Two impact modifiers, based respectively on polybutadiene (PB) and poly(butyl acrylate-co-styrene) (PBA), are compared in blends with four glassy polymers: polycarbonate (PC), poly(methyl methacrylate) (PMMA), poly(styrene-co-acrylonitrile) (PSAN), and poly(vinyl chloride) (PVC). Dynamic mechanical tests show glass transitions at about -80 °C in PB and -15 °C in PBA. Both modifiers have grafted PMMA shells, which are seen in the transmission electron microscope (TEM) to be about 10 nm thick. The two-stage PB particles have 200-nm-diameter polybutadiene cores, whereas the three-stage PBA particles have 260-nm-diameter PMMA cores, with 20-nm thick PBA rubber inner shells. Under tension, the PB particles cavitate to form single voids on reaching a critical volume strain, and subsequently offer little resistance to dilatation. By contrast, tensile tests performed in situ in the TEM show that the PBA shells form fibrils that are anchored to the rigid core, and act as constraints on further dilatation: the stresses developed in the PBA fibrils can be sufficient to draw fibrils from both the PMMA core and the PSAN matrix. There is evidence that the PMMA shells can debond from the matrix both in cryogenic fracture and in fatigue at 23 °C. Tensile dilatometry shows that the PB particles cavitate at higher strains than the PBA particles, but that the PB particles then cause a rapid volume increase, leading to a low strain at break. By contrast, the PBA particles produce a more controlled dilatation, and higher strains to break. Later papers in this series treat the mechanical and rheological behavior of these blends in more detail.
The influence of impact modifiers composed of an elastomer-based core and a poly(methyl methacrylate) (PMMA) shell on the melt flow properties of different thermoplastics has been studied, using both steady-state and dynamic viscosity measurements. The melt viscosities of the rubber-toughened blends were similar to those of the matrix polymers, over the range of shear rates commonly applied during melt processing. In the case of the matrix polymers, viscosity curves obtained under dynamic conditions coincided with those obtained under steady-state conditions. However, for blends the two curves show a slight divergence at low strain rates, where yielding is observed.
The aim of this project was to study the efficacy of current methods of quality control and quality assurance for ultra-high molecular weight polyethylene (UHMWPE) products, and find improvements where possible. Intrinsic viscosity (IV) tests were performed on three grades of polyethylene with weight average relative molar masses w of about 6 × 105, 5.0 × 106 and 9.0 × 106. Results from three laboratories showed substantial scatter, probably because different methods were used to make and test solutions. Tensile tests were carried out to 600 % extension at 150 °C under both constant applied load and constant Hencky strain rate, on compression mouldings made by a leading manufacturer of ultra-high molecular weight polyethylene. They gave low values of w, suggesting incomplete entanglement at ‘grain boundaries’ between powder particles. Results from conventional melt-rheology tests are presented, and their relevance to quality control and assurance is discussed. Attempts to calculate molecular weights from these data met with limited success because of extended relaxation times. Suggestions are made for improving international standards for IV testing of UHMWPE, by investigating the various factors that can cause significant errors, and by introducing methods for checking the homogeneity (and hence validity) of the solutions tested. Part 2 addresses characterization of crystallinity and structure. Part 3 covers mechanical properties, and Part 4 focuses on the sporadic crack propagation behaviour exhibited by all three grades of UHMWPE in fatigue tests on 10 mm thick compact tension specimens.
Three grades of polyethylene, with weight-average relative molar masses, , of approximately 0.6 × 106, 5 × 106, and 9 × 106, were supplied as compression mouldings by a leading manufacturer of ultra-high molecular weight polyethylene (UHMWPE). They were code-named PE06, PE5, and PE9, respectively. Specimens cut from these mouldings were subjected to a wide range of mechanical tests at 23 °C. In tensile tests, deformation was initially elastic and dominated by crystallinity, which was highest in PE06. Beyond the yield point, entanglement density became the dominant factor, and at 40 % strain, the rising stress–strain curves for PE5 and PE9 crossed the falling PE06 curve. Fracture occurred at strains above 150 %. Differences in stress–strain behaviour between PE5 and PE9 were relatively small. A similar pattern of behaviour was observed in wear tests; wear resistance showed a marked increase when was raised from 0.6 × 106 to 5 × 106, but there was no further increase when it was raised to 9 × 106. It is concluded that the unexpected similarity in behaviour between PE5 and PE9 was due to incomplete consolidation during moulding, which led to deficiencies in entanglement at grain boundaries; they were clearly visible on the surfaces of both tensile and wear specimens. Fatigue crack growth in 10 mm thick specimens was so severely affected by inadequate consolidation that it forms the basis for a separate report – Part 4 in this series.
Fatigue tests were carried out on compression mouldings supplied by a leading polymer manufacturer. They were made from three batches of ultra-high molecular weight polyethylene (UHMWPE) with weight-average relative molar masses, , of about 0.6 × 106, 5 × 106 and 9 × 106. In 10 mm thick compact tension specimens, crack propagation was so erratic that it was impossible to follow standard procedure, where crack-tip stress intensity amplitude, ΔK, is raised incrementally, and the resulting crack propagation rate, da/dN, increases, following the Paris equation, where a is crack length and N is number of cycles. Instead, most of the tests were conducted at fixed high values of ΔK. Typically, da/dN then started at a high level, but decreased irregularly during the test. Micrographs of fracture surfaces showed that crack propagation was sporadic in these specimens. In one test, at ΔK = 2.3 MPa m0.5, there were crack-arrest marks at intervals Δa of about 2 μm, while the number of cycles between individual growth steps increased from 1 to more than 1000 and the fracture surface showed increasing evidence of plastic deformation. It is concluded that sporadic crack propagation was caused by energy-dissipating crazing, which was initiated close to the crack tip under plane strain conditions in mouldings that were not fully consolidated. By contrast, fatigue crack propagation in 4 mm thick specimens followed the Paris equation approximately. The results from all four reports on this project are reviewed, and the possibility of using fatigue testing as a quality assurance procedure for melt-processed UHMWPE is discussed.