Investigation of the polyurethane chain length influence on the molecular dynamics in networks crosslinked by hyperbranched polyester

Several non-conventional polyurethane (PU) networks crosslinked with hyperbranched polyester (Boltorn^®H40) were synthesised with an aim to determine an influence of the PU chain length on molecular relaxations in such systems. The PU chain length was regulated by changing the macrodiol length or by changing the number of the repeating macrodiol/diisocyanate units n. Molecular dynamics were investigated by broadband dielectric spectroscopy and by dynamic mechanical analysis. It was found that the macrodiol length has a strong influence on the glass transition and the α-relaxation, and also on the crystallization. By contrast, the changes of n practically do not affect the molecular relaxations. This effect was explained by the formation of a physical network by hydrogen bonds between urethane groups, controlling the molecular mobility. The rheological measurements have shown, that at temperatures above 150 °C, when hydrogen bonds were thermally destroyed, not only macrodiol length but also n had strong influence on the flowing point.     

Dielectric and viscoelastic relaxations in poly(dicyclohexyl itaconate)

The relaxation spectrum of poly(dicyclohexyl itaconate) (PDCHI) was studied by dynamic mechanical, DC dielectric and thermally stimulated current measurements. Four relaxations, α, β, γ and δ, were obtained. The only method by which all four peaks were observed is that of dynamic dielectric measurements because of the broad range of frequencies employed. The β, γ and δ relaxations were characterized by the activation energy in a relaxation map. A tentative explanation of the molecular origin of each absorption is proposed. In the case of the α relaxation we have used two transformations, one from the permittivity to polarizability and the second from compliance to deformability in order to make evident the existence of this relaxation.     

The ‘wet dog’ effect in polymers as seen by thermoluminescence

It is shown that maxima of the thermoluminescence (TL) glow curve obtained from irradiated polymer containing molecularly dispersed chromophore coincide with the sub-T_g molecular relaxations, what can be related to the so called ‘wet dog’ effect. Good correlation has been found between the positions of the TL maxima and the molecular β- and γ-relaxations in different poly(alkyl methacrylate)s (alkyl=methyl, ethyl, n-butyl), and polystyrene doped with various chromophores: pyrene, carbazole and perylene. Additionally δ-relaxation has been detected at very low temperatures. The positions of the maxima in the TL spectra are independent of the used chromophore. In spite of the observed coincidence, the activation energies of the detrapping processes determined from the TL experiments are lower than the activation energies of the corresponding molecular relaxations determined from the dielectric spectroscopy. Spectral analyses of the light emitted at temperatures close to the TL maxima show that the ratio between excimeric and monomeric emissions is higher at higher temperatures, reflecting higher ability of the chromophore molecules to form excimers.     

Dynamic relaxation characteristics of polymer nanocomposites based on poly(ether imide) and poly(methyl methacrylate)

The dynamic relaxation characteristics of poly(ether imide) and poly(methyl methacrylate) nanocomposites based on native and surface-modified (i.e., hydrophobic) fumed silicas were investigated by dynamic mechanical analysis and dielectric spectroscopy. The nanocomposites displayed a dual glass transition behavior in the dynamic mechanical studies encompassing a bulk polymer glass transition (close to T_g for the unfilled polymer), and a second, higher-temperature transition reflecting relaxation of polymer chain segments constrained owing to their proximity to the particle surface. The position and intensity of the higher-temperature transition varied with particle loading and surface chemistry, and reflected the relative populations of segments constrained or immobilized at the particle-polymer interface. Dielectric measurements, which were used to probe the time-temperature response across the local sub-glass relaxations, indicated no variation in relaxation characteristics with particle loading.     

Dielectric properties of halar,an alternating copolymer of ethylene and chlorotrifluoroethylene

Dielectric properties of Halar, a predominantly alternating 1 : 1 copolymer of ethylene (E) and chlorotrifluoroethylene (CTFE), have been obtained as a function of temperature (?100 to +175°C), frequency (10²–10⁶ Hz), and thermal history. The dielectric loss index (ε″), related to heat dissipation in electrical applications, shows no major change between 25 and 175°C. However, a significant increase in (ε″) between +25°C and ?100°C is not considered detrimental for the applications. Activation energies (δE) for the three major relaxations (α-, β-, and γ-) in both mechanical and dielectric experiments are similar, thus suggesting a similar phase origin of the molecular relaxations in the two techniques. In dielectric analysis, the lowest temperature γ-relaxation is the strongest while it is the weakest in mechanical technique. It is proposed that, in dielectric experiments, only the CTFE groups participate and due to restricted mobility at low temperatures (i.e., γ-relaxation), the dissipation factor or relaxation strength is maximum.     

Properties of (BA)n-B type block copolymers of butadiene and dimethyl itaconate prepared using macroazonitrile initiators

Multi-block copolymers of the (BA)_n-B type, where A is poly(dimethyl itaconate) and B is polybutadiene, were synthesised using a macroazonitrile initiator. This was prepared by the reaction of 4, 4′ azobis (4-cyanopentanoyl chloride) with hydroxyl terminated polybutadienes. and subsequent decomposition of the azo group in the presence of dimethyl itaconate monomer yielded the block copolymer. Measurement of their glass transition temperatures revealed that the copolymers formed two phases. The dynamic thermomechanical properties were measured and this demonstrated that in the temperature range 290–400K, the glassy poly(dimethyl itaconate) blocks acted as crosslinking sites for the elastomeric polybutadiene blocks and that the materials behaved like typical elastoplastic block copolymers. Property variation was obtained when the ratio of polybutadiene to poly(dimethyl itaconate) in the copolymers was altered.     

Thermally stimulated discharge current studies on low-temperature relaxations in polycarbonate

The β-relaxation in polycarbonate has been investigated by the thermally stimulated discharge current (TSC) technique. The polarization of the β-peak in polycarbonate is shown to be uniform. Two broad peaks centered at 130° and 200°K were observed. Furthermore, two single relaxation processes were resolved for the lower temperature peak. The high temperature peak was also resolved into two peaks, however, only one of them was a single relaxation process. The individual peaks satisfied the dipolar theory, and the three peaks are associated with activation energies of 0.24, 0.27, and 0.47 eV, and temperatures of the peak maxima were 121°, 131°, and 193°K, respectively. The mechanism attributed to each peak is discussed and does not appear to contradict the results of conventional dielectric and mechanical relaxation and NMR measurements on the β-relaxation in polycarbonate.     

Dielectric and dynamic mechanical relaxation behaviour of poly(ethylene 2,6-naphthalene dicarboxylate). II. Semicrystalline oriented films

The dielectric and dynamic mechanical behaviour of bi-stretched non-treated and annealed semicrystalline poly(ethylene 2,6-naphthalene dicarboxylate) (PEN) films are studied as a function of different morphologies obtained by thermal treatments at temperatures close to the melting temperature of a semicrystalline film. Differential scanning calorimetry (DSC) shows that the glass transition temperatures do not change significantly with the thermal treatment for bi-stretched films. However, the melting temperatures and the degree of crystallinity increase with the value of annealing temperature. Both dielectric relaxation spectroscopy (DRS) and dynamic mechanical analysis (DMA) display three relaxation processes. In order of decreasing temperature, can be observed: the α-relaxation due to the glass transition, the β^∗-process assigned to cooperative molecular motions of the naphthalene groups which aggregate and the β-relaxation due to local fluctuations of the carbonyl groups. The α-relaxation process shifts to higher temperatures for the 250 and 260 °C treated bi-stretched semicrystalline samples compared to the sample thermally treated at 240 °C according to DRS data but shifts to lower temperatures according to the DMA measurements for the three annealed samples. This discrepency results from the different sensitivity of each methods with regards to the release of orientation. At a fixed frequency the temperature associated to β^∗-relaxation is lower for the non-treated bi-stretched semicrystalline samples than for the treated ones using DMA but no difference can be seen in DRS. The associated apparent activation energies are rather high which suggest cooperative motions. It is assumed that the orientation of the samples prevents coupling between the naphthalene groups due to the stretched chain configuration in the amorphous phase. The activation energy for the β-process given by DRS is independent of the thermal treatment and the value agrees with those found for poly(ethylene terephthalate) (PET) and amorphous PEN. Evidence of the decrease of orientation in the sample with thermal treatment can be seen via the onset of mobility, both by DRS and DMA. Thus, the orientation induces a greater change of properties compared to the crystalline samples obtained from the thermal treatment of an amorphous sample. Finally, a three phase model is proposed since there is evidence of a rigid amorphous phase present in PEN biaxially stretched samples which was favoured by the dependence of dielectric relaxation strengths on the degree of crystallinity for the β^∗- and α-relaxation.     

Preparation of poly(tert-butyl acrylate-g-styrene) as precursors of amphiphilic graft copolymers: 2. Relaxation processes and mechanical behavior

Viscoelastic relaxations of four poly(tert-butyl acrylate-g-styrene) copolymers are studied over a wide range of temperatures. The temperature location and apparent activation energy of the distinct relaxations observed under tension mode are discussed. As grafted polystyrene content increases in the copolymer, microdomains of both components occur and, consequently, two relaxations associated with cooperative motions of either the acrylate backbone or the graft are observed. A bending deformation mode is also analyzed in the region of the glass transition of the two components to study the phase separation. Moreover, the glass transition temperature of the acrylic backbone is estimated by microhardness measurements. The relationship between microhardness and storage modulus is established either below or above the glass transition of the tert-butyl acrylate backbone.     

Comparative studies on effects of silica and titania nanoparticles on crystallization and complex segmental dynamics in poly(dimethylsiloxane)

Effects of in situ synthesized silica and titania nanoparticles, 5 and 20-40 nm in diameter, respectively, on glass transition and segmental dynamics of poly(dimethylsiloxane) networks were studied by employing differential scanning calorimetry, thermally stimulated depolarization currents and broadband dielectric relaxation spectroscopy techniques. Strong interactions between the well dispersed fillers and the polymer suppress crystallinity and affect significantly the evolution of the glass transition in the nanocomposites. Next to the α relaxation associated with the glass transition of the bulk amorphous polymer fraction, two more segmental relaxations were recorded, originating from polymer chains restricted between condensed crystal regions (α_c-relaxation) and the semi-bound polymer in an interfacial layer with strongly reduced mobility due to interactions with hydroxyls on the nanoparticle surface (α′ relaxation), respectively. Interactions with the polymer were found to be stronger in the case of titania than silica, leading to an estimated interaction length of around 2 nm for silica and at least double for titania nanocomposites.     

Dielectric relaxation of polyorganophosphazenes

Dielectric relaxation spectra of poly(bis-trifluoroethoxy phosphazene) (PBFP), poly(bis-n-propoxy phosphazene) (PBPP), and poly(bis-n-propylamino phosphazene) (PBPAP) were measured in wide temperature and frequency regions, and the -relaxation caused by micro-Brownian motion of segments in the rubbery state and the -relaxation due to the local motions of the polymer in the glassy region were observed. The dielectric spectra of PBFP at temperatures higher than the rubbery region exhibited a mesophase transition at 358 K. From conformation analysis according to the two-site model, it has been elucidated that the mechanism for -relaxation of these samples is hindered internal rotation of the side groups.     

Relaxation behavior of layered double hydroxides filled dangling chain-based polyurethane/polymethyl methacrylate nanocomposites

A series of dangling chain based-polyurethane/poly(methyl methacrylate) (DPU/PMMA) filled with exfoliated layered double hydroxides (LDH) were synthesized by methyl methacrylate in-situ intercalative polymerization. The dangling chains were introduced by using vegetable oils as chain extender. The effect of dangling chain and the contents of LDH on the molecular dynamics of DPU/PMMA was investigated by a combination of dynamic mechanical analysis and broadband dielectric relaxation spectroscopy. Compared with polyurethane/poly(methyl methacrylate) (PU/PMMA) without dangling chain, the glass transition temperature (T_g) of DPU/PMMA shifts to lower temperature and the segmental dynamics becomes faster. A plateau with a high loss factor value above T_g significantly broadens the damping temperature range due to the synergy effect between the dangling chains and LDH layers. In DPU/PMMA/LDH nanocomposites, the α-relaxation associated with the glass transition of the polymer matrix becomes slower with the increase of LDH content, which indicates a restricted molecular mobility in the interfacial regions between polymer and LDH. However, the local relaxations at relatively low temperature remain unaffected by dangling chain or the addition of LDH. When the LDH content increases, Maxwell–Wagner–Sillars (MWS) interfacial polarization process caused by charge accumulation at interfaces becomes faster because of the smaller mean distance d between the exfoliated LDH layers.     

Dielectric relaxation of poly(tetrafluoroethylene–perfluorovinyl ether) films

Dielectric constant and dielectric loss have been studied for poly(tetrafluoroethylene–perfluorovinyl ether) (PFA) films over a wide temperature range in the frequency range 0.1–100 kHz. Two relaxation peaks were observed, one at room temperature (α_a-relaxation) and the other in the range 170–140 K (β-relaxation), with activation energies of 143·2 and 16·4 kcal/mol, respectively. The β-absorption is attributed to the short segmental local mode motion of the main chains. The α_a-relaxation can be interpreted as due to large-scale conformational rearrangement. The Cole–Cole diagrams are given at different temperatures and the distribution parameters (ϵ₀–ϵ_∞) and (1–α) of the relaxation times were calculated. The X-ray diffraction pattern of PFA shows both a diffuse halo and sharp reflections, characteristic of amorphous and crystalline phases of conventional semicrystalline polymers. Also, no evidence of crystallinity in the films due to thermal treatment during dielectric measurements was observed. IR spectra revealed the absence of any new peaks after the heat treatment.     

Thermal and dynamic mechanical investigations on fiber-reinforced polypropylene composites

The thermal behavior and dynamic mechanical properties of isotactic polypropylene (PP) and reactor blend PP/ethylene-propylene copolymer (EPM), reinforced with different amounts of short glass fibers (GF) and/or polyester fibers (PETF), were investigated by differential scanning calorimetry (DSC) and dynamic mechanical thermoanalysis (DMTA) of imposed tensile load on rectangular film specimens. DSC measurements exhibited an increase of the crystallization temperature of PP in the presence of fibers, but indicated no change in its percentage of crystallinity. DMTA spectra revealed an increase in the stiffness and a decrease of the damping with increasing GF content. The positions of the primary relaxations of PP and EPM did not change, but a significant broadening of the α-relaxation in the crystalline phase was observed, due to the induced reinforcement and interfacial interactions. The addition of PETF to PP enhanced its damping values at low temperatures and promoted the α-transition. The DMTA behavior was studied in dependence on the preconditioning and the frequency excitation. Heat treatment changed the characteristics of the β-relaxation of PP, due to enhanced molecular motion of the polymer segments. The variation of frequency affected the secondary relaxations considerably and, in the presence of GF, the glass transitions. For the different relaxations, activation energies from peak shift and loss peak areas were determined. Experimental data of loss peaks were fitted to phenomenological equations. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1143–1154, 1997     

Evaluation of local polarity of polymer solids by a rigid fluorescent probe of carbazole-terephthalate cyclophane

A novel rigid fluorescent probe, carbazole-terephthalate cyclophane (Cz-TP) was applied to evaluate local dielectric constants (ε) of various polymer solids in a wide range of temperatures. For poly(vinylidene fluoride), the ε increased above the glass transition temperature (T_g), due to relaxations of the polar segment -(CH₂CF₂)- of the main chain. For poly(alkyl methacrylate)s, the ε increased above the T_g or the melting temperature of the side chain, where motions of the polar ester groups are activated. For cyanoethylated polymers, the ε increased owing to motions of the polar cyano groups at the end of the side chain and the ε corresponded to the dielectric constant evaluated by dielectric relaxation measurement at a high frequency, because the Cz-TP exciplex has a lifetime of tens of nanoseconds. For a cyanoethylated polymer with a high content of cyano groups, the ε was larger at low temperatures than the dielectric constant obtained by the macroscopic dielectric relaxation measurement. These results show that the Cz-TP molecule is a useful probe for evaluation of the local polarity in polymer solids over a wide temperature range and can detect even a small change in ε at transition temperatures such as glass transition, side-chain melting, and side-chain relaxation.     

Structure–property relationships in thermoplastic elastomers. IV. Dynamic mechanical relaxations in polydioxolane,polybutyltrioxocane, and poly(propylene oxide) polyurethanes

Dynamic mechanical measurements had been made on polyurethanes of a range of hard segment content (HSC) obtained from α,ω-dihydroxy derivatives of polydioxolane, polybutyltrioxocane, and poly(propylene oxide) of 2000–12,000 MW coupled with MDI and TDI with hydroxyethyl phthalamide chain extenders. N-methylated chain extender was used to investigate the effect of hydrogen bonding. A broad γ transition was observed between −100 and −115°C attributable to the local motion of methylene sequences with a distribution of relaxations. The β-transition between −55 and −72°C is influenced by the degree of hydration; the α-transition occurs at nearly the same temperatures for all the TPEs, independent of HSC and thermal history. The magnitude of the loss tangent peak is nearly proportional to the soft segment content; the peak corresponds to the glass transition. An α-transition at higher temperature is sensitive to the structure of soft segment, HSC, and thermal history. It is probably associated with the melting of some weakly ordered regions in the soft domain. The hard domain counterpart was observed at the next higher temperature as the ϵ-relaxation. The final large loss of storage modulus occurs at temperatures much below the melting transition.     

Glass transition behaviour of poly(ether ether ketone)/poly(aryl ether sulphone) blends: dynamic mechanical and dielectric relaxation studies

Blends of poly(ether ether ketone) (PEEK) and poly(aryl ether sulphone) (PES) have been prepared in the whole composition range. The molecular dynamics and α-relaxation behaviour of these materials have been studied using dynamic mechanical and dielectric relaxation spectroscopy. From dynamic mechanical relaxation studies, two α-relaxation peaks corresponding to the segmental relaxation process of pure components in the blend was observed. Also, it was found that the temperature at which α-process of the homopolymers occurs, shows a slight change with blend composition, corresponding to a PEEK-rich and PES-rich phase. The relaxation intensities of the homopolymers in the blend compared to that in pure state were approximately proportional to their respective content in the blend. From the phase composition of the respective phases obtained using Fox equation, it has been inferred that PEEK dissolves more in PES than vice-versa. The α-relaxation of PES could not be detected from dielectric relaxation spectroscopy because of the possible influence of dc conduction and electrode polarization losses. Otherwise, the α-relaxation behaviour of PEEK-rich phase observed from dielectric relaxation studies agree with those inferred from dynamic mechanical relaxation studies. Furthermore, activation energies for molecular motions (E_a) at the α-relaxation have also been determined using an Arrhenius form of equation and it has been found that E_a for both PEEK-rich and PES-rich phase show variation with composition. Similarly, the relaxation times associated with the mobility of relaxing species in both PEEK and PES are influenced in the blends. It is likely that these observations are related to some interactions and a partial segmental mixing between the blend components, which result in changes in the local molecular environment on blending.     

New comb-like poly(n-alkyl itaconate)s with crystalizable side chains

A series of poly(mono n-alkyl itaconate)s, poly(methyl n-alkyl itaconate)s and poly(di n-alkyl itaconate)s with n=12, 14, 16, 18 and 22 have been prepared by radical polymerization. NMR studies point out that poly(methyl n-alkyl itaconate)s and poly(di n-alkyl itaconate)s are mainly syndiotactic polymers whereas poly(mono n-alkyl itaconate)s are obtained as almost atactic polymers. The characterization performed by DSC, solid state ¹³C CP/MAS NMR and X-ray diffraction, indicates that the side chains of poly(mono n-alkyl itaconate)s and poly(methyl n-alkyl itaconate)s derivatives with more than 12 carbon atoms are able to crystallize in hexagonal lattices. In the case of poly(di n-alkyl itaconate)s, when the side chains contain 12 or more carbon atoms, they are able to crystallize also in hexagonal lattices.