Molecular mobility and crystallinity in polytetramethylene ether glycol in the bulk and as soft component in polyurethanes

We revisit molecular mobility and crystallinity in a series of Polyurethanes prepared with polytetramethylene ether glycol (PTMEG) with varying molecular weights as soft component, methylene diisocyanate (MDI) as diisocyanate component and butanediol as chain extender in close comparison to the properties of the respective macrodiols used as soft segments. Modulated differential scanning calorimetry (MDSC) was utilized to study the glass transition and in detail crystallization and melting. Thermally stimulated depolarization currents (TSDC), and dielectric relaxation spectroscopy (DRS) were used to investigate local dynamics, dynamic glass transition and indirectly, crystallinity and morphology. The dielectric data were evaluated through representation by contour plots in the Arrhenius plane. Glass transition temperature of the diols is practically unaffected by molecular weight due to H-bonding effect, while for the PUs it showed a decreasing dependence due to higher microphase separation. Results are also discussed in terms of fragility. Crystallization of PTMEG becomes more intense and stable with increasing molecular weight, while the reflection of its melting process on its dielectric response was also observed. A weak crystallization process in the Polyurethane with long soft segments was well resolved using MDSC. Evidence for the occurrence of spinodal decomposition before this crystallization was observed by means of DRS.     

Structure-electrical properties relationships of polymer composites filled with Fe-powder

Structure-properties relationships of composite materials, consisting of a polymer matrix and metal inclusions, is very important for designing new materials with desirable properties. In the present work the electrical and dielectric properties of several composites, consisting of a polymer matrix and iron (Fe) particles as filler, were investigated. Broadband dielectric relaxation spectroscopy measurements were carried out. The electrical behaviour of the composites is described in terms of the percolation theory. Percolation threshold values were calculated and the values of the dielectric permittivity critical exponent were found in good agreement with the theoretical ones. The influence of using different polymer matrices on the physical properties of the composites was also of particular interest. The results were related to the microstructure of the composites and a schematic model was proposed.     

Mechanical properties of rigid polyurethane composites reinforced with surface treated ultrahigh molecular weight polyethylene fibers

The mechanical properties of ultrahigh molecular weight polyethylene (UHMWPE) fibers reinforced rigid polyurethane (PU) composites were studied, and the effects of the fiber surface treatment and the mass fraction were discussed. Chromic acid was used to treat the UHMWPE fibers, and polyurethane composites were prepared with 0.1 to 0.6 wt% as‐received and treated UHMWPE fibers. Attenuated total reflection Fourier transform infrared demonstrated that oxygen‐containing functional groups were efficiently grafted to the fiber surface. The mechanical performance tests of the UHMWPE fibers/PU composites were conducted, and the results revealed that the treated UHMWPE fibers/PU composites had better tensile, compression, and bending properties than as‐received UHMWPE fibers/PU composites. Thermal gravimetric analyzer showed that the thermal stability of the treated fiber composites were improved. The interface bonding of PU composites were investigated by scanning electron microscopy and dynamic mechanical analysis, and the results indicated that the surface modification of UHMWPE fiber could improve the interaction between fiber and PU, which played a positive role in mechanical properties of composites.     

Synergistic effects on polyurethane/lead zirconate titanate/carbon black three-phase composites

Synergistic processes in hybrid composites have frequently been described in the literature over the past few years, opening doors to new studies and applications for this type of material. In this study, three-phase composites were obtained using polyurethane (PU) as the matrix, lead zirconate titanate (PZT) as the ferroelectric ceramic and carbon black (CB) as the conductive phase. The discussion is primarily focused on a comparison of the electrical, thermal and dielectric properties of three-phase composites with those of PU_CB and PU_PZT biphasic composites. The study describes a synergistic effect between the PU/PZT/CB phases involved in the generation of charges between the particles, implying better homogeneity of the composites as well as influence over the PU crystallization. The PU_CB conductivity profile showed a phenomenon of multi-step percolation thresholds attributed to the molecular structure and repulsive surface charge of CB particles. The surface charge phenomenon restricted the percolation curve analysis of the three-phase composites by means of classic percolation theory, shown by distortion of the critical exponents. The dielectric constant three-phase composites increased gradually as a function of CB in accordance with the percolation profile.     

Method of determination of dielectric relaxation characteristics of plasticized polystyrenes on the basis of calorimetric glass temperature

The dielectric loss measurements of different polystyrenes (fractions and blends) with different molecular weights (M _n 2000–125000 g/mol) were carried out in the frequency range 10^–2–10⁶ Hz and the temperature range of the glass process (60°–135°C, depending on the molecular weight). The measurements of the pure fractions showed that the half-width of the glass relaxation process of the different polystyrenes can be correlated by a straight line, if they are plotted versus the relaxation frequency maxima of the glass process, regardless of the difference in both their molecular weight and glass transition temperature. Moreover, the fine structure of the shape of the glass process of polystyrenes with different molecular weights was found to be the same when the glass process appears at the same relaxation frequency range. The addition of oligostyrenes or low molecular <10% wt additives to the high molecular weight polystyrene did not influence the shape of the glass process. The calorimetric glass transition temperature of polystyrene was found to be only dependent on the number average molecular weight as well as on the number of end groups, but not on the molecular weight distribution. The obtained experimental results were correlated to develop a method for the estimation of the dielectric relaxation characteristics (relaxation frequency as well as the shape parameters) of the glass process of plasticized polystyrenes based on the calorimetric glass transition temperature. A method for the analysis of the dielectric relaxation curves of mixtures of label and polymer is suggested.     

The role of interfacial chemistry and interactions in the dynamics of thermosetting polyurethane–multiwalled carbon nanotube composites at low filler contents

Acid-oxidized multiwalled carbon nanotubes (MWCNTs) were introduced into a polyurethane (PU) matrix at low filler levels (0.01–0.25 wt%) through either van der Waals or covalent interactions, and their glass transition dynamics using dynamic mechanical analysis and laser-interferometric creep rate spectroscopy was investigated. The nanocomposites reveal substantial impact on the PU glass transition dynamics, which depends on the nanotube content and type of interfacial interactions. The pronounced dynamic heterogeneity within the glass transition covering 200 °C range and the displacement of main PU relaxation maxima from around 0 to 80–140 °C were registered. The results are treated in the framework of chemical inhomogeneity, constrained dynamics effects, and different motional cooperativities. The peculiariaties of the glass transition dynamics in the composites are reflected in their dynamic and static mechanical properties, in particular a two- to threefold increase in modulus and tensile strength for the covalent interfacial interaction of MWCNTs with PU.     

Self-assembly and molecular dynamics of oligoindenofluorenes.

The optical properties, self-assembly mechanism, thermal properties, and the associated molecular dynamics of a series of stable blue-emitting oligoindenofluorenes up to the polymer were investigated by photoluminescence, wide-angle X-ray scattering, polarizing optical microscopy, differential scanning calorimetry, and dielectric spectroscopy. Oligomers of indenofluorenes possess high structural order and form smectic mesophases, as opposed to the nematic mesophases formed in the corresponding oligofluorenes. The alpha process associated with the liquid-to-glass transition displays an asymmetric broadening of relaxation times (non-Debye process), with a non-Arrhenius temperature dependence of relaxation times and a strong molecular weight dependence. The low dielectric loss and low ionic conductivity revealed the absence of ketone structural defects, which is consistent with the observed stable blue emission.     

Composites of kaolin and polydimethylsiloxane

Kaolin particles were surface-treated with isobutyltrimethoxysilane (IBTMS), hydrogenated tallow (HT), and a polyisobutyl chain-based stabilizer (SAP) to make composites with polydimethylsiloxane (PDMS). IBTMS did not cover the strong acid sites on the kaolin surface and as a result a cross-linking reaction occurred for silanol-terminated PDMS. The polyisobutyl chain of SAP was found to be incompatible with PDMS and this caused aggregation of the kaolin particles. HT was the most effective at dispersing the particles into silanol-terminated PDMS. The aggregation state of the composites was characterized using rheology and microscopy. Both showed the HT-treated particles were well-dispersed in low molecular weight silanol-terminated PDMS, and they were weakly flocculated in higher molecular weight silanol-terminated PDMS. However, the same particles aggregated when dispersed in methyl-terminated PDMS. It appears the silanol-terminated PDMS acted as costabilizer through interaction with the kaolin surface. Transverse relaxation NMR was used to probe mobility of the PDMS chains in the composites. This showed little dependence on surface treatment, aggregation state, or polymer end groups. For all samples, chain mobility decreased with increasing kaolin concentration.     

Effect of dispersion of CdSe quantum dots on phase transition,electrical and electro-optical properties of 4PP4OB

We prepared composites of a liquid crystalline material, 4-pentylphenyl 4-octyloxybenzoate (4PP4OB) and cadmium selenide quantum dots (CdSe-QDs) and investigated their thermodynamic, electro-optical and dielectric properties. The effect of QDs on transition temperature from isotropic to nematic and nematic to smectic A phases was evaluated in this study. The effect of CdSe-QDs inclusion on various display parameters on host liquid crystals was studied in the nematic phase. The electrical parameters of the composites – relative permittivity, dielectric anisotropy, dielectric loss and dielectric relaxation – were investigated in the nematic and smectic phases. The changes in dielectric parameters of the composites are explained in terms of Maier–Meier theory.     

Water sorption and electrical/dielectric properties of organic-inorganic polymer blends

Organic-inorganic polymer blends (OIPB) were obtained by reaction of organic and inorganic oligomers. The organic oligomer was synthesized with 2,4-toluene diisocyanate (TDI) and oligooxypropylene glycols (OPG) with various molecular weights (MW). The inorganic component was a water solution of sodium silicate. The OIPB obtained are hydrophilic and have great water sorption ability (the relative weight of sorbed water reaches 2000 %). The kinetics of water sorption and the changes of electrical conductivity during sorption were studied. Sorption ability, and mechanical, electrical and dielectric properties of OIPB depend on molecular weight of OPG: conductivity increases with increasing MW, whereas the sorption ability correlates with the mechanical properties. The influence of the inorganic phase content on the electrical and dielectric properties was studied as well.     

Transitions/relaxations in polyester adhesive/PET system

The correlations between the transitions and the dielectric relaxation processes of the oriented poly(ethylene terephthalate) (PET) pre-impregnated of the polyester thermoplastic adhesive have been investigated by differential scanning calorimetry (DSC) and dynamic dielectric spectroscopy (DDS). The thermoplastic polyester adhesive and the oriented PET films have been studied as reference samples. This study evidences that the adhesive chain segments is responsible for the physical structure evolution in the PET-oriented film. The transitions and dielectric relaxation modes’ evolutions in the glass transition region appear characteristic of the interphase between adhesive and PET film, which is discussed in terms of molecular mobility. The storage at room temperature of the adhesive tape involves the heterogeneity of the physical structure, characterized by glass transition dissociation. Thus, the correlation between the transitions and the dielectric relaxation processes evidences a segregation of the amorphous phases. Therefore, the physical structure and the properties of the material have been linked to the chemical characteristics.     

Molecular weight dependence of hybrid shish kebab structure in injection molded bar of polyethylene/inorganic whisker composites

In our previous work, a hybrid shish kebab structure, with polyethylene (PE) crystal lamellae periodically decorated on the surface of an inorganic whisker (SMCW) and aligned approximately perpendicular to the long axis of the whisker, has been observed in the injection molded bar of PE/SMCW composites. To investigate the effect of the molecular weight of the PE matrix on the formation of the hybrid shish kebab structure and the corresponding physical properties of HDPE/SMCW composites, in this work, three types of PE with different molecular weights were used to prepare the composites. They were first melt blended and then subjected to dynamic packing injection molding (DPIM), in which the prolonged shear was exerted on the melt during the solidification stage. An obvious hybrid shish kebab (HSK) structure, with PE crystal lamellae closely packed on the surface of the SMCW, was found in the samples with a low molecular weight PE (LMW-PE) matrix and a medium molecular weight PE (MMW-PE) matrix. However, in samples with a high molecular weight PE (HMW-PE) matrix, an incomplete HSK structure with PE crystal lamellae loosely decorated on the surface of the SMCW was observed. Furthermore, DSC results indicated that SMCW served as a good nucleating agent only for the composite with a LMW-PE matrix and the nucleation efficiency decreased with increasing PE molecular weight. Correspondingly, the tensile strength of the PE/SMCW composites was significantly improved by adding SMCW for the samples with a LMW-PE or MMW-PE matrix. Especially for samples with a LMW-PE matrix, the tensile strength was remarkably enhanced by the presence of only 1 wt % SMCW. For the composites with a HMW-PE matrix, the addition of SMCW had almost no reinforcing effect on the composites. The molecular weight dependence of the formation of HSK and property enhancement was discussed on the basis of the chain mobility and crystallization capability of the PE matrix.     

The influence of the molecular weight of DMC polyethers on the physical-mechanical properties of PU materials based on them

This article describes synthesis of polyurethane (PU) elastomers based on DMC polyethers. The influence of the molecular weight of DMC polyethers on the strength characteristics and mechanical hysteresis of model PU composites based on them is studied. It is shown that, when the molecular weight of DMC polyethers changes in the range of 2000–4000, the strength of PU materials dramatically increases, while a considerable improvement of elastic properties is observed when using polyethers with MW = 8.000 or higher.     

Dielectric relaxations in PEEK by combined dynamic dielectric spectroscopy and thermally stimulated current

The molecular dynamics of a quenched poly(ether ether ketone) (PEEK) was studied over a broad frequency range from 10^?3 to 10⁶ Hz by combining dynamic dielectric spectroscopy (DDS) and thermo-stimulated current (TSC) analysis. The dielectric relaxation losses ε′′_KK has been determined from the real part ε′_T(ω) thanks to Kramers–Kronig transform. In this way, conduction and relaxation processes can be analyzed independently. Two secondary dipolar relaxations, the γ and the β modes, corresponding to non-cooperative localized molecular mobility have been pointed out. The main α relaxation appeared close to the glass transition temperature as determined by DSC; it has been attributed to the delocalized cooperative mobility of the free amorphous phase. The relaxation times of dielectric relaxations determined with TSC at low frequency converge with relaxation times extracted from DDS at high frequency. This correlation emphasized continuity of mobility kinetics between vitreous and liquid state. The dielectric spectroscopy exhibits the α_c relaxation, near 443 K, which has been associated with the rigid amorphous phase confined by crystallites. This present experiment demonstrates coherence of the dynamics of the PEEK heterogeneous amorphous phase between glassy and liquid state and significantly improve the knowledge of molecular/dynamic structure relationships.     

Dielectric Relaxation Phenomena and Electric Properties of Conductive Composite Polyurethane/Polyaniline Films

Summary: Composite polyurethane/polyaniline (PU/PANI) films have been chemically prepared by oxidative in-situ polymerization of aniline inside the previously swelled PU film. Swelling kinetic studies have shown that for PU films the swelling degree of aniline is 25 wt.%. The dielectric and electrical properties of the composite films were measured using dielectric relaxation spectroscopy and four-probe method. Dielectric measurements as a function of temperature and frequency revealed the presence of a relaxation process for the composite PU/PANI-HCl film. This relaxation was explained in terms of interfacial polarization due to the double-layered structure of the composite film. The activation energy values found by dielectric and electrical measurements are close and this result confirms the conducting character of the PANI containing layer.     

Polyurethane cationomers. I. Structure–properties relationships

Polyurethane (PU) cationomers have been synthesized by quaternizing tertiary amine-containing linear polyurethanes using different quaternizers containing acid groups. The effect of chemical structure of PU cationomers on the physical properties was studied. The mechanical properties of PU cationomers were improved with decreasing molecular weight of poly(caprolactone) glycol, and increasing concentration of quaternary ammonium. Decreasing the carbon number in the alkyl group of the N-alkyl diethanol-amine chain-extenders, and using rigid symmetrical diisocyanates, the mechanical properties of the PU cationomers were increased. The effects of these factors on the glass transition temperature of PU cationomers were also examined. The mechanical properties of the PU cationomers decreased by immersion in water and recovered after removal of the water.     

聚吡咯/多壁碳纳米管及其聚氨酯导电复合材料的制备和性能

以羧基化多壁碳纳米管(MWCNTs)做模版剂,采用化学氧化法将吡咯(Py)在羧基化MWCNTs表面聚合制备PPy/MWCNTs导电材料,将其添加到溶剂型聚氨酯(PU)溶液中制备了PPy/MWCNTs/PU导电复合材料,研究了Py用量对PPy/MWCNTs及其PU复合材料性能的影响.研究表明,随Py用量的增加,PPy/MWCNTs的长度不变,管径增大,sp~2和sp~3杂化C含量先提高后减少,N的掺杂梯度降低,PPy/MWCNTs的导电率高于羧基化MWCNTs和PPy.当Py用量为羧基化MWCNTs的20%时,其导电率最大.PPy/MWCNTs中N元素的掺杂程度及其管径变化是引起PPy/MWCNTs/PU复合材料的性能不同的主要原因.增加Py用量,MWCNTs中亲水的羧基因对PPy掺杂而消耗,相同导电材料用量时纳米导电粒子数目相对减少,PPy/MWCNTs/PU复合材料的耐水性能提高,定向应力、储能模量和玻璃化温度降低,导电率先增加后减小.当Py用量为羧基化MWCNTs的15%时,导电率最大.     

Effect of chain length on fragility and thermodynamic scaling of the local segmental dynamics in poly(methylmethacrylate)

Local segmental relaxation properties of poly(methylmethacrylate) (PMMA) of varying molecular weight are measured by dielectric spectroscopy and analyzed in combination with the equation of state obtained from PVT measurements. Significant variations of glass transition temperature and fragility with molecular weight are observed. In accord with the general properties of glass-forming materials, single molecular weight dependent scaling exponent gamma is sufficient to define the mean segmental relaxation time taualpha and its distribution. This exponent can be connected to the Gruneisen parameter and related thermodynamic quantities, thus demonstrating the interrelationship between dynamics and thermodynamics in PMMA. Changes in the relaxation properties ("dynamic crossover") are observed as a function of both temperature and pressure, with taualpha serving as the control parameter for the crossover. At longer taualpha another change in the dynamics is apparent, associated with a decoupling of the local segmental process from ionic conductivity.     

Molecular Dynamics and Structure of Poly(Methyl Methacrylate) Chains Grafted from Barium Titanate Nanoparticles

Core−shell nanocomposites comprising barium titanate, BaTiO₃ (BTO), and poly(methyl methacrylate) (PMMA) chains grafted from its surface with varied grafting densities were prepared. BTO nanocrystals are high-k inorganic materials, and the obtained nanocomposites exhibit enhanced dielectric permittivity, as compared to neat PMMA, and a relatively low level of loss tangent in a wide range of frequencies. The impact of the molecular dynamics, structure, and interactions of the BTO surface on the polymer chains was investigated. The nanocomposites were characterized by broadband dielectric and vibrational spectroscopies (IR and Raman), transmission electron microscopy, differential scanning calorimetry, and nuclear magnetic resonance. The presence of ceramic nanoparticles in core–shell composites slowed down the segmental dynamic of PMMA chains, increased glass transition temperature, and concurrently increased the thermal stability of the organic part. It was also evidenced that, in addition to segmental dynamics, local β relaxation was affected. The grafting density influenced the self-organization and interactions within the PMMA phase, affecting the organization on a smaller size scale of polymeric chains. This was explained by the interaction of the exposed surface of nanoparticles with polymer chains.     

Preparation and characteristics of poly(benzoxazine-urethane)/graphene oxide composites: Toughness,mechanical and thermal properties

Poly(benzoxazine-urethane)/graphene oxide [poly(Bz-PU)/GO] composites were successfully prepared by blending benzoxazine (Bz) with graphene oxide (GO) and isocyanato (NCO)-terminated polyurethane prepolymer (PU), followed by thermally activated polymerization of the blends. The network was formed via the mutual reaction and intermolecular interaction among the hydroxyl of GO, NCO groups of PU and phenolic hydroxyl of Bz. The toughness shown from SEM images and tensile properties of polybenzoxazine (PBz) plastic composites can effectively be improved by alloying with PU and GO. The onset curing temperature and exothermic peak maximums of the polymerization obtained from differential scanning calorimetry decreased resulted from the GO addition. The thermogravimetric analysis showed that the incorporation of 0.5 wt% of GO slightly improved the thermal stability of poly(Bz-PU)/GO composites. Additionally, the storage modulus improved and the glass transition temperature (Tg) increased gradually as the increasing GO content not beyond a certain amount. Finally, the exothermic peaks of the polymerization were shifted to lower temperature, and the thermal stability increased for the ternary composites as the number average molecular weights (Mn) of polyol decreased.