Exploring the thermomechanical properties of peroxide/co-agent assisted thermoplastic vulcanizates through temperature scanning stress relaxation measurements

Temperature scanning stress relaxation (TSSR) measurement of peroxide vulcanized polymer blends of polypropylene (PP) and ultrahigh molecular-EPDM (UHM-EPDM) rubber has been performed to study the thermomechanical behavior of thermoplastic vulcanizates (TPVs). Co-agents play crucial roles in the enhancement of properties of TPVs. Different types of co-agents (Triallyl cyanurate-TAC; N, N-m-phenylene-dimaleimide-HVA2; zinc dimethacrylate-ZDMA; and in-situ formed zinc dimethacrylate-ZMA) have been explored in this work. TSSR study shows that higher T₅₀ and T₉₀ values have been achieved in ZMA co-agent assisted-TPV. Higher TSSR-index (RI) value was also found for the same co-agent ZMA, indicating higher elastic behavior. TSSR result supports the mechanical and rheological properties, and it is found that the ZMA and ZDMA show higher mechanical strength. Cross-linked-density calculated by modified Flory–Rehner equation and the cross-link-density as obtained from TSSR method have been compared and the trend was found to be the same. Stress relaxation study shows the slow relaxation-phenomena of the ZMA-TPV with slowest relaxation-time (θ_r) than the other TPVs, which correlates with superior material strength. Thermogravimetric analysis proves that there is a difference in degradation temperature of the blends at approximately 5–10°C. Ultrahigh molecular weight-EPDM/PP based TPVs reveal superior thermomechanical and physico-mechanical properties with ZMA and ZDMA co-agent over TAC and HVA2. These ultrahigh molecular weight-EPDM based TPVs can be used in automotive seals/strips, hoses, bellows, and 2 K-molds for automotive applications.     

Investigation of modified SEBS‐based thermoplastic elastomers by temperature scanning stress relaxation measurements

Thermoplastic elastomers (TPEs) based on poly(styrene‐b‐ethylene/butylene‐b‐styrene) (SEBS), modified with poly(2,6‐dimethyl‐1,4‐phenylene ether) (PPE), were investigated by a new testing method. The development and characterization of TPEs with improved temperature and oil resistance is a current area of research to extend the applications of TPEs, especially in the automotive industry. Thermal scanning stress relaxation (TSSR) was used to investigate the relaxation behavior of compounds containing SEBS, blended with extender oil, various amounts of PPE and in some cases with a thermoplastic polymer. Polyamide 12 (PA12) or polypropylene (PP) were used as the thermoplastic component. TSSR measurements were applied to detect relaxation changes in the glass transition region of the polystyrene blocks mixed with PPE. It was shown that the glass transition temperature increased with addition of PPE to the compound up to a limit of approximately 150°C, which corresponded to a weight fraction of PPE in the polystyrene (PS)‐block of 0.5. The increased glass transition temperature lead to SEBS‐based thermoplastic elastomer compounds with improved upper service temperatures. Phase images obtained by atomic force microscopy showed that the addition of PPE results in an increase of hard phase dimension. The addition of a thermoplastic polymer improved the mechanical properties and temperature resistance, but naturally decreased the elasticity of the compounds. Compounds containing PA12 exhibited an improved oil resistance. POLYM. ENG. SCI., 45:1498–1507, 2005. © 2005 Society of Plastics Engineers     

Dynamic stress relaxation behavior of nanogel filled elastomers

Long-time stress relaxation behavior of virgin elastomers, chemically crosslinked nanogels and nanogel filled elastomers was studied with the help of a dynamic mechanical analyzer. Sulfur crosslinked natural rubber and styrene butadiene rubber nanogels and nanocomposite gels were prepared and characterized using different methods. These gels were added in to the virgin elastomer matrix at different concentrations. Presence of crosslinked gels in elastomer matrix greatly influenced its stress relaxation behavior. The effect of draw ratio, gel loading and temperature on the stress relaxation behavior of elastomers was investigated in detail. It was found that virgin elastomers displayed extremely long-term relaxation processes and the time required to achieve equilibrium dramatically decreased with the increase in crosslink density in the case of gels. Time-temperature superposition studies revealed that stress relaxation process was accelerated and relaxation time reduced with a rise in temperature. Finally, experimental stress relaxation data were fitted with the empirical Chasset and Thirion equation with good agreement. From the fitting parameters, the characteristic relaxation time and the material parameter were estimated in order to understand the mechanism of the relaxation processes in the gels and the gel filled elastomers.     

Assessing thermomechanical properties of a reactive maleic anhydride grafted styrene-ethylene-butylene-styrene/thermoplastic polyurethane blend with temperature scanning stress relaxation method

The phenomenon of stress relaxation in thermoplastic elastomers (TPEs) is common and influences the end-use properties of polymers. Temperature scanning stress relaxation (TSSR) method extends an advanced method to study the stress relaxation of TPEs at elevated temperatures. A reactive blend system based on maleic anhydride grafted styrene-ethylene-butylene-styrene and thermoplastic polyurethane is explored for its relaxation behavior at temperature up to 200°C with TSSR meter. The relaxation spectrum revealed the transitions occurring in the blends as well as the extent of interfacial interaction present. Direct measurement of elasticity of the blends was obtained from the TSSR index (RI). Glass transition temperature of the samples was measured from dynamic mechanical analysis. The elastic nature of the blends was also pursued from the storage modulus values and results were in line with TSSR results. The density of crosslinks in the system was assessed with both TSSR and the conventional Flory-Rehner equation and a similar trend was obtained. Atomic force microscopy and scanning electron microscopy revealed the dispersed morphology of the blends.     

Mechanical,thermal, barrier,and rheological properties of poly(ether‐block‐amide) elastomer/organoclay nanocomposite prepared by melt blending

Polyether block amide (PEBA) elastomer‐organoclay nanocomposites were prepared by a melt mixing technique. The X‐ray diffraction and transmission electron microscope analysis indicated that the nanocomposite formed a partially exfoliated nanostructure in which the organoclay was dispersed uniformly throughout the matrix at the nanometer scale. The effect of organoclay on the melting temperature (T_m), glass transition temperature (T_g), crystallization temperature (T_c), and heat of fusion (ΔH_m) of the PEBA was determined by differential scanning calorimetry. Enhanced mechanical properties of the nanocomposites were observed from tensile and dynamic mechanical analysis. Thermal gravimetric analysis showed that the clay nanoparticles caused an increase in the thermal stability of the PEBA. Measurement of oxygen permeability and the degree of swelling in ASTM #3 oil indicated that the gas barrier properties and solvent resistance were greatly improved by the clay nanoparticles. Melt rheological studies revealed that the nanocomposites exhibited strong shear thinning behavior and a percolated network of the clay particles was formed. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Relaxation behavior and activation energy of relaxation for polyimide and polyimide–graphene nanocomposite

The relaxation behavior of polyimide and its nanocomposite containing 10 wt % of graphene was studied by using the dynamic mechanical spectrometer. Dynamic mechanical analysis of polyimide and its composite was performed as a function of temperature and frequency in the temperature range of 25–480 °C and frequency range between 0.05 and 100 Hz. The effect of increasing frequency of testing from 0.05 to 100 Hz is a significant shift from the glass transition temperature, T_g, to higher temperature from 360 °C at 0.05 Hz to 420 °C at 100 Hz. The tan δ peak height for both α and β transitions decreased with increasing test frequency from 0.24 at 0.05 Hz to 0.08 at 100 Hz, due to increasing restriction to chain motion. At any given testing frequency, the T_g for the composite was shown to be higher than that for the matrix by about 5–10 °C. The Arrhenius equation was used to calculate the activation energy for both α and β transitions. The activation for α and β transitions for the composite and polyimide matrix were determined to be 688 and 537 kJ/mol and 313 and 309 kJ/mol, respectively, indicating that a significant increase in the energy barrier to chain relaxation occurred as a result of reinforcement of polyimide with low weight fraction of graphene. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43684.     

Rheological and mechanical properties of polyurethane modified by BHET

The chemical structure of polyurethane modified by BHET is correlated with its mechanical and dynamic mechanical properties. Evaluation of this amorphous elastomer by means of stress–strain tests and transition temperature measurements reveals that incorporation of the BHET structure into the soft polyester segment affects the domain structure and, in turn, the entire mechanical behavior of polyurethane. It is also shown that polyurethane has a wide range of T_g and secondary transition temperature by varying the ratio of BHET to EG as well as the ratio of TDI to polyester polyol.     

Stress relaxation behavior of biaxially oriented poly(ethylene terephthalate)

The stress relaxation behavior of biaxially oriented semicrystalline poly(ethylene terephthalate) was studied by thermomechanical analysis. Experimental techniques were developed for thin films. Relaxation moduli were measured as a function of stress, time, and temperature. The relaxation modulus was shown to be independent of stress over the range tested. Rate of loss of the relaxation modulus was found to be a nonlinear function of time and temperature up to about 100°C, encompassing the T_g for the polymer. Over the temperature range of 100–120°C it was primarily temperature-dependent. An empirical time—temperature superposition showed that significant losses in modulus can occur at very short times. At temperatures above the T_g these losses can result in significantly reduced film physical properties.     

Effect of weakly interacting nanofiller on the morphology and viscoelastic response of polyolefins

Effect of silica nanofiller on the deformation response and morphology of low‐ and high‐density polyethylene (HDPE, LDPE) and isotactic polypropylene (PP) modified with fumed silica was investigated. The dynamic‐mechanical thermal spectroscopy, differential scanning calorimetry, optical microscopy, and density measurements were carried out to determine the temperature dependence of storage and loss moduli as well as nanocomposite morphology. It was demonstrated that the degree of matrix reinforcement is considerably affected by the extent of matrix crystallinity, especially, in the temperature range from (T_m–130°C) to T_m. Based on experimental evidence and literature review, it is proposed that this phenomenon may be attributed to the alpha‐mechanical relaxation process occurring above matrix T_g. As a result of adding silica into the melted matrix, mobility of chains in contact with silica particles became reduced. This caused substantial changes in morphology of these semicrystalline nanocomposites. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Mechanical properties and linear infrared dichroism of thin films of polyurethane nanocomposites

Morphological, mechanical, and Fourier transform infrared dichroic investigations were performed on neat polyurethane (PU) polymer matrix and PU+CaCO₃ nanocomposite thin films to determine how the nanofiller influenced the mechanical properties. The measurements were performed on strips that were cut from the prepared films in parallel and perpendicular directions with respect to the direction of film preparation. Optical microscopy of PU and the PU+CaCO₃ nanocomposite revealed the strain‐induced transition from a continuous spherulitic morphology to a fiberlike structure. The stress–strain behavior of the neat PU and PU+CaCO₃ nanocomposite films showed significant differences at large strain regimes. The experimental results suggest that the mechanical properties were strongly related to the orientational behavior of the separated phases. The orientation of the hard and soft segments was analyzed by the orientation function calculated from the IR absorbances. A correlation between the orientations of segments, tensile properties, and hardness of the investigated polymer films was established. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Mechanical hysteresis of a polyether polyurethane thermoplastic elastomer

The mechanical hysteresis of a polyether polyurethane thermoplastic elastomer was studied as a function of temperature, percent strain, and deformation energy. Hysteresis values remained small at low temperatures when the extent of the sample deformation did not disrupt the glassy matrix. This was readily evident at temperatures below the glass transition temperature, T_g of the polymer where the material did not formally yield. At temperatures above the T_g of the polymer, hysteresis remained small even at substantial strains levels and demonstrated the capabilities of the hard segment domains to act as physical crosslinks. At elevated temperatures, percent hysteresis increased as the hydrogen-bonded hard segment domains weakened. When mechanical hysteresis was considered on the basis of constant deformation energies, hysteresis values reached a maximum in the vicinity of the T_g of the polymer. These maxima existed as a consequence of two opposing trends: the decreasing resiliency of the polymer as it becomes a glass and the increase in the resistance of that glass to undergo deformations sufficient to cause plastic flow. Finally, a hysteresis response surface constructed as a function of deformation energy and temperature was found to be sensitive to both the strain-induced crystallization of the rubbery soft segment matrix and to the strain-induced yielding of the glassy soft segment matrix.     

Viscoplastic deformation of an epoxy resin at elevated temperatures

The tensile behavior under monotonic loading and stress‐relaxation testing of an epoxy resin has been studied. Experimental data at various strain rates and three temperatures from ambient up to just below T_g were performed, to study the transition from the brittle behavior to a ductile and therefore viscoplastic one. Dynamic mechanical analysis was applied to study the glass transition region of the material. Furthermore, a three‐dimensional viscoplastic model was used to simulate the experimental results. This model incorporates all features of yield, strain softening, strain hardening, and rate/temperature dependence. The multiplicative decomposition of the deformation tensor into an elastic and viscoplastic part has also been applied, following the element arrangement in the mechanical model. A stress‐dependent viscosity was controlling the stress–strain material behavior, involving model parameters, calculated from the Eyring plots. A new equation for the evolution of the activation volume with deformation was proposed, based on a probability density function. The model capability was further verified by applying the same set of parameters to predict with a good accuracy the stress‐relaxation data as well. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2027–2033, 2006     

Condition monitoring of a thermally aged hydroxy‐terminated polybutadiene (HTPB)/isophorone diisocyanate (IPDI) elastomer by nuclear magnetic resonance cross‐polarization recovery times

A hydroxy‐terminated polybutadiene (HTPB)/isophorone diisocyanate (IPDI) elastomer is commonly used as propellant binder material. The thermal degradation of the binder is believed to be an important parameter governing the performance of the propellant. The aging of these binders can be monitored by mechanical property measurements, such as modulus or tensile elongation. These techniques, however, are not easily adapted to binder agents that are dispersed throughout a propellant. In this paper we investigated solid‐state nuclear magnetic resonance (NMR) relaxation times as a means to predict the mechanical properties of the binder as a function of aging time. Proton (¹H) spin–lattice and spin–spin relaxation times were insensitive to the degree of thermal degradation of the elastomer. Apparently, these relaxation times depend on localized motions that are only weakly correlated with mechanical properties. A strong correlation was found between the ¹³C cross‐polarization (CP) NMR time constant, T_cp, and the tensile elongation at break of the elastomer as a function of aging time. A ramped‐amplitude CP experiment was less sensitive to imperfections in setting critical instrumental parameters for this mobile material. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 453–459, 2001     

Temperature-triggered three-dimensional network formation in graphene–polybutadiene nanocomposite

Since the invention of vulcanization in the early 19th century, the study on potential factors affecting the crosslink network formation and the corresponding changes in the initial physiochemical attributes of elastomer has been the subject of prime interest. Where several investigations highlight the mechanism and kinetics of the crosslink network formation, the exclusive effect of compounding ingredients, such as filler, plasticizer, and anti-oxidant, is still being pursued. In this direction, we report preparation and characterization of cis-1,4-polybutadiene (PB)–graphene (G) nanocomposite and highlight a phenomenon in which graphene induces the spontaneous chemical reactions in the cis-1,4-polybutadiene elastomer matrix triggered at 170 °C temperature. PB–G nanocomposites were prepared by a fairly simple solution mixing and precipitation process, and such nanocomposites were analytically investigated using several characterization techniques. The differential scanning calorimetry analysis shows the evidence of reactions via exothermic peak transition at ~170 °C temperature. Dynamic mechanical thermal analysis and stress–strain analysis suggest improvement in the initial physiochemical attributes of elastomer. The equilibrium swelling study quantifies the network structure that formed during the spontaneous reactions induced by graphene. Nuclear magnetic resonance (¹H-NMR) and Raman spectroscopic analysis suggest clear deviation in the pristine chemical structure of cis-1,4-PB elastomer and graphene, respectively. We believe that the spontaneous chemical reactions led to the formation of a three-dimensional network within the PB elastomer. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48209.     

Synthesis and characterization of polyacrylamide‐calcium carbonate and polyacrylamide‐calcium sulfate nanocomposites

Polyacrylamide‐calcium carbonate (PAM/CaCO₃) and polyacrylamide‐calcium sulfate (PAM/CaSO₄) nanocomposites were prepared via solution‐mixing technique. The resulting PAM‐based nanocomposites with various CaCO₃ and CaSO₄ nanoparticles contents (0–4% w/w) were investigated. Nanoparticles of CaCO₃ and CaSO₄ were synthesized by in situ deposition technique. In this technique, the surface modification of nanoparticles was performed by nonionic polymeric surfactant. The particle size of nanoparticles was recognized by X‐ray diffraction and scanning electron microscope (SEM) analysis which confirms that the particle has diameter of 25–33 nm. As prepared, nanocomposites films (thickness, 40‐μm) were characterized by Fourier transform infrared (FT‐IR), SEM, and energy‐dispersive X‐ray spectroscopy (EDS). FT‐IR shows the chemical structure of nanocomposites where as SEM analysis suggested that the nanofillers dispersed well in polymer matrix and EDS shows the elemental composition of the nanocomposite samples. Thermal properties of the nanocomposites were studied by using differential scanning calorimetric analysis. The PAM/CaCO₃ and PAM/CaSO₄ nanocomposites showed a higher glass transition temperature and a better thermal stability compared to the pure PAM. The glass transition temperature (T_g) of nanocomposites increases with increase in content of nanoparticles. It may be owing to the interaction between inorganic and organic components. POLYM. COMPOS.,, 2012. © 2012 Society of Plastics Engineers     

Domain structure and time-dependent properties of a crosslinked urethane elastomer

The morphology of a chemically crosslinked urethane elastomer is correlated with its time-dependent mechanical properties. Evaluation of this amorphous elastomer by electron microscopy and small-angle x-ray scattering reveals that incompatible chain segments cluster into separate microphases having a periodicity in electron density of about 90 Å. This observed domain structure is similar to that seen previously in uncrosslinked, thermoplastic urethane elastomers. As in earlier studies on such linear system, thermal pretreatment of the crosslinked elastomer causes a time-dependent change in its room temperature modulus. However, the magnitude of this modulus change (about 20%) is generally less than observed previously with the linear systems. Another contrast with previous findings is that this time-dependent phenomenon is apparently not caused by thermally activated changes in microphase segregation. Rather, the observed time dependence in modulus is believed to be caused by molecular relaxation resulting in densification of amorphous packing within the hard-segment domains. The validity of this proposed mechanism is supported by differential scanning calorimetry experiments showing evidence of enthalpy relaxation during room-temperature aging of the elastomer. This relaxation is qualitatively similar to that observed previously during sub-T_g annealing of single-phase glassy polymers.     

Prediction of long‐term mechanical properties of PVDF/BaTiO3 nanocomposite

Low elastic modulus of polyvinylidene fluoride (PVDF) is a major drawback that can be compensated by adding nanoparticles. This work reports the long‐term mechanical behavior of PVDF nanocomposite containing BaTiO₃ nanoparticle that is evaluated by creep test. The nanocomposite morphology was characterized by scanning and transmission electron microscopy techniques. The dynamic mechanical analysis (DMA) was employed to study the viscoelastic behavior of nanocomposite in a wide range of temperatures and frequencies. According to the creep tests, nanocomposite reduced the rate of the creep compliance at different temperatures. Moreover, the creep compliance for the nanocomposite sample decreased slightly in comparison with neat PVDF. Comparing the Burger's model and experimental results, the elastic and viscous parameters revealed the exactly opposite behavior with increasing temperature. The effect of frequencies on storage moduli of samples was investigated based on time–temperature superposition (TTS) method. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40596.     

Gelatin/montmorillonite hybrid nanocomposite. I. Preparation and properties

Gelatin/montmorillonite (MMT) hybrid nanocomposite was directly prepared with unmodified MMT and gelatin aqueous solution. Thermal and mechanical properties of the composite were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and tensile tests. The results indicated that an intercalated or partially exfoliated nanocomposite could be achieved, and the properties of the composite were significantly improved. A T_g peak of high temperature disappeared in the DSC curve of the composite, and the thermogravity and thermally decomposed rate decreased obviously. The tensile strength and Young's modulus were also improved notably, which varied with MMT content, as well as the pH of gelatin matrix. Meanwhile, SEM photographs showed a plasticizing trend of gelatin fracture surface due to intercalation with MMT. Furthermore, the wet mechanical behavior was initially studied. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1189–1194, 2002     

Intercalation and exfoliation behavior of epoxy resin/curing agent/montmorillonite nanocomposite

The epoxy resin/curing agent/montmorillonite nanocomposite was prepared by a casting and curing process. The intercalation and exfoliation behaviors of epoxy resin in the presence of organophilic montmorillonite were investigated by X‐ray diffraction (XRD) and dynamic mechanical thermal analysis (DMTA). For the diethylenetriamine curing agent, the intercalated nanocomposite was obtained; and the exfoliated nanocomposite would be formed for tung oil anhydride curing agent. The curing condition does not affect the resulting kind of composite, both intercalation or exfoliation. For intercalated nanocomposite, the glass transition temperature T_g, measured by DMTA and affected by the curing temperature of matrix epoxy resin is corresponded to that of epoxy resin without a gallery. The α′ peak of the loss tangent will disappear if adding montmorillonite into the composite. It was also found that the T_g of the exfoliated nanocomposite decreases with increasing montmorillonite loading. © 2002 John Wiley & Sons, Inc. J Appl Polym Sci 84: 842–849, 2002; DOI 10.1002/app.10354     

Characterization of polymer-coated optical fibers using a torsion pendulum

A freely oscillating torsion pendulum has been used to characterize the dynamic mechanical behavior of single polymer-coated optical fibers. The dynamical mechanical spectra of the polymer coatings exhibit a glass transition temperature (T_g), a cryogenic glassy-state relaxation (T_sec), and another cryogenic relaxation that is attributed to water present in the coating (TH₂O). The shear modulus (G′) of the coating was computed from the shear moduli of the composite specimen and the core, assuming that the coating and core deform through the same angle on oscillation. The glassy-state modulus was the same for both thin and thick coatings, although the intensity of the damping peaks, as measured by the logarithmic decrement, increased with coating thickness. Comparison of the dynamic mechanical behavior of a coated optical fiber and of a free film cast from the same reactive components shows that the polymer itself can absorb water at ambient conditions and display a mechanical relaxation at cryogenic temperatures. The T., H₂O and T_sec relaxations are coupled with respect to their intensities. Latent chemical reactivity was found in one coating above its maximum temperature of cure. In this, the temperature of cure determines the glass transition temperature.