Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “polymer films”

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 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Deuteration Effects on the Physical and Optoelectronic Properties of Donor–Acceptor Conjugated Polymers

The significant differences in scattering cross sections between deuterium and protium are unique to neutron scattering techniques and have been a long-standing area of interest within the neutron scattering community. Researchers have explored selective deuteration to manipulate scattering contrast in soft matter systems, leading to the widespread use of deuterium labeling in materials development. As deuteration changes the atomic mass, it alters physical properties such as molecular volume, polarizability, and polarity, which in turn may affect noncovalent interactions and crystal ordering. Despite previous studies, there remains a limited understanding of how deuteration impacts donor–acceptor (DA) conjugated polymers. To address this, we synthesized deuterated DPP polymers and systematically investigated the effects of side-chain deuteration on their thermal stability, crystal packing, morphology, and optoelectronic properties. We found that deuteration increased the melting and crystallization temperatures of DPP polymers, although it did not significantly alter their morphology, molecular packing, or charge mobility. These properties were assessed by using atomic force microscopy (AFM), X-ray scattering, and thin-film transistor device measurements, respectively, for DPP polymers. Our work shows that deuterium labeling could be a powerful method for controlling scattering length density, enabling neutrons to study the structure and dynamics of conjugated polymers without impacting their electronic performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Unraveling the Unconventional Order of a High-Mobility Indacenodithiophene-Benzothiadiazole Copolymer

We report a new class of donor–acceptor (D-A) copolymers found to produce high charge carrier mobilities competitive with amorphous silicon (>1 cm 2 V –1 s –1 ) exhibit the puzzling microstructure of substantial local order, however lacking long-range order and crystallinity previously deemed necessary for achieving high mobility. Here, we demonstrate the application of low-dose transmission electron microscopy to image and quantify the nanoscale and mesoscale organization of an archetypal D-A copolymer across areas comparable to electronic devices (≈9 μm 2 ). The local structure is spatially resolved by mapping the backbone (001) spacing reflection, revealing nanocrystallites of aligned polymer chains throughout nearly the entire film. Analysis of the nanoscale structure of its ordered domains suggests significant short- and medium-range order and preferential grain boundary orientations. Moreover, we provide insights into the rich, interconnected mesoscale organization of this new family of D-A copolymers by analysis of the local orientational spatial autocorrelations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Polymer-Based Thermally Stable Chemiresistive Sensor for Real-Time Monitoring of NO 2 Gas Emission

Here, we present a thermally stable, mechanically compliant, and sensitive polymer-based NO 2 gas sensor design. Interconnected nanoscale morphology driven from spinodal decomposition between conjugated polymers tethered with polar side chains and thermally stable matrix polymers offers judicious design of NO 2 -sensitive and thermally tolerant thin films. The resulting chemiresitive sensors exhibit stable NO 2 sensing even at 170 °C over 6 h. Controlling the density of polar side chains along conjugated polymer backbone enables optimal design for coupling high NO 2 sensitivity, selectivity, and thermal stability of polymer sensors. Lastly, thermally stable films are used to implement chemiresistive sensors onto flexible and heat-resistant substrates and demonstrate a reliable gas sensing response even after 500 bending cycles at 170 °C. Such unprecedented sensor performance as well as environmental stability are promising for real-time monitoring of gas emission from vehicles and industrial chemical processes.

47 OTHER INSTRUMENTATION↗
DOE OSTI2023

Mechanical, Morphological, and Charge Transport Properties of NDI Polymers with Variable Built‐in Π‐Conjugation Lengths Probed by Simulation and Experiment

Abstract Mechanically deformable polymeric semiconductors are a key material for fabricating flexible organic thin‐film transistors (FOTFTs)—the building block of electronic circuits and wearable electronic devices. However, for many π‐conjugated polymers achieving mechanical deformability and efficient charge transport remains challenging. Here the effects of polymer backbone bending stiffness and film microstructure on mechanical flexibility and charge transport are investigated via experimental and computational methods for a series of electron‐transporting naphthalene diimide (NDI) polymers having differing extents of π‐conjugation. The results show that replacing increasing amounts of the π‐conjugated comonomer dithienylvinylene (TVT) with the π‐nonconjugated comonomer dithienylethane (TET) in the backbone of the fully π‐conjugated polymeric semiconductor, PNDI‐TVT 100 (yielding polymeric series PNDI‐TVT x , 100 ≥x≥ 0), lowers backbone rigidity, degree of texturing, and π–π stacking interactions between NDI moieties. Importantly, this comonomer substitution increases the mechanical robustness of PNDI‐TVT x while retaining efficient charge transport. Thus, reducing the TVT content of PNDI‐TVT x suppresses film crack formation and dramatically stabilizes the field‐effect electron mobility upon bending (e.g., 2 mm over 2000 bending cycles). This work provides a route to tune π–π stacking in π‐conjugated polymers while simultaneously promoting mechanical flexibility and retaining good carrier mobility in FOTFTs.

Chemistry↗
DOE OSTI2023

Biodegradable High-Molecular-Weight Poly(pentylene adipate- co -terephthalate): Synthesis, Thermo-Mechanical Properties, Microstructures, and Biodegradation

Poly(pentylene adipate-co-terephthalate) (PPAT) is a promising biobased and biodegradable polymer that can replace polyethylene in flexible packaging films where biodegradability is desired. High-molecular-weight (100K–145 KDa) aliphatic–aromatic polyester PPAT was successfully synthesized, and the effects of reaction conditions on molecular weight were reported. PPAT polyesters were characterized for polymer compositions, number-average unit length, thermal transitions, and rheological properties. PPAT compression-molded films were characterized for crystallinity and tensile properties to correlate micro- and macroproperties. PPAT compression-molded films exhibited up to a 76% higher tensile modulus than compression-molded films from poly(butylene adipate-co-terephthalate) (PBAT), making PPAT films potentially comparable with compression-molded films from linear low-density polyethylene (LLDPE). Finally, PPAT is biodegradable in soil and freshwater environments with estimated 90% biodegradation times of 504–580 and 604–845 days, respectively, while PBAT takes 971 days in soil and 395 days in freshwater.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Molecular interactions that drive morphological and mechanical stabilities in organic solar cells

Morphological and mechanical stabilities of organic solar cells (OSCs) are of paramount importance to ensure long-lived devices. However, the fundamental drivers of these stability metrics and their competing relationship have yet to be well defined. Here, in this work, several high-performance polymers and small molecule acceptors (SMAs) are considered to assist in the development of a comprehensive view of the molecular drivers of, and interrelationships between, morphological and mechanical stabilities. We find that the SMAs drive much of the embrittlement and diffusion characteristics in the blend films. However, the heterointeraction of the SMA and polymer, probed through dynamic mechanical analysis, is a key contributing factor to the film toughness. The heterointeraction energy is ideally maximally negative (i.e., repulsive), deviating from the geometric mean of the homointeraction energy. These findings assist in introducing a framework to understand the active layer stability and highlight material properties that lead to morphologically stable and physically robust OSCs.

14 SOLAR ENERGY↗
DOE OSTI2020

Beyond Substrates: Strain Engineering of Ferroelectric Membranes

Strain engineering in perovskite oxides provides for dramatic control over material structure, phase, and properties, but is restricted by the discrete strain states produced by available high-quality substrates. Here, using the ferroelectric BaTiO3, production of precisely strain-engineered, substrate-released nanoscale membranes is demonstrated via an epitaxial lift-off process that allows the high crystalline quality of films grown on substrates to be replicated. In turn, fine structural tuning is achieved using interlayer stress in symmetric trilayer oxide-metal/ferroelectric/oxide-metal structures fabricated from the released membranes. Additionally, in devices integrated on silicon, the interlayer stress provides deterministic control of ordering temperature (from 75 to 425 °C) and releasing the substrate clamping is shown to dramatically impact ferroelectric switching and domain dynamics (including reducing coercive fields to <10 kV cm-1 and improving switching times to <5 ns for a 20 µm diameter capacitor in a 100-nm-thick film). In devices integrated on flexible polymers, enhanced room-temperature dielectric permittivity with large mechanical tunability (a 90% change upon ±0.1% strain application) is demonstrated. This approach paves the way toward the fabrication of ultrafast CMOS-compatible ferroelectric memories and ultrasensitive flexible nanosensor devices, and it may also be leveraged for the stabilization of novel phases and functionalities not achievable via direct epitaxial growth.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Tackling P3HT:Y‐Series Miscibility Through Advanced Processing for Tunable Aggregation

Abstract Polymer and small molecule blend thin films are of strong interest for organic electronics and particularly organic solar cells. The high miscibility in blends of ordinary P3HT and state‐of‐the‐art Y‐series non‐fullerene acceptors (NFAs) suppresses phase separation and aggregation challenging successful charge separation and transport. In a recent work, current‐induced doping (CID) is introduced, a method to precisely control the aggregation of Poly(3‐hexylthiophene) (P3HT) in solution. The highly ordered pre‐aggregation in solution is used here to control the P3HT aggregation in neat films and blends with Y12 (BTP‐4F‐12). This results in a 25‐fold increase in hole mobility in P3HT organic field‐effect transistor (OFET) devices and tunability of the P3HT aggregate quality in the presence of Y12 over large ranges. At the same time, particularly the Y12 long‐range ordering is heavily suppressed by increasing P3HT aggregation. However, solvent vapor annealing (SVA) leads to an extraordinarily high Y12 ordering, changes in the crystal orientation of Y12, and a further improvement of P3HT aggregation. A broad range of different degrees of aggregation of both materials can therefore be obtained in the final thin films solely by changing processing parameters without changing the composition of the material system.

Chemistry↗
DOE OSTI2022

Improved Polypropylene Thermoformability through Polyethylene Layering

Due to its low cost, stiffness, and recyclability, isotactic polypropylene (iPP) is an excellent candidate for packaging applications. However, iPP is notoriously difficult to thermoform due to its low melt strength. The addition of just 10 thin layers of high-molecular-weight, linear low-density polyethylene (LLDPE) into iPP sheets by coextrusion significantly increased extensional viscosity and reduced sag. Both LLDPE and iPP were metallocene-catalyzed with excellent adhesion as measured in our previous work. Here, we performed a series of hot tensile tests and sheet sag measurements to determine the properties of the iPP sheet and the multilayer sheet between 130 and 180 °C. To evaluate the thermoformability of these multilayer sheets, truncated conical cups were positive vacuum formed at different temperatures and heating times, and the crush strength was measured. Cups that released easily from the mold with good shape retention and a crush strength within 80% of the maximum value were used to define a temperature–time thermoformability window. We estimated the maximum stress that occurred during the thermoforming process to be 5 MPa. Layer thicknesses before and after thermoforming were used to estimate an average strain of 0.78. The thin LLDPE layers decreased the yield stress below 5 MPa. This enabled thermoforming at sheet temperatures as low as 150 °C. The immiscible LLDPE interfaces increased extensional viscosity, which decreased sag in the multilayer sheets compared to iPP. This broadened the thermoforming range to temperatures as high as 180 °C and allowed longer heating times. These highly thermoformable, layered sheets may be recycled as iPP since they contain only 8% of LLDPE.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Automated tabletop exfoliation and identification of monolayer graphene flakes

Over the past two decades, graphene has been intensively studied because of its remarkable mechanical, optical, and electronic properties. Initial studies were enabled by manual “Scotch Tape” exfoliation; nearly two decades later, this method is still widely used to obtain chemically pristine flakes of graphene and other 2D van der Waals materials. Unfortunately, the yield of large, pristine flakes with uniform thickness is inconsistent. Thus, significant time and effort are required to exfoliate and locate flakes suitable for fabricating multilayer van der Waals heterostructures. Here, we describe a relatively affordable tabletop device (the “eXfoliator”) that can reproducibly control key parameters and largely automate the exfoliation process. In a typical exfoliation run, the eXfoliator produces 3 or more large (≥ 400 μm 2 ) high-quality graphene monolayer flakes, allowing new users to produce such flakes at a rate comparable to manual exfoliation by an experienced user. Furthermore, we use an automated mapping system and a computer vision algorithm to locate candidate flakes. Our results provide a starting point for future research efforts to identify more precisely which parameters matter for the success of exfoliation and to optimize them.

47 OTHER INSTRUMENTATION↗
DOE OSTI2021

Barrier film constructions and methods of making same

A barrier film including a substrate; a base polymer layer adjacent to the substrate; an oxide layer adjacent to the base polymer layer; a adhesion-modifying layer adjacent to the oxide layer; and a top coat polymer layer adjacent to the adhesion-modifying layer. An optional inorganic layer can be applied over the top coat polymer layer. The inclusion of a adhesion-modifying layer provides for enhanced resistance to moisture and improved peel strength adhesion of the top coat polymer layer to the underlying barrier stack layers.

Spagnola, Joseph C.↗
DOE OSTI2024

Anion exchange membrane and methods of making and using the same

Anion exchange membrane and methods of making and using the same. In one embodiment, the anion exchange membrane may be made by a method that includes a two-step polymerization. In the first step, an α-olefin monomer containing a pendant halide, such as 8-bromo-1-octene, may be polymerized by Ziegler-Natta polymerization to form a first polymer portion, the first polymer portion being a homopolymer. In the second step, the polymerization is charged with a non-functionalized α-olefin monomer, such as ethylene, thereby forming a second polymer portion, the second polymer being a copolymer made up predominantly of the non-functionalized olefin monomer. If desired, a small amount of an α-olefin monomer containing a crosslinking functionality may be included in the first and/or second steps. Following the two-step polymerization, the polymer is fabricated into a thin film. Thereafter, the thin film may be functionalized by replacing the pendant halides with pendant cations.

Strasser, Derek J.↗
DOE OSTI2025

Delineating Confinement Regimes for Nafion Thin Films via Simultaneous QCM-D and Spectroscopic Ellipsometry

Proton-conducting ionomers used in electrodes of electrochemical devices form nanometer-scale films covering metallic catalyst surfaces, wherein they experience confinement and interfacial effects absent in the bulk polymer. This confinement alters the physical properties of the ionomer film, which is postulated to increase the density and is attributed to the transport limitations observed in fuel-cell electrodes. Despite studies showing reduced swelling, no systematic measurement has validated this phenomenon by demonstrating both densification and stiffening as the film gets thinner. Here, this study aims to fill this gap by reporting the humidity-driven changes in swelling, mass uptake, and density of Nafion ionomer films cast at varying thicknesses (10–320 nm) onto a gold-plated sensor. The films were simultaneously probed during humidification using spectroscopic ellipsometry (SE) and a quartz crystal microbalance with dissipation (QCM-D), which allowed for determination of the density and shear stiffness. The effects of confinement were prominently observed below ∼30 nm, with films showing increased density along with decreased swelling and mass uptake during hydration. In addition, the confined films show a negative excess volume upon initial water sorption, implying a larger proportion of absorbed water might bound to ionic groups in accord with notion of localized densification.

Espinet, Kevin B. [University of California, Berke↗
DOE OSTI2025

Full-film dry transfer of MBE-grown van der Waals materials

Abstract Molecular beam epitaxy (MBE) has been used to create high-quality, large-scale two-dimensional van der Waals (2D vdW) materials. However, due to the strong adhesion between the substrate and deposited materials, the peel-off and dry transfer of MBE-grown vdW films onto other substrates has been challenging. This limits the study and use of MBE films for heterogeneous integration including stacked and twisted heterostructures. In this work, we develop a polymer-assisted dry transfer method and successfully perform full-film transfer of various MBE-grown 2D vdW materials including transition metal dichalcogenides, topological insulators and 2D magnets. In particular, we transfer air-sensitive 2D magnets, characterize their magnetic properties, and compare them with as-grown materials. The results show that the transfer technique does not degrade the magnetic properties, with the Curie temperature and hysteresis loops exhibiting similar behaviors after the transfer. Our results enable further development of heterogeneous integration of 2D vdW materials based on MBE growth.

Li, Ziling (ORCID:0000000203537036)↗
DOE OSTI2020

Electron‐Deficient and Quinoid Central Unit Engineering for Unfused Ring‐Based A 1 –D–A 2 –D–A 1 ‐Type Acceptor Enables High Performance Nonfullerene Polymer Solar Cells with High V oc and PCE Simultaneously

Abstract Here, a pair of A 1 –D–A 2 –D–A 1 unfused ring core‐based nonfullerene small molecule acceptors (NF‐SMAs), BO2FIDT‐4Cl and BT2FIDT‐4Cl is synthesized, which possess the same terminals (A 1 ) and indacenodithiophene unit (D), coupling with different fluorinated electron‐deficient central unit (difluorobenzoxadiazole or difluorobenzothiadiazole) (A 2 ). BT2FIDT‐4Cl exhibits a slightly smaller optical bandgap of 1.56 eV, upshifted highest occupied molecular orbital energy levels, much higher electron mobility, and slightly enhanced molecular packing order in neat thin films than that of BO2FIDT‐4Cl . The polymer solar cells (PSCs) based on BT2FIDT‐4Cl:PM7 yield the best power conversion efficiency (PCE) of 12.5% with a V oc of 0.97 V, which is higher than that of BO2FIDT‐4Cl ‐based devices (PCE of 10.4%). The results demonstrate that the subtle modification of A 2 unit would result in lower trap‐assisted recombination, more favorable morphology features, and more balanced electron and hole mobility in the PM7:BT2FIDT‐4Cl blend films. It is worth mentioning that the PCE of 12.5% is the highest value in nonfused ring NF‐SMA‐based binary PSCs with high V oc over 0.90 V. These results suggest that appropriate modulation of the quinoid electron‐deficient central unit is an effective approach to construct highly efficient unfused ring NF‐SMAs to boost PCE and V oc simultaneously.

Zhang, Chao↗