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This research has been concerned with investigating stress cracking phenomena which occur when thermoplastic polyurethanes (TPU's) are immersed in seawater at low temperatures. The investigation was concerned with testing the following hypothesis: a) that cracking of TPU was due to environmental stress cracking (ESC) and/or b) due to structure and morphology changes which occur during the ageing period. The combined effects of polyurethane chemical backbone, domain structure and crystallinity on stress cracking in TPU were studied. Further, the investigation concerned itself with studying, on stress cracking, the effects of storage conditioning the TPU granules prior to processing, the processing conditions and various postcuring treatments of TPU. Characterisation and analytical techniques employed to study the structure of TPU's investigated consisted of thermal analysis and X-ray diffraction. Molecular weight distribution was studied by gel permeation chromatography and solution viscosity techniques. Processing'was evaluated by melt flow index (MFI), injection moulding and extrusion. A new accelerated ageing test for environmental stress cracking has been developed which uses high pressures. Also, a new type of ESC chemical class of reagent which relates the hydrogen bonding parameter of the ESC agent to that of the TPU's has been discovered and a theory developed. A test method has been designed to measure, in active environments, the existence of a critical strain for all the TPU examined whether commercial or laboratory synthesised materials. Results show that the stress cracking in TPU's is due to the following events: (a) a large reduction in molecular weight due to the processing, and (b) the combined effects of applied stresses and the hydrolysis of the polymer. Molecular weight reduction in TPU's and their resistance to ESe was also found dependent on the preconditioning history of unprocessed TPU granules, as well as any postcuring operations applied to the processed materials. It has been established that, the ESe resistance of TPU's can be improved by (i) optimising processing conditions, (ii) by insertion of slight crosslinking or by selecting certain types of diisocyanates, specifically p~phenylene diisocyanate, and trans 1,4-cyclohexane diisocyanate. A mechanism to explain ESe of TPU's inactive and mild environments is also proposed.

No description available.

Environmental stress cracking (ESC) can result in catastrophic failure of polyethylene (PE) structures without any visible warning. The use of PE in more demanding applications, such as trenchless piping, can accelerate ESC failure of the material. Besides public safety issues, the replacement and remediation of these failed polyethylene structures also cost both in money and labour. This thesis is part of a collaborative project between the disciplines of chemical and civil engineering to study environmental stress cracking resistance (ESCR) of polyethylene. By combining structural mechanics and (micro)molecular science, new insights into the ESCR behaviour of polyethylene could be achieved. The test commonly used for determining ESCR of polyethylene can be time consuming and rather imprecise. In our study a new testing method has been developed which compares ESCR of resins based on the more direct measure of “hardening stiffness” rather than strain-hardening modulus. Our new method is much simpler than those proposed previously because it is conducted under ambient conditions and does not require specialized equipment for true stress-strain measurements. Comparisons between the conventional ESCR test method and the strain hardening test show that strain hardening can be used to rank ESCR of polyethylene in a reliable fashion. The strain hardening test developed in this thesis has the potential to replace the standard ESCR test that has been in use in industry for the past twenty five years. Most ESCR research has so far focused on bridging-tie-molecules as the main source of inter-lamellar connections. We take a fresh approach and demonstrate in this thesis that physical chain entanglements also contribute to the formation of inter-lamellar linkages. Chain entanglements in the melt state are known to be preserved in the polymer upon solidification, therefore, rheological determination of the molecular weight between entanglements (Me) is used as a measure of chain entanglements for PE. A lower Me value means a higher number of entanglements in the system. The inversely proportional relationship between Me and ESCR indicates that low network mobility due to increasing number of chain entanglements increases ESCR of PE. With the understanding that strain hardening is related to ESCR of polyethylene, the relationship between chain entanglements and tensile strain hardening has also been investigated. By combining experimental observations and parallel micromechanical modeling results, the presence of physical chain entanglements in the amorphous phase was demonstrated to be the factor controlling the strain hardening behaviour of polyethylene. Studies of the effect of inter-lamellar linkages on ESCR of polyethylene have traditionally focused on changes in the amorphous phase. In this thesis, percentage crystallinity and lamella thickness of polyethylene resins were studied to determine their effects on ESCR. The study of the effect of the crystalline phase on ESCR was extended to investigate the lateral surface characteristics of the lamella. An increase in ESCR was observed with increases in lateral lamella area of resins. It was postulated that a larger lateral lamella area results in a higher probability of formation of inter-lamellar linkages. This increase in phase interconnectivity directly results in an increasing ESCR for the resins. Finally, in order to facilitate practical applications of polyethylene (especially in pipes), attempts were made to develop a predictive tool for the quantitative estimation of the long-term ESCR of polyethylene based on the short-term notched constant load test (NCLT). Although previous work on slow crack growth models showed little sensitivity to crack activation energy, the ESC model pursued herein was found to be exponentially dependent on this parameter. Further refinement of the ESC model is needed but the modeling investigation proved fruitful in highlighting several other relationships amongst chemical, physical and mechanical properties of PE resins, such as, that between ESC crack activation energy and the α-relaxation energy of polyethylene.

Environmental stress cracking (ESC) can result in catastrophic failure of polyethylene (PE) structures without any visible warning. The use of PE in more demanding applications, such as trenchless piping, can accelerate ESC failure of the material. Besides public safety issues, the replacement and remediation of these failed polyethylene structures also cost both in money and labour. This thesis is part of a collaborative project between the disciplines of chemical and civil engineering to study environmental stress cracking resistance (ESCR) of polyethylene. By combining structural mechanics and (micro)molecular science, new insights into the ESCR behaviour of polyethylene could be achieved. The test commonly used for determining ESCR of polyethylene can be time consuming and rather imprecise. In our study a new testing method has been developed which compares ESCR of resins based on the more direct measure of “hardening stiffness” rather than strain-hardening modulus. Our new method is much simpler than those proposed previously because it is conducted under ambient conditions and does not require specialized equipment for true stress-strain measurements. Comparisons between the conventional ESCR test method and the strain hardening test show that strain hardening can be used to rank ESCR of polyethylene in a reliable fashion. The strain hardening test developed in this thesis has the potential to replace the standard ESCR test that has been in use in industry for the past twenty five years. Most ESCR research has so far focused on bridging-tie-molecules as the main source of inter-lamellar connections. We take a fresh approach and demonstrate in this thesis that physical chain entanglements also contribute to the formation of inter-lamellar linkages. Chain entanglements in the melt state are known to be preserved in the polymer upon solidification, therefore, rheological determination of the molecular weight between entanglements (Me) is used as a measure of chain entanglements for PE. A lower Me value means a higher number of entanglements in the system. The inversely proportional relationship between Me and ESCR indicates that low network mobility due to increasing number of chain entanglements increases ESCR of PE. With the understanding that strain hardening is related to ESCR of polyethylene, the relationship between chain entanglements and tensile strain hardening has also been investigated. By combining experimental observations and parallel micromechanical modeling results, the presence of physical chain entanglements in the amorphous phase was demonstrated to be the factor controlling the strain hardening behaviour of polyethylene. Studies of the effect of inter-lamellar linkages on ESCR of polyethylene have traditionally focused on changes in the amorphous phase. In this thesis, percentage crystallinity and lamella thickness of polyethylene resins were studied to determine their effects on ESCR. The study of the effect of the crystalline phase on ESCR was extended to investigate the lateral surface characteristics of the lamella. An increase in ESCR was observed with increases in lateral lamella area of resins. It was postulated that a larger lateral lamella area results in a higher probability of formation of inter-lamellar linkages. This increase in phase interconnectivity directly results in an increasing ESCR for the resins. Finally, in order to facilitate practical applications of polyethylene (especially in pipes), attempts were made to develop a predictive tool for the quantitative estimation of the long-term ESCR of polyethylene based on the short-term notched constant load test (NCLT). Although previous work on slow crack growth models showed little sensitivity to crack activation energy, the ESC model pursued herein was found to be exponentially dependent on this parameter. Further refinement of the ESC model is needed but the modeling investigation proved fruitful in highlighting several other relationships amongst chemical, physical and mechanical properties of PE resins, such as, that between ESC crack activation energy and the α-relaxation energy of polyethylene.

ABSTRACT Injection stretch blow moulded PET bottles are the most widely used container type for carbonated soft drinks. PET offers excellent clarity, good mechanical and barrier properties, and ease of processing. Typically, these bottles have a petaloid-shaped base, which gives good stability to the bottle and it is the most appropriate one for beverage storage. However, the base is prone to environmentally induced stress cracking and this a major concern to bottle manufacturers. The object of this study is to explain the occurrence of stress cracking, and to prevent it by optimising both the geometry of the petaloid base and the processing parameters during bottle moulding. A finite element model of the petaloid shape is developed in CATIA V5 R14, and used to predict the von Mises stress in the bottle base for different combinations of three key dimensions of the base: foot length, valley width, and clearance. The combination of dimensions giving the minimum stress is found by a statistical analysis approach using an optimisation and design of experiments software package ECHIP-7. A bottle mould was manufactured according to the optimum base geometry and PET bottles are produced by injection stretch blow moulding (ISBM). In order to minimise the stresses at the bottom of the bottle, the ISBM process parameters were reviewed and the effects of both the stretch rod movement and the temperature profile of the preform were studied by means of the process simulation software package (Blow View version 8.2). Simulated values of the wall thickness, stress, crystallinity, molecular orientation and biaxial ratio in the bottle base were obtained. The process parameters, which result in low stress and uniform material in the bottle base, are regarded as optimum operating conditions. In the evaluation process of the optimum bottle base, bottles with standard (current) and optimized (new) base were produced under the same process conditions via a two-stage ISBM machine. In order to compare both the bottles, environmental stress crack resistance, top load strength, burst pressure strength, thermal stability test as well as crystallinity studies ¬¬¬via modulated differential scanning calorimetry (MDSC) and morphology studies via environmental scanning electron microscopy (ESEM) and optical microscopy were conducted. In this study carried out, the new PET bottle with the optimised base significantly decreased the environmental stress cracking occurrence in the bottom of the bottle. It is found that the bottle with optimised base is stronger than the bottle with standard base against environmental stress cracking. The resistance time against environmental stress cracking are increased by about % 90 under the same operating process conditions used for standard (current) bottles; and by % 170 under the optimised process conditions where the preform re-heating temperature is set to 105 oC.

The interaction between poly(ether ether ketone) (PEEK) and three solvents (i.e., methylene chloride, tetrahydrofuran, and acetone) was studied by means of several complementary techniques. A series of eleven 0.3 mm thick PEEK films was produced. Each film had a certain crystallinity index and crystal morphology, as revealed by optical microscopy, differential scanning calorimetry (DSC), and wide angle X-ray scattering (WAXS). Dynamic solvent uptake measurements were performed on each film with the three solvents. Methylene chloride swelled both amorphous and semi-crystalline PEEK to high degrees, while tetrahydrofuran and acetone swelled amorphous PEEK only. After desorption, the samples were carefully analyzed to characterize solvent-induced crystallization (SINC), which occurred in amorphous PEEK exposed to all three solvents. Diffusion of methylene chloride and tetrahydrofuran in amorphous PEEK was observed in fractured specimens by scanning electron microscopy, while SINC was followed by DSC. The SINC process was found to be diffusion controlled. Diffusion of both solvents through the polymeric film took place in the first third of the equilibrium time, while swelling occurred in the remaining time. The mechanical properties of all solvent-exposed PEEK films were tested by three types of experiment (i.e., glass cone technique, microtensile tests, and tensile test in the environmental scanning electron microscope (ESEM)), which were first verified with another semi-crystalline thermoplastic polymer, isotactic polypropylene. PEEK specimens were stressed in the inside of glass cones and immersed in a series of solvents. Differences among solvent uptakes of stressed and unstressed specimens were explained in terms of crazing and SINC. Microtensile tests were performed on completely swollen PEEK specimens. Plasticization and delocalized crazing were found in the case of amorphous PEEK exposed to the three solvents and semi-crystalline PEEK exposed to methylene chloride, while classical crazing occurred in the other specimens. Finally, an amorphous PEEK specimen was swollen in acetone and stretched in the ESEM in acetone vapor. A very ductile deformation was observed, which occurred at the necked region between two notches. The results are discussed in terms of T_g depression and plasticization. / Ph. D.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2006. / This study concerns the phenomenon of environmental stress cracking resistance (ESCR) in three impact polypropylene copolymers (IPPCs). The main purpose was to correlate the ESCR with their properties such as microstructure, molecular weight (MW), molecular weight distribution (MWD), crystallinity and morphology. Initially the selection of a suitable test method and an active stress cracking agent (SCA) were the preliminary concerns. The Bell telephone test was used to evaluate SCAs, while a published procedure for determining ESCR of ethylene based plastics was adapted for the purpose of this study. Isopropanol was selected as SCA. Polymers were fully characterized by FTIR, 13C NMR, DSC and high temperature GPC. Optical microscopy was used to investigate craze formation and crack growth, and scanning electron microscopy (SEM) was used to study the morphology of the polymers. Since IPPCs are known to have multi-fraction copolymeric structures and each of these fractions has significantly different average properties, fractions were selectively removed from the materials, either by solvent extraction at room temperature, or by TREF fractionation. The effect of removing these fractions on the ESCR was determined. The effect of the molecular composition of the three IPPCs on the ESCR of these materials, as well as the effect of the removal of the selected molecular fractions on the ESCR, morphology and molecular characteristics are discussed and compared. Conclusions are drawn as to the factors controlling ESCR in these materials.

Sulfide Stress Cracking (SSC) resistance of the newly developed API-X100 High Strength Low Alloy (HSLA) steel was investigated in the NACE TM0177 "A" solution. The NACE TM0177 "A" solution is a hydrogen sulfide (H2S) saturated solution containing 5.0 wt.% sodium chloride (NaC1) and 0.5 wt.% acetic acid (CH3COOH). The aim of this thesis was to study the effect of microstructure, non-metallic inclusions and alloying elements of the X100 on H2S corrosion and SSC susceptibility. The study was conducted by means of electrochemical polarization techniques and constant load (proof ring) testing. Microstructural analysis and electrochemical polarization results for X100were compared with those for X80, an older generation HSLA steel. Uniaxial constant load SSC testing was conducted using X100 samples and the results were compared with those reported for older generation HSLA steels. Addition of H2S to the NACE TM0177 "A" solution increased the corrosion rate of X100from 51.6 to 96.7 mpy. The effect of H2S on the corrosion rate was similar for X80. The corrosion rate for X80 increased from 45.2 to 80.2 mpy when H2S was added to the test solution. Addition of H2S enhanced the anodic kinetics by forming a catalyst (FeHSads) on the metal surface and as a result, shifted the anodic polarization curve to more current densities. Moreover, the cathodic half cell potential increased due to the decrease in pH, from 2.9 to 2.7, which shifted the cathodic polarization curve to more current densities. The increase in both the anodic and cathodic currents, after H2S addition, caused the rise in the corrosion current density. In H2S saturated NACE TM-0177 "A" solution, the X100 steel corrosion rate was higher than the X80 steel by 20%. Longer phase boundaries and larger nonmetallic inclusions in the X100 microstructure generated more areas with dissimilar corrosion potentials and therefore, a stronger driving force for corrosion. Higher density of second phase regions and larger nonmetallic inclusions acted as an increased cathode area on the X100 surface which increased the cathodic current density and consequently, increased the corrosion current density. Proof ring tests on the X100 gave a threshold stress value, C5th, of 46% YS, 343.1 MPa(49.7 ksi). The main failure was caused by SSC cracking. SSC nucleated at corrosion pits on the metal surface and microcracks in the metal body and propagated perpendicular to the applied stress. Hydrogen Induced Cracking (HIC) was observed in the X100. HIC cracks nucleated at banded martensite-ferrite interfaces and propagated along the rolling direction parallel to the applied tensile stress through the softer ferrite phase. When compared to older HSLA grades, the X100 tested in this study had a high SSC susceptibility and therefore, is not be recommended for H2S service applications. The high X100 SSC susceptibility was caused by the material high corrosion rates in H2Smedia which formed corrosion pits that acted as crack initiation sites on the metal surface and provided more hydrogen that migrated into the steel. In addition, the X100 inhomogeneous microstructure provided a high density of hydrogen traps in front of the main crack tip which promoted SSC microcrack formation inside the metal. Microcracks in the metal body connected with the main crack tip that originated from corrosion pits which assisted SSC propagation.