High-Pressure Crystallization
of Glass-Forming Liquids at Varying
Thermodynamic Conditions
Karolina Adrjanowicz
Abstract A liquid is called “glass-forming” when it can avoid crystallization
on cooling and become a disordered solid called a glass. Glasses have unique
properties and highly promising applications. However, it is a longstanding open
scientific question what makes a liquid crystallize easily in one case, and form a
stable glass in another. This research focuses on the crystallization tendency of
glass-forming liquids and effective ways of tuning it. To provide a new insight
into the crystallization phenomenon, we have taken full advantage of the fact
that a phase space for every system is not one- but two-dimensional. Therefore, temperature T and pressure p are used as two independent thermodynamic variables to control and affect the crystallization outcome. The scientific
target was to give an insight into the crystallization phenomenon at a fundamental level. To do so, experimental studies at varying thermodynamic conditions were carried out with the use of dielectric spectroscopy. This includes (i)
a pioneering approach which allows to separately control molecular mobility
and thermodynamic driving force towards crystallization, (ii) development of the
time-pressure-transformation (TPT) and continuous-decompression-transformation
(CDT) diagrams as the pressure analogs for time-temperature-transformation (TTT)
and continuous-heating-transformation (CHT) diagrams which can be used to
describe crystallization/vitrification tendencies of the molecular systems under nonisothermal or non-isobaric conditions, (iii) investigation on the effect of path dependence and (iv) enantiomeric composition on the crystallization tendency of the
glass-forming liquids. The results gained from this study are of great scientific
and practical importance. First, they improve our knowledge on the crystallization behavior of molecular glass-forming systems under varying thermodynamic
conditions and second, demonstrate effective strategies which can be used to
control/modify the crystallization outcome by ably control of T and p when moving
through the phase diagram.
K. Adrjanowicz (B)
Institute of Physics, University of Silesia, 75 Pulku Piechoty 1, 41-500 Chorzow, Poland
e-mail: karolina.adrjanowicz@us.edu.pl
SMEBI, 75 Pulku Piechoty 1a, 41-500 Chorzow, Poland
© Springer Nature Switzerland AG 2020
T. A. Ezquerra and A. Nogales (eds.), Crystallization as Studied
by Broadband Dielectric Spectroscopy, Advances in Dielectrics,
https://doi.org/10.1007/978-3-030-56186-4_2
23
of Glass-Forming Liquids at Varying
Thermodynamic Conditions
Karolina Adrjanowicz
Abstract A liquid is called “glass-forming” when it can avoid crystallization
on cooling and become a disordered solid called a glass. Glasses have unique
properties and highly promising applications. However, it is a longstanding open
scientific question what makes a liquid crystallize easily in one case, and form a
stable glass in another. This research focuses on the crystallization tendency of
glass-forming liquids and effective ways of tuning it. To provide a new insight
into the crystallization phenomenon, we have taken full advantage of the fact
that a phase space for every system is not one- but two-dimensional. Therefore, temperature T and pressure p are used as two independent thermodynamic variables to control and affect the crystallization outcome. The scientific
target was to give an insight into the crystallization phenomenon at a fundamental level. To do so, experimental studies at varying thermodynamic conditions were carried out with the use of dielectric spectroscopy. This includes (i)
a pioneering approach which allows to separately control molecular mobility
and thermodynamic driving force towards crystallization, (ii) development of the
time-pressure-transformation (TPT) and continuous-decompression-transformation
(CDT) diagrams as the pressure analogs for time-temperature-transformation (TTT)
and continuous-heating-transformation (CHT) diagrams which can be used to
describe crystallization/vitrification tendencies of the molecular systems under nonisothermal or non-isobaric conditions, (iii) investigation on the effect of path dependence and (iv) enantiomeric composition on the crystallization tendency of the
glass-forming liquids. The results gained from this study are of great scientific
and practical importance. First, they improve our knowledge on the crystallization behavior of molecular glass-forming systems under varying thermodynamic
conditions and second, demonstrate effective strategies which can be used to
control/modify the crystallization outcome by ably control of T and p when moving
through the phase diagram.
K. Adrjanowicz (B)
Institute of Physics, University of Silesia, 75 Pulku Piechoty 1, 41-500 Chorzow, Poland
e-mail: karolina.adrjanowicz@us.edu.pl
SMEBI, 75 Pulku Piechoty 1a, 41-500 Chorzow, Poland
© Springer Nature Switzerland AG 2020
T. A. Ezquerra and A. Nogales (eds.), Crystallization as Studied
by Broadband Dielectric Spectroscopy, Advances in Dielectrics,
https://doi.org/10.1007/978-3-030-56186-4_2
23