3.1 Characterization of Particle Size and Zeta Potential
Firstly, the Z-average size and PDI of Re/mDA-CNCs when redispersing into DI water are shown in Table 1. The Z-average size and PDI of original CNCs are 110 nm and 0.213, respectively. However, it is observed from Fig. 3a that the original CNC powder via direct vacuum drying cannot be redispersed. The Z-average size and PDI of Re/mDA-CNCs when redispersed in DI water gradually decrease with the increasing of DA amount (Table 1), indicating the improved redispersion properties of Re/mDA-CNCs at higher DA amount. The Z-average size gradually approaches the size of original CNCs, and the particle size gradually become uniform. The Z-average size and PDI of Re/0.4DA-CNCs are 109 nm and 0.213, respectively. This indicates that Re/0.4DA-CNCs can be restored to its original size when redispersed in water. The size of Re/0.5DA-CNCs with higher DA amount do not change, indicating that the cationic groups of DA are attracted to the negative charges on CNC surface by opposite charges attracting, effectively reducing the number of H-bonding formed through -OH groups in CNC intramolecular, the schematic illustration for preparation and mechanism of Re/mDA-CNCs was shown in Fig. 1. And allowing the redispersion of Re/0.4DA-CNCs.
Furthermore, it can be seen from Table 1 that the Zeta potential of original CNCs is -45.9 mV and the Zeta potential of Re/mDA-CNCs gradually decreases with the addition of DA. The reason is due to the fact that DA is a surfactant composed of cationic groups and hydrophobic groups (C6H5- \ R-O-R (R') \ R-NH-R', which is shown in Fig.4). During the dehydration of CNCs, the electrostatic repulsion between the hydrophobic groups on the DA surface and -OH groups on the CNC surface leads to the neutralization of the cationic groups in DA with -OH groups on the surface of CNCs, which provides more opportunities to reduce the number of H-bonding formed through -OH groups in CNC intramolecular. The Zeta potential of Re/0.4DA-CNCs is -46.2 mV when dissolved in water (Table 1), which is slightly lower than that of original CNCs. The reason is that cationic groups in DA are attracted onto -OH groups on the CNC surface, consequently block the formation of H-bonding formed by -OH groups in CNC intramolecular. In addition, the hydrophobic parts in DA also rearrange on CNCs surface and extend outside, which improves the hydrophilicity and interface compatibility of CNCs. Therefore, DA acts as a H-bonding blocker and dispersant in the redispersion process. The Re/0.4DA-CNC powder is redispersed to the original size when redispersed in water without affecting the basic properties of CNCs.
Table 1 Z-average, PDI and Zeta potential of Re/mDA-CNCs
Samples
|
Z-average (d. nm)
|
PDI
|
Zeta Potential (mV)
|
Original CNCs
|
111
|
0.213
|
-45.9
|
Re/0.1DA-CNCS
|
154
|
0.314
|
-50.5
|
Re/0.2DA-CNCS
|
126
|
0.312
|
-48.7
|
Re/0.3DA-CNCS
|
119
|
0.285
|
-47.1
|
Re/0.4DA-CNCS
|
112
|
0.214
|
-46.2
|
Re/0.5DA-CNCS
|
112
|
0.213
|
-46.1
|
Note: The relative error of Z-average and Zeta potential measurement are ± 1 nm and ± 0.2 mV, respectively.
3.2 Morphology Characteristics of Re/mDA-CNCs
We observed the cross-sectional morphology of Re/mDA-CNC film and the original CNC film. The original CNC film shows a dense layered structure, which indicates that the -OH groups in CNC intramolecular “self-assembly” through H-bonding to form chiral nematic liquid crystal during drying (Fig.2a) (Ates et al. 2020). The self-assembly behavior of CNCs is hindered with the addition of DA, leading to surface disintegration of Re/mDA-CNC film with an increase in DA amount. When the amount of DA is 0.1%, the Re/0.1DA-CNC film still maintains a good layered structure (Fig.2b). The layered structure is gradually broken and the cross section shows convex and concave morphology when 0.2% DA are added (Fig.2c), and the presence of DA is considered to be the main reason for the cracking of layered structure. When the amount of DA is greater than 0.4%, the “self-assembled” layered structure is completely destroyed (Fig.2e), and the CNCs are dispersed randomly throughout the CNC-DA matrix. The reason for the destruction of the “self-assembly” structure is that the electrostatic repulsion between the hydrophobic groups of DA and -OH groups on the CNC surface causes the cationic groups in DA to be attracted to -OH groups on the CNC surface, resulting in the decrease in the number of H-bonding formed between -OH groups in CNC intramolecular due to the reduction in the number of -OH groups, which is consistent with the change in Zetapotential. It can be seen that DA plays a critical role in chemically shielding and dispersing in the redispersion process of Re/mDA-CNCs.
3.3 Dispersion Stability of Re/mDA-CNCs
As shown in Fig. 3a, the samples 1, 2, 3 are the original CNC suspensions, the dried Re/0.4DA-CNC redispersion suspensions and the CNC powder redispersion suspensions, respectively. The dried Re/0.4DA-CNC redispersion suspension had been stored for 7 days and still remained uniform and transparent with no visible aggregations. There is no significant difference from the original CNC suspension (No. 1 in Fig.3a), and the Tyndall effect was still clearly observed after 7 days of storing. In contrast, the redispersed suspension of CNC powder is cloudier and has visible solid particles. The fact that solid particles settle rapidly to the bottom within a short time shows that CNC cannot be redispersed.
The dispersion stability of original CNC suspension and the redispersed Re/0.4DA-CNC suspension is evaluated by Turbiscan technique. Fig. 3b and Fig. 3c are the back-scattering spectra of original CNC suspension and the redispersed Re/0.4DA-CNC suspension measured by the stability analyzer. The lines with different color in Fig.3 represent each measurement time, and the higher the absolute value of the difference in the back-scattering signal (ΔBS), the more pronounced the instability of the system. The presence of a small amount of flocculation in the original CNC suspension is caused by the floating phenomenon, resulting in a very low concentration (0-1.7 mm) of CNCs at the bottom of cuvette. This makes the bottom of cuvette slightly clear, causing the scattered light intensity to become weaker. As the measurement time increasing, the original flocculation of CNC suspension floats on the upper part of cuvette (37.5-40 mm), causing enhanced back-scattering light intensity in the spectrum. In comparison, the back-scattering light intensity of Re/0.4DA-CNC suspension at the bottom of cuvette is stable (Fig. 3c), and the particle size becomes increasingly homogeneous under the effect of shear stress. As time increases, the redispersed Re/0.4DA-CNCs floats to the upper layer, which is responsible for the increased back-scattering light intensity at the top (37.5-40 mm). It can be concluded from the analysis of dispersion stability that Re/0.4DA-CNC suspension shows an excellent stability by adding 0.4% DA, indicating that the flocculation of CNC particles decreases.
Moreover, the hydrophobicity of Re/0.4DA-CNC film is better than that of the origin CNC film. It can be seen from Fig. 3d that the water contact angle of original CNC film is 71.60°, and the water contact angle of Re/0.4DA-CNC film is 72.80° (Fig. 3e). This is due to the interaction between the cationic groups in DA and -OH groups on the CNC surface, reducing the amount of -OH groups, while the hydrophobic groups in DA rearrange on the CNC surface, which causes the increase in CNC hydrophobicity. It is demonstrated that the use of DA is not only beneficial to the preparation of Re/mDA-CNCs but also to the changes in the interfacial compatibility of CNCs and the increase in the water contact angle.
3.4 FT-IR Analysis
The functional groups of original CNC powder and Re/0.4DA-CNC powder were analyzed by using a FT-IR spectrometer, and the main characteristic peaks of cellulose are shown in the spectrum of CNCs in Fig. 4. The absorption peaks locate at 3,365 cm-1 (-OH stretching) (He et al. 2018), 2,891 cm-1 (C-H stretching) (Aguilar-Sanchez et al. 2020), 1,024 cm-1 (-C-O-C asymmetric stretching vibration), 1,324 cm-1 (C-H stretching vibration of cellulose -CH and -CH2) and 1,665 cm-1 (deformation vibration of O-H caused by moisture change in cellulose), respectively (Cheng et al. 2018; Guo et al. 2017; Nigmatullin et al. 2020). The peaks at 1,442 cm-1 and 1,324 cm-1 belong to -CH2 bending vibration and in-plane -CH bending vibration, respectively. Additionally, 1,058 cm-1 are attributed to -C-O stretching vibration, which are consistent with the characteristic peaks in the references (Li et al. 2018b). Compared to the original CNC film, the sharp new absorption peaks of Re/0.4DA-CNC film at 1545 cm-1 and 1738cm-1 are ascribed to the typical stretching vibration of C6H5- and the stretching vibration caused by -C=O (the presence of ester groups or carbonyl groups of -COOH in DA) (Huang et al. 2020; Ly and Mekonnen 2020), respectively. These groups play a key role in regulating the hydrophobicity and interfacial compatibility of CNCs. Moreover, the absorption peak at 746 cm-1 belongs to the bending vibration of -(CH2)n- in long-chain alkyl groups (Li et al. 2018a). The results reveal that the DA is successfully introduced into the CNC surface and does not change the basic chemical structure of the CNCs.
3.5 XRD Analysis
Fig. 5 shows the XRD pattern of original CNC powder and Re/0.4DA-CNC powder. It can be seen that the characteristic peaks of Re/0.4DA-CNC powder have not significant change compared with that of the original CNC powder, which indicates that the Re/0.4DA-CNC powder does not change the crystalline structure of cellulose I. The diffraction peaks of original CNC powder and Re/0.4DA-CNC powder appear at 2θ=15.1°, 16.8°, 22.5° and 34.7°, corresponding to the (1-10), (110), (200) and (004) cellulose crystal planes, respectively (Shang et al. 2019; Velásquez-Cock et al. 2018). The crystallinity of the original CNC powder and Re/0.4DA-CNC powder is calculated to be 78.26% and 78.07%, respectively. The crystallinity of Re/0.4DA-CNC powder is appropriately equal to that of the original CNC powder. It can be inferred that the addition of DA weakens the bonding force between the CNCs and reduces the number of H-bonding formed by -OH groups “self-assembly” in the CNC intramolecular, leading to the reduction in CNC cornification degree. The decrease in water retention value of Re/mDA-CNCs is due to the change in CNC interface compatibility caused by hydrophobic groups in DA.
3.6 TG-DTG Analysis
TG analysis for the original CNC powder and Re/0.4DA-CNC powder is illustrated in Fig.6a. There are some differences in the thermogravimetric curves of two samples. The free water is removed from the samples at the 50-160℃, where a slightly weight loss occurs for all samples. At the vitrification transition stage of 160-250℃, the samples begin to degrade, resulting in a small amount of weight loss. At 260-390℃, the glycosidic bonding of cellulose is severely broken. At 390℃, the weight loss of CNC powder and Re/0.4DA-CNC powder is 71% and 69%, respectively. At this stage, the electrostatic repulsion between hydrophobic groups and -OH groups in Re/0.4DA-CNCs leads to the neutralization of cationic groups and -OH groups in DA-CNC matrix. Thereby, the redispersed Re/0.4DA-CNCs prepared by adding DA can effectively reduce the number of H-bonding formed by the “self-assembly” of -OH within the CNC intramolecular.
Fig. 6b shows the DTG curves of the original CNC powder and Re/0.4DA-CNC powder. The Re/0.4DA-CNC powder has a degradation peak at 270°C, indicating that this stage is the degradation of glycosidic bonding in Re/0.4DA-CNCs. In this case, the thermal decomposition temperature difference between Re/0.4DA-CNC powder and the original CNC powder is within 50°C. The results show that the higher the intermolecular H-bonding content, the higher the thermal decomposition temperature and the better the thermal stability. The decrease in thermal stability of Re/0.4DA-CNCs is due to the decrease in the number of H-bonding formed by -OH groups within CNC intramolecular.