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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.

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At least 1,081 records · Page 60
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Impact of Cation Insertion on Semiconducting Polymer Thin Films toward Electrochemical Energy Conversion

Semiconducting polymers are being explored for electrochemical and photoelectrochemical energy transformation and storage applications. For these applications, it is critical to understand how ion insertion from the electrolyte into polymer electrodes modulates the polymer electronic structure and electron doping levels. Here, this study explores electrochemical cation insertion in the n-type conjugated redox polymer P90, composed of alternating naphthalene diimide (NDI) acceptor and bithiophene (T2) donor units, where the NDI units are functionalized with heptaethylene glycol (HEG, 90%) and 2-octyl dodecyl (OD, 10%) side chains. By combining in situ techniques (UV-vis absorption and Raman spectroscopies with electrochemistry), structural analysis using ex situ grazing-incidence wide-angle X-ray scattering (GIWAXS), and density functional theory (DFT) calculations, we reveal that dications enable negative polaron and bipolaron formation in the P90 at less reducing potentials while supporting more bipolaron formation than the monocations; moreover, larger dications with smaller hydrated radii increase the maximum P90 electron doping level. We also determine that the monocations lead to more thermodynamically stabilized polarons compared with the dications. These findings highlight the critical role of cation identity in tuning electrochemical charging, charge stabilization, and electronic structure of n-type conjugated redox polymers, providing guidance on the rational design of polymer-based (photo)electrochemical applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Effects of Residual Solvent Molecules Facilitating the Infiltration Synthesis of ZnO in a Nonreactive Polymer

Infiltration synthesis, the atomic-layer-deposition-based organic–inorganic material hybridization technique that enables unique hybrid composites with improved material properties and inorganic nanostructures replicated from polymer templates, is shown to be driven by the binding reaction between reactive chemical groups of polymers and perfusing vapor-phase material precursors. Here in this paper, we discover that residual solvent molecules from polymer processing can react with infiltrating material precursors to enable the infiltration synthesis of metal oxides in a nonreactive polymer. The systematic study, which combines in situ quartz crystal microgravimetry, polarization-modulated infrared reflection–absorption spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy, shows that the ZnO infiltration synthesis in nominally nonreactive SU-8 polymer is mediated by residual processing solvent cyclopentanone, a cyclic ketone whose Lewis-basic terminal carbonyl group can react with the infiltrating Lewis-acidic Zn precursor diethylzinc (DEZ). In addition, we find favorable roles of residual epoxy rings in the SU-8 film in further assisting the infiltration synthesis of ZnO. Lastly, the discovered rationale not only improves the understanding of infiltration synthesis mechanism, but also potentially expands its application to more diverse polymer systems for the generation of unique functional organic–inorganic hybrids and inorganic nanostructures.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Tuning the Cross-Linker Crystallinity of a Stretchable Polymer Semiconductor

The cross-linking of conjugated polymers has been shown to be an effective strategy to improve its elastic properties to give deformable semiconductors for plastic electronics. Although there have been extensive studies of the structural requirements of the polymer host for good film ductility, no work to date has focused on the relevance of the structural design or chemistry of these cross-linker additives. In this study, urethane groups and tertiary carbon atoms are inserted into the alkyl backbone of perfluorophenyl azide-based cross-linkers to investigate the importance of cross-linker crystallinity with respect to polymer morphology and hence mechanical and electrical properties. Linear cross-linkers with hydrogen bonding from urethane groups readily phase separate and recrystallize in the polymer network to form cross-linked domains that obstruct the strain distribution of the polymer film. Branch cross-linkers with tertiary carbon on the other hand form an evenly cross-linked network in the polymer blend stemming from excellent miscibility and show a 4-fold increase in fracture strain. Furthermore, a stable hole mobility of 0.2 cm 2 V –1 s –1 is achieved up to ε = 100%, and a stable hole mobility of 0.1 cm 2 V –1 s –1 after 2000 cycles of ε = 25% on fully stretchable organic field-effect transistors.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Atomistic Scale Analysis of the Carbonization Process for C/H/O/N-Based Polymers with the ReaxFF Reactive Force Field

During the carbonization process of raw polymer precursors, graphitic structures can evolve. The presence of these graphitic structures affects mechanical properties of the carbonized carbon fibers. To gain a better understanding of the chemistry behind the evolution of these structures, we performed atomistic-scale simulations using the ReaxFF reactive force field. Three different polymers were considered as a precursor: idealized ladder PAN (polyacrylonitrile), a proposed oxidized PAN, and poly(p-phenylene- 2,6-benzobisoxazole). We determined the underlying molecular details of polymer conversion into a carbon fiber structure. Because these are C/H/O/ N-based polymers, we first developed an improved force field for C/H/O/N chemistry based on the density functional theory data with a particular focus on N2 formation kinetics and its interactions with polymer-associated radicals formed during the carbonization process. Then, using this improved force field, we performed atomistic-scale simulations of the initial stage of the carbonization process for the considered polymers. On the basis of our simulation data, the molecular pathways for the formation of low-molecular-weight gas species and all-carbon ring formation were determined. We also examined the possible alignment of the developed all-carbon 6-membered ring clusters, which is crucial for the further graphitic structure evolution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Origins of Electrostriction in Poly(vinylidene fluoride)-Based Ferroelectric Polymers

Although electrostriction is ubiquitous for dielectric polymers, giant electrostriction has not been observed until relaxor ferroelectric (RFE) poly(vinylidene fluoride) (PVDF)-based polymers are achieved. However, the exact origin for giant electrostriction in these polymers has not been fully understood. By studying the electrostriction in the uniaxially stretched films of a ferroelectric poly(VDF-co-trifluoroethylene) [P(VDF-TrFE)] random copolymer and an RFE poly(VDF-co-TrFE-co-chlorotrifluoroethylene) [P(VDF-TrFE-CTFE)] random terpolymer in this work, we confirmed that ferroelectric switching with large hysteresis, such as in the case of P(VDF-TrFE), was not genuine electrostriction. By decreasing large ferroelectric domains to the nanometer scale (i.e., 2–3 nm), such as in the case of the P(VDF-TrFE-CTFE) terpolymer, electrostriction with low hysteresis could be achieved. Here, two origins of the large electrostriction in these polymers were identified. The first was the mechano-electrostriction due to the poling field-induced conformation transformation of oriented polymer chains. The second was the electric repulsion of electrically aligned nanodomains. These effects could occur in both crystals and the oriented amorphous fraction, which links between the nanocrystals and the isotropic amorphous fraction. When the poling field was relatively low (e.g., <40 MV/m), the mechano-electrostriction was the major contribution and the electric repulsion effect was a minor contribution to electrostriction. Meanwhile, a strong temperature dependence of the low-field electrostriction coefficient was observed. Finally, we found an empirical inverse relationship between the electrostriction coefficient and the product of Young’s modulus and dielectric constant. The knowledge obtained from this study provides an insightful understanding of the electrostriction mechanism in PVDF-based electroactive polymers, which will find potential applications in sensors and actuators for wearable electronics and soft robotics.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Universal Relationship between Conductivity and Solvation-Site Connectivity in Ether-Based Polymer Electrolytes

In this paper, we perform a joint experimental and computational study of ion transport properties in a systematic set of linear polyethers synthesized via acyclic diene metathesis (ADMET) polymerization. We measure ionic conductivity, σ, and glass transition temperature, T g , in mixtures of polymer and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt. While T g is known to be an important factor in the ionic conductivity of polymer electrolytes, recent work indicates that the number and proximity of lithium ion solvation sites in the polymer also play an important role, but this effect has yet to be systematically investigated. Here, adding aliphatic linkers to a poly(ethylene oxide) (PEO) backbone lowers T g and dilutes the polar groups; both factors influence ionic conductivity. To isolate these effects, we introduce a two-step normalization scheme. In the first step, Vogel–Tammann–Fulcher (VTF) fits are used to calculate a temperature-dependent reduced conductivity, σ r (T), which is defined as the conductivity of the electrolyte at a fixed value of T – T g . In the second step, we compute a nondimensional parameter f exp , defined as the ratio of the reduced molar conductivity of the electrolyte of interest to that of a reference polymer (PEO) at a fixed salt concentration. We find that f exp depends only on oxygen mole fraction, x 0 , and is to a good approximation independent of temperature and salt concentration. Molecular dynamics simulations are performed on neat polymers to quantify the occurrences of motifs that are similar to those obtained in the vicinity of isolated lithium ions. Finally, we show that f exp is a linear function of the simulation-derived metric of connectivity between solvation sites. From the relationship between σ r and f exp we derive a universal equation that can be used to predict the conductivity of ether-based polymer electrolytes at any salt concentration and temperature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Microstructural Evolution of the Thin Films of a Donor–Acceptor Semiconducting Polymer Deposited by Meniscus-Guided Coating

Crucial to the development and refinement of organic electronics is a fundamental understanding of how deposition processes affect the active material’s resulting microstructure in the thin film. Meniscus-guided coating (MGC) methods are attractive because of their amenability to high-throughput, industrially relevant continuous processes like roll-to-roll deposition, but the mechanism of solid film formation has not been elucidated and is valuable for the precise control of thin-film morphology and thus ultimate device performance. Here, in this work, we investigate the microstructural evolution of thin films of a diketopyrrolopyrrole–terthiophene donor–acceptor polymer semiconductor using both in situ and ex situ X-ray diffraction methods. On the basis of a comparison of disorder between the film bulk and the top surface and a depth profiling of the out-of-plane orientation of crystallites, we find that faster coating speeds introduce more disorder into the resulting films because the stochastic nucleation of disordered crystallites at the meniscus air–liquid interface becomes more dominant than substrate-mediated nucleation. Our results suggest that there exist three separate deposition regimes—namely the shear-dominate, disorder-dominate, and Landau–Levich–Derjaguin regimes—revealed by observing both polymer alignment via dry film thickness and optical dichroism, a property sensitive to the flow and shear fields. At low coating speeds, the shear strain imparted upon the solution directly induces polymer alignment, causing an increase in dichroism as a function of coating speed. When solvent evaporation becomes too rapid as coating speeds increase, a decrease in the dichroic ratio is observed before the classical Landau–Levich–Derjaguin regime occurs at the highest coating speeds, resulting in isotropic films. The preservation of out-of-plane crystalline texture throughout the thickness of the films is seen only for lower coating speeds, and a study of different deposition temperatures similarly indicates that the lower overall solvent evaporation is conducive to this process. Increased paracrystalline disorder (i.e., peak broadening) is observed by grazing-incidence wide-angle X-ray diffraction at the top interface of the dry films and at higher coating speeds. Together, these results indicate that more rapid solvent evaporation at higher coating speeds causes increased disorder, which can cause the nucleation of misaligned crystallites, affect the dichroic ratio, and may frustrate the alignment of polymer molecules in the amorphous regions of the film. Finally, because the polymer studied and the deposition technique used are representative models, these results are likely general for aggregating, semicrystalline donor–acceptor polymers deposited with MGC.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Electronic and Morphological Studies of Conjugated Polymers Incorporating a Disk-Shaped Polycyclic Aromatic Hydrocarbon Unit

As more research findings have shown the correlation between ordering in organic semiconductor thin films and device performance, it is becoming more essential to exercise control of the ordering through structural tuning. Many recent studies have focused on the influence of side chain engineering on polymer packing orientation in thin films. However, the impact of the size and conformation of aromatic surfaces on thin film ordering has not been investigated in great detail. Here we introduce a disk-shaped polycyclic aromatic hydrocarbon building block with a large π surface, namely, thienoazacoronenes (TACs), as a donor monomer for conjugated polymers. Here, a series of medium bandgap conjugated polymers have been synthesized by copolymerizing TAC with electron donating monomers of varying size. The incorporation of the TAC unit in such semiconducting polymers allows a systematic investigation, both experimentally and theoretically, of the relationships between polymer conformation, electronic structure, thin film morphology, and charge transport properties. Field effect transistors based on these polymers have shown good hole mobilities and photoresponses, proving that TAC is a promising building block for high performance optoelectronic materials.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Dithieno[3,2-c:3′,2′‑ h ][2,6]naphthyridine-4,9(5H,10H)-dione-Based Conjugated Polymers for High Stable n‑Type Organic Electrochemical Transistors

Amide/imide-based conjugated polymers have been utilized as n-type OECT materials and have demonstrated promising device performance. However, their performance remains insufficient in terms of both efficiency and stability, which limits their practical applications. The development of conjugated polymers based on amide and imide groups represents a promising approach to address this issue. Here, in this study, we introduced dithieno­[3,2-c:3′,2′-h]­[2,6]­naphthyridine-4,9­(5H,10H)-dione (TVTDA) into the design of the OECT materials for the first time. By copolymerizing it with (E)-2,2′-(ethene-1,2-diyl)­bis­(thiophene-3-carbonitrile), we prepared two polymers, TVTDA-2CNTVT-ST and TVTDA-2CNTVT-BR, which contain linear or branched ethylene glycol side chains, respectively. OECT devices based on these polymers demonstrate n-type charge transport characteristics, achieving promising μC* values of 7.17 and 26.5 F cm –1 V –1 s –1 for TVTDA-2CNTVT-ST and TVTDA-2CNTVT-BR, respectively. The higher electron mobility and μC* of TVTDA-2CNTVT-BR can be attributed to its mixed edge-on and face-on stacking mode, larger crystalline coherence length, and larger domain size in the thin film. To our delight, the OECT devices based on both polymers exhibit good operational stability after operating in an aqueous solution for 2000 s, with current retention rates exceeding 93%, representing the high level among the OECT devices based on amide/imide-conjugated polymers. Our study demonstrates that the TVTDA unit holds great potential for constructing high-performance n-type OECT materials.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Systematic computational and experimental investigation of lithium-ion transport mechanisms in polyester-based polymer electrolytes

Understanding the mechanisms of lithium-ion transport in polymers is crucial for the design of polymer electrolytes. We combine modular synthesis, electrochemical characterization, and molecular simulation to investigate lithium-ion transport in a new family of polyester-based polymers and in poly(ethylene oxide) (PEO). Theoretical predictions of glass-transition temperatures and ionic conductivities in the polymers agree well with experimental measurements. Interestingly, both the experiments and simulations indicate that the ionic conductivity of PEO, relative to the polyesters, is far higher than would be expected from its relative glass-transition temperature. The simulations reveal that diffusion of the lithium cations in the polyesters proceeds via a different mechanism than in PEO, and analysis of the distribution of available cation solvation sites in the various polymers provides a novel and intuitive way to explain the experimentally observed ionic conductivities. This work provides a platform for the evaluation and prediction of ionic conductivities in polymer electrolyte materials.

25 ENERGY STORAGE↗
DOE OSTI2019

Brush-Like Polymers and Entanglements: From Linear Chains to Filaments

Dynamics of melts and solutions of high molecular weight polymers and biopolymers is controlled by topological constraints (entanglements) imposing a sliding chain motion along an effective confining tube. For linear chains, the tube size is determined by universal packing number P e , the number of polymer strands within a confining tube that is required for chains to entangle. In this work, we show that in melts of brush-like (graft) polymers, consisting of linear chain backbones with grafted side chains, P e is not a universal number and depends on the molecular architecture. Specifically, we use coarse-grained molecular dynamics simulations to demonstrate that the packing number is a nonmonotonic function of the ratio R nsc /R ng of the size of the side chains R nsc to that of the backbone spacer between neighboring grafting points R ng . This parameter characterizes the degree of mutual interpenetration between side chains of the same macromolecule. We demonstrate that P e of brush-like polymers first decreases with increasing side chain grafting density in the dilute side chain regime (R nsc < R ng ), then begins to increase in the regime of overlapping side chains (R nsc > R ng ), approaching the value for linear chains in the limit of densely grafted side chains. This dependence of the packing number reflects a crossover from chain-like entanglements in systems with loosely grafted side chains (comb-like polymers) to entanglements between flexible filaments (bottlebrush-like polymers). Our simulation results are in agreement with the experimental data for the dependence of a plateau modulus on the molecular architecture of graft poly(n-butyl acrylates) and poly(norbornene)-graft-poly(lactide) melts.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Conformational Order in Aggregates of Conjugated Polymers

With the abundant variety and increasing chemical complexity of conjugated poly-friers proliferating the field of organic semiconductors, it has become increasingly important to correlate the polymer molecular structure with its mesoscale conformational and morphological attributes. For instance, it is unknown which combinations of chemical moieties and periodicities predictably produce mesoscale ordering. Interestingly) not all ordered morphologies result in efficient devices. In this work we have parametrized accurate classical force-fields and used these to compute the conformational and aggregation characteristics of single strands of common conjugated polymers. Molecular dynamics trajectories are shown to reproduce experimentally observed polymeric ordering, concluding that efficient organic photovoltaic devices span a range of polymer conformational classes, and suggesting that the solution-phase morphologies have far-reaching effects. Encouragingly, these simulations indicate that despite the wide-range of conformational classes present in successful devices, local molecular ordering, and not long-range crystallinity, appears to be the necessary requirement for efficient devices. Finally, we examine what makes a "good" solvent for conjugated polymers, concluding that dispersive pi-electron solvent-polymer interactions, and not the electrostatic potential of the backbone interacting with the solvent, are what primarily determine a polymer's solubility in a particular solvent, and consequently its morphological characteristics.

Jackson, Nicholas E.↗
DOE OSTI2020

Single-Crystal Polycationic Polymers Obtained by Single-Crystal-to-Single-Crystal Photopolymerization

The efficient preparation of single-crystalline ionic polymers and fundamental understanding of their structure–property relationships at the molecular level remains a challenge in chemistry and materials science. Herein, we observe the single-crystal structure of a highly ordered polycationic polymer (polyelectrolyte) and its proton conductivity. The polyelectrolyte single crystals can be prepared on a gram-scale in quantitative yield, by taking advantage of an ultraviolet/sunlight-induced topochemical polymerization, from a tricationic monomer—a self-complementary building block possessing a preorganized conformation. A single-crystal-to-single-crystal photopolymerization was revealed unambiguously by in situ single-crystal X-ray diffraction analysis, which was also employed to follow the progression of molecular structure from the monomer, to a partially polymerized intermediate, and, finally, to the polymer itself. Collinear polymer chains are held together tightly by multiple Coulombic interactions involving counterions to form two-dimensional lamellar sheets (1 nm in height) with sub-nanometer pores (5 Å). The polymer is extremely stable under 254 nm light irradiation and high temperature (above 500 K). The extraordinary mechanical strength and environmental stability—in combination with its impressive proton conductivity (~3 × 10 –4 S cm –1 )—endow the polymer with potential applications as a robust proton-conducting material. By marrying supramolecular chemistry with macromolecular science, the outcome represents a major step toward the controlled synthesis of single-crystalline polyelectrolyte materials with perfect tacticity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Controlled ionic conductivity via tapered block polymer electrolytes

We present the design of novel solid electrolytes using tapered block polymers (TBPs). In this work, we synthesize a series of TBPs via atom transfer radical polymerization (ATRP) consisting of rigid polystyrene and ion-conducting poly(oligo-oxyethylene methacrylate) segments and explore the role of tapered interfaces on ion transport. Previous studies on TBPs have shown that manipulating the taper composition in block polymers can reduce the unfavorable polymer–polymer interactions between blocks, enabling the design for highly-processable (lower order–disorder transition temperature) polymer electrolytes. Herein, we demonstrate that the taper profile and taper volume fraction significantly impact the glass transition temperatures (Tgs) in block polymer electrolytes, thus affecting the ionic conductivity. Additionally, we find that the normal-tapered materials with ≈60 vol% tapering exhibit remarkable improvements in ionic conductivity (increase ≈190% at 20 °C and increase ≈90% at 80 °C) in comparison to their non-tapered counterparts. Overall, our TBPs, with controllable interfacial interactions, present an exciting opportunity for the fabrication of cost-effective, highly-efficient, and stable energy storage membranes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Dynamic assembly of polymer nanotube networks via kinesin powered microtubule filaments

In this study, we describe for the first time how biological nanomotors may be used to actively self-assemble mesoscale networks composed of diblock copolymer nanotubes. The collective force generated by multiple kinesin nanomotors acting on a microtubule filament is large enough to overcome the energy barrier required to extract nanotubes from polymer vesicles comprised of poly(ethylene oxide-b-butadiene) in spite of the higher force requirements relative to extracting nanotubes from lipid vesicles. Nevertheless, large-scale polymer networks were dynamically assembled by the motors. These networks displayed enhanced robustness, persisting more than 24 h post-assembly (compared to 4–5 h for corresponding lipid networks). The transport of materials in and on the polymer membranes differs substantially from the transport on analogous lipid networks. Specifically, our data suggest that polymer mobility in nanotubular structures is considerably different from planar or 3D structures, and is stunted by 1D confinement of the polymer subunits. Moreover, quantum dots adsorbed onto polymer nanotubes are completely immobile, which is related to this 1D confinement effect and is in stark contrast to the highly fluid transport observed on lipid tubules.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2016

Assembly of polythiophenes on responsive polymer microgels for the highly selective detection of ammonia gas

For this study, a class of smart composite materials based on the assembly of conjugated polymers on responsive polymer microgels has been prepared. We have chosen poly(3-((2-(2-methoxyethoxy)ethoxy)methyl)-thiophene) as the model conjugated polymer and an ammonia-responsive microgel of phenoxazinium-functionalized poly(N-isopropylacrylamide-co-propargyl acrylate) as the model template. Under this design, the composite materials can combine the electrical conductivity of the conjugated polymers and the ammonia recognisability of the ammonia-responsive polymer microgels; the cooperation of these properties allows the reversible control of electrical conductivity by ammonia gas. Those composite materials can not only adapt to ammonia gas, but also convert changes in the concentration of ammonia into conductance, allowing the electrical detection of ammonia gas with high selectivity. This makes the composite materials different from the conductive polymer platforms reported previously, which may also respond to non-ammonia gases and the response induced by non-ammonia gases is close to that induced by ammonia gas. Using these composite materials as sensing materials for the electrical detection of ammonia gas, the detection limit can reach as low as 1.1 ppb. Finally, these features enable their use for the electrical detection of ammonia in breath.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Structure-induced switching of interpolymer adhesion at a solid–polymer melt interface

In this paper, we report a link between the interfacial structure and adhesive property of homopolymer chains physically adsorbed (i.e., via physisorption) onto solids. Polyethylene oxide (PEO) was used as a model and two different chain conformations of the adsorbed polymer were created on silicon substrates via the well-established Guiselin's approach: “flattened chains” which lie flat on the solid and are densely packed, and “loosely adsorbed polymer chains” which form bridges jointing up nearby empty sites on the solid surface and cover the flattened chains. We investigated the adhesion properties of the two different adsorbed chains using a custom-built adhesion testing device. Bilayers of a thick PEO overlayer on top of the flattened chains or loosely adsorbed chains were subjected to the adhesion test. The results revealed that the flattened chains do not show any adhesion even with the chemically identical free polymer on top, while the loosely adsorbed chains exhibit adhesion. Neutron reflectivity experiments corroborated that the difference in the interfacial adhesion is not attributed to the interfacial brodening at the free polymer–adsorbed polymer interface. Instead, coarse-grained molecular dynamics simulation results suggest that the tail parts of the loosely adsorbed chains act as “connector molecules”, bridging the free chains and substrate surface and improving the interfacial adhesion. Finally, these findings not only shed light on the structure–property relationship at the interface, but also provide a novel approach for developing sticking/anti-sticking technologies through precise control of the interfacial polymer nanostructures.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Enhanced resistance to decay of imprinted nanopatterns in thin films by bare nanoparticles compared to polymer-grafted nanoparticles

We extend a previous study on the influence of nanoparticles on the decay of nanoimprinted polymer film patterns to compare the effects of “bare” silica (SiO 2 ) nanoparticles and SiO 2 nanoparticles with grafted polymer layers having the same chemical composition as the polymer matrix. This method involves nanoimprinting substrate-supported polymer films using a pattern replicated from a digital versatile disc (DVD), and then annealing the patterned polymer nanocomposite films at elevated temperatures to follow the decay of the topographic surface pattern with time by atomic force microscopy imaging after quenching. We quantified the relaxation of the pattern height (“slumping”) and determined the relaxation time τ for this pattern decay process as a function of nanoparticle filler type and concentration to determine how nanoparticle additives influence relative film stability. Attractive interactions between the bare nanoparticles and the polymer matrix significantly enhance the thermal resilience of the nanopatterns to decay, compared to those of the particle brushes, wherein the particle core interactions are screened from the matrix via the brush layer. A novel aspect of this method is that it readily lends itself to in situ film relaxation measurements in a manufacturing context. We observe that the relaxation time of the pattern relaxation exhibits entropy–enthalpy compensation in the free energy parameters governing the pattern relaxation process as a function of temperature, irrespective of the NP system used, consistent with our previous experimental and computational studies.

36 MATERIALS SCIENCE↗