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Organically modified ZnAl Layered Double Hydroxides (ZnAl-LDH) was synthesized and melt blended with polyethylene to obtain nanocomposites. The resulting morphology was investigated by a combination of Differential Scanning Calorimetry (DSC), Small and Wide-angle X-ray scattering (SAXS and WAXS) and dielectric relaxation spectroscopy (DRS). The arrangement (intercalation) of polyethylene chains between LDH stacks was investigated employing SAXS. The homogeneity of the nanocomposites and average number of stack size (4–6 layers) were determined using scanning microfocus SAXS (BESSY II). DSC and WAXS results show that the degree of crystallinity decreases linearly with the increasing content of LDH. The extrapolation of this dependence to zero estimates a limiting concentration of ca. 45% LDH where the crystallization of PE is completely suppressed by the nanofiller. The dielectric spectra of the nanocomposites show several relaxation processes which are discussed in detail. The intensity of the dynamic glass transition (β-relaxation) increases with the concentration of LDH. This is attributed to the increasing concentration of the exchanged anion sodium dodecylbenzene sulfonate (SDBS) which is adsorbed at the LDH layers. Therefore, a detailed analysis of the β-relaxation provides information about the structure and the molecular dynamics in the interfacial region between the LDH layers and the polyethylene matrix which is otherwise dielectrically invisible (low dipole moment).
The influence of distinct carbon based nanofillers: expanded graphite (EG), conducting carbon black (CB), thermally reduced graphene oxide (TRGO) and multi-walled carbon nanotubes (CNT) on the thermal, dielectric, electrical and rheological properties of polybutylene terephthalate (PBT) was examined. The glass transition temperature (Tg) of PBT nanocomposites is independent of the filler type and content. The carbon particles act as nucleation agents and significantly affect the melting temperature (Tm), the crystallization temperature (Tc) and the degree of crystallinity of PBT composites. PBT composites with EG show insulating behaviour over the tested concentration range of 0.5 to 2 wt.-% and hardly changed rheological behaviour. CB, CNT and TRGO induce electrical conductivity to their particular PBT composites by forming a conducting particle network within the polymer matrix. CNT reached the percolation threshold at the lowest concentration (<0.5 wt.-%), followed by TRGO (<1 wt.-%) and CB (<2 wt.-%). With the formation of a particle network, the flow behaviour of composites with CB, CNT and TRGO is affected, i.e., a flow limit occurs and the melt viscosity increases. The degree of influence of the carbon nanofillers on the rheological properties of PBT composites follows the same order as for electrical conductivity. Electrical and rheological results suggest an influence attributed to the particle dispersion, which is proposed to follow the order of EG<< CB<TRGO<CNT.
Polymer based nanocomposites by melt blending of synthesized ZnAl-Layered Double Hydroxide (ZnAl-LDH) and polypropylene (PP) were investigated by temperature modulated differential scanning calorimetry (TMDSC). The LDH was organically modified by using a surfactant, sodium dodecylbenzene sulfonate (SDBS) to increase the interlayer spacing of the LDH, so that polymer segments can intercalate the inter layer galleries. The glass transition temperature (Tg) and the thermal relaxation strength (Δcp) were determined. The Tg remains constant for concentration till 12 wt% of LDH and a slight reduction of 3 K might be observed for 16 wt% LDH but within the experimental error. The thermal relaxation strength decreases indicating reduction in the amount of mobile polymer segments from amorphous fraction. This finding is supported by the increase in the rigid amorphous fraction (RAF) which is attributed to the polymer molecules which are in close proximity to the crystals and the LDH sheets, as they hinder their mobility. This is analyzed in detail and related to the dielectric relaxation spectroscopy (BDS) results.
A composite prepared from aerosil A380 and the liquid crystal (LC) 4-hexyl-4'-cyanophenyl benzoate (CP6B) was investigated by broadband dielectric spectroscopy in a large temperature range. The selected high silica density (ca. 7 g aerosil/1 g of CP6B) allows the observation of a thin layer (two-monolayer structure) adsorbed on the surface of the silica particles. For the composite one relaxation process is observed at frequencies much lower than that of the processes found for bulk CP6B. It is assigned to the dynamics of the molecules in the surface layer. The temperature dependence of its relaxation rates obeys the Vogel-Fulcher-Tammann law, which is characteristic for glass-forming liquids. The quasi 2D character of the observed glassy dynamics in the surface layer is discussed. The temperature dependence of the CP6B relaxation in the composite is compared with that of related hexylcyanobiphenyl molecules in the surface layer of aerosil composite with a similar concentration.
Epoxy-Based Nanocomposites—What Can Be Learned from Dielectric and Calorimetric Investigations?
(2022)
Epoxy-based nanocomposites are promisingmaterials for industrial applications (i.e., aerospace, marine, and automotive industries) due to their extraordinary mechanical and thermal properties. Regardless of the broad field of applications, there is still a considerable need to identify their structure–property relationships. Here, a detailed dielectric and calorimetric (DSC and fast scanning calorimetry) study on different epoxy-based nanocomposites was performed. Bisphenol A diglycidyl ether (DGEBA) cured with diethylenetriamine (DETA) was employed as the polymeric matrix, which was reinforced with three diverse nanofillers that exhibit different interaction strengths with the epoxy matrix (halloysite nanotubes, surface modified halloysite nanotubes, and taurine-modified layered double hydroxide). The structure, molecular mobility, and vitrification behavior are discussed in detail, focusing on the intrinsic structural and dynamic heterogeneity, as well as interfacial properties.
Superglassy polymers with a large fractional free volume have emerged as novel materials with a broad range of applications, especially in the field of membrane separations. Highly permeable addition-type substituted polynorbornenes with high thermal resistance and chemical stability are among the most promising materials. The major obstacle for extending the practical membrane application is their strong tendency to physical aging, leading to a partial decline in their superior transport performance over time. In the present study, broadband dielectric spectroscopy with complementary X-ray scattering techniques were employed to reveal changes in microporous structure, molecular mobility, and conductivity by systematic
comparison of two polynorbornenes with different numbers of trimethylsilyl side groups. Their response upon heating (aging) was compared in terms of structure, dynamics, and charge transport behavior. Furthermore, a detailed analysis of the observed
Maxwell−Wagner−Sillars polarization at internal interfaces provides unique information about the microporous structure in the
solid films. The knowledge obtained from the experiments will guide and unlock potential in synthesizing addition-type polynorbornenes with versatile properties.
The molecular dynamics of two addition type polynorbornenes, exo-PNBSiand PTCNSi1, bearing microporosity has been investigated by broadbanddielectric spectroscopy, fast scanning calorimetry, and neutron scattering. Bothpolymers have the same side groups but different backbones. Due to theirfavorable transport properties, these polymers have potential applications inseparation membranes for gases. It is established in literature that molecularfluctuations are important for the diffusion of small molecules through poly-mers. For exo-PNBSi, two dielectric processes are observed, which are assignedto Maxwell/Wagner/Sillars (MWS) process due to blocking of charge carriersat internal voids or pore walls. For PTCNSi1, one MWS-polarization process isfound. This points to a bimodal pore-size distribution for exo-PNBSi. A glasstransition for exo-PNBSi and for PTCNSi1 could be evidenced for the first timeusing fast scanning calorimetry. For Tgand the corresponding apparent activa-tion energy, higher values were found for PTCNSi1 compared to exo-PNBSi.For both polymers, the neutron scattering data reveal one relaxation process.This process is mainly assigned to methyl group rotation probably overlayedby carbon–carbon torsional fluctuations.