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  1. Article ; Online: Physical aging in molecular glasses beyond the α relaxation.

    Di Lisio, Valerio / Stavropoulou, Vasiliki-Maria / Cangialosi, Daniele

    The Journal of chemical physics

    2023  Volume 159, Issue 6

    Abstract: The description of kinetics of physical aging, namely the slow evolution of a glass thermodynamic state toward equilibrium, generally relies on the exclusive role of the main α relaxation. Here, we study the kinetics of physical aging over a wide ... ...

    Abstract The description of kinetics of physical aging, namely the slow evolution of a glass thermodynamic state toward equilibrium, generally relies on the exclusive role of the main α relaxation. Here, we study the kinetics of physical aging over a wide temperature range in five small molecules interacting via van der Waals forces monitoring the time evolution of the glass enthalpic state. To this aim, we employ fast scanning calorimetry, which permits exploring a wide range of aging times. To challenge the role of the α relaxation in the description of physical aging, we employ a model-independent approach, based on the time to reach equilibrium, and a modified version of the single parameter aging model. The latter accounts for the non-linearity of aging making use of the so-called density scaling approach to describe the dependence of the α relaxation time on the glass thermodynamic state. We show that the α relaxation is generally adequate to describe aging at temperatures close to the glass transition and, for lower temperatures, the latest stages of equilibration. In contrast, at low aging temperatures, it fails to catch a wide portion of the time-dependent evolution of the glass thermodynamic state, which is found to be much faster than predicted considering only the α relaxation. Hence, our results and analysis provide compelling arguments that the description of glass equilibration under a wide range of aging conditions is conveyed by different molecular mechanisms, beyond the mere role of the α relaxation.
    Language English
    Publishing date 2023-08-08
    Publishing country United States
    Document type Journal Article
    ZDB-ID 3113-6
    ISSN 1089-7690 ; 0021-9606
    ISSN (online) 1089-7690
    ISSN 0021-9606
    DOI 10.1063/5.0157994
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  2. Article: High throughput optimization procedure to characterize vitrification kinetics

    Abate, Anabella A. / Cangialosi, Daniele / Napolitano, Simone

    Thermochimica acta. 2022 Jan., v. 707

    2022  

    Abstract: We present VITRIFAST, a high throughput optimization procedure to characterize the vitrification kinetics based on calorimetric measurements. By analyzing the temperature dependence of specific heat capacity, the method determines the fictive temperature, ...

    Abstract We present VITRIFAST, a high throughput optimization procedure to characterize the vitrification kinetics based on calorimetric measurements. By analyzing the temperature dependence of specific heat capacity, the method determines the fictive temperature, Tf, and the enthalpy change during physical aging, ΔH, within only a few seconds. We tested VITRIFAST on the low molecular weight glass-former o−terphenyl (OTP) and on an archetypal glass forming polymer, polystyrene (PS), by analyzing the outcome of two classical sets of experiments. By means of fast scanning calorimetry (FSC), we characterized the vitrification kinetics in a wide range of cooling rates and the isothermal physical aging after vitrification at a given rate. In less than 3 minutes, our method could process 18 different calorimetric scans and provided values of Tf and ΔH in excellent agreement with those reported in the literature. VITRIFAST can be employed in the analysis of the temperature dependence of any type of second order derivative of free energy and represents a tremendous advance in the data analysis of calorimetric scans. The method is particularly helpful for fast scanning calorimetry users, considering the extremely large number of heat capacity scans recorded by this technique within a few minutes.
    Keywords Gibbs free energy ; calorimetry ; enthalpy ; glass ; heat ; molecular weight ; polystyrenes ; specific heat ; temperature ; vitrification
    Language English
    Dates of publication 2022-01
    Publishing place Elsevier B.V.
    Document type Article
    ZDB-ID 1500974-9
    ISSN 0040-6031
    ISSN 0040-6031
    DOI 10.1016/j.tca.2021.179084
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  3. Article ; Online: Decoupling of Glassy Dynamics from Viscosity in Thin Supported Poly(

    Chowdhury, Mithun / Monnier, Xavier / Cangialosi, Daniele / Priestley, Rodney D

    ACS polymers Au

    2022  Volume 2, Issue 5, Page(s) 333–340

    Abstract: We utilized fast scanning calorimetry to characterize the glass transition temperature ( ...

    Abstract We utilized fast scanning calorimetry to characterize the glass transition temperature (
    Language English
    Publishing date 2022-06-30
    Publishing country United States
    Document type Journal Article
    ISSN 2694-2453
    ISSN (online) 2694-2453
    DOI 10.1021/acspolymersau.2c00010
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  4. Article ; Online: Reaching the Ideal Glass in Polymer Spheres: Thermodynamics and Vibrational Density of States.

    Monnier, Xavier / Colmenero, Juan / Wolf, Marcel / Cangialosi, Daniele

    Physical review letters

    2021  Volume 126, Issue 11, Page(s) 118004

    Abstract: The existence of an ideal glass and the resolution to the Kauzmann paradox is a long-standing open question in materials science. To address this problem, we exploit the ability of glasses with large interfacial area to access low energy states. We ... ...

    Abstract The existence of an ideal glass and the resolution to the Kauzmann paradox is a long-standing open question in materials science. To address this problem, we exploit the ability of glasses with large interfacial area to access low energy states. We submit aggregates of spheres of a polymeric glass former to aging well below their glass transition temperature, T_{g}; and characterize their thermodynamic state by calorimetry, and the vibrational density of state (VDOS) by inelastic neutron scattering (INS). We show that, when aged at appropriate temperatures, glassy spheres attain a thermodynamic state corresponding to an ideal glass in time scales of about one day. In this state, the boson peak, underlying the deviation from the Debye level of the VDOS, is essentially suppressed. Our results are discussed in the framework of the link between the macroscopic thermodynamic state of glasses and their vibrational properties.
    Language English
    Publishing date 2021-04-02
    Publishing country United States
    Document type Journal Article
    ZDB-ID 208853-8
    ISSN 1079-7114 ; 0031-9007
    ISSN (online) 1079-7114
    ISSN 0031-9007
    DOI 10.1103/PhysRevLett.126.118004
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  5. Article ; Online: Physical aging of hydroxypropyl methylcellulose acetate succinate

    Seo, Yejoon / Zuo, Biao / Cangialosi, Daniele / Priestley, Rodney D

    Soft matter

    2022  Volume 18, Issue 43, Page(s) 8331–8341

    Abstract: Amorphous solid dispersions (ASDs) utilize the kinetic stability of the amorphous state to stabilize drug molecules within a glassy polymer matrix. Therefore, understanding the glassy-state stability of the polymer excipient is critical to ASD design and ...

    Abstract Amorphous solid dispersions (ASDs) utilize the kinetic stability of the amorphous state to stabilize drug molecules within a glassy polymer matrix. Therefore, understanding the glassy-state stability of the polymer excipient is critical to ASD design and performance. Here, we investigated the physical aging of hydroxypropyl methylcellulose acetate succinate (HPMCAS), a commonly used polymer in ASD formulations. We found that HPMCAS exhibited conventional physical aging behavior when annealed near the glass transition temperature (
    MeSH term(s) Drug Stability ; Methylcellulose/chemistry ; Excipients/chemistry ; Polymers/chemistry ; Solubility
    Chemical Substances hydroxypropylmethylcellulose acetate succinate (71138-97-1) ; Methylcellulose (9004-67-5) ; Excipients ; Polymers
    Language English
    Publishing date 2022-11-09
    Publishing country England
    Document type Journal Article
    ZDB-ID 2191476-X
    ISSN 1744-6848 ; 1744-683X
    ISSN (online) 1744-6848
    ISSN 1744-683X
    DOI 10.1039/d2sm01189a
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  6. Article ; Online: Length Scale of Molecular Motions Governing Glass Equilibration in Hyperquenched and Slow-Cooled Polystyrene.

    Luo, Jintian / Wang, Xiang / Tong, Ben / Li, Zhiqiang / Rocchi, Lorenzo Augusto / Di Lisio, Valerio / Cangialosi, Daniele / Zuo, Biao

    The journal of physical chemistry letters

    2024  Volume 15, Issue 2, Page(s) 357–363

    Abstract: Polymer glasses attain thermodynamic equilibrium owing to structural relaxation at various length scales. Herein, calorimetry experiments were conducted to trace the macroscopic relaxation of slow-cooled (SC) and hyperquenched (HQ) polystyrene (PS) ... ...

    Abstract Polymer glasses attain thermodynamic equilibrium owing to structural relaxation at various length scales. Herein, calorimetry experiments were conducted to trace the macroscopic relaxation of slow-cooled (SC) and hyperquenched (HQ) polystyrene (PS) glasses and based on detailed comparisons with molecular dynamics probed by dye reorientation, we discussed the possible molecular process governing the equilibration of PS glasses near the glass transition temperatures (
    Language English
    Publishing date 2024-01-04
    Publishing country United States
    Document type Journal Article
    ISSN 1948-7185
    ISSN (online) 1948-7185
    DOI 10.1021/acs.jpclett.3c03263
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  7. Article: Effect of molecular weight on vitrification kinetics and molecular mobility of a polymer glass confined at the microscale

    Monnier, Xavier / Cangialosi, Daniele

    Thermochimica acta. 2019 July, v. 677

    2019  

    Abstract: We employ fast scanning calorimetry (FSC) to investigate how varying the molecular weight interferes in the vitrification kinetics and molecular mobility of micrometric poly(4-tert-butyl styrene) (PtBS). In line with recent results, we find marked ... ...

    Abstract We employ fast scanning calorimetry (FSC) to investigate how varying the molecular weight interferes in the vitrification kinetics and molecular mobility of micrometric poly(4-tert-butyl styrene) (PtBS). In line with recent results, we find marked negative deviations of the fictive temperature Tf, that is, the metric employed to characterize vitrification kinetics, with the sample size and for all molecular weights. In contrast, the molecular mobility remains size independent and bulk-like. This implies that vitrification kinetics and molecular mobility are decoupled. Furthermore, quantifying the magnitude of such decoupling through the Frenkel–Kobeko–Reiner approach, indicates that this is more pronounced in the high molecular weight samples than in the low molecular weight PtBS employed in the present work.
    Keywords calorimetry ; glass ; molecular weight ; polymers ; styrene ; temperature ; vitrification
    Language English
    Dates of publication 2019-07
    Size p. 60-66.
    Publishing place Elsevier B.V.
    Document type Article
    ZDB-ID 1500974-9
    ISSN 0040-6031
    ISSN 0040-6031
    DOI 10.1016/j.tca.2019.01.011
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  8. Article ; Online: Thermodynamic Ultrastability of a Polymer Glass Confined at the Micrometer Length Scale.

    Monnier, Xavier / Cangialosi, Daniele

    Physical review letters

    2018  Volume 121, Issue 13, Page(s) 137801

    Abstract: We employ fast scanning calorimetry to assess the thermodynamic state attained after a given cooling rate and the molecular mobility of glassy poly(4-tert-butylstyrene) confined at the micrometer length scale. We show that, for such a large confinement ... ...

    Abstract We employ fast scanning calorimetry to assess the thermodynamic state attained after a given cooling rate and the molecular mobility of glassy poly(4-tert-butylstyrene) confined at the micrometer length scale. We show that, for such a large confinement length scale, thermodynamic states with a fictive temperature (T_{f}) 80 K below the polymer glass transition temperature (T_{g}) are attained, which allows to bypass the geological timescales required for bulk glasses. Access to such states is promoted by a fast mechanism of equilibration. Importantly, the tremendous T_{f} decrease takes place while the molecular mobility remains bulklike, indicating marked decoupling between vitrification kinetics and molecular mobility.
    Language English
    Publishing date 2018-05-17
    Publishing country United States
    Document type Journal Article
    ZDB-ID 208853-8
    ISSN 1079-7114 ; 0031-9007
    ISSN (online) 1079-7114
    ISSN 0031-9007
    DOI 10.1103/PhysRevLett.121.137801
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  9. Article ; Online: Direct observation of desorption of a melt of long polymer chains.

    Monnier, Xavier / Napolitano, Simone / Cangialosi, Daniele

    Nature communications

    2020  Volume 11, Issue 1, Page(s) 4354

    Abstract: Tuning the thermodynamic state of a material has a tremendous impact on its performance. In the case of polymers placed in proximity of a solid wall, this is possible by annealing above the glass transition temperature, ... ...

    Abstract Tuning the thermodynamic state of a material has a tremendous impact on its performance. In the case of polymers placed in proximity of a solid wall, this is possible by annealing above the glass transition temperature, T
    Language English
    Publishing date 2020-08-28
    Publishing country England
    Document type Journal Article
    ZDB-ID 2553671-0
    ISSN 2041-1723 ; 2041-1723
    ISSN (online) 2041-1723
    ISSN 2041-1723
    DOI 10.1038/s41467-020-18216-y
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  10. Article ; Online: Size-dependent vitrification in metallic glasses.

    Di Lisio, Valerio / Gallino, Isabella / Riegler, Sascha Sebastian / Frey, Maximilian / Neuber, Nico / Kumar, Golden / Schroers, Jan / Busch, Ralf / Cangialosi, Daniele

    Nature communications

    2023  Volume 14, Issue 1, Page(s) 4698

    Abstract: Reducing the sample size can profoundly impact properties of bulk metallic glasses. Here, we systematically reduce the length scale of Au and Pt-based metallic glasses and study their vitrification behavior and atomic mobility. For this purpose, we ... ...

    Abstract Reducing the sample size can profoundly impact properties of bulk metallic glasses. Here, we systematically reduce the length scale of Au and Pt-based metallic glasses and study their vitrification behavior and atomic mobility. For this purpose, we exploit fast scanning calorimetry (FSC) allowing to study glassy dynamics in an exceptionally wide range of cooling rates and frequencies. We show that the main α relaxation process remains size independent and bulk-like. In contrast, we observe pronounced size dependent vitrification kinetics in micrometer-sized glasses, which is more evident for the smallest samples and at low cooling rates, resulting in more than 40 K decrease in fictive temperature, T
    Language English
    Publishing date 2023-08-04
    Publishing country England
    Document type Journal Article
    ZDB-ID 2553671-0
    ISSN 2041-1723 ; 2041-1723
    ISSN (online) 2041-1723
    ISSN 2041-1723
    DOI 10.1038/s41467-023-40417-4
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