retardant properties of PLA composite. BC reduced flexural properties while co-addition of AHP enhanced bonding between PLA and BC, improving strength and ductility properties. Adding AHP drastically reduced the heat release rate and total heat release of the composites by 72.2% compared with pure PLA. The formation of carbonized surface layers in the BC/PLA/AHP composites effectively improved the fire performance index (FPI) and reduced the fire growth index (FGI). Flame-retardant performance was significantly improved with limiting oxygen index (LOI) of BC/PLA/AHP composite increased to 31 vol%, providing a V-0 rating in UL-94 vertical flame test. Adding AHP promoted earlier initial thermal degradation of the surface of BC/PLA/AHP composites with a carbon residue rate up to 40.3%, providing a protective layer of char. Further raw material and char residue analysis are presented in Part II of this series.

It is of great significance to develop green, sustainable additives to improve the thermal stability and flame retardancy of biopolymers. In this work, a synergistic modification of P/N elements to bamboo biochar (mBC) was successfully achieved by grafting a reaction of phytic acid and urea with preoxidized bamboo biochar. Fourier transform infrared spectroscopy, X-ray diffraction, nuclear magnetic resonance and scanning electron microscope determinations of the mBC demonstrated a successive grafting of phytic acid and urea to the originally porous surface. The ground mBC was blended with polylactic acid (PLA) to prepare mBC/PLA composites by extrusion and hot pressing. Mechanical strength studies showed a compromise in rigidity, which might originate from the mBC overdose and its limited miscibility with the resin. The thermogravimetric results supported the fact that the enhancement of thermal stability and flame retardancy of the composites with the mBC dosage, which showed that the mBC dosage in the PLA composites was not only lower than that of the conventional flame retardants, but also outperformed the counterparts using BC modified by inorganic phosphoric acid and urea. The mBC was prone to accelerate the earlier decomposition of the composites (30 °C lower in decomposition) and generate a continuous, dense residual carbon layer, which provides an effective shield resisting the mass and heat transfer between the combustion area and the underlying composite matrix. Only 10 wt% of mBC dosage could achieve a V-0 rating (UL94) for the composite, with a higher limiting oxygen index up to 28.3% compared to 20.7% for that of the virgin PLA; the cone colorimetric results also suggested that the flame retardancy had been greatly improved for all composites. In this work, biobased P-/N-containing bamboo biochar would be expected as a nontoxic biochar-based flame retardant that serves as green filler in polymer composites.

A cooperative flame-retardant system based on natural intumescent-grafted bamboo charcoal (BC) and chitosan (CS) was developed for polylactic acid (PLA) with improved flame retardancy and minimal decline in strength properties. Chitosan (CS) as an adhesion promoter improved the interfacial compatibility between graft-modified bamboo charcoal (BC-m) and PLA leading to enhanced tensile properties by 11.11% and 8.42%, respectively for tensile strength and modulus. At 3 wt.% CS and 30 wt.% BC-m, the crystallinity of the composite increased to 38.92%, or 43 times that of pure PLA (0.9%). CS promotes the reorganization of the internal crystal structure. Thermogravimetric analysis showed significantly improved material retention of PLA composites in nitrogen and air atmosphere. Residue rate for 5 wt.% CS and 30 wt.% BC-m was 29.42% which is 55.1% higher than the theoretical value of 18.97%. Flammability tests (limiting oxygen index-LOI and UL-94) indicated significantly improved flame retardancy and evidence of cooperation between CS and BC-m, with calculated cooperative effectiveness index(Ce) >1. From CONE tests, the peak heat release rate (pHRR) and total heat release (THR) were reduced by 26.9% and 30.5%, respectively, for 3% CS + 20% BC-m in PLA compared with adding 20% BC-m alone. Analysis of carbon residue morphology, chemical elements and structure suggest CS and BC-m form a more stable char containing pyrophosphate. This char provides heat insulation to inhibit complete polymer pyrolysis, resulting in improved flame retardancy of PLA composites. Optimal mix may be recommended at 20% BC-m + 3% CS to balance compatibility, composite strength properties and flame retardance.

A superhydrophobic stainless steel mesh (called “mesh” in short) is an ideal device to solve oil pollution accidents by oil–water separation. However, its widespread application is prevented by complicated preparation, weak durability, and particularly poor mechanical strength. It is well known that the used adhesives play a key role in the mechanical strength of superhydrophobic coatings. In this study, polyvinylidene fluoride (PVDF) and polydimethylsiloxanes (PDMSs) were respectively used as adhesives and lignin-nanocellulose crystal (L-CNC) particles as main structure materials to prepare L-CNC coated superhydrophobic meshes. Moreover, the meshes coated with L-CNC/PVDF and L-CNC/PDMS were compared with respect to the properties of wettability, sandpaper abrasion, oil–water separation, etc. The results showed that the L-CNC/PVDF-coated mesh had a higher water contact angle (WCA = 154.2°) than the L-CNC/PDMS-coated one (WCA = 152.6°), but worse abrasion resistance. Both of them showed high-efficiency oil/water separation with collection rates above 94.5% and stable reusable ability as the oil collection rates for toluene was still above 93.8% after reusing thirty times, meanwhile showing good heat, UV, acid and alkaline resistance properties.