Search NASA⌕ Search

SEARCH · Search NASA

Results for “PLURONICS”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 73 records · Page 4

Self-Assembly of a Triblock Copolymer in the Presence of a Rigid Conjugated Polyelectrolyte

The properties of conducting polymers are strongly influenced by structural changes induced by long-range order, which can be achieved by using block copolymers that self-assemble into crystalline structures. These blends result in unique mesophases distinct from the pure components with self-assembly behavior modulated by solution conditions and polymer architectures. High-throughput small-angle X-ray scattering data of aqueous Pluronic P123 (PEO 20 –PPO 70 –PEO 20 ) and conjugated polyelectrolyte poly[3-(potassium-4-butanoate) thiophene-2,5-diyl] (PPBT) blends at various concentrations and temperatures were automatically classified into phase maps by autophasemap, an unsupervised statistical analysis algorithm. The outlined phase boundaries revealed that adding PPBT to high P123 concentrations induced a transition from cubicly ordered spherical micelles to hexagonally packed cylindrical micelles. Shear alignment via rheological small-angle neutron scattering of the blends produced monolithic oriented cubic and hexagonal crystal gels. Furthermore, these insights into the self-assembly of conductive polymer blends will aid in the design of soft materials with tunable structural and electronic properties.

36 MATERIALS SCIENCE↗

Morphology Control of Carbon-Free Spinel NiCo 2 O 4 Catalysts for Enhanced Bifunctional Oxygen Reduction and Evolution in Alkaline Media

Spinel NiCo 2 O 4 is considered a promising precious metal-free catalyst that is also carbon-free for oxygen electrocatalysis. Current efforts mainly focus on optimal chemical doping and substituent to tune its electronic structures for enhanced activity. Here, we study its morphology control and elucidate the morphology-dependent catalyst performance for bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Three types of NiCo 2 O 4 catalysts with significantly distinct morphologies were prepared using temple-free, Pluronic-123 (P-123) soft, and SiO 2 hard templates, respectively, via hydrothermal methods following by a calcination. While the hard-template yields sphere-like dense structures, soft-template assists the formation of a unique nano-needle cluster assembly containing abundant meso- and macro pores. Furthermore, the effect of morphology of NiCo 2 O 4 on their corresponding bifunctional catalytic performance was systematically investigated. The flower-like nano-needle assembly NiCo 2 O 4 catalyst via the soft template method exhibited the highest catalytic activity and stability for both ORR and OER. In particular, it exhibited an onset and half-wave potentials of 0.94 and 0.82 V vs. RHE, respectively, for the ORR in alkaline media. Although it is still inferior to Pt, the NiCo 2 O 4 represents one of the best ORR catalyst compared to other reported carbon-free oxides. Meanwhile, remarkable OER activity and stability were achieved with an onset potential of 1.48 V and a current density of 15 mA/cm 2 at 1.6 V, showing no activity loss after 20,000 potential cycles (0 to 1.9 V). The demonstrated stability is even superior to Ir for the OER. The morphology-controlled approach provides an effective solution to create a robust 3D architecture with increased surface areas and enhanced mass transfer. More importantly, the soft template can yield high degree of spinel crystallinity with ideal stoichiometric ratios between Ni and Co, thus promoting structural integrity with enhanced electrical conductivity and catalytic properties.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Two-Step Thermoresponsive Ultrafiltration Membranes from Polymerization of Lyotropic Liquid Crystals

Here, in this study, we present the fabrication of a two-step thermoresponsive ultrafiltration (UF) membrane through polymerization of a lyotropic liquid crystal (LLC). A mixture of commercially available Pluronic F 127 block copolymer, water (containing ammonium persulfate as the initiator), and polymerizable oil (n-butyl acrylate/ethylene glycol dimethacrylate) is used to create an LLC with a lamellar structure, as characterized by cross-polarized light microscopy and atomic force microscopy. Differential scanning calorimetry is employed to evaluate the thermoresponsive behavior of the polymerized LLC (polyLLC). Two-step thermoresponsiveness (~35 and ~50 °C) of the polyLLC is observed due to the lower critical solution temperature (LCST) of F 127 and melting of the crystalline structure of the polyethylene oxide (PEO) chains of the F 127 surfactant. In the next step, the obtained mesophase is cast on a nonwoven polyester support sheet followed by thermal polymerization. The hydration capacity, water flux, water flux recovery after fouling, and molecular weight cutoff (MWCO) of the obtained membrane are evaluated at different temperatures to examine its thermoresponsiveness. The experimental results reveal that the UF membrane has a reversible thermoresponsive behavior at the LCST and PEO melting of polyLLC. Additionally, the cleaning efficiency of the fouled membrane can be enhanced by using its thermoresponsive behavior, resulting in an extended lifetime of the product. Furthermore, the MWCO of the membrane can be altered with temperature due to the pore size change with temperature stimulus.

36 MATERIALS SCIENCE↗

A lyotropic liquid crystal-templated nanofiltration membrane with thermo- and pH-responsive 3D transport pathway

We produce controlled nanostructured membranes from cross-linking of self-assembled diacrylated poloxamers. At sufficiently high concentrations, poloxamers form lyotropic liquid crystals (LLCs), such as lamellar (L α ), cubic packing of spherical micelles, and hexagonal packing of rod-like micelles in water (H 1 ). We use the H 1 phase as a template to produce orderly packed nanofibrous membranes. The obtained membrane has a continuous 3D transport pathway and can alter its nanofiltration (NF) properties in response to changes in temperature and pH. The formulation includes Pluronic P84-diacrylate (P84DA), a thermoresponsive component that acts as both macromer and structure-directing amphiphile. P84DA facilitates changes in membrane pore size with temperature due to its thermoresponsiveness when it is in contact with water. Furthermore, the precursor contains acrylic acid (AAc) as the charged component, which upon copolymerization with P84DA, not only enables ion separation through Donnan exclusion but also imparts pH-responsive behavior for the separation of ionic species. The membrane performance is studied and compared with a commercial NF membrane (NF270). We show that the synthesized NF membrane has separation properties adjustable with temperature and pH with exceptional resistance to fouling by various solutes due to its highly hydrophilic surface. Furthermore, the membrane shows an outstanding sulfate over chloride ion selectivity, which is a requirement for salt fractionation applications. Deducted from separate experiments, the ideal chloride/sulfate selectivity for magnesium cation is about 2.38 at low ionic strengths. This study is done on a model system to show the capability of incorporating pH-responsiveness in LLC templated membranes, in which the pH-responsive range can be designed by changing the charged groups of comonomer in the formulation.

36 MATERIALS SCIENCE↗

Flash Graphene from Plastic Waste

In this work, an approach to upcycling plastic waste (PW) products is presented. The method relies on flash Joule heating (FJH) to convert PW into flash graphene (FG). In addition to FG, the process results in the formation of carbon oligomers, hydrogen, and light hydrocarbons. In order to make high quality graphene, a sequential alternating current (AC) and direct current (DC) flash is used. Here, the FJH process requires no catalyst and works for PW mixtures, which makes the process suitable for handling landfill PW. The energy required to convert PW to FG is ~ 23 kJ/g or ~ $125 in electricity per ton of PW, potentially making this process economically attractive for scale-up. The FG was characterized by Raman spectroscopy and had a I 2D /I G peak ratio up to 6 with a low-intensity D band. Moreover, transmission electron microscopy and X-ray diffraction analysis show that the FG is turbostratic with an interlayer spacing of 3.45 Å. The large interlayer spacing will facilitate its dispersion in liquids and composites. Analysis of FG dispersions in 1% Pluronic aqueous solution shows that concentrations up to 1.2 mg/mL can be achieved. The carbon oligomers that distilled from the process were characterized by Fourier-transform infrared spectroscopy and have chemical structures similar to the starting PW. Initial analysis of gas phase products shows the formation of considerable amounts of hydrogen along with other light hydrocarbons. Since graphene is naturally occurring and it shows a low toxicity profile, this could be an environmentally beneficial method to upcycle PE.

54 ENVIRONMENTAL SCIENCES↗

Accelerated Synthesis of Ordered Mesoporous Carbons Using Plasma

Conventional ordered mesoporous carbon (OMC) production usually requires long processing times in the carbonization step to achieve desired temperatures through controlled ramps. To enable expedited materials discovery, developing advanced manufacturing capability with significantly improved throughput is highly desired. Current approaches for accelerating the synthesis of OMCs include using microwave and Joule heating. However, both methods rely on the introduction of additional components, such as microwave absorbers and electrically conductive agents, within the bulk materials to impart the ability to reach high carbonization temperatures. This work demonstrates accelerated synthesis and functionalization of OMCs through the use of a dielectric barrier discharge plasma, where carbonization can be accomplished within 15 min using 30 W plasma sources, representing more than an order of magnitude increase in polymer-to-carbon conversion kinetics compared to that of a traditionally pyrolyzed analogue. Particularly, the ability of performing rapid carbonization without the use of additional substrates within the OMC precursor systems is advantageous. A systematic investigation of how plasma power, time, and gas atmosphere impact the resulting OMC pore textures and properties is performed, demonstrating the broad applicability of plasma-enabled carbonization methods. Furthermore, we demonstrate that the plasma treatment strategy can be extended to incorporate heteroatoms into the carbon framework by introducing ammonia gas, resulting in OMCs with a nitrogen content up to 4.7 at %, as well as non-Pluronic templating systems for synthesizing OMC with pore sizes larger than 10 nm. As employing a plasma source for materials pyrolysis is an industrially relevant approach, our system can be extended toward scaled synthesis of OMCs with much faster production rates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tuning the Optical Properties of Mesoporous TiO2 Films by Nanoscale Engineering

Introducing mesoscale pores into spincoated titanium dioxide films, prepared by spincoating different sol-gel precursor solutions on silicon substrates and subsequent annealing at 350 C, 400 C or 450 C, respectively, affects several optical properties of the material. The change in refractive index observed for different mesoporous anatase films directly correlates with changes in pore size, but is also in a more complex manner influenced by the film thickness and the density of pores within the films. Additionally, the band gap of the films is blueshifted by the stress the introduction of pores exerts on the inorganic matrix. The differently sized pores were templated by Pluronic{reg_sign} block copolymers in the solgel solutions and tuned by employing different annealing temperatures for the film preparation. This study focused on elucidating the effect different templating materials (F127 and P123) have on the pore size of the final mesoporous titania film, and on understanding the relation of varying polymer concentration (taking P123 as an example) in the sol-gel solution to the pore concentration and size in the resultant titania film. Titania thin film samples or corresponding titanium dioxide powders were characterized by X-ray diffraction, nitrogen adsorption, ellipsometery, UV/Vis spectrometry and other techniques to understand the interplay between mesoporosity and optical properties.

36 MATERIALS SCIENCE↗

Pore orientation effects on the kinetics of mesostructure loss in surfactant templated titania thin films

The mesostructure loss kinetics are measured as a function of the orientation of micelles in 2D hexagonal close packed (HCP) columnar mesostructured titania thin films using in situ grazing incidence small angle x-ray scattering (GISAXS). Complementary supporting information is provided by ex situ scanning electron microscopy. Pluronic surfactant P123 acts as the template to synthesize HCP structured titania thin films. When the glass substrates are modified with crosslinked P123, the micelles of the HCP mesophase align orthogonal to the films, whereas a mix of parallel and orthogonal alignment is found on unmodified glass. The rate of mesostructure loss of orthogonally oriented (o-HCP) thin films (~60 nm thickness) prepared on modified substrate is consistently found to be less by a factor of 2.5 ± 0.35 than that measured for mixed orientation HCP films on unmodified substrates. The activation energy for mesostructure loss is only slightly greater for films on modified glass (155 ± 25 kJ/mol -1 ) than on unmodified (128 kJ/mol -1 ), which implies that the rate difference stems a greater activation entropy for mesostructure loss in o-HCP titania films. Nearly perfect orthogonal orientation of micelles on modified surfaces contributes to the lower rate of mesostructure loss by supporting the anisotropic stresses that develop within the films during annealing due to continuous curing, sintering and crystallization into the anatase phase during high temperature calcination (>450 °C). Because the film thickness dictates the propagation of orientation throughout the films and the degree of confinement, thicker (~250 nm) films cast onto P123-modified substrates have a much lower activation energy for mesostructure loss (89 ± 27 kJ/mol -1 ) due to the mix of orientations found in the films. Thus, in conclusion, this kinetic study shows that thin P123- templated o-HCP titania films are not only better able to achieve good orthogonal alignment of 3 the mesophase relative to thicker films or films on unmodified substrates, but that alignment of the mesophase in the films stabilizes the mesophase against thermally-induced mesostructure loss.

36 MATERIALS SCIENCE↗

Manipulating the architecture of Pd@Pt nanostructures through metal-selective capping agent interactions

Pluronic F127 and NaBr were used during co-reduction of Pd and Pt precursors to achieve octopodal and dendritic Pd@Pt nanoparticles selectively through preferential capping interactions. We demonstrate that two capping agents can be used to independently manipulate the growth regimes of metals in the synthesis of bimetallic nanostructures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Highly active atomically dispersed CoN 4 fuel cell cathode catalysts derived from surfactant-assisted MOFs: carbon-shell confinement strategy

Development of platinum group metal (PGM)-free catalysts for oxygen reduction reaction (ORR) is essential for affordable proton exchange membrane fuel cells. Herein, a new type of atomically dispersed Co doped carbon catalyst with a core–shell structure has been developed via a surfactant-assisted metal–organic framework approach. The cohesive interactions between the selected surfactant and the Co-doped zeolitic imidazolate framework (ZIF-8) nanocrystals lead to a unique confinement effect. During the thermal activation, this confinement effect suppressed the agglomeration of Co atomic sites and mitigated the collapse of internal microporous structures of ZIF-8. Among the studied surfactants, Pluronic F127 block copolymer led to the greatest performance gains with a doubling of the active site density relative to that of the surfactant-free catalyst. According to density functional theory calculations, unlike other Co catalysts, this new atomically dispersed Co–N–C@F127 catalyst is believed to contain substantial CoN 2+2 sites, which are active and thermodynamically favorable for the four-electron ORR pathway. The Co–N–C@F127 catalyst exhibits an unprecedented ORR activity with a half-wave potential (E 1/2 ) of 0.84 V (vs. RHE) as well as enhanced stability in the corrosive acidic media. It also demonstrated high initial performance with a power density of 0.87 W cm–2 along with encouraging durability in H 2 –O 2 fuel cells. The atomically dispersed Co site catalyst approaches that of the Fe–N–C catalyst and represents the highest reported PGM-free and Fe-free catalyst performance.

25 ENERGY STORAGE↗

Elasticity and yielding of mesophases of block copolymers in water–oil mixtures

Here, amphiphilic block copolymers self-assemble at the water/oil interface to form different mesomorphic structures, such as lamellar, micellar cubic, normal hexagonal, and reverse hexagonal structures. Usually, these structures are polycrystalline and the value of their elastic modulus depends on the average orientation of their constituent's single crystals. We introduce a model to predict the elastic modulus and yielding of mesophases from their characteristic length and intermicellar interactions. Shear modulus of each structure is measured as a function of deformation (strain). Zero-shear modulus, G 0 , depends on the inverse of the intermicellar distance with a power law model. The power law index for each structure is approximately n + 2 where n is the degree of confinement in the mesophase: 1 for lamellar, 2 for both normal and reverse hexagonal, and 3 for micellar cubic structures. Rheological properties of different mesophases of Pluronic P84 in the presence of water and p -xylene are used as a case study. The model is found to be in good agreement with experimental data in the linear viscoelastic region. When compared to experimental data, the yield strain value obtained from the model is one order of magnitude higher than the limit of the linear viscoelastic regime and close to the strain at the cross-over point of storage and loss moduli. Frequency sweep measurements are done to characterize the relaxation and cooperative model behaviors of each mesophase structure.

36 MATERIALS SCIENCE↗

Initiator-dependent kinetics of lyotropic liquid crystal-templated thermal polymerization

In this study, we examine the polymerization kinetics with different thermal initiators in lamellar and hexagonal lyotropic liquid crystal (LLC) structures directed by Pluronic L64. Ammonium persulfate is used to initiate the polymerization from the water phase, whereas azobisisobutyronitrile and benzoyl peroxide are employed to commence the reaction through the monomer phase. While the mesophase structure remains intact for all the initiation systems, the kinetics of polymerization and conversion vary significantly. The obtained differential scanning calorimetry (DSC) results reveal that, under same conditions, initiation from water (IFW) system results in enhanced reaction rates as well as higher monomer conversions compared to initiation from oil (IFO) one. Higher termination rate in LLC nanoconfinements induces lower reaction rates in IFO system. Moreover, our work on different LLC structures show that the effect of nanoconfinement on polymerization rate can be minimized through IFW. Chemorheology not only confirms the results obtained from DSC, but also shows that, in similar monomer conversions, the polymers obtained from IFW system exhibit an improved mechanical properties over the samples produced though IFO process.

36 MATERIALS SCIENCE↗

Diffusion characteristics of water molecules in a lamellar structure formed by triblock copolymers

The distribution and diffusion of water molecules are playing important roles in determining self-assembly and transport properties of polymeric systems. Small-angle neutron scattering (SANS) experiments and molecular dynamics (MD) simulation have been applied to understand the distribution of water molecules and their dynamics in the lamellar membrane formed by Pluronic L62 block copolymers. Penetration of water molecules into the polyethylene oxide (PEO) layers of the membranes has been estimated using scattering length density (SLD) profiles obtained from SANS measurements, which agree well with the molecular distribution observed from MD simulations. The water diffusion coefficient at different regions of the lamellar membrane was further investigated using MD simulation. The diffusion characteristic shows a transition from normal to anomalous diffusion as the position of the water molecule changes from the bulk to PEO and to the polypropylene oxide (PPO) layer. Here we find that water molecules within the PEO or PPO layers follow subdiffusive dynamics, which can be interpreted by the model of fractional Brownian motion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development and characterization of acrylated palm oil nanoparticles using ionizing radiation

In this study, the utilization of radiation crosslinking methods which are known as intermolecular and intramolecular crosslinking for the formation of nanoparticles of Acrylated Palm Oil (APO) in the microemulsion system that also consists of Pluronic F-127 (PF-127) surfactant was demonstrated. This microemulsion system was subjected to the ionizing radiation i.e. gamma irradiation at different doses to form the crosslinked APO nanoparticles. The effects of radiation doses on the size of APO nanoparticles were investigated using the Dynamic Light Scattering (DLS) method and their images were viewed using the Transmission Electron Microcrospy (TEM). The Fourier Transform Infra-Red (FTIR) spectroscopy was used to characterize the chemical structure and the crosslinking conversion of carbon-carbon double bond (-C = C-) of the APO nanoparticles after irradiation. As a result, the size of the APO nanoparticle decreased when the irradiation dose increased. Reduce in size might be due to the effect of intramolecular crosslinking reaction of the APO nanoparticles during irradiation process. Meanwhile, the intramolecular -C C- crosslinking conversion percentage was increased at doses below 1kGy before decreasing at the higher dose that might due to the intermolecular crosslinking of the macromolecules. This study showed that radiation crosslinking methods of polymerization and crosslinking in the microemulsion were found to be promising for the synthesis of nanoparticles.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

The dynamical crossover in attractive colloidal systems

We study the dynamical arrest in an adhesive hard-sphere colloidal system. We examine a micellar suspension of the Pluronic-L64 surfactant in the temperature (T) and volume fraction (ϕ) phase diagram. According to mode-coupling theory (MCT), this system is characterized by a cusp-like singularity and two glassy phases: an attractive glass (AG) phase and a repulsive glass (RG) phase. The T − ϕ phase diagram of this system as confirmed by a previous series of scattering data also exhibits a Percolation Threshold (PT) line, a reentrant behavior (AG-liquid-RG), and a glass-to-glass transition. The AG phase can be generated out of the liquid phase by using T and ϕ as control parameters. We utilize viscosity and nuclear magnetic resonance (NMR) techniques. NMR data confirm all the characteristic properties of the colloidal system phase diagram and give evidence of the onset of a fractal-like percolating structure at a precise threshold. The MCT scaling laws used to study the shear viscosity as a function of ϕ and T show in both cases a fragile-to-strong liquid glass-forming dynamic crossover (FSC) located near the percolation threshold where the clustering process is fully developed. These results suggest a larger thermodynamic generality for this phenomenon, which is usually studied only as a function of the temperature. We also find that the critical values of the control parameters, coincident with the PT line, define the locus of the FSC. In the region between the FSC and the glass transition lines the system dynamics are dominated by clustering effects. We thus demonstrate that it is possible, using the conceptual framework provided by extended mode-coupling theory, to describe the way a system approaches dynamic arrest, taking into account both cage and hopping effects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Versatile magnetometer assembly for characterizing magnetic properties of nanoparticles

We constructed a versatile magnetometer assembly for characterizing iron oxide nanoparticles. The magnetometer can be operated at room temperature or inside a cryocooler at temperatures as low as 6 K. The magnetometer’s sensor can be easily exchanged and different detection electronics can be used. We tested the assembly with a non-cryogenic commercial Hall sensor and a benchtop multimeter in a four-wire resistance measurement scheme. A magnetic moment sensitivity of 8.5 × 10{sup −8} Am{sup 2} was obtained with this configuration. To illustrate the capability of the assembly, we synthesized iron oxide nanoparticles coated with different amounts of a triblock copolymer, Pluronic F-127, and characterized their magnetic properties. We determined that the polymer coating does not affect the magnetization of the particles at room temperature and demonstrates that it is possible to estimate the average size of coating layers from measurements of the magnetic field of the sample.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Unbiased particle conformation extraction from scattering spectra using orthonormal basis expansions

A strategy is outlined for quantitatively evaluating the particle density profiles from small-angle scattering spectra of dilute solutions. The approach employs an orthonormal basis function expansion method, enabling the determination of characteristic mass distributions in self-assembled structures without the need for a specific structural model. Through computational benchmarking, the efficacy of this approach is validated by effectively reconstructing the density profile of soft-ball systems with varying fuzziness from their scattering signatures. Further, the feasibility of the method is demonstrated by fitting small-angle neutron scattering data obtained from Pluronic L64 micelles at different temperatures. This proposed approach is both simple and analytical, eliminating the requirement for a presumptive structural model in scattering analysis. The new method could therefore facilitate quantitative descriptions of complex nanoscopic structures inherent to numerous soft-matter systems using small-angle scattering techniques.

36 MATERIALS SCIENCE↗

Synthesis of mesoporous silica using a mineral silica source

Abstract Mesoporous silica has been applied in catalysis, separations, and drug delivery. It has generally been made using organosilicon precursors such as tetraethyl orthosilicate. For sustainability, it is necessary to find readily accessible mineral sources for making mesoporous silica. In this work, we demonstrate the successful synthesis of mesoporous silica with 10 nm average pore size using the mineral forsterite (Mg 2 SiO 4 ) as a silica source, providing a potentially cheaper and more Earth‐friendly route to making technologically important porous silica materials. Pure forsterite was synthesized by a solid‐state chemistry route at 1000°C and underwent dissolution–reprecipitation in aqueous hydrochloric acid containing the soft template surfactant, Pluronic P123. Variations of initial reaction pH (−0.2 to 0.6), reaction time (12–24 h), reaction temperature (50 to 90°C), and silica precursor (forsterite and fumed silica) were performed. The mesoporous silica aged at 70°C for 24 h had the highest porosity, with a surface area of 735 m 2 /g and a pore volume of 1.4 ml/g, comparable to mesoporous silica made using conventional starting materials. This novel geomimetic synthesis route supports the possibility of analogous formation of structured (mesoporous or zeolitic) silica in nature under abiotic or prebiotic conditions.

Materials Science↗