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At least 73 records · Page 4

Dynamic Mechanical Characterization of Thin Film Polymer Nanocomposites

Many new materials are being produced for aerospace applications with the objective of maximizing certain ideal properties without sacrificing others. Polymer composites in various forms and configurations are being developed in an effort to provide lighter weight construction and better thermal and electrical properties and still maintain adequate strength and stability. To this end, thin film polymer nanocomposites, synthesized for the purpose of influencing electrical conductivity using metal oxide particles as filler without incurring losses in mechanical properties, were examined to determine elastic modulus and degree of dispersion of particles. The effects of various metal oxides on these properties will be discussed.

Herring, Helen M.↗

Beyond nothingness in the formation and functional relevance of voids in polymer films

Abstract Voids—the nothingness—broadly exist within nanomaterials and impact properties ranging from catalysis to mechanical response. However, understanding nanovoids is challenging due to lack of imaging methods with the needed penetration depth and spatial resolution. Here, we integrate electron tomography, morphometry, graph theory and coarse-grained molecular dynamics simulation to study the formation of interconnected nanovoids in polymer films and their impacts on permeance and nanomechanical behaviour. Using polyamide membranes for molecular separation as a representative system, three-dimensional electron tomography at nanometre resolution reveals nanovoid formation from coalescence of oligomers, supported by coarse-grained molecular dynamics simulations. Void analysis provides otherwise inaccessible inputs for accurate fittings of methanol permeance for polyamide membranes. Three-dimensional structural graphs accounting for the tortuous nanovoids within, measure higher apparent moduli with polyamide membranes of higher graph rigidity. Our study elucidates the significance of nanovoids beyond the nothingness, impacting the synthesis‒morphology‒function relationships of complex nanomaterials.

36 MATERIALS SCIENCE↗

Additive-Induced Morphology Change of Polymer Film Enables Enhanced Charge Mobility and Faster Organic Electrochemical Transistor Switching

Conjugated polymers (CPs) play an important role in organic electrochemical transistors (OECTs) for bioelectronics and related applications, where they serve as channel materials. Currently, most successful polymers for CPs are re-engineered from traditional CPs by replacing hydrophobic alkyl side chains with hydrophilic ethylene glycol or ionic groups. Frustratingly, the enhanced ion transport often compromises the charge mobility of the original CP. In this work, we present an additive-mediated method to construct a modified poly(3-hexylthiophene) (P3HT) film to enable efficient ion migration. The additive is designed with a cleavable diazo group that releases nitrogen and 2-methoxyethanol, a volatile compound, to alter the P3HT film morphology. OECTs based on the film exhibit improved response times. Interestingly, the process also enhances the crystallinity of P3HT, leading to higher hole mobility compared with pristine P3HT. This study proposes an in situ strategy to achieve the functionality of the OMIEC via morphological regulation, offering a promising route to simultaneously enhance both ion accessibility and charge mobility.

Organic polymers↗

Fiber-Optic Sensor Would Monitor Growth of Polymer Film

A proposed optoelectronic sensor system would measure the increase in thickness of a film of parylene (a thermoplastic polymer made from para-xylene) during growth of the film in a vapor deposition process. By enabling real-time monitoring of film thickness, the system would make it possible to identify process conditions favorable for growth and to tailor the final thickness of the film with greater precision than is now possible. The heart of the sensor would be a pair of fiber-optic Fabry-Perot interferometers, depicted schematically in the figure. (In principle, a single such interferometer would suffice. The proposal calls for the use of two interferometers for protective redundancy and increased accuracy.) Each interferometer would include a light source, a fiber-optic coupler, and photodetectors in a control box outside the deposition chamber. A single-mode optical fiber for each interferometer would run from inside the control box to a fused-silica faceplate in a sensor head. The sensory tips of the optical fibers would be polished flush with the free surface of the faceplate. In preparation for use, the sensor head would be mounted with a hermetic seal in a feed-through port in the deposition chamber, such that free face of the faceplate and the sensory tips of the optical fibers would be exposed to the deposition environment. During operation, light would travel along each optical fiber from the control box to the sensor head. A small portion of the light would be reflected toward the control box from the end face of each fiber. Once growth of the parylene film started, a small portion of the light would also be reflected toward the control box from the outer surface of the film. In the control box, the two reflected portions of the light beam would interfere in one of the photodetectors. The difference between the phases of the interfering reflected portions of the light beam would vary in proportion to the increasing thickness of the film and the known index of refraction of the film, causing the photodetector reading to vary in proportion to a known sinusoidal function of film thickness. Electronic means of monitoring this variation and the corresponding variation in phase and thickness are well established in the art of interferometry. Hence, by tracking the cumulative change in phase difference from the beginning of deposition, one could track the growing thickness of the film to within a small fraction of a wavelength of light.

Beamesderfer, Michael↗

Monitoring Photodeposition of Polymer Films from Diacetylene Monomer Solutions Using In Situ Real-Time Spectroscopic Ellipsometry

Photodeposition of thin polymer (PDAMNA) films from diacetylene monomer (DAMNA) solutions onto gold coated silica substrates with UV light was studied using the technique of in-situ real time spectroscopic ellipsometry. The dielectric function of PDAMNA was determined; and the thickness of the growing PDAMNA films over a 4 hour time interval was determined using a linear regression fit of the experimental data to a homogeneous four phase optical model. It was found that stirring the solution dramatically lowers the rate of film deposition, suggesting that convection can affect the attachment kinetics of the film to the substrate. Lastly, the morphology of the PDAMNA films was examined using non-contact mode atomic force microscopy.

Hui, Du↗

Polymer film exhibits thermal and radiation stability

Aromatic/heterocyclic polymers /Pyrrones/ have the ability to absorb large quantities of photolytic, thermal and radiolytic energies while retaining their useful properties. They are prepared from the room temperature reaction of tetraamines and tetraacids.

Bell, V. L., Jr.↗

Post-Flight Analysis of Selected Fluorocarbon and Other Thin Film Polymer Specimens Flown on MISSE-5

Twenty thin film specimens were flown on M1SSE-5 as a cooperative effort between several organizations. This presentation will report results of initial inspections and post-flight measurements of the optical properties and recession of these materials due to the approx.13 month exposure period on the exterior of the International Space Station. These specimens were located on the "anti-solar" side of the MISSE-5 container and received a low number of Equivalent Sun Hours of solar UV exposure. Profilometry and/or ATF measurements will be conducted to determine thickness changes and atomic oxygen-induced recession rates Six of the specimens were covered with thin Kapton films, 0.1 and 0.3 mil in thickness. The 0.1 mil Kapton was almost completely eroded, suggesting that the atomic oxygen fluence is <8 x 10(exp 19) atoms/sq cm, similar to levels experienced during Space Shuttle materials experiments in the 1980's and 1990's. A comparison of results from MISSE-5 and Space Shuttle experiments will be included for those materials common to both the short and long-term exposures.

DeGroh, Kim↗

Resonant Tender X-ray Diffraction for Disclosing the Molecular Packing of Paracrystalline Conjugated Polymer Films

The performance of optoelectronic devices based on conjugated polymers is critically dependent upon molecular packing; however, the paracrystalline nature of these materials limits the amount of information that can be extracted from conventional X-ray diffraction. Resonant diffraction (also known as anomalous diffraction) occurs when the X-ray energy used coincides with an X-ray absorption edge in one of the constituent elements in the sample. The rapid changes in diffraction intensity that occur as the X-ray energy is varied across an absorption edge provide additional information that is lost in a conventional nonresonant experiment. Taking advantage of the fact that many conjugated polymers contain sulfur as heteroatoms, here we reveal pronounced resonant diffraction effects at the sulfur K-edge with a particular focus on the well-studied electron transporting polymer poly([N,N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)), P(NDI2OD-T2). The observed behavior is found to be consistent with the theory of resonant diffraction, and by simulating the energy-dependent peak intensity based on proposed crystal structures for P(NDI2OD-T2), we find that resonant diffraction can discriminate between different crystalline packing structures. The utilization of resonant diffraction opens up a new way to unlock important microstructural information about conjugated polymers for which only a handful of diffraction peaks are typically available.

36 MATERIALS SCIENCE↗

The Role of Side Chains and Hydration on Mixed Charge Transport in n ‐Type Polymer Films

Abstract Introducing ethylene glycol (EG) side chains to a conjugated polymer backbone is a well‐established synthetic strategy for designing organic mixed ion‐electron conductors (OMIECs). However, the impact that film swelling has on mixed conduction properties has yet to be scoped, particularly for electron‐transporting (n‐type) OMIECs. Here, the authors investigate the effect of the length of branched EG chains on mixed charge transport ofn‐type OMIECs based on a naphthalene‐1,4,5,8‐tetracarboxylic‐diimide‐bithiophene backbone. Atomic force microscopy (AFM), grazing‐incidence wide‐angle X‐ray scattering (GIWAXS), and scanning tunneling microscopy (STM) are used to establish the similarities between the common‐backbone films in dry conditions. Electrochemical quartz crystal microbalance with dissipation monitoring (EQCM‐D) and in situ GIWAXS measurements reveal stark changes in film swelling properties and microstructure during electrochemical doping, depending on the side chain length. It is found that even in the loss of the crystallite content upon contact with the aqueous electrolyte, the films can effectively transport charges and that it is rather the high water content that harms the electronic interconnectivity within the OMIEC films. These results highlight the importance of controlling water uptake in the films to impede charge transport inn‐type electrochemical devices.

Chemistry↗

Tribological properties of polymer films and solid bodies in a vacuum environment

The tribological properties of ten different polymer based materials were evaluated in a vacuum environment to determine their suitability for possible lubrication applications in a space environment, such as might be encountered on the proposed space station. A pin-on-disk tribometer was used and the polymer materials were evaluated either as solid body disks or as films applied to 440C HT stainless steel disks. A 440C HT stainless steel hemispherically tipped pin was slid against the polymer materials. For comparison, similar tests were conducted in a controlled air atmosphere of 50 percent relative humidity air. In most instances, the polymer materials lubricated much better under vacuum conditions than in air. Thus, several of the materials show promise as lubricants for vacuum applications. Friction coefficients of 0.05 or less and polymer material wear rates of up to 2 orders of magnitude less than in air were obtained. One material showed considerable promise as a traction drive material. Relatively high friction coefficients (0.36 to 0.52) and reasonably low wear rates were obtained in vacuum.

Fusaro, Robert L.↗

Tribological properties of polymer films and solid bodies in a vacuum environment

The tribological properties of ten different polymer based materials were evaluated in a vacuum environment to determine their suitability for possible lubrication applications in a space environment, such as might be encountered on the proposed Space Station. A pin-on-disk tribometer was used and the polymer materials were evaluated either as solid body disks or as films applied to 440C HT stainless steel disks. A 440C HT stainless steel hemispherically tipped pin was slid against the polymer materials. For comparison, similar tests were conducted in a controlled air atmosphere of 50 percent relative humidity air. In most instances, the polymer materials lubricated much better under vacuum conditions than in air. Thus, several of the materials show promise as lubricants for vacuum applications. Friction coefficients of 0.05 or less and polymer material wear rates of up to 2 orders of magnitude less than in air were obtained. One material showed considerable promise as a traction drive material. Relative high friction coefficients (0.36 to 0.52) and reasonably low wear rates were obtained in vacuum.

Fusaro, Robert L.↗

Charge carrier transport in thin conjugated polymer films: influence of morphology and polymer/substrate interactions

The performance of conjugated polymer (CP)-based electronic devices relies on optimal charge carrier mobilities, which are determined by monomeric architecture, degree of polymerization, chain conformation, and the nano- and mesoscale morphologies. With regard to the latter, we discuss two effects that have received limited attention in the literature, yet important for device performance optimization: (1) the role of morphological disorder and of CP/substrate interactions on the in-plane and out-of-plane carrier transport in CPs; (2) the impact of morphological disorder on charge transfer at the CP/substrate interface. The emergence of film thickness-dependent carrier mobilities, varying over two orders of magnitude within a length scale of 200 nm, and band-bending phenomena, extending tens of nanometers within the CP, are associated with these effects. These findings suggest areas for further research in order to enable widespread applications of next-generation CP-based devices.

36 MATERIALS SCIENCE↗

Co-polymer films for sensors

Embodiments include a sensor comprising a co-polymer, the co-polymer comprising a first monomer and a second monomer. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is polystyrene and the second monomer is poly-2-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium benzylamine chloride. Other embodiments are described and claimed.

Ryan, Margaret A.↗

Co-polymer Films for Sensors

Embodiments include a sensor comprising a co-polymer, the co-polymer comprising a first monomer and a second monomer. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is polystyrene and the second monomer is poly-2-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium benzylamine chloride. Other embodiments are described and claimed.

Ryan, Margaret A.↗

Reducing dielectric loss and enhancing electrical insulation for multilayer polymer films by nanoconfined ion transport under high poling electric fields

High temperature polar polymers have demonstrated potential for good thermal stability and high dielectric constant at the same time. However, polarization of contaminated impurity ions in polar polymers, even at the ppm level, can significantly increase the dielectric loss at high temperature and low frequencies. One effective strategy to mitigate this problem is to multilayer them with a high temperature nonpolar dielectric polymer to confine impurity ion transport at the nanometer scale. In this study, confined ion transport in high temperature polycarbonate (HTPC)/poly(vinylidene fluoride) (PVDF) multilayer films under high AC electric fields was studied using a direct analytical simulation method. Different from the ion transport under low fields, the ion diffusion model failed to describe the ion transport under high electric fields. An exponential ion distribution profile, which was observed for the DC poling situation, was employed to implement the direct analytical simulation. Confined impurity ion transport under high AC fields was quantitatively understood. As the AC field increased, the mobile ion concentration decreased whereas the diffusion coefficient increased. The decrease of mobile ion concentration was explained by the blockage of impurity ions by the HTPC layers. This knowledge helped in the determination of optimal conditions to polarize impurity ions from the PVDF layers into the HTPC layers. After cooling below the glass transition temperature of HTPC, polarized impurity ions were locked inside the HTPC layers. As a result, increased discharge efficiency and enhanced electrical insulation (i.e., increased dielectric breakdown strength) were achieved for the polarized multilayer films.

36 MATERIALS SCIENCE↗

Comparison of effects from gamma, e-beam and X-ray radiation on multilayer polymer films used in biopharmaceutical devices by chemometric treatment of spectroscopic data

The present study investigated the effects of gamma-ray, electron beam, and X-ray radiation on polymers in EVA/EVOH/EVA multilayer films. Spectroscopic methods, including FTIR and UV–Vis, were employed in conjunction with chemometric treatments such as PCA, SIMPLISMA treatments, and PLS models. The feasibility of dose prediction on multilayer film, given a known dose, is attainable across various irradiation technologies. Both gamma ray and X-ray exhibit comparable effects on the multilayer film, and it is feasible to anticipate the dose released on the film by utilizing UV–Vis spectra or infrared spectra for gamma ray or X-ray of a predetermined dose.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Polaron absorption in aligned conjugated polymer films: breakdown of adiabatic treatments and going beyond the conventional mid-gap state model

This study provides the first experimental polarized intermolecular and intramolecular optical absorption components of field-induced polarons in regioregular poly(3-hexylthiophene-2,5-diyl), rr-P3HT, a polymer semiconductor. Highly aligned rr-P3HT thin films were prepared by a high temperature shear-alignment process that orients polymer backbones along the shearing direction. rr-P3HT in-plane molecular orientation was measured by electron diffraction, and out-of-plane orientation was measured through series of synchrotron X-ray scattering techniques. Then, with molecular orientation quantified, polarized charge modulation spectroscopy was used to probe mid-IR polaron absorption in the ℏω = 0.075 — 0.75 eV range and unambiguously assign intermolecular and intramolecular optical absorption components of hole polarons in rr-P3HT. This data represents the first experimental quantification of these polarized components and allowed long-standing theoretical predictions to be compared to experimental results. The experimental data is discrepant with predictions of polaron absorption based on an adiabatic framework that works under the Born–Oppenheimer approximation, but the data is entirely consistent with a more recent nonadiabatic treatment of absorption based on a modified Holstein Hamiltonian. This nonadiabatic treatment was used to show that both intermolecular and intramolecular polaron coherence break down at length scales significantly smaller than estimated structural coherence in either direction. Importantly, this strongly suggests that polaron delocalization is fundamentally limited by energetic disorder in rr-P3HT.

36 MATERIALS SCIENCE↗