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Test methods including OM, SEM, TEM, DSC, SAXS, WAXS, and IR were used to characterise supra-molecular structure in three batches of polyethylene (PE), which had weight-average relative molar masses M ¯ w ${\overline{M}}_{\text{w}}$ of approximately 0.6 × 106, 5 × 106, and 9 × 106. They were applied to compression mouldings made by the polymer manufacturer. Electron microscopy showed that powders formed in the polymerization reactor consisted of irregularly shaped grains between 50 and 250 μm in diameter. Higher magnification revealed that each grain was an aggregate, composed of particles between 0.4 and 0.8 μm in diameter, which were connected by long, thin fibrils. In compression mouldings, lamellar thicknesses ranged from 7 to 23 nm. Crystallinity varied between 70 and 75 % in reactor powder, but was lower in compression mouldings. Melting peak temperatures ranged from 138 to 145 °C, depending on processing history. DMTA showed that the glass transition temperature θg was −120 °C for all three grades of polyethylene. IR spectroscopy found negligibly small levels of oxidation and thermal degradation in mouldings. Optical microscopy revealed the presence of visible fusion defects at grain boundaries. It is concluded that relatively weak defects can be characterized using optical microscopy, but there is a need for improved methods that can detect less obvious fusion defects. [ABSTRACT FROM AUTHOR]

Three grades of polyethylene, with weight-average relative molar masses, M ‾ W ${\bar{M}}_{\text{W}}$ , 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 M ‾ W ${\bar{M}}_{\text{W}}$ 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. [ABSTRACT FROM AUTHOR]

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, M ¯ W ${\overline{M}}_{\mathrm{W}}$ , 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. [ABSTRACT FROM AUTHOR]

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 M ̅ $̅{M}$ 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 M ̅ $̅{M}$ 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. [ABSTRACT FROM AUTHOR]

The master curves of a series of aliphatic polycarbonates (APCs) with different lengths of methylene segments in the repeat unit were obtained by dynamic rheological measurements. The plateau modulus and entanglement molecular weight were determined and cross-checked by different methods. Though having distinct difference in chemical structure of repeat units, both APCs and bisphenol-A polycarbonates have the similar entanglement weight and entanglement spacing. On the other side, the plateau modulus decreases with increasing the length of the side group of aliphatic polycarbonates with different side-chain lengths in the literature. The packing length model can explain the relationship between chain structure and entanglements. [ABSTRACT FROM AUTHOR]

Poly(methyl methacrylate) (PMMA) exhibits significantly tacticity-dependent properties, e.g. the glass transition temperature (T g), the characteristic ratio (C ∞), the specific volume and the gas permeability coefficient. Syndiotactic (s) PMMA is the most peculiar, exhibiting complex α - β relaxations. We first make brief reviews about key experimental facts of s -PMMA relaxations: 1) unusual α - β split; 2) tacticity dependence of T g ; 3) discrepancy between chain stiffness and T g. Based on the chain conformation analysis of Vacatello and Flory in 1986, and combined with the experimental results from dielectric spectroscopy (DS), dynamic-mechanical analysis (DMA), nuclear magnetic resonance (NMR), we have demonstrated that the molecular origin of the peculiar α - β relaxations resulted from the all-trans extended conformations which are predominant in syndiotactic PMMA. This local extended (and curved) structure, as a bigger jumping unit, induces the formation of domains with slow dynamics. The percolation of slow domains causes the freezing of the large-amplitude motion of main chains, and then a novel α transformation occurs at a higher temperature eventually. The high-specific volume state below T g provides a space for the constraint rotation of ester groups, showing a strong β relaxation even far from the T g. Therefore, many related experimental phenomena, e.g. the tacticity-dependence of properties, the effect of α- methyl, the effect of side-chain n-alkyl, the effect of molecular weight, and otherwise are easily resolved. Since adjacent bond angles are unequal in all-trans extended conformations, the backbone is curved, hence the s -PMMA chain tends to form quasi-cyclic structure, leading to the reversely correlation between the overall chain size (C ∞) and the local stiffness (T g). Lastly, the impact of these findings on the glass theory is presented in conclusions. [Display omitted] • Molecular origin of the peculiar α - β relaxations results from the all-trans extended conformationsin s -PMMA. • The local extended -structure, as a bigger jumping unit, induces the formation of domains with slow dynamics. • The local stiffness instead of the overall chain size determines the occurrence of the glass transition. • Molecular image of s -PMMA relaxations provides insights to understand the precise nature of the glass transition. [ABSTRACT FROM AUTHOR]