Two Different Surface Properties of Regenerated Cellulose due to Structural Anisotropy

Yamane, Chihiro; Aoyagi, Takeshi; Ago, Mariko; Sato, K.; Okajima, Kunihiko; Takahashi, Toshisada

doi:10.1295/polymj.pj2005187

Cited by 207 publications

(170 citation statements)

References 16 publications

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“…[31][32][33] There are several observations that suggest that hydrophobic interactions are decisive for the behavior of cellulose in aqueous systems: 34 -In the structure of cellulose there is a clear segregation into polar (OH) and nonpolar (CH) patches, and thus a clear amphiphilicity. [35][36][37][38] Due to the hydrophobic properties of the glucopyranose plane, the cellulose chains can stack via hydrophobic interactions and can form a sheet-like structure ( Fig. 1).…”

Section: Hydrogen Bonding Vs Hydrophobic Interactionsmentioning

confidence: 99%

The relevance of structural features of cellulose and its interactions to dissolution, regeneration, gelation and plasticization phenomena

Lindman

Medronho

Alves

et al. 2017

Phys. Chem. Chem. Phys.

195

109

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aCellulose is the most abundant polymer and a very important renewable resource. Since cellulose cannot be shaped by melting, a major route for its use for novel materials, new chemical compounds and renewable energy must go via the solution state. Investigations during several decades have led to the identification of several solvents of notably different character. The mechanisms of dissolution in terms of intermolecular interactions have been discussed from early work but, even on fundamental aspects, conflicting and opposite views appear. In view of this, strategies for developing new solvent systems for various applications have remained obscure. There is for example a strong need for using forest products for higher value materials and for environmental and cost reasons to use water-based solvents. Several new water-based solvents have been developed recently but there is no consensus regarding the underlying mechanisms. Here we wish to address the most important mechanisms described in the literature and confront them with experimental observations. A broadened view is helpful for improving the current picture and thus cellulose derivatives and phenomena such as fiber dissolution, swelling, regeneration, plasticization and dispersion are considered. In addition to the matter of hydrogen bonding versus hydrophobic interactions, the role of ionization as well as some applications of new knowledge gained are highlighted.

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Section: Hydrogen Bonding Vs Hydrophobic Interactionsmentioning

confidence: 99%

The relevance of structural features of cellulose and its interactions to dissolution, regeneration, gelation and plasticization phenomena

Lindman

Medronho

Alves

et al. 2017

Phys. Chem. Chem. Phys.

195

109

View full text Add to dashboard Cite

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“…In other words, (110) plane was oriented perpendicular to the film, because (11 -0) and (110) planes intersect almost vertically. According to earlier papers (Yamane et al, 2006;Kiyose et al, 2007), the orientation of the crystal planes takes place through the next three steps: (ⅰ), formation of cellulose molecular sheets; (ⅱ), stacking of the molecular sheets to form planar crystal; and (ⅲ), shrinkage of coagulating films perpendicular to the film surface brings planar orientation of the crystal planes. Although the diffraction intensity from the blend was slightly lower than that from the cellulose film, both types of films had similar diffraction profiles with each other.…”

Section: Filmsmentioning

confidence: 99%

Structure and Properties of Cellulose-Starch Blend Films Regenerated from Aqueous Sodium Hydroxide Solution

Miyamoto

Yamane

Seguchi

et al. 2009

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It was reported in 1984 that cellulose could be dissolved in aqueous sodium hydroxide solution when the intramolecular hydrogen bonds of cellulose were partially broken down by physical treatments such as steam explosion. Although there have been many studies on alkali-soluble cellulose, little is known about cellulose blends made from aqueous sodium hydroxide solution. Therefore, we investigated the structure and properties of cellulose-starch blend films regenerated from the solution. The blends had a porous structure with an average pore size increased from 1 to 6 μm with increased starch content. These pores were observed separately from each other, leading to high water and oil absorbencies of these blend films (the oil absorbency of the blend film containing 50 % starch was over 400 %, ten times that of cellulose film). The results of X-ray measurements, dynamic viscoelastic measurements, enzyme etching, and iodine staining suggested that cellulose and starch were miscible in the amorphous regions but incompatible in the crystalline regions of the cellulose-starch blend films.

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“…Looking into the crystal structure of cellulose, it is inferred that indeed C-H and C-O bonds are distinctly segregated and therefore cellulose molecules have an intrinsic structural anisotropy (Biermann et al 2001;Yamane et al 2006;Diddens et al 2008). Computer simulations have revealed that hydrophobic interactions contribute strongly to cellulose-cellulose attractions (Bergenstråhle et al 2010).…”

Section: Amphiphilicity and Charges Control The Dissolution And Regenmentioning

confidence: 99%

The Subtleties of Dissolution and Regeneration of Cellulose: Breaking and Making Hydrogen Bonds

Lindman

Medronho

2015

BioRes

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Cellulose dissolution and regeneration are old topics that have recently gained renewed attention. This is reflected in both applications -earlier and novel -and in scientific controversies. There is a current discussion in the literature on the balance between hydrogen bonding and hydrophobic interactions in controlling the solution behavior of cellulose. Some of the key ideas are recalled. Keywords Challenges and OpportunitiesIt is evident that today's society is placing an increasing demand on materials, which, in turn, is leading to a "carbon shortage" in certain industries. Industries need to become more resource-conscious and make use of what already exists, namely using other renewable and sustainable resources. The agro-forestal and related industries can indeed raise many resource challenges for society and suppliers in the near future. In this context, it is thus predicable that cellulose, as a widely abundant and versatile biopolymer, will assume a leading role. Cellulose is found in many different forms and applications. However, in some of these applications, cellulose dissolution and regeneration are key (and challenging) aspects. Due to the complexity of the biopolymeric network as well as to the partially crystalline structure and extended noncovalent interactions among molecules, chemical processing of cellulose is rather difficult. A wide variety of suitable solvents for cellulose is already available (Medronho and Lindman 2014). Nevertheless, most solvent systems have important limitations, and there is an intense activity in both industrial and academic research aiming to optimize existing solvents and develop new ones. The problem of obtaining a picture of molecular processes is not trivial since cellulose solvents are of remarkably different nature, and thus the understanding of the subtle balance between the different interactions involved becomes non-trivial. Thermodynamics and Kinetics"Cellulose itself is insoluble in water due to the many and strong hydrogen bonds". This and other similar statements have been extensively repeated in specialized literature. Furthermore, it is typically argued that "the key to the solution of this problem of cellulose solubility is to search for a solvent that can destroy effectively the interchain hydrogen bonding in cellulose". It is unquestionable that in solid cellulose there are multiple hydrogen bonds between the molecules that need to be broken in order to achieve dissolution. However, cellulose molecules are not transferred from the solid state to a

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Two Different Surface Properties of Regenerated Cellulose due to Structural Anisotropy

Cited by 207 publications

References 16 publications

The relevance of structural features of cellulose and its interactions to dissolution, regeneration, gelation and plasticization phenomena

The relevance of structural features of cellulose and its interactions to dissolution, regeneration, gelation and plasticization phenomena

Structure and Properties of Cellulose-Starch Blend Films Regenerated from Aqueous Sodium Hydroxide Solution

The Subtleties of Dissolution and Regeneration of Cellulose: Breaking and Making Hydrogen Bonds

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