Dissolution enthalpies of cellulose in ionic liquids

Parviainen, Helena; Parviainen, Arno; Virtanen, Tommi; Kilpeläinen, Ilkka; Ahvenainen, Patrik; Serimaa, Ritva; Grönqvist, Stina; Maloney, Thaddeus; Maunu, Sirkka Liisa

doi:10.1016/j.carbpol.2014.07.001

Cited by 40 publications

(43 citation statements)

References 33 publications

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“…Recently,P arviainen et al [27] reported the use of differential scanningcalorimetry (DSC) for the determination of the enthalpy of cellulose dissolution in three ILs. The measurements were performed on cellulose pastes in IL.…”

Section: Resultsmentioning

confidence: 99%

“…The measurements were performed on cellulose pastes in IL. [27] Of course, since enthalpy is an extensive thermodynamic property,a ny measurement of the value for enthalpy of cellulose dissolution must provide results that respond to the amount of cellulose dissolved in the medium. swellinga nd decrystallization) upon mixing cellulose and ILs for the sample preparation for the DSCa nalysis.…”

Section: Resultsmentioning

confidence: 99%

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Understanding Cellulose Dissolution: Energetics of Interactions of Ionic Liquids and Cellobiose Revealed by Solution Microcalorimetry

Oliveira

Rinaldi

2015

ChemSusChem

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In this report, the interactions between fifteen selected ionic liquids (ILs) and cellobiose (CB) are examined by high-precision solution microcalorimetry. The heat of mixing (Δmix H) of CB and ILs, or CB and IL/molecular solvent (MS) solutions, provides the first ever-published measure of the affinity of CB with ILs. Most importantly, we found that there is a very good correlation between the nature of the results found for Δmix H(CB) and the solubility behavior of cellulose. This correlation suggests that Δmix H(CB) offers a good estimate of the enthalpy of dissolution of cellulose even in solvents in which cellulose is insoluble. Therefore, the current findings open up new horizons for unravelling the intricacies of the thermodynamic factors accounting for the spontaneity of cellulose dissolution in ILs or IL/MS solutions.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Understanding Cellulose Dissolution: Energetics of Interactions of Ionic Liquids and Cellobiose Revealed by Solution Microcalorimetry

Oliveira

Rinaldi

2015

ChemSusChem

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“…If the relative differences are small, however, the methods will not show the same differences in relative crystallinity. This negative cc cellulose/glucose content, NMR nuclear magnetic resonance, PL plant material, WD unprocessed wood material, PP processed pulp, MCC microcrystalline cellulose, PT perpendicular transmission, ST symmetrical transmission, SR symmetrical reflection a Dixon et al (2015) b Borrega et al (2015) c Parviainen et al (2014) d Testova et al (2014) e Leppänen et al (2009) f Approximate cellulose content g Jeoh et al (2007) Cellulose (2016) As shown in the result section, differences in sample crystallinity values obtained with the Segal method can also be due to differences in crystallite sizes. A positive correlation between the crystallite size and the Segal crystallinity value has also been shown by Nam et al (2016).…”

Section: Discussionmentioning

confidence: 99%

“…Samples of low-and medium-density balsa (86 and 159 g/cm 3 , respectively) , spruce-pine sulphite pulp and nata de coco (Parviainen et al 2014), birch pulp (Testova et al 2014), bamboo (Dixon et al 2015), and MCC from birch sulphite, poplar kraft and cotton linters (Leppänen et al 2009) were analyzed. The published properties of these samples are summarized in Online Resource 1.…”

Section: Samplesmentioning

confidence: 99%

Comparison of sample crystallinity determination methods by X-ray diffraction for challenging cellulose I materials

2016

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Cellulose crystallinity assessment is important for optimizing the yield of cellulose products, such as bioethanol. X-ray diffraction is often used for this purpose for its perceived robustness and availability. In this work, the five most common analysis methods (the Segal peak height method and those based on peak fitting and/or amorphous standards) are critically reviewed and compared to two-dimensional Rietveld refinement. A larger (n ¼ 16) and more varied collection of samples than previous studies have presented is used. In particular, samples (n ¼ 6) with low crystallinity and small crystallite sizes are included. A good linear correlation (r 2 ! 0:90) between the five most common methods suggests that they agree on large-scale crystallinity differences between samples. For small crystallinity differences, however, correlation was not seen for samples that were from distinct sample sets. The least-squares fitting using an amorphous standard shows the smallest crystallite size dependence and this method combined with perpendicular transmission geometry also yielded values closest to independently obtained cellulose crystallinity values. On the other hand, these values are too low according to the Rietveld refinement. All analysis methods have weaknesses that should be considered when assessing differences in sample crystallinity.

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“…It is also believed that a solvent which can dissolve cellulose must be able to destroy its crystalline structure (Ramos et al 2005). However, cellulose dissolution is not constrained only because of crystallinity and lack of accessibility of chains (Parviainen et al 2014). It has been proposed that the difficulty in dissolving cellulose fibers could emanate from an unknown long range ordering or interaction that must be disrupted prior to dissolution (Isogai and Atalla 1998).…”

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confidence: 98%

Cellulose dissolution: insights on the contributions of solvent-induced decrystallization and chain disentanglement

2016

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The dissolution of cellulose is a critical step for the efficient utilization of this renewable resource as a starting material for the synthesis of high value-added functional polymers and chemicals and also for biofuel production. The recalcitrance of semicrystalline cellulose microfibrils presents a major barrier to cellulose dissolution. Despite research efforts, important aspects of cellulose dissolution such as solvent-induced decrystallization and chain disentanglement are not well-understood. Here we address these fundamental issues with the practical goal of gaining insights into the swelling and dissolution of cellulose that cannot be obtained from macroscopic experimental data. To this end, we have used a newly-developed phenomenological model that captures the phenomena governing the dissolution of semicrystalline polymers as well as the thermodynamics and kinetics of dissolution. This model fits well experimental data for swelling and dissolution of cotton fibers in the ionic liquid [bmim]Cl, and allows the quantification of two important aspects, i.e., solvent effectiveness in cellulose (1) decrystallization and (2) chain disentanglement, the balance of which controls the mechanism and kinetics of cellulose dissolution. The activation parameters of cellulose decrystallization, estimated using the obtained decrystallization constant values, reveal that the decrystallization of cellulose in [bmim]Cl is associated with positive enthalpy and entropy and it is also very sensitive to temperature. When the solvent effectiveness in the disruption of cellulose crystals is relatively lower than its ability to disentangle the chains, the kinetics of dissolution are controlled by decrystallization. Furthermore, conditions that facilitate cellulose chain disentanglement, in addition to increasing the rate of dissolution, can result in faster decrystallization. The solvent effectiveness in chain disentanglement is the only factor that determines the decrease of the cellulose fiber radius. In cases where the fiber dissolution rate is lower than the decrystallization rate, the dissolution of cellulose is mostly controlled by the solvent ability to disentangle the chains. The insights obtained from this study improve the understanding of cellulose-solvent interactions underlying decrystallization and disentanglement and their contributions in controlling the kinetics of cellulose swelling and dissolution.

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Dissolution enthalpies of cellulose in ionic liquids

Cited by 40 publications

References 33 publications

Understanding Cellulose Dissolution: Energetics of Interactions of Ionic Liquids and Cellobiose Revealed by Solution Microcalorimetry

Understanding Cellulose Dissolution: Energetics of Interactions of Ionic Liquids and Cellobiose Revealed by Solution Microcalorimetry

Comparison of sample crystallinity determination methods by X-ray diffraction for challenging cellulose I materials

Cellulose dissolution: insights on the contributions of solvent-induced decrystallization and chain disentanglement

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