Spatial-temporal light modulation by a liquid crystal-polymer photoconductor structure with conjugate bonds

NASA Astrophysics Data System (ADS)

Sliusar', A. V.; Myl'Nikov, V. S.

1991-11-01

A method is proposed for the spatial-temporal modulation of light by a polymer photoconductor-liquid crystal structure using conjugate-bond organic polymers as photosensitive elements. The preparation of such structures and their modulation characteristics are described. It is shown that the spectral absorption and photosensitivity characteristics of the structures are largely determined by the heat treament of the polymer film. Sensitivity limits of a modulator using a polyacrylonitrile film are 5 x 10 exp -6 J/sq cm and 5 x 10 exp -4 W/sq cm for the write and read light, respectively.

Release of DNA from polyelectrolyte multilayers fabricated using 'charge-shifting' cationic polymers: tunable temporal control and sequential, multi-agent release.

PubMed

Sun, Bin; Lynn, David M

2010-11-20

We report an approach to the design of multilayered polyelectrolyte thin films (or 'polyelectrolyte multilayers', PEMs) that can be used to provide tunable control over the release of plasmid DNA (or multiple different DNA constructs) from film-coated surfaces. Our approach is based upon methods for the layer-by-layer assembly of DNA-containing thin films, and exploits the properties of a new class of cationic 'charge-shifting' polymers (amine functionalized polymers that undergo gradual changes in net charge upon side chain ester hydrolysis) to provide control over the rates at which these films erode and release DNA. We synthesized two 'charge-shifting' polymers (polymers 1 and 2) containing different side chain structures by ring-opening reactions of poly(2-alkenyl azlactone)s with two different tertiary amine functionalized alcohols (3-dimethylamino-1-propanol and 2-dimethylaminoethanol, respectively). Subsequent characterization revealed large changes in the rates of side chain ester hydrolysis for these two polymers; whereas the half-life for the hydrolysis of the esters in polymer 1 was ~200 days, the half-life for polymer 2 was ~6 days. We demonstrate that these large differences in side chain hydrolysis make possible the design of PEMs that erode and promote the surface-mediated release of DNA either rapidly (e.g., over ~3 days for films fabricated using polymer 2) or slowly (e.g., over ~1 month for films fabricated using polymer 1). We demonstrate further that it is possible to design films with release profiles that are intermediate to these two extremes by fabricating films using solutions containing different mixtures of these two polymers. This approach can thus expand the usefulness of these two polymers and achieve a broader range of DNA release profiles without the need to synthesize polymers with new structures or properties. Finally, we demonstrate that polymers 1 and 2 can be used to fabricate multilayered films with hierarchical structures that promote the sequential release of two different DNA constructs with separate and distinct release profiles (e.g., the release of a first construct over a period of ~3 days, followed by the sustained release of a second for a period of ~70 days). With further development, this approach could contribute to the design of functional thin films and surface coatings that provide sophisticated control over the timing and the order of the release of two or more DNA constructs (or other agents) of interest in a range of biomedical contexts. Copyright © 2010 Elsevier B.V. All rights reserved.

Precursors for the polymer-assisted deposition of films

DOEpatents

McCleskey, Thomas M.; Burrell, Anthony K.; Jia, Quanxi; Lin, Yuan

2013-09-10

A polymer assisted deposition process for deposition of metal oxide films is presented. The process includes solutions of one or more metal precursor and soluble polymers having binding properties for the one or more metal precursor. After a coating operation, the resultant coating is heated at high temperatures to yield metal oxide films. Such films can be epitaxial in structure and can be of optical quality. The process can be organic solvent-free.

Electrical memory characteristics of a nondoped pi-conjugated polymer bearing carbazole moieties.

PubMed

Park, Samdae; Lee, Taek Joon; Kim, Dong Min; Kim, Jin Chul; Kim, Kyungtae; Kwon, Wonsang; Ko, Yong-Gi; Choi, Heungyeal; Chang, Taihyun; Ree, Moonhor

2010-08-19

Poly[bis(9H-carbazole-9-ethyl)dipropargylmalonate] (PCzDPM) is a novel pi-conjugated polymer bearing carbazole moieties that has been synthesized by polymerization of bis(9H-carbazole-9-ethyl)dipropargylmalonate with the aid of molybdenum chloride solution as the catalyst. This polymer is thermally stable up to 255 degrees C under a nitrogen atmosphere and 230 degrees C in air ambient; its glass-transition temperature is 147 or 128 degrees C, depending on the polymer chain conformation (helical or planar structure). The charge-transport characteristics of PCzDPM in nanometer-scaled thin films were studied as a function of temperature and film thickness. PCzDPM films with a thickness of 15-30 nm were found to exhibit very stable dynamic random access memory (DRAM) characteristics without polarity. Furthermore, the polymer films retain DRAM characteristics up to 180 degrees C. The ON-state current is dominated by Ohmic conduction, and the OFF-state current appears to undergo a transition from Ohmic to space-charge-limited conduction with a shallow-trap distribution. The ON/OFF switching of the devices is mainly governed by filament formation. The filament formation mechanism for the switching process is supported by the metallic properties of the PCzDPM film, which result in the temperature dependence of the ON-state current. In addition, the structure of this pi-conjugated polymer was found to vary with its thermal history; this change in structure can affect filament formation in the polymer film.

Linking Precursor Alterations to Nanoscale Structure and Optical Transparency in Polymer Assisted Fast-Rate Dip-Coating of Vanadium Oxide Thin Films

PubMed Central

Glynn, Colm; Creedon, Donal; Geaney, Hugh; Armstrong, Eileen; Collins, Timothy; Morris, Michael A.; Dwyer, Colm O’

2015-01-01

Solution processed metal oxide thin films are important for modern optoelectronic devices ranging from thin film transistors to photovoltaics and for functional optical coatings. Solution processed techniques such as dip-coating, allow thin films to be rapidly deposited over a large range of surfaces including curved, flexible or plastic substrates without extensive processing of comparative vapour or physical deposition methods. To increase the effectiveness and versatility of dip-coated thin films, alterations to commonly used precursors can be made that facilitate controlled thin film deposition. The effects of polymer assisted deposition and changes in solvent-alkoxide dilution on the morphology, structure, optoelectronic properties and crystallinity of vanadium pentoxide thin films was studied using a dip-coating method using a substrate withdrawal speed within the fast-rate draining regime. The formation of sub-100 nm thin films could be achieved rapidly from dilute alkoxide based precursor solutions with high optical transmission in the visible, linked to the phase and film structure. The effects of the polymer addition was shown to change the crystallized vanadium pentoxide thin films from a granular surface structure to a polycrystalline structure composed of a high density of smaller in-plane grains, resulting in a uniform surface morphology with lower thickness and roughness. PMID:26123117

Smart Polymer Surfaces

DTIC Science & Technology

2009-02-27

films: Inhibition of dewetting in thin polymer films”, Carroll, Gregory T., Sojka, Melissa E., Lei, Xuegong, Turro, Nicholas J., Koberstein, Jeffrey T...at Sandia was that the polymer films, designed to have specific interactions with particular warfare agents, would dewet the surface of a surface...crosslinking or dewetting . Patterned dewetting constitutes a completely new way of generating micro thin film structures that might be useful in

Near-field optical technique applied for investigation of the characteristics of polymer fiber and waveguide structures.

PubMed

Ming, Hai; Tang, Lin; Sun, Xiaohong; Zhang, Jiangying; Wang, Pei; Lu, Yonghua; Bai, Ming; Guo, Yang; Xie, Aifang; Zhang, Zebo

2004-01-01

This article summarizes the near-field optical technique applied for investigating the characteristics of polymer fiber and waveguide structures. The near-field optical technique is used to analyze multimode interference structures of fiber. The localized fluctuation of the transmission caused by fractal cluster is carried out in Nd3+- and Eu3+-doped polymer fiber and film by means of a scanning near-field optical microscopy. The near-field optical spectrum of Nd3+-doped polymer fiber is investigated. The topography and near-field intensity images of Azo-polymer liquid crystal film for waveguide are obtained simultaneously.

Investigation of the Effect of the Tortuous Pore Structure on Water Diffusion through a Polymer Film Using Lattice Boltzmann Simulations.

PubMed

Gebäck, Tobias; Marucci, Mariagrazia; Boissier, Catherine; Arnehed, Johan; Heintz, Alexei

2015-04-23

Understanding how the pore structure influences the mass transport through a porous material is important in several applications, not the least in the design of polymer film coatings intended to control drug release. In this study, a polymer film made of ethyl cellulose and hydroxypropyl cellulose was investigated. The 3D structure of the films was first experimentally characterized using confocal laser scanning microscopy data and then mathematically reconstructed for the whole film thickness. Lattice Boltzmann simulations were performed to compute the effective diffusion coefficient of water in the film and the results were compared to experimental data. The local porosities and pore sizes were also analyzed to determine how the properties of the internal film structure affect the water effective diffusion coefficient. The results show that the top part of the film has lower porosity, lower pore size, and lower connectivity, which results in a much lower effective diffusion coefficient in this part, largely determining the diffusion rate through the entire film. Furthermore, the local effective diffusion coefficients were not proportional to the local film porosity, indicating that the results cannot be explained by a single tortuosity factor. In summary, the proposed methodology of combining microscopy data, mass transport simulations, and pore space analysis can give valuable insights on how the film structure affects the mass transport through the film.

Radiation damage in polymer films from grazing-incidence X-ray scattering measurements

DOE PAGES

Vaselabadi, Saeed Ahmadi; Shakarisaz, David; Ruchhoeft, Paul; ...

2016-02-16

Grazing-incidence X-ray scattering (GIXS) is widely used to analyze the crystallinity and nanoscale structure in thin polymer films. However, ionizing radiation will generate free radicals that initiate cross-linking and/or chain scission, and structural damage will impact the ordering kinetics, thermodynamics, and crystallinity in many polymers. We report a simple methodology to screen for beam damage that is based on lithographic principles: films are exposed to patterns of x-ray radiation, and changes in polymer structure are revealed by immersing the film in a solvent that dissolves the shortest chains. The experiments are implemented with high throughput using the standard beam linemore » instrumentation and a typical GIXS configuration. The extent of damage (at a fixed radiation dose) depends on a range of intrinsic material properties and experimental variables, including the polymer chemistry and molecular weight, exposure environment, film thickness, and angle of incidence. The solubility switch for common polymers is detected within 10-60 sec at ambient temperature, and we verified that this first indication of damage corresponds with the onset of network formation in glassy polystyrene and a loss of crystallinity in polyalkylthiophenes. Therefore, grazing-incidence x-ray patterning offers an efficient approach to determine the appropriate data acquisition times for any GIXS experiment.« less

Fabrication of photonic band gap materials

DOEpatents

Constant, Kristen; Subramania, Ganapathi S.; Biswas, Rana; Ho, Kai-Ming

2002-01-15

A method for forming a periodic dielectric structure exhibiting photonic band gap effects includes forming a slurry of a nano-crystalline ceramic dielectric or semiconductor material and monodisperse polymer microspheres, depositing a film of the slurry on a substrate, drying the film, and calcining the film to remove the polymer microspheres therefrom. The film may be cold-pressed after drying and prior to calcining. The ceramic dielectric or semiconductor material may be titania, and the polymer microspheres may be polystyrene microspheres.

Directed Self-Assembly in "Breath Figure" Templating of Melamine-Based Amphiphilic Copolymers: Effect of Hydrophilic End-Chain on Honeycomb Film Formation and Wetting.

PubMed

Yin, Hongyao; Feng, Yujun; Billon, Laurent

2018-01-09

Amphiphilic copolymers are widely used in the fabrication of hierarchically honeycomb-structured films through a "breath figure" (BF) process because the hydrophilic block plays a key role in stabilising water templating. However, the hydrophilic monomers reported are mainly confined to acrylic acid and its derivatives, which largely limits understanding of the formation of BF arrays and the introduction of additional functions on porous films. The relationship between polymer composition, film microstructure and surface properties are also less documented. Herein, a novel melamine-based hydrophilic moiety, N-[3-({3-[(4,6-bis{[3-(dimethylamino)propyl]amino}-1,3,5-triazin-2yl)amino]propyl}(methyl)amino)propyl]methacrylamide (ANME), was incorporated into polystyrene (PS) chains by combining atom-transfer radical polymerisation and post-modification to afford three well-defined end-functionalised PS-PANME derivatives. These polymers were used to fabricate honeycomb films through the BF technique. Both inner and outer microstructures of the films were characterised by optical microscopy, AFM and SEM. Polymer hydrophilicity is enhanced upon increasing the PANME content, which results in variation of the film microstructure and porosity, and provokes a transition from Cassie-Baxter to Wenzel behaviour. Furthermore, the surface wettability of as-prepared honeycomb films and corresponding pillared films is mainly governed by film morphology, rather than by the properties of the polymers. Knowledge of the relationships between polymer composition and film structure, as well as surface wettability, is beneficial to design and prepare hierarchically porous films with desirable structures and properties. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel Effects of Compressed CO 2 Molecules on Structural Ordering and Charge Transport in Conjugated Poly(3-hexylthiophene) Thin Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, Naisheng; Sendogdular, Levent; Sen, Mani

We report the effects of compressed CO 2 molecules as a novel plasticization agent for poly(3- hexylthiophene) (P3HT) conjugated polymer thin films. In-situ neutron reflectivity experiment demonstrated the excess sorption of CO 2 molecules in the P3HT thin films (about 40 nm in thickness) at low pressure (P = 8.2 MPa) under the isothermal condition of T = 36 °C, which is far below the polymer bulk melting point. The results evidenced that these CO 2 molecules accelerated the crystallization process of the polymer on the basis of ex-situ grazing incidence Xray diffraction measurements after drying the films via rapidmore » depressurization to atmospheric pressure: not only the out-of-plane lamellar ordering of the backbone chains but also intra-plane π-π stacking of the side chains were significantly improved, when compared to those in the control P3HT films subjected to conventional thermal annealing (at T = 170 °C). Electrical measurements elucidated that the CO 2-annealed P3HT thin films exhibited enhanced charge carrier mobility along with decreased background charge carrier concentration and trap density compared to those in the thermally annealed counterpart. This is attributed to the CO 2-induced increase in polymer chain mobility that can drive the detrapping of molecular oxygen and healing of conformational defects in the polymer thin film. Given the universality of the excess sorption of CO 2regardless of the type of polymers, the present findings suggest that the CO 2 annealing near the critical point can be useful as a robust processing strategy for improving structural and electrical characteristics of other semiconducting conjugated polymers and related systems such as polymer: fullerene bulk heterojunction films.tion films.« less

Novel Effects of Compressed CO 2 Molecules on Structural Ordering and Charge Transport in Conjugated Poly(3-hexylthiophene) Thin Films

DOE PAGES

Jiang, Naisheng; Sendogdular, Levent; Sen, Mani; ...

2016-10-06

We report the effects of compressed CO 2 molecules as a novel plasticization agent for poly(3- hexylthiophene) (P3HT) conjugated polymer thin films. In-situ neutron reflectivity experiment demonstrated the excess sorption of CO 2 molecules in the P3HT thin films (about 40 nm in thickness) at low pressure (P = 8.2 MPa) under the isothermal condition of T = 36 °C, which is far below the polymer bulk melting point. The results evidenced that these CO 2 molecules accelerated the crystallization process of the polymer on the basis of ex-situ grazing incidence Xray diffraction measurements after drying the films via rapidmore » depressurization to atmospheric pressure: not only the out-of-plane lamellar ordering of the backbone chains but also intra-plane π-π stacking of the side chains were significantly improved, when compared to those in the control P3HT films subjected to conventional thermal annealing (at T = 170 °C). Electrical measurements elucidated that the CO 2-annealed P3HT thin films exhibited enhanced charge carrier mobility along with decreased background charge carrier concentration and trap density compared to those in the thermally annealed counterpart. This is attributed to the CO 2-induced increase in polymer chain mobility that can drive the detrapping of molecular oxygen and healing of conformational defects in the polymer thin film. Given the universality of the excess sorption of CO 2regardless of the type of polymers, the present findings suggest that the CO 2 annealing near the critical point can be useful as a robust processing strategy for improving structural and electrical characteristics of other semiconducting conjugated polymers and related systems such as polymer: fullerene bulk heterojunction films.tion films.« less

Methods and Materials for Selective Modification of Photopatterned Polymer Films.

DTIC Science & Technology

1999-06-28

reactivity templates (see below) formed by patterned irradiation of polymer films. In particular, the invention describes binding materials and processes ...image of the attached functional group) or that region of the polymer film left unexposed and unchanged during the aforementioned patterning process ...invention are accomplished by the structures and processes hereinafter 15 described. An aspect of the present invention is a process for modifying a

Electron irradiation effects on partially fluorinated polymer films: Structure-property relationships

NASA Astrophysics Data System (ADS)

Nasef, Mohamed Mahmoud; Dahlan, Khairul Zaman M.

2003-04-01

The effects of electron beam irradiation on two partially fluorinated polymer films i.e. poly(vinylidene fluoride) (PVDF) and poly(ethylene-tetrafluoroethylene) copolymer (ETFE) are studied at doses ranging from 100 to 1200 kGy in air at room temperature. Chemical structure, thermal and mechanical properties of irradiated films are investigated. FTIR show that both PVDF and ETFE films undergo similar changes in their chemical structures including the formation of carbonyl groups and double bonding. The changes in melting and crystallisation temperatures ( Tm and Tc) in both irradiated films are functions of irradiation dose and reflect the disorder in the chemical structure caused by the competition between crosslinking and chain scission. The heat of melting (Δ Hm) and the degree of crystallinity ( Xc) of PVDF films show no significant changes with the dose increase, whereas those of ETFE films are reduced rapidly after the first 100 kGy. The tensile strength of PVDF films is improved by irradiation compared to its rapid deterioration in ETFE films, which stemmed from the degradation prompted by the presence of radiation sensitive tetrafluoroethylene (TFE) comonomer units. The elongation at break of both films drops gradually with the dose increase indicating the formation of predominant crosslinked structures at high doses. However, the response of each polymer to crosslinking and main chain scission at various irradiation doses varies from PVDF to ETFE films.

High Precision Metal Thin Film Liftoff Technique

NASA Technical Reports Server (NTRS)

Brown, Ari D. (Inventor); Patel, Amil A. (Inventor)

2015-01-01

A metal film liftoff process includes applying a polymer layer onto a silicon substrate, applying a germanium layer over the polymer layer to create a bilayer lift off mask, applying a patterned photoresist layer over the germanium layer, removing an exposed portion of the germanium layer, removing the photoresist layer and a portion of the polymer layer to expose a portion of the substrate and create an overhanging structure of the germanium layer, depositing a metal film over the exposed portion of the substrate and the germanium layer, and removing the polymer and germanium layers along with the overlaying metal film.

Characterizing the local optoelectronic performance of organic solar cells with scanning-probe microscopy

NASA Astrophysics Data System (ADS)

Coffey, David C.

2007-12-01

Conjugated polymers, small molecules, and colloidal semiconductor nanocrystals are promising materials for use in low-cost, thin-film solar cells. The photovoltaic performance of these materials, however, is highly dependent on film structure, and directly correlating local film structures with device performance remains challenging. This dissertation describes several techniques we have developed to probe and control the local optoelectronic properties of organic semiconducting films. First, with an aim of rapidly fabricating photovoltaic films with varying morphology, we demonstrate that Dip-Pen Nanolithography (DPN) can be used to control nanoscale phase separation with sub-150 nm lateral resolution in polymer films that are 20--80 nm thick. This control is based on writing monolayer chemical templates that nucleate phase separation, and we use this technique to study heterogeneous nucleation in thin films. Second, we use time-resolved electrostatic force microscopy (trEFM) to measure photoexcited charge in polymer films with a resolution of 100 nm and 100 mus. We show that such data can predict the external quantum efficiencies of polymer photodiodes, and can thus link device performance with local optoelectronic properties. When applied to the study of blended polyfluorene films, we show that domain centers can buildup charge faster then domain interfaces, which indicates that polymer/polymer blend devices should be modeled as having impure donor/acceptor domains. Third, we use photoconductive atomic force microscopy (pcAFM) to map local photocurrents with 20 nm-resolution in polymer/fullerene solar cells- achieving an order of magnitude better resolution than previous techniques. We present photocurrent maps under short-circuit conditions (zero applied bias), as well as under various applied voltages. We find significant variations in the short-circuit current between regions that appear identical in AFM topography. These variations occur from one domain to another, as well as on larger length scales incorporating multiple domains. Our results suggest that organic solar cells can be significantly improved with better donor/acceptor structuring.

Demonstrating the feasibility of monitoring the molecular-level structures of moving polymer/silane interfaces during silane diffusion using SFG.

PubMed

Chen, Chunyan; Wang, Jie; Loch, Cheryl L; Ahn, Dongchan; Chen, Zhan

2004-02-04

In this paper, the feasibility of monitoring molecular structures at a moving polymer/liquid interface by sum frequency generation (SFG) vibrational spectroscopy has been demonstrated. N-(2-Aminoethyl)-3-aminopropyltrimethoxysilane (AATM, NH2(CH2)2NH(CH2)3Si(OCH3)3) has been brought into contact with a deuterated poly(methyl methacrylate) (d-PMMA) film, and the interfacial silane structure has been monitored using SFG. Upon initial contact, the SFG spectra can be detected, but as time progresses, the spectral intensity changes and finally disappears. Additional experiments indicate that these silane molecules can diffuse into the polymer film and the detected SFG signals are actually from the moving polymer/silane interface. Our results show that the molecular order of the polymer/silane interface exists during the entire diffusion process and is lost when the silane molecules traverse through the thickness of the d-PMMA film. The loss of the SFG signal is due to the formation of a new disordered substrate/silane interface, which contributes no detectable SFG signal. The kinetics of the diffusion of the silane into the polymer have been deduced from the time-dependent SFG signals detected from the AATM molecules as they diffuse through polymer films of different thickness.

Strong thin membrane structure. [solar sails

NASA Technical Reports Server (NTRS)

Frazer, R. E. (Inventor)

1979-01-01

A continuous process is described for producing strong lightweight structures for use as solar sails for spacecraft propulsion by radiation pressure. A thin reflective coating, such as aluminum, is applied to a rotating cylinder. A nylon mesh, applied over the aluminum coating, is then coated with a polymerizing material such as a para-xylylene monomer gas to polymerize as a film bound to the mesh and the aluminum. An emissivity increasing material such as chromium or silicon monoxide is applied to the polymer film to disperse such material colloidally into the growing polymer film, or to the final polymer film. The resulting membrane structure is then removed from the cylinder. Alternately, the membrane structure can be formed by etching a substrate in the form of an organic film such as a polymide, or a metal foil, to remove material from the substrate and reduce its thickness. A thin reflective coating (aluminum) is applied on one side of the substrate, and an emissivity increasing coating is applied on the reverse side of the substrate.

Role of Near Substrate and Bulk Polymer Morphology on Out-of-Plane Space-Charge Limited Hole Mobility.

PubMed

Turner, Johnathan; Gadisa, Abay

2016-12-07

Charge transport is a central issue in all types of organic electronic devices. In organic films, charge transport is crucially limited by film microstructure and the nature of the substrate/organic interface interactions. In this report, we discuss the influence of active layer thickness on space-charge limited hole transport in pristine polymer and polymer/fullerene bulk heterojunction thin films (∼15-300 nm) in a diode structure. According to the results, the out-of-plane hole mobility in pristine polymers is sensitive to the degree of polymer chain aggregation. Blending the polymers with a fullerene molecule does not change the trend of hole mobility if the polymer tends to make an amorphous structure. However, employing an aggregating polymer in a bulk heterojunction blend gives rise to a marked difference in charge carrier transport behavior compared to the pristine polymer and this difference is sensitive to active layer thickness. In aggregating polymer films, the thickness-dependent interchain interaction was found to have direct impact on hole mobility. The thickness-dependent mobility trend was found to correspond well with the trend of fill factors of corresponding bulk heterojunction solar cells. This investigation has a vital implication for material design and the development of efficient organic electronic devices, including solar cells and light-emitting diodes.

Design of Polymers with Semiconductor, NLO and Structural Properties.

DTIC Science & Technology

1991-04-22

polymer thin films. + 14 KV Needle electrod Polymer layer ITO electrode Substrate Heater and temperature control unit The second harmonic coefficients of...the solubily and processability through utilization of derivitization and precursor routes we have been able to form the first optical quality films...ethylene spacer, and therefore 14 possesses a great degree of solubility in organic solvents, necessary for the fabrication of optical quality thin films

ITO-MgF2 Film Development for PowerSphere Polymer Surface Protection

NASA Technical Reports Server (NTRS)

Hambourger, Paul D.; Kerslake, Thomas W.; Waters, Deborah L.

2004-01-01

Multi-kilogram class microsatellites with a PowerSphere electric power system are attractive for fulfilling a variety of potential NASA missions. However, PowerSphere polymer surfaces must be coated with a film that has suitable electrical sheet resistivity for electrostatic discharge control, be resistant to atomic oxygen attack, be transparent to ultraviolet light for composite structure curing and resist ultraviolet light induced darkening for efficient photovoltaic cell operation. In addition, the film must be tolerant of polymer layer folding associated with launch stowage of PowerSphere inflatable structures. An excellent film material candidate to meet these requirements is co-sputtered, indium oxide (In2O3) - tin oxide (SnO2), known as 'ITO', and magnesium fluoride (MgF2). While basic ITO-MgF2 film properties have been the subject of research over the last decade, further research is required in the areas of film durability for space-inflatable applications and precise film property control for large scale commercial production. In this paper, the authors present film durability results for a folded polymer substrate and film resistance to vacuum UV darkening. The authors discuss methods and results in the area of film sheet resistivity measurement and active control, particularly dual-channel, plasma emission line measurement of ITO and MgF2 plasma sources. ITO-MgF2 film polymer coupon preparation is described as well as film deposition equipment, procedures and film characterization. Durability testing methods are also described. The pre- and post-test condition of the films is assessed microscopically and electrically. Results show that an approx. 500A ITO-18vol% MgF2 film is a promising candidate to protect PowerSphere polymer surfaces for Earth orbit missions. Preliminary data also indicate that in situ film measurement methods are promising for active film resistivity control in future large scale production. Future film research plans are also discussed.

Development of biodegradable metaloxide/polymer nanocomposite films based on poly-ε-caprolactone and terephthalic acid.

PubMed

Varaprasad, Kokkarachedu; Pariguana, Manuel; Raghavendra, Gownolla Malegowd; Jayaramudu, Tippabattini; Sadiku, Emmanuel Rotimi

2017-01-01

The present investigation describes the development of metal-oxide polymer nanocomposite films from biodegradable poly-ε-caprolactone, disposed poly(ethylene terephthalate) oil bottles monomer and zinc oxide-copper oxide nanoparticles. The terephthalic acid and zinc oxide-copper oxide nanoparticles were synthesized by using a temperature-dependent precipitation technique and double precipitation method, respectively. The terephthalic acid synthesized was confirmed by FTIR analysis and furthermore, it was characterized by thermal analysis. The as-prepared CuO-ZnO nanoparticles structure was confirmed by XRD analysis and its morphology was analyzed by SEM/EDS and TEM. Furthermore, the metal-oxide polymer nanocomposite films have excellent mechanical properties, with tensile strength and modulus better than pure films. The metal-oxide polymer nanocomposite films that were successfully developed show a relatively brighter colour when compared to CuO film. These new metal-oxide polymer nanocomposite films can replace many non-degradable plastics. The new metal-oxide polymer nanocomposite films developed are envisaged to be suitable for use in industrial and domestic packaging applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Ultrathin Au film on polymer surface for surface plasmon polariton waveguide application

NASA Astrophysics Data System (ADS)

Liu, Tong; Ji, Lanting; He, Guobing; Sun, Xiaoqiang; Wang, Fei; Zhang, Daming

2017-11-01

Formation of laterally continuous ultrathin gold films on polymer substrates is a technological challenge. In this work, the vacuum thermal evaporation method is adopted to form continuous Au films in the thickness range of 7-17 nm on polymers of Poly(methyl-methacrylate-glycidly-methacrylate) and SU-8 film surface without using the adhesion or metallic seeding layers. Absorption spectrum, scanning electron microscope and atomic force microscope images are used to characterize the Au film thickness, roughness and optical loss. The result shows that molecular-scale structure, surface energy and electronegativity have impacts on the Au film morphology on polymers. Wet chemical etching is used to fabricate 7-nm thick Au stripes embedded in polymer claddings. These long-range surface plasmon polariton waveguides demonstrate the favorable morphological configurations and cross-sectional states. Through the end-fire excitation method, propagation losses of 6-μm wide Au stripes are compared to theoretical values and analyzed from practical film status. The smooth, patternable gold films on polymer provide potential applications to plasmonic waveguides, biosensing, metamaterials and optical antennas.

Fabrication of multilayered conductive polymer structures via selective visible light photopolymerization

NASA Astrophysics Data System (ADS)

Cullen, Andrew T.; Price, Aaron D.

2017-04-01

Electropolymerization of pyrrole is commonly employed to fabricate intrinsically conductive polymer films that exhibit desirable electromechanical properties. Due to their monolithic nature, electroactive polypyrrole films produced via this process are typically limited to simple linear or bending actuation modes, which has hindered their application in complex actuation tasks. This initiative aims to develop the specialized fabrication methods and polymer formulations required to realize three-dimensional conductive polymer structures capable of more elaborate actuation modes. Our group has previously reported the application of the digital light processing additive manufacturing process for the fabrication of three-dimensional conductive polymer structures using ultraviolet radiation. In this investigation, we further expand upon this initial work and present an improved polymer formulation designed for digital light processing additive manufacturing using visible light. This technology enables the design of novel electroactive polymer sensors and actuators with enhanced capabilities and brings us one step closer to realizing more advanced electroactive polymer enabled devices.

Investigations on the Mechanical Properties of Conducting Polymer Coating-Substrate Structures and Their Influencing Factors

PubMed Central

Wang, Xi-Shu; Tang, Hua-Ping; Li, Xu-Dong; Hua, Xin

2009-01-01

This review covers recent advances and work on the microstructure features, mechanical properties and cracking processes of conducting polymer film/coating- substrate structures under different testing conditions. An attempt is made to characterize and quantify the relationships between mechanical properties and microstructure features. In addition, the film cracking mechanism on the micro scale and some influencing factors that play a significant role in the service of the film-substrate structure are presented. These investigations cover the conducting polymer film/coating nucleation process, microstructure-fracture characterization, translation of brittle-ductile fractures, and cracking processes near the largest inherent macromolecule defects under thermal-mechanical loadings, and were carried out using in situ scanning electron microscopy (SEM) observations, as a novel method for evaluation of interface strength and critical failure stress. PMID:20054470

An Unconventional Approach to Photomobile Composite Polymer Films.

PubMed

Castagna, Riccardo; Nucara, Luca; Simoni, Francesco; Greci, Lucedio; Rippa, Massimo; Petti, Lucia; Lucchetta, Daniele E

2017-04-01

Photomobile polymer (Pmp) films are fabricated by using a cheap and fast process. The working mechanism of the Pmp-film motion under illumination is explained. Details concerning the film structure and formation are given. Two related applications regarding light-induced caterpillar-miming motion and photocontrolled electrical switches are proposed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study of multilayer polymer materials after ionization treatment

NASA Astrophysics Data System (ADS)

Tarasyuk, V. T.; Semkina, A. A.; Solovyeva, V. I.; Fedotova, D. D.; Strokova, N. E.; Malenko, D. M.; Baranov, O. V.; Bakumenko, A. V.; Puchkov, S. N.; Prokopenko, A. V.

2017-12-01

Electron-beam technologies of food products processing involves the use of modern packaging materials in form of polymer films of different composition. The objective of the research is to study the impact of accelerated electrons on the structure of the polymeric packaging materials used for storage of agricultural products. It was investigated radiation exposure on film material PE/PA (80/20) with a thickness of 80 mkm. This film used for storage of vegetables and fruits and has the necessary indicators for gas and vapor permeability. Electron beam treatment of the films was performed on a compact radiation sterilization installation with local bio-protection with electron energy of 5 MeV. A polymer films were irradiated with doses from 1 to 10 kGy. Changing the structure of the film composition was monitored by IR spectrometry. As a result of irradiation by accelerated electrons with doses up to 18 kGy is established that the polymer film is modification of the polymeric material in the form of a partial degradation with subsequent intra-molecular crosslinking. This improves the physico-mechanical properties in the transverse direction, and such film can be used for food packaging before electron-beam treatment.

Enhancing the thermal dissipation of a light-converting composite for quantum dot-based white light-emitting diodes through electrospinning nanofibers

NASA Astrophysics Data System (ADS)

Zheng, Huai; Lei, Xiang; Cheng, Ting; Liu, Sheng; Zeng, Xiaoliang; Sun, Rong

2017-06-01

Quantum dots (QDs) have been developed as one of the most promising light-converting materials for white light-emitting diodes (LEDs). In current QD-based LED packaging structures, composites of QDs and polymers are used as light-converting layers. However, the ultralow thermal conductivity of such composites seriously hinders the dissipation of QD-generating heat. In this paper, we demonstrate a method to enhance the thermal dissipation of QD-polymer composites through electrospinning polymer nanofibers. QD-polymer films embedded by electrospun nanofibers were prepared. Benefitting from aligned polymer chains in the electrospun nanofibers, the through-panel and in-panel thermal conductivities of the proposed QD-polymer film increased by 39.9% and 423.1%, respectively, compared to traditional QD-polymer film. The proposed and traditional QD-polymer films were both packaged on chip on board (CoB) LEDs for experimental comparison. Compared to traditional QD-polymer film, the luminous flux and luminous efficiency of the LEDs were increased by up to 51.8% and 42.9% by the proposed QD-polymer film under a current of 800 mA, respectively. With an increase in the driving current from 20-800 mA, the correlated color temperature (CCT) variation decreased by 72.7%. The maximum temperatures in the QD-polymer films were reduced from 419 K-411 K under a driving current of 200 mA.

Highlights of 10th plasma chemistry meeting

NASA Technical Reports Server (NTRS)

Kitamura, K.; Hashimoto, H.; Hozumi, K.

1981-01-01

The chemical structure is given of a film formed by plasma polymerization from pyridine monomers. The film has a hydrophilic chemical structure, its molecular weight is 900, and the molecular system is C55H50N10O3. The electrical characteristics of a plasma polymerized film are described. The film has good insulating properties and was successfully applied as video disc coating. Etching resistance properties make it possible to use the film as a resist in etching. The characteristics of plasma polymer formed from monomers containing tetramethyltin are discussed. The polymer is in film form, displays good adhesiveness, is similar to UV film UV 35 in light absorption and is highly insulating.

Structure of Irreversibly Adsorbed Star Polymers

NASA Astrophysics Data System (ADS)

Akgun, Bulent; Aykan, Meryem Seyma; Canavar, Seda; Satija, Sushil K.; Uhrig, David; Hong, Kunlun

Formation of irreversibly adsorbed polymer chains on solid substrates have a huge impact on the wetting, glass transition, aging and polymer chain mobility in thin films. In recent years there has been many reports on the formation, kinetics and dynamics of these layers formed by linear homopolymers. Recent studies showed that by varying the number of polymer arms and arm molecular weight one can tune the glass transition temperature of thin polymer films. Using polymer architecture as a tool, the behavior of thin films can be tuned between the behavior of linear chains and soft colloids. We have studied the effect of polymer chain architecture on the structure of dead layer using X-ray reflectivity (XR) and atomic force microscopy. Layer thicknesses and densities of flattened and loosely adsorbed chains has been measured for linear, 4-arm, and 8-arm star polymers with identical total molecular weight as a function of substrate surface energy, annealing temperature and annealing time. Star polymers have been synthesized using anionic polymerization. XR measurements showed that 8-arm star PS molecules form the densest and the thickest dead layers among these three molecules.

The numerical simulation and experiment on extrusion roller embossing of light diffusion plate with micro-structure

NASA Astrophysics Data System (ADS)

Zang, Gongzheng; Fu, Zhihong; Zhang, Lei; Wan, Yue

2018-01-01

Extrusion roller embossing process has demonstrated the ability to produce polymer film with micro-structure. However the influence of various parameters on the forming quality has not been understood clearly. In this paper, a light diffusion plate with semi cylindrical micro-structure array as the research object, the influence of the main processing parameters such as roller speed, pressuring distance and polymer film temperature to the rolling quality was investigated in detail by simulation and experimental methods. The results show that the thickness of the light diffusion plate and the micro-structure fitting diameter increases with the increasing of the roll speed and the polymer film temperature, and decreases with the increasing of the pressing distance. Besides, the simulation results conformed well to the experimental results.

Polythiophene thin films by surface-initiated polymerization: Mechanistic and structural studies

DOE PAGES

Youm, Sang Gil; Hwang, Euiyong; Chavez, Carlos A.; ...

2016-06-15

The ability to control nanoscale morphology and molecular organization in organic semiconducting polymer thin films is an important prerequisite for enhancing the efficiency of organic thin-film devices including organic light-emitting and photovoltaic devices. The current “top-down” paradigm for making such devices is based on utilizing solution-based processing (e.g., spin-casting) of soluble semiconducting polymers. This approach typically provides only modest control over nanoscale molecular organization and polymer chain alignment. A promising alternative to using solutions of presynthesized semiconducting polymers pursues instead a “bottom-up” approach to prepare surface-grafted semiconducting polymer thin films by surface-initiated polymerization of small-molecule monomers. Herein, we describe themore » development of an efficient method to prepare polythiophene thin films utilizing surface-initiated Kumada catalyst transfer polymerization. In this study, we provided evidence that the surface-initiated polymerization occurs by the highly robust controlled (quasi-“living”) chain-growth mechanism. Further optimization of this method enabled reliable preparation of polythiophene thin films with thickness up to 100 nm. Extensive structural studies of the resulting thin films using X-ray and neutron scattering methods as well as ultraviolet photoemission spectroscopy revealed detailed information on molecular organization and the bulk morphology of the films, and enabled further optimization of the polymerization protocol. One of the remarkable findings was that surface-initiated polymerization delivers polymer thin films showing complex molecular organization, where polythiophene chains assemble into lateral crystalline domains of about 3.2 nm size, with individual polymer chains folded to form in-plane aligned and densely packed oligomeric segments (7-8 thiophene units per each segment) within each domain. Achieving such a complex mesoscale organization is virtually impossible with traditional methods relying on solution processing of presynthesized polymers. Another significant advantage of surface-confined polymer thin films is their remarkable stability toward organic solvents and other processing conditions. In addition to controlled bulk morphology, uniform molecular organization, and stability, a unique feature of the surface-initiated polymerization is that it can be used for the preparation of large-area uniformly nanopatterned polymer thin films. Lastly, this was demonstrated using a combination of particle lithography and surface-initiated polymerization. In general, surface-initiated polymerization is not limited to polythiophene but can be also expanded toward other classes of semiconducting polymers and copolymers.« less

Interfacial Properties of Thin Films of Poly(vinyl ether)s with Architectural Design in Water

NASA Astrophysics Data System (ADS)

Oda, Yukari; Itagaki, Nozomi; Sugimoto, Sin; Kawaguchi, Daisuke; Matsuno, Hisao; Tanaka, Keiji

Precise design of primary structure and architecture of polymers leads to the well-defined structure, unique physical properties, and excellent functions not only in the bulk but also at the interfaces. We here constructed functional polymer interfaces in water based on the architectural design of poly(vinyl ether)s with oxyethylene side-chains (POEVE). A branched polymer with POEVE parts was preferentially segregated at the air interface in the matrix of poly(methyl methacrylate). As an alternative way to prepare the POEVE surface, the cross-linked hydrogel thin films were prepared. The moduli of the hydrogel films near the water interfaces, which were examined by force-distance curve measurements using atomic force microscopy, were greatly sensitive to the cross-linking density of the polymers. Diffuse interfaces of POEVE chains at the water interface make it possible to prevent the platelet adhesion on the films.

Dynamics of Poly(methyl methacrylate) and Polystyrene Thin Films on Hydrophobic and Hydrophilic Surfaces

NASA Astrophysics Data System (ADS)

Tsige, Mesfin

While an extensive literature dealing with the structure and dynamics of polymers at surfaces and interfaces exist, there has been a paucity of information regarding the length scale of the influence of the surface on polymer mobility and its dependence on polymer-surface interaction. To address this issue, we have investigated using molecular dynamics simulations the dynamics of PMMA and PS films of similar system sizes on two different surfaces as a function of film thickness, polymer molecular weight, and temperature. The dynamics of the polymer chains in the film on two different surfaces will be discussed in the context of a three-layer model. This work was supported by NSF Grant DMR1410290.

Simulated Space Vacuum Ultraviolet (VUV) Exposure Testing for Polymer Films

NASA Technical Reports Server (NTRS)

Dever, Joyce A.; Pietromica, Anthony J.; Stueber, Thomas J.; Sechkar, Edward A.; Messer, Russell K.

2002-01-01

Vacuum ultraviolet (VUV) radiation of wavelengths between 115 and 200 nm produced by the sun in the space environment can cause degradation to polymer films producing changes in optical, mechanical, and chemical properties. These effects are particularly important for thin polymer films being considered for ultra-lightweight space structures, because, for most polymers, VUV radiation is absorbed in a thin surface layer. NASA Glenn Research Center has developed facilities and methods for long-term ground testing of polymer films to evaluate space environmental VUV radiation effects. VUV exposure can also be used as part of sequential simulated space environmental exposures to determine combined damaging effects. This paper will describe the effects of VUV on polymer films and the necessity for ground testing. Testing practices used at Glenn Research Center for VUV exposure testing will be described including characterization of the VUV radiation source used, calibration procedures traceable to the National Institute of Standards and Technology (NIST), and testing techniques for VUV exposure of polymer surfaces.

Dewetting of Thin Polymer Films

NASA Astrophysics Data System (ADS)

Dixit, P. S.; Sorensen, J. L.; Kent, M.; Jeon, H. S.

2001-03-01

DEWETTING OF THIN POLYMER FILMS P. S. Dixit,(1) J. L. Sorensen,(2) M. Kent,(2) H. S. Jeon*(1) (1) Department of Petroleum and Chemical Engineering, New Mexico Institute of Mining and Technology, 801 Leroy Place, Socorro, NM 87801, jeon@nmt.edu (2) Department 1832, Sandia National Laboratories, Albuquerque, NM. Dewetting of thin polymer films is of technological importance for a variety of applications such as protective coatings, dielectric layers, and adhesives. Stable and smooth films are required for the above applications. Above the glass transition temperature (Tg) the instability of polymer thin films on a nonwettable substrate can be occurred. The dewetting mechanism and structure of polypropylene (Tg = -20 ^circC) and polystyrene (Tg = 100 ^circC) thin films is investigated as a function of film thickness (25 Åh < 250 Åand quenching temperature. Contact angle measurements are used in conjunction with optical microscope to check the surface homogeneity of the films. Uniform thin films are prepared by spin casting the polymer solutions onto silicon substrates with different contact angles. We found that the stable and unstable regions of the thin films as a function of the film thickness and quenching temperature, and then constructed a stability diagram for the dewetting of thin polymer films. We also found that the dewetting patterns of the thin films are affected substantially by the changes of film thickness and quenching temperature.

Thickness Dependence of Failure in Ultra-thin Glassy Polymer Films

NASA Astrophysics Data System (ADS)

Bay, Reed; Shimomura, Shinichiro; Liu, Yujie; Ilton, Mark; Crosby, Alfred

The physical properties of polymer thin films change as the polymer chains become confined. Similar changes in mechanical properties have been observed, though these critical properties have only been explored a limited extent and with indirect methods. Here, we use a recently developed method to measure the complete uniaxial stress strain relationship of polymer thin films of polystyrene films (PS, Mw =130kg/mol, 490kg/mol, and 853kg/mol) as a function of thickness (20 nm-220nm). In this method, we hold a `dog-bone' shaped film on water between a flexible cantilever and a movable rigid boundary, measuring force-displacement from the cantilever deflection. From our measurements, we find that the modulus decreases as the PS chains become confined. The PS thin films exhibit ``ideal perfectly plastic'' behavior due to crazing, which differs from the typical brittle response of bulk PS. The draw stress due to crazing decreases with film thickness. These results provide new fundamental insight into how polymer behavior is altered due to structural changes in the entangled polymer network upon confinement. NSF DMR 1608614.

Water Vapor Permeation of Metal Oxide/Polymer Coated Plastic Films

NASA Astrophysics Data System (ADS)

Numata, Yukihiro; Oya, Toshiyuki; Kuwahara, Mitsuru; Ito, Katsuya

Barrier performance to water vapor permeation of ceramic coated layers deposited on flexible polymer films is of great interest to food packaging, medical device packaging and flat panel display industries. In this study, a new type film in which a ceramic layer is deposited on a polymer coated film was proposed for lower water vapor permeation. It is important how to control interfacial properties between each layer and film for good barrier performance. Several kinds of polymer coated materials were prepared for changing surface free energy of the films before and after depositing the ceramic layer. The ceramic layer, which is composed of mixed material of SiO2 and Al2O3, was adopted under the same conditions. The following results were obtained; 1) Water vapor permeation is not related to the surface energy of polymer coated films, 2) After depositing the ceramic layer, however, a strong correlation is observed between the water vapor permeation and surface free energy. 3) The phenomenon is considered that the polarity of the polymer layers plays a key role in changing the structure of ceramic coated layers.

Direct Fabrication of Inkjet-Printed Dielectric Film for Metal-Insulator-Metal Capacitors

NASA Astrophysics Data System (ADS)

Cho, Cheng-Lin; Kao, Hsuan-ling; Wu, Yung-Hsien; Chang, Li-Chun; Cheng, Chun-Hu

2018-01-01

In this study, an inkjet-printed dielectric film that used a polymer-based SU-8 ink was fabricated for use in a metal-insulator-metal (MIM) capacitor. Thermal treatment of the inkjet-printed SU-8 polymer film affected its surface morphology, chemical structure, and surface wettability. A 20-min soft-bake at 60°C was applied to eliminate inkjet-printed bubbles and ripples. The ultraviolet-exposed SU-8 polymer film was crosslinked at temperatures between 120°C and 220°C and became disordered at 270°C, demonstrated using Fourier-transform infrared spectroscopy. A maximum SU-8 polymer film hard-bake temperature of 120°C was identified, and a printing process was subsequently employed because the appropriate water contact angle of the printed film was 79°. Under the appropriate inkjet printing conditions, the two-transmission-line method was used to extract the dielectric and electrical properties of the SU-8 polymer film, and the electrical behavior of the fabricated MIM capacitor was also characterized.

Influence of film structure on the dewetting kinetics of thin polymer films in the solvent annealing process.

PubMed

Zhang, Huanhuan; Xu, Lin; Lai, Yuqing; Shi, Tongfei

2016-06-28

On a non-wetting solid substrate, the solvent annealing process of a thin polymer film includes the swelling process and the dewetting process. Owing to difficulties in the in situ analysis of the two processes simultaneously, a quantitative study on the solvent annealing process of thin polymer films on the non-wetting solid substrate is extremely rare. In this paper, we design an experimental method by combining spectroscopic ellipsometry with optical microscopy to achieve the simultaneous in situ study. Using this method, we investigate the influence of the structure of swollen film on its dewetting kinetics during the solvent annealing process. The results show that for a thin PS film with low Mw (Mw = 4.1 kg mol(-1)), acetone molecules can form an ultrathin enriched layer between the PS film and the solid substrate during the swelling process. The presence of the acetone enriched layer accounts for the exponential kinetic behavior in the case of a thin PS film with low Mw. However, the acetone enriched layer is not observed in the case of a thin PS film with high Mw (Mw = 400 kg mol(-1)) and the slippage effect of polymer chains is valid during the dewetting process.

Correlation between Hierarchical Structure and Processing Control of Large-area Spray-coated Polymer Solar Cells toward High Performance

PubMed Central

Huang, Yu-Ching; Tsao, Cheng-Si; Cha, Hou-Chin; Chuang, Chih-Min; Su, Chun-Jen; Jeng, U-Ser; Chen, Charn-Ying

2016-01-01

The formation mechanism of a spray-coated film is different from that of a spin-coated film. This study employs grazing incidence small- and wide-angle X-ray Scattering (GISAXS and GIWAXS, respectively) quantitatively and systematically to investigate the hierarchical structure and phase-separated behavior of a spray-deposited blend film. The formation of PCBM clusters involves mutual interactions with both the P3HT crystal domains and droplet boundary. The processing control and the formed hierarchical structure of the active layer in the spray-coated polymer/fullerene blend film are compared to those in the spin-coated film. How the different post-treatments, such as thermal and solvent vapor annealing, tailor the hierarchical structure of the spray-coated films is quantitatively studied. Finally, the relationship between the processing control and tailored BHJ structures and the performance of polymer solar cell devices is established here, taking into account the evolution of the device area from 1 × 0.3 and 1 × 1 cm2. The formation and control of the special networks formed by the PCBM cluster and P3HT crystallites, respectively, are related to the droplet boundary. These structures are favorable for the transverse transport of electrons and holes. PMID:26817585

Structure and Properties of Azobenzene Thin-Films

NASA Astrophysics Data System (ADS)

Allen, R. A.

1987-09-01

Available from UMI in association with The British Library. A number of monomer and polymer materials, all containing the azobenzene group, have been deposited as Langmuir-Blodgett (LB) multilayers and their structures and physical properties studied. LB films of two monomeric materials exhibited liquid crystal phase changes that were investigated by optical microscopy and X-ray diffraction. Multilayers built up from one of the materials exhibited a phase change upon aging and this demonstrated that the LB technique had produced a structure that was not the equilibrium state. A monomer material possessing a fluorocarbon chain was found to initially deposit as an LB film in a Z-type manner, but changed to Y-type deposition with increasing multilayer thickness. A correlation was observed between this behaviour and the surface potential changes that were brought about when deposition took place on an aluminium substrate. The feasibility of building up alternating multilayers of monomer and polymer materials was demonstrated. Combining these two classes of material in the same LB film may confer on it the mechanical durability of the polymers and the highly ordered structure and potentially interesting physical properties of the monomer. The structures developed here may prove to have high second harmonic generation capabilities. Polymer materials were built up into relatively thick Y-type LB multilayers and studied by X-ray diffraction. Only poorly defined layered structures were found. Polymer materials were also cast into thin films from the melt and from solution. One of the compounds developed a high degree of anisotropy in its structure after exposure to linearly polarised white light. A birefringence of up to Deltan = 0.21 was measured. In contrast, LB films formed from the same material could not be ordered in the same manner and this appeared to result from the very close packing that takes place in such structures.

Quantitative estimation of film forming polymer-plasticizer interactions by the Lorentz-Lorenz Law.

PubMed

Dredán, J; Zelkó, R; Dávid, A Z; Antal, I

2006-03-09

Molar refraction as well as refractive index has many uses. Beyond confirming the identity and purity of a compound, determination of molecular structure and molecular weight, molar refraction is also used in other estimation schemes, such as in critical properties, surface tension, solubility parameter, molecular polarizability, dipole moment, etc. In the present study molar refraction values of polymer dispersions were determined for the quantitative estimation of film forming polymer-plasticizer interactions. Information can be obtained concerning the extent of interaction between the polymer and the plasticizer from the calculation of molar refraction values of film forming polymer dispersions containing plasticizer.

Redox active polymer devices and methods of using and manufacturing the same

DOEpatents

Johnson, Paul; Bautista-Martinez, Jose Antonio; Friesen, Cody; Switzer, Elise

2018-06-05

The disclosed technology relates generally to apparatus comprising conductive polymers and more particularly to tag and tag devices comprising a redox-active polymer film, and method of using and manufacturing the same. In one aspect, an apparatus includes a substrate and a conductive structure formed on the substrate which includes a layer of redox-active polymer film having mobile ions and electrons. The conductive structure further includes a first terminal and a second terminal configured to receive an electrical signal therebetween, where the layer of redox-active polymer is configured to conduct an electrical current generated by the mobile ions and the electrons in response to the electrical signal. The apparatus additionally includes a detection circuit operatively coupled to the conductive structure and configured to detect the electrical current flowing through the conductive structure.

A pH/enzyme-responsive polymer film consisting of Eudragit FS 30 D and arabinoxylane as a potential material formulation for colon-specific drug delivery system.

PubMed

Rabito, Mirela Fulgencio; Reis, Adriano Valim; Freitas, Adonilson dos Reis; Tambourgi, Elias Basile; Cavalcanti, Osvaldo Albuquerque

2012-01-01

Polymer film based on pH-dependent Eudragit FS 30 D acrylic polymer in association with arabinoxylane, a polysaccharide issued from gum psyllium, was produced by way of solvent casting. Physical-chemical characterization of the polymer film samples was performed by means of thermogravimetry (TGA), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). Furthermore, water-equilibrium swelling index (I(s)) and weight loss of the films in KCl buffer solution of pH 1.2, in KH(2)PO(4) buffer solution of pH 5.0, or in KH(2)PO(4) buffer solution of pH 5.0 consisting of 4% enzyme Pectinex 3X-L (w/v) were also carried out for the film characterization. No chemical interactions between the Eudragit FS 30 D and the arabinoxylane polymer chains were evidenced, thus suggesting that the film-forming polymer structure was obtained from a physical mixture of both polymers. The arabinoxylane-loader films showed a more pronounced weight loss after their immersion in buffer solution containing enzyme Pectinex 3X-L. The introduction of the arabinoxylane makes the film more susceptible to undergo an enzymatic degradation. This meant that the enzyme-dependent propriety issued from the arabinoxylane has been imprinted into the film formulation. This type of polymer film is an interesting system for applications in colon-specific drug delivery system.

Multilayer polymer dielectric films for hollow glass waveguides

NASA Astrophysics Data System (ADS)

Kendall, Wesley; Harrington, James A.

2018-02-01

Hollow glass waveguides (HGWs) have been extensively investigated for the transmission of broadband, high-power radiation, particularly in the mid-infrared. One area of particular interest is the deposition of dielectric thin films within the hollow core of the HGW in order to reduce the losses at desired wavelengths. By implementing a thin film multilayer structure with high index mismatch between adjacent films, it is possible to dramatically improve the losses of the waveguides due to the thin film interference effect. Existing multilayer film research has utilized heavy metal halides, which although provide considerable index contrast, are toxic and unsuitable for clinical applications in which they are often used. Polymer dielectric thin films provide desirable optical properties for HGWs but are hindered by solvent compatibility in the deposition procedure. This work demonstrates implementation of a polymer multilayer dielectric thin film stack within a HGW, using ChemoursTM Teflon AF (n = 1.29) as the low-index material and polystyrene (n = 1.59) as the high-index material. These two polymers were deposited using liquid phase techniques within a HGW; the absorption spectra of waveguide as each layer was deposited on was analyzed in the mid-IR with an FTIR, and straight and bending losses were measured on a CO2 laser. Appreciable losses were realized with the addition of the second polymer film and the interference bands red-shifted with the second layer, suggesting the successful creation of the multilayer structure.

Electrically and chemically tunable soft-solid block copolymer structural color (Conference Presentation)

NASA Astrophysics Data System (ADS)

Park, Cheolmin

2016-09-01

1D photonic crystals based on the periodic stacking of two different dielectric layers have been widely studied due to their potential use in low-power reflective mode displays, e-books and sensors, but the fabrication of mechanically flexible polymer structural color (SC) films, with electro-active color switching, remains challenging. Here, we demonstrate free-standing electric field tunable ionic liquid swollen block copolymer films. Placement of a polymer/ionic liquid (IL) film-reservoir adjacent to a self-assembled poly(styrene-block-quaternized 2vinyl pyridine) (PS-b-QP2VP) copolymer SC film allowed the development of R, G and B full-color SC block copolymer films by swelling of the QP2VP domains by the ionic liquid associated with water molecules. The IL-polymer/BCP SC film is mechanically flexible with excellent color stability over several days at ambient conditions. The selective swelling of the QP2VP domains could be controlled by both the ratio of the IL to a polymer in the gel-like IL reservoir layer and by an applied voltage in the range of -3V to +6V using a metal/IL reservoir/SC film/IL reservoir/metal capacitor type device.

Implantable polymer/metal thin film structures for the localized treatment of cancer by Joule heating

NASA Astrophysics Data System (ADS)

Kan-Dapaah, Kwabena; Rahbar, Nima; Theriault, Christian; Soboyejo, Wole

2015-04-01

This paper presents an implantable polymer/metal alloy thin film structure for localized post-operative treatment of breast cancer. A combination of experiments and models is used to study the temperature changes due to Joule heating by patterned metallic thin films embedded in poly-dimethylsiloxane. The heat conduction within the device and the surrounding normal/cancerous breast tissue is modeled with three-dimensional finite element method (FEM). The FEM simulations are used to explore the potential effects of device geometry and Joule heating on the temperature distribution and lesion (thermal dose). The FEM model is validated using a gel model that mimics biological media. The predictions are also compared to prior results from in vitro studies and relevant in vivo studies in the literature. The implications of the results are discussed for the potential application of polymer/metal thin film structures in hyperthermic treatment of cancer.

Multilevel Investigation of Charge Transport in Conjugated Polymers.

PubMed

Dong, Huanli; Hu, Wenping

2016-11-15

Conjugated polymers have attracted the world's attentions since their discovery due to their great promise for optoelectronic devices. However, the fundamental understanding of charge transport in conjugated polymers remains far from clear. The origin of this challenge is the natural disorder of polymers with complex molecular structures in the solid state. Moreover, an effective way to examine the intrinsic properties of conjugated polymers is absent. Optoelectronic devices are always based on spin-coated films. In films, polymers tend to form highly disordered structures at nanometer to micrometer length scales due to the high degree of conformational freedom of macromolecular chains and the irregular interchain entanglement, thus typically resulting in much lower charge transport properties than their intrinsic performance. Furthermore, a subtle change of processing conditions may dramatically affect the film formation-inducing large variations in the morphology, crystallinity, microstructure, molecular packing, and alignment, and finally varying the effective charge transport significantly and leading to great inconsistency over an order of magnitude even for devices based on the same polymer semiconductor. Meanwhile, the charge transport mechanism in conjugated polymers is still unclear and its investigation is challenging based on such complex microstructures of polymers in films. Therefore, how to objectively evaluate the charge transport and probe the charge transport mechanism of conjugated polymers has confronted the world for decades. In this Account, we present our recent progress on multilevel charge transport in conjugated polymers, from disordered films, uniaxially aligned thin films, and single crystalline micro- or nanowires to molecular scale, where a derivative of poly(para-phenylene ethynylene) with thioacetyl end groups (TA-PPE) is selected as the candidate for investigation, which could also be extended to other conjugated polymer systems. Our systematic investigations demonstrated that 3-4 orders higher charge transport properties could be achieved with the improvement of polymer chain order and confirmed efficient charge transport along the conjugated polymer backbones. Moreover, with downscaling to molecular scale, many novel phenomena were observed such as the largely quantized electronic structure for an 18 nm-long TA-PPE and the modulation of the redox center of tetrathiafulvalene (TTF) units on tunneling charge transport, which opens the door for conjugated polymers used in nanometer quantum devices. We hope the understanding of charge transport in PPE and its related conjugated polymer at multilevel scale in this Account will provide a new method to sketch the charge transport properties of conjugated polymers, and new insights into the combination of more conjugated polymer materials in the multilevel optoelectronic and other related functional devices, which will offer great promise for the next generation of electronic devices.

Structure Formation of Ultrathin PEO Films at Solid Interfaces—Complex Pattern Formation by Dewetting and Crystallization

PubMed Central

Braun, Hans-Georg; Meyer, Evelyn

2013-01-01

The direct contact of ultrathin polymer films with a solid substrate may result in thin film rupture caused by dewetting. With crystallisable polymers such as polyethyleneoxide (PEO), molecular self-assembly into partial ordered lamella structures is studied as an additional source of pattern formation. Morphological features in ultrathin PEO films (thickness < 10 nm) result from an interplay between dewetting patterns and diffusion limited growth pattern of ordered lamella growing within the dewetting areas. Besides structure formation of hydrophilic PEO molecules, n-alkylterminated (hydrophobic) PEO oligomers are investigated with respect to self-organization in ultrathin films. Morphological features characteristic for pure PEO are not changed by the presence of the n-alkylgroups. PMID:23385233

Role of Polymer Segregation on the Mechanical Behavior of All-Polymer Solar Cell Active Layers.

PubMed

Balar, Nrup; Xiong, Yuan; Ye, Long; Li, Sunsun; Nevola, Daniel; Dougherty, Daniel B; Hou, Jianhui; Ade, Harald; O'Connor, Brendan T

2017-12-20

An all-polymer bulk heterojunction (BHJ) active layer that removes the use of commonly used small molecule electron acceptors is a promising approach to improve the thermomechanical behavior of organic solar cells. However, there has been limited research on their mechanical properties. Here, we report on the mechanical behavior of high-performance blade-coated all-polymer BHJ films cast using eco-friendly solvents. The mechanical properties considered include the elastic modulus, crack onset strain, and cohesive fracture energy. We show that the mechanical behavior of the blend is largely unaffected by significant changes in the segregation characteristics of the polymers, which was varied systematically through solvent formulation. In comparison to a polymer:fullerene BHJ counterpart, the all-polymer films were found to have lower stiffness and increased ductility. Yet, the fracture energy of the all-polymer films is not significantly improved compared to that of the polymer:fullerene films. This study highlights that improved mechanical behavior of all-polymer systems cannot be assumed, and that details of the molecular structure, molecular weight, and film morphology play an important role in both the optoelectronic and mechanical properties. Furthermore, we show that simple composite modeling provides a predictive tool for the mechanical properties of the polymer blend films, providing a framework to guide future optimization of the mechanical behavior.

Communication: The simplified generalized entropy theory of glass-formation in polymer melts.

PubMed

Freed, Karl F

2015-08-07

While a wide range of non-trivial predictions of the generalized entropy theory (GET) of glass-formation in polymer melts agree with a large number of observed universal and non-universal properties of these glass-formers and even for the dependence of these properties on monomer molecular structure, the huge mathematical complexity of the theory precludes its extension to describe, for instance, the perplexing, complex behavior observed for technologically important polymer films with thickness below ∼100 nm and for which a fundamental molecular theory is lacking for the structural relaxation. The present communication describes a hugely simplified version of the theory, called the simplified generalized entropy theory (SGET) that provides one component necessary for devising a theory for the structural relaxation of thin polymer films and thereby supplements the first required ingredient, the recently developed Flory-Huggins level theory for the thermodynamic properties of thin polymer films, before the concluding third step of combining all the components into the SGET for thin polymer films. Comparisons between the predictions of the SGET and the full GET for the four characteristic temperatures of glass-formation provide good agreement for a highly non-trivial model system of polymer melts with chains of the structure of poly(n-α olefins) systems where the GET has produced good agreement with experiment. The comparisons consider values of the relative backbone and side group stiffnesses such that the glass transition temperature decreases as the amount of excess free volume diminishes, contrary to general expectations but in accord with observations for poly(n-alkyl methacrylates). Moreover, the SGET is sufficiently concise to enable its discussion in a standard course on statistical mechanics or polymer physics.

Communication: The simplified generalized entropy theory of glass-formation in polymer melts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Freed, Karl F.

2015-08-07

While a wide range of non-trivial predictions of the generalized entropy theory (GET) of glass-formation in polymer melts agree with a large number of observed universal and non-universal properties of these glass-formers and even for the dependence of these properties on monomer molecular structure, the huge mathematical complexity of the theory precludes its extension to describe, for instance, the perplexing, complex behavior observed for technologically important polymer films with thickness below ∼100 nm and for which a fundamental molecular theory is lacking for the structural relaxation. The present communication describes a hugely simplified version of the theory, called the simplifiedmore » generalized entropy theory (SGET) that provides one component necessary for devising a theory for the structural relaxation of thin polymer films and thereby supplements the first required ingredient, the recently developed Flory-Huggins level theory for the thermodynamic properties of thin polymer films, before the concluding third step of combining all the components into the SGET for thin polymer films. Comparisons between the predictions of the SGET and the full GET for the four characteristic temperatures of glass-formation provide good agreement for a highly non-trivial model system of polymer melts with chains of the structure of poly(n-α olefins) systems where the GET has produced good agreement with experiment. The comparisons consider values of the relative backbone and side group stiffnesses such that the glass transition temperature decreases as the amount of excess free volume diminishes, contrary to general expectations but in accord with observations for poly(n-alkyl methacrylates). Moreover, the SGET is sufficiently concise to enable its discussion in a standard course on statistical mechanics or polymer physics.« less

Chain Conformation near the Buried Interface in Nanoparticle-Stabilized Polymer Thin Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barkley, Deborah A.; Jiang, Naisheng; Sen, Mani

It is known that when nanoparticles are added to polymer thin films, they often migrate to the film-substrate interface and form an “immobile interfacial layer”, which has been believed as the origin of suppression of dewetting. We here report an alternative mechanism of dewetting suppression from the structural aspect of a polymer. Dodecane thiol-functionalized gold (Au) nanoparticles embedded in PS thin films prepared on Si substrates were used as a model. It was found that thermal annealing promotes irreversible polymer adsorption onto the substrate surface along with the surface migration of the nanoparticles. We also revealed that the surface migrationmore » causes additional nanoconfined space for the adsorbed polymer chains. As a result, the self-organization process of the strongly adsorbed polymer chains on the solid surface was so hindered that the chain conformations were randomized and expanded in the film normal direction. Here, the resultant chain conformation allows the interpenetration between free chains and the adsorbed chains, promoting adhesion and hence stabilizing the thin film.« less

Chain Conformation near the Buried Interface in Nanoparticle-Stabilized Polymer Thin Films

DOE PAGES

Barkley, Deborah A.; Jiang, Naisheng; Sen, Mani; ...

2017-09-26

It is known that when nanoparticles are added to polymer thin films, they often migrate to the film-substrate interface and form an “immobile interfacial layer”, which has been believed as the origin of suppression of dewetting. We here report an alternative mechanism of dewetting suppression from the structural aspect of a polymer. Dodecane thiol-functionalized gold (Au) nanoparticles embedded in PS thin films prepared on Si substrates were used as a model. It was found that thermal annealing promotes irreversible polymer adsorption onto the substrate surface along with the surface migration of the nanoparticles. We also revealed that the surface migrationmore » causes additional nanoconfined space for the adsorbed polymer chains. As a result, the self-organization process of the strongly adsorbed polymer chains on the solid surface was so hindered that the chain conformations were randomized and expanded in the film normal direction. Here, the resultant chain conformation allows the interpenetration between free chains and the adsorbed chains, promoting adhesion and hence stabilizing the thin film.« less

Polarized emission from light-emitting electrochemical cells using uniaxially oriented polymer thin films of poly(9,9-dioctylfluorene-co-bithiophene)

NASA Astrophysics Data System (ADS)

Miyazaki, Masumi; Sakanoue, Tomo; Takenobu, Taishi

2018-03-01

Uniaxially oriented poly(9,9-dioctylfluorene-co-bithiophene) (F8T2) films were prepared on rubbed polyimide substrates and applied to emitting layers of light-emitting electrochemical cells (LECs). The layered structure of the uniaxially oriented F8T2 film and ionic liquid electrolytes enabled us to demonstrate LEC operations with high anisotropic characteristics both in emission and charge transport. Polarized electroluminescence (EL) from electrochemically induced p-n junctions in the uniaxially oriented F8T2 was obtained. The dichroic ratios of EL were the same as those of photoluminescence, suggesting that the doping process into the oriented F8T2 did not interrupt the polymer ordering. This indicates the usefulness of the layered structure of the polymer/electrolyte for the fabrication of LECs based on highly oriented polymer films. In addition, uniaxially oriented F8T2 was found to show reduced threshold energy in optically pumped amplified spontaneous emission. These demonstrations suggest the advantage of uniaxially oriented polymer-based LECs for potential application in future electrically pumped lasers.

Structural and optical characterization of PVA:KMnO4 based solid polymer electrolyte

NASA Astrophysics Data System (ADS)

Abdullah, Omed Gh.; Aziz, Shujahadeen B.; Rasheed, Mariwan A.

Solid polymer electrolyte films of polyvinyl alcohol (PVA) doped with a different weight percent of potassium permanganate (KMnO4) were prepared by standard solution cast method. XRD and FTIR techniques were performed for structural study. Complex formation between the PVA polymer and KMnO4 salt was confirmed by Fourier transform infrared (FTIR) spectroscopy. The description of crystalline nature of the solid polymer electrolyte films has been confirmed by XRD analysis. The UV-Visible absorption spectra were analyzed in terms of absorption formula for non-crystalline materials. The fundamental optical parameters such as optical band gap energy, refractive index, optical conductivity, and dielectric constants have been investigated and showed a clear dependence on the KMnO4 concentration. The observed value of optical band gap energy for pure PVA is about 6.27 eV and decreases to a value 3.12 eV for the film sample formed with 4 wt% KMnO4 salt. The calculated values of refractive index and the dielectric constants of the polymer electrolyte films increase with increasing KMnO4 content.

Enhanced Self-Organized Dewetting of Ultrathin Polymer Blend Film for Large-Area Fabrication of SERS Substrate.

PubMed

Zhang, Huanhuan; Xu, Lin; Xu, Yabo; Huang, Gang; Zhao, Xueyu; Lai, Yuqing; Shi, Tongfei

2016-12-06

We study the enhanced dewetting of ultrathin Polystyrene (PS)/Poly (methyl methacrylate) (PMMA) blend films in a mixed solution, and reveal the dewetting can act as a simple and effective method to fabricate large-area surface-enhanced Raman scattering (SERS) substrate. A bilayer structure consisting of under PMMA layer and upper PS layer forms due to vertical phase separation of immiscible PS/PMMA during the spin-coating process. The thicker layer of the bilayer structure dominates the dewetting structures of PS/PMMA blend films. The diameter and diameter distribution of droplets, and the average separation spacing between the droplets can be precisely controlled via the change of blend ratio and film thickness. The dewetting structure of 8 nm PS/PMMA (1:1 wt%) blend film is proved to successfully fabricate large-area (3.5 cm × 3.5 cm) universal SERS substrate via deposited a silver layer on the dewetting structure. The SERS substrate shows good SERS-signal reproducibility (RSD < 7.2%) and high enhancement factor (2.5 × 10 7 ). The enhanced dewetting of polymer blend films broadens the application of dewetting of polymer films, especially in the nanotechnology, and may open a new approach for the fabrication of large-area SERS substrate to promote the application of SERS substrate in the rapid sensitive detection of trace molecules.

Enhanced Self-Organized Dewetting of Ultrathin Polymer Blend Film for Large-Area Fabrication of SERS Substrate

PubMed Central

Zhang, Huanhuan; Xu, Lin; Xu, Yabo; Huang, Gang; Zhao, Xueyu; Lai, Yuqing; Shi, Tongfei

2016-01-01

We study the enhanced dewetting of ultrathin Polystyrene (PS)/Poly (methyl methacrylate) (PMMA) blend films in a mixed solution, and reveal the dewetting can act as a simple and effective method to fabricate large-area surface-enhanced Raman scattering (SERS) substrate. A bilayer structure consisting of under PMMA layer and upper PS layer forms due to vertical phase separation of immiscible PS/PMMA during the spin-coating process. The thicker layer of the bilayer structure dominates the dewetting structures of PS/PMMA blend films. The diameter and diameter distribution of droplets, and the average separation spacing between the droplets can be precisely controlled via the change of blend ratio and film thickness. The dewetting structure of 8 nm PS/PMMA (1:1 wt%) blend film is proved to successfully fabricate large-area (3.5 cm × 3.5 cm) universal SERS substrate via deposited a silver layer on the dewetting structure. The SERS substrate shows good SERS-signal reproducibility (RSD < 7.2%) and high enhancement factor (2.5 × 107). The enhanced dewetting of polymer blend films broadens the application of dewetting of polymer films, especially in the nanotechnology, and may open a new approach for the fabrication of large-area SERS substrate to promote the application of SERS substrate in the rapid sensitive detection of trace molecules. PMID:27922062

Structural and morphological modifications of polymer thin film in the presence of nonsolvent

DOE Office of Scientific and Technical Information (OSTI.GOV)

Talukdar, Hrishikesh, E-mail: hiasst@yahoo.in; Kundu, Sarathi

Thin films of sodium poly(acrylic acid) salt (Na-PAA) have been investigated to obtain the modification of the out-of-plane structure and surface morphology in the presence of toluene which is considered as nonsolvent for Na-PAA. X-ray reflectivity analysis show that the out-of-plane thickness of the Na-PAA film increases if the film is kept for longer time inside the toluene. For the thicker film the effect of toluene is more pronounced than the thinner one. Surface morphology obtained from the atomic force microscopy shows that the top surface becomes relatively rough after the dipping of the Na-PAA film inside toluene. Although toluenemore » is nonsolvent for Na-PAA molecules, however, the effect of restructuring of the nanometer-thick polymer film cannot be ignored. The reason for such structural modification has been proposed.« less

Polyethylene-Carbon Nanotube Composite Film Deposited by Cold Spray Technique

NASA Astrophysics Data System (ADS)

Ata, Nobuhisa; Ohtake, Naoto; Akasaka, Hiroki

2017-10-01

Carbon nanotubes (CNTs) are high-performance materials because of their superior electrical conductivity, thermal conductivity, and self-lubrication, and they have been studied for application to polymer composite materials as fillers. However, the methods of fabricating polymer composites with CNTs, such as injection molding, are too complicated for industrial applications. We propose a simple cold spray (CS) technique to obtain a polymer composite of polyethylene (PE) and CNTs. The composite films were deposited by CS on polypropylene and nano-porous structured aluminum substrates. The maximum thickness of the composite film was approximately 1 mm. Peaks at G and D bands were observed in the Raman spectra of the films. Scanning electron microscopy images of the film surface revealed that PE particles were melted by the acceleration gas and CNTs were attached with melted PE. The PE particles solidified after contact with the substrate. These results indicate that PE-CNT composite films were successfully deposited on polypropylene and nano-porous structured aluminum substrates by CS.

Influence of UV irradiation on hydroxypropyl methylcellulose polymer films

NASA Astrophysics Data System (ADS)

Rao, B. Lakshmeesha; Shivananda, C. S.; Shetty, G. Rajesha; Harish, K. V.; Madhukumar, R.; Sangappa, Y.

2018-05-01

Hydroxypropyl Methylcellulose (HPMC) biopolymer films were prepared by solution casting technique and effects of UV irradiation on the structural and optical properties of the polymer films were analysed using X-ray Diffraction and UV-Visible studies. From XRD data, the microcrystalline parameters (crystallite size (LXRD) and crystallinity (Xc)) were calculated and found to be decreasing with UV irradiation due to photo-degradation process. From the UV-Vis absorption data, the optical bandgap (Eg), average numbers of carbon atoms per conjugation length (N) of the polymer chain and the refractive index (n) at 550 nm (average wavelength of visible light) of virgin and UV irradiated HPMC films were calculated. With increase in UV exposure time, the optical bandgap energy (Eg) increases, and hence average number of carbon atoms per conjugation length (N) decreases, supports the photo-degradation of HPMC polymer films. The refractive index of the HPMC films decreases after UV irradiation, due to photo-degradation induced chain rearrangements.

High energy density and efficiency achieved in nanocomposite film capacitors via structure modulation

NASA Astrophysics Data System (ADS)

Zeng, Yi; Shen, Zhong-Hui; Shen, Yang; Lin, Yuanhua; Nan, Ce-Wen

2018-03-01

Flexible dielectric polymer films with high energy storage density and high charge-discharge efficiency have been considered as promising materials for electrical power applications. Here, we design hierarchical structured nanocomposite films using nonlinear polymer poly(vinylidene fluoride-HFP) [P(VDF-HFP)] with inorganic h-boron nitride (h-BN) nanosheets by electrospinning and hot-pressing methods. Our results show that the addition of h-BN nanosheets and the design of the hierarchical multilayer structure in the nanocomposites can remarkably enhance the charge-discharge efficiency and energy density. A high charge-discharge efficiency of 78% and an energy density of 21 J/cm3 can be realized in the 12-layered PVDF/h-BN nanocomposite films. Phase-field simulation results reveal that the spatial distribution of the electric field in these hierarchical structured films affects the charge-discharge efficiency and energy density. This work provides a feasible route, i.e., structure modulation, to improve the energy storage performances for nanocomposite films.

Formation of surface relief grating in polymers with pendant azobenzene chromophores as studied by AFM/UFM

NASA Astrophysics Data System (ADS)

Kulikovska, Olga; Gharagozloo-Hubmann, Kati; Stumpe, Joachim; Huey, Bryan D.; Bliznyuk, Valery N.

2012-12-01

We studied peculiarities of the structural reconstruction within holographically recorded gratings on the surface of several different amorphous azobenzene-containing polymers. Under illumination with a light interference pattern, two processes take place in this type of polymer. The first process is the light-induced orientation of azobenzene units perpendicular to the polarization plane of the incident light. The second one is a transfer of macromolecules along the grating vector (i.e. perpendicular to the grating lines). These two processes result in the creation of a volume orientation grating (alternating regions of different direction or degree of molecular orientation) and a surface relief grating (SRG)—i.e. modulation of film thickness. One can assume that both orientation of molecules and their movement might change the local mechanical properties of the material. Therefore, formation of the SRG is expected to result also in modulation of the local stiffness of the polymer film. To reveal and investigate these stiffness changes within the grating, spin-coated polymer films were prepared and the gratings were recorded on them in two different ways: with an orthogonal circular or orthogonal linear polarization of two recording light beams. A combination of atomic force microscopy (AFM) and ultrasonic force microscopy (UFM) techniques was applied for SRG development monitoring. We demonstrate that formation of the phase gratings depends on the chemical structure of polymers being used, polymer film thickness, and recording parameters, with the height of grating structures (depth of modulation) increasing with both the exposure time and the film thickness. UFM images suggest that the slopes of the topographic peaks in the phase gratings exhibit an increased stiffness with respect to the grating depressions.

Fabrication of porous hierarchical polymer/ceramic composites by electron irradiation of organic/inorganic polymers: route to a highly durable, large-area superhydrophobic coating.

PubMed

Lee, Eun Je; Kim, Jae Joon; Cho, Sung Oh

2010-03-02

Polymer/ceramic composite films with micro- and nanocombined hierarchical structures are fabricated by electron irradiation of poly(methyl methacrylate) (PMMA) microspheres/silicone grease. Electron irradiation induces volume contraction of PMMA microspheres and simultaneously transforms silicone grease into a ceramic material of silicon oxycarbide with many nanobumps. As a result, highly porous structures that consist of micrometer-sized pores and microparticles decorated with nanobumps are created. The fabricated films with the porous hierarchical structure exhibit good superhydrophobicity with excellent self-cleaning and antiadhesion properties after surface treatment with fluorosilane. In addition, the porous hierarchical structures are covered with silicon oxycarbide, and thus the superhydrophobic coatings have high hardness and strong adhesion to the substrate. The presented technique provides a straightforward route to producing large-area, mechanically robust superhydrophobic films on various substrate materials.

Structure-processing-property correlations in thin films of conjugated polymer nanocomposites and blends

NASA Astrophysics Data System (ADS)

Sreeram, Arvind

Conjugated polymers have found several applications in recent years, in energy conversion and storage devices such as organic light emitting diodes, solar cells, batteries, and super capacitors. Thin films of polymers used for these applications need to be mechanically and thermally stable to withstand the harsh operating conditions. Although there is significant information on the optoelectronic properties of many of these polymers, there are only few studies on their mechanical properties. There is little information in the literature on how processing of these films influence mechanical properties. In the first part of this study, poly(p-phenylene vinylene) (PPV) films were prepared by thermolytic conversion of poly[p -phenylene (tetrahydrothiophenium)ethylene chloride] precursor films, at different temperatures and the kinetics of reaction was investigated using thermogravimetry and Fourier transform infrared (FTIR) spectroscopy. The mechanical properties of the films, studied using nanoindentation, showed a dependence on the extent of conversion and chemical composition of the films. The presence of chemical defects (e.g., carbonyl groups, detected using FTIR spectroscopy), was also found to have a noticeable effect on the modulus and hardness of the films. The storage modulus, E', and plasticity decreased with an increase in conversion, whereas the loss modulus, E", showed the opposite trend. Both the precursor and the fully-converted PPV films were found to have significantly lower E" than E', consistent with the glassy nature of the polymers at room temperature. In the second part of the study, polyacetylene films were synthesized by acid-catalyzed dehydration reaction of poly(vinyl alcohol) (PVA) precursor films. The kinetics of this reaction was monitored by thermogravimetry. The chemical structure of the conjugated polymer films was characterized by Raman and IR spectroscopy. Polyacetylene films incorporated with 1-propyl-3-methylimidazolium ionic liquid (IL) could be obtained in a single step reaction. The incorporation of IL in the film, not only greatly improved its mechanical properties, by acting as a plasticizer, but also imparted a dual mechanism of charge transport. The segments of conjugated double bonds imparted electronic conductivity to the films, and the IL resulted in ionic conductivity. The presence of both electronic and ionic conduction pathways in the films was confirmed by electrochemical impedance spectroscopy (EIS). These IL-imbibed conjugated polymer films are promising as materials for electrochemical energy conversion and storage. In the third part of this work, conjugated polymer films containing multiwalled carbon nanotubes (MWNT) and graphene nanoplatelets (GNP) were synthesized and characterized. PPV--MWNT nanocomposite films and PA--GNP nanocomposite films were characterized using a variety of analytical techniques including transmission electron microscopy, quasistatic and dynamic nanoindentaiton, electrochemical impedance spectroscopy, and cyclic voltammetry. Potential application of these films is in electrochemical supercapacitors.

Polymer poling characterization using second harmonic generation (SHG)

NASA Astrophysics Data System (ADS)

Tellier, Gildas; Averty, Dominique; Blart, Errol; Boisrobert, Christian; Gundel, Hartmut; Le Tacon, Sylvain; Monnereau, Cyrille; Odobel, Fabrice; Seveno, Raynald

2006-04-01

Several polymer molecules have structures which are suitable for the non-linear optic applications. We report on the design and fabrication of a high performance electro-optic modulator made of polymer thin films. The polymer we study contains a chromophore based on Disperse Red One covalently grafted to a host-matrix. The polymer materials are deposited in thin layers on a glass substrate by chemical solution deposition, either by spin-coating or by dip-coating. The thickness of the films is ranging from a hundred nanometers to several micrometers. Initially, the polymer molecules are randomly oriented and the films are isotropic, hence no electro-optic effect can be observed. In order to break the symmetry and align the chromophores, the films are submitted to the so-called corona poling process. As a result, their structure become non-centrosymmetric and the second-order susceptibility is no longer zero. The corona poling method consists of applying a high electric field to the polymer by means of a needle electrode, placed above the polymer film which is posed on a grounded sample support electrode. Thermal regulation of the support electrode allows to control the temperature during the poling of the films. Once the poling process has been established, a chemical cross-linking function is thermally activated in order to fix the orientation of the chromophores in the polymer matrix. The orientation and its stability in time is evaluated with a Second Harmonic Generation measurement set-up using the Makers Fringes configuration. We studied the influence of the poling temperature, the distance between the corona needle electrode and the sample, the high voltage applied, and the duration of the poling process on the efficiency of chromophore orientation in order to optimize the poling procedure. Finally, aging of poled polymer samples has been investigated at elevated temperatures, confirming the stability of the cross-linking process.

Strong thin membrane structure for use as solar sail comprising substrate with reflective coating on one surface and an infra red emissivity increasing coating on the other surface

NASA Technical Reports Server (NTRS)

Frazer, Robert E. (Inventor)

1982-01-01

Production of strong lightweight membrane structure by applying a thin reflective coating such as aluminum to a rotating cylinder, applying a mesh material such as nylon over the aluminum coating, coating the mesh overlying the aluminum with a polymerizing material such as a para-xylylene monomer gas to polymerize as a film bound to the mesh and the aluminum, and applying an emissivity increasing material such as chromium and silicon monoxide to the polymer film to disperse such material colloidally into the growing polymer film, or applying such material to the final polymer film, and removing the resulting membrane structure from the cylinder. Alternatively, such membrane structure can be formed by etching a substrate in the form of an organic film such as a polyimide, or a metal foil, to remove material from the substrate and reduce its thickness, applying a thin reflective coating such as aluminum on one side of the substrate and applying an emissivity increasing coating such as chromium and silicon monoxide on the reverse side of the substrate.

Controlling Au Nanorod Dispersion in Thin Film Polymer Blends

NASA Astrophysics Data System (ADS)

Hore, Michael J. A.; Composto, Russell J.

2012-02-01

Dispersion of Au nanorods (Au NRs) in polymer thin films is studied using a combination of experimental and theoretical techniques. Here, we incorporate small volume fractions of polystyrene-functionalized Au NRs (φrod 0.05) into polystyrene (PS) thin films. By controlling the ratio of the brush length (N) to that of the matrix polymers (P), we can selectively obtain dispersed or aggregated Au NR structures in the PS-Au(N):PS(P) films. A dispersion map of these structures allows one to choose N and P to obtain either uniformly dispersed Au NRs or aggregates of closely packed, side-by-side aligned Au NRs. Furthermore, by blending poly(2,6-dimethyl-p-phenylene oxide) (PPO) into the PS films, we demonstrate that the Au nanorod morphology can be further tuned by reducing depletion-attraction forces and promoting miscibility of the Au NRs. These predictable structures ultimately give rise to tunable optical absorption in the films resulting from surface plasmon resonance coupling between the Au NRs. Finally, self-consistent field theoretic (SCFT) calculations for both the PS-Au(N):PS(P) and PS-Au(N):PS(P):PPO systems provide insight into the PS brush structure, and allow us to interpret morphology and optical property results in terms of wet and dry PS brush states.

Determination of active layer morphology in all-polymer photovoltaic cells

DOE PAGES

Mulderig, Andrew J.; Jin, Yan; Yu, Fei; ...

2017-08-18

This paper investigates the structure of films spin-coated from blends of the semiconducting polymers poly(3-hexylthiophene-2,5-diyl) (P3HT) and poly{2,6-[4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene]-alt-4,7(2,1,3-benzo­thiadiazole)} (PCPDTBT). Such blends are of potential use in all-polymer solar cells in which both the acceptor and the donor material generate excitons to contribute to the photocurrent. Prompted by threefold performance gains seen in polymer/fullerene and polymer blend solar cells upon addition of pristine graphene, devices are prepared from P3HT/PCPDTBT blends both with and without graphene. This report focuses on the morphology of the active layer since this is of critical importance in determining performance. Small-angle neutron scattering (SANS) is utilized tomore » study this polymer blend with deuterated P3HT to provide contrast and permit the investigation of buried structure in neat and graphene-doped films. SANS reveals the presence of P3HT crystallites dispersed in an amorphous blend matrix of P3HT and PCPDTBT. The crystallites are approximately disc shaped and do not show any evidence of higher-order structure or aggregation. While the structure of the films does not change with the addition of graphene, there is a perceptible effect on the electronic properties and energy conversion efficiency in solar cells made from such films. Finally, determination of the active layer morphology yields crucial insight into structure–property relationships in organic photovoltaic devices.« less

Determination of active layer morphology in all-polymer photovoltaic cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mulderig, Andrew J.; Jin, Yan; Yu, Fei

This paper investigates the structure of films spin-coated from blends of the semiconducting polymers poly(3-hexylthiophene-2,5-diyl) (P3HT) and poly{2,6-[4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']dithiophene]-alt-4,7(2,1,3-benzo­thiadiazole)} (PCPDTBT). Such blends are of potential use in all-polymer solar cells in which both the acceptor and the donor material generate excitons to contribute to the photocurrent. Prompted by threefold performance gains seen in polymer/fullerene and polymer blend solar cells upon addition of pristine graphene, devices are prepared from P3HT/PCPDTBT blends both with and without graphene. This report focuses on the morphology of the active layer since this is of critical importance in determining performance. Small-angle neutron scattering (SANS) is utilized tomore » study this polymer blend with deuterated P3HT to provide contrast and permit the investigation of buried structure in neat and graphene-doped films. SANS reveals the presence of P3HT crystallites dispersed in an amorphous blend matrix of P3HT and PCPDTBT. The crystallites are approximately disc shaped and do not show any evidence of higher-order structure or aggregation. While the structure of the films does not change with the addition of graphene, there is a perceptible effect on the electronic properties and energy conversion efficiency in solar cells made from such films. Finally, determination of the active layer morphology yields crucial insight into structure–property relationships in organic photovoltaic devices.« less

High strength films from oriented, hydrogen-bonded "graphamid" 2D polymer molecular ensembles.

PubMed

Sandoz-Rosado, Emil; Beaudet, Todd D; Andzelm, Jan W; Wetzel, Eric D

2018-02-27

The linear polymer poly(p-phenylene terephthalamide), better known by its tradename Kevlar, is an icon of modern materials science due to its remarkable strength, stiffness, and environmental resistance. Here, we propose a new two-dimensional (2D) polymer, "graphamid", that closely resembles Kevlar in chemical structure, but is mechanically advantaged by virtue of its 2D structure. Using atomistic calculations, we show that graphamid comprises covalently-bonded sheets bridged by a high population of strong intermolecular hydrogen bonds. Molecular and micromechanical calculations predict that these strong intermolecular interactions allow stiff, high strength (6-8 GPa), and tough films from ensembles of finite graphamid molecules. In contrast, traditional 2D materials like graphene have weak intermolecular interactions, leading to ensembles of low strength (0.1-0.5 GPa) and brittle fracture behavior. These results suggest that hydrogen-bonded 2D polymers like graphamid would be transformative in enabling scalable, lightweight, high performance polymer films of unprecedented mechanical performance.

Organometallic Polymeric Conductors

NASA Technical Reports Server (NTRS)

Youngs, Wiley J.

1997-01-01

For aerospace applications, the use of polymers can result in tremendous weight savings over metals. Suitable polymeric materials for some applications like EMI shielding, spacecraft grounding, and charge dissipation must combine high electrical conductivity with long-term environmental stability, good processability, and good mechanical properties. Recently, other investigators have reported hybrid films made from an electrically conductive polymer combined with insulating polymers. In all of these instances, the films were prepared by infiltrating an insulating polymer with a precursor for a conductive polymer (either polypyrrole or polythiophene), and oxidatively polymerizing the precursor in situ. The resulting composite films have good electrical conductivity, while overcoming the brittleness inherent in most conductive polymers. Many aerospace applications require a combination of properties. Thus, hybrid films made from polyimides or other engineering resins are of primary interest, but only if conductivities on the same order as those obtained with a polystyrene base could be obtained. Hence, a series of experiments was performed to optimize the conductivity of polyimide-based composite films. The polyimide base chosen for this study was Kapton. 3-MethylThiophene (3MT) was used for the conductive phase. Three processing variables were identified for producing these composite films, namely time, temperature, and oxidant concentration for the in situ oxidation. Statistically designed experiments were used to examine the effects of these variables and synergistic/interactive effects among variables on the electrical conductivity and mechanical strength of the films. Multiple linear regression analysis of the tensile data revealed that temperature and time have the greatest effect on maximum stress. The response surface of maximum stress vs. temperature and time (for oxidant concentration at 1.2 M) is shown. Conductivity of the composite films was measured for over 150 days in air at ambient temperature. The conductivity of the films dropped only half an order of magnitude in that time. Films aged under vacuum at ambient temperature diminished slightly in conductivity in the first day, but did not change thereafter. An experimental design approach will be applied to maximize the efficiency of the laboratory effort. The material properties (initial and long term) will also be monitored and assessed. The experimental results will add to the existing database for electrically conductive polymer materials. Attachments: 1) Synthesis Crystal Structure, and Polymerization of 1,2:5,6:9,10-Tribenzo-3,7,11,13-tetradehydro(14) annulene. 2) Reinvestigation of the Photocyclization of 1,4-Phenylene Bis(phenylmaleic anhydride): Preparation and Structure of (5)Helicene 5,6:9,10-Dianhydride. 3) Preparation and Structure Charecterization of a Platinum Catecholate Complex Containing Two 3-Ethynyltheophone Groups. and 4) Rigid-Rod Polymers Based on Noncoplanar 4,4'-Biphenyldiamines: A Review of Polymer Properties vs Configuration of Diamines.

Inverse opal photonic crystal of chalcogenide glass by solution processing.

PubMed

Kohoutek, Tomas; Orava, Jiri; Sawada, Tsutomu; Fudouzi, Hiroshi

2011-01-15

Chalcogenide opal and inverse opal photonic crystals were successfully fabricated by low-cost and low-temperature solution-based process, which is well developed in polymer films processing. Highly ordered silica colloidal crystal films were successfully infilled with nano-colloidal solution of the high refractive index As(30)S(70) chalcogenide glass by using spin-coating method. The silica/As-S opal film was etched in HF acid to dissolve the silica opal template and fabricate the inverse opal As-S photonic crystal. Both, the infilled silica/As-S opal film (Δn ~ 0.84 near λ=770 nm) and the inverse opal As-S photonic structure (Δn ~ 1.26 near λ=660 nm) had significantly enhanced reflectivity values and wider photonic bandgaps in comparison with the silica opal film template (Δn ~ 0.434 near λ=600 nm). The key aspects of opal film preparation by spin-coating of nano-colloidal chalcogenide glass solution are discussed. The solution fabricated "inorganic polymer" opal and the inverse opal structures exceed photonic properties of silica or any organic polymer opal film. The fabricated photonic structures are proposed for designing novel flexible colloidal crystal laser devices, photonic waveguides and chemical sensors. Copyright © 2010 Elsevier Inc. All rights reserved.

Dithiopheneindenofluorene (TIF) Semiconducting Polymers with Very High Mobility in Field-Effect Transistors.

PubMed

Chen, Hu; Hurhangee, Michael; Nikolka, Mark; Zhang, Weimin; Kirkus, Mindaugas; Neophytou, Marios; Cryer, Samuel J; Harkin, David; Hayoz, Pascal; Abdi-Jalebi, Mojtaba; McNeill, Christopher R; Sirringhaus, Henning; McCulloch, Iain

2017-09-01

The charge-carrier mobility of organic semiconducting polymers is known to be enhanced when the energetic disorder of the polymer is minimized. Fused, planar aromatic ring structures contribute to reducing the polymer conformational disorder, as demonstrated by polymers containing the indacenodithiophene (IDT) repeat unit, which have both a low Urbach energy and a high mobility in thin-film-transistor (TFT) devices. Expanding on this design motif, copolymers containing the dithiopheneindenofluorene repeat unit are synthesized, which extends the fused aromatic structure with two additional phenyl rings, further rigidifying the polymer backbone. A range of copolymers are prepared and their electrical properties and thin-film morphology evaluated, with the co-benzothiadiazole polymer having a twofold increase in hole mobility when compared to the IDT analog, reaching values of almost 3 cm 2 V -1 s -1 in bottom-gate top-contact organic field-effect transistors. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Elongated phase separation domains in spin-cast polymer blend thin films characterized using a panoramic image.

PubMed

Zhang, Hong; Okamura, Yosuke

2018-02-14

Polymer thin films with micro/nano-structures can be prepared by a solvent evaporation induced phase separation process via spin-casting a polymer blend, where the elongated phase separation domains are always inevitable. The striation defect, as a thickness nonunifomity in spin-cast films, is generally coexistent with the elongated domains. Herein, the morphologies of polymer blend thin films are recorded from the spin-cast center to the edge in a panoramic view. The elongated domains are inclined to appear at the ridge regions of striations with increasing radial distance and align radially, exhibiting a coupling between the phase separation morphology and the striation defect that may exist. We demonstrate that the formation of elongated domains is not attributed to shape deformation, but is accomplished in situ. A possible model to describe the initiation and evolution of the polymer blend phase separation morphology during spin-casting is proposed.

Ultrasonic-assisted synthesis of phosphorus graphene oxide/poly (vinyl alcohol) polymer and surface resistivity research of phosphorus graphene oxide/poly (vinyl alcohol) film.

PubMed

Li, Jihui; Li, Yongshen; Niu, Shuai; Li, Ning

2017-05-01

In this paper, phosphorus graphene oxide/poly (vinyl alcohol) polymer (PGO/PVA polymer) was synthesized by PGO and PVA via the esterification in the case of faint acidity and the ultrasound irradiation and characterized; moreover, phosphorus graphene oxide/poly (vinyl alcohol) film (PGO/PVA film) was prepared by PGO/PVA polymer and characterized; also, the surface resistivity of PGO/PVA film was investigated in the case of the different amount of PGO. Based on those, it had been found that PGO reacted with PVA to produce PGO/PVA polymer via the esterification under the ultrasonic-assisted condition, and PGO/PVA polymer was structured by 2D lattice of PGO and the chain of PVA connected in the form of six-member lactone ring and phosphonic ester, and PGO/PVA film was constituted by PGO/PVA polymer, and surface resistivity of 0.00, 0.75, 1.50, 2.25 and 3.00wt% of PGO/PVA film were 6.85×10 8 , 2.98×10 8 , 1.42×10 6 , 7.66×10 4 and 1.29×10 5 Ω/sq, respectively. Copyright © 2016 Elsevier B.V. All rights reserved.

Enhanced thermal stability of a polymer solar cell blend induced by electron beam irradiation in the transmission electron microscope.

PubMed

Bäcke, Olof; Lindqvist, Camilla; de Zerio Mendaza, Amaia Diaz; Gustafsson, Stefan; Wang, Ergang; Andersson, Mats R; Müller, Christian; Kristiansen, Per Magnus; Olsson, Eva

2017-05-01

We show by in situ microscopy that the effects of electron beam irradiation during transmission electron microscopy can be used to lock microstructural features and enhance the structural thermal stability of a nanostructured polymer:fullerene blend. Polymer:fullerene bulk-heterojunction thin films show great promise for use as active layers in organic solar cells but their low thermal stability is a hindrance. Lack of thermal stability complicates manufacturing and influences the lifetime of devices. To investigate how electron irradiation affects the thermal stability of polymer:fullerene films, a model bulk-heterojunction film based on a thiophene-quinoxaline copolymer and a fullerene derivative was heat-treated in-situ in a transmission electron microscope. In areas of the film that exposed to the electron beam the nanostructure of the film remained stable, while the nanostructure in areas not exposed to the electron beam underwent large phase separation and nucleation of fullerene crystals. UV-vis spectroscopy shows that the polymer:fullerene films are stable for electron doses up to 2000kGy. Copyright © 2016 Elsevier B.V. All rights reserved.

Enhanced thermal stability of a polymer solar cell blend induced by electron beam irradiation in the transmission electron microscope.

PubMed

Bäcke, Olof; Lindqvist, Camilla; de Zerio Mendaza, Amaia Diaz; Gustafsson, Stefan; Wang, Ergang; Andersson, Mats R; Müller, Christian; Kristiansen, Per Magnus; Olsson, Eva

2017-02-01

We show by in situ microscopy that the effects of electron beam irradiation during transmission electron microscopy can be used to lock microstructural features and enhance the structural thermal stability of a nanostructured polymer:fullerene blend. Polymer:fullerene bulk-heterojunction thin films show great promise for use as active layers in organic solar cells but their low thermal stability is a hindrance. Lack of thermal stability complicates manufacturing and influences the lifetime of devices. To investigate how electron irradiation affects the thermal stability of polymer:fullerene films, a model bulk-heterojunction film based on a thiophene-quinoxaline copolymer and a fullerene derivative was heat-treated in-situ in a transmission electron microscope. In areas of the film that exposed to the electron beam the nanostructure of the film remained stable, while the nanostructure in areas not exposed to the electron beam underwent large phase separation and nucleation of fullerene crystals. UV-vis spectroscopy shows that the polymer:fullerene films are stable for electron doses up to 2000kGy. Copyright © 2017 Elsevier B.V. All rights reserved.

Copper cladding on polymer surfaces by ionization-assisted deposition

NASA Astrophysics Data System (ADS)

Kohno, Tomoki; Tanaka, Kuniaki; Usui, Hiroaki

2018-03-01

Copper thin films were prepared on poly(ethylene terephthalate) (PET) and polyimide (PI) substrates by an ionization-assisted vapor deposition method. The films had a polycrystalline structure, and their crystallite size decreased with increasing ion acceleration voltage V a. Ion acceleration was effective in reducing the surface roughness of the films. Cross-sectional transmission electron microscopy revealed that the copper/polymer interface showed increased corrugation with increasing V a. The increase in V a also induced the chemical modification of polymer chains of the PET substrate, but the PI substrate underwent smaller modification after ion bombardment. Most importantly, the adhesion strength between the copper film and the PET substrate increased with increasing V a. It was concluded that ionization-assisted deposition is a promising technique for preparing metal clad layers on flexible polymer substrates.

Alumina/polymer-coated nanocrystals with extremely high stability used as a color conversion material in LEDs

NASA Astrophysics Data System (ADS)

Woo, Ju Yeon; Lee, Jongsoo; Han, Chang-Soo

2013-12-01

The long-term stability of quantum dot (QD)-based devices under harsh environmental conditions has been a critical bottleneck to be resolved for commercial use. Here, we demonstrate an extremely stable QD/alumina/polymer hybrid structure by combining internal atomic layer deposition (ALD) infilling with polymer encapsulation. ALD infilling and polymer encapsulation of QDs synergistically prohibit the degradation of QDs in terms of optical, thermal and humid attacks. Our hybrid QD/alumina/polymer film structure showed no noticeable reduction in photoluminescence even in a commercial grade test (85% humidity at 85 ° C) over 28 days. In addition, we successfully fabricated a QD-based light-emitting device with excellent long-term stability by incorporating hybrid QD/alumina/polymer film as a color conversion material on light-emitting diode chips.

Structure and morphology of magnetron sputter deposited ultrathin ZnO films on confined polymeric template

NASA Astrophysics Data System (ADS)

Singh, Ajaib; Schipmann, Susanne; Mathur, Aakash; Pal, Dipayan; Sengupta, Amartya; Klemradt, Uwe; Chattopadhyay, Sudeshna

2017-08-01

The structure and morphology of ultra-thin zinc oxide (ZnO) films with different film thicknesses on confined polymer template were studied through X-ray reflectivity (XRR) and grazing incidence small angle X-ray scattering (GISAXS). Using magnetron sputter deposition technique ZnO thin films with different film thicknesses (<10 nm) were grown on confined polystyrene with ∼2Rg film thickness, where Rg ∼ 20 nm (Rg is the unperturbed radius of gyration of polystyrene, defined by Rg = 0.272 √M0, and M0 is the molecular weight of polystyrene). The detailed internal structure, along the surface/interfaces and the growth direction of the system were explored in this study, which provides insight into the growth procedure of ZnO on confined polymer and reveals that a thin layer of ZnO, with very low surface and interface roughness, can be grown by DC magnetron sputtering technique, with approximately full coverage (with bulk like electron density) even in nm order of thickness, in 2-7 nm range on confined polymer template, without disturbing the structure of the underneath template. The resulting ZnO-polystyrene hybrid systems show strong ZnO near band edge (NBE) and deep-level (DLE) emissions in their room temperature photoluminescence spectra, where the contribution of DLE gets relatively stronger with decreasing ZnO film thickness, indicating a significant enhancement of surface defects because of the greater surface to volume ratio in thinner films.

Oriented Liquid Crystalline Polymer Semiconductor Films with Large Ordered Domains.

PubMed

Xue, Xiao; Chandler, George; Zhang, Xinran; Kline, R Joseph; Fei, Zhuping; Heeney, Martin; Diemer, Peter J; Jurchescu, Oana D; O'Connor, Brendan T

2015-12-09

Large strains are applied to liquid crystalline poly(2,5-bis(3-tetradecylthiophen-2yl)thieno(3,2-b)thiophene) (pBTTT) films when held at elevated temperatures resulting in in-plane polymer alignment. We find that the polymer backbone aligns significantly in the direction of strain, and that the films maintain large quasi-domains similar to that found in spun-cast films on hydrophobic surfaces, highlighted by dark-field transmission electron microscopy imaging. The highly strained films also have nanoscale holes consistent with dewetting. Charge transport in the films is then characterized in a transistor configuration, where the field effect mobility is shown to increase in the direction of polymer backbone alignment, and decrease in the transverse direction. The highest saturated field-effect mobility was found to be 1.67 cm(2) V(-1) s(-1), representing one of the highest reported mobilities for this material system. The morphology of the oriented films demonstrated here contrast significantly with previous demonstrations of oriented pBTTT films that form a ribbon-like morphology, opening up opportunities to explore how differences in molecular packing features of oriented films impact charge transport. Results highlight the role of grain boundaries, differences in charge transport along the polymer backbone and π-stacking direction, and structural features that impact the field dependence of charge transport.

Universal lab on a smartphone: a research of TiOPc thin film as a light dependence electrode

NASA Astrophysics Data System (ADS)

Lin, PoHan; Hsu, Y. H.; Lee, C. K.

2014-02-01

In this paper, we study the photoconductivity of a polymer-based TiOPc (Titanium Oxide Phthalocyanine) thin-film for the development of a multi-opto-piezoelectric-valve-array. Using a polymer-based TiOPc thin film to serve as the electrode and a structural layer of a piezoelectric polymer, P(VDF-TrFE) poly[(vinylidenefluoride-co-trifluoroethylene], an optical control valve-array could be developed for manipulating multiple microdroplets for the application of digital microfluidic. In this ongoing project, the dependency of the light intensity, thickness, and composition of spin-coated polymer-based TiOPc thin-film was studied. The experimental finding suggested that a 14 to 55 times resistivity change could be achieved by controlling the film thickness to be between 0.9 μm and 1.5 μm with TiOPc concentration of 20% and 30% w/w compositions.

Structures and properties of poly(3-alkylthiophene) thin-films fabricated though vapor-phase polymerization.

PubMed

Back, Ji-Woong; Song, Eun-Ah; Lee, Keum-Joo; Lee, Youn-Kyung; Hwang, Chae-Ryong; Jo, Sang-Hyun; Jung, Woo-Gwang; Kim, Jin-Yeol

2012-02-01

Organic semiconducting polymer thin-films of 3-hexylthiophene, 3-octylthiophene, 3-decylthiophene, containing highly oriented crystal were fabricated by gas-phase polymerization using the CVD technique. These poly(3-alkylthiophene) films had a crystallinity up to 80%, and possessed a Hall mobility up to 10 cm2/Vs. The degree of crystalinity and the mobility values increased as the alkyl chain length increased. The crystal structure of the polymers was composed of stacked layers constructed by a side-by-side arrangement of alkyl chains and in-plane pi-pi stacking. These thin films are capable of being applied to organic electronics as the active materials used in thin-film transistors and organic photovoltaic cells.

Directed Self-Organization of Polymer-Grafted Nanoparticles in Polymer Thin Films

NASA Astrophysics Data System (ADS)

Zhang, Ren

The controlled organization of nanoparticle (NP) constituents into superstructures of well-defined shape, composition and connectivity represents a continuing challenge in the development of novel hybrid materials for many technological applications. Surface modification of NPs with grafted polymer ligands has emerged as a versatile means to control the interaction and organization of particle constituents in polymer-matrix composite materials. In this study, by incorporating polymer-grafted nanoparticles (PGNPs) into polymeric thin films, we aim to understand and control the spatial organization of PGNPs through the interactions between polymer brush layer and matrix chains. As model systems, we investigate thermodynamic behaviors of polystyrene-tethered gold nanoparticles (denoted as AuPS) dispersed in polymer thin film matrices with identical and different chemical compositions (PS and PMMA, respectively), and evaluate the influence of external perturbation fields on directed organization of nanofillers. With the presence of unfavorable enthalpic interactions between grafted and free polymer chains (i.e. AuPS/ PMMA blend thin films), phase-separated structures are generated upon thermal annealing, characterized with morphologies ranging from discrete droplets to spinodal structures, which is consistent with composition-dependent classic binary polymer blends phase separation. The phase separation kinetics of AuPS/ PMMA blends exhibit distinct features compared to the parent PS/ PMMA homopolymer blends. We further illustrate phase-separated AuPS-rich domains can be directed into unidirectionally aligned anisotropic structures through soft-shear dynamic zone annealing (DZA-SS) process with tunable domain aspect ratios. To exert exquisite control over the shape, size and location of phase-separated PGNP domains, topographically patterned elastomer confinement is introduced to PGNP/ polymer blend thin films during thermal annealing. When the phase-separated lengthscale coincides with confined pattern dimension, long-range ordered submicron-sized AuPS domains are generated in PMMA matrices with dense and well-dispersed nanoparticle distribution. Furthermore, preferential segregation of AuPS nanoparticles at patterned mesa regions can be induced in PS matrices where enthalpic interactions are absent. This selective segregation is achieved due to the local perturbation of grafted chains when confined in a restricted space. The efficiency of this particle segregation process within patterned mesa-trench films can be tuned by changing the relative entropic confinement effects on grafted and matrix chains. This physical pattern directed PGNP organization strategy is applicable to versatile pattern geometries and nanoparticle compositions.

Resonant infrared laser deposition of polymer-nanocomposite materials for optoelectronic applications

NASA Astrophysics Data System (ADS)

Park, Hee K.; Schriver, Kenneth E.; Haglund, Richard F.

2011-11-01

Polymers find a number of potentially useful applications in optoelectronic devices. These include both active layers, such as light-emitting polymers and hole-transport layers, and passive layers, such as polymer barrier coatings and light-management films. This paper reports the experimental results for polymer films deposited by resonant infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE) and resonant infrared pulsed laser deposition (RIR-PLD) for commercial optoelectronic device applications. In particular, light-management films, such as anti-reflection coatings, require refractive-index engineering of a material. However, refractive indices of polymers fall within a relatively narrow range, leading to major efforts to develop both low- and high-refractive-index polymers. Polymer nanocomposites can expand the range of refractive indices by incorporating low- or high-refractive-index nanoscale materials. RIR-MAPLE is an excellent technique for depositing polymer-nanocomposite films in multilayer structures, which are essential to light-management coatings. In this paper, we report our efforts to engineer the refractive index of a barrier polymer by combining RIR-MAPLE of nanomaterials (for example, high refractive-index TiO2 nanoparticles) and RIR-PLD of host polymer. In addition, we report on the properties of organic and polymer films deposited by RIR-MAPLE and/or RIR-PLD, such as Alq3 [tris(8-hydroxyquinoline) aluminum] and PEDOT:PSS [poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate)]. Finally, the challenges and potential for commercializing RIR-MAPLE/PLD, such as industrial scale-up issues, are discussed.

Formation of biodegradated polymers as components of future composite materials on the basis of shape memory alloy of medical appointment

NASA Astrophysics Data System (ADS)

Nasakina, E. O.; Baikin, A. S.; Sergiyenko, K. V.; Kaplan, M. A.; Konushkin, S. V.; Yakubov, A. D.; Izvin, A. V.; Sudarchikova, M. A.; Sevost’yanov, M. A.; Kolmakov, A. G.

2018-04-01

The processes of formation of polymer polylactide or polyglycylidactide films for the subsequent creation of a layered composite with a biodegradable layer on the basis of a nickel-free shape memory alloy TiNbTaZr are studied. The structure of the samples was determined using an SEM. The correspondence of morphology of surfaces of and the substrate itself is noted. High adhesion of the polymer to the future basis of the developed composite material is supposed. The formed films is homogeneous and amorphous throughout the polymer volume. By varying the volume of solutions, it is possible to obtain films of a given thickness for any type of polymer, its molecular weight, and the solution concentration of the polymer in chloroform. Poly (glycolide-lactide) should be more plastic than polylactide.

Unlocking the Structure and Dynamics of Thin Polymeric Films

DTIC Science & Technology

2016-11-13

AFRL-AFOSR-JP-TR-2016-0092 Unlocking the Structure and Dynamics of Thin Polymeric Films Andrew Whittaker THE UNIVERSITY OF QUEENSLAND Final Report 11...Final 3. DATES COVERED (From - To)  15 Jun 2015 to 16 Jun 2016 4. TITLE AND SUBTITLE Unlocking the Structure and Dynamics of Thin Polymeric Films 5a...the interfacial structure that are inherent in thin films affects how polymers behave. A number of technically relevant polymeric systems were

Why we need to look beyond the glass transition temperature to characterize the dynamics of thin supported polymer films.

PubMed

Zhang, Wengang; Douglas, Jack F; Starr, Francis W

2018-05-29

There is significant variation in the reported magnitude and even the sign of [Formula: see text] shifts in thin polymer films with nominally the same chemistry, film thickness, and supporting substrate. The implicit assumption is that methods used to estimate [Formula: see text] in bulk materials are relevant for inferring dynamic changes in thin films. To test the validity of this assumption, we perform molecular simulations of a coarse-grained polymer melt supported on an attractive substrate. As observed in many experiments, we find that [Formula: see text] based on thermodynamic criteria (temperature dependence of film height or enthalpy) decreases with decreasing film thickness, regardless of the polymer-substrate interaction strength ε. In contrast, we find that [Formula: see text] based on a dynamic criterion (relaxation of the dynamic structure factor) also decreases with decreasing thickness when ε is relatively weak, but [Formula: see text] increases when ε exceeds the polymer-polymer interaction strength. We show that these qualitatively different trends in [Formula: see text] reflect differing sensitivities to the mobility gradient across the film. Apparently, the slowly relaxing polymer segments in the substrate region make the largest contribution to the shift of [Formula: see text] in the dynamic measurement, but this part of the film contributes less to the thermodynamic estimate of [Formula: see text] Our results emphasize the limitations of using [Formula: see text] to infer changes in the dynamics of polymer thin films. However, we show that the thermodynamic and dynamic estimates of [Formula: see text] can be combined to predict local changes in [Formula: see text] near the substrate, providing a simple method to infer information about the mobility gradient.

Stacking metal nano-patterns and fabrication of moth-eye structure

NASA Astrophysics Data System (ADS)

Taniguchi, Jun

2018-01-01

Nanoimprint lithography (NIL) can be used as a tool for three-dimensional nanoscale fabrication. In particular, complex metal pattern structures in polymer material are demanded as plasmonic effect devices and metamaterials. To fabricate of metallic color filter, we used silver ink and NIL techniques. Metallic color filter was composed of stacking of nanoscale silver disc patterns and polymer layers, thus, controlling of polymer layer thickness is necessary. To control of thickness of polymer layer, we used spin-coating of UV-curable polymer and NIL. As a result, ten stacking layers with 1000 nm layer thickness was obtained and red color was observed. Ultraviolet nanoimprint lithography (UV-NIL) is the most effective technique for mass fabrication of antireflection structure (ARS) films. For the use of ARS films in mobile phones and tablet PCs, which are touch-screen devices, it is important to protect the films from fingerprints and dust. In addition, as the nanoscale ARS that is touched by the hand is fragile, it is very important to obtain a high abrasion resistance. To solve these problems, a UV-curable epoxy resin has been developed that exhibits antifouling properties and high hardness. The high abrasion resistance ARS films are shown to withstand a load of 250 g/cm2 in the steel wool scratch test, and the reflectance is less than 0.4%.

Dewetting of thin polymer films: an X-ray scattering study

NASA Astrophysics Data System (ADS)

Müller-Buschbaum, P.; Stamm, M.

1998-06-01

The surface morphology of different dewetting states of thin polymer films (polystyrene) on top of silicon substrates was investigated. With diffuse X-ray scattering in the region of total external reflection a high in-plane resolution was achieved. We observe a new nano-dewetting structure which coexists with the well known mesoscopic dewetting structures of holes, cellular pattern and drops. This nano-dewetting structure consists of small dimples with a diameter in the nanometer range. It results from the dewetting of a remaining ultra-thin polymer layer and can be explained with theoretical predictions of spinodal decomposition. The experimental results of the scattering study are confirmed with scanning-force microscopy measurements.

Understanding temperature tuning of the all polymer co-extruded laser

NASA Astrophysics Data System (ADS)

Crescimanno, Michael; Andrews, Jim; Aviles, Michael; Dawson, Nathan; Petrus, Joshua; Mazzocco, Anthony; Singer, Ken; Baer, Eric; Song, Hyunmin

2012-10-01

We investigate the effects of elevated temperatures on a few types of all-polymer multilayer films that were fabricated using a co-extrusion melt-process technique. We report on the anisotropic thermal expansion of the multilayer films, which affects the photonic crystal structure via constituent wise induced anisotropic strains and a change in the relative refractive indices. In addition to the characterization of these films in the temperature range of approximately 20-95 degrees C, we show the application to non-contact temperature sensing and wavelength tuning of all polymer Distributed FeedBack (DFB) lasers and Distributed Bragg Reflector (DBR) lasers.

Dielectric breakdown in silica-amorphous polymer nanocomposite films: the role of the polymer matrix.

PubMed

Grabowski, Christopher A; Fillery, Scott P; Westing, Nicholas M; Chi, Changzai; Meth, Jeffrey S; Durstock, Michael F; Vaia, Richard A

2013-06-26

The ultimate energy storage performance of an electrostatic capacitor is determined by the dielectric characteristics of the material separating its conductive electrodes. Polymers are commonly employed due to their processability and high breakdown strength; however, demands for higher energy storage have encouraged investigations of ceramic-polymer composites. Maintaining dielectric strength, and thus minimizing flaw size and heterogeneities, has focused development toward nanocomposite (NC) films; but results lack consistency, potentially due to variations in polymer purity, nanoparticle surface treatments, nanoparticle size, and film morphology. To experimentally establish the dominant factors in broad structure-performance relationships, we compare the dielectric properties for four high-purity amorphous polymer films (polymethyl methacrylate, polystyrene, polyimide, and poly-4-vinylpyridine) incorporating uniformly dispersed silica colloids (up to 45% v/v). Factors known to contribute to premature breakdown-field exclusion and agglomeration-have been mitigated in this experiment to focus on what impact the polymer and polymer-nanoparticle interactions have on breakdown. Our findings indicate that adding colloidal silica to higher breakdown strength amorphous polymers (polymethyl methacrylate and polyimide) causes a reduction in dielectric strength as compared to the neat polymer. Alternatively, low breakdown strength amorphous polymers (poly-4-vinylpyridine and especially polystyrene) with comparable silica dispersion show similar or even improved breakdown strength for 7.5-15% v/v silica. At ∼15% v/v or greater silica content, all the polymer NC films exhibit breakdown at similar electric fields, implying that at these loadings failure becomes independent of polymer matrix and is dominated by silica.

Real-time x-ray scattering study of the initial growth of organic crystals on polymer brushes

DOE Office of Scientific and Technical Information (OSTI.GOV)

An, Sung Yup; Ahn, Kwangseok; Kim, Doris Yangsoo

2014-04-21

We studied the early-stage growth structures of pentacene organic crystals grown on polymer brushes using real-time x-ray scattering techniques. In situ x-ray reflectivity and atomic force microscopy analyses revealed that at temperatures close to the glass transition temperature of polymer brush, the pentacene overlayer on a polymer brush film showed incomplete condensation and 3D island structures from the first monolayer. A growth model based on these observations was used to quantitatively analyze the real-time anti-Bragg x-ray scattering intensities measured during pentacene growth to obtain the time-dependent layer coverage of the individual pentacene monolayers. The extracted total coverage confirmed significant desorptionmore » and incomplete condensation in the pentacene films deposited on the polymer brushes. These effects are ascribed to the change in the surface viscoelasticity of the polymer brushes around the glass transition temperature.« less

Structure of water at zwitterionic copolymer film-liquid water interfaces as examined by the sum frequency generation method.

PubMed

Kondo, Takuya; Nomura, Kouji; Gemmei-Ide, Makoto; Kitano, Hiromi; Noguchi, Hidenori; Uosaki, Kohei; Saruwatari, Yoshiyuki

2014-01-01

A copolymer film composed of zwitterionic carboxymethylbetaine (CMB) and n-butyl methacrylate (BMA), Poly(CMB-r-BMA), was cast on a flat plane of an octadecyltrichlorosilane (ODS)-modified fused quartz prism with a semi-cylindrical shape. CH stretching of the polymer film and O-H stretching of water at the surface of the film were examined using the sum frequency generation (SFG) technique. The C-H stretching band of the cast film, indicating a gauche defect of the film, was affected by the contact medium including dry nitrogen, water vapor-saturated nitrogen and liquid water. In contrast, the C-H stretching of an octadecyl group introduced onto the quartz prism for stable attachment of the cast film was not significantly changed by the contact medium. The O-H stretching band indicated that water molecules at the surface of the Poly(CMB-r-BMA) film in contact with liquid water were not greatly oriented in comparison with those at the surfaces of a bare prism, an ODS SAM-modified prism, and a prism covered with a PolyBMA film or a copolymer film of BMA and methacrylic acid or 2-(dimethylamino)ethyl methacrylate. A similar small perturbation of the structure of water was previously observed in the vicinity of water-soluble zwitterionic polymers and zwitterionic copolymer films using Raman and attenuated total reflection infrared spectroscopies, respectively. A distinct effect of charge neutralization to diminish the perturbation of the structure of interfacial water around polymer materials was suggested. Copyright © 2013 Elsevier B.V. All rights reserved.

Generation of conductivity through transfer charge properties, for polyesters and polyamides with characteristic functional groups

NASA Astrophysics Data System (ADS)

Gonzalez, Carmen; Tagle, Luis Hernan; Terraza, Claudio A.; Barriga, Andres; Cabrera, A. L.; Volkmann, Ulrich G.

2011-03-01

Electro-optic properties of σ -conjugated polymers, as polysilylene; are associated with electron conjugation in the silicon atom, which allows a significant delocalization of electrons along of the chain. Thus, the conductivity is intimately connected to the mobility of charge carriers, which in turn depends on the structure and morphology of the system. We report the characterization of polyesters (PEFs) and polyamides (PAFs). Film thicknesses were obtained by ellipsometry. The vibration frequencies of the groups were determined by FT-IR and corroborated by Raman spectroscopy. Structural information was obtained from X-Ray diffraction (XRD). The structural and surface morphology were studied by scanning electron microscope (SEM). Electrical conductivity of the polymers was measured before and after exposure to iodine vapor, for films of different thicknesses. Morphological differentiation was studied by energy dispersive microscopy (EDX), showing a regular distribution of iodine within the polymer. Preliminary conductivity measurements showed adverse effects when oxidation of the polymer films is induced These effects are related to a certain grade of disorder within the system

Symmetry Breaking in Side Chains Leading to Mixed Orientations and Improved Charge Transport in Isoindigo-alt-Bithiophene Based Polymer Thin Films.

PubMed

Xue, Guobiao; Zhao, Xikang; Qu, Ge; Xu, Tianbai; Gumyusenge, Aristide; Zhang, Zhuorui; Zhao, Yan; Diao, Ying; Li, Hanying; Mei, Jianguo

2017-08-02

The selection of side chains is important in design of conjugated polymers. It not only affects their intrinsic physical properties, but also has an impact on thin film morphologies. Recent reports suggested that a face-on/edge-on bimodal orientation observed in polymer thin films may be responsible for a three-dimensional (3D) charge transport and leads to dramatically improved mobility in donor-acceptor based conjugated polymers. To achieve a bimodal orientation in thin films has been seldom explored from the aspect of molecular design. Here, we demonstrate a design strategy involving the use of asymmetric side chains that enables an isoindigo-based polymer to adopt a distinct bimodal orientation, confirmed by the grazing incidence X-ray diffraction. As a result, the polymer presents an average high mobility of 3.8 ± 0.7 cm 2 V -1 s -1 with a maximum value of 5.1 cm 2 V -1 s -1 , in comparison with 0.47 and 0.51 cm 2 V -1 s -1 obtained from the two reference polymers. This study exemplifies a new strategy to develop the next generation polymers through understanding the property-structure relationship.

Using a micro-molding process to fabricate polymeric wavelength filters

NASA Astrophysics Data System (ADS)

Chuang, Wei-Ching; Lee, An-Chen; Ho, Chi-Ting

2008-08-01

A procedure for fabricating a high aspect ratio periodic structure on a UV polymer at submicron order using holographic interferometry and molding processes is described. First, holographic interferometry using a He-Cd (325 nm) laser was used to create the master of the periodic line structure on an i-line sub-micron positive photoresist film. A 20 nm nickel thin film was then sputtered on the photoresist. The final line pattern on a UV polymer was obtained from casting against the master mold. Finally, a SU8 polymer was spun on the polymer grating to form a planar waveguide or a channel waveguide. The measurement results show that the waveguide length could be reduced for the waveguide having gratings with a high aspect ratio.

Highly crystalline films of PCPDTBT with branched side chains by solvent vapor crystallization: influence on opto-electronic properties.

PubMed

Fischer, Florian S U; Trefz, Daniel; Back, Justus; Kayunkid, Navaphun; Tornow, Benjamin; Albrecht, Steve; Yager, Kevin G; Singh, Gurpreet; Karim, Alamgir; Neher, Dieter; Brinkmann, Martin; Ludwigs, Sabine

2015-02-18

PCPDTBT, a marginally crystallizable polymer, is crystallized into a new crystal structure using solvent-vapor annealing. Highly ordered areas with three different polymer-chain orientations are identified using TEM/ED, GIWAXS, and polarized Raman spectroscopy. The optical and structural properties differ significantly from films prepared by standard device preparation protocols. Bilayer solar cells, however, show similar performance. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Selectively Patterning Polymer Opal Films via Microimprint Lithography.

PubMed

Ding, Tao; Zhao, Qibin; Smoukov, Stoyan K; Baumberg, Jeremy J

2014-11-01

Large-scale structural color flexible coatings have been hard to create, and patterning color on them is key to many applications, including large-area strain sensors, wall-size displays, security devices, and smart fabrics. To achieve controlled tuning, a micro-imprinting technique is applied here to pattern both the surface morphology and the structural color of the polymer opal films (POFs). These POFs are made of 3D ordered arrays of hard spherical particles embedded inside soft shells. The soft outer shells cause the POFs to deform upon imprinting with a pre-patterned stamp, driving a flow of the soft polymer and a rearrangement of the hard spheres within the films. As a result, a patterned surface morphology is generated within the POFs and the structural colors are selectively modified within different regions. These changes are dependent on the pressure, temperature, and duration of imprinting, as well as the feature sizes in the stamps. Moreover, the pattern geometry and structural colors can then be further tuned by stretching. Micropattern color generation upon imprinting depends on control of colloidal transport in a polymer matrix under shear flow and brings many potential properties including stretchability and tunability, as well as being of fundamental interest.

Synthesis and characterization thin films of conductive polymer (PANI) for optoelectronic device application

NASA Astrophysics Data System (ADS)

Jarad, Amer N.; Ibrahim, Kamarulazizi; Ahmed, Nasser M.

2016-07-01

In this work we report preparation and investigation of structural and optical properties of polyaniline conducting polymer. By using sol-gel in spin coating technique to synthesize thin films of conducting polymer polyaniline (PANI). Conducting polymer polyaniline was synthesized by the chemical oxidative polymerization of aniline monomers. The thin films were characterized by technique: Hall effect, High Resolution X-ray diffraction (HR-XRD), Fourier transform infrared (FTIR) spectroscopy, Field emission scanning electron microscopy (FE-SEM), and UV-vis spectroscopy. Polyaniline conductive polymer exhibit amorphous nature as confirmed by HR-XRD. The presence of characteristic bonds of polyaniline was observed from FTIR spectroscopy technique. Electrical and optical properties revealed that (p-type) conductivity PANI with room temperature, the conductivity was 6.289×10-5 (Ω.cm)-1, with tow of absorption peak at 426,805 nm has been attributed due to quantized size of polyaniline conducting polymer.

Structure-property relation in HPMC polymer films plasticized with Sorbitol

NASA Astrophysics Data System (ADS)

Prakash, Y.; Somashekarappa, H.; Mahadevaiah, Somashekar, R.

2013-06-01

A correlation study on physical and mechanical properties of Hydroxy propyl-methylcellulose (HPMC) polymer films plasticized with different weight ratio of Sorbitol, prepared using solution casting method, was carried out using wide angle X-ray technique and universal testing machine. It is found that the crystallanity decreases as the concentration of Sorbitol increases up to a certain concentration and there afterwards increases. Measured Physical Properties like tensile strength decreases and elongation (%) increases indicating increase in the flexibility of the films. These observations confirm the correlation between microstructal parameters and mechanical properties of films. These films are suitable for packaging food products.

Rapid prototyping of all-solution-processed multi-lengthscale electrodes using polymer-induced thin film wrinkling

PubMed Central

Gabardo, Christine M.; Adams-McGavin, Robert C.; Fung, Barnabas C.; Mahoney, Eric J.; Fang, Qiyin; Soleymani, Leyla

2017-01-01

Three-dimensional electrodes that are controllable over multiple lengthscales are very important for use in bioanalytical systems that integrate solid-phase devices with solution-phase samples. Here we present a fabrication method based on all-solution-processing and thin film wrinkling using smart polymers that is ideal for rapid prototyping of tunable three-dimensional electrodes and is extendable to large volume manufacturing. Although all-solution-processing is an attractive alternative to vapor-based techniques for low-cost manufacturing of electrodes, it often results in films suffering from low conductivity and poor substrate adhesion. These limitations are addressed here by using a smart polymer to create a conformal layer of overlapping wrinkles on the substrate to shorten the current path and embed the conductor onto the polymer layer. The structural evolution of these wrinkled electrodes, deposited by electroless deposition onto a nanoparticle seed layer, is studied at varying deposition times to understand its effects on structural parameters such as porosity, wrinkle wavelength and height. Furthermore, the effect of structural parameters on functional properties such as electro-active surface area and surface-enhanced Raman scattering is investigated. It is found that wrinkling of electroless-deposited thin films can be used to reduce sheet resistance, increase surface area, and enhance the surface-enhanced Raman scattering signal. PMID:28211898

Rapid prototyping of all-solution-processed multi-lengthscale electrodes using polymer-induced thin film wrinkling

NASA Astrophysics Data System (ADS)

Gabardo, Christine M.; Adams-McGavin, Robert C.; Fung, Barnabas C.; Mahoney, Eric J.; Fang, Qiyin; Soleymani, Leyla

2017-02-01

Three-dimensional electrodes that are controllable over multiple lengthscales are very important for use in bioanalytical systems that integrate solid-phase devices with solution-phase samples. Here we present a fabrication method based on all-solution-processing and thin film wrinkling using smart polymers that is ideal for rapid prototyping of tunable three-dimensional electrodes and is extendable to large volume manufacturing. Although all-solution-processing is an attractive alternative to vapor-based techniques for low-cost manufacturing of electrodes, it often results in films suffering from low conductivity and poor substrate adhesion. These limitations are addressed here by using a smart polymer to create a conformal layer of overlapping wrinkles on the substrate to shorten the current path and embed the conductor onto the polymer layer. The structural evolution of these wrinkled electrodes, deposited by electroless deposition onto a nanoparticle seed layer, is studied at varying deposition times to understand its effects on structural parameters such as porosity, wrinkle wavelength and height. Furthermore, the effect of structural parameters on functional properties such as electro-active surface area and surface-enhanced Raman scattering is investigated. It is found that wrinkling of electroless-deposited thin films can be used to reduce sheet resistance, increase surface area, and enhance the surface-enhanced Raman scattering signal.

Self-organization processes in polysiloxane block copolymers, initiated by modifying fullerene additives

NASA Astrophysics Data System (ADS)

Voznyakovskii, A. P.; Kudoyarova, V. Kh.; Kudoyarov, M. F.; Patrova, M. Ya.

2017-08-01

Thin films of a polyblock polysiloxane copolymer and their composites with a modifying fullerene C60 additive are studied by atomic force microscopy, Rutherford backscattering, and neutron scattering. The data of atomic force microscopy show that with the addition of fullerene to the bulk of the polymer matrix, the initial relief of the film surface is leveled more, the larger the additive. This trend is associated with the processes of self-organization of rigid block sequences, which are initiated by the field effect of the surface of fullerene aggregates and lead to an increase in the number of their domains in the bulk of the polymer matrix. The data of Rutherford backscattering and neutron scattering indicate the formation of additional structures with a radius of 60 nm only in films containing fullerene, and their fraction increases with increasing fullerene concentration. A comparative analysis of the data of these methods has shown that such structures are, namely, the domains of a rigid block and are not formed by individual fullerene aggregates. The interrelation of the structure and mechanical properties of polymer films is considered.

Effect of plasticizer on surface of free films prepared from aqueous solutions of salts of cationic polymers with different plasticizers

NASA Astrophysics Data System (ADS)

Bajdik, János; Fehér, Máté; Pintye-Hódi, Klára

2007-06-01

Acquisition of a more detailed understanding of all technological processes is currently a relevant tendency in pharmaceutical technology and hence in industry. A knowledge of film formation from dispersion of polymers is very important during the coating of solid dosage forms. This process and the structure of the film can be influenced by different additives. In the present study, taste-masking films were prepared from aqueous citric acid solutions of a cationic polymer (Eudragit ® E PO) with various hydrophilic plasticizers (glycerol, propylene glycol and different poly(ethylene glycols)). The mechanical properties, film thickness, wetting properties and surface free energy of the free films were studied. The aim was to evaluate the properties of surface of free films to predict the arrangement of macromolecules in films formed from aqueous solutions of salts of cationic polymers. A high molecular weight of the plasticizer decreased the work of deformation. The surface free energy and the polarity were highest for the film without plasticizer; the hydrophilic additives decreased these parameters. The direction of the change in polarity (a hydrophilic component caused a decrease in the polarity) was unexpected. It can be explained by the change in orientation of the macromolecules, a hydrophobic surface being formed. Examination of the mechanical properties and film thickness can furnish additional results towards a knowledge of film formation by this not frequently applied type of polymer from aqueous solution.

Benchtop fabrication of microfluidic systems based on curable polymers with improved solvent compatibility.

PubMed

Hashimoto, Michinao; Langer, Robert; Kohane, Daniel S

2013-01-21

This paper describes a general scheme to fabricate microchannels from curable polymers on a laboratory benchtop. Using the scheme described here, benchtop fabrication of SU-8 microfluidic systems was demonstrated for the first time, and their compatibility with organic solvents was demonstrated. The fabrication process has three major stages: 1) transferring patterns of microchannels to polymer films by molding, 2) releasing the patterned film and creating inlets and outlets for fluids, and 3) sealing two films together to create a closed channel system. Addition of a PDMS slab supporting the polymer film provided structural integrity during and after fabrication, allowing manipulation of the polymer films without fracturing or deformation. SU-8 channels fabricated according to this scheme exhibited solvent compatibility against continuous exposure to acetone and ethylacetate, which are incompatible with native PDMS. Using the SU-8 channels, continuous generation of droplets of ethylacetate, and templated synthesis of poly (lactic-co-glycolic acid) (PLGA) microparticles, both with stable size, were demonstrated continuously over 24 h, and at intervals over 75 days.

Polymer subtrates for dry-coupled ultrasonic transducers

NASA Astrophysics Data System (ADS)

Komsky, Igor N.

2003-07-01

Dry-coupled inspection techniques are very important for applications on components with non-uniform surfaces and for inspections of advanced materials or coatings that are porous or otherwise sensitive to the application of water, gel, or some other ultrasonic couplants. To overcome the problems associated with the liquid coupling medium, a number of polymer films have been developed to transmit the ultrasound through a dry interface. These materials are very flexible so even low pressure loading is sufficient to adapt the films to the irregular inspection surfaces. Several polymer films have been evaluated to develop dry-coupled substrates for transducer modules. The modules will be utilized to detect and characterize fatigue cracks and corrosion spots in the aircraft structures. Ultrasonic properties of the polymer films were measured and compared with the properties of plastic or rubber-like materials commonly used for ultrasonic applications. Experiments have been carried out to analyze propagation of longitudinal and shear waves in the films. Two different types of the ultrasonic modules with the flexible polymer substrates are being developed. The influence of the surface condition on the module performance was evaluated for both types of the modules.

Ultrasonically assisted single screw extrusion, film blowing and film casting of LLDPE/clay and PA6/clay nanocomposites

NASA Astrophysics Data System (ADS)

Niknezhad, Setareh

The major objective of this study was to investigate the effect of ultrasonic treatment on the dispersion of modified clay particles in LLDPE and PA6 matrices and the final properties of nanocomposites. LLDPE and PA6 are two polymers that are widely used in packaging industry. Blown and cast films were manufactured from the prepared nanocomposites. To achieve one step film processing, an online ultrasonic film casting was developed. Ultrasonic waves caused high-energy mixing and dispersion due to the acoustic cavitation, causing the clay agglomorates to separate into individual platelets in polymer matrix. Ultrasonic waves also broke down the polymer molecular chains reducing viscosity of the melt, facilating dispersion of the clay platelets throughout the matrix. Ultrasound also led to a breakage of the clay platelets reducing the particle size and improving their distribution. Clay particles acted as a heterogenous nucleation agent generating smaller size polymer crystals. In turn, these improved different properties including mechanical properties, oxygen permeability and transparency of films. In LLDPE/clay 20A nanocomposites, the effect of ultrasound was more obvious at higher clay loadings. Exfoliated structure for ultrasonically treated nanocomposites containing 2.5, 5 and 7.5 wt% of clay 20A and highly intercalated structure for ultrasonically treated nanocomposites containing 10 wt% of clay 20A were achieved. However, in blown films, the exfoliated structure transferred to the intercalated structure due to the addition of more shear and thermal degradation of surfactants of the clay particles. While, manufacturing cast films using the new developed online ultrasonic cast film machine revealed the exfoliated structure with ultrasonic treatment till 7.5 wt% of clay loadings. Cast films of nanocomposites containing 5 wt% of clay loadings were also prepared with addition of different compatibilizers. The compatibilizer containing higher amount of grafted maleic anhydride (MA) affected mechanical properties and oxygen permeability with ultrasonic treatment to higher extent. However, use of compatibilizers led to a higher die pressure and resulted in opaque cast films. The mechanical properties were in agreement with crystallinity of samples. The exfoliated structure was achieved for PA6/clay 30B nanocomposites prepared using ultrasonically assisted single screw extrusion except for untreated nanocomposites containing 10 wt% of clay 30B. Untreated 92.5/7.5 and 90/10 PA6/clay 30B blown films showed the intercalated structure, but the exfoliated structure was achieved with ultrasonic treatment. All cast films of PA6/clay 30B showed the exfoliated structure. FTIR spectroscopy along with XRD results confirmed the existence of alpha and gamma-type crystals in the cast films, with clay particles favoring the formation of gamma-type crystals, and ultrasonic treatment favoring the formation of alpha-type crystals. Both parameters increased crystallinity of cast films improving their mechanical properties and oxygen permeability.

Photoluminescence Imaging of Polyfluorene Surface Structures on Semiconducting Carbon Nanotubes: Implications for Thin Film Exciton Transport.

PubMed

Hartmann, Nicolai F; Pramanik, Rajib; Dowgiallo, Anne-Marie; Ihly, Rachelle; Blackburn, Jeffrey L; Doorn, Stephen K

2016-12-27

Single-walled carbon nanotubes (SWCNTs) have potential to act as light-harvesting elements in thin film photovoltaic devices, but performance is in part limited by the efficiency of exciton diffusion processes within the films. Factors contributing to exciton transport can include film morphology encompassing nanotube orientation, connectivity, and interaction geometry. Such factors are often defined by nanotube surface structures that are not yet well understood. Here, we present the results of a combined pump-probe and photoluminescence imaging study of polyfluorene (PFO)-wrapped (6,5) and (7,5) SWCNTs that provide additional insight into the role played by polymer structures in defining exciton transport. Pump-probe measurements suggest exciton transport occurs over larger length scales in films composed of PFO-wrapped (7,5) SWCNTs, compared to those prepared from PFO-bpy-wrapped (6,5) SWCNTs. To explore the role the difference in polymer structure may play as a possible origin of differing transport behaviors, we performed a photoluminescence imaging study of individual polymer-wrapped (6,5) and (7,5) SWCNTs. The PFO-bpy-wrapped (6,5) SWCNTs showed more uniform intensity distributions along their lengths, in contrast to the PFO-wrapped (7,5) SWCNTs, which showed irregular, discontinuous intensity distributions. These differences likely originate from differences in surface coverage and suggest the PFO wrapping on (7,5) nanotubes produces a more open surface structure than is available with the PFO-bpy wrapping of (6,5) nanotubes. The open structure likely leads to improved intertube coupling that enhances exciton transport within the (7,5) films, consistent with the results of our pump-probe measurements.

[Effect of annealing temperature on the crystallization and spectroscopic response of a small-molecule semiconductor doped in polymer film].

PubMed

Yin, Ming; Zhang, Xin-Ping; Liu, Hong-Mei

2012-11-01

The crystallization properties of the perylene (EPPTC) molecules doped in the solid film of the derivative of polyfluorene (F8BT) at different annealing temperatures, as well as the consequently induced spectroscopic response of the exciplex emission in the heterojunction structures, were studied in the present paper. Experimental results showed that the phase separation between the small and the polymer molecules in the blend film is enhanced with increasing the annealing temperature, which leads to the crystallization of the EPPTC molecules due to the strong pi-pi stacking. The size of the crystal phase increases with increasing the annealing temperature. However, this process weakens the mechanisms of the heterojunction configuration, thus, the total interfacial area between the small and the polymer molecules and the amount of exciplex are reduced significantly in the blend film. Meanwhile, the energy transfer from the polymer to the small molecules is also reduced. As a result, the emission from the exciplex becomes weaker with increasing the annealing temperature, whereas the stronger emission from the polymer molecules and from the crystal phase of the small molecules can be observed. These experimental results are very important for understanding and tailoring the organic heterojunction structures. Furthermore, this provides photophysics for improving the performance of photovoltaic or solar cell devices.

Electrochemical synthesis of Sm2O3 nanoparticles: Application in conductive polymer composite films for supercapacitors.

PubMed

Mohammad Shiri, Hamid; Ehsani, Ali; Jalali Khales, Mina

2017-11-01

A novel electrosynthetic method was introduced to synthesize of Sm 2 O 3 nanoparticles and furthermore, for improving the electrochemical performance of conductive polymer, hybrid POAP/Sm 2 O 3 films have then been fabricated by POAP electropolymerization in the presence of Sm 2 O 3 nanoparticles as active electrodes for electrochemical supercapacitors. The structure, morphology, chemical composition of Sm 2 O 3 nanoparticles was examined. Surface and electrochemical analyses have been used for characterization of Sm 2 O 3 and POAP/Sm 2 O 3 composite films. Different electrochemical methods including galvanostatic charge discharge experiments, cyclic voltammetry and electrochemical impedance spectroscopy have been applied to study the system performance. The supercapacity behavior of the composite film was attributed to the (i) high active surface area of the composite, (ii) charge transfer along the polymer chain due to the conjugation form of the polymer and finally (iii) synergism effect between conductive polymer and Sm 2 O 3 nanoparticles. Copyright © 2017 Elsevier Inc. All rights reserved.

Structurally-driven Enhancement of Thermoelectric Properties within Poly(3,4-ethylenedioxythiophene) thin Films

PubMed Central

Petsagkourakis, Ioannis; Pavlopoulou, Eleni; Portale, Giuseppe; Kuropatwa, Bryan A.; Dilhaire, Stefan; Fleury, Guillaume; Hadziioannou, Georges

2016-01-01

Due to the rising need for clean energy, thermoelectricity has raised as a potential alternative to reduce dependence on fossil fuels. Specifically, thermoelectric devices based on polymers could offer an efficient path for near-room temperature energy harvesters. Thus, control over thermoelectric properties of conducting polymers is crucial and, herein, the structural, electrical and thermoelectric properties of poly(3,4-ethylenedioxythiophene) (PEDOT) thin films doped with p-toluenesulfonate (Tos) molecules were investigated with regards to thin film processing. PEDOT:Tos thin films were prepared by in-situ polymerization of (3,4-ethylenedioxythiophene) monomers in presence of iron(III) p-toluenesulfonate with different co-solvents in order to tune the film structure. While the Seebeck coefficient remained constant, a large improvement in the electrical conductivity was observed for thin films processed with high boiling point additives. The increase of electrical conductivity was found to be solely in-plane mobility-driven. Probing the thin film structure by Grazing Incidence Wide Angle X-ray Scattering has shown that this behavior is dictated by the structural properties of the PEDOT:Tos films; specifically by the thin film crystallinity combined to the preferential edge-on orientation of the PEDOT crystallites. Consequentially enhancement of the power factor from 25 to 78.5 μW/mK2 has been readily obtained for PEDOT:Tos thin films following this methodology. PMID:27470637

Structurally-driven Enhancement of Thermoelectric Properties within Poly(3,4-ethylenedioxythiophene) thin Films.

PubMed

Petsagkourakis, Ioannis; Pavlopoulou, Eleni; Portale, Giuseppe; Kuropatwa, Bryan A; Dilhaire, Stefan; Fleury, Guillaume; Hadziioannou, Georges

2016-07-29

Due to the rising need for clean energy, thermoelectricity has raised as a potential alternative to reduce dependence on fossil fuels. Specifically, thermoelectric devices based on polymers could offer an efficient path for near-room temperature energy harvesters. Thus, control over thermoelectric properties of conducting polymers is crucial and, herein, the structural, electrical and thermoelectric properties of poly(3,4-ethylenedioxythiophene) (PEDOT) thin films doped with p-toluenesulfonate (Tos) molecules were investigated with regards to thin film processing. Tos thin films were prepared by in-situ polymerization of (3,4-ethylenedioxythiophene) monomers in presence of iron(III) p-toluenesulfonate with different co-solvents in order to tune the film structure. While the Seebeck coefficient remained constant, a large improvement in the electrical conductivity was observed for thin films processed with high boiling point additives. The increase of electrical conductivity was found to be solely in-plane mobility-driven. Probing the thin film structure by Grazing Incidence Wide Angle X-ray Scattering has shown that this behavior is dictated by the structural properties of the Tos films; specifically by the thin film crystallinity combined to the preferential edge-on orientation of the PEDOT crystallites. Consequentially enhancement of the power factor from 25 to 78.5 μW/mK(2) has been readily obtained for Tos thin films following this methodology.

Multilevel organization in hybrid thin films for optoelectronic applications.

PubMed

Vohra, Varun; Bolognesi, Alberto; Calzaferri, Gion; Botta, Chiara

2009-10-20

In this work we report two simple approaches to prepare hybrid thin films displaying a high concentration of zeolite crystals that could be used as active layers in optoelectronic devices. In the first approach, in order to organize nanodimensional zeolite crystals of 40 nm diameter in an electroactive environment, we chemically modify their external surface and play on the hydrophilic/hydrophobic forces. We obtain inorganic nanocrystals that self-organize in honeycomb electroluminescent polymer structures obtained by breath figure formation. The different functionalizations of the zeolite surface result in different organizations inside the cavities of the polymeric structure. The second approach involving soft-litography techniques allows one to arrange single dye-loaded zeolite L crystals of 800 nm of length by mechanical loading into the nanocavities of a conjugated polymer. Both techniques result in the formation of thin hybrid films displaying three levels of organization: organization of the dye molecules inside the zeolite nanochannels, organization of the zeolite crystals inside the polymer cavities, and micro- or nanostructuration of the polymer.

Photonic Shape Memory Polymer with Stable Multiple Colors

PubMed Central

2017-01-01

A photonic shape memory polymer film that shows large color response (∼155 nm) in a wide temperature range has been fabricated from a semi-interpenetrating network of a cholesteric polymer and poly(benzyl acrylate). The large color response is achieved by mechanical embossing of the photonic film above its broad glass transition temperature. The embossed film, as it recovers to its original shape on heating through the broad thermal transition, exhibits multiple structural colors ranging from blue to orange. The relaxation behavior of the embossed film can be fully described using a Kelvin–Voigt model, which reveals that the influence of temperature on the generation of colors is much stronger than that of time, thereby producing stable multiple colors. PMID:28840717

Polymer based nanocomposites with nanofibers and exfoliated clay

NASA Technical Reports Server (NTRS)

Meador, Michael A.; Reneker, Darrell H.

2005-01-01

Polymer solutions, containing clay sheets, were electrospun into nanofibers and microfibers that contained clay sheets inside. Controllable removal of polymer by plasma etching from the surface of fibers revealed the arrangement of clay. The shape, flexibility, size distribution and arrangement of clay sheets were observed by transmission and scanning electron microscopy. The clay sheets were partially aligned in big fibers with normal direction of clay sheets perpendicular to fiber axis. Crumpling of clay sheets inside fibers was observed when the fiber diameter was comparable to the lateral size of clay sheets. Single sheets of clay were observed both by catching clay sheets dispersed in water with electrospun nanofiber mats and by the deliberate removal of most of the polymer in the fibers. Thin, flexible gas barrier films, that are reasonably strong, were assembled from clay sheets and polymer nanofibers. Structure of composite films was characterized with scanning electron microscopy. Continuous film of clay sheets were physically attached to the surface of fiber mats. Spincoating film of polymer and clay sheets was reinforced by electrospun fiber scaffold. Certain alignment of clay sheets was observed in the vicinity of fibers.

Improving energy conversion efficiency for triboelectric nanogenerator with capacitor structure by maximizing surface charge density.

PubMed

He, Xianming; Guo, Hengyu; Yue, Xule; Gao, Jun; Xi, Yi; Hu, Chenguo

2015-02-07

Nanogenerators with capacitor structures based on piezoelectricity, pyroelectricity, triboelectricity and electrostatic induction have been extensively investigated. Although the electron flow on electrodes is well understood, the maximum efficiency-dependent structure design is not clearly known. In this paper, a clear understanding of triboelectric generators with capacitor structures is presented by the investigation of polydimethylsiloxane-based composite film nanogenerators, indicating that the generator, in fact, acts as both an energy storage and output device. Maximum energy storage and output depend on the maximum charge density on the dielectric polymer surface, which is determined by the capacitance of the device. The effective thickness of polydimethylsiloxane can be greatly reduced by mixing a suitable amount of conductive nanoparticles into the polymer, through which the charge density on the polymer surface can be greatly increased. This finding can be applied to all the triboelectric nanogenerators with capacitor structures, and it provides an important guide to the structural design for nanogenerators. It is demonstrated that graphite particles with sizes of 20-40 nm and 3.0% mass mixed into the polydimethylsiloxane can reduce 34.68% of the effective thickness of the dielectric film and increase the surface charges by 111.27% on the dielectric film. The output power density of the triboelectric nanogenerator with the composite polydimethylsiloxane film is 3.7 W m(-2), which is 2.6 times as much as that of the pure polydimethylsiloxane film.

Biophysical elucidation of the mechanism of enhanced drug release and topical delivery from polymeric film-forming systems.

PubMed

Garvie-Cook, Hazel; Frederiksen, Kit; Petersson, Karsten; Guy, Richard H; Gordeev, Sergey N

2015-08-28

The effect of incorporating the lipidic medium-chain triglyceride (MCT) into polymeric film-forming systems (FFS) for topical drug delivery has been evaluated. First, the in vitro release of betamethasone-17-valerate (BMV), a representative dermatological drug, was determined from FFS comprising either hydrophobic polyacrylate co-polymers, or hydrophilic hydroxypropyl cellulose, with and without MCT. Release was enhanced from both polymers in the presence of MCT. Atomic force microscopy imaging and nanoindentation of FFS with MCT revealed two-phase structured films with softer inclusions (0.5 to 4μm in diameter) surrounded by a more rigid structure. Chemical mapping with Raman micro-spectroscopy showed that MCT was primarily confined to the inclusions within the polymer, which predominated in the surrounding film. BMV was distributed throughout the film but was more concentrated outside the inclusions. Furthermore, while BMV dissolved better into the hydrophobic films, it was more soluble in the MCT inclusions in hydrophilic films, suggesting its increased availability for diffusion from these softer regions of the polymer and explaining the release enhancement observed. Second, ex vivo skin penetration studies clearly revealed that uptake of BMV was higher from hydrophobic FFS than that from the more hydrophilic polymer due, at least in part, to the superior anti-nucleation efficiency of the former. Drug was quickly taken up into the SC from which it then diffused continuously over a sustained period into the lower, viable skin layers. In the presence of MCT, the overall uptake of BMV was increased and provides the basis for further optimisation of FFS as simple, convenient and sustained formulations for topical therapy. Copyright © 2015 Elsevier B.V. All rights reserved.

Topographic measurement of buried thin-film interfaces using a grazing resonant soft x-ray scattering technique

NASA Astrophysics Data System (ADS)

Gann, Eliot; Watson, Anne; Tumbleston, John R.; Cochran, Justin; Yan, Hongping; Wang, Cheng; Seok, Jaewook; Chabinyc, Michael; Ade, Harald

2014-12-01

The internal structures of thin films, particularly interfaces between different materials, are critical to system properties and performance across many disciplines, but characterization of buried interface topography is often unfeasible. In this work, we demonstrate that grazing resonant soft x-ray scattering (GRSoXS), a technique measuring diffusely scattered soft x rays from grazing incidence, can reveal the statistical topography of buried thin-film interfaces. By controlling and predicting the x-ray electric field intensity throughout the depth of the film and simultaneously the scattering contrast between materials, we are able to unambiguously identify the microstructure at different interfaces of a model polymer bilayer system. We additionally demonstrate the use of GRSoXS to selectively measure the topography of the surface and buried polymer-polymer interface in an organic thin-film transistor, revealing different microstructure and markedly differing evolution upon annealing. In such systems, where only indirect control of interface topography is possible, accurate measurement of the structure of interfaces for feedback is critically important. While we demonstrate the method here using organic materials, we also show that the technique is readily extendable to any thin-film system with elemental or chemical contrasts exploitable at absorption edges.

Controlled release of tocopherols from polymer blend films

NASA Astrophysics Data System (ADS)

Obinata, Noe

Controlled release packaging has great potential to increase storage stability of foods by releasing active compounds into foods continuously over time. However, a major limitation in development of this technology is the inability to control the release and provide rates useful for long term storage of foods. Better understanding of the factors affecting active compound release is needed to overcome this limitation. The objective of this research was to investigate the relationship between polymer composition, polymer processing method, polymer morphology, and release properties of active compounds, and to provide proof of principle that compound release is controlled by film morphology. A natural antioxidant, tocopherol was used as a model active compound because it is natural, effective, heat stable, and soluble in most packaging polymers. Polymer blend films were produced from combination of linear low density polyethylene (LLDPE) and high density polyethylene (HDPE), polypropylene (PP), or polystyrene (PS) with 3000 ppm mixed tocopherols using conventional blending method and innovative blending method, smart blending with a novel mixer using chaotic advection. Film morphologies were visualized with scanning electron microscopy (SEM). Release of tocopherols into 95% ethanol as a food simulant was measured by UV/Visible spectrophotometry or HPLC, and diffusivity of tocopherols in the polymers was estimated from this data. Polymer composition (blend proportions) and processing methods have major effects on film morphology. Four different types of morphologies, dispersed, co-continuous, fiber, and multilayer structures were developed by either conventional extrusion or smart blending. With smart blending of fixed polymer compositions, different morphologies were progressively developed with fixed polymer composition as the number of rod rotations increased, providing a way to separate effects of polymer composition and morphology. The different morphologies obtained using conventional and smart blending greatly affected tocopherol release. Strong correlation was observed between morphology and release rate: multilayer, slow release; co-continuous and fiber, moderate; disperse: fast release. Results indicate that morphology can be manipulated by polymer composition and processing method, and release rates of tocopherols are varied with polymer morphology. Manipulating polymer compositions and film morphologies may provide a means to control the release of tocopherols from food contact films.

Incorporating allylated lignin-derivatives in thiol-ene gel-polymer electrolytes.

PubMed

Baroncini, Elyse A; Stanzione, Joseph F

2018-07-01

Growing environmental and economic concerns as well as the uncertainty that accompanies finite petrochemical resources contributes to the increase in research and development of bio-based, renewable polymers. Concurrently, industrial and consumer demand for smaller, safer, and more flexible technologies motivates a global research effort to improve electrolytic polymer separators in lithium-ion batteries. To incorporate the aromatic structural advantages of lignin, a highly abundant and renewable resource, into gel-polymer electrolytes, lignin-derived molecules, vanillyl alcohol and gastrodigenin are functionalized and UV-polymerized with multi-functional thiol monomers. The resulting thin, flexible, polymer films possess glass transition temperatures ranging from -42.1°C to 0.3°C and storage moduli at 25°C ranging from 1.90MPa to 10.08MPa. The crosslinked polymer films swollen with electrolyte solution impart conductivities in the range of 7.04×10 -7 to 102.73×10 -7 Scm -1 . Thiol molecular weight has the most impact on the thermo-mechanical properties of the resulting films while polymer crosslink density has the largest effect on conductivity. The conducting abilities of the bio-based gel-polymer electrolytes in this study prove the viability of lignin-derived feedstock for use in lithium-ion battery applications and reveal structurally and thermally desirable traits for future work. Copyright © 2018 Elsevier B.V. All rights reserved.

Crystalline Stratification in Semiconducting Polymer Thin Film Quantified by Grazing Incidence X-ray Scattering

NASA Astrophysics Data System (ADS)

Gann, Eliot; Caironi, Mario; Noh, Yong-Young; Kim, Yun-Hi; McNeill, Christopher R.

The depth dependence of crystalline structure within thin films is critical for many technological applications, but has been impossible to measure directly using common techniques. In this work, by monitoring diffraction peak intensity and location and utilizing the highly angle-dependent waveguiding effects of X-rays near grazing incidence we quantitatively measure the thickness, roughness and orientation of stratified crystalline layers within thin films of a high-performance semiconducting polymer. In particular, this diffractive X-ray waveguiding reveals a self-organized 5-nm-thick crystalline surface layer with crystalline orientation orthogonal to the underlying 65-nm-thick layer. While demonstrated for an organic semiconductor film, this approach is applicable to any thin film material system where stratified crystalline structure and orientation can influence important interfacial processes such as charge injection and field-effect transport.

Space Environmentally Stable Polyimides and Copolyimides

NASA Technical Reports Server (NTRS)

Watson, Kent A.; Connell, John W.

2000-01-01

Polyimides with a unique combination of properties including low color in thin films, atomic oxygen (AO), ultra-violet (UV) radiation resistance, solubility in organic solvents in the imide form, high glass transition (T(sub g)) temperatures and high thermal stability have been prepared and characterized. The polymers were prepared by reacting a novel aromatic diamine with aromatic dianhydrides in a polar aprotic solvent. The solubility of the polymers in the imide form as well as the color density of thin films were dependent upon the chemical structure of the dianhydride. Several thin films (25-50 mm thick) prepared by solution casting of amide acid or imide solutions exhibited very low color and high optical transparency (approximately 90%) as determined by UV/visible spectroscopy. The polymers exhibited T(sub g)s >200 C depending upon the structure of the dianhydride and temperatures of 5% weight loss approximately 500C in air as determined by dynamic thermogravimetric analysis. Thin films coated with silver/inconel were exposed to a high fluence of AO and 1000 equivalent solar hours of UV radiation. The effects of these exposures on optical properties were minor. These space environmentally durable polymers are potentially useful in a variety of applications on spacecraft such as thin film membranes on antennas, second-surface mirrors, thermal/optical coatings and multi-layer thermal insulation (MLI) blanket materials. The chemistry, physical and mechanical properties of the polymers as well as their responses to AO and UV exposure will be discussed.

Biodegradable polymer film as a source for formation of human fetal retinal pigment epithelium spheroids.

PubMed

Rezai, K A; Farrokh-Siar, L; Botz, M L; Godowski, K C; Swanbom, D D; Patel, S C; Ernest, J T

1999-05-01

To evaluate the attachment of human fetal rctinal pigment epithelial (HFRPE) cells to a biodegradable polymer film with subsequent formation of spheroids in vitro. Ten biodegradable polymer films with different compositions were examined for their physical properties and ease of manipulation under a dissecting microscope. The film with the most suitable handling characteristics was chosen, and a purely isolated sheet of HFRPE cells was attached to it. The purity of the cells was assessed by their pigmentation and expression of cytokeratin. Proliferation was assessed by incorporation of 5-bromo-2'-deoxyuridine (BrdtJ). Cellular structure was analyzed under light and electron microscopes, and the functional capability of the cells was evaluated by rod outer segment (ROS) phagocytosis. The polymer film with composition 50:50 poly (DL-lactide) (PLA)/poly (DL-lactide-co-glycolide) (PLG) with an inherent viscosity of 1.03 dl/g was found to be the most suitable for handling under the microscope. Sheets of HFRPE cells attached to the polymer films within 48 hours and began to form spheroids. All the isolated cells were pigmented and expressed cytokeratin. They possessed a cuboidal morphology, numerous apical microvilli, and no sign of dedifferentiation. HFRPE cells produced extracellular matrix (collagen filaments) on their basal side, filling the cavities of the polymer film. The cells subsequently proliferated, incorporated BrdU, migrated onto the culture plate to form monolayers, and phagocytized ROS. Biodegradable polymer films can be used as a scaffold for the adhesion of the HFRPE sheet and formation of spheroids. Spheroids represent a source of high density and well-differentiated HFRPE cells that are easy to transfer. Furthermore, the stricture of the membrane makes it suitable for additional applications.

Space environmental effects on polymeric materials

NASA Technical Reports Server (NTRS)

Kiefer, Richard L.; Orwoll, Robert A.

1987-01-01

A study is presented of the effect of radiation on polymers. It helps to estimate the impact of the space environment on composite structures. Two commercially available polymer films were used; a polyetherimide, and a polysulfone. Both films were irradiated in vacuum with 85 KeV electron. Properties of the films before and after irradiation were monitored by tensile elongation measurements, ultraviolet/visible spectroscopy, glass transition temperature measurements, gel permeation chromatography, and infrared spectroscopy. The results of these characterizations are presented and briefly discussed.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Youm, Sang Gil; Hwang, Euiyong; Chavez, Carlos A.

The ability to control nanoscale morphology and molecular organization in organic semiconducting polymer thin films is an important prerequisite for enhancing the efficiency of organic thin-film devices including organic light-emitting and photovoltaic devices. The current “top-down” paradigm for making such devices is based on utilizing solution-based processing (e.g., spin-casting) of soluble semiconducting polymers. This approach typically provides only modest control over nanoscale molecular organization and polymer chain alignment. A promising alternative to using solutions of presynthesized semiconducting polymers pursues instead a “bottom-up” approach to prepare surface-grafted semiconducting polymer thin films by surface-initiated polymerization of small-molecule monomers. Herein, we describe themore » development of an efficient method to prepare polythiophene thin films utilizing surface-initiated Kumada catalyst transfer polymerization. In this study, we provided evidence that the surface-initiated polymerization occurs by the highly robust controlled (quasi-“living”) chain-growth mechanism. Further optimization of this method enabled reliable preparation of polythiophene thin films with thickness up to 100 nm. Extensive structural studies of the resulting thin films using X-ray and neutron scattering methods as well as ultraviolet photoemission spectroscopy revealed detailed information on molecular organization and the bulk morphology of the films, and enabled further optimization of the polymerization protocol. One of the remarkable findings was that surface-initiated polymerization delivers polymer thin films showing complex molecular organization, where polythiophene chains assemble into lateral crystalline domains of about 3.2 nm size, with individual polymer chains folded to form in-plane aligned and densely packed oligomeric segments (7-8 thiophene units per each segment) within each domain. Achieving such a complex mesoscale organization is virtually impossible with traditional methods relying on solution processing of presynthesized polymers. Another significant advantage of surface-confined polymer thin films is their remarkable stability toward organic solvents and other processing conditions. In addition to controlled bulk morphology, uniform molecular organization, and stability, a unique feature of the surface-initiated polymerization is that it can be used for the preparation of large-area uniformly nanopatterned polymer thin films. Lastly, this was demonstrated using a combination of particle lithography and surface-initiated polymerization. In general, surface-initiated polymerization is not limited to polythiophene but can be also expanded toward other classes of semiconducting polymers and copolymers.« less

Symmetry Breaking in Side Chains Leading to Mixed Orientations and Improved Charge Transport in Isoindigo- alt -Bithiophene Based Polymer Thin Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xue, Guobiao; Zhao, Xikang; Qu, Ge

The selection of side chains is important in design of conjugated polymers. It not only affects their intrinsic physical properties, but also has an impact on thin film morphologies. Recent reports suggested that a face-on/edge-on bimodal orientation observed in polymer thin films may be responsible for a three-dimensional (3D) charge transport and leads to dramatically improved mobility in donor–acceptor based conjugated polymers. To achieve a bimodal orientation in thin films has been seldom explored from the aspect of molecular design. Here, we demonstrate a design strategy involving the use of asymmetric side chains that enables an isoindigo-based polymer to adoptmore » a distinct bimodal orientation, confirmed by the grazing incidence X-ray diffraction. As a result, the polymer presents an average high mobility of 3.8 ± 0.7 cm2 V–1 s–1 with a maximum value of 5.1 cm2 V–1 s–1, in comparison with 0.47 and 0.51 cm2 V–1 s–1 obtained from the two reference polymers. This study exemplifies a new strategy to develop the next generation polymers through understanding the property-structure relationship.« less

Dynamics in thin folded polymer films

NASA Astrophysics Data System (ADS)

Croll, Andrew; Rozairo, Damith

Origami and Kirigami inspired structures depend on a complex interplay between geometry and material properties. While clearly important to the overall function, very little attention has focused on how extreme curvatures and singularities in real materials influence the overall dynamic behaviour of folded structures. In this work we use a set of three polymer thin films in order to closely examine the interaction of material and geometry. Specifically, we use polydimethylsiloxane (PDMS), polystyrene (PS) and polycarbonate (PC) thin films which we subject to loading in several model geometries of varying complexity. Depending on the material, vastly different responses are noted in our experiments; D-cones can annihilate, cut or lead to a crumpling cascade when pushed through a film. Remarkably, order can be generated with additional perturbation. Finally, the role of adhesion in complex folded structures can be addressed. AFOSR under the Young Investigator Program (FA9550-15-1-0168).

Structural, microstructural and electrochemical properties of dispersed-type polymer nanocomposite films

NASA Astrophysics Data System (ADS)

Arya, Anil; Sharma, A. L.

2018-01-01

Free-standing solid polymer nanocomposite (PEO-PVC)  +  LiPF6-TiO2 films have been prepared through a standard solution-cast technique. The improvement in structural, microstructural and electrochemical properties has been observed on the dispersion of nanofiller in polymer salt complex. X-ray diffraction studies clearly reflect the formation of complex formation, as no corresponding salt peak appeared in the diffractograms. The Fourier transform infrared analysis suggested clear and convincing evidence of polymer-ion, ion-ion and polymer-ion-nanofiller interaction. The highest ionic conductivity of the prepared solid polymer electrolyte (SPE) films is ~5  ×  10-5 S cm-1 for 7 wt.% TiO2. The linear sweep voltammetry provides the electrochemical stability window of the prepared SPE films, about ~3.5 V. The ion transference number has been estimated, t ion  =  0.99 through the DC polarization technique. Dielectric spectroscopic studies were performed to understand the ion transport process in polymer electrolytes. All solid polymer electrolytes possess good thermal stability up to 300 °C. Differential scanning calorimetry analysis confirms the decrease of the melting temperature and signal of glass transition temperature with the addition of nanofiller, which indicates the decrease of crystallinity of the polymer matrix. An absolute correlation between diffusion coefficient (D), ion mobility (µ), number density (n), double-layer capacitance (C dl), glass transition temperature, melting temperature (T m), free ion area (%) and conductivity (σ) has been observed. A convincing model to study the role of nanofiller in a polymer salt complex has been proposed, which supports the experimental findings. The prepared polymer electrolyte system with significant ionic conductivity, high ionic transference number, and good thermal and voltage stability could be suggested as a potential candidate as electrolyte cum separator for the fabrication of a rechargeable lithium-ion battery system.

Assessment and formation mechanism of laser-induced periodic surface structures on polymer spin-coated films in real and reciprocal space.

PubMed

Rebollar, Esther; Pérez, Susana; Hernández, Jaime J; Martín-Fabiani, Ignacio; Rueda, Daniel R; Ezquerra, Tiberio A; Castillejo, Marta

2011-05-03

In this work we evaluate the potential of grazing incidence X-ray scattering techniques in the investigation of laser-induced periodic surface structures (LIPSSs) in a series of strongly absorbing model spin-coated polymer films which are amorphous, such as poly(ethylene terephthalate), poly(trimethylene terephthalate), and poly(carbonate bisphenol A), and in a weaker absorbing polymer, such as semicrystalline poly(vinylidene fluoride), over a narrow range of fluences. Irradiation was performed with pulses of 6 ns at 266 nm, and LIPSSs with period lengths similar to the laser wavelength and parallel to the laser polarization direction are formed by devitrification of the film surface at temperatures above the characteristic glass transition temperature of the polymers. No crystallization of the surface is induced by laser irradiation, and crystallinity of the material prevents LIPSS formation. The structural information obtained by both atomic force microscopy and grazing incidence small-angle X-ray scattering (GISAXS) correlates satisfactorily. Comparison of experimental and simulated GISAXS patterns suggests that LIPSSs can be well described considering a quasi-one-dimensional paracrystalline lattice and that irradiation parameters have an influence on the order of such a lattice.

Design of 3D scaffolds for tissue engineering testing a tough polylactide-based graft copolymer.

PubMed

Dorati, R; Colonna, C; Tomasi, C; Genta, I; Bruni, G; Conti, B

2014-01-01

The aim of this research was to investigate a tough polymer to develop 3D scaffolds and 2D films for tissue engineering applications, in particular to repair urethral strictures or defects. The polymer tested was a graft copolymer of polylactic acid (PLA) synthesized with the rationale to improve the toughness of the related PLA homopolymer. The LMP-3055 graft copolymer (in bulk) demonstrated to have negligible cytotoxicity (bioavailability >85%, MTT test). Moreover, the LMP-3055 sterilized through gamma rays resulted to be cytocompatible and non-toxic, and it has a positive effect on cell biofunctionality, promoting the cell growth. 3D scaffolds and 2D film were prepared using different LMP-3055 polymer concentrations (7.5, 10, 12.5 and 15%, w/v), and the effect of polymer concentration on pore size, porosity and interconnectivity of the 3D scaffolds and 2D film was investigated. 3D scaffolds got better results for fulfilling structural and biofunctional requirements: porosity, pore size and interconnectivity, cell attachment and proliferation. 3D scaffolds obtained with 10 and 12.5% polymer solutions (3D-2 and 3D-3, respectively) were identified as the most suitable construct for the cell attachment and proliferation presenting pore size ranged between 100 and 400μm, high porosity (77-78%) and well interconnected pores. In vitro cell studies demonstrated that all the selected scaffolds were able to support the cell proliferation, the cell attachment and growth resulting to their dependency on the polymer concentration and structural features. The degradation test revealed that the degradation of polymer matrix (ΔMw) and water uptake of 3D scaffolds exceed those of 2D film and raw polymer (used as control reference), while the mass loss of samples (3D scaffold and 2D film) resulted to be controlled, they showed good stability and capacity to maintain the physical integrity during the incubation time. © 2013.

Constructive spin-orbital angular momentum coupling can twist materials to create spiral structures in optical vortex illumination

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barada, Daisuke; Center for Optical Research and Education; Juman, Guzhaliayi

It was discovered that optical vortices twist isotropic and homogenous materials, e.g., azo-polymer films to form spiral structures on a nano- or micro-scale. However, the formation mechanism has not yet been established theoretically. To understand the mechanism of the spiral surface relief formation in the azo-polymer film, we theoretically investigate the optical radiation force induced in an isotropic and homogeneous material under irradiation using a continuous-wave optical vortex with arbitrary topological charge and polarization. It is revealed that the spiral surface relief formation in azo-polymer films requires the irradiation of optical vortices with a positive (negative) spin angular momentum andmore » a positive (negative) orbital angular momentum (constructive spin-orbital angular momentum coupling), i.e., the degeneracy among the optical vortices with the same total angular momentum is resolved.« less

Anisotropic elasticity of quasi-one-component polymer nanocomposites.

PubMed

Voudouris, Panayiotis; Choi, Jihoon; Gomopoulos, Nikos; Sainidou, Rebecca; Dong, Hongchen; Matyjaszewski, Krzysztof; Bockstaller, Michael R; Fytas, George

2011-07-26

The in-plane and out-of-plane elastic properties of thin films of "quasi-one-component" particle-brush-based nanocomposites are compared to those of "classical" binary particle-polymer nanocomposite systems with near identical overall composition using Brillouin light scattering. Whereas phonon propagation is found to be independent of the propagation direction for the binary particle/polymer blend systems, a pronounced splitting of the phonon propagation velocity along the in-plane and out-of-plane film direction is observed for particle-brush systems. The anisotropic elastic properties of quasi-one-component particle-brush systems are interpreted as a consequence of substrate-induced order formation into layer-type structures and the associated breaking of the symmetry of the film. The results highlight new opportunities to engineer quasi-one-component nanocomposites with advanced control of structural and physical property characteristics based on the assembly of particle-brush materials.

Photoluminescence Imaging of Polyfluorene Surface Structures on Semiconducting Carbon Nanotubes: Implications for Thin Film Exciton Transport

DOE PAGES

Hartmann, Nicolai F.; Pramanik, Rajib; Dowgiallo, Anne-Marie; ...

2016-12-06

Single-walled carbon nanotubes (SWCNTs) have potential to act as light-harvesting elements in thin film photovoltaic devices, but performance is in part limited by the efficiency of exciton diffusion processes within the films. Factors contributing to exciton transport can include film morphology encompassing nanotube orientation, connectivity, and interaction geometry. Such factors are often defined by nanotube surface structures that are not yet well understood. We present the results of a combined pump-probe and photoluminescence imaging study of polyfluorene (PFO)-wrapped (6,5) and (7,5) SWCNTs that provide additional insight into the role played by polymer structures in defining exciton transport. The pump-probe measurementsmore » suggest exciton transport occurs over larger length scales in films composed of PFO-wrapped (7,5) SWCNTs, compared to those prepared from PFO-bpy-wrapped (6,5) SWCNTs. To explore the role the difference in polymer structure may play as a possible origin of differing transport behaviors, we performed a photoluminescence imaging study of individual polymer-wrapped (6,5) and (7,5) SWCNTs. The PFO-bpy-wrapped (6,5) SWCNTs showed more uniform intensity distributions along their lengths, in contrast to the PFO-wrapped (7,5) SWCNTs, which showed irregular, discontinuous intensity distributions. These differences likely originate from differences in surface coverage and suggest the PFO wrapping on (7,5) nanotubes produces a more open surface structure than is available with the PFO-bpy wrapping of (6,5) nanotubes. Furthermore, the open structure likely leads to improved intertube coupling that enhances exciton transport within the (7,5) films, consistent with the results of our pump-probe measurements.« less

Photoluminescence Imaging of Polyfluorene Surface Structures on Semiconducting Carbon Nanotubes: Implications for Thin Film Exciton Transport

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hartmann, Nicolai F.; Pramanik, Rajib; Dowgiallo, Anne-Marie

Single-walled carbon nanotubes (SWCNTs) have potential to act as light-harvesting elements in thin film photovoltaic devices, but performance is in part limited by the efficiency of exciton diffusion processes within the films. Factors contributing to exciton transport can include film morphology encompassing nanotube orientation, connectivity, and interaction geometry. Such factors are often defined by nanotube surface structures that are not yet well understood. We present the results of a combined pump-probe and photoluminescence imaging study of polyfluorene (PFO)-wrapped (6,5) and (7,5) SWCNTs that provide additional insight into the role played by polymer structures in defining exciton transport. The pump-probe measurementsmore » suggest exciton transport occurs over larger length scales in films composed of PFO-wrapped (7,5) SWCNTs, compared to those prepared from PFO-bpy-wrapped (6,5) SWCNTs. To explore the role the difference in polymer structure may play as a possible origin of differing transport behaviors, we performed a photoluminescence imaging study of individual polymer-wrapped (6,5) and (7,5) SWCNTs. The PFO-bpy-wrapped (6,5) SWCNTs showed more uniform intensity distributions along their lengths, in contrast to the PFO-wrapped (7,5) SWCNTs, which showed irregular, discontinuous intensity distributions. These differences likely originate from differences in surface coverage and suggest the PFO wrapping on (7,5) nanotubes produces a more open surface structure than is available with the PFO-bpy wrapping of (6,5) nanotubes. Furthermore, the open structure likely leads to improved intertube coupling that enhances exciton transport within the (7,5) films, consistent with the results of our pump-probe measurements.« less

Tailoring surface properties of ArF resists thin films with functionally graded materials (FGM)

NASA Astrophysics Data System (ADS)

Takemoto, Ichiki; Ando, Nobuo; Edamatsu, Kunishige; Fuji, Yusuke; Kuwana, Koji; Hashimoto, Kazuhiko; Funase, Junji; Yokoyama, Hiroyuki

2007-03-01

Our recent research effort has been focused on new top coating-free 193nm immersion resists with regard to leaching of the resist components and lithographic performance. We have examined methacrylate-based resins that control the surface properties of ArF resists thin films by surface segregation behavior. For a better understanding of the surface properties of thin films, we prepared the six resins (Resin 1-6) that have three types fluorine containing monomers, a new monomer (Monomer A), Monomer B and Monomer C, respectively. We blended the base polymer (Resin 0) with Resin (1-6), respectively. We evaluated contact angles, surface properties and lithographic performances of the polymer blend resists. The static and receding contact angles of the resist that contains Resin (1-6) are greater than that of the base polymer (Resin 0) resist. The chemical composition of the surface of blend polymers was investigated with X-ray photoelectron spectroscopy (XPS). It was shown that there was significant segregation of the fluorine containing resins to the surface of the blend films. We analyzed Quantitative Structure-Property Relationships (QSPR) between the surface properties and the chemical composition of the surface of polymer blend resists. The addition of 10 wt% of the polymer (Resin 1-6) to the base polymer (Resin 0) did not influence the lithographic performance. Consequently, the surface properties of resist thin films can be tailored by the appropriate choice of fluorine containing polymer blends.

Cyclopentadithiophene-Benzothiadiazole Donor-Acceptor Polymers as Prototypical Semiconductors for High-Performance Field-Effect Transistors.

PubMed

Li, Mengmeng; An, Cunbin; Pisula, Wojciech; Müllen, Klaus

2018-05-15

Donor-acceptor (D-A) conjugated polymers are of great interest as organic semiconductors, because they offer a rational tailoring of the electronic properties by modification of the donor and acceptor units. Nowadays, D-A polymers exhibit field-effect mobilities on the order of 10 -2 -10 0 cm 2 V -1 s -1 , while several examples showed a mobility over 10 cm 2 V -1 s -1 . The development of cyclopentadithiophene-benzothiadiazole (CDT-BTZ) copolymers one decade ago represents an important step toward high-performance organic semiconductors for field-effect transistors. The significant rise in field-effect mobility of CDT-BTZ in comparison to the existing D-A polymers at that time opened the door to a new research field with a large number of novel D-A systems. From this point, the device performance of CDT-BTZ was gradually improved by a systematic optimization of the synthesis and polymer structure as well as by an efficient solution processing into long-range ordered thin films. The key aspect was a comprehensive understanding of the relation between polymer structure and solid-state organization. Due to their fundamental role for the field of D-A polymers in general, this Account will for the first time explicitly focus on prototypical CDT-BTZ polymers, while other reviews provide an excellent general overview on D-A polymers. The first part of this Account discusses strategies for improving the charge carrier transport, focusing on chemical aspects. Improved synthesis as an essential stage toward high purity, and high molecular weight is a prerequisite for molecular order. The modification of substituents is a further crucial feature to tune the CDT-BTZ packing and self-assembly. Linear alkyl side chains facilitate intermolecular π-stacking interactions, while branched ones increase solubility and alter the polymer packing. Additional control over the supramolecular organization of CDT-BTZ polymers is introduced by alkenyl substituents via their cis-trans isomerization. The last discussed chemical concept is based on heteroatom variation within the CDT unit. The relationships found experimentally for CDT-BTZ between polymer chemical structure, solid-state organization, and charge carrier transport are explained by means of theoretical simulations. Besides the effects of molecular design, the second part of this Account discusses the processing conditions from solution. The film microstructure, defined as a mesoscopic domain organization, is critically affected by solution processing. Suitable processing techniques allow the formation of a long-range order and a uniaxial orientation of the CDT-BTZ chains, thus lowering the trapping density of grain boundaries for charge carriers. For instance, alignment of the CDT-BTZ polymer by dip-coating yields films with a pronounced structural and electrical anisotropy and favors a fast migration of charge carriers along the conjugated backbones in the deposition direction. By using film compression with the assistance of an ionic liquid, one even obtains CDT-BTZ films with a band-like transport and a transistor hole mobility of 10 cm 2 V -1 s -1 . This device performance is attributed to large domains in the compressed films being formed by CDT-BTZ with longer alkyl chains, which establish a fine balance between polymer interactions and growth kinetics during solvent evaporation. On the basis of the prototypical semiconductor CDT-BTZ, this Account provides general guidelines for achieving high-performance polymer transistors by taking into account the subtle balance of synthetic protocol, molecular design, and processing.

Microstructured polymer films by X-ray lithographic exposure and grafting

NASA Astrophysics Data System (ADS)

Gürsel, Selmiye A.; Padeste, Celestino; Solak, Harun H.; Scherer, Günther G.

2005-07-01

Recently we reported on a new technique to generate micro- and nanostructured polymer materials by the combination of selective irradiation of polymer substrates with X-rays and subsequent grafting of a second polymer. Here we focus on the spatially defined grafting throughout the thickness of poly(ethylene-alt-tetrafluoroethylene) (ETFE) and poly (tetrafluoroethylene-co-hexafluoropropylene) (FEP) films using X-ray irradiation through a metal mask, followed by grafting with styrene. Calculations of the transmission of X-rays through the polymer as a function of the wavelength have revealed that energy deposition within the substrate material, which should control the density of created radicals, can be selected in a wide range. Depending on the used wavelength the radicals are created either near the surface or in the bulk of the sample. First experiments demonstrated spatially defined grafting through a 100 μm thick ETFE film and 25 μm thick FEP film. The achieved graft level depends on the irradiation dose as well as on the grafting parameters such as concentration, temperature and time. The precision of structure definition within the film depends on the properties of the X-ray source, the metal mask and the grafting process. The presented process allows controlled grafting through fluoropolymer films with micrometer resolution and local modification of the properties of the films, such as ion conductivity, diffusion of specific molecules or optical properties.

A comparison of tackified, miniemulsion core-shell acrylic latex films with corresponding particle-blend films: structure-property relationships.

PubMed

Canetta, Elisabetta; Marchal, Jeanne; Lei, Chun-Hong; Deplace, Fanny; König, Alexander M; Creton, Costantino; Ouzineb, Keltoum; Keddie, Joseph L

2009-09-15

Tackifying resins (TRs) are often added to pressure-sensitive adhesive films to increase their peel strength and adhesion energy. In waterborne adhesives, the TR is dispersed in water using surfactants and then blended with colloidal polymers in water (i.e., latex). In such waterborne systems, there are problems with the colloidal stability and difficulty in applying coatings of the particle blends; the films are often hydrophilic and subject to water uptake. Here, an alternative method of making waterborne, tackified adhesives is demonstrated. The TR is incorporated within the core of colloidal polymer particles via miniemulsion polymerization. Atomic force microscopy (AFM) combined with force spectroscopy analysis reveals there is heterogeneity in the distribution of the TR in films made from particle blends and also in films made from miniemulsion polymers. Two populations, corresponding to TR-rich and acrylic-rich components, were identified through analysis of the AFM force-displacement curves. The nanoscale maximum adhesion force and adhesion energy were found to be higher in a miniemulsion film containing 12 wt % tackifying resin in comparison to an equivalent blended film. The macroscale tack and viscoelasticity are interpreted by consideration of the nanoscale structure and properties. The incorporation of tackifying resin through a miniemulsion polymerization process not only offers clear benefits in the processing of the adhesive, but it also leads to enhanced adhesion properties.

Humidity versus photo-stability of metal halide perovskite films in a polymer matrix.

PubMed

Manshor, Nurul Ain; Wali, Qamar; Wong, Ka Kan; Muzakir, Saifful Kamaluddin; Fakharuddin, Azhar; Schmidt-Mende, Lukas; Jose, Rajan

2016-08-21

Despite the high efficiency of over 21% reported for emerging thin film perovskite solar cells, one of the key issues prior to their commercial deployment is to attain their long term stability under ambient and outdoor conditions. The instability in perovskite is widely conceived to be humidity induced due to the water solubility of its initial precursors, which leads to decomposition of the perovskite crystal structure; however, we note that humidity alone is not the major degradation factor and it is rather the photon dose in combination with humidity exposure that triggers the instability. In our experiment, which is designed to decouple the effect of humidity and light on perovskite degradation, we investigate the shelf-lifetime of CH3NH3PbI3 films in the dark and under illumination under high humidity conditions (Rel. H. > 70%). We note minor degradation in perovskite films stored in a humid dark environment whereas upon exposure to light, the films undergo drastic degradation, primarily owing to the reactive TiO2/perovskite interface and also the surface defects of TiO2. To enhance its air-stability, we incorporate CH3NH3PbI3 perovskite in a polymer (poly-vinylpyrrolidone, PVP) matrix which retained its optical and structural characteristics in the dark for ∼2000 h and ∼800 h in room light soaking, significantly higher than a pristine perovskite film, which degraded completely in 600 h in the dark and in less than 100 h when exposed to light. We attribute the superior stability of PVP incorporated perovskite films to the improved structural stability of CH3NH3PbI3 and also to the improved TiO2/perovskite interface upon incorporating a polymer matrix. Charge injection from the polymer embedded perovskite films has also been confirmed by fabricating solar cells using them, thereby providing a promising future research pathway for stable and efficient perovskite solar cells.

First-Principles Predictions of Near-Edge X-ray Absorption Fine Structure Spectra of Semiconducting Polymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Su, Gregory M.; Patel, Shrayesh N.; Pemmaraju, C. D.

The electronic structure and molecular orientation of semiconducting polymers in thin films determine their ability to transport charge. Methods based on near-edge X-ray absorption fine structure (NEXAFS) spectroscopy can be used to probe both the electronic structure and microstructure of semiconducting polymers in both crystalline and amorphous films. However, it can be challenging to interpret NEXAFS spectra on the basis of experimental data alone, and accurate, predictive calculations are needed to complement experiments. Here, we show that first-principles density functional theory (DFT) can be used to model NEXAFS spectra of semiconducting polymers and to identify the nature of transitions inmore » complicated NEXAFS spectra. Core-level X-ray absorption spectra of a set of semiconducting polymers were calculated using the excited electron and core-hole (XCH) approach based on constrained-occupancy DFT. A comparison of calculations on model oligomers and periodic structures with experimental data revealed the requirements for accurate prediction of NEXAFS spectra of both conjugated homopolymers and donor–acceptor polymers. The NEXAFS spectra predicted by the XCH approach were applied to study molecular orientation in donor–acceptor polymers using experimental spectra and revealed the complexity of using carbon edge spectra in systems with large monomeric units. The XCH approach has sufficient accuracy in predicting experimental NEXAFS spectra of polymers that it should be considered for design and analysis of measurements using soft X-ray techniques, such as resonant soft X-ray scattering and scanning transmission X-ray microscopy.« less

A Treatise on Acoustic Radiation. Volume 2. Acoustic Transducers

DTIC Science & Technology

1983-01-01

ORIFICE INERTANCE ..................... 327 4.1 INTRODUCTION TO POLYMER FILM TRANSDUCERS ................................................. 331 4.2...PHENOMENOLOGICAL THEORY OF PIEZOELECTRICITY IN POLYMER FILMS ...... 331 4.3 STRUCTURE AND PROPERTIES OF PVF 2 IN 31 MODE...capacity C(fl0ow)) and inteprets it as the free capacity (CO + CMoT). Similarly at a frequency "far enough" above fa (say 2fa, or 4f.) one again measures

Structural Evolution of Low-Molecular-Weight Poly(ethylene oxide)-block-polystyrene Diblock Copolymer Thin Film

PubMed Central

Huang, Xiaohua

2013-01-01

The structural evolution of low-molecular-weight poly(ethylene oxide)-block-polystyrene (PEO-b-PS) diblock copolymer thin film with various initial film thicknesses on silicon substrate under thermal annealing was investigated by atomic force microscopy, optical microscopy, and contact angle measurement. At film thickness below half of the interlamellar spacing of the diblock copolymer (6.2 nm), the entire silicon is covered by a polymer brush with PEO blocks anchored on the Si substrate due to the substrate-induced effect. When the film is thicker than 6.2 nm, a dense polymer brush which is equal to half of an interlamellar layer was formed on the silicon, while the excess material dewet this layer to form droplets. The droplet surface was rich with PS block and the PEO block crystallized inside the bigger droplet to form spherulite. PMID:24302862

Fabrication of reduced graphene oxide nanosheets doped PVA composite films for tailoring their opto-mechanical properties

NASA Astrophysics Data System (ADS)

Aslam, Muhammad; Kalyar, Mazhar Ali; Raza, Zulfiqar Ali

2017-06-01

Laminar graphene nanosheets have raised passionate attention due to their incredible physico-chemical properties. Its wide-scale, high-yield production at low-cost has made it possible to produce top class promising versatile polymer nanocomposites. Reduced graphene oxide (RGO) nanosheets were incorporated to prepare optically tunable and high mechanical strength polymer nanocomposite films. RGO-doped poly(vinyl alcohol) (PVA) nanocomposite films were prepared via solution casting. Low level RGO doping significantly altered the structural, optical and mechanical properties of pure PVA films. Most of the band structure parameters like direct/indirect band gap, band tail, refractive index, dielectric constant, optical conductivity and dispersion parameters were investigated in detail for the first time. Tauc's, Wemple-DiDomenico, Helpin-Tsai and mixture rule models were employed to investigate optical and mechanical parameters. The applied models reinforced the experimental results in the present study. Advanced analytical techniques were engaged to characterize the nanocomposites films.

INK-JET PRINTING OF PF6 FOR OLED APPLICATIONS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Burrasca, G.; Fasolino, T.; Miscioscia, R.

2008-08-28

In the last years there has been much interest in applying ink-jet printing (IJP) technology to the deposition of several materials for organic electronics applications, including metals, polymers and nanoparticles dispersions on flexible substrates. The aim of this work is to study the effect of ink-jet deposition of polymer films in the manufacturing of OLED devices comparing their performances to standard technologies. The ink-jet printed polymer is introduced in an hybrid structure in which other layers are deposited by vacuum thermal evaporation. The electrical and optical properties of the obtained devices are investigated.OLEDs with the same structure were fabricated bymore » spin-coating a polymer film by the same solution used as ink. Results have been compared to the above ones to determine how the deposition method affects the device optoelectronic properties.« less

Epitaxial ternary nitride thin films prepared by a chemical solution method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luo, Hongmei; Feldmann, David M; Wang, Haiyan

2008-01-01

It is indispensable to use thin films for many technological applications. This is the first report of epitaxial growth of ternary nitride AMN2 films. Epitaxial tetragonal SrTiN2 films have been successfully prepared by a chemical solution approach, polymer-assisted deposition. The structural, electrical, and optical properties of the films are also investigated.

Silicon containing electroconductive polymers and structures made therefrom

NASA Technical Reports Server (NTRS)

Nagasubramanian, Ganesan (Inventor); Distefano, Salvador (Inventor); Liang, Ranty H. (Inventor)

1991-01-01

An electropolymerized film comprised of polymers and copolymers of a monomer is formed on the surface of an anode. The finished structures have superior electrical and mechanical properties for use in applications such as electrostatic dissipation and for the reduction of the radar cross section of advanced aircraft.

Structurally colored biopolymer thin films for detection of dissolved metal ions in aqueous solution

NASA Astrophysics Data System (ADS)

Cathell, Matthew David

Natural polymers, such as the polysaccharides alginate and chitosan, are noted sorbents of heavy metals. Their polymer backbone structures are rich in ligands that can interact with metal ions through chelation, electrostatics, ion exchange and nonspecific mechanisms. These water-soluble biopolymer materials can be processed into hydrogel thin films, creating high surface area interfaces ideal for binding and sequestering metal ions from solution. By virtue of their uniform nanoscale dimensions (with thicknesses smaller than wavelengths of visible light) polymer thin films exhibit structure-based coloration. This phenomenon, frequently observed in nature, causes the transparent and essentially colorless films to reflect light in a wide array of colors. The lamellar film structures act as one-dimensional photonic crystals, allowing selective reflection of certain wavelengths of light while minimizing other wavelengths by out-of-phase interference. The combination of metal-binding and reflective properties make alginate and chitosan thin films attractive candidates for analyte sensing. Interactions with metal ions can induce changes in film thicknesses and refractive indices, thus altering the path of light reflected through the film. Small changes in dimensional or optical properties can lead to shifts in film color that are perceivable by the unaided eye. These thin films offer the potential for optical sensing of toxic dissolved materials without the need for instrumentation, external power or scientific expertise. With the use of a spectroscopic ellipsometer and a fiber optic reflectance spectrometer, the physical and optical characteristics of biopolymer thin films have been characterized in response to 50 ppm metal ion solutions. It has been determined that metal interactions can lead to measurable changes in both film thicknesses and effective refractive indices. The intrinsic response behaviors of alginate and chitosan, as well as the responses of modified derivatives of these materials, have been investigated. It has been found that the natural metal selectivity of biopolymer films can be tuned and refined by adjusting the ligand environment through backbone modification. Other investigations have also been undertaken, including in situ monitoring of biopolymer---metal interactions and quantification of thin film metal-binding capacities.

Material properties of novel polymeric films

NASA Astrophysics Data System (ADS)

Kim, Gene

This dissertation will study the material properties of two types of novel polymer films (polyelectrolyte multilayer films and photolithographic polymer films). The formation of polylelectrolyte multilayer films onto functionalized aluminum oxide surfaces and functionalized poly(ethylene terephthaltate) (PET) were studied. Functionalization of the aluminum oxide surfaces was achieved via silane coupling. Functionalization of PET surfaces was achieved via hydrolysis and amidation. Surface characterization techniques such as X-ray photoelectron spectroscopy (XPS) and dynamic contact angle measurements were used to monitor the polyelectrolyte multilayer formation. Mechanical properties of the aluminum oxide supported polyelectrolyte multilayer films were tested using a simplified peel test. XPS was used to analyze the surfaces before and after peel. Single lap shear joint specimens were constructed to test the adhesive shear strength of the PET-supported polyelectrolyte multilayer film samples with the aid of a cyanoacrylate adhesive. The adhesive shear strength and its relation with the type of functionalization, number of polyelectrolyte layers, and the effect of polyelectrolyte conformation using added salt were explored. Also, characterization on the single lap joints after adhesive failure was carried out to determine the locus of failure within the multilayers by using XPS and SEM. Two types of photolithographic polymers were formulated and tested. These two polymers (photocrosslinkable polyacrylate (PUA), and a photocrosslinkable polyimide (HRP)) were used to investigate factors that would affect the structural integrity of these particular polymers under environmental variables such as processing (time, UV cure, pressure, and temperature) and ink exposure. Thermomechanical characterization was carried out to see the behavior of these two polymers under these environmental variables. Microscopic techniques were employed to study the morphological behavior of the two polymer systems. Also, unique in-house characterization methods such as the vibrational holographic interferometry to measure residual stress in these polymer coatings upon processing, and the environmental tensile tester (ETT) to measure ink diffusion and swelling stresses were used to further characterize these two polymers.

Self-assembled morphologies of an amphiphilic Y-shaped weak polyelectrolyte in a thin film.

PubMed

Mu, Dan; Li, Jian-Quan; Feng, Sheng-Yu

2017-11-29

Different from the self-assembly of neutral polymers, polyelectrolytes self-assemble into smaller aggregates with a more loosely assembled structure, which results from the repulsive forces acting between similar electrical compositions with the introduction of ions. The Y-shaped weak polyelectrolytes self-assemble into a core-shell type cylindrical structure with a hexagonal arrangement in a thin film, whose thickness is smaller than the gyration radius of the polymer chain. The corresponding formation mechanism consists of enrichment of the same components, adjustment of the shape of the aggregate, and the subsequent separation into individual aggregates. With the increase in the thickness of the thin film until it exceeds the gyration radius of the polymer chain, combined with the greater freedom of movement along the direction of thin film thickness, the self-assembled structure changes into a micellar structure. Under confinement, the repulsive force to the polymeric components is weakened by the repulsive forces among polyelectrolyte components with like charges, and this helps in generating aggregates with more uniform size and density distribution. In particular, when the repulsive force between the walls and the core forming components is greater than that between the walls and the shell forming components, such asymmetric confinement produces a crossed-cylindrical structure with nearly perpendicular arrangement of two cylinder arrays. Similarly, a novel three-crossed cylinder morphology is self-assembled upon removal of confinement.

The production of ultrathin polyimide films for the solar sail program and Large Space Structures Technology (LSST): A feasibility study

NASA Technical Reports Server (NTRS)

Forester, R. H.

1978-01-01

Polyimide membranes of a thickness range from under 0.01 micron m to greater than 1 micron m can be produced at an estimated cost of 50 cents per sq m (plus the cost of the polymer). The polymer of interest is dissolved in a solvent which is solube in water. The polymer or casting solution is allowed to flow down an inclined ramp onto a water surface where a pool of floating polymer develops. The solvent dissolves into the water lowering the surface tension of the water on equently, the contact angle of the polymer pool is very low and the edge of the pool is very thin. The solvent dissolves from this thin region too rapidly to be replenished from the bulk of the pool and a solid polymer film forms. Firm formation is rapid and spontaneous and the film spreads out unaided, many feet from the leading edge of the pool. The driving force for this process is the exothermic solution of the organic solvent from the polymer solution into the water.

Thermomechanical Properties and Glass Dynamics of Polymer-Tethered Colloidal Particles and Films

PubMed Central

2017-01-01

Polymer-tethered colloidal particles (aka “particle brush materials”) have attracted interest as a platform for innovative material technologies and as a model system to elucidate glass formation in complex structured media. In this contribution, Brillouin light scattering is used to sequentially evaluate the role of brush architecture on the dynamical properties of brush particles in both the individual and assembled (film) state. In the former state, the analysis reveals that brush–brush interactions as well as global chain relaxation sensitively depend on grafting density; i.e., more polymer-like behavior is observed in sparse brush systems. This is interpreted to be a consequence of more extensive chain entanglement. In contrast, the local relaxation of films does not depend on grafting density. The results highlight that relaxation processes in particle brush-based materials span a wider range of time and length scales as compared to linear chain polymers. Differentiation between relaxation on local and global scale is necessary to reveal the influence of molecular structure and connectivity on the aging behavior of these complex systems. PMID:29755139

Thermomechanical Properties and Glass Dynamics of Polymer-Tethered Colloidal Particles and Films.

PubMed

Cang, Yu; Reuss, Anna N; Lee, Jaejun; Yan, Jiajun; Zhang, Jianan; Alonso-Redondo, Elena; Sainidou, Rebecca; Rembert, Pascal; Matyjaszewski, Krzysztof; Bockstaller, Michael R; Fytas, George

2017-11-14

Polymer-tethered colloidal particles (aka "particle brush materials") have attracted interest as a platform for innovative material technologies and as a model system to elucidate glass formation in complex structured media. In this contribution, Brillouin light scattering is used to sequentially evaluate the role of brush architecture on the dynamical properties of brush particles in both the individual and assembled (film) state. In the former state, the analysis reveals that brush-brush interactions as well as global chain relaxation sensitively depend on grafting density; i.e., more polymer-like behavior is observed in sparse brush systems. This is interpreted to be a consequence of more extensive chain entanglement. In contrast, the local relaxation of films does not depend on grafting density. The results highlight that relaxation processes in particle brush-based materials span a wider range of time and length scales as compared to linear chain polymers. Differentiation between relaxation on local and global scale is necessary to reveal the influence of molecular structure and connectivity on the aging behavior of these complex systems.

Polymer coating behavior of Rayleigh-SAW resonators with gold electrode structure for gas sensor applications.

PubMed

Avramov, Ivan D; Länge, Kerstin; Rupp, Swen; Rapp, Bastian; Rapp, Michael

2007-01-01

Results from systematic polymer coating experiments on surface acoustic wave (SAW) resonators and coupled resonator filters (CRF) on ST-cut quartz with a corrosion-proof electrode structure entirely made of gold (Au) are presented and compared with data from similar SAW devices using aluminium (Al) electrodes. The recently developed Au devices are intended to replace their earlier Al counterparts in sensor systems operating in highly reactive chemical gas environments. Solid parylene C and soft poly[chlorotrifluoroethylene-co-vinylidene fluoride] (PCFV) polymer films are deposited under identical conditions onto the surface of Al and Au devices. The electrical performance of the Parylene C coated devices is monitored online during film deposition. The PCVF coated devices are evaluated after film deposition. The experimental data show that the Au devices can stand up to 40% thicker solid films for the same amount of loss increase than the Al devices and retain better resonance and phase characteristics. The frequency sensitivities of Au and Al devices to parylene C deposition are nearly identical. After coating with soft PCFV sensing film, the Au devices provide up to two times higher gas sensitivity when probed with cooling agent, octane, or tetrachloroethylene.

Inelastic deformation of plasma polymerised thin films facilitated by transient dense plasma focus irradiation

NASA Astrophysics Data System (ADS)

Grant, Daniel S.; Rawat, Rajdeep S.; Bazaka, Kateryna; Jacob, Mohan V.

2017-09-01

The high degree of crosslinking present in plasma polymerised thin films, coupled with their high molecular weight, imbues these films with properties similar to those of thermosetting polymers. For instance, such films tend to be relatively hard, insoluble, and to date have not exhibited plasticity when subjected to elevated temperatures. In this paper it is demonstrated that plasma polymers can, in fact, undergo plastic deformation in response to the application of extremely short-lived thermal treatment delivered by a dense plasma focus device, as evidenced by the evolution of bubble-like structures from the thin film. This finding suggests new avenues for texturing plasma thin films, and synthesising cavities that may find utility as thermal insulators or domains for material encapsulation.

The Structures of Fibronectin Adsorbed on Polyelectrolyte Thin Films

NASA Astrophysics Data System (ADS)

Shin, Kwanwoo; Satija, Sushil; Fang, Xiao-Hua; Li, Bin-Quan; Nadine, Pernodet; Miriam, Rafailovich; Sokolov, Jonathan; Arach, Goldar; Roser, Steve

2002-03-01

We have shown that it is possible to form a fibrilar network of fibronectin on a polyelectrolyte polymer film whose dimensions are similar to those reported on the extra cellular matrix. The fibronectin network was observed to form only when the charge density of the polymer was in excess of the natural charge density of the cell wall. Furthermore, the self-organized fibronectin layer was much thicker than the polymer film, indicating that long ranged interaction may play a key role in the assembly process. It is therefore important to understand the structure of the polymer layer/protein interface. Here we report on a neutron reflectivity study where we explore the structure of the polyelectrolyte layer, in this case sulfonated polystyrene (PSS_x.), with varying degree of sulfonation (x<30%), as a function of sulfur content and counter ion concentration. These results are then correlated with systemic study of the adsorption and the multilayer formation of fibronectin as a function of incubation time for various sulfonation levels of PSS_x. Furthermore, the surface charge on the substrates can be strongly influenced by the presence of salt ions, it is important to understand changes due to electrostatic interactions occurring in the various salt conditions. Complementary X-ray reflection was used to determine the salt density profile associating with the internal ionic polymer matrix. This work was funded in part of the NSF-MRSEC program.

Inorganic-polymer-derived dielectric films

DOEpatents

Brinker, C. Jeffrey; Keefer, Keith D.; Lenahan, Patrick M.

1987-01-01

A method of coating a substrate with a thin film of a polymer of predetermined porosity comprises depositing the thin film on the substrate from a non-gelled solution comprising at least one hydrolyzable metal alkoxide of a polymeric network forming cation, water, an alcohol compatible with the hydrolysis and the polymerization of the metal alkoxide, and an acid or a base, prior to depositing the film, controlling the structure of the polymer for a given composition of the solution exclusive of the acid or base component and the water component, (a) by adjusting each of the water content, the pH, and the temperature to obtain the desired concentration of alkoxide, and then adjusting the time of standing of the solution prior to lowering the temperature of the solution, and (b) lowering the temperature of the solution after the time of standing to about 15 degrees C. or lower to trap the solution in a state in which, after the depositing step, a coating of the desired porosity will be obtained, and curing the deposited film at a temperature effective for curing whereby there is obtained a thin film of a polymer of a predetermined porosity and corresponding pore size on the substrate.

Real-time Analysis of the Enzymatic Biodegradation of Polyhydroxyalkanoate Thin Films Using Microfabricated Polymer Microstructures

NASA Astrophysics Data System (ADS)

Delfaus, Stephen; Latuga, Brian M.; Morse, Clinton; McCarney, Evan R.; Rossini, Connie J.; Augustine, Brian H.; Flythe, Michael D.; Rowe, Sean; Baron, Stephen F.; Dennis, Douglas E.

2003-11-01

In-situ atomic force microscopy (AFM) allows for the real-time acquisition and analysis of materials undergoing biological and chemical alterations. A co-polymer blend of poly 3-hydroxybutyrate / poly 3-hydroxyvalerate P(3HB-3HV) were spun-cast onto glass slides to create thin films with film thickness of 40 nm. This polymer is naturally biodegradable by a variety of bacterially produced enzymes. In this study, these materials were degraded by an untyped and concentrated Strptomyces sp. enzyme produced from soil. Using liquid-cell AFM in contact mode, we were able to observe biodegradation uniformly across the surface of the P(3HB-3HV) films beginning within 2 min of introduction of the enzyme. Height standards have been developed using microcontact printing of self assembled monolayers and selective dewetting to produce P(3HB-3HV) structures with dimensions as small as 10 mm. We will discuss the use of microfabricated height standards to measure biodegradation kinetics in these polymers.

Molecular organization in MAPLE-deposited conjugated polymer thin films and the implications for carrier transport characteristics

DOE PAGES

Dong, Ban Xuan; Li, Anton; Strzalka, Joseph; ...

2016-09-18

The morphological structure of poly(3-hexylthiophene) (P3HT) thin films deposited by both Matrix Assisted Pulsed Laser Evaporation (MAPLE) and solution spin-casting methods are investigated. We found that the MAPLE samples possessed a higher degree of disorder, with random orientations of polymer crystallites along the side-chain stacking, π-π stacking, and conjugated backbone directions. Furthermore, the average molecular orientations and relative degrees of crystallinity of MAPLE-deposited polymer films are insensitive to the chemistries of the substrates onto which they were deposited; this is in stark contrast to the films prepared by the conventional spin-casting technique. In spite of the seemingly unfavorable molecular orientations andmore » the highly disordered morphologies, the in-plane charge carrier transport characteristics of the MAPLE samples are comparable to those of spin-cast samples, exhibiting similar transport activation energies (56 meV versus 54 meV) to those reported in the literature for high mobility polymers.« less

Molecular organization in MAPLE-deposited conjugated polymer thin films and the implications for carrier transport characteristics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dong, Ban Xuan; Li, Anton; Strzalka, Joseph

The morphological structure of poly(3-hexylthiophene) (P3HT) thin films deposited by both Matrix Assisted Pulsed Laser Evaporation (MAPLE) and solution spin-casting methods are investigated. We found that the MAPLE samples possessed a higher degree of disorder, with random orientations of polymer crystallites along the side-chain stacking, π-π stacking, and conjugated backbone directions. Furthermore, the average molecular orientations and relative degrees of crystallinity of MAPLE-deposited polymer films are insensitive to the chemistries of the substrates onto which they were deposited; this is in stark contrast to the films prepared by the conventional spin-casting technique. In spite of the seemingly unfavorable molecular orientations andmore » the highly disordered morphologies, the in-plane charge carrier transport characteristics of the MAPLE samples are comparable to those of spin-cast samples, exhibiting similar transport activation energies (56 meV versus 54 meV) to those reported in the literature for high mobility polymers.« less

PLASMA POLYMER FILMS AS ADHESION PROMOTING PRIMERS FOR ALUMINUM SUBSTRATES. PART I: CHARACTERIZATION OF FILMS AND FILM/SUBSTRATE INTERFACES

EPA Science Inventory

Plasma polymerized hexamethyldisiloxane (HMDSO) films (~800 Å in thickness) were deposited onto aluminum substrates (6111-T4 alloy) in radio frequency (RF) and microwave (MW) powered reactors to be used as primers for structural adhesive bonding. Processing variables such as sub...

Controlled bending and folding of a bilayer structure consisting of a thin stiff film and a heat shrinkable polymer sheet

NASA Astrophysics Data System (ADS)

Cui, Jianxun; Adams, John G. M.; Zhu, Yong

2018-05-01

Bending pre-designed flat sheets into three-dimensional (3D) structures is attracting much interest, as it provides a simple approach to make 3D devices. Here we report controlled bending and folding of a bilayer structure consisting of a heat shrinkable polymer sheet and a thin stiff film (not thermally responsive). Upon heating, the prestrained polymer sheet shrinks, leading to bending or folding of the bilayer. We studied the effect of relative dimensions of the two layers on the bending behavior and demonstrated the transition from longitudinal bending to transverse bending of the bilayer strip. Transverse bending was utilized to fold origami structures, including several flat letters, a crane, and a corrugated metal sheet via Miura-ori folding. We developed a method to further control the bending orientation based on bio-inspired anisotropic bending stiffness. By bending the metal foil in different orientations, several structures were obtained, including cylindrical surfaces and left-handed/right-handed helical structures.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrova, V. A.; Orekhov, A. S.; Chernyakov, D. D.

A method for preparing multilayer film composites based on chitosan has been developed by the example of polymer pairs: chitosan–hyaluronic acid, chitosan–alginic acid, and chitosan–carrageenan. The structure of the composite films is characterized by X-ray diffractometry and scanning electron microscopy. It is shown that the deposition of a solution of hyaluronic acid, alginic acid, or carrageenan on a chitosan gel film leads to the formation of a polyelectrolyte complex layer at the interface, which is accompanied by the ordering of chitosan chains in the surface region; the microstructure of this layer depends on the nature of contacting polymer pairs.

Removable polytetrafluoroethylene template based epitaxy of ferroelectric copolymer thin films

NASA Astrophysics Data System (ADS)

Xia, Wei; Chen, Qiusong; Zhang, Jian; Wang, Hui; Cheng, Qian; Jiang, Yulong; Zhu, Guodong

2018-04-01

In recent years ferroelectric polymers have shown their great potentials in organic and flexible electronics. To meet the requirements of high-performance and low energy consumption of novel electronic devices and systems, structural and electrical properties of ferroelectric polymer thin films are expected to be further optimized. One possible way is to realize epitaxial growth of ferroelectric thin films via removable high-ordered polytetrafluoroethylene (PTFE) templates. Here two key parameters in epitaxy process, annealing temperature and applied pressure, are systematically studied and thus optimized through structural and electrical measurements of ferroelectric copolymer thin films. Experimental results indicate that controlled epitaxial growth is realized via suitable combination of both parameters. Annealing temperature above the melting point of ferroelectric copolymer films is required, and simultaneously moderate pressure (around 2.0 MPa here) should be applied. Over-low pressure (around 1.0 MPa here) usually results in the failure of epitaxy process, while over-high pressure (around 3.0 MPa here) often results in residual of PTFE templates on ferroelectric thin films.

Healing of polymer interfaces: Interfacial dynamics, entanglements, and strength

NASA Astrophysics Data System (ADS)

Ge, Ting; Robbins, Mark O.; Perahia, Dvora; Grest, Gary S.

2014-07-01

Self-healing of polymer films often takes place as the molecules diffuse across a damaged region, above their melting temperature. Using molecular dynamics simulations we probe the healing of polymer films and compare the results with those obtained for thermal welding of homopolymer slabs. These two processes differ from each other in their interfacial structure since damage leads to increased polydispersity and more short chains. A polymer sample was cut into two separate films that were then held together in the melt state. The recovery of the damaged film was followed as time elapsed and polymer molecules diffused across the interface. The mass uptake and formation of entanglements, as obtained from primitive path analysis, are extracted and correlated with the interfacial strength obtained from shear simulations. We find that the diffusion across the interface is significantly faster in the damaged film compared to welding because of the presence of short chains. Though interfacial entanglements increase more rapidly for the damaged films, a large fraction of these entanglements are near chain ends. As a result, the interfacial strength of the healing film increases more slowly than for welding. For both healing and welding, the interfacial strength saturates as the bulk entanglement density is recovered across the interface. However, the saturation strength of the damaged film is below the bulk strength for the polymer sample. At saturation, cut chains remain near the healing interface. They are less entangled and as a result they mechanically weaken the interface. Chain stiffness increases the density of entanglements, which increases the strength of the interface. Our results show that a few entanglements across the interface are sufficient to resist interfacial chain pullout and enhance the mechanical strength.

Significantly improved dielectric performances of nanocomposites via loading two-dimensional core-shell structure Bi2Te3@SiO2 nanosheets

NASA Astrophysics Data System (ADS)

Chen, Jianwen; Wang, Xiucai; Yu, Xinmei; Fan, Yun; Duan, Zhikui; Jiang, Yewen; Yang, Faquan; Zhou, Yuexia

2018-07-01

Polymer/semiconductor-insulator nanocomposites can display high dielectric constants with a relatively low dissipation factor under low electric fields, and thus seem to promising for high energy density capacitors. Here, a novel nanocomposite films is developed by loading two-dimensional (2D) core-shell structure Bi2Te3@SiO2 nanosheets in the poly (vinylidene fluoride-hexafluoro propylene) (P(VDF-HFP)) polymer matrix. The 2D Bi2Te3 nanosheets were prepared through simple microwave-assisted method. The experimental results suggesting that the SiO2 shell layer between the fillers and polymer matrix could effectively improve the dielectric constant, dielectric loss, AC conductivity, and breakdown strength of composites films. The composite films load with 10 vol.% 2D Bi2Te3@SiO2 nanosheets exhibits a high dielectric constant of 70.3 at 1 kHz and relatively low dielectric loss of 0.058 at 1 kHz. The finite element simulation of electric field and electric current density distribution revealed that the SiO2 shell layer between the fillers and polymer matrix could effectively improve the energy loss, local electric field strength, and breakdown strength of composite films. Therefore, this work will provide a promising route to achieve high-performance capacitors.

Functional patterned coatings by thin polymer film dewetting.

PubMed

Telford, Andrew M; Thickett, Stuart C; Neto, Chiara

2017-12-01

An approach for the fabrication of functional polymer surface coatings is introduced, where micro-scale structure and surface functionality are obtained by means of self-assembly mechanisms. We illustrate two main applications of micro-patterned polymer surfaces obtained through dewetting of bilayers of thin polymer films. By tuning the physical and chemical properties of the polymer bilayers, micro-patterned surface coatings could be produced that have applications both for the selective attachment and patterning of proteins and cells, with potential applications as biomaterials, and for the collection of water from the atmosphere. In all cases, the aim is to achieve functional coatings using approaches that are simple to realize, use low cost materials and are potentially scalable. Copyright © 2017 Elsevier Inc. All rights reserved.

Optical properties of Sr3B2O6:Dy3+/PMMA polymer nanocomposites

NASA Astrophysics Data System (ADS)

Khursheed, Sumara; Kumar, Vinay; Singh, Vivek K.; Sharma, Jitendra; Swart, H. C.

2018-04-01

The paper presents a facile way to synthesize luminescent polymer nanocomposite (PNC) films consisting of nanophosphors (NPs) of rare earth ions doped alkaline earth borates (Sr3B2O6:Dy3+) dispersed in a polymer (PMMA) matrix via a solution casting method and the results of their detailed structural and optical properties measurements. The PNC films were characterized using X-ray diffraction (XRD), Photoluminescence (PL), and differential scanning calorimetry (DSC). The crystallinity of the dispersed NPs did not suffer on account of being dispersed in the PMMA. The Rhombohedral structure and the formation of a single phase of Sr3B2O6:Dy3+ were confirmed by the XRD data of both the NP powders and the PNC films with an average particle size of 43 nm. Also, the observed PL emission and excitation spectra of the PNC films amply suggested that embedding of the nanophosphors in the PMMA matrix preserves their typical luminescence emission. The chromaticity coordinates (x = 0.37, y = 0.39) of the PNC films also validated the yellowish white emission of the nanophosphor. DSC scans on the PMMA only and the Sr3B2O6:Dy3+/PMMA films suggested an increase in the thermal stability of the PNC films as compared to pure PMMA although no significant change in the glass transition temperature was observed.

Mechanisms of charge transport and resistive switching in composite films of semiconducting polymers with nanoparticles of graphene and graphene oxide

NASA Astrophysics Data System (ADS)

Berestennikov, A. S.; Aleshin, A. N.

2017-11-01

We have investigated the effect of the resistive switching in the composite films based on polyfunctional polymers - PVK, PFD and PVC mixed with particles of Gr and GO with the concentration of ˜ 1 - 3 wt.%. We have developed the solution processed hybrid memory structures based on PVK and GO particles composite films. The effect of the resistive switching in Al/PVK(PFD; PVC):Gr(GO)/ITO/PET structures manifests itself as a sharp change of the electrical resistance from a low-conducting state to a relatively high-conducting state when applying a bias to Al-ITO electrodes of ˜ 0.2-0.4 V. It has been established that a sharp conductivity jump characterized by S-shaped current-voltage curves and the presence of their hysteresis occurs upon applying a voltage pulse to the Au/PVK(PFD; PVC):Gr(GO)/ITO/PET structures, with the switching time in the range from 1 to 30 μs. The mechanism of resistive switching associated with the processes of capture and accumulation of charge carriers by Gr(GO) particles introduced into the matrixes of the PVK polymer due to the reduction/oxidation processes. The possible mechanisms of energy transfer between organic and inorganic components in PVK(PFD; PVC):GO(Gr) films causes increase mobility are discussed. Incorporating of Gr (GO) particles into the polymer matrix is a promising route to enhance the performance of hybrid memory structures, as well as it is an effective medium for memory cells.

Impact of solvents and supercritical CO2 drying on the morphology and structure of polymer-based biofilms

NASA Astrophysics Data System (ADS)

Causa, Andrea; Salerno, Aurelio; Domingo, Concepción; Acierno, Domenico; Filippone, Giovanni

2014-05-01

In the present work, two-dimensional systems based on biodegradable polymers such as poly(ɛ-caprolactone) (PCL), poly(ethylene oxide) (PEO) and polylactic acid (PLA) are fabricated by means of a sustainable approach which consists in inducing phase separation in solutions of such polymers and "green" solvents, namely ethyl lactate (EL) and ethyl acetate (EA). The extraction of the solvent is promoted by a controlled drying process, which is performed in either air or supercritical CO2. The latter can indeed act as both an antisolvent, which favors the deposition of the polymer by forming a mixture with EL and EA, and a plasticizing agent, whose solvation and transport properties may considerably affect the microstructure and crystallinity of the polymer films. The morphological, topographical and crystalline properties of the films are tailored through a judicial selection of the materials and the processing conditions and assessed by means of thermal analyses, polarized optical microscopy, scanning electron microscopy and confocal interferometric microscopy. The results show that the morphological and crystalline properties of the films are strongly dependent on the choice of both the polymer/solvent system and the operating conditions during the drying step. In particular, the morphological, topographical and thermal properties of films prepared starting from highly crystalline polymers, namely PCL and PEO, are greatly affected by the crystallization of the material. Conversely, the less crystalline PLA forms almost completely amorphous films.

Current progress and technical challenges of flexible liquid crystal displays

NASA Astrophysics Data System (ADS)

Fujikake, Hideo; Sato, Hiroto

2009-02-01

We focused on several technical approaches to flexible liquid crystal (LC) display in this report. We have been developing flexible displays using plastic film substrates based on polymer-dispersed LC technology with molecular alignment control. In our representative devices, molecular-aligned polymer walls keep plastic-substrate gap constant without LC alignment disorder, and aligned polymer networks create monostable switching of fast-response ferroelectric LC (FLC) for grayscale capability. In the fabrication process, a high-viscosity FLC/monomer solution was printed, sandwiched and pressed between plastic substrates. Then the polymer walls and networks were sequentially formed based on photo-polymerization-induced phase separation in the nematic phase by two exposure processes of patterned and uniform ultraviolet light. The two flexible backlight films of direct illumination and light-guide methods using small three-primary-color light-emitting diodes were fabricated to obtain high-visibility display images. The fabricated flexible FLC panels were driven by external transistor arrays, internal organic thin film transistor (TFT) arrays, and poly-Si TFT arrays. We achieved full-color moving-image displays using the flexible FLC panel and the flexible backlight film based on field-sequential-color driving technique. Otherwise, for backlight-free flexible LC displays, flexible reflective devices of twisted guest-host nematic LC and cholesteric LC were discussed with molecular-aligned polymer walls. Singlesubstrate device structure and fabrication method using self-standing polymer-stabilized nematic LC film and polymer ceiling layer were also proposed for obtaining LC devices with excellent flexibility.

Enhanced magnetoelectric coupling in a composite multiferroic system via interposing a thin film polymer

NASA Astrophysics Data System (ADS)

Xiao, Zhuyun; Mohanchandra, Kotekar P.; Lo Conte, Roberto; Ty Karaba, C.; Schneider, J. D.; Chavez, Andres; Tiwari, Sidhant; Sohn, Hyunmin; Nowakowski, Mark E.; Scholl, Andreas; Tolbert, Sarah H.; Bokor, Jeffrey; Carman, Gregory P.; Candler, Rob N.

2018-05-01

Enhancing the magnetoelectric coupling in a strain-mediated multiferroic composite structure plays a vital role in controlling magnetism by electric fields. An enhancement of magnetoelastic coupling between ferroelectric single crystal (011)-cut [Pb(Mg1/3Nb2/3)O3](1-x)-[PbTiO3]x (PMN-PT, x≈ 0.30) and ferromagnetic polycrystalline Ni thin film through an interposed benzocyclobutene polymer thin film is reported. A nearly twofold increase in sensitivity of remanent magnetization in the Ni thin film to an applied electric field is observed. This observation suggests a viable method of improving the magnetoelectric response in these composite multiferroic systems.

Novel processing to produce polymer/ceramic nanocomposites by atomic layer deposition

NASA Astrophysics Data System (ADS)

Liang, Xinhua

Polymeric materials can be greatly influenced by nanoscale inclusions of inorganic materials. The main goal of this thesis is to fabricate novel polymer/ceramic composite materials for two different applications using atomic layer deposition (ALD) or molecular layer deposition (MLD) methods. One is to produce well-dispersed polymer/ceramic nanocomposites with improved barrier properties for packaging applications. The other is to produce porous polymer/ceramic composites with improved bioactivity for tissue engineering applications. ALD has been successfully utilized for the conformal and uniform deposition of ultra-thin alumina and titania films on primary micron-sized polymer particles. The mechanism to initiate alumina and titania ALD on polymer particles without chemical functional groups was confirmed. A nucleation period was needed for both alumina and titania ALD on high density polyethylene (HDPE) particles and no nucleation period was needed for alumina ALD on polymethyl methacrylate particles. Titania ALD films deposited at low temperatures had an amorphous structure and showed much weaker photoactivity than common pigment-grade anatase TiO2 particles. Highly uniform and conformal ultra-thin aluminum alkoxide (alucone) polymer films were deposited on primary silica and titania nanoparticles using MLD in a fluidized bed reactor. The deposition chemistry and properties of alucone MLD films were investigated. The photoactivity of pigment-grade TiO2 particles was quenched after 20 cycles of an alucone MLD film, but the films shrank and decomposed in the presence of water, which decreased the passivation effect of the photoactivity of TiO2 particles. Well-dispersed polymer/ceramic nanocomposites were obtained by extruding alumina ALD coated HDPE particles. The diffusion coefficient of the fabricated nanocomposite membranes can be reduced by half with the inclusion of 7.3 vol.% alumina flakes. However, a corresponding increase in permeability was also observed due to the voids formed at or near the interface of the polymer and alumina flakes during the extrusion process. Efforts to improve the barrier properties of the membranes included 3-aminopropyltriethoxysilane treatment and coating alucone MLD films on alumina coated particles prior to extrusion. The porous polymer/ceramic particles were synthesized by depositing ultra-thin alumina or titania films on highly porous poly(styrene-divinylbenzene) particles using a low-temperature ALD process. Analytical characterization revealed that conformal alumina and titania films were grown on internal and external polymer particle surfaces, and the pore filling mechanism was a uniform coating of the pore walls. The ALD layers can improve the bioactivity and protein adsorption of the polymer substrates.

Controlling Film Morphology in Conjugated Polymer

PubMed Central

Park, Lee Y.; Munro, Andrea M.; Ginger, David S.

2009-01-01

We study the effects of patterned surface chemistry on the microscale and nanoscale morphology of solution-processed donor/acceptor polymer-blend films. Focusing on combinations of interest in polymer solar cells, we demonstrate that patterned surface chemistry can be used to tailor the film morphology of blends of semiconducting polymers such as poly-[2-(3,7-dimethyloctyloxy)-5-methoxy-p-phenylenevinylene] (MDMO-PPV), poly-3-hexylthiophene (P3HT), poly[(9,9-dioctylflorenyl-2,7-diyl)-co-benzothiadiazole)] (F8BT), and poly(9,9-dioctylfluorene-co-bis-N,N’-(4-butylphenyl)-bis-N,N’-phenyl-1,4-phenylendiamine) (PFB) with the fullerene derivative, [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). We present a method for generating patterned, fullerene-terminated monolayers on gold surfaces, and use microcontact printing and Dip-Pen Nanolithography (DPN) to pattern alkanethiols with both micro- and nanoscale features. After patterning with fullerenes and other functional groups, we backfill the rest of the surface with a variety of thiols to prepare substrates with periodic variations in surface chemistry. Spin coating polymer:PCBM films onto these substrates, followed by thermal annealing under nitrogen, leads to the formation of structured polymer films. We characterize these films with Atomic Force Microscopy (AFM), Raman spectroscopy, and fluorescence microscopy. The surface patterns are effective in guiding phase separation in all of the polymer:PCBM systems investigated, and lead to a rich variety of film morphologies that are inaccessible with unpatterned substrates. We demonstrate our ability to guide pattern formation in films thick enough of be of interest for actual device applications (up to 200 nm in thickness) using feature sizes as small as 100 nm. Finally, we show that the surface chemistry can lead to variations in film morphology on length scales significantly smaller than those used in generating the original surface patterns. The variety of behaviors observed and the wide range of control over polymer morphology achieved at a variety of different length scales have important implications for the development of bulk heterojunction solar cells. PMID:18983150

Coupling of microphase separation and dewetting in weakly segregated diblock co-polymer ultrathin films.

PubMed

Yan, Derong; Huang, Haiying; He, Tianbai; Zhang, Fajun

2011-10-04

We have studied the coupling behavior of microphase separation and autophobic dewetting in weakly segregated poly(ε-caprolactone)-block-poly(L-lactide) (PCL-b-PLLA) diblock co-polymer ultrathin films on carbon-coated mica substrates. At temperatures higher than the melting point of the PLLA block, the co-polymer forms a lamellar structure in bulk with a long period of L ∼ 20 nm, as determined using small-angle X-ray scattering. The relaxation procedure of ultrathin films with an initial film thickness of h = 10 nm during annealing has been followed by atomic force microscopy (AFM). In the experimental temperature range (100-140 °C), the co-polymer dewets to an ultrathin film of itself at about 5 nm because of the strong attraction of both blocks with the substrate. Moreover, the dewetting velocity increases with decreasing annealing temperatures. This novel dewetting kinetics can be explained by a competition effect of the composition fluctuation driven by the microphase separation with the dominated dewetting process during the early stage of the annealing process. While dewetting dominates the relaxation procedure and leads to the rupture of the ultrathin films, the composition fluctuation induced by the microphase separation attempts to stabilize them because of the matching of h to the long period (h ∼ 1/2L). The temperature dependence of these two processes leads to this novel relaxation kinetics of co-polymer thin films. © 2011 American Chemical Society

Electro-Optically Active Monomers: Synthesis and Characterization of Thin Films of Liquid Crystalline Substituted Polyacetylenes

NASA Technical Reports Server (NTRS)

Duran, R. S.

1995-01-01

The overall objective of this study was the description of the behavior of mesogen substituted acetylene monomers and polymers in monolayer films at the air/water interface and as multilayer films including the formation of such films. Fundamental knowledge to be gained would include the effect of balancing hydrophilic and hydrophobic tendencies in a molecule more complex than the classical fatty acids or lipids. The effect of molecular shape on the packing and thus the ultimate stability of monolayers formed from these new molecules was explored. The work takes on the challenge of preorienting monomers in well-ordered arrays prior to attempting polymerization with the hope that order would be preserved in any resulting polymer. New knowledge gained with regard to the acetylenic monomers includes processing of the acetylene monomer into multi-layer films, followed by the design and synthesis of a second generation of improved monomer structure for superior LBK film transfer properties. A third generation of acetylenic monomer was synthesized which approaches more closely the goal of solid state polymerization of these materials. A parallel study took a different approach. The materials are pre-formed poly(phenylene-acetylene) polymers so questions about reactivity are mute. The materials are a variation on the well-known hairy-rod polymers with regard to their Langmuir film-forming properties. Overall, the goal was to demonstrate that these polymers could be processed into NLO materials with novel polar order.

Chemical vapor deposition and characterization of polysilanes polymer based thin films and their applications in compound semiconductors and silicon devices

NASA Astrophysics Data System (ADS)

Oulachgar, El Hassane

As the semiconductors industry is moving toward nanodevices, there is growing need to develop new materials and thin films deposition processes which could enable strict control of the atomic composition and structure of thin film materials in order to achieve precise control on their electrical and optical properties. The accurate control of thin film characteristics will become increasingly important as the miniaturization of semiconductor devices continue. There is no doubt that chemical synthesis of new materials and their self assembly will play a major role in the design and fabrication of next generation semiconductor devices. The objective of this work is to investigate the chemical vapor deposition (CVD) process of thin film using a polymeric precursor as a source material. This process offers many advantages including low deposition cost, hazard free working environment, and most importantly the ability to customize the polymer source material through polymer synthesis and polymer functionalization. The combination between polymer synthesis and CVD process will enable the design of new generation of complex thin film materials with a wide range of improved chemical, mechanical, electrical and optical properties which cannot be easily achieved through conventional CVD processes based on gases and small molecule precursors. In this thesis we mainly focused on polysilanes polymers and more specifically poly(dimethylsilanes). The interest in these polymers is motivated by their distinctive electronic and photonic properties which are attributed to the delocalization of the sigma-electron along the Si-Si backbone chain. These characteristics make polysilane polymers very promising in a broad range of applications as a dielectric, a semiconductor and a conductor. The polymer-based CVD process could be eventually extended to other polymer source materials such as polygermanes, as well as and a variety of other inorganic and hybrid organic-inorganic polymers. This work has demonstrated that a polysilane polymeric source can be used to deposit a wide range of thin film materials exhibiting similar properties with conventional ceramic materials such as silicon carbide (SiC), silicon oxynitride (SiON), silicon oxycarbide (SiOC) silicon dioxide (SiO2) and silicon nitride (Si3N4). The strict control of the deposition process allows precise control of the electrical, optical and chemical properties of polymer-based thin films within a broad range. This work has also demonstrated for the first time that poly(dimethylsilmaes) polymers deposited by CVD can be used to effectively passivate both silicon and gallium arsenide MOS devices. This finding makes polymer-based thin films obtained by CVD very promising for the development of high-kappa dielectric materials for next generation high-mobility CMOS technology. Keywords. Thin films, Polymers, Vapor Phase Deposition, CVD, Nanodielectrics, Organosilanes, Polysilanes, GaAs Passivation, MOSFET, Silicon Oxynitride, Integrated Waveguide, Silicon Carbide, Compound Semiconductors.

Ultrasonic-assisted preparation of graphene oxide carboxylic acid polyvinyl alcohol polymer film and studies of thermal stability and surface resistivity.

PubMed

Li, Yongshen; Li, Jihui; Li, Yuehai; Li, Yali; Song, Yunan; Niu, Shuai; Li, Ning

2018-01-01

In this paper, flake graphite, nitric acid and acetic anhydride are used to prepare graphene oxide carboxylic acid (GO-COOH) via an ultrasonic-assisted method, and GO-COOH and polyvinyl alcohol polymer (PVA) are used to synthesize graphene oxide carboxylic acid polyvinyl alcohol polymer (GO-COOPVA) via the ultrasonic-assisted method, and GO-COOPVA is used to manufacture graphene oxide carboxylic acid polyvinyl alcohol polymer film (GO-COOPVA film) via a solidification method, and the structure and morphology of GO-COOH, GO-COOPVA and GO-COOPVA film are characterized, and the thermal stability and surface resistivity are measured in the case of the different amount of GO-COOH. Based on the characterization and measurement, it has been successively confirmed and attested that carboxyl groups implant on 2D lattice of GO to form GO-COOH, and GO-COOH and PVA have the esterification reaction to produce GO-COOPVA, and GO-COOPVA consists of 2D lattice of GO-COOH and the chain of PVA connected in the form of carboxylic ester, and GO-COOPVA film is composed of GO-COOPVA, and the thermal stability of GO-COOPVA film obviously improves in comparison with PVA film, and the surface resistivity of GO-COOPVA film clearly decreases. Copyright © 2017 Elsevier B.V. All rights reserved.

Evaluation of structural and optical properties of Ce3+ ions doped (PVA/PVP) composite films for new organic semiconductors

NASA Astrophysics Data System (ADS)

Ali, F. M.; Kershi, R. M.; Sayed, M. A.; AbouDeif, Y. M.

2018-06-01

Polymer blend films based on Polyvinyl alcohol (PVA)/Poly(vinylpyrrolidone) (PVP) doped with different concentration of cerium ions [(PVA/PVP)-x wt.% Ce3+] (x = 3%, 5%, 10% and 15%) were prepared by the conventional solution casting technique. The characteristics of the prepared polymer composite films were studied using X-ray diffraction (XRD), FT-IR and UV-Vis. spectroscopy. The XRD patterns of the investigated samples revealed a clear reduction on the structural parameters such as crystallinity degree and cluster size D of the doped PVA/PVP blend films compared with the virgin one whereas there is no big difference in the d spacing of the product composite films. Significant changes in FT-IR spectra are observed which reveal an interactions between the cerium ions and PVA/PVP blends. The absorption spectra in the ultraviolet-visible region showed a wide red shift in the fundamental absorption edge of (PVA/PVP)-x wt. % Ce3+ composites. The optical gap Eg gradually decreased from 4.54 eV for the undoped PVA/PVP film to 3.10 eV by increasing Ce3+ ions content. The optical dispersion parameters have been analyzed according to Wemple-Didomenico single oscillator model. The dispersion energy Ed, the single oscillator energy Eo, the average inter-band oscillator wavelength λo and the static refractive index no are strongly affected by cerium ions doping. Cerium ions incorporation in PVA/PVP blend films leads to a significant increase in the refractive index and decrease in the optical gap. These results are likely of great important in varieties of applications including polymer waveguides, organic semiconductors, polymer solar cells and optoelectronics devices.

Structure and Barrier Properties of Multinanolayered Biodegradable PLA/PBSA Films: Confinement Effect via Forced Assembly Coextrusion.

PubMed

Messin, Tiphaine; Follain, Nadège; Guinault, Alain; Sollogoub, Cyrille; Gaucher, Valérie; Delpouve, Nicolas; Marais, Stéphane

2017-08-30

Multilayer coextrusion processing was applied to produce 2049-layer film of poly(butylene succinate-co-butylene adipate) (PBSA) confined against poly(lactic acid) (PLA) using forced assembly, where the PBSA layer thickness was about 60 nm. This unique technology allowed to process semicrystalline PBSA as confined polymer and amorphous PLA as confining polymer in a continuous manner. The continuity of PBSA layers within the 80/20 wt % PLA/PBSA layered films was clearly evidenced by atomic force microscopy (AFM). Similar thermal events to the reference films were revealed by thermal studies; indicating no diffusion of polymers during the melt-processing. Mechanical properties were measured for the multilayer film and the obtained results were those expected considering the fraction of each polymer, revealing the absence of delamination in the PLA/PBSA multinanolayer film. The confinement effect induced by PLA led to a slight orientation of the crystals, an increase of the rigid amorphous fraction (RAF) in PBSA with a densification of this fraction without changing film crystallinity. These structural changes allowed to strongly improve the water vapor and gas barrier properties of the PBSA layer into the multilayer film up to two decades in the case of CO 2 gas. By confining the PBSA structure in very thin and continuous layers, it was then possible to improve the barrier performances of a biodegradable system and the resulting barrier properties were successfully correlated to the effect of confinement on the microstructure and the chain segment mobility of the amorphous phase. Such investigation on these multinanolayers of PLA/PBSA with the aim of evidencing relationships between microstructure implying RAF and barrier performances has never been performed yet. Besides, gas and water permeation results have shown that the barrier improvement obtained from the multilayer was mainly due to the reduction of solubility linked to the reduction of the free volume while the tortuosity effect, as usually expected, was not really observed. This work brings new insights in the field of physicochemical behaviors of new multilayer films made of biodegradable polyesters but also in interfacial processes due to the confinement effect induced in these multinanolayer structures obtained by the forced assembly coextrusion. This original coextrusion process was a very advantageous technique to produce eco-friendly materials with functional properties without the help of tie layer, additives, solvents, surface treatments, or inorganic fillers.

Manipulating polymers and composites from the nanoscopic to microscopic length scales

NASA Astrophysics Data System (ADS)

Gupta, Suresh

2008-10-01

This thesis focuses on the manipulation of polymers and composites on length scales ranging from the nanoscopic to microscopic. In particular, on the microscopic length scale electric fields were used to produce instabilities at the air surface and at polymer interfaces that lead to novel three dimensional structures and patterns. On the nanoscopic length scale, the interaction of ligands attached to nanoparticles and polymer matrix were used to induce self-assembly processes that, in turn, lead to systems that self-heal, self-corral, or are patterned. For manipulation at the micron length scale, electrohydrodynamic instabilities were used in trilayer system composed of a layer of poly(methyl methacrylate) (PMMA), a second layer of polystyrene (PS) and a third layer of air. Dewetting of the polymer at the substrate at the polymer/polymer interface under an applied electric field was used to generate novel three dimensional structures. Also, electrohydrodynamic instabilities were used to pattern thin polymer films in conjunction with ultrasonic vibrations and patterned upper electrodes. Self-assembly processes involving polymers and nanoparticles offer a unique means of generating pattern materials or materials that self heal. Simple polymer/nanoparticle composites were investigated. Here, in the absence of interactions between the poly(ethylene oxide) ligands attached to the nanoparticles and PMMA polymer matrix, the opportunity to generate self-healing systems was opened. The size of the nanoparticle was varied and the effect on diffusion of nanoparticle in the polymer matrix was studied. CdSe nanorods were also assembled on a substrate templated with or guided by microphase separated diblock copolymers. The nanorods were incorporated in the diblock copolymer thin films by spin coating the co-solution of nanorods and polymer, surface adsorption of nanorods on to the patterned diblock copolymer films and surface reconstruction of PS/PMMA diblock copolymer thin film. Further, the interactions between the PMMA polymer matrix and the tri n-octyl phosphine oxide ligands attached to an anisotropic nanoparticle, i.e. nanorods, were used to influence the dispersion of the nanorods in the polymer. This led to a novel assembly, termed self-corralling where under an applied electric field highly oriented, highly ordered arrays of nanorods form. Further, self corralling of nanorods was directed by chemically patterned substrates.

Structural Effects of Gating Poly(3-hexylthiophene) through an Ionic Liquid

DOE PAGES

Guardado, Jesus O.; Salleo, Alberto

2017-07-17

Ionic liquids are increasingly employed as dielectrics to generate high charge densities and enable low-voltage operation with organic semiconductors. But, effects on structure and morphology of the active material are not fully known, particularly for permeable semiconductors such as conjugated polymers, in which ions from the ionic liquid can enter and electrochemically dope the semicrystalline film. In order to understand when ions enter, where they go, and how they affect the film, thin films of the archetypal semiconducting polymer, poly(3-hexylthiophene), are electrochemically doped with 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, the archetypal ionic liquid. High-resolution, ex situ X-ray diffraction measurements and complete pole figuresmore » reveal changes with applied voltage, cycling, and frequency in lattice spacing, crystallite orientation, and crystallinity in the bulk and at the buried interface. Dopant ions penetrate the film and enter the crystallites at sufficiently high voltages and low frequencies. Upon infiltrating crystallites, ions permanently expand lamellar stacking and contract pi-stacking. Cycling amplifies these effects, but higher frequencies mitigate the expansion of bulk crystallites as ions are hindered from entering crystallites. Furthermore, this mechanistic understanding of the structural effects of ion penetration will help develop models of the frequency and voltage impedance response of electrochemically doped conjugated polymers and advance electronic applications.« less

Structural Effects of Gating Poly(3-hexylthiophene) through an Ionic Liquid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guardado, Jesus O.; Salleo, Alberto

Ionic liquids are increasingly employed as dielectrics to generate high charge densities and enable low-voltage operation with organic semiconductors. But, effects on structure and morphology of the active material are not fully known, particularly for permeable semiconductors such as conjugated polymers, in which ions from the ionic liquid can enter and electrochemically dope the semicrystalline film. In order to understand when ions enter, where they go, and how they affect the film, thin films of the archetypal semiconducting polymer, poly(3-hexylthiophene), are electrochemically doped with 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, the archetypal ionic liquid. High-resolution, ex situ X-ray diffraction measurements and complete pole figuresmore » reveal changes with applied voltage, cycling, and frequency in lattice spacing, crystallite orientation, and crystallinity in the bulk and at the buried interface. Dopant ions penetrate the film and enter the crystallites at sufficiently high voltages and low frequencies. Upon infiltrating crystallites, ions permanently expand lamellar stacking and contract pi-stacking. Cycling amplifies these effects, but higher frequencies mitigate the expansion of bulk crystallites as ions are hindered from entering crystallites. Furthermore, this mechanistic understanding of the structural effects of ion penetration will help develop models of the frequency and voltage impedance response of electrochemically doped conjugated polymers and advance electronic applications.« less

Development and characterization of carrageenan/grapefruit seed extract composite films for active packaging.

PubMed

Kanmani, Paulraj; Rhim, Jong-Whan

2014-07-01

Carrageenan-based antimicrobial films were developed by incorporation of grape fruit seed extract (GSE) at different concentration into the polymer using a solvent casing method and their physical, mechanical, and antimicrobial properties were examined. The carrageenan/GSE composite films appeared yellowish tint due to the polyphenolic compounds in the GSE. SEM analysis showed rough surface with sponge like structures on the cross section of the films. FT-IR results indicated at GSE had good compatibility with carrageenan. The amorphous structure of polymer films was not changed by the incorporation of GSE. But, the addition of GSE increased moisture content, water vapor permeability, and surface hydrophilicity of the films. The tensile strength and elastic modulus decreased with increasing content of GSE, however, the elongation at break increased significantly up to 6.6μg/mL of GSE then decreased thereafter. Thermal stability of the films was not influenced by GSE incorporation. The carrageenan/GSE composite films exhibited great antibacterial activity against food borne pathogens. These results suggest that the carrageenan-based composite films have a high potential for being used as an antimicrobial or active food packaging applications. Copyright © 2014 Elsevier B.V. All rights reserved.

Optically transparent/colorless polyimides

NASA Technical Reports Server (NTRS)

Stclair, A. K.; Stclair, T. L.; Slemp, W.; Ezzell, K. S.

1985-01-01

Several series of linear aromatic polyimide films have been synthesized and characterized with the objective of obtaining maximum optical transparency. Two approaches have been used as part of this structure-property relationship study. The first approach is to vary the molecular structure so as to separate chromophoric centers and reduce electronic interactions between polymer chains to lower the intensity of color in the resulting polymer films. A second and concurrent approach is to perform polymerizations with highly purified monomers. Glass transition temperatures of thermally cured polyimide films are obtained by thermomechanical analysis and thermal decomposition temperatures are determined by thermogravimetric analysis. Transmittance UV-visible spectra of the polyimide films are compared to that of a commercial polyimide film. Fully imidized films are tested for solubility in common organic solvents. The more transparent films prepared in this study are evaluated for use on second-surface mirror thermal control coating systems. Lightly colored to colorless films are characterized by UV-visible spectroscopy before and after exposure to 300 equivalent solar hours UV irradiation and varying doses of 1 MeV electron irradiation. The effects of monomer purity, casting solvent and cure atmosphere on polyimide film transparency are also investigated.

Proceedings of the International Symposium on Nonlinear Optical Polymers for Soldier Survivability (1st), Held in Natick, Massachusetts on June 13-14, 1989

DTIC Science & Technology

1990-09-01

Film Fabrication for Optical Second Harmonic Generation * Dr. Geoffrey A. Lindsay, Naval Weapons Center, et al. Corona-Onset Poling of New Side...having the required structures: Polyanilines and derivatives, polyazobenzenes and derivatives and polypyrroles. These polymers are generally...phase polymerization of the monomers on substrates of polyvinyl alcohol or polyvinylpyrrolidone. These films will be evaluated in a facility that

Effect of fractal silver electrodes on charge collection and light distribution in semiconducting organic polymer films

DOE PAGES

Chamousis, Rachel L.; Chang, Lilian; Watterson, William J.; ...

2014-08-21

Living organisms use fractal structures to optimize material and energy transport across regions of differing size scales. Here we test the effect of fractal silver electrodes on light distribution and charge collection in organic semiconducting polymer films made of P3HT and PCBM. The semiconducting polymers were deposited onto electrochemically grown fractal silver structures (5000 nm × 500 nm; fractal dimension of 1.71) with PEDOT:PSS as hole-selective interlayer. The fractal silver electrodes appear black due to increased horizontal light scattering, which is shown to improve light absorption in the polymer. According to surface photovoltage spectroscopy, fractal silver electrodes outperform the flatmore » electrodes when the BHJ film thickness is large (>400 nm, 0.4 V photovoltage). Photocurrents of up to 200 microamperes cm -2 are generated from the bulk heterojunction (BHJ) photoelectrodes under 435 nm LED (10–20 mW cm -2) illumination in acetonitrile solution containing 0.005 M ferrocenium hexafluorophosphate as the electron acceptor. In conclusion, the low IPCE values (0.3–0.7%) are due to slow electron transfer to ferrocenium ion and due to shunting along the large metal–polymer interface. Overall, this work provides an initial assessment of the potential of fractal electrodes for organic photovoltaic cells.« less

Perpendicularly Aligned, Anion Conducting Nanochannels in Block Copolymer Electrolyte Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arges, Christopher G.; Kambe, Yu; Suh, Hyo Seon

Connecting structure and morphology to bulk transport properties, such as ionic conductivity, in nanostructured polymer electrolyte materials is a difficult proposition because of the challenge to precisely and accurately control order and the orientation of the ionic domains in such polymeric films. In this work, poly(styrene-block-2-vinylpyridine) (PSbP2VP) block copolymers were assembled perpendicularly to a substrate surface over large areas through chemical surface modification at the substrate and utilizing a versatile solvent vapor annealing (SVA) technique. After block copolymer assembly, a novel chemical vapor infiltration reaction (CVIR) technique selectively converted the 2-vinylpyridine block to 2-vinyl n-methylpyridinium (NMP+ X-) groups, which aremore » anion charge carriers. The prepared block copolymer electrolytes maintained their orientation and ordered nanostructure upon the selective introduction of ion moieties into the P2VP block and post ion-exchange to other counterion forms (X- = chloride, hydroxide, etc.). The prepared block copolymer electrolyte films demonstrated high chloride ion conductivities, 45 mS cm(-1) at 20 degrees C in deionized water, the highest chloride ion conductivity for anion conducting polymer electrolyte films. Additionally, straight-line lamellae of block copolymer electrolytes were realized using chemoepitaxy and density multiplication. The devised scheme allowed for precise and accurate control of orientation of ionic domains in nanostructured polymer electrolyte films and enables a platform for future studies that examines the relationship between polymer electrolyte structure and ion transport.« less

Manufacturing polymer thin films in a micro-gravity environment

NASA Technical Reports Server (NTRS)

Vera, Ivan

1987-01-01

This project represents Venezuela's first scientific experiment in space. The apparatus for the automatic casting of two polymer thin films will be contained in NASA's Payload No. G-559 of the Get Away Special program for a future orbital space flight in the U.S. Space Shuttle. Semi-permeable polymer membranes have important applications in a variety of fields, such as medicine, energy, and pharmaceuticals and in general fluid separation processes, such as reverse osmosis, ultrafiltration, and electrodialysis. The casting of semi-permeable membranes in space will help to identify the roles of convection in determining the structure of these membranes.

Orienting semi-conducting π-conjugated polymers.

PubMed

Brinkmann, Martin; Hartmann, Lucia; Biniek, Laure; Tremel, Kim; Kayunkid, Navaphun

2014-01-01

The present review focuses on the recent progress made in thin film orientation of semi-conducting polymers with particular emphasis on methods using epitaxy and shear forces. The main results reported in this review deal with regioregular poly(3-alkylthiophene)s and poly(dialkylfluorenes). Correlations existing between processing conditions, macromolecular parameters and the resulting structures formed in thin films are underlined. It is shown that epitaxial orientation of semi-conducting polymers can generate a large palette of semi-crystalline and nanostructured morphologies by a subtle choice of the orienting substrates and growth conditions. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dielectric property study of poly(4-vinylphenol)-graphene oxide nanocomposite thin film

NASA Astrophysics Data System (ADS)

Roy, Dhrubojyoti

2018-05-01

Thin film capacitor device having a sandwich structure of indium tin oxide (ITO)-coated glass/polymer or polymer nanocomposite /silver has been fabricated and their dielectric and leakage current properties has been studied. The dielectric properties of the capacitors were characterized for frequencies ranging from 1 KHz to 1 MHz. 5 wt% Poly(4-vinylphenol)(PVPh)-Graphene (GO) nanocomposite exhibited an increase in dielectric constant to 5.6 and small rise in dielectric loss to around˜0.05 at 10 KHz w.r.t polymer. The DC conductivity measurements reveal rise of leakage current in nanocomposite.

Rapid assessment of crystal orientation in semi-crystalline polymer films using rotational zone annealing and impact of orientation on mechanical properties

DOE PAGES

Ye, Changhuai; Wang, Chao; Wang, Jing; ...

2017-08-17

Crystal orientation in semi-crystalline polymers tends to enhance their performance, such as increased yield strength and modulus, along the orientation direction. Zone annealing (ZA) orients the crystal lamellae through a sharp temperature gradient that effectively directs the crystal growth, but the sweep rate (V ZA) of this gradient significantly impacts the extent of crystal orientation. Here in this work, we demonstrate rotational zone annealing (RZA) as an efficient method to elucidate the influence of V ZA on the crystal morphology of thin films in a single experiment using isotactic poly(1-butene), PB-1, as a model semi-crystalline polymer. These RZA results aremore » confirmed using standard, serial linear ZA to tune the structure from an almost unidirectional oriented morphology to weakly oriented spherulites. The overall crystallinity is only modestly changed in comparison to isothermal crystallization (maximum of 55% from ZA vs. 48% for isothermal crystallization). However, the average grain size increases and the spherulites become anisotropic from ZA. Due to these structural changes, the Young's modulus of the oriented films, both parallel and perpendicular to the spherulite orientation direction, is significantly increased by ZA. The modulus does become anisotropic after ZA due to the directionality in the crystal structure, with more than a threefold increase in the modulus parallel to the orientation direction for the highest oriented film in comparison to the modulus from isothermal crystallization. Lastly, RZA enables rapid identification of conditions to maximize orientation of crystals in thin polymer films, which could find utility in determining conditions to improve crystallinity and performance in organic electronics.« less

Rapid assessment of crystal orientation in semi-crystalline polymer films using rotational zone annealing and impact of orientation on mechanical properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ye, Changhuai; Wang, Chao; Wang, Jing

Crystal orientation in semi-crystalline polymers tends to enhance their performance, such as increased yield strength and modulus, along the orientation direction. Zone annealing (ZA) orients the crystal lamellae through a sharp temperature gradient that effectively directs the crystal growth, but the sweep rate (V ZA) of this gradient significantly impacts the extent of crystal orientation. Here in this work, we demonstrate rotational zone annealing (RZA) as an efficient method to elucidate the influence of V ZA on the crystal morphology of thin films in a single experiment using isotactic poly(1-butene), PB-1, as a model semi-crystalline polymer. These RZA results aremore » confirmed using standard, serial linear ZA to tune the structure from an almost unidirectional oriented morphology to weakly oriented spherulites. The overall crystallinity is only modestly changed in comparison to isothermal crystallization (maximum of 55% from ZA vs. 48% for isothermal crystallization). However, the average grain size increases and the spherulites become anisotropic from ZA. Due to these structural changes, the Young's modulus of the oriented films, both parallel and perpendicular to the spherulite orientation direction, is significantly increased by ZA. The modulus does become anisotropic after ZA due to the directionality in the crystal structure, with more than a threefold increase in the modulus parallel to the orientation direction for the highest oriented film in comparison to the modulus from isothermal crystallization. Lastly, RZA enables rapid identification of conditions to maximize orientation of crystals in thin polymer films, which could find utility in determining conditions to improve crystallinity and performance in organic electronics.« less

Effects of Molecular Structure and Packing Order on the Stretchability of Semicrystalline Conjugated Poly(Tetrathienoacene-diketopyrrolopyrrole) Polymers

DOE PAGES

Lu, Chien; Lee, Wen-Ya; Gu, Xiaodan; ...

2016-12-23

The design of polymer semiconductors possessing high charge transport performance, coupled with good ductility, remains a challenge. Understanding the distribution and behavior of both crystalline domains and amorphous regions in conjugated polymer films, upon an applied stress, shall provide general guiding principles to design stretchable organic semiconductors. Structure–property relationships (especially in both side chain and backbone engineering) are investigated for a series of poly(tetrathienoacene-diketopyrrolopyrrole) polymers. It is observed that the fused thiophene diketopyrrolopyrrole-based polymer, when incorporated with branched side chains and an additional thiophene spacer in the backbone, exhibits improved mechanical endurance and, in addition, does not show crack propagationmore » until 40% strain. Furthermore, this polymer exhibits a hole mobility of 0.1 cm2 V -1 s -1 even at 100% strain or after recovered from strain, which reveals prominent continuity and viscoelasticity of the polymer thin film. In conclusion, it is also observed that the molecular packing orientations (either edge-on or face-on) significantly affect the mechanical compliance of the polymer films. The improved stretchability of the polymers is attributed to both the presence of soft amorphous regions and the intrinsic packing arrangement of its crystalline domains.« less

Effects of Molecular Structure and Packing Order on the Stretchability of Semicrystalline Conjugated Poly(Tetrathienoacene-diketopyrrolopyrrole) Polymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu, Chien; Lee, Wen-Ya; Gu, Xiaodan

The design of polymer semiconductors possessing high charge transport performance, coupled with good ductility, remains a challenge. Understanding the distribution and behavior of both crystalline domains and amorphous regions in conjugated polymer films, upon an applied stress, shall provide general guiding principles to design stretchable organic semiconductors. Structure–property relationships (especially in both side chain and backbone engineering) are investigated for a series of poly(tetrathienoacene-diketopyrrolopyrrole) polymers. It is observed that the fused thiophene diketopyrrolopyrrole-based polymer, when incorporated with branched side chains and an additional thiophene spacer in the backbone, exhibits improved mechanical endurance and, in addition, does not show crack propagationmore » until 40% strain. Furthermore, this polymer exhibits a hole mobility of 0.1 cm2 V -1 s -1 even at 100% strain or after recovered from strain, which reveals prominent continuity and viscoelasticity of the polymer thin film. In conclusion, it is also observed that the molecular packing orientations (either edge-on or face-on) significantly affect the mechanical compliance of the polymer films. The improved stretchability of the polymers is attributed to both the presence of soft amorphous regions and the intrinsic packing arrangement of its crystalline domains.« less

The effect of axial ion parameters on the properties of glow discharge polymer in T2B/H2 plasma

NASA Astrophysics Data System (ADS)

Ai, Xing; He, Xiao-Shan; Huang, Jing-Lin; He, Zhi-Bing; Du, Kai; Chen, Guo

2018-03-01

Glow discharge polymer (GDP) films were fabricated using plasma-enhanced chemical vapor deposition. The main purpose of this work was to explore the correlations of plasma parameters with the surface morphology and chemical structure of GDP films. The intensities of main positive ions and ion energy as functions of axial distances in T2B/H2 plasma were diagnosed using energy-resolved mass spectrometry. The surface morphology and chemical structure were characterized as functions of axial distances using a scanning electron microscope and Fourier transform infrared spectroscopy, respectively. As the axial distance increases, both the intensities of positive ions and high energy ions decreases, and dissociation weakens while polymerization enhances. This leads to the weakening of the cross-linking structure of GDP films and the formation of dome defects on films. Additionally, high energy ions could introduce a strong etching effect to form etching pits. Therefore, an axial distance of about 20 mm was found to be the optimal plasma parameter to prepare the defect-free GDP films. These results could help one to find the optimal plasma parameters for GDP film deposition.

Fire-retardant epoxy polymers

NASA Technical Reports Server (NTRS)

Akawie, R. I.; Bilow, N.; Giants, T. W.

1978-01-01

Phosphorus atoms in molecular structure of epoxies make them fire-retardant without degrading their adhesive strength. Moreover, polymers are transparent, unlike compounds that contain arsenic or other inorganics. They have been used to bond polyvinylfluoride and polyether sulfone films onto polyimide glass laminates.

Combined Mechanical and Electrical Study of Polymers of Biological Origin

NASA Astrophysics Data System (ADS)

Zsoldos, G.; Szoda, K.; Marossy, K.

2017-02-01

Thermally Simulated Depolarization Current measurement is an excellent but not widely used method for identifying relaxation processes in polymers. The DMA method is used here to analyze the mechanical changes depend on temperature in biopolymers. The two techniques take advantage of the energy changes involved in the various phase transitions of certain polymer molecules. This allows for several properties of the material to be ascertained; melting points, enthalpies of melting, crystallization temperatures, glass transition temperatures and degradation temperatures. The examined biopolymer films are made from biological materials such as proteins and polysaccharides. These materials have gained wide usage in pharmaceutical, medical and food areas. The uses of biopolymer films depend on their structure and mechanical properties. This work is based on pectin and gelatin films. The films were prepared by casting. The casting technique used aqueous solutions in each case of sample preparation. The manufacturing process of the pectin and gelatin films was a single stage solving process.

Elucidation of band structure of charge storage in conducting polymers using a redox reaction.

PubMed

Contractor, Asfiya Q; Juvekar, Vinay A

2014-07-01

A novel technique to investigate charge storage characteristics of intrinsically conducting polymer films has been developed. A redox reaction is conducted on a polymer film on a rotating disk electrode under potentiostatic condition so that the rate of charging of the film equals the rate of removal of the charge by the reaction. The voltammogram obtained from the experiment on polyaniline film using Fe(2+)/Fe(3+) in HCl as the redox system shows five distinct linear segments (bands) with discontinuity in the slope at specific transition potentials. These bands are the same as those indicated by electron spin resonance (ESR)/Raman spectroscopy with comparable transition potentials. From the dependence of the slopes of the bands on concentration of ferrous and ferric ions, it was possible to estimate the energies of the charge carriers in different bands. The film behaves as a redox capacitor and does not offer resistance to charge transfer and electronic conduction.

Elaboration of m-cresol polyamide12/ polyaniline composite films for antistatic applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mezdour, D.; Tabellout, M.; Bardeau, J.-F

2013-12-16

The present work deals with the preparation of transparent antistatic films from an extreme dilution of an intrinsically conducting polymer (ICP) with not coloured polymers. Our approach is based on the chemical polymerization of a very thin layer of Polyaniline (PANI) around particles of an insulating polymer (PA12). Films were obtained by dissolving the synthesized core-shell particles in m-Cresol. The electric property and structure relationships were investigated by using dielectric relaxation spectroscopy, X-ray diffraction and micro-Raman spectroscopy. Composite films exhibited a well established dc conductivity over all the frequency range for 10 wt. % of PANI concentration related to themore » conductive properties of the PANI clusters. X-ray diffraction data show broader and lower intensity of PA12 peaks when increasing PANI content, probably due to the additional doping effect of m- cresol. The doping of PA12/PANI films with Dodecyl benzene sulfonic acid (DBSA) was unequivocally verified by Raman spectroscopy.« less

Swelling kinetics and electrical charge transport in PEDOT:PSS thin films exposed to water vapor.

PubMed

Sarkar, Biporjoy; Jaiswal, Manu; Satapathy, Dillip K

2018-06-06

We report the swelling kinetics and evolution of the electrical charge transport in poly(3,4-ethylene dioxythiophene) polystyrene sulfonate (PEDOT:PSS) thin films subjected to water vapor. Polymer films swell by the diffusion of water vapor and are found to undergo structural relaxations. Upon exposure to water vapor, primarily the hygroscopic PSS shell, which surrounds the conducting PEDOT-rich cores, takes up water vapor and subsequently swells. We found that the degree of swelling largely depends on the PEDOT to PSS ratio. Swelling driven microscopic rearrangement of the conducting PEDOT-rich cores in the PSS matrix strongly influences the electrical charge transport of the polymer film. Swelling induced increase as well as decrease of electrical resistance are observed in polymer films having different PEDOT to PSS ratio. This anomalous charge transport behavior in PEDOT:PSS films is reconciled by taking into account the contrasting swelling behavior of the PSS and the conducting PEDOT-rich cores leading to spatial segregation of PSS in films with PSS as a minority phase and by a net increase in mean separation between conducting PEDOT-rich cores for films having abundance of PSS.

Swelling kinetics and electrical charge transport in PEDOT:PSS thin films exposed to water vapor

NASA Astrophysics Data System (ADS)

Sarkar, Biporjoy; Jaiswal, Manu; Satapathy, Dillip K.

2018-06-01

We report the swelling kinetics and evolution of the electrical charge transport in poly(3,4-ethylene dioxythiophene) polystyrene sulfonate (PEDOT:PSS) thin films subjected to water vapor. Polymer films swell by the diffusion of water vapor and are found to undergo structural relaxations. Upon exposure to water vapor, primarily the hygroscopic PSS shell, which surrounds the conducting PEDOT-rich cores, takes up water vapor and subsequently swells. We found that the degree of swelling largely depends on the PEDOT to PSS ratio. Swelling driven microscopic rearrangement of the conducting PEDOT-rich cores in the PSS matrix strongly influences the electrical charge transport of the polymer film. Swelling induced increase as well as decrease of electrical resistance are observed in polymer films having different PEDOT to PSS ratio. This anomalous charge transport behavior in PEDOT:PSS films is reconciled by taking into account the contrasting swelling behavior of the PSS and the conducting PEDOT-rich cores leading to spatial segregation of PSS in films with PSS as a minority phase and by a net increase in mean separation between conducting PEDOT-rich cores for films having abundance of PSS.

Self-Assembling Brush Polymers Bearing Multisaccharides.

PubMed

Lee, Jongchan; Kim, Jin Chul; Lee, Hoyeol; Song, Sungjin; Kim, Heesoo; Ree, Moonhor

2017-06-01

Three different series of brush polymers bearing glucosyl, maltosyl, or maltotriosyl moiety at the bristle end are successfully prepared by using cationic ring-opening polymerization and two sequential postmodification reactions. All brush polymers, except for the polymer containing 100 mol% maltotriosyl moiety, demonstrate the formation of multibilayer structure in films, always providing saccharide-enriched surface. These self-assembling features are remarkable, regarding the bulkiness of saccharide moieties and the kink in the bristle due to the triazole linker. The saccharide-enriched film surfaces reveal exceptionally high specific binding affinity to concanavalin A but suppress nonspecific binding of plasma proteins severely. Overall, the brush polymers bearing saccharide moieties of various kinds in this study are highly suitable materials for biomedical applications including biosensors. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

'Breath figure' PLGA films as implant coatings for controlled drug release

NASA Astrophysics Data System (ADS)

Ponnusamy, Thiruselvam

The breath figure method is a versatile and facile approach of generating ordered micro and nanoporous structures in polymeric materials. When a polymer solution (dissolved in a high vapor pressure organic solvent) is evaporated out in the presence of a moist air stream, the evaporative cooling effect causes the condensation and nucleation of water droplets onto the polymer solution surface. This leads to the formation of an imprinted porous structure upon removal of the residual solvent and water. The facile removal of the water droplet template leaving its structural imprint is a specifically appealing aspect of the breath figure film technology. The first part of the dissertation work involves the fabrication of drug loaded breath figure thin films and its utilization as a controlled drug release carrier and biomaterial scaffold. In a single fabrication step, single layer/multilayer porous thin films were designed and developed by combining the breath figure process and a modified spin or dip coating technique. Using biodegradable polymers such as poly (lactic-co-glycolic acid) (PLGA) and poly (ethylene glycol) (PEG), drug loaded films were fabricated onto FDA approved medical devices (the Glaucoma drainage device and the Surgical hernia mesh). The porosity of the films is in the range of 2-4 microm as characterized by scanning electron microscope. The drug coated medical implants were characterized for their surface and bulk morphology, the degradation rate of the film, drug release rate and cell cytotoxicity. The results suggest that the use of breath figure morphologies in biodegradable polymer films adds an additional level of control to drug release. In comparison to non-porous films, the breath figure films showed an increased degradation and enhanced drug release. Furthermore, the porous nature of the film was investigated as a biomaterial scaffold to construct three dimensional in vitro tissue model systems. The breath figure film with interconnected pores facilitates cell infiltration and tissue remodelling in vitro, suggesting its high potential in regenerative medicine and tissue engineering applications. In the second part of the dissertation, the versatility of breath figure polymers was explored as a reverse template to create micropatterned soft materials. Unlike traditional lithographic masters, the breath figure assembly is a simple and cost-effective approach to create micro/nano sized "bead" like uniform patterns on the surface of hydrogels and biopolymers. By incorporating iron nanoparticles into the pores, this technique was extended to form hydrogels decorated with nanoparticles specifically in the pattern. The morphology features and the functional characteristics were demonstrated through scanning electron microscopy. The potential applications of these micro-fabricated materials in biosensors and cell culture substrates are outlined.

Ion beam sputtering of fluoropolymers. [etching polymer films and target surfaces

NASA Technical Reports Server (NTRS)

Sovey, J. S.

1978-01-01

Ion beam sputter processing rates as well as pertinent characteristics of etched targets and films are described. An argon ion beam source was used to sputter etch and deposit the fluoropolymers PTFE, FEP, and CTFE. Ion beam energy, current density, and target temperature were varied to examine effects on etch and deposition rates. The ion etched fluoropolymers yield cone or spire-like surface structures which vary depending upon the type of polymer, ion beam power density, etch time, and target temperature. Sputter target and film characteristics documented by spectral transmittance measurements, X-ray diffraction, ESCA, and SEM photomicrographs are included.

Process for preparing essentially colorless polyimide film containing phenoxy-linked diamines

NASA Technical Reports Server (NTRS)

Stclair, A. K.; Stclair, T. L.

1986-01-01

A polyimide film that is approximately 90% transparent at 500 nm, useful for thermal protective coatings and solar cells, and the processes for preparing the same by thermal and chemical conversion are disclosed. An essential feature for achieving maximum optical transparency films requires utilizing recrystallized and/or sublimated specific aromatic diamines and dianhydride monomers and introducing phenoxy or thiophenyl separator groups and isomeric m,m' or o,p'-oriented diamines into the polymer molecular structure. The incorporation of these groups in the polymer structure serves to separate the chromaphoric centers and reduce the formation of inter-chain and intra-chain charge transfer complexes which normally cause absorptions in the UV-visible range. The films may be obtained by hand, brushing, casting, or spraying a layer of polyamic acid solutions onto a surface and thermally converting the applied layer to the polyimide, or the polyamic acid solution can be chemically converted to the polyimide, subsequentially dissolved in an organic solvent, and applied as a polyimide film layer with the solvent therein thermally removed.

Structural phase study in un-patterned and patterned PVDF semi-crystalline films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pramod, K., E-mail: rameshg.phy@pondiuni.edu.in; Gangineni, Ramesh Babu, E-mail: rameshg.phy@pondiuni.edu.in

2014-04-24

This work explores the structural phase studies of organic polymer- polyvinylidene fluoride (PVDF) thin films in semi-crystallized phase and nano-patterned PVDF thin films. The nanopatterns are transferred with the CD layer as a master using soft lithography technique. The semi-crystalline PVDF films were prepared by a still and hot (SH) method, using a homemade spin coater that has the proficiency of substrate heating by a halogen lamp. Using this set up, smooth PVDF thin films in semi-crystalline α-phase were prepared using 2-Butanone as solvent. XRD, AFM and confocal Raman microscope have been utilized to study the structural phase, crystallinity andmore » quality of the films.« less

Treatments to induce the nucleation and growth of apatite-like layers on polymeric surfaces and foams.

PubMed

Reis, R L; Cunha, A M; Fernandes, M H; Correia, R N

1997-12-01

In this work, a bioactive glass is used as a percusor of calcium-phosphate (Ca-P) film deposition onto several polymer-based materials. Both bioinert (high molecular weight polyethylene, HMWPE), and biodegradable (corn starch-based blends, SEVA-C) polymers, unreinforced or reinforced with hydroxylapatite (HA), were coated by the very simple proposed route. Also polyurethane (PU) foams, with an open-cell structure, were mineralized by the proposed method. In fact, it was possible to induce the growth of the Ca-P films not only at the surface, but also in the bulk of the PU foam. These cellular materials are intended for cancellous bone replacement applications. The morphology of the formed films was strongly dependent on the used substrate, its polar character, and on the presence of HA in its composition, as observed by SEM. Nevertheless, a well defined needly like structure was observed in all samples at high magnifications. The Ca:P ratios of the films were between 1.5 and 1.7, i.e. in the range of tricalcium phosphate-hydroxylapatite. Raman spectroscopy and thin-film x-ray diffraction (XRD) evidenced the formation of mostly amorphous calcium-phosphate films. After scraping the coating from the polymer surface and heat-treating the resulting powder at 1000 degrees C for 1 h, HA and beta-tricalcium phosphate (TCP) typical peaks were found on XRD patterns.

Superhydrophobic polymeric films with hierarchical structures produced by nanoimprint (NIL) and plasma roughening

NASA Astrophysics Data System (ADS)

Durret, Jérôme; Szkutnik, Pierre-David; Frolet, Nathalie; Labau, Sebastien; Gourgon, Cécile

2018-07-01

The structuration of various polymeric films has been studied to create superhydrophobic surfaces. Nanoimprint lithography and/or plasma etching processes with CF4/Ar have been used on FEP, PMMA and PET polymer films. On the one hand, the effect of the CF4/Ar gases, the input power and the plasma treatment duration have been investigated in terms of etching and fluorination degree, and XPS analyses are precisely discussed. On the other hand, wettability performances were characterized. Relationships between the contact angle, the contact angle hysteresis and the surface structures have been investigated. The wetting behaviors and the transition between the Wenzel and the Cassie-Baxter states was discussed as a function of the roughness. We have prepared each studied polymer films in transparent and flexible superhydrophobic surfaces whose contact angle are ∼160° and hysteresis are ∼2°. A short plasma treatment time (10 s) is sufficient to obtain a superhydrophobic behavior on FEP and PMMA. Results indicate that hierarchical structures allow a more stable superhydrophobic state regarding inhomogeneities. Moreover, the use of plasma etching is suggested to overcome some limitations of the NIL in the case of structures with a high aspect ratio. Finally, a quick and large surface fabrication method for superhydrophobic films is detailed.

Selective Template Wetting Routes to Hierarchical Polymer Films: Polymer Nanotubes from Phase-Separated Films via Solvent Annealing.

PubMed

Ko, Hao-Wen; Cheng, Ming-Hsiang; Chi, Mu-Huan; Chang, Chun-Wei; Chen, Jiun-Tai

2016-03-01

We demonstrate a novel wetting method to prepare hierarchical polymer films with polymer nanotubes on selective regions. This strategy is based on the selective wetting abilities of polymer chains, annealed in different solvent vapors, into the nanopores of porous templates. Phase-separated films of polystyrene (PS) and poly(methyl methacrylate) (PMMA), two commonly used polymers, are prepared as a model system. After anodic aluminum oxide (AAO) templates are placed on the films, the samples are annealed in vapors of acetic acid, in which the PMMA chains are swollen and wet the nanopores of the AAO templates selectively. As a result, hierarchical polymer films containing PMMA nanotubes can be obtained after the AAO templates are removed. The distribution of the PMMA nanotubes of the hierarchical polymer films can also be controlled by changing the compositions of the polymer blends. This work not only presents a novel method to fabricate hierarchical polymer films with polymer nanotubes on selective regions, but also gives a deeper understanding in the selective wetting ability of polymer chains in solvent vapors.

Polymer blend effect on molecular alignment induced by contact freezing of mesogenic phthalocyanine

NASA Astrophysics Data System (ADS)

Kitagawa, Takahiro; Fiderana Ramananarivo, Mihary; Fujii, Akihiko; Ozaki, Masanori

2018-04-01

The polymer blend effect in the fabrication of uniaxially oriented thin films of a mesogenic phthalocyanine, 1,4,8,11,15,18,22,25-octahexylphthalocyanine (C6PcH2), by contact freezing was studied. Contact freezing was induced by thermal stimulation to a supercooled liquid crystal state of the mixture of C6PcH2 and poly(3-hexylthiophene) (P3HT). With the blending of P3HT with C6PcH2 at an appropriate blend ratio, the cracks observed in a pure C6PcH2 film disappeared while maintaining the uniaxial alignment of C6PcH2. The polymer blend effect was discussed by taking the anisotropic optical absorption and molecular stacking structure in the thin films into consideration.

Composite materials obtained by the ion-plasma sputtering of metal compound coatings on polymer films

NASA Astrophysics Data System (ADS)

Khlebnikov, Nikolai; Polyakov, Evgenii; Borisov, Sergei; Barashev, Nikolai; Biramov, Emir; Maltceva, Anastasia; Vereshchagin, Artem; Khartov, Stas; Voronin, Anton

2016-01-01

In this article, the principle and examples composite materials obtained by deposition of metal compound coatings on polymer film substrates by the ion-plasma sputtering method are presented. A synergistic effect is to obtain the materials with structural properties of the polymer substrate and the surface properties of the metal deposited coatings. The technology of sputtering of TiN coatings of various thicknesses on polyethylene terephthalate films is discussed. The obtained composites are characterized by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), atomic force microscopy (AFM), and scanning tunneling microscopy (STM) is shown. The examples of application of this method, such as receiving nanocomposite track membranes and flexible transparent electrodes, are considered.

Diels-Alder Trapping of Photochemically Generated o-Xylenols: Application in the Synthesis of Novel Organic Molecules and Polymers

NASA Technical Reports Server (NTRS)

Meador, Michael A.

2003-01-01

Bis(o-xylenol) equivalents are useful synthetic intermediates in the construction of polymers and hydroxyl substituted organic molecules which can organize by hydrogen bonded self-assembly into unique supramolecular structures. These polymers and supramolecular materials have potential use as coatings and thin films in aerospace, electronic and biomedical applications.

Macroscopic monolayer of plasmon coupled gold nanoparticles on mirror for fluorescence enhancement

NASA Astrophysics Data System (ADS)

Kaydashev, V. E.; Zolotukhin, P.; Belanova, A.; Anokhin, A. S.; Zharinov, V. S.; Kaidashev, E. M.

2018-04-01

We study an ability of a large quasi-homogeneous monolayer of Au plasmon coupled nanoparticles separated from continuous Au film by polymer spacer to enhance a fluorescence of adsorbed molecular species. A fluorescence response of Methylene Blue molecules is studied as a function of polymer film thickness. A change of plasmonic properties of a system, its ability to enhance a fluorescence and the possible heating of a structure upon light absorption are discussed.

Structural modification in the formation of starch - silver nanocomposites

NASA Astrophysics Data System (ADS)

Begum, S. N. Suraiya; Aswal, V. K.; Ramasamy, Radha Perumal

2016-05-01

Polymer based nanocomposites have gained wide applications in field of battery technology. Starch is a naturally occurring polysaccharide with sustainable properties such as biodegradable, non toxic, excellent film forming capacity and it also act as reducing agent for the metal nanoparticles. In our research various concentration of silver nitrate (AgNO3) was added to the starch solution and films were obtained using solution casting method. Surface electron microscope (SEM) of the films shows modifications depending upon the concentration of AgNO3. Small angle neutron scattering (SANS) analysis showed that addition of silver nitrate modifies the starch to disc like structures and with increasing the AgNO3 concentration leads to the formation of fractals. This research could benefit battery technology where solid polymer membranes using starch is used.

Effect of polymer matrix on structure of Se particles formed in aqueous solutions during redox process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Suvorova, E. I., E-mail: suvorova@ns.crys.ras.ru; Klechkovskaya, V. V.

2010-12-15

Transmission electron microscopy and X-ray energy dispersive microanalysis study of the structure of particles formed during the reduction of Se(IV) to Se(0) in aqueous solutions in the presence of amphiphilic polymers showed the formation of Se/polymer composite particles. The content of carbon inside the particles can be as large as 80 at %. Polymers deeply influence the structure of particles. Depending on polymers, the composite particles may be unstable with time and they spontaneously evolve from Se/polymer composite particles to crystalline particles of monoclinic Se. For the stable ones, addition of bacterial cellulose Acetobacter xylinum gel-film can induce crystallization inmore » the particles which expel the polymeric material. The Se/polymer composite particles and Se crystalline particles exhibit different sensitivity to electron irradiation and stiffness.« less

Laboratory Analysis of Polymer Thin Films for Planetary Balloons and Gossamer Structures

NASA Technical Reports Server (NTRS)

Sterling, Jerry; Fairbrother, Debora A.

2004-01-01

Commercially available polymer thin fdms with thickness of 15 microns or less were evaluated for potential application as the gas envelope material of balloons and other inflated vehicles. Films on this thickness scale are of interest for Earth and Mars ballooning as well as many gossamer space structures. Due to the uniqueness of these missions relative to typical uses of these materials, application-specific materials properties measurements were made. We evaluated numerous polymer chemistries, plus a few variations within one chemistry. The data show that there are often trade-offs among the different materials, such as with polyesters and polyimides having greater stiffness (modulus) but lower tear propagation resistance than polyethylene. Sections of polyethylene films can be joined by heat sealing, while adhesives and their accompanying mass penalty must be used with polyesters and polyimides. When the analysis temperature is reduced to 190 K, polyethylenes display dramatically increased stiffness and yield point, while the increase for other materials is more modest. The data also show that manufacturing processes can significantly affect film properties. To emphasize the need for application-specific properties assessment, we discuss two recent applications using these materials.

Fabrication of multilayered thin films via spin-assembly

DOEpatents

Chiarelli, Peter A.; Robinson, Jeanne M.; Casson, Joanna L.; Johal, Malkiat S.; Wang, Hsing-Lin

2007-02-20

An process of forming multilayer thin film heterostructures is disclosed and includes applying a solution including a first water-soluble polymer from the group of polyanionic species, polycationic species and uncharged polymer species onto a substrate to form a first coating layer on the substrate, drying the first coating layer on the substrate, applying a solution including a second water-soluble polymer from the group of polyanionic species, polycationic species and uncharged polymer species onto the substrate having the first coating layer to form a second coating layer on the first coating layer wherein the second water-soluble polymer is of a different material than the first water-soluble polymer, and drying the second coating layer on the first coating layer so as to form a bilayer structure on the substrate. Optionally, one or more additional applying and drying sequences can be repeated with a water-soluble polymer from the group of polyanionic species, polycationic species and uncharged polymer species, so that a predetermined plurality of layers are built up upon the substrate.

Transparent oxygen and water vapor barriers for flexible electronics using semi-crystalline polymer matrix thin films

NASA Astrophysics Data System (ADS)

Sehgal, Akhil

Electronic components such as organic light emitting diodes (OLED) and photo-voltaics have been of more focus with the advancement of technology. These electronics are susceptible to degradable in the presence of gases such as water vapor and oxygen. Being that these gases are constituents of the atmosphere and can be found in nearly every environment, certain protocols must take place to mitigate the issues that occur. New generation electronics are sensitive to oxidation and corrosion in the presence of extremely low concentrations of moisture and oxygen and therefore the development and improvements of gas barriers are vital for advancements in electronics technology. The improvements of appliances such as flexible solar cells and OLEDs require barriers that need to be flexible in order to achieve high longevity. The area of research has been focused on designing flexible polymer films with composite nanoparticles and cross-linking agents that have low permeability to moisture and oxygen gas. The polymers studied are in the family of methacrylates. Due to the properties of methacrylate polymers, it has been proposed that they are capable of having efficient barrier properties due to their ability to cross link and form crystalline structures with low chain mobility. The change in intensities of the FTIR peaks of different functional groups indicates the cross-linking and crystallinity of the polymer films. The UV-Vis data indicates high transparency of the films. SEM images of the films show continuous and well cured surfaces with minimal deviations, pores and defects. The addition of cross-linking agents and nanoparticles increased polymerization and cross-linking of the methacrylate polymer chains, therefore increasing inter-chain density and long range order. The incorporation of these additives increased the crystallinity of the films and by decreasing the distances and number of voids between polymer chains along with having minimal sorption sites for gases to bond to, the ability of gases such as moisture and oxygen to penetrate through the films has decreased.

Antimicrobial activity of biopolymer-antibiotic thin films fabricated by advanced pulsed laser methods

NASA Astrophysics Data System (ADS)

Cristescu, R.; Popescu, C.; Dorcioman, G.; Miroiu, F. M.; Socol, G.; Mihailescu, I. N.; Gittard, S. D.; Miller, P. R.; Narayan, R. J.; Enculescu, M.; Chrisey, D. B.

2013-08-01

We report on thin film deposition by matrix assisted pulsed laser evaporation (MAPLE) of two polymer-drug composite thin film systems. A pulsed KrF* excimer laser source (λ = 248 nm, τ = 25 ns, ν = 10 Hz) was used to deposit composite thin films of poly(D,L-lactide) (PDLLA) containing several gentamicin concentrations. FTIR spectroscopy was used to demonstrate that MAPLE-transferred materials exhibited chemical structures similar to those of drop cast materials. Scanning electron microscopy data indicated that MAPLE may be used to fabricate thin films of good morphological quality. The activity of PDLLA-gentamicin composite thin films against Staphylococcus aureus bacteria was demonstrated using drop testing. The influence of drug concentration on microbial viability was also assessed. Our studies indicate that polymer-drug composite thin films prepared by MAPLE may be used to impart antimicrobial activity to implants, medical devices, and other contact surfaces.

Electro-synthesis of novel nanostructured PEDOT films and their application as catalyst support

PubMed Central

2011-01-01

Poly(3,4-ethylenedioxythiophene) (PEDOT) films doped with nitric and chlorine ions have been electrochemically deposited simply by a one-step electrochemical method in an aqueous media in the absence of any surfactant. The fabricated PEDOT films were characterized by scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy. The results indicate that the hierarchical structured PEDOT film doped with nitric ions displays a 'lunar craters' porous morphology consisting of PEDOT nano-sheets with a thickness of less than 2 nm. The effect of counter ions on the electro-polymerization, the electrochemistry, and the morphology of the polymer film was studied. Compared with PEDOT film doped with nitric acid, PEDOT film deposited in the presence of chlorine ions shows irregular morphology and less electrochemical activity. The specific nanostructure of the polymer was further studied as catalyst support for platinum nanoparticles to methanol electro-oxidation. PMID:21711871

Laser-induced atomic assembling of periodic layered nanostructures of silver nanoparticles in fluoro-polymer film matrix

NASA Astrophysics Data System (ADS)

Bagratashvili, V. N.; Rybaltovsky, A. O.; Minaev, N. V.; Timashev, P. S.; Firsov, V. V.; Yusupov, V. I.

2010-05-01

Fluorinated acrylic polymer (FAP) films have been impregnated with silver precursor (Ag(hfac)COD) by supercritical fluid technique and next irradiated with laser (λ = 532 nm). Laser-chemically reduced Ag atoms have been assembled into massifs of Ag nanoparticles (3 - 8 nm) in FAP/Ag(hfac)COD films matrix in the form of periodic layered nanostructures (horizontal to film surface) with unexpectedly short period (90 - 180 nm). The wavelet analysis of TEM images reveals the existence of even shorter-period structures in such films. Photolysis with non-coherent light or pyrolysis of FAP/Ag(hfac)COD film results in formation of Ag nanoparticles massifs but free of any periodic nanoparticle assemblies. Our interpretation of the observed effect of laser formation of short-period nano-sized Ag nanoparticle assemblies is based on self-enhanced interference process in the course of modification of optical properties of film.

Nanoscale porosity in polymer films: fabrication and therapeutic applications

PubMed Central

Bernards, Daniel A.; Desai, Tejal A.

2011-01-01

This review focuses on current developments in the field of nanostructured bulk polymers and their application in bioengineering and therapeutic sciences. In contrast to well-established nanoscale materials, such as nanoparticles and nanofibers, bulk nanostructured polymers combine nanoscale structure in a macroscopic construct, which enables unique application of these materials. Contemporary fabrication and processing techniques capable of producing nanoporous polymer films are reviewed. Focus is placed on techniques capable of sub-100 nm features since this range approaches the size scale of biological components, such as proteins and viruses. The attributes of these techniques are compared, with an emphasis on the characteristic advantages and limitations of each method. Finally, application of these materials to biofiltration, immunoisolation, and drug delivery are reviewed. PMID:22140398

Adsorbed Polymer Nanolayers on Solids: Mechanism, Structure and Applications

NASA Astrophysics Data System (ADS)

Sen, Mani Kuntal

In this thesis, by combining various advanced x-ray scattering, spectroscopic and other surface sensitive characterization techniques, I report the equilibrium polymer chain conformations, structures, dynamics and properties of polymeric materials at the solid-polymer melt interfaces. Following the introduction, in chapter 2, I highlight that the backbone chains (constituted of CH and CH2 groups) of the flattened polystyrene (PS) chains preferentially orient normal to the weakly interactive substrate surface via thermal annealing regardless of the initial chain conformations, while the orientation of the phenyl rings becomes randomized, thereby increasing the number of surface-segmental contacts (i.e., enthalpic gain) which is the driving force for the flattening process of the polymer chains even onto a weakly interactive solid. In chapter 3, I elucidate the flattened structures in block copolymer (BCP) thin films where both blocks lie flat on the substrate, forming a 2D randomly phase-separated structure irrespective of their microdomain structures and interfacial energetics. In chapter 4, I reveal the presence of an irreversibly adsorbed BCP layer which showed suppressed dynamics even at temperatures far above the individual glass transition temperatures of the blocks. Furthermore, this adsorbed BCP layer plays a crucial role in controlling the microdomain orientation in the entire film. In chapter 5, I report a radically new paradigm of designing a polymeric coating layer of a few nanometers thick ("polymer nanolayer") with anti-biofouling properties.

Fabrication of refractive index distributions in polymer using a photochemical reaction

NASA Astrophysics Data System (ADS)

Kada, Takeshi; Obara, Atsushi; Watanabe, Toshiyuki; Miyata, Seizo; Liang, Chuan Xin; Machida, Hideaki; Kiso, Koichi

2000-01-01

We demonstrate that a photochemical reaction can create various distributions of refractive index in polymer. When the polymer containing a photochemically active material is irradiated by UV light, the photochemical reaction which breaks the π-conjugated system in the material and decreases its linear polarizability can reduce refractive index of the polymer. We prepared a PMMA film added DMAPN ((4-N,N-dimethylaminophenyl)-N'-phenylnitrone) with a rate of 23 wt % by use of spin coating. Electronic structural change of DMAPN and refractive indices of the film before and after UV irradiation were evaluated by UV absorption spectra and m-line method, respectively. The UV irradiation decreased λmax at 380 nm in the absorption spectra, which is attributed to nitrone, and the refractive indices exponentially with irradiation time. The change of refractive indices reached 0.028. The refractive index profile upon depth of the film was investigated by measuring refractive indices of stacked DMAPN/PMMA films. When UV with a power of 10.7 mW/cm2 irradiated upon three stacked DMAPN/PMMA films for 35 s, variation of the refractive index change showed a quadratic profile. The refractive index profile with various irradiation time can be accounted with the combination of the chemical kinetics with the steady state approximation and Lambert-Beer's law. Thus, the photochemical reaction can be used to control the refractive index distribution in polymer.

High barrier multilayer packaging by the coextrusion method: The effect of nanocomposites and biodegradable polymers on flexible film properties

NASA Astrophysics Data System (ADS)

Thellen, Christopher T.

The objective of this research was to investigate the use of nanocomposite and multilayer co-extrusion technologies for the development of high gas barrier packaging that is more environmentally friendly than many current packaging system. Co-extruded bio-based and biodegradable polymers that could be composted in a municipal landfill were one direction that this research was aimed. Down-gauging of high performance barrier films using nanocomposite technology and co-extrusion was also investigated in order to reduce the amount of solid waste being generated by the packaging. Although the research is focused on military ration packaging, the technologies could easily be introduced into the commercial flexible packaging market. Multilayer packaging consisting of poly(m-xylylene adipamide) nanocomposite layers along with adhesive and tie layers was co-extruded using both laboratory and pilot-scale film extrusion equipment. Co-extrusion of biodegradable polyhydroxyalkanoates (PHA) along with polyvinyl alcohol (PVOH) and tie layers was also accomplished using similar co-extrusion technology. All multilayer films were characterized for gas barrier, mechanical, and thermal properties. The biodegradability of the PVOH and PHA materials in a marine environment was also investigated. The research has shown that co-extrusion of these materials is possible at a research and pilot level. The use of nanocomposite poly(m-xylylene adipamide) was effective in down-gauging the un-filled barrier film to thinner structures. Bio-based PHA/PVOH films required the use of a malefic anhydride grafted PHA tie layer to improve layer to layer adhesion in the structure to avoid delamination. The PHA polymer demonstrated a high rate of biodegradability/mineralization in the marine environment while the rate of biodegradation of the PVOH polymer was slower.

The Role of Nanofillers in Polymer Nanocomposites

NASA Astrophysics Data System (ADS)

Xu, Di

Polymer nanocomposites have been widely used in many fields. By introducing nanoparticles as fillers, researchers are able to get reinforced materials and new materials with novel properties, such as stronger mechanics, enhanced optical properties and improved conductivity. Though experimental techniques have rapidly advanced to enable better control of materials at atomic level, there is still a lack of a fundamental understanding of the dynamics and structure-properties relations in polymer nanocomposites. In this thesis, we use computer simulations to study the molecular structure and connections between microstate to macro properties of a variety of nanocomposites. Our goal is to understand the role of nanofillers in complex nanocomposite systems and to assist nanocomposite design. Nanoplatelet fillers, such as clays, have shown superior effects on the properties of polymer gels. We used molecular dynamic simulation to study nanoplatelet-filled composite gel system, in which short-range attraction exists between the polymer and nanoplatelet fillers. We show that the polymers and nanoplatelet fillers formed organic-inorganic networks with nanoplatelets acting as crosslink junctions, and the network eventually percolates the system as fillers reached a critical concentration. Stress auto-correlation and step-strain test were applied to investigate the mechanical properties; the results show the simulated composites changed from fluid-like to solid-like. The mechanical changes were consistent with the percolation transition, and gelation mechanism was therefore believed to be similar to those pure polymer physical gels. It was observed platelets aggregated into a local intercalation structure, which significantly differs from typical spherical fillers. This unique intercalation structure was examined by radial distribution function and ordering parameters. We discussed how intercalation would affect the properties of the platelet composites by comparing them with spherical fillers. Nanofillers have been widely used in polymer blends to improve the interfacial compatibility of otherwise immiscible polymers. In the second system, we investigated the interfacial behavior of binary polymer blends with different types of fillers. The interfacial tension and shear resistance were studied as a function of filler-polymer interaction, filler concentration and species of fillers. We found filler-polymer interaction is the key factor to improve the interfacial compatibility. The results show that nanofillers reduce both interfacial tension and interfacial slip at strong filler-polymer interaction. The effects of nanofillers however differ significantly from each other by their shapes. We analyzed the structure of nanofillers at the interface and their effects on the interfacial behaviors. The self-assembly of polymers into a columnar structure, while subject to a thin film environment, provides an economic route to fabricate polymer solar cell (PSC) with high conversion efficiency. In our work, we showed that two immiscible polymer segregates into to a percolating columnar structure when confined to a thin film. By adding nanofillers, with specific functionality, we can template the segregation of nanofillers to the polymer-polymer interface. We prove this process is surface tension driven and is a result that is particular for thin film geometries, where the thickness is under critical value. The results provide a theoretical basis for the column structure forming in a self-assembled PSC system, and can help to select polymer candidates that optimize PSC efficiency. These studies serve as theoretical guideline for engineering novel nanocomposites, and could lead to the design of materials with new and improved properties.

Comparison of molecular orientation and phase transition behaviors in the two kinds of ordered ultrathin films of reversed duckweed polymer ES-3 studied by infrared grazing reflection-absorption spectroscopy

NASA Astrophysics Data System (ADS)

Wang, Qiang; Xu, Weiqing; Zhao, Bing

2003-03-01

A multilayer LB film and a casting film of reversed duckweed polymer ES-3 on Au-evaporated glass slides were investigated by Fourier Transform infrared grazing reflection-absorption spectroscopy. It is found that the two kinds of ordered ultrathin films have different orientation of alkyl chains, nearly perpendicular to the substrate surface for the LB film while rather tilted for the casting film. The studies on their thermal transition behaviors indicate that both of the films have three phase transition processes, respectively, occurring near 65, 105 and 140 °C for the former while near 80, 105 and 140 °C for the latter, but show different transition behavior in the each corresponding transition process. It is referred that at room temperature there are island-like domain structures formed in the LB film, but no ones in the casting film; however, the latter can form the domain structures between the first two transition points due to the desorption of solvents. The formation of domain structure seems to play two important roles, one of which is to make alkyl chains more perpendicular to the substrate surface, and the other to make alkyl chains more packed closely. Thermal cyclic experiments reveal that neither of the films could return to its original state after thermal cyclic treatment up to the temperature, which is above the third transition point, although its alkyl chain becomes highly ordered again.

New Synthesis Of Poly(1,3,4-Oxadiazoles)

NASA Technical Reports Server (NTRS)

Connell, John W.; Hergenrother, Paul M.; Wolf, Peter

1992-01-01

Synthesis via aromatic nucleophilic displacement yields new high-molecular-weight polymers. Polymers exhibited good mechanical and thermal properties. Synthetic route provided high-molecular-weight POX of new chemical structure, potentially more economical. Availability of large variety of activated aromatic dihalides, facilitates variation of chemical structures. Exhibit properties making them useful as films. Also useful in coatings, adhesives, moldings, and composites.

Polymethacrylate Polymers with Appended Aluminum(III)-Tetraphenylporphyrins: Synthesis, Characterization and Evaluation as Macromolecular Ionophores for Electrochemical and Optical Fluoride Sensors

PubMed Central

Wang, Lin; Meyerhoff, Mark E.

2008-01-01

The synthesis and characterization of a novel polymethacylate polymer with covalently linked Al(III)-tetraphenylporphyrin (Al(III)-TPP) groups is reported. The new polymer is examined as a potential macromolecular ionophore for the preparation of polymeric membrane-based potentiometric and optical fluoride selective sensors. To prepare the polymer, an Al(III) porphyrin monomer modified with a methacrylate functionality is synthesized, allowing insertion into a polymethacrylate block copolymer (methyl methacrylate and decyl methacrylate) backbone. The resulting polymer can then be incorporated, along with appropriate additives, into conventional plasticized poly(vinyl chloride) films for testing electrochemical and optical fluoride response properties. The covalent attachment of the Al(III)-TPP ionophore to the copolymer matrix provides potentiometric sensors that exhibit significant selectivity for fluoride ion with extended lifetimes (compared to ion-selective membrane electrodes formulated with conventional free Al(III)-TPP structure). However, quite surprisingly, the attachment of the ionophore to the polymer does not eliminate the interaction of Al(III)-TPP structures to form dimeric species within the membrane phase in the presence of fluoride ion. Such interactions are confirmed by UV/visible spectroscopy of the blended polymeric films. Use of the new polymer-Al(III)-TPP conjugates to prepare optical fluoride sensors by co-incorporating a lipophilic pH indicator (4’,5’-dibromofluorescein octadecyl ester; ETH7075) is also examined and the resulting optical sensing films are shown to exhibit excellent selectivity for fluoride, with the potential for prolonged operational lifetime. PMID:18298973

Can deformation of a polymer film with a rigid coating model geophysical processes?

NASA Astrophysics Data System (ADS)

Volynskii, A. L.; Bazhenov, S. L.

2007-12-01

The structural and mechanical behavior of polymer films with a thin rigid coating is analyzed. The behavior of such systems under applied stress is accompanied by the formation of a regular wavy surface relief and by regular fragmentation of the coating. The above phenomena are shown to be universal. Both phenomena (stress-induced development of a regular wavy surface relief and regular fragmentation of the coating) are provided by the specific features of mechanical stress transfer from a compliant soft support to a rigid thin coating. The above phenomena are associated with a specific structure of the system, which is referred to as “a rigid coating on a soft substratum” system (RCSS). Surface microrelief in RCSS systems is similar to the ocean floor relief in the vicinity of mid-oceanic ridges. Thus, the complex system composed of a young oceanic crust and upper Earth's mantle may be considered as typically “a solid coating on a soft substratum” system. Specific features of the ocean floor relief are analyzed in terms of the approach advanced for the description of the structural mechanical behavior of polymer films with a rigid coating. This analysis allowed to estimate the strength of an ocean floor.

Ultrathin Polymer Films, Patterned Arrays, and Microwells

NASA Astrophysics Data System (ADS)

Yan, Mingdi

2002-05-01

The ability to control and tailor the surface and interface properties of materials is important in microelectronics, cell growth control, and lab-on-a-chip devices. Modification of material surfaces with ultrathin polymer films is attractive due to the availability of a variety of polymers either commercially or by synthesis. We have developed two approaches to the attachment of ultrathin polymer films on solid substrates. In the first method, a silane-functionalized perfluorophenyl azide (PFPA-silane) was synthesized and used to covalently immobilize polymer thin films on silicon wafers. Silanization of the wafer surface with the PFPA-silane introduced a monolayer of azido groups which in turn covalently attached the polymer film by way of photochemically initiated insertion reactions. The thickness of the film could be adjusted by the type and the molecular weight of the polymer. The method is versatile due to the general C-H and/or N-H insertion reactions of crosslinker; and therefore, no specific reactive functional groups on the polymers are required. Using this method, a new type of microwell array was fabricated from covalently immobilized polymer thin films on flat substrates. The arrays were characterized with AFM, XPS, and TOF-SIMS. The second method describes the attachment of polymer thin films on solid substrates via UV irradiation. The procedure consisted of spin-coating a polymer film and irradiating the film with UV light. Following solvent extraction, a thin film remained. The thickness of the film, from a few to over a hundred nanometers, was controlled by varying solution concentration and the molecular weight of the polymer.

Healing of polymer interfaces: Interfacial dynamics, entanglements, and strength

DOE PAGES

Ge, Ting; Robbins, Mark O.; Perahia, Dvora; ...

2014-07-25

Self-healing of polymer films often takes place as the molecules diffuse across a damaged region, above their melting temperature. Using molecular dynamics simulations we probe the healing of polymer films and compare the results with those obtained for thermal welding of homopolymer slabs. These two processes differ from each other in their interfacial structure since damage leads to increased polydispersity and more short chains. A polymer sample was cut into two separate films that were then held together in the melt state. The recovery of the damaged film was followed as time elapsed and polymer molecules diffused across the interface.more » The mass uptake and formation of entanglements, as obtained from primitive path analysis, are extracted and correlated with the interfacial strength obtained from shear simulations. We find that the diffusion across the interface is signifcantly faster in the damaged film compared to welding because of the presence of short chains. Though interfacial entanglements increase more rapidly for the damaged films, a large fraction of these entanglements are near chain ends. As a result, the interfacial strength of the healing film increases more slowly than for welding. For both healing and welding, the interfacial strength saturates as the bulk entanglement density is recovered across the interface. However, the saturation strength of the damaged film is below the bulk strength for the polymer sample. At saturation, cut chains remain near the healing interface. They are less entangled and as a result they mechanically weaken the interface. When the strength of the interface saturates, the number of interfacial entanglements scales with the corresponding bulk entanglement density. Chain stiffness increases the density of entanglements, which increases the strength of the interface. Our results show that a few entanglements across the interface are sufficient to resist interfacial chain pullout and enhance the mechanical strength.« less

Confinement induced densification in supported unentangled polymer films

NASA Astrophysics Data System (ADS)

Pradipkanti, L.; Satapathy, Dillip K.

2017-05-01

We report the densification phenomena inunentangled and low-molecular weight polystyrene (PS) thin films supported on solid substrates having thickness from 25 nm to 230 nm. The mass density of the thin polymer films were extracted from X-ray reflectivity profiles and also from the refractive index by using Clausius and Mossotti equation. The mass densityof polymeris found to increasesignificantly with decrease in film thickness below ten times the radius of gyration of the polymer. The net increase in mass density of the polymer film upon reduction in thickness is discussed in terms of three-layer model and the presence of unentangled polymer chains. We conjecture that, the densification of ultra-thin polymer films can strongly alter the polymer conformations at film/substrate interface.

Gibbs Ensemble Simulations of the Solvent Swelling of Polymer Films

NASA Astrophysics Data System (ADS)

Gartner, Thomas; Epps, Thomas, III; Jayaraman, Arthi

Solvent vapor annealing (SVA) is a useful technique to tune the morphology of block polymer, polymer blend, and polymer nanocomposite films. Despite SVA's utility, standardized SVA protocols have not been established, partly due to a lack of fundamental knowledge regarding the interplay between the polymer(s), solvent, substrate, and free-surface during solvent annealing and evaporation. An understanding of how to tune polymer film properties in a controllable manner through SVA processes is needed. Herein, the thermodynamic implications of the presence of solvent in the swollen polymer film is explored through two alternative Gibbs ensemble simulation methods that we have developed and extended: Gibbs ensemble molecular dynamics (GEMD) and hybrid Monte Carlo (MC)/molecular dynamics (MD). In this poster, we will describe these simulation methods and demonstrate their application to polystyrene films swollen by toluene and n-hexane. Polymer film swelling experiments, Gibbs ensemble molecular simulations, and polymer reference interaction site model (PRISM) theory are combined to calculate an effective Flory-Huggins χ (χeff) for polymer-solvent mixtures. The effects of solvent chemistry, solvent content, polymer molecular weight, and polymer architecture on χeff are examined, providing a platform to control and understand the thermodynamics of polymer film swelling.

Electric Charge Accumulation in Polar and Non-Polar Polymers under Electron Beam Irradiation

NASA Astrophysics Data System (ADS)

Nagasawa, Kenichiro; Honjoh, Masato; Takada, Tatsuo; Miyake, Hiroaki; Tanaka, Yasuhiro

The electric charge accumulation under an electron beam irradiation (40 keV and 60 keV) was measured by using the pressure wave propagation (PWP) method in the dielectric insulation materials, such as polar polymeric films (polycarbonate (PC), polyethylene-naphthalate (PEN), polyimide (PI), and polyethylene-terephthalate (PET)) and non-polar polymeric films (polystyrene (PS), polypropylene (PP), polyethylene (PE) and polytetrafluoroethylene (PTFE)). The PE and PTFE (non-polar polymers) showed the properties of large amount of electric charge accumulation over 50 C/m3 and long saturation time over 80 minutes. The PP and PS (non-polar polymer) showed the properties of middle amount of charge accumulation about 20 C/m3 and middle saturation time about 1 to 20 minutes. The PC, PEN, PI and PET (polar polymers) showed the properties of small amount of charge accumulation about 5 to 20 C/m3 and within short saturation time about 1.0 minutes. This paper summarizes the relationship between the properties of charge accumulation and chemical structural formula, and compares between the electro static potential distribution with negative charged polymer and its chemical structural formula.

Controlled fragmentation of multimaterial fibres and films via polymer cold-drawing.

PubMed

Shabahang, Soroush; Tao, Guangming; Kaufman, Joshua J; Qiao, Yangyang; Wei, Lei; Bouchenot, Thomas; Gordon, Ali P; Fink, Yoel; Bai, Yuanli; Hoy, Robert S; Abouraddy, Ayman F

2016-06-23

Polymer cold-drawing is a process in which tensile stress reduces the diameter of a drawn fibre (or thickness of a drawn film) and orients the polymeric chains. Cold-drawing has long been used in industrial applications, including the production of flexible fibres with high tensile strength such as polyester and nylon. However, cold-drawing of a composite structure has been less studied. Here we show that in a multimaterial fibre composed of a brittle core embedded in a ductile polymer cladding, cold-drawing results in a surprising phenomenon: controllable and sequential fragmentation of the core to produce uniformly sized rods along metres of fibre, rather than the expected random or chaotic fragmentation. These embedded structures arise from mechanical-geometric instabilities associated with 'neck' propagation. Embedded, structured multimaterial threads with complex transverse geometry are thus fragmented into a periodic train of rods held stationary in the polymer cladding. These rods can then be easily extracted via selective dissolution of the cladding, or can self-heal by thermal restoration to re-form the brittle thread. Our method is also applicable to composites with flat rather than cylindrical geometries, in which case cold-drawing leads to the break-up of an embedded or coated brittle film into narrow parallel strips that are aligned normally to the drawing axis. A range of materials was explored to establish the universality of this effect, including silicon, germanium, gold, glasses, silk, polystyrene, biodegradable polymers and ice. We observe, and verify through nonlinear finite-element simulations, a linear relationship between the smallest transverse scale and the longitudinal break-up period. These results may lead to the development of dynamical and thermoreversible camouflaging via a nanoscale Venetian-blind effect, and the fabrication of large-area structured surfaces that facilitate high-sensitivity bio-detection.

Controlled fragmentation of multimaterial fibres and films via polymer cold-drawing

NASA Astrophysics Data System (ADS)

Shabahang, Soroush; Tao, Guangming; Kaufman, Joshua J.; Qiao, Yangyang; Wei, Lei; Bouchenot, Thomas; Gordon, Ali P.; Fink, Yoel; Bai, Yuanli; Hoy, Robert S.; Abouraddy, Ayman F.

2016-06-01

Polymer cold-drawing is a process in which tensile stress reduces the diameter of a drawn fibre (or thickness of a drawn film) and orients the polymeric chains. Cold-drawing has long been used in industrial applications, including the production of flexible fibres with high tensile strength such as polyester and nylon. However, cold-drawing of a composite structure has been less studied. Here we show that in a multimaterial fibre composed of a brittle core embedded in a ductile polymer cladding, cold-drawing results in a surprising phenomenon: controllable and sequential fragmentation of the core to produce uniformly sized rods along metres of fibre, rather than the expected random or chaotic fragmentation. These embedded structures arise from mechanical-geometric instabilities associated with ‘neck’ propagation. Embedded, structured multimaterial threads with complex transverse geometry are thus fragmented into a periodic train of rods held stationary in the polymer cladding. These rods can then be easily extracted via selective dissolution of the cladding, or can self-heal by thermal restoration to re-form the brittle thread. Our method is also applicable to composites with flat rather than cylindrical geometries, in which case cold-drawing leads to the break-up of an embedded or coated brittle film into narrow parallel strips that are aligned normally to the drawing axis. A range of materials was explored to establish the universality of this effect, including silicon, germanium, gold, glasses, silk, polystyrene, biodegradable polymers and ice. We observe, and verify through nonlinear finite-element simulations, a linear relationship between the smallest transverse scale and the longitudinal break-up period. These results may lead to the development of dynamical and thermoreversible camouflaging via a nanoscale Venetian-blind effect, and the fabrication of large-area structured surfaces that facilitate high-sensitivity bio-detection.

Vacuum-integrated electrospray deposition for highly reliable polymer thin film.

PubMed

Park, Soohyung; Lee, Younjoo; Yi, Yeonjin

2012-10-01

Vacuum electrospray deposition (ESD) equipment was designed to prepare polymer thin films. The polymer solution can be injected directly into vacuum system through multi-stage pumping line, so that the solvent residues and ambient contaminants are highly reduced. To test the performance of ESD system, we fabricated organic photovoltaic cells (OPVCs) by injecting polymer solution directly onto the substrate inside a high vacuum chamber. The OPVC fabricated has the structure of Al∕P3HT:PCBM∕PEDOT:PSS∕ITO and was optimized by varying the speed of solution injection and concentration of the solution. The power conversion efficiency (PCE) of the optimized OPVC is 3.14% under AM 1.5G irradiation without any buffer layer at the cathode side. To test the advantages of the vacuum ESD, we exposed the device to atmosphere between the deposition steps of the active layer and cathode. This showed that the PCE of the vacuum processed device is 24% higher than that of the air exposed device and confirms the advantages of the vacuum prepared polymer film for high performance devices.

Diffusion, swelling, cross linkage study and mechanical properties of ZnO doped PVA/NaAlg blend polymer nanocomposite

NASA Astrophysics Data System (ADS)

Guruswamy, B.; Ravindrachary, V.; Shruthi, C.; Hegde, Shreedatta; Sagar, Rohan N.

2018-04-01

ZnO nano particles were synthesized using a chemical precipitation method. Pure and ZnO nano particle doped PVA-NaAlg blend composite films were prepared using solution casing method. Structural information of these composites was studied using FTIR. Diffusion kinetics of these polymer blend composite were studied using Flory-Huggins theory. Using these diffusion studies, cross-linking density and swelling properties of the films were analyzed. Mechanical properties of these composite are also studied.

Understanding Coatings that Protect Plasmonic Structures for Materials Characterization and Detection and Identification of Chemical, Biological and Explosive Agents

DTIC Science & Technology

2013-04-11

in the top monomolecular layer of a blend film using mass spectrometry. This technique we call Surface Layer-Matrix Assisted Laser Desorption...C., Foster, M.D. “Probing Surface Concentration of Cyclic/linear Blend Films Using Surface MALDI-TOF Mass Spectrometry,” Dept. of Polymer Science...Isotopically Labeled Species in a Polymer Blend Using Tip Enhanced Raman Spectroscopy, ACS Macro Letters (11 2012) TOTAL: 2 Books Number of Manuscripts

Investigating the effects of polymer molecular weight and non-solvent content on the phase separation, surface morphology and hydrophobicity of polyvinyl chloride films

NASA Astrophysics Data System (ADS)

Khoryani, Zahra; Seyfi, Javad; Nekoei, Mehdi

2018-01-01

The main aim of this research is to study the effects of polymer molecular weight as well as non-solvent concentration on the phase separation, surface morphology and wettability of polyvinyl chloride (PVC) films. Gel permeation chromatography (GPC) results showed that the Mn of the used PVC grades is 6 × 104, 8.7 × 104 and 1.26 × 105 g/mol. It was found that a proper combination of polymer molecular weight and non-solvent content could result in superhydrophobic and self-cleaning behaviors. Scanning electron microscopy (SEM) results demonstrated that addition of ethanol causes the polymer chains to be severely aggregated at the films' surface forming strand-like structures decorated by nano-scale polymer spheres. The polymer molecular weight was found to affect the degree of porosity which is highly influential on the hydrophobicity of the films. The mechanism of phase separation process was also discussed and it was found that the instantaneous demixing is the dominant mechanism once higher contents of non-solvent were used. However, a delayed demixing mechanism was detected when the lower molecular weight PVC has been used which resulted in a pore-less and dense skin layer. Differential scanning calorimetry was also utilized to study the crystallization and glass transition behavior of samples.

High proton conductivity in the molecular interlayer of a polymer nanosheet multilayer film.

PubMed

Sato, Takuma; Hayasaka, Yuta; Mitsuishi, Masaya; Miyashita, Tokuji; Nagano, Shusaku; Matsui, Jun

2015-05-12

High proton conductivity was achieved in a polymer multilayer film with a well-defined two-dimensional lamella structure. The multilayer film was prepared by deposition of poly(N-dodecylacryamide-co-acrylic acid) (p(DDA/AA)) monolayers onto a solid substrate using the Langmuir-Blodgett technique. Grazing-angle incidence X-ray diffraction measurement of a 30-layer film of p(DDA/AA) showed strong diffraction peaks in the out-of-plane direction at 2θ = 2.26° and 4.50°, revealing that the multilayer film had a highly uniform layered structure with a monolayer thickness of 2.0 nm. The proton conductivity of the p(DDA/AA) multilayer film parallel to the layer plane direction was 0.051 S/cm at 60 °C and 98% relative humidity with a low activation energy of 0.35 eV, which is comparable to perfluorosulfonic acid membranes. The high conductivity and low activation energy resulted from the formation of uniform two-dimensional proton-conductive nanochannels in the hydrophilic regions of the multilayer film. The proton conductivity of the multilayer film perpendicular to the layer plane was determined to be 2.1 × 10(-13) S/cm. Therefore, the multilayer film showed large anisotropic conductivity with an anisotropic ratio of 2.4 × 10(11).

Structural perturbations of azurin deposited on solid matrices as revealed by trp phosphorescence.

PubMed Central

Gabellieri, E; Strambini, G B

2001-01-01

The phosphorescence emission of Cd-azurin from Pseudomonas aeruginosa was used as a probe of possible perturbations in the dynamical structure of the protein core that may be induced by protein-sorbent and protein-protein interactions occurring when the macromolecule is deposited into amorphous, thin solid films. Relative to the protein in aqueous solution, the spectrum is unrelaxed and the phosphorescence decay becomes highly heterogeneous, the average lifetime increasing sharply with film thickness and upon its dehydration. According to the lifetime parameter, adsorption of the protein to the substrate is found to produce a multiplicity of partially unfolded structures, an influence that propagates for several protein layers from the surface. Among the substrates used for film deposition, hydrophilic silica, dextran, DEAE-dextran, dextran sulfate, and hydrophobic octodecylamine, the perturbation is smallest with dextran sulfate and largest with octodecylamine. The destabilizing effect of protein-protein interactions, as monitored on 50-layer-thick films, is most evident at a relative humidity of 75%. Stabilizing agents were incorporated to attenuate the deleterious effects of protein aggregation. Among them, the most effective in preserving a more native-like structure are the disaccharides sucrose and trehalose in dry films and the polymer dextran in wet films. Interestingly, the polymer was found to achieve maximum efficacy at sensibly lower additive/protein ratios than the sugars. PMID:11325742

Mapping the structural order of laser-induced periodic surface structures in thin polymer films by microfocus beam grazing incidence small-angle X-ray scattering.

PubMed

Martín-Fabiani, Ignacio; Rebollar, Esther; García-Gutiérrez, Mari Cruz; Rueda, Daniel R; Castillejo, Marta; Ezquerra, Tiberio A

2015-02-11

In this work we present an accurate mapping of the structural order of laser-induced periodic surface structures (LIPSS) in spin-coated thin polymer films, via a microfocus beam grazing incidence small-angle X-ray scattering (μGISAXS) scan, GISAXS modeling, and atomic force microscopy imaging all along the scanned area. This combined study has allowed the evaluation of the effects on LIPSS formation due to nonhomogeneous spatial distribution of the laser pulse energy, mapping with micrometric resolution the evolution of the period and degree of structural order of LIPSS across the laser beam diameter in a direction perpendicular to the polarization vector. The experiments presented go one step further toward controlling nanostructure formation in LIPSS through a deep understanding of the parameters that influence this process.

High-intensity pulse light sintering of silver nanowire transparent films on polymer substrates: the effect of the thermal properties of substrates on the performance of silver films.

PubMed

Jiu, Jinting; Sugahara, Tohru; Nogi, Masaya; Araki, Teppei; Suganuma, Katsuaki; Uchida, Hiroshi; Shinozaki, Kenji

2013-12-07

Silver nanowire (AgNW) films with a random mesh structure have attracted considerable attention as high-performance flexible transparent electrodes that can replace the expensive and brittle ITO-sputtered films widely used in displays, touch screens, and solar cells. Methods such as heating, pressure treatment, and light treatment are usually used to obtain an optically transparent and electrically conductive film comparable to those of commercial ITO. However, the adhesion between the AgNW film and the substrate is so weak that other overcoatings or extra treatments are necessary. Here, a high-intensity pulsed light (HIPL) sintering technique was developed to rapidly and simply sinter the AgNW film and thus achieve strong adhesion and even high conductivity on these flexible polymer substrates which will be widely applied to the printing of electronic devices. The conductivity of the AgNW film closely depended on the thermal performance of substrates, and the adhesion was determined by the soft state of the substrate surface originating from the glass transition or melting of substrates with light intensity. The rapid sintering technique can be popularized to fabricate new devices on these polymer substrates by considering the thermal properties of the substrate to improve the performance of devices.

Preparation and analysis of multilayer composites based on polyelectrolyte complexes

NASA Astrophysics Data System (ADS)

Petrova, V. A.; Orekhov, A. S.; Chernyakov, D. D.; Baklagina, Yu. G.; Romanov, D. P.; Kononova, S. V.; Volod'ko, A. V.; Ermak, I. M.; Klechkovskaya, V. V.; Skorik, Yu. A.

2016-11-01

A method for preparing multilayer film composites based on chitosan has been developed by the example of polymer pairs: chitosan-hyaluronic acid, chitosan-alginic acid, and chitosan-carrageenan. The structure of the composite films is characterized by X-ray diffractometry and scanning electron microscopy. It is shown that the deposition of a solution of hyaluronic acid, alginic acid, or carrageenan on a chitosan gel film leads to the formation of a polyelectrolyte complex layer at the interface, which is accompanied by the ordering of chitosan chains in the surface region; the microstructure of this layer depends on the nature of contacting polymer pairs.

Second harmonic generation and photochromic grating in polyurethane films containing diazo isoxazole chromophore

NASA Astrophysics Data System (ADS)

Marański, Krzysztof; Kucharski, Stanisław; Ortyl, Ewelina; Nunzi, Jean-Michel; Ahmadi-Kandjani, Sohrab; Dabos-Seignon, Sylvie; Chan, Siu-Wai; Barille, Regis

2008-08-01

The chromophoric intermediate: 2,2'-({4-[( E)-(5-methylisoxazol-3-yl)diazenyl]phenyl}-imino)diethanol was used in polyaddition reaction with di-isocyanate to obtain a new polyurethane polymeric material showing nonlinear optical and photochromic properties. The maximum absorption band of the polymer film was at 418 nm. The illumination of the film with crossed beams of the 488 nm Ar + laser yielded surface relief grating of regular structure. Measurement of the frequency doubling signal with 1064 nm laser indicated the polymer as interesting material for photooptical applications. The measured nonlinear optical coefficient, d33, reached 90.2 pm/V.

Precise Side-Chain Engineering of Thienylenevinylene-Benzotriazole-Based Conjugated Polymers with Coplanar Backbone for Organic Field Effect Transistors and CMOS-like Inverters.

PubMed

Lee, Min-Hye; Kim, Juhwan; Kang, Minji; Kim, Jihong; Kang, Boseok; Hwang, Hansu; Cho, Kilwon; Kim, Dong-Yu

2017-01-25

Two donor-acceptor (D-A) alternating conjugated polymers based on thienylenevinylene-benzotriazole (TV-BTz), PTV6B with a linear side chain and PTVEhB with a branched side chain, were synthesized and characterized for organic field effect transistors (OFETs) and complementary metal-oxide-semiconductor (CMOS)-like inverters. According to density functional theory (DFT), polymers based on TV-BTz exhibit a coplanar and rigid structure with no significant twists, which could cause to an increase in charge-carrier mobility in OFETs. Alternating alkyl side chains of the polymers impacted neither the band gap nor the energy level. However, it significantly affected the morphology and crystallinity when the polymer films were thermally annealed. To investigate the effect of thermal annealing on the morphology and crystallinity, we characterized the polymer films using atomic force microscopy (AFM) and 2D-grazing incidence X-ray diffraction (2D-GIWAXD). Fibrillary morphologies with larger domains and increased crystallinity were observed in the polymer films after thermal annealing. These polymers exhibited improved charge-carrier mobilities in annealed films at 200 °C and demonstrated optimal OFET device performance with p-type transport characteristics with charge-carrier mobilities of 1.51 cm 2 /(V s) (PTV6B) and 2.58 cm 2 /(V s) (PTVEhB). Furthermore, CMOS-like inorganic (ZnO)-organic (PTVEhB) hybrid bilayer inverter showed that the inverting voltage (V inv ) was positioned near the ideal switching point at half (1/2) of supplied voltage (V DD ) due to fairly balanced p- and n-channels.

Application of α-amylase as a novel biodemulsifier for destabilizing amphiphilic polymer-flooding produced liquid treatment.

PubMed

Jiang, Jiatong; Wu, Hairong; Lu, Yao; Ma, Tao; Li, Zhe; Xu, Derong; Kang, Wanli; Bai, Baojun

2018-07-01

The performance and de-emulsification mechanism of α-amylase, a novel environmental friendly biodemulsifier in petroleum industry, was investigated at room temperature. The effects of α-amylase on the viscosity of amphiphilic polymer solution and de-emulsification rate were studied by changing the concentration of α-amylase, temperature and salinity. Polymer molecular weight, Zeta potential, interfacial film strength and interfacial tension were measured to investigate the de-emulsification mechanism of α-amylase. The results show that α-amylase is an efficient biodemulsifier to increase the de-emulsification rate of amphiphilic polymer emulsions. Hydrolysis of α-amylase to amphiphilic polymers destroys the structure of the amphiphilic polymer, thereby reduces the viscosity and the interfacial film strength of the system. Once de-emulsification is completed, the lower layer, i.e. the emulsified layer, will be clear. Thus, α-amylase can be applied as an effective de-emulsifier for amphiphilic polymer-stabilized O/W emulsion. Copyright © 2018 Elsevier Ltd. All rights reserved.

Laser-induced porous graphene films from commercial polymers

NASA Astrophysics Data System (ADS)

Lin, Jian; Peng, Zhiwei; Liu, Yuanyue; Ruiz-Zepeda, Francisco; Ye, Ruquan; Samuel, Errol L. G.; Yacaman, Miguel Jose; Yakobson, Boris I.; Tour, James M.

2014-12-01

The cost effective synthesis and patterning of carbon nanomaterials is a challenge in electronic and energy storage devices. Here we report a one-step, scalable approach for producing and patterning porous graphene films with three-dimensional networks from commercial polymer films using a CO2 infrared laser. The sp3-carbon atoms are photothermally converted to sp2-carbon atoms by pulsed laser irradiation. The resulting laser-induced graphene (LIG) exhibits high electrical conductivity. The LIG can be readily patterned to interdigitated electrodes for in-plane microsupercapacitors with specific capacitances of >4 mF cm-2 and power densities of ~9 mW cm-2. Theoretical calculations partially suggest that enhanced capacitance may result from LIG’s unusual ultra-polycrystalline lattice of pentagon-heptagon structures. Combined with the advantage of one-step processing of LIG in air from commercial polymer sheets, which would allow the employment of a roll-to-roll manufacturing process, this technique provides a rapid route to polymer-written electronic and energy storage devices.

Laser-induced porous graphene films from commercial polymers

PubMed Central

Lin, Jian; Peng, Zhiwei; Liu, Yuanyue; Ruiz-Zepeda, Francisco; Ye, Ruquan; Samuel, Errol L. G.; Yacaman, Miguel Jose; Yakobson, Boris I.; Tour, James M.

2014-01-01

Synthesis and patterning of carbon nanomaterials cost effectively is a challenge in electronic and energy storage devices. Here report a one-step, scalable approach for producing and patterning porous graphene films with 3-dimensional networks from commercial polymer films using a CO2 infrared laser. The sp3-carbon atoms are photothermally converted to sp2-carbon atoms by pulsed laser irradiation. The resulting laser-induced graphene (LIG) exhibits high electrical conductivity. The LIG can be readily patterned to interdigitated electrodes for in-plane microsupercapacitors with specific capacitances of >4 mF·cm−2 and power densities of ~9 mW·cm−2. Theoretical calculations partially suggest that enhanced capacitance may result from LIG’s unusual ultra-polycrystalline lattice of pentagon-heptagon structures. Combined with the advantage of one-step processing of LIG in air from commercial polymer sheets, which would allow the employment of a roll-to-roll manufacturing process, this technique provides a rapid route to polymer-written electronic and energy storage devices. PMID:25493446

Small-angle light scattering symmetry breaking in polymer-dispersed liquid crystal films with inhomogeneous electrically controlled interface anchoring

DOE Office of Scientific and Technical Information (OSTI.GOV)

Loiko, V. A., E-mail: loiko@ifanbel.bas-net.by; Konkolovich, A. V.; Zyryanov, V. Ya.

2017-03-15

We have described the method of analyzing and reporting on the results of calculation of the small-angle structure of radiation scattered by a polymer-dispersed liquid crystal film with electrically controlled interfacial anchoring. The method is based on the interference approximation of the wave scattering theory and the hard disk model. Scattering from an individual liquid crystal droplet has been described using the anomalous diffraction approximation extended to the case of droplets with uniform and nonuniform interface anchoring at the droplet–polymer boundary. The director field structure in an individual droplet is determined from the solution of the problem of minimizing themore » volume density of the free energy. The electrooptical effect of symmetry breaking in the angular distribution of scattered radiation has been analyzed. This effect means that the intensities of radiation scattered within angles +θ{sub s} and–θ{sub s} relative to the direction of illumination in the scattering plane can be different. The effect is of the interference origin and is associated with asymmetry of the phase shift of the wavefront of an incident wave from individual parts of the droplet, which appears due to asymmetry of the director field structure in the droplet, caused by nonuniform anchoring of liquid crystal molecules with the polymer on its surface. This effect is analyzed in the case of normal illumination of the film depending on the interfacial anchoring at the liquid crystal–polymer interface, the orientation of the optical axes of droplets, their concentration, sizes, anisometry, and polydispersity.« less

Towards developing an efficient sensitive element for trinitrotoluene detection: TiO2 thin films functionalized with molecularly imprinted copolymer films

NASA Astrophysics Data System (ADS)

Lazau, Carmen; Iordache, Tanta-Verona; Florea, Ana-Mihaela; Orha, Corina; Bandas, Cornelia; Radu, Anita-Laura; Sarbu, Andrei; Rotariu, Traian

2016-10-01

In this study, TiO2 films were successfully grown in-situ onto a FTO substrate by a hydrothermal method, using TiCl4 as Ti precursor, and further on functionalized with a 2,4,6-trinitrotoluene-molecularly imprinted polymer (TNT-MIP) film as a preliminary step in developing a trinitrotoluene (TNT) reusable sensor to overcome the international security issues. For investigating the TiO2 film thickness, crystalline structure and morphology, the films were autoclaved at 200 °C at different times. The X-ray diffraction showed that TiO2 films possessed a rutile structure, with no cracks visible by atomic force microscopy (AFM), and the films morphology observed by scanning electron microscopy (SEM) was highly dependent upon the hydrothermal treatment time. Yet, the TiO2 films with a more porous surface were more suitable for TNT-MIP film deposit. Rheology of precursor polymer film solutions, based on poly (acrylonitrile-co-acrylic acid), poly (acrylonitrile-co-methacrylic acid) or poly (acrylonitrile- co-itaconic acid), and the structure and adherence of TNT-MIP films were investigated in order to establish the correct recipe of the MIP. The removal yield of TNT from the imprinted films, the thickness, the porosity and the compatibility with the inorganic TiO2 film were adequate for the poly (acrylonitrile-co-acrylic acid) system with an acrylonitrile: acrylic acid practical ratio of 86.1:13.9 (wt./wt.). Farmore, AFM morphology corroborated with SEM results highlighted the effect of TNT imprinting in the copolymer matrix as the surface of the imprinted layer was quite different from that of the non-imprinted layer.

Selective Metallization of Well Aligned PS-b-P2VP Block Copolymers in Thin Films and in Confined Geometries

NASA Astrophysics Data System (ADS)

Sievert, James D.; Watkins, James J.; Russell, Thomas P.

2006-03-01

Well aligned, microphase-separated structures of styrene-2-vinylpyridine block copolymers are being used as templates for macromolecule-metal nanocomposites. These composites are either prepared as thin films or confined in nanoporous aluminum oxide membranes. Under optimal conditions, templates are prepared as thin films or confined nanorods and metallized without disturbing the ordered structure. We have developed a procedure that deposits metal within the polymer using supercritical carbon dioxide-soluble metal precursors. The use of supercritical carbon dioxide allows for selective metallization of the polymer at or below the glass transition, without disrupting the morphology. In addition, similar procedures have been investigated using metal salts and acids. Using these techniques, metals and metal-sulfides including silver, gold, platinum and zinc sulfide have been selectively deposited.

Polymer based plasmonic elements with dye molecules

NASA Astrophysics Data System (ADS)

Zhang, Douguo; Wang, Xiangxian; Chen, Yikai; Han, Lu; Wang, Pei; Ming, Hai

2012-11-01

Recently, dielectric loaded surface plasmons (SPs) elements are inducing highly interesting in the field of nanooptics, which are composed of dielectric nanostructures fabricated on a metallic thin film. This configuration will provide a route to novel integrated micro-optical devices and components combining photonics and electronics on the same chip. The advantages are easy fabrication, easy integration, and also the potential to realizing active plasmonic devices. In this talk, we will present our recent work in this field. Polymer (PMMA) nano-structures are fabricated on a silver film by the electron beam lithography (EBL) and laser interference lithography. These nano-structures are used to manipulate the behaviors of the SPs, such as converging, diverging, and guiding the propagation of SPs in subwavelength scale. Except for the pure PMMA nano-structures, dye materials (Rhodamine B, RhB) doped PMMA structures are also fabricated on the silver film. The RhB molecules will work as the active medium to excite the SPs or compensation the loss of SPs wave. The dye doped PMMA nanostructure provides a choice to realize active plasmonic elements, such as SPs Bragg gratings. On the other hand, the interaction between the fluorescence molecules and SPs will give rise to some new optical phenomena, such as directional fluorescence emission, anisotropic fluorescence emission. These polymer based plasmonic structures are investigated with a home-built leakage radiation microscopy (LRM).

Electrochemical Analysis of Conducting Polymer Thin Films

PubMed Central

Vyas, Ritesh N.; Wang, Bin

2010-01-01

Polyelectrolyte multilayers built via the layer-by-layer (LbL) method has been one of the most promising systems in the field of materials science. Layered structures can be constructed by the adsorption of various polyelectrolyte species onto the surface of a solid or liquid material by means of electrostatic interaction. The thickness of the adsorbed layers can be tuned precisely in the nanometer range. Stable, semiconducting thin films are interesting research subjects. We use a conducting polymer, poly(p-phenylene vinylene) (PPV), in the preparation of a stable thin film via the LbL method. Cyclic voltammetry and electrochemical impedance spectroscopy have been used to characterize the ionic conductivity of the PPV multilayer films. The ionic conductivity of the films has been found to be dependent on the polymerization temperature. The film conductivity can be fitted to a modified Randle’s circuit. The circuit equivalent calculations are performed to provide the diffusion coefficient values. PMID:20480052

Conformational Phase Diagram for Polymers Adsorbed on Ultrathin Nanowires

NASA Astrophysics Data System (ADS)

Vogel, Thomas; Bachmann, Michael

2010-05-01

We study the conformational behavior of a polymer adsorbed at an attractive stringlike nanowire and construct the complete structural phase diagram in dependence of the binding strength and effective thickness of the nanowire. For this purpose, Monte Carlo optimization techniques are employed to identify lowest-energy structures for a coarse-grained model of a polymer in contact with the nanowire. Among the representative conformations in the different phases are, for example, compact droplets attached to the wire and also nanotubelike monolayer films wrapping it in a very ordered way. We here systematically analyze low-energy shapes and structural order parameters to elucidate the transitions between the structural phases.

Conformational phase diagram for polymers adsorbed on ultrathin nanowires.

PubMed

Vogel, Thomas; Bachmann, Michael

2010-05-14

We study the conformational behavior of a polymer adsorbed at an attractive stringlike nanowire and construct the complete structural phase diagram in dependence of the binding strength and effective thickness of the nanowire. For this purpose, Monte Carlo optimization techniques are employed to identify lowest-energy structures for a coarse-grained model of a polymer in contact with the nanowire. Among the representative conformations in the different phases are, for example, compact droplets attached to the wire and also nanotubelike monolayer films wrapping it in a very ordered way. We here systematically analyze low-energy shapes and structural order parameters to elucidate the transitions between the structural phases.

Spontaneous wrinkling in azlactone-based functional polymer thin films in 2D and 3D geometries for guided nanopatterning

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ramanathan, Muruganathan; Lokitz, Bradley S.; Messman, Jamie M.

We report a simple, one step process for developing wrinkling patterns in azlactone-based polymer thin films and brushes in 2D and 3D surfaces. The polymer used in this work wrinkles spontaneously upon deposition and solidification on a substrate without applying any external strain to the substrate, with the mode of deposition defining the direction of the wrinkles. Wrinkle formation is shown to occur on a variety of substrates over large areas. We also find that a very thin brush-like layer of an azlactone-containing block copolymer also exhibits wrinkled topology. Given the spontaneity and versatility of wrinkle formation, we further demonstratemore » two proofs-of-concept, i) that these periodic wrinkled structures are not limited to planar surfaces, but are also developed in complex geometries including tubes, cones and other 3D structures; and ii) that this one-step wrinkling process can be used to guide the deposition of metal nanoparticles and quantum dots, creating a periodic, nanopatterned film.« less

Atomic layer deposited oxide films as protective interface layers for integrated graphene transfer

NASA Astrophysics Data System (ADS)

Cabrero-Vilatela, A.; Alexander-Webber, J. A.; Sagade, A. A.; Aria, A. I.; Braeuninger-Weimer, P.; Martin, M.-B.; Weatherup, R. S.; Hofmann, S.

2017-12-01

The transfer of chemical vapour deposited graphene from its parent growth catalyst has become a bottleneck for many of its emerging applications. The sacrificial polymer layers that are typically deposited onto graphene for mechanical support during transfer are challenging to remove completely and hence leave graphene and subsequent device interfaces contaminated. Here, we report on the use of atomic layer deposited (ALD) oxide films as protective interface and support layers during graphene transfer. The method avoids any direct contact of the graphene with polymers and through the use of thicker ALD layers (≥100 nm), polymers can be eliminated from the transfer-process altogether. The ALD film can be kept as a functional device layer, facilitating integrated device manufacturing. We demonstrate back-gated field effect devices based on single-layer graphene transferred with a protective Al2O3 film onto SiO2 that show significantly reduced charge trap and residual carrier densities. We critically discuss the advantages and challenges of processing graphene/ALD bilayer structures.

Hybrid microfabrication of nanofiber-based sheets and rods for tissue engineering applications.

PubMed

Park, Suk-Hee; Kim, Min Sung; Lee, Dasom; Choi, Yong Whan; Kim, Deok-Ho; Suh, Kahp-Yang

2013-12-01

Electrospun nanofibers have been developed into a variety of forms for tissue engineering scaffolds to regulate the cellular functions guided by nanotopographical cues. Here, we have successfully fabricated nanofiber-based scaffold complexes of rod and sheet type by combining the three microfabrication techniques of electrospinning, spin coating, and polymer melt deposition. It was demonstrated that this hybrid fabrication could produce uniaxially aligned nanofiber scaffolds supported by a thin film, allowing for a mechanically enforced substrate for cell culture as well as facile scaffold manipulation. The results of cell analysis indicated that nanofibers on spin-coated films could provide contact guidance effects on cells and retain them even after manipulation. As an application of the cell-laden nanofiber film, we built a rod-type structure by rolling up the film around a mechanically supporting core microfiber, which was incorporated by polymer melt deposition. A biocompatible and biodegradable polymer, polycaprolactone, was used throughout the processes and thus could be used as a directly implantable substitute in tissue regeneration.

High temperature arc-track resistant aerospace insulation

NASA Technical Reports Server (NTRS)

Dorogy, William

1994-01-01

The topics are presented in viewgraph form and include the following: high temperature aerospace insulation; Foster-Miller approach to develop a 300 C rated, arc-track resistant aerospace insulation; advantages and disadvantages of key structural features; summary goals and achievements of the phase 1 program; performance goals for selected materials; materials under evaluation; molecular structures of candidate polymers; candidate polymer properties; film properties; and a detailed program plan.

Humidity-dependent compression-induced glass transition of the air–water interfacial Langmuir films of poly(D,L-lactic acid- ran-glycolic acid) (PLGA)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Hyun Chang; Lee, Hoyoung; Jung, Hyunjung

2015-08-26

Constant rate compression isotherms of the air–water interfacial Langmuir films of poly(D,L-lactic acid- ran-glycolic acid) (PLGA)show a distinct feature of an exponential increase in surface pressure in the high surface polymer concentration regime. We have previously demonstrated that this abrupt increase in surface pressure is linked to the glass transition of the polymer film, but the detailed mechanism of this process is not understood. In order to obtain a molecular-level understanding of this behavior, we performed extensive characterizations of the surface mechanical, structural and rheological properties of Langmuir PLGA films at the air–water interface, using combined experimental techniques including themore » Langmuir film balance, X-ray reflectivity and double-wall-ring interfacial rheometry methods.« less

Overcoming Film Quality Issues for Conjugated Polymers Doped with F4TCNQ by Solution Sequential Processing: Hall Effect, Structural, and Optical Measurements.

PubMed

Scholes, D Tyler; Hawks, Steven A; Yee, Patrick Y; Wu, Hao; Lindemuth, Jeffrey R; Tolbert, Sarah H; Schwartz, Benjamin J

2015-12-03

We demonstrate that solution-sequential processing (SqP) can yield heavily doped pristine-quality films when used to infiltrate the molecular dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) into pure poly(3-hexylthiophene) (P3HT) polymer layers. Profilometry measurements show that the SqP method produces doped films with essentially the same surface roughness as pristine films, and 2-D grazing-incidence wide-angle X-ray scattering (GIWAXS) confirms that SqP preserves both the size and orientation of the pristine polymer's crystallites. Unlike traditional blend-cast F4TCNQ/P3HT doped films, our sequentially processed layers have tunable and reproducible conductivities reaching as high as 5.5 S/cm even when measured over macroscopic (>1 cm) distances. The high conductivity and superb film quality allow for meaningful Hall effect measurements, which reveal p-type conduction and carrier concentrations tunable from 10(16) to 10(20) cm(-3) and hole mobilities ranging from ∼0.003 to 0.02 cm(2) V(-1) s(-1) at room temperature over the doping levels examined.

High Energy Density in Azobenzene-based Materials for Photo-Thermal Batteries via Controlled Polymer Architecture and Polymer-Solvent Interactions.

PubMed

Jeong, Seung Pyo; Renna, Lawrence A; Boyle, Connor J; Kwak, Hyunwook S; Harder, Edward; Damm, Wolfgang; Venkataraman, Dhandapani

2017-12-19

Energy densities of ~510 J/g (max: 698 J/g) have been achieved in azobenzene-based syndiotactic-rich poly(methacrylate) polymers. The processing solvent and polymer-solvent interactions are important to achieve morphologically optimal structures for high-energy density materials. This work shows that morphological changes of solid-state syndiotactic polymers, driven by different solvent processings play an important role in controlling the activation energy of Z-E isomerization as well as the shape of the DSC exotherm. Thus, this study shows the crucial role of processing solvents and thin film structure in achieving higher energy densities.

Study of series-connected polymer tandem solar cells based on a highly efficient donor material of PTB7-Th

NASA Astrophysics Data System (ADS)

Zang, Yue; Gao, Xiumin; Xin, Qing; Lin, Jun; Zhao, Jufeng

2017-06-01

A highly efficient donor polymer, PTB7-Th, combined with acceptor fullerene PC71BM was introduced as the subcell in the series-connected tandem devices to achieve high-performance polymer tandem solar cells. Design of the device architecture was investigated using modeling and simulation methods to identify the optimal structure and to predict performance of the tandem cells. To address the challenge of current matching between the constituent subcells, the effect of active layer thickness, different device structure, and use of ultrathin Ag film were analyzed. It was found that the distribution of optical intensity in the tandem structure can be optimized through the optical spacer effect of interfacial layers and micro-cavity effect derived from the embedded ultrathin Ag film. Our results indicate that the efficient light utilization with appropriate subcells can allow achievement of power conversion efficiency of 12%, which can be 25% higher than that of a single cell of PTB7-Th.

Preparation Nano-Structure Polytetrafluoroethylene (PTFE) Functional Film on the Cellulose Insulation Polymer and Its Effect on the Breakdown Voltage and Hydrophobicity Properties

PubMed Central

Liu, Cong; Li, Yanqing; Liao, Ruijin; Liao, Qiang; Tang, Chao

2018-01-01

Cellulose insulation polymer is an important component of oil-paper insulation, which is widely used in power transformer. The weight of the cellulose insulation polymer materials is as high as tens of tons in the larger converter transformer. Excellent performance of oil-paper insulation is very important for ensuring the safe operation of larger converter transformer. An effective way to improve the insulation and the physicochemical property of the oil impregnated insulation pressboard/paper is currently a popular research topic. In this paper, the polytetrafluoroethylene (PTFE) functional film was coated on the cellulose insulation pressboard by radio frequency (RF) magnetron sputtering to improve its breakdown voltage and the hydrophobicity properties. X-ray photoelectron spectroscopy (XPS) results show that the nano-structure PTFE functional film was successfully fabricated on the cellulose insulation pressboard surface. The scanning electron microscopy (SEM) and X-ray diffraction (XRD) present that the nanoscale size PTFE particles were attached to the pressboard surface and it exists in the amorphous form. Atomic force microscopy (AFM) shows that the sputtered pressboard surface is still rough. The rough PTFE functional film and the reduction of the hydrophilic hydroxyl of the surface due to the shielding effect of PTFE improve the breakdown and the hydrophobicity properties of the cellulose insulation pressboard obviously. This paper provides an innovative way to improve the performance of the cellulose insulation polymer. PMID:29883376

Preparation Nano-Structure Polytetrafluoroethylene (PTFE) Functional Film on the Cellulose Insulation Polymer and Its Effect on the Breakdown Voltage and Hydrophobicity Properties.

PubMed

Hao, Jian; Liu, Cong; Li, Yanqing; Liao, Ruijin; Liao, Qiang; Tang, Chao

2018-05-21

Cellulose insulation polymer is an important component of oil-paper insulation, which is widely used in power transformer. The weight of the cellulose insulation polymer materials is as high as tens of tons in the larger converter transformer. Excellent performance of oil-paper insulation is very important for ensuring the safe operation of larger converter transformer. An effective way to improve the insulation and the physicochemical property of the oil impregnated insulation pressboard/paper is currently a popular research topic. In this paper, the polytetrafluoroethylene (PTFE) functional film was coated on the cellulose insulation pressboard by radio frequency (RF) magnetron sputtering to improve its breakdown voltage and the hydrophobicity properties. X-ray photoelectron spectroscopy (XPS) results show that the nano-structure PTFE functional film was successfully fabricated on the cellulose insulation pressboard surface. The scanning electron microscopy (SEM) and X-ray diffraction (XRD) present that the nanoscale size PTFE particles were attached to the pressboard surface and it exists in the amorphous form. Atomic force microscopy (AFM) shows that the sputtered pressboard surface is still rough. The rough PTFE functional film and the reduction of the hydrophilic hydroxyl of the surface due to the shielding effect of PTFE improve the breakdown and the hydrophobicity properties of the cellulose insulation pressboard obviously. This paper provides an innovative way to improve the performance of the cellulose insulation polymer.

Wrinkling and folding of nanotube-polymer bilayers

NASA Astrophysics Data System (ADS)

Semler, Matthew R.; Harris, John M.; Hobbie, Erik K.

2014-07-01

The influence of a polymer capping layer on the deformation of purified single-wall carbon nanotube (SWCNT) networks is analyzed through the wrinkling of compressed SWCNT-polymer bilayers on polydimethylsiloxane. The films exhibit both wrinkling and folding under compression and we extract the elastoplastic response using conventional two-plate buckling schemes. The formation of a diffuse interpenetrating nanotube-polymer interface has a dramatic effect on the nanotube layer modulus for both metallic and semiconducting species. In contrast to the usual percolation exhibited by the pure SWCNT films, the capped films show a crossover from "composite" behavior (the modulus of the SWCNT film is enhanced by the polymer) to "plasticized" behavior (the modulus of the SWCNT film is reduced by the polymer) as the SWCNT film thickness increases. For almost all thicknesses, however, the polymer enhances the yield strain of the nanotube network. Conductivity measurements on identical films suggest that the polymer has a modest effect on charge transport, which we interpret as a strain-induced polymer penetration of interfacial nanotube contacts. We use scaling, Flory-Huggins theory, and independently determined nanotube-nanotube and nanotube-polymer Hamaker constants to model the response.

In situ X-ray study of the structural evolution of gold nano-domains by spray deposition on thin conductive P3HT films.

PubMed

Al-Hussein, M; Schindler, M; Ruderer, M A; Perlich, J; Schwartzkopf, M; Herzog, G; Heidmann, B; Buffet, A; Roth, S V; Müller-Buschbaum, P

2013-02-26

Gold (Au) nanoparticles are deposited from aqueous solution onto one of the most used conductive polymers, namely poly(3-hexylthiophene) (P3HT), using airbrush deposition. We report on the structure formation and packing of the Au nanoparticles after a 5 s spray cycle. In situ grazing incidence small-angle X-ray scattering (GISAXS) measurements with 20 ms time resolution allow a real-time observation of the emergence and evolution of the microstructure during a spray cycle and subsequent solvent evaporation. The results reveal multistage nanoscale ordering of the Au nanoparticles during the spray cycle. Further ex situ atomic force microscopy measurements of the sprayed films showed the formation of Au monolayer islands on top of the polymer film. Our study suggests that the solvent-substrate interaction as well as solvent evaporation kinetics are important factors that need to be taken into consideration in order to grow a compact uniform monolayer film for the fabrication of ultrathin films using airbrush deposition.

Highly ordered gold nanotubes using thiols at a cleavable block copolymer interface.

PubMed

Ryu, Ja-Hyoung; Park, Soojin; Kim, Bokyung; Klaikherd, Akamol; Russell, Thomas P; Thayumanavan, S

2009-07-29

We have prepared functionalized nanoporous thin films from a polystyrene-block-polyethylene oxide block copolymer, which was made cleavable due to the intervening disulfide bond. The cleavage reaction of the disulfide bond leaves behind free thiol groups inside the nanopores of polystyrene thin film. This nanoporous thin film can be used as a template for generating gold nanoring structures. This strategy can provide a facile method to form a highly ordered array of biopolymer or metal-polymer composite structures.

The influence of polymer architectures on the dewetting behavior of thin polymer films: from linear chains to ring chains.

PubMed

Wang, Lina; Xu, Lin; Liu, Binyuan; Shi, Tongfei; Jiang, Shichun; An, Lijia

2017-05-03

The dewetting behavior of ring polystyrene (RPS) film and linear polystyrene (LPS) film on silanized Si substrates with different grafting densities and PDMS substrate was investigated. Results showed that polymer architectures greatly influenced the dewetting behavior of the thin polymer film. On the silanized Si substrate with 69% grafting density, RPS chains exhibited stronger adsorption compared with LPS chains, and as a result the wetting layer formed more easily. For LPS films, with a decreased annealing temperature, the stability of the polymer film changed from non-slip dewetting via apparent slip dewetting to apparently stable. However, for RPS films, the polymer film stability switched from apparent slip dewetting to apparently stable. On the silanized Si substrate with 94% grafting density, the chain adsorption became weaker and the dewetting processes were faster than that on the substrate with 69% grafting density at the same experimental temperature for both the LPS and RPS films. Moreover, on the PDMS substrate, LPS films always showed non-slip dewetting, while the dewetting kinetics of RPS films switched from non-slip dewetting to slip dewetting behaviour. Forming the wetting layer strongly influenced the stability and dewetting behavior of the thin polymer films.

Computational modeling of in vitro biological responses on polymethacrylate surfaces

PubMed Central

Ghosh, Jayeeta; Lewitus, Dan Y; Chandra, Prafulla; Joy, Abraham; Bushman, Jared; Knight, Doyle; Kohn, Joachim

2011-01-01

The objective of this research was to examine the capabilities of QSPR (Quantitative Structure Property Relationship) modeling to predict specific biological responses (fibrinogen adsorption, cell attachment and cell proliferation index) on thin films of different polymethacrylates. Using 33 commercially available monomers it is theoretically possible to construct a library of over 40,000 distinct polymer compositions. A subset of these polymers were synthesized and solvent cast surfaces were prepared in 96 well plates for the measurement of fibrinogen adsorption. NIH 3T3 cell attachment and proliferation index were measured on spin coated thin films of these polymers. Based on the experimental results of these polymers, separate models were built for homo-, co-, and terpolymers in the library with good correlation between experiment and predicted values. The ability to predict biological responses by simple QSPR models for large numbers of polymers has important implications in designing biomaterials for specific biological or medical applications. PMID:21779132

Structure, dielectric, thermal and I-V studies of electron beam irradiated PVDF-HFP/LiClO4 electrolyte film

NASA Astrophysics Data System (ADS)

Yesappa, L.; Niranjana, M.; Ashokkumar, S. P.; Vijeth, H.; Basappa, M.; Ganesh, S.; Devendrappa, H.

2018-05-01

The effect of electron beam (EB) irradiation on polymer electrolyte (PVDF-HFP: LiClO4=90:10, PHL10) films prepared by solution casting method. FT-IR confirms the complexation between salt and polymer upon EB dose. Degradation of polymer and decrease in % of crystallinity from 50.10 to 40.96 at 2θ=19.90° at 120 kGy dose indicates increased amorphousity confirmed by XRD. The TGA result show decrease in Tm from 460 °C to 418 °C is leads to degradation of polymer chain at higher dosage. The dielectric parameters have been determined and observed decreasing trend with increased frequency as well as temperature due to increase the mobility of charge carrier confirms the capacitive nature. I-V plots exhibit an ohmic behavior with applied voltage and irradiation dose. The results notice the change in polymer properties upon irradiation.

Fabrication of raised and inverted SU8 polymer waveguides

NASA Astrophysics Data System (ADS)

Holland, Anthony S.; Mitchell, Arnan; Balkunje, Vishal S.; Austin, Mike W.; Raghunathan, Mukund K.

2005-01-01

Polymer films with high optical transmission have been investigated for making optical devices for several years. SU8 photoresist and optical adhesives have been investigated for use as thin films for optical devices, not what they were originally designed for. Optical adhesives are typically a one component thermoset polymer and are convenient to use for making thin film optical devices such as waveguides. They are prepared in minutes as thin films unlike SU8, which has to be carefully thermally cured over several hours for optimum results. However SU8 can be accurately patterned to form the geometry of structures required for single mode optical waveguides. SU8 in combination with the lower refractive index optical adhesive films such as UV15 from Master Bond are used to form single and multi mode waveguides. SU8 is photopatternable but we have also used dry etching of the SU8 layer or the other polymer layers e.g. UV15 to form the ribs, ridges or trenches required to guide single modes of light. Optical waveguides were also fabricated using only optical adhesives of different refractive indices. The resolution obtainable is poorer than with SU8 and hence multi mode waveguides are obtained. Loss measurements have been obtained for waveguides of different geometries and material combinations. The process for making polymer waveguides is demonstrated for making large multi mode waveguides and microfluidic channels by scaling the process up in size.

Impedance analysis on PVA/PVP: GO blend nanocomposite polymer films

NASA Astrophysics Data System (ADS)

Rao, M. C.; Basha, S. K. Shahenoor; Kumar, B. Ranjit

2018-05-01

Nanocomposite polymer films have been prepared by doping Graphene oxide (GO) in PVA/PVP blend polymers by solution cast technique. AC conductivity studies were performed on to the prepared nanocomposite films and the maximum ionic conductivity is found to be 6.13x10-4 Scm-1 for (0.30:0.3) wt% of nanocomposite polymer film at room temperature. The maximum ionic conductivity of nanocomposite polymer films of PVA/PVP: GO holds great promise in potential applications.

Towards Biomimicking Wood: Fabricated Free-standing Films of Nanocellulose, Lignin, and a Synthetic Polycation

PubMed Central

Pillai, Karthik; Navarro Arzate, Fernando; Zhang, Wei; Renneckar, Scott

2014-01-01

Woody materials are comprised of plant cell walls that contain a layered secondary cell wall composed of structural polymers of polysaccharides and lignin. Layer-by-layer (LbL) assembly process which relies on the assembly of oppositely charged molecules from aqueous solutions was used to build a freestanding composite film of isolated wood polymers of lignin and oxidized nanofibril cellulose (NFC). To facilitate the assembly of these negatively charged polymers, a positively charged polyelectrolyte, poly(diallyldimethylammomium chloride) (PDDA), was used as a linking layer to create this simplified model cell wall. The layered adsorption process was studied quantitatively using quartz crystal microbalance with dissipation monitoring (QCM-D) and ellipsometry. The results showed that layer mass/thickness per adsorbed layer increased as a function of total number of layers. The surface coverage of the adsorbed layers was studied with atomic force microscopy (AFM). Complete coverage of the surface with lignin in all the deposition cycles was found for the system, however, surface coverage by NFC increased with the number of layers. The adsorption process was carried out for 250 cycles (500 bilayers) on a cellulose acetate (CA) substrate. Transparent free-standing LBL assembled nanocomposite films were obtained when the CA substrate was later dissolved in acetone. Scanning electron microscopy (SEM) of the fractured cross-sections showed a lamellar structure, and the thickness per adsorption cycle (PDDA-Lignin-PDDA-NC) was estimated to be 17 nm for two different lignin types used in the study. The data indicates a film with highly controlled architecture where nanocellulose and lignin are spatially deposited on the nanoscale (a polymer-polymer nanocomposites), similar to what is observed in the native cell wall. PMID:24961302

Thermoplastic composite matrices with improved solvent resistance

NASA Technical Reports Server (NTRS)

Hergenrother, P. M.; Jensen, B. J.; Havens, S. J.

1984-01-01

In order to improve solvent resistance of aromatic thermoplastic polymers, ethynyl-terminated aromatic sulfone polymers (ETS), sulfone/ester polymers (SEPE) containing pendent ethynyl groups, and phenoxy resin containing pendent ethynyl groups are synthesized. Cured polysulfones and phenoxy resins containing ethynyl groups on the ends or pendent on the molecules exhibited systematic behavior in solvent resistance, film flexibility, and toughness as a function of crosslink density. The film and composite properties of a cured solvent-resistant ETS were better than those of a commercially available solvent sensitive polysulfone. The study was part of a NASA program to better understand the trade-offs between solvent resistance, processability and mechanical properties which may be useful in designing composite structures for aerospace vehicles.

Formation mechanism of photo-induced nested wrinkles on siloxane-photomonomer hybrid film

DOE Office of Scientific and Technical Information (OSTI.GOV)

Suzuki, Kazumasa; International Laboratory of Materials Science and Nanotechnology; Laboratorio di Scienz

Nested wrinkle structures, hierarchical surface wrinkles of different periodicities of sub-μm and tens-μm, have been fabricated on a siloxane-photomonomer hybrid film via a photo-induced surface polymerization of acrylamide. The formation mechanism of the nested wrinkle structures is examined based on a time-dependent structure observation and chemical composition analyses. In-situ observation of the evolving surface structure showed that sub-μm scale wrinkles first formed, subsequently the tens-μm scale ones did. In-situ FT-IR analysis indicated that the nested wrinkles formation took place along with the development of siloxane network of under layer. A cross sectional observation of the film revealed that the filmmore » was composed of three layers. FT-IR spectra of the film revealed that the surface and interior layers were polyacrylamide rich layer and siloxane-polymer rich layer, respectively. The intermediate layer formed as a diffusion layer by migration of acrylamide from interior to the surface. These three layers have different chemical compositions and therefore different mechanical characteristics, which allows the wrinkle formation. Shrinkage of siloxane-polymer interior layers, as a result of polycondensation of siloxane network, induced mechanical instabilities at interlayers, to form the nested wrinkle structures.« less

Synthesis and characterization of Au-MWCNT/PEDOT: PSS composite film for optoelectronic applications

NASA Astrophysics Data System (ADS)

Jasna, M.; Anjana, R.; Jayaraj, M. K.

2017-08-01

Recently, flexible organic optoelectronics have got great attention because of their light weight, mechanical flexibility and cost effective fabrication process. Conjugated polymers like PEDOT: PSS are widely used for the transparent electrode applications due to its chemical stability, high conductivity, flexibility and optical transparency in the visible region. Conductivity of the PEDOT: PSS polymer can be enhanced by adding organic solvents or conducting nano fillers like CNT, graphene, etc. Carbon nanotubes are good nano fillers to enhance the conductivity and mechanical strength of PEDOT: PSS composite film. Inthe present work, the effect of gold nano particles in PEDOT: PSS/CNT composite is studied. The conductivity enhancement in PEDOT: PSS/CNT thin films can be attributed to the formation of CNT network in the polymer matrix and conformational change of the PEDOT from benzoid to quinoid structure. Even though the conductivity was enhanced, the transparency of the composite thin films decreased with increase in CNT concentration. To overcome this problem, gold nano particles were attached to CNT walls via chemical route. AuMWCNT/PEDOT: PSS composite films were prepared by spin coating method. TEM images confirmed the decoration of gold nano particles on CNT walls. Electrical and optical properties of the composite films were studied. This simple solution processed conducting films are suitable for optoelectronic applications

Thin film-coated polymer webs

DOEpatents

Wenz, Robert P.; Weber, Michael F.; Arudi, Ravindra L.

1992-02-04

The present invention relates to thin film-coated polymer webs, and more particularly to thin film electronic devices supported upon a polymer web, wherein the polymer web is treated with a purifying amount of electron beam radiation.

Molecular-dynamics simulations of crosslinking and confinement effects on structure, segmental mobility and mechanics of filled elastomers

NASA Astrophysics Data System (ADS)

Davris, Theodoros; Lyulin, Alexey V.

2016-05-01

The significant drop of the storage modulus under uniaxial deformation (Payne effect) restrains the performance of the elastomer-based composites and the development of possible new applications. In this paper molecular-dynamics (MD) computer simulations using LAMMPS MD package have been performed to study the mechanical properties of a coarse-grained model of this family of nanocomposite materials. Our goal is to provide simulational insights into the viscoelastic properties of filled elastomers, and try to connect the macroscopic mechanics with composite microstructure, the strength of the polymer-filler interactions and the polymer mobility at different scales. To this end we simulate random copolymer films capped between two infinite solid (filler aggregate) walls. We systematically vary the strength of the polymer-substrate adhesion interactions, degree of polymer confinement (film thickness), polymer crosslinking density, and study their influence on the equilibrium and non-equilibrium structure, segmental dynamics, and the mechanical properties of the simulated systems. The glass-transition temperature increases once the mesh size became smaller than the chain radius of gyration; otherwise it remained invariant to mesh-size variations. This increase in the glass-transition temperature was accompanied by a monotonic slowing-down of segmental dynamics on all studied length scales. This observation is attributed to the correspondingly decreased width of the bulk density layer that was obtained in films whose thickness was larger than the end-to-end distance of the bulk polymer chains. To test this hypothesis additional simulations were performed in which the crystalline walls were replaced with amorphous or rough walls.

Organic Thin Films Deposited by Emulsion-Based, Resonant Infrared, Matrix-Assisted Pulsed Laser Evaporation: Fundamentals and Applications

NASA Astrophysics Data System (ADS)

Ge, Wangyao

Thin film deposition techniques are indispensable to the development of modern technologies as thin film based optical coatings, optoelectronic devices, sensors, and biological implants are the building blocks of many complicated technologies, and their performance heavily depends on the applied deposition technique. Particularly, the emergence of novel solution-processed materials, such as soft organic molecules, inorganic compounds and colloidal nanoparticles, facilitates the development of flexible and printed electronics that are inexpensive, light weight, green and smart, and these thin film devices represent future trends for new technologies. One appealing feature of solution-processed materials is that they can be deposited into thin films using solution-processed deposition techniques that are straightforward, inexpensive, high throughput and advantageous to industrialize thin film based devices. However, solution-processed techniques rely on wet deposition, which has limitations in certain applications, such as multi-layered film deposition of similar materials and blended film deposition of dissimilar materials. These limitations cannot be addressed by traditional, vacuum-based deposition techniques because these dry approaches are often too energetic and can degrade soft materials, such as polymers, such that the performance of resulting thin film based devices is compromised. The work presented in this dissertation explores a novel thin film deposition technique, namely emulsion-based, resonant infrared, matrix-assisted pulsed laser evaporation (RIR-MAPLE), which combines characteristics of wet and dry deposition techniques for solution-processed materials. Previous studies have demonstrated the feasibility of emulsion-based RIR-MAPLE to deposit uniform and continuous organic, nanoparticle and blended films, as well as hetero-structures that otherwise are difficult to achieve. However, fundamental understanding of the growth mechanisms that govern emulsion-based RIR-MAPLE is still missing, which increases the difficulty of using rational design to improve the performance of initial RIR-MAPLE devices that have been demonstrated. As a result, it is important to study the fundamentals of emulsion-based RIR-MAPLE in order to provide insight into the long-term prospects for this thin film deposition technique. This dissertation explores the fundamental deposition mechanisms of emulsion-based RIR-MAPLE by considering the effects of the emulsion target composition (namely, the primary solvent, secondary solvent, and surfactant) on the properties of deposited polymer films. The study of primary solvent effects on hydrophobic polymer deposition helps identify the unique method of film formation for emulsion-based RIR-MAPLE, which can be described as cluster-by-cluster deposition of emulsified particles that yields two levels of ordering (i.e., within the clusters and among the clusters). The generality of this film formation mechanism is tested by applying the lessons learned to hydrophilic polymer deposition. Based on these studies, the deposition design rules to achieve smooth polymer films, which are important for different device applications, are identified according to the properties of the polymer. After discussion of the fundamental deposition mechanisms, three applications of emulsion-based RIR-MAPLE, namely thin film deposition of organic solar cells, polymer/nanoparticle hybrid solar cells, and antimicrobial/fouling-release multifunctional films, are studied. The work on organic solar cells identifies the ideal deposition mode for blended films with nanoscale domain sizes, as well as demonstrates the relationships among emulsion target composition, film properties, and corresponding device performance. The studies of polymer/nanoparticle hybrid solar cells demonstrate precise control of colloidal nanoparticle deposition, in which the integrity of nanoparticles is maintained and a distinct film morphology is achieved when co-deposited with polymers. Finally, the application of antimicrobial and fouling-release multifunctional films demonstrates the importance of blended film deposition with nanoscale phase separation, a key feature to achieving reusable bio-films that can kill bacteria when illuminated with ultraviolet light. Thus, this dissertation provides great insight to the fundamentals of emulsion-based RIR-MAPLE, serves as a valuable reference for future development, and paves the pathway for wider adoption of this unique thin film deposition technique, especially for organic solar cells.

The influence of guaifenesin and ketoprofen on the properties of hot-melt extruded polyethylene oxide films.

PubMed

Crowley, Michael M; Fredersdorf, Anke; Schroeder, Britta; Kucera, Shawn; Prodduturi, Suneela; Repka, Michael A; McGinity, James W

2004-08-01

Films containing polyethylene oxide (PEO) and a model drug, either guaifenesin (GFN) or ketoprofen (KTP), were prepared by hot-melt extrusion. The thermal properties of the hot-melt extruded films were investigated using differential scanning calorimetry (DSC). Scanning electron microscopy (SEM) was used to examine the surface morphology of the films, and wide angle X-ray diffraction (XRD) was used to investigate the crystalline properties of the polymer, drugs and physical mixtures as well as the solid state structure of the films. The stability of the polymer was studied using gel permeation chromatography. The mechanical properties, including percent elongation and tensile strength of the films, were determined on an Instron according to American Society for Testing Materials (ASTM) procedures. The Hansen solubility parameter was calculated using the Hoftyzer or van Krevelen method to estimate the likelihood of drug--polymer miscibility. Both GFN and KTP were stable during the extrusion process. Melting points corresponding to the crystalline drugs were not observed in the films. Crystallization of GFN on the surface of the film was observed at all concentrations studied, however KTP crystallization did not occur until reaching the 15% level. Guaifenesin and ketoprofen were found to decrease drive load, increase PEO stability and plasticize the polymer during extrusion. The Hansen solubility parameters predicted miscibility between PEO and KTP and poor miscibility between PEO and GFN. The predictions of the solubility parameters were in agreement with the XRD and SEM results. The percent elongation decreased with increasing GFN concentrations and significantly increased with increasing levels of KTP. Both GFN and KTP decreased the tensile strength of the extruded film.

Effect of gamma radiation on low density polyethylene (LDPE) films: optical, dielectric and FTIR studies.

PubMed

Moez, A Abdel; Aly, S S; Elshaer, Y H

2012-07-01

The low density polyethylene (LDPE) films were irradiated with gamma radiation in the dose range varied from 20 to 400 kGy. The induced changes in the chemical structure and dielectric properties for the irradiated films were investigated. The structure modifications: crystallinity as well as possible molecular changes of the polymer were recognized using Fourier Transform Infrared Spectroscopy (FTIR). The optical results were determined from transmission, reflection and absorption spectra for these films. The dielectric properties of these films were calculated using optical methods. Result indicates small variation in crystallinity which could be increased or decreased depending on the relative importance of the structural and chemical changes. Copyright © 2012 Elsevier B.V. All rights reserved.

Graphene Oxide Monolayer as a Compatibilizer at the Polymer-Polymer Interface for Stabilizing Polymer Bilayer Films against Dewetting.

PubMed

Kim, Tae-Ho; Kim, Hyeri; Choi, Ki-In; Yoo, Jeseung; Seo, Young-Soo; Lee, Jeong-Soo; Koo, Jaseung

2016-12-06

We investigate the effect of adding graphene oxide (GO) sheets at the polymer-polymer interface on the dewetting dynamics and compatibility of immiscible polymer bilayer films. GO monolayers are deposited at the poly(methyl methacrylate) (PMMA)-polystyrene (PS) interface by the Langmuir-Schaefer technique. GO monolayers are found to significantly inhibit the dewetting behavior of both PMMA films (on PS substrates) and PS films (on PMMA substrates). This can be interpreted in terms of an interfacial interaction between the GO sheets and these polymers, which is evidenced by the reduced contact angle of the dewet droplets. The favorable interaction of GO with both PS and PMMA facilitates compatibilization of the immiscible polymer bilayer films, thereby stabilizing their bilayer films against dewetting. This compatibilization effect is verified by neutron reflectivity measurements, which reveal that the addition of GO monolayers broadens the interface between PS and the deuterated PMMA films by 2.2 times over that of the bilayer in the absence of GO.

Effect of Core-shell Ceria/Poly(Vinylpyrrolidone) (PVP) Nanoparticles Incorporated in Polymer Films and Their Optical Properties (2): Increasing the Refractive Index

PubMed Central

Itoh, Toshio; Uchida, Toshio; Izu, Noriya; Shin, Woosuck

2017-01-01

We investigated the preparation of well-dispersed core-shell ceria-poly(vinylpyrrolidone) (PVP) nanoparticles with an average particle size of around 20 nm which were used to produce a hybrid film with a polymer coating of dipentaerythritol hexaacrylate (DPHA). We obtained good dispersion of the nanoparticles in a mixed solvent of 48% 1-methoxy-2-propanol (MP), 32% 3-methoxy-3-methyl-1-butanol (MMB), and 20% methyl i-butyl ketone (MIBK). An ink of the polymer coating consisting of 68.7 wt% nanoparticles and 31.3 wt% DPHA with a polymerization initiator was prepared using this solvent mixture. The surface of the hybrid film showed low roughness and the nanoparticles formed a densely packed structure in the DPHA matrix. The resulting coating possessed excellent transparency and a high refractive index of 1.69. PMID:28773070

Strong Photonic-Band-Gap Effect on the Spontaneous Emission in 3D Lead Halide Perovskite Photonic Crystals.

PubMed

Zhou, Xue; Li, Mingzhu; Wang, Kang; Li, Huizeng; Li, Yanan; Li, Chang; Yan, Yongli; Zhao, Yongsheng; Song, Yanlin

2018-03-25

Stimulated emission in perovskite-embedded polymer opal structures is investigated. A polymer opal structure is filled with a perovskite, and perovskite photonic crystals are prepared. The spontaneous emission of the perovskite embedded in the polymer opal structures exhibits clear signatures of amplified spontaneous emission (ASE) via gain modulation. The difference in refractive-index contrast between the perovskite and the polymer opal is large enough for retaining photonic-crystals properties. The photonic band gap has a strong effect on the fluorescence emission intensity and lifetime. The stimulated emission spectrum exhibits a narrow ASE rather than a wide fluorescence peak in the thin film. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photo-Induced Self-Condensation, A Technique For Fabricating Organic Lightguide Structures

NASA Astrophysics Data System (ADS)

Franke, H.; Heuer, W.

1986-11-01

Planar lightguides have been fabricated from mixtures of the polymer PMMA with benzoin type photoinitiators. Using conventional UV-photolithography 2 dimensional refractive index patterns were recorded in the polymer films. Thickness and refractive index of the organic lightguides were determined by m-line spectroscopy. The achieved refractive index changes increased with increasing photoinitiator concentrations. For high concentrations (< 70 %) the film refractive index could be increased via UV exposure by Δn = 0.03. Thermal treatment at below 100°C caused the out diffusion of the unexposed photoinitiator and completion of the photochemically induced reaction in the exposed parts of the film. Thus refractive index patterns (Δn < 0.05) could be developed and fixed.

Ion beam deposition of amorphous carbon films with diamond like properties

NASA Technical Reports Server (NTRS)

Angus, John C.; Mirtich, Michael J.; Wintucky, Edwin G.

1982-01-01

Carbon films were deposited on silicon, quartz, and potassium bromide substrates from an ion beam. Growth rates were approximately 0.3 micron/hour. The films were featureless and amorphous and contained only carbon and hydrogen in significant amounts. The density and carbon/hydrogen ratio indicate the film is a hydrogen deficient polymer. One possible structure, consistent with the data, is a random network of methylene linkages and tetrahedrally coordinated carbon atoms.

Structural evolution under uniaxial drawing of Poly(D, L-lactide) Films

NASA Astrophysics Data System (ADS)

Stoclet, Grégory; Lefebvre, Jean-Marc; Seguela, Roland

2009-03-01

Aliphatic polyesters are an important class of biodegradable polymers. They have drawn particular attention in the last few years as food packaging materials because they can be derived from renewable resources. Among this family, polylactide (PLA) is considered as one of the most promising ``green'' polymer for use as a substitute to petroleum-based polymers. In the present work, we investigate the mechanical behaviour of amorphous poly(D, L-lactide) films in relation to the structural evolution upon stretching at various draw temperatures (Td) above the glass transition temperature. Examination of the drawing behaviour shows that PLA initially behaves like a rubbery material until a true strain of the order of 1. Strain hardening occurs beyond this strain level, up to film fracture. Such strain hardening is generally ascribed to a strain induced crystallization phenomenon. In the present case, it is clearly more pronounced for Td = 90 C than for Td = 70 C. The corresponding structural evolutions are investigated by means of WAXS. The diffraction patterns reveal the marked influence of draw temperature. Indeed for Td = 70 C a mesophase is induced whereas strain-induced crystallisation takes place at Td = 90 C. Further work is in progress, in order to elucidate mesophase development and mechanical response.

Enhancing performing characteristics of organic semiconducting films by improved solution processing

DOEpatents

Bazan, Guillermo C; Moses, Daniel; Peet, Jeffrey; Heeger, Alan J

2014-05-13

Improved processing methods for enhanced properties of conjugated polymer films are disclosed, as well as the enhanced conjugated polymer films produced thereby. Addition of low molecular weight alkyl-containing molecules to solutions used to form conjugated polymer films leads to improved photoconductivity and improvements in other electronic properties. The enhanced conjugated polymer films can be used in a variety of electronic devices, such as solar cells and photodiodes.

Microstructure synthesis control of biological polyhydroxyalkanoates with mass spectrometry

NASA Astrophysics Data System (ADS)

Pederson, Erik Norman

Polyhydroxyalkanoates (PHA's) are a class of biologically produced polymers, or plastic, that is synthesized by various microorganisms. PHA's are made from biorenewable resources and are fully biodegradable and biocompatible, making them an environmentally friendly green polymer. A method of incorporating polymer microstructure into the PHA synthesized in Ralstonia eutropha was developed. These microstructures were synthesized with polyhydroxybutyrate (PHB) and poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) as the polymer domains. To synthesize the PHB V copolymer, the additional presence of valerate was required. To control valerate substrate additions to the bioreactor, an off-gas mass spectrometry (MS) feedback control system was developed. Important process information including the cell physiology, growth kinetics, and product formation kinetics in the bioreactor was obtained with MS and used to control microstructure synthesis. The two polymer microstructures synthesized were core-shell granules and block copolymers. Block copolymers control the structure of the individual polymer chains while core-shell granules control the organization of many polymer chains. Both these microstructures result in properties unattainable by blending the two polymers together. The core-shell structures were synthesized with controlled domain thickness based on a developed model. Different block copolymers compositions were synthesized by varying the switching time of the substrate pulses responsible for block copolymer synthesis. The block copolymers were tested to determine their chemical properties and cast into films to determine the materials properties. These block copolymer films possessed new properties not achieved by copolymers or blends of the two polymers.

Bioinspired Non-iridescent Structural Color from Polymer Blend Thin Films

NASA Astrophysics Data System (ADS)

Nallapaneni, Asritha; Shawkey, Matthew; Karim, Alamgir

Colors exhibited in biological species are either due to natural pigments, sub-micron structural variation or both. Structural colors thus exhibited can be iridescent (ID) or non-iridescent (NID) in nature. NID colors originate due to interference and coherent scattering of light with quasi-ordered micro- and nano- structures. Specifically, in Eastern Bluebird (Sialia sialis) these nanostructures develop as a result of phase separation of β-keratin from cytoplasm present in cells. We replicate these structures via spinodal blend phase separation of PS-PMMA thin films. Colors of films vary from ultraviolet to blue. Scattering of UV-visible light from selectively leeched phase separated blends are studied in terms of varying domain spacing (200nm to 2 μm) of film. We control these parameters by tuning annealing time and temperature. Angle-resolved spectroscopy studies suggest that the films are weakly iridescent and scattering from phase-separated films is more diffused when compared to well-mixed films. This study offers solutions to several color-based application in paints and coatings industry.

NMR Investigations of Structure and Dynamics in Polymers for Energy Storage Applications

NASA Astrophysics Data System (ADS)

Greenbaum, Steven

Materials innovation is needed to realize major progress in energy storage capacity for lithium batteries and capacitors. Polymers hold considerable promise as ion conducting media in batteries and electrochemical capacitors and as dielectrics in thin film capacitors. Structural studies of materials utilized in lithium battery technology are hampered by the lack of long-range order found in well-defined crystalline phases. Powder x-ray diffraction yields structural parameters that have been averaged over hundreds of lattice sites, and is unable to provide structural information about amorphous phases. Our laboratory uses solid state nuclear magnetic resonance (NMR) methods to investigate structural and chemical aspects of lithium ion cathodes, anodes, electrolytes, interfaces and interphases. NMR is element- (nuclear-) specific and sensitive to small variations in the immediate environment of the ions being probed, for example Li+, and in most cases is a reliably quantitative spectroscopy in that the integrated intensity of a particular spectral component is directly proportional to the number of nuclei in the corresponding material phase. NMR is also a powerful tool for probing ionic and molecular motion in lithium battery electrolytes with a dynamic range spanning some ten orders of magnitude through spin-lattice relaxation and self-diffusion measurements. Broadband relaxometry based on Fast Field Cycling NMR (FFCNMR) methods can span three to four of these orders of magnitude in a single set of measurements. Results of several recent NMR investigations performed on our lab will be presented. We explore the ion transport mechanism in polyether-based and lithium polymer electrolytes and those based on other base polymers, in particular, the extent to which ionic motion is coupled to polymer segmental motion. Polycarbonates are being considered as a possible replacement for polypropylene in high power thin film capacitors due to their favorable dielectric properties. We investigate the effects of incorporation of two types of additives in the polymer film on the ring-flip motions corresponding to the γ relaxation: (i) high dielectric constant ceramic particles; (ii) polar organic diluent molecules, The low frequency realm of broadband relaxometry allows meaningful comparison with dielectric relaxation studies of these samples performed by collaborators. Work Supported in part by the U.S. Office of Naval Research.

Self-assembly Columnar Structure in Active Layer of Bulk Heterojunction Solar Cell

NASA Astrophysics Data System (ADS)

Pan, Cheng; Segui, Jennifer; Yu, Yingjie; Li, Hongfei; Akgun, Bulent; Satijia, Sushil. K.; Gersappe, Dilip; Nam, Chang-Yong; Rafailovich, Miriam

2012-02-01

Bulk Heterojunction (BHJ) polymer solar cells are an area of intense interest due to their flexibility and relatively low cost. However, due to the disordered inner structure in active layer, the power conversion efficiency of BHJ solar cell is relatively low. Our research provides the method to produce ordered self-assembly columnar structure within active layer of bulk heterojunction (BHJ) solar cell by introducing polystyrene (PS) into the active layer. The blend thin film of polystyrene, poly (3-hexylthiophene-2,5-diyl) (P3HT) and [6,6]-phenyl C61 butyric acid methyl ester (PCBM) at different ratio are spin coated on substrate and annealed in vacuum oven for certain time. Atomic force microscopy (AFM) images show uniform phase segregation on the surface of polymer blend thin film and highly ordered columnar structure is then proven by etching the film with ion sputtering. TEM cross-section technology is also used to investigate the column structure. Neutron reflectometry was taken to establish the confinement of PCBM at the interface of PS and P3HT. The different morphological structures formed via phase segregation will be correlated with the performance of the PEV cells to be fabricated at the BNL-CFN.

Correlating Transport with Nanostructure and Chemical Identity in Radical Polymer Conducting Glasses

NASA Astrophysics Data System (ADS)

Boudouris, Bryan; Rostro, Lizbeth; Baradwaj, Aditya; Hay, Martha

2015-03-01

Radical polymers are an emerging class of macromolecules that are composed of non-conjugated backbones which bear stable radical groups at the pendant positions. Because of these stable radical sites, these glassy materials are able to conduct charge in the solid state through a series of oxidation-reduction (redox) reactions. Importantly, the redox-active behavior is controlled by both the local chemical environment of the radical polymer groups and by the nanoscale structure of the materials. Here, we demonstrate that proper control of the pendant group chemical functionality allows for the fabrication of transparent and conducting amorphous thin films which have solid-state hole mobility and electrical conductivity values on the same order as those seen in common conjugated, semicrystalline polymer systems [e.g., poly(3-hexylthiophene) (P3HT)]. Furthermore, we show that control of the nanostructure of the materials aids in facilitating transport in these radical polymer thin films. In turn, we implement simultaneous spectroscopic and electrical characterization measurements in order to elucidate the exact mechanism of charge transport in radical polymers. Finally, we demonstrate that, because there is ready control over the molecular properties of these materials, developing bendable and stretchable transparent conducting thin films is relatively straightforward with this unique class of organic electronic materials.

Chemical copatterning strategies using azlactone-based block copolymers

DOE PAGES

Masigol, Mohammadali; Barua, Niloy; Retterer, Scott T.; ...

2017-09-01

Interfaces can be modified with azlactone-functional polymers in order to manipulate the chemical surface reactivity. Azlactone groups are highly reactive toward amine, thiol, and alcohol nucleophiles, providing a versatile coupling chemistry for secondary surface modification. Azlactone-based surface polymers have been explored in numerous applications, including chemical and biological capture, sensing, and cell culture. These applications often require that the polymer is copatterned within a chemically or biologically inert background; however, common fabrication methods degrade azlactone groups during processing steps or result in polymer films with poorly controlled thicknesses. Here, the authors develop fabrication strategies using parylene lift-off and interface-directed assemblymore » methods to generate microscale patterns of azlactone-based block copolymer in chemically or biologically inert backgrounds. The functionality of azlactone groups was preserved during fabrication, and patterned films appeared as uniform, 80–120nm brushlike films. The authors also develop a patterning approach that uses a novel microcontact stamping method to generate cross-linked, three-dimensional structures of azlactone-based polymers with controllable, microscale thicknesses. The authors identify the benefits of each approach and expect these polymers and patterning strategies to provide a versatile toolbox for developing synthetic interfaces with tuned chemical and physical features for sensing, cell culture, or material capture applications.« less

Chemical copatterning strategies using azlactone-based block copolymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Masigol, Mohammadali; Barua, Niloy; Retterer, Scott T.

Interfaces can be modified with azlactone-functional polymers in order to manipulate the chemical surface reactivity. Azlactone groups are highly reactive toward amine, thiol, and alcohol nucleophiles, providing a versatile coupling chemistry for secondary surface modification. Azlactone-based surface polymers have been explored in numerous applications, including chemical and biological capture, sensing, and cell culture. These applications often require that the polymer is copatterned within a chemically or biologically inert background; however, common fabrication methods degrade azlactone groups during processing steps or result in polymer films with poorly controlled thicknesses. Here, the authors develop fabrication strategies using parylene lift-off and interface-directed assemblymore » methods to generate microscale patterns of azlactone-based block copolymer in chemically or biologically inert backgrounds. The functionality of azlactone groups was preserved during fabrication, and patterned films appeared as uniform, 80–120nm brushlike films. The authors also develop a patterning approach that uses a novel microcontact stamping method to generate cross-linked, three-dimensional structures of azlactone-based polymers with controllable, microscale thicknesses. The authors identify the benefits of each approach and expect these polymers and patterning strategies to provide a versatile toolbox for developing synthetic interfaces with tuned chemical and physical features for sensing, cell culture, or material capture applications.« less

Laser Fabrication of Polymer Ferroelectric Nanostructures for Nonvolatile Organic Memory Devices.

PubMed

Martínez-Tong, Daniel E; Rodríguez-Rodríguez, Álvaro; Nogales, Aurora; García-Gutiérrez, Mari-Cruz; Pérez-Murano, Francesc; Llobet, Jordi; Ezquerra, Tiberio A; Rebollar, Esther

2015-09-09

Polymer ferroelectric laser-induced periodic surface structures (LIPSS) have been prepared on ferroelectric thin films of a poly(vinylidene fluoride-trifluoroethylene) copolymer. Although this copolymer does not absorb light at the laser wavelength, LIPSS on the copolymer can be obtained by forming a bilayer with other light-absorbing polymers. The ferroelectric nature of the structured bilayer was proven by piezoresponse force microscopy measurements. Ferroelectric hysteresis was found on both the bilayer and the laser-structured bilayer. We show that it is possible to write ferroelectric information at the nanoscale. The laser-structured ferroelectric bilayer showed an increase in the information storage density of an order of magnitude, in comparison to the original bilayer.

The Evolution of Thin-Film Structure in pi-Conjugated System: Implications for Devices

DTIC Science & Technology

2015-07-09

dependent, polymer self - assembly (Chem Matls, 2015). The results provide vital insights into factors leading to organized conjugated polymer nanostructures...34Liquid Crystalline Poly(3-hexylthiophene) Solutions Revisited: Role of Time- dependent Self - Assembly ", Chemistry of Materials (2015), 27(7), 2687-2694...period (if none, report none): For the first time, we demonstrated that π-conjugated polymers self - assemble and exhibit liquid crystal ordering

Polymer blend lithography for metal films: large-area patterning with over 1 billion holes/inch(2).

PubMed

Huang, Cheng; Förste, Alexander; Walheim, Stefan; Schimmel, Thomas

2015-01-01

Polymer blend lithography (PBL) is a spin-coating-based technique that makes use of the purely lateral phase separation between two immiscible polymers to fabricate large area nanoscale patterns. In our earlier work (Huang et al. 2012), PBL was demonstrated for the fabrication of patterned self-assembled monolayers. Here, we report a new method based on the technique of polymer blend lithography that allows for the fabrication of metal island arrays or perforated metal films on the nanometer scale, the metal PBL. As the polymer blend system in this work, a mixture of polystyrene (PS) and poly(methyl methacrylate) (PMMA), dissolved in methyl ethyl ketone (MEK) is used. This system forms a purely lateral structure on the substrate at controlled humidity, which means that PS droplets are formed in a PMMA matrix, whereby both phases have direct contact both to the substrate and to the air interface. Therefore, a subsequent selective dissolution of either the PS or PMMA component leaves behind a nanostructured film which can be used as a lithographic mask. We use this lithographic mask for the fabrication of metal patterns by thermal evaporation of the metal, followed by a lift-off process. As a consequence, the resulting metal nanostructure is an exact replica of the pattern of the selectively removed polymer (either a perforated metal film or metal islands). The minimum diameter of these holes or metal islands demonstrated here is about 50 nm. Au, Pd, Cu, Cr and Al templates were fabricated in this work by metal PBL. The wavelength-selective optical transmission spectra due to the localized surface plasmonic effect of the holes in perforated Al films were investigated and compared to the respective hole diameter histograms.

Processing Solvent Dependent Morphology of Diketopyrrolopyrrole (DPP) based Low Band Gap Polymer and PCBM Blends

NASA Astrophysics Data System (ADS)

Ferdous, Sunzida; Liu, Feng; Russell, Thomas

2013-03-01

Solution processing of polymer semiconductors is widely used for fabrication of low cost organic solar cells. Recently, mixed solvent systems or additive based systems for fabricating polymer solar cells have proven to be beneficial for obtaining high performance devices with multi-length scale morphologies. To control the morphology during the processing step, one needs to understand the effect of solvent as it evaporates to form the final thin film structure. In this study, we used diketopyrrolopyrrole (DPP) based low band gap polymer and phenyl-C71-butyric acid methyl ester (PCBM) blend in a series of mixed solvent systems consisting of a good solvent for both of the active material components, as well as different solvents that are good solvents for PCBM, but poor solvents for the polymer. Different evaporation times of the poor solvents during the drying process, and different solubility of the polymer in these poor solvents as well as their interaction with the substrate play an important role in the final morphology. In-situ GIWAXS studies were performed to observe the evolution of the structure as the solvent evaporates. The final morphologies of the thin film devices were also characterized by AFM, TEM, and various x-ray scattering techniques to correlate the morphology with the obtained device performances.

Optical Anisotropy and Waveguiding in Thin Films of a Conjugated Polymer Which Exhibits Stimulated Emission.

NASA Astrophysics Data System (ADS)

Miller, E. Kirk; McGehee, Michael; Diaz-Garcia, Maria; Srikant, V.; Heeger, Alan J.

1998-03-01

We report variable angle spectroscopic ellipsometry (VASE) measurements on thin films of poly(2-butyl-5(2-ethyl-hexyl)-1,4- phenylenevinylene) (BuEH-PPV) in the spectral region below the electronic absorption edge. We find that the films are best described as uniaxially anisotropic, with the optical axis perpendicular to the plane of the film, consistent with the notion that the polymer chains lie preferentially in the plane of the film. Due to the anisotropic distribution of chromophores, the in-plane index of refraction is found to be significantly higher and more dispersive than the out-of- plane index, implying a higher effective index for transverse-electric (TE) waveguide modes than for the corresponding transverse- magnetic (TM) modes. The implications of these data for amplified spontaneous emission (ASE) experiments and in-plane laser structures are discussed.

Tape method of forming a thin layer of doped lanthanum chromite particles and of bonding such on an electrode

DOEpatents

Richards, Von L.; Singhal, Subhash C.; Pal, Uday B.

1992-01-01

A combustible polymer film, useful for application of an interconnection on an electrode is made by: (1) providing doped LaCro.sub.3 particles; (2) dispersing doped LaCrO.sub.3 particles in a solvent, to provide a dispersion; (3) screening the dispersion to provide particles in the range of from 30 micrometers to 80 micrometers; (4) admixing a fugitive polymer with the particles; (5) casting the dispersion to provide a film; (6) drying the film; and (7) stripping the film. The film can then be applied to a porous, preheated electrode top surface, and then electrochemical vapor depositing a dense skeletal LaCrO.sub.3 structure, between and around the doped LaCrO.sub.3 particles. Additional solid oxide electrolyte and fuel electrode layers can then be added to provide a fuel cell.

Tape method of forming a thin layer of doped lanthanum chromite particles and of bonding such on an electrode

DOEpatents

Richards, V.L.; Singhal, S.C.; Pal, U.B.

1992-07-21

A combustible polymer film, useful for application of an interconnection on an electrode is made by: (1) providing doped LaCro[sub 3] particles; (2) dispersing doped LaCrO[sub 3] particles in a solvent, to provide a dispersion; (3) screening the dispersion to provide particles in the range of from 30 micrometers to 80 micrometers; (4) admixing a fugitive polymer with the particles; (5) casting the dispersion to provide a film; (6) drying the film; and (7) stripping the film. The film can then be applied to a porous, preheated electrode top surface, and then a dense skeletal LaCrO[sub 3] structure is electrochemically vapor deposited between and around the doped LaCrO[sub 3] particles. Additional solid oxide electrolyte and fuel electrode layers can then be added to provide a fuel cell. 4 figs.

Effects of fluid shear stress on polyelectrolyte multilayers by neutron scattering studies

DOE PAGES

Singh, Saurabh; Junghans, Ann; Watkins, Erik; ...

2015-02-17

The structure of layer-by-layer (LbL) deposited nanofilm coatings consists of alternating polyethylenimine (PEI) and polystyrenesulfonate (PSS) films deposited on a single crystal quartz substrate. LbL-deposited nanofilms were investigated by neutron reflectomery (NR) in contact with water in the static and fluid shear stress conditions. The fluid shear stress was applied through a laminar flow of the liquid parallel to the quartz/polymer interface in a custom-built solid–liquid interface cell. The scattering length density profiles obtained from NR results of these polyelectrolyte multilayers (PEM), measured under different shear conditions, showed proportional decrease of volume fraction of water hydrating the polymers. For themore » highest shear rate applied (ca. 6800 s –1) the water volume fraction decreased by approximately 7%. The decrease of the volume fraction of water was homogeneous through the thickness of the film. Since there were not any significant changes in the total polymer thickness, it resulted in negative osmotic pressures in the film. The PEM films were compared with the behavior of thin films of thermoresponsive poly(N-isopropylacrylamide) (pNIPAM) deposited via spin-coating. The PEM and pNIPAM differ in their interactions with water molecules, and they showed opposite behaviors under the fluid shear stress. In both cases the polymer hydration was reversible upon the restoration of static conditions. Furthermore, a theoretical explanation is given to explain this difference in the effect of shear on hydration of polymeric thin films.« less

The role of ultra-fast solvent evaporation on the directed self-assembly of block polymer thin films

NASA Astrophysics Data System (ADS)

Drapes, Chloe; Nelson, G.; Grant, M.; Wong, J.; Baruth, A.

The directed self-assembly of nano-structures in block polymer thin films viasolvent vapor annealing is complicated by several factors, including evaporation rate. Solvent vapor annealing exposes a disordered film to solvent(s) in the vapor phase, increasing mobility and tuning surface energy, with the intention of producing an ordered structure. Recent theoretical predictions reveal the solvent evaporation affects the resultant nano-structuring. In a competition between phase separation and kinetic trapping during drying, faster solvent removal can enhance the propagation of a given morphology into the bulk of the thin film down to the substrate. Recent construction of a purpose-built, computer controlled solvent vapor annealing chamber provides control over forced solvent evaporation down to 15 ms. This is accomplished using pneumatically actuated nitrogen flow into and out of the chamber. Furthermore, in situ spectral reflectance, with 10 ms temporal resolution, monitors the swelling and evaporation. Presently, cylinder-forming polystyrene-block-polylactide thin films were swollen with 40% (by volume) tetrahydrofuran, followed by immediate evaporation under a variety of designed conditions. This includes various evaporation times, ranging from 15 ms to several seconds, and four unique rate trajectories, including linear, exponential, and combinations. Atomic force microscopy reveals specific surface, free and substrate, morphologies of the resultant films, dependent on specific evaporation conditions. Funded by the Clare Boothe Luce Foundation and Nebraska EPSCoR.

PLASMA POLYMER FILMS AS ADHESION PROMOTING PRIMERS FOR ALUMINUM. PART II: STRENGTH AND DURABILITY OF LAP JOINTS

EPA Science Inventory

Plasma polymerized hexamethyldisiloxane (HMDSO) films (~800 A in thickness) were deposited onto 6111-T4 aluminum substrates in radio frequency and microwave powered reactors and used as primers for structural adhesive bonding. Processing variables such as substrate pre-treatment,...

Rheological properties of PLGA film-based implants: correlation with polymer degradation and SPf66 antimalaric synthetic peptide release.

PubMed

Santoveña, A; Alvarez-Lorenzo, C; Concheiro, A; Llabrés, M; Fariña, J B

2004-02-01

This paper reports on the rheological properties of poly(D,L-lactic-co-glycolic acid) polymers (PLGA) dispersions used to form films and of the implants prepared by compression of SPf66 antimalaric peptide between several films, before application and during drug release. 25% PLGA (M(w)=48,000Da) dispersions in dichloromethane showed viscous Newtonian behaviour, being easy flowing and adaptable to the moulds. Evolution of viscoelastic properties, polymer molecular weight, and SPf66 release pattern from the implants immersed in various media was evaluated. Oscillatory shear test showed that freshly prepared implants have an elastic modulus, G', greater than the viscous modulus, G", being both practically independent of angular frequency. After 6 weeks immersion in a pH 7.4 phosphate buffer, G' and G" increased in almost one order of magnitude, despite of a significant polymer degradation. Polymer molecular weight decreased slowly during the first 10 days of immersion (a similar pattern was obtained at pHs 2 and 7.4) and then the degradation process accelerated (degradation index on day 7 equals to 0.89, and on day 14 equals to 16.5). SPf66 release profile followed a pattern similar to that of the polymer degradation index. These observations are explained in terms of changes in polymer structure and conformation that happen in the implant.

Vapor deposition routes to conformal polymer thin films

PubMed Central

Moni, Priya; Al-Obeidi, Ahmed

2017-01-01

Vapor phase syntheses, including parylene chemical vapor deposition (CVD) and initiated CVD, enable the deposition of conformal polymer thin films to benefit a diverse array of applications. This short review for nanotechnologists, including those new to vapor deposition methods, covers the basic theory in designing a conformal polymer film vapor deposition, sample preparation and imaging techniques to assess film conformality, and several applications that have benefited from vapor deposited, conformal polymer thin films. PMID:28487816

Modification of Side Chains of Conjugated Molecules and Polymers for Charge Mobility Enhancement and Sensing Functionality.

PubMed

Liu, Zitong; Zhang, Guanxin; Zhang, Deqing

2018-06-19

Organic semiconductors have received increasing attentions in recent years because of their promising applications in various optoelectronic devices. The key performance metric for organic semiconductors is charge carrier mobility, which is governed by the electronic structures of conjugated backbones and intermolecular/interchain π-π interactions and packing in both microscopic and macroscopic levels. For this reason, more efforts have been paid to the design and synthesis of conjugated frameworks for organic semiconductors with high charge mobilities. However, recent studies manifest that appropriate modifications of side chains that are linked to conjugated frameworks can improve the intermolecular/interchain packing order and boost charge mobilities. In this Account, we discuss our research results in context of modification of side chains in organic semiconductors for charge mobility enhancement. These include the following: (i) The lengths of alkyl chains in sulfur-rich thiepin-fused heteroacences can dramatically influence the intermolecular arrangements and orbital overlaps, ushering in different hole mobilities. Inversely, the lamellar stacking modes of alkyl chains in naphthalene diimide (NDI) derivatives with tetrathiafulvalene (TTF) units are affected by the structures of conjugated cores. (ii) The steric hindrances owing to the bulky branching chains can be weakened by partial replacement of the branching alkyl chains with linear ones for diketopyrrolopyrrole (DPP)-based D (donor)-A (acceptor) conjugated polymers. Such modification of side chains makes the polymer backbones more planar and thus interchain packing order and charge mobilities are improved. The incorporation of hydrophilic tri(ethylene glycol) (TEG) chains into the polymers also leads to improved interchain packing order. In particular, the polymer in which TEG side chains are distributed uniformly exhibits relatively high charge mobility without thermal annealing. (iii) The incorporation of urea groups in the side chains induces the polymer chains to pack more orderly and form large domains because of the additional H-bonding among urea groups. Accordingly, thin film mobilities of the conjugated D-A polymers with side chains entailing urea groups are largely boosted in comparison with those of polymers of the same backbones with either branching alkyl chains or branching/linear alkyl chains. (iv) The torsions of branching alkyl chains in conjugated D-A polymers can be inhibited to some extent upon incorporation of tiny amount of NMe 4 I in the thin film. As a result, the polymer thin films with NMe 4 I exhibit improved crystallinity, and charge mobilities can be boosted by more than 20 times. (v) Side chains with functional groups in the conjugated polymers can endow the thin film field-effect transistors (FETs) with sensing functionality. FETs with the conjugated polymer with -COOH groups in the side chains show sensitive, selective, and fast responses toward ammonia and amines, while FETs with the ultrathin films of the polymer containing tetra(ethylene glycol) (TEEG) in the side chains can sense alcohol vapors (in particular ethanol vapor) sensitively and selectively with fast response.

Discrimination of saturated alkanes and relevant volatile compounds via the utilization of a conceptual fluorescent sensor array based on organoboron-containing polymers.

PubMed

Qi, Yanyu; Xu, Wenjun; Kang, Rui; Ding, Nannan; Wang, Yelei; He, Gang; Fang, Yu

2018-02-21

This work reports a conceptual sensor array for the highly discriminative analysis of 20 clinically and environmentally relevant volatile small organic molecules (VSOMs), including saturated alkanes and common solvents, in the air at room temperature. For the construction of the sensor array, a four coordinated, non-planar mono-boron complex and four relevant polymers are synthesized. Based on the polymers and the use of different substrates, 8 fluorescent films have been fabricated. Integration of the film-based sensors results in the sensor array, which demonstrates unprecedented discriminating capability toward the VSOMs. Moreover, for the signal molecule of lung cancer, n -pentane, the response time is less than 1 s, the experimental detection limit is lower than 3.7 ppm, and after repeating the tests over 50 times no observable degradation was observed. The superior sensing performance is partially ascribed to the tetrahedral structure of the boron centers in the polymers as it may produce molecular channels in the films, which are a necessity for fast and reversible sensing. In addition, the polarity of the micro-channels may endow the films with additional selectivity towards the analytes. The design as demonstrated provides an effective strategy to improve the sensing performance of fluorescent films to very challenging analytes, such as saturated alkanes.

Low-temperature oxidizing plasma surface modification and composite polymer thin-film fabrication techniques for tailoring the composition and behavior of polymer surfaces

NASA Astrophysics Data System (ADS)

Tompkins, Brendan D.

This dissertation examines methods for modifying the composition and behavior of polymer material surfaces. This is accomplished using (1) low-temperature low-density oxidizing plasmas to etch and implant new functionality on polymers, and (2) plasma enhanced chemical vapor deposition (PECVD) techniques to fabricate composite polymer materials. Emphases are placed on the structure of modified polymer surfaces, the evolution of polymer surfaces after treatment, and the species responsible for modifying polymers during plasma processing. H2O vapor plasma modification of high-density polyethylene (HDPE), low-density polyethylene (LDPE), polypropylene (PP), polystyrene (PS), polycarbonate (PC), and 75A polyurethane (PU) was examined to further our understanding of polymer surface reorganization leading to hydrophobic recovery. Water contact angles (wCA) measurements showed that PP and PS were the most susceptible to hydrophobic recovery, while PC and HDPE were the most stable. X-ray photoelectron spectroscopy (XPS) revealed a significant quantity of polar functional groups on the surface of all treated polymer samples. Shifts in the C1s binding energies (BE) with sample age were measured on PP and PS, revealing that surface reorganization was responsible for hydrophobic recovery on these materials. Differential scanning calorimetry (DSC) was used to rule out the intrinsic thermal properties as the cause of reorganization and hydrophobic recovery on HDPE, LDPE, and PP. The different contributions that polymer cross-linking and chain scission mechanisms make to polymer aging effects are considered. The H2O plasma treatment technique was extended to the modification of 0.2 microm and 3.0 microm track-etched polycarbonate (PC-TE) and track-etched polyethylene terephthalate (PET-TE) membranes with the goal of permanently increasing the hydrophilicity of the membrane surfaces. Contact angle measurements on freshly treated and aged samples confirmed the wettability of the membrane surfaces was significantly improved by plasma treatment. XPS and SEM analyses revealed increased oxygen incorporation onto the surface of the membranes, without any damage to the surface or pore structure. Contact angle measurements on a membrane treated in a stacked assembly suggest the plasma effectively modified the entire pore cross section. Plasma treatment also increased water flux through the membranes, with results from plasma modified membranes matching those from commercially available hydrophilic membranes (treated with wetting agent). Mechanisms for the observed modification are discussed in terms of OH and O radicals implanting oxygen functionality into the polymers. Oxidizing plasma systems (O2, CO2, H2O vapor, and formic acid vapor) were used to modify track-etched polycarbonate membranes and explore the mechanisms and species responsible for etching polycarbonate during plasma processing. Etch rates were measured using scanning electron microscopy; modified polycarbonate surfaces were further characterized using x-ray photoelectron spectroscopy and water contact angles. Etch rates and surface characterization results were combined with optical emission spectroscopy data used to identify gas-phase species and their relative densities. Although the oxide functionalities implanted by each plasma system were similar, the H2O vapor and formic acid vapor plasmas yielded the lowest contact angles after treatment. The CO2, H2O vapor, and formic acid vapor plasma-modified surfaces were, however, found to be similarly stable one month after treatment. Overall, etch rate correlated directly to the relative gas-phase density of atomic oxygen and, to a lesser extent, hydroxyl radicals. PECVD of acetic acid vapor (CH3COOH) was used to deposit films on PC-TE and silicon wafer substrates. The CH3COOH films were characterized using XPS, wCA, and SEM. This modification technique resulted in continuous deposition and self-limiting deposition of a-CxO yHz films on Si wafers and PC-TE, respectively. The self-limiting deposition on PC-TE revealed that resulting films have minimal impact on 3D PC structures. This technique would allow for more precise fabrication of patterned or nano-textured PC. PECVD is used to synthesize hydrocarbon/fluorocarbon thin films with compositional gradients by continuously changing the ratio of gases in a C 3F8/H2 plasma. The films are characterized using variable angle spectroscopic ellipsometry (VASE), Fourier transform infrared spectroscopy (FTIR), XPS, wCA, and SEM. These methods revealed that shifting spectroscopic signals can be used to characterize organization in the deposited film. Using these methods, along with gas-phase diagnostics, film chemistry and the underlying deposition mechanisms are elucidated, leading to a model that accurately predicts film thickness.

Langmuir Films of Flexible Polymers Transferred to Aqueous/Liquid Crystal Interfaces Induce Uniform Azimuthal Alignment of the Liquid Crystal

PubMed Central

Kinsinger, Michael I.; Buck, Maren E.; Meli, Maria-Victoria; Abbott, Nicholas L.; Lynn, David M.

2009-01-01

We reported recently that amphiphilic polymers can be assembled at interfaces created between aqueous phases and thermotropic liquid crystals (LCs) in ways that (i) couple the organization of the polymer to the order of the LC and (ii) respond to changes in the properties of aqueous phases that can be characterized as changes in the optical appearance of the LC. This investigation sought to characterize the behavior of aqueous-LC interfaces decorated with uniaxially compressed thin films of polymers transferred by Langmuir-Schaefer (LS) transfer. Here, we report physicochemical characterization of interfaces created between aqueous phases and the thermotropic LC 4-cyano-4’-pentylbiphenyl (5CB) decorated with Langmuir films of a novel amphiphilic polymer (polymer 1), synthesized by the addition of hydrophobic and hydrophilic side chains to poly(2-vinyl-4,4’-dimethylazlactone). Initial characterization of this system resulted in the unexpected observation of uniform azimuthal alignment of 5CB after LS transfer of the polymer films to aqueous-5CB interfaces. This paper describes characterization of Langmuir films of polymer 1 hosted at aqueous-5CB interfaces as well as the results of our investigations into the origins of the uniform ordering of the LC observed upon LS transfer. Our results, when combined, support the conclusion that uniform azimuthal alignment of 5CB is the result of long-range ordering of polymer chains in the Langmuir films (in a preferred direction orthogonal to the direction of compression) that is generated during uniaxial compression of the films prior to LS transfer. Although past studies of Langmuir films of polymers at aqueous-air interfaces have demonstrated that in-plane alignment of polymer backbones can be induced by uniaxial compression, these past reports have generally made use of polymers with rigid backbones. One important outcome of this current study is thus the observation of anisotropy and long-range order in Langmuir films of a novel flexible polymer. A second important outcome is the observation that the existence, extent, and dynamics of this order can be identified and characterized optically by transfer of the Langmuir film to a thin film of LC. Additional characterization of Langmuir films of two other flexible polymers [poly(methyl methacrylate) and poly(vinyl stearate)] using this method also resulted in uniform azimuthal alignment of 5CB, suggesting that the generation of long-range order in uniaxially compressed Langmuir films of polymers may also occur more generally over a broader range of polymers with flexible backbones. PMID:19836025

Extremely fast and highly selective detection of nitroaromatic explosive vapours using fluorescent polymer thin films.

PubMed

Demirel, Gokcen Birlik; Daglar, Bihter; Bayindir, Mehmet

2013-07-14

A novel sensing material based on pyrene doped polyethersulfone worm-like structured thin film is developed using a facile technique for detection of nitroaromatic explosive vapours. The formation of π-π stacking in the thin fluorescent film allows a highly sensitive fluorescence quenching which is detectable by the naked eye in a response time of a few seconds.

Fluorinated bottlebrush polymers based on poly(trifluoroethyl methacrylate): Synthesis and characterizations

DOE PAGES

Xu, Yuewen; Wang, Weiyu; Wang, Yangyang; ...

2015-11-25

Bottlebrush polymers are densely grafted polymers with long side-chains attached to a linear polymeric backbone. Their unusual structures endow them with a number of unique and potentially useful properties in solution, in thin films, and in bulk. Despite the many studies of bottlebrushes that have been reported, the structure–property relationships for this class of materials are still poorly understood. In this contribution, we report the synthesis and characterization of fluorinated bottlebrush polymers based on poly(2,2,2-trifluoroethyl methacrylate). The synthesis was achieved by atom transfer radical polymerization (ATRP) using an α-bromoisobutyryl bromide functionalized norbornene initiator, followed by ring-opening metathesis polymerization (ROMP) usingmore » a third generation Grubbs’ catalyst (G3). Rheological characterization revealed that the bottlebrush polymer backbones remained unentangled as indicated by the lack of a rubbery plateau in the modulus. By tuning the size of the backbone of the bottlebrush polymers, near-spherical and elongated particles representing single brush molecular morphologies were observed in a good solvent as evidenced by TEM imaging, suggesting a semi-flexible nature of their backbones in dilute solutions. Thin films of bottlebrush polymers exhibited noticeably higher static water contact angles as compared to that of the macromonomer reaching the hydrophobic regime, where little differences were observed between each bottlebrush polymer. Further investigation by AFM revealed that the surface of the macromonomer film was relatively smooth; in contrast, the surface of bottlebrush polymers displayed certain degrees of nano-scale roughness (R q = 0.8–2.4 nm). The enhanced hydrophobicity of these bottlebrushes likely results from the preferential enrichment of the fluorine containing end groups at the periphery of the molecules and the film surface due to the side chain crowding effect. Furthermore, our results provide key information towards the design of architecturally tailored fluorinated polymers with desirable properties.« less

Gold coatings on polymer laser induced periodic surface structures: assessment as substrates for surface-enhanced Raman scattering.

PubMed

Rebollar, Esther; Sanz, Mikel; Pérez, Susana; Hernández, Margarita; Martín-Fabiani, Ignacio; Rueda, Daniel R; Ezquerra, Tiberio A; Domingo, Concepción; Castillejo, Marta

2012-12-05

We report on the fabrication of gold coated nanostructured polymer thin films and on their characterization as substrates for surface enhanced Raman spectroscopy (SERS). Laser induced periodic surface structures (LIPSS) were obtained on thin polymer films of poly(trimethylene terephthalate) (PTT) upon laser irradiation with the fourth harmonic of a Nd:YAG laser (266 nm, pulse duration 6 ns) resulting in a period close to the incident wavelength. The nanostructured polymer substrates were coated with a nanoparticle assembled gold layer by pulsed laser deposition using the fifth harmonic of a Nd:YAG laser (213 nm, pulse duration 15 ns). Different deposition times resulted in thicknesses from a few nanometres up to several tens of nanometres. Analysis by atomic force microscopy and grazing incident small angle X-ray scattering showed that gold coating preserved the LIPSS relief. The capabilities of the produced nanostructures as substrates for SERS have been investigated using benzenethiol as a test molecule. The SERS signal is substantially larger than that observed for a gold-coated flat substrate. Advantages of this new type of SERS substrates are discussed.

The role of regioregularity, crystallinity, and chain orientation on electron transport in a high-mobility n-type copolymer.

PubMed

Steyrleuthner, Robert; Di Pietro, Riccardo; Collins, Brian A; Polzer, Frank; Himmelberger, Scott; Schubert, Marcel; Chen, Zhihua; Zhang, Shiming; Salleo, Alberto; Ade, Harald; Facchetti, Antonio; Neher, Dieter

2014-03-19

We investigated the correlation between the polymer backbone structural regularity and the charge transport properties of poly{[N,N'-bis(2-octyldodecyl)-1,4,5,8-naphthalenediimide-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} [P(NDI2OD-T2)], a widely studied semiconducting polymer exhibiting high electron mobility and an unconventional micromorphology. To understand the influence of the chemical structure and crystal packing of conventional regioregular P(NDI2OD-T2) [RR-P(NDI2OD-T2)] on the charge transport, the corresponding regioirregular polymer RI-P(NDI2OD-T2) was synthesized. By combining optical, X-ray, and transmission electron microscopy data, we quantitatively characterized the aggregation, crystallization, and backbone orientation of all of the polymer films, which were then correlated to the electron mobilities in electron-only diodes. By carefully selecting the preparation conditions, we were able to obtain RR-P(NDI2OD-T2) films with similar crystalline structure along the three crystallographic axes but with different orientations of the polymer chains with respect to the substrate surface. RI-P(NDI2OD-T2), though exhibiting a rather similar LUMO structure and energy compared with the regioregular counterpart, displayed a very different packing structure characterized by the formation of ordered stacks along the lamellar direction without detectible π-stacking. Vertical electron mobilities were extracted from the space-charge-limited currents in unipolar devices. We demonstrate the anisotropy of the charge transport along the different crystallographic directions and how the mobility depends on π-stacking but is insensitive to the degree or coherence of lamellar stacking. The comparison between the regioregular and regioirregular polymers also shows how the use of large planar functional groups leads to improved charge transport, with mobilities that are less affected by chemical and structural disorder with respect to classic semicrystalline polymers such as poly(3-hexylthiophene).

Microcontact printing for patterning carbon nanotube/polymer composite films with electrical conductivity.

PubMed

Ogihara, Hitoshi; Kibayashi, Hiro; Saji, Tetsuo

2012-09-26

Patterned carbon nanotube (CNT)/acrylic resin composite films were prepared using microcontact printing (μCP). To prepare ink for μCP, CNTs were dispersed into propylene glycol monomethyl ether acetate (PGMEA) solution in which acrylic resin and a commercially available dispersant (Disperbyk-2001) dissolved. The resulting ink were spin-coated onto poly(dimethylsiloxane) (PDMS) stamps. By drying solvent components from the ink, CNT/polymer composite films were prepared over PDMS stamps. Contact between the stamps and glass substrates provided CNT/polymer composite patternings on the substrates. The transfer behavior of the CNT/polymer composite films depended on the thermal-treatment temperature during μCP; thermal treatment at temperatures near the glass-transition temperature (T(g)) of the acrylic resin was effective to form uniform patternings on substrates. Moreover, contact area between polymer and substrates also affect the transfer behavior. The CNT/polymer composite films showed high electrical conductivity, despite the nonconductivity of polymer components, because CNTs in the films were interconnected. The electrical conductivity of the composite films increased as CNT content in the film became higher; as a result, the composite patternings showed almost as high electrical conductivity as previously reported CNT/polymer bulk composites.

Impact of the titania nanostructure on charge transport and its application in hybrid solar cells

NASA Astrophysics Data System (ADS)

Koffman-Frischknecht, Alejandro; Gonzalez, Fernando; Plá, Juan; Violi, Ianina; Soler-Illia, Galo J. A. A.; Perez, M. Dolores

2018-02-01

Porous titania films are widely studied in a number of optoelectronic applications due to its favorable optical and electronic characteristics. Mesoporous titania thin films (MTTFs) with tunable pore size, pore order, accessibility and crystallinity are of interest in electronic devices due to the potential for optimization of the desired characteristics for charge separation and carrier transport. In this work, several MTTFs were prepared by sol-gel chemistry with different structural properties tuned by post-synthesis thermal treatment. The effect of the structural properties (pore diameter, order and accessibility) on the electrical properties of the material was studied by films fabrication onto a transparent conducting electrode, ITO, such that it enables optoelectronic applications. The performance as photoanode was explored by the fabrication of hybrid polymer (P3HT): titania solar cells. Not only does structural properties affect polymer impregnation inside the titania pores as expected and hence impacts charge separation at the interface, but also the thermal treatment affects crystallinity and the films electronic properties. A more complete picture about the electronic properties of the different MTTFs prepared in this work was studied by mobility measurement by space charge limited current and impedance spectroscopy.

Novel adhesive properties of poly(ethylene-oxide) adsorbed nanolayers

NASA Astrophysics Data System (ADS)

Zeng, Wenduo

Solid-polymer interfaces play crucial roles in the multidisciplinary field of nanotechnology and are the confluence of physics, chemistry, biology, and engineering. There is now growing evidence that polymer chains irreversibly adsorb even onto weakly attractive solid surfaces, forming a nanometer-thick adsorbed polymer layer ("adsorbed polymer nanolayers"). It has also been reported that the adsorbed layers greatly impact on local structures and properties of supported polymer thin films. In this thesis, I aim to clarify adhesive and tribological properties of adsorbed poly(ethylene-oxide) (PEO) nanolayers onto silicon (Si) substrates, which remain unsolved so far. The adsorbed nanolayers were prepared by the established protocol: one has to equilibrate the melt or dense solution against a solid surface; the unadsorbed chains can be then removed by a good solvent, while the adsorbed chains are assumed to maintain the same conformation due to the irreversible freezing through many physical solid-segment contacts. I firstly characterized the formation process and the surface/film structures of the adsorbed nanolayers by using X-ray reflectivity, grazing incidence X-ray diffraction, and atomic force microscopy. Secondly, to compare the surface energy of the adsorbed layers with the bulk, static contact angle measurements with two liquids (water and glycerol) were carried out using a optical contact angle meter equipped with a video camera. Thirdly, I designed and constructed a custom-built adhesion-testing device to quantify the adhesive property. The experimental results provide new insight into the microscopic structure - macroscopic property relationship at the solid-polymer interface.

Solvent-vapor-assisted dewetting of prepatterned thin polymer films: control of morphology, order, and pattern miniaturization.

PubMed

Bhandaru, Nandini; Goohpattader, Partho Sarathi; Faruqui, Danish; Mukherjee, Rabibrata; Sharma, Ashutosh

2015-03-17

Ultrathin (<100 nm) unstable polymer films exposed to a solvent vapor dewet by the growth of surface instability, the wavelength (λ) of which depends on the film thickness (h(f)). While the dewetting of a flat polymer thin film results in random structures, we show that the dewetting of a prepatterned film results in myriad ordered mesoscale morphologies under specific conditions. Such a film undergoes rupture over the thinnest parts when the initial local thickness of these zones (h(rm)) is lower than a limiting thickness h(lim) ≈ 10 nm. Additionally, the width of the pattern grooves (l(s)) must be wider than λ(s) corresponding to a flat film having a thickness of h(rm) for pattern-directed dewetting to take place over surface-tension-induced flattening. We first present an experimentally obtained morphology phase diagram that captures the conditions where a transition from surface-tension-induced flattening to pattern-directed-rupture takes place. Subsequently, we show the versatility of this technique in achieving a variety of aligned mesopatterns starting from a prepatterned film with simple grating geometry. The morphology of the evolving patterns depends on several parameters such as the initial film thickness (h(f)), prepattern amplitude (h(st)), duration of solvent vapor exposure (SVE), and wettability of the stamp used for patterning. Periodic rupture of the film at regular intervals imposes directionality on the evolving patterns, resulting in isolated long threads/cylindrical ridges of polymers, which subsequently disintegrate into an aligned array of droplets due to Rayleigh-Plateau instability under specific conditions. Other patterns such as a double periodic array of droplets and an array of holes are also possible to obtain. The evolution can be interrupted at any intermediate stage by terminating the solvent vapor annealing, allowing the creation of pattern morphology on demand. The created patterns are significantly miniaturized in size as compared to features obtained from dewetting a flat film with the same hf.

Confinement and the Glass Transition Temperature in Supported Polymer Films: Molecular Weight, Repeat Unit Modification, and Cooperativity Length Scale Investigations

NASA Astrophysics Data System (ADS)

Mundra, Manish K.

2005-03-01

It is well known that the glass transition temperatures, Tgs, of supported polystyrene (PS) films decrease dramatically with decreasing film thickness below 60-80 nm. However, a detailed understanding of the cause of this effect is lacking. We have investigated the impact of several parameters, including polymer molecular weight (MW), repeat unit structure, and the length scale of cooperatively rearranging regions in bulk. There is no significant effect of PS MW on the Tg-confinement effect over a range of 5,000 to 3,000,000 g/mol. In contrast, the strength of the Tg reduction and the onset of the confinement effect increase dramatically upon changing the polymer from PS to poly(4-tert-butylstyrene) (PTBS), with PTBS exhibiting a Tg reduction relative to bulk at a thickness of 300-400 nm. PTBS also shows a Tg reduction relative to bulk of 47 K in a 21-nm-thick film, more than twice that observed in a PS film of identical thickness. Characterization of the length scale of cooperatively rearranging regions has been done by differential scanning calorimetry but reveals at best a limited correlation with the confinement effect.

Free-Standing Conducting Polymer Films for High-Performance Energy Devices.

PubMed

Li, Zaifang; Ma, Guoqiang; Ge, Ru; Qin, Fei; Dong, Xinyun; Meng, Wei; Liu, Tiefeng; Tong, Jinhui; Jiang, Fangyuan; Zhou, Yifeng; Li, Ke; Min, Xue; Huo, Kaifu; Zhou, Yinhua

2016-01-18

Thick, uniform, easily processed, highly conductive polymer films are desirable as electrodes for solar cells as well as polymer capacitors. Here, a novel scalable strategy is developed to prepare highly conductive thick poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (HCT-PEDOT:PSS) films with layered structure that display a conductivity of 1400 S cm(-1) and a low sheet resistance of 0.59 ohm sq(-1). Organic solar cells with laminated HCT-PEDOT:PSS exhibit a performance comparable to the reference devices with vacuum-deposited Ag top electrodes. More importantly, the HCT-PEDOT:PSS film delivers a specific capacitance of 120 F g(-1) at a current density of 0.4 A g(-1). All-solid-state flexible symmetric supercapacitors with the HCT-PEDOT:PSS films display a high volumetric energy density of 6.80 mWh cm(-3) at a power density of 100 mW cm(-3) and 3.15 mWh cm(-3) at a very high power density of 16160 mW cm(-3) that outperforms previous reported solid-state supercapacitors based on PEDOT materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Manufacturing and application of a fully polymeric electrophoresis chip with integrated polyaniline electrodes.

PubMed

Henderson, Rowan D; Guijt, Rosanne M; Haddad, Paul R; Hilder, Emily F; Lewis, Trevor W; Breadmore, Michael C

2010-07-21

This work describes the development of a fully polymeric microchip with integrated polymeric electrodes suitable for performing microchip electrophoresis. The polymer electrodes were fabricated in a thin film of the conducting polymer, polyaniline (PANI), by flash lithography using a studio camera flash and a transparency mask. During flash welding, exposed regions welded into non-conducting regions forming a conducting polymer circuit in the non-exposed regions. Using a structured layer of dry film photoresist for sealing, a polydimethylsiloxane (PDMS) substrate containing channels and reservoirs was bound to the PANI film to form an integrated microfluidic device. The conducting regions of the PANI film were shown to be capable of carrying the high voltages of up to 2000 V required for chip electrophoresis, and were stable for up to 30 minutes under these conditions. The PANI electrodes were used for the electrophoretic separation of three sugars labelled with 8-amino-1,3,6-pyrenetrisulfonic acid (APTS) in the dry film resist-PDMS hybrid device. Highly efficient separations comparable to those achieved in similar microchips using platinum electrodes confirm the potential of polyaniline as a new material suitable for high voltage electrodes in Lab-on-a-chip devices.

Expandable and retractable self-rolled structures based on metal/polymer thin film for flow sensing

NASA Astrophysics Data System (ADS)

Zhu, Jianzhong; White, Carl; Saadat, Mehdi; Bart-Smith, Hilary

2015-11-01

Most aquatic animals such as fish rely heavily on their ability of detect and respond to ambient flows in order to explore and inhabit various habitats or survive predator-prey encounters. Fish utilize neuromasts in their skin surface and lateral lines in their bodies to align themselves while swimming upstream for migration, avoid obstacles, reduce locomotion cost, and detect flow variations caused by potential predators. In this study, a thin film MEMS sensor analogous to a fish neuromast has been designed for flow sensing. Residual stress arises in many thin film materials during processing. Metal and polymer thin film materials with a significant difference in elastic modular were chosen to form a multiple-layer structure. Upon releasing, the structure rolls into a tube due to mechanical property mismatch. The self-rolled tube can expand or retract, depending on the existence of external force such as flow. An embedded strain sensor detects the deformation of the tube and hence senses the ambient flow. Numerical simulations were conducted to optimize the structural design. Experiments were performed in a flow tank to quantify the performance of the sensor. This research is supported by the Office of Naval Research under the MURI Grant N00014-14-1-0533.

Directed ordering of phase separated domains and dewetting of thin polymer blend films on a topographically patterned substrate.

PubMed

Bhandaru, Nandini; Karim, Alamgir; Mukherjee, Rabibrata

2017-07-21

Substrate pattern guided self-organization of ultrathin and confined polymeric films on a topographically patterned substrate is a useful approach for obtaining ordered meso and nano structures over large areas, particularly if the ordering is achieved during film preparation itself, eliminating any post-processing such as thermal or solvent vapor annealing. By casting a dilute solution of two immiscible polymers, polystyrene (PS) and polymethylmethacrylate (PMMA), from a common solvent (toluene) on a topographically patterned substrate with a grating geometry, we show the formation of self-organized meso patterns with various degrees of ordering. The morphology depends on both the concentration of the dispensed solution (C n ) and the blend composition (R B ). Depending on the extent of dewetting during spin coating, the final morphologies can be classified into three distinct categories. At a very low C n the solution dewets fully, resulting in isolated polymer droplets aligned along substrate grooves (Type 1). Type 2 structures comprising isolated threads with aligned phase separated domains along each substrate groove are observed at intermediate C n . A continuous film (Type 3) is obtained above a critical concentration (C n *) that depends on R B . While the extent of ordering of the domains gradually diminishes with an increase in film thickness for Type 3 patterns, the size of the domains remains much smaller than that on a flat substrate, resulting in significant downsizing of the features due to the lateral confinement imposed on the phase separation process by the topographic patterns. Finally, we show that some of these structures exhibit excellent broadband anti-reflection (AR) properties.

Infrared-spectroscopic single-shot laser mapping ellipsometry: Proof of concept for fast investigations of structured surfaces and interactions in organic thin films

NASA Astrophysics Data System (ADS)

Furchner, Andreas; Kratz, Christoph; Gkogkou, Dimitra; Ketelsen, Helge; Hinrichs, Karsten

2017-11-01

We present a novel infrared-spectroscopic laser mapping ellipsometer based on a single-shot measurement concept. The ellipsometric set-up employs multiple analyzers and detectors to simultaneously measure the sample's optical response under different analyzer azimuths. An essential component is a broadly tunable quantum cascade laser (QCL) covering the important marker region of 1800-1540 cm-1. The ellipsometer allows for fast single-wavelength as well as spectroscopic studies with thin-film sensitivity at temporal resolutions of 60 ms per wavelength. We applied the single-shot mapping ellipsometer for the characterization of metal-island enhancement surfaces as well as of molecular interactions in organic thin films. In less than 3 min, a linescan with 1600 steps revealed profile and infrared-enhancement properties of a gradient gold-island film for sensing applications. Spectroscopic measurements were performed to probe the amide I band of thin films of poly(N-isopropylacrylamide) [PNIPAAm], a stimuli-responsive polymer for bioapplications. The QCL spectra agree well with conventional FT-IR ellipsometric results, showing different band components associated with hydrogen-bond interactions between polymer and adsorbed water. Multi-wavelength ellipsometric maps were used to analyze homogeneity and surface contaminations of the polymer films.

Ultrasonic-assisted synthesis of polyvinyl alcohol/phytic acid polymer film and its thermal stability, mechanical properties and surface resistivity.

PubMed

Li, Jihui; Li, Yongshen; Song, Yunna; Niu, Shuai; Li, Ning

2017-11-01

In this paper, polyvinyl alcohol/phytic acid polymer (PVA/PA polymer) was synthesized through esterification reaction of PVA and PA in the case of acidity and ultrasound irradiation and characterized, and PVA/PA polymer film was prepared by PVA/PA polymer and characterized, and the influence of dosage of PA on the thermal stability, mechanical properties and surface resistivity of PVA/PA polymer film were researched, and the influence of sonication time on the mechanical properties of PVA/PA polymer film was investigated. Based on those, it was concluded that the hydroxyl group on the chain of PVA and the phosphonic group on PA were connected together in the form of phosphonate bond, and the hydroxyl group on the chain of PVA were connected together in the form of ether bond after the intermolecular dehydration; in the meantime, it was also confirmed that PVA/PA polymer film prepared from 1.20mL of PA not only had the high thermal stability and favorable ductility but also the low surface resistivity in comparison with PVA/PA polymer film with 0.00mL of PA, and the ductility of PVA/PA polymer film was very sensitive to the sonication time. Copyright © 2017. Published by Elsevier B.V.

Radiation effects on ETFE polymer exposed to glow discharge

NASA Astrophysics Data System (ADS)

Minamisawa, Renato Amaral; Abidzina, Volha; de Almeida, Adelaide; Budak, Satilmis; Tereshko, I.; Elkin, I.; Ila, Daryush

2007-08-01

The polymer ethylenetetrafluoroethylene (ETFE) is composed of alternating ethylene and tetrafluoroethylene segments. Because it has applications in areas such as medical physics and industrial coatings, there is a great interest in surface modification studies of ETFE polymer. When this material is exposed to ionizing radiation it suffers damage that depends on the type, energy and intensity of the irradiation. In order to determine the radiation damage mechanism from exposure to low voltage plasma, ETFE films were exposed to residual gas plasma in glow discharge regime to a fluence of 2 × 1017 ions/cm2. Irradiated films were analyzed with optical absorption photospectrometry, Fourier transform infrared (FTIR) and Raman spectroscopy to determine the chemical nature of the structural changes caused by low energy glow discharge.

Localized entrapment of green fluorescent protein within nanostructured polymer films

NASA Astrophysics Data System (ADS)

Ankner, John; Kozlovskaya, Veronika; O'Neill, Hugh; Zhang, Qiu; Kharlampieva, Eugenia

2012-02-01

Protein entrapment within ultrathin polymer films is of interest for applications in biosensing, drug delivery, and bioconversion, but controlling protein distribution within the films is difficult. We report on nanostructured protein/polyelectrolyte (PE) materials obtained through incorporation of green fluorescent protein (GFP) within poly(styrene sulfonate)/poly(allylamine hydrochloride) multilayer films assembled via the spin-assisted layer-by-layer method. By using deuterated GFP as a marker for neutron scattering contrast we have inferred the architecture of the films in both normal and lateral directions. We find that films assembled with a single GFP layer exhibit a strong localization of the GFP without intermixing into the PE matrix. The GFP volume fraction approaches the monolayer density of close-packed randomly oriented GFP molecules. However, intermixing of the GFP with the PE matrix occurs in multiple-GFP layer films. Our results yield new insight into the organization of immobilized proteins within polyelectrolyte matrices and open opportunities for fabrication of protein-containing films with well-organized structure and controllable function, a crucial requirement for advanced sensing applications.

Preparation of polystyrene brush film by radical chain-transfer polymerization and micromechanical properties

NASA Astrophysics Data System (ADS)

Zhao, Jing; Chen, Miao; An, Yanqing; Liu, Jianxi; Yan, Fengyuan

2008-12-01

A radical chain-transfer polymerization technique has been applied to graft-polymerize brushes of polystyrene (PSt) on single-crystal silicon substrates. 3-Mercapto-propyltrimethoxysilane (MPTMS), as a chain-transfer agent for grafting, was immobilized on the silicon surface by a self-assembling process. The structure and morphology of the graft-functionalized silicon surfaces were characterized by the means of contact-angle measurement, ellipsometric thickness measurement, Fourier transformation infrared (FTIR) spectroscopy, and atomic force microscopy (AFM). The nanotribological and micromechanical properties of the as-prepared polymer brush films were investigated by frictional force microscopy (FFM), force-volume analysis and scratch test. The results indicate that the friction properties of the grafted polymer films can be improved significantly by the treatment of toluene, and the chemically bonded polystyrene film exhibits superior scratch resistance behavior compared with the spin-coated polystyrene film. The resultant polystyrene brush film is expected to develop as a potential lubrication coating for microelectromechanical systems (MEMS).

Assessment of femtosecond laser induced periodic surface structures on polymer films.

PubMed

Rebollar, Esther; Vázquez de Aldana, Javier R; Martín-Fabiani, Ignacio; Hernández, Margarita; Rueda, Daniel R; Ezquerra, Tiberio A; Domingo, Concepción; Moreno, Pablo; Castillejo, Marta

2013-07-21

In this work we present the formation of laser induced periodic surface structures (LIPSS) on spin-coated thin films of several model aromatic polymers including poly(ethylene terephthalate), poly(trimethylene terephthalate) and poly carbonate bis-phenol A upon irradiation with femtosecond pulses of 795 and 265 nm at fluences well below the ablation threshold. LIPSS are formed with period lengths similar to the laser wavelength and parallel to the direction of the laser polarization vector. Formation of LIPSS upon IR irradiation at 795 nm, a wavelength at which the polymers absorb weakly, contrasts with the absence of LIPSS in this spectral range upon irradiation with nanosecond pulses. Real and reciprocal space characterization of LIPSS obtained by Atomic Force Microscopy (AFM) and Grazing Incidence Small Angle X-ray Scattering (GISAXS), respectively, yields well correlated morphological information. Comparison of experimental and simulated GISAXS patterns suggests that LIPSS can be suitably described considering a quasi-one-dimensional paracrystalline lattice and that irradiation parameters have an influence on the order of such a lattice. Fluorescence measurements, after laser irradiation, provide indirect information about dynamics and structure of the polymer at the molecular level. Our results indicate that the LIPSS are formed by interference of the incident and surface scattered waves. As a result of this process, heating of the polymer surface above its glass transition temperature takes place enabling LIPSS formation.

Transparent ITO electrode in the polymer network liquid crystal variable optical attenuator

NASA Astrophysics Data System (ADS)

Zhang, Xindong; Dong, Wei; Liu, Caixia; Chen, Yinghua; Ruan, Shengping; Zhang, Shuang; Guo, Wenbin; Yang, Dong; Han, Lin; Chen, Weiyou

2004-05-01

Indium tin oxide (ITO) films as transparent conductors have caused a great deal of interest due to their prominent electro-optical behavior. This paper describes a study of the properties of ITO thin films that are used for a new type variable optical attenuator using polymer network liquid crystal (PNLC). The mechanism of PNLC optical attenuator operation is that the light from the input fiber is scattered when no voltage is applied, and the light passes through the attenuator when sufficient voltage is applied. So the ITO thin films can provide transparent electrodes for PNLC. They were deposited under various preparation conditions using the radio-frequency (rf) magnetron sputtering technique. Here discuss the results of the structural, electrical and optical properties of the ITO films. The paper presents some experimental results obtained in laboratory.

Characterization of ethylcellulose and hydroxypropyl methylcellulose thin films deposited by matrix-assisted pulsed laser evaporation

NASA Astrophysics Data System (ADS)

Palla-Papavlu, A.; Rusen, L.; Dinca, V.; Filipescu, M.; Lippert, T.; Dinescu, M.

2014-05-01

In this study is reported the deposition of hydroxypropyl methylcellulose (HPMC) and ethylcellulose (EC) by matrix-assisted pulsed laser evaporation (MAPLE). Both HPMC and EC were deposited on silicon substrates using a Nd:YAG laser (266 nm, 5 ns laser pulse and 10 Hz repetition rate) and then characterized by atomic force microscopy and Fourier transform infrared spectroscopy. It was found that for laser fluences up to 450 mJ/cm2 the structure of the deposited HPMC and EC polymer in the thin film resembles to the bulk. Morphological investigations reveal island features on the surface of the EC thin films, and pores onto the HPMC polymer films. The obtained results indicate that MAPLE may be an alternative technique for the fabrication of new systems with desired drug release profile.

Exploring ways to control the properties of polymer thin films

NASA Astrophysics Data System (ADS)

Clough, Andrew R.

Understanding the causes of deviations from bulk-like properties observed in polymer thin films is of interest both from a fundamental standpoint and in order to tailor the properties of polymer thin films used by industry as coatings and in the production of microelectronic devices. As thicknesses are decreased below 100 nm, interfacial effects start to become important. In addition, a confinement effect occurs when the film thickness becomes comparable to the unperturbed size of the polymer chain. In this thesis, we modify polymer films in a controllable way in order to study how some of these properties may be related and potentially adjusted. One of these properties is the glass transition temperature, which is seen to vary with the film thickness for films thinner than 100 nm. While there appears to be a consensus that the variation is attributable to the interactions the polymer has with the film interfaces, important questions concerning how the observed changes may affect the onset of large scale, liquid-like motions in the films have been seldom investigated. We modify the substrate interface with grafted polymer chains, which is known to instill interfacial slippage, to investigate the relation, if any, between the glass transition temperature and large scale chain motions in the films. As another part of the effort to find ways to control the properties of polymer films, we study the effect of swelling films with solvents of different qualities. Studies have shown that modifying the solvent quality used when preparing films by spin-coating, in which solvent from a polymer solution is rapidly removed to form thin uniform films, can affect some properties by modifying the degree of inter-chain entanglement in the film. As it is often difficult to spin-coat films when the solvent is poor, we investigate whether solvent swelling can also be used to modify this entanglement. We find that solvent swelling is able to modify the degree of entanglement in the films. Most importantly, swelling with a poor solvent allows us to reduce the degree of inter-chain entanglement, bringing the film further from equilibrium.

Polymer films

DOEpatents

Granick, Steve; Sukhishvili, Svetlana A.

2004-05-25

A film contains a first polymer having a plurality of hydrogen bond donating moieties, and a second polymer having a plurality of hydrogen bond accepting moieties. The second polymer is hydrogen bonded to the first polymer.

Polymer films

DOEpatents

Granick, Steve [Champaign, IL; Sukhishvili, Svetlana A [Maplewood, NJ

2008-12-30

A film contains a first polymer having a plurality of hydrogen bond donating moieties, and a second polymer having a plurality of hydrogen bond accepting moieties. The second polymer is hydrogen bonded to the first polymer.

Three-compartment model for contaminant accumulation by semipermeable membrane devices

USGS Publications Warehouse

Gale, Robert W.

1998-01-01

Passive sampling of dissolved hydrophobic contaminants with lipid (triolein)-containing semipermeable membrane devices (SPMDs) has been gaining acceptance for environmental monitoring. Understanding of the accumulation process has employed a simple polymer film-control model of uptake by the polymer-enclosed lipid, while aqueous film control has been only briefly discussed. A more complete three-compartment model incorporating both aqueous film (turbulent-diffusive) and polymer film (diffusive) mass transfer is developed here and is fit to data from accumulation studies conducted in constant-concentration, flow-through dilutors. This model predicts aqueous film control of the whole device for moderate to high Kow compounds, rather than polymer film control. Uptake rates for phenanthrene and 2,2‘,5,5‘-tetrachlorobiphenyl were about 4.8 and 4.2 L/day/standard SPMD, respectively. Maximum 28 day SPMD concentration factors of 30 000 are predicted for solutes with log Kow values of >5.5. Effects of varying aqueous and polymer film thicknesses and solute diffusivities in the polymer film are modeled, and overall accumulation by the whole device is predicted to remain under aqueous film control, although accumulation in the triolein may be subject to polymer film control. The predicted half-life and integrative response of SPMDs to pulsed concentration events is proportional to log KSPMD.

Mapping nanoscale effects of localized noise-source activities on photoconductive charge transports in polymer-blend films.

PubMed

Shekhar, Shashank; Cho, Duckhyung; Cho, Dong-Guk; Yang, Myungjae; Hong, Seunghun

2018-05-18

We develolped a method to directly image the nanoscale effects of localized noise-source activities on photoconducting charge transports in domain structures of phase-separated polymer-blend films of Poly(9,9-di-n-octylfluorenyl-2,7-diyl) and Poly(9,9-di-n-octylfluorene-alt-benzothiadiazole). For the imaging, current and noise maps of the polymer-blend were recorded using a conducting nanoprobe in contact with the surface, enabling the conductivity (σ) and noise-source density (N T ) mappings under an external stimulus. The blend-films exhibited the phase-separation between the constituent polymers at domains level. Within a domain, high σ (low N T ) and low σ (high N T ) regions were observed, which could be associated with the ordered and disordered regions of a domain. In the N T maps, we observed that noise-sources strongly affected the conduction mechanism, resulting in a scaling behavior of σ ∝ [Formula: see text] in both ordered and disordered regions. When a blend film was under an influence of an external stimulus such as a high bias or an illumination, an increase in the σ was observed, but that also resulted in increases in the N T as a trade-off. Interestingly, the Δσ versus ΔN T plot exhibited an unusual scaling behavior of Δσ ∝ [Formula: see text] which is attributed to the de-trapping of carriers from deep traps by the external stimuli. In addition, we found that an external stimulus increased the conductivity at the interfaces without significantly increasing their N T , which can be the origin of the superior performances of polymer-blend based devices. These results provide valuable insight about the effects of noise-sources on nanoscale optoelectronic properties in polymer-blend films, which can be an important guideline for improving devices based on polymer-blend.

Mapping nanoscale effects of localized noise-source activities on photoconductive charge transports in polymer-blend films

NASA Astrophysics Data System (ADS)

Shekhar, Shashank; Cho, Duckhyung; Cho, Dong-Guk; Yang, Myungjae; Hong, Seunghun

2018-05-01

We develolped a method to directly image the nanoscale effects of localized noise-source activities on photoconducting charge transports in domain structures of phase-separated polymer-blend films of Poly(9,9-di-n-octylfluorenyl-2,7-diyl) and Poly(9,9-di-n-octylfluorene-alt-benzothiadiazole). For the imaging, current and noise maps of the polymer-blend were recorded using a conducting nanoprobe in contact with the surface, enabling the conductivity (σ) and noise-source density (N T) mappings under an external stimulus. The blend-films exhibited the phase-separation between the constituent polymers at domains level. Within a domain, high σ (low N T) and low σ (high N T) regions were observed, which could be associated with the ordered and disordered regions of a domain. In the N T maps, we observed that noise-sources strongly affected the conduction mechanism, resulting in a scaling behavior of σ ∝ {{N}{{T}}}-0.5 in both ordered and disordered regions. When a blend film was under an influence of an external stimulus such as a high bias or an illumination, an increase in the σ was observed, but that also resulted in increases in the N T as a trade-off. Interestingly, the Δσ versus ΔN T plot exhibited an unusual scaling behavior of Δσ ∝ {{Δ }}{{N}{{T}}}0.5, which is attributed to the de-trapping of carriers from deep traps by the external stimuli. In addition, we found that an external stimulus increased the conductivity at the interfaces without significantly increasing their N T, which can be the origin of the superior performances of polymer-blend based devices. These results provide valuable insight about the effects of noise-sources on nanoscale optoelectronic properties in polymer-blend films, which can be an important guideline for improving devices based on polymer-blend.

Fibronectin and bovine serum albumin adsorption and conformational dynamics on inherently conducting polymers: a QCM-D study.

PubMed

Molino, Paul J; Higgins, Michael J; Innis, Peter C; Kapsa, Robert M I; Wallace, Gordon G

2012-06-05

Quartz crystal microbalance with dissipation monitoring (QCM-D) was employed to characterize the adsorption of the model proteins, bovine serum albumin (BSA) and fibronectin (FN), to polypyrrole doped with dextran sulfate (PPy-DS) as a function of DS loading and surface roughness. BSA adsorption was greater on surfaces of increased roughness and was above what could be explained by the increase in surface area alone. Furthermore, the additional mass adsorbed on the rough films was concomitant with an increase in the rigidity of the protein layer. Analysis of the dynamic viscoelastic properties of the protein adlayer reveal BSA adsorption on the rough films occurs in two phases: (1) arrival and initial adsorption of protein to the polymer surface and (2) postadsorption molecular rearrangement to a more dehydrated and compact conformation that facilitates further recruitment of protein to the polymer interface, likely forming a multilayer. In contrast, FN adsorption was independent of surface roughness. However, films prepared from solutions containing the highest concentration of DS (20 mg/mL) demonstrated both an increase in adsorbed mass and adlayer viscoelasticity. This is attributed to the higher DS loading in the conducting polymer film resulting in presentation of a more hydrated molecular structure indicative of a more unfolded and bioactive conformation. Modulating the redox state of the PPy-DS polymers was shown to modify both the adsorbed mass and viscoelastic nature of FN adlayers. An oxidizing potential increased both the total adsorbed mass and the adlayer viscoelasticity. Our findings demonstrate that modification of polymer physicochemical and redox condition alters the nature of protein-polymer interaction, a process that may be exploited to tailor the bioactivity of protein through which interactions with cells and tissues may be controlled.

Hybrid Composites for LH2 Fuel Tank Structure

NASA Technical Reports Server (NTRS)

Grimsley, Brian W.; Cano, Roberto J.; Johnston, Norman J.; Loos, Alfred C.; McMahon, William M.

2001-01-01

The application of lightweight carbon fiber reinforced plastics (CFRP) as structure for cryogenic fuel tanks is critical to the success of the next generation of Reusable Launch Vehicles (RLV). The recent failure of the X-33 composite fuel tank occurred in part due to microcracking of the polymer matrix, which allowed cryogen to permeate through the inner skin to the honeycomb core. As part of an approach to solve these problems, NASA Langley Research Center (LaRC) and Marshall Space Flight Center (MSFC) are working to develop and investigate polymer films that will act as a barrier to the permeation of LH2 through the composite laminate. In this study two commercially available films and eleven novel LaRC films were tested in an existing cryogenics laboratory at MSFC to determine the permeance of argon at room temperature. Several of these films were introduced as a layer in the composite to form an interleaved, or hybrid, composite to determine the effects on permeability. In addition, the effects of the interleaved layer thickness, number, and location on the mechanical properties of the composite laminate were investigated. In this initial screening process, several of the films were found to exhibit lower permeability to argon than the composite panels tested.

Structural properties of atactic polystyrene adsorbed onto solid surfaces.

PubMed

Tatek, Yergou B; Tsige, Mesfin

2011-11-07

In the present work, we are studying the local conformation of chains in a thin film of polystyrene adsorbed on a solid substrate by using atomistically detailed simulations. The simulations are carried out by using the readily available and massively parallel molecular dynamics code known as LAMMPS. In particular, a special emphasis is given to the density and orientation of side chains (which consist of phenyl groups and methylene units) at solid/polymer and polymer/vacuum interfaces. Three types of substrates were used in our study: α-quartz, graphite, and amorphous silica. Our investigation was restricted to atactic polystyrene. Our results show that the density and structural properties of side chains depend on the type of surface. An excess of phenyl rings is observed near the α-quartz substrate while the film adsorbed on graphite is depleted in C(6)H(5). Moreover, the orientation of the rings and methylene units on the substrate/film interface show a strong dependence on the type of the substrate, while the rings at the film/vacuum interface show a marked tendency to point outward, away from the film. The results we obtained are in a large part in good agreement with previous experimental and simulation results.

Nonlinear Layer-by-Layer Films: Effects of Chain Diffusivity on Film Structure and Swelling

DOE PAGES

Selin, Victor; Ankner, John F.; Sukhishvili, Svetlana A.

2017-08-09

Here in this paper, we report on the role of molecular diffusivity in the formation of nonlinearly growing polyelectrolyte multilayers (nlPEMs). Electrostatically bound polyelectrolyte multilayers were assembled from poly(methacrylic acid) (PMAA) as a polyanion and quaternized poly(2-(dimethylamino)ethyl methacrylate) (QPC) as a polycation. Film growth as measured by ellipsometry was strongly dependent on the time allowed for each polymer deposition step, suggesting that the diffusivities of the components are crucial in controlling the rate of film growth. Uptake of polyelectrolytes within nlPEMs was relatively slow and occurred on time scales ranging from minutes to hours, depending on the film thickness. Spectroscopicmore » ellipsometry measurements with nlPEM films exposed to aqueous solutions exhibited high (severalfold) degrees of film swelling and different swelling values for films exposed to QPC or PMAA solutions. FTIR spectroscopy showed that the average ionization of film-assembled PMAA increased upon binding of QPC and decreased upon binding of PMAA, in agreement with the charge regulation mechanism for weak polyelectrolytes. The use of neutron reflectometry (NR) enabled quantification of chain intermixing within the film, which was drastically enhanced when longer times were allowed for polyelectrolyte deposition. Diffusion coefficients of the polycation derived from the uptake rates of deuterated chains within hydrogenated films were of the order of 10 –14 cm 2/s, i.e., 5–6 orders of magnitude smaller than those found for diffusion of free polymer chains in solution. Exchange of the polymer solutions to buffer inhibited film intermixing. Taken together, these results contribute to understanding the mechanism of the growth of nonlinear polyelectrolyte multilayers and demonstrate the possibility of controlling film intermixing, which is highly desirable for potential future applications.« less

Using in-situ polymerization of conductive polymers to enhance the electrical properties of solution-processed carbon nanotube films and fibers.

PubMed

Allen, Ranulfo; Pan, Lijia; Fuller, Gerald G; Bao, Zhenan

2014-07-09

Single-walled carbon nanotubes/polymer composites typically have limited conductivity due to a low concentration of nanotubes and the insulating nature of the polymers used. Here we combined a method to align carbon nanotubes with in-situ polymerization of conductive polymer to form composite films and fibers. Use of the conducting polymer raised the conductivity of the films by 2 orders of magnitude. On the other hand, CNT fiber formation was made possible with in-situ polymerization to provide more mechanical support to the CNTs from the formed conducting polymer. The carbon nanotube/conductive polymer composite films and fibers had conductivities of 3300 and 170 S/cm, respectively. The relatively high conductivities were attributed to the polymerization process, which doped both the SWNTs and the polymer. In-situ polymerization can be a promising solution-processable method to enhance the conductivity of carbon nanotube films and fibers.

Electrical Transfer Function and Poling Mechanisms for Nonlinear Optical Polymer Modulators

NASA Technical Reports Server (NTRS)

Watson, Michael Dale

2004-01-01

Electro-Optic Polymers hold great promise in increased electro-optic coefficients as compared to their inorganic corollaries. Many researchers have focused on quantum chemistry to describe how the dipoles respond to temperature and electric fields. Much work has also been done for single layer films to confirm these results. For optical applications, waveguide structures are utilized to guide the optical waves in 3 layer stacks. Electrode poling is the only practical poling method for these structures. This research takes an electrical engineering approach to develop poling models and electrical and optical transfer functions of the waveguide structure. The key aspect of the poling model is the large boundary charge density deposited during the poling process. The boundary charge density also has a large effect on the electrical transfer function which is used to explain the transient response of the system. These models are experimentally verified. Exploratory experiment design is used to study poling parameters including time, temperature, and voltage. These studies verify the poling conditions for CLDX/APC and CLDZ/APEC guest host electro optic polymer films in waveguide stacks predicted by the theoretical developments.

Effects of swelling on the viscoelastic properties of polyester films made from glycerol and glutaric acid

USDA-ARS?s Scientific Manuscript database

Viscoelastic properties have been determined for poly(glycerol-co-glutaric acid) films synthesized from Lewis acid-catalyzed polyesterifications. The polymers were prepared by synthesizing polymer gels that were subsequently cured at 125 degrees C to form polymer films. The polymers were evaluated ...

Conjunction of Conducting Polymer Nanostructures with Macroporous Structured Graphene Thin Films for High-Performance Flexible Supercapacitors.

PubMed

Memon, Mushtaque A; Bai, Wei; Sun, Jinhua; Imran, Muhammad; Phulpoto, Shah Nawaz; Yan, Shouke; Huang, Yong; Geng, Jianxin

2016-05-11

Fabrication of hybridized structures is an effective strategy to promote the performances of graphene-based composites for energy storage/conversion applications. In this work, macroporous structured graphene thin films (MGTFs) are fabricated on various substrates including flexible graphene papers (GPs) through an ice-crystal-induced phase separation process. The MGTFs prepared on GPs (MGTF@GPs) are recognized with remarkable features such as interconnected macroporous configuration, sufficient exfoliation of the conductive RGO sheets, and good mechanical flexibility. As such, the flexible MGTF@GPs are demonstrated as a versatile conductive platform for depositing conducting polymers (CPs), e.g., polyaniline (PAn), polypyrrole, and polythiophene, through in situ electropolymerization. The contents of the CPs in the composite films are readily controlled by varying the electropolymerization time. Notably, electrodeposition of PAn leads to the formation of nanostructures of PAn nanofibers on the walls of the macroporous structured RGO framework (PAn@MGTF@GPs): thereafter, the PAn@MGTF@GPs display a unique structural feature that combine the nanostructures of PAn nanofibers and the macroporous structures of RGO sheets. Being used as binder-free electrodes for flexible supercapacitors, the PAn@MGTF@GPs exhibit excellent electrochemical performance, in particular a high areal specific capacity (538 mF cm(-2)), high cycling stability, and remarkable capacitive stability to deformation, due to the unique electrode structures.

Structural, Thermal, Physical, Mechanical, and Barrier Properties of Chitosan Films with the Addition of Xanthan Gum.

PubMed

de Morais Lima, Maria; Carneiro, Lucia Cesar; Bianchini, Daniela; Dias, Alvaro Renato Guerra; Zavareze, Elessandra da Rosa; Prentice, Carlos; Moreira, Angelita da Silveira

2017-03-01

Films based on chitosan and xanthan gum were prepared using casting technique aiming to investigate the potential of these polymers as packaging materials. Six formulations of films were studied varying the proportion of chitosan and xanthan gum: 100:0 (chitosan:xanthan gum, w/w, C100XG0 film); 90:10 (chitosan:xanthan gum, w/w, C90XG10 film); 80:20 (chitosan:xanthan gum, w/w, C80XG20 film); 70:30 (chitosan:xanthan gum, w/w, C70XG30 film); 60:40 (chitosan:xanthan gum, w/w, C60XG40 film); and 50:50 (chitosan:xanthan gum, w/w, C50XG50 film). The total quantity of solids (chitosan and xanthan gum) in the filmogenic solution was 1.5 g per 100 mL of aqueous solution for all treatments, according to the proportion of each polymer. The films were evaluated by their functional groups, structural, thermal, morphological, physical, mechanical, and barrier properties. All films have presented endothermic peaks in the range of 122 to 175 °C and broad exothermic peaks above 200 °C, which were assigned to the melting temperature and thermal decomposition, respectively. These results demonstrated that films with xanthan gum have the highest T m and Δ m H. The films containing higher content of xanthan gum show also the highest tensile strength and the lowest elongation. Xanthan gum addition did not affect the water vapor permeability, solubility, and moisture of films. This set of data suggests the formation of chitosan-xanthan complexes in the films. © 2017 Institute of Food Technologists®.

Spray forming polymer membranes, coatings and films

DOEpatents

McHugh, Kevin M.; Watson, Lloyd D.; McAtee, Richard E.; Ploger, Scott A.

1993-01-01

A method of forming a polymer film having controlled physical and chemical characteristics, wherein a plume of nebulized droplets of a polymer or polymer precursor is directed toward a substrate from a converging/diverging nozzle having a throat at which the polymer or a precursor thereof is introduced and an exit from which the nebulized droplets of the polymer or precursor thereof leave entrained in a carrier gas. Relative movement between the nozzle and the substrate is provided to form a polymer film. Physical and chemical characteristics can be controlled by varying the deposition parameters and the gas and liquid chemistries. Semipermeable membranes of polyphosphazene films are disclosed, as are a variety of other polymer systems, both porous and non-porous.

Spray forming polymer membranes, coatings and films

DOEpatents

McHugh, K.M.; Watson, L.D.; McAtee, R.E.; Ploger, S.A.

1993-10-12

A method is described for forming a polymer film having controlled physical and chemical characteristics, wherein a plume of nebulized droplets of a polymer or polymer precursor is directed toward a substrate from a converging/diverging nozzle having a throat at which the polymer or a precursor thereof is introduced and an exit from which the nebulized droplets of the polymer or precursor thereof leave entrained in a carrier gas. Relative movement between the nozzle and the substrate is provided to form a polymer film. Physical and chemical characteristics can be controlled by varying the deposition parameters and the gas and liquid chemistries. Semipermeable membranes of polyphosphazene films are disclosed, as are a variety of other polymer systems, both porous and non-porous. 4 figures.

Enhanced energy density and thermostability in polyimide nanocomposites containing core-shell structured BaTiO3@SiO2 nanofibers

NASA Astrophysics Data System (ADS)

Wang, Junchuan; Long, Yunchen; Sun, Ying; Zhang, Xueqin; Yang, Hong; Lin, Baoping

2017-12-01

High energy density polymer nanocomposites with high-temperature resistance are quite desirable for film capacitors and many other power electronics. In this study, polyimide-based (PI) nanocomposite films containing the core-shell structured barium titanate@silicon dioxide (BT@SiO2) nanofibers have been successfully synthesized by the solution casting method. In the BT@SiO2/PI nanocomposite films, the dielectric permittivity as well as the breakdown strength increase significantly. The SiO2 shell layers with moderate dielectric permittivity could effectively mitigate the local field concentration induced by the large mismatch between the dielectric permittivity of BT and PI, which contributes to the enhancement of the breakdown strength of the PI nanocomposite films. As a result, the PI nanocomposite film filled with 3 vol% BT@SiO2 nanofibers exhibits a maximal energy density of 2.31 J cm-3 under the field of 346 kV/mm, which is 62% over the pristine PI (1.42 J cm-3 at 308 kV/mm) and about 200% greater than the best commercial polymer, i.e. biaxially oriented polypropylenes (BOPP) (≈1.2 J cm-3). The thermogravimetric analysis results indicate that the BT@SiO2/PI nanocomposite films have good thermal stability below 500 °C.

Optically transparent super-hydrophobic thin film fabricated by reusable polyurethane-acrylate (PUA) mold

NASA Astrophysics Data System (ADS)

Park, J.-S.; Park, J.-H.; Lee, D.-W.

2018-02-01

In this paper, we describe a simple manufacturing method for producing an optically transparent super-hydrophobic polymer thin film using a reusable photo-curable polymer mold. Soluble photoresist (PR) molds were prepared with under-exposed and under-baked processes, which created unique hierarchical micro/nano structures. The reverse phase of the PR mold was replicated on the surface of polydimethylsiloxane (PDMS) substrates. The unique patterns on the replicated PDMS molds were successfully transferred back to the UV curable polyurethane-acrylate (PUA) using a laboratory-made UV exposure system. Continuous production of the super-hydrophobic PDMS thin film was demonstrated using the reusable PUA mold. In addition, hydrophobic nano-silica powder was sprayed onto the micro/nano structured PDMS surfaces to further improve hydrophobicity. The fabricated PDMS thin films with hierarchical surface texturing showed a water contact angle  ⩾150°. Excellent optical transmittance within the range of visible light of wavelengths between 400-800 nm was experimentally confirmed using a spectrophotometer. High efficiency of the super-hydrophobic PDMS film in optical transparency was also confirmed using solar panels. The fabricated PUA molds are very suitable for use in roll-to-roll or roll-to-plate systems which allow continuous production of super-hydrophobic thin films with an excellent optical transparency.

Hierarchical templating in deposition of semi-covalently imprinted inverse opal polythiophene film for femtomolar determination of human serum albumin.

PubMed

Dabrowski, Marcin; Cieplak, Maciej; Sharma, Piyush Sindhu; Borowicz, Pawel; Noworyta, Krzysztof; Lisowski, Wojciech; D'Souza, Francis; Kuhn, Alexander; Kutner, Wlodzimierz

2017-08-15

Nanostructured artificial receptor materials with unprecedented hierarchical structure for determination of human serum albumin (HSA) are designed and fabricated. For that purpose a new hierarchical template is prepared. This template allowed for simultaneous structural control of the deposited molecularly imprinted polymer (MIP) film on three length scales. A colloidal crystal templating with optimized electrochemical polymerization of 2,3'-bithiophene enables deposition of an MIP film in the form of an inverse opal. Thickness of the deposited polymer film is precisely controlled with the number of current oscillations during potentiostatic deposition of the imprinted poly(2,3'-bithiophene) film. Prior immobilization of HSA on the colloidal crystal allows formation of molecularly imprinted cavities exclusively on the internal surface of the pores. Furthermore, all binding sites are located on the surface of the imprinted cavities at locations corresponding to positions of functional groups present on the surface of HSA molecules due to prior derivatization of HSA molecules with appropriate functional monomers. This synergistic strategy results in a material with superior recognition performance. Integration of the MIP film as a recognition unit with a sensitive extended-gate field-effect transistor (EG-FET) transducer leads to highly selective HSA determination in the femtomolar concentration range. Copyright © 2017 Elsevier B.V. All rights reserved.

Plasma deposited polymers as gas sensitive films

NASA Astrophysics Data System (ADS)

Radeva, E.; Georgieva, V.; Lazarov, J.; Vergov, L.; Donkov, N.

2012-03-01

The possibility is presented of producing thin plasma polymers with desired properties by using nanofillers. Composite films are synthesized from a mixture of hexamethyldisiloxane (HMDSO) and detonation nanodiamond particles (DNDs). The chemical structure of the composite consists of DNDs distributed in the polymer matrix. The effect of DNDs on the humidity and ammonia sorptive properties of the polymers obtained is studied by measuring the mass changes as a result of gas sorption by using a quartz crystal microbalance (QCM). The results show that, in view of building a sensing element for measuring humidity, ammonia or other gases, it is possible to maximize the sensor sensitivity to a certain gas by using an appropriate concentration of DNDs in HMDSO. Thus, a high degree of sensor sensitivity, together with short response time and minimum hysteresis, can be achieved. Composites of plasma-polymerized HMDSO with DNDs can be used as gas sensitive layers for the development of quartz resonator sensors.

How Much Do Ultrathin Polymers with Intrinsic Microporosity Swell in Liquids?

PubMed

Ogieglo, Wojciech; Ghanem, Bader; Ma, Xiaohua; Pinnau, Ingo; Wessling, Matthias

2016-10-06

As synthetic membrane materials, polymers with intrinsic microporosity (PIMs) have demonstrated unprecedented permeation and molecular-separation properties. Here, we report the swelling characteristics of submicron-thick supported films of spirobisindane-based PIMs, PIM-1 and PIM-6FDA-OH, for six organic solvents and water using in situ spectroscopic ellipsometry. Surprisingly, PIMs swell significantly in most organic solvents, with swelling factors (SF = h swollen /h dry ) as high as 2.5. This leads to the loss of the ultrarigid character of the polymer and produces equilibrated liquid-like swollen films. Filling of the excess frozen-in fractional free volume with liquid was discovered next to swelling-induced polymer matrix dilation. Water hardly swells the polymer matrix, but it penetrates into the intrinsic microporous structure. This study is the first to provide fundamental swelling data for PIMs, leading to better comprehension of their permeation properties. Such an understanding is indispensable for applications such as solvent filtration, natural-gas separation, and ion retention in flow batteries.

Building a road map for tailoring multilayer polyelectrolyte films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ankner, John Francis; Bardoel, Agatha A; Sukishvili, Svetlana

2012-01-01

Researchers are moving a step closer to a definite road map for building layer-by-layer (LbL) assembled polyelectrolyte films, with the assistance of the Liquids Reflectometer at Oak Ridge National Laboratory's Spallation Neutron Source, in Oak Ridge, Tennessee. Scientists using the liquids reflectometer have successfully taken snapshots in close to real time of these multilayered structures for different applications when they modify the structure and function parameters. Polyelecrolytes are polymers that carry charge in aqueous solutions. They contain chemical groups that dissociate in water, making such polymers charged. Most polyelectrolytes are water soluble. They are important components in foods, soaps, shampoos,more » and cosmetics products. They show promise for such environmental work as oil recovery and water treatment. Polyelectrolytes are compelling because researchers can chemically modify how they interact with water for multiple applications. When two types of polyelectrolytes of opposite charge are assembled at a surface in a sequential way using the LbL assembly technique, 'the result is the forming of surface films, useful for coatings, biomedical implants and devices, controlling adhesion of biological molecules, and controlling delivery of therapeutic molecules from surfaces,' said Svetlana Sukhishvili of the Stevens Institute of Technology in New Jersey, the lead chemist on the collaboration. 'Medical doctors often prefer to deliver multiple therapeutic compounds from the coatings in a time-resolved manner,' Sukhishvili said. 'To assist them, material scientists need to learn how to build coatings in which polymer layering will not be compromised when exposed to normal physiological conditions.' 'Being able to control these properties, understanding how what you do to the materials affects their properties, this allows you to apply them to situations where interacting with an environment is very helpful, whether in a biological context or any other kind of water soluble context,' said John Ankner, lead instrument scientist for the Liquids Reflectometer. Ankner said that when several parameters are systematically altered, that allows researchers to map out the whole range of structures in the polymer. 'This work really sets a road map for how to get started with synthesizing polyelectrolyte materials for specific applications. Then, one can say, ok, this methylated material, the one that is 30% charged, is going to be what we want to use for a particular application.' The ORNL collaboration with the Stevens Institute has been conducting a series of experiments at the SNS to study layered film stratification in these polymers. Researchers stitch the polyelectrolyte chains in the LbL films together through what is called ionic pairing and arrange them within fuzzy, ultrathin layers that lie parallel to a solid surface substrate. Exposure of these films to aqueous solutions that contain salt (i.e., conditions that imitate real life) can compromise this film layering, as the salt ions act to weaken the ionic pairing that binds such layers together. So salt solutions are of key interest in studying how to make such layers for use in human applications. In the first research, Ankner, Sukhishvili and her student Li Xu looked at the effects of the layering of two types of LbL films of changing the charge density with a salt solution, and of blocking access to a charged site by nearby groups. The films were composed of positively charged variants of PDMA, a methyl polymer, and PDEA, an ethyl polymer. The other component of both systems is the ion exchanger polystyrene sulfonate (PSS) which features a fixed negative charge. First, a silicon substrate was dipped into solutions of PDMA and PDEA in dilute sodium chloride for a fixed time. Depending on the deposition time and the concentration of the solution, a nanometer-thick monolayer of the polymer adsorbs to the silicon surface. The film buildup is then continued by depositing a layer of PSS, and the cycle is repeated. The PDMA (methyl)/PSS and PDEA (ethyl)/PSS films were then annealed in varying concentrations of aqueous salt solutions. The chemists wanted to know if in these multi-layer cake-like assemblies, the structure can be systematically altered by varying the salt concentration, time in solution, and ultimately other environmental parameters, such as temperature or pH. Neutron reflectivity of the layered films exhibits the quality of the layering, in particular the concentration of the layers and how intermixed they are with adjacent layers. In this research, neutron reflectivity data from films built from 10%, 40%, and 100% charged PDMA or PDEA polyelectrolytes and 100% charged PSS were quantitatively compared to predicted, layered arrangements until the models produced reflectivity patterns matching those of the data.« less

Polymeric Thin Films for Organic Electronics: Properties and Adaptive Structures

PubMed Central

Cataldo, Sebastiano; Pignataro, Bruno

2013-01-01

This review deals with the correlation between morphology, structure and performance of organic electronic devices including thin film transistors and solar cells. In particular, we report on solution processed devices going into the role of the 3D supramolecular organization in determining their electronic properties. A selection of case studies from recent literature are reviewed, relying on solution methods for organic thin-film deposition which allow fine control of the supramolecular aggregation of polymers confined at surfaces in nanoscopic layers. A special focus is given to issues exploiting morphological structures stemming from the intrinsic polymeric dynamic adaptation under non-equilibrium conditions. PMID:28809362

Method and apparatus for measuring micro structures, anisotropy and birefringence in polymers using laser scattered light

DOEpatents

Grek, Boris; Bartolick, Joseph; Kennedy, Alan D.

2000-01-01

A method and apparatus for measuring microstructures, anistropy and birefringence in polymers using laser scattered light includes a laser which provides a beam that can be conditioned and is directed at a fiber or film which causes the beam to scatter. Backscatter light is received and processed with detectors and beam splitters to obtain data. The data is directed to a computer where it is processed to obtain information about the fiber or film, such as the birefringence and diameter. This information provides a basis for modifications to the production process to enhance the process.

Efficient protein-repelling thin films regulated by chain mobility of low-Tg polymers with increased stability via crosslinking

NASA Astrophysics Data System (ADS)

Zhang, Jinghui; Huang, Zhiwei; Liu, Dan

2017-12-01

Polymer thin films are generally employed as coatings on implants to prevent protein adsorption. Polymer chain mobility and surface softness have been found to contribute to the protein resistance, but also bring film instability in a liquid protein medium. We investigated the protein resistance ability of three low-Tg polymers, including hydrophobic polymers polyisoprene (PI), poly(n-butyl methacrylate) (PnBMA) and hydrophilic polyethylene oxide (PEO), by overcoming the instability issue with crosslinking. We found that the Tgs of PI and PEO can be increased to around 0 °C after crosslinking. The remained strong chain mobility of both films can still resist protein adsorption regardless the hydrophobicity, yet greatly increases the film stability under an aqueous circumstance. The PnBMA film increased its Tg to around room temperature after crosslinking, which deteriorated the protein-resistance ability having the surface covered by BSA molecules. Our results support that the chain mobility of a polymer film plays an important role in resisting protein adsorption due to the increased entropy associated with more mobile polymer chains. By tune the degree of crosslinking, the stability of polymer in aqueous environment can be increased while the protein resistant ability can be remained. Our results provide a new strategy to design polymer materials for effective antifouling.

Modeling the mechanical properties of ultra-thin polymer films [Structural modeling of films of atomic scale thickness

DOE PAGES

Espinosa-Loza, Francisco; Stadermann, Michael; Aracne-Ruddle, Chantel; ...

2017-11-16

A modeling method to extract the mechanical properties of ultra-thin films (10–100 nm thick) from experimental data generated by indentation of freestanding circular films using a spherical indenter is presented. The relationship between the mechanical properties of the film and experimental parameters including load, and deflection are discussed in the context of a constitutive material model, test variables, and analytical approaches. As a result, elastic and plastic regimes are identified by comparison of finite element simulation and experimental data.

Modeling the mechanical properties of ultra-thin polymer films [Structural modeling of films of atomic scale thickness

DOE Office of Scientific and Technical Information (OSTI.GOV)

Espinosa-Loza, Francisco; Stadermann, Michael; Aracne-Ruddle, Chantel

A modeling method to extract the mechanical properties of ultra-thin films (10–100 nm thick) from experimental data generated by indentation of freestanding circular films using a spherical indenter is presented. The relationship between the mechanical properties of the film and experimental parameters including load, and deflection are discussed in the context of a constitutive material model, test variables, and analytical approaches. As a result, elastic and plastic regimes are identified by comparison of finite element simulation and experimental data.

Self-assembly of block copolymers on topographically patterned polymeric substrates

DOEpatents

Russell, Thomas P.; Park, Soojin; Lee, Dong Hyun; Xu, Ting

2016-05-10

Highly-ordered block copolymer films are prepared by a method that includes forming a polymeric replica of a topographically patterned crystalline surface, forming a block copolymer film on the topographically patterned surface of the polymeric replica, and annealing the block copolymer film. The resulting structures can be used in a variety of different applications, including the fabrication of high density data storage media. The ability to use flexible polymers to form the polymeric replica facilitates industrial-scale processes utilizing the highly-ordered block copolymer films.

Inexpensive, rapid fabrication of polymer-film microfluidic autoregulatory valve for disposable microfluidics.

PubMed

Zhang, Xinjie; Zhu, Zhixian; Ni, Zhonghua; Xiang, Nan; Yi, Hong

2017-06-01

This work presents the fabrication of a microfluidic autoregulatory valve which is composed of several layers of thin polymer films (i.e., polyvinyl chloride (PVC), polyethylene terephthalate (PET) double-sided tape, and polydimethylsiloxane (PDMS)). Briefly, pulsed UV laser is employed to cut the microstructures of through grooves or holes in the thermoplastic polymer films, and then the polymer-film valves are precisely assembled through laminating the PDMS membranes to the thermoplastic polymer films through the roll-lamination method. The effective bonding between the PVC film and the PDMS membrane is realized using the planar seal method, and the valve is sandwiched and compressed by a home-made housing to achieve the good seal effect. Then, the flow performances of the prototype valve are examined, and constant flow autoregulation is realized under the static or dynamic test pressures. The long-term response of the valve is also studied and minimum flow-rate decrements are found over a long actuation time. The fabrication method proposed in this work is successful for the low-cost and fast prototyping of the polymer-film valve. We believe our method will also be broadly applicable for fabrication of other low-cost and disposable polymer-film microfluidic devices.

Making molecular balloons in laser-induced explosive boiling of polymer solutions.

PubMed

Leveugle, Elodie; Sellinger, Aaron; Fitz-Gerald, James M; Zhigilei, Leonid V

2007-05-25

The effect of the dynamic molecular rearrangements leading to compositional segregation is revealed in coarse-grained molecular dynamics simulations of short pulse laser interaction with a polymer solution in a volatile matrix. An internal release of matrix vapor at the onset of the explosive boiling of the overheated liquid is capable of pushing polymer molecules to the outskirts of a transient bubble, forming a polymer-rich surface layer enclosing the volatile matrix material. The results explain unexpected "deflated balloon" structures observed in films deposited by the matrix-assisted pulsed laser evaporation technique.

Structure and size of ions electrochemically doped in conducting polymer

NASA Astrophysics Data System (ADS)

Kaneto, Keiichi; Hata, Fumito; Uto, Sadahito

2018-05-01

Among electroactive polymers (EAPs) for softactuators, conducting polymers have been intensively studied because of the large strain and stress caused by a low voltage operation. A larger deformation is desirable to extend their cycle life by reducing the operation voltage, and this is advantageous for their potential use in wider applications. The deformation is generated by the insertion of ions by electrochemical oxidation; hence, the magnitude of the strain depends on the bulkiness of the ions in the electrolytes. It is important, therefore, to clarify the structure and size of the ions during the electrochemical cycle, in order to achieve better performance of actuation. Anion and cation sizes (radii) in polypyrrole (PPy) film have been estimated using the precise measurement of strain against the amount of charge injected during the electrochemical cycles, assuming isotropic deformation of the film. The anion size was estimated using an anion-drive film, which was electrodeposited in TBABF4/methyl benzoate. The film was electrochemically cycled in sodium electrolytes, and the strain was measured simultaneously using a laser displacement meter. The cation size was obtained using a cation-drive film, being electropolymerized in aqueous dodecylbenzene sulfonic (DBS) acid. The cation-drive film was cycled in chloride electrolytes and measured the strain. The Cl-, Br-, NO3- , BF4- , and ClO4- radii were found to be approximately 235, 245, 250, 270 and 290 pm, respectively. The radii of K+, Na+ and Li+ were approximately 230, 237 and 274 pm, respectively. The results were discussed and took the crystalline ion radius and hydrated ion radius (Stokes radius) into consideration. It was found that the structure and size of the anions were slightly larger than the crystalline ion radius. Contrary to the anions, the cation radii were close to the hydrated ion radius, being larger than the crystalline ion radius.

MISSE 6 Polymer Film Tensile Experiment

NASA Technical Reports Server (NTRS)

Miller, Sharon K. R.; Dever, Joyce A.; Banks, Bruce A.; Waters, Deborah L.; Sechkar, Edward; Kline, Sara

2010-01-01

The Polymer Film Tensile Experiment (PFTE) was flown as part of Materials International Space Station Experiment 6 (MISSE 6). The purpose of the experiment was to expose a variety of polymer films to the low Earth orbital environment under both relaxed and tension conditions. The polymers selected are those commonly used for spacecraft thermal control and those under consideration for use in spacecraft applications such as sunshields, solar sails, and inflatable and deployable structures. The dog-bone shaped samples of polymers that were flown were exposed on both the side of the MISSE 6 Passive Experiment Container (PEC) that was facing into the ram direction (receiving atomic oxygen, ultraviolet (UV) radiation, ionizing radiation, and thermal cycling) and the wake facing side (which was supposed to have experienced predominantly the same environmental effects except for atomic oxygen which was present due to reorientation of the International Space Station). A few of the tensile samples were coated with vapor deposited aluminum on the back and wired to determine the point in the flight when the tensile sample broke as recorded by a change in voltage that was stored on battery powered data loggers for post flight retrieval and analysis. The data returned on the data loggers was not usable. However, post retrieval observation and analysis of the samples was performed. This paper describes the preliminary analysis and observations of the polymers exposed on the MISSE 6 PFTE.

The impact of fullerenes on the ordering of polyacrylonitrile during nanocomposites formation

DOE PAGES

Imel, Adam E.; Dadmun, Mark D.

2015-08-18

The production of polymer nanocomposites from solution consists of the mixing of the polymer and nanoparticle in solution and subsequent evaporation of the solvent. Here, we examine the formation of polyacrylonitrile and C60 fullerene nanocomposites, with a focus on monitoring these two steps.This study indicates that the nanoparticles are individually dispersed with the polymer chains in solution prior to deposition and in the final film. As the solution becomes more concentrated, the nanoparticles are sequestered to the outer edges of the polymer crystals, altering the detected crystal structure. The self-assembled structure of the crystalline polymer is directed by the additionmore » of C 60 and manifests itself as a peak in small-angle X-ray scattering on a length scale of ~150 . Moreover, our results suggest that the non-covalent molecular interactions between C60 and polyacrylonitrile matrix are sufficiently strong to alter the self-assembled morphology of the polymer and the meso- and nanoscale structures in the nanocomposite.« less

Construction of conducting polymer/cytochrome C/thylakoid membrane based photo-bioelectrochemical fuel cells generating high photocurrent via photosynthesis.

PubMed

Cevik, Emre; Carbas, Buket Bezgin; Senel, Mehmet; Yildiz, Huseyin Bekir

2018-08-15

In this study, a photo-bioelectrochemical fuel cell was constructed for photocurrent generation by illuminating the electrodes within an aqueous solution. In this purpose, gold electrode was coated with poly 4-(4H-Dithieno [3,2-b:2',3'-d]pyrol-4-yl) aniline, P(DTP-Ph-NH 2 ) conductive polymer film by using electrochemical polymerization. Then, P(DTP-Ph-NH 2 ) conductive polymer film coated surface was electrochemically modified with cytochrome C which covalently linked onto the surface via bis-aniline functionality of the polymer film and formed crosslinked-structure. The thylakoid membrane was attached on the surface of this electrode by using bissulfosaxinimidyl suberate (BS 3 ) and used as photo-anode in photo-bioelectrochemical fuel cell. The photo-cathode of the photo-bioelectrochemical fuel cell fabrication was followed by the modification of conductive polymer poly[5-(4H-dithieno [3,2-b:2',3'-d]pyrol-4-yl) naphtalene-1-amine] film coating, glutaraldehyde activation, and bilirubin oxidase enzyme immobilization. During the photosynthesis occurring in thylakoid membrane under the light, water was oxidized and separated; while oxygen was released in anode side, the cathode side was reduced the oxygen gas into the water via a bio-electro-catalytic method. The cytochrome C was used for binding of thylakoid membrane to the electrode surface and play an important role for transferring of electrons released as a result of photosynthesis. Copyright © 2018 Elsevier B.V. All rights reserved.

Effect of Energy Alignment, Electron Mobility, and Film Morphology of Perylene Diimide Based Polymers as Electron Transport Layer on the Performance of Perovskite Solar Cells.

PubMed

Guo, Qiang; Xu, Yingxue; Xiao, Bo; Zhang, Bing; Zhou, Erjun; Wang, Fuzhi; Bai, Yiming; Hayat, Tasawar; Alsaedi, Ahmed; Tan, Zhan'ao

2017-03-29

For organic-inorganic perovskite solar cells (PerSCs), the electron transport layer (ETL) plays a crucial role in efficient electron extraction and transport for high performance PerSCs. Fullerene and its derivatives are commonly used as ETL for p-i-n structured PerSCs. However, these spherical small molecules are easy to aggregate with high annealing temperature and thus induce morphology stability problems. N-type conjugated polymers are promising candidates to overcome these problems due to the tunable energy levels, controllable aggregation behaviors, and good film formation abilities. Herein, a series of perylene diimide (PDI) based polymers (PX-PDIs), which contain different copolymeried units (X), including vinylene (V), thiophene (T), selenophene (Se), dibenzosilole (DBS), and cyclopentadithiophene (CPDT), are introduced as ETL for p-i-n structured PerSCs. The effect of energy alignment, electron mobility, and film morphology of these ETLs on the photovoltaic performance of the PerSCs are fully investigated. Among the PX-PDIs, PV-PDI demonstrates the deeper LUMO energy level, the highly delocalized LUMO electron density, and a better planar structure, making it the best electron transport material for PerSCs. The planar heterojunction PerSC with PV-PDI as ETL achieves a power conversion efficiency (PCE) of 10.14%, among the best values for non-fullerene based PerSCs.

In situ monitoring of laser-induced periodic surface structures formation on polymer films by grazing incidence small-angle X-ray scattering.

PubMed

Rebollar, Esther; Rueda, Daniel R; Martín-Fabiani, Ignacio; Rodríguez-Rodríguez, Álvaro; García-Gutiérrez, Mari-Cruz; Portale, Giuseppe; Castillejo, Marta; Ezquerra, Tiberio A

2015-04-07

The formation of laser-induced periodic surface structures (LIPSS) on model spin-coated polymer films has been followed in situ by grazing incidence small-angle X-ray scattering (GISAXS) using synchrotron radiation. The samples were irradiated at different repetition rates ranging from 1 up to 10 Hz by using the fourth harmonic of a Nd:YAG laser (266 nm) with pulses of 8 ns. Simultaneously, GISAXS patterns were acquired during laser irradiation. The variation of both the GISAXS signal with the number of pulses and the LIPSS period with laser irradiation time is revealing key kinetic aspects of the nanostructure formation process. By considering LIPSS as one-dimensional paracrystalline lattice and using a correlation found between the paracrystalline disorder parameter, g, and the number of reflections observed in the GISAXS patterns, the variation of the structural order of LIPSS can be assessed. The role of the laser repetition rate in the nanostructure formation has been clarified. For high pulse repetition rates (i.e., 10 Hz), LIPSS evolve in time to reach the expected period matching the wavelength of the irradiating laser. For lower pulse repetition rates LIPSS formation is less effective, and the period of the ripples never reaches the wavelength value. Results support and provide information on the existence of a feedback mechanism for LIPSS formation in polymer films.

Touch-mode capacitive pressure sensor with graphene-polymer heterostructure membrane

NASA Astrophysics Data System (ADS)

Berger, Christian; Phillips, Rory; Pasternak, Iwona; Sobieski, Jan; Strupinski, Wlodek; Vijayaraghavan, Aravind

2018-01-01

We describe the fabrication and characterisation of a touch-mode capacitive pressure sensor (TMCPS) with a robust design that comprises a graphene-polymer heterostructure film, laminated onto the silicon dioxide surface of a silicon wafer, incorporating a SU-8 spacer grid structure. The spacer grid structure allows the flexible graphene-polymer film to be partially suspended above the substrate, such that a pressure on the membrane results in a reproducible deflection, even after exposing the membrane to pressures over 10 times the operating range. Sensors show reproducible pressure transduction in water submersion at varying depths under static and dynamic loading. The measured capacitance change in response to pressure is in good agreement with an analytical model of clamped plates in touch mode. The device shows a pressure sensitivity of 27.1 +/- 0.5 fF Pa-1 over a pressure range of 0.5 kPa-8.5 kPa. In addition, we demonstrate the operation of this device as a force-touch sensor in air.

Molecular engineered conjugated polymer with high thermal conductivity

PubMed Central

Song, Bai; Lee, Elizabeth M. Y.; Gleason, Karen K.

2018-01-01

Traditional polymers are both electrically and thermally insulating. The development of electrically conductive polymers has led to novel applications such as flexible displays, solar cells, and wearable biosensors. As in the case of electrically conductive polymers, the development of polymers with high thermal conductivity would open up a range of applications in next-generation electronic, optoelectronic, and energy devices. Current research has so far been limited to engineering polymers either by strong intramolecular interactions, which enable efficient phonon transport along the polymer chains, or by strong intermolecular interactions, which enable efficient phonon transport between the polymer chains. However, it has not been possible until now to engineer both interactions simultaneously. We report the first realization of high thermal conductivity in the thin film of a conjugated polymer, poly(3-hexylthiophene), via bottom-up oxidative chemical vapor deposition (oCVD), taking advantage of both strong C=C covalent bonding along the extended polymer chain and strong π-π stacking noncovalent interactions between chains. We confirm the presence of both types of interactions by systematic structural characterization, achieving a near–room temperature thermal conductivity of 2.2 W/m·K, which is 10 times higher than that of conventional polymers. With the solvent-free oCVD technique, it is now possible to grow polymer films conformally on a variety of substrates as lightweight, flexible heat conductors that are also electrically insulating and resistant to corrosion. PMID:29670943

A novel fabrication method for surface integration of metal structures into polymers (SIMSIP)

NASA Astrophysics Data System (ADS)

Carrion-Gonzalez, Hector

Recently developed flexible electronics applications require that the thin metal films embedded on elastomer substrates also be flexible. These electronic systems are radically different in terms of performance and functionality than conventional silicon-based devices. A key question is whether the metal deposited on flexible films can survive large strains without rupture. Cumbersome macro-fabrication methods have been developed for functional and bendable electronics (e.g., interconnects) encapsulated between layers of polymer films. However, future electronic applications may require electronic flexible devices to be in intimate contact with curved surfaces (e.g., retinal implants) and to be robust enough to withstand large and repeated mechanical deformations. In this research, a novel technique for surface integration of metal structures into polymers (SIMSIP) was developed. Surface embedding, as opposed to placing metal on polymers, provides better adherence while leaving the surface accessible for contacts. This was accomplished by first fabricating the micro-scale metal patterns on a quartz or Teflon mother substrate, and then embedding them to a flexible polyimide thin film. The technique was successfully used to embed micro-metal structures of gold (Au), silver (Ag), and copper (Cu) into polyimide films without affecting the functional properties of the either the metals or the polymers. Experimental results confirm the successful surface-embedding of metal structures as narrow as 0.6 microm wide for different geometries commonly used in circuit design. Although similar approaches exist in literature, the proposed methodology provides a simpler and more reliable way of producing flexible circuits/electronics that is also suitable for high volume manufacturing. In order to demonstrate the flexibility of metal interconnects fabricated using the SIMSIP technique, multiple Au electrodes (5 microm and 2.5 microm wide) were tested using the X-theta bending methodology. The X-theta bending test captures data on the electrical resistivity of micro Au electrodes fabricated using the proposed SIMSIP technique by bending them at different angles between 0o and 180o up to 50 times. The data shows that the electrical resistivity of the Au electrodes remains constant (<1% variation) despite the interconnects being repeatedly subjected to extreme tensile and compressive forces during the X-theta bending test. These results are significant from the perspective of flexible electronics and biotechnology applications since the fabricated thin films exhibit significant electrical stability, reliability and wear resistance. These surface-embedded, flexible, and mechanically stable metal interconnects will enable the further development of new electronic products with applications in biotechnology (e.g., e-skin), space exploration (e.g., satellites), and microelectronics (e.g., flat panel displays). The SIMSIP technique is also a suitable process for the nanofabrication of flexible electronic devices in applications that require intimate contact with bendable curved surfaces (e.g., retinal implants).

Dual Imprinted Polymer Thin Films via Pattern Directed Self-Organization.

PubMed

Grolman, Danielle; Bandyopadhyay, Diya; Al-Enizi, Abdullah; Elzatahry, Ahmed; Karim, Alamgir

2017-06-21

Synthetic topographically patterned films and coatings are typically contoured on one side, yet many of nature's surfaces have distinct textures on different surfaces of the same object. Common examples are the top and bottom sides of the butterfly wing or lotus leaf, onion shells, and the inside versus outside of the stem of a flower. Inspired by nature, we create dual (top and bottom) channel patterned polymer films. To this end, we first develop a novel fabrication method to create ceramic line channel relief structures by converting the oligomeric residue of stamped poly(dimethylsiloxane) (PDMS) nanopatterns on silicon substrates to glass (SiOx, silica) by ultraviolet-ozone (UVO) exposure. These silica patterned substrates are flow coated with polystyrene (PS) films and confined within an identically patterned top confining soft PDMS elastomer film. Annealing of the sandwich structures drives the PS to rapidly mold fill the top PDMS pattern in conjunction with a dewetting tendency of the PS on the silica pattern. Varying the film thickness h, from less than to greater than the pattern height, and varying the relative angle between the top-down and bottom-up patterned confinement surfaces create interesting uniform and nonuniform digitized defects in PS channel patterns, as also a defect-free channel regime. Our dual patterned polymer channels provide a novel fabrication route to topographically imprinted Moiré patterns (whose applications range from security encrypting holograms to sensitive strain gauges), and their basic laser light diffractions properties are illustrated and compared to graphical simulations and 2D-FFT of real-space AFM channel patterns. While traditional "geometrical" and "fringe" Moiré patterns function by superposition of two misaligned optical patterned transmittance gratings, our topographic pattern gratings are quite distinct and may allow for more unique holographic optical characteristics with further development.

Supramolecular structure formation of Langmuir-Blodgett films of comblike precursor and polyimide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goloudina, S. I., E-mail: goloudina@mail.ru; Luchinin, V. V.; Rozanov, V. V.

2013-03-15

The surface structure of Langmuir-Blodgett films of a comblike polyimide precursor-a rigid-chain polyamic acid alkylamine salt bearing multichains of tertiary amine-and films of the corresponding polyimide were studied by atomic force microscopy (AFM). An analysis of the images of the surface of three-layer films revealed a domain structure. It was found that the Langmuir-Blodgett film formation of the precursor occurs as a result of the layer-by-layer deposition of two-dimensional domains (composed of polyamic acid salt molecules on the water surface) onto a substrate. The formation of domains in a monolayer is associated with the chemical structure of the precursor, tomore » be more precise, with the rigidity of the main chain and the presence of closely spaced aliphatic side chains in the polymer chain, whose total cross-section area is close to the surface area of the projection onto the plane of the repeating unit of the main chain. Polyimide films inherit the domain structure of the precursor films; the inhomogeneity of the film thickness substantially decreases, whereas the domain size and character of their distribution in the film remain unchanged.« less

Biodegradable starch-based polymeric materials

NASA Astrophysics Data System (ADS)

Suvorova, Anna I.; Tyukova, Irina S.; Trufanova, Elena I.

2000-05-01

The effects of low-molecular-weight additives, temperature and mechanical action on the structure and properties of starch are discussed. Special attention is given to mixtures of starch with synthetic polymers, e.g., co-polymers of ethylene with vinyl acetate, vinyl alcohol, acrylic acid, cellulose derivatives and other natural polymers. These mixtures can be used in the development of novel environmentally safe materials (films, coatings, packaging materials) and various articles for short-term use. The bibliography includes 105 references.

Capillary bending of a thin polymer film floating on a liquid bath

NASA Astrophysics Data System (ADS)

Twohig, Timothy; Croll, Andrew B.

Thin elastic films and shells are very important in schemes for the encapsulation and protection of fluids from their environment. Capillary origami is a particularly poignant example of how useful fluid/film structures can be formed. The interactions of fluids on thin-films which themselves lie on another surface (fluid or low friction solid) need to be studied if the differences from fluid-fluid and fluid-solid film interfaces are to be fully appreciated. In this experiment, we examine the triple line that occurs when a fluid is resting on a thin polymer film which is itself floating on a second fluid. The top fluid has a high-energy air/fluid interface which can be minimized by deforming the film in a manner that reduces the total air/fluid interface. We create a one-dimensional experiment in order to isolate the basic physics that occurs as the tension of the top fluid pulls on the thin film. Notably, the 1D geometry removes all the complexity incurred by thin films in biaxial stress states (such as wrinkling, folding and crumpling) from the problem. AFOSR under the Young Investigator Program (FA9550-15-1-0168).

Novel conjugates of peptides and conjugated polymers for optoelectronics and neural interfaces

NASA Astrophysics Data System (ADS)

Bhagwat, Nandita

Peptide-polymer conjugates are a novel class of hybrid materials that take advantage of each individual component giving the opportunity to generate materials with unique physical, chemical, mechanical, optical, and electronic properties. In this dissertation peptide-polymer conjugates for two different applications are discussed. The first set of peptide-polymer conjugates were developed as templates to study the intermolecular interactions between electroactive molecules by manipulating the intermolecular distances at nano-scale level. A PEGylated, alpha-helical peptide template was employed to effectively display an array of organic chromophores (oxadiazole containing phenylenevinylene oligomers, Oxa-PPV). Three Oxa-PPV chromophores were strategically positioned on each template, at distances ranging from 6 to 17 A from each other, as dictated by the chemical and structural properties of the peptide. The Oxa-PPV modified PEGylated helical peptides (produced via Heck coupling strategies) were characterized by a variety of spectroscopic methods. Electronic contributions from multiple pairs of chromophores on a scaffold were detectable; the number and relative positioning of the chromophores dictated the absorbance and emission maxima, thus confirming the utility of these polymer--peptide templates for complex presentation of organic chromophores. The rest of the thesis is focused on using poly(3,4-alkylenedioxythiophene) based conjugated polymers as coatings for neural electrodes. This thiophene derivative is of considerable current interest for functionalizing the surfaces of a wide variety of devices including implantable biomedical electronics, specifically neural bio-electrodes. Toward these ends, copolymer films of 3,4-ethylenedioxythiophene (EDOT) with a carboxylic acid functional EDOT (EDOTacid) were electrochemically deposited and characterized as a systematic function of the EDOTacid content (0, 25, 50, 75, and 100%). The chemical surface characterization of the films confirmed the presence of both EODT and EDOTacid units. Cyclic voltammetry showed that the films had comparable charge storage capacities regardless of their composition. The morphology of the films varied depending on the monomer feed ratio. Thus we were able to develop a method for synthesizing electrically active carboxylic acid functional poly(3,4-ethylenedioxythiophene) copolymer films with tunable hydrophilicities and surface morphologies. For longer lifetime devices incorporating a biomolecule via covalent immobilization techniques are preferred over physical adsorption or entrapment. We took advantage of the carboxylic acid group on the PEDOTacid copolymer films to modify the surface of these films with a laminin based peptide, the nonapeptide sequence CDPGYIGSR. XPS and toluidine blue O assay proved the presence of the peptide on the surface and electrochemical analysis demonstrated unaltered properties of the peptide modified films. The bioactivity of the peptide along with the need of a spacer molecule for cell adhesion and differentiation was tested using the rat pheochromocytoma (PC12) cells. Films modified with the longest poly(ethylene glycol) spacer used in this study, a 3 nm long molecule, demonstrated the best attachment and neurite outgrowth compared to films with peptides with no spacer and a 1 nm spacer, PEG3. The films with PEG10-CDPGYISGR covalently modified to the surface demonstrated 11.5% neurite expression with the mean neurite length of 90 microm. Along with the acid functionalized PEDOT films, vinyl terminated ProDOT films were also investigated as coatings for neural electrodes. The vinyl group was successfully modified with a RGD peptide via thiol-ene click chemistry. Both the acid and vinyl functional conducting polymer films provide an effective approach to biofunctionalize conducting polymer films.

21 CFR 175.320 - Resinous and polymeric coatings for polyolefin films.

Code of Federal Regulations, 2014 CFR

2014-04-01

... film over one or both sides of a base film produced from one or more of the basic olefin polymers complying with § 177.1520 of this chapter. The base polyolefin film may contain optional adjuvant substances... Limitations (i) Resins and polymers: Acrylic acid polymer and its ethyl or methyl esters Acrylamide...

A Review: Origins of the Dielectric Properties of Proteins and Potential Development as Bio-Sensors

PubMed Central

Bibi, Fabien; Villain, Maud; Guillaume, Carole; Sorli, Brice; Gontard, Nathalie

2016-01-01

Polymers can be classified as synthetic polymers and natural polymers, and are often characterized by their most typical functions namely their high mechanical resistivity, electrical conductivity and dielectric properties. This bibliography report consists in: (i) Defining the origins of the dielectric properties of natural polymers by reviewing proteins. Despite their complex molecular chains, proteins present several points of interest, particularly, their charge content conferring their electrical and dielectric properties; (ii) Identifying factors influencing the dielectric properties of protein films. The effects of vapors and gases such as water vapor, oxygen, carbon dioxide, ammonia and ethanol on the dielectric properties are put forward; (iii) Finally, potential development of protein films as bio-sensors coated on electronic devices for detection of environmental changes particularly humidity or carbon dioxide content in relation with dielectric properties variations are discussed. As the study of the dielectric properties implies imposing an electric field to the material, it was necessary to evaluate the impact of frequency on the polymers and subsequently on their structure. Characterization techniques, on the one hand dielectric spectroscopy devoted for the determination of the glass transition temperature among others, and on the other hand other techniques such as infra-red spectroscopy for structure characterization as a function of moisture content for instance are also introduced. PMID:27527179

Note: Setup for chemical atmospheric control during in situ grazing incidence X-ray scattering of printed thin films

DOE PAGES

Pröller, Stephan; Moseguí González, Daniel; Zhu, Chenhuii; ...

2017-06-01

In order to tailor the assembling of polymers and organic molecules, a deeper understanding of the kinetics involved in thin film production is necessary. While post-production characterization only provides insight on the final film structure, more sophisticated experimental setups are needed to probe the structure formation processes in situ during deposition. The drying kinetics of a deposited organic thin film strongly influences the assembling process on the nanometer scale. Lastly, this work presents an experimental setup that enables fine control of the atmosphere composition surrounding the sample during slot die coating, while simultaneously probing the film formation kinetics using inmore » situ grazing incidence X-ray scattering and spectroscopy.« less

A method for fabricating a micro-structured surface of polyimide with open and closed pores

NASA Astrophysics Data System (ADS)

Ma, Yong-Won; Oh, Jae Yong; Ahn, Seokyoung; Shin, Bo Sung

2016-08-01

A new approach for fabricating open and closed porous structures based on laser processing is presented. Liquid polyimide (PI) was mixed with azodicarbonamide which is a chemical blowing agent (CBA), and the mixture was spin-coated and pre-cured in order to fabricate solid PI films. Porous PI was prepared by irradiating PI films mixed with azodicarbonamide. The PI film with azodicarbonamide was etched by using laser ablation, and the azodicarbonamide was decomposed due to the heat induced by the absorbed laser energy. At higher laser beam irradiation, more pores were fabricated due to the resulting increase in the CBA decomposition from 27 mJ/cm2 to 40 mJ/cm2 per single pulse. A fluence of about 50 mJ/cm2 resulted in fewer and larger open pores, which were formed by the coalescence of small pores. In contrast, a closed porous structure was fabricated at a fluence of less than 1 mJ/cm2 because PI was barely etched. The proposed method can be used to create open and closed porous structures selectively and is not limited to thermosetting polymers, but is also effective with thermoplastic polymers.

Formation of nanocrystalline diamond in polymer like carbon films deposited by plasma CVD.

PubMed

Bhaduri, A; Chaudhuri, P

2009-09-01

Conventional plasma enhanced chemical vapour deposition (PECVD) method is generally not suitable for the growth of nanocrystalline diamond (NCD) films. However, our study shows that conditions favourable for powder formation help to grow large amount of nanocrystallites in conventional PECVD. With CH4 as the carbon source gas, dilution with Ar and moderate (50 W) rf power enhances formations of powders (nanoparticles) and C2 dimers within the plasma. On the other hand, with pure CH4 or with hydrogen diluted CH4, powder formation as also NCD growth is hindered. It is proposed that the nanoparticles formed in the plasma act as the "islands" while the C2 dimers are the "seeds" for the NCD growth. The structure of the films deposited on the grounded anode under different conditions of dilution has been studied. It is observed that with high Ar dilution the films contain NCD embedded in polymer like carbon (PLC) matrix.

Scanning Tunneling Microscopy analysis of space-exposed polymer films

NASA Technical Reports Server (NTRS)

Kalil, Carol R.; Young, Philip R.

1993-01-01

The characterization of the surface of selected space-exposed polymer films by Scanning Tunneling Microscopy (STM) is reported. Principles of STM, an emerging new technique for materials analysis, are reviewed. The analysis of several films which received up to 5.8 years of low Earth orbital (LEO) exposure onboard the NASA Long Duration Exposure Facility (LDEF) is discussed. Specimens included FEP Teflon thermal blanket material, Kapton film, and several experimental polymer films. Ultraviolet and atomic oxygen-induced crazing and erosion are described. The intent of this paper is to demonstrate how STM is enhancing the understanding of LEO space environmental effects on polymer films.

Efficient upconversion polymer-inorganic nanocomposite thin film emitters prepared by the double beam matrix assisted pulsed laser evaporation (DB-MAPLE)

NASA Astrophysics Data System (ADS)

Darwish, Abdalla M.; Burkett, Allan; Blackwell, Ashley; Taylor, Keylantra; Walker, Vernell; Sarkisov, Sergey; Koplitz, Brent

2014-09-01

We report on fabrication and investigation of optical and morphological properties of highly efficient (a quantum yield of 1%) upconversion polymer-inorganic nanocomposite thin film emitters prepared by the new technique of double beam matrix assisted pulsed laser evaporation (DB-MAPLE). Polymer poly(methyl methacrylate) (PMMA) host was evaporated on a silicon substrate using a 1064-nm pulsed laser beam using a target made of frozen (to the temperature of liquid nitrogen) solution of PMMA in chlorobenzene. Concurrently, the second 532-nm pulsed beam from the same laser was used to impregnate the polymer host with the inorganic nanoparticulate made of the rare earth upconversion compounds NaYF4: Yb3+, Er3+, NaYF4: Yb3+, Ho3+, and NaYF4: Yb3+, Tm3+. The compounds were initially synthesized using the wet process, baked, and compressed in solid pellet targets. The proposed DB-MAPLE method has the advantage of making highly homogeneous nanocomposite films with precise control of the doping rate due to the optimized overlapping of the plumes produced by the ablation of the organic and inorganic target with the infrared and visible laser beams respectively. X-ray diffraction, electron and atomic force microscopy, and optical fluorescence spectroscopy indicated that the inorganic nanoparticulate preserved its crystalline structure and upconversion properties (strong emission in green, red, and blue bands upon illumination with 980-nm laser diode) after being transferred from the target in the polymer nanocomposite film. The produced films can be used in applications varying from the efficiency enhancement of the photovoltaic cells, optical sensors and biomarkers to anti-counterfeit labels.

Analysis of Fluorinated Polyimides Flown on the Materials International Space Station Experiment

NASA Technical Reports Server (NTRS)

Finckenor, M. M.; Rodman, L.; Farmer, B.

2015-01-01

This Technical Memorandum documents the results from the Materials on International Space Station Experiment (MISSE) series involving fluorinated polyimide films analyzed at NASA Marshall Space Flight Center. These films may be used in thermal control, sunshield, solar sail, solar concentrator, and other lightweight polymer film applications. Results include postflight structural integrity, visual observations, determination of atomic oxygen erosion yield, and optical property changes as compared to preflight values.

Effect of ultraviolet radiation in the photo-oxidation of High Density Polyethylene and Biodegradable Polyethylene films

NASA Astrophysics Data System (ADS)

Martínez-Romo, A.; González Mota, R.; Bernal, J. J. Soto; Frausto Reyes, C.; Rosales Candelas, I.

2015-01-01

One of the most widely used plastics in the world is the High density polyethylene (HDPE), it is a stable material due to its carbon-carbon bonds, causing their slow degradation; which is why we are looking for alternative ways to accelerate the degradation process of this polymer. An alternative is the addition of oxidized groups in its molecular structure, which results in the development of polymers susceptible to biodegradation (PE-BIO). In this paper, HDPE and PE-BIO films were exposed to UV-B radiation (320-280 nm) at different exposure times, 0-60 days. The effects of UV radiation in samples of HDPE and PE-BIO were characterized using infrared spectroscopy with attenuated total reflectance (ATR). The results show that the exposed materials undergo changes in their molecular structure, due to the infrared bands formed which corresponds to the photo-oxidation of HDPE and PE films when submitted to UV-B radiation.

Ferrocene pixels by laser-induced forward transfer: towards flexible microelectrode printing

NASA Astrophysics Data System (ADS)

Mitu, B.; Matei, A.; Filipescu, M.; Palla Papavlu, A.; Bercea, A.; Lippert, T.; Dinescu, M.

2017-03-01

The aim of this work is to demonstrate the potential of laser-induced forward transfer (LIFT) as a printing technology, alternative to standard microfabrication techniques, in the area of flexible micro-electrode fabrication. First, ferrocene thin films are deposited onto fused silica and fused silica substrates previously coated with a photodegradable polymer film (triazene polymer) by matrix assisted pulsed laser evaporation (MAPLE). The morphology and chemical structure of the ferrocene thin films deposited by MAPLE has been investigated by atomic force microscopy and Fourier transformed infrared spectroscopy, and no structural damage occurs as a result of the laser deposition. Second, LIFT is applied to print for the first time ferrocene pixels and lines onto flexible polydimethylsiloxane (PDMS) substrates. The ferrocene pixels and lines are flawlessly transferred onto the PDMS substrates in air at room temperature, without the need of additional conventional photolithography processes. We believe that these results are very promising for a variety of applications ranging from flexible electronics to lab-on-a-chip devices, MEMS, and medical implants.

Molecular-Level Control of Ciclopirox Olamine Release from Poly(ethylene oxide)-Based Mucoadhesive Buccal Films: Exploration of Structure-Property Relationships with Solid-State NMR.

PubMed

Urbanova, Martina; Gajdosova, Marketa; Steinhart, Miloš; Vetchy, David; Brus, Jiri

2016-05-02

Mucoadhesive buccal films (MBFs) provide an innovative way to facilitate the efficient site-specific delivery of active compounds while simultaneously separating the lesions from the environment of the oral cavity. The structural diversity of these complex multicomponent and mostly multiphase systems as well as an experimental strategy for their structural characterization at molecular scale with atomic resolution were demonstrated using MBFs of ciclopirox olamine (CPX) in a poly(ethylene oxide) (PEO) matrix as a case study. A detailed description of each component of the CPX/PEO films was followed by an analysis of the relationships between each component and the physicochemical properties of the MBFs. Two distinct MBFs were identified by solid-state NMR spectroscopy: (i) at low API (active pharmaceutical ingredient) loading, a nanoheterogeneous solid solution of CPX molecularly dispersed in an amorphous PEO matrix was created; and (ii) at high API loading, a pseudoco-crystalline system containing CPX-2-aminoethanol nanocrystals incorporated into the interlamellar space of a crystalline PEO matrix was revealed. These structural differences were found to be closely related to the mechanical and physicochemical properties of the prepared MBFs. At low API loading, the polymer chains of PEO provided sufficient quantities of binding sites to stabilize the CPX that was molecularly dispersed in the highly amorphous semiflexible polymer matrix. Consequently, the resulting MBFs were soft, with low tensile strength, plasticity, and swelling index, supporting rapid drug release. At high CPX content, however, the active compounds and the polymer chains simultaneously cocrystallized, leaving the CPX to form nanocrystals grown directly inside the spherulites of PEO. Interfacial polymer-drug interactions were thus responsible not only for the considerably enhanced plasticity of the system but also for the exclusive crystallization of CPX in the thermodynamically most stable polymorphic form, Form I, which exhibited reduced dissolution kinetics. The bioavailability of CPX olamine formulated as PEO-based MBFs can thus be effectively controlled by inducing the complete dispersion and/or microsegregation and nanocrystallization of CPX olamine in the polymer matrix. Solid-state NMR spectroscopy is an efficient tool for exploring structure-property relationships in these complex pharmaceutical solids.

Alternative Thieno[3,2-b][1]benzothiophene Isoindigo Polymers for Solar Cell Applications.

PubMed

Neophytou, Marios; Bryant, Daniel; Lopatin, Sergei; Chen, Hu; Hallani, Rawad K; Cater, Lewis; McCulloch, Iain; Yue, Wan

2018-03-05

This work reports the synthesis, characterization, photophysical, and photovoltaic properties of five new thieno[3,2-b][1]benzothiophene isoindigo (TBTI)-containing low bandgap donor-acceptor conjugated polymers with a series of comonomers and different side chains. When TBTI is combined with different electron-rich moieties, even small structural variations can have significant impact on thin film morphology of the polymer:phenyl C70 butyric acid methyl ester (PCBM) blends. More importantly, high-resolution electron energy loss spectroscopy is used to investigate the phase-separated bulk heterojunction domains, which can be accurately and precisely resolved, enabling an enhanced correlation between polymer chemical structure, photovoltaic device performance, and morphology. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Understanding and Controlling Nanoscale Morphology in Self-Assembled Semiconducting Materials

NASA Astrophysics Data System (ADS)

Kang, Hyeyeon

Self-assembled semiconducting materials have been rapidly developed for a range of applications. This work aims to control the morphology of nanostructured semiconductors to understand how their functions arise from the structural properties. The first part of this dissertation focuses on the formation of a bulk-heterojunction (BHJ) in the active layer of organic photovoltaics (OPV). A BHJ is a bicontinuous interpenetrating network of organic components. The phase separation of the electron donor and the acceptor is required to achieve a BHJ structure in the nanostructured morphology, which promotes an efficient charge transportation. The use of solvent additive is one of the strategies to control the spontaneous phase separation during the film formation. Low vapor pressure solvent additives are introduced to a polymer casting solution in a sequentially processed OPV system, to study the swelling effect on the phase separation. In particular, the change in crystallinity and vertical mixing will be intensively studied upon polymer swelling. As another strategy, we introduce a molecular structure change to fullerene derivatives. A small structural variation leads to a large enough contrast of their surface energy, which is attributed to different vertical phase separation in the active layer. It eventually allows us to examine photovoltaic performance and device physics. In the second part, mesoporous inorganic films are investigated by preparation from a nanocrystal solution or sol-gel precursors for solar energy applications. Mesoporous nanocrystal-based titania is synthesized for inorganic/organic hybrid solar cells. The effect of surface modification is examined by anchoring a fullerene derivative on to titania surface. 3D interconnected mesoporous tantalum nitride films are prepared via sol-gel method as photoanodes in solar water splitting. The simple synthetic method using polymer template enables us to successfully prepare nitride films with excellent pore periodicity. The porous tantalum nitride film is examined with photoelectrochemical measurement to investigate the correlation between nanostructuring and photocatalytic activity. For the final part of this dissertation, porous cobalt ferrite and cadmium sulfide films are studied using ellipsometric porosimetry. Understanding the nature of their pores allows us to tune the intrinsic properties of the materials or prove the newly designed synthetic method.

Large-scale fabrication of polymer/Ag core-shell nanorod array as flexible SERS substrate by combining direct nanoimprint and electroless deposition

NASA Astrophysics Data System (ADS)

Liu, Sisi; Xu, Zhimou; Sun, Tangyou; Zhao, Wenning; Wu, Xinghui; Ma, Zhichao; Xu, Haifeng; He, Jian; Chen, Cunhua

2014-06-01

We demonstrate a highly sensitive surface-enhanced Raman scattering (SERS) substrate, which consists of Ag nanoparticles (NPs) assembled on the surface of a nanopatterned polymer film. The fabrication route of a polymer/Ag core-shell nanorod (PACSN) array employed a direct nanoimprint technique to create a high-resolution polymer nanorod array. The obtained nanopatterned polymer film was subjected to electroless deposition to form a sea-cucumber-like Ag shell over the surface of the polymer nanorod. The morphology and structures of PACSNs were analyzed by using scanning electron microscopy and X-ray diffraction. The as-synthesized PACSNs exhibited a remarkable SERS activity and Raman signal reproducibility to rhodamine 6G, and a concentration down to 10-12 M can be identified. The effect of electroless deposition time of Ag NPs onto the polymer nanorod surface was investigated. It was found that the electroless deposition time played an important role in SERS activity. Our results revealed that the combination of direct nanoimprint and electroless deposition provided a convenient and cost-effective way for large-scale fabrication of reliable SERS substrates without the requirement of expensive instruments.

Shear sensitive monomer-polymer laminate structure and method of using same

NASA Technical Reports Server (NTRS)

Singh, Jag J. (Inventor); Eftekhari, Abe (Inventor); Parmar, Devendra S. (Inventor)

1993-01-01

Monomer cholesteric liquid crystals have helical structures which result in a phenomenon known as selective reflection, wherein incident white light is reflected in such a way that its wavelength is governed by the instantaneous pitch of the helix structure. The pitch is dependent on temperature and external stress fields. It is possible to use such monomers in flow visualization and temperature measurement. However, the required thin layers of these monomers are quickly washed away by a flow, making their application time dependent for a given flow rate. The laminate structure according to the present invention comprises a liquid crystal polymer substrate attached to a test surface of an article. A light absorbing coating is applied to the substrate and is thin enough to permit bonding steric interaction between the liquid crystal polymer substrate and an overlying liquid crystal monomer thin film. Light is directed through and reflected by the liquid crystal monomer thin film and unreflected light is absorbed by the underlying coating. The wavelength of the reflected light is indicative of the shear stress experienced by the test surface. Novel aspects of the invention include its firm bonding of a liquid crystal monomer to a model and its use of a coating to reduce interference from light unreflected by the monomer helical structure.

Morphological evolution of thin polymer film on chemically patterned substrates

NASA Astrophysics Data System (ADS)

Singh, Satya Pal

2018-05-01

In this paper work, pattern formation in ultra thin polymer film, adsorbed on chemically patterned substrates, is reported under strong confinement. The observations indicate for the strong influence of the surface attraction over evolution of spindoal waves, leading to the flattening of the film. But, the film appears to be torn apart in strip or nano fiber like structures, because of coalescences of the monomers at the free ends of the chains. The beads at the free ends of the chain are relatively more mobile. The chain diffusion towards attractive part of the chemically patterned surfaces is clearly seen. Prewetting or crystallization like phenomena seems to appear resulting into formation of strips with coexistence of molten phase drops at the top of the ruptured film. The investigation mimics spindoal dewetting because of the fact that the rupturing occurs in case of strong attractive surface. The investigation is of technical importance as it highlights the formation of nano scale strips and fibers though in a quasi equilibrium case.

Patterning of ultrathin polymethylmethacrylate films by in-situ photodirecting of the Marangoni flow

NASA Astrophysics Data System (ADS)

Elashnikov, Roman; Fitl, Premysl; Svorcik, Vaclav; Lyutakov, Oleksiy

2017-02-01

Laser heating and Marangoni flow result in the formation of surface structures with different geometries and shape on thin polymer films. By laser beam irradiation combined with a sample movement the solid polymethylmethacrylate (PMMA) films are heated and undergo phase transition which leads to a material flow. Since the laser beam has a non-linear distribution of energy, the PMMA film is heated inhomogeneously and a surface tension gradient in a lateral direction is introduced. During this procedure additional phenomena such as "reversible" or cyclic polymer flow also take place. The careful choice of experimental conditions enables the preparation of patterns with sophisticated geometries and with hierarchical pattern organization. Depending on initial PMMA film thickness and speed of the sample movement line arrays are created, which can subsequently be transformed into the crimped lines or system of circular holes. In addition, the introduction of a constant acceleration in the sample movement or a laser beam distortion enables the preparation of regularly crimped lines, ordered hexagonal holes or overlapped plates.

Chemical Fabrication Used to Produce Thin-Film Materials for High Power-to- Weight-Ratio Space Photovoltaic Arrays

NASA Technical Reports Server (NTRS)

Hepp, Aloysius F.; Rybicki, George C.; Raffaelle, Ryne P.; Harris, Jerry D.; Hehemann, David G.; Junek, William; Gorse, Joseph; Thompson, Tracy L.; Hollingsworth, Jennifer A.; Buhro, William E.

2000-01-01

The key to achieving high specific power (watts per kilogram) space solar arrays is the development of a high-efficiency, thin-film solar cell that can be fabricated directly on a flexible, lightweight, space-qualified durable substrate such as Kapton (DuPont) or other polyimide or suitable polymer film. Cell efficiencies approaching 20 percent at AM0 (air mass zero) are required. Current thin-film cell fabrication approaches are limited by either (1) the ultimate efficiency that can be achieved with the device material and structure or (2) the requirement for high-temperature deposition processes that are incompatible with all presently known flexible polyimide or other polymer substrate materials. Cell fabrication processes must be developed that will produce high-efficiency cells at temperatures below 400 degrees Celsius, and preferably below 300 degress Celsius to minimize the problems associated with the difference between the coefficients of thermal expansion of the substrate and thin-film solar cell and/or the decomposition of the substrate.

DC magnetron sputtered polyaniline-HCl thin films for chemical sensing applications.

PubMed

Menegazzo, Nicola; Boyne, Devon; Bui, Holt; Beebe, Thomas P; Booksh, Karl S

2012-07-03

Thin films of conducting polymers exhibit unique chemical and physical properties that render them integral parts in microelectronics, energy storage devices, and chemical sensors. Overall, polyaniline (PAni) doped in acidic media has shown metal-like electronic conductivity, though exact physical and chemical properties are dependent on the polymer structure and dopant type. Difficulties arising from poor processability render production of doped PAni thin films particularly challenging. In this contribution, DC magnetron sputtering, a physical vapor deposition technique, is applied to the preparation of conductive thin films of PAni doped with hydrochloric acid (PAni-HCl) in an effort to circumvent issues associated with conventional thin film preparation methods. Samples manufactured by the sputtering method are analyzed along with samples prepared by conventional drop-casting. Physical characterization (atomic force microscopy, AFM) confirm the presence of PAni-HCl and show that films exhibit a reduced roughness and potentially pinhole-free coverage of the substrate. Spectroscopic evidence (UV-vis, FT-IR, and X-ray photoelectron spectroscopy (XPS)) suggests that structural changes and loss of conductivity, not uncommon during PAni processing, does occur during the preparation process. Finally, the applicability of sputtered films to gas-phase sensing of NH(3) was investigated with surface plasmon resonance (SPR) spectroscopy and compared to previous contributions. In summary, sputtered PAni-HCl films exhibit quantifiable, reversible behavior upon exposure to NH(3) with a calculated LOD (by method) approaching 0.4 ppm NH(3) in dry air.

A molecular scale perspective: Monte Carlo simulation for rupturing of ultra thin polymer film melts

NASA Astrophysics Data System (ADS)

Singh, Satya Pal

2017-04-01

Monte Carlo simulation has been performed to study the rupturing process of thin polymer film under strong confinement. The change in mean square displacement; pair correlation function; density distribution; average bond length and microscopic viscosity are sampled by varying the molecular interaction parameters such as the strength and the equilibrium positions of the bonding, non-bonding potentials and the sizes of the beads. The variation in mean square angular displacement χθ = [ < Δθ2 > - < Δθ>2 ] fits very well to a function of type y (t) = A + B *e-t/τ. This may help to study the viscous properties of the films and its dependence on different parameters. The ultra thin film annealed at high temperature gets ruptured and holes are created in the film mimicking spinodal dewetting. The pair correlation function and density profile reveal rich information about the equilibrium structure of the film. The strength and equilibrium bond length of finite extensible non-linear elastic potential (FENE) and non-bonding Morse potential have clear impact on microscopic rupturing of the film. The beads show Rouse or repetition motion forming rim like structures near the holes created inside the film. The higher order interaction as dipole-quadrupole may get prominence under strong confinement. The enhanced excluded volume interaction under strong confinement may overlap with the molecular dispersion forces. It can work to reorganize the molecules at the bottom of the scale and can imprint its signature in complex patterns evolved.

Dispersing nanoparticles in a polymer film via solvent evaporation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheng, Shengfeng; Grest, Gary S.

Large-scale molecular dynamics simulations are used to study the dispersion of nanoparticles (NPs) in a polymer film during solvent evaporation. As the solvent evaporates, a dense polymer-rich skin layer forms at the liquid/vapor interface, which is either NP rich or poor depending on the strength of the NP/polymer interaction. When the NPs are strongly wet by the polymer, the NPs accumulate at the interface and form layers. However, when the NPs are only partially wet by the polymer, most NPs are uniformly distributed in the bulk of the polymer film, with the dense skin layer serving as a barrier tomore » prevent the NPs from moving to the interface. Furthermore, our results point to a possible route to employ less favorable NP/polymer interactions and fast solvent evaporation to uniformly disperse NPs in a polymer film, contrary to the common belief that strong NP/polymer attractions are needed to make NPs well dispersed in polymer nanocomposites.« less

Dispersing nanoparticles in a polymer film via solvent evaporation

DOE PAGES

Cheng, Shengfeng; Grest, Gary S.

2016-05-19

Large-scale molecular dynamics simulations are used to study the dispersion of nanoparticles (NPs) in a polymer film during solvent evaporation. As the solvent evaporates, a dense polymer-rich skin layer forms at the liquid/vapor interface, which is either NP rich or poor depending on the strength of the NP/polymer interaction. When the NPs are strongly wet by the polymer, the NPs accumulate at the interface and form layers. However, when the NPs are only partially wet by the polymer, most NPs are uniformly distributed in the bulk of the polymer film, with the dense skin layer serving as a barrier tomore » prevent the NPs from moving to the interface. Furthermore, our results point to a possible route to employ less favorable NP/polymer interactions and fast solvent evaporation to uniformly disperse NPs in a polymer film, contrary to the common belief that strong NP/polymer attractions are needed to make NPs well dispersed in polymer nanocomposites.« less

21 CFR 175.320 - Resinous and polymeric coatings for polyolefin films.

Code of Federal Regulations, 2012 CFR

2012-04-01

... coating is applied as a continuous film over one or both sides of a base film produced from one or more of the basic olefin polymers complying with § 177.1520 of this chapter. The base polyolefin film may... as are provided: List of substances Limitations (i) Resins and polymers: Acrylic acid polymer and its...

21 CFR 175.320 - Resinous and polymeric coatings for polyolefin films.

Code of Federal Regulations, 2013 CFR

2013-04-01

... coating is applied as a continuous film over one or both sides of a base film produced from one or more of the basic olefin polymers complying with § 177.1520 of this chapter. The base polyolefin film may... as are provided: List of substances Limitations (i) Resins and polymers: Acrylic acid polymer and its...

A novel double-layer molecularly imprinted polymer film based surface plasmon resonance for determination of testosterone in aqueous media

NASA Astrophysics Data System (ADS)

Tan, Yuan; Jing, Lijing; Ding, Yonghong; Wei, Tianxin

2015-07-01

This work aimed to prepare a novel double-layer structure molecularly imprinted polymer film (MIF) on the surface plasmon resonance (SPR) sensor chips for detection of testosterone in aqueous media. The film was synthesized by in-situ UV photo polymerization. Firstly, the modification of gold surface of SPR chip was performed by 1-dodecanethiol. Then double-layer MIF was generated on the 1-dodecanethiol modified gold surface. The non-modified and imprinted surfaces were characterized by atomic force microscopy (AFM), fourier transform infrared (FTIR) spectroscopy and contact angle measurements. Analysis of SPR spectroscopy showed that the imprinted sensing film displayed good selectivity for testosterone compared to other analogues and the non-imprinted polymer film (NIF). Within the concentrations range of 1 × 10-12-1 × 10-8 mol/L, the coupling angle changes of SPR were linear with the negative logarithm of testosterone concentrations (R2 = 0.993). Based on a signal/noise ratio of three, the detection limit was estimated to be 10-12 mol/L. Finally, the developed MIF was successfully applied to the seawater detection of testosterone. The results in the experiments suggested that a combination of SPR sensing with MIF was a promising alternative method for detection of testosterone in aqueous media.

Photocurrent generation in carbon nitride and carbon nitride/conjugated polymer composites.

PubMed

Byers, Joshua C; Billon, Florence; Debiemme-Chouvy, Catherine; Deslouis, Claude; Pailleret, Alain; Semenikhin, Oleg A

2012-09-26

The semiconductor and photovoltaic properties of carbon nitride (CNx) thin films prepared using a reactive magnetron cathodic sputtering technique were investigated both individually and as composites with an organic conjugated polymer, poly(2,2'-bithiophene) (PBT). The CNx films showed an increasing thickness as the deposition power and/or nitrogen content in the gas mixture increase. At low nitrogen content and low deposition power (25-50 W), the film structure was dominated by the abundance of the graphitic sp(2) regions, whereas at higher nitrogen contents and magnetron power CNx films started to demonstrate semiconductor properties, as evidenced by the occurrence of photoconductivity and the development of a space charge region. However, CNx films alone did not show any reproducible photovoltaic properties. The situation changed, however, when CNx was deposited onto conjugated PBT substrates. In this configuration, CNx was found to function as an acceptor material improving the photocurrent generation both in solution and in solid state photovoltaic devices, with the external quantum efficiencies reaching 1% at high nitrogen contents. The occurrence of the donor-acceptor charge transfer was further evidenced by suppression of the n-doping of the PBT polymer by CNx. Nanoscale atomic force microscopy (AFM) and current-sensing AFM data suggested that CNx may form a bulk heterojunction with PBT.

Degradation of PVC/rPLA Thick Films in Soil Burial Experiment

NASA Astrophysics Data System (ADS)

Nowak, Bożena; Rusinowski, Szymon; Chmielnicki, Blazej; Kamińska-Bach, Grażyna; Bortel, Krzysztof

2016-10-01

Some of the biodegradable polymers can be blended with a synthetic polymer to facilitate their biodegradation in the environment. The objective of the study was to investigate the biodegradation of thick films of poly(vinyl chloride)/recycled polylactide (PVC/rPLA). The experiments were carried out in the garden soil or in the mixture of garden soil and hydrocarbon-contaminated soil under laboratory conditions. Since it is widely accepted that the biosurfactants secreted by microorganisms enable biotransformation of various hydrophobic substances in the environment, it was assumed that the use of contaminated soil, rich in biosurfactant producing bacteria, may accelerate biodegradation of plastics. After the experimental period, the more noticeable weight loss of polymer films was observed after incubation in the garden soil. However, more pronounced changes in the film surface morphology and chemical structure as well as decrease of tensile strength were observed after incubation of films in the mixture of garden and contaminated soil. It turned out that as a result of competition between two distinct groups of microorganisms present in the mixture of garden and hydrocarbon-contaminated soils the number of microorganisms and their activity were lower than the activity of indigenous microflora of garden soil as well as the amount of secreted biosurfactants towards plastics.

Unique cohesive nature of the β1-isomer of [70]PCBM fullerene on structures and photovoltaic performances of bulk heterojunction films with PffBT4T-2OD polymers.

PubMed

Umeyama, Tomokazu; Igarashi, Kensho; Sakamaki, Daisuke; Seki, Shu; Imahori, Hiroshi

2018-01-04

The effects of regioisomer and diastereomer separations of [70]PCBM on structures and photovoltaic properties of PffBT4T-2OD:[70]PCBM blend films have systematically been investigated for the first time. Decreasing the amount of a diastereomer of β-[70]PCBM with high aggregation tendency (β 1 -[70]PCBM) improved the photovoltaic performances.

3-dimensional free standing micro-structures by proton beam writing of Su 8-silver nanoParticle polymeric composite

NASA Astrophysics Data System (ADS)

Igbenehi, H.; Jiguet, S.

2012-09-01

Proton beam lithography a maskless direct-write lithographic technique (well suited for producing 3-Dimensional microstructures in a range of resist and semiconductor materials) is demonstrated as an effective tool in the creation of electrically conductive freestanding micro-structures in an Su 8 + Nano Silver polymer composite. The structures produced show non-ohmic conductivity and fit the percolation theory conduction model of tunneling of separated nanoparticles. Measurements show threshold switching and a change in conductivity of at least 4 orders of magnitude. The predictable range of protons in materials at a given energy is exploited in the creation of high aspect ratio, free standing micro-structures, made from a commercially available SU8 Silver nano-composite (GMC3060 form Gersteltec Inc. a negative tone photo-epoxy with added metallic nano-particles(Silver)) to create films with enhanced electrical properties when exposed and cured. Nano-composite films are directly written on with a finely focused MeV accelerated Proton particle beam. The energy loss of the incident proton beams in the target polymer nano- composite film is concentrated at the end of its range, where damage occurs; changing the chemistry of the nano-composite film via an acid initiated polymerization - creating conduction paths. Changing the energy of the incident beams provide exposed regions with different penetration and damage depth - exploited in the demonstrated cantilever microstructure.

The Chemical and Physical Properties of Pyrrole-Based Conducting Polymers: The Characterization of As-Grown Films by X-Ray Photoemission Spectroscopy.

DTIC Science & Technology

1983-04-07

has been the subject of the most extensive experimental and theoretical investigations because in this particular polymer bond-alternation defects6...systems2 3 " 2 4 that such structures can arise from simultaneous core electron photoionization and valence electron excitation ("shake up") or ionization...34shake off"). While structures on the high energy side of the direct photoionization peak could also arise from characteristic energy losses (Le

Hydrothermal Growth of ZnO Nanowires on UV-Nanoimprinted Polymer Structures.

PubMed

Park, Sooyeon; Moore, Sean A; Lee, Jaejong; Song, In-Hyouk; Farshchian, Bahador; Kim, Namwon

2018-05-01

Integration of zinc oxide (ZnO) nanowires on miniaturized polymer structures can broaden its application in multi-functional polymer devices by taking advantages of unique physical properties of ZnO nanowires and recent development of polymer microstructures in analytical systems. In this paper, we demonstrate the hydrothermal growth of ZnO nanowires on polymer microstructures fabricated by UV nanoimprinting lithography (NIL) using a polyurethane acrylate (PUA). Since PUA is a siloxane-urethane-acrylate compound containing the alpha-hydroxyl ketone, UV-cured PUA include carboxyl groups, which inhibit and suppress the nucleation and growth of ZnO nanowires on polymer structures. The presence of carboxyl groups in UV-cured PUA was substantiated by Fourier transform infrared spectroscopy (FTIR), and a Ag thin film was deposited on the nanoimprinted polymer structures to limit their inhibitive influence on the growth of ZnO nanowires. Furthermore, the naturally oxidized Ag layer (Ag2O) reduced crystalline lattice mismatches at the interface between ZnO-Ag during the seed annealing process. The ZnO nanowires grown on the Ag-deposited PUA microstructures were found to have comparable morphological characteristics with ZnO nanowires grown on a Si wafer.

RESEARCH ON THE ELECTRONIC AND OPTICAL PROPERTIES OF POLYMER AND OTHER ORGANIC MOLECULAR THIN FILMS

DOE Office of Scientific and Technical Information (OSTI.GOV)

ALEXEI G. VITUKHNOVSKY; IGOR I. SOBELMAN - RUSSIAN ACADEMY OF SCIENCES

1995-09-06

Optical properties of highly ordered films of poly(p-phenylene) (PPP) on different substrates, thin films of mixtures of conjugated polymers, of fullerene and its composition with polymers, molecular J-aggregates of cyanine dyes in frozen matrices have been studied within the framework of the Agreement. Procedures of preparation of high-quality vacuum deposited PPP films on different substrates (ITO, Si, GaAs and etc.) were developed. Using time-correlated single photon counting technique and fluorescence spectroscopy the high quality of PPP films has been confirmed. Dependence of structure and optical properties on the conditions of preparation were investigated. The fluorescence lifetime and spectra of highlymore » oriented vacuum deposited PPP films were studied as a function of the degree of polymerization. It was shown for the first time that the maximum fluorescence quantum yield is achieved for the chain length approximately equal to 35 monomer units. The selective excitation of luminescence of thin films of PPP was performed in the temperature range from 5 to 300 K. The total intensity of luminescence monotonically decreases with decreasing temperature. Conditions of preparation of highly cristallyne fullerene C{sub 60} films by the method of vacuum deposition were found. Composites of C{sub 60} with conjugated polymers PPV and polyacetylene (PA) were prepared. The results on fluorescence quenching, IR and resonant Raman spectroscopy are consistent with earlier reported ultrafast photoinduced electron transfer from PPV to C{sub 60} and show that the electron transfer is absent in the case of the PA-C{sub 60} composition. Strong quenching of PPV fluorescence was observed in the PPV-PA blends. The electron transfer from PPV to PA can be considered as one of the possible mechanisms of this quenching. The dynamics of photoexcitations in different types of J-aggregates of the carbocyanine dye was studied at different temperatures in frozen matrices. The optical properties of relatively simple J-aggregates with pure intrasegment relaxation, which they have found, may clarify the problem of the relationship between intrasegment and intersegment processes in the formation of luminescent states in more complicated conjugated polymers, which is important for construction of electroluminescence and photosensitive devices.« less

Synthesis of hydrazone functionalized epoxy polymers for non-linear optical device applications

NASA Astrophysics Data System (ADS)

Singh, Rajendra K.

A series of twelve, thermally crosslinkable, epoxy polymers bearing covalently attached NLO-active hydrazone chromophores were synthesized. The primary focus was on the synthesis of two series of NLO-active hydroxy functionalized hydrazone chromophores. The first series, called the monohydroxy series (Hydrazones I--VI) comprised of six monohydroxy functionalized hydrazones and the second series consisted of six dihydroxy functionalized hydrazones (Hydrazones VII--XII). These hydrazone chromophores were then grafted, via the hydroxy functionality, on to a commercial epoxy polymer to obtain twelve NLO-active soluble prepolymers. The grafting reaction yields multiple secondary hydroxyl sites due to opening of the epoxide rings and these hydroxyl groups were used for further crosslinking by formulating the prepolymers with a blocked polyisocyanate commercial crosslinker. This formulation was spin coated on glass slides to form 2--2.5 m m thick uniform, defect free, transparent films. The films were corona poled, above their Tg, to align the chromophores in a noncentrosymmetric fashion and simultaneously complete the thermal cure that results in a highly crosslinked network. Finally the thermal characteristics of the second order nonlinearity of the twelve polymers are compared to illustrate the key structure-property relationships underlying the performance of the films.

Tribochemical synthesis of nano-lubricant films from adsorbed molecules at sliding solid interface: Tribo-polymers from α-pinene, pinane, and n-decane

NASA Astrophysics Data System (ADS)

He, Xin; Barthel, Anthony J.; Kim, Seong H.

2016-06-01

The mechanochemical reactions of adsorbed molecules at sliding interfaces were studied for α-pinene (C10H16), pinane (C10H18), and n-decane (C10H22) on a stainless steel substrate surface. During vapor phase lubrication, molecules adsorbed at the sliding interface could be activated by mechanical shear. Under the equilibrium adsorption condition of these molecules, the friction coefficient of sliding steel surfaces was about 0.2 and a polymeric film was tribochemically produced. The synthesis yield of α-pinene tribo-polymers was about twice as much as pinane tribo-polymers. In contrast to these strained bicyclic hydrocarbons, n-decane showed much weaker activity for tribo-polymerization at the same mechanical shear condition. These results suggested that the mechanical shear at tribological interfaces could induce the opening of the strained ring structure of α-pinene and pinane, which leads to polymerization of adsorbed molecules at the sliding track. On a stainless steel surface, such polymerization reactions of adsorbed molecules do not occur under typical surface reaction conditions. The mechanical properties and boundary lubrication efficiency of the produced tribo-polymer films are discussed.

Orientational behavior of thin films of poly(3-methylthiophene) on platinium: A FTIR and near edge x-ray absorption fine structure (NEXAFS) study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, X.Q.; Chen, J.; Hale, P.D.

1988-01-01

Near edge x-ray absorption fine structure (NEXAFS) and infrared reflection-absorption spectroscopy (IRRAS) have been used to study the orientational behavior of thin films of poly(3-methylthiophene) electrochemically polymerized on a platinum surface. Clear orientational effects, with the thiophene rings predominantly oriented parallel to the platinum surface, were observed when the thickness of the polymer films were within a few hundred /angstrom/A. It was found that more highly ordered films were produced at lower polymerization potential (1.4V vs SCE) than at higher potential (1.8V vs SCE). 5 refs., 4 figs., 2 tabs.

Biological preconcentrator

DOEpatents

Manginell, Ronald P [Albuquerque, NM; Bunker, Bruce C [Albuquerque, NM; Huber, Dale L [Albuquerque, NM

2008-09-09

A biological preconcentrator comprises a stimulus-responsive active film on a stimulus-producing microfabricated platform. The active film can comprise a thermally switchable polymer film that can be used to selectively absorb and desorb proteins from a protein mixture. The biological microfabricated platform can comprise a thin membrane suspended on a substrate with an integral resistive heater and/or thermoelectric cooler for thermal switching of the active polymer film disposed on the membrane. The active polymer film can comprise hydrogel-like polymers, such as poly(ethylene oxide) or poly(n-isopropylacrylamide), that are tethered to the membrane. The biological preconcentrator can be fabricated with semiconductor materials and technologies.

Evaluation of high temperature structural adhesives for extended service, phase 5

NASA Technical Reports Server (NTRS)

Hendricks, C. L.; Hill, S. G.; Hale, J. N.; Dumars, W. G.

1987-01-01

The evaluation of 3 experimental polymers from NASA-Langley and a commercially produced polymer from Mitsui Toatsu Chemicals as high temperature structural adhesives is presented. A polyphenylquinoxaline (PPQ), polyimide (STPI/LaRC-2), and a polyarylene ether (PAE-SO2) were evaluated as metal-to-metal adhesives. Lap shear, crack extension, and climbing drum peel specimens were fabricated from all three polymers and tested after thermal, combined thermal/humidity, and stressed hydraulic fluid (Skydrol) exposure. The fourth polymer, LARC-TPI was evaluated as an adhesive for titanium honeycomb sandwich structure. All three experimental polymers performed well as metal-to-metal adhesives from 219 K (-65 F) to 505 K (450 F), including humidity exposure. Structural adhesive strength was also maintained at 505 K for a minimum of 3000 hours. LaRC-TPI was evaluated as a high temperature (505 K) adhesive for titanium honeycomb sandwich structure. The LaRC-TPI bonding process development concentrated on improving the honeycomb core-to-skin bond. The most promising approach of those evaluated combined a LaRC-TPI polymer solution with a semi-crystalline LaRC-TPI powder for adhesive film fabrication and fillet formation.

Changes induced by UV radiation in the presence of sodium benzoate in films formulated with polyvinyl alcohol and carboxymethyl cellulose.

PubMed

Villarruel, S; Giannuzzi, L; Rivero, S; Pinotti, A

2015-11-01

This work was focused on: i) developing single and blend films based on carboxymethyl cellulose (CMC) and polyvinyl alcohol (PVOH) studying their properties, ii) analyzing the interactions between CMC and PVOH and their modifications UV-induced in the presence of sodium benzoate (SB), and iii) evaluating the antimicrobial capacity of blend films containing SB with and without UV treatment. Once the blend films with SB were exposed to UV radiation, they exhibited lower moisture content as well as a greater elongation at break and rougher surfaces compared to those without treatment. Considering oxygen barrier properties, the low values obtained would allow their application as packaging with selective oxygen permeability. Moreover, the characteristics of the amorphous phase of the matrix prevailed with a rearrangement of the structure of the polymer chain, causing a decrease of the crystallinity degree. These results were supported by X-rays and DSC analysis. FT-IR spectra reflected some degree of polymer-polymer interaction at a molecular level in the amorphous regions. The incorporation of sodium benzoate combined with UV treatment in blend films was positive from the microbial point of view because of the growth inhibition of a wide spectrum of microorganisms. From a physicochemical perspective, the UV treatment of films also changed their morphology rendering them more insoluble in water, turning the functionalized blend films into a potential material to be applied as food packaging. Copyright © 2015 Elsevier B.V. All rights reserved.

Microstructural aspects in steel fiber reinforced acrylic emulsion polymer modified concrete

NASA Astrophysics Data System (ADS)

Hazimmah, Dayang; Ayob, Afizah; Sie Yee, Lau; Chee Cung, Wong

2018-03-01

Scanning electron microscope observations of polymer-free and polymer-modified cements have shown that the polymer particles are partitioned between the inside of hydrates and the surface of anhydrous cement grains. For optimum dosage of acrylic emulsion polymer with 2.5%, the C-S-H gel in this structure is finer and more acicular. Some polymer adheres or deposit on the surface of the C-S-H gel. The presence of acrylic emulsion polymer confines the ionic diffusion so that the Ca(OH)2 crystallized locally to form fine crystals. The void in the structures seems to be smaller but no polymer films appears to be bridging the walls of pores although many polymer bonds or C-S-H spread into the pore spaces. In addition to porosity reduction, acrylic emulsion polymer modified the hydration products in the steel fiber -matrix ITZ. The hydration product C-S-H appeared as a needle like shape. The needle-shaped C-S-H increases and gradually formed the gel, with needles growing into the pore space. The phenomenon is more obvious as curing age increased.

Interpenetrating polymer network ion exchange membranes and method for preparing same

DOEpatents

Alexandratos, Spiro D.; Danesi, Pier R.; Horwitz, E. Philip

1989-01-01

Interpenetrating polymer network ion exchange membranes include a microporous polymeric support film interpenetrated by an ion exchange polymer and are produced by absorbing and polymerizing monomers within the support film. The ion exchange polymer provides ion exchange ligands at the surface of and throughout the support film which have sufficient ligand mobility to extract and transport ions across the membrane.

The in situ synthesis of PbS nanocrystals from lead(II) n-octylxanthate within a 1,3-diisopropenylbenzene–bisphenol A dimethacrylate sulfur copolymer

PubMed Central

Bear, J. C.; Mayes, A. G.; Parkin, I. P.; O'Brien, P.

2017-01-01

The synthesis of lead sulfide nanocrystals within a solution processable sulfur ‘inverse vulcanization’ polymer thin film matrix was achieved from the in situ thermal decomposition of lead(II) n-octylxanthate, [Pb(S2COOct)2]. The growth of nanocrystals within polymer thin films from single-source precursors offers a faster route to networks of nanocrystals within polymers when compared with ex situ routes. The ‘inverse vulcanization’ sulfur polymer described herein contains a hybrid linker system which demonstrates high solubility in organic solvents, allowing solution processing of the sulfur-based polymer, ideal for the formation of thin films. The process of nanocrystal synthesis within sulfur films was optimized by observing nanocrystal formation by X-ray photoelectron spectroscopy and X-ray diffraction. Examination of the film morphology by scanning electron microscopy showed that beyond a certain precursor concentration the nanocrystals formed were not only within the film but also on the surface suggesting a loading limit within the polymer. We envisage this material could be used as the basis of a new generation of materials where solution processed sulfur polymers act as an alternative to traditional polymers. PMID:28878986

Sorption Behavior of Compressed CO2 and CH4 on Ultrathin Hybrid Poly(POSS-imide) Layers.

PubMed

Raaijmakers, Michiel J T; Ogieglo, Wojciech; Wiese, Martin; Wessling, Matthias; Nijmeijer, Arian; Benes, Nieck E

2015-12-09

Sorption of compressed gases into thin polymeric films is essential for applications including gas sensors and membrane based gas separation. For glassy polymers, the sorption behavior is dependent on the nonequilibrium status of the polymer. The uptake of molecules by a polymer is generally accompanied by dilation, or swelling, of the polymer material. In turn, this dilation can result in penetrant induced plasticization and physical aging that affect the nonequilibrium status of the polymer. Here, we investigate the dilation and sorption behavior of ultrathin membrane layers of a hybrid inorganic-organic network material that consists of alternating polyhedral oligomeric silsesquioxane and imide groups, upon exposure to compressed carbon dioxide and methane. The imide precursor contains fluoroalkene groups that provide affinity toward carbon dioxide, while the octa-functionalized silsesquioxane provides a high degree of cross-linking. This combination allows for extremely high sorption capacities, while structural rearrangements of the network are hindered. We study the simultaneous uptake of gases and dilation of the thin films at high pressures using spectroscopic ellipsometry measurements. Ellipsometry provides the changes in both the refractive index and the film thickness, and allows for accurate quantification of sorption and swelling. In contrast, gravimetric and volumetric measurements only provide a single parameter; this does not allow an accurate correction for, for instance, the changes in buoyancy because of the extensive geometrical changes of highly swelling films. The sorption behavior of the ultrathin hybrid layers depends on the fluoroalkene group content. At low pressure, the apparent molar volume of the gases is low compared to the liquid molar volume of carbon dioxide and methane, respectively. At high gas concentrations in the polymer film, the apparent molar volume of carbon dioxide and methane exceeds that of the liquid molar volume, and approaches that of the gas phase. The high sorption capacity and reversible dilation characteristics of the presented materials provide new directions for applications including gas sensors and gas separation membranes.

Nonlinear optical thin films

NASA Technical Reports Server (NTRS)

Leslie, Thomas M.

1993-01-01

A focused approach to development and evaluation of organic polymer films for use in optoelectronics is presented. The issues and challenges that are addressed include: (1) material synthesis, purification, and the tailoring of the material properties; (2) deposition of uniform thin films by a variety of methods; (3) characterization of material physical properties (thermal, electrical, optical, and electro-optical); and (4) device fabrication and testing. Photonic materials, devices, and systems were identified as critical technology areas by the Department of Commerce and the Department of Defense. This approach offers strong integration of basic material issues through engineering applications by the development of materials that can be exploited as the active unit in a variety of polymeric thin film devices. Improved materials were developed with unprecedented purity and stability. The absorptive properties can be tailored and controlled to provide significant improvement in propagation losses and nonlinear performance. Furthermore, the materials were incorporated into polymers that are highly compatible with fabrication and patterning processes for integrated optical devices and circuits. By simultaneously addressing the issues of materials development and characterization, keeping device design and fabrication in mind, many obstacles were overcome for implementation of these polymeric materials and devices into systems. We intend to considerably improve the upper use temperature, poling stability, and compatibility with silicon based devices. The principal device application that was targeted is a linear electro-optic modulation etalon. Organic polymers need to be properly designed and coupled with existing integrated circuit technology to create new photonic devices for optical communication, image processing, other laser applications such as harmonic generation, and eventually optical computing. The progression from microscopic sample to a suitable film-forming material in a working device is a complex, multifaceted endeavor. It requires close attention to maintaining the optical properties of the electro-optic active portion of the polymer while manipulating the polymer structure to obtain the desired secondary polymer properties.

Effects of anhydrous AlCl3 dopant on the structural, optical and electrical properties of PVA-PVP polymer composite films

NASA Astrophysics Data System (ADS)

Shanmugam, G.; Krishnakumar, V.

2018-05-01

Polymer composite films based on PVA-PVP with AlCl3 as the dopant at different concentrations were prepared using solution casting technique. XRD patterns reveal the increase in amorphousity of the films with AlCl3 doping. Optical absorption studies exhibit that the values of optical absorption coefficient, direct and indirect optical band gaps are found to decrease with increase in AlCl3 concentration. It confirms the charge transfer in complexes between the polymer and the dopant. The dielectric studies show the increase in dielectric constant at low frequency with increasing AlCl3 concentration and temperature. The ac conductivity and ionic conductivity increase with the AlCl3 content and the maximum value at room temperature is found to be 6.89 × 10-4 and 8.05 × 10-5 S/cm for higher AlCl3 doped PVA-PVP film. The estimated ionic conductivity value is three or four orders of magnitude greater than those obtained in the certain representative polymer-salt complexes as reported earlier. Electrical modulus plots confirm the removal of electrode polarization and the low conductivity relaxation time with Al doping. The activation energy estimated from the temperature dependent dc conductivity plot is agreed well with the migration energy calculated from the temperature dependent electric modulus plot.

Atomistic simulations of bulk, surface and interfacial polymer properties

NASA Astrophysics Data System (ADS)

Natarajan, Upendra

In chapter I, quasi-static molecular mechanics based simulations are used to estimate the activation energy of phenoxy rings flips in the amorphous region of a semicrystalline polyimide. Intra and intermolecular contributions to the flip activation energy, the torsional cooperativity accompanying the flip, and the effect of the flip on the motion in the glassy bulk state, are looked at. Also, comparison of the weighted mean activation energy is made with experimental data from solid state NMR measurements; the simulated value being 17.5 kcal/mol., while the experimental value was observed to be 10.5 kcal/mol. Chapter II deals with construction of random copolymer thin films of styrene-butadiene (SB) and styrene-butadiene-acrylonitrile (SBA). The structure and properties of the free surfaces presented by these thin films are analysed by, the atom mass density profiles, backbone bond orientation function, and the spatial distribution of acrylonitrile groups and styrene rings. The surface energies of SB and SBA are calculated using an atomistic equation and are compared with experimental data in the literature. In chapter III, simulations of polymer-polymer interfaces between like and unlike polymers, specifically cis-polybutadiene (PBD) and atatic polypropylene (PP), are presented. The structure of an incompatible polymer-polymer interface, and the estimation of the thermodynamic work of adhesion and interfacial energy between different incompatible polymers, form the focus here. The work of adhesion is calculated using an atomistic equation and is further used in a macroscopic equation to estimate the interfacial energy. The interfacial energy is compared with typical values for other immiscible systems in the literature. The interfacial energy compared very well with interfacial energy values for a few other immiscible hydrocarbon pairs. In chapter IV, the study proceeds to look at the interactions between nonpolar and polar small molecules with SB and SBA thin film surfaces. Toluene, hexadecane and water molecules are separately simulated to interact with SB and SBA surfaces in vacuum. The energetics of interaction are calculated atomistically and used in the atomistic equation to calculate the interfacial energy or the interaction energy. Comparisons with experimental data are not made due to the small concentrations of the molecules on the polymer surface. However, fundamental understanding of the structure of the system and the breakup of the energetics are provided by such a study.

Grazing-incidence small angle x-ray scattering studies of nanoscale polymer gratings

NASA Astrophysics Data System (ADS)

Doxastakis, Manolis; Suh, Hyo Seon; Chen, Xuanxuan; Rincon Delgadillo, Paulina A.; Wan, Lingshu; Williamson, Lance; Jiang, Zhang; Strzalka, Joseph; Wang, Jin; Chen, Wei; Ferrier, Nicola; Ramirez-Hernandez, Abelardo; de Pablo, Juan J.; Gronheid, Roel; Nealey, Paul

2015-03-01

Grazing-Incidence Small Angle X-ray Scattering (GISAXS) offers the ability to probe large sample areas, providing three-dimensional structural information at high detail in a thin film geometry. In this study we exploit the application of GISAXS to structures formed at one step of the LiNe (Liu-Nealey) flow using chemical patterns for directed self-assembly of block copolymer films. Experiments conducted at the Argonne National Laboratory provided scattering patterns probing film characteristics at both parallel and normal directions to the surface. We demonstrate the application of new computational methods to construct models based on scattering measured. Such analysis allows for extraction of structural characteristics at unprecedented detail.

Investigation of the influence of the composition on mechanical properties of polylactide

NASA Astrophysics Data System (ADS)

Baikin, A. S.; Sevostyanov, M. A.; Nasakina, E. O.; Sergienko, K. V.; Kaplan, M. A.; Konushkin, S. V.; Kolmakova, A. A.; Yakubov, A. D.; Kolmakov, A. G.

2018-04-01

In this paper we describe the creation of films from polylactide. Studied the mechanical properties of developed polymer films of polylactide. The effect of the molecular weight of polylactide on the mechanical properties of the resulting polymer films is shown. The dependence of the mechanical properties of polylactide films on the polymer concentration in chloroform was studied. The possibility of creating biodegradable films with specified mechanical properties is shown.

Studies on the high electronic energy deposition in polyaniline thin films

NASA Astrophysics Data System (ADS)

Deshpande, N. G.; Gudage, Y. G.; Vyas, J. C.; Singh, F.; Sharma, Ramphal

2008-05-01

We report here the physico-chemical changes brought about by high electronic energy deposition of gold ions in HCl doped polyaniline (PANI) thin films. PANI thin films were synthesized by in situ polymerization technique. The as-synthesized PANI thin films of thickness 160 nm were irradiated using Au7+ ion of 100 MeV energy at different fluences, namely, 5 × 1011 ions/cm2 and 5 × 1012 ions/cm2, respectively. A significant change was seen after irradiation in electrical and photo conductivity, which may be related to increased carrier concentration, and structural modifications in the polymer film. In addition, the high electronic energy deposition showed other effects like cross-linking of polymer chains, bond breaking and creation of defect sites. AFM observations revealed mountainous type features in all (before and after irradiation) PANI samples. The average size (diameter) and density of such mountainous clusters were found to be related with the ion fluence. The AFM profiles also showed change in the surface roughness of the films with respect to irradiation, which is one of the peculiarity of the high electronic energy deposition technique.

Simulated glass transition of poly(ethylene oxide) bulk and film: a comparative study.

PubMed

Wu, Chaofu

2011-09-29

Stepwise cooling molecular dynamics (MD) simulations have been carried out on the bulk and film models for poly(ethylene oxide) (PEO) to understand glass transition of amorphous polymer films. Three types of properties--density, energy, and dynamics--are computed and plotted against the temperature for the two systems. It has been confirmed that all these properties can reveal glass transition in both PEO bulk and film systems. All the determined glass transition temperatures (T(g)'s) drop in the same order of magnitude to the experimental data available. Among various methods, the T(g)'s obtained from the density and energy data are close to each other if the same space regions are defined, which can suggest the same free volume theory, and dynamic T(g)'s obtained from mean-squared displacements (MSDs) are highest, which can suggest the kinetic theory for structural relaxation. Consistently, all these T(g)'s obtained using different methods show that the T(g)'s of PEO film are lower than those of PEO bulk. The free surface layers of polymer films dictate this offset. © 2011 American Chemical Society

Investigation of ITO free transparent conducting polymer based electrode

NASA Astrophysics Data System (ADS)

Sharma, Vikas; Sapna, Sachdev, Kanupriya

2016-05-01

The last few decades have seen a significant improvement in organic semiconductor technology related to solar cell, light emitting diode and display panels. The material and structure of the transparent electrode is one of the major concerns for superior performance of devices such as OPV, OLED, touch screen and LCD display. Commonly used ITO is now restricted due to scarcity of indium, its poor mechanical properties and rigidity, and mismatch of energy levels with the active layer. Nowadays DMD (dielectric-metal-dielectric) structure is one of the prominent candidates as alternatives to ITO based electrode. We have used solution based spin coated polymer layer as the dielectric layer with silver thin film embedded in between to make a polymer-metal-polymer (PMP) structure for TCE applications. The PMP structure shows low resistivity (2.3 x 10-4Ω-cm), high carrier concentration (2.9 x 1021 cm-3) and moderate transparency. The multilayer PMP structure is characterized with XRD, AFM and Hall measurement to prove its suitability for opto-electronic device applications.

Organic conductive films for semiconductor electrodes

DOEpatents

Frank, Arthur J.

1984-01-01

According to the present invention, improved electrodes overcoated with conductive polymer films and preselected catalysts are provided. The electrodes typically comprise an inorganic semiconductor overcoated with a charge conductive polymer film comprising a charge conductive polymer in or on which is a catalyst or charge-relaying agent.

Comparative static curing versus dynamic curing on tablet coating structures.

PubMed

Gendre, Claire; Genty, Muriel; Fayard, Barbara; Tfayli, Ali; Boiret, Mathieu; Lecoq, Olivier; Baron, Michel; Chaminade, Pierre; Péan, Jean Manuel

2013-09-10

Curing is generally required to stabilize film coating from aqueous polymer dispersion. This post-coating drying step is traditionally carried out in static conditions, requiring the transfer of solid dosage forms to an oven. But, curing operation performed directly inside the coating equipment stands for an attractive industrial application. Recently, the use of various advanced physico-chemical characterization techniques i.e., X-ray micro-computed tomography, vibrational spectroscopies (near infrared and Raman) and X-ray microdiffraction, allowed new insights into the film-coating structures of dynamically cured tablets. Dynamic curing end-point was efficiently determined after 4h. The aim of the present work was to elucidate the influence of curing conditions on film-coating structures. Results demonstrated that 24h of static curing and 4h of dynamic curing, both performed at 60°C and ambient relative humidity, led to similar coating layers in terms of drug release properties, porosity, water content, structural rearrangement of polymer chains and crystalline distribution. Furthermore, X-ray microdiffraction measurements pointed out different crystalline coating compositions depending on sample storage time. An aging mechanism might have occur during storage, resulting in the crystallization and the upward migration of cetyl alcohol, coupled to the downward migration of crystalline sodium lauryl sulfate within the coating layer. Interestingly, this new study clearly provided further knowledge into film-coating structures after a curing step and confirmed that curing operation could be performed in dynamic conditions. Copyright © 2013 Elsevier B.V. All rights reserved.

Preparation, Structural and Dielectric Properties of Solution Grown Polyvinyl Alcohol(PVA) Film

NASA Astrophysics Data System (ADS)

Nangia, Rakhi; Shukla, Neeraj K.; Sharma, Ambika

2017-08-01

Flexible dielectrics with high permittivity have been investigated extensively due to their applications in electronic industry. In this work, structural and electrical characteristics of polymer based film have been analysed. Poly vinyl alcohol (PVA) film was prepared by solution casting method. X-ray diffraction (XRD) characterization technique is used to investigate the structural properties. The semi-crystalline nature has been determined by the analysis of the obtained XRD pattern. Electrical properties of the synthesized film have been analysed from the C-V and I-V curves obtained at various frequencies and temperatures. Low conductivity values confirm the insulating behaviour of the film. However, it is found that conductivity increases with temperature. Also, the dielectric permittivity is found to be higher at lower frequencies and higher temperatures, that proves PVA to be an excellent dielectric material which can be used in interface electronics. Dielectric behaviour of the film has been explained based on dipole orientations to slow and fast varying electric field. However further engineering can be done to modulate the structural, electrical properties of the film.

Diverse 2D structures obtained by adsorption of charged ABA triblock copolymer on different surfaces

NASA Astrophysics Data System (ADS)

Kontturi, Katri S.; Vesterinen, Arja-Helena; Seppälä, Jukka; Laine, Janne

2012-11-01

In the larger context of 2D polymeric structures, the morphologies obtained by adsorption and subsequent drying of charged, ABA type amphiphilic triblock copolymer of poly[2-(dimethylamino)ethyl metacrylate] (PDMAEMA) and poly(propylene oxide) (PPO) were investigated with atomic force microscopy and X-ray photoelectron spectroscopy as well as in situ adsorption analysis with quartz crystal microbalance with dissipation monitoring. Hydrophilic silica and hydrophobic polystyrene (PS) were used as substrates for adsorption. The structures emerging from the self-assembly of adsorbing polymer were profoundly influenced by composition of the aqueous solution and the choice of substrate. When adsorbed from dilute polymer solution where the concentration is so low that the polymer does not yet show surface-active behavior, the triblock copolymer unimers associated on hydrophilic silica surface forming large, irregular clustered aggregates, with sizes increasing with electrolyte concentration of the solution. On a hydrophobic PS substrate, on the other hand, unimers spread much more evenly, forming clear surface patterns. The roughness of these patterned structures was tuned with the electrolyte concentration of the solution. Adsorption from a more concentrated polymer solution, where the surface-activity of the polymer is perceptible, resulted in the formation of a smooth film with complete coverage over the hydrophilic silica substrate when the electrolyte concentration was high. On PS, on the other hand, nucleation of evenly scattered globular, disk-like micelles was induced. Besides the dry film morphology, the even distribution of the irreversibly adsorbed polymer over the PS surface was likely to serve as an optimal platform for the build-up of reversible hydrophobically bound multilayers at high electrolyte concentration. The multilayer formation was reversible because a decrease in the electrolyte concentration of the solution re-introduces strong electrostatic repulsion between the multilayered polymer coils which results in breakdown of the layer.

One-dimensional rigid film acoustic metamaterials

NASA Astrophysics Data System (ADS)

Ma, Fuyin; Wu, Jiu Hui; Huang, Meng

2015-11-01

We have designed a 1D film-type acoustic metamaterial structure consisting of several polymer films directly stacked on each other. It is experimentally revealed that the mass density law can be broken by such structures in the low frequency range. By comparing the sound transmission loss (STL) curves of structures with different numbers of cycles, materials and incident sound directions, several physical properties of the 1D film-type acoustic metamaterial are revealed, which consist of cyclical effects, surface effects and orientation effects. It is suggested that the excellent low frequency sound insulation capacity is influenced by both the cycle number and the stiffness of the film surface. Meanwhile, the surface effect plays a dominant role among these physical properties. Due to the surface acoustic property, for structures with a particular combination form, the STL dominated by the cyclical effects may reach saturation with increasing number of construction periods. Moreover, in some cases, the sound insulation ability is diverse for different sound incidence directions. This kind of 1D film-type periodic structure with these special physical properties provides a new concept for the regulation of sound waves.

Rheological and structural characterisation of film-forming solutions and biodegradable edible film made from kefiran as affected by various plasticizer types.

PubMed

Ghasemlou, Mehran; Khodaiyan, Faramarz; Oromiehie, Abdulrasoul

2011-11-01

The rheological properties of kefiran film-forming solutions, as well as the structural characterisation of the resulting films, were investigated as a function of various plasticizer types. The behaviours of the storage (G') and loss (G″) moduli as a function of frequency were typical of gel-like material, with the G' higher than the G″. Kefiran-based films, which may find application as edible films, were prepared by a casting and solvent-evaporation method. Possible interaction between the adjacent chains in the kefiran polymer and various plasticizers was proven by Fourier-transform infrared spectroscopy (FT-IR). The crystallinity of plasticized kefiran film was also analysed using X-ray diffraction (XRD); this revealed an amorphous-crystalline structure. These results were explained by the film's microstructure, which was analysed by atomic force microscopy (AFM) and scanning electron microscopy (SEM). The present study has helped determine possible interactions of kefiran, plasticizer and water molecules in determining film properties. Copyright © 2011 Elsevier B.V. All rights reserved.

Testing of Flexible Ballutes in Hypersonic Wind Tunnels for Planetary Aerocapture

NASA Technical Reports Server (NTRS)

Buck, Gregory M.

2007-01-01

Studies were conducted for the In-Space Propulsion (ISP) Ultralightweight Ballute Technology Development Program to increase the technical readiness level of inflatable decelerator systems for planetary aerocapture. The present experimental study was conducted to develop the capability for testing lightweight, flexible materials in hypersonic facilities. The primary objectives were to evaluate advanced polymer film materials in a high-temperature, high-speed flow environment and provide experimental data for comparisons with fluid-structure interaction modeling tools. Experimental testing was conducted in the Langley Aerothermodynamics Laboratory 20-Inch Hypersonic CF4 and 31-Inch Mach 10 Air blowdown wind tunnels. Quantitative flexure measurements were made for 60 degree half angle afterbody-attached ballutes, in which polyimide films (1-mil and 3- mil thick) were clamped between a 1/2-inch diameter disk and a base ring (4-inch and 6-inch diameters). Deflection measurements were made using a parallel light silhouette of the film surface through an existing schlieren optical system. The purpose of this paper is to discuss these results as well as free-flying testing techniques being developed for both an afterbody-attached and trailing toroidal ballute configuration to determine dynamic fluid-structural stability. Methods for measuring polymer film temperature were also explored using both temperature sensitive paints (for up to 370 C) and laser-etched thin-film gages.

Testing of Flexible Ballutes in Hypersonic Wind Tunnels for Planetary Aerocapture

NASA Technical Reports Server (NTRS)

Buck, Gregory M.

2006-01-01

Studies were conducted for the In-Space Propulsion (ISP) Ultralightweight Ballute Technology Development Program to increase the technical readiness level of inflatable decelerator systems for planetary aerocapture. The present experimental study was conducted to develop the capability for testing lightweight, flexible materials in hypersonic facilities. The primary objectives were to evaluate advanced polymer film materials in a high-temperature, high-speed flow environment and provide experimental data for comparisons with fluid-structure interaction modeling tools. Experimental testing was conducted in the Langley Aerothermodynamics Laboratory 20-Inch Hypersonic CF4 and 31-Inch Mach 10 Air blowdown wind tunnels. Quantitative flexure measurements were made for 60 degree half angle afterbody-attached ballutes, in which polyimide films (1-mil and 3-mil thick) were clamped between a 1/2-inch diameter disk and a base ring (4-inch and 6-inch diameters). Deflection measurements were made using a parallel light silhouette of the film surface through an existing schlieren optical system. The purpose of this paper is to discuss these results as well as free-flying testing techniques being developed for both an afterbody-attached and trailing toroidal ballute configuration to determine dynamic fluid-structural stability. Methods for measuring polymer film temperature were also explored using both temperature sensitive paints (for up to 370 C) and laser-etched thin-film gages.

Fabrication of efficient graphene-doped polymer/fullerene bilayer organic solar cells in air using spin coating followed by ultrasonic vibration post treatment

NASA Astrophysics Data System (ADS)

Zabihi, Fatemeh; Chen, Qianli; Xie, Yu; Eslamian, Morteza

2016-12-01

In this work, in an attempt to improve the performance and lifetime of organic solar cells, P3HT photon absorbing polymer was doped with graphene (G) nano-sheets, to make light harvesting G-P3HT composite thin film. The composite this film was then employed as the donor of a bilayer organic solar cell with the structure of glass/ITO/PEDOT:PSS/G-P3HT/C60/Al. The reference P3HT:PCBM bulk heterojunction solar cell was also fabricated for comparison. All solution-processed layers were made by spin coating in humid air (Shanghai, China); C60 and Al were deposited by thermal evaporation. An effective mechanical treatment approach developed by the authors, i.e. the application of forced ultrasonic vibration on the wet spun-on films, was used to improve the dispersion of graphene in G-P3HT composite films to obtain a uniform nanostructure. This mechanical method eliminates tedious and expensive chemical steps, currently performed to engineer the structure of organic solar cells. It is evidenced that the G-P3HT composite thin films, post treated by ultrasonic vibration at the optimum vibration duration, possess superior electrical conductivity, charge carrier mobility and density, uniform surface potential distribution, and lower surface roughness, compared to those of P3HT and G-P3HT thin films made without vibration. The results show significant improvement in the power conversion efficiency (PCE) of vibration-treated G-P3HT/C60 cell (PCE = 5.17%, the highest reported for this structure), substantiating the strong positive effect of using graphene and forced vibration for the fabrication of P3HT active layer in the bilayer cell structure.

The effect of polymer architecture on the interdiffusion in thin polymer films

NASA Astrophysics Data System (ADS)

Caglayan, Ayse; Yuan, Guangcui; Satija, Sushil K.; Uhrig, David; Hong, Kunlun; Akgun, Bulent

Branched polymer chains have been traditionally used in industrial applications as additives. Recently they have found applications in electrochromic displays, lithography, biomedical coatings and targeting multidrug resistant bacteria. In some of these applications where they are confined in thin layers, it is important to understand the relation between the mobility and polymer chain architecture to optimize the processing conditions. Earlier interdiffusion measurements on linear and cyclic polymer chains demonstrated the key role of chain architecture on mobility. We have determined the vertical diffusion coefficients of the star polystyrene chains in thin films as a function of number of polymer arms, molecular weight per arm, and film thickness using neutron reflectivity (NR) and compare our results with linear chains of identical total molecular weight. Bilayer samples of 4-arm and 8-arm protonated polystyrenes (hPS) and deuterated polystyrenes (dPS) were used to elucidate the effect of polymer chain architecture on polymer diffusion. NR measurements indicate that the mobility of polymer chains in thin films get faster as the number of polymer arms increases and the arm molecular weight decreases. Both star polymers showed faster interdiffusion compared to their linear analog. Diffusion coefficient of branched PS chains has a weak dependence on the film thickness.

Developing Novel Fluorescent Materials with Near Infrared Emission by Using m-Phenylene

NASA Technical Reports Server (NTRS)

Pang, Yi; Liao, Ling; Meador, Michael A.

2003-01-01

Our research focuses on development of novel p-conjugated polymers with desired emission. In the current study, the structure of a highly green-emitting poly[(m-phenylenevinylene)- alt-( p-phenylenevinylene)] has been modified by increasing the content of p-phenylene to achieve red- and infrared-emission. The polymer is synthesized via Wittig-Horner condensation, which is known to lead to trans-olefin linkage. The polymer is soluble in common organic solvents such as toluene, chloroform and THF. The spectroscopic properties of the polymer in both solution and film states will be discussed in comparison with its model compound.

Understanding the effect of nanoporosity on optimizing the performance of self-healing materials for anti-corrosion applications

NASA Astrophysics Data System (ADS)

Sellaiyan, S.; Smith, S. V.; Hughes, A. E.; Miller, A.; Jenkins, D. R.; Uedono, A.

2011-01-01

The chromate-based epoxy primer film was prepared on glass and metal surfaces using various graded doctor blades. The quality and consistency of the films was assessed using scanning electron microscopy and the porosity within the film characterized by positron annihilation lifetime spectroscopy. The positron lifetime (τ) distribution for the epoxy polymer matrix was resolved using the CONTIN program. The free volume was found from the ortho-positronium component. The optimum thickness for the films was established for future structure/activity studies.

Study on Buckling of Stiff Thin Films on Soft Substrates as Functional Materials

NASA Astrophysics Data System (ADS)

Ma, Teng

In engineering, buckling is mechanical instability of walls or columns under compression and usually is a problem that engineers try to prevent. In everyday life buckles (wrinkles) on different substrates are ubiquitous -- from human skin to a rotten apple they are a commonly observed phenomenon. It seems that buckles with macroscopic wavelengths are not technologically useful; over the past decade or so, however, thanks to the widespread availability of soft polymers and silicone materials micro-buckles with wavelengths in submicron to micron scale have received increasing attention because it is useful for generating well-ordered periodic microstructures spontaneously without conventional lithographic techniques. This thesis investigates the buckling behavior of thin stiff films on soft polymeric substrates and explores a variety of applications, ranging from optical gratings, optical masks, energy harvest to energy storage. A laser scanning technique is proposed to detect micro-strain induced by thermomechanical loads and a periodic buckling microstructure is employed as a diffraction grating with broad wavelength tunability, which is spontaneously generated from a metallic thin film on polymer substrates. A mechanical strategy is also presented for quantitatively buckling nanoribbons of piezoelectric material on polymer substrates involving the combined use of lithographically patterning surface adhesion sites and transfer printing technique. The precisely engineered buckling configurations provide a route to energy harvesters with extremely high levels of stretchability. This stiff-thin-film/polymer hybrid structure is further employed into electrochemical field to circumvent the electrochemically-driven stress issue in silicon-anode-based lithium ion batteries. It shows that the initial flat silicon-nanoribbon-anode on a polymer substrate tends to buckle to mitigate the lithiation-induced stress so as to avoid the pulverization of silicon anode. Spontaneously generated submicron buckles of film/polymer are also used as an optical mask to produce submicron periodic patterns with large filling ratio in contrast to generating only ˜100 nm edge submicron patterns in conventional near-field soft contact photolithography. This thesis aims to deepen understanding of buckling behavior of thin films on compliant substrates and, in turn, to harness the fundamental properties of such instability for diverse applications.

Hydrophilization and hydrophobic recovery in polymers obtained by casting of polymer solutions on water surface.

PubMed

Bormashenko, Edward; Chaniel, Gilad; Gendelman, Oleg

2014-12-01

We demonstrate the possibility of hydrophilization of polymer films in situ under the process of their preparation. The polymer surface is hydrophilized when the polymer solution is spread on the water surface and the solvent is evaporated. Essential hydrophilization of the polymer surface is achieved under this process. We relate the observed hydrophilization of polymer films to the dipole-dipole interaction of the polar moieties of polymer chains with highly polar water molecules. The dipole-dipole interaction between water molecules and polar groups of polymer chains, orienting the polar groups of a polymer, may prevail over the London dispersion forces. The process, reported in the paper, allows to manufacture the films in which the hydrophilic moieties of the polymer molecule are oriented toward the polymer/air interface. It is demonstrated that even such traditionally extremely hydrophobic polymers as polydimethylsiloxane can be markedly hydrophilized. This hydrophilization, however, does not persist forever. After removal from the water surface, hydrophobic recovery was observed, i.e. polymer films restored their hydrophobicity with time. The characteristic time of the hydrophobic recovery is on the order of magnitude of hours. Copyright © 2014 Elsevier Inc. All rights reserved.

Organic conductive films for semiconductor electrodes

DOEpatents

Frank, A.J.

1984-01-01

According to the present invention, improved electrodes overcoated with conductive polymer films and preselected catalysts are provided. The electrodes typically comprise an inorganic semiconductor over-coated with a charge conductive polymer film comprising a charge conductive polymer in or on which is a catalyst or charge-relaying agent.

Hot pen and laser writable photonic polymer films

NASA Astrophysics Data System (ADS)

Moirangthem, Monali; Stumpel, Jelle E.; Alp, Baran; Teunissen, Pit; Bastiaansen, Cees W. M.; Schenning, Albertus P. H. J.

2016-03-01

An orange-reflecting photonic polymer film has been fabricated based on a hydrogen-bonded cholesteric liquid crystalline (CLC) polymer consisting of non-reactive (R)-(+)-3-methyladipic acid as the chiral dopant. This polymer film can be patterned easily by evaporating the chiral dopant at specific locations with a hot pen or a laser beam. Removal of chiral dopant leads to a decrease in the helical pitch at the heat treated areas leading to a change in color from orange to green revealing a high contrast pattern. The photonic patterns are irreversible and stable at ambient conditions. This makes such a CLC polymer film interesting as writable photonic paper.

The effect of confinement on the crystalline microstructure of polymer: fullerene bulk heterojunctions

DOE PAGES

Ashraf, A.; Dissanayake, D. M. N. M.; Eisaman, M. D.

2015-07-01

We investigate the effect of confinement on the coherence length and the crystalline microstructure of the polymer component of polymer: fullerene bulk heterojunction thin films using grazing incidence wide angle x-ray scattering. We find that the polymer crystallite size decreases and the alignment of the molecules along the surface normal increases, as the thin-film thickness is reduced from 920nm to < 20nm and approaches the thin-film confinement regime. Furthermore, we find that the polymer crystallite size near the surface (air interface) is lower than the crystallite size in the bulk or the bottom (substrate interface) of bulk heterojunction films thickermore » than the confinement regime. Variation in polymer crystallite size can cause changes in charge carrier mobility and recombination rates, which in turn affect the performance of bulk heterojunction thin film devices such as photovoltaics and photodetectors« less

Stability Enhancement of Polymeric Sensing Films Using Fillers

NASA Technical Reports Server (NTRS)

Lin, Brian; Shevade, Abhijit; Ryan, Margaret Amy; Kisor, Adam; Yen, Shiao-Pin; Manatt, Kenneth; Homer, Margie; Fleurial, Jean-Pierre

2006-01-01

Experiments have shown the stability enhancement of polymeric sensing films on mixing the polymer with colloidal filler particles (submicron-sized) of carbon black, silver, titanium dioxide, and fumed silicon dioxide. The polymer films are candidates for potential use as sensing media in micro/nano chemical sensor devices. The need for stability enhancement of polymer sensing films arises because such films have been found to exhibit unpredictable changes in sensing activity over time, which could result in a possible failure of the sensor device. The changes in the physical properties of a polymer sensing film caused by the sorption of a target molecule can be measured by any of several established transduction techniques: electrochemical, optical, calorimetric, or piezoelectric, for example. The transduction technique used in the current polymer stability experiments is based on piezoelectric principles using a quartz-crystal microbalance (QCM). The surface of the QCM is coated with the polymer, and the mass uptake by the polymer film causes a change in the oscillating frequency of the quartz crystal. The polymer used for the current study is ethyl cellulose. The polymer/ polymer composite solutions were prepared in 1,3 dioxolane solvent. The filler concentration was fixed at 10 weight percent for the composites. The polymer or polymer composite solutions were cast on the quartz crystal having a fundamental frequency of about 6 MHz. The coated crystal was subjected to a multistage drying process to remove all measurable traces of the solvent. In each experiment, the frequency of oscillation was measured while the QCM was exposed to clean, dry, flowing air for about 30 minutes, then to air containing a known concentration of isopropanol for about 30 minutes, then again to clean dry air for about 30 minutes, and so forth. This cycle of measurements for varying isopropanol concentrations was repeated at intervals for several months. The figure depicts some of the sensing film stability results for ethyl cellulose polymer, ethyl cellulose-carbon black, and ethyl cellulose-silicon dioxide composite systems. An ethyl cellulose film exhibited a marked decline in response in the first few months of study and settled to a steady average response after about four months. However, response varied widely around the average response for ethyl cellulose film. In contrast, ethyl cellulose- carbon black and ethyl cellulose-silicon dioxide composites also declined in the early months, but showed more repeatable sensing film activity after the initial decline. Similar trends were observed in experiments for ethyl cellulose-titanium dioxide and ethyl cellulose-silver composites.

Preparation of poly(vinyl alcohol)/chitosan/starch blends and studies on thermal and surface properties

NASA Astrophysics Data System (ADS)

Nasalapure, Anand V.; Chalannavar, Raju K.; Malabadi, Ravindra B.

2018-05-01

Biopolymers are abundantly available from its natural sources of extraction. Chitosan(CH) is one of the widely used natural polymer which is perspective natural polysaccharide. Natural polymer blend with synthetic polymer enhances property of the material such as polyvinyl alcohol (PVA). PVA is nontoxic degradable synthetic polymer and very good film forming polymer. In this study prepared hybrid based film by adding starch into Chitosan/PVA which slighlty increased the surface and thermal property of ternary blend film.

Structure-property correlations of ion-containing polymers for fuel cell applications

NASA Astrophysics Data System (ADS)

Sproll, Véronique; Nagy, Gergely; Gasser, Urs; Balog, Sandor; Gustavsson, Sanna; Schmidt, Thomas J.; Gubler, Lorenz

2016-01-01

In order to investigate the structure-property correlations of grafted proton conducting membranes, the model system consisting of an ETFE base film grafted with polystyrene and subsequent sulfonation (ETFE-g-PSSA) along with crosslinked derivatives ETFE-g-P(SSA-co-DiPB) were synthesized. The characteristics of the final membranes were characterized by PFG-NMR diffusometry, in-plane conductivity and by investigations of the dimensional changes of the grafted membranes. The collected data were correlated with the inherent anisotropy of the ETFE base film.

Charge-flow structures as polymeric early-warning fire alarm devices. M.S. Thesis; [metal oxide semiconductors

NASA Technical Reports Server (NTRS)

Sechen, C. M.; Senturia, S. D.

1977-01-01

The charge-flow transistor (CFT) and its applications for fire detection and gas sensing were investigated. The utility of various thin film polymers as possible sensing materials was determined. One polymer, PAPA, showed promise as a relative humidity sensor; two others, PFI and PSB, were found to be particularly suitable for fire detection. The behavior of the charge-flow capacitor, which is basically a parallel-plate capacitor with a polymer-filled gap in the metallic tip electrode, was successfully modeled as an RC transmission line. Prototype charge-flow transistors were fabricated and tested. The effective threshold voltage of this metal oxide semiconductor was found to be dependent on whether surface or bulk conduction in the thin film was dominant. Fire tests with a PFI-coated CFT indicate good sensitivity to smouldering fires.

Spectroscopic properties of (PVA+ZnO):Mn{sup 2+} polymer films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rani, Ch.; Raju, D. Siva; Bindu, S. Hima

2015-05-15

Electron Paramagnetic Resonance (EPR), optical absorption and infrared spectral studies have been carried out on Mn{sup 2+} ions doped in poly(vinyl alcohol) complexed with zinc oxide polymer films prepared by solution cast technique. The EPR spectra of 1 mol% Mn{sup 2+} ions doped polymer complex (PVA+ZnO) at room temperature exhibit sextet hyperfine structure (hfs), centered at 2.01. The spin-Hamiltonian parameter values indicate that the ground state of Mn{sup 2+} ion in d{sup 5} and the site symmetry around Mn{sup 2+} ions in tetragonally distorted octa hedral site. The optical absorption spectra exhibits two bands centered at 275nm at 437nm. Themore » FTIR spectrum exhibits bands characteristic of stretching and banding vibrations of O-H, C-H and C=C groups.« less

Water-Stable Nanoporous Polymer Films with Excellent Proton Conductivity.

PubMed

Wang, Zhengbang; Liang, Cong; Tang, Haolin; Grosjean, Sylvain; Shahnas, Artak; Lahann, Joerg; Bräse, Stefan; Wöll, Christof

2018-03-01

Achieving high values for proton conductivity in a material critically depends on providing hopping sites arranged in a regular fashion. Record values reported for regular, molecular crystals cannot yet be reached by technologically relevant systems, and the best values measured for polymer membranes suited for integration into devices are almost two orders of magnitude lower. Here, an alternative polymer membrane synthesis strategy based on the chemical modification of surface-mounted, monolithic, crystalline metal-organic framework thin films is demonstrated. Due to chemical crosslinking and subsequent removal of metal ions, these surface-mounted gels (SURGELs) are found to exhibit high proton conductivity (0.1 S cm -1 at 30 °C and 100% RH (relative humidity). These record values are attributed to the highly ordered polymer network structure containing regularly spaced carboxylic acid side groups. These covalently bound organic frameworks outperform conventional, ion-conductive polymers with regard to ion conductivity and water stability. Pronounced water-induced swelling, which causes severe mechanical instabilities in commercial membranes, is not observed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Graphene Oxide-Polymer Composite Langmuir Films Constructed by Interfacial Thiol-Ene Photopolymerization

NASA Astrophysics Data System (ADS)

Luo, Xiaona; Ma, Kai; Jiao, Tifeng; Xing, Ruirui; Zhang, Lexin; Zhou, Jingxin; Li, Bingbing

2017-02-01

The effective synthesis and self-assembly of graphene oxide (GO) nanocomposites are of key importance for a broad range of nanomaterial applications. In this work, a one-step chemical strategy is presented to synthesize stable GO-polymer Langmuir composite films by interfacial thiol-ene photopolymerization at room temperature, without use of any crosslinking agents and stabilizing agents. It is discovered that photopolymerization reaction between thiol groups modified GO sheets and ene in polymer molecules is critically responsible for the formation of the composite Langmuir films. The film formed by Langmuir assembly of such GO-polymer composite films shows potential to improve the mechanical and chemical properties and promotes the design of various GO-based nanocomposites. Thus, the GO-polymer composite Langmuir films synthesized by interfacial thiol-ene photopolymerization with such a straightforward and clean manner, provide new alternatives for developing chemically modified GO-based hybrid self-assembled films and nanomaterials towards a range of soft matter and graphene applications.

In situ ultra-small-angle X-ray scattering study under uniaxial stretching of colloidal crystals prepared by silica nanoparticles bearing hydrogen-bonding polymer grafts

DOE PAGES

Ishige, Ryohei; Williams, Gregory A.; Higaki, Yuji; ...

2016-04-19

A molded film of single-component polymer-grafted nanoparticles (SPNP), consisting of a spherical silica core and densely grafted polymer chains bearing hydrogen-bonding side groups capable of physical crosslinking, was investigated byin situultra-small-angle X-ray scattering (USAXS) measurement during a uniaxial stretching process. Static USAXS revealed that the molded SPNP formed a highly oriented twinned face-centered cubic (f.c.c.) lattice structure with the [11-1] plane aligned nearly parallel to the film surface in the initial state. Structural analysis ofin situUSAXS using a model of uniaxial deformation induced by rearrangement of the nanoparticles revealed that the f.c.c. lattice was distorted in the stretching direction inmore » proportion to the macroscopic strain until the strain reached 35%, and subsequently changed into other f.c.c. lattices with different orientations. The lattice distortion and structural transition behavior corresponded well to the elastic and plastic deformation regimes, respectively, observed in the stress–strain curve. The attractive interaction of the hydrogen bond is considered to form only at the top surface of the shell and then plays an effective role in cross-linking between nanoparticles. The rearrangement mechanism of the nanoparticles is well accounted for by a strong repulsive interaction between the densely grafted polymer shells of neighboring particles.« less

Flexible and conductive MXene films and nanocomposites with high capacitance

DOE PAGES

Ling, Zheng; Ren, Chang E.; Zhao, Meng-Qiang; ...

2014-11-11

MXenes, a new family of 2D materials, combine hydrophilic surfaces with metallic conductivity. Delamination of MXene produces single-layer nanosheets with thickness of about a nanometer and lateral size of the order of micrometers. The high aspect ratio of delaminated MXene renders it promising nanofiller in multifunctional polymer nanocomposites. In this study, Ti 3C 2T x MXene was mixed with either a charged polydiallyldimethylammonium chloride (PDDA) or an electrically neutral polyvinyl alcohol (PVA) to produce Ti 3C 2T x/polymer composites. The as-fabricated composites are flexible and have electrical conductivities as high as 2.2 × 10 4 S/m in the case ofmore » the Ti 3C 2T x/PVA composite film and 2.4 × 10 5 S/m for pure Ti 3C 2T x films. The tensile strength of the Ti 3C 2T x/PVA composites was significantly enhanced compared with pure Ti 3C 2T x or PVA films. The intercalation and confinement of the polymer between the MXene flakes not only increased flexibility but also enhanced cationic intercalation, offering an impressive volumetric capacitance of ~530 F/cm 3 for MXene/PVA-KOH composite film at 2 mV/s. Finally, to our knowledge, this study is a first, but crucial, step in exploring the potential of using MXenes in polymer-based multifunctional nanocomposites for a host of applications, such as structural components, energy storage devices, wearable electronics, electrochemical actuators, and radiofrequency shielding, to name a few.« less

Tuning Fano resonances with a nano-chamber of air.

PubMed

Chen, Jianjun; He, Keke; Sun, Chengwei; Wang, Yujia; Li, Hongyun; Gong, Qihuang

2016-05-15

By designing a polymer-film-coated asymmetric metallic slit structure that only contains one nanocavity side-coupled with a subwavelength plasmonic waveguide, the Fano resonance is realized in the experiment. The Fano resonance originates from the interference between the narrow resonant spectra of the radiative light from the nanocavity and the broad nonresonant spectra of the directly transmitted light from the slit. The lateral dimension of the asymmetric slit is only 825 nm. Due to the presence of the soft polymer film, a nano-chamber of air is constructed. Based on the opto-thermal effect, the air volume in the nano-chamber is expanded by a laser beam, which blueshifts the Fano resonance. This tunable Fano resonance in such a submicron slit structure with a nano-chamber is of importance in the highly integrated plasmonic circuits.

Mode and polarization state selected guided wave spectroscopy of orientational anisotrophy in model membrane cellulosic polymer films: relevance to lab-on-a-chip

NASA Astrophysics Data System (ADS)

Andrews, Mark P.; Kanigan, Tanya

2007-06-01

Orientation anisotropies in structural properties relevant to the use of cellulosic polymers as membranes for lab-on-chips were investigated for cellulose acetate (CA) and regenerated cellulose (RC) films deposited as slab waveguides. Anisotropy was probed with mode and polarization state selected guided wave Raman spectroscopy. CA exhibits partial chain orientation in the plane of the film, and this orientation is independent of sample substrate and film preparation conditions. RC films also show in-plane anisotropy, where the hexose sugar rings lie roughly in the plane of the film. Explanations are given of the role of artifacts in interpreting waveguide Raman spectra, including anomalous contributions to Raman spectra that arise from deviations from right angle scattering geometry, mode-dependent contributions to longitudinal electric field components and TE<-->TM mode conversion. We explore diffusion profiles of small molecules in cellulosic films by adaptations of an inverse-Wentzel-Kramers-Brillouin (iWKB) recursive, noninteger virtual mode index algorithm. Perturbations in the refractive index distribution, n(z), are recovered from the measured relative propagation constants, neffective,m, of the planar waveguide. The refractive index distribution then yields the diffusion profile.

Coulombic interactions on the deposition and rotational mobility distributions of dyes in polyelectrolyte multilayer thin films.

PubMed

Li, Ye; Yip, Wai Tak

2004-12-07

We employed negatively charged fluorescein (FL), positively charged rhodamine 6G (R6G), and neutral Nile Red (NR) as molecular probes to investigate the influence of Coulombic interaction on their deposition into and rotational mobility inside polyelectrolyte multilayer (PEM) films. The entrapment efficiency of the dyes reveals that while Coulombic repulsion has little effect on dye deposition, Coulombic attraction can dramatically enhance the loading efficiency of dyes into a PEM film. By monitoring the emission polarization of single dye molecules in polyethylenimine (PEI) films, the percentages of mobile R6G, NR, and FL were determined to be 87 +/- 4%, 76 +/- 5%, and 68 +/- 3%, respectively. These mobility distributions suggest that cationic R6G enjoys the highest degree of rotational freedom, whereas anionic FL shows the least mobility because of Coulombic attraction toward cationic PEI. Regardless of charges, this high percentage of mobile molecules is in stark contrast to the 5-40% probe mobility reported from spun-cast polymer films, indicating that our PEI films contain more free volume and display richer polymer dynamics. These observations demonstrate the potential of using isolated fluorescent probes to interrogate the internal structure of a PEM film at a microscopic level.

Structural Studies of dielectric HDPE+ZrO2 polymer nanocomposites: filler concentration dependences

NASA Astrophysics Data System (ADS)

Nabiyev, A. A.; Islamov, A. Kh; Maharramov, A. M.; Nuriyev, M. A.; Ismayilova, R. S.; Doroshkevic, A. S.; Pawlukojc, A.; Turchenko, V. A.; Olejniczak, A.; Rulev, M. İ.; Almasan, V.; Kuklin, A. I.

2018-03-01

Structural properties of HDPE+ZrO2 polymer nanocomposites thin films of 80-100μm thicknesses were investigated using SANS, XRD, Laser Raman and FTIR spectroscopy. The mass fraction of the filler was 1, 3, 10, and 20%. Results of XRD analysis showed that ZrO2 powder was crystallized both in monoclinic and in cubic phase under normal conditions. The percentages of monoclinic and cubic phase were found to be 99.8% and 0.2%, respectively. It was found that ZrO2 nanoparticles did not affect the main crystal and chemical structure of HDPE, but the degree of crystallinity of the polymer decreases with increasing concentration of zirconium oxide. SANS experiments showed that at ambient conditions ZrO2 nanoparticles mainly distributed like mono-particles in the polymer matrix at all concentrations of filler.The structure of HDPE+ZrO2 does not changes up to 132°C at 1-3% of filler, excepting changing of the polymer structure at temperatures upper 82°C. At high concentrations of filler 10-20% the aggregation of ZrO2 nanoparticles occurs, forming domains of 2.5μm. The results of Raman and FTIR spectroscopy did not show additional specific chemical bonds between the filler and the polymer matrix. New peaks formation was not observed. These results suggest that core-shell structure does not exist in the polymer nanocomposite system.

Correlating Polymer Crystals via Self-Induced Nucleation

NASA Astrophysics Data System (ADS)

Reiter, Günter

Crystallizable polymers often form multiple stacks of uniquely oriented lamellae, which have good registry despite being separated by amorphous fold surfaces. These correlations require multiple synchronized, yet unidentified, nucleation events. Here, we demonstrate that in thin films of isotactic polystyrene, the probability of generating correlated lamellae is controlled by the branched morphology of a single primary lamella. The nucleation density ns of secondary lamellae is found to be dependent on the width of the branches of the primary lamella. This relation is independent of molecular weight, crystallization temperature, and film thickness. We propose a nucleation mechanism based on the insertion of polymers into a branched primary lamellar crystal. Even in single crystals, characterized by faceted structures with a well-defined envelope reflecting the underlying crystal unit cell, polymers are folded and thus in a meta-stable state. Annealing such meta-stable single crystals allowed to unveil the initial morphological framework of a dendritic single crystal, i.e. the initial stages of growth.

Humidity influence on atomic force microscopy electrostatic nanolithography

NASA Astrophysics Data System (ADS)

Lyuksyutov, Sergei; Juhl, Shane; Vaia, Richard

2006-03-01

The formation and sustainability of water menisci and bridges between solid dielectric surface and nano-asperity under external electrostatic potential is a mystery, which must be adequately explained. The goal of our study is twofold: (i) To address the influence of an ambient humidity through the water meniscus formation on the nanostructure formation in soften polymeric surfaces; (ii) Estimate an electric charge generation and transport inside the water meniscus in vicinity of nanoscale asperity taking into consideration an induced water ionization in strong non-uniform electric field of magnitude up to 10^10 Vm-1. It is suspected that strong electric field inside a polymer matrix activates the hoping mechanism of conductivity. The electrons are supplied by tunneling of conductive tip, and also through water ionization. Electric current associated with these free carriers produces Jule heating of a small volume of polymer film heating it above the glass transition temperature. Nanostructures are created by mass transport of visco-elastic polymer melt enabling high structure densities on polymer film.

Studies on structural, thermal and AC conductivity scaling of PEO-LiPF6 polymer electrolyte with added ionic liquid [BMIMPF6

NASA Astrophysics Data System (ADS)

Chaurasia, S. K.; Saroj, A. L.; Shalu, Singh, V. K.; Tripathi, A. K.; Gupta, A. K.; Verma, Y. L.; Singh, R. K.

2015-07-01

Preparation and characterization of polymer electrolyte films of PEO+10wt.% LiPF6 + xwt.% BMIMPF6 (1-butyl-3-methylimidazolium hexafluorophosphate) containing dopant salt lithium hexafluorophosphate (LiPF6) and ionic liquid (BMIMPF6) having common anion PF6 - are reported. The ionic conductivity of the polymer electrolyte films has been found to increase with increasing concentration of BMIMPF6 in PEO+10 wt.% LiPF6 due to the plasticization effect of ionic liquid. DSC and XRD results show that the crystallinity of polymer electrolyte decreases with BMIMPF6 concentration which, in turn, is responsible for the increase in ionic conductivity. FTIR spectroscopic study shows the complexation of salt and/or ionic liquid cations with the polymer backbone. Ion dynamics behavior of PEO+LiPF6 as well as PEO+LiPF6 + BMIMPF6 polymer electrolytes was studied by frequency dependent conductivity, σ(f) measurements. The values σ(f) at various temperatures have been analyzed in terms of Jonscher power law (JPL) and scaled with respect to frequency which shows universal power law characteristics at all temperatures.

Evaluation of biocompatibility and toxicity of biodegradable poly (DL-lactic acid) films

PubMed Central

Li, Rui-Yun; Liu, Zhi-Gang; Liu, Huan-Qiu; Chen, Lei; Liu, Jian-Feng; Pan, Yue-Hai

2015-01-01

Regeneration and functional recovery of nerves after peripheral nerve injury is the key to peripheral nerve repair. One of the putative therapeutic strategies is to use anti-adhesion polymer films, made of polymeric biomaterials. Recently, a novel biodegradable poly (DL-lactic acid) (PDLLA) film has been prepared using a method of phase transformation with biodegradable polylactic acid polymer as the substrate. This novel, anti-adhesion film has a porous structure, which provides better mechanical properties, better flexibility, more complete diffusion through the polymer of tissue biologic factors like growth factors, and more controllable degradation compared to traditional non-porous films. Little is known, however, about the in vitro and in vivo biocompatibility and cytotoxicity of this type of PDLLA film. Therefore, our aim was to evaluate the biocompatibility and cytotoxicity of this novel PDLLA film using various experimental methods, including a skin irritation test, MTT analysis, and the mouse bone marrow cell micronucleus test, as well as hematology or clinical chemistry measurements in rats after receiving sciatic nerve transection and anastomosis with wrapping of the anastomosis with DLLA films. We demonstrated that exposure to PDLLA film extracts did not generate apparent erythema or edema in rabbit skin and had no effect on the proliferation of Vero cells. Additionally, treatment with PDLLA film extracts did not alter the incidence of micronucleated polychromatic erythrocytes as compared with saline Treated group. Furthermore, implantation of PDLLA film did not alter liver or renal function as measured by serum levels of ALT, AST, TP, A/G, Cr, and BUN, and pathologic examinations showed that implantation of PDLLA film did not cause pathologic changes to the rat liver, kidney, pancreas, or spleen. Taken together, these results suggest that PDLLA films have excellent biocompatibility and no obvious toxicity in vivo, and may be used to prevent nerve adhesion, thereby promoting nerve regeneration. PMID:26396667

Space and surface charge behavior analysis of charge-eliminated polymer films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oda, Tetsuji; Takashima, Kazunori; Ichiyama, Shinichiro

1995-12-31

Charge behavior of corona-charged or charge eliminated polymer films being dipped in the city water were studied. They were polytetrafluoroethylene (PTFE teflon{trademark}), polypropylene (PP), low density or high density polyethylene (LDPE or HDPE) thin films which are as grown (native) or plasma-processed. The plasma processing at low pressure was tested as antistatic processing. Charge elimination was done by being dipped in alcohol or city water. TSDC analysis and surface charge profile measurement were done for both charged and charge eliminated polymer films. Surface charge density of plasma processed polymer films just after corona charging is roughly the same as thatmore » of an original film. There is little difference between surface charge density profile of a native film and that of a plasma processed film. A large hetero current peak of TSDC was observed at room temperature for a processed film. It was found that the hetero peak disappears after charge elimination process. A pressure pulse wave method by using a pulse-driven piezoelectric PVDF polymer film as a piezoelectric actuator was newly developed to observe real space charge distribution. A little difference of internal space charge distribution between the plasma processed film and the native one after corona charging is found.« less

Combination process of diamond machining and roll-to-roll UV-replication for thin film micro- and nanostructures

NASA Astrophysics Data System (ADS)

Väyrynen, J.; Mönkkönen, K.; Siitonen, S.

2016-09-01

Roll-to-roll (R2R) ultraviolet (UV) curable embossing replication process is a highly accurate and cost effective way to replicate large quantities of thin film polymer parts. These structures can be used for microfluidics, LED-optics, light guides, displays, cameras, diffusers, decorative, laser sensing and measuring devices. In the R2R UV-process, plastic thin film coated with UV-curable lacquer, passes through an imprinting embossing drum and is then hardened by an UV-lamp. One key element for mastering this process is the ability to manufacture a rotating drum containing micro- and nanostructures. Depending on the pattern shapes, the drum can be directly machined by diamond machining or it can be done through wafer level lithographical process. Due to the shrinkage of UV-curable lacquer, the R2R drum pattern process needs to be prototyped few times, in order to get the desired performance and shape from the R2R produced part. To speed up the prototyping and overall process we have developed a combination process where planar diamond machining patterns are being turned into a drum roller. Initially diamond machined patterns from a planar surface are replicated on a polymer sheet using UV-replication. Secondly, a nickel stamper shim is grown form the polymer sheet and at the end the stamper is turned into a roller and used in the R2R process. This process allows various micro milled, turned, grooved and ruled structures to be made at thin film products through the R2R process. In this paper, the process flow and examples of fabricating R2R embossed UVcurable thin film micro- and nanostructures from planar diamond machined patterns, is reported.

Investigation of the influence of the composition on mechanical properties poly(glycolide-DL-lactide)

NASA Astrophysics Data System (ADS)

Baikin, A. S.; Sevostyanov, M. A.; Nasakina, E. O.; Sergienko, K. V.; Kaplan, M. A.; Konushkin, S. V.; Kolmakova, A. A.; Yakubov, A. D.; Kolmakov, A. G.

2018-04-01

In this paper we describe the creation of films from poly (glycolide-DL-lactide). Studied the mechanical properties of developed polymer films of poly (glycolide-DL-lactide). The effect of the molecular weight of poly (glycolide-DL-lactide) on the mechanical properties of the resulting polymer films is shown. The dependence of the mechanical properties of poly (glycolide-DL-lactide) films on the polymer concentration in chloroform was studied. The possibility of creating biodegradable films with specified mechanical properties is shown.

Control of Porosity in Ladder Polymers by Solvent-induced Aggregation

NASA Astrophysics Data System (ADS)

Brady, Michael; Gamo, Eri; Wang, Cheng; Xia, Yan

Porous polymers hold promise as materials for gas absorption, membranes, and organic electronics. In all of these applications, attaining in-plane ordering of backbones and thus porous free volume impacts the ability to adsorb gas, selectively filter molecules, and conduct charges. In this work, hard and soft x-ray scattering and soft x-ray spectroscopy are of focus to study the pore structure, induced by the solution-driven aggregation of ladder polymer thin films made of LP-1 and LP-2. Using GISAXS and AFM it is shown that thermal annealing drives the growth of crystallites in thin films. Due to the completely sp2nature of the ladder polymer backbones, it is expected that backbones are extremely stiff and thus preventing them from packing once left in a metastable state following casting. Therefore, the combination of GIWAXS and GISAXS will be shown to be critical in correctly understanding how pores develop in this 700 m2/g sorbent (N2). Finally, application in CO2/N2 separation membranes towards carbon sequestration will be presented that show gas selectivity is achieved through heteroatom incorporation and polymer blending. In this talk, focus will be placed on state-of-the-art x-ray scattering and spectroscopy, highlighting the importance of chemically sensitive structural information enabled by the combination of spectroscopy and scattering at play with the use of resonant soft x-rays.

Graphene Oxide Filled Lignin/Starch Polymer Bionanocomposite: Structural, Physical, and Mechanical Studies.

PubMed

Aqlil, Meryem; Moussemba Nzenguet, Annie; Essamlali, Younes; Snik, Asmae; Larzek, Mohamed; Zahouily, Mohamed

2017-12-06

In this study, graphene oxide (GO) was investigated as a potential nanoreinforcing agent in starch/lignin (ST/L) biopolymer matrix. Bionanocomposite films based on ST/L blend matrix and GO were prepared by solution-casting technique of the corresponding film-forming solution. The structures, morphologies, and properties of bionanocomposite films were characterized by Fourier transform infrared (FTIR), thermal gravimetric analysis (TGA), ultraviolet-visible (UV-vis), SEM, and tensile tests. The experimental results showed that content of GO have a significant influence on the mechanical properties of the produced films. The results revealed that the interfacial interaction formed in the bionanocomposite films improved the compatibility between GO fillers and ST/L matrix. The addition of GO also reduced moisture uptake (Mu) and water vapor permeability of ST/L blend film. In addition, TGA showed that the thermal stability of bionanocomposite films was better than that of neat starch film. These findings confirmed the effectiveness of the proposed approach to produce biodegradable films with enhanced properties, which may be used in packaging applications.

A bifractal nature of reticular patterns induced by oxygen plasma on polymer films

NASA Astrophysics Data System (ADS)

Bae, Junwan; Lee, I. J.

2015-05-01

Plasma etching was demonstrated to be a promising tool for generating self-organized nano-patterns on various commercial films. Unfortunately, dynamic scaling approach toward fundamental understanding of the formation and growth of the plasma-induced nano-structure has not always been straightforward. The temporal evolution of self-aligned nano-patterns may often evolve with an additional scale-invariance, which leads to breakdown of the well-established dynamic scaling law. The concept of a bifractal interface is successfully applied to reticular patterns induced by oxygen plasma on the surface of polymer films. The reticular pattern, composed of nano-size self-aligned protuberances and underlying structure, develops two types of anomalous dynamic scaling characterized by super-roughening and intrinsic anomalous scaling, respectively. The diffusion and aggregation of short-cleaved chains under the plasma environment are responsible for the regular distribution of the nano-size protuberances. Remarkably, it is uncovered that the dynamic roughening of the underlying structure is governed by a relaxation mechanism described by the Edwards-Wilkinson universality class with a conservative noise. The evidence for the basic phase, characterized by the negative roughness and growth exponents, has been elusive since its first theoretical consideration more than two decades ago.

Structural modification in the formation of starch – silver nanocomposites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Begum, S. N. Suraiya; Ramasamy, Radha Perumal, E-mail: perumal.ramasamy@gmail.com; Aswal, V. K.

Polymer based nanocomposites have gained wide applications in field of battery technology. Starch is a naturally occurring polysaccharide with sustainable properties such as biodegradable, non toxic, excellent film forming capacity and it also act as reducing agent for the metal nanoparticles. In our research various concentration of silver nitrate (AgNO{sub 3}) was added to the starch solution and films were obtained using solution casting method. Surface electron microscope (SEM) of the films shows modifications depending upon the concentration of AgNO{sub 3}. Small angle neutron scattering (SANS) analysis showed that addition of silver nitrate modifies the starch to disc like structuresmore » and with increasing the AgNO{sub 3} concentration leads to the formation of fractals. This research could benefit battery technology where solid polymer membranes using starch is used.« less

Grafting of styrene into pre-irradiated fluoropolymer films: Influence of base material and irradiation temperature

NASA Astrophysics Data System (ADS)

Lappan, Uwe; Geißler, Uwe; Gohs, Uwe; Uhlmann, Steffi

2010-10-01

In this study, the influence of irradiation temperature on mechanical properties of three fluoropolymers and on grafting of styrene into the polymers by the pre-irradiation method was investigated. Electron paramagnetic resonance spectroscopy and infrared spectroscopy were used to characterize the irradiated polymers regarding trapped radical species and changes in the chemical structure, respectively. For poly(tetrafluoroethylene-co-perfluoropropyl vinyl ether) (PFA) the irradiation temperature was found to be an important factor for tensile strength and elongation at break of the pre-irradiated film. No strong effect of irradiation temperature on the mechanical properties was noticed for poly(tetrafluoroethylene-co-ethylene) (ETFE); however the yield of grafting drops at high irradiation temperatures. Finally, mechanical properties of poly(tetrafluoroethylene) (PTFE) were found to be dramatically altered, even if the film was irradiated at elevated temperature.

Cationic antimicrobial polymers and their assemblies.

PubMed

Carmona-Ribeiro, Ana Maria; de Melo Carrasco, Letícia Dias

2013-05-10

Cationic compounds are promising candidates for development of antimicrobial agents. Positive charges attached to surfaces, particles, polymers, peptides or bilayers have been used as antimicrobial agents by themselves or in sophisticated formulations. The main positively charged moieties in these natural or synthetic structures are quaternary ammonium groups, resulting in quaternary ammonium compounds (QACs). The advantage of amphiphilic cationic polymers when compared to small amphiphilic molecules is their enhanced microbicidal activity. Besides, many of these polymeric structures also show low toxicity to human cells; a major requirement for biomedical applications. Determination of the specific elements in polymers, which affect their antimicrobial activity, has been previously difficult due to broad molecular weight distributions and random sequences characteristic of radical polymerization. With the advances in polymerization control, selection of well defined polymers and structures are allowing greater insight into their structure-antimicrobial activity relationship. On the other hand, antimicrobial polymers grafted or self-assembled to inert or non inert vehicles can yield hybrid antimicrobial nanostructures or films, which can act as antimicrobials by themselves or deliver bioactive molecules for a variety of applications, such as wound dressing, photodynamic antimicrobial therapy, food packing and preservation and antifouling applications.

Cationic Antimicrobial Polymers and Their Assemblies

PubMed Central

Carmona-Ribeiro, Ana Maria; de Melo Carrasco, Letícia Dias

2013-01-01

Cationic compounds are promising candidates for development of antimicrobial agents. Positive charges attached to surfaces, particles, polymers, peptides or bilayers have been used as antimicrobial agents by themselves or in sophisticated formulations. The main positively charged moieties in these natural or synthetic structures are quaternary ammonium groups, resulting in quaternary ammonium compounds (QACs). The advantage of amphiphilic cationic polymers when compared to small amphiphilic molecules is their enhanced microbicidal activity. Besides, many of these polymeric structures also show low toxicity to human cells; a major requirement for biomedical applications. Determination of the specific elements in polymers, which affect their antimicrobial activity, has been previously difficult due to broad molecular weight distributions and random sequences characteristic of radical polymerization. With the advances in polymerization control, selection of well defined polymers and structures are allowing greater insight into their structure-antimicrobial activity relationship. On the other hand, antimicrobial polymers grafted or self-assembled to inert or non inert vehicles can yield hybrid antimicrobial nanostructures or films, which can act as antimicrobials by themselves or deliver bioactive molecules for a variety of applications, such as wound dressing, photodynamic antimicrobial therapy, food packing and preservation and antifouling applications. PMID:23665898

PTFE-nanocomposites structure and wear-resistance changing in various methods of structural modification

NASA Astrophysics Data System (ADS)

Mashkov, Yu K.; Ruban, A. S.; Rogachev, E. A.; Chemisenko, O. V.

2018-01-01

Conditions of polymer materials usage containing nanoelements as modifiers significantly affect the requirements for their physic-mechanical and tribological properties. However, the mechanisms of nanoparticles effect to the polymers tribotechnical properties have not been studied enough. The article aim is to analyze the results of studying polytetrafluoroethylene modified with cryptocrystalline graphite and silicon dioxide and to determine the effectiveness of the modification methods used and methods for further improving filled PTFE mechanical and tribotechnical properties. The effect of modifiers to PCM supramolecular structure was analyzed with SEM methods. The results of modifying the PCM samples surface by depositing a copper film with ion-vacuum deposition methods and changing the structural-phase composition and tribological characteristics are considered. The findings make possible to characterize the physicochemical processes under frictional interaction in metal polymer tribosystems.