Polyimides and their derivatives for gas separation applications

High performance polymers are of interest for high temperature gas separations, especially for the sequestration of carbon dioxide. A new family of high performance imide polymers (VTEC, RBI Inc.) has been identified as a material class containing the potential building blocks needed for a successful membrane capture material. The VTEC polyimides possess the desired thermal properties (up to 500 °C) and are robust and flexible even after multiple thermal cycles (up to 400 °C). A critical variable when working with the glassy polymers is their moisture content. It has been found that water entrapped within the polymer matrix (either as hydration molecules attached to salts in the polymer, left over solvent, or physisorbed) can also cause the polymer to change dramatically. Additionally presence of molecular water in the polymer’s void volume has been validated through Positron Annihilation Lifetime (PAL) spectroscopy. In this presentation, polymer characterization and gas-separation testing results will be discussed

Drastic enhancement of carbon dioxide adsorption in fluoroalkyl-modified poly(allylamine)

Polyamine-based carbon dioxide sorbents suffer from a seesaw relationship between amine content and amine efficiency. High polyamine loadings equate to increased amine contents, but often at the expense of amine efficiency. Carbon dioxide mass transport in compact polymers is severely limited, especially at ambient temperature. High polymer contents curtail diffusion pathways, hindering CO2 from reaching and reacting with the numerous amine functions. Here, we overcome this issue using poly(allylamine) (PAA) grafted with short fluoroalkyl chains and then cross-linked with C60. As experimentally evidenced by positron annihilation lifetime spectroscopy, the incorporation of fluoroalkyl chains generates free volume elements that act as additional diffusion pathways within the material. The inclusion of void volume in fluoroalkyl-functionalized PAA sorbents results in radically increased CO2 uptakes and amine efficiencies in diluted gas streams at room temperature, including simulated air. We speculate that the hydrophobic fluorinated functions interfere with the strong amine hydrogen bonding network disrupting and consequently altering the packing and conformation of the polymer chains. The evidence presented here is a blueprint for the development of more efficient amine-based CO2 sorbents. This journal i

Constraint methods for determining pathways and free energy of activated processes

Activated processes from chemical reactions up to conformational transitions of large biomolecules are hampered by barriers which are overcome only by the input of some free energy of activation. Hence, the characteristic and rate-determining barrier regions are not sufficiently sampled by usual simulation techniques. Constraints on a reaction coordinate r have turned out to be a suitable means to explore difficult pathways without changing potential function, energy or temperature. For a dense sequence of values of r, the corresponding sequence of simulations provides a pathway for the process. As only one coordinate among thousands is fixed during each simulation, the pathway essentially reflects the system's internal dynamics. From mean forces the free energy profile can be calculated to obtain reaction rates and insight in the reaction mechanism. In the last decade, theoretical tools and computing capacity have been developed to a degree where simulations give impressive qualitative insight in the processes at quantitative agreement with experiments. Here, we give an introduction to reaction pathways and coordinates, and develop the theory of free energy as the potential of mean force. We clarify the connection between mean force and constraint force which is the central quantity evaluated, and discuss the mass metric tensor correction. Well-behaved coordinates without tensor correction are considered. We discuss the theoretical background and practical implementation on the example of the reaction coordinate of targeted molecular dynamics simulation. Finally, we compare applications of constraint methods and other techniques developed for the same purpose, and discuss the limits of the approach

Comparison of Aromatic Dithiophoshinic and Phosphinic Acid Derivatives for Minor Actinide Extraction

A new extractant for the separation of actinide(III) and lanthanide(III), bis(otrifluoromethylphenyl) phosphinic acid (O-PA) was synthesized. The synthetic route employed mirrors one that was employed to produce the sulfur containing analog bis(otrifluoromethylphenyl) dithiophosphinic acid (S-PA). Multinuclear NMR spectroscopy was used for elementary characterization of the new O-PA derivative. This new O-PA extractant was used to perform Am(III)/Eu(III) separations and the results were directly compared to those obtained in identical separation experiments using S-PA, an extractant that is known to exhibit separation factors of ~100,000 at low pH. The separations data are presented and discussed in terms comparing the nature of the oxygen atom as a donor to that of the sulfur atom in extractants that are otherwise identical

Momentum dependent mean-field dynamics of compressed nuclear matter and neutron stars

Nuclear matter and compact neutron stars are studied in the framework of the non-linear derivative (NLD) model which accounts for the momentum dependence of relativistic mean-fields. The generalized form of the energy-momentum tensor is derived which allows to consider different forms of the regulator functions in the NLD Lagrangian. The thermodynamic consistency of the NLD model is demonstrated for arbitrary choice of the regulator functions. The NLD approach describes the bulk properties of the nuclear matter and compares well with microscopic calculations and Dirac phenomenology. We further study the high density domain of the nuclear equation of state (EoS) relevant for the matter in $\beta$-equilibrium inside neutron stars. It is shown that the low density constraints imposed on the nuclear EoS and by the momentum dependence of the Schr\"odinger-equivalent optical potential lead to a maximum mass of the neutron stars around $M \simeq 2 M_{\odot}$ which accommodates the observed mass of the J1614-2230 millisecond radio pulsar.Comment: 25 pages, 11 figures, accepted for publication in Nuclear Physics

The History of Makassan Trepang Fishing and Trade

The Malayan term trepang describes a variety of edible holothurians commonly known as sea cucumbers. Although found in temperate and tropical marine waters all over the world, the centre of species diversity and abundance are the shallow coastal waters of Island Southeast Asia. For at least 300 years, trepang has been a highly priced commodity in the Chinese market. Originally, its fishing and trade was a specialized business, centred on the town of Makassar in South Sulawesi (Indonesia). The rise of trepang fishing in the 17th century added valuable export merchandize to the rich shallow seas surrounding the islands of Southeast Asia. This enabled local communities to become part of large trading networks and greatly supported their economic development. In this article, we follow Makassan trepang fishing and trading from its beginning until the industrialization of the fishery and worldwide depletion of sea cucumbers in the 20th century. Thereby, we identify a number of characteristics which trepang fishing shares with the exploitation of other marine resources, including (1) a strong influence of international markets, (2) the role of patron-client relationships which heavily influence the resource selection, and (3) the roving-bandit-syndrome, where fishermen exploit local stocks of valuable resources until they are depleted, and then move to another area. We suggest that understanding the similarities and differences between historical and recent exploitation of marine resources is an important step towards effective management solutions

Positron Annihilation Spectroscopy of High Performance Polymer Films under CO2 Pressure

Positron annihilation Lifetime and Doppler broadening measurements are reported for six polymer films as a function of carbon dioxide absolute pressure ranging from 0 to 45 psi. Since the polymer films were thin and did not absorb all positrons, corrections were made in the lifetime analysis for the absorption of positrons in the positron source and sample holder using the Monte Carlo transport code MCNP. Different polymers are found to behave differently. Some polymers studied form positronium and some, such as the polyimide structures, do not. For those samples that form positronium an interpretation in terms of free volume is possible; for those that don’t form positronium, further work is needed to determine how best to describe the behavior in terms of the bulk positron annihilation parameters. Some polymers exhibit changes in positron lifetime and intensity under CO2 pressure which may be described by the Henry or Langmuir sorption models, while the positron response of other polymers is rather insensitive to the CO2 pressure. The results demonstrate the usefulness of positron annihilation spectroscopy in investigating the sorption of CO2 into various polymers at pressures up to about 3 atm