Effect of molecular weight on secondary Newtonian plateau at high shear rates for linear isotactic melt blown polypropylenes

In this work, three melt blown grades of isotactic linear polypropylenes, with weight average molecular weights between 56 250–75 850 g/mol, have been characterized at 230 °C over a very wide shear rate range (10–107 1/s) by using conventional rotational and twin bore capillary rheometry equipped with novel orifice die, and by an instrumented capillary nozzle on an injection molding machine. A low shear rate primary Newtonian plateau, a pseudoplastic region and a well developed secondary Newtonian plateau (occurring between 2·106−7·106 1/s) were identified for all the polypropylene melts. Flow activation energy at low (E0) and high (E∞) shear rates was found to be 56.590 kJ/mol and 25.204 kJ/mol, respectively. Considering the typical value of pressure sensitivity coefficient for polypropylene melt, β = 20.00 GPa−1, and measured flow activation energy at the secondary Newtonian plateau, E∞ = 25.204 kJ/mol, it was found that the effect of viscous dissipation and pressure is mutually cancelled, i.e. that the measured viscosity data can be considered as the true material property within the whole applied shear rate range. For the first time, it has been revealed that the secondary Newtonian viscosity, η∞, depends linearly on the weight average molecular weight, Mw, in log-log scale as η∞=1.19·10−6Mw 1.084. The observed slope close to 1 between η∞ and Mw suggests that polymer chains in the melt are disentangled at the secondary Newtonian plateau region. This conclusion is supported by the experimental observation that the high shear rate flow activation energy E∞ for given PP melts is comparable with the flow activation energy of PP like oligomer (squalane, C30H62; 2,6,10,15,19,23-hexamethyltetracosane). The measured flow data were fitted by six different viscosity models, from which two, namely Modified Carreau and Quemada models, were suggested here for the first time. It has been found that the accuracy of utilized models to describe the measured data is the highest for the newly suggested models and decreases in the following order: Modified Quemada model, Modified Carreau model, Carreau-Yasuda model, Cross model, Generalized Quemada model and Carreau model. © 2017 Elsevier B.V.16-05886S, GACR, Grantová Agentura České RepublikyGrant Agency of the Czech Republic [16-05886S

Effect of molecular weight, branching and temperature on dynamics of polypropylene melts at very high shear rates

Dynamics of linear polypropylene (L-PP) and long-chain branched polypropylene (LCB-PP) miscible blends, having weight average molecular weight between 64 and 78 kg/mol, was investigated via high shear rate rheology. Results obtained were compared with the corresponding data for L-PP. High-shear rate secondary Newtonian plateaus, η∞, were identified at three different temperatures for well entangled L-PP/LCB-PP blends above shear rates of 2·106 1/s and their dependence on weight average molecular weight, Mw, was successfully related as η∞(T)=K∞(T)·Mw n with the exponent n = 1.010. Interestingly, the temperature dependant proportionality constant K∞ was found to be about 10–20% lower for the blend in comparison with the pure L-PP whereas the parameter n was found to be the same for both systems. The average values of high-shear rate flow activation energy, E∞, for the blends was found to be slightly lower than for pure L-PP and comparable with low-shear rate flow activation energy of PP like oligomer squalane (C30H62; 2,6,10,15,19,23-hexamethyltetracosane). This suggests that polymer chains are fully disentangled at very high shear rates and chain branching can enhance the flow in this regime due to smaller coil size and higher availability of the free volume (i.e. lower monomeric friction coefficient) in comparison with their linear counterparts. © 2018 Elsevier LtdGrant Agency of the Czech Republic [16-05886S

Visualisation and analysis of polyethylene coextrusion melt flow

Polymer melts experience complex, time variant, stress and deformation fields on their passage through fixed geometries in many conversion operations. Flow complexity is further increased in operations involving the co-joining of two or more melt streams where one confining boundary is moving and viscoelastic. Such a complex situation arises in coextrusion processes. This work covers experimental studies on polyethylene melt flows in complex coextrusion geometries with a view to understanding the stress fields involved and their effects on flow stability. A 30°1coextrusion geometry is studied using two extrusion arrangements. In one arrangement a single extruder is used to feed a 'bifurcated' die design wherein the melt stream is split prior to, and rejoined after, a divider plate in the die. In the other design melt streams are delivered to, and converged at 30°, using two independent extruders. In a second die melt streams are brought together at 90°. In each die arrangement melt flow in the confluent region and die land to the die exit was observed through side windows of a visualisation cell. Velocity ratios of the two melt streams were varied and layer thickness ratios producing instability are determined for each melt for a variety of flow conditions. Stress and velocity fields in the coextrusion arrangements were quantified using stress birefringence and particle image velocimetry techniques. The study demonstrates conclusively that wave type interfacial instability occurred in the coextrusion geometries when the same low density polyethylene melt is used in each stream. This observation occurred at specific, repeatable, stream layer ratios in each die arrangement. The complex flows were numerical modelled using a modified Leonov model and Flow 2000P software. There was reasonable agreement between modelled at experimentally determined stress fields. Modelling however provided far more detailed stress gradient information than could be resolved from the optical techniques. A total normal stress difference (TNSD) sign criterion was used to predict the critical layer ratio for the onset of the interfacial instability in one die arrangement and good agreement between theory and experiment has been obtained. The study conclusively demonstrates wave type interfacial instability in the coextrusion process is not caused by process perturbations potentially introduced by extruder screw rotation but is associated with process-history dependant differences in melt elasticity. © 2009 American Institute of Physics

A depositional model for spherulitic carbonates associated with alkaline, volcanic lakes

The South Atlantic Aptian ‘Pre-salt’ reservoirs are formed by a combination of spherulitic carbonates and Mg-rich clays accumulated in volcanic alkaline lake settings with exotic chemistries. So far, outcrop analogues characterised by metre-thick successions deposited in lacustrine scenarios are elusive so disentangling the genesis of spherulitic carbonates represents a major scientific challenge with business impact. In particular the controls on spatial distribution and the environment of spherulitic facies formation remain poorly constrained, little studied, and hotly debated. To shed light on this conundrum, a spherulitic carbonate-rich, alkaline volcanic lacustrine succession has been analysed at outcrop scale: the Carboniferous East Kirkton Limestone (Scotland). Despite clays being very scarce and limited to layers of amorphous Mg-Si minerals, a diverse array of spherulitic calcitic components were formed, including coated grains, crusts, and build-ups. This setting enables the mechanisms of spherulitic calcite development and the patterns of sediment accumulation to be explored in a geobiological and hydrochemical scenario similar to the ‘Pre-Salt’ subsurface occurrences but divorced from clay influence. The integration of logs, borehole data, outcrop photomosaics and petrographic observations collectively allowed the reconstruction of a depositional model for the East Kirkton lacustrine succession. In this model, calcite spherule nucleation took place at the sediment-water interface in the littoral zone, driven by the co-occurrence of 1) high alkalinity, 2) Ca-Mg rich hydrochemistry, and 3) microbial-derived colloidal exopolymeric substances. These environmental conditions permitted the coeval development of spherulitic cementstone build-ups and spherulitic grainstone-packstone within the wave-agitated zone, and the accumulation of floatstones and laminites of spherulitic grains in deeper lake regions by means of downslope reworking. This model is consistent with the previously documented microbial bloom occurrences and highlights the need to better understand the complex ‘microbe-solution’ interactions before any reliable facies model is envisaged

Are spherulitic lacustrine carbonates an expression of large-scale mineral carbonation? : A case study from the East Kirkton Limestone, Scotland

BP Exploration Co. is thanked for funding, and particularly the Carbonate Team for supporting this research and for fruitful discussions. West Lothian Council and Scottish Natural Heritage are thanked for allowing access and permission for sampling the site. The Core Store Team at BGS Keyworth is particularly acknowledged for their assistance. Mark Anderson, Tony Sinclair (University of Hull), and Bouk Lacet (VU University Amsterdam) are thanked for technical support. Anne Kelly (SUERC) for carrying out the Strontium Isotope analyses. Mark Tyrer is thanked for his advice on PHREEQC modelling.Peer reviewedPostprin

Twenty-three unsolved problems in hydrology (UPH) – a community perspective

This paper is the outcome of a community initiative to identify major unsolved scientific problems in hydrology motivated by a need for stronger harmonisation of research efforts. The procedure involved a public consultation through on-line media, followed by two workshops through which a large number of potential science questions were collated, prioritised, and synthesised. In spite of the diversity of the participants (230 scientists in total), the process revealed much about community priorities and the state of our science: a preference for continuity in research questions rather than radical departures or redirections from past and current work. Questions remain focussed on process-based understanding of hydrological variability and causality at all space and time scales. Increased attention to environmental change drives a new emphasis on understanding how change propagates across interfaces within the hydrological system and across disciplinary boundaries. In particular, the expansion of the human footprint raises a new set of questions related to human interactions with nature and water cycle feedbacks in the context of complex water management problems. We hope that this reflection and synthesis of the 23 unsolved problems in hydrology will help guide research efforts for some years to come

Evaluating the Effects of SARS-CoV-2 Spike Mutation D614G on Transmissibility and Pathogenicity.

Global dispersal and increasing frequency of the SARS-CoV-2 spike protein variant D614G are suggestive of a selective advantage but may also be due to a random founder effect. We investigate the hypothesis for positive selection of spike D614G in the United Kingdom using more than 25,000 whole genome SARS-CoV-2 sequences. Despite the availability of a large dataset, well represented by both spike 614 variants, not all approaches showed a conclusive signal of positive selection. Population genetic analysis indicates that 614G increases in frequency relative to 614D in a manner consistent with a selective advantage. We do not find any indication that patients infected with the spike 614G variant have higher COVID-19 mortality or clinical severity, but 614G is associated with higher viral load and younger age of patients. Significant differences in growth and size of 614G phylogenetic clusters indicate a need for continued study of this variant

The James Webb Space Telescope Mission

Twenty-six years ago a small committee report, building on earlier studies, expounded a compelling and poetic vision for the future of astronomy, calling for an infrared-optimized space telescope with an aperture of at least $4m$. With the support of their governments in the US, Europe, and Canada, 20,000 people realized that vision as the $6.5m$ James Webb Space Telescope. A generation of astronomers will celebrate their accomplishments for the life of the mission, potentially as long as 20 years, and beyond. This report and the scientific discoveries that follow are extended thank-you notes to the 20,000 team members. The telescope is working perfectly, with much better image quality than expected. In this and accompanying papers, we give a brief history, describe the observatory, outline its objectives and current observing program, and discuss the inventions and people who made it possible. We cite detailed reports on the design and the measured performance on orbit.Comment: Accepted by PASP for the special issue on The James Webb Space Telescope Overview, 29 pages, 4 figure

Relationships between outdoor time, physical activity, sedentary time, and body mass index in children : a 12-country study

Purpose: This study investigated the relationship between outdoor time and physical activity (PA), sedentary time (SED), and body mass index z scores among children from 12 lower-middle-income, upper-middle-income, and high-income countries. Methods: In total, 6478 children (54.4% girls) aged 9-11 years participated. Outdoor time was self-reported, PA and SED were assessed with ActiGraph GT3X+ accelerometers, and height and weight were measured. Data on parental education, neighborhood collective efficacy, and accessibility to neighborhood recreation facilities were collected from parent questionnaires. Country latitude and climate statistics were collected through national weather data sources. Gender-stratified multilevel models with parental education, climate, and neighborhood variables as covariates were used to examine the relationship between outdoor time, accelerometry measures, and body mass index z scores. Results: Each additional hour per day spent outdoors was associated with higher moderate-to vigorous-intensity PA (boys: +2.8 min/d; girls: +1.4 min/d), higher light-intensity PA (boys: +2.0 min/d; girls: +2.3 min/d), and lower SED (boys: -6.3 min/d; girls: -5.1 min/d). Effect sizes were generally weaker in lower-middle-income countries. Outdoor time was not associated with body mass index z scores. Conclusions: Outdoor time was associated with higher PA and lower SED independent of climate, parental education, and neighborhood variables, but effect sizes were small. However, more research is needed in low-and middle-income countries

Proportion of children meeting recommendations for 24-hour movement guidelines and associations with adiposity in a 12-country study

Background: The Canadian 24-h movement guidelines were developed with the hope of improving health and future health outcomes in children and youth. The purpose of this study was to evaluate adherence to the 3 recommendations most strongly associated with health outcomes in new 24-h movement guidelines and their relationship with adiposity (obesity and body mass index z-score) across countries participating in the International Study of Childhood Obesity, Lifestyle and the Environment (ISCOLE). Methods: Cross-sectional results were based on 6128 children aged 9-11years from the 12 countries of ISCOLE. Sleep duration and moderate-to-vigorous physical activity (MVPA) were assessed using accelerometry. Screen time was measured through self-report. Body weight and height were measured. Body mass index (BMI, kgm2) was calculated, and BMI z-scores were computed using age- and sex-specific reference data from the World Health Organization. Obesity was defined as a BMI z-score>+2 SD. Meeting the overall 24-h movement guidelines was defined as: 9 to 11h/night of sleep, ≤2h/day of screen time, and at least 60min/day of MVPA. Age, sex, highest parental education and unhealthy diet pattern score were included as covariates in statistical models. Associations between meeting vs. not meeting each single recommendation (and combinations) with obesity were assessed with odds ratios calculated using generalized linear mixed models. A linear mixed model was used to examine the differences in BMI z-scores between children meeting vs. not meeting the different combinations of recommendations. Results: The global prevalence of children meeting the overall recommendations (all three behaviors) was 7%, with children from Australia and Canada showing the highest adherence (15%). Children meeting the three recommendations had lower odds ratios for obesity compared to those meeting none of the recommendations (OR=0.28, 95% CI 0.18-0.45). Compared to not meeting the 24-h movement recommendations either independently or combined, meeting them was significantly associated with a lower BMI z-score. Whenever the MVPA recommendation was included in the analysis the odds ratios for obesity were lower. Conclusions: For ISCOLE participants meeting these 3 healthy movement recommendations the odds ratios of being obese or having high BMI z-scores were lower. However, only a small percentage of children met all recommendations. Future efforts should aim to find promising ways to increase daily physical activity, reduce screen time, and ensure an adequate night's sleep in children. Trial registration: The International Study of Childhood Obesity, Lifestyle and the Environment (ISCOLE) was registered at ClinicalTrials.gov (Identifier NCT01722500) (October 29, 2012)