Two-phase water model in the cellulose network of paper

Conti, Allegra; Palombo, Marco; Parmentier, Alexandra; Poggi, Giovanna; Baglioni, Piero; Luca, Francesco De

doi:10.1007/s10570-017-1338-2

Cited by 11 publications

(12 citation statements)

References 22 publications

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“…[5,6] Water in cellulose is organized in two phases, which are characterized by different confining environments: one phase is characterized by mobile water (phase-1) and is assigned to ADs located in elementary fibrils at, or close to, fibre surfaces; the other, characterized by less mobile water (phase-2), is confined in microfibril ADs located at fibre cores. [3,[7][8][9][10] This model agrees with the widespread phenomenological characterization of water in cellulose structures.…”

Section: Introductionsupporting

confidence: 74%

“…This means that hydrolysis results in the opening of the structure, with a significant increase in pore size of ADs located in elementary fibrils at fibre surfaces, which are accessible to acids, as already shown elsewhere. [9,10] It is also worth noting that the increase in the confining size of water can also allow for the penetration of pollutants inside paper, which may result in new degradation mechanisms, or enhance the acidification process itself. [54][55][56] The diffraction patterns of the acidified samples are reported in Figure 4.…”

Section: Resultsmentioning

confidence: 99%

“…New insight into the changes in the macromolecular network of cellulose after acid-catalyzed hydrolysis has been recently obtained using nuclear magnetic resonance (NMR) diffusometry. [9,10] In this work, we have used NMR relaxation and diffraction measurements to monitor the changes in acidic paper due to the application of a deacidification based on calcium hydroxide nanoparticles. Those changes were also monitored during a 2-week ageing at high temperature and relative humidity used to favour the depolymerization of cellulose in untreated, acidic, and deacidified paper.…”

Section: Introductionmentioning

confidence: 99%

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Detection of acidic paper recovery after alkaline nanoparticle treatment by 2D NMR relaxometry

Poggi

Parmentier²,

Nourinaeini

et al. 2020

Magnetic Reson in Chemistry

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Cellulose‐based artefacts are highly prone to degradation, especially in the presence of acidic compounds, which trigger the depolymerization of cellulose chains and lead to a loss in the original mechanical resistance of the material. Calcium hydroxide nanoparticles dispersed in organic solvent have been recently proposed for the deacidification of cellulose‐based artworks. In this work, changes induced on paper by a deacidification treatment, following an acidification bath, were studied by nuclear magnetic resonance (NMR) relaxometry and by the so‐called NMR diffraction of water trapped in the cellulose network. The deacidification treatment modifies intrachain and interchain bonds in hydrolyzed and degraded cellulose, leading to a buffered cellulose network configuration, which is similar to that characterizing the untreated reference sample in terms of relaxation parameters. Overall, calcium hydroxide nanoparticles are demonstrated effective in hindering the degradation of cellulose induced by acids and ageing in strong environmental conditions, even from the standpoint of cellulose network arrangement. It is worth noting, too, that the unilateral NMR device used for the relaxation measurements may represent a powerful tool for the preservation of cellulose‐based artworks because it allows for the monitoring of the conservation status of cellulose in a completely non‐invasive manner.

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Section: Introductionsupporting

confidence: 74%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Detection of acidic paper recovery after alkaline nanoparticle treatment by 2D NMR relaxometry

Poggi

Parmentier²,

Nourinaeini

et al. 2020

Magnetic Reson in Chemistry

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“…Even though cellulose is a relatively stable polymer, it is known to undergo degradation and the most important degradation mechanism is acid-catalysed hydrolysis of the β-1,4-glycosidic bond [3][4][5], resulting in a decrease of the DP and, consequently, a decrease of the mechanical resistance of the material. New insights into the changes in the macromolecular network of cellulose after acid-catalysed hydrolysis were obtained using NMR diffusometry and relaxometry [6,7]. The degradation of cellulose-based material, which may take place at room temperature, is due to environmental and endogenous factors.…”

Section: Introductionmentioning

confidence: 99%

Nanomaterials for Combined Stabilisation and Deacidification of Cellulosic Materials—The Case of Iron-Tannate Dyed Cotton

et al. 2020

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The conservation of textiles is a challenge due to the often fast degradation that results from the acidity combined with a complex structure that requires remediation actions to be conducted at several length scales. Nanomaterials have lately been used for various purposes in the conservation of cultural heritage. The advantage with these materials is their high efficiency combined with a great control. Here, we provide an overview of the latest developments in terms of nanomaterials-based alternatives, namely inorganic nanoparticles and nanocellulose, to conventional methods for the strengthening and deacidification of cellulose-based materials. Then, using the case of iron-tannate dyed cotton, we show that conservation can only be addressed if the mechanical strengthening is preceded by a deacidification step. We used CaCO3 nanoparticles to neutralize the acidity, while the stabilisation was addressed by a combination of nanocellulose, and silica nanoparticles, to truly tackle the complexity of the hierarchical nature of cotton textiles. Silica nanoparticles enabled strengthening at the fibre scale by covering the fibre surface, while the nanocellulose acted at bigger length scales. The evaluation of the applied treatments, before and after an accelerated ageing, was assessed by tensile testing, the fibre structure by SEM and the apparent colour changes by colourimetric measurements.

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“…It has been recently proposed that water in cellulose is arranged in two phases characterized by different confining environments, both involving ADs (Conti et al 2014(Conti et al , 2017. A phase characterized by more mobile water (phase-1) is assigned to ADs located in elementary fibrils at fiber surfaces, while less mobile water (phase-2) is confined in microfibril ADs located at fiber cores (Mu ¨ller et al 2000;Schuster et al 2003;Zhao et al 2007;Conti et al 2017). This model accounts well for experimental data, and it fully agrees with the widespread phenomenological characterization of water in cellulose structures reported in the literature.…”

Section: Introductionmentioning

confidence: 99%

Reconditioning acidic and artificially aged cellulose with alkaline nanoparticles: an NMR diffusometry study

Nourinaeini

Poggi

Parmentier³

et al. 2020

Cellulose

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The prominent degradation mechanism of cellulose is the acid-catalyzed hydrolysis of glycosidic bonds, which results in the decrease of the degree of polymerization (DP) and, macroscopically, in the dramatic decay of the mechanical resistance of cellulose-based materials. Alkaline nanoparticles in organic solvents have been recently proposed for the deacidification of cellulose-based artworks. Their effectiveness has been demonstrated in previous studies, by pH and DP measurements, colorimetric and thermal analyses. Herein, the changes in the cellulosic network following an acidification bath and a consequent deacidification treatment using Ca(OH) 2 nanoparticles, have been investigated by NMR selfdiffusion dynamics of water and related to the changes of samples' DPs. The deacidification treatment modifies intra-and inter-chain interactions, leading to a buffered cellulose network configuration similar to that characterizing the untreated reference sample in terms of diffusive parameters and confining environment. Such results are plausibly due to a rearrangement in connectivity of the cellulosic network, even though with a different physical fingerprint with respect to the reference sample. The analysis of tortuosity of the cellulosic network in acidic and deacidified samples confirms this conclusion, further corroborating the idea that calcium hydroxide nanoparticles are an effective tool to hamper the degradation of cellulose induced by acids and aging in strong environmental conditions, even from the standpoint of cellulose network arrangement.

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Two-phase water model in the cellulose network of paper

Cited by 11 publications

References 22 publications

Detection of acidic paper recovery after alkaline nanoparticle treatment by 2D NMR relaxometry

Detection of acidic paper recovery after alkaline nanoparticle treatment by 2D NMR relaxometry

Nanomaterials for Combined Stabilisation and Deacidification of Cellulosic Materials—The Case of Iron-Tannate Dyed Cotton

Reconditioning acidic and artificially aged cellulose with alkaline nanoparticles: an NMR diffusometry study

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