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At least 145 records · Page 8

Process for preparing composite articles from composite fiber blends

A composite article is prepared by forming a continuous tow of continuous carbon fibers, forming a continuous tow of thermoplastic polymer fibers, uniformly and continuously spreading the thermoplastic polymer fibers to a selected width, uniformly and continuously spreading the carbon fiber tow to a width that is essentially the same as the selected width for the thermoplastic polymer fiber tow, intermixing the tows intimately, uniformly and continuously, in a relatively tension-free state, continuously withdrawing the intermixed tow and applying the tow to a mold and heating the tow.

McMahon, Paul E.↗

Thermal Conductivity of Polyimide/Carbon Nanofiller Blends

Ultem(TM) was mixed with three different carbon-based nanofillers in efforts to increase the thermal conductivity of the polymer. After initial mixing, the nanocomposites were extruded or processed via the Laboratory Mixing Molder (LMM) process. High resolution scanning electron microscopy (HRSEM) revealed significant alignment of the nanofillers in the extruded samples. Thermal conductivity measurements were made both in the direction and perpendicular to the direction of alignment of nanofillers as well as for unaligned samples. It was found that the largest improvement in thermal conductivity was achieved in the case of aligned samples when the measurement was performed in the direction of alignment. Unaligned samples also showed a significant improvement in thermal conductivity and may be useful in applications when it is not possible to align the nanofiller. However the improvements in thermal conductivity did not approach those expected based on a rule of mixtures. This is likely due to poor phonon transfer through the matrix.

Delozier, D. M.↗

Modified Phenylethynyl Containing Imides for Secondary Bonding: Non-Autoclave, Low Temperature Processable Adhesives

As part of a program to develop structural adhesives for high performance aerospace applications, research continued on the development of modified phenylethynyl containing imides, LaRC(trademark)MPEIs. In previous reports, the polymer properties were controlled by varying the molecular weight, the amount of branching, and the phenylethynyl content and by blending with low molecular weight materials. This research involves changing the flexibility in the copolyimide backbone of the branched, phenylethynyl terminated adhesives. These adhesives exhibit excellent processability at pressures as low as 15 psi and temperatures as low as 288 C. The Ti/Ti lap shear specimens are processable in an autoclave or a temperature programmable oven under a vacuum bag at 288-300 C without external pressure. The cured polymers exhibit high mechanical properties and excellent solvent resistance. The chemistry and properties of these adhesives are presented.

Dezern, James F.↗

Assembling Vertical Block Copolymer Nanopores via Solvent Vapor Annealing on Homopolymer-Functionalized Substrates

Utilizing the self-assembly of block copolymers with large Flory–Huggins interaction parameters (χ) for nanofabrication is a formidable challenge due to the attendant large surface energy differences between the blocks. This work reports a robust protocol for the fabrication of thin films with highly ordered cylindrical nanopore arrays via the self-assembly of an asymmetric poly(styrene-block-4-vinylpyridine) (PS-b-P4VP) diblock copolymer blended with a P4VP homopolymer. The desired vertical domain orientation is achieved at the air–polymer interface by controlled solvent vapor annealing (SVA) using acetone, a solvent with weak selectivity for PS over P4VP, and at the substrate interface by functionalization using a hydroxy-terminated poly(2-vinylpyridine) (P2VP-OH) homopolymer brush. In contrast, the vertical cylinder orientation is unstable during acetone SVA on substrates functionalized using hydroxy-terminated poly(methyl methacrylate) (PMMA-OH). Although PMMA exhibits more balanced interfacial energies between PS and P4VP than P2VP in the dry state, it is also swollen more selectively by acetone. We hypothesize that the nearly balanced solvent swelling of the three polymers (P2VP, P4VP, and PS) stabilizes the vertical cylinder orientation, while unbalanced swelling (PMMA > P4VP and PS) does not. Here we further characterize pore formation by addition of a P4VP homopolymer and its postassembly extraction using ethanol, revealing a narrow window of pore size tunability. Notably, minimal differences in nanopore morphologies are observed for P4VP volume fractions as high as 0.1, regardless of the P4VP molar mass. However, further increasing the P4VP volume fraction results in domain reorientation or macrophase separation when its molar mass is less than or greater than the P4VP block molar mass, respectively. Using a P4VP homopolymer that is nearly equal in length to the P4VP block enables the fabrication of well-ordered arrays of vertical, through-film nanopores with high aspect ratios (>10), small periods (<23 nm), and diameters less than 10 nm.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Some observations in high pressure rheology of lubricants

Experimental data are presented on viscosity, elastic shear modulus, and limiting shear stress of 12 liquid lubricants. It is shown that transition histories do affect the limiting shear stress of the materials in the form of isothermal compression resulting in a lower density and lower limiting stress than isobaric cooling. The measured limiting shear stress agrees with EHD traction data at slide-to-roll ratios of 0.1 or more. In pressure viscosity measurements of the polymer solutions, it is found that for some temperatures, the pressure viscosity coefficient of the blend is slightly less than that of the base, which results in the crossing of the viscosity-pressure isotherms at high pressures.

Bair, S.↗

Antimisting kerosene: Base fuel effects, blending and quality control techniques

The problems associated with blending of the AMK additive with Jet A, and the base fuel effects on AMK properties are addressed. The results from the evaluation of some of the quality control techniques for AMK are presented. The principal conclusions of this investigation are: significant compositional differences for base fuel (Jet A) within the ASTM specification DI655; higher aromatic content of the base fuel was found to be beneficial for the polymer dissolution at ambient (20 C) temperature; using static mixer technology, the antimisting additive (FM-9) is in-line blended with Jet A, producing AMK which has adequate fire-protection properties 15 to 20 minutes after blending; degradability of freshly blended and equilibrated AMK indicated that maximum degradability is reached after adequate fire protection is obtained; the results of AMK degradability as measured by filter ratio, confirmed previous RAE data that power requirements to decade freshly blended AMK are significantly higher than equilibrated AMK; blending of the additive by using FM-9 concentrate in Jet A produces equilibrated AMK almost instantly; nephelometry offers a simple continuous monitoring capability and is used as a real time quality control device for AMK; and trajectory (jet thurst) and pressure drop tests are useful laboratory techniques for evaluating AMK quality.

Yavrouian, A. H.↗

Vapor-Phase Heteroatom Incorporation into Semiconductive Molecular-Scale Magic-Size Clusters

Magic-size metal chalcogenide clusters of molecular size exhibit well-defined structure and unique properties that might be further expanded with the incorporation or substitution of a second metal. Here, we report the postmodification of magic-size clusters synthesized in polymer thin films via exposure to volatile metal organic precursors commonly utilized for atomic layer deposition. Exposure of In 6 S 6 (CH 3 ) 6 clusters to dimethylcadmium results in exposure-dependent incorporation of Cd 2+ , which extends the optical absorbance of the clusters into the visible spectrum. The mechanism for Cd 2+ incorporation is consistent with Cd 2+ replacement of In 3+ that includes methyl ligand removal to maintain charge neutrality. Even for clusters embedded in a polymer matrix, ligand loss leads to sintering and transformation into larger nanoscale aggregates with zinc blende-type structure. The extent of Cd incorporation can be modulated by varying the process temperature and volatile metal organic exposure as well as the choice of volatile metal organic precursor. A computational thermodynamic analysis of heteroatom incorporation for several metals and chemistries reveals that both the stability of the substituted cluster and the favorability of reaction byproducts jointly determine the favorability of cation incorporation.

atomic layer deposition↗

Safer Electrolytes for Lithium-Ion Cells

A number of nonvolatile, low-flammability liquid oligomers and polymers based on aliphatic organic carbonate molecular structures have been found to be suitable to be blended with ethylene carbonate to make electrolytes for lithium-ion electrochemical cells. Heretofore, such electrolytes have often been made by blending ethylene carbonate with volatile, flammable organic carbonates. The present nonvolatile electrolytes have been found to have adequate conductivity (about 2 mS/cm) for lithium ions and to remain liquid at temperatures down to -5 C. At normal charge and discharge rates, lithiumion cells containing these nonvolatile electrolytes but otherwise of standard design have been found to operate at current and energy densities comparable to those of cells now in common use. They do not perform well at high charge and discharge rates -- an effect probably attributable to electrolyte viscosity. Cells containing the nonvolatile electrolytes have also been found to be, variously, nonflammable or at least self-extinguishing. Hence, there appears to be a basis for the development of safer high-performance lithium-ion cells.

Kejha, Joe↗

HyBlend Collaborative Research Partnership (CRADA Final Report)

This agreement assembles a multi-lab, multi-industry team to address high-priority research topics related to the blending of hydrogen (H2) into the U.S. natural gas (NG) pipeline network. There are four main research objectives: 1. Compatibility of metals (SNL) – Develop general principles for operation of HyBlend™ delivery systems in the context of structural integrity and assess the role of gas impurities on degradation of metal pipelines. 2. Compatibility of polymers (PNNL) – Assess gas impurities in HyBlend for polymer pipeline degradation and lifetime predictions. 3. Life cycle analysis (LCA) (ANL) – Analyze the life cycle of technology pathways for hydrogen and NG blends, as well as alternative pathways. 4.Techno-economic analysis (TEA) (NREL) – Quantify the costs and opportunities for hydrogen production and blending with the NG network, as well as alternative pathways.

08 HYDROGEN↗

Electroconductive PET/SWNT Films by Solution Casting

The market for electrically conductive polymers is rapidly growing, and an emerging pathway for attaining these materials is via polymer-carbon nanotube (CNT) nanocomposites, because of the superior properties of CNTs. Due to their excellent electrical properties and anisotropic magnetic susceptibility, we expect CNTs could be easily aligned to maximize their effectiveness in imparting electrical conductivity to the polymer matrix. Single-walled carbon nanotubes (SWNT) were dispersed in a polyethylene terephthalate (PET) matrix by solution blending then cast onto a glass substrate to create thin, flexible films. Various SWNT loading concentrations were implemented (0.5, 1.0, and 3.0 wt.%) to study the effect of additive density. The processing method was repeated to produce films in the presence of magnetic fields (3 and 9.4 Tesla). The SWNTs showed a high susceptibility to the magnetic field and were effectively aligned in the PET matrix. The alignment was characterized with Raman spectroscopy. Impedance spectroscopy was utilized to study the electrical behavior of the films. Concentration and dispersion seemed to play very important roles in improving electrical conductivity, while alignment played a secondary and less significant role. The most interesting result proved to be the effect of a magnetic field during processing. It appears that a magnetic field may improve dispersion of unmodified SWNTs, which seems to be more important than alignment. It was concluded that SWNTs offer a good option as conductive, nucleating filler for electroconductive polymer applications, and the utilization of a magnetic field may prove to be a novel method for CNT dispersion that could lead to improved nanocomposite materials.

Steinert, Brian W.↗

Synthesis and Properties of Poly(vinyl chloride)- b -polyethylene Multiblock Copolymers through the Hydrodechlorination of PVC with Silylium Ions

Polymer compatibilizers stabilize the interface between two immiscible polymers to allow for a material that improves properties for additional use. Chlorinated polyethylene (CPE) is a common compatibilizer, yet there does not exist a synthetic pathway either from monomers or via the functionalization of polyethylene (PE) to yield a polymer that has a controlled chlorine amount and primary structure along the polymer chain. Herein, we report a series of novel block copolymers of poly(vinyl chloride) (PVC) and PE, synthesized through selective hydrodechlorination of PVC. Contrary to CPE, the full range of chlorination can be obtained and the block number can be altered. Interfacial adhesion studies reveal samples with competitive compatibilization of PVC/polyolefin elastomer blends (POE). In conclusion, this method shows that post-polymerization modification can be a strategic top-down synthesis to achieve high performance polymers.

Wood, Zachary A. [Univ. of Southern California, Lo↗

Simulated space environmental effects on some experimental high performance polymers

Organic polymeric materials are currently being considered for long term use (more than 10 years) in structural (adhesives and composite matrices) and functional (films and coatings) applications on spacecraft. Although organic polymers have been utilized successfully in short term missions, the long term durability of these materials in space is of concern. As part of a NASA effort on high performance polymers for potential space applications, various experimental polymeric materials recently synthesized at NASA Langley Research Center were evaluated under simulated space environmental conditions. Experimental resins from blends of acetylene terminated materials, poly(arylene ether)s and low color polyimides were exposed to high energy electron and ultraviolet radiation in an attempt to simulate space environmental effects. Thin films, neat resin moldings and carbon fiber reinforced composites were exposed and the effect on certain polymer properties were determined. This paper reviews recent research involving the effects of various radiation exposures on the physical, optical and mechanical properties of several experimental polymer systems.

Connell, John W.↗

Closed‐Loop Recycling of Mixed Plastics of Polyester and CO 2 ‐Based Polycarbonate to a Single Monomer

Abstract Physical blending is an effective strategy for tailoring polymeric materials to specific application requirements. However, physically blended mixed plastics waste adds additional barriers in mechanical or chemical recycling. This difficulty arises from the intricate requirement for meticulous sorting and separation of the various polymers in the inherent incompatibility of mixed polymers during recycling. To overcome this impediment, this work furthers the emerging single‐monomer – multiple‐materials approach through the design of a bifunctional monomer that can not only orthogonally polymerize into two different types of polymers – specifically lactone‐based polyester and CO 2 ‐based polycarbonate – but the resultant polymers and their mixture can also be depolymerized back to the single, original monomer when facilitated by catalysis. Specifically, the lactone/epoxide hybrid bifunctional monomer (BiL O ) undergoes ring‐opening polymerization through the lactone manifold to produce polyester, PE(BiL O ), and is also applied to ring‐opening copolymerization with CO 2 , via the epoxide manifold, to yield polycarbonate, PC(BiL O ). Remarkably, a one‐pot recycling process of a BiL O ‐derived PE/PC blend back to the constituent monomer BiL O in >99 % selectivity was achieved with a superbase catalyst at 150 °C, thereby effectively obviating the requirement for sorting and separation typically required for recycling of mixed polymers.

Shi, Changxia↗

Closed‐Loop Recycling of Mixed Plastics of Polyester and CO 2 ‐Based Polycarbonate to a Single Monomer

Abstract Physical blending is an effective strategy for tailoring polymeric materials to specific application requirements. However, physically blended mixed plastics waste adds additional barriers in mechanical or chemical recycling. This difficulty arises from the intricate requirement for meticulous sorting and separation of the various polymers in the inherent incompatibility of mixed polymers during recycling. To overcome this impediment, this work furthers the emerging single‐monomer – multiple‐materials approach through the design of a bifunctional monomer that can not only orthogonally polymerize into two different types of polymers – specifically lactone‐based polyester and CO 2 ‐based polycarbonate – but the resultant polymers and their mixture can also be depolymerized back to the single, original monomer when facilitated by catalysis. Specifically, the lactone/epoxide hybrid bifunctional monomer (BiL O ) undergoes ring‐opening polymerization through the lactone manifold to produce polyester, PE(BiL O ), and is also applied to ring‐opening copolymerization with CO 2 , via the epoxide manifold, to yield polycarbonate, PC(BiL O ). Remarkably, a one‐pot recycling process of a BiL O ‐derived PE/PC blend back to the constituent monomer BiL O in >99 % selectivity was achieved with a superbase catalyst at 150 °C, thereby effectively obviating the requirement for sorting and separation typically required for recycling of mixed polymers.

Chemistry↗

Material Response Analysis of PICA-NuSil at the Hypersonic Materials Environmental Test System

Phenolic impregnated carbon ablator (PICA) is a thermal protection system (TPS) that gained heritage during the Stardust mission and is the baseline TPS material for expeditions to Mars (e.g., Mars Science Laboratory and Mars 2020).1 PICA is friable; therefore, a polysiloxane resin (NuSil CV-1144-0) is deposited onto the surface of flight hardware before assembly, test, and launch operations (ATLO) to mitigate particle shedding. Furthermore, the Mars Science Laboratory (MSL) and Mars 2020 heatshields were instrumented with an array of thermocouple plugs (MEDLI Integrated Sensor Plugs or MISP) designed to measure the in-depth thermal response of PICA during flight. Post-flight analysis of MISP data suggests that recession was lower than predicted, and NuSil is suspected as a reasonable cause. NuSil primarily consists of a copolymer blend of dimethyl and diphenyl-substituted polysiloxane resin. Four decades of research in the field of polymer-derived ceramics demonstrate that polysiloxane resins form oxidation-resistant silicon oxycarbide materials at pyrolysis temperatures as low as 800 °C. -2 Furthermore, silicon oxycarbide materials exhibit excellent thermal stability at relatively high-temperatures (< 1200 °C) but eventually decompose via carbothermal reduction. -3 Therefore, it is reasonable to suggest that NuSil forms an oxidation-resistant thermal barrier coating on the TPS surface and influences the material response during atmospheric entry. Evidence for this notion was observed during prior arc-jet testing at both the Aerodynamic Heating Facility (AHF) and the Panel Test Facility (PTF) at the NASA Ames Research Center. Articles of PICA were subjected to testing in airflow, and a temperature discontinuity was recorded at the surface of coupons coated with NuSil. A glassy coating was observed to form at the surface in shear flow configurations (wedge and panel) under moderate heat fluxes. Furthermore, state-of-the-art material response models have yet to account for the underlying physics and chemistry of the temperature discontinuity. To this end, a pathfinder test campaign was executed at the Hypersonic Materials Environmental Test System (HyMETS) to enhance the fundamental understanding of PICA-NuSil ablation phenomena and provide a preliminary data set to aid in the development of material response models.

PICA↗

Electrolyte Immersion Increases Photoconductivity in a Model Polymer Photocathode

Immersing polymer solar cells in aqueous electrolyte for photoelectrochemical (PEC) hydrogen production is likely to cause photophysical changes that could present both challenges and opportunities for engineering functional and durable devices. Herein we study the bulk heterojunction blend poly(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl)-alt-(2-(((2-ethylhexyl)oxy)carbonyl)-3-fluorothieno[3,4-b]thiophene-4,6-diyl):poly(N,N'-di(2-octyldodecyl)naphthalene-1,8:4,5-bis(dicarboximide)-2,6-diyl)-alt-(2,2-bithiophene-5,5'-diyl) (PTB7-Th:N2200) excited-state dynamics in electrolyte from femtosecond to millisecond time scales using pump-probe microwave conductivity and absorption spectroscopy. While the blend swells very little, electrolyte exposure increases the microwave-frequency mobility and possibly the yield of photogenerated charges while also decreasing crystallinity. These results indicate an enhancement in key performance metrics, implying that any limitations on the performance of PEC test devices do not arise from active layer-electrolyte interactions. For the PTB7-Th:N2200 blend or similar photocathode systems, our results indicate that improving the interfacial kinetics and/or the carrier lifetime should be prioritized, not protecting the active layer from the electrolyte. Since this observation may not be universal to all polymer systems, future research should focus on identifying their limiting photophysical processes. electrolyte.

14 SOLAR ENERGY↗

Characterizations of Enriched Metallic Single-Walled Carbon Nanotubes in Polymer Composite

Using different processing conditions, we disperse the single-walled carbon nanotube (SWNT) into the polymethyl methacrylate (PMMA) to form composites. In the melt-blended sample, the SWNTs originally semiconducting - became predominantly metallic after dispersion into the melt-blended composite. The interaction of the PMMA and SWNT is investigated by the polarized Raman studies. The structure changes in the PMMA and SWNT shows that the anisotropic interactions are responsible for SWNT electronic density of states (DOS) changes. The increased metallic SWNT percentage is confirmed by the conductivity and dielectric constant measurements .

Chen, Bin↗

Ionic Polyimides: New High Performance Polymers for Additive Manufacturing

There is currently a very limited set of engineering polymers that have been demonstrated as viable for use in 3-D printing. Additive manufacturing of custom components will require a much larger array of polymers, especially those with physical, thermal, chemical, and mechanical properties that can be tailor-made. The development of ‘Ionic Polyimides’ offers a solution to this shortage by combining the well understood and widely accepted properties of conventional polyimides, with a new approach to polymer synthesis. Polyimides and polymeric ionic liquids (poly(ILs)) are at the forefront of advanced polymer materials, each with their own set of advantages and disadvantages. While it is clear that more types of polymer materials are needed for fused deposition modeling (FDM) additive manufacturing, there is a need to explore these classes of materials. The synthesis process developed by the Bara Research Group at the University of Alabama allows full control over polymer structure, nanostructure, thermal, electrical, and physical properties making them a prime candidate for use in the additive manufacturing process. Furthermore, the new process allows us to tailor-make a high strength polymer that can be used to fabricate filament feedstock instead of pellets for 3D printing. The primary objective of this proposal is to determine the relationship between molecular structure, physical properties, and performance of ionic polyimides. Further, we seek to determine their utility as materials suitable for additive manufacturing of components used in aerospace vehicles, with an emphasis on characterizing and simulating their thermal behaviors and properties. This proposal addresses the need for fundamental research on a customizable polymer filament feedstock for 3-D printing with tailor-made properties potentially making it superior to the commercial blends offered in industry today. The deliverables for this project are the creation of a database that will detail the relationships between the molecular structure and physical properties for the ionic polyimide of interest (e.g. Tg/Tm (Glass Transition Temperature divided by Melting Point)) relative to different ionic polyimide structures). This new database will provide a “road map” to the development of the first generation of materials and ultimately proof-of-concept.

Jackson, Enrique↗