| Citation: |
AN Bang, SUN Wenye, LI Guangying, et al. Effect of glycerol polymerization degree on the structure and humidity response of cellulose nanocrystals composite iridescent films[J]. Acta Materiae Compositae Sinica, 2024, 41(12): 6740-6749. DOI: 10.13801/j.cnki.fhclxb.20240415.001
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In order to investigate the effect of glycerol with different polymerization degrees on mechanical and humidity response of cellulose nanocrystalls (CNC), CNC were mixed with glycerol, triglycerol, hexamylglycerol and decaglycerol at different mass ratios to prepared a series of CNC/polyglycerol composite iridescent films by evaporation-induced self-assembly. The effect of glycerol polymerization degrees on structural color, mechanical and humidity response property of CNC composite iridescence film was systematically studied. The iridescent color of the composite iridescent film is blueshifted with the increase of the degree of polymerization due to the decrease of pitch of CNC chiral nematic sturcture, the maximum reflective wavelength decreases by up to 40 nm. The addition of glycerol (and polyglycerol) significantly improved the humidity response ability of CNC films. For the composite film with the same amount of addition, the lower the degree of polymerization of polyglycerol, the stronger the humidity response ability and the redder in high humidity enviroment. The color of 20wt% sample with glycerol change from cyan to red in relative humidity 98%, redshift about 170 nm. Compared with pure CNC film, the mechanical properties of the composite films were significantly improved. And compared with glycerol, the elongation at break and the tensile strength of decaglycerol composite films increased by 1.58 times and 2.48 times, respectively.
Cellulose nanocrystals (CNC) are natural biological and renewable photonic crystals, and the tunable structural color of CNC composite films has been widely researched. But the effect of the additive’s polymerization degree on the structural color and humidity response has not been reported. Glycerol with different polymerization degree was compound with CNC to form composite iridescence films and structural color, mechanical and humidity response of films was systematically studied.
CNC composite iridescence films were prepared by evaporation-induced self-assembly through mixing CNC suspension with polyglycerol with different polymerization degree. The structural color of CNC composite film can be adjusted by the amount of polyglycerol. The difference between different polyglycerol were compared under the same conditions. And the effect of polymerization degree of polyglycerol on the optical properties, mechanical and humidity response of the composite film were researched.
The reflectance spectra show that the structural color of CNC composite films was redshift with the content of polyglycerol increase, it was also verified by the increased size of periodic ordered micro-structure observe form SEM, which is associated with the reflected wavelength by the Segal’s empirical formula. The reflectance peak of CNC composite films was blueshift with the increase of polymerization degree of polyglycerol when the content of polyglycerol constant. The results showed that the pitch of the composite film was proportional to the amount of polyglycerol, and the polymerization degree was inversely proportional. All the CNC composite films formed orderly chiral nematic phase structures, and the left-hand assembly of CNC was clearly seen in SEM images. This long-term ordered periodic structure is the origin of the structural color of CNC composite film, and the size of its periodic structure determines the structural color. The periodic structure size of the CNC composite films increased with the content of polyglycerol increased, but compared with the same amount of glycerol, the size of periodic structure of decaglycerol decreased, which was consistent with the reflectance spectra results. The addition of polyglycerol significantly improved the mechanical properties of the composite iridescence film. With the increase of glycerol polymerization degree, the elongation at break and the tensile strength of the composite iridescence film increase, which is due to the increase of the force between the long molecular chains. Compared with CNC/G20(CNC composite film with 20 wt% glycerol addition), the elongation at break and tensile strength of CNC/10G20(CNC composite film with 20 wt% glycerol addition) were increased by 1.58 times and 2.48 times, respectively. The addition of polyglycerol introduced humidity response to the CNC iridescence film. The redshift of the CNC composite films with different (polyglycerol) was decreased with the increase of the polymerization degree of (polyglycerol) under different relative humidity (35%, 70%, 85% and 98%), indicating that the humidity response ability was decreased. It also can be seen from the FTIR spectra that the peak value of the CNC composite film at 1030cm-1 decreased with the increase of (polyglycerol) polymerization degree, indicating that the number of primary hydroxyl groups in the composite film decreased. It’s mainly caused by glycerol polymerization, the condensation between the primary hydroxyl groups forms ether bonds with the polymerization of glycerol. And the decrease of the number of hydroxyl groups leads to the decrease of its hydrophilic ability, and finally the humidity response ability decreases.Conclusions: The addition of polyglycerol can precisely adjust the structural color of CNC iridescence film and increase the mechanical properties significantly. Moreover, polyglycerol introduced humidity response ability to CNC iridescence. With the increase of the degree of polymerization of polyglycerol, its mechanical properties increased, but its ability to adjust the structural color and humidity response gradually decreased.
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