Short-chain polymer rigidity due to the Debye process of monohydroxy alcohols

Abstract

In addition to the ubiquitous structural relaxation of viscous supercooled liquids, monohydroxy alcohols and several other hydrogen-bonded systems display a strong single-exponential electrical low-frequency absorption. So far, this so-called Debye process could be observed only using dielectric techniques. Exploiting a combination of broad-band and high-resolution rheology experiments for three isomeric octanols, unambiguous mechanical evidence for the Debye process is found. Its spectral signature is similar to the viscoelastic fingerprint of small-chain polymers, enabling us to estimate the effective molecular weight for the supramolecular structure formed by the studied monohydroxy alcohols. This finding opens the venue for the application of further non-dielectric techniques directed at unraveling the microscopic nature of the Debye process and for an understanding of this phenomenon in terms of polymer concepts.

12 pages, 4 figures

References in corpus (3)

• Hydrogen-bond equilibria and life times in a supercooled monohydroxy alcohol
• Investigation of the shear-mechanical and dielectric relaxation processes in two mono-alcohols close to the glass transition
• Debye relaxation and 250 K anomaly in glass forming monohydroxy alcohols

Cited by in corpus (15)

• Dipole-dipole correlations and the Debye process in the dielectric response of non-associating glass forming liquids
• Identification of structural relaxation in the dielectric response of water
• On the Nature of the Debye-Process in Monohydroxy Alcohols: 5-Methyl-2-Hexanol Investigated by Depolarized Light Scattering and Dielectric Spectroscopy
• Intermolecular Cross-Correlations in the Dielectric Response of Glycerol
• Slow rheological mode in glycerol and glycerol-water mixtures
• Supramolecular structures in monohydroxy alcohols: Insights from shear-mechanical studies of a systematic series of octanol structural isomers
• Molecular mechanism of the Debye relaxation in monohydroxy alcohols revealed from rheo-dielectric spectroscopy
• On the Spectral Shape of the Structural Relaxation in Deeply Supercooled Liquids
• Linking the dielectric Debye process in 2-ethyl-1-hexanol to its density fluctuations
• Local dielectric response in 1-propanol: $\alpha$-relaxation versus relaxation of mesoscale structures
• A systematic study of the isothermal crystallization of the mono-alcohol n-butanol monitored by dielectric spectroscopy
• Model for the alpha and beta shear-mechanical properties of supercooled liquids and its comparison to squalane data
• Insights into the Non-exponential Behaviour of the Dielectric Debye-like Relaxation in Monoalcohols
• Piezo-Electric Shear Rheometry: Further developments in experimental implementation and data extraction
• Competing Supramolecular Structures: Dielectric and Rheological Spectroscopy on Glycerol/Propanol Mixtures