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Abstract Aggregation‐induced emission (AIE) luminogens are attractive dyes to probe polymer properties that depend on changes in chain mobility and free volume. When embedded in polymers the restriction of intramolecular motion (RIM) can lead to their photoluminescence quantum yield (PLQY) strong enhancement if local microviscosity increases (lowering of chain mobility and free volume). Nonetheless, measuring PLQY during stimuli, i.e. heat or mechanical stress, is technically challenging; thus, emission intensity is commonly used instead, assuming its direct correlation with the PLQY. Here, by using fluorescence lifetime as an absolute fluorescence parameter, it is demonstrated that this assumption can be invalid in many commonly encountered conditions. To this aim, different polymers are loaded with tetraphenylenethylene (TPE) and characterized during the application of thermal and mechanical stress and physical aging. Under these conditions, polymer matrix transparency variation is observed, possibly due to local changes in refractive index and to the formation of microfractures. By combining different characterization techniques, it is proved that scattering can affect the apparent emission intensity, while lifetime measurements can be used to ascertain whether the observed phenomenon is due to modifications of the photophysical properties of AIE dyes (RIM effect) or to alterations in the matrix optical properties.

Metallic glass formers are a relatively new entry in glass physics, which has attracted large interest in both physics and materials science communities due to the unique mechanical and structural properties of these materials. Physical aging is however one of the main obstacle to their widespread use as it affects their properties at all length scales. The knowledge of the microscopic mechanisms inducing aging and relaxation is therefore extremely important for both fundamental and applied sciences. In this article we present a review of the recent advances made with the X-ray photon correlation spectroscopy technique on the study of the collective particle motion and physical aging in metallic glasses at the atomic level. We show that a careful tuning of the sample preparation or the application of specific thermal protocols have the potential to drive the glass into more aged or rejuvenated microscopic configurations with different stabilities.

Abstract Background To explore whether differences between men and women in the sensitivity to (strength of the association) and/or in the exposure to determinants (prevalence) contribute to the difference in physical functioning, with women reporting more limitations. Methods Data of the Doetinchem Cohort Study was used (n = 5856, initial ages 26–70 years), with follow-up measurements every 5 years (up to 20). Physical functioning (subscale SF-36, range:0–100), sex (men or women) and a number of socio-demographic, lifestyle- and health-related determinants were assessed. Mixed-model multivariable analysis was used to investigate differences between men and women in sensitivity (interaction term with sex) and in exposure (change of the sex difference when adjusting) to determinants of physical functioning. Results The physical functioning score among women was 6.55 (95%CI:5.48,7.61) points lower than among men. In general, men and women had similar determinants, but pain was more strongly associated with physical functioning (higher sensitivity), and also more prevalent among women (higher exposure). The higher exposure to low educational level and not having a paid job also contributed to the lower physical functioning score among women. In contrast, current smoking, mental health problems and a low educational level were more strongly associated with a lower physical functioning score among men and lower physical activity and higher BMI were more prevalent among men. Conclusions Although important for physical functioning among both men and women, our findings provide no indications for reducing the difference in physical functioning by promoting a healthy lifestyle but stress the importance of differences in pain, work and education.

Physical aging deals with slow property changes over time caused by molecular rearrangements. This is relevant for non-crystalline materials such as polymers and inorganic glasses, both in production and during subsequent use. The Narayanaswamy theory from 1971 describes physical aging—an inherently nonlinear phenomenon—in terms of a linear convolution integral over the so-called material time ξ. The resulting “Tool–Narayanaswamy (TN) formalism” is generally recognized to provide an excellent description of physical aging for small, but still highly nonlinear, temperature variations. The simplest version of the TN formalism is single-parameter aging according to which the clock rate dξ/dt is an exponential function of the property monitored. For temperature jumps starting from thermal equilibrium, this leads to a first-order differential equation for property monitored, involving a system-specific function. The present paper shows analytically that the solution to this equation to first order in the temperature variation has a universal expression in terms of the zeroth-order solution, R0(t). Numerical data for a binary Lennard–Jones glass former probing the potential energy confirm that, in the weakly nonlinear limit, the theory predicts aging correctly from R0(t) (which by the fluctuation–dissipation theorem is the normalized equilibrium potential-energy time-autocorrelation function).

Optimizing the pigment volume concentration of zinc phosphate pigments can protect Al alloy 6101 from alkaline media. Additionally, zinc phosphate pigments form a shielding film on the substrate and facilitate stopping the penetration of aggressive corrosion ions. The efficiency of eco-friendly zinc phosphate pigments is almost 98% during the corrosion analysis. A comparative study of physical aging of neat epoxy and Zinc Phosphate (ZP) pigment-modified epoxy coatings on Al alloy 6101 was conducted in Xi’an, China, for one year in all four seasons, where in summer for 3 months, results degraded more due to high UV radiation and humidity; it is found that peeling force of ZP pigments modified epoxy coatings is 50% higher of than that of the neat epoxy coatings though both peel-off adhesion strength and scratch test visibility decreased in both coatings; The electrochemical resistance of ZP pigments modified epoxy coatings is about 30% higher of than that of neat epoxy coatings, the corrosion rate of ZP pigments modified epoxy coatings is about 70% lower of than that of neat epoxy coatings, moreover the gloss retention is 20% higher in the modified epoxy; Optical surface observation of the coatings showed that the ZP modified epoxy coating could effectively restrict the crack and shrinkage in coatings after aging experimentation in the natural environment.

Abstract Background This study explores whether a sex difference in sensitivity to (strength of the association) and/or in exposure to (prevalence) determinants of gait speed contributes to the observed lower gait speed among older women compared to men. Methods Data from the Longitudinal Aging Study Amsterdam (LASA) were used. In total 2407 men and women aged 55–81 years were included, with baseline measurements in 1992/2002 and follow-up measurements every 3–4 years for 15/25 years. Multivariable mixed model analysis was used to investigate sex differences in sensitivity (interaction term with sex) and in exposure to (change of the sex difference when adjusted) socio-demographic, lifestyle, social and health determinants of gait speed. Results Women had a 0.054 m/s (95 % CI: 0.076 − 0.033, adjusted for height and age) lower mean gait speed compared to men. In general, men and women had similar determinants of gait speed. However, higher BMI and lower physical activity were more strongly associated with lower gait speed in women compared to men (i.e. higher sensitivity). More often having a lower educational level, living alone and having more chronic diseases, pain and depressive symptoms among women compared to men also contributed to observed lower gait speed in women (i.e. higher exposure). In contrast, men more often being a smoker, having a lower physical activity and a smaller personal network size compared to women contributed to a lower gait speed among men (i.e. higher exposure). Conclusions Both a higher sensitivity and higher exposure to determinants of gait speed among women compared to men contributes to the observed lower gait speed among older women. The identified (modifiable) contributing factors should be taken into account when developing prevention and/or treatment strategies aimed to enhance healthy physical aging. This might require a sex-specific approach in both research and clinical practice, which is currently often lacking.

The first commercial hollow fiber and flat sheet gas separation membranes were produced in the late 1970s from the glassy polymers polysulfone and poly(vinyltrimethyl silane), respectively, and the first industrial application was hydrogen recovery from ammonia purge gas in the ammonia synthesis loop. Membranes based on glassy polymers (polysulfone, cellulose acetate, polyimides, substituted polycarbonate, and poly(phenylene oxide)) are currently used in various industrial processes, such as hydrogen purification, nitrogen production, and natural gas treatment. However, the glassy polymers are in a non-equilibrium state; therefore, these polymers undergo a process of physical aging, which is accompanied by the spontaneous reduction of free volume and gas permeability over time. The high free volume glassy polymers, such as poly(1-trimethylgermyl-1-propyne), polymers of intrinsic microporosity PIMs, and fluoropolymers Teflon® AF and Hyflon® AD, undergo significant physical aging. Herein, we outline the latest progress in the field of increasing durability and mitigating the physical aging of glassy polymer membrane materials and thin-film composite membranes for gas separation. Special attention is paid to such approaches as the addition of porous nanoparticles (via mixed matrix membranes), polymer crosslinking, and a combination of crosslinking and addition of nanoparticles.

Epoxy systems are widely used as matrix resins for fiber reinforced polymers (FRP) and, therefore, often have to withstand harsh environmental conditions. Especially in marine and offshore environments, moisture or direct water contact leads to water absorption into the epoxy resin. As a result, the mechanical properties change during application. Since diffusion at room or colder temperatures is slow, industry and academia typically use accelerated aging methods at elevated temperatures for durability prediction. However, as the water-polymer interaction is a complex combination of plasticization, physical aging, and molecular interaction, all of these mechanisms are expected to be affected by the ambient temperature. To reveal the impact of aging time and temperature on the thermo-mechanical properties of an amine-epoxy system, this publication includes various hygrothermal aging conditions, like water bath and relative humidity aging at temperatures ranging from 8°C to 70°C and relative humidity from 20% to 90%. Thus, it is demonstrated via long-term aging, DMTA and FTIR investigations that, e.g., strength, stiffness, strain to failure, and the glass transition temperature (Tg) can differ significantly depending on aging time and temperature. For example, it can be shown that water absorption at cold temperatures leads to the strongest and longest-lasting reduction in strength, although the maximum water absorption amount is lower than at higher temperatures. For the application, this means that strength differences of up to 26% can be obtained, depending on the aging method selected. Furthermore, it can be shown that conventional prediction models, such as Eyring correlation, which consider the mobility of the molecular structure for the prediction of thermo-mechanical properties, can only be used to a limited extent for prediction in hygrothermal aging. The reasons for this are seen to be, in particular, the different characteristics of the water-polymer interactions depending on the aging temperature. While plasticization dominates in cold conditions, relaxation and strong water-molecule bonds predominate in warm conditions.

The effect of physical aging on the viscoelastic (VE) behavior of epoxy resin is investigated experimentally performing strain-controlled tests at various temperatures on specimens aged at different temperatures (TA) for different times (tA). The aging effect is analyzed using as a framework Schapery's type of thermo-aging-rheologically simple (T-A-R simple) VE model that contains aging-state and test-temperature dependent shift factor. Experiments show that in first approximation, the shift factor can be presented as the product of aging related shift factor aA and temperature related factor aT. It is found that for short aging times the change rate of the aging shift factor with tA does not depend on TA, whereas for long tA at high TA the rate increases. Shift factors alone are not able to explain differences in relaxation curves for almost “fully” aged specimens aged at different high TA, It is shown that a T-A-R complex VE model with two additional aging-dependent functions can describe the observed discrepancies.

The influence of thermal-oxidative aging on flexural property of carbon fiber bismaleimide resin composites was investigated via three point flexural test. The mass loss behavior, fracture morphology, dynamic mechanical property and IR spectrum of the composites were analyzed at different aging time. The results show that with the increase of aging time, the mass loss rate at 100℃ aging temperature gradually tends to stabilize and the mass loss rate at 180℃ aging temperature gradually increases. There is only physical aging at 100℃ aging temperature and no new substance is generated; but at the aging temperature 180℃, the chemical aging occurs and results in thermal aging and oxidation reactions, causing the degradation of matrix and interface properties. The influence of thermal-oxidative aging on flexural strength of composites is greater than flexural modulus.

Abstract Polyethylene terephthalate (PET) is the most important mass‐produced thermoplastic polyester used as a packaging material. Recently, thermophilic polyester hydrolases such as TfCut2 from Thermobifida fusca have emerged as promising biocatalysts for an eco‐friendly PET recycling process. In this study, postconsumer PET food packaging containers are treated with TfCut2 and show weight losses of more than 50% after 96 h of incubation at 70 °C. Differential scanning calorimetry analysis indicates that the high linear degradation rates observed in the first 72 h of incubation is due to the high hydrolysis susceptibility of the mobile amorphous fraction (MAF) of PET. The physical aging process of PET occurring at 70 °C is shown to gradually convert MAF to polymer microstructures with limited accessibility to enzymatic hydrolysis. Analysis of the chain‐length distribution of degraded PET by nuclear magnetic resonance spectroscopy reveals that MAF is rapidly hydrolyzed via a combinatorial exo‐ and endo‐type degradation mechanism whereas the remaining PET microstructures are slowly degraded only by endo‐type chain scission causing no detectable weight loss. Hence, efficient thermostable biocatalysts are required to overcome the competitive physical aging process for the complete degradation of postconsumer PET materials close to the glass transition temperature of PET.

Mixed-matrix membranes (MMMs) are membranes that are composed of polymers embedded with inorganic particles. By combining the polymers with the inorganic fillers, improvements can be made to the permeability compared to the pure polymer membranes due to new pathways for gas transport. However, the fillers, such as hyper cross-linked polymers (HCP), can also help to reduce the physical aging of the MMMs composed of a glassy polymer matrix. Here we report the synthesis of two novel HCP fillers, based on the Friedel–Crafts reaction between a tetraphenyl methane monomer and a bromomethyl benzene monomer. According to the temperature and the solvent used during the reaction (dichloromethane (DCM) or dichloroethane (DCE)), two different particle sizes have been obtained, 498 nm with DCM and 120 nm with DCE. The change in the reaction process also induces a change in the surface area and pore volumes. Several MMMs have been developed with PIM-1 as matrix and HCPs as fillers at 3% and 10wt % loading. Their permeation performances have been studied over the course of two years in order to explore physical aging effects over time. Without filler, PIM-1 exhibits the classical aging behavior of polymers of intrinsic microporosity, namely, a progressive decline in gas permeation, up to 90% for CO2 permeability. On the contrary, with HCPs, the physical aging at longer terms in PIM-1 is moderated with a decrease of 60% for CO2 permeability. 13C spin-lattice relaxation times (T1) indicates that this slowdown is related to the interactions between HCPs and PIM-1.

Poly(N-isopropylacrylamide) (PNIPA), as a smart polymer, can be applied for drug delivery systems. This amorphous polymer can be exposed on a structural recovery process during the storage and transport of medicaments. For the physical aging times up to one year, the structural recovery for PNIPA was studied by advanced thermal analysis. The structural recovery process occurred during the storage of amorphous PNIPA below glass transition and could be monitored by the differential scanning calorimetry (DSC). The enthalpy relaxation (recovery) was observed as overshoot in change heat capacity at the glass transition region in the DSC during heating scan. The physical aging of PNIPA was studied isothermally at 400.15 K and also in the non-isothermal conditions. For the first time, the structural recovery process was analyzed in reference to absolute heat capacity and integral enthalpy in frame of their equilibrium solid and liquid PNIPA.

The ductile-brittle transition behaviour of organo modified montmorillonite-based Poly(lactic acid) films (PLA/o-MMT) was analysed using the Essential Work of Fracture (EWF) methodology, Small Punch Tests (SPT) and Enthalpy relaxation analysis. While the EWF methodology could only be applied successfully to de-aged samples, small punch test (SPT) was revealed as more effective for a mechanical characterization during the transient behaviour from ductile to brittle. According to differential scanning calorimetry (DSC) results, physical aging at 30°C of PLA/o-MMT samples exhibited slower enthalpy relaxation kinetics as compared to the pristine polymer. Although all samples exhibited an equivalent thermodynamic state after being stored one week at 30°C, significant differences were observed in the mechanical performances. These changes could be attributed to the toughening mechanisms promoted by o-MMT.

This study explores the effect of physical aging and/or crystallization on the supersaturation potential and crystallization kinetics of amorphous active pharmaceutical ingredients (APIs). Spray-dried, fully amorphous indapamide, metolazone, glibenclamide, hydrocortisone, hydrochlorothiazide, ketoconazole, and sulfathiazole were used as model APIs. The parameters used to assess the supersaturation potential and crystallization kinetics were the maximum supersaturation concentration (Cmax,app), the area under the curve (AUC), and the crystallization rate constant (k). These were compared for freshly spray-dried and aged/crystallized samples. Aged samples were stored at 75% relative humidity for 168 days (6 months) or until they were completely crystallized, whichever came first. The solid-state changes were monitored with differential scanning calorimetry, Raman spectroscopy, and powder X-ray diffraction. Supersaturation potential and crystallization kinetics were investigated using a tenfold supersaturation ratio compared to the thermodynamic solubility using the µDISS Profiler. The physically aged indapamide and metolazone and the minimally crystallized glibenclamide and hydrocortisone did not show significant differences in their Cmax,app and AUC when compared to the freshly spray-dried samples. Ketoconazole, with a crystalline content of 23%, reduced its Cmax,app and AUC by 50%, with Cmax,app being the same as the crystalline solubility. The AUC of aged metolazone, one of the two compounds that remained completely amorphous after storage, significantly improved as the crystallization kinetics significantly decreased. Glibenclamide improved the most in its supersaturation potential from amorphization. The study also revealed that, besides solid-state crystallization during storage, crystallization during dissolution and its corresponding pathway may significantly compromise the supersaturation potential of fully amorphous APIs.

The effect of a quenching treatment applied on heated cast sheet extruded films of two poly(lactic acid) (PLA) commercial grades, with different optical purities, was studied. The thermal and mechanical properties of the films, as well as their fracture behavior, were assessed by differential scanning calorimetry (DSC), tensile tests, and the essential work of fracture (EWF) approach. The heating-quenching treatment causes a de-aging effect with an increase in the free volume of polymer chains evidenced by a decrease in the glass transition temperature (Tg) and a decrease in the tensile stiffness and yield stress. As a result, there is an abrupt increase in ductility, finding a dramatic change in the fracture behavior, from brittle to ductile. The use of digital image correlation (DIC) of the strain field analysis during fracture testing has allowed relating the decrease on the yield stress promoted by quenching with the crack propagation kinetics. The use of the EWF method to characterize the fracture toughness of PLA has allowed to measure this enhancement on toughness, finding that the specific essential work of fracture (we) and the plastic term (βwp) parameters increased 120% and 1200%, respectively, after the quenching process.

The in-plane (plane stress) fracture toughness of two polyester (PET, PETG) sheets were assessed using the essential work of fracture (EWF) method after thermal and hygrothermal aging performed just below glass temperature. This ensured that physical aging takes place. On the aged sheets the yield stress (σy), enthalpy relaxation (ΔH) and EWF parameters were determined. It was observed that the essential work of fracture component related to the specific yielding (we,y) is suitable for assessing physical aging - independently of the humidity content. A good linear correlations exists between we,y, σy and ΔH.