Aging Of Polycarbonate Research Articles

Modeling and tracing of polycarbonate (PC) degradation in soil microcosm with a PC microplastics quantification method based on pyrolysis GC–MS

Understanding the migration and transformation of polycarbonate (PC) plastic wastes in the natural environment is crucial for assessing their environmental impact and bioremediation. In this study, PC plastic degradation was modeled and traced in soil microcosm by investigating physiochemical properties changes of PC, the formation of microplastics, and changes in soil microbial communities. Notably, PC microplastics quantification method was also successfully devised by pyrolysis gas chromatography mass spectrometry and also applied herein. Through gel permeation chromatography analysis, the molecular weight of the naturally aged PC film obviously reduced, whereas no change for unaged ones. After 12 months of soil burial, the surface corrosion and holes formation were emerged on the surfaces of both PC films in the non-sterilized soil harboring indigenous microorganisms by scanning electron microscope. The worsened thermal stability of both PC films in non-sterilized soil was demonstrated by thermogravimetric analysis. Meanwhile, the presence of increased hydroxyl group absorption and decreased carbonyl peak highlighted molecular chain breakage in both PC films by Fourier transform infrared spectroscopy. In particular, all the changes were more significant in aged PC than unaged ones. Furthermore, the increase of quantified PC microplastics on the surface of PC film in the non-sterilized soil accompanied the decreasing of microbial diversity and the enrichment of potential functional microorganisms. These findings revealed that the combination of natural aging and indigenous microbes exhibited a noticeable performance in PC plastics degradation in soil microcosm, providing new insights into the degradation mechanism of PC plastic wastes in the natural environment.

Effects of Aging in an Aqueous Solution of NaCl on Impact Strength and Structure of Bisphenol A Polycarbonate

The responses of the impact strength and structure of bisphenol A polycarbonate (PC) to aging in a 5 wt% aqueous solution of NaCl were studied in detail. The results of the Izod notched impact test showed that the impact strength decreased from 71.1 kJ/m2 to 17.5 kJ/m2 after an aging time of only 1 day in the aqueous solution of NaCl. The surface appearance of the aged PC observed by polarizing optical microscopy indicated that a large number of microvoids formed, and the size and number of these microvoids increased substantially with an increase in the aging time. The glass transition temperature, measured by differential scanning calorimetry, underwent a slight decrease after aging in the NaCl solution. In addition, no crystallization could be inferred from the heating curves. Thermal gravimetric analysis showed that the thermal decomposition temperature moved to a lower temperature, and the changes of the NaCl solution pH values indicated that hydrolysis was the dominant mechanism of degradation during aging in the aqueous solution of NaCl. Furthermore, the presence of NaCl accelerated the hydrolysis during the early stages of aging. A ductile-brittle transition caused by aging was inferred from observations of fracture surfaces using scanning electron microscopy.

Thermoplastique Degradation under Heat and Irradiation

The aim of the article is to highlight the effect of the environment on the properties of a polycarbonate (PC). It consists in aging this material under Ultra-violet (UV) combined with temperature for different periods of time, and to reveal the physicochemical and mechanical changes caused by aging. PC is a highly valued technical material for its various important characteristics and low cost. It finds its application in various fields but mainly in those whose requirements are the transparency and the impact resistance. The physicochemical and mechanicals characterizations of the marketed polycarbonate are necessary in order to highlight its intrinsic properties and to develop strategies that can improve its lifespan. In this work, we highlight the physicochemical and mechanical characteristics of virgin and aged polycarbonate. For this, analytical techniques and mechanical tests were used. A comparison of the characteristics revealed the combined effects of temperature and ultraviolet rays.

Ageing affects microplastic toxicity over time: Effects of aged polycarbonate on germination, growth, and oxidative stress of Lepidium sativum

Plastic has been an environmental pollutant far longer than claimed by the first reports surfacing in 1979, meaning some plastic materials have been decaying in nature for decades. Nevertheless, the threat posed to biota is not fully understood, especially from aged microplastic. The question considered in this study was whether the adverse effects of new plastic differ from those of old plastic material. Therefore, the morphological and physiological effects on Lepidium sativum with exposure to both new and aged polycarbonate were considered against a known stressor leaching from polycarbonate with time, bisphenol-A. Exposure to new and short-term aged polycarbonate (up to 80 days) elicited the most severe effects such as germination inhibition, reduced seedling growth, decreased chlorophyll concentrations, and increased catalase activity. These adverse effects in L. sativum associated with polycarbonate exposure were reduced as a function of the ageing time applied to the polycarbonate. The chemical substances that lend new polycarbonate material its toxicity were likely leached with time during the ageing process. Based on the results obtained, temperature and humidity based artificial ageing significantly reduced the phytotoxicity of the microplastic particles.

Sorption and leaching behaviors between aged MPs and BPA in water: The role of BPA binding modes within plastic matrix

Due to the hydrophobicity and large specific surface area microplastics (MPs) have become the vector for the migration of environmental organic pollutants. Environmental aging process affects the physiochemical structure of MPs and their corresponding environmental behaviors, in which the effect of bisphenol A (BPA) binding mode within plastic matrix on aging behaviors of MPs is not reported. In this work, the structural properties and BPA sorption behaviors of low density polyethylene (LDPE) MPs with BPA additives and polycarbonate (PC) MPs with BPA monomers exposed to three types of artificial accelerated aging processes including UV/H2O, UV/H2O2, and UV/Cl2 systems were comparatively investigated. Virgin LDPE and PC exhibited obvious leakage of BPA additives or monomers. Aged LDPE had stronger sorption ability towards BPA in water environment with no observed leakage of BPA additives. While, aged PC had extremely high leakage of BPA monomers, which is similar to virgin PCs and was proved to be a persistent source of BPA release. The BPA sorption on aged LDPE or leaching from aged PC was influenced by aging processes, water pH, salinity, co-existing estradiol (E2), and water sources. This study reveals the potential ecological and environmental risks of MPs containing toxic additives/monomers during aging processes from a new perspective.

The Influence of New and Artificial Aged Microplastic and Leachates on the Germination of Lepidium sativum L.

With the increase in environmental monitoring and assessing, we are gaining insight into the extent of microplastic pollution in our environment. The threat posed by microplastics to biota could come, e.g., from leached substances. As some plastic materials have been decaying in nature for extended periods already, the toxic effects of leaching compounds need to be investigated. It is furthermore essential to understand the adverse effects of new plastic and how these effects differ from the effects elicited by old plastic material. Therefore, in the present study, the effects of exposure to leachates from new and artificial aged polycarbonate as well as new and aged polycarbonate granules on various germination parameters of Lepidium sativum were studied. Germination, root, and shoot length, as well as the calculated germination rate index as a measure for germination speed, was negatively influenced in substrate-free and substrate containing exposures. From an ecological and agricultural point of view, this implies possible yield losses with less germinating seeds, slower plant germination speed, and smaller seedlings in general.

Evolution of mechanical and barrier properties of thermally aged polycarbonate films

Polycarbonate (PC) films of two different grades (Macrolon® LED 2245 and Macrolon® AL 2447) were elaborated and thermally aged at 100, 120 and 140 °C during intermediate and long times of aging. The physical aging effect on the film properties was analyzed by infrared spectroscopy, water contact angle, thermal and tensile tests, and water and gas permeation and sorption measurements. The effect of thermal treatment on PC properties was revealed, especially for the film aged at 120 °C. Aging caused a continual increase of PC glass transition temperature and relaxation enthalpy, an increase in Young's modulus and yield strength values and a decrease in the elongation at break. These results were attributed to the reduction of the free volume because of the PC conformational changes.The film barrier properties using liquid water and gas (N2, O2 and CO2) molecules as probes were studied in order to highlight the free volume evolution. It was shown that physical aging caused a reduction of water and gas permeability. This fact was mainly explained by the decrease of the solubility coefficient with the aging time increase.

High fidelity computational characterization of the mechanical response of thermally aged polycarbonate

A representative all-atom molecular dynamics (MD) system of polycarbonate (PC) is built and conditioned to capture and predict the behaviours of PC in response to a broad range of thermo-mechanical loadings for various thermal aging. The PC system is constructed to have a distribution of molecular weights comparable to a widely used commercial PC (LEXAN 9034), and thermally conditioned to produce models for aged and unaged PC. The MD responses of these models are evaluated through comparisons to existing experimental results carried out at much lower loading rates, but done over a broad range of temperatures and loading modes. These experiments include monotonic extension/compression/shear, unilaterally and bilaterally confined compression, and load-reversal during shear. It is shown that the MD simulations show both qualitative and quantitative similarity with the experimental response. The quantitative similarity is evaluated by comparing the dilatational response under bilaterally confined compression, the shear flow viscosity and the equivalent yield stress. The consistency of the in silico response to real laboratory experiments strongly suggests that the current PC models are physically and mechanically relevant and potentially can be used to investigate thermo-mechanical response to loading conditions that would not easily be possible. These MD models may provide valuable insight into the molecular sources of certain observations, and could possibly offer new perspectives on how to develop constitutive models that are based on better understanding the response of PC under complex loadings. To this latter end, the models are used to predict the response of PC to complex loading modes that would normally be difficult to do or that include characteristics that would be difficult to measure. These include the responses of unaged and aged PC to unilaterally confined extension/compression, cyclic uniaxial/shear loadings, and saw-tooth extension/compression/shear.

Migration Characteristics and Degradation Kinetics of Bisphenol A

This paper study the migration characteristics and degradation kinetics of bisphenol A using TGA - gas chromatography - mass spectrometry and found that bisphenol A polycarbonate in the thermal oxidative aging conditions of 130 °C de-gradated to bisphenol A. At the range of 0 h to 120 h, the bisphenol A content of environmental hormones increased with time. When it reached 120 h, bisphenol A environmental hormone content decreased slightly with aging time. The content of bisphenol A reached 495mg/kg when the thermal oxidative aging time was 168 h, which was decreased compared to the content of 442mg/kg at 120 h. Polycarbonate thermal decomposition kinetics study showed that the thermal decomposition of polycarbonate can be divided into three phases. The first thermal decomposition occurred at the range of 415° C to 425 ° C, the polycarbonate end groups fracture of the second stage at 493.6°C , the main fracture of the main chain rearrangement and crosslinking, and the third stage at 598.7°C, the degradation of the chain continues to decompose and the decomposition of the crosslinked carbon precursor; thermal oxidation aging of polycarbonate decreased the heat stability and promote the thermal decomposition of polycarbonate. Comparing the oxidation induction period, thermal weight loss rate and activation energy of polycarbonate before and after thermal oxidative aging, it c found that the thermal stability of the hot oxygen aging of polycarbonate is reduced.

ポリカーボネートの熱老化に関する研究

ポリカーボネートの熱老化に関する研究

Dynamic fracture analysis of aged glassy polycarbonate by the method of caustics

The purpose of this work is to investigate the dynamic fracture properties of glassy polycarbonate (PC) with different aging times. The optical method of caustics is adopted in which the shadow spot patterns are recorded by a high speed camera during the dynamic fracture process. Then, the dynamic crack propagation, the stress intensity factor (SIF) and the dynamic fracture toughness of aged PC are obtained through an analysis of the characteristic size of caustic pattern. Moreover, by combining with the investigation of the fracture surface and the energy release rate analysis, the influence of aging time on the dynamic fracture behavior is discussed. Results show that the dynamic fracture toughness and critical energy release rate of PC decreases with aging time for short aging times, whereas they have little change or even increase for longer aging times. Therefore, aging modifies the mechanical properties especially the dynamic fracture properties of PC nonlinearly, not linearly as generally thought of.

Anisotropic loss of toughness with physical aging of work toughened polycarbonate

We have studied the response of mechanically toughened and physically aged polycarbonate primarily using Charpy impact and ultrasonic wave speed measurements. The toughening was conducted through plastic compression on as‐received PC. The Charpy impact tests showed anisotropic toughening, both in the absorbed energy and in the mode of fracture. The amount of toughening with plastic compression, even though anisotropic, is centered around the response of annealed and quenched samples, which represent the response of an unaged PC. There was an anisotropic drop in the toughness of some samples with aging. The time of this drop was uncorrelated in the different directions and disappeared for the highly toughened samples. This transition was bimodal and statistically distributed between either a fully ductile or a fully brittle failure. As the samples were prepared in a manner to remove induced residual stresses, this drop in toughening may be associated with an intrinsic anisotropic thermal aging of the deformed material. POLYM. ENG. SCI., 54:794–804, 2014. © 2013 Society of Plastics Engineers

Physical aging and deformation kinetics of polycarbonate

AbstractConsidering the current view that physical aging of glasses results in an increase of activation barriers to plastic deformation, it is surprising that, until now, no influence of physical aging was observed experimentally on the temperature dependence of plastic deformation in polymeric glasses. This study evaluates why such an influence has not been found, and it is shown that detailed analysis of a set of uniaxial compression data on polycarbonate (PC) at different strain rates and temperatures leads to the conclusion that a significant influence indeed exists. As a consequence, the Eyring activation energy depends on the aging history of the material. These experimental observations are rationalized in terms of a simple physical interpretation of the aging phenomenon. The article also contains a discussion of the apparent deaging of amorphous polymers induced by large‐strain plastic deformation. This discussion is of key importance here, because this study compares yield stresses of aged PC with those of mechanically deaged, or rejuvenated, PC. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012

Study on the changing regularity of structure and properties of PC aged outdoor in western areas of China

AbstractAs an important engineering material, polycarbonate (PC) has been used widely. When exposed to the environment, PC will have aging process, which will reduce its performance and efficiency. This article studies the changing regularities of PCs structure and properties of ageing in western areas of China by measuring the change of intrinsic viscosity (IV), thermal decomposition temperature, glass transition temperature, and the groups within PC. The analysis of its IV, DSC, and thermo gravimetric analysis exhibited the same changing regularity, i.e., the aged PC (in Lasa, Yuli, and Jiangjin) experienced degradation and crosslinking, while degradation occurred earlier in the process of ageing, crosslinking predominated in later period. In addition, the results of UV absorption spectra and infrared absorption spectra showed the evidence of decomposition of the ester groups, resulting in the production of alcohol and phenol. And the results of mechanical tests indicated that the ductility disappeared mainly in the first year of outdoor aging. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Aging behavior and lifetime modeling for polycarbonate

In this paper, polycarbonate (PC) as a material candidate for solar absorber applications is investigated as to the aging behavior at different temperatures in air and water. The aging conditioning was performed in air in the temperature range from 120 to 140 °C and in water between 70 and 95 °C. Tensile tests were performed on unaged and aged PC film specimens at ambient temperature using strain-to-break values as a performance indicator for the degree of aging. For PC the effect of aging was found to strongly depend on the aging conditions. Activation energy based lifetime prediction models according to various methods described in the literature were applied. The activation energies and corresponding lifetime predictions for the temperature range from 40 to 60 °C in water and from 90 to 110 °C in air derived from these models are compared and interpreted as to their practical relevance.

Load and depth sensing indentation as a tool to monitor a gradient in the mechanical properties across a polymer coating: A study of physical and chemical aging effects

AbstractLoad and depth sensing indentation has been used to characterize the elastic modulus and hardness of various polycarbonate films. This analytical technique is shown to be extremely suitable for the determination of gradients in these mechanical properties. Furthermore, it is demonstrated that such a gradient exists over a length of micrometers in chemically aged polycarbonate, but it is virtually absent in physically aged polycarbonate. From these results, it is concluded that, although the first 100 nm cannot be probed, physical aging occurs homogeneously throughout the bulk of the sample. However, chemical aging starts at the surface and moves progressively into the bulk of the material. From the study of these films, it appears that for the interpretation of these measurements, knowledge about the amount of creep occurring during the measurements and about the mechanical properties of the substrate on which these films are applied is needed. Creep can be measured with the same indenter through the application of a constant load for a period of time. Load and depth sensing indentation appears to be a powerful method for studying the physical and chemical aging of polymers. It is especially valuable for coatings and films for which conventional tensile testing is problematic. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1628–1639, 2004

Positron Annihilation Lifetime Spectroscopy to Study the Structural Relaxation of PC Far Below the Glass Transition Temperature

We report the dynamics of the physical aging of polycarbonate (PC) far below Tg by means of positron annihilation lifetime spectroscopy (PALS). This technique is able to detect the isothermal relaxation of the free volume after rejuvenation above Tg. The isothermal relaxation was done at different temperatures far below Tg and for different aging times. The free volume relaxation results were modeled according to a phenomenological model presented by Struik, so as to obtain the equilibrium relaxation times of the aging process at each aging temperature. The results suggest two possible scenarios for aging far below Tg: a) the relaxation process of PC is dominated by the � process, although the fast modes of theprocess remain present even at the lowest investigated temperature; b) an Arrhenius type process, resulting from cooperative dynamics of several � processes, determines the aging far below Tg.

FTIR investigation of structural modifications during low-temperature ageing of polycarbonate

Conformational changes are sought during low-temperature ageing of solution-cast films of BPA-polycarbonate, by observing the conformationally sensitive IR aromatic breathing band at 1600 cm−1. Preliminary results using the carbonyl band at 1775 cm−1 had shown some indication of ageing-induced changes in the distribution of conformations. The present results obtained on the 1600 cm−1 band show no indication whatever of conformational rearrangements. This result, at variance with observations of conformational rearrangements accompanying sub-Tg annealing, lends support to the concept that sub-Tg annealing and low temperature ageing are two distinct processes.

Physical aging of polycarbonate investigated by dynamic viscoelasticity

The physical aging of polycarbonate was investigated with dynamic viscoelastic measurements. Physical aging was observed for samples aged at 110 °C (QA) and room temperature (QP) after being quenched from the molten state. The shapes of the temperature dispersion curves of the dynamic viscoelastic functions (E', E, and tan 8) of the QA and QP samples changed with aging time in a temperature range below the glass-transition temperature (T g ). However, at temperatures close to but below T g , the curves for the aged samples merged into the curve of the quenched sample at a temperature denoted T H , T H increased with aging time. The experimental results suggest that the aged sample has a memory of having been quenched and that as the sample approaches the equilibrium state, this memory is lost. Differential scanning calorimetry thermograms showed an endothermic peak below T g for the QA samples. The peak temperature (T P ) also increased with aging time. T H and T P of the QA samples were approximately the same. The increase of both T H and T P with aging time indicates that the structure of the polymeric chain in the glassy state relaxes over larger segment scale lengths because the scale of the movable segments is related to temperature.

Modelling the nonlinear viscoelastic behavior of amorphous glassy polymers

Constitutive equations are derived for the nonlinear viscoelastic response of glassy polymers at isothermal loading with small strains. The model is based on the concept of temporary networks, where the rates of breakage and reformation for active chains depend on the specific entropy production. It is demonstrated that the stress-strain relations with a dissipation-driven internal clock adequately predict an apparent aging of polycarbonate observed in dynamic tests on stretched specimens.