Abstract
Size distributions of cellulose nanocrystals (CNCs), extracted from softwood pulp via strong sulfuric acid hydrolysis, exhibit large variability when analyzed from transmission electron microscopy (TEM) images. In this article, the causes of this variability are studied and discussed. In order to obtain results comparable with those reported, a reference material of CNCs (CNCD-1) was used to evaluate size distribution. CNC TEM specimens were prepared as-stained and dried with a rapid-flushing staining method or hydrated and embedded in vitreous ice with the plunge-freezing method. Several sets of bright-field TEM (BF-TEM), annular dark-field scanning TEM (ADF-STEM) and cryogenic-TEM (cryo-TEM) images were acquired for size distribution analysis to study the contributing factors. The rapid-flushing staining method was found to be the most effective for contrast enhancement of CNCs, not only revealing the helical structure of single CNCs but also resolving the laterally jointed CNCs. During TEM specimen preparation, CNCs were fractionated on TEM grids driven by the coffee-ring effect, as observed from contrast variation of CNCs with a stain-depth gradient. From the edge to the center of the TEM grids, the width of CNCs increases, while the aspect ratio (length to width) decreases. This fractionated dispersion of CNCs suggests that images taken near the center of a droplet would give a larger mean width. In addition to particle fractionation driven by the coffee-ring effect, the arrangement and orientation of CNC particles on the substrate significantly affect the size measurement when CNC aggregation cannot be resolved in images. The coexistence of asymmetric cross-section CNC particles introduces a large variation in size measurement, as TEM images of CNCs are mixed projections of the width and height of particles. As a demonstration of how this contributes to inflated size measurement, twisted CNC particles, rectangular cross-section particles and end-to-end jointed CNCs were revealed in reconstructed three-dimensional (3D) micrographs by electron tomography (ET).
Highlights
Cellulose nanocrystals (CNCs) are crystalline particles derived from naturally abundant plant or animal cellulose sources via strong acid hydrolysis
The results show 28% of CNCs with an approximately symmetric transverse cross-section and the remainder with an asymmetric cross-section [17]
BF-transmission electron microscopy (TEM) images with a pixel size of 2048 × 2048 were acquired on a Gatan slow-scan camera with pixel resolution at selected magnifications calibrated with a standard specimen
Summary
Cellulose nanocrystals (CNCs) are crystalline particles derived from naturally abundant plant or animal cellulose sources (wood, cotton, tunicate and bacteria, etc.) via strong acid hydrolysis. Compared with bulk cellulose with greater amorphous fractions, CNCs exhibit a higher aspect ratio (length-to-width) with the reactive surface of hydroxyl side groups, a greater axial elastic modulus and unique liquid crystalline properties. These properties, along with their natural abundance and biocompatibility, make CNCs attractive for many industrial applications, such as sustainable energy and electronics, biomedical engineering, water treatment, etc. The mean width (7.5 nm) measured in TEM is still approximately twice the mean height (3.4 nm) measured in AFM This may indicate that not all CNC particles are composed of single crystallites, CNC particles are composed of single crystallites in different sizes or CNCs are laterally jointed bundles. The major factors influencing the size distribution of CNCs will be discussed in depth based on observations and analysis
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