Environmental stress cracking of polyethylene

Modification of the Griffith theory for the presence of liquids has been shown to explain some facets of the environmental stress cracking of polyethylene. In the absence of intercrystalline links and tie molecules, we find that one important factor is the interfacial tension generated between the spherulite boundary and the liquid environment. Judicious incorporation of silanes into polyethylene appear to reduce the tendency to stress cracking by modifying the interfacial tensions between the environment and the polymer.     

Environmental stress cracking of low-density polyethylene in normal alcohols

Fracture mechanics was used to investigate the environmental stress cracking of low-density polyethylene with 4.0 melt flow index. Annealed samples were prepared; a single edge notch was made and then the samples were fractured under constant load in four different liquid alcohols. The relation between the stress intensity factor K and the crack speed a˙ has been investigated. The log a˙ vs. logK curves are influenced not only by temperature but also by the alcohol used as the environment. This influence has been studied in detail. The conclusions are as follows: the crack speed at high K is determined by the diffusion mechanism, and this mechanism cannot be explained in terms of hydrodynamics but can be explained in terms of thermally activated molecular motion. On the other hand, the crack speed at low K is strongly related to the plasticization and the stress relaxation of the crack tip material.     

Influence of wetting properties of the liquid on environmental stress cracking of polyethylene at high stress

It has previously been shown that, under high stress and consequently at short times to failure, a major factor governing the environmental stress cracking (ESC) of polyethylene is the ability of a liquid environment to penetrate a growing fissure at a sufficiently high speed to maintain contact with the fracture front. In this earlier study, viscosity was shown to play a significant role in this kinetic effect. The purpose of the present paper is to demonstrate that another property of the solid–liquid system influencing ESC under these high stress conditions is the spreading coefficient of the liquid on the polymer—the parameter defining the tendency of the liquid to wet the polyethylene. It has been shown that the spreading coefficient can be considered as a force and this force in conjunction with atmospheric pressure constitutes the force necessary to drive the liquid into the growing crack.     

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.     

Environmental stress cracking of polyethylene: Analysis of the three zones of behavior and determination of crack-front dimensions

Previous work has shown that in the environmental stress cracking (ESC) of polyethylene, there are three major zones of behavior depending on the applied stress and the nature of the liquid environment. These three zones correspond to “pure” ESC (zone 1), ESC controlled by the speed of penetration of the liquid within a growing crack (zone 2), and behavior as in the absence of liquid (zone 3). Analysis of the transitions between zones has shown that, in the present case, a given liquid will either be capable of giving rise to all three types of behavior depending on the stress applied, or will be totally inactive. A related analysis has enabled the order of magnitude of the dimensions of the crack tip to be estimated and this has been found to be in the range of a micron.     

Temperature effects in the environmental stress cracking of polyethylene

An already existing model describing three types of behavior in the environmental stress cracking (ESC) of polyethylene (PE) subjected to uniaxial tensile loading at 25°C has been extended to cover the temperature range 25-50°C. Three effects have been observed and are found to be qualitatively consistent with the model. The transition between “pure” ESC (zone 1) and liquid-flow-controlled behavior (zone 2) occurs at shorter times for higher temperatures—an effect mainly due to reduced liquid viscosity. “Pure” ESC is less temperature dependent than failure occurring without the liquid playing a significant role (zone 3). This has been attributed to a compensation of reduced mechanical resistance of the polymer at higher temperatures, by reduced stress concentrations at the crack tip due to local absorption of the liquid. The transition time between zones 2 and 3 increases with temperature. Although it is surprising at first sight, this effect is shown to be compatible with the ESC model.     

Environmental stress cracking resistance of polyethylene: The use of CRYSTAF and SEC to establish structure–property relationships

Nineteen commercial high‐density polyethylene resins made with different polymerization processes and catalyst types were analyzed by high‐temperature size exclusion chromatography and crystallization analysis fractionation. The information obtained with these characterization techniques on the polymer chain structure was correlated to environmental stress cracking resistance. Environmental stress cracking resistance increases when the molecular weight and concentration of polymer chains that crystallize in trichlorobenzene between 75 and 85 °C increase. Polymer chains present in this crystallization range are assumed to act as tie molecules between crystal lamellae. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1267–1275, 2000     

Correlation between environmental stress cracking and liquid sorption for low-swelling liquids

The environmental stress cracking (ESC) of polyethylene has been studied under conditions of dynamic equilibrium with the liquid for low-swelling liquids. Even among active ESC agents, there is a clear relative order of efficiency. It has been shown that the liquid becomes less efficient with increasing equilibrium swelling. This fact has been attributed to local plasticization of the crack front leading, in turn, to a reduction in the high-stress concentrations associated with a wedge-shaped crack. Some semiquantitative ideas are proposed in an attempt to explain the relation between ESC efficiency and volume/volume sorption.     

Effects of loading conditions and temperature on environmental stress cracking of low-density polyethylene

Fracture mechanics was used to investigate the environmental stress cracking (ESC) of low density polyethylene (LDPE). Annealed and quenched samples were prepared; a single edge notch was made and the samples were fractured under constant load in a liquid methanol environment. The relation between the stress intensity factor K and the crack speed ? has been investigated. There is a large difference between annealed and quenched samples in the variation of this relation with temperature and applied load. The cause of this difference is discussed in detail. We propose that thermally activated molecular motion is essential to ESC of the annealed LDPE while stress concentration contributes markedly to ESC of the quenched LDPE.     

Structural and rheological property relationship of bimodal polyethylene with improved environment stress cracking resistance

Five bimodal polyethylene samples with different molecular parameters were studied in order to understand the incidence of molecular architecture on the environment stress cracking resistance (ESCR). The results showed that the tensile strain hardening stiffness at low strain rate was shown to be a fast and reliable indicator for evaluating ESCR of polyethylene. The reduction of chain dimension from phase separation would lead to the decrease of the possibility for a molecular in melt to form a tie molecular but an increasing number of short chain branch content was shown to increases strain hardening stiffness or tie chains. Physical chain entanglements were established as another source of inter-lamellar linkages that contribute to ESCR of polyethylene. Within the similar branch content and no phase separation, due to an increasing in plateau modulus was shown to increases hardening stiffness or ESCR of resins.     

Environmental stress cracking of poly(vinyl chloride) in alkaline solutions

The environmental stress cracking (ESC) effects on PVC of various high pH sodium hydroxide environments have been studied. The behaviour of PVC specimens in air and pH 12, 13, 13.5 and 14.39 sodium hydroxide solutions has been examined under three-point bend, tensile and creep conditions. Two parameters were used in three-point bend testing to determine the effect of an applied strain and high pH environment on the stability of PVC, namely time to craze initiation and width of crazing. It was found that, in general, crazing occurred sooner and to a greater degree with increasing strain and pH, although there was some evidence that craze growth was most rapid at pH 13.5. The results also indicated a critical strain value of 1.5–1.6%, below which crazing was not observed in any of these alkaline environments. Creep and tensile testing revealed that the time for which a PVC specimen was immersed in the environment was very important in determining the severity of the environmental effect. Creep tests at elevated temperatures showed that the time for the effects to be manifest decreased with increasing temperature. Creep rates were highest in pH 13.5 sodium hydroxide solution indicating that this was the most hostile of the environments considered.     

Ionic liquid integrated polyethylene glycol (PEG)-based quasi-solid electrolyte for efficiency enhancement of dye-sensitized solar cell

Journal of Solid State Electrochemistry - We are presenting herein the effect of using three different cell electrolytes namely: (a) propylene carbonate containing 0.2 M LiI and...     

Low-temperature radiation-induced cracking of liquid hydrocarbons

Conditions of chain cracking reactions in liquid hydrocarbons at lowered temperatures are discussed subject to contribution of the long-living radiation-excited molecular states. It is predicted that chain reactions of hydrocarbon degradation can proceed without thermal activation at the high dose rates of ionizing irradiation. In this process, both initiation and propagation of the chain are caused only by the action of radiation. Experimental verification has allowed observation of low-temperature chain cracking reactions in high-viscous oil.     

Testing plastics for resistance to environmental stress cracking

Methods of test for measuring the resistance of plastics to environmental stress cracking are critically reviewed. Particularly consideration is given to the relative merits of constant strain and constant stress tests and the most suitable procedure for the generation of design data discussed. Note is taken of the position regarding national and international standardisation.     

Catalytic cracking of polyethylene waste in horizontal tube reactor

In this study catalytic and thermal cracking of polyethylene waste were investigated in continued tube reactor system. HZSM-5 and equilibrium FCC type catalysts were tested. Both the resistance to deactivation and the regeneration process of the catalyst were studied. Reaction temperature of 545 °C and residence time of 20 min were used during the cracking treatment. The reaction products were analyzed and the textural properties of catalysts were also determined. It was found that after the first reaction run the FCC catalyst lost 75% of its cracking activity, in case of HZSM-5 the rate of deactivation was higher. The cracking activity of catalyst could be improved by regeneration process with only 2-3% compared to the coked catalyst. The isomerisation effect of the catalysts was also observed. The effect of coked FCC catalyst could be improved by the regeneration process with 50% in case of HZSM-5 it was only 25%.     

Mechanism of stress cracking of poly(ethylene terephthalate) beverage bottles: A method for the prevention of stress cracking based on water hardness

A recently described bottle test method was used to evaluate the dependence of stress crack failure of poly(ethylene terephthalate) (PET) carbonated soft drink bottles on water hardness. Although the industry belief is that water hardness is irrelevant to stress cracking, it was found that hardness ions exert a tremendous positive impact by deactivating water alkalinity through precipitation as harmless carbonate minerals. This mitigating effect of hardness means that no complete understanding of stress cracking as a function of alkalinity is possible without also considering water hardness. A useful concept is that of excess alkalinity, which is defined as alkalinity that is not precipitated during solution evaporation. Limiting excess alkalinity by using water with sufficient hardness is an effective means of stress crack prevention in PET soft drink bottles. Evaluation of compositions which are typical of those used for lubricating PET bottles on production conveyors showed that the role of these compositions in stress cracking was that of spectators, that is, they neither cause failure if water does not otherwise cause it, nor stop failure if water otherwise causes it.     

Criteria of efficiency of cellulose acetate plasticization

Using cellulose acetate plastics as an example, it was shown that the search for the optimal concentrations of plasticizers should take into account the compatibility of components, as well as the thermophysical and mechanical properties of plasticized polymers. It was suggested that the temperature range of durability of a plastic, i.e., the difference between its glass-transition and brittle temperatures, be used as a plasticization efficiency criterion. Plasticizers that are well compatible with a polymer at processing temperatures but show a limited compatibility at its service temperatures make it possible to manufacture goods with an extended durable temperature range.     

Catalytic cracking of polyethylene over nanocrystalline HZSM-5: Catalyst deactivation and regeneration study

In this work, catalytic cracking of low density polyethylene (LDPE) over nanocrystalline HZSM-5 zeolite in a batch reactor at 340 °C was carried out with the aim of study both the catalyst resistance to deactivation and the catalyst regeneration process. For looking into the catalyst deactivation, consecutive polyethylene cracking experiments were carried out. Subsequently, the same reactions has been also performed but by regenerating the zeolite after each experiment by promoting coke combustion at 550 °C under air flow. Zeolites used were two samples of nanocrystalline HZSM-5 with very different textural properties (sample A, with most of its surface corresponding to zeolitic micropores and sample B with a considerable amount of external surface, mesopores and super-micropores) in order to study the effect of their textural properties in the deactivation and regeneration experiments. Although conversion and activity values reached over both samples are quite high taking into account the mild conditions used, sample B shows a very much higher initial activity than A due to its improved textural properties. In both samples two different deactivation mechanisms occur: a reversible deactivation by coke deposition removable by the regeneration procedure, and an irreversible or permanent deactivation by other factors. Deactivation of sample B occurs faster due to the higher amount of coke deposited on this material. However, the improved textural properties of this catalyst supposes an advantage for the regeneration process, since coke deposited either on the external surface or on the super-micropores and mesopores, makes easier the regeneration procedure.     

A test method for the determination of the stress cracking effects of liquid environments on thermoplastics by measurement of critical strain

The stress cracking effect of liquids on thermoplastic materials can be quantified by measuring the critical strain to cause cracking or crazing. The critical strain is ideally defined as the value of applied strain, for a given material and liquid combination, below which no cracking or crazing occurs. A method is described for the determination of critical strain using a simple straining jig. A strain gauge extensometer attached directly to the specimen is used to accurately monitor the applied strain while visual observation of the sample is used to record the time to crack or craze.Critical strain values measured by this technique are quoted for various alcohols and ketones in contact with polycarbonate and compared with literature values.