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      Mechanically Robust, Flame-Retardant Poly(lactic acid) Biocomposites via Combining Cellulose Nanofibers and Ammonium Polyphosphate

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          Abstract

          Expanding the application range of flame-retardant polymer biocomposites remains a huge challenge for a sustainable society. Despite largely enhanced flame retardancy, until now the resultant poly(lactic acid) (PLA) composites still suffer reduced tensile strength and impact toughness due to improper material design strategies. We, herein, demonstrate the design of a green flame retardant additive (ammonium polyphosphate (APP)@cellulose nanofiber (CNF)) via using the cellulose nanofibers (CNFs) as the green multifunctional additives hybridized with ammonium polyphosphate (APP). The results show that PLA composite with 5 wt % loading of APP@CNF can pass the UL-94 V-0 rating, besides a high limited oxygen index of 27.5%, indicative of a significantly enhanced flame retardancy. Moreover, the 5 wt % of APP@CNF enables the impact strength (σ i) of the PVA matrix to significantly improve from 7.63 to 11.8 kJ/m 2 (increase by 54%), in addition to a high tensile strength of 50.3 MPa for the resultant flame-retardant PLA composite. The enhanced flame retardancy and mechanical strength performances are attributed to the improved dispersion of APP@CNF and its smaller phase size within the PLA matrix along with their synergistic effect between APP and CNF. This work opens up a facile innovative methodology for the design of high-performance ecofriendly flame retardants and their advanced polymeric composites.

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          Most cited references32

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          Optically Transparent Composites Reinforced with Networks of Bacterial Nanofibers

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            Elastic modulus and stress-transfer properties of tunicate cellulose whiskers.

            Experimental deformation micromechanics of natural cellulose fibers using Raman spectroscopy and X-ray diffraction have been widely reported. However, little has been published on the direct measurements of the mechanical properties, and in particular the elastic modulus, of the highly crystalline material in the native state. Here we report on measurements of the elastic modulus of tunicate cellulose using a Raman spectroscopic technique. A dispersed sample of the material is deformed using a four-point bending test, and a shift in a characteristic Raman band (located at 1095 cm(-1)) is used as an indication of the stress in the material. Relatively little intensity change of the Raman band located at 1095 cm(-1) is shown to occur for samples oriented parallel and perpendicular to the polarization direction of the laser, as compared to a highly oriented flax sample. This indicates that the tunicate sample is a two-dimensional in-plane random network of fibers. By use of this result, the Raman shift, and calibrations with strain from other materials, it is shown that the modulus of the material is very high, at about 143 GPa, and a lack of Raman band broadening is thought to be due to the fact that there is pure crystalline deformation occurring without the effect of crystalline/amorphous fractions. A strain sensitivity of the shift in the 1095-cm(-1) Raman peak for this specimen is shown to be -2.4 +/- 0.2 cm(-1)/%. A molecular mechanics approach, using computer simulation and an empirical force field, was used to predict the modulus of a highly oriented chain of the material, and this is found to be 145 GPa, which is in agreement with the experimental data. However, by use of a normal-mode analysis, it is found that a number of modes have positions close to the central positions of the experimental Raman band. One in particular is found to shift at a rate of 2.5 cm(-1)/%, but due to the complex nature of the structure, it is not entirely conclusive that this band is representative of the experimental findings.
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              Cellulose nanocrystals vs. cellulose nanofibrils: a comparative study on their microstructures and effects as polymer reinforcing agents.

              Both cellulose nanocrystals (CNCs) and cellulose nanofibrils (CNFs) are nanoscale cellulose fibers that have shown reinforcing effects in polymer nanocomposites. CNCs and CNFs are different in shape, size and composition. This study systematically compared their morphologies, crystalline structure, dispersion properties in polyethylene oxide (PEO) matrix, interactions with matrix, and the resulting reinforcing effects on the matrix polymer. Transparent PEO/CNC and PEO/CNF nanocomposites comprising up to 10 wt % nanofibers were obtained via solution casting. Scanning electron microscopy (SEM), wide-angle X-ray diffraction (WXRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), dynamic mechanical analyzer (DMA), and tensile testing were used to examine the above-mentioned properties of nanocellulose fibers and composites. At the same nanocellulose concentration, CNFs led to higher strength and modulus than did CNCs due to CNFs' larger aspect ratio and fiber entanglement, but lower strain-at-failure because of their relatively large fiber agglomerates. The Halpin-Kardos and Ouali models were used to simulate the modulus of the composites and good agreements were found between the predicted and experimental values. This type of systematic comparative study can help to develop the criteria for selecting proper nanocellulose as a biobased nano-reinforcement material in polymer nanocomposites.
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                Author and article information

                Journal
                ACS Omega
                ACS Omega
                ao
                acsodf
                ACS Omega
                American Chemical Society
                2470-1343
                25 May 2018
                31 May 2018
                : 3
                : 5
                : 5615-5626
                Affiliations
                []School of Chemical Engineering and Technology, Harbin Institute of Technology , 92 West Dazhi Street, Nangang District, Harbin 150001, China
                []Department of Materials, College of Engineering, Zhejiang A & F University , 666 Wusu Street, Linan District, Hangzhou 311300, China
                [§ ]Center for Future Materials, University of Southern Queensland , West Street, Toowoomba, Queensland 4350, Australia
                Author notes
                [* ]E-mail: pingansong@ 123456gmail.com (P.S.).
                [* ]E-mail: menglinh@ 123456hit.edu.cn (L.M.).
                Article
                10.1021/acsomega.8b00540
                6641890
                31458762
                92dc4a28-6eed-498a-bc8e-508eda4dfdba
                Copyright © 2018 American Chemical Society

                This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.

                History
                : 21 March 2018
                : 15 May 2018
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                ao-2018-00540q

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