On the time for fold surfaces to order during the crystallization of polyethylene from the melt and its dependence on molecular parameters

New experiments underpin the interpretation of the basic division in crystallization behaviour of polyethylene in terms of whether or not there is time for the fold surface to order before the next molecular layer is added at the growth front. For typical growth rates, in Regime 11, polyethylene lamellae form with disordered {001} fold surfaces then transform, with lamellar thickening and twisting, towards the more-ordered condition found for slower crystallization in Regime 1, in which lamellae form with and retain {201} fold surfaces. Several linear and linear-low-density polyethylenes have been used to show that, for the same polymer crystallized alone or in a blend, the growth rate at which the change in initial lamellar condition occurs is reasonably constant thereby supporting the concept of a specific time for surfaces to attain the ordered {201}) state. This specific time, in the range from milliseconds to seconds, increases with molecular length, and in linear-low-density polymer, for higher branch contents. (c) 2006 Elsevier Ltd. All rights reserved.

Architectural effect on the surface tension of an ABA triblock copolymer melt

The excess surface energy of lamellae formed by an ABA triblock copolymer melt oriented parallel to a neutral surface is evaluated using self-consistent field theory (SCFT). Consistent with experiments and previous SCFT calculations, we find a preference for the A-rich domains at the surface, which can only be attributed to the architectural asymmetry between the A and B blocks. The behavior was previously attributed to a loss of bridging configurations that occurs when the B-domain resides at the surface. Here we demonstrate that it is actually the presence of chain ends that reduces the excess surface energy of an A-rich domain relative that of a B-rich domain.

Factors controlling the distribution of ozone in the West African lower troposphere during the AMMA (African Monsoon Multidisciplinary Analysis) wet season campaign

Ozone and its precursors were measured on board the Facility for Airborne Atmospheric Measurements (FAAM) BAe 146 Atmospheric Research Aircraft during the monsoon season 2006 as part of the African Monsoon Multidisciplinary Analysis (AMMA) campaign. One of the main features observed in the west African boundary layer is the increase of the ozone mixing ratios from 25 ppbv over the forested area (south of 12° N) up to 40 ppbv over the Sahelian area. We employ a two-dimensional (latitudinal versus vertical) meteorological model coupled with an O3-NOx-VOC chemistry scheme to simulate the distribution of trace gases over West Africa during the monsoon season and to analyse the processes involved in the establishment of such a gradient. Including an additional source of NO over the Sahelian region to account for NO emitted by soils we simulate a mean NOx concentration of 0.7 ppbv at 16° N versus 0.3 ppbv over the vegetated region further south in reasonable agreement with the observations. As a consequence, ozone is photochemically produced with a rate of 0.25 ppbv h−1 over the vegetated region whilst it reaches up to 0.75 ppbv h−1 at 16° N. We find that the modelled gradient is due to a combination of enhanced deposition to vegetation, which decreases the ozone levels by up to 11 pbbv, and the aforementioned enhanced photochemical production north of 12° N. The peroxy radicals required for this enhanced production in the north come from the oxidation of background CO and CH4 as well as from VOCs. Sensitivity studies reveal that both the background CH4 and partially oxidised VOCs, produced from the oxidation of isoprene emitted from the vegetation in the south, contribute around 5–6 ppbv to the ozone gradient. These results suggest that the northward transport of trace gases by the monsoon flux, especially during nighttime, can have a significant, though secondary, role in determining the ozone gradient in the boundary layer. Convection, anthropogenic emissions and NO produced from lightning do not contribute to the establishment of the discussed ozone gradient.

Genotype and fungicide effects on late-season root growth of winter wheat

The aim of this work was to investigate differences among genotypes in post-anthesis root growth and distribution of modern UK winter wheat cultivars, and the effects of fungicide applications. Post-anthesis root growth of up to six cultivars of winter wheat (Triticum aestivum L.), given either one or three applications of fungicide, was studied in field experiments during two seasons. Total root mass remained unchanged between GS63 (anthesis) and GS85, but root length increased significantly from 14.7 to 31.4 km m(2) in one season. Overall, there was no evidence for a decline in either root mass or length during grain filling. Root mass as a proportion of total plant mass was about 0.05 at GS85. There were significant differences among cultivars in root length and mass especially below 30 cm. Malacca had the smallest root length and Savannah the largest, and Shamrock had a significantly larger root system below 40 cm in both seasons. Fungicide applied at ear emergence had no significant effect on root mass in either season but increased root length (P < 0.01) in the more disease-prone season. By maintaining a green canopy for longer, fungicide applied at flag leaf emergence may have resulted in delayed senescence of the root system and contributed to the post-anthesis maintenance of root mass and length.

Effects of triazole and strobilurin fungicide programmes, with and without late-season nitrogen fertiliser, on the baking quality of Malacca winter wheat

Field experiments were conducted over 3 years to study the effect of applying triazole and strobilurin fungicides on the bread-making quality of Malacca winter wheat. Averaged over all years the application of a fungicide programme increased yields, particularly when strobilurin fungicides were applied. Reductions in protein concentration, sulphur concentration, Hageberg failing number and loaf volumes also occurred as the amount of fungicide applied increased. However, there were no deleterious effects of fungicide application on sodium dodecyl sulphate (SDS) sedimentation volumes, N:S ratios or dough theology. Effects of fungicide application on bread-making quality were not product specific. Therefore, it appears that new mechanisms to explain strobilurin effects on bread-making quality do not need to be invoked. Where reductions in protein concentration did occur they could be compensated for by a late-season application of nitrogen either as granular ammonium nitrate at flag leaf emergence or foliar urea at anthesis. These applications, however, sometimes increased the N:S ratio of the extracted flour and failed to improve loaf volume. Multiple regression analysis revealed that main effects of year, flour protein concentration and N:S ratio could explain 93% of the variance in loaf volume caused by season, fungicide and nitrogen treatments. However, an equally good fit was achieved by just including sulphur concentration with year. (C) 2004 Elsevier Ltd. All rights reserved.

Dichrostachys cinerea and Acacia nilotica fruits as dry season feed supplements for goats in a semi-arid environment: Summary of a DFID funded project in Zimbabwe

Indehiscent fruits of six tree species, common in Matabeleland were examined in in vitro and in vivo trials. The results for two of them, Acacia nilotica and Dichrostachys cinerea are presented here. Acacia nilotica-contained more total phenolics than D. cinerea, but less nitrogen (N) and fibre (ADF and NDF). After 48 h incubation, in vitro OMD of both species was increased by PEG and NaOH or wood ash treatment, except when NaOH or wood ash were used in combination with PEG with D. cinerea fruits. DM intake, DMD were lowest and N-retention negative in goats fed A. nilotica as supplement. However when fed a supplement of D. cinerea, untreated or treated with PEG or NaOH, digestibility and N-retention were highest, and similar to a commercial goat meal, with the untreated fruit. In a trial in which milking does were supplemented with D. cinerea fruits, for 65 before and 65 days after kidding, kid birthweight and weaning weight were increased by supplementation. Deaths of twin-born kids were lowest in the supplemented but unmilked group. Supplementation with D. cinerea fruit resulted in improved goat performance. The only treatment applied of practical significance, wood ash, is currently being tested in an in vivo study. More research is required on detoxification of tannins, especially with A. nilotica. (c) 2005 Elsevier B.V. All rights reserved.

The optimum temperature for long-season cropping in the everbearing strawberry 'Everest'

The prolonged season of everbearing strawberries causes vegetative growth and fruiting to coincide, so the influence of the environment on the balance of assimilate partitioning between vegetative and reproductive growth is important for optimised long-season production. Fruiting patterns were evaluated over three seasons for the everbearing strawberry 'Everest'. A range of temperatures (15-27 degrees C) was studied in the first season to establish a temperature response curve. Detailed transfer treatments in the second and third seasons gave insight into heat-induced cropping troughs ('thermo-dormancy'). The detrimental effect on yield of thermo-dormancy was prevented by cool night-time temperature during the periods of heat stress, a treatment that resulted in the largest total fruit fresh weight and overall yield. The highest yields were recorded for plants grown between 18 and 23 degrees C. At higher temperatures fruit number increased, but fruit weight decreased. The importance of night-time temperature in optimising long-season fruit production has significance for commercial production, in which protected cropping tends to increase average temperature through the season.

Analysis of shade and temperature effects on assimilate partitioning in the everbearing strawberry 'Everest' as the basis for optimised long-season fruit production

Growth patterns and cropping were evaluated over the season for the everbearing strawberry 'Everest' at a range of temperatures (15-27degreesC) in two light environments (ambient and 50% shade). The highest yield was recorded for unshaded plants grown at 23degreesC, but the optimum temperature for vegetative growth was 15degreesC. With increasing temperature fruit number increased, but fruit weight decreased. Fruit weight was also significantly reduced by shade, and although 'Everest' showed a degree of shade tolerance in vegetative growth, yield was consistently reduced by shade. Shade also reduced the number of crowns developed by the plants over the course of the season, emphasising that crown number was ultimately the limiting factor for yield potential. We conclude that, in contrast to Junebearers which partition more assimilates to fruit at temperatures around 15degreesC (Le Miere et al., 1998), optimised cropping in the everbearer 'Everest' is achieved at the significantly higher temperature of 23degreesC. These findings have significance for commercial production, in which protection tends to reduce light levels but increase average temperature throughout the season.

Melt structure and its transformation by sequential crystallization of the two blocks within poly(L-lactide)-block-poly(epsilon-caprolactone) double crystalline diblock copolymers

Sequential crystallization of poly(L-lactide) (PLLA) followed by poly(epsilon-caprolactone) (PCL) in double crystalline PLLA-b-PCL diblock copolymers is studied by differential scanning calorimetry (DSC), polarized optical microscopy (POM), wide-angle X-ray scattering (WAXS) and small-angle X-ray scattering (SAXS). Three samples with different compositions are studied. The sample with the shortest PLLA block (32 wt.-% PLLA) crystallizes from a homogeneous melt, the other two (with 44 and 60% PLLA) from microphase separated structures. The microphase structure of the melt is changed as PLLA crystallizes at 122 degrees C (a temperature at which the PCL block is molten) forming spherulites regardless of composition, even with 32% PLLA. SAXS indicates that a lamellar structure with a different periodicity than that obtained in the melt forms (for melt segregated samples). Where PCL is the majority block, PCL crystallization at 42 degrees C following PLLA crystallization leads to rearrangement of the lamellar structure, as observed by SAXS, possibly due to local melting at the interphases between domains. POM results showed that PCL crystallizes within previously formed PLLA spherulites. WAXS data indicate that the PLLA unit cell is modified by crystallization of PCL, at least for the two majority PCL samples. The PCL minority sample did not crystallize at 42 degrees C (well below the PCL homopolymer crystallization temperature), pointing to the influence of pre-crystallization of PLLA on PCL crystallization, although it did crystallize at lower temperature. Crystallization kinetics were examined by DSC and WAXS, with good agreement in general. The crystallization rate of PLLA decreased with increase in PCL content in the copolymers. The crystallization rate of PCL decreased with increasing PLLA content. The Avrami exponents were in general depressed for both components in the block copolymers compared to the parent homopolymers. Polarized optical micrographs during isothermal crystalli zation of (a) homo-PLLA, (b) homo-PCL, (c) and (d) block copolymer after 30 min at 122 degrees C and after 15 min at 42 degrees C.

Factors controlling the distribution of ozone in the West African lower troposphere during the AMMA (African Monsoon Multidisciplinary Analysis) wet season campaign

Ozone and its precursors were measured on board the Facility for Airborne Atmospheric Measurements (FAAM) BAe 146 Atmospheric Research Aircraft during the monsoon season 2006 as part of the African Monsoon Multidisciplinary Analysis (AMMA) campaign. One of the main features observed in the west African boundary layer is the increase of the ozone mixing ratios from 25 ppbv over the forested area (south of 12 degrees N) up to 40 ppbv over the Sahelian area. We employ a two-dimensional ( latitudinal versus vertical) meteorological model coupled with an O-3-NOx-VOC chemistry scheme to simulate the distribution of trace gases over West Africa during the monsoon season and to analyse the processes involved in the establishment of such a gradient. Including an additional source of NO over the Sahelian region to account for NO emitted by soils we simulate a mean NOx concentration of 0.7 ppbv at 16 degrees N versus 0.3 ppbv over the vegetated region further south in reasonable agreement with the observations. As a consequence, ozone is photochemically produced with a rate of 0.25 ppbv h(-1) over the vegetated region whilst it reaches up to 0.75 ppbv h(-1) at 16 degrees N. We find that the modelled gradient is due to a combination of enhanced deposition to vegetation, which decreases the ozone levels by up to 11 pbbv, and the aforementioned enhanced photochemical production north of 12 degrees N. The peroxy radicals required for this enhanced production in the north come from the oxidation of background CO and CH4 as well as from VOCs. Sensitivity studies reveal that both the background CH4 and partially oxidised VOCs, produced from the oxidation of isoprene emitted from the vegetation in the south, contribute around 5-6 ppbv to the ozone gradient. These results suggest that the northward transport of trace gases by the monsoon flux, especially during nighttime, can have a significant, though secondary, role in determining the ozone gradient in the boundary layer. Convection, anthropogenic emissions and NO produced from lightning do not contribute to the establishment of the discussed ozone gradient.

Effects of triazole and strobilurin fungicide programmes, with and without late-season nitrogen fertiliser, on the baking quality of Malacca winter wheat

Field experiments were conducted over 3 years to study the effect of applying triazole and strobilurin fungicides on the bread-making quality of Malacca winter wheat. Averaged over all years the application of a fungicide programme increased yields, particularly when strobilurin fungicides were applied. Reductions in protein concentration, sulphur concentration, Hageberg failing number and loaf volumes also occurred as the amount of fungicide applied increased. However, there were no deleterious effects of fungicide application on sodium dodecyl sulphate (SDS) sedimentation volumes, N:S ratios or dough theology. Effects of fungicide application on bread-making quality were not product specific. Therefore, it appears that new mechanisms to explain strobilurin effects on bread-making quality do not need to be invoked. Where reductions in protein concentration did occur they could be compensated for by a late-season application of nitrogen either as granular ammonium nitrate at flag leaf emergence or foliar urea at anthesis. These applications, however, sometimes increased the N:S ratio of the extracted flour and failed to improve loaf volume. Multiple regression analysis revealed that main effects of year, flour protein concentration and N:S ratio could explain 93% of the variance in loaf volume caused by season, fungicide and nitrogen treatments. However, an equally good fit was achieved by just including sulphur concentration with year. (C) 2004 Elsevier Ltd. All rights reserved.

Melt brushes of diblock copolymer

Using self-consistent field theory (SCFT), we investigate the morphologies formed by a melt brush of AB diblock copolymers grafted to a flat substrate by their B ends. In addition to a laterally uniform morphology, SCFT predicts three ordered morphologies exhibiting different periodic patterns at the air surface: a hexagonal array of A-rich dots, an alternating sequence of A- and B-rich stripes, and a hexagonal pattern of B-rich dots. When the phase diagram of the tethered film is plotted as a function of A/B incompatibility, $\chi N$, and diblock composition, $f$, it resembles the bulk phase diagram with the periodic phases converging to a mean-field critical point at weak segregation. The periodic-phase region in the phase diagram shrinks with increasing grafting density and expands when the air surface acquires an affinity for the grafted B blocks.