Volume 92, Issue 9

Almost thirty years ago the criteria that are currently used to verify claims for the discovery of a new element were set down by the comprehensive work of a Transfermium Working Group, TWG, jointly established by IUPAC and IUPAP. The recent completion of the naming of the 118 elements in the first seven periods of the Periodic Table of the Elements was considered as an opportunity for a review of these criteria in the light of the experimental and theoretical advances in the field. In late 2016 the Unions decided to establish a new Joint Working Group, JWG, consisting of six members determined by the Unions. A first meeting of the JWG was in May 2017. One year later this report was finished. In a first part the works and conclusions of the TWG and the Joint Working Parties, JWP, deciding on the discovery of the now named elements are summarized. Possible experimental developments for production and identification of new elements beyond the presently known ones are estimated. Criteria and guidelines for establishing priority of discovery of these potential new elements are presented. Special emphasis is given to a description for the application of the criteria and the limits for their applicability.

Interlaboratory comparison on the determination of the molecular composition of humic substances (HS) was undertaken in the framework of IUPAC project 2016-015-2-600. The analysis was conducted using high resolution mass spectrometry, nominally, Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) with electrospray ionization. Six samples of HS from freshwater, soil, and leonardite were used for this study, including one sample of humic acids (HA) from coal (leonardite), two samples of soil HA (the sod-podzolic soil and chernozem), two samples of soil fulvic acids (FA) (the sod-podzolic soil and chernozem), and one sample of freshwater humic acids (the Suwannee River). The samples were analyzed on five different FTICR MS instruments using the routine conditions applied in each participating laboratory. The results were collected as mass lists, which were further assigned formulae for the determination of molecular composition. The similarity of the obtained data was evaluated using appropriate statistical metrics. The results have shown that direct comparison of discrete stoichiometries assigned to the mass lists obtained by the different laboratories yielded poor results with low values of the Jaccard similarity score – not exceeding 0.56 (not more than 56 % of the similar peaks). The least similarity was observed for the aromatics-rich HA samples from leonardite (coal) and the chernozem soil, which might be connected to difficulties in their ionization. The reliable similarity among the data obtained in this intercomparison study was achieved only by transforming a singular point (stoichiometry) in van Krevelen diagram into a sizeable pixel (a number of closely located stoichiometries), which can be calculated from the population density distribution. The conclusion was made that, so far, these are descriptors of occupation density distribution, which provide the metrics compliant with the data quality requirements, such as the reproducibility of the data measurements on different instruments.

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 × 10 5 , 5.0 × 10 6 and 9.0 × 10 6 . 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.

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 × 10 6 , 5 × 10 6 , and 9 × 10 6 . 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 θ g 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.

Three grades of polyethylene, with weight-average relative molar masses, M ‾ W ${\bar{M}}_{\text{W}}$ , of approximately 0.6  ×  10 6 , 5  ×  10 6 , and 9  ×  10 6 , 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  ×  10 6 to 5  ×  10 6 , but there was no further increase when it was raised to 9  ×  10 6 . 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, M ¯ W ${\overline{M}}_{\mathrm{W}}$ , of about 0.6 × 10 6 , 5 × 10 6 and 9 × 10 6 . 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, Δ K , is raised incrementally, and the resulting crack propagation rate, d a /d N , 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 Δ K . Typically, d a /d N 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 Δ K  = 2.3 MPa m 0.5 , there were crack-arrest marks at intervals Δ a o f 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.