Transition Behavior of Cellulose Nanocrystal Networks Induced by Nanoconfined Water

IF 6.2 Q2 ENERGY & FUELS
Siyuan Liu, Dan Xu, Chenyang Cai, Xizhou Cecily Zhang, Loren B. Andreas, Zengbin Wang, Qun Song, Jiaxiu Wang, Catalin R. Picu, Kai Zhang
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Abstract

Hydrogen bonding (HB) is essential for the mechanical properties of cellulose-based materials. However, the plastification of cellulose nanocrystals (CNC) caused by the transition of HB in the presence of water is still insufficiently understood. In this work, the rigid–soft transition of nanoconfined chains in non-ordered regions of CNC surfaces is quantitively described by comparing their strain behaviors with amorphous cellulose. Moreover, this softening (referred to as the “hydro-glass transition”) with increasing relative humidity (RH) is explored, and a threshold RH value (RHt) is identified to characterize the transition. The phenomenon is attributed to the monolayer to multilayer adsorption and eventually capillary condensation of water molecules in wedged mesopores of the CNC films. This triggers a rapid transition of HB from cellulose–cellulose to cellulose–water type in the vicinity of RHt. The hydro-glass transition is promoted by higher temperatures, for example, RHt at 65 °C decreases to 50%. In addition, the presence of surface groups with lower acid dissociation constant (comparing SO3 and OH/COO moieties) also accelerates this hydro-glass transition process. Thus, a detailed understanding of the thermodynamic changes in hydrogen-bonded nanoconfined polymer chains in the presence of humidity, with implications for developing nanomaterials with RH-controlled properties, is provided.

Abstract Image

纳米水诱导纤维素纳米晶网络的转变行为
氢键(HB)对纤维素基材料的机械性能至关重要。然而,纤维素纳米晶体(CNC)的塑化是由HB在水的存在下的转变引起的,目前还没有得到充分的了解。在这项工作中,通过比较它们与无定形纤维素的应变行为,定量描述了CNC表面非有序区域纳米约束链的刚软转变。此外,研究了随着相对湿度(RH)的增加,这种软化(称为“水-玻璃转变”),并确定了一个阈值RH值(RHt)来表征这种转变。这一现象是由于CNC薄膜的楔状介孔中的水分子从单层到多层吸附并最终发生毛细凝聚。这触发了HB在RHt附近从纤维素-纤维素到纤维素-水型的快速转变。较高的温度促进了水玻璃转变,例如,65℃时的RHt降低到50%。此外,具有较低酸解离常数的表面基团的存在(比较 SO3−和 OH/COO−基团)也加速了这种水玻璃转变过程。因此,对氢键纳米聚合物链在湿度条件下的热力学变化有了详细的了解,这对开发具有rh控制特性的纳米材料具有重要意义。
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来源期刊
CiteScore
8.20
自引率
3.40%
发文量
0
期刊介绍: Advanced Energy and Sustainability Research is an open access academic journal that focuses on publishing high-quality peer-reviewed research articles in the areas of energy harvesting, conversion, storage, distribution, applications, ecology, climate change, water and environmental sciences, and related societal impacts. The journal provides readers with free access to influential scientific research that has undergone rigorous peer review, a common feature of all journals in the Advanced series. In addition to original research articles, the journal publishes opinion, editorial and review articles designed to meet the needs of a broad readership interested in energy and sustainability science and related fields. In addition, Advanced Energy and Sustainability Research is indexed in several abstracting and indexing services, including: CAS: Chemical Abstracts Service (ACS) Directory of Open Access Journals (DOAJ) Emerging Sources Citation Index (Clarivate Analytics) INSPEC (IET) Web of Science (Clarivate Analytics).
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