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At least 1,135 records · Page 63

Synthesis of poly(3,4-ethylenedioxythuophene) derivatives using three-armed conjugated cross-linker and its thermoelectric properties

Conducting polymer based thermoelectric systems are very effective at harvesting electricity from waste heat with low-temperature gradients relative to environmental temperature. However, although various studies concerning the doping effect exist, there are insufficient reports on the effect of the change in polymer chain structure on the thermoelectric properties. Here we demonstrate different poly(3,4-ethylenedioxythiophene) (PEDOT)-derivative chain structures (such as linear, two-dimensional, co-polymer), by varying the amount of three-armed conjugated cross-linker (1,3,5-tri(2-thienyl)-benzene (TTB)). Further, at a small amount of TTB addition (until 0.5 mM), the electrochemical charge transport of the PEDOT films increased without shift of the UV–Vis absorbing property. However, from higher than 0.5 mM TTB, electrochemical charge transport decreased with blue shift of the UV–Vis absorbing curve. Moreover, the power factor of the PEDOT-derivative films without TTB to a small amount of TTB (0.5 mM) was improved from (27.03 to 49.43) µWm -1 K -2 , and at higher than 0.5 mM TTB concentration, was diminished, respectively, because a small amount of TTB enhanced the π–π interaction of the polymer chains without disrupting the conjugation, while excess TTB molecules blocked conjugation of the polymer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding the Impacts of Support–Polymer Interactions on the Dynamics of Poly(ethyleneimine) Confined in Mesoporous SBA-15

Supported amines are a promising class of CO 2 sorbents offering large uptake capacities and fast uptake rates. Additionally, among supported amines, poly(ethyleneimine) (PEI) physically impregnated in the mesopores of SBA-15 silica is widely used. Within these composite materials, the chain dynamics and morphologies of PEI strongly influence the CO 2 capture performance, yet little is known about chain and macromolecule mobility in confined pores. Here, we probe the impact of the support–PEI interactions on the dynamics and structures of PEI at the support interface and the corresponding impact on CO 2 uptake performance, which yields critical structure–property relationships. The pore walls of the support are grafted with organosilanes with different chemical end groups to differentiate interaction modes (spanning from strong attraction to repulsion) between the pore surface and PEI. Combinations of techniques, such as quasi-elastic neutron scattering (QENS), 1 H T 1 –T 2 relaxation correlation solid-state NMR, and molecular dynamics (MD) simulations, are used to comprehensively assess the physical properties of confined PEI. We hypothesized that PEI would have faster dynamics when subjected to less attractive or repulsive interactions. However, we discover that complex interfacial interactions resulted in complex structure–property relationships. Indeed, both the chain conformation of the surface-grafted chains and of the PEI around the surface influenced the chain mobility and CO 2 uptake performance. By coupling knowledge of the dynamics and distributions of PEI with CO 2 sorption performance and other characteristics, we determine that the macroscopic structures of the hybrid materials dictate the first rapid CO 2 uptake, and the rate of CO 2 sorption during the subsequent gradual uptake stage is determined by PEI chain motions that promote diffusive jumps of CO 2 through PEI-packed domains.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Lightweight, Flexible Solar Cells on Stainless Steel Foil and Polymer for Space and Stratospheric Applications

The availability of low-cost, lightweight and reliable photovoltaic (PV) modules is an important component in reducing the cost of satellites and spacecraft. In addition, future high-power spacecraft will require lightweight PV arrays with reduced stowage volume. In terms of the requirements for low mass, reduced stowage volume, and the harsh space environment, thin film amorphous silicon (a-Si) alloy cells have several advantages over other material technologies (1). The deposition process is relatively simple, inexpensive, and applicable to large area, lightweight, flexible substrates. The temperature coefficient has been found to be between -0.2 and -0.3 %/degC for high-efficiency triple-junction a-Si alloy cells, which is superior for high temperature operation compared to crystalline Si and triple-junction GaAs/InGaP/Ge devices at 0.53 %/degC and 0.45 %/degC, respectively (2). As a result, the reduction in efficiency at high temperature typical in space conditions is less for a-Si alloy cells than for their crystalline counterparts. Additionally, the a-Si alloy cells are relatively insensitive to electron and proton bombardment. We have shown that defects that are created by electrons with energies between 0.2 to 2 MeV with fluence up to 1x10(exp 15) e/sq cm and by protons with energy in the range 0.3 MeV to 5 MeV with fluence up to 1x10(exp 13) p/sq cm can be annealed out at 70 C in less than 50 hours (1). Further, modules incorporating United Solar s a-Si alloy cells have been tested on the MIR space station for 19 months with only minimal degradation (3). For stratospheric applications, such as the high altitude airship, the required PV arrays are typically of considerably higher power than current space arrays. Airships typically have a large area available for the PV, but weight is of critical importance. As a result, low cost and high specific power (W/kg) are key factors for airship PV arrays. Again, thin-film a-Si alloy solar cell technology is well suited to such applications.

Beernink, Kevin↗

Novel High Barrier Films for Packaging Food and Medicine

Long manned missions require food packaging to maintain food safety, nutrition, and acceptability for the length of 3-5 years1,2 while the shelf life assigned by NASA for current provisions is 18-24 months1. The focus of this design project was to make a polymer film specifically to function as a high oxygen barrier to later be included in an improved multi-layer packaging system of other specialized polymers with capabilities to allow for a 5-year shelf-life. To qualify as a high oxygen barrier film and to be a successful design for the future packaging, the resulting film is required to have an oxygen transmission rate (OTR) less than 0.06 cc/ m2/24 hr/atm, the standard for the current packaging3. This new film was designed to have a decreased permeability by increasing the “tortuous path” a gas molecule travels to permeate through a film. The increase in the “tortuous path” of a gas molecule is accomplished by introducing a 2D material additive. The additive chosen for this project was hexagonal boron nitride (h-BN) which exfoliates into boron nitride nanosheets (BNNs). Nylon 6 was chosen as the candidate for the matrix. This project is required to determine the best methods to synthesize the sample film and then to test the OTR of the film to determine if this design was successful. This project examined methods for pulverizing polymer resin pellets, h-BN exfoliation, and film fabrication using a hot press. This report includes the exfoliation and analysis of h-BN, procedural preparations for films, and a modeling study of estimated OTR of the h-BN/Nylon. The work in this report did not yield a high barrier composite film because of the laboratory closure in response to COVID -19 guidance but provides a concise method of the additive preparation and film synthesis. This gives a good starting point for future research in high barrier films by 2D additive composites.

Polymer, Nylon, PET, boron nitride, nanocomposite↗

Effects of Specimen Geometry on Flatwise Tensile Strength

The through-thickness or flatwise strength of a uniaxial polymer matrix composite was investigated with several test specimen geometries and starting plate thicknesses. The use of thinner plates is desirable to save material and lower costs during materials development programs. The various configurations gave similar results with the exception of thin, straight-sided specimens. Thin specimens tended to provide invalid results per ASTM International D7291; however, the addition of a large, shallow radius improved the results. The Weibull distribution provided a good fit to the combined data.

Polymer matrix composite↗

Polyether-polyester graft copolymer

Described is a polyether graft polymer having improved solvent resistance and crystalline thermally reversible crosslinks. The copolymer is prepared by a novel process of anionic copolymerization. These polymers exhibit good solvent resistance and are well suited for aircraft parts. Previous aromatic polyethers, also known as polyphenylene oxides, have certain deficiencies which detract from their usefulness. These commercial polymers are often soluble in common solvents including the halocarbon and aromatic hydrocarbon types of paint thinners and removers. This limitation prevents the use of these polyethers in structural articles requiring frequent painting. In addition, the most popular commercially available polyether is a very high melting plastic. This makes it considerably more difficult to fabricate finished parts from this material. These problems are solved by providing an aromatic polyether graft copolymer with improved solvent resistance and crystalline thermally reversible crosslinks. The graft copolymer is formed by converting the carboxyl groups of a carboxylated polyphenylene oxide polymer to ionic carbonyl groups in a suitable solvent, reacting pivalolactone with the dissolved polymer, and adding acid to the solution to produce the graft copolymer.

Bell, Vernon L.↗

Thermally Induced Structural Transitions in Epoxy Thermoset Polymer Networks and Their Spectroscopic Responses

The polymer network structure of epoxy thermosets plays a significant role in its final material properties. However, the effects of mild thermal exposure on these network structures are poorly studied. In this work, wide-angle X-ray scattering was used to investigate the polymer network structure of two epoxy thermosets: homopolymerized bisphenol A (BPA) epoxy resin and BPA epoxy resin cured with a polyether amine hardener (BPA/T-403). Using density functional theory and wide-angle X-ray scattering, insights into the polymer network structure were obtained. Diffraction features were determined to originate from hardener-to-hardener molecular distance, perpendicular π–π stacking of aromatic p-phenylene rings, and the average carbon–carbon distance in the polymer. Thermal exposure was found to permanently alter these structural features for both thermosets, with an increase in the π–π stacking distance. Homopolymerized BPA had an additional decrease in the hardener-to-hardener distance. These structural alterations were found to be detectable using Fourier transform infrared spectroscopy and Raman spectroscopy, with changes in the hardener-to-hardener distance having the largest variations in the resulting spectra specifically at the aromatic and ether frequencies.

36 MATERIALS SCIENCE↗

Zero-cost corrections to influence functional coefficients from bath response functions

Recent work has shown that it is possible to circumvent the calculation of the spectral density and directly generate the coefficients of the discretized influence functionals using data from classical trajectory simulations. However, the accuracy of this procedure depends on the validity of the high temperature approximation. In this work, an alternative derivation based on the Kubo formalism is provided. This enables the calculation of additional correction terms that increases the range of applicability of the procedure to lower temperatures. Because it is based on the Kubo-transformed correlation function, this approach allows the direct use of correlation functions obtained from methods such as ring-polymer molecular dynamics and centroid molecular dynamics in determining the influence functional coefficients for subsequent system-solvent simulations. The accuracy of the original procedure and the corrected procedure is investigated across a range of parameters. It is interesting that the correction term comes at zero additional cost. Furthermore, it is possible to improve upon the correction using zero-cost physical intuition and heuristics making the method even more accurate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Self‐Propelling Macroscale Sheets Powered by Enzyme Pumps

Abstract Nanoscale enzymes anchored to surfaces act as chemical pumps by converting chemical energy released from enzymatic reactions into spontaneous fluid flow that propels entrained nano‐ and microparticles. Enzymatic pumps are biocompatible, highly selective, and display unique substrate specificity. Utilizing these pumps to trigger self‐propelled motion on the macroscale has, however, constituted a significant challenge and thus prevented their adaptation in macroscopic fluidic devices and soft robotics. Using experiments and simulations, we herein show that enzymatic pumps can drive centimeter‐scale polymer sheets along directed linear paths and rotational trajectories. In these studies, the sheets are confined to the air/water interface. With the addition of appropriate substrate, the asymmetric enzymatic coating on the sheets induces chemically driven, buoyancy flows that controllably propel the sheet's motion on the air/water interface. The directionality and speed of the motion can be tailored by changing the pattern of the enzymatic coating, type of enzyme, and nature and concentration of the substrate. This work highlights the utility of biocompatible enzymes for generating motion in macroscale fluidic devices and robotics and indicates their potential utility for in vivo applications.

Song, Jiaqi↗

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↗

Additive manufacturing of strong silica sand structures enabled by polyethyleneimine binder

Abstract Binder Jet Additive Manufacturing (BJAM) is a versatile AM technique that can form parts from a variety of powdered materials including metals, ceramics, and polymers. BJAM utilizes inkjet printing to selectively bind these powder particles together to form complex geometries. Adoption of BJAM has been limited due to its inability to form strong green parts using conventional binders. We report the discovery of a versatile polyethyleneimine (PEI) binder for silica sand that doubled the flexural strength of parts to 6.28 MPa compared with that of the conventional binder, making it stronger than unreinforced concrete (~4.5 MPa) in flexural loading. Furthermore, we demonstrate that PEI in the printed parts can be reacted with ethyl cyanoacrylate through a secondary infiltration, resulting in an increase in flexural strength to 52.7 MPa. The strong printed parts coupled with the ability for sacrificial washout presents potential to revolutionize AM in various applications including construction and tooling.

36 MATERIALS SCIENCE↗

Additive manufacturing of high explosives with inert dilution for wave shaping and detonation velocity grading

The performance of a high explosive charge is highly influenced by the detonation velocity and any inherent internal structure. Additively manufactured (AM) high explosive charges allow for a precisely engineered internal structure and the selective placement of discrete or graded volumes of a tailored material, which are unachievable by conventional means. The dilution of a solid explosive by an inert additive for detonation velocity reduction is herein evaluated for a method of material extrusion called a direct-ink-write AM, where an 1,3,5,7-tetranitro-1,3,5,7-tetrazoctane-based ultraviolet -curable energetic-binder paste explosive was diluted by the inert density mock 5-iodo-2′-deoxyuridine for use in the manufacture of multi-material explosive charges. The explosive ink was characterized for printing by rheological and particle size measurements, and the detonation velocities for 0–40 wt. % inert diluent were found to have a continuous linear reduction in detonation velocity down to 14.3% difference. A two-component 3D plane wave explosive lens with 8.038 km/s “fast” and 7.491 km/s “slow” diluted ink in an internal cone demonstrated a reduced time of breakout at the output face from 361 to 53 ns. A linearly graded “fast–slow–fast” cylinder was successfully printed and fired, showing engineered control along the length of the charge as the detonation velocity dropped from 7.851 to 6.700 km/s and then recovered to 7.241 km/s. The extreme control over the internal composition of a high explosive charge via a dual-material extruder/mixer challenges conventional manufacturing approaches and opens new avenues for engineered detonation wavefronts, high explosive charge performance, and new applications.

36 MATERIALS SCIENCE↗

Interfacial electroneutrality controls transport of asymmetric salts through charge-patterned mosaic membranes

Membranes that selectively enhance target solute permeation while rejecting competing species are essential for precision separations. This study introduces charge-patterned mosaic membranes (CMMs) that selectively transport divalent asymmetric salts by leveraging a net-neutral membrane–solution interface. This mechanism, dictated by the charge ratio of positive and negative domains on the membrane surface and the balance of cations and anions in the salt, is supported by analytical, numerical, and experimental results. Analytical solutions identified cationic domain coverages (f + ) of 33%, 50%, and 66% as optimal for the selective transport of +2:−1 salts, +1:−1 salts, and +1:−2 salts, respectively, under conditions where the pattern size (L) is significantly larger than the Debye length. Numerical simulations and experiments using CMMs with alternating charged-stripes inkjet-printed onto nanostructure copolymer substrates confirmed these findings. By varying stripe widths to control f + , pressure-driven filtration experiments demonstrated selective enrichment of MgCl 2 and K 2 SO 4 at the predicted f + values, with deviations from these values leading to salt rejection. These results highlight the pivotal role of a net-neutral interface in enabling asymmetric salt enrichment. This study positions CMMs as a versatile platform for tuning ion selectivity, addressing challenges in resource recovery, water treatment, and precision separations.

additive manufacturing↗

A Novel Low-Cost Method of Manufacturing Nb3Sn Superconductors with Multiple-Tin-Tube Sources (CRADA FRA-2008-0001 Final Report)

In order to successfully sustain a fusion reaction, peak magnetic fields on the order of 12-13 Tesla will be required. Magnetic fields of this magnitude can only be accomplished by advanced superconductors such as Nb3Sn. However, the economic success of a fusion machine will depend on further improvements in the cost-performance of the Nb3Sn conductor. This project will develop a novel, low-cost, multiple-tin-tube process as a new manufacturing approach for large-scale Nb3Sn-conductor production. The process will be suitable for the efficient production of larger strands (0.83 mm), consistent with ITER (International Thermonuclear Experimental Reactor) specifications. In Phase I, Cu/Nb composites were manufactured and shaped into sub-elements. These sub-elements were tin-coated by electroplating, assembled into a precise-fit restack billet tube, and drawn to 0.83 mm diameter. In Phase II, the process will be scaled-up to full production levels. The improved Nb3Sn conductor should have an immediate benefit for high-field magnet applications. A prototype fusion machine, based on a cost effective Nb3Sn conductor, would have enormous economic and social benefits. In addition, the conductor should be applicable to nuclear magnetic resonance (NMR), which has requirements for use in chemical research, biochemistry, pharmaceutical chemistry, polymer science, petroleum research, agricultural chemistry, and medicine. Leszek Motowidlo, Principal Investigator, will be responsible for the overall coordination of the effort. He and others of SupraMagnetics staff will design and fabricate protoype PIT Nb3Sn conductors for evaluation at Fermilab. Emanuela Barzi will be responsible for the Fermilab subcontract and will coordinate and supervise critical current testing Nb3Sn strands and cable fabrication and evaluation.

43 PARTICLE ACCELERATORS↗

Direct Ink Write and Processing of Complex 3D Marine Compatible Structures with Calcium Carbonate Slurries

Ocean acidification heavily impacts marine ecosystems by reducing calcification. Many coral-algae symbiotic relationships are in jeopardy due to the destruction of coral reefs. Here, a ceramic ink compatible with the direct ink write additive manufacturing technique was formulated and used to print marine compatible structures that could grow algae and restore that relationship. A diacrylate polymer was mixed with calcium carbonate, a material that comprises a coral skeleton, to create a slurry with shear thinning properties. Rheology studies were conducted to confirm printing properties and characterize the slurry. Printed parts demonstrated strong control over print features, including size and infill design. Various infill patterns and percentages were attempted to optimize printability and potential algae growth. Thermogravimetric analysis helped determine a logical burnout and sintering procedure to avoid large cracking. This project developed a printable and sinter-able calcium carbonate ceramic slurry for complex marine-compatible structures and algae growth. This research was conducted in the support of the Eco Reef project.

36 MATERIALS SCIENCE↗

Study of dynamic emission spectra from lubricant films in an elastohydrodynamic contact using Fourier transform spectroscopy

Infrared emission spectra were obtained through a diamond window from lubricating fluids in an operating sliding elastohydrodynamic contact and analyzed by comparison with static absorption spectra under similar pressures. Different loads, shear rates and temperatures were used. Most of the spectra exhibited polarization characteristics, indicating directional alignment of the lubricant in the EHD contact. Among the fluids studied were a "traction" fluid, an advanced ester, and their mixtures, a synthetic paraffin, a naphthenic reference fluid (N-1), both neat and containing 1 percent of p-tricresyl phosphate as an anti-wear additive, and a C-ether. Traction properties were found to be nearly proportional to mixture composition for traction fluid and ester mixtures. The anti-wear additive reduced traction and fluid temperature under low loads but increased them under higher loads, giving rise to formation of a friction polymer.

Lauer, J. L.↗

LDEF fiber optic exposure experiment

Ten fiber optic cable samples of different types were exposed in low Earth orbit for over 5.5 years on the Long Duration Exposure Facility (LDEF). Four of the samples were mounted externally, and the remaining six were internal, under approximately .5 gc/sq m of aluminum. The experiment was recovered in January of 1990, and laboratory evaluation of the effects of the exposure has continued since. An increase in loss, presumed to be from radiation darkening, aging effects on polymer materials used in cabling, unique contamination effects on connector terminations, and micrometeoroid impacts were observed on some of the samples. In addition, the dependence of sample loss was measured as a function of temperature before and after the flight. All cable samples were functional, and the best exhibited no measurable change in performance, indicating that conventional fiber optic cables can perform satisfactorily in spacecraft. Experimental results obtained to date will be presented and discussed.

Johnston, Alan R.↗