Coupled effect of ageing and temperature in the mechanical behaviour of a polyamide

The present work is concerned with the thermo-mechanical analysis of a particular aliphatic polyamide with long alkyl chains used in the internal sheath of flexible pipes. The main focus is to analyse the coupled influence of temperature and ageing on its mechanical behaviour and fracture. Fracture and tensile tests were performed over a wide range of temperature (from −5 °C to 90 °C) and of corrected inherent viscosity (between 1.0 dl/g and 1.8 dl/g). For higher values of the CIV, the material presents superplastic behaviour, but the behaviour tends to be brittle for lower values of the inherent viscosity and temperature. A general model is proposed for the uniaxial behaviour (valid for a wide range of temperature and inherent viscosity) and also for the fracture behaviour. Experiments are compared with the model predictions and show good agreement.     

Low velocity impact and pseudo-ductile behaviour of carbon/glass/epoxy and carbon/glass/PMMA hybrid composite laminates for aircraft application at service temperature

Carbon/glass hybrid composite (CGHC) laminates are some of the most promising composites for lightweight applications. Sometimes these laminates are used in warm environment, such as aircraft frame structures, and this may affect their performance. In order to investigate this issue, the present research aims to study the effect of temperatures on the impact behavior and pseudo-ductile behaviour of CGHC in presence of different types of thermosets “epoxy” and thermoplastic “acrylic poly-methyl methacrylate-PMMA”. The experiments were started with making of CGHC laminates from different stacking sequences of unidirectional carbon and woven glass fibre layers, using a vacuum-assisted resin transfer method followed by curing treatment. In addition to CGHC laminates, four other neat batches (Carbon/epoxy, Carbon/PMMA, Glass/epoxy, Glass/PMMA) were prepared for comparison. The low velocity impact behaviour of the fabricated panels was evaluated at high temperatures (60 °C and 80 °C) according to ISO 6603-2 standard, using drop tower, while pseudo-ductile behaviour and ductility index (DI) of the specimens were estimated based on the measured total energy and elastic energy. Also, the low-velocity impact response was modeled mathematically based on a modified energy-balance model to predict the absorbed energies. Finally, the failure mechanisms were examined using optical microscope to determine the influence of these damage growth on DI of the composites under different temperatures. The results showed that the impact energy response of both hybrid composites i.e. epoxy and PMMA was stable even as the temperature rose, however, carbon/glass/PMMA exhibited better performance compared with carbon/glass/epoxy with an increase in impact energy response estimated at 50% (25 °C) and 53% (80 °C). Also, the pseudo-ductile phenomenon was strongly evident, which facilitates the predictablility of failure.     

Tension behaviour of HNBR and FKM elastomers for a wide range of temperatures

This article presents uniaxial tension tests of three different elastomer compounds commonly applied as seal materials in the oil and gas industry. The tests were performed at five different temperatures, ranging from −20 to 150 °C. Optical measurements were used to ensure high quality stress–strain data. The material samples were exposed to a cyclic deformation history, enabling the viscoelastic behaviour to be explored. A considerable effect of temperature changes was found, with a pronounced increase of stiffness and viscosity for the lowest temperatures. A dip in the stress–strain curve was seen for one of the hydrogenated nitrile butadiene rubbers tested at low temperatures. Matrix-particle debonding simulations qualitatively described this stress dip. For the tests performed at the highest temperatures, a considerable number encountered material failure.     

Constitutive model calibration of the time and temperature-dependent behavior of high density polyethylene

HDPE is commonly used in pipelines and piping for industrial and societal infrastructure. Like most polymers, HDPE's mechanical properties are sensitive to temperature and show time dependent properties. The temperature effect on both the short and long term compressive and tensile behavior of HDPE, in a combined manner, have not been investigated thoroughly in the past. Especially the constitutive behavior of HDPE, incorporating temperature effects on its long and short term behavior, could be essential when designing such infrastructural components. Hence, the temperature effect on the short and long term response in tension and compression of HDPE is investigated in this study. The short term tensile and compressive stress-strain behavior at 23, 40, 60, and 80 °C were obtained through experiments at constant displacement rate and temperature. Tensile and compressive stress relaxation (e.g. long term) behavior at 23, 40, 50, 60, 70, and 80 °C were investigated through stress relaxation tests. The experimental results from the short term tests showed that both the tensile and compression moduli and yield strength of HDPE decrease linearly with the increase in temperature. It is also shown from the long term test that relaxation modulus in tension and compression are highly dependent on temperature. Based on the experimental results, the constitutive three network model (TNM) was calibrated and implemented in a FEA model, which was then validated through a three point bending (3 PB) relaxation test with a prescribed temperature profile. The FEA model and the calibrated model results agree markedly well with the experimental results, which indicates that the model can be used reliably to predict the temperature dependent short and long term behavior of HDPE in design and analysis of HDPE components.     

Temperature and variable strain rate sensitivity in recycled HDPE

The recycling of post-consumer plastics and their utilization as raw materials to develop value-added products has become an important goal worldwide. The present work is concerned with the thermo-mechanical analysis of recycled high-density polyethylene (HDPE) under uniaxial tensile loading. The main focus is to propose a one-dimensional phenomenological model able to describe the influence of temperature and strain rate on the mechanical behavior. Tensile tests were performed over a wide range of temperatures (from 25°C to 100°C). Each experiment was performed under controlled strain rate varying from 7.25 × 10⁻⁵ s⁻¹ to 7.25 × 10⁻³ s⁻¹ in steps. It is shown that only one tensile test performed at three different temperatures is necessary to fully identify experimentally all material parameters that arise in the theory. Thus, with this experimental procedure, the number of tests used to evaluate the mechanical properties of recycled HDPE is significantly reduced. The experiments are compared with the model predictions and show good agreement.     

Design of toughened PLA based material for application in structures subjected to severe loading conditions. Part 2. Quasi-static tensile tests and dynamic mechanical analysis at ambient and moderately high temperature

The suitability of a ternary composition 58 wt% polylactide (PLA) - 25 wt% poly (methyl methacrylate) (PMMA) - 17 wt% Impact modifier (Biomax^®Strong - BS) for use in technical parts subjected to severe loading conditions continues to be investigated. Previous work has demonstrated that PLA-PMMA-BS composition presents very appealing tensile properties at ambient temperature over a wide range of strain-rate, and can compete with petro-sourced blends for use in highly-loaded technical parts. Attention is paid now to its mechanical behavior at moderately high temperature (up to 60 °C), through tensile tests and dynamic mechanical analyses. Results highlight the improvement of mechanical properties in the considered range of temperature, thanks to the presence of PMMA in the blend, and prove that PLA-PMMA-BS composition can be suitable for use in technical parts subjected to high strain-rate and/or moderately high temperature.     

Study of the morphology,thermal and mechanical properties of irradiated isotactic polypropylene films

Thin films of isotactic polypropylene (iPP) are of great economical importance and their production is quite challenging due to the need of very fast uniaxial or biaxial expansion. During the expansion, critical problems usually arise, like structure disruption, shear thinning, causing material, energy and time losses. This work aims to study the surface morphology and compare the thermal, mechanical properties of PP films irradiated by gamma ray in an acetylene atmosphere after uniaxial expansion. PP films were made by compression molding at 190 °C with cooling in water at room temperature and irradiated by gamma ray, at (5, 12.5 and 20 kGy) under acetylene atmosphere. After irradiation the samples were submitted to thermal treatment at 90 °C for 1 h and then stretched out at 170 °C using an Instron machine. The surface of PP films, pristine and modified, (i.e., irradiated), was studied using optical microscopy (OM) and scanning electron microscopy (SEM). The changes in morphology, crystallinity and tensile parameters, like yield stress, rupture stress and elongation strain of the PP with irradiation dose were investigated. The results showed some evidences of gel formation due to crosslinking and/or long chain branching induced by radiation.     

Tensile properties of semi-crystalline thermoplastic polymers: Effects of temperature and strain rates

This work deals with the study of temperature and time dependency of tensile properties of a PA 12-based polymer. The range of variation of parameters in experiments was linked to in-service conditions of components manufactured with this material (temperature interval from ?25 °C to 50 °C and average strain-rate magnitudes from 0.00028 s^?1 to 9.4 s^?1). For tests with different temperatures and low speed, an electro-mechanical machine, Zwick Z250, equipped with an incremental extensometer was used. To study the effect of strain rate at medium speeds, a servo-hydraulic system, Schenk PC63M, equipped with a strain-gauge extensometer was used, while at high speeds a servo-hydraulic machine, Instron VHS 160/20, equipped with a high-speed camera for strain evaluation by digital image correlation was employed. The changes of the rate of deformation with strain as well as elastic modulus variation with strain were studied. An increase in the elastic modulus and yield strength was observed with a drop in temperature and an increase in the strain-rate, temperature having a stronger influence on the variation of mechanical properties. The collected data was assembled in an elasto-plastic material model for finite-element simulations capable of rendering temperature- and strain-rate-dependency. The model was implemented in the commercial software Abaqus, yielding accurate results for all tests.     

The possibility of using beef tallow biodiesel as a viscosity reference material

This study analyses the possibility of using beef tallow biodiesel transesterified with ethanol, provided by Universidade Federal Fluminense, as a viscosity reference material for biodiesels. The quantity viscosity was measured with capillary viscometers, according to Brazilian standards, in a temperature range between 20 °C and 40 °C for characterisation, and at 40 °C for homogeneity, in short-term stability (90 days) and long-term stability (450 days). Thirty-nine samples were stored, 9 at 45 °C, 6 at 4 °C and 24 at 20 °C. The behaviour of viscosity is analysed considering the estimated uncertainty of measurements for characterisation, homogeneity and stability. The reason to study a transesterified biofuel with ethanol lies in the fact that it is easy to produce this fluid from sugarcane in Brazil.     

Dynamic mechanical analysis of ethylene tetrafluoroethylene (ETFE) foils in use for transparent membrane buildings

Glass transition temperature and tan delta (the ratio of loss modulus to storage modulus) are indispensable parameters for determining appropriate application range of ETFE foils. In this study, ETFE foils in terms of specimen number, material direction and thickness were investigated with dynamic mechanical analysis (DMA) over a temperature range of -70-100 °C at frequencies of 0.1, 1, and 10 Hz. Glass transition temperatures were obtained with storage modulus, loss modulus and tan delta curves. It is found that frequency effect on glass transition temperature was proportional and that frequency effect was more significant than material direction effect. Moreover, a comparison study showed that elastic modulus determined with quasi-static experiments was greater than storage modulus calculated with dynamic mechanical experiments. To propose suitable glass transition temperature ranges for engineering application, an approach to determine confidence interval based on statistical analysis was employed. The resulting intervals with confidence coefficient of 95% were 31.2–32.7 °C, 60.5–66.4 °C and 79.6–83.3 °C for storage modulus, loss modulus and tan delta, respectively. In general, this study could provide useful observations and values for evaluating dynamic mechanical properties of ETFE foils.     

Solid-state mechanical properties of crystalline drugs and excipients

Thermal mechanical analysis (TMA) of crystalline drugs and excipients in their pre-melt temperature range performed in this study corroborate their newly found linear dielectric conductivity properties with temperature. TMA of crystalline active pharmacy ingredients (APIs) or excipients shows softening at 30–100 °C below the calorimetric melting phase transition, which is also observed by dielectric analysis (DEA). Acetophenetidin melts at 135 °C as measured calorimetrically by DSC, but softens under a low mechanical stress at 95 °C. At this pre-melting temperature, the crystals collapse under the applied load, and the TMA probe shows rapid displacement. The mechanical properties yield a softening structure and cause a dimensionally slow disintegration resulting in a sharp dimensional change at the melting point. In order to incorporate these findings into a structure–property relationship, several United States Pharmacopeia (USP) melting-point standard drugs were evaluated by TMA, DSC, and DEA, and compared to the USP standard melt temperatures. The USP standard melt temperature for vanillin (80 °C) [1], acetophenetidin (135 °C) [2], and caffeine (235 °C) [3] are easily verified calorimetrically via DSC. The combined thermal analysis techniques allow for a wide variety of the newly discovered physical properties of drugs and excipients.     

Experimental and numerical investigation of yielding phenomena in a shape memory polymer subjected to cyclic tension at various strain rates

This paper presents experimental and numerical results of a polyurethane shape memory polymer (SMP) subjected to cyclic tensile loading. The goal was to investigate the polymer yielding phenomena based on the effects of thermomechanical coupling. Mechanical characteristics were obtained with a testing machine, whereas the SMP temperature accompanying its deformation process was simultaneously measured in a contactless manner with an infrared camera. The SMP glass transition temperature was approximately 45 °C; therefore, when tested at room temperature, the polymer is rigid and behaves as solid material. The stress and related temperature changes at various strain rates showed how the SMP yield limit evolved in subsequent loading-unloading cycles under various strain rates. A two-phase model of the SMP was applied to describe its mechanical response in cyclic tension. The 3D Finite Element model of a tested specimen was used in simulations. Good agreement between the model predictions and experimental results was observed for the first tension cycle.     

New insight into dynamic mechanical relaxation in N-butyl-N-(2-nitroxy-ethyl) nitramine plasticized nitrocellulose through molecular dynamic simulations

We performed dynamic mechanical analysis (DMA) on nitrocellulose (NC) plasticized by an insensitive plasticizer N-butyl-N-(2-nitroxy-ethyl)nitramine (Bu-NENA). NC/Bu-NENA blend shows two mechanical relaxation processes in the temperature ranges of???50 to???40 °C and 30?~?40 °C, and their variations with deformation frequencies were studied. To explore further the effect of temperature on relaxation, the binary mixture model of NC/Bu-NENA was constructed, and molecular dynamic simulations were conducted. The simulated mean square displacements (MSD) show abrupt increase in the temperature range of???50 to???40 °C and 30?~?40 °C, which are consistent with those of the two relaxation processes observed in the DMA curves. Moreover, the free volume (V_free) and torsion energy obtained from molecular dynamic simulations exhibit distinct increase at the temperature above 30 °C and???50 °C respectively, reflecting the sudden enhancements on the mobility of polymer chain elements and the rotation of molecular bonds. Furthermore, the radial distribution function (RDF) associated with the intermolecular interactions reveals that the intensities of both hydrogen bond and van der Waals forces decrease with the increase of temperature, which is responsible for the decrease of storage modulus at high temperature. These computational and experimental studies reveal guidance to strengthening the NC base propellants in broad temperature range.

     

Experimental set-up for determination of the large-strain tensile behaviour of polymers at low temperatures

In this study, we present a method to determine the large-strain tensile behaviour of polymers at low temperatures using a purpose-built temperature chamber made of polycarbonate (PC). This chamber allows for several cameras during testing. In our case, two digital cameras were utilized to monitor the two perpendicular surfaces of the test sample. Subsequently, the pictures were analysed with digital image correlation (DIC) software to determine the strain field on the surface of the specimen. In addition, a thermal camera was used to monitor self-heating during loading. It is demonstrated that the PC chamber does not influence the stress-strain curve as determined by DIC. Applying this set-up, a semi-crystalline cross-linked low-density polyethylene (XLPE) under quasi-static tensile loading has been successfully analysed using DIC at four different temperatures (25 °C, 0 °C, −15 °C, −30 °C). At the lower temperatures, the conventional method of applying a spray-paint speckle failed due to embrittlement and cracking of the spray-paint speckle when the tensile specimen deformed. An alternative method was developed utilising white grease with a black powder added as contrast. The results show a strong increase in both the Young’s modulus and the flow stress for decreasing temperatures within the experimental range. We also observe that although the XLPE material is practically incompressible at room temperature, the volumetric strains reach a value of about 0.1 at the lower temperatures.     

Effects of simulation conditions on antibacterial performance of polypropylene and polystyrene doped with HPQM antibacterial agent

2-Hydroxypropyl-3-piperazinyl-quinoline carboxylic acid methacrylate (HPQM) antibacterial agent in two different forms, solid form (HPQM-supported Neusilin absorbance; HPQM-neu) and liquid form (HPQM dissolved in deionized water; HPQM-water), were added to polypropylene (PP) and polystyrene (PS). The antibacterial performance against Escherichia coli and mechanical properties of the specimens were investigated. The effects of simulated conditions, including immersion in water (at room temperature and 80 °C), immersion in surfactant solution (at room temperature and 80 °C) and exposure to UV aging, on the antibacterial performance of specimens were also studied. The results showed that the optimal HPQM concentration for PP/HPQM-neu and PP/HPQM-water were 500 and 750 ppm, respectively, in order to reach 99.9% E. coli bacteria reduction, but those for PS/HPQM-neu and PS/HPQM-water were 1250 ppm. Addition of HPQM in both forms to PP and PS did not change the mechanical performance. HPQM-water was more appropriate and effective for antibacterial peformance for PP and PS than HPQM-neu. Immersion of all specimens in water and detergent solution (at room temperature and 80 °C) and UV aging decreased the antibacterial performance at different rates, the effect being very pronounced for the specimens with HPQM-neu.     

Thermal,mechanical and dielectric behaviour of poly(aryl ether ketone) with low melting temperature

New poly(aryl ether ketone)s (PAEKs) with a low melting temperature (relative to PEEK) are of interest in order to simplify the manufacturing of high-performance polymers or composites. In this study, we propose to investigate the physical properties of a new PAEK from Victrex, namely PAEK LM. Combinations of thermal analyses were used as follows: standard and modulated temperature differential scanning calorimetry, dynamic mechanical analysis, dynamic dielectric analysis and guarded hot plate technique. We found that the global mechanical, dielectric and thermal properties are very similar to the PEEK reference. The glass transition temperature was observed in the same range than PEEK (∼ 150 °C) while the melting temperature T_m was measured at 307 °C for PAEK LM which is about 35 °C below the melting temperature of PEEK. The degree of crystallinity of PAEK LM was found to be 27% while for PEEK it is 38%, depending on the processing conditions. This work explored crystalline structure–property relationships to explain the behaviour of PAEK LM.

     

Size effect of silica nanoparticles on thermal decomposition of PMMA

The size effect of silica nanoparticles (SiO₂) on thermal decomposition of poly(methylmethacrylate) (PMMA) was investigated by the controlled rate thermogravimetry. Thermal degradation temperature of PMMA–SiO₂ composites depended on both fraction and size of SiO₂, the thermal degradation temperature of 23 nm (diameter) SiO₂–PMMA (6.1 wt%) was 13.5 °C higher than that of PMMA. The thermal stabilities of 17 nm SiO₂–PMMA (3.2 wt%) and 13 nm SiO₂–PMMA (4.8 wt%) were 21 and 23 °C, respectively, higher than that of PMMA without SiO₂. The degree of degradation improvement was increased linearly with the surface area of SiO₂. The number of surface hydroxyl group in unit volume of SiO₂ particle increased with increasing the specific surface area of SiO₂, and the interaction between hydroxide group of SiO₂ and carbonyl group of PMMA had an important role to improve the thermal stability of PMMA.     

Polymer gel electrolytes based on oligomeric polyether/cross-linked PMMA blends prepared via in situ polymerization

Very-low-vapor-pressure oligomeric polyether electrolytes blended with and dimensionally stabilized by cross-linked poly(methyl methacrylate) (PMMA) are prepared via in situ polymerization. The synthesized polymer gel electrolytes (PGEs) are freestanding films with excellent dimensional stability, mechanical integrity and strength. They exhibit high ionic conductivity at room temperature reaching 4.3 × 10⁻⁴ S/cm for the highest conducting sample and exceptional thermal stability. The oligomeric polyether and PMMA appear to have molecular level interaction in the blends and the PGEs remain a single phase from at least −50 to 200 °C, potentially enabling their application in advanced batteries in wide temperature ranges. The novel in situ polymerization process allows precise control of the composition of the PGEs and can enable in situ fabrication of advanced cells.     

Glucose Oxidase-dextran Conjugates with Enhanced Stabilities Against Temperature and pH

Multipoint covalent bonding of glucose oxidase (EC 1.1.3.4) to hydrophilic natural polymer dextran and optimization of procedures to obtain, with enhanced temperature and pH stabilities, were studied. Purified enzyme was conjugated with various molecular weight dextrans (17.5, 75, and188 kD) in a ratio of 20:1, 10:1, 1:1, 1:5, 1:10, 1:15, and 1:20. After 1 h of incubation at pH 7, the activities of purified enzyme and conjugates were determined at different temperatures (25°C, 30°C, 35°C, 40°C, 50°C, 60°C, 70°C, and 80°C), and the results were evaluated for thermal resistance. Increases in temperature from 25°C to 50°C did not change the activities of the conjugates. The conjugate, which was prepared with 75 kDa dextran in a molar ratio of 1:5, showed the highest thermal resistance and even the activity still remains at 80°C at pH 7.0. This conjugate also displayed activity in a wide pH range (pH 4.0–7.0) at high temperatures. Conjugate, which was synthesized with 75 kDa dextran in a molar ratio of 1:5, appears to be feasible and useful for biotechnological applications.     

Kinetics of Lime Pretreatment of Sugarcane Bagasse to Enhance Enzymatic Hydrolysis

The objective of this work was to determine the optimum conditions of sugarcane bagasse pretreatment with lime to increase the enzymatic hydrolysis of the polysaccharide component and to study the delignification kinetics. The first stage was an evaluation of the influence of temperature, reaction time, and lime concentration in the pretreatment performance measured as glucose release after hydrolysis using a 2³ central composite design and response surface methodology. The maximum glucose yield was 228.45 mg/g raw biomass, corresponding to 409.9 mg/g raw biomass of total reducing sugars, with the pretreatment performed at 90°C, for 90 h, and with a lime loading of 0.4 g/g dry biomass. The enzymes loading was 5.0 FPU/dry pretreated biomass of cellulase and 1.0 CBU/dry pretreated biomass of β-glucosidase. Kinetic data of the pretreatment were evaluated at different temperatures (60°C, 70°C, 80°C, and 90°C), and a kinetic model for bagasse delignification with lime as a function of temperature was determined. Bagasse composition (cellulose, hemicellulose, and lignin) was measured, and the study has shown that 50% of the original material was solubilized, lignin and hemicellulose were selectively removed, but cellulose was not affected by lime pretreatment in mild temperatures (60–90°C). The delignification was highly dependent on temperature and duration of pretreatment.