Elastic properties of the hydrogen-bonded liquid and glassy glycerol under high pressure: comparison with propylene carbonate

Lyapin, A. G.; Gromnitskaya, E. L.; Danilov, I. V.; Бражкин, В. В.

doi:10.1039/c7ra06165j

Cited by 18 publications

(13 citation statements)

References 51 publications

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“…From the DSC experiments we detected a glass transition temperature (T g ) at −70.8°C for the pure GC and at −61.3°C for the KF saturated solution. A similar behavior was reported for glycerol and PC [32,33]. The heat flow signal suggests the presence of an enthalpic recovery associated to the glass transition.…”

Section: Differential Scanning Calorimetrysupporting

confidence: 60%

The curious effect of potassium fluoride on glycerol carbonate. How salts can influence the structuredness of organic solvents

Sarri

Tatini

Ambrosi

et al. 2018

Journal of Molecular Liquids

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Glycerol carbonate (4-hydroxymethyl-1,3-dioxolan-2-one, shortly GC) is a dense, viscous, water soluble solvent. The high dielectric constant and dipole moment make it a suitable non-aqueous green solvent for several salts in different applications. GC dissolves significant amounts of inorganic salts such as KF. The saturation of GC with KF leads to the formation of a viscous liquid at room temperature. In this paper, we report on conductivity, rheology, differential scanning calorimetry and infrared spectroscopy experiments that indicate the formation of a glassy liquid where GC molecules and KF ion pairs are intercalated in a firm and ordered bidimensional structure, stabilized by hydrogen bonding and strong ion-dipole interactions.

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Section: Differential Scanning Calorimetrysupporting

confidence: 60%

The curious effect of potassium fluoride on glycerol carbonate. How salts can influence the structuredness of organic solvents

Sarri

Tatini

Ambrosi

et al. 2018

Journal of Molecular Liquids

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“…0.33, typical for H-bonding liquids like glycerol, are assumed. 34 This (see SI for details) still vastly underestimates the experimental results, even if combined with the mentioned approximation of chain stretching (Figure 3a).…”

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confidence: 76%

“…For the matrix modulus, the classical entangled rubber modulus is used and Poisson’s ratio of cross-linked PDMS (σ m = 0.495) is taken from the literature . For the clusters, G f = 3 × 10 9 Pa, typical for glassy systems, and σ f = 0.33, typical for H-bonding liquids like glycerol, are assumed . This (see SI for details) still vastly underestimates the experimental results, even if combined with the mentioned approximation of chain stretching (Figure a).…”

mentioning

confidence: 99%

Turning Rubber into a Glass: Mechanical Reinforcement by Microphase Separation

Treß

Xing

et al. 2021

ACS Macro Lett.

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Supramolecular associations provide a promising route to functional materials with properties such as self-healing, easy recyclability or extraordinary mechanical strength and toughness. The latter benefit especially from the transient character of the formed network, which enables dissipation of energy as well as regeneration of the internal structures. However, recent investigations revealed intrinsic limitations in the achievable mechanical enhancement. This manuscript presents studies of a set of telechelic polymers with hydrogen-bonding chain ends exhibiting an extraordinarily high, almost glass-like, rubbery plateau. This is ascribed to the segregation of the associative ends into clusters and formation of an interfacial layer surrounding these clusters. An approach adopted from the field of polymer nanocomposites provides a quantitative description of the data and reveals the strongly altered mechanical properties of the polymer in the interfacial layer. These results demonstrate how employing phase separating dynamic bonds can lead to the creation of high-performance materials.

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“…The full expression of each matrix can be found in Maurer et al 63 To analyze the mechanical reinforcement, we used the mechanical ILM with the interfacial layer thickness taken from the BDS measurements (Figure 12b). We assumed that the Poisson's ratio and the modulus of the functional group cluster are the same as in the hydrogen bonding system in glycerol, 64 that is, ∼0.33 and 3 GPa, respectively. The Poisson's ratio of the PDMS matrix and of the interfacial layer was assumed to be 0.495, which is the same as that of neat PDMS.…”

Section: Shear Rheologymentioning

confidence: 99%

Critical Role of the Interfacial Layer in Associating Polymers with Microphase Separation

Samanta

Treß

et al. 2021

Macromolecules

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Polymers with dynamic (transient) bonds, often called associating polymers, have been attracting significant attention in recent years due to their unique viscoelastic properties, self-healing ability, and recyclability. Nevertheless, understanding the mechanisms and the factors controlling their macroscopic properties remains limited due to the higher complexity introduced by the dynamic bonds. In this study, small-angle X-ray scattering (SAXS), broadband dielectric spectroscopy (BDS), and rheology were applied to unravel the structure and dynamics of telechelic associating polymers with different molecular weights. SAXS measurements revealed phase separation of the functional end groups with an average cluster size of ∼2–3 nm and the distance between clusters controlled by the chain length. Borrowing the interfacial layer model analysis of BDS data from the polymer nanocomposite field, we demonstrated the presence of an interfacial polymer layer with a thickness of ∼0.7–0.9 nm surrounding these clusters. Rheological measurements showed quantitatively that the presence of the interfacial layer significantly alters the viscoelastic behavior of these materials, indicating the crucial role of the interfacial layer in defining the macroscopic mechanical properties of the studied telechelic materials. The presented results emphasize that phase separation of the functional groups in associating polymers leads to very significant changes of the viscoelastic properties, opening a promising avenue in the design of novel functional materials.

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Elastic properties of the hydrogen-bonded liquid and glassy glycerol under high pressure: comparison with propylene carbonate

Abstract: We compare elastic properties of the liquid and glassy glycerol and propylene carbonate as the archetypal molecular glass formers with and without hydrogen bonding.

Cited by 18 publications

References 51 publications

The curious effect of potassium fluoride on glycerol carbonate. How salts can influence the structuredness of organic solvents

The curious effect of potassium fluoride on glycerol carbonate. How salts can influence the structuredness of organic solvents

Turning Rubber into a Glass: Mechanical Reinforcement by Microphase Separation

Critical Role of the Interfacial Layer in Associating Polymers with Microphase Separation

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