Influence of thermooxidative aging on the static and dynamic mechanical properties of long‐glass‐fiber‐reinforced polyamide 6 composites

The static and dynamic mechanical properties, thermal behaviors, and morphology of pure long‐glass‐fiber‐reinforced samples [polyamide 6 (PA6)/long glass fiber (LGF)] with different thermal exposure times at 160°C were studied by comparison with stabilized samples in this study. The aging mechanism of the PA6/LGF samples under heat and oxygen was studied with the methods of thermal Fourier transform infrared (FTIR), differential scanning calorimetry, dynamic mechanical analysis, scanning electron microscopy (SEM), and so on. The results indicate that the static mechanical strength, melting temperature, and crystallization temperature decreased because of the decomposition of the macromolecular chain of PA6 resin and the debonding of the interface between the glass fibers and matrix. The glass‐transition temperature and crystallinity also increased and decreased, respectively, after aging. The macromolecular chain decomposition dominated in the subsequent aging process; this resulted in many sharp and brittle microcracks appearing on the surfaces of the aged samples, as shown by SEM and the FTIR spectra. The existence of stabilizers endowed the PA6/LGF composites with better retention of static and dynamic mechanical properties. The reason was that the metal ions of the copper salt antioxidant acted as an anti‐aging catalyst in the reinforced PA6 system. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39594.     

Effects of prior aging at 288°C in air and in argon environments on creep response of PMR‐15 neat resin

The creep behavior of PMR‐15 neat resin, a polyimide thermoset polymer, aged in air and in argon environments at 288°C for up to 1000 h was evaluated. Creep tests were performed at 288°C at creep stress levels of 10 and 20 MPa. Creep periods of at least 25‐h in duration were followed by 50‐h periods of recovery at zero stress. Prior isothermal aging increased the elastic modulus and significantly decreased the polymer's capacity to accumulate creep strain. The aging environment had little influence on creep and recovery behaviors. However, aging in air dramatically degraded the tensile strength of the material. Dynamic mechanical analysis revealed an increase in the glass transition temperature from ∼330°C to ∼336°C after 1000 h in argon or in air at 288°C. The rise in the glass transition temperature with aging time is attributed to an increase in the crosslink density of the PMR‐15 polyimide. Increase in the crosslink density due to aging in both air and argon environments is likely behind the changes in the elastic modulus and the decreased capacity for inelastic straining. A visibly damaged surface layer of ∼0.16 mm thickness was observed in specimens aged in air for 1000 h. Results indicate that the unoxidized core material governs the overall mechanical response, whereas the oxidized surface layer causes a decrease in tensile strength by acting as a crack initiation site and promoting early failures. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Evolution of the amorphous fraction of PEEK during annealing at atmospheric and high pressure above the glass transition temperature

The constrained fraction of the amorphous phase of semi‐crystalline polymers is in an out‐of‐equilibrium state so that "physical aging"‐like features can be observed (e.g., by calorimetry) even above the glass transition temperature. This was already addressed in the literature in several semi‐crystalline polymers at atmospheric pressure. Despite the well‐known influence of pressure on molecular mobility, the pressure‐sensitivity of these microstructure rearrangements has never been tackled. This study focuses on annealing in highly pressurized Poly‐Ether‐Ether‐Ketone (PEEK), compared with atmospheric pressure. The phenomenon is tracked by ex‐situ Differential Scanning Calorimetry (DSC). A significant influence of pressure is evidenced, without any complete equivalence with temperature. Indeed, pressure seems to confine rearrangements within spatially limited domains. The stability and coexistence of reorganization processes upon successive annealings is also investigated. Finally, relationships between constrained and free amorphous phase rearrangements are discussed via the different glass transition shifts observed after atmospheric or high pressure annealing. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1148‐1157, 2013     

Characterization of a thermoset by thermal analysis techniques: Criterion to assign the value of the α‐transition temperature by dielectric analysis

A cured thermoset composed of diglycidyl ether of bisphenol A and m‐xylylene diamine as the cure agent was studied with different thermal analysis techniques, including differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and dielectric analysis (DEA). DSC was used to measure the glass‐transition temperature and to check the absence of the heat of reaction. DMA and DEA were used to show the existence of two transitions in the temperature range of −100 to 240°C. The transition at a low temperature corresponded to the β transition. The second one, at a higher temperature, was associated with an α transition. The β transition followed Arrhenius behavior, whereas the α transition followed Vogel behavior. For an analysis of the α transition, different equations, such as the Havriliak–Negami, Vogel, and Williams–Landel–Ferry equations, were used. Important differences related to the fitting parameters were found that depended on the type of equation and the operation mode used. For this reason, a new method for calculating the α‐transition temperature was examined. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2027–2037, 2005     

Enthalpy relaxation of photopolymerized multilayered thiol‐ene films

Multilayered thiol‐ene network films with two and three different components were fabricated by spin coating and photopolymerization. The distinctive glass transition temperatures of each layer component were observed at corresponding glass transition regions of each bulk sample. Sub‐T_g aging of 10‐, 21‐, and 32‐layered thiol‐ene films was investigated in terms of enthalpy relaxation. Enthalpy relaxation of each layer component occurred independently and presented the characteristic time and temperature dependency. Overlapped unsymmetrical bell‐shaped enthalpy relaxation distribution having peak maximum at T_g‐10°C of each layer component was observed, resulting in broad distribution of enthalpy relaxation over wide temperature range. In addition, enthalpy relaxation of each layer component in the multilayered thiol‐ene films was significantly accelerated comparing to that of bulk thiol‐ene samples. Dynamic mechanical thermal properties of multilayered thiol‐ene films also showed two and three separated glass transition temperature. However, for 32‐layered thiol‐ene film consisting of three different layer components, glass transition and damping region are overlapped and the width is extended more than 100°C. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

X‐ray diffraction,Raman, and differential thermal analyses of the thermal aging of a Kevlar®‐PBI blend fabric

A previous study of the effects of thermal aging on the tensile properties of a fabric made of a 60–40 wt % blend of Kevlar and PBI fibers has shown that exposure to elevated temperatures between 190 and 320°C results in a rapid decrease in tensile breaking force retention. In this article, X‐ray diffraction and Raman spectroscopy analyses were carried out to evaluate the consequences of thermal aging on the material's crystallinity. Differential thermal analyses were also undertaken to examine the evolution of the glass transition temperature of PBI following thermal exposure. X‐ray diffraction profiles show a gradual increase in the crystallinity with temperature and aging time, whereas a complete disappearance of spectral lines for aged samples in Raman analysis suggests instead a decrease in crystallinity as a consequence of exposure to elevated temperatures. The seemingly contradictory outcome obtained when using the two techniques led to the proposal of a new, alternative hypothesis to explain the observed results. This hypothesis involves two simultaneous events that occur during thermal aging: the increase of crystallite size in the direction parallel to coplanar sheets, and the disruption of the crystalline lattice in the direction perpendicular to those sheets. The glass transition temperature of PBI was found to shift towards the lower temperatures after thermal aging, a phenomenon that can be associated with random polymer chain scission caused by thermal aging. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

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     

Evaluation of the tensile properties and thermal stability of ultrahigh‐molecular‐weight polyethylene fibers

The thermal stability of ultrahigh‐molecular‐weight polyethylene (UHMWPE) should be paid attention in its applications, although the fiber has excellent flexible tensile properties. The measurements for two kinds of UHMWPE fibers, Dyneema SK65 (The Netherlands) and ZHF (Beijing, China), were carried out at different annealing temperatures and for different aging times. Experimental and regression analysis results showed that the aging behavior of the fibers followed an exponential attenuation with the annealing temperature and aging time. The critical temperature for the safe use of the fibers was equal to or lower than 70°C and depended on the glass‐transition temperature; this was validated by tensile tests. The difference between the two fibers in the thermal properties resulted from the intrinsic supermolecular structures of the two fibers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 310–315, 2005     

Environmental aging of cold‐cured epoxy‐silica hybrids prepared by sol−gel process

The article investigates the effects of long term environmental aging on thermal and mechanical properties of epoxy‐silica hybrids. These nanostructured materials, prepared by non‐aqueous sol‐gel process and in situ generation of nanosilica during epoxy curing at room temperature, present the potential to be used as cold‐cured adhesives for civil engineering and Cultural Heritage applications. A specifically developed conditioning procedure for these cold‐cured nanostructured materials was applied before moisture/water absorption tests. The work evidenced the superior durability of the studied epoxy‐silica hybrid, which kept its performances in severe, but realistic, environmental conditions with respect to traditional epoxy adhesives. The reduction in the glass transition temperature and mechanical properties of the studied epoxy‐silica hybrid, observed in the first weeks of environmental aging, was followed by a significant recovery. This was attributed to two concomitant phenomena: the reactivation of the incomplete curing reactions in the epoxy domains and the continuation of the condensation reactions in the siloxane domains activated by the absorbed water. Finally, the Fickian behavior, presented by the studied epoxy‐silica hybrid, was used as an indirect indication of the homogeneity of achieved microstructure, with well dispersed silica nanostructures in the epoxy network. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40093.     

Aging of the Binders GAP-N100 and HTPB-IPDI Investigated by Torsion-DMA

The aging of the binders GAP-N100 and HTPB-IPDI was investigated by DMA in torsion mode to find out the changes in the storage shear modulus G′(ω), loss shear modulus G″(ω) and in the glass transition temperature T_G. The forced sinusodial deformation method was used with measuring frequencies between 0.1 Hz and 56.2 Hz. A measurement temperature range between −100°C and +50°C was applied. The DMA instrument was a Rheometrics Dynamical Spectrometer, type RDS II/7700. Non-aged GAP-N100 shows a well defined steep glass transition between −40°C and −25°C, which is found with aged samples also but shifted to higher temperatures. The glass transition of the binder HTPB-IPDI lies between −70°C and −10°C, but HTPB-IPDI has not a well defined glass transition. With aging it looses its glass transition, which can be seen by a smoothing out of the transition step in the curve G′(ω)=f(T). The behaviour and the differences of these binders are explainable on a molecular basis. The systematic shift of the glass transition temperature of the non-aged and aged GAP-N100 as well as of the non-aged HTPB-IPDI is describable by the Williams-Landel-Ferry equation. This equation was used to extrapolate the values of the glass transition temperatures to shear rates possible during operational use of propellants.     

Ultraviolet light absorber mobility in crosslinked coatings: Experiments and modeling

The diffusion of an ultraviolet absorber (UVA) across a concentration step change in an acrylic melamine clearcoat was measured via micro-ultraviolet spectroscopy. Concentration profiles were obtained after diffusion times of 4–200 h at steady temperatures of 70, 80, and 90 °C. The glass transition temperature of the coating was measured via dynamic mechanical analysis for each time–temperature pair, and T_g was observed to increase with thermal aging, with a faster rate of increase at higher aging temperatures. The change in T_g was modeled using a first-order dependence on the deviation from a long-time T_g asymptote. The diffusion coefficient was then represented by a free volume expression, and the combination provided an accurate model of the measured concentration profiles. The time-dependent increases in glass transition temperature helped to explain why UVA diffusion does not alleviate concentration gradients created by photooxidation under natural weathering conditions.     

Effects of storage aging on the cure kinetics of T700/BMI prepregs for advanced composites

The effects of room temperature aging on the cure kinetics of a bismaleimide (BMI) matrix prepreg have been characterized by different time and storage conditions. The study has focused on the stability of BMI matrix carbon fiber prepregs, when exposed to controlled environmental conditions before being used in composite manufacturing. The effects of aging on reactivity, glass transition temperature, and process window have been investigated by differential scanning calorimetrer through dynamic and isothermal tests. A theoretical kinetic model for epoxy matrix prepregs, developed in previous studies, has been applied to the cure of both aged and virgin BMI matrix. The model is able to satisfactorily describe the effect of processing variables such as temperature and degree of cure during the curing of the composite under different conditions (curing temperature and heating rate). The effects of diffusion‐controlled phenomena on the cure kinetics, associated with changes in glass transition temperature as a function of the degree of cure, have been taken into account in the formulation of an nth‐order kinetic model. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Synthesis and characterization of poly(vinyl 2,4,6‐trinitrophenylacetal) as a new energetic binder

Poly(vinyl alcohol) was modified by an aldehyde acetal reaction with 2,4,6‐trinitrophenylacetaldehyde to give a new energetic polymer poly(vinyl 2,4,6‐trinitrophenylacetal) (PVTNP). The structure of PVTNP was characterized by elemental analysis, ultraviolet–visible spectroscopy, Fourier transform infrared spectroscopy, and nuclear magnetic resonance spectra. The glass‐transition temperature of PVTNP was evaluated by differential scanning calorimetry (DSC), and the thermal stability of PVTNP was tested by differential thermal analysis (DTA) and thermogravimetric analysis (TGA). DSC traces showed that the PVTNP polymer had one single glass‐transition temperature at 105.3°C. DTA and TGA curves showed that the thermooxidative degradation of PVTNP in air was a three‐step reaction, and the percentage of degraded PVTNP reached nearly 100% at 650°C. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Self‐healing materials for structural applications

Self‐healing materials for structural applications offer considerable practical benefits because they would allow to overcome the difficulties connected to damage diagnosis and repair. In this article, a process active at very low temperature for the repair of damaged structural material is shown. The self‐repair function is based on the metathesis polymerization of ENB activated by Hoveyda–Grubbs' first generation catalyst. The self‐healing epoxy mixture, containing the catalyst powder allows a cure temperature up to 180°C. Dynamic mechanical analysis was used to determine mechanical parameters. The autorepair composite shows a high modulus in a wide temperature range, a glass transition temperature at about 100°C and a self‐healing efficiency of about 95%. POLYM. ENG. SCI., 54:777–784, 2014. © 2013 Society of Plastics Engineers     

Effect of physical aging on the microstructure and dynamic mechanical properties of poly(ether sulfone) copolymer

Effects of physical aging on the submicroscopic structure and dynamic mechanical properties of amorphous poly(ether sulfone) copolymer film were studied by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and electron‐microscopy measurements. Heat flow responses were measured after annealing the amorphous samples obtained, by quenching the melt into an ice‐water bath close to but below the glass transition temperature. The extent of aging is related to the supercooling from the glass transition temperature and to the aging time. The activation energy of the aging process was estimated by the Williams–Watt expression (Williams and Watts, Trans Faraday Soc 1970, 66, 80). A systematic study of the influence of aging on the dynamic mechanical properties of poly(ether sulfone) copolymer has also been made. During isothermal annealing, the increase of the temperature of tan δ peak for the α and β′ relaxation with aging time has been observed. The aging in the zone of the β peak has also been investigated and an interpretation of the results was proposed on the basis of foregone theories. The result of electron‐microscopy investigation indicates that poly(ether sulfone) copolymer has formed a local order structure during the physical aging. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 530–534, 2006     

Ultraporous poly(lactic acid) scaffolds with improved mechanical performance using high‐pressure molding and salt leaching

A novel processing technique, i.e. high‐pressure compression molding/salt leaching, was developed to fabricate ultraporous poly(lactic acid) (PLA) scaffolds. The optimized composition was studied in relation to the porosity, pore morphology, thermal property, and mechanical performance of the PLA scaffolds. At a porogen (CaCO₃) content of 90 wt %, the scaffolds have an interconnected open pore structure and a porosity above 80%. It was truly interesting that the structural stability of high‐pressure molded scaffolds was remarkably improved based on the fact that its glass transition temperature (83.5°C) increased about 20°C, as compared to that of the conventional compression‐molded PLA (60°C), which is not far from physiological temperature (～37°C) at the risk of structural relaxation or physical aging. More importantly, the mechanical performance of PLA scaffolds was drastically enhanced under optimized processing conditions. At pressure and temperature of 1000 MPa and 190°C, the porous PLA scaffolds attained a storage modulus of 283.7 MPa, comparable to the high‐end value of trabecular bone (250 MPa) ever reported. In addition, our prepared PLA scaffolds showed excellent cellular compatibility and biocompatibility in vitro tests, further suggesting that the high‐pressure molded PLA scaffolds have high potential for bone tissue engineering applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3509–3520, 2013     

Aging behavior of a hot‐cured epoxy system

The thermal and hydro‐thermal aging of a hot‐cured epoxy system (diglycidylether of bisphenol A (DGEBA) + dicyandiamide (DDA)) in the glassy state is revisited using DSC and IR attenuated total reflection spectroscopy. Because of the diffusion of DDA from the solid particles into the liquid DGEBA matrix, curing produces a highly crosslinked amorphous matrix that contains low crosslinked amorphous regions. After full curing, the network possesses a relatively low molecular mobility and no residual reactive groups. Thermal and hydro‐thermal loading is performed at 60°C, well below the principal glass transition temperature (T_g1 = 171°C). Both aging regimes cause significant chemical and structural changes to the glassy epoxy. It undergoes a phase separation of relatively mobile segments inside the low mobile matrix, providing a second glass transition that shifts from T_g2 = 86–114°C within 108 days of aging. This phase separation is reversible on heating into the viscoelastic state. Hydro‐thermal aging leads to a reversible and a nonreversible plasticizing effect as well. On thermal aging, no chemical changes are observed but hydro‐thermal aging causes significant chemical modifications in the epoxy system. These modifications are identified as a partial degradation of crosslinks produced by the cyano groups of the DDA and correspond to the nonreversible plasticitation. These changes in the cured epoxy should exert an influence on the mechanical properties of an adhesive bond. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Testing of polysulfone for applications in nuclear facilities

Polysulfone Tecason S samples, designed for use in nuclear facilities, were aged under different conditions to simulate their long‐term use in nuclear power plants. The specimens, with thicknesses of 4 mm, were irradiated with ⁶⁰Co γ rays in oxygen and/or in air at different temperatures and thermally aged at 180°C. For all samples, the glass‐transition temperature, the stepwise change in the heat capacity at the glass‐transition temperature, and the oxidative induction temperature were measured with differential scanning calorimetry. Simultaneously, the mechanical properties were determined and correlated with the results obtained by differential scanning calorimetry. Although the material was aged under very harsh conditions (irradiation in oxygen with absorbed doses up to 500 kGy and thermal aging at 180°C up to 115 days), the detected changes were relatively small. Nevertheless, a tendency of the glass‐transition temperature and oxidative induction temperature to decrease with advanced material degradation was evident. The color changes of the cross‐sectional slices of some samples clearly indicated that the degradation was due to diffusion‐limited oxidation not homogeneously distributed throughout the sample bulk. In addition, samples from the near surface layers and from the center of the sample were examined. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and nonlinear optical properties of a novel X‐type polyester containing dicyanovinylnitroresorcinoxy groups with enhanced thermal stability of dipole alignment

A novel X‐type polyester (5) containing 4‐(2′,2′‐dicyanovinyl)‐6‐nitroresorcinoxy groups as nonlinear optical (NLO) chromophores, which constitute parts of the polymer backbone, was prepared and characterized. Polyester 5 is soluble in common organic solvents such as N,N‐dimethylformamide and acetone. Polyester 5 shows thermal stability up to 300 °C from thermogravimetric analysis with a glass transition temperature obtained from differential scanning calorimetry of near 108 °C. The second harmonic generation (SHG) coefficient (d₃₃) of poled polymer films at the 1064 nm fundamental wavelength is 2.99 pm V^?1. The dipole alignment exhibits thermal stability even at 7 °C above the glass transition temperature, and no significant SHG decay is observed below 115 °C due to the partial main‐chain character of the polymer structure, which is acceptable for NLO device applications. © 2013 Society of Chemical Industry     

The effect of isothermal aging on transverse crack development in carbon fiber reinforced cross-ply laminates

An investigation into the effect of isothermal aging on the development of transverse cracks in cross-ply laminates of two high temperature composite systems was performed. The composite materials investigated were BASF X5260/640–800 and DuPont Avimid K/IM6. Changes in the glass transition temperature, composite weight loss, crack density, and mode I intralaminar fracture toughness were monitored during isothermal aging in air at 177°C for up to 2232 h. The two laminate configurations used in this study include two variations of the generic cross-ply configuration [0₂/90_n]_s, in which n equals 1 and 2. The results of this investigation show that a layer of degraded material forms at the surface of the X5260/640–800 bismaleimide laminates and that the thickness of the degraded layer increases with aging time. After 744 h of aging, transverse cracks form in the surface plies and an increasing crack density evolves as aging time is increased; however, transverse cracks do not form in the inner 90° ply groups with aging during the time period investigated. The Avimid K/IM6 thermoplastic polyimide laminates, which show evidence of cracking prior to aging, do not exhibit any significant change in crack density with aging. The results of the aging experiments also show that the bismaleimide system exhibits a weight loss of 1.5% and an increase in glass transition temperature from 250°C to 300°C after 2232 h of aging at 177°C, while the thermoplastic polyimide system shows a weight loss of only 0.05% and an increase in glass transition temperature from 280 to 285°C after 2232 h. Changes in the resistance to crack formation are also seen in these materials during aging. The mode I intralaminar fracture toughness, a measure of resistance to transverse crack formation, shows a 50% decrease after aging for 2232 h for the bismaleimide system, while the behavior exhibited by the thermoplastic polyimide shows little evidence of a reduction.