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Dynamics in Geometrical Confinement pp 213–245Cite as

Molecular Mobility and Phase Transformations of Several Low Molecular Weight Glass Formers Confined to Nanoporous Silica Matrices

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Part of the book series: Advances in Dielectrics ((ADVDIELECT))

Abstract

The dynamical behavior of three low molecular weight glass formers confined to nanostructured mesoporous silica (100 % Si) with pore sizes ranging from 2.8 to 8.6 nm, is probed by Dielectric Relaxation Spectroscopy (DRS). The confined guests embrace different classes of materials: a surfactant, Triton X-100, a liquid crystal, E7 nematic mixture and the pharmaceutical drug, Ibuprofen. All three glass formers show two distinct dynamical domains inside the pores, as revealed by the detection of both bulk-like and surface processes. The latter is characterized by a slower mobility than the bulk-like process and the temperature dependence follows the characteristic Vogel-Fulcher-Tammann-Hesse (VFTH) law indicating a glassy dynamics of the molecules anchored to the pore surface. In the case of E7, the Vogel temperature (T\(_{0})\) of this process is size dependent, decreasing with increasing pore size, which is taken as a finite size effect. Concerning the bulk-like process, assigned to the glassy dynamics of the molecules in the middle of the pore, the confinement effect becomes stronger depending on the material as follows: (1) Triton X-100, undergoing almost no change in the glass transition temperature (T\(_{g})\), only a slight increase \(\sim \)3 K is observed; (2) E7, with a maximum decrease of 10 K in T\(_{\mathrm{g}}\) compared to the bulk temperature for a pore size of 6.8 nm; and (3) Ibuprofen, which shows not only a higher decrease in the glass transition temperature, \(\sim \)30 K when confined to a pore size of 3.6 nm (MCM-41), but also its temperature dependence of relaxation times varies from VFTH to Arrhenius like, which is interpreted as 3.6 nm being a dimension that interferes with the length scale of cooperativity. Moreover, two secondary relaxations are detected in the pharmaceutical drug, the more local one being insensitive to confinement while the second process, taken as the precursor of the glass transition, becomes more mobile relatively to the respective process in bulk Ibuprofen. The results confirm that molecular dynamics of the probed low molecular weight guests confined into nanostructured mesoporous hosts is controlled by a counterbalance between confinement and surface effects.

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Abbreviations

BJH:

Barrett-Joyner-Halenda

CM:

Coupling model

CN:

Cyano group

CPG:

controlled pore glasses

DSC:

Differential scanning calorimetry

DRS:

Dielectric relaxation spectroscopy

FTIR:

Fourier transform infrared spectroscopy

HN:

Havriliak- Negami

JG:

Johari-Goldstein

LCs:

Liquid-crystals

MWS:

Maxwell-Wagner-Sillars

NMR:

Nuclear magnetic resonance

M\(_{\mathrm{W}}\) :

Molecular weight

T\(_{\mathrm{g}}\) :

Glass transition temperature

T\(_{\mathrm{IN}}\) :

Isotropic to nematic transition

T\(_{0}\) :

Vogel Temperature

TEM:

Transmission electron microscopy

TEOS:

Tetraethoxysilane

TGA:

Thermogravimetric analysis

VFTH:

Vogel-Fulcher-Tamman-Hesse

XRD:

\(\mathrm{X}\)-ray diffraction

\(\Delta \upvarepsilon \) :

Dielectric strength

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Acknowledgments

M. Dionísio dedicates this chapter to J. J. Moura Ramos and G. Williams who introduce her in the dielectrics world. The authors deeply acknowledge the fruitful collaboration with Prof. Dr. Andreas Schönhals by the use of broadband dielectric equipment to investigate confined Ibuprofen and E7, being grateful by his deeply knowledge in this matter whose papers supports a significant part of the work here presented. Our collaboration started in 2006 in the framework of the PhD of A. R. Brás, which grant SFRH/BD/23829/2005 is also acknowledged. The authors also acknowledged the careful reading and revision of this chapter by Professor Friedrich Kremer. Financial support for the work here reported was provided through the projects PTDC/CTM//64288/2006 and PTDC/CTM/098979/2008 implemented within the framework of the Programme “Promover a Produção Científica, o Desenvolvimento Tecnológico e a Inovação 002: Investigação Científica e Tecnológica (3599-PPCDTI)” financed by Fundação para a Ciência e Tecnologia (FCT).

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Authors and Affiliations

  1. REQUIMTE/CQFB, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516, Caparica, Portugal

    M. Dionísio, N. T. Correia & A. R. Brás

  2. Unité Matériaux Et Transformations (UMET), UMR CNRS 8207, UFR de Physique, BAT P5, Université Lille Nord de France, 59655, Villeneuve d’Ascq Cedex, France

    N. T. Correia

  3. Jülich Centre for Neutron Science (JCNS-1) and Institute for Complex Systems (ICS-1), Forschungszentrum Jülich, 52425, Jülich, Germany

    A. R. Brás

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  1. M. Dionísio
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  3. A. R. Brás
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Correspondence to M. Dionísio .

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  1. Group of Molecular Physics, University of Leipzig, Leipzig, Germany

    Friedrich Kremer

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Dionísio, M., Correia, N.T., Brás, A.R. (2014). Molecular Mobility and Phase Transformations of Several Low Molecular Weight Glass Formers Confined to Nanoporous Silica Matrices. In: Kremer, F. (eds) Dynamics in Geometrical Confinement. Advances in Dielectrics. Springer, Cham. https://doi.org/10.1007/978-3-319-06100-9_9

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