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Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

CN 11-5981/TQ

Postal Subscription Code 80-969

2018 Impact Factor: 2.809

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Front. Chem. Sci. Eng.    2019, Vol. 13 Issue (1) : 59-69    https://doi.org/10.1007/s11705-018-1712-0
RESEARCH ARTICLE
Preparation of lignin/TiO2 nanocomposites and their application in aqueous polyurethane coatings
Dongjie Yang1, Shengyu Wang1, Ruisheng Zhong1, Weifeng Liu1(), Xueqing Qiu1,2()
1. School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, China
2. State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou 510640, China
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Abstract

A simple method using a water soluble lignin quaternary ammonium salt (LQAS) and TiO2 has been developed for the preparation of lignin/TiO2 nanocomposites in an aqueous medium under mild conditions. The LQAS/TiO2 nanocomposites contain well-dispersed small particles with excellent ultraviolet (UV) shielding abilities and good compatibilities with waterborne polyurethane (WPU). When the LQAS/TiO2 nanocomposites were blended with WPU, the UV absorbance and the tensile ductility of the WPU increased significantly. The composite WPU hybrid film containing 6 wt-% LQAS/TiO2 nanocomposite had the highest visible light transmittance and had excellent ultraviolet aging properties. After 192 h of UV light irradiation, the tensile strength of the composite film was above 8 MPa and the elongation at break was 800%. This work highlights new possibilities for the utilization of alkali lignin.
Keywords lignin      TiO2      nanocomposite particle      polyurethane film     
Corresponding Author(s): Weifeng Liu,Xueqing Qiu   
Just Accepted Date: 09 February 2018   Online First Date: 19 April 2018    Issue Date: 25 February 2019
 Cite this article:   
Dongjie Yang,Shengyu Wang,Ruisheng Zhong, et al. Preparation of lignin/TiO2 nanocomposites and their application in aqueous polyurethane coatings[J]. Front. Chem. Sci. Eng., 2019, 13(1): 59-69.
 URL:  
https://academic.hep.com.cn/fcse/EN/10.1007/s11705-018-1712-0
https://academic.hep.com.cn/fcse/EN/Y2019/V13/I1/59
Fig.1  The preparation method for the LQAS/TiO2 nanocomposites
Fig.2  FTIR spectra of AL and LQAS-50
LQAS-50 /g H2O /mL H2SO4 /mL Tetrabutyl titanate /mL Ethanol /mL Particle size /mL
1.5 2.5 2 10 30 >1 µm
1 2.5 2 10 30 >500 nm
0.5 2.5 2 10 30 >500 nm
0.5 3.5 2 10 30 328.5
0.5 4.5 2 10 30 257.2
0.5 6.5 2 10 30 243.3
0.5 6.5 1.5 10 30 314.6
0.5 6.5 1 10 30 190.2
0.5 6.5 0.5 10 30 258.0
Tab.1  Effect of different preparation conditions on the particle size of LQAS/TiO2 nanocomposites
Fig.3  TGA/DSC curves of LQAS-60/TiO2
Sample Lignin content/%
LQAS-50/TiO2 34.5
LQAS-60/TiO2 35.3
LQAS-70/TiO2 33.6
LQAS-80/TiO2 32.8
Tab.2  Lignin content for the LQAS/TiO2 nanocomposites
Fig.4  XRD patterns of TiO2 and LQAS/TiO2 nanocomposites
Sample Cell parameters Crystallinity/%
a /Å b /Å c /Å
TiO2 4.59 4.59 2.96 85.9
LQAS-50/TiO2 3.78 3.78 9.52 4.10
LQAS-60/TiO2 3.77 3.77 9.50 4.55
LQAS-70/TiO2 3.79 3.79 9.51 3.69
LQAS-80/TiO2 3.79 3.78 9.51 3.41
LQAS-60/TiO2 (180 °C) 3.77 3.78 9.49 26.8
Tab.3  Cell parameters and the crystallinity of the LQAS/TiO2 nanocomposites
Fig.5  SEM images of TiO2 and LQAS/TiO2 nanocomposites (a) TiO2, (b) LQAS-50/TiO2, (c) LQAS-60/TiO2, (d) LQAS-70/TiO2, and (e) LQAS-80/TiO2
Fig.6  TEM images of TiO2 and LQAS/TiO2 nanocomposites (a) TiO2, (b) LQAS-50/TiO2, (c) LQAS-60/TiO2, (d) LQAS-70/TiO2, and (e) LQAS-80/TiO2
Fig.7  Particle size distributions in the LQAS/TiO2 nanocomposites
Sample Average size /nm
TiO2 150.0
LQAS-50/TiO2 191.2
LQAS-60/TiO2 184.5
LQAS-70/TiO2 195.7
LQAS-80/TiO2 198.6
Tab.4  The average size of the LQAS/TiO2 nanocomposites
Fig.8  N2 adsorption-desorption isotherms of TiO2 and the LQAS/TiO2 nanocomposites
Fig.9  BJH pore size distribution curves of TiO2 and the LQAS/TiO2 nanocomposites
Sample BET specific surface area /(m2?g?1)
TiO2 53.8
LQAS-50/TiO2 321.4
LQAS-60/TiO2 339.7
LQAS-70/TiO2 299.9
LQAS-80/TiO2 284.3
Tab.5  BET specific surface areas of TiO2 and the LQAS/TiO2 nanocomposites
Fig.10  Ti2p XPS spectra test for TiO2 and LQAS-60/TiO2
Fig.11  SEM images of the WPU-based blended films: (a) WPU+ 6 wt-% TiO2, (b) WPU+ 4.2 wt-% TiO2 + 1.8 wt-% LQAS-60, (c) WPU+ LQAS-50/TiO2, (d) WPU+ LQAS-60/TiO2, (e) WPU+ LQAS-70/TiO2, (f) WPU+ LQAS-80/TiO2
Fig.12  UV-Vis transmittance spectra of the WPU-based blended films
Fig.13  Digital photos of the WPU-based blended films: (a) WPU+ 6 wt-% TiO2, (b) WPU+ 4.2 wt-% TiO2 +1.8 wt-% LQAS-60, (c) WPU+ 6 wt-% LQAS-60/TiO2
Sample Tensile strength /MPa Elongation at break /%
WPU 22.4 ± 1.0 510 ± 25
WPU+ 6 wt-% TiO2 25.6 ± 0.7 440 ± 27
WPU+ 4.2 wt-% TiO2+1.8 wt-% LQAS-60 17.4 ± 0.8 362 ± 25
WPU+ 6 wt-% LQAS-50/TiO2 13.6 ± 0.2 961 ± 24
WPU+ 6 wt-% LQAS-60/TiO2 14.1 ± 0.6 1066 ± 25
WPU+ 6 wt-% LQAS-70/TiO2 13.5 ± 0.4 833 ± 25
WPU+ 6 wt-% LQAS-80/TiO2 13.1 ± 0.2 824 ± 25
WPU+ 6 wt-% LQAS-60/TiO2 (180 °C) 18.6 ± 0.4 889 ± 25
Tab.6  Mechanical properties of WPU-based blended films
Fig.14  The mechanical properties of the WPU-based blended films during UV aging process
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