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.     

Elasto-viscoplastic behaviour of a polyvinylidene fluoride (PVDF) in tension

The present paper is concerned with the plasticity of a polyvinylidene fluoride (PVDF) in tension. Strain rate strongly influences the plastic behaviour, but the variation of the elastic properties is almost negligible within the range of strain rates considered in the study (from 1.6 × 10⁻⁴ s⁻¹ up to 1.6 × 10⁻¹ s⁻¹). In particular, the yield stress and the ultimate tensile strength are strongly rate-dependent. A one-dimensional elasto-viscoplastic phenomenological model is proposed and analysed. Despite the nonlinearity of the model equations, only one tensile test performed with variable strain rate is sufficient to identify all material parameters. Model predictions are compared with experiments showing good agreement.     

Chain rupture and tensile deformation of polyamide 6 fibers

Summary The tensile deformation of polyamide 6 fibers gives rise to irreversible changes of its tensile properties, which apparently arise from chain rupture. This molecular failure process is usually analyzed by means of the ESR-spectroscopy. The number of ruptured chains, as obtained by this method, is, however, much too small to account for the changes of the tensile properties and for the observed strong decrease of the average molecular weight. Based on studies on energy dissipation, on structural as well on spectroscopical investigations we come to the conclusion that chain rupture is mainly responsible for the irreversible changes of the tensile properties. The dissipation of energy can be accounted for in terms of the energy release on chain rupture and energetic interactions with neighboring segments, in agreement with the data on the molecular weight decrease. The spectroscopically determined number of ruptured chains is governed by a fast recombination of the free radicals.

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Zusammenfassung Eine Deformation von Polyamid 6 Fasern führt zu irreversiblen Veränderungen in den mechanischen Eigenschaften, die offensichtlich durch Kettenbrüche verursacht werden. Dieser molekulare Versagensprozeß wird gewöhnlich mittels der ESR-Spektroskopie analysiert. Die hierdurch erhaltene Anzahl an Kettenbrüchen ist jedoch viel zu gering, um sowohl die Veränderungen in den mechanischen Eigenschaften als auch die starke Abnahme des mittleren Molekulargewichtes erklären zu können. Auf der Grundlage unserer Untersuchungen zur Energiedissipation, aus Streuexperimenten und spektroskopischen Untersuchungen kommen wir zu dem Schluß, daß Kettenbrüche für die Veränderungen der Eigenschaften allein verantwortlich sind. Die Energiedissipation läßt sich vollständig auf die Energiefreisetzung beim Kettenbruch und energetische Wechselwirkungen mit umgebenden Segmenten zurückführen, in Einklang mit den Ergebnissen zur Molekulargewichtserniedrigung. Die spektroskopisch bestimmte Anzahl an Kettenbrüchen wird durch eine schnelle Rekombination der freien Radikale beeinträchtigt.

     

Effect of cyclic loading on tensile properties of PC and PC/ABS

The effects of cyclic loading on tensile fracture properties of polycarbonate (PC) and the alloy of polycarbonate and acrylonitrile-butadiene-styrene (PC/ABS) are experimentally investigated in the paper. Two digital cameras are used to record simultaneously the tensile deformation of specimens and the large deformation and the necking process of these polymers are discussed. Two lateral contractions are not identical at the later tensile stages and the contraction ratios in each lateral direction are related with the tensile strains in axial direction on width and thickness surface. The curvature radiuses at the minimum section during necking process are shown. The volume increases during necking process and then decreases gradually. The yield stress and fracture stress of PC/ABS are lower than that of PC. The degradation of the fracture stress and fracture strain due to the application of cyclic loading is larger for PC than that for PC/ABS, and these can be used to explain qualitatively why PC has higher fatigue crack growth rate than PC/ABS.     

Study of ionizing radiation on the properties of polyamide 6 with fiberglass reinforcement

The use of polymers reinforced with fiberglass is becoming more and more common in the switches for household industries. These compounds perform a good tension resistance to the impact and the humidity absorption being used at the present time and also are in the automobile industry in parts underneath the hood, especially in the radiator frames. The aim of this work is to study the effect of ionizing radiation on the properties of polyamide 6 with fiberglass reinforcement and undergone to different irradiation doses. Samples were prepared and irradiated on JOB 188 accelerator with an electron beam energy of 1.5 MeV in air with different doses and a dose rate of 27.99 kGy/h. Afterward, the properties of the non-irradiated and irradiated polyamide 6 with fiberglass reinforcement were evaluated.     

Potentiodynamic and cyclic voltammetric behaviour of a lead electrode in NaOH solution

Summary The electrochemical behaviour of lead in NaOH solution was studied by potentiodynamic and cyclic voltammetric techniques in combination with X-ray diffraction analysis. The active dissolution of lead involves a small shoulderA1 followed by a peakA1 prior to a passive region. The shoulderA1 is assigned to the electroformation of a Pb(OH)₂ film, whereas peakA1 is due to the formation of PbO. Beyond the passive region, the current density increases again, forming a small shoulderA2 and a peakA2 prior to the oxygen evolution potential. The shoulderA2 and the peakA2 are correlated to the electrooxidation of PbO to Pb₃O₄ and PbO₂, respectively. The intensity of the anodic peaks increases with increasing alkali concentration, temperature and scan rate. In cyclic voltammetry, the reverse scan shows two cathodic peaksC1 andC2 which are correlated to the electroreduction of PbO and PbO₂ respectively, to Pb.

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Potentiodynamisches und cyclovoltammetrisches Verhalten einer Bleielektrode in NaOH-Lösung

Zusammenfassung Das elektrochemische Verhalten von Blei in NaOH wurde mittels potentiodynamischer und cyclovoltammetrischer Techniken unter Zuhilfenahme der Röntgenbeugungsanalyse untersucht. Die aktive Auflösung von Blei verläuft über eine SchulterA1, die von einem einer passiven Region vorgelagerten PeakA1 gefolgt wird. Die SchulterA1 wird der elektrochemischen Bildung eines Pb(OH)₂-Films, der PeakA1 der Bildung von PbO zugeschrieben. Jenseits der passiven Region steigt die Stromdichte wieder an, und vor Erreichen des Sauerstoffpotentials treten eine kleine SchulterA2 und ein PeakA2 auf, die mit der Elektrooxidation von PbO zu Pb₃O₄ und PbO₂ korrelieren. Analog dazu beobachtet man in der cyclischen Voltammetrie zwei kathodische PeaksC1 undC2, die der Elektroreduktion von PbO und PbO₂ zu Pb entsprechen. Die Intensität der anodischen Peaks steigt mit steigender Alkalikonzentration, Temperatur und Scangeschwindigkeit.

     

Thermodynamic properties affect the molecular motion of novolac type phenolic resin blended with polyamide

The effect of association reaction length on the substantial increase of molecular motion as well as entropy (−TΔS_m) of phenolic-polyamide blends is investigated with the ¹³C solid-state NMR and DSC. The H-bonding strength by forming the phenolic-polyamide interaction is great enough to overcome the breaking off the self-association of phenolic. With respect to decreasing the association reaction, the polyamide resonance intensity of ¹³C solid-state NMR spectra is weakened due to the reduction of the cross-polarization efficiency at a high mobile sample. The glass transition temperature of phenolic-polyamide blend as well as T^H_1ρ value from NMR experiments is also decreased. The decreasing strength of H-bonding resulting from blending causes higher entropy (−TΔS_m) and higher molecular mobility of the phenolic-polyamide blends. Accordingly, the polyamide-66 possesses higher H-bonding force and exhibits more mobile role in this phenolic/polyamide blends family. It can be concluded that the molecular segmental motion and entropy are progressively decreased while increasing the inter-association force of the polyamide within the miscible window.     

Effects of reprocessing on the structure and properties of polyamide 6 nanocomposites

PA6 based nanocomposites (NCs) were reprocessed by repeated injection moulding to find out whether reprocessing is possible in these materials by means of the observation of the changes in the structure and mechanical properties. The studied variables were (a) the number of cycles (1-5), (b) the origin of the NC: either laboratory mixed or commercial and (c) the processing temperature (230 °C and 270 °C). Neat PA6 was also reprocessed as a reference material. In spite of the colour change, the Young's modulus, the solid state characteristics and the dispersion level were preserved upon reprocessing. The lack of change of chemical nature observed by FTIR, and the observed decreases in viscosity indicated that the main effect of reprocessing was a decrease in the molecular weight. At 230 °C the decreases in viscosity were smaller after reprocessing, and almost no change was seen in the structural parameters and properties. The decrease in the molecular weight after reprocessing at 270 °C leads to lower ductility and mainly to a decrease in the ability of the nPA6 matrix to cold draw. However, no change of the interphase conditions or agglomeration of the OMMT was detected and the NCs remained clearly ductile; thus, revealing a lack of deterioration of the interface and the ability of the NCs for recycling.     

FTIR spectroscopy study of the interaction between fibre of polyamide 6 and iodine

The IR spectra of several samples of polyamide 6 fibres treated with solutions of different concentrations of iodine and potassium iodide were studied. The IR spectra of their respective iodine desorptions, obtained by means of treatment with sodium thiosulphate, were also studied. The spectral changes observed are related to variations in the polymorphic crystalline α and γ forms of the polyamide, which demonstrate the formation of a complex between the tri-iodide ion and the polymer during the iodine sorption process and a structural change during desorption.     

Structure and properties of an hybrid system based on bisphenol A polycarbonate modified by A polyamide 6/organoclay nanocomposite

Blends of poly(carbonate of bisphenol A) (PC) with minute amounts of a nanocomposite based in polyamide 6 (PA6) with a layered organoclay (nPA6) were obtained upon melt mixing by varying the contents of both nPA6 and organoclay. The ternary nanocomposites (NC) were composed of a PC-rich matrix with some mixed PA6 present, and by a neat nPA6 dispersed phase. Upon dissolution of the matrix of the NC’s, the dispersed phase showed a highly fibrillar morphology that resembled that of thermoplastic/liquid crystalline polymer (LCP) blends. The cryogenically fractured surfaces observed by SEM showed a very fine particle size that was attributed to the presence of PA6 in the matrix and indicated a low interfacial tension. The Young’s modulus behaviour is proposed to be a consequence of the slight orientation of the PC-rich matrix and the highly fibrillated and oriented nPA6 dispersed phase. The important reinforcement effect of the dispersed phase is attributed to the additive effects of its large degree of orientation, and the reinforcing effect of the organoclay.     

HPLC study of the physicochemical characteristics of reverse-osmosis separation on a polyamide membrane material

Summary The fundamental characteristics of reverse osmosis on a polymer membrane have been correlated with HPLC experimental conditions by using the membrane material as a column packing. Twelve formulas were used to calculate the physicochemical characteristics of the reverse-osmosis separation process and it was found that these characteristics can be determined on the basis of retention (t _R, V_R) and partition coefficient (K) of the solute in HPLC. It seems that HPLC is an effective tool for studying the physicochemical nature of reverse-osmosis separations and the characteristics of the polymer membrane.     

Mechanism of the temperature-dependent degradation of polyamide 66 films exposed to water

Experiments were performed to elucidate the degradation mechanism of hot-pressed polyamide 66 upon exposure to water. For films exposed to water over the temperature range 25 °C-90 °C, degradation was monitored using FTIR and solid-state ¹³C NMR spectroscopies. The data are consistent with a mechanism in which (1) a radical is formed on the methylene carbon adjacent to the amide nitrogen, (2) this radical reacts with oxygen to form a hydroperoxide, and (3) the hydroperoxide decomposes to form an imide or a hydroxylated amide, both of which may cleave leading to chain scission. Water appears to facilitate degradation by increasing the flexibility of the polymer matrix through swelling rather than acting as a reactive species, at least at the early stages of the process. An apparent activation energy of 15 ± 2 kJ/mol is observed for the early stages of degradation, suggesting that segmental motions in the polymer associated with water and oxygen sorption or inter-chain radical reactions are indeed key components of the degradation process.     

2,4-Dinitrophenol as an activating reagent in a facile preparation of cyclic phosphate triesters

2,4-Dinitrophenol was employed with benzyloxy-bis-(diisopropylamino)phosphine to synthesise the cyclic phosphate derivatives of a series of alkane diols (HO-(CH₂)_n-OH, n=2-6) in good isolated yields. Tetrazole and DNP were compared by ³¹P NMR spectroscopy for their ability to catalyse the cyclisation at the P(III) stage. Investigation of the phosphate triester stability under various oxidation and chromatographic conditions resulted in the optimisation of the isolation procedures of the chemically unstable cyclic compounds. Conditions for debenzylation were developed to yield the corresponding cyclic phosphodiesters quantitatively. The methodology was further applied to the preparation and isolation of the cyclic phosphate derivative of a carbohydrate.     

Influences of hyperbranched polyethylenimine on the reactive compatibilization of polycarbonate/polyamide blends

The influences of hyperbranched polyethylenimine(h PEI), which possesses many reactive amino end-groups, on the blending properties of bisphenol-A polycarbonate(PC) and amorphous polyamide(a PA) were systematically investigated. Scanning electron microscopy(SEM) and differential scanning calorimetry(DSC) were used to observe the effect of h PEI on morphologies of PC and a PA phases in bulk blends. While the interfacial fracture toughness between planar PC and a PA layers with and without h PEI was studied by using augmented double cantilever beam(ADCB) method. Results show that the compatibility in PC/a PA blends can be significantly improved by adding a small amount of h PEI, mainly due to the interchange reactions between the polymers leading to the formation of block copolymers, cross-linked polymers and molecules with other constitutions. The augmented double cantilever beam experiments showed that the reactive process drastically reinforced the interfacial adhesion between planar layers of PC and a PA. However, degradation takes place during annealing at 180 °C, which was responsible for the production of small molar mass species of PC.     

Analysis of the antioxidant activity of an indole library: cyclic voltammetry versus ROS scavenging activity

The electrochemical behavior of an indole library of compounds, including several tryptophan and tryptamine derivatives previously demonstrated to be active against several reactive oxygen species (ROS), was investigated. For this purpose, a voltammetry study was undertaken and the oxidation potential was correlated to the scavenging activity reported for the studied indoles. All the compounds showed an oxidation potential peak lower than that observed for indole (Epox = 1.035 V), but higher than that described for the antioxidant melatonin (Epox = 0.715 V). The electrochemical behavior showed a high correlation with the scavenging activity of peroxyl radical, for selected compounds.     

Effect of surface orientation on the tribological properties of laser sintered polyamide 12

Experiments have been carried out to determine the tribological properties of laser sintered polyamide 12 (PA12). The effect of surface orientation on the wear properties was studied, which showed anisotropic behaviour. Laser sintered specimens were polished to achieve better surface finish for the wear tests. Tribological testing results showed that the wear resistance was greater and the coefficient of friction was smaller for the side surfaces as compared to the top surfaces. Experimental details and possible reasons for the results obtained are further discussed in the paper.     

Water as an efficient medium for the synthesis of cyclic carbonate

Herein, we report a novel method for the synthesis of cyclic carbonate in water. By tuning the amount of water, cycloaddition of CO₂ to epoxide in aqueous medium leads to cyclic carbonates with moderate to excellent yields and high selectivities. In addition, the presence of water could remarkably improve the activity of ionic liquids by which the turnover frequency of the reaction is about 4-5 times higher in the presence than in the absence of water. The relationship between the higher catalytic reactivity and water was proposed.     

Solid-state morphology,structure, and tensile properties of polyethylene/polyamide/nanoclay blends: Effect of clay fraction

The effect of nanoclay fraction on the linear and non-linear tensile properties of a polyethylene/polyamide 12 blend with droplet morphology was investigated. All ternary blends were prepared at a fixed polyamide (PA) weight fraction of 20%, and at clay volume fractions varying from 0.5 to 2.5% relative to PA. Scanning electron microscopy and transmission electron microscopy were used to characterize the morphology of the blends and the clay interphase structure. The nanoclay content was shown to strongly influence both linear and non-linear tensile properties. Young's modulus, elongation at yield, yield strength, tensile strength and elongation at break as a function of clay fraction were studied and discussed in terms of morphological changes and strain-induced structural reorganization of the clay interphase.