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At least 325 records · Page 18

Polymers from Levoglucosenone and Other Anhydrosugars (CRADA Final Report)

The goal of this work is to identify promising drop-in or novel polymers that can be produced from levoglucosenone (LGO), CyreneTM, or other anhydrous sugars. LGO is a potentially important feedstock for polymers produced from renewable sources and can be produced in high yields by the company Circa from the pyrolysis of cellulose and biomass. NLR has a long history with anhydrosugars, pyrolysis and biomass-based polymers and has recently developed machine learning (ML) tools for predicting polymer properties. The DOE has recently supported efforts to identify coproducts from pyrolysis of biomass and their use in the production of performance advantaged polymers. DOE is also supporting the development of ML and molecular modeling for predicting and understanding polymer properties. NLR will leverage this expertise and experience to map out the pathways to polymers from LGO, use ML to identify the properties of novel polymers and estimate the market application space. From this effort NLR will deliver a summary report that outlines the most promising pathways based on quantitative and qualitative metrics for producing polymers from LGO.

09 BIOMASS FUELS↗

Synthesis of hyperbranched polymer films via electrodeposition and oxygen-tolerant surface-initiated photoinduced polymerization

Hypothesis Hyperbranched polymers, not only possess higher functionality, but are also easier to prepare compared to dendrimers and dendric polymers. Combining electrodeposition and surface-initiated photoinduced electron transfer-reversible addition-fragmentation chain transfer (SI-PET-RAFT) polymerization is hypothesized to be a novel strategy for preparing hyperbranched polymer films on conductive surfaces without degassing. Experiments In this study, polymer brush grafted films with four different architectures (i.e. linear, branched, linear- block -branched, and branched- block -linear) were prepared on gold-coated glass substrates using electrodeposition, followed by SI-PET-RAFT polymerization. The resulting film structure and thickness, surface topology, absorption property, and electrochemical behavior were confirmed by spectroscopy, microscopy, microbalance technique, and impedance measurement. Findings These hyperbranched polymer brushes were capable of forming a thicker but more uniformly covered films compared to linear polymer brush films, demonstrating that hyperbranched polymer films can be potentially useful for fabricating protective polymer coatings on various conductive surfaces.

36 MATERIALS SCIENCE↗

Carboxylating Elastomer via Thiol‐Ene Click Reaction to Improve Miscibility with Conjugated Polymers for Mechanically Robust Organic Solar Cells with Efficiency of 19%

Abstract Incorporating flexible insulating polymers is a straightforward strategy to enhance the mechanical properties of rigid conjugated polymers, enabling their use in flexible electronic devices. However, maintaining electronic characteristics simultaneously is challenging due to the poor miscibility between insulating polymers and conjugated polymers. This study introduces the carboxylation of insulating polymers as an effective strategy to enhance miscibility with conjugated polymers via surface energy modulation and hydrogen bonding. The carboxylated elastomer, synthesized via a thiol‐ene click reaction, closely matches the surface energy of the conjugated polymer. This significantly improves the mechanical properties, achieving a high crack‐onset strain of 21.48%, surpassing that (5.93%) of the unmodified elastomer:conjugated polymer blend. Upon incorporating the carboxylated elastomer into PM6:L8‐BO‐based organic solar cells, an impressive power conversion efficiency of 19.04% is attained, which top‐performs among insulating polymer‐incorporated devices and outperforms devices with unmodified elastomer or neat PM6:L8‐BO. The superior efficiency is attributed to the optimized microstructures and enhanced crystallinity for efficient and balanced charge transport, and suppressed charge recombination. Furthermore, flexible devices with 5% carboxylated elastomer exhibit superior mechanical stability, retaining ≈88.9% of the initial efficiency after 40 000 bending cycles at a 1 mm radius, surpassing ≈83.5% for devices with 5% unmodified elastomer.

Chemistry↗

Achieving High Alignment of Conjugated Polymers by Controlled Dip-Coating

Realizing high polymer chain orientation and ordered thin-film microstructures is beneficial for efficient charge transport of conjugated polymers. However, achieving a high alignment degree remains a challenge due to the sensitive nature of polymers to the processing conditions. By simply varying concentrations during a dip-coating method, the component of polymer aggregates that adopt the planar backbones is enlarged and the ensuing assembly process is promoted. Herein, highly oriented polymer thin films of an isoindigo-based conjugated polymer (PII-2T) are prepared to enhance polymer orientation resulting in a drastic booming in carrier mobilities of organic field-effect-transistors (OFETs). The maximum mobility from aligned polymer films increases by up to 8.3 cm 2 V -1 s -1 , which is tenfold beyond the value evaluated from the unaligned direction or traditional spin-coated samples. The enhanced orientation can also reduce the adverse effects of the contact resistance and facilitate charge transport in transistors. This work demonstrates that the highly aligned conjugated polymer films can be approached by the dip-coating method while offers a latent cornerstone toward understanding the critical role of processing-related parameters in determining morphology of solution-coated thin films.

36 MATERIALS SCIENCE↗

Rewritable Surface‐Grafted Polymer Brushes with Dynamic Covalent Linkages

Abstract Surface grafting of polymer brushes drastically modifies surface properties, including wettability, compatibility, responsiveness, etc. A broad variety of functionalities can be introduced to the surface via different types of polymers. Bringing together properties of two or more types of polymer brushes to one surface opens up even more possibilities in brush‐modified materials. However, while it is generally feasible to introduce several chemical compositions along the brushes via copolymerization, it is challenging to vary the types of polymer brushes along a surface. Although previous studies have demonstrated binary brushes via orthogonal polymerization techniques or partial deactivation/regrafting, they commonly limit the number of polymer types to two. Here, we propose a strategy to introduce dynamic covalent diketoenamine linkages at the root of polymer brushes. The grafting density could be precisely tuned during surface functionalization. The surface‐anchored polymer brushes were cleaved by the addition of small molecule amines. New polymer brushes can be regrafted from the surface following refunctionalization of exposed sites. The maneuverability allows tuning of the types and densities of the polymer brushes, pointing the way to the preparation of a new generation of well‐defined brush‐modified materials with mixed grafts, with potential applications in the design of smart materials and surfaces.

Cui, Feichen↗

SANS quantification of bound water in water-soluble polymers across multiple concentration regimes

Contrast-variation small-angle neutron scattering (CV-SANS) is a widely used technique for quantifying hydration water in soft matter systems, but it is predominantly applied in the dilute regime or for systems with a well-defined structure factor. Here, CV-SANS was used to quantify the number of hydration water molecules associating with three water-soluble polymers with different critical solution temperatures and types of water–solute interactions in dilute, semidilute, and concentrated solution through the exploration of novel methods of data fitting and analysis. Multiple SANS fitting workflows with varying levels of model assumptions were evaluated and compared to give insight into SANS model selection. These fitting pathways ranged from general, model-free algorithms to more standard form and structure factor fitting. In addition, Monte Carlo bootstrapping was evaluated as a method to estimate parameter uncertainty through simulation of technical replicates. The most robust fitting workflow for dilute solutions was found to be form factor fitting without CV-SANS ( i.e. polymer in 100% D 2 O). For semidilute and concentrated solutions, while the model-free approach can be mathematically defined for CV-SANS data, the addition of a structure factor imposes physical constraints on the optimization problem, suggesting that the optimal fitting pathway should include appropriate form and structure factor models. The measured hydration numbers were consistent with the number of tightly bound water molecules associated with each monomer unit, and the concentration dependence of the hydration number was largely governed by the chemistry-specific interactions between water and polymer. Polymers with weaker water–polymer interactions ( i.e. those with fewer hydration water molecules) were found to have more bound water at higher concentrations than those with stronger water–polymer interactions due to the increase in the number of forced water–polymer contacts in the concentrated system. This SANS-based method to count hydration water molecules can be applied to polymers in any concentration regime, which will lead to improved understanding of water–polymer interactions and their impact on materials design.

36 MATERIALS SCIENCE↗

Machine learning-assisted profiling of a kinked ladder polymer structure using scattering

Ladder polymers consisting of fused rings in the backbone have very limited conformational freedom, which results in very different properties from traditional linear polymers. However, accurately determining their size and chain conformations from solution scattering remains a challenge. Their chain conformations of kinked ladder polymers are largely governed by the structures and relative orientations or configurations of the repeat units, unlike conventional polymer chains whose bending angles between repeat units follow a unimodal Gaussian distribution. Meanwhile, traditional scattering models for polymer chains do not account for these unique structural features. This work introduces a novel approach that integrates machine learning with Monte Carlo simulations to construct a model that can describe the geometry of a type of kinked CANAL ladder polymers. We first develop a Monte Carlo simulation model for sampling the configuration space of CANAL ladder polymers, where each repeat unit is modeled as a biaxial segment. Then, we establish a machine learning-assisted scattering analysis framework based on Gaussian Process Regression. Finally, we conduct small-angle neutron scattering experiments on a CANAL ladder polymer solution to apply our approach. Our method uncovers structural features of such ladder polymers that conventional methods fail to capture.

Ding, Lijie [Oak Ridge National Laboratory (ORNL),↗

Small Angle X-Ray Scattering and Polymers

Polymers are some of the most versatile and useful materials on this planet. Properties of polymers are a result of their processing history, chemical makeup, and physical structure. Therefore, characterization is necessary to develop new polymer formulations and processes. Many established techniques for polymer characterization are destructive, and alternative methods that don’t destroy samples are in high demand. Thermal analysis techniques such as differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) yield important characteristic information for polymer samples while destroying the sample. Non-destructive strategies such as X ray diffraction (XRD) or small angle X-ray scattering (SAXS) can also find polymer characteristics while preserving a sample’s attributes. Sample preservation is desirable when investigating novel formulation and processing methods. SAXS analysis will be done on two different polymers: polyethylene, and a triblock copolymer. Using these two polymers allows for confidence between tests as polyethylene is very common, and well understood. Polyethylene analysis will be done first, and when methods have been refined so that the SAXS data matches accepted thermal analysis values for HDPE, there will be confidence to use the same analysis on block copolymers. Block copolymers remain relatively unexplored, so SAXS data will yield valuable information on their characteristics. Understanding the mechanical properties of these polymers is paramount to their application in upcycling, a process by which waste plastic can be converted into a higher value commodity. For this project, the upcycling process will be done via 3-dimensional (3d) printing.

36 MATERIALS SCIENCE↗

Accessibility and Mechanical Stability of Nanoporous Zinc Oxide and Aluminum Oxide Coatings Synthesized via Infiltration of Polymer Templates

The conformal nanoporous inorganic coatings with accessible pores that are stable under applied thermal and mechanical stresses represent an important class of materials used in the design of sensors, optical coatings, and biomedical systems. Here, we synthesize porous AlO x and ZnO coatings by the sequential infiltration synthesis (SIS) of two types of polymers that enable the design of porous conformal coatings—polymers of intrinsic microporosity (PIM) and block co-polymer (BCP) templates. Using quartz crystal microbalance (QCM), we show that alumina precursors infiltrate both polymer templates four times more efficiently than zinc oxide precursors. Using the quartz crystal microbalance (QCM) technique, we provide a comprehensive study on the room temperature accessibility to water and ethanol of pores in block copolymers (BCPs) and porous polymer templates using polystyrene-block-poly-4-vinyl pyridine (PS75-b-P4VP25) and polymers of intrinsic microporosity (PIM-1), polymer templates modified by swelling, and porous inorganic coatings such as AlO x and ZnO synthesized by SIS using such templates. Importantly, we demonstrate that no structural damage occurs in inorganic nanoporous AlO x and ZnO coatings synthesized via infiltration of the polymer templates during the water freezing/melting cycling tests, suggesting excellent mechanical stability of the coatings, even though the hardness of the inorganic nanoporous coating is affected by the polymer and precursor selections. We show that the hardness of the coatings is further improved by their annealing at 900 °C for 1 h, though for all the cases except ZnO obtained using the BCP template, this annealing has a negligible effect on the porosity of the material, as is confirmed by the consistency in the optical characteristics. These findings unravel new potential for the materials being used across various environment and temperature conditions.

36 MATERIALS SCIENCE↗

Process for crosslinking methylene-containing aromatic polymers with ionizing radiation

A process for crosslinking aromatic polymers containing radiation-sensitive methylene groups (-CH2-) by exposing the polymers to ionizing radiation thereby causing crosslinking of the polymers through the methylene groups is described. Crosslinked polymers are resistant to most organic solvents such as acetone, alcohols, hydrocarbons, methylene, chloride, chloroform, and other halogenated hydrocarbons, to common fuels and to hydraulic fluids in contrast to readily soluble uncrosslinked polymers. In addition, the degree of crosslinking of the polymers depends upon the percentage of the connecting groups which are methylene which ranges from 5 to 50 pct and preferably from 25 to 50 pct of the connecting groups, and is also controlled by the level of irradiation which ranges from 25 to 1000 Mrads and preferably from 25 to 250 Mrads. The temperature of the reaction conditions ranges from 25 to 200 C and preferably at or slightly above the glass transition temperature of the polymer. The crosslinked polymers are generally more resistant to degradation at elevated temperatures such as greater than 150 C, have a reduced tendency to creep under load, and show no significant embrittlement of parts fabricated from the polymers.

Bell, Vernon L.↗

Effect of Polymer Electrode Morphology on Performance of a Lithium/Polypyrrole Battery

A variety of conducting polymer batteries were described in the recent literature. In this work, a Li/Polypyrrole secondary battery is described. The effect of controlling the morphology of the polymer on enhancement of counterion diffusion in the polymer phase is explored. A method of preparing conducting polymers was developed which yields high surface area per unit volume of electrode material. A porous membrane is used as a template in which to electrochemically polymerize pyrrole, then the membrane is dissolved, leaving the polymer in a fibrillar form. Conventionally, the polymer is electrochemically polymerized as a dense polymer film on a smooth Pt disk electrode. Previous work has shown that when the polymer is electrochemically polymerized in fribrillar form, charge transport rates are faster and charge capacities are greater than for dense, conventionally grown films containing the same amount of polymer. The purpose is to expand previous work by further investigating the possibilities of the optimization of transport rates in polypyrrole films by controlling the morphology of the films. The utility of fibrillar polypyrrole as a cathode material in a lithium/polymer secondary battery is then assessed. The performance of the fibrillar battery is compared to the performance of an analogous battery which employed a conventionally grown polypyrrole film. The study includes a comparison of cyclic voltammetry, shape of charge/discharge curves, discharge time and voltage, cycle life, coulombic efficiencies, charge capacities, energy densities, and energy efficiencies.

Nicholson, Marjorie Anne↗

JTEC monograph on biodegradable polymers and plastics in Japan: Research, development, and applications

A fact-finding team of American scientists and engineers visited Japan to assess the status of research and development and applications in biodegradable polymers. The visit was sponsored by the National Science Foundation and industry. In Japan, the team met with representatives of 31 universities, government ministries and institutes, companies, and associations. Japan's national program on biodegradable polymers and plastics evaluates new technologies, testing methods, and potential markets for biodegradables. The program is coordinated by the Biodegradable Plastics Society of Japan, which seeks to achieve world leadership in biodegradable polymer technology and identify commercial opportunities for exploiting this technology. The team saw no major new technology breakthroughs. Japanese scientists and engineers are focusing on natural polymers from renewable resources, synthetic polymers, and bacterially-produced polymers such as polyhydroxyalkanoates, poly(amino acids), and polysaccharides. The major polymers receiving attention are the Zeneca PHBV copolymers, Biopol(registered trademark), poly(lactic acid) from several sources, polycaprolactone, and the new synthetic polyester, Bionolle(registered trademark), from Showa High Polymer. In their present state of development, these polymers all have major deficiencies that inhibit their acceptance for large-scale applications.

Lenz, Robert W.↗

A Sensitive Technique Using Atomic Force Microscopy to Measure the Low Earth Orbit Atomic Oxygen Erosion of Polymers

Polymers such as polyimide Kapton and Teflon FEP (fluorinated ethylene propylene) are commonly used spacecraft materials due to their desirable properties such as flexibility, low density, and in the case of FEP low solar absorptance and high thermal emittance. Polymers on the exterior of spacecraft in the low Earth orbit (LEO) environment are exposed to energetic atomic oxygen. Atomic oxygen erosion of polymers occurs in LEO and is a threat to spacecraft durability. It is therefore important to understand the atomic oxygen erosion yield (E, the volume loss per incident oxygen atom) of polymers being considered in spacecraft design. Because long-term space exposure data is rare and very costly, short-term exposures such as on the shuttle are often relied upon for atomic oxygen erosion determination. The most common technique for determining E is through mass loss measurements. For limited duration exposure experiments, such as shuttle experiments, the atomic oxygen fluence is often so small that mass loss measurements can not produce acceptable uncertainties. Therefore, a recession measurement technique has been developed using selective protection of polymer samples, combined with postflight atomic force microscopy (AFM) analysis, to obtain accurate erosion yields of polymers exposed to low atomic oxygen fluences. This paper discusses the procedures used for this recession depth technique along with relevant characterization issues. In particular, a polymer is salt-sprayed prior to flight, then the salt is washed off postflight and AFM is used to determine the erosion depth from the protected plateau. A small sample was salt-sprayed for AFM erosion depth analysis and flown as part of the Limited Duration Candidate Exposure (LDCE-4,-5) shuttle flight experiment on STS-51. This sample was used to study issues such as use of contact versus non-contact mode imaging for determining recession depth measurements. Error analyses were conducted and the percent probable error in the erosion yield when obtained by the mass loss and recession depth techniques has been compared. The recession depth technique is planned to be used to determine the erosion yield of 42 different polymers in the shuttle flight experiment PEACE (Polymer Erosion And Contamination Experiment) planned to fly in 2002 or 2003.

deGroh, Kim K.↗

Photo-Curing: UV Radiation curing of polymers

The Polymers Branch of the Materials Division is dedicated to the development of high-performance for a variety of applications. Areas of significant interest include high- temperature polymers, low density, and high strength insulating materials, conductive polymers, and high density polymer electrolytes. This summer our group is working diligently on a photo-curing project. There is interest in the medical community feel the need for a new and improved balloon that will be used for angioplasty (a form of heart surgery). This product should maintain flexibility but add many other properties. Like possibly further processability and resistance to infection. Our group intends on coming up with this product by using photo-enolization (or simply, photo-curing) by Diels-Alder trapping. The main objective was to synthesize a series of new polymers by Diels-Alder cycloaddition of photoenols with more elastomeric properties. Our group was responsible for performing the proper photo-curing techniques of the polymers with diacrylates and bismaleimides, synthesizing novel monomers, and evaluating experimental results. We attempted to use a diacrylate to synthesize the polymer because of previous research done within the Polymers Branch here at NASA. Most acrylates are commercially available, have more elastometric properties than a typical rigid aromatic structure has and they contain ethylene oxides in the middle of their structure that create extensive flexibility. The problem we encountered with the acrylates is that they photo chemically and thermally self polymerize and create diradicals at low temperatures; these constraints caused a lot of unnecessary side reactions. We want to promote solely, diketone polymerization because this type of polymerization has the ability to cause very elastic polymers. We chose to direct our attention towards the usage of maleimides because they are known for eliminating these unnecessary side reactions.

Inman, Christina A.↗

MISSE PEACE Polymers: An International Space Station Environmental Exposure Experiment Being Conducted

As part of the Materials International Space Station Experiment (MISSE), 41 different polymers are being exposed for approximately 1 1/2 years to the low-Earth-orbit (LEO) environment on the exterior of the International Space Station. MISSE is a materials flight experiment sponsored by the Air Force Research Lab/Materials Lab and NASA, and is the first external experiment on the space station. A similar set of 41 polymers will be flown as part of the Polymer Erosion and Contamination Experiment (PEACE) a shuttle flight experiment that is being developed at the NASA Glenn Research Center collaboratively with the Hathaway Brown School for girls. Therefore, these 41 polymers are collectively called the MISSE PEACE Polymers. The purpose of the MISSE PEACE Polymers experiment is to determine how durable polymers are in the LEO space environment where spacecraft, such as the space station, orbit. Polymers are commonly used as spacecraft materials because of their desirable properties such as good flexibility, low density, and certain electrical properties or optical properties (such as a low solar absorptance and high thermal emittance). Two examples of the use of polymers on the exterior of spacecraft exposed to the space environment include metalized Teflon FEP (fluorinated ethylene propylene, DuPont) thermal control materials on the Hubble Space Telescope, and polyimide Kapton (DuPont) solar array blankets.

deGroh, Kim K.↗

Understanding Thermal Transport in Polymer –Silver Nanowire Composites

Understanding thermal transport across filler-polymer interfaces and filler-filler contacts within polymer composites is of great importance for better thermal design of the composites that are widely used in high-performance heat exchangers, energy storage devices, and flexible electronics. Over the past several decades, considerable progress has been made in improving the thermal conductivity of polymer composites, but several key questions concerning the influence of interfacial thermal resistance, or Kapitza resistance, still remain. Firstly, the thermal properties of these composites are highly dependent on thermal transport through the filler network and its contacts. For metallic nanofillers, the thermal conductivity is often estimated using the Wiedemann-Franz law based on electrical conductivity; however, it remains a question whether the Wiedemann-Franz law still holds at nanoscale contacts. Through investigation of silver nanowires of varying sizes, we were able to demonstrate that the Lorenz number for silver nanowire increases with decreasing nanowire diameter. Examination of the corresponding electrical and thermal conductivities indicate that these changes are due to that the relative contribution of phonons becomes more significant as a result of elastic stiffening. Furthermore, we show that for silver nanowires, the contact thermal resistance is ~8 times lower than that of multi-walled carbon nanotube (MWCNT) of similar diameters. Additionally, through systematic studies of electrospun polymer-silver nanowire composite nanofibers, we investigated the impact of interface morphology on the thermal conductivity enhancement of the composite system and probed the value of the Kapitza resistance for individual polymer-filler interfaces. For polymer nanofibers containing continuous, single silver nanowires, the thermal conductivity increases linearly with increasing volume fraction of silver, which is consistent with the prediction of percolation theory for samples above the percolation limit. By comparing this linear trend to the measured thermal conductivities of composite nanofibers with more complex structures, we were able to determine the resistance associated with any additional polymer-filler boundaries. In doing so we find that the thermal boundary resistance for polyvinylpyrrolidone (PVP)–silver interfaces is significantly lower than that of comparable polymer-MWCNT composite systems.Together our studies provide new insights into thermal transport in polymer nanocomposites and should help facilitate the design of high performance polymeric thermal interface material.

Thermal transport↗

Understanding Thermal Transport in Polymer - Silver Nanowire Composites

Understanding thermal transport across filler-polymer interfaces and filler-filler contacts within polymer composites is of great importance for better thermal design of the composites that are widely used in high-performance heat exchangers, energy storage devices, and flexible electronics. Over the past several decades, considerable progress has been made in improving the thermal conductivity of polymer composites, but several key questions concerning the influence of interfacial thermal resistance, or Kapitza resistance, still remain. Firstly, the thermal properties of these composites are highly dependent on thermal transport through the filler network and its contacts. For metallic nanofillers, the thermal conductivity is often estimated using the Wiedemann-Franz law based on electrical conductivity; however, it remains a question whether the Wiedemann-Franz law still holds at nanoscale contacts. Through investigation of silver nanowires of varying sizes, we were able to demonstrate that the Lorenz number for silver nanowire increases with decreasing nanowire diameter. Examination of the corresponding electrical and thermal conductivities indicate that these changes are due to that the relative contribution of phonons becomes more significant as a result of elastic stiffening. Furthermore, we show that for silver nanowires, the contact thermal resistance is ~8 times lower than that of multi-walled carbon nanotube (MWCNT) of similar diameters. Additionally, through systematic studies of electrospun polymer-silver nanowire composite nanofibers, we investigated the impact of interface morphology on the thermal conductivity enhancement of the composite system and probed the value of the Kapitza resistance for individual polymer-filler interfaces. For polymer nanofibers containing continuous, single silver nanowires, the thermal conductivity increases linearly with increasing volume fraction of silver, which is consistent with the prediction of percolation theory for samples above the percolation limit. By comparing this linear trend to the measured thermal conductivities of composite nanofibers with more complex structures, we were able to determine the resistance associated with any additional polymer-filler boundaries. In doing so we find that the thermal boundary resistance for polyvinylpyrrolidone (PVP)–silver interfaces is significantly lower than that of comparable polymer-MWCNT composite systems. Together our studies provide new insights into thermal transport in polymer nanocomposites and should help facilitate the design of high performance polymeric thermal interface material.

Matthew L. Fitzgerald↗

Thermally-rearranged polymer blends for gas separation membranes

Polymer blends comprising an ortho-functionalized polyimide homo or copolymer and a polybenzimidazole homo or copolymer, wherein the ortho-functionalized polyimide thermally rearranges to a polymer comprising a phenylene heterocyclic group, such as, polybenzoxazole, polybenzothiazole, polybenzimidazole and/or other heterocyclic structure upon heating. Also disclosed are method of forming a polymer blend comprising dissolving an ortho-functionalized polyimide homo or copolymer and a polybenzimidazole homo or copolymer in a solvent, and optional compatibilizer, to form a polymer solution; contacting a support with the polymer solution; and evaporating the solvent to provide a thin layer comprising the polymer blend on the support. Further, methods of heat treating these polymer blends to thermally rearrange the disclosed polyimides are disclosed, as are the polymer blends prepared thereby. Methods of using these polymer blends to separate gases are also disclosed.

Freeman, Benny D.↗