Electronic Supplementary Information (ESI) available: XRD and FTIR spectra of pretreated bamboo pulp, AFM micrographs and height profiles of CNC I, CNC II and CNC: I→II and their properties (Table S1), XRD spectra for different PLA/CNC polymorph films at 1wt% CNC loading. See Cellulose nanocrystals (CNCs) using different polymorphs of cellulose were fabricated from raw bamboo pulp through alkali treatment followed by acid hydrolysis. The effect of CNC polymorphs, namely CNC I, CNC II and CNC:I→II (CNC II from cellulose I), on its morphology, crystal structure, degree of hydrogen bonding and thermal stability were studied. These polymorphs were dispersed in polylactic acid (PLA) films using casting evaporation approach and their effect on the structural, thermal, mechanical and barrier properties of the PLA were investigated. The CNC polymorphs differ significantly in their reinforcement capability and ability to form percolated network. Incorporation of CNC II and CNC: I→II significantly improved the Young's modulus of composites (by ~72%). However, their elongation at break significantly decreased compared to CNC I, due to high hydroxyl functionality, which forms entangled hydrogen bonded network within the polymer matrix, leading to improvement in mechanical as well as barrier properties. The theoretically calculated moduli of composites using Halpin Kardos, Cox-Krenchel and Ouali models showed good agreement for CNC I,CNC II and CNC:I→II respectively, albeit at higher aspect ratio. All three CNCs showed the capability to form percolated network, the occurrence and stability of which varied with the type of polymorphs. Therefore, the current study provides an insight towards selection of appropriate polymorphs for fabrication of CNC reinforced high performance poly (lactic acid) based bionanocomposites.
This paper reports a single-step co-precipitation method for the fabrication of magnetic cellulose nanocrystals (MGCNCs) with high iron oxide nanoparticle content (∼51 wt % loading) adsorbed onto cellulose nanocrystals (CNCs). X-ray diffraction (XRD), Fourier transform infrared (FTIR), and Raman spectroscopic studies confirmed that the hydroxyl groups on the surface of CNCs (derived from the bamboo pulp) acted as anchor points for the adsorption of Fe3O4 nanoparticles. The fabricated MGCNCs have a high magnetic moment, which is utilized to orient the magnetoresponsive nanofillers in parallel or perpendicular orientations inside the polylactic acid (PLA) matrix. Magnetic-field-assisted directional alignment of MGCNCs led to the incorporation of anisotropic mechanical, thermal, and electrical properties in the fabricated PLA-MGCNC nanocomposites. Thermomechanical studies showed significant improvement in the elastic modulus and glass-transition temperature for the magnetically oriented samples. Differential scanning calorimetry (DSC) and XRD studies confirmed that the alignment of MGCNCs led to the improvement in the percentage crystallinity and, with the absence of the cold-crystallization phenomenon, finds a potential application in polymer processing in the presence of magnetic field. The tensile strength and percentage elongation for the parallel-oriented samples improved by ∼70 and 240%, respectively, and for perpendicular-oriented samples, by ∼58 and 172%, respectively, in comparison to the unoriented samples. Furthermore, its anisotropically induced electrical and magnetic properties are desirable for fabricating self-biased electronics products. We also demonstrate that the fabricated anisotropic PLA-MGCNC nanocomposites could be laminated into films with the incorporation of directionally tunable mechanical properties. Therefore, the current study provides a novel noninvasive approach of orienting nontoxic bioderived CNCs in the presence of low magnetic fields, with potential applications in the manufacturing of three-dimensional composites with microstructural features comparable to biological materials for high-performance engineering applications.
In this study, we successfully demonstrate single-step industrially scalable reactive extrusion of polylactic acid (PLA)/ cellulose nanocrystal (CNC)-based cast films which leads to reduced necking, improved processability, melt strength, and rheological behavior. PLA chains grafted onto CNCs, formed cross-linked gel-like structures of high molecular weight (M w ≈ 150−245 kDa), with varying grafting efficiency (14%−67%) or gel-fraction yield (16%− 69%), depending on the type of compatibilizers used. The reactively processed films show reduction in both oxygen properties (20%− 65%) and water vapor barrier properties (27%−50%), along with improved thermomechanical properties. These films finds potential applications for the storage of oil-and dairy-based products, which show shelf lives of ∼5 months and ∼2 weeks, respectively, and are within the standard migration limits, as per the set legislations. Therefore, the present study provides a novel, easily processable extrusion-based approach for manufacturing sustainable PLA/ CNC-based green and eco-friendly films with improved recyclability, biodegradability, and nontoxicity for potential applications as food packages on a commercial scale.
This article reports a novel fabrication
of branched cum cross-linked
poly(lactic acid) (PLA) with nanosilk fibroin with graft chain topology
by reactive extrusion process. It could be possible by the addition
of a small amount of radical initiator (dicumyl peroxide (DCP)). Grafting
of silk nanocrystals (SNCs) on PLA macromolecules that provides remarkable
improvement in the rheological and thermal properties of the latter
are confirmed by 1H NMR and Fourier transform infrared
investigation. Significant improvement is observed in zero shear viscosities,
and the crossover point shifts to lower frequencies as compared to
the branched and cross-linked PLA system. Along with SNC grafting,
the crystallization process is also enhanced and stable crystals appeared
during cooling, which results in a single melting peak. The rate of
crystallization of PLA has been improved although the percentage crystallinity
reduces with DCP content, as higher grafting and cross-linking restricts
the chain segmental motion, which is critical for crystallization
process. Furthermore, SNC grafting increases the reprocessability
performance of PLA and provides higher rheological properties as compared
to the branched and cross-linked PLA at all reprocessing cycles.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.