Preparation and characteristics of TEMPO-oxidized cellulose nanofibrils from bamboo pulp and their oxygen-barrier application in PLA films

doi:10.1007/s11705-017-1673-8

Front. Chem. Sci. Eng.

2017, Vol. 11

Issue (4) : 554-563 https://doi.org/10.1007/s11705-017-1673-8

RESEARCH ARTICLE

Preparation and characteristics of TEMPO-oxidized cellulose nanofibrils from bamboo pulp and their oxygen-barrier application in PLA films

Bozhen Wu¹, Biyao Geng^2,³, Yufei Chen^2,³, Hongzhi Liu^2,³(

), Guangyao Li³(

), Qiang Wu^2,³(

)

¹. College of Materials Science and Engineering, Zhejiang University of Technology, Hangzhou 310014, China
². Zhejiang Provincial Collaborative Innovation Center for Bamboo Resources and High-efficiency Utilization, Hangzhou 311300, China
³. School of Engineering, Zhejiang Agriculture & Forestry University, Hangzhou 311300, China

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Abstract

Bleached bamboo kraft pulp was pretreated by 2,2,6,6-tetramethylpiperidine-1-oxy radical (TEMPO)-mediated oxidation using a TEMPO/NaBr/NaClO system at pH= 10 in water to facilitate mechanical disintegration into TEMPO-oxidized cellulose nanofibrils (TO-CNs). A series of TO-CNs with different carboxylate contents were obtained by varying amounts of added NaClO. An increase in carboxylate contents results in aqueous TO-CN dispersions with higher yield, zeta potential values, and optical transparency. When carboxylate groups are introduced, the DP_v value of the TO-CNs remarkably decreases and then levels off. And the presence of hemicellulose in the pulp is favorable to TEMPO oxidization. After the oxidization, the native cellulose I crystalline structure and crystal size of bamboo pulp are almost maintained. TEM micrographs revealed that the degree of nanofibrillation is directly proportional to the carboxylate contents. With increasing carboxylate contents, the free-standing TO-CN films becomes more transparent and mechanically stronger. The oxygen permeability of PLA films drastically decreases from 355 for neat PLA to 8.4 mL·m⁻²·d⁻¹ after coating a thin layer of TO-CN with a carboxylate content of 1.8 mmol·g⁻¹. Therefore, inexpensive and abundant bamboo pulp would be a promising starting material to isolate cellulose nanfibrils for oxygen-barrier applications.

Keywords bamboo TEMPO cellulose nanofibrils oxygen barrier

Corresponding Author(s): Hongzhi Liu,Guangyao Li,Qiang Wu

Just Accepted Date: 04 July 2017 Issue Date: 06 November 2017

Cite this article:

Bozhen Wu,Biyao Geng,Yufei Chen, et al. Preparation and characteristics of TEMPO-oxidized cellulose nanofibrils from bamboo pulp and their oxygen-barrier application in PLA films[J]. Front. Chem. Sci. Eng., 2017, 11(4): 554-563.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-017-1673-8
https://academic.hep.com.cn/fcse/EN/Y2017/V11/I4/554

Fig.1 Relationships between the amounts of NaClO added in the TEMPO/NaBr/NaClO oxidation of bamboo bleached kraft pulp and either carboxylate (-COO^?Na⁺) content or DP_v of TO-CN aqueous dispersions

Fig.2 Relationships between the carboxylate (-COO^?Na⁺) contents and either yields of TO-CNs or zeta potential values of TO-CN aqueous dispersions

Fig.3 Light transmittance spectra of various TO-CN dispersions prepared through mechanical homogenization of bamboo kraft pulp

Fig.4 FT-IR spectra of bamboo bleached kraft pulp and its derived TO-CNs

Fig.5 XRD spectra of pulp and various TO-CN filmsprepared from TEMPO-oxidized bamboo bleached kraft pulp

Tab.1 Crystalline data of various TO-CN films prepared from bamboo bleached kraft pulp

Fig.6 TEM images of various TO-CNs prepared from bamboo kraft pulp: (a) TO-CN 0.5, (b) TO-CN 1.0, and (c) TO-CN 1.8

Fig.7 Width distributions of various TO-CNs: (a) TO-CN 0.5, (b) TO-CN 1.0, and (c) TO-CN 1.8

Fig.8 Light transmittance spectra of various TO-CN films (~20?µm in thickness) derived from bamboo kraft pulp

Fig.9 Typical tensile stress-strain curves of various TO-CN films

Tab.2 Mechanical property data of different TO-CN films from the bamboo pulp^a)

Fig.10 Oxygen permeability of neat 50? mm thick PLA film and the ones coated with 1? mm thick TO-CN layers

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