Aspects of physical aging,mechanical rejuvenation,and thermal annealing in a new copolyester

Long‐term effects of physical aging and mechanical rejuvenation are monitored through dynamic mechanical properties of an amorphous glassy polymer. These phenomena are investigated through dynamic mechanical testing that evaluates in situ the evolution of the storage modulus with time during annealing and physical aging. Comparisons are made on samples with different thermal histories and mechanical treatment (rejuvenation). The polymer characterized in this contribution is a new commercially available copolyester under the tradename of Tritan?. The results are discussed in context to different aging rates obtained from the various thermal and mechanical treatments; both measurements of aging rates are compared. POLYM. ENG. SCI., 55:1941–1950, 2015. © 2014 Society of Plastics Engineers     

Aging of HTPB/Al/AP Rocket Propellant Formulations Investigated by DMA Measurements

Three HTPB‐based rocket propellant formulations containing ammonium perchlorate and aluminum particles, with different aluminum content and particle size, have been manufactured. The study has focused on the change of mechanical properties with aging time by using dynamic mechanical analysis (DMA). Therefore, propellant formulations underwent an accelerated aging program, in air (RH<10 %), between 60 °C and 90 °C with aging time adjusted to a thermal equivalent load of 15 to 20 years at 25 °C. DMA investigations revealed distinct changes in the shape of the loss factor curve. These curves were modeled with three exponentially modified Gaussian (EMG) functions in order to get the molecular interpretation of the involved aging phenomena by separating the binder fractions with different mobility. Aging of propellant formulations can be followed by considering only two parameters: the areas of the second and third loss factor transition peaks (A₂, A₃), and the corresponding maximum temperature values of the assigned Gauss peaks (Tc₂, Tc₃).     

Dynamic mechanical properties of extruded nylon–wood composites

Dynamic mechanical properties determine the potential end use of a newly developed extruded nylon–wood composite in under‐the‐hood automobile applications. In this article, the dynamic mechanical properties of extruded nylon–wood composites were characterized using a dynamic mechanical thermal analyzer (DMTA) to determine storage modulus, glass transition temperature (T_g), physical aging effects, long‐term performance prediction, and comparisons to similar products. The storage modulus of the nylon–wood composite was found to be more temperature stable than pure nylon 66. The T_g range of the nylon–wood composite was found to be between 23 and 56°C, based on the decrease in storage modulus. A master curve was constructed based on the creep curves at various temperatures from 30 to 80°C. The results show that the relationship between shift factors and temperature follows Arrhenius behavior. Nylon–wood composites have good temperature‐dependent properties. Wood fillers reduced the physical aging effects on nylon in the wood composites. The comparison of the nylon–wood composite with other similar products shows that nylon–wood composites are a promising low cost material for industrial applications. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Dispersion of multiwalled carbon nanotubes in thermoplastic elastomer gels: Morphological,rheological, and electrical properties

An investigation was reported here with an aim to prepare nanocomposite thermoplastic elastomer gels by dissolving polystyrene‐b‐poly(ethylene/butylene)‐b‐polystyrene (SEBS) triblock copolymer in selective hydrocarbon oils with the presence of multiwalled carbon nanotubes (MWCNTs). The properties related to morphology, viscoelasticity, electrical and mechanical properties, and thermal stability were explored and discussed. Dynamic rheological measurements of the resultant nanocomposite thermoplastic elastomer gels (NCTPEGs) confirmed that addition of MWCNTs affects the linear viscoelastic properties in which dynamic storage and loss moduli increase to some extent. At a temperature between 30°C and 40°C below the gel point the NCTPEGs have dynamic storage modulus greater than loss modulus (G′ and G″), thereby indicating that at room temperature a physical network is still present despite the addition of MWCNTs. The morphological properties revealed that MWCNTs were dispersed and exfoliated within the swollen TPE. The incorporation of small quantity of MWCNTs improved the thermal stability and mechanical properties of NCTPEGs. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Isothermal physical aging of a fully cured epoxy—amine thermosetting system

The rate and effects of isothermal physical aging of a fully cured epoxy—amine/glass fiber composite specimen were studied for a wide range of isothermal aging temperatures (−180 to 200°C) using a freely oscillating torsion pendulum technique: torsional braid analysis (TBA). As assigned from the maxima in the mechanical loss vs. temperature, the glass transition temperature, T_g, was 182°C (0.9 Hz), and the principal glassy-state secondary transition temperature, T_β, was ≈ −30°C (1.9 Hz). Plots of the increase in the isothermal modulus and of the decrease in the isothermal mechanical loss were linear vs. log aging time; their slopes provided aging rates. It was found that the isothermal aging rate varies with isothermal aging temperature (T_a) and that there are two maxima in the aging rate vs. T_a. A correlation presumably exists between the two maxima in the aging rate and the two transitions. This is not surprising since mechanical loss maxima (i.e., transitions) and aging rate maxima both correspond to specific, localized, and restricted submolecular motions. Effects after isothermal physical aging were investigated vs. temperature in terms of change of modulus of the specimen. The effect of isothermal aging existed primarily in a narrow temperature region localized about T_a. The majority of the isothermal aging effect can be eliminated by heating to temperatures above T_a, but below T_g. Theoretical and practical implications of this observation are discussed. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 55–67, 1997     

Environmental aging of the Ti-6Al-4V/FM-5 polyimide. adhesive bonded system: implications of physical and chemical aging on durability

Ti-6A1-4V/FM-5 polyimide adhesively bonded double cantilever beam (DCB) specimens were aged for 12 months at elevated temperatures (177°C and 204°C) in one of three different environments: ambient atmospheric air pressure and reduced air pressures of 2 psi (13.8 kPa) and 0.2 psi (1.38 kPa), to assess bond durability. The FM-5 polyimide adhesive (Tg~ 250°C) is based on a polyimide developed by NASA Langley Research Center and is produced by Cytec Industries, Inc. Bonds aged for different times were tested to measure the critical strain energy release rate as a function of the temperature and environment. The greatest loss in bond strength occurred after aging in air at 204°C. Following thermal rejuvenation of the aged bonds at 300°C for 2 h, part of the strength loss could be recovered. This strength recovery was attributed to the reversal of physical aging in the adhesive resin. Further evidence for physical aging, which is a thermo-reversible phenomenon, was obtained from tests conducted on neat resin specimens using DMA (dynamic mechanical analysis) and DSC (differential scanning calorimetry). The unrecovered portion of the loss in bond strength following longer-term aging was attributed to chemical aging/degradation of the bonded 'system'. The 'system' in this study includes the adherends, the adhesive, the surface pretreatment (chromic acid anodization, CAA), and their respective interphase/interface regions. Evidence for chemical aging was also seen from weight loss, and Soxhlet extraction data on neat resin specimens.     

Dynamic mechanical behavior of copolymers containing carbon black

The storage and loss moduli of random copolymers of styrene and butyl methacrylate containing carbon black of varied surface area were determined by dynamic mechanical analysis at several temperatures about 100°C above the glass-transition temperature, T_g. At low frequencies, the pure polymers exhibit linear double log plots of moduli against frequency, with slopes of unity and approaching two for G″ and G′, respectively. With the addition of carbon black filler, both G′ and G″ become independent of frequency and temperature at low frequencies, consistent with yield behavior arid the formation of a carbon black network. The limiting dynamic complex modulus exceeds the yield stress from steady shear rheology, perhaps indicating the extent of the carbon black network, which was highest for low-molecular-weight copolymer and polystyrene. The filled random copolymers behaved Theologically like similarly filled polystyrenes of comparable molecular weights. Plasticization effects observed in the steady shear rheology of filled copolymers containing small concentrations of carbon black were not observed in dynamic mechanical analysis, although dynamic moduli converge at high frequency.     

Dynamic mechanical properties of polypropylene composites filled with ultrafine particles

The dynamic moduli of isotactic polypropylene (PP) filled with ultrafine SiO₂ and micron sized glass particles are measured in the temperature range 30–130°C at frequency 10 Hz. The storage moduli of PP composites, E′_c, increase with filler content and decreasing filler size in the whole range of temperature. The loss moduli of PP composites, E″_c, increase with filler content and decreasing filler size above 40°C. The intensity of the broad despersion which appears at ca. 60°C increases with filler content and decreasing filler size. By assuming that the energy is not dissipated in the effective volume, namely, filler volume plus that of immobilized interfacial region, the effective volume fraction is evaluated from the relative loss modulus, E″_cE″₀ at 60°C. The effective volume fraction increases with filler content and decreasing filler size. The effect of addition of ultrafine particles on the broad dispersion at ca. 60°C resembles the effect of increasing crystallinity of pure PP. It is concluded that the broad dispersion which appeared at ca. 60°C seemed to be assigned to the grain boundary of PP composities or crystalline boundary of pure PP.     

Erasure below glass‐transition temperature of effect of isothermal physical aging in fully cured epoxy/amine thermosetting system

The erasure below the glass‐transition temperature (T_g) of the effect of isothermal physical aging (at aging temperature T_a) in a fully cured epoxy/amine thermosetting system is investigated using the torsional braid analysis (TBA) dynamic mechanical analysis technique and the differential scanning calorimetry (DSC) technique. From the TBA temperature scans, the intensity of the localized perturbation of the moduli in the vicinity of the T_a (90°C), due to isothermal physical aging, is decreased by heating to below the T_g (T_g∞ = 177°C), indicating that the physical aging effect can be eliminated by heating to below the T_g. The isothermal aging effect in the vicinity of the T_a is almost completely eliminated by heating to 50°C above the T_a (i.e., 140°C); however, a competing aging effect occurs above T_a at higher temperatures during the heating. Erasure below T_g of the isothermal physical aging effect is inferred from DSC experiments from the diminished relaxation enthalpy in the vicinity of the T_g, which is measured from the difference in areas between the aged (T_a = 150°C) and deaged thermograms. A comparison of the TBA and DSC results is made. Implications on the heterogeneous nature of the amorphous glassy state of polymers are discussed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 396–404, 2001     

The rheological behavior and dynamic mechanical properties of syndiotactic 1,2‐polybutadiene

The rheological behavior and the dynamic mechanical properties of syndiotactic 1,2‐polybutadiene (sPB) were investigated by a rotational rheometer (MCR‐300) and a dynamic mechanical analyzer (DMA‐242C). Rheological behavior of sPB‐830, a sPB with crystalline degree of 20.1% and syndiotactic content of 65.1%, showed that storage modulus (G′) and loss modulus (G″) decreased, and the zero shear viscosity (η₀) decreased slightly with increasing temperature when measuring temperatures were lower than 160°C. However, G′ and G″ increased at the end region of relaxation curves with increasing temperature and η₀ increased with increasing temperature as the measuring temperatures were higher than 160°C. Furthermore, critical crosslinked reaction temperature was detected at about 160°C for sPB‐830. The crosslinked reaction was not detected when test temperature was lower than 150°C for measuring the dynamic mechanical properties of sample. The relationship between processing temperature and crosslinked reaction was proposed for the sPB‐830 sample. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Elevated temperature aging of HIPS

The effects of aging at 85°C on a rubber-modified polystyrene (HIPS) have been studied as a function of aging time in both air and nitrogen. Four different types of physical measurements were carried out on the aged samples. These included mechanical relaxation measurements, tensile stress–strain measurements, creep measurements at several stresses, and measurements of fatigue lifetime under applied tension–compression stress. Aging in nitrogen is largely a physical aging process and results in higher modulus, higher tensile strength, and longer delay times to the onset of accelerating creep deformation. But tensile ductility and fatigue lifetime tend to reduce, and there is no change in location of T_g of the rubber phase. Aging in air involves both chemical and physical aging, and the changes that occur depend on which process dominates. For long-time aging of 150 h or more, the rubber-phase T_g is shifted to higher temperatures and the associated loss peak is broadened due to crosslinking. Also, the tensile strength, tensile ductility, creep delay time, and fatigue life all reduce. These effects are attributed to oxidative attack and embrittlement. SEM micrographs reveal variations in fracture surface morphology due to the mode of testing and to the aging medium.     

Dual glassy relaxations in physically aged semi‐crystalline poly(L‐lactic acid)

Semi‐crystalline poly(L ‐lactic acid) (PLLA) was physically aged below the glass transition temperature for various times to investigate its amorphous phase behavior. During a differential scanning calorimetry heating scan, dual enthalpy recovery endotherms were found to appear in the glass transition region of PLLA, aged at 52 °C, of a particular degree of crystallinity (X_c) within a definite range. Below the lower X_c limit, only the low endotherm corresponding to the free amorphous phase was observed; above the upper X_c limit, only the high endotherm corresponding to the constrained amorphous phase was observed. Dual tan δ peaks in dynamic mechanical analysis confirmed the coexistence of the dual amorphous phases. Both lower and upper limits of the X_c range increased with an increase in isothermal crystallization temperature from the melt. Long‐term physical aging at 52 °C, which did not affect X_c, allowed the evolution of the free amorphous phase to the constrained amorphous phase in PLLA with X_c within the definite range. The effects of physical aging at various temperatures on the enthalpy recovery endotherms were also investigated. Copyright © 2011 Society of Chemical Industry     

Accelerated crystallization of poly(L‐lactide) by physical aging

The low‐temperature physical aging of amorphous poly(L ‐lactide) (PLLA) at 25–50°C below glass transition temperature (T_g) was carried out for 90 days. The physical aging significantly increased the T_g and glass transition enthalpy, but did not cause crystallization, regardless of aging temperature. The nonisothermal crystallization of PLLA during heating was accelerated only by physical aging at 50°C. These results indicate that the structure formed by physical aging only at 50°C induced the accelerated crystallization of PLLA during heating, whereas the structure formed by physical aging at 25 and 37°C had a negligible effect on the crystallization of PLLA during heating, except when the physical aging at 37°C was continued for the period as long as 90 days. The mechanism for the accelerated crystallization of PLLA by physical aging is discussed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

The effect of modification on structure and dynamic mechanical behavior during the processing of acrylic fiber to stabilized fiber

Polyacrylonitrile (PAN) fibers pretreated with potassium permanganate have reduced the time required for stabilization, and also improved mechanical properties of the resultant carbon fibers. In this study, the effect of modification on the stabilization process and the dynamic mechanical properties of PAN fibers have been examined. The beta peak appeared at about 125°C on the loss tangent curves caused by molecular motion in the PAN fiber. Appearing at about 254°C, the alpha peak is attributed to chemical reactions and molecular motion in the formation of the crystalline phase of stabilized fibers. The alpha peak of the modified PAN fiber had lower absorption and had a smaller peak in the temperature range of 212–239°C. This indicated that potassium permanganate acts as a catalyst to lower the reaction temperature by about 20°C of the initial cyclization reaction. The dynamic storage modulus analysis indicated that modified PAN fibers have a lower initial transition temperature and that formation of the ladder polymer is gradual and steady.     

Effect of hydrothermal aging on the thermo‐mechanical properties of a composite dental prosthetic material

The aim of this investigation was to evaluate the long‐tern effects of aging in water on the physical properties of a new class of commercially available dental polymer composites. The selected product consists of a bisphenol a glycidyl methacrylate (Bis‐GMA) resin diluted with triethylene glycol dimethacrylate (TEGDMA) and reinforced with long E‐glass fibers, specifically developed for prosthetic dental bridges. Samples were prepared according to a standard procedure suggested by the producer, and aged in water at 37°C and 70°C up to 32 weeks. Samples were periodically tested in order to assess their mass variation, static flexural modulus and strength, fatigue resistance, and dynamic mechanical thermal behavior. Experimental results evidenced that aging caused two simultaneous phenomena, having opposite effects on the specimen mass. In fact, composites absorbed a certain amount of water (up to 0.8 wt% at 37°C and 1.2 wt% at 70°C) but at the same time a mass loss was detected, which could be attributed to a release of unreacted monomeric species and fragments generated by polymer chain degradation (especially at 70°C). Flexural strength strongly decreased during aging in water, reaching 80% and 45% of the initial value for samples aged for 32 weeks at 37 and 70°C, respectively. Aging practically does not affect flxural modulus, while a sensible reduction of the material fatigue life was observed. Glass transition temperature and the relative activation energy were markedly influenced by the aging in water with effects related to the water uptake and mass loss phenomena.     

Effect of natural fibers on thermal and mechanical properties of natural fiber polypropylene composites studied by dynamic mechanical analysis

The present study deals with the effects of natural fibers on thermal and mechanical properties of natural fiber polypropylene composites using dynamic mechanical analysis. Composites of polypropylene and various natural fibers including kenaf fibers, wood flour, rice hulls, and newsprint fibers were prepared at 25 and 50% (by weight) fiber content levels. One and two percent maleic anhydride grafted polypropylene was also used as the compatibilizer for composites containing 25 and 50% fibers, respectively. Specimens for dynamic mechanical analysis tests were cut out of injection‐molded samples and were tested over a temperature range of ?60 to +120°C. Frequency of the oscillations was fixed at 1 Hz and the strain amplitude was 0.1%, which was well within the linear viscoelastic region. The heating rate was 2°C/min for all temperature scan tests. Storage modulus (E′), loss modulus (E″), and mechanical loss factor (tan δ) were collected during the test and were plotted versus temperature. An increase in storage and loss moduli and a decrease in the mechanical loss factor were observed for all composites indicating more elastic behavior of the composites as compared with the pure PP. Changes in phase transition temperatures were monitored and possible causes were discussed. Results indicated that glass transition was slightly shifted to lower temperatures in composites. α transition temperature was higher in the case of composites and its intensity was higher as well. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4341–4349, 2006     

Dynamic mechanical properties of Al2O3/poly(ether ether ketone) composites

The dynamic mechanical properties of high‐performance polymer matrix composites based on semicrystalline poly(ether ether ketone) (PEEK) and aluminum oxide (Al₂O₃) were evaluated in the temperature range of 30–250°C with a three‐point‐bending mode at a frequency of 1 Hz. The storage modulus and loss modulus changed significantly with the variation of the Al₂O₃ content in the PEEK matrix. The Al₂O₃ reinforcement was more pronounced above the glass‐transition temperature (T_g). A composite containing 60 wt % (33 vol %) Al₂O₃ exhibited about a 78% increase in the storage modulus at 50°C and about a 200% increase at 200°C. However, there was no significant change in the mechanical loss factor and T_g associated with the peak of the mechanical loss factor or loss modulus with the addition of Al₂O₃. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 568–575, 2007     

Physical aging deep in the glassy state of a fully cured polyimide

Physical aging of a fully cured polyimide/glass fiber specimen has been investigated deep in the glassy state using a freely oscillating torsion pendulum (TBA). A single specimen, the physical aging effects of which could be erased by heating to above T_g = 304°C (0.8 Hz), could be used for all experiments. Data were obtained during isothermal aging at different aging temperatures, T_α, (from 10°C to T_g) and during subsequent temperature scans (T_α to 5 to 315°C). The aging rate depended upon the value of T_α relative to both T_g and the β-relaxation temperature, T_β = 139°C (1.3 Hz). Changes in thermomechanical behavior due to aging were localized about T_α. This suggests that only an intermediate portion of the relaxation spectrum participates in, and is affected by, isothermal physical aging. It follows, and is observed, that the intensity of the β-relaxation mechanical loss peak is perturbed most significantly by aging at T_α near T_β. The effect of isothermal aging deep in the glassy state could be essentially eliminated by heating to below T_g. © 1992 John Wiley & Sons, Inc.