Polymer co-crystalline films for photonics

Daniel, Christophe; Albunia, Alexandra R.; D’Aniello, Concetta; Rizzo, Paola; Venditto, Vincenzo; Guerra, Gaetano

doi:10.2971/jeos.2009.09037

Cited by 9 publications

(3 citation statements)

References 45 publications

(48 reference statements)

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“…This strong L dependence of E a is probably because longer molecules are more strongly constrained, as mentioned above. Control of the dynamics can be essential for the functionalization of sPS by introducing not only polar molecules [ 23 ] but also various functional ones such as single molecular magnet, [ 24 ] dichroic pigment, [ 25 ] fluorescent molecules, [ 26 ] etc. The strong L dependence of the guest dynamics shown in Figures 5 and 6 will be important information for developing such a research field.…”

Section: Resultsmentioning

confidence: 99%

Dielectric Relaxation Behavior of Halobenzene Confined in the δ‐Phase of Syndiotactic Polystyrene

Urakawa

Kobayashi

Inoue

et al. 2023

Macromolecular Symposia

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Syndiotactic polystyrene (sPS) incorporates low-mass guest molecules to form a co-crystalline structure, the 𝜹-phase, in which the guest molecules are confined within a nanosized space. Under such spatial constraints, what factors determine the dynamics of the guest molecules? This is an interesting question and needs to be clarified toward the functionalization of sPS/functional guest systems. In this study, the size effect of the guest molecules and use monosubstituted halobenzenes (fluorobenzene, chlorobenzene, bromobenzene, and iodobenzene) to systematically change the molecular size is focussed. Since halobenzene has a large electric dipole moment, dielectric relaxation measurements can effectively detect its molecular motion. This study aims to identify the guest dynamics in the 𝜹-phase by dielectric relaxation measurement and examines the molecular length dependence of the rotational relaxation times and their activation energies.

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Section: Resultsmentioning

confidence: 99%

Dielectric Relaxation Behavior of Halobenzene Confined in the δ‐Phase of Syndiotactic Polystyrene

Urakawa

Kobayashi

Inoue

et al. 2023

Macromolecular Symposia

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“…Moreover, sPS is able to form different kinds of co-crystalline (clathrate) phases with a large number of guest molecules which can be incorporated in the cavities between the helices of the crystalline region of the and forms (Tarallo et al, 2010a(Tarallo et al, ,b, 2011. The clathrate forms are not only interesting for applications, when active guests can be incorporated in the sPS films, leading to advanced materials for optical and magnetic applications (Giordano et al, 2005;Stegmaier et al, 2005;Daniel et al, 2009;Rizzo et al, 2010), but may offer a unique advantage in the case when neutron scattering methods are used for the investigation of the microstructure and microdynamics of such materials; the neutron scattering length density (SLD) of the crystalline regions can be varied by loading D and H isotopologues of the guest molecules in the crystalline cages of the form and channels of the form while working with deuterated sPS matrix. This advantage has already been demonstrated in some previous small-angle neutron scattering (SANS) studies (Kaneko et al, 2013(Kaneko et al, , 2014.…”

Section: Introductionmentioning

confidence: 99%

Extended Q-range small-angle neutron scattering to understand the morphology of proton-exchange membranes: the case of the functionalized syndiotactic-polystyrene model system

Schiavone,

Lamparelli,

Daniel

et al. 2023

J Appl Cryst

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Semi-crystalline polymers exhibit microphase separation into crystalline and amorphous domains characterized by multiple structural levels with sizes ranging from ångströms to hundreds of nanometres. The combination of small-angle (SANS) and wide-angle (WANS) neutron scattering on the same beamline enables reliable in situ characterization of such materials under application-relevant conditions, with the unique advantage of contrast variation by controlled labelling, allowing the structure of such multi-component systems to be resolved in detail. This paper reports a structural analysis performed on deuterated polymer membranes based on syndiotactic polystyrene (sPS) using an extended Q-range SANS and WANS combination, always with the same neutron scattering instrument, either a pinhole SANS diffractometer installed at a research reactor or a `small- and wide-angle' time-of-flight diffractometer installed at a neutron spallation source. sPS is a semi-crystalline material that becomes hydrophilic and proton conducting when suitable functionalization is achieved by thin film sulfonation, and can form various co-crystalline complexes (clathrates) with small organic molecules stored in the crystalline phase as guests in the vacancies between the polymer helices. Therefore, this material is interesting not only for its conducting properties but also for its versatility as a model system to evaluate the usefulness of extended Q-range neutron scattering in such studies. Variation of neutron contrast was achieved in the amorphous hydrophilic phase by using H2O or D2O to hydrate the membranes and in the crystalline phase by loading the clathrates with deuterated or protonated guest molecules. The experimental approach, the advantages and limitations of the two types of instrumentation used in such analyses, and the main results obtained with respect to the structural characterization of sulfonated sPS membranes under different hydration and temperature conditions are reported, and the potential of this method for similar structural studies on other semi-crystalline polymeric materials is discussed.

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“…In particular, for s‐PS, two nanoporous crystalline phases (δ and ε) have been discovered, which can absorb several guest molecules producing clathrate and intercalate co‐crystals. Films presenting s‐PS/active‐guest co‐crystals have been proposed as advanced materials for optical, magnetic, and ferroelectric applications.…”

Section: Introductionmentioning

confidence: 99%

Sulfonated syndiotactic polystyrene: sorption of ionic liquid in the amorphous phase and of organic guests in the crystalline phase

Dembna

Venditto

Albunia

et al. 2012

Polymers for Advanced Techs

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Fourier Transform Infrared spectroscopy (FTIR) and Wide-Angle X-Ray Diffraction (WAXD) measurements have\ud clearly established the occurrence of a dual sorption ability of sulfonated syndiotactic polystyrene samples, which\ud exhibit the nanoporous d crystalline phase. In fact, large uptake (up to 20–30 wt%) of ionic liquid (IL; e.g. 1-ethyl-\ud 3-methylimidazolium dicyanamide) occurs only in the hydrophilic amorphous sulfonated phases and does not disturb\ud the hydrophobic nanoporous crystalline d phase. On the other hand, a large uptake of organic guests (e.g. naphthalene)\ud occurs prevailingly in the nanoporous hydrophobic crystalline phase, independently of the presence of the IL in the amorphous\ud phase, eventually leading to the formation of syndiotactic polystyrene co-crystalline phases. The thermal stability\ud of IL can be largely increased by their inclusion in the amorphous phase of sulfonated syndiotactic polystyrene films

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Polymer co-crystalline films for photonics

Cited by 9 publications

References 45 publications

Dielectric Relaxation Behavior of Halobenzene Confined in the δ‐Phase of Syndiotactic Polystyrene

Dielectric Relaxation Behavior of Halobenzene Confined in the δ‐Phase of Syndiotactic Polystyrene

Extended Q-range small-angle neutron scattering to understand the morphology of proton-exchange membranes: the case of the functionalized syndiotactic-polystyrene model system

Sulfonated syndiotactic polystyrene: sorption of ionic liquid in the amorphous phase and of organic guests in the crystalline phase

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