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At least 235 records · Page 13

First Ever Polymer Flood Field Pilot To Enhance The Recovery Of Heavy Oils On Alaska’s North Slope - Pushing Ahead One Year Later

In June 2018 the team embarked on an ambitious project to address the slow development pace of Alaska’s 20+ billion barrels heavy oil resource via the first ever polymer flood pilot. Following the successful commencement of the pilot in August 2018, the field demonstration, supporting laboratory experiments and numerical simulation have steadily progressed. A significant amount of valuable data and lessons learned have been collected, and are reported in this paper. The ongoing pilot and the research activities is making headway toward the primary objective of validating the use of polymer flooding for extracting heavy oil in Alaska’s challenging environment. The pilot is conducted in two pre-existing pairs of horizontal injectors and producers in an isolated fault block of the Schrader Bluff heavy oil reservoir at the Milne Point Field. A customized polymer blending and pumping unit injects HPAM polymer at a concentration of 1,750 ppm to achieve a target viscosity of 45 cP. Supporting coreflood laboratory experiments have focused on quantification of polymer retention in the rock, and effect of injection water salinity, polymer, and their combinations on oil recovery. The injection and production response of the pilot flood pattern is utilized to develop a history matched reservoir simulation model for forecasting oil recovery beyond the pilot. Finally, specially designed laboratory experiments address anticipated operating concerns regarding post-polymer breakthrough such as oil-water separation efficiency and polymer induced fouling of heater tubes. Polymer has been injected continuously since startup except for two short equipment modification shutdowns, and more recently a prolonged disruption due to polymer hydration issues at the J-pad field site. Cumulatively, over 600,000 lbs. of polymer has been injected, corresponding to ~7%PV. The two producers show significant decrease in the water cut, gradually increasing oil rate, and no polymer breakthrough. Two main observations from the coreflood are a significant uncertainty in polymer retention values, and positive oil recovery response to low salinity water (2,600 mg/liter TDS). The heterogeneity in the flood pattern presents some challenges in obtaining a robust history matched simulation model. Experimental results on produced fluids treatment indicate the formation of a dense polymer deposit, at certain conditions, on heating tubes that can negatively impact the heat transfer efficiency. The scientific knowledge, including the lessons learned during unanticipated shutdowns, quality control, logistics and field data that is being acquired from this effort has referential value for other planned EOR projects. Finally, by all indications, the polymer field pilot is steadily progressing toward achieving the ultimate goal of unlocking the massive heavy oil resources on Alaska North Slope (ANS).

Dandekar, Abhijit↗

Imide/arylene ether copolymers with pendent trifluoromethyl groups

A series of imide/arylene ether block copolymers were prepared using an arylene ether block containing a hexafluoroisopropylidene group and an imide block containing a hexafluoroisopropylidene and a trifluoromethyl group in the polymer backbone. The copolymers were characterized and mechanical properties were determined and compared to the homopolymers.

Jensen, Brian J.↗

Self-assembled elastomers with molecularly encoded tissue-like softness, strain-adaptive stiffening and coloration

The invention generally relates to linear-bottlebrush-linear copolymer blocks and methods of making and using same. The disclosed copolymer blocks can be useful in, for example, the formation of polymer networks that replicate biological stress-strain behavior. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present invention.

Sheiko, Sergei↗

Spontaneous assembly of hierarchical phases

We report the grand promise of self-assembly is the creation of target nanostructures through spontaneous molecular organization, a process that is — in principle — simpler and more scalable than laborious top-down nanofabrication methods. Yet self-assembly faces a fundamental challenge: the structures that form thermodynamically tend to minimize surface area and maximize symmetry; the most readily-accessible structures are thus quite simple. Block copolymer (BCP) self-assembly, for example, takes advantage of the chemical incompatibility along a polymer backbone to drive local phase separation; frustrated assembly leads to a nanoscale morphology whose unit cell is dictated by chain architecture. Canonical BCPs (linear chains with two blocks) form alternating lamellae and hexagonally-packed cylinders in a straightforward manner; but more exotic phases require additional control, for example directing the assembly using external forces, such as shear or chemical templates. An elegant alternative is to use synthetic methods to design more sophisticated chain architectures, which may give rise to new morphologies. An outstanding challenge is to achieve morphological control without undue synthetic burden. Sun et al. now report in Nature Nanotechnology the design and synthesis of novel triblock copolymers that give rise to structural order at multiple length scales, thereby forming complex and hierarchical nanoscale phases.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Synthesis and Characterization of Methacrylamide-Based Block Random Copolymers via Amine Functionalization of Polystyrene- Block -Poly(Pentafluorophenyl Methacrylate) Toward Enhanced Amenability to Manufacturing Criteria in Nanolithography

Recent interest in manipulating the chemistry of block copolymers (BCPs) to manage the covarying properties necessary to meet manufacturing criteria in nanolithography has resulted in the development and expansion of the A-block-(B-random-C) BCP architecture, where the random block allows for the decoupling of thermodynamic and wetting properties. Previous reports of such BCPs have used click chemistry to create the desired random block, but all such instances possess additional functional groups that are susceptible to undesirable side reactions upon annealing, such as cross-linking and surface grafting. This study reports the substitution reaction of polystyrene-block-poly(pentafluorophenyl methacrylate) (PS-b-PPFMA) with primary amines. The resulting methacrylamide structure of the functionalized random block has only an amide linkage between the attached functional group and the polymer backbone, thereby omitting any sources of side reactions within the BCP. The outcomes of this report also demonstrate the enhanced thermal stability of these materials by virtue of their stable amide bonds. A range of random copolymer compositions is assessed to develop BCPs in which the random block has approximately the same surface energy as the PS block. These BCPs can self-assemble into perpendicular lamellae and are therefore promising candidates for directed self-assembly.

block copolymers↗

Tubulin Double Helix: Lateral and Longitudinal Curvature Changes of Tubulin Protofilament

By virtue of their native structures, tubulin dimers are protein building blocks that are naturally pre-programmed to assemble into cytoskeletal polymers known as microtubules (MTs). Here we demonstrate polycation-directed (i.e. electrostatically tunable) assembly of tubulins through tubulin protofilament conformational changes in the longitudinal and lateral directions, creating novel tubulin double helices and various tubular architectures. Synchrotron small angle X-ray scattering and transmission electron microscopy reveal a remarkable range of nanoscale assembly structures: single- and double-layered double-helix tubulin tubules. The phase transitions from MTs into the new assemblies are dependent on the size and concentration of polycations. Two characteristic scales that determine the number of observed phases are the size of polycation compared to the size of tubulin (≈4 nm) and MT diameter (≈25 nm). This work suggests the feasibility of “programmable breakdown” of protein nanotubes, tearing MTs into double-stranded tubulins and building up previously undiscovered nanostructures, by using polycations with scissor- and glue-like properties. Importantly, we define a new role of tubulins as two-dimensionally shape-controllable building blocks for novel supramolecular architectures. Furthermore, these findings provide insight into the design of protein-based functional materials, for example, as metallization templates for nanoscale electronic devices, kinesin motor-driving molecular screws, and anticancer drug delivery vehicles.

2D shape‐control↗

Chamber For Testing Polymers In Oxygen Plasma

Apparatus holds polymer specimen at constant temperature while exposing it to oxygen plasma. Copper tube (part of cooling coil) extends into plasma chamber, supporting copper block and thermoelectric module on which specimen mounted. Copper block made small - 4.4 by 3.8 by 1.6 cm - having little effect on plasma. Used to evaluate resistances of polymer materials to plasma environments, and for analysis of gases produced by attack of plasma on polymer specimen.

Whitaker, Ann F.↗

Effect of Molecular Weight and Layer Thickness on Dielectric Breakdown Strength of Neat and Homopolymer Swollen Lamellar Block Copolymer Films

Designing next-generation lightweight pulsed power devices hinges on understanding the factors influencing the energy storage performance of dielectric materials. Polymer dielectric films have a quadratic dependence of energy storage on the voltage breakdown strength and strategies to enhance the breakdown strength are expected to yield a path toward high energy storage densities. Highly stratified lamellar block copolymer (L-BCP) films of model polystyrene-b-polymethylmethacrylate (PS-b-PMMA) exhibited as much as ~50% enhancement in breakdown voltage (E BD ), (225 % increase in stored energy density, U~ E BD 2 ), compared to unordered as-cast L-BCP films. Such an energy density using amorphous polymer is on par with industry-standard semi-crystalline biaxially oriented polypropylene (BOPP), and as such a notable development in the field. This work develops a deeper understanding of the molecular mechanisms of E BD enhancement in L-BCP films, due to combination of interface formation and spatial isolation of the chain ends into segregated zones. We further confirm the role of chain ends in the breakdown process blending a low M n L-BCP with matched M n homopolymers to attain same layer spacing as neat L-BCP of higher M n . E BD shows a significant decrease at low homopolymer fractions due to increased net chain end density within swollen ordered L-BCP domains in wet-brush regime, followed by increased E BD due to layer thickness increase via segregated “interphase layer” formation by excess homopolymers. Notably, E BD of homopolymer swollen L-BCPs is always lower than neat L-BCP of the same domain spacing, due to overall adverse chain ends contribution from homopolymers. These findings provide important selection rules for L-BCPs for designing next-generation flexible electronics with high energy density solid-state BCP film capacitors.

36 MATERIALS SCIENCE↗

First Ever Polymer Flood Field Pilot to Enhance the Recovery of Heavy Oils on Alaska North Slope – Producer Responses and Operational Lessons Learned

The US Department of Energy and Hilcorp Alaska, LLC are jointly cosponsoring a field pilot project entitled “First Ever Field Pilot on Alaska’s North Slope to Validate the Use of Polymer Floods for Heavy Oil Enhanced Oil Recovery (EOR).” The objective of this pilot is to perform a field experiment to validate the use of an advanced polymer flooding technology to unlock the vast heavy oil resources on Alaska North Slope (ANS). Two pairs of horizontal injection and production wells have been deployed in an isolated fault block of the Schrader Bluff heavy oil reservoir at the Milne Point Field to conduct a polymer flood pilot which was designed to acquire field performance data to optimize polymer flood design in the Schrader Bluff heavy oil reservoirs on ANS. Hydrolyzed polyacrylamide (HPAM) polymer injection started on August 28, 2018 using a custom made polymer mixing and pumping unit. Polymer solution properties such as concentration, viscosity, and filter ratio, have been closely monitored and adjusted as necessary. Operational procedures have been improved to ensure adequate injectivity and polymer propagation through the formation. Oil and water production is tested frequently to monitor water cut performance, and produced water is sampled and analyzed for polymer content. Tracers were pumped pre and post polymer injection startup to compare polymer flood breakthrough timing and sweep efficiency. Polymer injectivity of the horizontal wells drilled in the Schrader Bluff NB sand is found to be sufficient to replace the reservoir production voidage although there were some declines as high viscosity polymer swept the near wellbore region. Production data show significant reduction in water cut and the oil production rate has stabilized. No polymer production has been confirmed from the two horizontal producers after 22 months of polymer injection into the two supporting horizontal injectors. Tracer data show very low sweep efficiencies with waterflood alone, whereas significant improvement has been achieved with polymer flood. Many operational lessons have been learned and improvements have been made regarding polymer mixing, pumping, and onsite quality control, particularly in a challenging Arctic environment. Adequate polymer injection rate can be achieved with diligent monitoring and quality assurance of the properties of the injected polymer solution.

Ning, Samson↗

Polymers derived from 2,2′-bisimidazoles

Disclosed are compositions derived from 2,2′bisimidazoles building blocks and methods of making the same. The disclosed compositions are capable of withstanding temperatures up to 600° C. and substantially flame resistant.

Bara, Jason E.↗

Characterization of the Heat Extraction Capability of a Compliant, Sliding, Thermal Interface for Use in a High Temperature, Vacuum Microgravity Furnace

Much of the material science gained in microgravity research requires processing a sample in a high performance furnace. One such furnace currently being designed is the Quench Module Insert (QMI). The Principle Investigators, for whom the furnace is proposed, require high temperature gradients in their cylindrical samples to achieve the science objectives. One of the components critical to achieving high sample axial temperature gradients in the Quench Module Insert is a high performance cold zone to extract the heat from the sample. This cold zone employs a compliant, sliding thermal interface based on a Vel-Therm felt. This felt provides a conductive path between the Sample Cartridge Assembly (SCA) exterior surface and the interior surface of the water cooled chill block while allowing movement of the sample relative to the chill block. The Vel-Therm felt is composed of long polymer-based fibers affixed to a thin flexible substrate layer. The fibers are oriented perpendicular to this substrate giving the felt the appearance of a velvet fabric. The Vel-Therm felt heat extraction capability was quantified in earlier tests performed in an inert gas environment. The current activity, described in this paper, is intended to characterize the extraction capability of Vel-Therm felt in a vacuum environment similar to the QMI environment. This testing is necessary to quantify the thermal performance of the Vel-Therm felt and the sensitivity of that performance to key variables. The data derived from these tests will be incorporated into the current thermal models to improve the quality of the models and reduce uncertainty of the analytical results. In addition, the data will be used to help select the appropriate Vel-Therm felt and set proper operating limits as well as assess the performance range of the furnace. The objective of this test is to measure the heat extraction rate of the Vel-Therm felt as specified by the effective heat transfer coefficient. Therefore, the test setup was designed to force the bulk of the heat transfer through the area where the Vel-Therm felt was applied. A heat source, consisting of a ceramic heating element encased in a Copper (Cu) housing is mounted on four isolated support rods. A 6-layer molybdenum radiation shield is used to insulate against heat loss from the heater and prevent heat exchange between the hot and cold sides of the test apparatus. The Vel-Therm felt is affixed to the surface of the cold sink, a water-cooled Cu chill block. An adjustable plate supports and isolates the cold sink from above and is used to control the amount of the deflection of the Vel- Therm when in contact with the Cu heating element housing. The primary means of establishing the power being conducted through the felt is to measure the energy being transferred to the water passing through the chill block. Analysis was performed to support the assumption that the source and sink surfaces were approximately isothermal under the specific test conditions. As a check on the amount of power passing through the felt, the power supplied to the heater was also measured. Thermocouples were strategically located throughout the test apparatus for measurement purposes. A bell jar was lowered over the assembly to impose vacuum conditions. Currently, variables tested have been fiber compression and fiber type and surface temperatures (both the hot and cold side temperatures are hypothesized to be important to the performance of the Vel-Therm.) Selected runs were repeated to ensure consistency and repeatability. Results obtained thus far reveal that Vel-Therm performance is significantly degraded by fibers being exposed to high compression. It also shows that performance is somewhat negatively impacted by previous compression, thereby, raising the question of repeatability. In addition, early results show a significant dependence on temperature. A computer aided mathematical analysis of the test setup is ongoing. The results will be correlated to actual results. The correlation will examine such details as parasitic loses, conduction down the power leads and many other concerns.

Bellomy-Ezell, Jenny↗

Revealing the working mechanism of a multi-functional block copolymer binder for lithium-sulfur batteries

The lithium-sulfur (Li-S) battery is one of the most promising substitutes for current energy storage systems because of its low cost, high theoretical capacity, and high energy density. However, the high solubility of intermediate products (i.e., lithium polysulfides) and the resultant shuttle effect lead to rapidly fading capacity and a low coulombic efficiency, which hinder the practical application of Li-S batteries. In this study, block copolymers are constructed with both an ethylene oxide unit and a styrene unit and then used as binders for Li-S batteries. Electrochemical performance improvements are attributed to the synergistic effects contributed by the different units of the block copolymer. Here, the ethylene oxide unit traps polysulfide, which bonds strongly with the intermediate lithium polysulfide, and enhances the transport of lithium ions to reach high capacity. Meanwhile, the styrene unit maintains cathode integrity by improving the mechanical properties and elasticity of the constructed block copolymer to accommodate the large volume changes. By enabling multiple functions via different units in the polymer chain, high sulfur utilization is achieved, polysulfide diffusion is confined, and the shuttle effect is suppressed during the cycle life of Li-S batteries, as revealed by operando ultraviolet–visible spectroscopy and S K-edge X-ray absorption spectroscopy.

25 ENERGY STORAGE↗

Development of polyphenylquinoxaline graphite composites

The potential of polyphenylquinoxaline (PPQ)/graphite composites to serve as structural material at 316 C (600 F)has been demonstrated using a block copolymer, BlCo(13), PPQ derivative. Initially, thirteen polyphenylquinoxalines were evaluated. From this work, four candidate polymers were selected for preliminary evaluation as matrices for HMS graphite fiber reinforced composites. The preliminary composite evaluation enabled selection of one of the four polymers for advanced composite preparation and testing. Using an experimentally established cure schedule for each of the four polymers, preliminary laminates of 50% resin volume content, prepared without postcure, were tested for flexure strength and modulus, interlaminar shear strength (short beam), and tensile strength and modulus at ambient temperature. A block copolymer (Bl Co 13) derived from one mole p-bis (phenylglyoxalyl) benzene, one fourth mole 3,3'-diaminobenzidine and three-fourths mole 3,3', 4,4'-tetraminobenzophenone was selected for extensive study. Tensile, flexural, and interlaminar shear values were obtained after aging and testing postcured BlCo(13) laminates at 316 C (600 F). The potential of PPQ/graphite laminates to serve as short term structural materials at temperatures up to 371 C (700 F) was demonstrated through weight loss experiments.

Hoggatt, J. T.↗

Polymer Crosslinked 3-D Assemblies of Nanoparticles: Mechanically Strong Lightweight Porous Materials

In analogy to supramolecular assemblies, which are pursued because of properties above and beyond those of the individual molecules, self-standing monolithic three-dimensional assemblies of nanoparticles also have unique properties attributed to their structure. For example, ultra low-density 3-D assemblies of silica nanoparticles, known as silica aerogels, are characterized by large internal void space, high surface area and very low thermal conductivity. Aerogels, however, are also extremely fragile materials, limiting their application to a few specialized environments, e.g., in nuclear reactors as Cerenkov radiation detectors, in space (refer to NASA's Stardust Program) and aboard certain planetary vehicles (thermal insulators on Mars Rovers in 1997 and 2004). The fragility problem is traced to well-defined weak points in the aerogel skeletal framework, the interparticle necks. Using the surface functionality of the nanoparticle building blocks as a focal point, we have directed attachment of a conformal polymer coating over the entire framework, rendering all necks wider. Thus, although the bulk density may increase only by 3x, the mesoporosity (pores in the range 2-50 nm) remains unchanged, while the strength of the material increases by up to 300... Having addressed the fragility problem, aerogels are now robust materials, and a variety of applications, ranging from thermal/acoustic insulators to catalyst supports, to platform for sensors, and dielectrics are all within reach. Our approach employs molecular science to manipulate nanoscopic matter for achieving useful macroscopic properties, and in our view it resides at the core of what defines nanotechnology. In that spirit, this technology is expandable in three directions. Thus, we have already crosslinked successfully amine-modified silica, and we anticipate that more rich chemistry will be realized by been creative with the nanoparticle surface modifiers. On the other hand, although we do not expect orders-of-magnitude increase in strength, nevertheless, by varying the polymer we expect to impart other properties such as hydrophobicity, thermal stability and perhaps electrical conductivity. Besides polymers, crosslinkers will include metals and ceramics (e.g., through POSS precursors). Finally, network morphology directs load dissipation, and of approximately 30 different crosslinked oxide aerogels, vanadia, whose structure is fibrous rather than particulate, yields a much stronger (by 4..) material than silica of the same density. It seems imperative to implement control of network morphology, even through templating.

Leventis, Nicholas↗

18.6% Efficiency All-Polymer Solar Cells Enabled by a Wide Bandgap Polymer Donor Based on Benzo[1,2-d:4,5-d']bisthiazole

The limited selection of wide bandgap polymer donors for all-polymer solar cells (all-PSCs) is a bottleneck problem restricting their further development and remains poorly studied. In this work, a new wide bandgap polymer, namely PBBTz-Cl, is designed and synthesized by bridging the benzobisthiazole acceptor block and chlorinated benzodithiophene donor block with thiophene units for application as an electron donor in all-PSCs. PBBTz-Cl not only possesses wide bandgap and deep energy levels but also displays strong absorption, high-planar structure, and good crystallinity, making it a promising candidate for application as a polymer donor in organic solar cells. When paired with the narrow bandgap polymer acceptor PY-IT, a fibril-like morphology forms, which facilitates exciton dissociation and charge transport, contributing to a power conversion efficiency (PCE) of 17.15% of the corresponding all-PSCs. Moreover, when introducing another crystalline polymer acceptor BTP-2T2F into the PBBTz-Cl:PY-IT host blend, the absorption ditch in the range of 600–750 nm is filled, and the blend morphology is further optimized with the trap density reducing. As a result, the ternary blend all-PSCs achieve a significantly improved PCE of 18.60%, which is among the highest values for all-PSCs to date.

36 MATERIALS SCIENCE↗

Design and Synthesis of Novel Block Copolymers for Efficient Opto-Electronic Applications

It has been predicted that nano-phase separated block copolymer systems containing electron rich donor blocks and electron deficient acceptor blocks may facilitate the charge carrier separation and migration in organic photovoltaic devices due to improved morphology in comparison to polymer blend system. This paper presents preliminary data describing the design and synthesis of a novel Donor-Bridge-Acceptor (D-B-A) block copolymer system for potential high efficient organic optoelectronic applications. Specifically, the donor block contains an electron donating alkyloxy derivatized polyphenylenevinylene (PPV), the acceptor block contains an electron withdrawing alkyl-sulfone derivatized polyphenylenevinylene (PPV), and the bridge block contains an electronically neutral non-conjugated aliphatic hydrocarbon chain. The key synthetic strategy includes the synthesis of each individual block first, then couple the blocks together. While the donor block stabilizes and facilitates the transport of the holes, the acceptor block stabilizes and facilitates the transport of the electrons, the bridge block is designed to hinder the probability of electron-hole recombination. Thus, improved charge separation and stability are expected with this system. In addition, charge migration toward electrodes may also be facilitated due to the potential nano-phase separated and highly ordered block copolymer ultra-structure.

Sun, Sam-Shajing↗

Miktoarm Star Polymers: Synthesis and Applications

Polymers with precisely controlled structure and function are in high demand across a diverse array of applications spanning the life sciences and nanotechnology. One prototypical example is a class of branched block copolymers known as miktoarm stars (μ-stars), which contain two or more arm compositions connected at a common junction. Miktoarm stars have attracted considerable attention since their physical properties can be different from conventional linear block copolymers. This perspective highlights the latest developments and historical context in the field of miktoarm star polymers, including design strategies, synthetic techniques, and advanced characterization tools used to avoid common preparation pitfalls and tailor properties for emerging applications. Furthermore, our contemporary perspective on μ-star polymers is a resource for inspiring future research into this exciting class of materials at the intersection of chemistry, physics, and advanced technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗