Self-assembling behavior in decane solution of potential wax crystal nucleators based on poly(co-olefins)

The control of the precipitation and gelation of long chain paraffins from oil remains an enduring technological challenge regarding the processing and recovery of refined fuels and waxy crudes. Wax crystal modifiers based on polyethylene -poly(ethylene-propylene) (PE-PEP) diblock copolymers function as efficient nucleators for wax crystals in middle distillate fuels. These diblock polymers self-assemble in oil to form expansive platelike aggregates consisting of a PE core cloaked behind the amorphous PEP brush layer. The PE core thus promotes nucleation of solubilized long chain alkanes. Additional candidate structures for wax crystal nucleators include linear and star copolyolefins where the composition variation signals the alteration between crystalline and amorphous segments. This study focuses upon the self-assembling behavior in solution of these materials. The characteristics of the single chains and the aggregates formed at lower temperatures were determined via small-angle neutron scattering. Both plates and needlelike structures were found. The placement of the amorphous and crystalline blocks in the arms of the star shaped polymers was found to influence the architecture of the self-assembled micelles. As a point of comparison a commercial copolymer of ethylene-vinyl acetate (EVA) was also investigated. The EVA material was found to be relatively "undisciplined" in comparison to the structurally more uniform anionically prepared counterparts

Interaction of paraffin wax gels with random crystalline/amorphous hydrocarbon copolymers

The control mechanisms involved in the modification of wax crystal dimensions in crude oils and refined fuels are of joint scientific and practical interest. An understanding of these mechanisms allows strategies to be developed that lead to decreases in crude oil pour points or (for refined fuels) cold filter plugging points. The attainment of these goals involves the control and modification of wax crystals that spontaneously form in mixed hydrocarbon systems upon decreasing temperature. This work reports on the influence of random crystalline-amorphous block copolymers (ethylene-butene) upon the rheology of model oils. In a parallel fashion small-angle neutron scattering was exploited to gain microscopic insight as to how added poly(ethylene-butene) copolymers modify the wax crystal structures. The copolymers with different contents of polyethylene are highly selective with respect to wax crystal modification. Thus, the copolymer with the highest crystalline tendency is more efficient for the larger wax molecules while the less crystalline one is more efficient for the lower waxes

Interaction of paraffin wax gels with ethylene/vinyl acetate copolymers

The commercial grades of ethylene/vinyl acetate (EVA) co-polymers have found application as pour point" depressants in refined fuels. This study focuses on their behavior as additives to crude oils, where the intent is to reduce the yield stress of the gels that can form when the oil exits the reservoir. The model crude oils consisted of 4 wt % wax in decane. At EVA dosage levels of similar to200 ppm, the reduction in yield stress is 3 orders of magnitude for the C-36 wax, whereas the reduction is 1 order of magnitude for C-32 and only 3-fold for the C-28 wax. This decrease in efficiency with decreasing wax carbon number indicates that the EVA materials would not provide an adequate reduction in yield stress to ensure against gelation in pipeline transport. Neutron scattering studies, as a function of temperature, of the self-assembly of the EVA co-polymers show dramatically different aggregated structures in decane. The EVA with the lowest ethylene content shows scattering that increases with a power-law exponent of similar to1.6. This scattering behavior is typical for weakly aggregating polymer gels. In contrast, the EVA with the higher ethylene content shows a transition from surface scattering (found for strongly segregated objects) to a plateau whose height is dependent on temperature. Micrographs of the wax crystal morphology indicate that the ethylene-poor EVA alters the wax crystal habit at higher concentrations more effectively than does its higher-ethylene-content counterpart, whereas the latter EVA grade seems to form more wax crystals at low concentrations

Multi-method study of the Middle Pleistocene loess–palaeosol sequence of Köndringen, SW Germany

Loess–palaeosol sequences (LPSs) remain poorly investigated in the southern part of the Upper Rhine Graben but represent an important element to understand the environmental context controlling sediment dynamics in the area. A multi-method approach applied to the LPS at Köndringen reveals that its formation occurred during several glacial–interglacial cycles. Field observations, as well as colour, grain size, magnetic susceptibility, organic carbon, and carbonate content measured in three profiles at 5 cm resolution, provide detailed stratigraphical information. Only minor parts of the LPS are made up of loess sediment, whereas the major parts are polygenetic palaeosols and pedosediments of varying development that are partly intersected, testifying to a complex local geomorphic evolution. The geochronological framework is based on 10 cm resolution infrared-stimulated luminescence (IRSL) screening combined with 18 multi-elevated-temperature post-IR IRSL ages. The luminescence ages indicate that two polygenetic, truncated Luvisols formed during marine isotope stages (MISs) 9(–7?) and MIS 5e, whereas unaltered loess units correspond to the last glacial (MISs 5d–2) and MIS 8. The channel-like structure containing the two truncated Luvisols cuts into &gt; 2 m thick pedosediments apparently deposited during MIS 12. At the bottom of the LPS, a horizon with massive carbonate concretions (loess dolls) occurs, which may correspond to at least one older interglacial.</p

Bulk and Boundary Critical Behavior at Lifshitz Points

Lifshitz points are multicritical points at which a disordered phase, a homogeneous ordered phase, and a modulated ordered phase meet. Their bulk universality classes are described by natural generalizations of the standard $\phi^4$ model. Analyzing these models systematically via modern field-theoretic renormalization group methods has been a long-standing challenge ever since their introduction in the middle of the 1970s. We survey the recent progress made in this direction, discussing results obtained via dimensionality expansions, how they compare with Monte Carlo results, and open problems. These advances opened the way towards systematic studies of boundary critical behavior at $m$-axial Lifshitz points. The possible boundary critical behavior depends on whether the surface plane is perpendicular to one of the $m$ modulation axes or parallel to all of them. We show that the semi-infinite field theories representing the corresponding surface universality classes in these two cases of perpendicular and parallel surface orientation differ crucially in their Hamiltonian's boundary terms and the implied boundary conditions, and explain recent results along with our current understanding of this matter.Comment: Invited contribution to STATPHYS 22, to be published in the Proceedings of the 22nd International Conference on Statistical Physics (STATPHYS 22) of the International Union of Pure and Applied Physics (IUPAP), 4--9 July 2004, Bangalore, Indi

Clearance of materials from accelerator facilities

A new Technical Standard that supports the clearance of materials and equipment (personal property) from U.S. Department of Energy (DOE) accelerator facilities has been developed. The Standard focuses on personal property that has the potential to be radiologically impacted by accelerator operations. It addresses material clearance programs and protocols for off-site releases without restriction on use. Common metals with potential volumetric activation are of main interest with technical bases provided in Appendices of the Standard. The clearance protocols in the Standard include three elements: 1) clearance criteria, 2) process knowledge, and 3) measurement methods. This paper presents the technical aspects of the new Standard, discusses operational experience gained in clearance of materials and equipment from several accelerator facilities at SLAC and examples as to how this Standard can be applied to benefit the entirety of the DOE Accelerator Complex

Improving polymeric microemulsions with block copolymer polydispersity

Recent experiments have demonstrated that block copolymers are capable of stabilizing immiscible homopolymer blends producing bicontinuous microemulsion. The stability of these polymeric alloys requires the copolymer to form flexible, nonattractive monolayers along the homopolymer interfaces. We predict that copolymer polydispersity can substantially and simultaneously improve the monolayers in both of these respects. Furthermore, polydispersity should provide similar improvements in systems, such as colloidal suspensions and polymer/clay composites, that utilize polymer brushes to suppress attractive interactions