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For inorganic/polymer nanocomposites a so-called Rigid Amorphous Phase (RAF) is formed in the interfacial region by adsorption of polymer segments onto the nanoparticles. The segmental dynamics of RAF is expected to be altered, as compared to the pure matrix, which might percolate to the entire system, affecting the overall nanocomposite properties. A combination of two relaxation spectroscopy techniques (Broadband Dielectric Spectroscopy (BDS) and Temperature Modulated DSC (TMDSC)) as well as Fast Scanning Calorimetry (FSC) was employed to investigate the structure and molecular mobility of nanocomposites based on Epoxy and Layered Doubled Hydroxides with different nanoparticle content. First, BDS investigations proved the existence of a process, which is present only for nanocomposites, assigned to the dynamics of polymer segments within RAF. Second, the amount of RAF was quantified by analyzing the change of specific heat capacity step of nanocomposites, comparing to the pure material. Thirdly, the glass transition of nanocomposites was studied with FSC, applying high heating rates (0.5-10 kK/s). Considering that all techniques probe essentially the same molecular process, an activation plot was constructed, delivering a complete picture of the molecular mobility and structure of the polymer nanocomposites including RAF.
Over the past decades research on the molecular dynamics of miscible polymer blends is of topical interest in the literature, to understand the segmental mobility of individual components, as it is affected by blending. In general, miscible polymer blends exhibit a complex dynamic behavior. For an A/B blend the relaxation times of component A and component B are affected by the spatial local compositional heterogeneity, present in binary systems on a microscopic level, regardless of the macroscopic homogeneity. Here, a combination of broadband dielectric and specific heat spectroscopy was employed to study the dynamically asymmetric PVME/PS blend with seven different compositions, focusing on samples with high PS contents. Considering that PS is dielectrically invisible, BDS is a powerful technique to study the response of PVME, as it is affected by PS segments. Here, three separate relaxation processes were found by dielectric investigations, related to confined or constrained PVME segments due to the spatial local compositional heterogeneities, which is in contrary to the previous literature findings [1]. Moreover, the dielectric data was compared with results obtained by specific heat spectroscopy, where a fourth relaxation process was found, due to the cooperative fluctuations of PVME and PS.
[1] Colmenero, J., Arbe, A. Soft Matter, 2007, 3, 1474.
The molecular mobility of the highly asymmetric miscible blend poly(vinyl methyl ether)/polystyrene was investigated by broadband dielectric (frequency range 10^-1 Hz – 10^9 Hz) and specific heat spectroscopy (frequency range 10^1 Hz – 10^4 Hz). The dielectric spectra revealed a complex molecular dynamic behavior, where three different relaxation processes were observed. At temperatures below the glass transition temperature an α´-relaxation was found, with an Arrhenius-like temperature dependence of its relaxation rates. It is assigned to localized fluctuations of the confined PVME segments within a frozen glassy matrix dominated by PS. Above the thermal glass transition temperature two processes with a VFT behavior of their relaxation rates were detected called α1- and α2-relaxation, both originating from PVME dipoles fluctuating in PS-rich environments, however with diverse PS concentrations. The relevant length scales for the processes are assumed to be different, corresponding to the Kuhn segment length for the former relaxation and to the CRR for the latter one. The observed multiple glassy dynamics result from spatial local compositional heterogeneities on a microscopic level. Additionally, SHS investigations were performed for the first time for this system, proving an existence of a fourth relaxation process (α3-relaxation) due to the cooperative fluctuations of both PS and PVME segments. The separation between the thermal α3- and dielectric α2-relaxation increases dramatically with increasing polystyrene concentration, proving that the thermal response is dominated by PS.
Broadband dielectric spectroscopy in the frequency range from 10-1 to 109 Hz is employed to revisit the segmental dynamics of the miscible blend system poly(vinyl methyl ether)/polystyrene (PVME/PS) in dependence on the composition firstly in the bulk state. Here especially the case of high polystyrene concentrations is considered. It is important to note that only the molecular dynamics of PVME segments as affected by PS is observed because the dipole moment of polystyrene is negligible. Three relaxation processes are found which are due to fluctuations of differently constrained or confined PVME segments. The degree of the confinement of PVME segments due to PS is discussed in dependence on the composition.
Further a spatial confinement is considered by investigating thin films of the PVME/PS blend where the film thickness was varied from 100 nm down to 5 nm. Two concentrations of PVME/PS (50/50 wt% and 25/75 wt%) are investigated. To measure nanometer thick films a novel electrode system based on nanostructured electrodes was employed. Nanostructured electrodes can be considered as a cut-edge technology in dielectric spectroscopy. The relaxation spectra of the films showed multiple processes which are discussed in dependence on the film thickness.
For inorganic/polymer nanocomposites a so-called Rigid Amorphous Phase (RAF) is formed in the interfacial region by adsorption of polymer segments onto the nanoparticles. The segmental dynamics of RAF is expected to be altered, as compared to the pure matrix, which might percolate into the entire system, affecting the overall nanocomposite properties. A combination of two relaxation spectroscopy techniques (Broadband Dielectric Spectroscopy (BDS) and Specific Heat Spectroscopy (SHS) in a form of Temperature Modulated DSC (TMDSC)) as well as Fast Scanning Calorimetry (FSC) was employed to investigate the structure and molecular mobility of nanocomposites based on Epoxy and Layered Doubled Hydroxides with different nanoparticle content.
First, BDS investigations proved the existence of a process, which is present only for nanocomposites, assigned to the dynamics of polymer segments within RAF. Second, the amount of RAF was quantified by analyzing the change of specific heat capacity step of nanocomposites, comparing to the pure material.
Thirdly, the glass transition of nanocomposites was studied with FSC, applying high heating rates (500-10 000 K/s). Considering that all techniques probe essentially the same molecular process, an activation plot was constructed, delivering a complete picture of the molecular mobility and structure of the polymer nanocomposites including RAF.
Polymers at interfaces play a major role in a broad variety of applications ranging from engineering purposes (for instance polymer based nanocomposites) to high tech implications (for instance light emitting diodes). Here the glass transition and glassy dynamics is considered for epoxy-based nanocomposite with Layered Double Hydroxide nanofiller and for thin films of a misicble polymer blend of PVME/PS with thicknesses down to 7 nm. The materials are investigated by spectroscopic techniques (broadband and specific heat spectroscopy), as well as by fast scanning calorimetry and small- and wide-angle X-ray scattering.
We show that complex physical and chemical interactions between boehmite nanoparticles and epoxy drastically affect matrix properties, which in the future will provide tuning of material properties for further optimization in applications from automotive to aerospace. We utilize intermodulation atomic force microscopy (ImAFM) for probing local stiffness of both particles and polymer matrix. Stiff particles are expected to increase total stiffness of nanocomposites and the stiffness of polymer should remain unchanged. However, ImAFM revealed that stiffness of matrix in epoxy/boehmite nanocomposite is significantly higher than unfilled epoxy. The stiffening effect of the boehmite on epoxy also depends on the particle concentration. To understand the mechanism behind property alteration induced by boehmite nanoparticles, network architecture is investigated using dynamic mechanical thermal analysis (DMTA). It was revealed that although with 15 wt% boehmite nanoparticles the modulus at glassy state increases, crosslinking density of epoxy for this composition is drastically low.
Nanocomposites based on MgAL layered double hydroxides (LDH) and an epoxy resin were prepared and investigated by a combination of complementary methods. As epoxy resin Bisphenol A diglycidyl ether (DGEBA) was used with Diethylenetriamine as curing agent. The LDH was modified with taurine, which acts as an additional crosslinking agent due to its amine groups. The epoxy resin was cured in a presence of the nanofiller, which was added to the system in various concentrations. X-ray scattering, by combination of SAXS and WAXS was used to characterize the morphology of the obtained nanocomposites. These investigations show that the filler is distributed in the matrix as small stacks of ca. 10 layers. The molecular dynamics of the system, as probe for structure, was investigated by broadband dielectric spectroscopy. In addition to the - and -relaxation (dynamic glass transition), characteristic for the unfilled materials, a further process was found which was assigned to localized fluctuations of segments physically adsorbed or chemically bonded to the nanoparticles. The dielectric -relaxation is shifted to higher temperatures for the nanocomposites in comparison to the pure material but depends weakly on the content of nanoparticles. Further, for the first time Flash DSC was employed to a thermosetting system to investigate the glass transition behavior of the nanocomposites. The heating rates were converted in to relaxation rates. For low concentrations of the nanofiller the thermal data overlap more or less with that of the pure epoxy. For higher concentrations the thermal data are shifted significantly to higher temperatures. This is discussed in terms the cooperativity approach to the glass transition.
Two epoxy-based nanocomposites with different nanofillers (layered double hydroxide and boehmite) were investigated employing temperature modulated DSC, flash DSC and broadband dielectric spectroscopy. Detailed investigation on the molecular mobility of the two systems showed the effect of the fillers on the structure of the bulk epoxy matrix and the interface formed at the polymer/particle interface
Based on the three-phase model of semi-crystalline polymers, we determined all phase fractions of the NiAl-LDH/PLLA nanocomposites in dependence on the concentration of the nanofiller. Moreover, the rigid amorphous fraction (RAF) was separated into the RAFcrystal and the RAFfiller unbiasedly. A detailed comparison to the related nanocomposite system MgAl-LDH/PLLA was made considering that Mg and Ni have different atomic weights. As a first result is was found that NiAl-LDH/PLLA displays a higher crystallization rate compared to MgAl-LDH/PLLA, which is related to the different morphologies of the two nanocomposite systems. For both systems RAFcrystal increases with increasing concentration of the nanofiller. This means in the case of the nanocomposite not each crystal produces the same amount of RAF, as often assumed. Also, RAFfiller increases with the concentration for both systems but in a different way. This is discussed considering again the different morphologies of both nanocomposites.