A kinetic effect in the environmental stress cracking of polyethylene due to liquid viscosity

An Interesting kinetic effect in the environmental stress cracking (E.S.C.) of polyethylene has been observed, in which the liquid viscosity plays an important role. E.S.C. of a low density, high melt index polyethylene due to silicone oils has been studied using constant load creep experiments. For relatively low stresses, it has been found that the time to fracture is independent of the viscosity of the silicone oil, all other factors being approximately equal. However, at high stresses, the time to fracture increases with increasing viscosity for a given stress. This effect has been shown to be due to the relative ease with which the liquid penetrates a growing crack and thus always be at the crack front. Times to fracture for viscous liquids at high stresses are longer since crack propagation continues partially with and partially without liquid contact, fracture rate being much slower when not in the presence of the liquid.     

Hydrothermal ageing of radiation cured epoxy resin-polyether sulfone blends as matrices for structural composites

The hydrothermal ageing of epoxy-thermoplastic blends, used as matrices for carbon fibre composites, cured by electron beam, has been studied. Two different thermoplastic percentages have been adopted. A suitable choice of both curing process and formulation parameters allows to carry out irradiation at mild temperature with several advantages, coming from a “non thermal” process, for both the final properties of the materials and the environment. Nevertheless the occurring of vitrification phenomena needs the use of a short thermal treatment after irradiation on the already solid materials, in order to complete the cure reactions. Radiation cured epoxy based matrices have been subjected to a thermal and moisture absorption ageing treatment and its influence on the thermal and mechanical properties has been investigated through dynamic mechanical thermal analysis and fracture toughness tests. The results have been interpreted on the basis of the different curing degree reached by the investigated systems and in the light of their morphological structures. Plasticization, thermal curing and degradation reactions occur in different extent depending on the kind of the material. In particular, for fracture properties, a better resistance to ageing is shown by the system at higher thermoplastic concentration.     

Relationships between microstructure and pitting corrosion of ADI in sodium chloride solution

Austempered ductile iron (ADI) has complex microstructure containing a multiphase matrix (called ‘ausferrite’), graphite spheres and oxide inclusions. The corrosion resistance of ADI is related to its microstructure which is determined by heat treatment parameters (like austempering temperature, austempering time, austenitising temperature and austenitising time). In the present paper, the electrochemical behaviour and corrosion resistance of ADI have been investigated by means of the electrochemical microcell technique and classical electrochemical measurements in sodium chloride solution. Particular attention has been paid to the influence of austempering temperature on the microstructure and pitting corrosion. It has been shown that ADI austempered at 430 °C has upper ausferritic microstructure and reveals a better corrosion resistance in sodium chloride solution than ADI austempered at 280 °C. Moreover, the corrosion resistance increases as the volume fracture of ferrite increases and the carbon content of austenite decreases. The good corrosion behaviour of ADI austempered at 430 °C was also related to the good coarsening of the austenite grains and broad ferrite needles (less ferrite/austenite interfaces). It has been demonstrated that silicon is the alloying element hindering the anodic dissolution of the alloy.     

Characterizing fracture energy of proton exchange membranes using a knife slit test

Pinhole formation in proton exchange membranes (PEM) may be caused by a process of flaw formation and crack propagation within membranes exposed to cyclic hygrothermal loading. Fracture mechanics can be used to characterize the propagation process, which is thought to occur in a slow, time‐dependent manner under cyclic loading conditions, and believed to be associated with limited plasticity. The intrinsic fracture energy has been used to characterize the fracture resistance of polymeric material with limited viscoelastic and plastic dissipation, and has been found to be associated with long‐term durability of polymeric materials. Insight into this limiting value of fracture energy may be useful in characterizing the durability of proton exchange membranes, including the formation of pinhole defects. In an effort to collect fracture data with limited plasticity, a knife slit test was adapted to measure fracture energies of PEMs, resulting in fracture energies that were two orders of magnitude smaller than those obtained with other fracture test methods. The presence of a sharp knife blade reduces crack tip plasticity, providing fracture energies that may be more representative of the intrinsic fracture energies of the thin membranes. Three commercial PEMs were tested to evaluate their fracture energies (G_c) at temperatures ranging from 40 to 90 °C and humidity levels varying from dry to 90% relative humidity (RH). Experiments were also conducted with membrane specimens immersed in water at various temperatures. The time temperature moisture superposition principle was applied to generate fracture energy master curves plotted as a function of reduced cutting rate based on the humidity and temperature conditions of the tests. The shift with respect to temperature and humidity suggests that the slitting process is viscoelastic in nature. Also such shifts were found to be consistent with those obtained from constitutive tests such as stress relaxation. The fracture energy is more sensitive to temperature than on humidity. The master curves converge at the lowest reduced cutting rates, suggesting similar intrinsic fracture energies; but diverge at higher reduced cutting rates to significantly different fracture energies. Although the relationship between G_c and ultimate mechanical durability has not been established, the test method may hold promise for investigating and comparing membrane resistance to failure in fuel cell environments. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 333–343, 2010     

Special fracture mechanics specimens for multilayer plastic pipes testing

Pipes consisting of layers of different materials (multilayer pipes) are considered. The fracture toughness value of the main pipe is taken into account as a parameter relevant to fracture assessment connected with the resistance of pipe material against slow crack growth. With the aim of simplifying estimation of main pipe material fracture toughness, non-homogeneous test specimens cut directly from multi-layer pipes are suggested and numerically analysed. The values of the corresponding stress intensity factor K_I and biaxiality factors B are calculated for the case of two and three layer test specimens. Based on the results obtained, the transferability of fracture toughness values measured on laboratory specimens to pipe systems is discussed. It is shown that in most cases of multi-layer commercial pipes and routine fracture toughness measurements the values of the stress intensity factor calculated on the basis of homogeneous specimens can be used.     

Transport in ceria electrolytes modified with sintering aids: effects on oxygen reduction kinetics

Small (2 mol%) cobalt oxide additions to ceria-gadolinia (CGO) materials considerably improve sinterability, making it possible to obtain ceramics with 95–99% density and sub-micrometre grain sizes at 1,170–1,370 K. The addition of Co causes a significant shift of the electrolytic domain to lower pO₂. This modification to the minor electronic conductivity of the electrolyte material has influence on the cathodic oxygen reduction reaction. The impedance technique is shown to provide information not only about polarisation resistance, but also about the active electrode area from analysis of the current constriction resistance. It is demonstrated that this current constriction resistance can be related to the minor electronic contributions to total conductivity in these materials. A simple imbedded grid approach gives control of the contact area allowing the properties of the electrolyte materials to be studied. A much lower polarisation resistance for the Co-containing CGO electrolyte is observed, which can be clearly attributed to an increased three-phase reaction area in the Co-containing material, as a consequence of elevated p-type conductivity.     

Effect of mechanical pre-conditioning on fracture resistance of polypropylene

The effect of externally applied mechanical pre-conditioning,i.e.pre-impact treatment,on the fracture resistance was investigated for polypropylene(PP).Impact strength was obtained via notched and/or unnotched samples.It has been shown that the pre-impact treatment is favorable to the improvement of the fracture resistance.The impact strength increases linearly with the applied pre-impact energy.Both optical and SEM results show that there are at least two possible mechanisms for the improvement of the fracture resistance.One is the crack blunting effect which is introduced to notched sample by pre-impact treatment,reducing the sensitivity of PP to the applied notch.The other is the formation of large amount of microvoids induced by pre-impact treatment,which changes the stress distribution and induces intensive plastic deformation of PP at the second impact measurement,leading to the improvement of the fracture resistance.     

Clays as selective catalysts in organic synthesis

Suitably modified smectite clays can be very selective catalysts for a wide range of organic reactions. While it has long been known that such materials can act as Bronsted and Lewis acids, it has been shown recently that they are also effective Diels-Alder catalysts. A selection of illustrative reactions is given which emphasises their wide range of use, their selectivity, and the ease of work-up after reaction. In each case, mechanistic information is presented, e.g., on the site of reaction (whether interlayer or surface), rate determining steps, etc. The regiochemical consequences of the restricted reaction space are stressed.Based on material presented at the Fourth International Symposium on Inclusion Phenomena and the Third International Symposium on Cyclodextrins, Lancaster, U.K., 20–25 July 1986.     

Cyclic tests on cracked round bars as a quick tool to assess the long term behaviour of thermoplastics and elastomers

The aim of this work is to demonstrate the applicability of the cracked round bar test recently developed for PE-HD to other polymeric materials. The main advantage of this new test method are rather short testing times for PE-HD materials used in long-term applications such as piping. Therefore, this test is of high interest for other polymers used in similar applications.Five thermoplastic materials used for plumbing (PE-HD, PP-B, PB, PVC-U, PA12), a technical polymer (POM) and an elastomeric material (H-NBR) have been tested. Scanning electron microscopy has been applied to investigate fracture surfaces.Results show that the test method seems to be basically applicable to all tested materials. Most materials showed similar fracture behaviour as postulated in literature, despite the high acceleration factor of the cyclic CRB test.     

Influence of block composition on crack toughness behaviour of styrene-b-(styrene-random-butadiene)-b-styrene triblock copolymers

The deformation and fracture behaviour of symmetric and asymmetric styrene-b-(styrene-random-butadiene)-b-styrene (S-SB-S) triblock copolymers with variations in their molecular architectures in terms of their outer PS block and the random SB middle block composition ratios have been investigated using essential work of fracture approach based on post yield fracture mechanics concept. The present investigations on crack resistance behaviour of these S-(S/B)-S triblock copolymers where effective interaction parameter (χ_eff) is systematically varied through the variation of block compositions and architecture is in continuation to our earlier communicated short article highlighting the phase behaviour-morphology and mechanical property interrelation. The crack initiation and propagation behaviours are correlated to morphology and dynamic mechanical properties as obtained from TEM, SAXS and DMA measurements. The influence of interaction parameter (χ-parameter) space which has been manipulated through the variation of block compositions has clearly manifested in their morphologies and in their mechanical properties. Further the kinetic aspects of fracture mechanical response have also been investigated where all the materials have clearly revealed block composition dependence. SEM analysis was carried out to understand the fracture modes prior to failure.     

Recent progresses on solution-processed silver nanowire based transparent conducting electrodes for organic solar cells

Organic photovoltaics (OPVs) are considered as a future alternative for conventional silicon based solar cells, owing to their low cost, ease of production and high-throughput. The transparent conducting electrode (TCE) is a fundamental component of OPVs. Traditionally, indium tin oxide (ITO) has been mainly utilized as a TCE in OPV applications due to its relatively high transparency and low sheet resistance. However, increasing demand for the optoelectronic devices has led to large fluctuations in ITO prices in the past decade and ITO is known to account more than 50% of the total cost of OPV devices. Thus, it is believed that development of solution-processable alternative materials is of great importance in reducing the cost of OPVs. Numerous materials, including silver nanowires, carbon nanotubes, graphene and conducting polymers, have been offered as replacements for ITO. This article reviews recent progress on fabrication of TCE via solution based coating techniques of silver nanowires (Ag NWs). In addition, performance of the Ag NWs based TCE in OPVs is summarized. Finally, we explore the future outlook for Ag NWs based TCE at the end of the review.     

Intercalated clay nanocomposites: Morphology,mechanics, and fracture behavior

Intercalated nanocomposites of modified montmorillonite clays in a glassy epoxy were prepared by crosslinking with commercially available aliphatic diamine curing agents. These materials are shown to have improved Young's modulus but corresponding reductions in ultimate strength and strain to failure. The results were consistent with most particulate‐filled systems. The macroscopic compressive behavior was unchanged, although the failure mechanisms in compression varied from the unmodified samples. The fracture toughness of these materials was investigated and improvements in toughness values of 100% over unmodified resin were demonstrated. The fracture‐surface topology was examined using scanning electron and tapping‐mode atomic force microscopies and shown to be related to the clay morphology of the system. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 1137–1146, 2001     

High-modulus polydiacetylene single-crystal fibers

The relationship between structure and mechanical properties of polydiactetylene single-crystal fibers has been studied in detail. It is shown by transmission electron microscopy that the fibers have a high degree of internal perfection, with the polymer molecules aligned parallel to the fiber axes. The fibers of the dicarbazolyl derivative investigated were found to have a Young's modulus of 45 GPa and fracture strengths of up to 1.5 GPa, the strengths being controlled by defects such as surface steps. It is shown that the stiffness of the polymer backbone is similar to that of polyethylene, and the theoretical strength of the polydiacetylene singlecrystal fibers is determined to be about 3 GPa, corresponding to a fracture strain of between 6 and 8% and a force required to break molecules to the order of 3 nN. The derivative studied is also found to have good thermal stability, not degrading below 300°C, and excellent creep resistance up to at least 100°C. The possibility of using the single-crystal fibers in composites is also discussed.     

Instrumented Macroindentation Techniques for Polymers and Composites – Mechanical Properties,Fracture Toughness and Time-Dependent Behaviour as a Function of the Temperature

An innovative cooling and heating device has been successfully applied to an instrumented macrohardness testing machine in close collaboration with the company Zwick/Roell. The prototype allows the local time-dependent analysis of mechanical properties such as Martens hardness and indentation modulus, as well as fracture toughness and creep and relaxation behaviour at temperatures ranging from −100 °C to +100 °C. On the basis of load–indentation depth, load–time or indentation depth–time diagrams, the indentation behaviour as a function of test speed and/or temperature (which has rarely been done for polymers in the macro-range of loading) depending on matrix and materials composition (amorphous/semicrystalline thermoplastics, epoxy resins, micro- and nanocomposites) has been analysed. Martens-hardness, indentation modulus on the one hand and creep compliance and relaxation modulus on the other have been found to be strongly temperature dependent. Adequate methods of indentation fracture mechanics have been enhanced for polymers and applied to determine the fracture toughness of very different polymer-based materials.     

Interlaminar Fracture Toughness Characterization of Laminated Composites: A Review

Abstract

Interlaminar fracture toughness had been the subject of great interest for several years and is still interesting to the research community. In this article, a comprehensive analysis of fracture toughness in FRP laminates is presented. Primarily, toughness studies are undertaken on glass and carbon fiber reinforced composites under mode-I and mode-II loading conditions. The fracture behavior and its failure pattern depend on a number of parameters: fiber sizing/coating, matrix modification, insert film, fiber volume fraction, stacking sequence, specimen geometry, loading rate and temperature change. In fact, a state-of-the-art process enables increasing fracture resistance with “matrix toughening by carbon nanotubes (CNT) inclusion”. It enables production of materials having ultra-high strength and low weight. The present study has highlighted the available techniques of CNT incorporation: mechanical mixing, grafting and interleaving. Other aspects, such as the dispersion level, matrix viscosity, fiber surface roughness, loading weight %, bonding strength with epoxy, height and density of grown CNT, energy absorption mechanism during delamination, etc., have been examined as well. Although a clear correlation of all these parameters with fracture toughness is hard to establish, there is growing understanding of the surface-grown CNTs and interleaving processes as they ensure significant increase in fracture toughness.     

A comparison of fracture and permanganic etching of polypyrrole films

The internal organization within electrochemically polymerized films of the conducting polymers polypyrrole p-toluene sulphonate and polypyrrole sulphate has been examined by scanning electron microscopy (SEM) following transverse fracture and permanganic etching of microtomed cross sections. X-ray scattering studies have shown these two materials to exhibit very different internal ordering: polypyrrole p-toluene sulphonate is thought as being anisotropic, with the counter ions and polypyrrole chains lying down preferentially in the plane of the work electrode, whereas polypyrrole sulphate is considered to be isotropic. Comparison of the internal textures following the two different preparative techniques shows significant differences. Whereas the morphology revealed in transverse fracture surfaces correlates closely with x-ray scattering data, etched surfaces exhibit a morphology that is in good agreement with the direct examination of sections prepared by ultramicrotomy. Despite the apparent contradiction in these two sets of data, a consistent picture of the true morphology (as revealed by permanganic etching) can be deduced and reconciled with the fracture surface micrographs. © 1996 John Wiley & Sons, Inc.     

“On the use of the essential work of fracture procedure in the determination of the fracture energy of tough polymeric materials”

The determination of the energy of fracture of tough polymeric materials in plane strain conditions by means of the essential work of fracture procedure has nowadays two open questions. The first is related to the ligament length that has to be used when the impact specimens break partially upon testing, and the second is related to the way to assure that the crack propagation occurs in an already yielded zone. The use of i) a “true ligament length” associated with only the broken area and ii) impact specimens yielded in the notch zone in a previous tensile test, are evaluated and proposed.     

Recent Advances on the Abrasion Resistance Enhancements and Applications of Superhydrophobic Materials

Researches on superhydrophobicity have been overwhelming and have shown great advantages in various fields. However, the abrasion resistance of superhydrophobic structures was usually poor, and they were easily damaged by external force or harsh environment, which greatly limited the applications of superhydrophobic surfaces. Much attention has been paid to improving the abrasion resistance of superhydrophobic materials by researchers. In this review, aimed at the advances on improving the abrasion resistance of superhydrophobic surfaces, it was summarized and compared three enhancement strategies including the reasonably design of micro-nano structures, the adoption of adhesives, and the preparation of self-healing surface. Finally, the applications of typical superhydrophobic materials with abrasion resistance were reviewed in various fields. In order to broaden the application fields of superhydrophobic materials, the abarasion resistance should be further improved. Therefore, we proposed the ideas for the future development of superhydrophobic materials with higher abrasion resistance. We hope that this review will provide a new approach to the preparation and development of stable superhydrophobic surfaces with higher abrasion resistance.     

The formation of cluster vibrations in imperfectly structured materials

The dynamics of cluster formation in imperfectly structured materials is discussed in terms of their evolution from a prepared state fluctuation. It is shown that this is accompanied by the generation of group oscillations of displacements in the centres/axes of motion of the cluster components. A fractional index defining the partitioning of the vibrational/librational energy between the group oscillations and the centre of motion vibrations is shown to be related to the structural regularity of the cluster. The generation of group oscillation has also been related to the change in configurational entropy attendant upon the irreversible formation of imperfectly structured clusters, expressed as the same fraction of the change arising from complete dissociation of the ideal state.     

Effect of processing on the environmental stress cracking resistance of high-impact polystyrene

Processing conditions have a strong effect on the final mechanical properties of products made of polymeric materials. Relevant phenomena most commonly include thermal stresses, physical ageing, frozen-in strains and molecular orientation. In this work, two different high-impact polystyrenes, processed by thermoforming, were considered: a “standard” one and a grade specifically resistant to Environmental Stress Cracking (ESC). The main effect induced by thermoforming was molecular orientation. The local degree of orientation was measured on a thermoformed product and its effect on the material ESC behavior in sunflower oil was studied. A Fracture Mechanics approach was applied to evaluate the fracture resistance of the two materials. Results show that a higher degree of orientation increases the fracture resistance in air but has no effect on the (expectedly lower) resistance in the active oil environment.