Hydrolysis of polycarbonate to yield BPA

Elevated temperatures and high humidity decrease the molecular weight and impact strength of polycarbonate. Hydrolysis of injection molded polycarbonate (PC) bars stored in glass containers at 85°C and 96% relative humidity (RH) produced brown surface crystals within 30 days. Aging of PC bars at 96% RH and temperatures of 70°C and lower for longer periods of time formed a brown liquid coating on the PC. X-ray, DSC, and GPC measurements indicated that about 70 wt% of the surface crystals were bisphenol A (BPA). The remaining portion of hydrolysis products appeared to be higher molecular weight oligomers of BPA. The brown liquid was composed of supercooled liquid BPA, BPA oligomers, and water. Initial growth of BPA on the surface of a PC bar took place at the interface between the PC and the glass wall of the container. Apparently a water soluble extract from the glass container accelerated the hydrolytic degradation of PC; nevertheless, hydrolysis of PC occurred in the absence of glass—although at a slower rate. Hydrolysis studies were carried out on several commercial PC formulations. The PC resin containing only a heat stabilizer was least affected. Of the fiame retardant grades, the brominated PC hydrolyzed less rapidly than these particular compositions containing alkali metal sulfonic acid salts. A glass fiber reinforced PC was less stable than its unfilled parent compound. A hydrolytic stabilizer was ineffective against the attack of water under these conditions.     

Growth of fatigue cracks in polycarbonate

The rapid increase in the rate of application of thermoplastics in engineering design problems and the interest in the structural use of these materials have resulted in the requirement of comprehensive information about the behaviour of thermoplastics when subjected to cyclic loading conditions. In addition to the “total fatigue life” data already available for many materials, attempts have been made to analyse the crack initiation and steady crack growth processes and determine the effects of parameters such as mean load, frequency and crack geometry on the rate of crack propagation. The results of an investigation of these aspects of fatigue crack growth in a brittle thermoplastic, polymethylmethacrylate (PMMA), have already been reported. In this paper, the results of a test program devised to study the behaviour, at room temperature and in air, of a polycarbonate, (PC), under similar loading conditions, are presented. Fracture Mechanics concepts have been used to analyse the results. It was found that a relationship of the form ?_N = β λⁿ already shown to predict the cyclic fatigue crack propagation rate in PMMA, is also applicable to polycarbonate. However, when the effects of frequency and loading rate were studied, it was found that after the magnitude of parameter K?( = ΔK/half the periodic time) exceeded 4000 lbf in. ^?3/2 s^?1, the influence of the mean level of stress intensity factor, K_m, became negligible in comparison to the effect of ΔK.     

Partial miscibility of poly(butylene terephthalate)/BPA polycarbonate melt blends

Summary Differential scanning calorimetry (DSC) measurements have been carried out on a number of poly(butylene terephthalate) (PBT)/BPA polycarbonate (PC) blends prepared by melt compounding and solution casting from hexafluoroisopropanol (HFIP). The results clearly indicate that appreciable mixing of the two polymers takes place in the melt phase whereas complete separation is observed in cast films. The failure of the casting procedure to mimic the melt blending results is related in part to liquid-liquid phase separation and to crystallization of both polymers from the casting solvent.     

A fatigue crack initiation map for polycarbonate

The mechanisms of fatigue crack initiation for various stress levels and thicknesses have been determined for single-edge notched specimens of polycarbonate and used to assemble a map. Three basic fatigue crack initiation mechanisms were identified and named as cooperative ductile (the damage zone formed ahead of crack consisting of yielded material), solo-crack brittle (very little damage zone development), and cooperative brittle (identified as a cloud of microcracks or crazes that developed at the notch tip). With a given applied stress and within the same failure mechanism, the values of the number of cycles to crack initiation decrease with increase in thickness. The transition from cooperative ductile to solo-crack brittle initiation mechanisms is sudden with increasing thickness. Transition from cooperative ductile to cooperative brittle with decreasing stress was less well defined. Regions where combinations of mechanisms were observed are also identified in the map. © 1993 John Wiley & Sons, Inc.     

Impact fatigue of a polycarbonate/acrylonitrile-butadiene-styrene blend

This study analyzes the impact properties of a polycarbonate/acrylanitrile-butadiene-styrene (PC/ABS) blend. The specimens were prepared under various injection molding conditions, including filling time, melting temperature, and mold temperature. Impact tests were performed with a Dynatup drop weight impact tester at different impact energies (10, 15, 20, 25 J). The fracture mechanism was examined with a scanning electron microscopy. The results indicated that the load-time history of the PC/ABS blend has approximately a sinusoidal form in impact. The best injection molding conditions are a filling time of 12 s, a melting temperature of 260°C and a mold temperature of 80°C. In this case, the specimen shows the highest energy absorbed in single impact, together with the highest impact number in impact fatigue. The impact number and the accumulation energy seem to follow an exponential curve as the impact energy decreases. The PC/ABS blend material clearly exhibited ductile fracture with a continuous reduction in strength by viscoplastic deformation. The higher the impact number, the higher the accumulation energy. The accumulation energy of impact fatigue with impact energy 10 J is about 35–45 times greater than the energy absorbed in single impact. Tearing, shear fracture, and plastic deformation are the major fracture mechanisms of the PC/ABS blend matrix in single impact and repeated impact conditions.     

The morphology and deformation behavior of poly(butylene terephthalate)/BPA polycarbonate blends

Summary In this communication the results of a series of recent studies of the morphology and deformation behavior of toughened poly(butylene terephthalate) (PBT)/BPA polycarbonate (PC) blends are briefly summarized. Several papers containing a more detailed account are currently in press (1–3). Among the unique morphological features of these blends are the consistent isolation of the core/shell impact modifier (IM) in the PC phase and the crystallization and phase separation of the PBT from the partially miscible PBT/PC melt on slow cooling. DSC studies provide corroborating evidence for melt miscibility of the two resins. The blends deform through a combination of cavitation and shear processes. In all cases cavitation occurs exclusively within the IM particles and is suppressed at higher PC concentrations and elevated temperatures.     

Polymer reaction in polycarbonate with Na2CO3

The recombination of polycarbonate (PC) chains has been researched as one of the studies on self‐repairing materials. The specimens, which included sodium carbonate and Tri(2,4‐di‐t‐buthylphenyl)phosphate, were treated at 120°C in a steam chamber and subsequently at 130°C under nitrogen atmosphere. The molecular weight of the specimen with 0.1 ppm of sodium carbonate increased during the subsequent treatment. The same tendency was observed when sodium carbonate was supplementally added to the specimen. In particular, the molecular weight little changed under severe condition when the concentration of sodium carbonate was controlled to be 100 to 1000 ppm. The result showed PC could be used as a self‐repairing material. The deterioration is expected to be minimized if the recovery rate is the same as the deterioration rate by applying these self‐repairing systems. The tensile strength, the transparency, and the reaction schemes are discussed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 920–926, 2004     

Impact fracture behavior of molecularly orientated polycarbonate sheets

The impact fracture behavior of molecularly orientated polycarbonate (PC) sheets was investigated. The molecular orientation was achieved via a newly developed equal channel angular extrusion (ECAE) process. Improvement in impact fracture propagation resistance was observed in the ECAE processed PC sheets. The improved impact resistance was found to be directly related to the changes in molecular orientation because of ECAE. The unique characteristics of the ECAE process for polymer extrusion are described. The potential benefits of ECAE in enhancing physical and mechanical properties of the extruded PC sheets are discussed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2060–2066, 2001     

Rheological interpretation of heat generation associated with fatigue of polycarbonate

Temperature change was measured of polycarbonate under monotonically increasing tensile and pulsating tensile loads. In the former case, the specimen temperature began to rise when an appreciable amount of viscoelastic strain was noticed on the stress—strain diagram. The rise, θ_v, could be formulated as a function of the viscoelastic strain, εv: In fatigue tests, the average temperature began to rise immediately after the decrease due to the thermoelastic effect. The amount of the heat generation, σ, was nearly constant for each cycle throughout the fatigue process and has a relation to the fatigue life, N_f, (α? a)·N_f = constant, where a is another adjustable constant. From a rheological aspect of dissipation energy, the equation is transformed to a relation between the viscoelastic strain and the fatigue life as εV^1/2 · N_f = constant, which is similar to the one for metals given by Manson and Coffin.⁶ The temperature rise in the fatigue was also related to the viscoelastic strain. The relation is of the same form as for static tension but less by a factor of one order.     

Degradation depth profiles and fracture of UV exposed polycarbonate

Abstract

Photodegradation depth profiles have been determined in 3 mm thick polycarbonate injection moulded bars using molecular mass measurements and an attempt made to relate the results to the fracture behaviour in uniaxial tensile tests. Unstabilised samples were compared with similar bars containing a commercial stabilising system. Although the presence of stabiliser restricted molecular mass degradation to a thin surface layer, with little degradation indicated beyond 0·1 mm from the exposed surface, the bars made from stabilised polymer embrittled at least as quickly as those made from unstabilised material, for which molecular mass degradation was evident at least up to 0·4 mm from the exposed surface. The as moulded compressive residual stresses near the surface of unstabilised polycarbonate bars increased in magnitude on UV exposure during the period in which embrittlement developed and may have partially countered the eects of molecular degradation, whereas little varition in the residual stress distribution with exposure was observed in stabilised polycarbonate.     

Temperature dependence of craze shape and fracture in polycarbonate

The shape of the craze at the tip of a loaded crack has been determined by optical microscopy for polycarbonate. The effect of temperature was examined, and measurements were made on samples of different molecular weight. In all cases the craze shape can be described to a good approximation by the Dugdale model for the plastic zone at a crack tip. The crack opening displacement depended on sample molecular weight, but was independent of temperature. Fracture toughness values deduced from the craze shape were in good agreement with plane strain fracture toughness obtained from direct cleavage fracture measurements, on the assumption that failure occurs by combined plane strain and plane stress fracture modes.     

Polymer crosslinking controlled by release of catalyst encapsulated in polycarbonate micro-spheres

EVA crosslinking by ester-silane exchange reaction, controlled by catalyst released from polycarbonate micro-particles, was studied from rheological experiments. Firstly, dibutyltin dilaurate in polycarbonate (PC) (DBTDL) catalyst was encapsulated in polycarbonate micro-particles by an emulsion process. These PC micro-particles have a trimodal size distribution with a mean diameter around 25 μm. Furthermore, scanning electronic microscopy analysis revealed that the DBTDL catalyst is homogeneously dispersed in PC micro-particles. This was verified by DSC experiments which showed a T_g equal to 72 °C for the DBTL micro-particles. Secondly, the deformation and break-up studies of PC micro-particles in molten EVA matrix showed that PC micro-particles can only break up in EVA matrix of high molecular weight (EVA28-03) and for temperatures higher than 200 °C. Thirdly, rheological experiments showed that the crosslink reaction is controlled by the diffusion rate of DBTDL from PC micro-particles. However, this diffusion rate was observed to be independent on either the temperature or the PC micro-particles size.     

Micromechanisms of interlaminar fracture and fatigue

The interlaminar fracture and fatigue properties of AS/3501-;6 graphite/epoxy are discussed from a mechanistic point of view. Particular emphasis is placed on the interaction between the loading mode and the local geometry of the interlaminar zone and on how this affects the stresses close to the crack tip and the resulting failure path. Delamination growth under Mode I loading is shown to depend on the likelihood of fiber bridging occurring and on how effective these bridged fibers are at diverting strain energy away from the crack tip. The Mode II behavior is controlled by both the work required to shear the fibers from the matrix and the ease with which tensile failure of the matrix between the fibers can occur.     

Some observations on fatigue and crazing of polycarbonate (bisphenol A)

Amorphous, unoriented polycarbonate (bisphenol A) films are cyclically fatigued at several tensile stress levels below their yield stress. The fatigued films have been investigated by X-ray scattering, density measurements, and dynamic mechanical tests (Rheovibron). The X-ray data suggest a decrease of the interchain distances in the fatigued films by about 1 %. In spite of this improved packing the overall density shows a decrease (of 0.08 %). The dynamic mechanical testing reveals shifts of both the and relaxation peaks towards lower temperatures. In addition, many of the fatigued film samples fracture at the cryogenic temperatures during the tests on the Rheovibron. These results lead to the conclusion that microvoids are formed in the fatigued polymer. The microvoids are distributed throughout the fatigued polymer and weaken the material.     

Effect of notches and glass fiber reinforcement on fatigue behavior of polycarbonate

In order to investigate the effect of a notch on the tensile properties of polycarbonate and 30% glass fiber-reinforced polycarbonate, two types of notched specimens were prepared. These notches were a sharp 60° notch and a dull notch with rounded tip 1.5 mm in radius at the base of the 60° notch. The notches decreased the tensile strength of polycarbonate. The sharp notch reduced tensile strength more effectively than the dull notch. In 30% glass fiber-reinforced polycarbonate, even the dull notch decreased the tensile strength considerably. Unnotched polycarbonate was subjected to cyclic tensile loading of 10⁴ cycles at 10 Hz, with varying cyclic stress. It was found that the elongation at break decreased rapidly with increase in cyclic stress. The notches considerably decreased the tensile fatigue strengths of polycarbonate and glass fiber-reinforced polycarbonate in 10⁴ cycles at 10 Hz.     

The effects of stress cracking on the fracture toughness of polycarbonate

The growth of crazes from a sharp crack in extruded polycarbonate sheets immersed in ethanol was measured. Below a critical level of the stress intensity factor craze growth was controlled by solvent diffusion through the end of the notch and fracture was prevented by craze arrest. Above a critical level, growth was controlled by either end diffusion or a combination of end diffusion and diffusion through the faces of the extruded sheet, and in both cases the final result was brittle fracture. The effects of annealing and quenching was studied at various sheet thicknesses. In thin specimens annealing and/or quenching had a significant effect on crack growth rate, which was predictable in terms of the state of stress. As the specimen thickness increased, causing a transition from plane stress to plane strain conditions, the previous thermal history had a diminishing effect on craze growth rate. The effects of thermal history and thickness on the fracture toughness of polycarbonate was also investigated. It was found that thickness was the more important variable and that at a ½ in. thickness the effects of thermal history were statistically insignificant. The effect of ethanol exposure on fracture toughness was studied. It was found that exposure to solvent initially caused an increase in k_IC with time to a maximum value, followed by a substantial decrease with time which eventually led to brittle fracture. This behavior was explained as a competition between plasticization of the crack tip and coalescence of crazes to form microcracks.     

Craze dissemination during fatigue fracture in polystyrene

Results of studies on fatigue fracture in polystyrene are reported. Experiments were carried out on tension-tension single edge notched specimens, 0.25 mm thick. Macroscopic studies involved the propagation of the crack and its associated active zone (or the so-called process zone) evolution. Microscopic studies consisted of fracture surface examination and quantitative characterization of the crazing distribution along the trailing edge and within the active zone. The width and length of the active zone increased monotonically during the quasi-static phase of crack layer growth. The crack growth kinetics followed an S-shaped curve. Analysis of crazing distribution showed that; (i) the distribution of crazing along the trailing edge of the active zone is related by a scaling parameter, (ii) the average crazing density along the trailing edge as well as within the active zone is constant, (iii) the specific energy of crazing evaluated here compares well with previously reported data. The results of this work support the form of self similarity of damage evolution adopted by the crack layer model, and that the specific energy of damage is a material constant.     

The effect of rolling orientation on the brittle-ductile transition in polycarbonate fracture

The effect of orientation on the brittle-ductile transition in rolled polycarbonate was examined. It has been believed that the brittle-ductile transition is governed by the residual stress at low reduction and the orientation at high reduction. But, our experimental results revealed that the brittle-ductile transition is caused by neither the residual stress nor orientation. It is proposed that the brittle-ductile transition may be ascribed to the morphological change which is produced during plastic deformation on rolling.     

Effect of molecular weight on craze shape and fracture toughness in polycarbonate

The shape of the craze at the tip of a crack has been studied using optical microscopy on polycarbonates of various molecular weights at ?30°C. For all molecular weights studied the craze shape was well approximated by the Dugdale plastic zone model and this model was used to calculate the craze stress and the release rate in plane strain. It was found that the craze dimensions, the craze stress and the strain energy release rate in plane strain all increased with increasing molecular weight. Fracture of macroscopic specimens showed a mixed mode fracture in all molecular weights. By studying the effect of thickness the strain energy release rate in plane strain was calculated for various molecular weights. Agreement was found between these values and those determined from the craze shape measurements. The overall strain energy release rate, the strain energy release rate in plane strain and the contributions from the plane stress mode increased with increasing molecular weight.     

Interlaminar fracture toughness and fatigue fracture of continuous fiber-reinforced polymer composites with carbon-based nanoreinforcements: a review

ABSTRACT

This review critically examines the recent developments in the use of carbon-based nanofillers as additional reinforcement to enhance the interlaminar properties of FRP composites. The low interlaminar strength of FRP composites results in delamination failure. The various nanoreinforcement strategies and their effect on fracture toughness, interlaminar shear strength (ILSS) and interlaminar fatigue are discussed in detail to prevent this delamination failure. Important findings on various factors that influence the interlaminar properties of multi-scale composites are presented by discussing various intrinsic and extrinsic toughening processes. Moreover, an overview of simulation techniques is provided to predict the delamination onset and propagation.