Structure-property interpretation of biological polyhydroxyalkanoates with different monomeric composition: Dielectric spectroscopy investigation

AbstractNon-linear dielectric spectroscopy (NLDS) is employed as an effective tool to study relaxation processes and phase transitions of a poly(vinylidenefluoride-trifluoroethylene-chlorofluoroethylene) (P(VDF-TrFE-CFE)) relaxor-ferroelectric (R-F) terpolymer in detail. Measurements of the non-linear dielectric permittivity $${\varepsilon _{2}^{'}}$$ ε 2 ′ reveal peaks at 30 and 80$$\,^\circ$$ ∘ C that cannot be identified in conventional dielectric spectroscopy. By combining the results from NLDS experiments with those from other techniques such as thermally stimulated depolarization and dielectric-hysteresis studies, it is possible to explain the processes behind the additional peaks. The former peak, which is associated with the mid-temperature transition, is found in all other vinylidene fluoride-based polymers and may help to understand the non-zero $$\varepsilon _\mathrm {2}^{'}$$ ε 2 ′ values that are detected on the paraelectric phase of the terpolymer. The latter peak can also be observed during cooling of P(VDF-TrFE) copolymer samples at 100$$\,^\circ$$ ∘ C and is due to conduction and space-charge polarization as a result of the accumulation of real charges at the electrode–sample interface.

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Broadband Dielectric Spectroscopy Study of Biobased Poly(alkylene 2,5-furanoate)s’ Molecular Dynamics

Polymers ◽

10.3390/polym12061355 ◽

2020 ◽

Vol 12 (6) ◽

pp. 1355 ◽

Cited By ~ 3

Author(s):

Michelina Soccio ◽

Daniel E. Martínez-Tong ◽

Giulia Guidotti ◽

Beatriz Robles-Hernández ◽

Andrea Munari ◽

...

Keyword(s):

Molecular Dynamics ◽

Dielectric Spectroscopy ◽

Relaxation Times ◽

Barrier Properties ◽

Polymer Processing ◽

Industrial Applications ◽

Structure Property ◽

Property Relations ◽

Broadband Dielectric Spectroscopy ◽

Segmental Relaxation

Poly(2,5-alkylene furanoate)s are bio-based, smart, and innovative polymers that are considered the most promising materials to replace oil-based plastics. These polymers can be synthesized using ecofriendly approaches, starting from renewable sources, and result into final products with properties comparable and even better than those presented by their terephthalic counterparts. In this work, we present the molecular dynamics of four 100% bio-based poly(alkylene 2,5-furanoate)s, using broadband dielectric spectroscopy measurements that covered a wide temperature and frequency range. We unveiled complex local relaxations, characterized by the simultaneous presence of two components, which were dependent on thermal treatment. The segmental relaxation showed relaxation times and strengths depending on the glycolic subunit length, which were furthermore confirmed by high-frequency experiments in the molten region of the polymers. Our results allowed determining structure–property relations that are able to provide further understanding about the excellent barrier properties of poly(alkylene 2,5-furanoate)s. In addition, we provide results of high industrial interest during polymer processing for possible industrial applications of poly(alkylene furanoate)s.

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Structure-property relations of liquid crystalline polymers

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100127013 ◽

1987 ◽

Vol 45 ◽

pp. 460-463

Author(s):

Linda C. Sawyer

Keyword(s):

Solid State ◽

Liquid Crystalline ◽

Structural Model ◽

Crystalline Polymer ◽

Liquid Crystalline Polymers ◽

Mechanical Anisotropy ◽

Structure Property ◽

Preparation Methods ◽

Crystalline Polymers ◽

Extended Chain

Recent liquid crystalline polymer (LCP) research has sought to define structure-property relationships of these complex new materials. The two major types of LCPs, thermotropic and lyotropic LCPs, both exhibit effects of process history on the microstructure frozen into the solid state. The high mechanical anisotropy of the molecules favors formation of complex structures. Microscopy has been used to develop an understanding of these microstructures and to describe them in a fundamental structural model. Preparation methods used include microtomy, etching, fracture and sonication for study by optical and electron microscopy techniques, which have been described for polymers. The model accounts for the macrostructures and microstructures observed in highly oriented fibers and films.Rod-like liquid crystalline polymers produce oriented materials because they have extended chain structures in the solid state. These polymers have found application as high modulus fibers and films with unique properties due to the formation of ordered solutions (lyotropic) or melts (thermotropic) which transform easily into highly oriented, extended chain structures in the solid state.

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Structure-property relationships of PE/PP sandwiched films

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100126998 ◽

1987 ◽

Vol 45 ◽

pp. 454-455

Author(s):

J. Petermann ◽

G. Broza ◽

U. Rieck ◽

A. Jaballah ◽

A. Kawaguchi

Keyword(s):

Mechanical Tests ◽

Polymer Materials ◽

Ionic Crystals ◽

Structure Property ◽

Polymer Systems ◽

Structure Property Relationships ◽

Oriented Films ◽

Materials Used ◽

Polymer Laminates ◽

Heated Glass

Oriented overgrowth of polymer materials onto ionic crystals is well known and recently it was demonstrated that this epitaxial crystallisation can also occur in polymer/polymer systems, under certain conditions. The morphologies and the resulting physical properties of such systems will be presented, especially the influence of epitaxial interfaces on the adhesion of polymer laminates and the mechanical properties of epitaxially crystallized sandwiched layers.Materials used were polyethylene, PE, Lupolen 6021 DX (HDPE) and 1810 D (LDPE) from BASF AG; polypropylene, PP, (PPN) provided by Höchst AG and polybutene-1, PB-1, Vestolen BT from Chemische Werke Hüls. Thin oriented films were prepared according to the method of Petermann and Gohil, by winding up two different polymer films from two separately heated glass-plates simultaneously with the help of a motor driven cylinder. One double layer was used for TEM investigations, while about 1000 sandwiched layers were taken for mechanical tests.

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Probing vacancies and structural distortions at individual defects in ceramics using EELS

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100165859 ◽

1996 ◽

Vol 54 ◽

pp. 678-679

Author(s):

D. J. Wallis ◽

N. D. Browning

Keyword(s):

Structural Information ◽

Core Loss ◽

Nearest Neighbors ◽

Ceramic Materials ◽

Scanning Transmission Electron Microscope ◽

Real Space ◽

Atomic Scale ◽

Structure Property ◽

Scanning Transmission ◽

Key Issues

In electron energy loss spectroscopy (EELS), the near-edge region of a core-loss edge contains information on high-order atomic correlations. These correlations give details of the 3-D atomic structure which can be elucidated using multiple-scattering (MS) theory. MS calculations use real space clusters making them ideal for use in low-symmetry systems such as defects and interfaces. When coupled with the atomic spatial resolution capabilities of the scanning transmission electron microscope (STEM), there therefore exists the ability to obtain 3-D structural information from individual atomic scale structures. For ceramic materials where the structure-property relationships are dominated by defects and interfaces, this methodology can provide unique information on key issues such as like-ion repulsion and the presence of vacancies, impurities and structural distortion.An example of the use of MS-theory is shown in fig 1, where an experimental oxygen K-edge from SrTiO3 is compared to full MS-calculations for successive shells (a shell consists of neighboring atoms, so that 1 shell includes only nearest neighbors, 2 shells includes first and second-nearest neighbors, and so on).

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Approaches for TEM imaging of cavitation in toughened nylon

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100153737 ◽

1989 ◽

Vol 47 ◽

pp. 352-353

Author(s):

Barbara A. Wood

Keyword(s):

Morphological Characteristics ◽

Structure Property ◽

Polymer Systems ◽

Selective Staining ◽

Structure Property Relationships ◽

Rubber Toughened ◽

Shear Yield ◽

Controversial Topic ◽

Selection Of ◽

Diamond Knife

A controversial topic in the study of structure-property relationships of toughened polymer systems is the internal cavitation of toughener particles resulting from damage on impact or tensile deformation.Detailed observations of the influence of morphological characteristics such as particle size distribution on deformation mechanisms such as shear yield and cavitation could provide valuable guidance for selection of processing conditions, but TEM observation of damaged zones presents some experimental difficulties.Previously published TEM images of impact fractured toughened nylon show holes but contrast between matrix and toughener is lacking; other systems investigated have clearly shown cavitated impact modifier particles. In rubber toughened nylon, the physical characteristics of cavitated material differ from undamaged material to the extent that sectioning of heavily damaged regions by cryoultramicrotomy with a diamond knife results in sections of greater than optimum thickness (Figure 1). The detailed morphology is obscured despite selective staining of the rubber phase using the ruthenium trichloride route to ruthenium tetroxide.

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