纤维素纳米晶的独特特征

M. Ioelovich
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摘要

本文采用一系列方法研究了纤维素纳米晶和游离纤维素纳米晶颗粒(CNCs)的结构特征和性能。研究表明,纤维素纳米晶具有三大显著特征。纤维素纳米晶的第一个显著特点是其棒状形状,具有相当高的长宽比和较低的渗流阈值。纳米结晶的第二个显著特点是其高度发达的比表面积,这导致棒状结晶自发结晶,并通过其横向平面聚集在一起。这种聚集过程在热力学上是有利的,因为它会导致纳米结晶的比表面积减小,热力学势能降低。纤维素纳米晶的第三个显著特点是其表层的副晶结构,这对晶格畸变、平面间距、参数和晶胞体积等结构特征有重大影响。除结构外,副晶部分还影响纤维素的重要物理和物理化学特性,如脱氘的可得性、纤维素碱化后 CII-异构体的含量、纳米晶的熔点等。通过推导相关方程,可以利用副晶部分的含量预测纳米晶体的结构特征和性质。
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DISTINCTIVE FEATURES OF CELLULOSE NANOCRYSTALLITES
In this paper, a set of methods was used to study the structural characteristics and properties of cellulose nanocrystallites and free cellulose nanocrystalline particles (CNCs). It was shown that cellulose nanocrystallites have three main distinctive features. The first distinctive feature of cellulose nanocrystallites is their rod-like shape with a quite high aspect ratio and a low percolation threshold. The second distinctive feature of nanocrystallites is their highly developed specific surface area that leads to the spontaneous crystallization and aggregation of rod-like crystallites by their lateral planes. This aggregation process is thermodynamically favorable because it leads to a decrease in the specific surface area of nanocrystallites and a reduction of the thermodynamic potential. The third distinctive feature of cellulose nanocrystallites is the paracrystalline structure of their surface layers, which significantly affects structural characteristics such as lattice distortion, interplanar spacings, parameters, and volume of the crystalline unit cell, etc. Along with structure, the paracrystalline fraction affects also important physical and physical-chemical properties of cellulose, such as accessibility to deuteration, the content of CII-allomorph after cellulose alkalization, melting point of nanocrystallites, etc. Correlation equations were derived that provide to predict the structural characteristics and properties of nanocrystallites using the content of the paracrystalline fraction.
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