A series of four cellulose nanocrystal (CNC) suspensions were prepared from bleached softwood kraft pulp using different conditions of sulfuric acid hydrolysis. The CNCs were identical in size (95 nm in length × 5 nm in width) but had different surface charges corresponding to the harshness of the hydrolysis conditions. Consequently, it was possible to isolate the effects of surface charge on the self-assembly and viscosity of the CNC suspensions across surface charges ranging from 0.27%S to 0.89%S. The four suspensions (never-dried, free of added electrolyte) all underwent liquid crystalline phase separation, but the concentration onset for the emergence of the chiral nematic phase shifted to higher values with increasing surface charge. Similarly, suspension viscosity was also influenced by surface charge, with suspensions of lower surface charge CNCs more viscous and tending to gel at lower concentrations. The properties of the suspensions were interpreted in terms of the increase in effective diameter of the nanocrystals due to the surface electrostatic repulsion of the negative sulfate half-esters, as modified by the screening effects of the H counterions in the suspensions. The results suggest that there is a threshold surface charge density (∼0.3%S) above which effective volume considerations are dominant across the concentration range relevant to liquid crystalline phase formation. Above this threshold value, phase separation occurs at the same effective volume fraction of CNCs (∼10 vol %), with a corresponding increase in critical concentration due to the decrease in effective diameter that occurs with increasing surface charge. Below or near this threshold value, the formation of end-to-end aggregates may favor gelation and interfere with ordered phase formation.
Recent
years have seen an increased interest toward utilizing biobased
and biodegradable materials for barrier packaging applications. Most
of the abovementioned materials usually have certain shortcomings
that discourage their adoption as a preferred material of choice.
Nanocellulose falls into such a category. It has excellent barrier
against grease, mineral oils, and oxygen but poor tolerance against
water vapor, which makes it unsuitable to be used at high humidity.
In addition, nanocellulose suspensions’ high viscosity and
yield stress already at low solid content and poor adhesion to substrates
create additional challenges for high-speed processing. Polylactic
acid (PLA) is another potential candidate that has reasonably high
tolerance against water vapor but rather a poor barrier against oxygen.
The current work explores the possibility of combining both these
materials into thin multilayer coatings onto a paperboard. A custom-built
slot-die was used to coat either microfibrillated cellulose or cellulose
nanocrystals onto a pigment-coated baseboard in a continuous process.
These were subsequently coated with PLA using a pilot-scale extrusion
coater. Low-density polyethylene was used as for reference extrusion
coating. Cationic starch precoating and corona treatment improved
the adhesion at nanocellulose/baseboard and nanocellulose/PLA interfaces,
respectively. The water vapor transmission rate for nanocellulose
+ PLA coatings remained lower than that of the control PLA coating,
even at a high relative humidity of 90% (38 °C). The multilayer
coating had 98% lower oxygen transmission rate compared to just the
PLA-coated baseboard, and the heptane vapor transmission rate reduced
by 99% in comparison to the baseboard. The grease barrier for nanocellulose
+ PLA coatings increased 5-fold compared to nanocellulose alone and
2-fold compared to PLA alone. This approach of processing nanocellulose
and PLA into multiple layers utilizing slot-die and extrusion coating
in tandem has the potential to produce a barrier packaging paper that
is both 100% biobased and biodegradable.
Cotton-source cellulose nanocrystals (CNCs) with a range of surface charge densities were fluorescently labeled with 5-(4, 6-dichlorotriazinyl) aminofluorescein (DTAF) in a facile, one-pot reaction under alkaline conditions. Three CNC samples were labeled: (I) anionic CNCs prepared by sulfuric acid hydrolysis with a sulfur content of 0.47 wt %, (II) a partially desulfated, sulfuric acid-hydrolyzed CNC sample, which was less anionic with an intermediate sulfur content of 0.21 wt %, and (III) uncharged CNCs prepared by HCl hydrolysis. The DTAF-labeled CNCs were characterized by dynamic light scattering, atomic force microscopy, fluorescence spectroscopy and microscopy, and polarized light microscopy. Fluorescent CNCs exhibited similar colloidal stability to the starting CNCs, with the exception of the HCl-hydrolyzed sample, which became less agglomerated after the labeling reaction. The degree of labeling depended on the sulfur content of the CNCs, indicating that the presence of sulfate half-ester groups on the CNC surfaces hindered labeling. The labeling reaction produced CNCs that had detectable fluorescence, without compromising the overall surface chemistry or behavior of the materials, an aspect relevant to studies that require a fluorescent cellulose substrate with intact native properties. The DTAF-labeled CNCs were proposed as optical markers for the dispersion quality of CNC-loaded polymer composites. Electrospun polyvinyl alcohol fibers loaded with DTAF-labeled CNCs appeared uniformly fluorescent by fluorescence microscopy, suggesting that the nanoparticles were well dispersed within the polymer matrix.
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