A complete atomistic model of molten polyethylene from neutron scattering data: a new methodology for polymer structure

A new approach to the study of the local organization in amorphous polymer materials is presented. The method couples neutron diffraction experiments that explore the structure on the spatial scale 1–20 Å with the reverse Monte Carlo fitting procedure to predict structures that accurately represent the experimental scattering results over the whole momentum transfer range explored. Molecular mechanics and molecular dynamics techniques are also used to produce atomistic models independently from any experimental input, thereby providing a test of the viability of the reverse Monte Carlo method in generating realistic models for amorphous polymeric systems. An analysis of the obtained models in terms of single chain properties and of orientational correlations between chain segments is presented. We show the viability of the method with data from molten polyethylene. The analysis derives a model with average C-C and C-H bond lengths of 1.55 Å and 1.1 Å respectively, average backbone valence angle of 112, a torsional angle distribution characterized by a fraction of trans conformers of 0.67 and, finally, a weak interchain orientational correlation at around 4 Å.

A detailed single chain model for molten poly(tetrafluoroethylene) from a novel structure refinement technique on neutron scattering data

We present a new methodology that couples neutron diffraction experiments over a wide Q range with single chain modelling in order to explore, in a quantitative manner, the intrachain organization of non-crystalline polymers. The technique is based on the assignment of parameters describing the chemical, geometric and conformational characteristics of the polymeric chain, and on the variation of these parameters to minimize the difference between the predicted and experimental diffraction patterns. The method is successfully applied to the study of molten poly(tetrafluoroethylene) at two different temperatures, and provides unambiguous information on the configuration of the chain and its degree of flexibility. From analysis of the experimental data a model is derived with CC and CF bond lengths of 1.58 and 1.36 Å, respectively, a backbone valence angle of 110° and a torsional angle distribution which is characterized by four isometric states, namely a split trans state at ± 18°, giving rise to a helical chain conformation, and two gauche states at ± 112°. The probability of trans conformers is 0.86 at T = 350°C, which decreases slightly to 0.84 at T = 400°C. Correspondingly, the chain segments are characterized by long all-trans sequences with random changes in sign, rather anisotropic in nature, which give rise to a rather stiff chain. We compare the results of this quantitative analysis of the experimental scattering data with the theoretical predictions of both force fields and molecular orbital conformation energy calculations.

Extracting quantitative structural parameters for disordered polymers from neutron scattering data

The organization of non-crystalline polymeric materials at a local level, namely on a spatial scale between a few and 100 a, is still unclear in many respects. The determination of the local structure in terms of the configuration and conformation of the polymer chain and of the packing characteristics of the chain in the bulk material represents a challenging problem. Data from wide-angle diffraction experiments are very difficult to interpret due to the very large amount of information that they carry, that is the large number of correlations present in the diffraction patterns.We describe new approaches that permit a detailed analysis of the complex neutron diffraction patterns characterizing polymer melts and glasses. The coupling of different computer modelling strategies with neutron scattering data over a wide Q range allows the extraction of detailed quantitative information on the structural arrangements of the materials of interest. Proceeding from modelling routes as diverse as force field calculations, single-chain modelling and reverse Monte Carlo, we show the successes and pitfalls of each approach in describing model systems, which illustrate the need to attack the data analysis problem simultaneously from several fronts.

Extracting and validating force fields for disordered polymeric materials from neutron scattering data

We present a new approach that allows the determination and refinement of force field parameters for the description of disordered macromolecular systems from experimental neutron diffraction data obtained over a large Q range. The procedure is based on tight coupling between experimentally derived structure factors and computer modelling. By separating the potential into terms representing respectively bond stretching, angle bending and torsional rotation and by treating each of them separately, the various potential parameters are extracted directly from experiment. The procedure is illustrated on molten polytetrafluoroethylene.

Extracting force fields for disordered polymeric materials from neutron scattering data

We present a new approach that allows the determination of force-field parameters for the description of disordered macromolecular systems from experimental neutron diffraction data obtained over a large Q range. The procedure is based on a tight coupling between experimentally derived structure factors and computer modelling. We separate the molecular potential into non-interacting terms representing respectively bond stretching, angle bending and torsional rotation. The parameters for each of the potentials are extracted directly from experimental data through comparison of the experimental structure factor and those derived from atomistic level molecular models. The viability of these force fields is assessed by comparison of predicted large-scale features such as the characteristic ratio. The procedure is illustrated on molten poly(ethylene) and poly(tetrafluoroethylene).

Modelling the structure of a polymer glass poly(methylmethacrylate) through neutron scattering experiments

Determination of the local structure of a polymer glass by scattering methods is complex due to the number of spatial and orientational correlations, both from within the polymer chain (intrachain) and between neighbouring chains (interchain), from which the scattering arises. Recently considerable advances have been made in the structural analysis of relatively simple polymers such as poly(ethylene) through the use of broad Q neutron scattering data tightly coupled to atomistic modelling procedures. This paper presents the results of an investigation into the use of these procedures for the analysis of the local structure of a-PMMA which is chemically more complex with a much greater number of intrachain structural parameters. We have utilised high quality neutron scattering data obtained using SANDALS at ISIS coupled with computer models representing both the single chain and bulk polymer system. Several different modelling approaches have been explored which encompass such techniques as Reverse Monte Carlo refinement and energy minimisation and their relative merits and successes are discussed. These different approaches highlight structural parameters which any realistic model of glassy atactic PMMA must replicate.

Eco-labeling, rents, sales prices and occupancy rates: do LEED and Energy Star labeled offices obtain multiple premiums?

Drawing upon an updated and expanded dataset of Energy Star and LEED labeled commercial offices, this paper investigates the effect of eco-labeling on rental rates, sale prices and occupancy rates. Using OLS and robust regression procedures, hedonic modeling is used to test whether the presence of an eco-label has a significant positive effect on rental rates, sale prices and occupancy rates. The study suggests that estimated coefficients can be sensitive to outlier treatment. For sale prices and occupancy rates, there are notable differences between estimated coefficients for OLS and robust regressions. The results suggest that both Energy Star and LEED offices obtain rental premiums of approximately 3%. A 17% sale price premium is estimated for Energy Star labeled offices but no significant sale price premium is estimated for LEED labeled offices. Surprisingly, no significant occupancy premium is estimated for Energy Star labeled offices and a negative occupancy premium is estimated for LEED labeled offices.

Retrieval of mesospheric electron densities using an optimal estimation inverse method

We present a new method to determine mesospheric electron densities from partially reflected medium frequency radar pulses. The technique uses an optimal estimation inverse method and retrieves both an electron density profile and a gradient electron density profile. As well as accounting for the absorption of the two magnetoionic modes formed by ionospheric birefringence of each radar pulse, the forward model of the retrieval parameterises possible Fresnel scatter of each mode by fine electronic structure, phase changes of each mode due to Faraday rotation and the dependence of the amplitudes of the backscattered modes upon pulse width. Validation results indicate that known profiles can be retrieved and that χ2 tests upon retrieval parameters satisfy validity criteria. Application to measurements shows that retrieved electron density profiles are consistent with accepted ideas about seasonal variability of electron densities and their dependence upon nitric oxide production and transport.

Tillage and herbicide treatments with inter-row cultivation influence weed densities and yield of three industrial crops

Field experiments were conducted in northern Greece in 2003 and 2004 to evaluate effects of tillage regimes (moldboard plowing, chisel plowing, and rotary tilling), cropping sequences(continuous cotton, cotton-sugar beet rotation,and continuous tobacco) and herbicide treatments with inter-row hand hoeing on weed population densities. Total weed densities were not affected by tillage treatment except that of barnyardgrass (Echinochloa crus-galli), which increased only in moldboard plowing treated plots during 2003. Redroot pigweed (Amaranthus retroflexus)and black nightshade (Solanum nigrum) densities were reduced in continuous cotton, while purple nutsedge (Cyperus rotundus), E. crus-galli, S. nigrum, and johnsongras(Sorghum halepense) densities were reduced in tobacco. A. retroflexus and S. nigrum were effectively controlled by all herbicide treatments with inter-row hand hoeing,whereas E. crus-galli was effectively reduced by herbicides applied to cotton and tobacco. S. halepense density reduction was a result of herbicide applied to tobacco with inter-row hand hoeing. Yield of all crops was higher under moldboard plowing and herbicide treatments. Pre-sowing and pre-emergence herbicide treatments in cotton and pre-transplant in tobacco integrated with inter-row cultivation resulted in efficient control of annual weed species and good crop yields. These observations are of practical relevance to crop selection by farmers in order to maintain weed populations at economically acceptable densities through the integration of various planting dates, sustainable herbicide use and inter-row cultivation; tools of great importance in integrated weed management systems. Keywords: cropping sequence, herbicide, integrated weed management, inter-row cultivation,tillage.

(Non)differentiability and asymptotics for potential densities of subordinators

For subordinators with positive drift we extend recent results on the structure of the potential measures and the renewal densities. Applying Fourier analysis a new representation of the potential densities is derived from which we deduce asymptotic results and show how the atoms of the Lévy measure translate into points of (non)differentiability of the potential densities.

The asymptotic behavior of densities related to the supremum of a stable process

If X is a stable process of index α∈(0, 2) whose Lévy measure has density cx−α−1 on (0, ∞), and S1=sup0x)∽Aα−1x−α as x→∞ and P(S1≤x)∽Bα−1ρ−1xαρ as x↓0. [Here ρ=P(X1>0) and A and B are known constants.] It is also known that S1 has a continuous density, m say. The main point of this note is to show that m(x)∽Ax−(α+1) as x→∞ and m(x)∽Bxαρ−1 as x↓0. Similar results are obtained for related densities.

Synthesis and crystal structure of a novel octa-aqua bridged star-shaped Ni4K complex

A penta-nuclear. star-shaped hetero-metallic compound containing a unique Ni4KO8 core has been synthesized. The X-ray single crystal structure analysis reveals that in the complex, [K(Ni(LH)(2))(4)(OH2)(8)](Br)(ClO4)(8)center dot 11H(2)O (LH=(CH3)(2)HN+(CH2)(3)N=CHC6H4O-) the eight coordinate central K+ ion is encapsulated by four terminal [Ni(LH)(2)](2+) units through the double water bridges between K+ and each Ni(II) ions.

Housing densities and consumer choice

From 2001, the construction of flats and high-density developments increased in England and the building of houses declined. Does this indicate a change in taste or is it a result of government planning policies? In this paper, an analysis is made of the long-term effects of the policy of constraint which has existed for the past 50 years but the increase in density is identified as occurring primarily after new, revised, planning guidance was issued in England in 2000 which discouraged low-density development. To substantiate this, it is pointed out that the change which occurred in England did not occur in Scotland where guidance was not changed to encourage high-density residential development. The conclusion that the change is the result of planning policies and not of a change in taste is confirmed by surveys of the occupants of new high-rise developments in Leeds. The new flat-dwellers were predominantly young and childless and expressed the intention, in the near future, when they could, of moving out of the city centre and into houses. From recent changes in guidance by the new coalition government, it is expected that the construction of flats in England will fall back to earlier levels over the next few years.

SANS/WANS time-resolving neutron scattering studies of polymer phase transitions using NIMROD

We use new neutron scattering instrumentation to follow in a single quantitative time-resolving experiment, the three key scales of structural development which accompany the crystallisation of synthetic polymers. These length scales span 3 orders of magnitude of the scattering vector. The study of polymer crystallisation dates back to the pioneering experiments of Keller and others who discovered the chain-folded nature of the thin lamellae crystals which are normally found in synthetic polymers. The inherent connectivity of polymers makes their crystallisation a multiscale transformation. Much understanding has developed over the intervening fifty years but the process has remained something of a mystery. There are three key length scales. The chain folded lamellar thickness is ~ 10nm, the crystal unit cell is ~ 1nm and the detail of the chain conformation is ~ 0.1nm. In previous work these length scales have been addressed using different instrumention or were coupled using compromised geometries. More recently researchers have attempted to exploit coupled time-resolved small-angle and wide-angle x-ray experiments. These turned out to be challenging experiments much related to the challenge of placing the scattering intensity on an absolute scale. However, they did stimulate the possibility of new phenomena in the very early stages of crystallisation. Although there is now considerable doubt on such experiments, they drew attention to the basic question as to the process of crystallisation in long chain molecules. We have used NIMROD on the second target station at ISIS to follow all three length scales in a time-resolving manner for poly(e-caprolactone). The technique can provide a single set of data from 0.01 to 100Å-1 on the same vertical scale. We present the results using a multiple scale model of the crystallisation process in polymers to analyse the results.