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.

Thermodynamics of the Electric Field Induced Orientation of Nematic Droplet/Polymer Films

NASA Astrophysics Data System (ADS)

Drzaic, Paul S.

1989-07-01

Films consisting of micron-sized nematic liquid crystal droplets dispersed in a polymer matrix (NCAP) represent an important new class of electro-optical devices. These films strongly scatter light in the tm powered state, but achieve a high degree of clarity when an electric field is applied. In this report we describe the aspects of liquid crystal and polymer composition that control the magnitude of the electric field required to orient the nematic droplets. The droplet shape is found to be an important factor in the electro-optical response of these films. In films deposited from aqueous solutions the nematic cavities in the film are usually oblate in nature, with the short axis perpendicular to the film plane. The nematic, which adopts a bipolar configuration within the cavity, is preferentially aligned so that each droplet's symmetry axis is aligned parallel to the film plane in the rest state, but rotates to lie parallel with the field in the powered state. Capacitance data is presented which supports this picture. It is shown that the nematic droplet shape can be a major factor in determining the thermodynamics of droplet orientation.

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.

Perpendicular Orientation Control without Interfacial Treatment of RAFT-Synthesized High-χ Block Copolymer Thin Films with Sub-10 nm Features Prepared via Thermal Annealing.

PubMed

Nakatani, Ryuichi; Takano, Hiroki; Chandra, Alvin; Yoshimura, Yasunari; Wang, Lei; Suzuki, Yoshinori; Tanaka, Yuki; Maeda, Rina; Kihara, Naoko; Minegishi, Shinya; Miyagi, Ken; Kasahara, Yuusuke; Sato, Hironobu; Seino, Yuriko; Azuma, Tsukasa; Yokoyama, Hideaki; Ober, Christopher K; Hayakawa, Teruaki

2017-09-20

In this study, a series of perpendicular lamellae-forming poly(polyhedral oligomeric silsesquioxane methacrylate-block-2,2,2-trifluoroethyl methacrylate)s (PMAPOSS-b-PTFEMAs) was developed based on the bottom-up concept of creating a simple yet effective material by tailoring the chemical properties and molecular composition of the material. The use of silicon (Si)-containing hybrid high-χ block copolymers (BCPs) provides easy access to sub-10 nm feature sizes. However, as the surface free energies (SFEs) of Si-containing polymers are typically vastly lower than organic polymers, this tends to result in the selective segregation of the inorganic block onto the air interface and increased difficulty in controlling the BCP orientation in thin films. Therefore, by balancing the SFEs between the organic and inorganic blocks through the use of poly(2,2,2-trifluoroethyl methacrylate) (PTFEMA) on the organic block, a polymer with an SFE similar to Si-containing polymers, orientation control of the BCP domains in thin films becomes much simpler. Herein, perpendicularly oriented BCP thin films with a χ eff value of 0.45 were fabricated using simple spin-coating and thermal annealing processes under ambient conditions. The thin films displayed a minimum domain size of L 0 = 11 nm, as observed via atomic force microscopy (AFM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Furthermore, directed self-assembly (DSA) of the BCP on a topographically prepatterned substrate using the grapho-epitaxy method was used to successfully obtain perpendicularly oriented lamellae with a half pitch size of ca. 8 nm.

A direct correlation of x-ray diffraction orientation distributions to the in-plane stiffness of semi-crystalline organic semiconducting films

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

Zhao, Bingxiao; Awartani, Omar; O'Connor, Brendan

2016-05-02

Large charge mobilities of semi-crystalline organic semiconducting films could be obtained by mechanically aligning the material phases of the film with the loading axis. A key element is to utilize the inherent stiffness of the material for optimal or desired alignment. However, experimentally determining the moduli of semi-crystalline organic thin films for different loading directions is difficult, if not impossible, due to film thickness and material anisotropy. In this paper, we address these challenges by presenting an approach based on combining a composite mechanics stiffness orientation formulation with a Gaussian statistical distribution to directly estimate the in-plane stiffness (transverse isotropy)more » of aligned semi-crystalline polymer films based on crystalline orientation distributions obtained by X-ray diffraction experimentally at different applied strains. Our predicted results indicate that the in-plane stiffness of an annealing film was initially isotropic, and then it evolved to transverse isotropy with increasing mechanical strains. This study underscores the significance of accounting for the crystalline orientation distributions of the film to obtain an accurate understanding and prediction of the elastic anisotropy of semi-crystalline polymer films.« less

Anisotropic Dye Adsorption and Anhydrous Proton Conductivity in Smectic Liquid Crystal Networks: The Role of Cross-Link Density, Order, and Orientation.

PubMed

Liang, Ting; van Kuringen, Huub P C; Mulder, Dirk J; Tan, Shuai; Wu, Yong; Borneman, Zandrie; Nijmeijer, Kitty; Schenning, Albertus P H J

2017-10-11

In this work, the decisive role of rigidity, orientation, and order in the smectic liquid crystalline network on the anisotropic proton and adsorbent properties is reported. The rigidity in the hydrogen-bonded polymer network has been altered by changing the cross-link density, the order by using different mesophases (smectic, nematic, and isotropic phases), whereas the orientation of the mesogens was controlled by alignment layers. Adding more cross-linkers improved the integrity of the polymer films. For the proton conduction, an optimum was found in the amount of cross-linker and the smectic organization results in the highest anhydrous proton conduction. The polymer films show anisotropic proton conductivity with a 54 times higher conductivity in the direction perpendicular to the molecular director. After a base treatment of the smectic liquid crystalline network, a nanoporous polymer film is obtained that also shows anisotropic adsorption of dye molecules and again straight smectic pores are favored over disordered pores in nematic and isotropic networks. The highly cross-linked films show size-selective adsorption of dyes. Low cross-linked materials do not show this difference due to swelling, which decreases the order and creates openings in the two-dimensional polymer layers. The latter is, however, beneficial for fast adsorption kinetics.

Novel Organic Field Effect Transistors via Nano-Modification

DTIC Science & Technology

2005-07-01

mobility by using two kinds of nano-scale films. One is to apply the photoalignment method on a nano-scale film to control the orientation of pentacene ...scale film (polymer electrolyte) to control moving of ions in/out an active semiconducor, pentacene or conducting polymer, for improving carrier...mobility. In this project, pentacene or a series of conducting polymers, such as the derivatives of PANI and P3HT will be patterned and manufactured in

Enhanced thermal conductance of polymer composites through embedding aligned carbon nanofibers

DOE PAGES

Nicholas, Roberts; Hensley, Dale K.; Wood, David

2016-07-08

The focus of this work is to find a more efficient method of enhancing the thermal conductance of polymer thin films. This work compares polymer thin films embedded with randomly oriented carbon nanotubes to those with vertically aligned carbon nanofibers. Thin films embedded with carbon nanofibers demonstrated a similar thermal conductance between 40–60 μm and a higher thermal conductance between 25–40 μm than films embedded with carbon nanotubes with similar volume fractions even though carbon nanotubes have a higher thermal conductivity than carbon nanofibers

Enhanced thermal conductance of polymer composites through embedding aligned carbon nanofibers

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

Nicholas, Roberts; Hensley, Dale K.; Wood, David

The focus of this work is to find a more efficient method of enhancing the thermal conductance of polymer thin films. This work compares polymer thin films embedded with randomly oriented carbon nanotubes to those with vertically aligned carbon nanofibers. Thin films embedded with carbon nanofibers demonstrated a similar thermal conductance between 40–60 μm and a higher thermal conductance between 25–40 μm than films embedded with carbon nanotubes with similar volume fractions even though carbon nanotubes have a higher thermal conductivity than carbon nanofibers

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.

Fluoropolymer Microstructure and Dynamics: Influence of Molecular Orientation Induced by Uniaxial Drawing

NASA Astrophysics Data System (ADS)

Miranda, Daniel; Yin, Chaoqing; Runt, James

Fluorinated semi-crystalline polymer films are attractive for dielectric film applications due to their chemical inertness, heat resistance, and high thermal stability. In the present investigation we explore the influence of orientation induced by uniaxial drawing on the crystalline microstructure and relaxation processes of poly(ethylene-tetrafluoroethylene) (ETFE), in order to ascertain how morphological control can benefit polymer dielectric design. When drawn below or near the Tg, the crystallinity of the drawn films is unchanged, and oriented amorphous structures and crystalline microfibrils form at high draw ratios. This orientation slows segmental relaxation, reflected by an increase in the dynamic Tg, and also delays the transition to the high temperature crystalline form of ETFE. When drawing above the Tg, the films undergo strain-induced crystallization at high draw ratios. For these films an increase in the dynamic Tg is also observed, in addition to a second segmental relaxation process, appearing as a shoulder on the primary process. We propose that this represents a contribution from a rigid amorphous fraction, having slowed chain dynamics. Supported by Office of Naval Research.

Casting Control of Floating-films into Ribbon-shape Structure by modified Dynamic FTM

NASA Astrophysics Data System (ADS)

Tripathi, A.; Pandey, M.; Nagamatsu, S.; Pandey, S. S.; Hayase, S.; Takashima, W.

2017-11-01

We have developed a new method to obtain Ribbon-shaped floating films via dynamic casting of floating-film and transfer method (dynamic-FTM). Dynamic-FTM is a unique method to prepare oriented thin-film of conjugated polymers (CPs) which is quick and easy. This method has several advantages as compared to the other conventional casting procedure to prepare oriented CP films. In the conventional dynamic FTM appearance of large scale circular orientation poses difficulty not only for practical applications but also hinders the detailed analysis of the orientation mechanism. In this present work, pros and cons of this newly proposed ribbon-shaped floating-film have been discussed in detail from those of the conventional floating-film prepared by dynamic-FTM.

Optical-strain characteristics of anisotropic polymer films fabricated from a liquid crystal diacrylate

NASA Astrophysics Data System (ADS)

Escuti, Michael J.; Cairns, Darran R.; Crawford, Gregory P.

2004-03-01

The optomechanical characteristics of oriented polymer films made from a photopolymerizable liquid crystal diacrylate (BASF LC242) were examined, with general implications for oriented films of similar materials being used and considered for display-component applications. The birefringence of these uniaxial films before and after polymerization was determined by measuring the retardation between crossed polarizers, (resulting in Δn=0.142±0.002 at 633 nm for the cured polymer films). Optical-strain characteristics were also determined by measuring the transmittance of the films between crossed polarizers at two wavelengths (612 and 633 nm) during the application of a monotonically increasing tensile strain. Under the conservative assumption that Poisson's ratio is constant for the relatively small strains in our experiment, we develop a strained-waveplate model to detect changes in birefringence directly from the modulation in transmittance with increasing strain. We show that strain applied along the axis of the polymer chains did not substantially affect the birefringence, and strain applied perpendicularly caused only a slight decrease (˜1% decrease for 10% strain). These results highlight the robustness of fully polymerized reactive mesogen optical films to withstand the moderate strains anticipated during manufacturing processes and in-service deformation caused by bending or impact.

Influence of the side chain and substrate on polythiophene thin film surface, bulk, and buried interfacial structures.

PubMed

Xiao, Minyu; Jasensky, Joshua; Zhang, Xiaoxian; Li, Yaoxin; Pichan, Cayla; Lu, Xiaolin; Chen, Zhan

2016-08-10

The molecular structures of organic semiconducting thin films mediate the performance of various devices composed of such materials. To fully understand how the structures of organic semiconductors alter on substrates due to different polymer side chains and different interfacial interactions, thin films of two kinds of polythiophene derivatives with different side-chains, poly(3-hexylthiophene) (P3HT) and poly(3-potassium-6-hexanoate thiophene) (P3KHT), were deposited and compared on various surfaces. A combination of analytical tools was applied in this research: contact angle goniometry and X-ray photoelectron spectroscopy (XPS) were used to characterize substrate dielectric surfaces with varied hydrophobicity for polymer film deposition; X-ray diffraction and UV-vis spectroscopy were used to examine the polythiophene film bulk structure; sum frequency generation (SFG) vibrational spectroscopy was utilized to probe the molecular structures of polymer film surfaces in air and buried solid/solid interfaces. Both side-chain hydrophobicity and substrate hydrophobicity were found to mediate the crystallinity of the polythiophene film, as well as the orientation of the thiophene ring within the polymer backbone at the buried polymer/substrate interface and the polymer thin film surface in air. For the same type of polythiophene film deposited on different substrates, a more hydrophobic substrate surface induced thiophene ring alignment with the surface normal at both the buried interface and on the surface in air. For different films (P3HT vs. P3KHT) deposited on the same dielectric substrate, a more hydrophobic polythiophene side chain caused the thiophene ring to align more towards the surface at the buried polymer/substrate interface and on the surface in air. We believe that the polythiophene surface, bulk, and buried interfacial molecular structures all influence the hole mobility within the polythiophene film. Successful characterization of an organic conducting thin film surface, buried interfacial, and bulk structures is a first crucial step in understanding the structure-function relationship of such films in order to optimize device performance. An in-depth understanding on how the side-chain influences the interfacial and surface polymer orientation will guide the future molecular structure design of organic semiconductors.

Temperature-independent zero-birefringence polymer for liquid crystal displays

NASA Astrophysics Data System (ADS)

Shikanai, M. D.; Tagaya, A.; Koike, Y.

2016-03-01

A polymer film that shows almost no orientational birefringence even when the polymer main chain is in an oriented state and almost no temperature dependence of orientational birefringence in the temperature range from around -40 to 85 °C was prepared. This temperature range is important because it is where in-car liquid crystal displays (LCDs) are generally used; therefore, it is desirable to have constant orientational birefringence over this range. We suggest a method to compensate for the intrinsic birefringence and temperature coefficient of intrinsic birefringence of individual polymers by copolymerizing monomers of homopolymers that display opposite signs of the two parameters described above. Analysis of four types of polymers, methyl methacrylate (MMA), 2,2,2-trifluoroethyl methacrylate, benzyl methacrylate (BzMA), and phenyl methacrylate (PhMA), reveal that they possess both positive and negative signs of their temperature coefficient of intrinsic birefringence. Using this approach, we prepare P(MMA/PhMA/BzMA) (39:23:38 wt. %), which exhibits almost no intrinsic birefringence and almost no temperature dependence of intrinsic birefringence. The retardation of this polymer film when drawn uniaxially scarcely changed (between 0.3 and 0.8 nm) between 12 and 70 °C, which is small enough not to cause image degradation in LCDs.

JPRS Report, Science & Technology, Japan, Selections from Future Industrial Technology Symposium.

DTIC Science & Technology

1988-08-01

pyrolyzed graphite ( HOPG ). X-ray diffraction photos of the biaxially stretched PPV films indicate that the films have been plane-oriented. It is...CRYSTALS OF TWO-DIMENSIONALLY CROSS-LINKED POLYMERS PRODUCED 8 ION-CROSSLINKING POLYMER COMPACTS EVALUATED 12 RECENT PROGRESS IN SYNTHETIC METALS...derived from 2,5-thienylene bis(methylene dimethyl sulfonium bromide). Highly conducting graphite films also have been obtained by pyrolysis of PPV and

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

Controlling Crystal Microstructure to Minimize Loss in Polymer Dielectrics

NASA Astrophysics Data System (ADS)

Miranda, Daniel; Iacob, Ciprian; Zhang, Shihai; Runt, James

Polymer dielectric films are of great importance for high performance capacitors. For these films it is critical to reduce dielectric loss, as it diminishes efficiency and contributes to waste heat generation during device operation. Here, a model semi-crystalline polymer, poly(ethylene naphthalate) (PEN), was used to examine how morphological factors inhibit chain relaxations responsible for loss. This was achieved by manipulating the extent of crystallization and the crystalline microstructure through a combination of annealing and uniaxial drawing, and investigating their effects on dielectric performance. Varying crystallization conditions influenced the dynamic Tg and extent of rigid amorphous fraction formation, but had a limited effect on loss magnitude. Film orientation however greatly reduced loss, through strain-induced crystallization and development of oriented amorphous mesophasic regions. Post-drawing annealing conditions were capable of further refining the crystal microstructure and, in turn, the dielectric properties. These findings demonstrate that semi-crystalline polymer morphology has a very strong influence on amorphous chain relaxations, and understanding how processing conditions affect morphology is critical to the rational design of polymer dielectrics. Office of Naval Research.

Piezoelectric Polymer Films for Application in Monitoring Devices

DTIC Science & Technology

1977-02-01

pulse is also evident, as is the decay rate of the pressure, and what appears to be a pronounced " dicrotic notch ," which is asso- ciated with heart valve...investigation of factors responsible for this remark- able behavior of an organic polymer. Commercial PVF 2 homopolymer and copolymer films were oriented by... factors such as changes in elastic modulus of the film with temperature, depolarization processes at the higher temperature, and pyroelectric effects

Freestanding, heat resistant microporous film for use in energy storage devices

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

Pekala, Richard W.; Cherukupalli, Srinivas; Waterhouse, Robert R.

Preferred embodiments of a freestanding, heat resistant microporous polymer film (10) constructed for use in an energy storage device (70, 100) implements one or more of the following approaches to exhibit excellent high temperature mechanical and dimensional stability: incorporation into a porous polyolefin film of sufficiently high loading levels of inorganic or ceramic filler material (16) to maintain porosity (18) and achieve low thermal shrinkage; use of crosslinkable polyethylene to contribute to crosslinking the polymer matrix (14) in a highly inorganic material-filled polyolefin film; and heat treating or annealing of biaxially oriented, highly inorganic material-filled polyolefin film above the meltingmore » point temperature of the polymer matrix to reduce residual stress while maintaining high porosity. The freestanding, heat resistant microporous polymer film embodiments exhibit extremely low resistance, as evidenced by MacMullin numbers of less than 4.5.« less

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.

Partial hydrophilic modification of biaxially oriented polypropylene film by an atmospheric pressure plasma jet with the allylamine monomer

NASA Astrophysics Data System (ADS)

Chen, W. X.; Yu, J. S.; Hu, W.; Chen, G. L.

2016-11-01

In this paper, the partial modification of the biaxially oriented polypropylene (BOPP) film for potential biological and packaging applications was achieved via hydrophilic modification using atmospheric pressure plasma jet (APPJ). In the APPJ system, the allylamine (ALA) monomer was polymerized on the BOPP surface by either the Ar/O2 or the He/O2 plasma. The results showed that plasmatic modification created many micro/nano sized holes on the BOPP film, which increased the surface roughness dramatically and the increased roughness enhanced the combining intensity between the BOPP film and the ALA polymer. However, such a plasmatic modification increased the water vapor permeability. The FTIR and XPS characterizations showed that the amine groups were grafted onto the BOPP film, and the contact angle of the BOPP film decreases from 98.5° to 8°. Compared with the BOPP films treated by the Ar or He plasma, the barrier property of the modified BOPP film increased significantly when the ALA polymer was incorporated. The bio-affinity/toxicity of ALA polymer was illustrated by the attachment of the cultured SMMC-7721 hepatoma cells on the modified BOPP film. The significant enhancement in the cell density indicated that modified BOPP film was highly bio-compatible and non-toxic, especially treated with the Ar/O2/ALA plasma.

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

Canevarolo, Sebastião V., E-mail: caneva@ufscar.br; Ravazzi, Camila; Silva, Jorge, E-mail: jorge.silva@ufscar.br

Polyethylene films are a common packaging material. The level and type of chain orientation in these films are a very important property which is of great care and concern of the converter personnel during the conformation process. Usually bi-orientation is the conventional procedure but when easy tear in one direction is needed mono-orientation is sought. This paper deal with the characterization of the crystalline orientation in films of polyethylene blends (HDPE/LLDPE) which have being oriented in two steps: initially the polymer was bi-oriented via extrusion-blown, cooled, and then in a second process hot stretched along the machine direction in ordermore » to produce mono-oriented films. In order to evaluate the orientation of the film, the polarization of the FT-IR beam was rotated 360° in steps of 5° by rotating the polarizer. In each step the absorbance spectrum was recorded and the corresponding dichroic ratio (DR) calculated after subtracting the baseline. With differential scanning calorimetry (DSC) was possible to infer about the changes in the morphology caused by the stretching.« less

Video-microscopy of NCAP films: the observation of LC droplets in real time

NASA Astrophysics Data System (ADS)

Reamey, Robert H.; Montoya, Wayne; Wong, Abraham

1992-06-01

We have used video-microscopy to observe the behavior of liquid crystal (LC) droplets within nematic droplet-polymer films (NCAP) as the droplets respond to an applied electric field. The textures observed at intermediate fields yielded information about the process of liquid crystal orientation dynamics within droplets. The nematic droplet-polymer films had low LC content (less than 1 percent) to allow the observation of individual droplets in a 2 - 6 micrometers size range. The aqueous emulsification technique was used to prepare the films as it allows the straightforward preparation of low LC content films with a controlled droplet size range. Standard electro-optical (E-O) tests were also performed on the films, allowing us to correlate single droplet behavior with that of the film as a whole. Hysteresis measured in E-O tests was visually confirmed by droplet orientation dynamics; a film which had high hysteresis in E-O tests exhibited distinctly different LC orientations within the droplet when ramped up in voltage than when ramped down in voltage. Ramping the applied voltage to well above saturation resulted in some droplets becoming `stuck'' in a new droplet structure which can be made to revert back to bipolar with high voltage pulses or with heat.

Thin HTSC films produced by a polymer metal precursor technique

NASA Astrophysics Data System (ADS)

Lampe, L. v.; Zygalsky, F.; Hinrichsen, G.

In precursors the metal ions are combined with acid groups of polymethacrylic acid (PMAA), polyacrylic acid (PAA) or novolac. Compared to thermal degradation temperature of pure polymers those of precursors are low. Precursors films were patterned by UV lithography. Diffractometric investigations showed that the c-axis oriented epitaxial films of YBa 2Cu 3O x and Bi 2Sr 2CaCu 2O x originated from amorphous metal oxide films, which were received after thermal degradation of the precursor. Transition temperatures and current densities were determined by electric resistivity measurements.

Characterization and measurement of polymer wear

NASA Technical Reports Server (NTRS)

Buckley, D. H.; Aron, P. R.

1984-01-01

Analytical tools which characterize the polymer wear process are discussed. The devices discussed include: visual observation of polymer wear with SEM, the quantification with surface profilometry and ellipsometry, to study the chemistry with AES, XPS and SIMS, to establish interfacial polymer orientation and accordingly bonding with QUARTIR, polymer state with Raman spectroscopy and stresses that develop in polymer films using a X-ray double crystal camera technique.

Effects of Polypropylene Orientation on Mechanical and Heat Seal Properties of Polymer-Aluminum-Polymer Composite Films for Pouch Lithium-Ion Batteries.

PubMed

Zeng, Fangxinyu; Chen, Jinyao; Yang, Feng; Kang, Jian; Cao, Ya; Xiang, Ming

2018-01-16

In this study, polyamide-aluminum foil-polypropylene (PA-Al-PP) composite films with different orientation status of the PP layer were prepared, and their morphology, tensile, peeling and heat seal behavior were studied. The comparative study of tensile and fracture behaviors of single-layer film of PA, Al and PP, as well as the composite films of PA-Al, PP-Al and PA-Al-PP revealed that in PA-Al-PP composite film, the PA layer with the highest tensile strength can share the tensile stress from the Al layer during stretching, while the PP layer with the lowest tensile strength can prevent further development of the small cracks on boundary of the Al layer during stretching. Moreover, the study of heat seal behavior suggested that both the orientation status and the heat seal conditions were important factors in determining the heat seal strength ( HSS ) and failure behavior of the sample. Four failure types were observed, and a clear correspondence between HSS and failure types was found. The results also elucidated that for the composite film, only in the cases where the tensile stress was efficiently released by each layer during HSS measurement could the composite film exhibit desired high HSS that was even higher than its tensile strength.

Theoretical investigation of confocal microscopy using an elliptically polarized cylindrical vector laser beam: Visualization of quantum emitters near interfaces

NASA Astrophysics Data System (ADS)

Boichenko, Stepan

2018-04-01

We theoretically study laser-scanning confocal fluorescence microscopy using elliptically polarized cylindrical vector excitation light as a tool for visualization of arbitrarily oriented single quantum dipole emitters located (1) near planar surfaces enhancing fluorescence, (2) in a thin supported polymer film, (3) in a freestanding polymer film, and (4) in a dielectric planar microcavity. It is shown analytically that by using a tightly focused azimuthally polarized beam, it is possible to exclude completely the orientational dependence of the image intensity maximum of a quantum emitter that absorbs light as a pair of incoherent independent linear dipoles. For linear dipole quantum emitters, the orientational independence degree higher than 0.9 can normally be achieved (this quantity equal to 1 corresponds to completely excluded orientational dependence) if the collection efficiency of the microscope objective and the emitter's total quantum yield are not strongly orientationally dependent. Thus, the visualization of arbitrarily oriented single quantum emitters by means of the studied technique can be performed quite efficiently.

Crystallization Mechanism and Charge Carrier Transport in MAPLE-Deposited Conjugated Polymer Thin Films

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

Dong, Ban Xuan; Strzalka, Joseph; Jiang, Zhang

Although spin casting and chemical surface reactions are the most common methods used for fabricating functional polymer films onto substrates, they are limited with regard to producing films of certain morphological characteristics on different wetting and nonwetting substrates. The matrix-assisted pulsed laser evaporation (MAPLE) technique offers advantages with regard to producing films of different morphologies on different types of substrates. Here, we provide a quantitative characterization, using X-ray diffraction and optical methods, to elucidate the additive growth mechanism of MAPLE-deposited poly(3-hexylthiophene) (P3HT) films on substrates that have undergone different surface treatments, enabling them to possess different wettabilities. We show thatmore » MAPLE-deposited films are composed of crystalline phases, wherein the overall P3HT aggregate size and crystallite coherence length increase with deposition time. A complete pole figure constructed from X-ray diffraction measurements reveals that in these MAPLE-deposited films, there exist two distinct crystallite populations: (i) highly oriented crystals that grow from the flat dielectric substrate and (ii) misoriented crystals that preferentially grow on top of the existing polymer layers. The growth of the highly oriented crystals is highly sensitive to the chemistry of the substrate, whereas the effect of substrate chemistry on misoriented crystal growth is weaker. The use of a self-assembled monolayer to treat the substrate greatly enhances the population and crystallite coherence length at the buried interfaces, particularly during the early stage of deposition. Furthermore, the evolution of the in-plane carrier mobilities during the course of deposition is consistent with the development of highly oriented crystals at the buried interface, suggesting that this interface plays a key role toward determining carrier transport in organic thin-film transistors.« less

Crystallization Mechanism and Charge Carrier Transport in MAPLE-Deposited Conjugated Polymer Thin Films

DOE PAGES

Dong, Ban Xuan; Strzalka, Joseph; Jiang, Zhang; ...

2017-11-23

Although spin casting and chemical surface reactions are the most common methods used for fabricating functional polymer films onto substrates, they are limited with regard to producing films of certain morphological characteristics on different wetting and nonwetting substrates. The matrix-assisted pulsed laser evaporation (MAPLE) technique offers advantages with regard to producing films of different morphologies on different types of substrates. Here, we provide a quantitative characterization, using X-ray diffraction and optical methods, to elucidate the additive growth mechanism of MAPLE-deposited poly(3-hexylthiophene) (P3HT) films on substrates that have undergone different surface treatments, enabling them to possess different wettabilities. We show thatmore » MAPLE-deposited films are composed of crystalline phases, wherein the overall P3HT aggregate size and crystallite coherence length increase with deposition time. A complete pole figure constructed from X-ray diffraction measurements reveals that in these MAPLE-deposited films, there exist two distinct crystallite populations: (i) highly oriented crystals that grow from the flat dielectric substrate and (ii) misoriented crystals that preferentially grow on top of the existing polymer layers. The growth of the highly oriented crystals is highly sensitive to the chemistry of the substrate, whereas the effect of substrate chemistry on misoriented crystal growth is weaker. The use of a self-assembled monolayer to treat the substrate greatly enhances the population and crystallite coherence length at the buried interfaces, particularly during the early stage of deposition. Furthermore, the evolution of the in-plane carrier mobilities during the course of deposition is consistent with the development of highly oriented crystals at the buried interface, suggesting that this interface plays a key role toward determining carrier transport in organic thin-film transistors.« less

Pressure sensor using liquid crystals

NASA Technical Reports Server (NTRS)

Parmar, Devendra S. (Inventor); Holmes, Harlan K. (Inventor)

1994-01-01

A pressure sensor includes a liquid crystal positioned between transparent, electrically conductive films (18 and 20), that are biased by a voltage (V) which induces an electric field (E) that causes the liquid crystal to assume a first state of orientation. Application of pressure (P) to a flexible, transparent film (24) causes the conductive film (20) to move closer to or farther from the conductive film (18), thereby causing a change in the electric field (E'(P)) which causes the liquid crystal to assume a second state of orientation. Polarized light (P.sub.1) is directed into the liquid crystal and transmitted or reflected to an analyzer (A or 30). Changes in the state of orientation of the liquid crystal induced by applied pressure (P) result in a different light intensity being detected at the analyzer (A or 30) as a function of the applied pressure (P). In particular embodiments, the liquid crystal is present as droplets (10) in a polymer matrix (12) or in cells (14) in a polymeric or dielectric grid (16) material in the form of a layer (13) between the electrically conductive films (18 and 20). The liquid crystal fills the open wells in the polymer matrix (12) or grid (16) only partially.

Mechanical properties of metal-organic frameworks: An indentation study on epitaxial thin films

NASA Astrophysics Data System (ADS)

Bundschuh, S.; Kraft, O.; Arslan, H. K.; Gliemann, H.; Weidler, P. G.; Wöll, C.

2012-09-01

We have determined the hardness and Young's modulus of a highly porous metal-organic framework (MOF) using a standard nanoindentation technique. Despite the very low density of these films, 1.22 g cm-3, Young's modulus reaches values of almost 10 GPa for HKUST-1, demonstrating that this porous coordination polymer is substantially stiffer than normal polymers. This progress in characterizing mechanical properties of MOFs has been made possible by the use of high quality, oriented thin films grown using liquid phase epitaxy on modified Au substrates.

Fluorescence lifetime, dipole orientation and bilayer polymer films

NASA Astrophysics Data System (ADS)

Ho, Xuan Long; Chen, Po-Jui; Woon, Wei-Yen; White, Jonathon David

2017-10-01

Bilayer films consisting of the optically transparent polymers, polystyrene (PS) and poly(methyl methacrylate) (PMMA) were spin-cast on glass substrates. The upper 13.5 nm layer (PS) was lightly doped with Rhodamine-6 G (RH6G) or MEH-PPV. While the fluorescence of MEH-PPV was independent of PMMA thickness, the lifetime of RH6G increased 3-fold as the underlying PMMA thickness increased from 0 to 500 nm while the collected flux decreased suggesting a reorientation of the smaller molecule's dipole with respect to the air-polymer interface with PMMA thickness. This suggests lifetime may find application for nondestructive thickness measurements of transparent films with sub-micron lateral resolution and large range.

Significantly Increasing the Ductility of High Performance Polymer Semiconductors through Polymer Blending.

PubMed

Scott, Joshua I; Xue, Xiao; Wang, Ming; Kline, R Joseph; Hoffman, Benjamin C; Dougherty, Daniel; Zhou, Chuanzhen; Bazan, Guillermo; O'Connor, Brendan T

2016-06-08

Polymer semiconductors based on donor-acceptor monomers have recently resulted in significant gains in field effect mobility in organic thin film transistors (OTFTs). These polymers incorporate fused aromatic rings and have been designed to have stiff planar backbones, resulting in strong intermolecular interactions, which subsequently result in stiff and brittle films. The complex synthesis typically required for these materials may also result in increased production costs. Thus, the development of methods to improve mechanical plasticity while lowering material consumption during fabrication will significantly improve opportunities for adoption in flexible and stretchable electronics. To achieve these goals, we consider blending a brittle donor-acceptor polymer, poly[4-(4,4-dihexadecyl-4H-cyclopenta[1,2-b:5,4-b']dithiophen-2-yl)-alt-[1,2,5]thiadiazolo[3,4-c]pyridine] (PCDTPT), with ductile poly(3-hexylthiophene). We found that the ductility of the blend films is significantly improved compared to that of neat PCDTPT films, and when the blend film is employed in an OTFT, the performance is largely maintained. The ability to maintain charge transport character is due to vertical segregation within the blend, while the improved ductility is due to intermixing of the polymers throughout the film thickness. Importantly, the application of large strains to the ductile films is shown to orient both polymers, which further increases charge carrier mobility. These results highlight a processing approach to achieve high performance polymer OTFTs that are electrically and mechanically optimized.

Effects of Polypropylene Orientation on Mechanical and Heat Seal Properties of Polymer-Aluminum-Polymer Composite Films for Pouch Lithium-Ion Batteries

PubMed Central

Chen, Jinyao; Yang, Feng; Kang, Jian; Cao, Ya; Xiang, Ming

2018-01-01

In this study, polyamide-aluminum foil-polypropylene (PA-Al-PP) composite films with different orientation status of the PP layer were prepared, and their morphology, tensile, peeling and heat seal behavior were studied. The comparative study of tensile and fracture behaviors of single-layer film of PA, Al and PP, as well as the composite films of PA-Al, PP-Al and PA-Al-PP revealed that in PA-Al-PP composite film, the PA layer with the highest tensile strength can share the tensile stress from the Al layer during stretching, while the PP layer with the lowest tensile strength can prevent further development of the small cracks on boundary of the Al layer during stretching. Moreover, the study of heat seal behavior suggested that both the orientation status and the heat seal conditions were important factors in determining the heat seal strength (HSS) and failure behavior of the sample. Four failure types were observed, and a clear correspondence between HSS and failure types was found. The results also elucidated that for the composite film, only in the cases where the tensile stress was efficiently released by each layer during HSS measurement could the composite film exhibit desired high HSS that was even higher than its tensile strength. PMID:29337881

Micro-orientation control of silicon polymer thin films on graphite surfaces modified by heteroatom doping

NASA Astrophysics Data System (ADS)

Shimoyama, Iwao; Baba, Yuji; Hirao, Norie

2017-05-01

Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy is applied to study orientation structures of polydimethylsilane (PDMS) films deposited on heteroatom-doped graphite substrates prepared by ion beam doping. The Si K-edge NEXAFS spectra of PDMS show opposite trends of polarization dependence for non irradiated and N2+-irradiated substrates, and show no polarization dependence for an Ar+-irradiated substrate. Based on a theoretical interpretation of the NEXAFS spectra via first-principles calculations, we clarify that PDMS films have lying, standing, and random orientations on the non irradiated, N2+-irradiated, and Ar+-irradiated substrates, respectively. Furthermore, photoemission electron microscopy indicates that the orientation of a PDMS film can be controlled with microstructures on the order of μm by separating irradiated and non irradiated areas on the graphite surface. These results suggest that surface modification of graphite using ion beam doping is useful for micro-orientation control of organic thin films.

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.

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.

Nanoconfinement: an effective way to enhance PVDF piezoelectric properties.

PubMed

Cauda, Valentina; Stassi, Stefano; Bejtka, Katarzyna; Canavese, Giancarlo

2013-07-10

The dimensional confinement and oriented crystallization are both key factors in determining the piezoelectric properties of a polymeric nanostructured material. Here we prepare arrays of one-dimensional polymeric nanowires showing piezoelectric features by template-wetting two distinct polymers into anodic porous alumina (APA) membranes. In particular, poly(vinylidene fluoride), PVDF, and its copolymer poly(vinylidene fluoride-trifluoroethylene), PVTF, are obtained in commercially available APA, showing a final diameter of about 200 nm and several micrometers in length, reflecting the templating matrix features. We show that the crystallization of both polymers into a ferroelectric phase is directed by the nanotemplate confinement. Interestingly, the PVDF nanowires mainly crystallize into the β-phase in the nanoporous matrix, whereas the reference thin film of PVDF crystallizes in the α nonpolar phase. In the case of the PVTF nanowires, needle-like crystals oriented perpendicularly to the APA channel walls are observed, giving insight on the molecular orientation of the polymer within the nanowire structure. A remarkable piezoelectric behavior of both 1-D polymeric nanowires is observed, upon recording ferroelectric polarization, hysteresis, and displacement loops. In particular, an outstanding piezoelectric effect is observed for the PVDF nanowires with respect to the polymeric thin film, considering that no poling was carried out. Current versus voltage (I-V) characteristics showed a consistent switching behavior of the ferroelectric polar domains, thus revealing the importance of the confined and oriented crystallization of the polymer in monodimensional nanoarchitectures.

High-Temperature Capacitor Polymer Films

NASA Astrophysics Data System (ADS)

Tan, Daniel; Zhang, Lili; Chen, Qin; Irwin, Patricia

2014-12-01

Film capacitor technology has been under development for over half a century to meet various applications such as direct-current link capacitors for transportation, converters/inverters for power electronics, controls for deep well drilling of oil and gas, direct energy weapons for military use, and high-frequency coupling circuitry. The biaxially oriented polypropylene film capacitor remains the state-of-the-art technology; however, it is not able to meet increasing demand for high-temperature (>125°C) applications. A number of dielectric materials capable of operating at high temperatures (>140°C) have attracted investigation, and their modifications are being pursued to achieve higher volumetric efficiency as well. This paper highlights the status of polymer dielectric film development and its feasibility for capacitor applications. High-temperature polymers such as polyetherimide (PEI), polyimide, and polyetheretherketone were the focus of our studies. PEI film was found to be the preferred choice for high-temperature film capacitor development due to its thermal stability, dielectric properties, and scalability.

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.

Thermally induced texture flip in semiconducting polymer stabilized by epitaxial relationship

NASA Astrophysics Data System (ADS)

O'Hara, Kathryn A.; Pokuri, Balaji S. S.; Takacs, Christopher J.; Beaujuge, Pierre M.; Ganapathysubramanian, Baskar; Chabinyc, Michael L.

The morphology of semiconducting polymer films has a large effect on the charge transport properties. Charges can move easily along the conjugated backbone and in the pi-pi stacking direction. However, transport through the film is determined by the connectivity between domains, which is not well understood. We previously observed quadrites in the polymer, PSBTBT, and proposed that the preferential overlap between lamellae may improve connectivity and provide an additional conduction pathway. Now, the presence of quadrites is revealed in another successful donor polymer, PBDTTPD, using high resolution transmission electron microscopy (HRTEM). A study of how side-chain substitution affects the epitaxial crossing is conducted by examining several PBDTTPD derivatives. The stability of the film texture with annealing is also examined as a function of quadrite formation. It has been shown that heating some semicrystalline polymers above the melting temperature and slow cooling can flip the lamellar texture from face-on to edge-on. We hypothesize that the orientation of lamellar crystallites in PBDTTPD films is stabilized by the epitaxial overlap between adjacent crystalline domains. This may have important implications for the electronic transport properties.

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.

Rapid and Efficient Redox Processes within 2D Covalent Organic Framework Thin Films

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

DeBlase, Catherine R.; Hernández-Burgos, Kenneth; Silberstein, Katharine E.

2015-03-24

Two-dimensional covalent organic frameworks (2D COFs) are ideally suited for organizing redox-active subunits into periodic, permanently porous polymer networks of interest for pseudocapacitive energy storage. Here we describe a method for synthesizing crystalline, oriented thin films of a redox-active 2D COF on Au working electrodes. The thickness of the COF film was controlled by varying the initial monomer concentration. A large percentage (80–99%) of the anthraquinone groups are electrochemically accessible in films thinner than 200 nm, an order of magnitude improvement over the same COF prepared as a randomly oriented microcrystalline powder. As a result, electrodes functionalized with oriented COFmore » films exhibit a 400% increase in capacitance scaled to electrode area as compared to those functionalized with the randomly oriented COF powder. These results demonstrate the promise of redox-active COFs for electrical energy storage and highlight the importance of controlling morphology for optimal performance.« less

Rapid and Efficient Redox Processes within 2D Covalent Organic Framework Thin Films

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

DeBlase, Catherine R.; Hernández-Burgos, Kenneth; Silberstein, Katharine E.

2015-02-17

Two-dimensional covalent organic frameworks (2D COFs) are ideally suited for organizing redox-active subunits into periodic, permanently porous polymer networks of interest for pseudocapacitive energy storage. Here we describe a method for synthesizing crystalline, oriented thin films of a redox-active 2D COF on Au working electrodes. The thickness of the COF film was controlled by varying the initial monomer concentration. A large percentage (80–99%) of the anthraquinone groups are electrochemically accessible in films thinner than 200 nm, an order of magnitude improvement over the same COF prepared as a randomly oriented microcrystalline powder. As a result, electrodes functionalized with oriented COFmore » films exhibit a 400% increase in capacitance scaled to electrode area as compared to those functionalized with the randomly oriented COF powder. These results demonstrate the promise of redox-active COFs for electrical energy storage and highlight the importance of controlling morphology for optimal performance.« 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.

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.

Improved electron transport properties of n-type naphthalenediimide polymers through refined molecular ordering and orientation induced by processing solvents.

PubMed

An, Yujin; Long, Dang Xuan; Kim, Yiho; Noh, Yong-Young; Yang, Changduk

2016-05-14

To determine the role played by the choice of processing solvents in governing the photophysics, microstructure, and charge carrier transport in naphthalenediimide (NDI)-based polymers, we have prepared two new NDI-bithiophene (T2)- and NDI-thienothiophene (TTh)-containing polymers with hybrid siloxane pentyl chains (SiC5) (P(NDI2SiC5-T2) and P(NDI2SiC5-TTh)). Among the various processing solvents studied here, the films prepared using chloroform exhibited far better electron mobilities (0.16 ± 0.1-0.21 ± 0.05 cm(2) V(-1) s(-1)) than the corresponding samples prepared from different solvents, exceeding one order of magnitude higher, indicating the significant influence of the processing solvent on the charge transport. Upon thin-film analysis using atomic force microscopy and grazing incidence X-ray diffraction, we discovered that molecular ordering and orientation are affected by the choice of the processing solvent, which is responsible for the change in the transport characteristics of this class of polymers.

Electric Field-Mediated Processing of Polymers. Appendix 1

NASA Technical Reports Server (NTRS)

Wnek, G. E.; Bowlin, G. L.; Haas, T. W.

2000-01-01

Significant opportunities exist for the processing of polymers (homopolymers and blends) using electric fields. We suggest that a broad range of properties can be achieved using a relatively small number of polymers, with electric fields providing the ability to tailor properties via the control of shape, morphology, and orientation. Specific attention is given to electrospinning, but we note that electroaerosol formation and field-modulated film casting represent additional processing options.

Confinement and Ordering of Au Nanorods in Polymer Films

NASA Astrophysics Data System (ADS)

Hore, Michael J. A.; Mills, Eric; Liu, Yu; Composto, Russell J.

2009-03-01

Ordered arrays of gold nanorods (Au NRs) possess interesting optical properties that might be utilized in future devices. Au NRs functionalized with a poly(ethylene glycol)-thiol brush are incorporated into homopolymer or block copolymer (BCP) films. NR distribution and orientational correlations are studied as a function of nanorod concentration and spacial confinement via Rutherford backscattering spectrometry (RBS) and transmission electron microscopy, respectively. In particular, differences in the degree of nanorod ordering are presented for PMMA homopolymer films (d ˜ 45 nm) versus PS-b-PMMA BCP films (L/2 ˜ 40 nm), where higher ordering is seen in the case of BCP films. At moderate volume fractions of NRs, φ = 1% to 10%, the degree of ordering is moderate, and increases with increasing φ . However, coexistence between regions of higher ordering and isotropic orientations is observed. In addition to the planar confinement considered above, orientation of Au NRs confined to cylindrical P2VP domains is studied in PS-b-P2VP BCP films.

Growth Of Oriented Crystals At Polymerized Membranes

DOEpatents

Charych, Deborah H. , Berman, Amir

2000-01-25

The present invention relates to methods and compositions for the growth and alignment of crystals at biopolymeric films. The methods and compositions of the present invention provide means to generate a variety of dense crystalline ceramic films, with totally aligned crystals, at low temperatures and pressures, suitable for use with polymer and plastic substrates.

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.

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.

Polymer dispersed nematic liquid crystal for large area displays and light valves

NASA Astrophysics Data System (ADS)

Drzaic, Paul S.

1986-09-01

A new electro-optical material based on nematic liquid crystal dispersed in a polymer matrix has recently been introduced by Fergason. This technology (termed NCAP, for nematic curvilinear aligned phase) is suitable for making very large area (thousands of square centimeter) light valves and displays. The device consists of micron size droplets of liquid crystal dispersed in and surrounded by a polymer film. Light passing through the film in the absence of an applied field is strongly forward scattered, giving a milky, translucent film. Application of an electric field across the liquid crystal/polymer film places the film in a highly transparent state. Pleochroic dyes may be employed in the system in order to achieve controllable light absorption as well as scattering. Microscopically, it is shown that the liquid-crystal director lies preferentially parallel to the polymer wall, leading to a bipolar-like configuration of the liquid-crystal directors within the droplet. The symmetry axes of the droplets are randomly oriented in the unpowered, scattering state, but align parallel to the field in the powered, transparent state. The electric field required to reorient a given droplet varies inversely with the diameter of that droplet, and it is shown that the macroscopic electro-optical properties of the film can be modeled if the distribution of liquid-crystal droplet sizes is known.

Titania Deposition on PMR-15

NASA Technical Reports Server (NTRS)

Meador, Mary B.; Sutter, James K.; Pizem, Hillel; Gershevitz, Olga; Goffer, Yossi; Frimer, Aryeh A.; Sukenik, Chaim N.; Sampathkumaran, Uma; Milhet, Xavier; McIlwain, Alan

2005-01-01

The formation, degree of crystallinity and adherence of dense titania (TiO2) thin film coatings on a high-temperature polyimide resin (PMR-15) can be influenced by the chemical composition of the polymer surface. Furthermore, solution deposition conditions can be adjusted to provide additional control over the morphology and crystallinity of the titania films. Recipes for solution-based titania deposition that used a slowly-hydrolyzing titanium fluoride salt in the presence of boric acid as a fluoride scavenger allowed growth of films up to 750 nm thick in 22 h. By adjusting solution pH and temperature, either amorphous titania or oriented crystalline anatase films could be formed. Surface sulfonate groups enhance the adhesion of solution-deposited oxide thin film coatings. While most sulfonation procedures severely damaged the PMR-15 surface, the use of chlorosulfonic acid followed by hydrolysis of the installed chlorosulfonyl groups provided effective surface sulfonation without significant surface damage. In some cases, the oxide deposition solution caused partial hydrolysis of the polymer surface, which itself was sufficient to allow adhesion of the titania film through chelation of titanium ions by exposed benzoic acid groups on the polymer surface.

Directed Self-Assembly of Block Copolymers for High Breakdown Strength Polymer Film Capacitors.

PubMed

Samant, Saumil P; Grabowski, Christopher A; Kisslinger, Kim; Yager, Kevin G; Yuan, Guangcui; Satija, Sushil K; Durstock, Michael F; Raghavan, Dharmaraj; Karim, Alamgir

2016-03-01

Emerging needs for fast charge/discharge yet high-power, lightweight, and flexible electronics requires the use of polymer-film-based solid-state capacitors with high energy densities. Fast charge/discharge rates of film capacitors on the order of microseconds are not achievable with slower charging conventional batteries, supercapacitors and related hybrid technologies. However, the current energy densities of polymer film capacitors fall short of rising demand, and could be significantly enhanced by increasing the breakdown strength (EBD) and dielectric permittivity (εr) of the polymer films. Co-extruded two-homopolymer component multilayered films have demonstrated much promise in this regard showing higher EBD over that of component polymers. Multilayered films can also help incorporate functional features besides energy storage, such as enhanced optical, mechanical, thermal and barrier properties. In this work, we report accomplishing multilayer, multicomponent block copolymer dielectric films (BCDF) with soft-shear driven highly oriented self-assembled lamellar diblock copolymers (BCP) as a novel application of this important class of self-assembling materials. Results of a model PS-b-PMMA system show ∼50% enhancement in EBD of self-assembled multilayer lamellar BCP films compared to unordered as-cast films, indicating that the breakdown is highly sensitive to the nanostructure of the BCP. The enhancement in EBD is attributed to the "barrier effect", where the multiple interfaces between the lamellae block components act as barriers to the dielectric breakdown through the film. The increase in EBD corresponds to more than doubling the energy storage capacity using a straightforward directed self-assembly strategy. This approach opens a new nanomaterial paradigm for designing high energy density dielectric materials.

Directed self-assembly of block copolymers for high breakdown strength polymer film capacitors

DOE PAGES

Samant, Saumil P.; Grabowski, Christopher A.; Kisslinger, Kim; ...

2016-03-04

Emerging needs for fast charge/discharge yet high-power, lightweight, and flexible electronics requires the use of polymer-film-based solid-state capacitors with high energy densities. Fast charge/discharge rates of film capacitors on the order of microseconds are not achievable with slower charging conventional batteries, supercapacitors and related hybrid technologies. However, the current energy densities of polymer film capacitors fall short of rising demand, and could be significantly enhanced by increasing the breakdown strength (E BD) and dielectric permittivity (ε r) of the polymer films. Co-extruded two-homopolymer component multilayered films have demonstrated much promise in this regard showing higher E BD over that ofmore » component polymers. Multilayered films can also help incorporate functional features besides energy storage, such as enhanced optical, mechanical, thermal and barrier properties. In this work, we report accomplishing multilayer, multicomponent block copolymer dielectric films (BCDF) with soft-shear driven highly oriented self-assembled lamellar diblock copolymers (BCP) as a novel application of this important class of self-assembling materials. Results of a model PS- b-PMMA system show ~50% enhancement in E BD of self-assembled multilayer lamellar BCP films compared to unordered as-cast films, indicating that the breakdown is highly sensitive to the nanostructure of the BCP. The enhancement in E BD is attributed to the “barrier effect”, where the multiple interfaces between the lamellae block components act as barriers to the dielectric breakdown through the film. The increase in E BD corresponds to more than doubling the energy storage capacity using a straightforward directed self-assembly strategy. Lastly, this approach opens a new nanomaterial paradigm for designing high energy density dielectric materials.« 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

Molecularly Oriented Polymeric Thin Films for Space Applications

NASA Technical Reports Server (NTRS)

Fay, Catharine C.; Stoakley, Diane M.; St.Clair, Anne K.

1997-01-01

The increased commitment from NASA and private industry to the exploration of outer space and the use of orbital instrumentation to monitor the earth has focused attention on organic polymeric materials for a variety of applications in space. Some polymeric materials have exhibited short-term (3-5 yr) space environmental durability; however, future spacecraft are being designed with lifetimes projected to be 10-30 years. This gives rise to concern that material property change brought about during operation may result in unpredicted spacecraft performance. Because of their inherent toughness and flexibility, low density, thermal stability, radiation resistance and mechanical strength, aromatic polyimides have excellent potential use as advanced materials on large space structures. Also, there exists a need for high temperature (200-300 C) stable, flexible polymeric films that have high optical transparency in the 300-600nm range of the electromagnetic spectrum. Polymers suitable for these space applications were fabricated and characterized. Additionally, these polymers were molecularly oriented to further enhance their dimensional stability, stiffness, elongation and strength. Both unoriented and oriented polymeric thin films were also cryogenically treated to temperatures below -184 C to show their stability in cold environments and determine any changes in material properties.

Controlling domain orientation of liquid crystalline block copolymer in thin films through tuning mesogenic chemical structures

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

Xie, He-Lou; Li, Xiao; Ren, Jiaxing

Controlling the macroscopic orientation of nanoscale periodic structures of amphiphilic liquid crystalline block copolymers (LC BCPs) is important to a variety of technical applications (e.g., lithium conducting polymer electrolytes). To study LC BCP domain orientation, a series of LC BCPs containing a poly(ethylene oxide) (PEO) block as a conventional hydrophilic coil block and LC blocks containing azobenzene mesogens is designed and synthesized. LC ordering in thin films of the BCP leads to the formation of highly ordered, microphase-separated nanostructures, with hexagonally arranged PEO cylinders. Substitution on the tail of the azobenzene mesogen is shown to control the orientation of themore » PEO cylinders. When the substitution on the mesogenic tails is an alkyl chain, the PEO cylinders have a perpendicular orientation to the substrate surface, provided the thin film is above a critical thickness value. In contrast, when the substitution on the mesogenic tails has an ether group the PEO cylinders assemble parallel to the substrate surface regardless of the film thickness value.« less

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.

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

Spectral Photosensitization of Optical Anisotropy in Solid Poly(Vinyl Cinnamate) Films

NASA Astrophysics Data System (ADS)

Kozenkov, V. M.; Spakhov, A. A.; Belyaev, V. V.; Chausov, D. N.; Chigrinov, V. G.

2018-04-01

The possibility and features of formation of sensitized photoinduced optical anisotropy in amorphous films of poly(vinyl cinnamate) and its derivative poly(vinyl-4-metoxicinnamate) under the action of polarized light (including light that is not absorbed by polymer macromolecules themselves) have been investigated. It is found that the effect of induced optical anisotropy is based on the transfer of electron excitation energy from donor (sensitizer) molecules to acceptor molecules and is observed in the course of phototopochemical biomolecular cyclization reaction of cinnamate fragments in polymer macromolecules. The detected photoinduced anisotropy in solid films of poly(vinyl cinnamate) and its derivative poly(vinyl-4-metoxicinnamate) ensures sensitized photo-orientation of low-molecular thermotropic liquid crystals.

Orientation-dependent structural and photocatalytic properties of LaCoO3 epitaxial nano-thin films

NASA Astrophysics Data System (ADS)

Zhang, Yan-ping; Liu, Hai-feng; Hu, Hai-long; Xie, Rui-shi; Ma, Guo-hua; Huo, Ji-chuan; Wang, Hai-bin

2018-02-01

LaCoO3 epitaxial films were grown on (100), (110) and (111) oriented LaAlO3 substrates by the polymer-assisted deposition method. Crystal structure measurement and cross-section observation indicate that all the LaCoO3 films are epitaxially grown in accordance with the orientation of LaAlO3 substrates, with biaxial compressive strain in the ab plane. Owing to the different strain directions of CoO6 octahedron, the mean Co-O bond length increases by different amounts in (100), (110) and (111) oriented films compared with that of bulk LaCoO3, and the (100) oriented LaCoO3 has the largest increase. Photocatalytic degradation of methyl orange indicates that the order of photocatalytic activity of the three oriented films is (100) > (111) > (110). Combined with analysis of electronic nature and band structure for LaCoO3 films, it is found that the change of the photocatalytic activity is closely related to the crystal field splitting energy of Co3+ and Co-O binding energy. The increase in the mean Co-O bond length will decrease the crystal field splitting energy of Co3+ and Co-O binding energy and further reduce the value of band gap energy, thus improving the photocatalytic activity. This may also provide a clue for expanding the visible-light-induced photocatalytic application of LaCoO3.

Characterizing Electric Field Exposed P3HT Thin Films Using Polarized-Light Spectroscopies

DOE PAGES

Bhattacharjee, Ujjal; Elshobaki, Moneim; Santra, Kalyan; ...

2016-06-23

P3HT (poly (3-hexylthiophene)) has been widely used as a donor in the active layer in organic photovoltaic devices. Although moderately high-power conversion efficiencies have been achieved with P3HT-based devices, structural details, such as the orientation of polymer units and the extent of H- and J-aggregation are not yet fully understood; and different measures have been taken to control the ordering in the material. One such measure, which we have exploited, is to apply an electric field from a Van de Graaff generator. We used fluorescence (to measure anisotropy instead of polarization, which is more commonly measured) and Raman spectroscopy tomore » characterize the order of P3HT molecules in thin films resulting from the field. We determine preferential orientations of the units in a thin film, consistent with observed hole mobility in thin-film-transistors, and observe that the apparent H-coupling strength changes when the films are exposed to oriented electrical fields during drying.« less

Diagnosis at a glance of biological non-Newtonian fluids with Film Interference Flow Imaging (FIFI)

NASA Astrophysics Data System (ADS)

Hidema, R.; Yamada, N.; Furukawa, H.

2012-04-01

In the human body, full of biological non-Newtonian fluids exist. For example, synovial fluids exist in our joints, which contain full of biopolymers, such as hyaluronan and mucin. It is thought that these polymers play critical roles on the smooth motion of the joint. Indeed, luck of biopolymers in synovial fluid cause joint pain. Here we study the effects of polymer in thin liquid layer by using an original experimental method called Film Interference Flow Imaging (FIFI). A vertically flowing soap film containing polymers is made as two-dimensional flow to observe turbulence. The thickness of water layer is about 4 μm sandwiched between surfactant mono-layers. The interference pattern of the soap film is linearly related to the flow velocity in the water layer through the change in the thickness of the film. Thus the flow velocity is possibly analyzed by the single image analysis of the interference pattern, that is, FIFI. The grid turbulence was made in the flowing soap films containing the long flexible polymer polyethyleneoxide (PEO, Mw=3.5x106), and rigid polymer hydroxypropyl cellulose (HPC, Mw > 1.0 x106). The decaying process of the turbulence is affected by PEO and HPC at several concentrations. The effects of PEO are sharply seen even at low concentrations, while the effects of HPC are gradually occurred at much higher concentration compared to the PEO. It is assumed that such a difference between PEO and HPC is due to the polymer stretching or polymer orientation under turbulence, which is observed and analyzed by FIFI. We believe the FIFI will be applied in the future to examine biological fluids such as synovial fluids quickly and quantitatively.

Quinuclidinium salt ferroelectric thin-film with duodecuple-rotational polarization-directions

NASA Astrophysics Data System (ADS)

You, Yu-Meng; Tang, Yuan-Yuan; Li, Peng-Fei; Zhang, Han-Yue; Zhang, Wan-Ying; Zhang, Yi; Ye, Heng-Yun; Nakamura, Takayoshi; Xiong, Ren-Gen

2017-04-01

Ferroelectric thin-films are highly desirable for their applications on energy conversion, data storage and so on. Molecular ferroelectrics had been expected to be a better candidate compared to conventional ferroelectric ceramics, due to its simple and low-cost film-processability. However, most molecular ferroelectrics are mono-polar-axial, and the polar axes of the entire thin-film must be well oriented to a specific direction to realize the macroscopic ferroelectricity. To align the polar axes, an orientation-controlled single-crystalline thin-film growth method must be employed, which is complicated, high-cost and is extremely substrate-dependent. In this work, we discover a new molecular ferroelectric of quinuclidinium periodate, which possesses six-fold rotational polar axes. The multi-axes nature allows the thin-film of quinuclidinium periodate to be simply prepared on various substrates including flexible polymer, transparent glasses and amorphous metal plates, without considering the crystallinity and crystal orientation. With those benefits and excellent ferroelectric properties, quinuclidinium periodate shows great potential in applications like wearable devices, flexible materials, bio-machines and so on.

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

Samant, Saumil P.; Grabowski, Christopher A.; Kisslinger, Kim

Emerging needs for fast charge/discharge yet high-power, lightweight, and flexible electronics requires the use of polymer-film-based solid-state capacitors with high energy densities. Fast charge/discharge rates of film capacitors on the order of microseconds are not achievable with slower charging conventional batteries, supercapacitors and related hybrid technologies. However, the current energy densities of polymer film capacitors fall short of rising demand, and could be significantly enhanced by increasing the breakdown strength (E BD) and dielectric permittivity (ε r) of the polymer films. Co-extruded two-homopolymer component multilayered films have demonstrated much promise in this regard showing higher E BD over that ofmore » component polymers. Multilayered films can also help incorporate functional features besides energy storage, such as enhanced optical, mechanical, thermal and barrier properties. In this work, we report accomplishing multilayer, multicomponent block copolymer dielectric films (BCDF) with soft-shear driven highly oriented self-assembled lamellar diblock copolymers (BCP) as a novel application of this important class of self-assembling materials. Results of a model PS-b-PMMA system show ~50% enhancement in E BD of self-assembled multilayer lamellar BCP films compared to unordered as-cast films, indicating that the breakdown is highly sensitive to the nanostructure of the BCP. The enhancement in E BD is attributed to the “barrier effect”, where the multiple interfaces between the lamellae block components act as barriers to the dielectric breakdown through the film. The increase in E BD corresponds to more than doubling the energy storage capacity using a straightforward directed self-assembly strategy. This approach opens a new nanomaterial paradigm for designing high energy density dielectric materials.« less

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

Samant, Saumil P.; Grabowski, Christopher A.; Kisslinger, Kim

Emerging needs for fast charge/discharge yet high-power, lightweight, and flexible electronics requires the use of polymer-film-based solid-state capacitors with high energy densities. Fast charge/discharge rates of film capacitors on the order of microseconds are not achievable with slower charging conventional batteries, supercapacitors and related hybrid technologies. However, the current energy densities of polymer film capacitors fall short of rising demand, and could be significantly enhanced by increasing the breakdown strength (E BD) and dielectric permittivity (ε r) of the polymer films. Co-extruded two-homopolymer component multilayered films have demonstrated much promise in this regard showing higher E BD over that ofmore » component polymers. Multilayered films can also help incorporate functional features besides energy storage, such as enhanced optical, mechanical, thermal and barrier properties. In this work, we report accomplishing multilayer, multicomponent block copolymer dielectric films (BCDF) with soft-shear driven highly oriented self-assembled lamellar diblock copolymers (BCP) as a novel application of this important class of self-assembling materials. Results of a model PS- b-PMMA system show ~50% enhancement in E BD of self-assembled multilayer lamellar BCP films compared to unordered as-cast films, indicating that the breakdown is highly sensitive to the nanostructure of the BCP. The enhancement in E BD is attributed to the “barrier effect”, where the multiple interfaces between the lamellae block components act as barriers to the dielectric breakdown through the film. The increase in E BD corresponds to more than doubling the energy storage capacity using a straightforward directed self-assembly strategy. Lastly, this approach opens a new nanomaterial paradigm for designing high energy density dielectric materials.« less

Optical characterization of thin nickel films on polymer substrates using reflectance difference spectroscopy

NASA Astrophysics Data System (ADS)

Rinnerbauer, V.; Schmidegg, K.; Hohage, M.; Sun, L. D.; Flores-Camacho, J. M.; Zeppenfeld, P.

2009-06-01

We have used reflectance difference spectroscopy (RDS) and its extension, azimuth-dependent RDS (ADRDS), to study the properties of sputtered and evaporated nickel films on biaxially oriented poly(ethylene terephtalate) (PET) films in a roll to roll web-coating process. From the full set of ADRDS spectra we extract and analyze both the intrinsic RDS spectra and the azimuthal orientation of the effective optical anisotropy of the samples. From the latter, contributions to the RDS spectra arising from the nickel layer and the PET substrate with different orientations of the optical eigenaxes can be inferred. We find an attenuation of the characteristic RDS signal of the PET substrate with increasing nickel film thickness which is in good agreement with the theoretical prediction. For film thicknesses above 20 nm another contribution to the RDS signal attributed to the optical anisotropy of the deposited nickel layers can be observed. Its strength depends on the deposition method, and is considerably larger for evaporated films than for sputtered ones. With increasing nickel film thickness, the azimuthal orientation of the sample anisotropy changes from the initial value of the PET substrate by about 20° toward the machine direction of the foil. We demonstrate that RDS is also a valuable tool for inline monitoring in the roll to roll process, as the attenuation of the RDS signal, under proper consideration of the orientation of the effective anisotropy, is a function of the film thickness and characteristic for the deposited material.

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.

Watching How Molecules Orient in a Surface Forces Apparatus, Using Confocal Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Jiang, Shan; Kim, Minsu; Bae, Sung Chul; Granick, Steve

2006-03-01

Much is known about surface forces, less about where they come from. This laboratory is engaged in direct vibrational spectroscopic measurements of how molecules orient in confined geometries. Regarding force measurements, PDMS (polydimethylsiloxane) was a model system for many years. In this study, we describe direct experiments using a novel version of confocal Raman spectroscopy. This experiment allows direct measurement of how the PDMS molecules orient under confinment as well as under subsequent shear. When the thickness of the fluid film is less than the unperturbed radius of gyration of the polymer, we obtain two novel findings: (a) linewidth analysis of peaks reveals that vibrational relaxation times are perturbed in this confined geometry; (b) orientation of the chain backbone is not everywhere the same within the molecularly-thin film; domains of various orientation are observed instead.

Understanding Interfacial Alignment in Solution Coated Conjugated Polymer Thin Films

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

Qu, Ge; Zhao, Xikang; Newbloom, Gregory M.

Domain alignment in conjugated polymer thin films can significantly enhance charge carrier mobility. However, the alignment mechanism during meniscus-guided solution coating remains unclear. Furthermore, interfacial alignment has been rarely studied despite its direct relevance and critical importance to charge transport. In this study, we uncover a significantly higher degree of alignment at the top interface of solution coated thin films, using a donor–acceptor conjugated polymer, poly(diketopyrrolopyrrole-co-thiopheneco- thieno[3,2- b]thiophene-co-thiophene) (DPP2T-TT), as the model system. At the molecular level, we observe in-plane π–π stacking anisotropy of up to 4.8 near the top interface with the polymer backbone aligned parallel to the coatingmore » direction. The bulk of the film is only weakly aligned with the backbone oriented transverse to coating. At the mesoscale, we observe a well-defined fibril-like morphology at the top interface with the fibril long axis pointing toward the coating direction. Significantly smaller fibrils with poor orientational order are found on the bottom interface, weakly aligned orthogonal to the fibrils on the top interface. The high degree of alignment at the top interface leads to a charge transport anisotropy of up to 5.4 compared to an anisotropy close to 1 on the bottom interface. We attribute the formation of distinct interfacial morphology to the skin-layer formation associated with high Peclet number, which promotes crystallization on the top interface while suppressing it in the bulk. As a result, we further infer that the interfacial fibril alignment is driven by the extensional flow on the top interface arisen from increasing solvent evaporation rate closer to the meniscus front.« less

Understanding Interfacial Alignment in Solution Coated Conjugated Polymer Thin Films

DOE PAGES

Qu, Ge; Zhao, Xikang; Newbloom, Gregory M.; ...

2017-08-01

Domain alignment in conjugated polymer thin films can significantly enhance charge carrier mobility. However, the alignment mechanism during meniscus-guided solution coating remains unclear. Furthermore, interfacial alignment has been rarely studied despite its direct relevance and critical importance to charge transport. In this study, we uncover a significantly higher degree of alignment at the top interface of solution coated thin films, using a donor–acceptor conjugated polymer, poly(diketopyrrolopyrrole-co-thiopheneco- thieno[3,2- b]thiophene-co-thiophene) (DPP2T-TT), as the model system. At the molecular level, we observe in-plane π–π stacking anisotropy of up to 4.8 near the top interface with the polymer backbone aligned parallel to the coatingmore » direction. The bulk of the film is only weakly aligned with the backbone oriented transverse to coating. At the mesoscale, we observe a well-defined fibril-like morphology at the top interface with the fibril long axis pointing toward the coating direction. Significantly smaller fibrils with poor orientational order are found on the bottom interface, weakly aligned orthogonal to the fibrils on the top interface. The high degree of alignment at the top interface leads to a charge transport anisotropy of up to 5.4 compared to an anisotropy close to 1 on the bottom interface. We attribute the formation of distinct interfacial morphology to the skin-layer formation associated with high Peclet number, which promotes crystallization on the top interface while suppressing it in the bulk. As a result, we further infer that the interfacial fibril alignment is driven by the extensional flow on the top interface arisen from increasing solvent evaporation rate closer to the meniscus front.« less

Orientation-dependent structural and photocatalytic properties of LaCoO3 epitaxial nano-thin films

PubMed Central

Zhang, Yan-ping; Hu, Hai-long; Xie, Rui-shi; Ma, Guo-hua; Huo, Ji-chuan; Wang, Hai-bin

2018-01-01

LaCoO3 epitaxial films were grown on (100), (110) and (111) oriented LaAlO3 substrates by the polymer-assisted deposition method. Crystal structure measurement and cross-section observation indicate that all the LaCoO3 films are epitaxially grown in accordance with the orientation of LaAlO3 substrates, with biaxial compressive strain in the ab plane. Owing to the different strain directions of CoO6 octahedron, the mean Co–O bond length increases by different amounts in (100), (110) and (111) oriented films compared with that of bulk LaCoO3, and the (100) oriented LaCoO3 has the largest increase. Photocatalytic degradation of methyl orange indicates that the order of photocatalytic activity of the three oriented films is (100) > (111) > (110). Combined with analysis of electronic nature and band structure for LaCoO3 films, it is found that the change of the photocatalytic activity is closely related to the crystal field splitting energy of Co3+ and Co–O binding energy. The increase in the mean Co–O bond length will decrease the crystal field splitting energy of Co3+ and Co–O binding energy and further reduce the value of band gap energy, thus improving the photocatalytic activity. This may also provide a clue for expanding the visible-light-induced photocatalytic application of LaCoO3. PMID:29515854

Orientation-dependent structural and photocatalytic properties of LaCoO3 epitaxial nano-thin films.

PubMed

Zhang, Yan-Ping; Liu, Hai-Feng; Hu, Hai-Long; Xie, Rui-Shi; Ma, Guo-Hua; Huo, Ji-Chuan; Wang, Hai-Bin

2018-02-01

LaCoO 3 epitaxial films were grown on (100), (110) and (111) oriented LaAlO 3 substrates by the polymer-assisted deposition method. Crystal structure measurement and cross-section observation indicate that all the LaCoO 3 films are epitaxially grown in accordance with the orientation of LaAlO 3 substrates, with biaxial compressive strain in the ab plane. Owing to the different strain directions of CoO 6 octahedron, the mean Co-O bond length increases by different amounts in (100), (110) and (111) oriented films compared with that of bulk LaCoO 3 , and the (100) oriented LaCoO 3 has the largest increase. Photocatalytic degradation of methyl orange indicates that the order of photocatalytic activity of the three oriented films is (100) > (111) > (110). Combined with analysis of electronic nature and band structure for LaCoO 3 films, it is found that the change of the photocatalytic activity is closely related to the crystal field splitting energy of Co 3+ and Co-O binding energy. The increase in the mean Co-O bond length will decrease the crystal field splitting energy of Co 3+ and Co-O binding energy and further reduce the value of band gap energy, thus improving the photocatalytic activity. This may also provide a clue for expanding the visible-light-induced photocatalytic application of LaCoO 3 .

Effects of Interphase Modification and Biaxial Orientation on Dielectric Properties of Poly(ethylene terephthalate)/Poly(vinylidene fluoride-co-hexafluoropropylene) Multilayer Films.

PubMed

Yin, Kezhen; Zhou, Zheng; Schuele, Donald E; Wolak, Mason; Zhu, Lei; Baer, Eric

2016-06-01

Recently, poly(vinylidene fluoride) (PVDF)-based multilayer films have demonstrated enhanced dielectric properties, combining high energy density and high dielectric breakdown strength from the component polymers. In this work, further enhanced dielectric properties were achieved through interface/interphase modulation and biaxial orientation for the poly(ethylene terephthalate)/poly(methyl methacrylate)/poly(vinylidene fluoride-co-hexafluoropropylene) [PET/PMMA/P(VDF-HFP)] three-component multilayer films. Because PMMA is miscible with P(VDF-HFP) and compatible with PET, the interfacial adhesion between PET and P(VDF-HFP) layers should be improved. Biaxial stretching of the as-extruded multilayer films induced formation of highly oriented fibrillar crystals in both P(VDF-HFP) and PET, resulting in improved dielectric properties with respect to the unstretched films. First, the parallel orientation of PVDF crystals reduced the dielectric loss from the αc relaxation in α crystals. Second, biaxial stretching constrained the amorphous phase in P(VDF-HFP) and thus the migrational loss from impurity ions was reduced. Third, biaxial stretching induced a significant amount of rigid amorphous phase in PET, further enhancing the breakdown strength of multilayer films. Due to the synergistic effects of improved interfacial adhesion and biaxial orientation, the PET/PMMA/P(VDF-HFP) 65-layer films with 8 vol % PMMA exhibited optimal dielectric properties with an energy density of 17.4 J/cm(3) at breakdown and the lowest dielectric loss. These three-component multilayer films are promising for future high-energy-density film capacitor applications.

Thin-film morphology of inkjet-printed single-droplet organic transistors using polarized Raman spectroscopy: effect of blending TIPS-pentacene with insulating polymer.

PubMed

James, David T; Kjellander, B K Charlotte; Smaal, Wiljan T T; Gelinck, Gerwin H; Combe, Craig; McCulloch, Iain; Wilson, Richard; Burroughes, Jeremy H; Bradley, Donal D C; Kim, Ji-Seon

2011-12-27

We report thin-film morphology studies of inkjet-printed single-droplet organic thin-film transistors (OTFTs) using angle-dependent polarized Raman spectroscopy. We show this to be an effective technique to determine the degree of molecular order as well as to spatially resolve the orientation of the conjugated backbones of the 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-Pentacene) molecules. The addition of an insulating polymer, polystyrene (PS), does not disrupt the π-π stacking of the TIPS-Pentacene molecules. Blending in fact improves the uniformity of the molecular morphology and the active layer coverage within the device and reduces the variation in molecular orientation between polycrystalline domains. For OTFT performance, blending enhances the saturation mobility from 0.22 ± 0.05 cm(2)/(V·s) (TIPS-Pentacene) to 0.72 ± 0.17 cm(2)/(V·s) (TIPS-Pentacene:PS) in addition to improving the quality of the interface between TIPS-Pentacene and the gate dielectric in the channel, resulting in threshold voltages of ∼0 V and steep subthreshold slopes.

Chlorination of low-band-gap polymers: Toward high-performance polymer solar cells

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

Mo, Daize; Wang, Huan; Chen, Hui

Here, halogenation is an effective way to tune the energy levels of organic semiconducting materials. To date, fluorination of organic semiconducting materials to fabricate polymer solar cells (PSCs) has been used far more than chlorination; however, fluorine exchange reactions suffer from low yields and the resulting fluorinated polymer always comes with higher price, which will greatly hinder their commercial applications. Herein, we designed and synthesized a series of chlorinated donor-acceptor (D-A) type polymers, in which benzo[1,2-b:4,5- b]dithiophene and chlorinated benzothiadiazole units are connected by thiophene π-bridges with an asymmetric alkyl chain. These chlorinated polymers showed deep highest occupied molecular orbitalmore » energy levels, which promoted the efficiency of their corresponding PSCs by increasing the device open circuit voltage. The asymmetric alkyl chain on the thiophene moieties gave the final polymer sufficient solubility for solution processing and strong π-π stacking in films allowed for high mobility. Although the introduction of a large chlorine atom increased the torsion angle of the polymer backbone, the chlorinated polymers maintained high crystallinity and a favorable backbone orientation in the blended films. These factors contributed to respectable device performances from thick-film devices, which showed PCEs as high as 9.11% for a 250 nm-thick active layer. These results demonstrate that chlorination is a promising method to fine tune the energy levels of conjugated polymers, and chlorinated benzothiadiazole may be a versatile building block in materials for efficient solar energy conversion.« less

Chlorination of low-band-gap polymers: Toward high-performance polymer solar cells

DOE PAGES

Mo, Daize; Wang, Huan; Chen, Hui; ...

2017-03-08

Here, halogenation is an effective way to tune the energy levels of organic semiconducting materials. To date, fluorination of organic semiconducting materials to fabricate polymer solar cells (PSCs) has been used far more than chlorination; however, fluorine exchange reactions suffer from low yields and the resulting fluorinated polymer always comes with higher price, which will greatly hinder their commercial applications. Herein, we designed and synthesized a series of chlorinated donor-acceptor (D-A) type polymers, in which benzo[1,2-b:4,5- b]dithiophene and chlorinated benzothiadiazole units are connected by thiophene π-bridges with an asymmetric alkyl chain. These chlorinated polymers showed deep highest occupied molecular orbitalmore » energy levels, which promoted the efficiency of their corresponding PSCs by increasing the device open circuit voltage. The asymmetric alkyl chain on the thiophene moieties gave the final polymer sufficient solubility for solution processing and strong π-π stacking in films allowed for high mobility. Although the introduction of a large chlorine atom increased the torsion angle of the polymer backbone, the chlorinated polymers maintained high crystallinity and a favorable backbone orientation in the blended films. These factors contributed to respectable device performances from thick-film devices, which showed PCEs as high as 9.11% for a 250 nm-thick active layer. These results demonstrate that chlorination is a promising method to fine tune the energy levels of conjugated polymers, and chlorinated benzothiadiazole may be a versatile building block in materials for efficient solar energy conversion.« less

Masked PDAMNA Film On Glass

NASA Technical Reports Server (NTRS)

1996-01-01

Polydiacetylenes are a unique class of highly conjugated organic polymers that are of interest for both electronic and photonic applications. Photodeposition from solutions is a novel process superior to those grown by conventional techniques. Evidence of this is seen when the films are viewed under a microscope; they exhibit small particles of solid polymer which form in the bulk solution, get transported by convection to the surface of the growing film, and become embedded. Also convection tends to cause the film thickness to be less uniform, and may even affect the molecular orientation of the films. The thrust of the research is to investigate in detail, both in 1-g and low-g, the effects of convection (and lack thereof) on this novel and interesting reaction. In this example, a portion of the substrate was blocked from exposure to the UV light by the mask, which was placed on the opposite side of the glass disk as the film, clearly demonstrating that photodeposition occurs only where the substrate is irradiated directly.

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).

Photomotility of polymers

PubMed Central

Wie, Jeong Jae; Shankar, M. Ravi; White, Timothy J.

2016-01-01

Light is distinguished as a contactless energy source for microscale devices as it can be directed from remote distances, rapidly turned on or off, spatially modulated across length scales, polarized, or varied in intensity. Motivated in part by these nascent properties of light, transducing photonic stimuli into macroscopic deformation of materials systems has been examined in the last half-century. Here we report photoinduced motion (photomotility) in monolithic polymer films prepared from azobenzene-functionalized liquid crystalline polymer networks (azo-LCNs). Leveraging the twisted-nematic orientation, irradiation with broad spectrum ultraviolet–visible light (320–500 nm) transforms the films from flat sheets to spiral ribbons, which subsequently translate large distances with continuous irradiation on an arbitrary surface. The motion results from a complex interplay of photochemistry and mechanics. We demonstrate directional control, as well as climbing. PMID:27830707

Incorporating poly(3-hexyl thiophene) into orthogonally aligned cylindrical nanopores of titania for optoelectronics

DOE PAGES

Nagpure, Suraj; Browning, James F.; Rankin, Stephen E.

2016-11-03

Here, the incorporation of hole conducting polymer poly(3-hexyl thiophene) (P3HT) into the 8-9 nm cylindrical nanopores of titania is investigated using films with a unique orthogonally oriented hexagonal close packed mesostructure. The films are synthesized using evaporation induced self-assembly (EISA) with Pluronic triblock copolymer F127 as the structure directing agent. The orthogonally oriented cylindrical nanopore structure was chosen over a cubic structure because confinement in uniform cylindrical channels is hypothesized to enhance hole conductivity of P3HT by inducing local polymer chain ordering. Orthogonal orientation of the cylindrical nanopores is achieved by modifying the substrate (FTO-coated glass slides) with crosslinked F127.more » After thermal treatment to remove organic templates from the films, P3HT is infiltrated into the nanopores by spin coating a 1 wt% P3HT solution in chlorobenzene onto the titania films followed by thermal annealing under vacuum at 200 °C. The results show that infiltration is essentially complete after 30 minutes of annealing, with little or no further infiltration thereafter. A final infiltration depth of ~14 nm is measured for P3HT into the nanopores of titania using neutron reflectometry measurements. Photoluminescence measurements demonstrate that charge transfer at the P3HT-TiO 2 interface improves as the P3HT is infiltrated into the pores, suggesting that an active organic-inorganic heterojuction is formed in the materials.« less

Incorporating poly(3-hexyl thiophene) into orthogonally aligned cylindrical nanopores of titania for optoelectronics

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

Nagpure, Suraj; Browning, James F.; Rankin, Stephen E.

Here, the incorporation of hole conducting polymer poly(3-hexyl thiophene) (P3HT) into the 8-9 nm cylindrical nanopores of titania is investigated using films with a unique orthogonally oriented hexagonal close packed mesostructure. The films are synthesized using evaporation induced self-assembly (EISA) with Pluronic triblock copolymer F127 as the structure directing agent. The orthogonally oriented cylindrical nanopore structure was chosen over a cubic structure because confinement in uniform cylindrical channels is hypothesized to enhance hole conductivity of P3HT by inducing local polymer chain ordering. Orthogonal orientation of the cylindrical nanopores is achieved by modifying the substrate (FTO-coated glass slides) with crosslinked F127.more » After thermal treatment to remove organic templates from the films, P3HT is infiltrated into the nanopores by spin coating a 1 wt% P3HT solution in chlorobenzene onto the titania films followed by thermal annealing under vacuum at 200 °C. The results show that infiltration is essentially complete after 30 minutes of annealing, with little or no further infiltration thereafter. A final infiltration depth of ~14 nm is measured for P3HT into the nanopores of titania using neutron reflectometry measurements. Photoluminescence measurements demonstrate that charge transfer at the P3HT-TiO 2 interface improves as the P3HT is infiltrated into the pores, suggesting that an active organic-inorganic heterojuction is formed in the materials.« less

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.

Enhanced dielectric properties due to space charge-induced interfacial polarization in multilayer polymer films

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

Chen, Xinyue; Tseng, Jung-Kai; Treufeld, Imre

We report that with the recent advancement of power electronics, polymer film capacitors have become increasingly important. However, the low temperature rating (up to 85 °C) and low energy density (5 J cm -3 at breakdown) of state-of-the-art biaxially oriented polypropylene (BOPP) films have been limiting factors for advanced power electronics. Based on our recent work, multilayer films (MLFs), which consist of a high energy density polymer [e.g., poly(vinylidene fluoride) (PVDF)] and a high breakdown/low loss polymer [e.g., polycarbonate (PC)], have shown potential to achieve high energy density (13–17 J cm -3), enhanced breakdown strength, high temperature tolerance, and lowmore » loss simultaneously. In this study, the dielectric properties of PC/PVDF 50/50 32- and 256-layer (32L and 256L) films were investigated. The breakdown strength of the 32L film was as high as 800 MV m -1 at room temperature, as compared to 600 MV m -1 of PVDF and 750 MV m-1 of PC. The temperature rating of the 32L film reached 120 °C, higher than that of BOPP. In addition, it was observed that the 32L film with thicker PC layers exhibited a higher breakdown strength and a lower DC conductivity than the 256L film with thinner PC layers at elevated temperatures. These differences were attributed to the difference in the interfacial polarization of space charges, which was further verified by thermally stimulated depolarization current spectroscopy. In conclusion, we conclude that interfacial polarization endows MLFs with the desirable dielectric properties for next generation film capacitors.« less

Enhanced dielectric properties due to space charge-induced interfacial polarization in multilayer polymer films

DOE PAGES

Chen, Xinyue; Tseng, Jung-Kai; Treufeld, Imre; ...

2017-09-15

We report that with the recent advancement of power electronics, polymer film capacitors have become increasingly important. However, the low temperature rating (up to 85 °C) and low energy density (5 J cm -3 at breakdown) of state-of-the-art biaxially oriented polypropylene (BOPP) films have been limiting factors for advanced power electronics. Based on our recent work, multilayer films (MLFs), which consist of a high energy density polymer [e.g., poly(vinylidene fluoride) (PVDF)] and a high breakdown/low loss polymer [e.g., polycarbonate (PC)], have shown potential to achieve high energy density (13–17 J cm -3), enhanced breakdown strength, high temperature tolerance, and lowmore » loss simultaneously. In this study, the dielectric properties of PC/PVDF 50/50 32- and 256-layer (32L and 256L) films were investigated. The breakdown strength of the 32L film was as high as 800 MV m -1 at room temperature, as compared to 600 MV m -1 of PVDF and 750 MV m-1 of PC. The temperature rating of the 32L film reached 120 °C, higher than that of BOPP. In addition, it was observed that the 32L film with thicker PC layers exhibited a higher breakdown strength and a lower DC conductivity than the 256L film with thinner PC layers at elevated temperatures. These differences were attributed to the difference in the interfacial polarization of space charges, which was further verified by thermally stimulated depolarization current spectroscopy. In conclusion, we conclude that interfacial polarization endows MLFs with the desirable dielectric properties for next generation film capacitors.« less

Microscopic signature of insulator-to-metal transition in highly doped semicrystalline conducting polymers in ionic-liquid-gated transistors

NASA Astrophysics Data System (ADS)

Tanaka, Hisaaki; Nishio, Satoshi; Ito, Hiroshi; Kuroda, Shin-ichi

2015-12-01

Electronic state of charge carriers, in particular, in highly doped regions, in thin-film transistors of a semicrystalline conducting polymer poly(2,5-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene), has been studied by using field-induced electron spin resonance (ESR) spectroscopy. By adopting an ionic-liquid gate insulator, a gate-controlled reversible electrochemical hole-doping of the polymer backbone is achieved, as confirmed from the change of the optical absorption spectra. The edge-on molecular orientation in the pristine film is maintained even after the electrochemical doping, which is clarified from the angular dependence of the g value. As the doping level increases, spin 1/2 polarons transform into spinless bipolarons, which is demonstrated from the spin-charge relation showing a spin concentration peak around 1%, contrasting to the monotonic increase in the charge concentration. At high doping levels, a drastic change in the linewidth anisotropy due to the generation of conduction electrons is observed, indicating the onset of metallic state, which is also supported by the temperature dependence of the spin susceptibility and the ESR linewidth. Our results suggest that semicrystalline conducting polymers become metallic with retaining their molecular orientational order, when appropriate doping methods are chosen.

Super-Robust Polylactide Barrier Films by Building Densely Oriented Lamellae Incorporated with Ductile in Situ Nanofibrils of Poly(butylene adipate-co-terephthalate).

PubMed

Zhou, Sheng-Yang; Huang, Hua-Dong; Ji, Xu; Yan, Ding-Xiang; Zhong, Gan-Ji; Hsiao, Benjamin S; Li, Zhong-Ming

2016-03-01

Remarkable combination of excellent gas barrier performance, high strength, and toughness was realized in polylactide (PLA) composite films by constructing the supernetworks of oriented and pyknotic crystals with the assistance of ductile in situ nanofibrils of poly(butylene adipate-co-terephthalate) (PBAT). On the basis that the permeation of gas molecules through polymer materials with anisotropic structure would be more frustrated, we believe that oriented crystalline textures cooperating with inerratic amorphism can be favorable for the enhancement of gas barrier property. By taking full advantage of intensively elongational flow field, the dispersed phase of PBAT in situ forms into nanofibrils, and simultaneously sufficient row-nuclei for PLA are induced. After appropriate thermal treatment with the acceleration effect of PBAT on PLA crystallization, oriented lamellae of PLA tend to be more perfect in a preferential direction and constitute into a kind of network interconnecting with each other. At the same time, the molecular chains between lamellae tend to be more extended. This unique structure manifests superior ability in ameliorating the performance of PLA film. The oxygen permeability coefficient can be achieved as low as 2 × 10(-15) cm(3) cm cm(-2) s(-1) Pa(-1), combining with the high strength, modulus, and ductility (104.5 MPa, 3484 MPa, and 110.6%, respectively). The methodology proposed in this work presents an industrially scalable processing method to fabricate super-robust PLA barrier films. It would indeed push the usability of biopolymers forward, and certainly prompt wider application of biodegradable polymers in the fields of environmental protection such as food packaging, medical packaging, and biodegradable mulch.

Thin Polymer Films with Continuous Vertically Aligned 1 nm Pores Fabricated by Soft Confinement

DOE PAGES

Feng, Xunda; Nejati, Siamak; Cowan, Matthew G.; ...

2015-12-03

Membrane separations are critically important in areas ranging from health care and analytical chemistry to bioprocessing and water purification. An ideal nanoporous membrane would consist of a thin film with physically continuous and vertically aligned nanopores and would display a narrow distribution of pore sizes. However, the current state of the art departs considerably from this ideal and is beset by intrinsic trade-offs between permeability and selectivity. We demonstrate an effective and scalable method to fabricate polymer films with ideal membrane morphologies consisting of submicron thickness films with physically continuous and vertically aligned 1 nm pores. The approach is basedmore » on soft confinement to control the orientation of a cross-linkable mesophase in which the pores are produced by self-assembly. The scalability, exceptional ease of fabrication, and potential to create a new class of nanofiltration membranes stand out as compelling aspects.« less

Protein immobilization on epoxy-activated thin polymer films: effect of surface wettability and enzyme loading.

PubMed

Chen, Bo; Pernodet, Nadine; Rafailovich, Miriam H; Bakhtina, Asya; Gross, Richard A

2008-12-02

A series of epoxy-activated polymer films composed of poly(glycidyl methacrylate/butyl methacrylate/hydroxyethyl methacrylate) were prepared. Variation in comonomer composition allowed exploration of relationships between surface wettability and Candida antartica lipase B (CALB) binding to surfaces. By changing solvents and polymer concentrations, suitable conditions were developed for preparation by spin-coating of uniform thin films. Film roughness determined by AFM after incubation in PBS buffer for 2 days was less than 1 nm. The occurrence of single CALB molecules and CALB aggregates at surfaces was determined by AFM imaging and measurements of volume. Absolute numbers of protein monomers and multimers at surfaces were used to determine values of CALB specific activity. Increased film wettability, as the water contact angle of films increased from 420 to 550, resulted in a decreased total number of immobilized CALB molecules. With further increases in the water contact angle of films from 55 degrees to 63 degrees, there was an increased tendency of CALB molecules to form aggregates on surfaces. On all flat surfaces, two height populations, differing by more than 30%, were observed from height distribution curves. They are attributed to changes in protein conformation and/or orientation caused by protein-surface and protein-protein interactions. The fraction of molecules in these populations changed as a function of film water contact angle. The enzyme activity of immobilized films was determined by measuring CALB-catalyzed hydrolysis of p-nitrophenyl butyrate. Total enzyme specific activity decreased by decreasing film hydrophobicity.

Paper-polymer composite devices with minimal fluorescence background.

PubMed

Wang, Chang-Ming; Chen, Chong-You; Liao, Wei-Ssu

2017-04-22

Polymer film incorporated paper-based devices show advantages in simplicity and rugged backing. However, their applications are restricted by the high fluorescence background interference of conventional laminating pouches. Herein, we report a straightforward approach for minimal fluorescence background device fabrication, in which filter paper was shaped and laminated in between two biaxially oriented polypropylene (OPP) and polyvinyl butyral (PVB) composite films. This composite film provides mechanical strength for enhanced device durability, protection from environmental contamination, and prevents reagent degradation. This approach was tested by the determination of copper ions with a fluorescent probe, while the detection of glucose was used to illustrate the improved device durability. Our results show that lamination by the polymer composite lengthens device lifetime, while allowing for fluorescence detection methods combination with greatly reduced fluorescent background widely present in commercially available lamination pouches. By the combination of rapid device prototyping with low cost materials, we believe that this composite design would further expand the potential of paper-based devices. Copyright © 2017 Elsevier B.V. All rights reserved.

Block Copolymer Directed Biomimetic Mineral Formation for Polymer Nanocomposites

NASA Astrophysics Data System (ADS)

Gleeson, Sarah; Yu, Tony; Chen, Xi; Marcolongo, Michele; Li, Christopher

Bone is a hierarchically structured biocomposite comprised of mineralized collagen fibrils. The mechanical properties of bone can be precisely tuned by the structure and morphology of the mineral nanocrystals as well as the organic collagen fibrils. Synthetic materials that can mimic the nanostructure of natural bone show promise to replicate bone's structural function, yet little is known about the mechanism of mineral formation. We previously have shown that hierarchically ordered polymer fibers control the distribution and orientation of hydroxyapatite, enhancing mechanical properties and biocompatibility. We demonstrate a new method for mineralization by forming block copolymer single crystal films of polycaprolactone-block-poly(acrylic acid) (PCL- b-PAA) so that lamellar anionic PAA nanodomains recruit mineral ions and provide one-dimensional confinement to induce orientation. The effect of the anionic domain dimensions on mineral content, orientation, and structure within the polymer matrix is shown. The mechanical properties of the nanocomposite are evaluated to determine the role of mineral orientation and crystallinity in composite strength. These results can be used to tailor the physical mineralization environment to create a more biomimetic bone material.

Effect of Backbone Chemistry on the Structure of Polyurea Films Deposited by Molecular Layer Deposition

DOE PAGES

Bergsman, David S.; Closser, Richard G.; Tassone, Christopher J.; ...

2017-01-01

An experimental investigation into the growth of polyurea films by molecular layer deposition was performed by examining trends in the growth rate, crystallinity, and orientation of chains as a function of backbone flexibility. Growth curves obtained for films containing backbones of aliphatic and phenyl groups indicate that an increase in backbone flexibility leads to a reduction in growth rate from 4 to 1 Å/cycle. Crystallinity measurements collected using grazing incidence X-ray diffraction and Fourier transform infrared spectroscopy suggest that some chains form paracrystalline, out-of-plane stacks of polymer segments with packing distances ranging from 4.4 to 3.7 Å depending on themore » monomer size. Diffraction intensity is largely a function of the homogeneity of the backbone. Near-edge X-ray absorption fine structure measurements for thin and thick samples show an average chain orientation of ~25° relative to the substrate across all samples, suggesting that changes in growth rate are not caused by differences in chain angle but instead may be caused by differences in the frequency of chain terminations. In conclusion, these results suggest a model of molecular layer deposition-based chain growth in which films consist of a mixture of upward growing chains and horizontally aligned layers of paracrystalline polymer segments.« less

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.

Microgravity

NASA Image and Video Library

1996-08-01

Polydiacetylenes are a unique class of highly conjugated organic polymers that are of interest for both electronic and photonic applications. Photodeposition from solutions is a novel process superior to those grown by conventional techniques. Evidence of this is seen when the films are viewed under a microscope; they exhibit small particles of solid polymer which form in the bulk solution, get transported by convection to the surface of the growing film, and become embedded. Also convection tends to cause the film thickness to be less uniform, and may even affect the molecular orientation of the films. The thrust of the research is to investigate in detail, both in 1-g and low-g, the effects of convection (and lack thereof) on this novel and interesting reaction. In this example, a portion of the substrate was blocked from exposure to the UV light by the mask, which was placed on the opposite side of the glass disk as the film, clearly demonstrating that photodeposition occurs only where the substrate is irradiated directly.

Assessment of Anisotropic Semiconductor Nanorod and Nanoplatelet Heterostructures with Polarized Emission for Liquid Crystal Display Technology.

PubMed

Cunningham, Patrick D; Souza, João B; Fedin, Igor; She, Chunxing; Lee, Byeongdu; Talapin, Dmitri V

2016-06-28

Semiconductor nanorods can emit linear-polarized light at efficiencies over 80%. Polarization of light in these systems, confirmed through single-rod spectroscopy, can be explained on the basis of the anisotropy of the transition dipole moment and dielectric confinement effects. Here we report emission polarization in macroscopic semiconductor-polymer composite films containing CdSe/CdS nanorods and colloidal CdSe nanoplatelets. Anisotropic nanocrystals dispersed in polymer films of poly butyl-co-isobutyl methacrylate (PBiBMA) can be stretched mechanically in order to obtain unidirectionally aligned arrays. A high degree of alignment, corresponding to an orientation factor of 0.87, was achieved and large areas demonstrated polarized emission, with the contrast ratio I∥/I⊥ = 5.6, making these films viable candidates for use in liquid crystal display (LCD) devices. To some surprise, we observed significant optical anisotropy and emission polarization for 2D CdSe nanoplatelets with the electronic structure of quantum wells. The aligned nanorod arrays serve as optical funnels, absorbing unpolarized light and re-emitting light from deep-green to red with quantum efficiencies over 90% and high degree of linear polarization. Our results conclusively demonstrate the benefits of anisotropic nanostructures for LCD backlighting. The polymer films with aligned CdSe/CdS dot-in-rod and rod-in-rod nanostructures show more than 2-fold enhancement of brightness compared to the emitter layers with randomly oriented nanostructures. This effect can be explained as the combination of linearly polarized luminescence and directional emission from individual nanostructures.

Solubility- and temperature-driven thin film structures of polymeric thiophene derivatives for high performance OFET applications

NASA Astrophysics Data System (ADS)

LeFevre, Scott W.; Bao, Zhenan; Ryu, Chang Y.; Siegel, Richard W.; Yang, Hoichang

2007-09-01

It has been shown that high charge mobility in solution-processible organic semiconductor-based field effect transistors is due in part to a highly parallel π-π stacking plane orientation of the semiconductors with respect to gate-dielectric. Fast solvent evaporation methods, generally, exacerbate kinetically random crystal orientations in the films deposited, specifically, from good solvents. We have investigated solubility-driven thin film structures of thiophene derivative polymers via spin- and drop-casting with volatile solvents of a low boiling point. Among volatile solvents examined, marginal solvents, which have temperature-dependent solubility for the semiconductors (e.g. methylene chloride for regioregular poly(3-alkylthiophene)s), can be used to direct the favorable crystal orientation regardless of solvent drying time, when the temperature of gate-dielectrics is held to relatively cooler than the warm solution. Grazing-incidence X-ray diffraction and atomic force microscopy strongly support that significant control of crystal orientation and mesoscale morphology using a "cold" substrate holds true for both drop and spin casting. The effects of physiochemical post-modificaiton on film crystal structures and morphologies of poly(9,9-dioctylfluorene-co-bithiophene) have also been investigated.

Helical instability in film blowing process: Analogy to buckling instability

NASA Astrophysics Data System (ADS)

Lee, Joo Sung; Kwon, Ilyoung; Jung, Hyun Wook; Hyun, Jae Chun

2017-12-01

The film blowing process is one of the most important polymer processing operations, widely used for producing bi-axially oriented film products in a single-step process. Among the instabilities observed in this film blowing process, i.e., draw resonance and helical motion occurring on the inflated film bubble, the helical instability is a unique phenomenon portraying the snake-like undulation motion of the bubble, having the period on the order of few seconds. This helical instability in the film blowing process is commonly found at the process conditions of a high blow-up ratio with too low a freezeline position and/or too high extrusion temperature. In this study, employing an analogy to the buckling instability for falling viscous threads, the compressive force caused by the pressure difference between inside and outside of the film bubble is introduced into the simulation model along with the scaling law derived from the force balance between viscous force and centripetal force of the film bubble. The simulation using this model reveals a close agreement with the experimental results of the film blowing process of polyethylene polymers such as low density polyethylene and linear low density polyethylene.

Electrospun Polymer Fibers for Electronic Applications

PubMed Central

Luzio, Alessandro; Canesi, Eleonora Valeria; Bertarelli, Chiara; Caironi, Mario

2014-01-01

Nano- and micro- fibers of conjugated polymer semiconductors are particularly interesting both for applications and for fundamental research. They allow an investigation into how electronic properties are influenced by size confinement and chain orientation within microstructures that are not readily accessible within thin films. Moreover, they open the way to many applications in organic electronics, optoelectronics and sensing. Electro-spinning, the technique subject of this review, is a simple method to effectively form and control conjugated polymer fibers. We provide the basics of the technique and its recent advancements for the formation of highly conducting and high mobility polymer fibers towards their adoption in electronic applications. PMID:28788493

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.

Development and application of variable angle internal reflection Raman spectroscopy for vibrationally specific depth-profiling of polymer thin films

NASA Astrophysics Data System (ADS)

Fontaine, Norman Henry

1997-10-01

Techniques which can be used to obtain depth-resolved information on the thermodynamics at polymer-polymer and polymer-wall interfaces, and of small molecule diffusion in polymers, are of particular interest to industry. Optical methods which are sensitive to molecular vibrations (such as internal reflection Raman spectroscopy) are advantageous because they can non- destructively probe molecular content, orientation, and polarity of the local environment in a sample. However, while optical internal reflection depth-profiling methods have been reported, they have never progressed beyond the demonstration stage. In this work, the theory and methodology of internal reflection spectroscopy are developed and optimized into a rigorous field-controlled spectroscopic technique. A novel asymmetric internal reflection element (IRE) is introduced which traps back-reflections, allowing precise evanescent and standing wave probe-field control in the sample for all angles of incidence. It is demonstrated that a Gaussian laser beam will best approximate an infinite homogeneous plane wave when the IRE/sample interface lies in the paraxial-Fraunhofer region (far- field) of the beam path. Calibration methods are presented, sources of systematic errors are identified, and the angular resolution limit (ARL) is introduced as a measure of the field control developed in a sample by any internal reflection method. A general model of Raman scattering and photon detection from multi-layer thin films is developed. A new and generalized operator based transfer matrix method is developed and applied to electromagnetic field and diffusion computations in multi-layer systems. Total internal reflection spectroscopy is extended to include sub-critical angles of incidence, where resonant field enhancements generate large and selective amplification of the probe-field intensity within the layers of the sample. Fitting these resonances to the model spectral intensities allows unique determination of the location of buried interfaces in micron-sized polymer multi-layers with nanometer scale precision and the refractive indices of the layers with precision of /Delta n/approx/pm 0.0001. The Raman active molecular content of each optically distinct layer of the film is determinable simultaneously with the optical properties. Resonant mode VAIRRS studies of poly(methyl methacrylate) films spun-cast from toluene and then dried under ambient conditions have shown evidence for toluene diffusion concurrent with a rotationally hindered relaxation of oriented ester side groups about the polymer backbone. Low temperature annealing (≈87oC) has shown evidence that this hindered rotational relaxation may be reversible. VAIRRS study of a polystyrene/poly(methyl methacrylate) bi-layer has detected evidence for toluene diffusion across the buried polymer-polymer interface.

Rechargeable lithium/polymer cathode batteries

NASA Astrophysics Data System (ADS)

Osaka, Tetsuya; Nakajima, Toshiki; Shiota, Koh; Owens, Boone B.

1989-06-01

Polypyrrole (PPy) and polyaniline (PAn) were investigated for cathode materials of rechargeable lithium batteries. PPy films prepared with PF6(-) anion and/or platinum substrate precoated with nitrile butadiene rubber (NBR) were excellent cathode materials because of rough and/or highly oriented film structure. PAn films were successfully prepared from non-aqueous propylene carbonate solution containing aniline, CF3COOH and lithium perchlorate. Its acidity strongly affects the anion doping-undoping behavior. The PAn cathode prepared in high acidic solution (e.g., 4:1 ratio of acid:aniline) gives the excellent battery performance.

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

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.

Dielectric Characterization of Mylar and The Effects of Doping Processes.

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

Belcher, Cami Beth

2016-11-01

Mylar® polymer is a bi-axially oriented polyethylene terephthalate (PET) polymer film used widely as a dielectric, specifically in capacitors. The dielectric characteristics of Mylar have been well studied and documented over the years; however, many of the mechanisms responsible for dielectric breakdown and failure are not understood for modified versions of the material. Previous studies on Mylar confirm that factors such as temperature, humidity, and voltage ramp rates can also have a significant effect on the dielectric properties and measurement of the dielectric properties. This study seeks to determine how dielectric properties, including permittivity, dielectric loss, and breakdown strength, aremore » affected by doping of the polymer. To do this, two types of Mylar films, virgin film and film doped with a small-molecule electron-acceptor, are tested. Both types of materials are tested under a variety of environmental and experimental conditions, including testing at elevated temperatures, varying relative humidity, and varying ramp rates in dielectric breakdown testing. Analysis of permittivity, dielectric loss, and breakdown strength will be presented comparing virgin and doped Mylar to gain insight into the effects of doping with electron-acceptor molecules on dielectric properties under these varying environmental and test conditions.« less

Self-Supported Crack-Free Conducting Polymer Films with Stabilized Wrinkling Patterns and Their Applications

PubMed Central

Xie, Jixun; Han, Xue; Ji, Haipeng; Wang, Juanjuan; Zhao, Jingxin; Lu, Conghua

2016-01-01

Self-supported conducting polymer films with controlled microarchitectures are highly attractive from fundamental and applied points of view. Here a versatile strategy is demonstrated to fabricate thin free-standing crack-free polyaniline (PANI)-based films with stable wrinkling patterns. It is based on oxidization polymerization of pyrrole inside a pre-wrinkled PANI film, in which the wrinkled PANI film is used both as a template and oxidizing agent for the first time. The subsequently grown polypyrrole (PPy) and the formation of interpenetrated PANI/PPy networks play a decisive role in enhancing the film integrity and the stability of wrinkles. This enhancing effect is attributed to the modification of internal stresses by the interpenetrated PANI/PPy microstructures. Consequently, a crack-free film with stable controlled wrinkles such as the wavelength, orientation and spatial location has been achieved. Moreover, the wrinkling PANI/PPy film can be removed from the initially deposited substrate to become free-standing. It can be further transferred onto target substrates to fabricate hierarchical patterns and functional devices such as flexible electrodes, gas sensors, and surface-enhanced Raman scattering substrates. This simple universal enhancing strategy has been extended to fabrication of other PANI-based composite systems with crack-free film integrity and stabilized surface patterns, irrespective of pattern types and film geometries. PMID:27827459

Fundamental and future prospects of printed ambipolar fluorene-type polymer light-emitting transistors for improved external quantum efficiency, mobility, and emission pattern

NASA Astrophysics Data System (ADS)

Kajii, Hirotake

2018-05-01

In this review, we focus on the improved external quantum efficiency, field-effect mobility, and emission pattern of top-gate-type polymer light-emitting transistors (PLETs) based on ambipolar fluorene-type polymers. A low-temperature, high-efficiency, printable red phosphorescent PLET based on poly(alkylfluorene) with modified alkyl side chains fabricated by a film transfer process is demonstrated. Device fabrication based on oriented films leads to an improved EL intensity owing to the increase in field-effect mobility. There are three factors that affect the transport of carriers, i.e., the energy level, threshold voltage, and mobility of each layer for heterostructure PLETs, which result in various emission patterns such as the line-shaped, multicolor and in-plane emission pattern in the full-channel area between source and drain electrodes. Fundamentals and future prospects in heterostructure devices are discussed and reviewed.

Structural Ordering of Semiconducting Polymers and Small-Molecules for Organic Electronics

NASA Astrophysics Data System (ADS)

O'Hara, Kathryn Allison

Semiconducting polymers and small-molecules can be readily incorporated into electronic devices such as organic photovoltaics (OPVs), thermoelectrics (OTEs), organic light emitting diodes (OLEDs), and organic thin film transistors (OTFTs). Organic materials offer the advantage of being processable from solution to form flexible and lightweight thin films. The molecular design, processing, and resulting thin film morphology of semiconducting polymers drastically affect the optical and electronic properties. Charge transport within films of semiconducting polymers relies on the nanoscale organization to ensure electronic coupling through overlap of molecular orbitals and to provide continuous transport pathways. While the angstrom-scale packing details can be studied using X-ray scattering methods, an understanding of the mesoscale, or the length scale over which smaller ordered regions connect, is much harder to achieve. Grain boundaries play an important role in semiconducting polymer thin films where the average grain size is much smaller than the total distance which charges must traverse in order to reach the electrodes in a device. The majority of semiconducting polymers adopt a lamellar packing structure in which the conjugated backbones align in parallel pi-stacks separated by the alkyl side-chains. Only two directions of transport are possible--along the conjugated backbone and in the pi-stacking direction. Currently, the discussion of transport between crystallites is centered around the idea of tie-chains, or "bridging" polymer chains connecting two ordered regions. However, as molecular structures become increasingly complex with the development of new donor-acceptor copolymers, additional forms of connectivity between ordered domains should be considered. High resolution transmission electron microscopy (HRTEM) is a powerful tool for directly imaging the crystalline grain boundaries in polymer and small-molecule thin films. Recently, structures comparable to quadrites were discovered in the semiconducting polymer, PSBTBT, where the angle of chain overlap could be predicted by the geometry of the backbone and alkyl side-chains. Such structures are hypothesized to improve the electronic connectivity and enable 3D transport. Now, it has been determined that another semiconducting polymer, PBDTTPD, forms cross-chain structures in thin films. PBDTTPD is a low band-gap donor-acceptor copolymer used in high efficiency OPVs. The effect of the alkyl side-chains on intercrystallite order is determined by examining three different derivatives of the PBDTTPD polymer with HRTEM. Additionally, the expansion and contraction of films during thermal annealing and slow cooling is monitored through in-situ grazing incidence wide-angle X-ray scattering (GIWAXS) measurements. Results show that minor variations in side-chain structure drive both crystallite orientation and the formation of crossed structures. Overall, these studies suggest design principles to continue to advance the field of organic electronics.

Electro-Optic Coefficients of Guest-Host Poled Polymers Containing Chromophores with Large First Hyperpolarizabilities: A Test of the Two-State, Oriented-Gas Model

NASA Technical Reports Server (NTRS)

Skindhoj, J.; Bourhill, G.; Gilmour, S.; Tiemann, B.; Mansour, K.; Perry, K.; Heng, L-T.; Marder, S.; Perry, J.

1994-01-01

the electro-optic r33, coefficients of poled poly(methylmethacrylate) films containing dyes with first hyperpolarizabilities that span nearly two orders of magnitude have been determined at 820 and 1300 nm by modulated ellipsometry.

Gas flow-field induced director alignment in polymer dispersed liquid crystal microdroplets deposited on a glass substrate

NASA Technical Reports Server (NTRS)

Parmar, D. S.; Singh, J. J.

1993-01-01

Polymer dispersed liquid crystal thin films have been deposited on glass substrates by the processes of polymerization and solvent evaporation induced phase separation. The electron and the optical polarization microscopies of the films reveal that PDLC microdroplets formed during the process of phase separation near the top surface of the film remain exposed and respond to shear stress due to air or gas flow on the surface. Optical response of the film to an air flow-induced shear stress input on the free surface has been measured. Director orientation in the droplets changes with the applied shear stress leading to time varying transmitted light intensity. Director dynamics of the droplet for an applied step shear stress has been discussed from free energy considerations. Results on the measurement of light transmission as a function of the gas flow parameter unambiguously demonstrate the potential of these systems for use as boundary layer and gas flow sensors.

Biodegradable multilayer barrier films based on alginate/polyethyleneimine and biaxially oriented poly(lactic acid).

PubMed

Gu, Chun-Hong; Wang, Jia-Jun; Yu, Yang; Sun, Hui; Shuai, Ning; Wei, Bing

2013-02-15

A layer-by-layer (LBL) approach was used to assemble alternating layers of sodium alginate (ALG)/polyethyleneimine (PEI) on biaxially oriented poly(lactic acid) (BOPLA) films in order to produce bio-based all-polymer thin films with low gas permeability. Increasing the depositing of ALG and PEI from 0 to 30 layers results in large thickness variations (from 0 to 3.92 μm). After 30 ALG/PEI layers are deposited, the resulting assembly has an OTR of 1.22 cm(3)/(m(2) day atm). When multiplied by thickness, the resulting oxygen permeability (OP) is found to be less than 3.8×10(-17) cm(3) cm/cm(2) s Pa, which is almost 3 orders of magnitude lower than that of uncoated BOPLA film (1.8×10(-14) cm(3)cm/cm(2) s Pa). At the same time, the resulting multilayer-coated BOPLA films maintain high optical clarity and tensile properties. This unique barrier thin film has become a promising alternative to non-biodegradable synthetic food packaging materials. Copyright © 2012 Elsevier Ltd. All rights reserved.

Acoustic method of investigating the material properties and humidity sensing behavior of polymer coated piezoelectric substrates

NASA Astrophysics Data System (ADS)

Caliendo, Cinzia

2006-09-01

The relative humidity (RH) sensing behavior of a polymeric film was investigated by means of polymer coated surface acoustic wave (SAW) delay lines implemented on single crystal piezoelectric substrates, such as quartz and LiNbO3, and on thin piezoelectric polycrystalline films, such as ZnO and AlN, on Si and GaAs. The same SAW delay line configuration was implemented on each substrate and the obtained devices' operating frequency was in the range of 105-156MHz, depending on the type of the substrate, on its crystallographic orientation, and on the SAW propagation direction. The surface of each SAW device was covered by the same type RH sensitive film of the same thickness and the RH sensitivity of each polymer coated substrate, i.e., the SAW relative phase velocity shift per RH unit changes, was investigated in the 0%—80% RH range. The perturbational approach was used to relate the SAW sensor velocity response to the RH induced changes in the physical parameters of the sensitive polymer film: the incremental change in the mass density and shear modulus of the polymer film per unit RH change were estimated. The shift of the bare SAW delay lines operating frequency induced by the presence of the polymer film, at RH =0% and at T =-10°C, allowed the experimental estimation of the mass sensitivity values of each substrate. These values were in good accordance with those reported in the literature and with those theoretically evaluated by exact numerical calculation. The shift of the bare SAW delay lines propagation loss induced by the polymer coating of the device surface, at RH =0% and at ambient temperature, allowed the experimental estimation of the elastic sensitivity of each substrate. These values were found in good accordance with those available from the literature. The temperature coefficient of delay and the electromechanical coupling coefficient of the bare substrates were also estimated. The membrane sensitivity to ethanol, methanol and isopropylic alcohol was tested by means of a high-frequency (670MHz) high-sensitivity Si /AlN resonator sensor.

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

Ishige, Ryohei; Williams, Gregory A.; Higaki, Yuji

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

Tilted Orientation of Photochromic Dyes with Guest-Host Effect of Liquid Crystalline Polymer Matrix for Electrical UV Sensing

PubMed Central

Ranjkesh, Amid; Park, Min-Kyu; Park, Do Hyuk; Park, Ji-Sub; Choi, Jun-Chan; Kim, Sung-Hoon; Kim, Hak-Rin

2015-01-01

We propose a highly oriented photochromic dye film for an ultraviolet (UV)-sensing layer, where spirooxazine (SO) derivatives are aligned with the liquid crystalline UV-curable reactive mesogens (RM) using a guest-host effect. For effective electrical UV sensing with a simple metal-insulator-metal structure, our results show that the UV-induced switchable dipole moment amount of the SO derivatives is high; however, their tilting orientation should be controlled. Compared to the dielectric layer with the nearly planar SO dye orientation, the photochromic dielectric layer with the moderately tilted dye orientation shows more than seven times higher the UV-induced capacitance variation. PMID:26729116

Synthesis of Stretchable Gold Films with Nanocracks: Stretched up to 120% Strain while Maintaining Conductivity

NASA Astrophysics Data System (ADS)

Yu, Mei; Wang, Chong; Yang, Cancan; Yu, Zhe

2017-11-01

With the great deformability of stretch, compression, bend and twisting, while preserving electrical property, metal films on elastomeric substrates have many applications for serving as bioelectrical interfaces. However, at present, most polymer-supported thin metal films reported rupture at small elongations (<10%). In this work, highly stretchable thin gold films were fabricated on PDMS substrates by a novel micro-processing technology. The as deposited films can be stretched by a maximum 120% strain while maintaining their electrical conductivity. Electrical characteristics of the gold films under single-cycle and multi-cycle stretch deformations are investigated in this work. SEM images imply that the gold films are under the structure of nanocracks. The mechanisms of the stretchability of the gold films can be explained by the nanocraks, which uniformly distribute with random orientation in the films.

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.

Second harmonic generation by all-optical poling and its relaxation in the polymer films containing azo sulfonamide chromophores

NASA Astrophysics Data System (ADS)

Ortyl, E.; Chan, S. W.; Nunzi, J.-M.; Kucharski, S.

2006-11-01

Polyurethane polymers containing azo sulfonamide chromophores were obtained by coupling reaction of the precursor polyurethane with corresponding diazonium salts. The chromophores, showing high hyperpolarizability value on molecular scale, were found to undergo orientation by all-optical poling method yielding macroscopic nonlinear optical response. The rate of generation and decay of the second-order nonlinear susceptibility was evaluated as a function of time. It was established that the polymers containing sulfonamide type chromophores showed higher stability of the nonlinear optical signal as compared with those modified with a nitro-acceptor groups of the Disperse Red type.

Orientation and Order in Shear-Aligned Thin Films of Cylinder-Forming Block Copolymers

NASA Astrophysics Data System (ADS)

Register, Richard

The regularity and tunability of the nanoscale structure in block copolymers makes their thin films attractive as nanolithographic templates; however, in the absence of a guiding field, self-assembly produces a polygrain structure with no particular orientation and a high density of defects. As demonstrated in the elegant studies of Ed Kramer and coworkers, graphoepitaxy can provide local control over domain orientation, with a dramatic reduction in defect density. Alternatively, cylindrical microdomains lying in the plane of the film can be aligned over macroscopic areas by applying shear stress at the film surface. In non-sheared films of polystyrene-poly(n-hexylmethacrylate) diblocks, PS-PHMA, the PS cylinder axis orientation relative to the surface switches from parallel to perpendicular as a function of film thickness; this oscillation is damped out as the fraction of the PS block increases, away from the sphere-cylinder phase boundary. In aligned films, thicknesses which possess the highest coverage of parallel cylinders prior to shear show the highest quality of alignment post-shear, as measured by the in-plane orientational order parameter. In well-aligned samples of optimal thickness, the quality of alignment is limited by isolated dislocations, whose density is highest at high PS contents, and by undulations in the cylinders' trajectories, whose impact is most severe at low PS contents; consequently, polymers whose compositions lie in the middle of the cylinder-forming region exhibit the highest quality of alignment. The dynamics of the alignment process are also investigated, and fit to a melting-recrystallization model which allows for the determination of two key alignment parameters: the critical stress needed for alignment, and an orientation rate constant. For films containing a monolayer of cylindrical domains, as PS weight fraction or overall molecular weight increases, the critical stress increases moderately, while the rate of alignment drastically decreases. As the number of layers of cylinders in the film increases, the critical stress decreases modestly, while the rate remains unchanged; substrate wetting condition has no measurable influence on alignment response. [Work of Raleigh Davis, in collaboration with Paul Chaikin.

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

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

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.

Vapor-phase deposition of regioregular and oriented poly(3-hexylthiophene) structures and novel nanostructured composites of interpenetrating poly(3-hexylthiophene) and polyaniline exhibiting full-color wavelength (400-1000 nm) photoluminescence

NASA Astrophysics Data System (ADS)

Biswas, A.; Bayer, I. S.; Karulkar, P. C.; Tripathi, A.; Avasthi, D. K.

2007-10-01

A promising solvent-free technique of electron-beam-assisted vapor-phase codeposition method is presented which allows uniform blending of different conjugated and nonconjugated polymers at the nanoscale. The technique allows direct incorporation of regioregular poly(3-hexylthiophene) (P3HT) polymer with different structural orientations into conventional and semiconducting polymers without fractionation or degradation of P3HT while maintaining the nanoscale morphology of deposited organic films. The results of fabricated novel nanostructured organic composites (˜100-200nm) comprising regioregular and oriented P3HT and different conjugated and nonconjugated polymers including selective assembly of P3HT nanonodules into a copolymer template are presented. We show a typical example of blending of P3HT and polyaniline (PANI) that formed a unique nanoscale morphology comprising interpenetrating networks of different shapes and sizes of nanospherulites (˜100nm) of P3HT in PANI. The so fabricated nanocomposites (˜200nm) exhibited remarkable broadband photoluminescence features covering the entire blue, green, and red wavelength regions between 400 and 1000nm. Such organic nanocomposites might be useful for flexible full-color screen flat panel displays and organic white-light solid-state lighting applications.

Simultaneous Increase in Open-Circuit Voltage and Efficiency of Fullerene-Free Solar Cells through Chlorinated Thieno[3,4- b ]thiophene Polymer Donor

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

Wang, Huan; Chao, Pengjie; Chen, Hui

The chlorinated polymer, PBTCl, has been found to be an efficient donor in nonfullerene polymer solar cells (PSCs), which showed a blue-shifted absorbance compared to that of its fluorine analogue (PTB7-th) and resulted in more complementary light absorption with a nonfullerene acceptor, such as ITIC. Meanwhile, chlorine substitution lowered the HOMO level of PBTCl, which increased the open-circuit voltage of the corresponding polymer-based devices. The 2D GIWAXS analysis illustrated that the PBTCl/ITIC blend film exhibited a “face-on” orientation and scattering features of both PBTCl and ITIC, suggesting that the blend of PBTCl and ITIC was phase-separated and formed individual crystallinemore » domains of the donor and acceptor, which promoted charge transfer in the bicontinuous film and eventually elevated the solar energy conversion efficiency. The PBTCl-based nonfullerene PSC exhibited a maximum PCE of 7.57% with a Voc of 0.91 V, which was an approximately 13% increasing in the PCE compared to that of the fluorine-analogue-based device.« less

Gas barrier properties of bio-inspired Laponite-LC polymer hybrid films.

PubMed

Tritschler, Ulrich; Zlotnikov, Igor; Fratzl, Peter; Schlaad, Helmut; Grüner, Simon; Cölfen, Helmut

2016-05-26

Bio-inspired Laponite (clay)-liquid crystal (LC) polymer composite materials with high clay fractions (>80%) and a high level of orientation of the clay platelets, i.e. with structural features similar to the ones found in natural nacre, have been shown to exhibit a promising behavior in the context of reduced oxygen transmission. Key characteristics of these bio-inspired composite materials are their high inorganic content, high level of exfoliation and orientation of the clay platelets, and the use of a LC polymer forming the organic matrix in between the Laponite particles. Each single feature may be beneficial to increase the materials gas barrier property rendering this composite a promising system with advantageous barrier capacities. In this detailed study, Laponite/LC polymer composite coatings with different clay loadings were investigated regarding their oxygen transmission rate. The obtained gas barrier performance was linked to the quality, respective Laponite content and the underlying composite micro- and nanostructure of the coatings. Most efficient oxygen barrier properties were observed for composite coatings with 83% Laponite loading that exhibit a structure similar to sheet-like nacre. Further on, advantageous mechanical properties of these Laponite/LC polymer composites reported previously give rise to a multifunctional composite system.

Examining the Self-Assembly of Rod-Coil Block Copolymers via Physics Based Polymer Models and Polarized X-Ray Scattering

NASA Astrophysics Data System (ADS)

Hannon, Adam; Sunday, Daniel; Windover, Donald; Liman, Christopher; Bowen, Alec; Khaira, Gurdaman; de Pablo, Juan; Delongchamp, Dean; Kline, R. Joseph

Photovoltaics, flexible electronics, and stimuli-responsive materials all require enhanced methodology to examine their nanoscale molecular orientation. The mechanical, electronic, optical, and transport properties of devices made from these materials are all a function of this orientation. The polymer chains in these materials are best modeled as semi-flexible to rigid rods. Characterizing the rigidity and molecular orientation of these polymers non-invasively is currently being pursued by using polarized resonant soft X-ray scattering (P-RSoXS). In this presentation, we show recent work on implementing such a characterization process using a rod-coil block copolymer system in the rigid-rod limit. We first demonstrate how we have used physics based models such as self-consistent field theory (SCFT) in non-polarized RSoXS work to fit scattering profiles for thin film coil-coil PS- b-PMMA block copolymer systems. We then show by using a wormlike chain partition function in the SCFT formulism to model the rigid-rod block, the methodology can be used there as well to extract the molecular orientation of the rod block from a simulated P-RSoXS experiment. The results from the work show the potential of the technique to extract thermodynamic and morphological sample information.

Polymer Nanocomposite Films: Dispersion of Polymer Grafted Nanorods and Optical Properties

NASA Astrophysics Data System (ADS)

Composto, Russell

2013-03-01

The thermodynamic factors that affect the dispersion of polymer-brush grafted gold nanorods (NR) in polymer matrix films have been studied by experiment and theory. When brush and matrix have a favorable interaction, such as poly(ethylene oxide) (PEO)-NR/ poly(methyl methacrylate) (PMMA) and polystyrene (PS)-NR / poly(2,6-dimethyl-p-phenylene oxide) (PPO), nanorods are uniformly dispersed. For PEO-NRs in PMMA, the NRs are regularly spaced and well dispersed, independent of the ratio of the degree of polymerization of the matrix (P) to that of the brush (N), namely P/N. As the NR volume fraction increases, the local orientation of the nanorods increases, whereas the macroscopic orientation remains isotropic. When the brush and matrix are similar (i.e., PS-NR / PS and PEO-NR / PEO), the nanorods randomly disperse for P/N < 2 (i.e., wet brush), but align side-by-side in aggregates for P/N > 2. UV-visible spectroscopy and discrete dipole approximation (DDA) calculations demonstrate that surface plasmon coupling leads to a blue shift in the longitudinal surface plasmon resonance (LSPR) as P/N increases. For P/N > 2, self-consistent field theory (SCFT) calculations and Monte Carlo (MC) simulations indicate that nanorod aggregation is caused by depletion-attraction forces. Starting with a dry brush system, namely, a PS matrix where P/N = 30, these attractive forces can be mediated by adding a compatibilizing agent (e.g., PPO) that drives the NRs to disperse. Finally, dry and wet brush behavior is observed for NR aspect ratios varying from 2.5 to 7. However, compared at the same volume fraction, long rods for the dry case exhibit much better local order than lower aspect ratio nanorods, suggesting that long rods may exhibit nematic-like ordering at higher loadings. NSF Polymer and CEMRI Programs.

Naphthodipyrrolidone (NDP) based conjugated polymers with high electron mobility and ambipolar transport properties

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

Zhang, Haichang; Zhang, Shuo; Mao, Yifan

Two novel donor–acceptor π-conjugated polymers based on naphthodipyrrolidone (NDP) were synthesized and characterized. The polymers possess low band gaps and suitable molecular orbital levels as ambipolar semiconductors. The thin film organic field effect transistor of NDP polymers exhibited ambipolar transport properties with a high electron mobility up to 0.67 cm 2 V –1 s –1. The grazing-incidence wide-angle X-ray scattering (GIWAXS) studies demonstrated that the polymer molecules pack into a long-range-ordered lamellar structure with isotropically oriented crystalline domains. Thermal annealing promoted edge-on lamellar stacking as evidenced by the increased diffraction intensity along the out-of-plane direction. In conclusion, the polymer withmore » NDP and bithiophene units achieved the best edge-on lamellar stacking after thermal annealing, which yielded the best electron transport performance in this work.« less

Naphthodipyrrolidone (NDP) based conjugated polymers with high electron mobility and ambipolar transport properties

DOE PAGES

Zhang, Haichang; Zhang, Shuo; Mao, Yifan; ...

2017-05-12

Two novel donor–acceptor π-conjugated polymers based on naphthodipyrrolidone (NDP) were synthesized and characterized. The polymers possess low band gaps and suitable molecular orbital levels as ambipolar semiconductors. The thin film organic field effect transistor of NDP polymers exhibited ambipolar transport properties with a high electron mobility up to 0.67 cm 2 V –1 s –1. The grazing-incidence wide-angle X-ray scattering (GIWAXS) studies demonstrated that the polymer molecules pack into a long-range-ordered lamellar structure with isotropically oriented crystalline domains. Thermal annealing promoted edge-on lamellar stacking as evidenced by the increased diffraction intensity along the out-of-plane direction. In conclusion, the polymer withmore » NDP and bithiophene units achieved the best edge-on lamellar stacking after thermal annealing, which yielded the best electron transport performance in this work.« less

Tips pentacene crystal alignment for improving performance of solution processed organic thin film transistors

NASA Astrophysics Data System (ADS)

He, Zhengran

A newly-developed p-type organic semiconductor 6,13-bis (triisopropylsilylethynyl) pentacene (TIPS pentacene) demonstrates various advantages such as high mobility, air stability and solution processibility, but at the same time its application is restricted by major issues, such as crystal misorientation and performance variation of organic thin-film transistors (OTFTs). This dissertation demonstrates several different approaches to address these issues. As a result, both crystal orientation and areal coverage can be effectively improved, leading to an enhancement of average mobility and performance consistency of OTFTs. Chapter 1 presents an introduction and background of this dissertation. Chapter 2 explores the usage of inorganic silica nanoparticles to manipulate the morphology of TIPS pentacene thin films and the performance of solution-processed organic OTFTs. The resultant drop-cast films yield improved morphological uniformity at ~10% SiO2 loading, which also leads to a 3-fold increase in average mobility and nearly 4-times reduction in the ratio of standard deviation of mobility (μStdev) to average mobility (μAvg). The experimental results suggest that the SiO2 nanoparticles mostly aggregate at TIPS pentacene grain boundaries, and that 10% nanoparticle concentration effectively reduces the undesirable crystal misorientation without considerably compromising TIPS pentacene crystallinity. Chapter 3 discusses the utilization of air flow to effectively reduce the TIPS pentacene crystal anisotropy and enhance performance consistency in OTFTs. Under air-flow navigation (AFN), TIPS pentacene forms thin films with improved crystal orientation and increased areal coverage, which subsequently lead to a four-fold increase of average hole mobility and one order of magnitude enhancement in performance consistency. Chapter 4 investigates the critical roles of lateral and vertical phase separation in the performance of the next-generation organic and hybrid electronic devices. A novel method is demonstrated here to switch between lateral and vertical phase separation in semiconducting TIPS pentacene/ polymer blend films by simply varying the alkyl length of the polyacrylate polymer component. The phase separation modes depend on intermolecular interactions between small molecule TIPS pentacene and polymer additives. The blend film with a dominant vertical phase separation exhibits a significant enhancement in average mobility and performance consistency of organic OTFTs. Chapter 5 demonstrates an effective approach to improve both charge transport and performance consistency in solution-processed OTFTs by blending TIPS pentacene with a series of small-molecule additives: 4-butylbenzoic acid (BBA), 4-hexylbenzoic acid (HBA), and 4-octylbenzoic acid (OBA). These three small molecules share a benzoic acid moiety, but have different length of hydrophobic tails. The self-assembled interfacial layer of small molecules on the gate oxide surface leads to uniform deposition of TIPS pentacene crystal seeds and facilitates TIPS pentacene to grow along the tilted orientation of substrate, which results in a film of enhanced crystal orientation and areal coverage. OTFTs based on TIPS pentacene/small molecule blends demonstrate greatly improved average hole mobility and performance consistency, which correlates with the length of hydrophobic tail of the small-molecule additives. Chapter 6 summarizes the conclusions of this dissertation and the related future work.

Borate cross-linked graphene oxide-chitosan as robust and high gas barrier films

NASA Astrophysics Data System (ADS)

Yan, Ning; Capezzuto, Filomena; Lavorgna, Marino; Buonocore, Giovanna G.; Tescione, Fabiana; Xia, Hesheng; Ambrosio, Luigi

2016-05-01

Chitosan (CS) is one of the most promising polymers due to its biocompatibility, biodegradability, and natural abundance. However, its poor mechanical and barrier properties make it difficult to satisfy a wide range of applications. Herein, borate ions, originating from the hydrolysis of sodium tetraborate decahydrate (borax), have been used to crosslink chitosan and graphene oxide (GO) nanocomposites. Chitosan films consisting of 1.0 wt% boron and 1.0 wt% GO exhibit a significant improvement in both the toughness and oxygen barrier properties compared to pristine chitosan. In particular the tensile strength of the samples after thermal treatment increases by ~160% compared to pristine chitosan, whereas their oxygen permeability reduces by ~90%. This is ascribed to the chemical crosslinking between chitosan and GO nanoplatelets through borate ions, as well as the formation of a layered morphology with graphene nanoplatelets oriented parallel to the sample surface. The exceptional robust and high gas barrier film has promising application in the packaging industry. The borate-crosslinking chemistry represents the potential strategy for improving properties of other polymer nanocomposites.Chitosan (CS) is one of the most promising polymers due to its biocompatibility, biodegradability, and natural abundance. However, its poor mechanical and barrier properties make it difficult to satisfy a wide range of applications. Herein, borate ions, originating from the hydrolysis of sodium tetraborate decahydrate (borax), have been used to crosslink chitosan and graphene oxide (GO) nanocomposites. Chitosan films consisting of 1.0 wt% boron and 1.0 wt% GO exhibit a significant improvement in both the toughness and oxygen barrier properties compared to pristine chitosan. In particular the tensile strength of the samples after thermal treatment increases by ~160% compared to pristine chitosan, whereas their oxygen permeability reduces by ~90%. This is ascribed to the chemical crosslinking between chitosan and GO nanoplatelets through borate ions, as well as the formation of a layered morphology with graphene nanoplatelets oriented parallel to the sample surface. The exceptional robust and high gas barrier film has promising application in the packaging industry. The borate-crosslinking chemistry represents the potential strategy for improving properties of other polymer nanocomposites. Electronic supplementary information (ESI) available: Detailed characterization methods and survey XPS spectra. See DOI: 10.1039/c6nr00377j

Molecular Packing of High-Mobility Diketo Pyrrolo-Pyrrole Polymer Semiconductors with Branched Alkyl Side Chains

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

X Zhang; L Richter; D DeLongchamp

We describe a series of highly soluble diketo pyrrolo-pyrrole (DPP)-bithiophene copolymers exhibiting field effect hole mobilities up to 0.74 cm{sup 2} V{sup -1} s{sup -1}, with a common synthetic motif of bulky 2-octyldodecyl side groups on the conjugated backbone. Spectroscopy, diffraction, and microscopy measurements reveal a transition in molecular packing behavior from a preferentially edge-on orientation of the conjugated plane to a preferentially face-on orientation as the attachment density of the side chains increases. Thermal annealing generally reduces both the face-on population and the misoriented edge-on domains. The highest hole mobilities of this series were obtained from edge-on molecular packingmore » and in-plane liquid-crystalline texture, but films with a bimodal orientation distribution and no discernible in-plane texture exhibited surprisingly comparable mobilities. The high hole mobility may therefore arise from the molecular packing feature common to the entire polymer series: backbones that are strictly oriented parallel to the substrate plane and coplanar with other backbones in the same layer.« less

The artefacts of radiochromic film dosimetry with flatbed scanners and their causation by light scattering from radiation-induced polymers.

PubMed

Schoenfeld, Andreas A; Poppinga, Daniela; Harder, Dietrich; Doerner, Karl-Joachim; Poppe, Bjoern

2014-07-07

Optical experiments and theoretical considerations have been undertaken in order to understand the causes of the 'orientation effect' and the 'parabola effect', the artefacts impairing the desired light absorption measurement on radiochromic EBT3 films with flatbed scanners. EBT3 films exposed to doses up to 20.9 Gy were scanned with an Epson Expression 10000XL flatbed scanner in landscape and portrait orientation. The horizontally and vertically polarized light components of the scanner were determined, and another Epson Expression 10000XL flatbed scanner was disassembled to examine its optical components. The optical properties of exposed and unexposed EBT3 films were studied with incident polarized and unpolarized white light, and the transmitted red light was investigated for its polarization and scattering properties including the distribution of the scattering angles. Neutral density filters were studied for comparison. Guidance was sought from the theory of light scattering from rod-like macromolecular structures. The drastic dose-dependent variation of the transmitted total light current as function of the orientation of front and rear polarizers, interpreted by light scattering theory, shows that the radiation-induced polymerization of the monomers of EBT3 films produces light scattering oscillators preferably polarized at right angles with the coating direction of the film. The directional distribution of the scattered light is partly anisotropic, with a preferred scattering plane at right angles with the coating direction, indicating light scattering from stacks of coherently vibrating oscillators piled up along the monomer crystals. The polyester carrier film also participates in these effects. The 'orientation' and 'parabola' artefacts due to flatbed scanning of radiochromic films can be explained by the interaction of the polarization-dependent and anisotropic light scattering from exposed and unexposed EBT3 films with the quantitative difference between the scanner's horizontally and vertically polarized light supply and with the limited directional acceptance of the scanner's light recording system.

Single clay sheets inside electrospun polymer nanofibers

NASA Astrophysics Data System (ADS)

Sun, Zhaohui

2005-03-01

Nanofibers were prepared from polymer solution with clay sheets by electrospinning. Plasma etching, as a well controlled process, was used to supply electrically excited gas molecules from a glow discharge. To reveal the structure and arrangement of clay layers in the polymer matrix, plasma etching was used to remove the polymer by controlled gasification to expose the clay sheets due to the difference in reactivity. The shape, flexibility, and orientation of clay sheets were studied by transmission and scanning electron microscopy. Additional quantitative information on size distribution and degree of exfoliation of clay sheets were obtained by analyzing electron micrograph of sample after plasma etching. Samples in various forms including fiber, film and bulk, were thinned by plasma etching. Morphology and dispersion of inorganic fillers were studied by electron microscopy.

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.

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.

Selective cell response on natural polymer bio-interfaces textured by femtosecond laser

NASA Astrophysics Data System (ADS)

Daskalova, A.; Trifonov, A.; Bliznakova, I.; Nathala, C.; Ajami, A.; Husinsky, W.; Declercq, H.; Buchvarov, I.

2018-02-01

This study reports on the evaluation of laser processed natural polymer-chitosan, which is under consideration as a biointerface used for temporary applications as skin and cartilage substitutes. It is employed for tissue engineering purposes, since it possesses a significant degree of biocompatibility and biodegradability. Chitosan-based thin films were processed by femtosecond laser radiation to enhance the surface properties of the material. Various geometry patterns were produced on polymer surfaces and employed to examine cellular adhesion and orientation. The topography of the modified zones was observed using scanning electron microscopy and confocal microscopy. Test of the material cytotoxicity was performed by evaluating the life/dead cell correlation. The obtained results showed that texturing with femtosecond laser pulses is appropriate method to initiate a predefined cellular response. Formation of surface modifications in the form of foams with an expansion of the material was created under laser irradiation with a number of applied laser pulses from N = 1-5. It is shown that irradiation with N > 5 results in disturbance of microfoam. Material characterization reveals a decrease in water contact angle values after laser irradiation of chitosan films. Consequently, changes in surface roughness of chitosan thin-film surface result in its functionalization. Cultivation of MC3T3 and ATMSC cells show cell orientational migration concerning different surface patterning. The influence of various pulse durations (varying from τ = 30-500 fs) over biofilms surface was examined regarding the evolution of surface morphology. The goal of this study was to define the optimal laser conditions (laser energy, number of applied pulses, and pulse duration) to alter surface wettability properties and porosity to improve material performance. The acquired set of results indicate the way to tune the surface properties to optimize cell-interface interaction.

Polymer-grafted gold nanorods in polymer thin films: Dispersion and plasmonic coupling

NASA Astrophysics Data System (ADS)

Hore, Michael-Jon Ainsley

This dissertation describes complementary experimental and theoretical studies to deter- mine the thermodynamic factors that affect the dispersion of polymer-grafted Au nanorods within polymer thin films. Au nanorods exhibit a uniform dispersion with a regular spacing for favorable brush / matrix interactions, such as poly(ethylene glycol) (PEG)-Au / poly(methyl methacrylate) (PMMA) and polystyrene (PS)-Au / poly(2,6-dimethyl-p-phenylene oxide) (PPO). For PEG-Au / PMMA, the nanorods are locally oriented and their dispersion is independent of the ratio of the degree of polymerization of the matrix (P) to that of the brush (N), α = P/N, whereas for chemically similar brush / matrix combinations, such as PS-Au / PS and PEG-Au / poly(ethylene oxide) (PEO), nanorods are randomly dispersed for α 2. For aggregated systems (α > 2), nanorods are found primarily within aggregates containing side-by-side aligned nanorods with a spacing that scales with N. UV-visible spectroscopy and discrete dipole approximation (DDA) calculations demonstrate that coupling between surface plasmons within the aggregates leads to a blue shift in the optical absorption as α increases, indicating the sensitivity of spectroscopy for determining nanorod dispersion in polymer nanocomposite films. Self-consistent field theory (SCFT) calculations and Monte Carlo (MC) simulations show that the aggregation of nanorods for α > 2 can be attributed to depletion-attraction forces caused by autophobic dewetting of the brush and matrix. Finally, miscible blends of PS and PPO are investigated as a route to control depletion-attraction interactions between PS-Au nanorods. Initially, nanorods aggregate in matrices having 50 vol. % PPO and then gradually disperse as PPO becomes the majority component. The brush and matrix density profiles, determined by SCFT, show that PPO segregates into the PS brush, and acts as a compatibilizer, which improves dispersion. As dispersion improves, coupling between surface plasmons is reduced, leading to a red shift in the optical absorption. The outcome of these systematic structure-property-modeling studies is the ability to control nanorod dispersion, orientation, and optical absorption by manipulating brush/matrix interactions and entropic depletion-attraction forces.

Morphology controls the thermoelectric power factor of a doped semiconducting polymer

PubMed Central

Patel, Shrayesh N.; Glaudell, Anne M.; Peterson, Kelly A.; Thomas, Elayne M.; O’Hara, Kathryn A.; Lim, Eunhee; Chabinyc, Michael L.

2017-01-01

The electrical performance of doped semiconducting polymers is strongly governed by processing methods and underlying thin-film microstructure. We report on the influence of different doping methods (solution versus vapor) on the thermoelectric power factor (PF) of PBTTT molecularly p-doped with FnTCNQ (n = 2 or 4). The vapor-doped films have more than two orders of magnitude higher electronic conductivity (σ) relative to solution-doped films. On the basis of resonant soft x-ray scattering, vapor-doped samples are shown to have a large orientational correlation length (OCL) (that is, length scale of aligned backbones) that correlates to a high apparent charge carrier mobility (μ). The Seebeck coefficient (α) is largely independent of OCL. This reveals that, unlike σ, leveraging strategies to improve μ have a smaller impact on α. Our best-performing sample with the largest OCL, vapor-doped PBTTT:F4TCNQ thin film, has a σ of 670 S/cm and an α of 42 μV/K, which translates to a large PF of 120 μW m−1 K−2. In addition, despite the unfavorable offset for charge transfer, doping by F2TCNQ also leads to a large PF of 70 μW m−1 K−2, which reveals the potential utility of weak molecular dopants. Overall, our work introduces important general processing guidelines for the continued development of doped semiconducting polymers for thermoelectrics. PMID:28630931

Ultra-thin passivating film induced by vinylene carbonate on highly oriented pyrolytic graphite negative electrode in lithium-ion cell

NASA Astrophysics Data System (ADS)

Matsuoka, O.; Hiwara, A.; Omi, T.; Toriida, M.; Hayashi, T.; Tanaka, C.; Saito, Y.; Ishida, T.; Tan, H.; Ono, S. S.; Yamamoto, S.

We investigated the influence of vinylene carbonate, as an additive molecule, on the decomposition phenomena of electrolyte solution [ethylene carbonate (EC)—ethyl methyl carbonate (EMC) (1:2 by volume) containing 1 M LiPF 6] on a highly oriented pyrolytic graphite (HOPG) negative electrode by using cyclic voltammetry (CV) and atomic force microscopy (AFM). Vinylene carbonate deactivated reactive sites (e.g. radicals and oxides at the defects and the edge of carbon layer) on the cleaved surface of the HOPG negative electrode, and prevented further decomposition of the other solvents there. Further, vinylene carbonate induced an ultra-thin film (less than 1.0 nm in thickness) on the terrace of the basal plane of the HOPG negative electrode, and this film suppressed the decomposition of electrolyte solution on the terraces of the basal plane. We consider that this ultra-thin passivating film is composed of a reduction product of vinylene carbonate (VC), and might have a polymer structure. These induced effects might explain how VC improves the life performance of lithium-ion cells.

Highly Oriented Atomically Thin Ambipolar MoSe2 Grown by Molecular Beam Epitaxy

PubMed Central

2017-01-01

Transition metal dichalcogenides (TMDCs), together with other two-dimensional (2D) materials, have attracted great interest due to the unique optical and electrical properties of atomically thin layers. In order to fulfill their potential, developing large-area growth and understanding the properties of TMDCs have become crucial. Here, we have used molecular beam epitaxy (MBE) to grow atomically thin MoSe2 on GaAs(111)B. No intermediate compounds were detected at the interface of as-grown films. Careful optimization of the growth temperature can result in the growth of highly aligned films with only two possible crystalline orientations due to broken inversion symmetry. As-grown films can be transferred onto insulating substrates, allowing their optical and electrical properties to be probed. By using polymer electrolyte gating, we have achieved ambipolar transport in MBE-grown MoSe2. The temperature-dependent transport characteristics can be explained by the 2D variable-range hopping (2D-VRH) model, indicating that the transport is strongly limited by the disorder in the film. PMID:28530829

Effect of orientation on electrically conducting thermoplastic composite properties

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

Genetti, W.B.; Grady, B.P.

1996-10-01

Properties of electrically conducting composites made from low density polyethylene (LDPE), high density polyethylene (HDPE), and polypropylene (PP) filled with nickel flake are being studied as a function of nickel concentration and draw ratio. The effect on electrical conduction, crystallinity, melt temperature, tensile modulus, and elongation at break are being tested. The melt temperature increases with increasing nickel concentration. The electrical conduction increases slowly with increased nickel concentration to the percolation volume fraction, then increases sharply. Orientation by uniaxial stretching of the films should allow conductive pathways to form throughout the polymer more easily by forcing particles closer together, thusmore » reducing the percolation volume fraction. This process could be caused by both alignment of the polymer chains and by stress induced crystallization that forces the particles into smaller amorphous regions.« less

Lithium secondary batteries: Role of polymer cathode morphology

NASA Astrophysics Data System (ADS)

Naoi, Katsuhiko; Osaka, Tetsuya; Owens, Boone B.

1988-06-01

Electrically conducting polymers have been utilized both as the cathode and as the electrolyte element of Li secondary cells. Polymer cathodes were limited in their suitability for batteries because of the low energy content associated with low levels of doping and the inclusion of complex ionic species in the cathode. Recent studies have indicated that doping levels up to 100 percent can be achieved in polyanilene. High doping levels in combination with controlled morphologies have been found to improve the energy and rate capabilities of polymer cathodes. A morphology-modifying technique was utilized to enhance the charge/discharge characteristics of Li/liquid electrolyte polypyrrole cells. The polymer is electropolymerized in a preferred orientation morphology when the substrate is first precoated with an insulating film of nitrile butadiene rubber (NBR). Modification of the kinetic behavior of the electrode results from variations in the chemical composition of the NBR.

Controlled Terahertz Birefringence in Stretched Poly(lactic acid) Films Investigated by Terahertz Time-Domain Spectroscopy and Wide-Angle X-ray Scattering.

PubMed

Iwasaki, Hotsumi; Nakamura, Madoka; Komatsubara, Nozomu; Okano, Makoto; Nakasako, Masayoshi; Sato, Harumi; Watanabe, Shinichi

2017-07-20

We report a correlation between the dielectric property and structure of stretched poly(lactic acid) (PLA) films, revealed by polarization-sensitive terahertz time-domain spectroscopy and two-dimensional (2D) wide-angle X-ray scattering (WAXS). The experiments evidence that the dielectric function of the PLA film becomes more anisotropic with increasing draw ratio (DR). This behavior is explained by a classical Lorentz oscillator model assuming polarization-dependent absorption. The birefringence can be systematically altered from 0 to 0.13 by controlling DR. The combination of terahertz spectroscopy and 2D WAXS measurement reveals a clear correlation between the birefringence in the terahertz frequency domain and the degree of orientation of the PLA molecular chains. These findings imply that the birefringence is a result of the orientation of the PLA chains with anisotropic macromolecular vibration modes. Because of a good controllability of the birefringence, polymer-based materials will provide an attractive materials system for phase retarders in the terahertz frequency range.

Investigation of drug release and matrix degradation of electrospun poly(DL-lactide) fibers with paracetanol inoculation.

PubMed

Cui, Wenguo; Li, Xiaohong; Zhu, Xinli; Yu, Guo; Zhou, Shaobing; Weng, Jie

2006-05-01

This study was aimed at assessing the potential use of electrospun fibers as drug delivery vehicles with focus on the different diameters and drug contents to control drug release and polymer fiber degradation. A drug-loaded solvent-casting polymer film was made with an average thickness of 100 microm for comparative purposes. DSC analysis indicated that electrospun fibers had a lower T(g) but higher transition enthalpy than solvent-casting polymer film due to the inner stress and high degree of alignment and orientation of polymer chains caused by the electrospinning process. Inoculation of paracetanol led to a further slight decrease in the T(g) and transition enthalpy. An in vitro drug release study showed that a pronounced burst release or steady release phase was initially observed followed by a plateau or gradual release during the rest time. Fibers with a larger diameter exhibited a longer period of nearly zero order release, and higher drug encapsulation led to a more significant burst release after incubation. In vitro degradation showed that the smaller diameter and higher drug entrapment led to more significant changes of morphologies. The electrospun fiber mat showed almost no molecular weight reduction, but mass loss was observed for fibers with small and medium size, which was characterized with surface erosion and inconsistent with the ordinarily polymer degrading form. Further wetting behavior analysis showed that the high water repellent property of electrospun fibers led to much slower water penetration into the fiber mat, which may contribute to the degradation profiles of surface erosion. The specific degradation profile and adjustable drug release behaviors by variation of fiber characteristics made the electrospun nonwoven mat a potential drug delivery system rather than polymer films and particles.

The origin of the flatbed scanner artifacts in radiochromic film dosimetry—key experiments and theoretical descriptions

NASA Astrophysics Data System (ADS)

Schoenfeld, Andreas A.; Wieker, Soeren; Harder, Dietrich; Poppe, Bjoern

2016-11-01

The optical origin of the lateral response and orientation artifacts, which occur when using EBT3 and EBT-XD radiochromic films together with flatbed scanners, has been reinvestigated by experimental and theoretical means. The common feature of these artifacts is the well-known parabolic increase in the optical density OD(x)  =  -log10 I(x)/I 0(x) versus offset x from the scanner midline (Poppinga et al 2014 Med. Phys. 41 021707). This holds for landscape and portrait orientations as well as for the three color channels. Dose-independent optical subjects, such as neutral density filters, linear polarizers, the EBT polyester foil and diffusive glass, also present the parabolic lateral artifact when scanned with a flatbed scanner. The curvature parameter c of the parabola function OD(x)  =  c 0  +  cx 2 is found to be a linear function of the dose, the parameters of which are influenced by the film orientation and film type, EBT3 or EBT-XD. The ubiquitous parabolic shape of function OD(x) is attributed (a) to the optical path-length effect (van Battum et al 2016 Phys. Med. Biol. 61 625-49), due to the increasing obliquity of the optical scanner light associated with increasing offset x from the scanner midline, and (b) and (c) to the partial polarization and scattering of the light leaving the film, which affect the ratio ~I(x)/{{I}0}(x) , thus making OD(x) increase with x 2. The orientation effect results from the changes of effects (b) and (c) associated with turning the film position, and thereby the orientation of the polymer structure of the sensitive film layer. In a comparison of experimental results obtained with selected optical subjects, the relative weights of the contributions of the optical path-length effect and the polarization and scattering of light leaving the films to the lateral response artifact have been estimated to be of the same order of magnitude. Mathematical models of these causes for the parabolic shape of function OD(x) are given as appendices.

The origin of the flatbed scanner artifacts in radiochromic film dosimetry-key experiments and theoretical descriptions.

PubMed

Schoenfeld, Andreas A; Wieker, Soeren; Harder, Dietrich; Poppe, Bjoern

2016-11-07

The optical origin of the lateral response and orientation artifacts, which occur when using EBT3 and EBT-XD radiochromic films together with flatbed scanners, has been reinvestigated by experimental and theoretical means. The common feature of these artifacts is the well-known parabolic increase in the optical density OD(x)  =  -log 10 I(x)/I 0 (x) versus offset x from the scanner midline (Poppinga et al 2014 Med. Phys. 41 021707). This holds for landscape and portrait orientations as well as for the three color channels. Dose-independent optical subjects, such as neutral density filters, linear polarizers, the EBT polyester foil and diffusive glass, also present the parabolic lateral artifact when scanned with a flatbed scanner. The curvature parameter c of the parabola function OD(x)  =  c 0   +  cx 2 is found to be a linear function of the dose, the parameters of which are influenced by the film orientation and film type, EBT3 or EBT-XD. The ubiquitous parabolic shape of function OD(x) is attributed (a) to the optical path-length effect (van Battum et al 2016 Phys. Med. Biol. 61 625-49), due to the increasing obliquity of the optical scanner light associated with increasing offset x from the scanner midline, and (b) and (c) to the partial polarization and scattering of the light leaving the film, which affect the ratio [Formula: see text], thus making OD(x) increase with x 2 . The orientation effect results from the changes of effects (b) and (c) associated with turning the film position, and thereby the orientation of the polymer structure of the sensitive film layer. In a comparison of experimental results obtained with selected optical subjects, the relative weights of the contributions of the optical path-length effect and the polarization and scattering of light leaving the films to the lateral response artifact have been estimated to be of the same order of magnitude. Mathematical models of these causes for the parabolic shape of function OD(x) are given as appendices.

Natural and synthetic mineral silicates as functional nanoparticles in polymer composites

NASA Astrophysics Data System (ADS)

Shao, Hua

A new strategy is described for the substantial enhancement of the barrier properties for both a thermoset epoxy polymer and a thermoplastic polyolefin by sandwiching a novel self-supported clay fabric film between thin polymer sheets. The success of this strategy is attributed to the high orientation of clay nanolayers in the paper-like clay fabric films and to the filling of the micro- or sub-micro sized voids between imperfectly tiled clay platelet edges by the polymer chains. Thermoplastic polyolefin-clay fabric film composites were fabricated by hot-pressing the clay films between two sheets of high density polyethylene (HDPE) films. The sandwiched composites exhibit more than a 30-fold decrease in O2 transmission rate with respect to the pure HDPE film. Impregnating the self-supported clay papers with epoxy pre-polymers successfully leads to thermoset composite films with more than 2-3 orders of magnitude reduction in O2 permeability in comparison to the pristine epoxy matrix. Owing to the promising use of synthetic Mg-saponite (denoted SAP) as epoxy polymer reinforcing agents, we investigated the cost-effective synthesis of SAP by replacing urea with sodium hydroxide as base source. Co-crystallization of new zeolite phases, such as garronite (denoted GIS) and cancrinite (denoted CAN), occurred along with SAP upon increasing the alkalinity of the reaction mixture. This finding represents the first example of the preparation of a CAN/SAP phase mixture. Moreover, pure-phase cancrinite with rod-like morphology up to several mum in length was synthesized under Mg-free conditions. Also, the Si/AI ratio within the synthesis gel has an influence on the chemical composition and textural properties of pure CAN crystals. Microporous cancrinite is a promising candidate for reinforcing epoxy polymers, considering that CAN represents a substantial fraction of the mixed CAN-SAP phase formed during the synthesis of saponite. Therefore, the reaction conditions (e.g. alkalinity, reaction temperature, and duration) were further expored in order to optimize the formation of small crystals of CAN (˜ 100 nm) with large external surface area and high pore volume. These textural features facilitate the homogeneous dispersion of cancrinite particles in epoxy matrices. In addition, a new phase sodalite (denoted SOD) was co-crystallized along with CAN in some cases, depending on reaction conditions. The synthetic zeolites CAN and SOD act as reinforcing agents for thermoset epoxy polymers owing in part to their small particle size, large surface area and high pore volume. The tensile strength, modulus and toughness of an epoxy matrix are simultaneously enhanced without the need for organic surface modification of zeolites. This finding represents the first example for which the mechanical properties of glassy epoxy composite are all improved through the use of a microporous zeolite as a functional inorganic nanoparticle.

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

Flexible Polymer/Metal/Polymer and Polymer/Metal/Inorganic Trilayer Transparent Conducting Thin Film Heaters with Highly Hydrophobic Surface.

PubMed

Kang, Tae-Woon; Kim, Sung Hyun; Kim, Cheol Hwan; Lee, Sang-Mok; Kim, Han-Ki; Park, Jae Seong; Lee, Jae Heung; Yang, Yong Suk; Lee, Sang-Jin

2017-09-27

Polymer/metal/polymer and polymer/metal/inorganic trilayer-structured transparent electrodes with fluorocarbon plasma polymer thin film heaters have been proposed. The polymer/metal/polymer and polymer/metal/inorganic transparent conducting thin films fabricated on a large-area flexible polymer substrate using a continuous roll-to-roll sputtering process show excellent electrical properties and visible-light transmittance. They also exhibit water-repelling surfaces to prevent wetting and to remove contamination. In addition, the adoption of a fluorocarbon/metal/fluorocarbon film permits an outer bending radius as small as 3 mm. These films have a sheet resistance of less than 5 Ω sq -1 , sufficient to drive light-emitting diode circuits. The thin film heater with the fluorocarbon/Ag/SiN x structure exhibits excellent heating characteristics, with a temperature reaching 180 °C under the driving voltage of 13 V. Therefore, the proposed polymer/metal/polymer and polymer/metal/inorganic transparent conducting electrodes using polymer thin films can be applied in flexible and rollable displays as well as automobile window heaters and other devices.

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.

Multiresponsive Kinematics and Robotics of Surface-Patterned Polymer Film.

PubMed

Liang, Shumin; Qiu, Xiaxin; Yuan, Jun; Huang, Wei; Du, Xuemin; Zhang, Lidong

2018-06-06

Soft robots, sensors, and energy harvesters require materials that are capable of converting external stimuli to visible deformations, especially when shape-programmable deformations are desired. Herein, we develop a polymer film that can reversibly respond to humidity, heating, and acetone vapors with the generation of shape-programmable large deformations. Poly(vinylidene fluoride) film, capable of providing acetone responsiveness, is designed with microchannel patterns created on its one side by using templates, and the microchannels-patterned side is then treated with hygroscopic 3-aminopropyltriethoxysilane (APTES) to give humidity/heating-responsive elements. The APTES-modified microchannels lead to anisotropic flexural modulus and hygroscopicity in the film, resulting in the shape-programmed kinematics depending on the orientations of surface microchannels. As the microchannels align at oblique/right angles with respect to the long axis of the film strips, the coiling/curling motions can be generated in response to the stimuli, and the better motion performances are found in humidity- and heating-driven systems. This material utilized in self-adaptive soft robots exhibits prominent toughness, powerful strength, and long endurance for converting humidity and heat to mechanical works including transportation of lightweight objects, automatic sensing cap, and mimicking crawling in nature. We thus believe that this material with shape-programmable multisensing capability might be suitable for soft machines and robotics.

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

Self-assembly of mesoscopically ordered chromatic polydiacetylene/silica nanocomposites

NASA Technical Reports Server (NTRS)

Lu, Y.; Yang, Y.; Sellinger, A.; Lu, M.; Huang, J.; Fan, H.; Haddad, R.; Lopez, G.; Burns, A. R.; Sasaki, D. Y.;

Simultaneous Increase in Open-Circuit Voltage and Efficiency of Fullerene-Free Solar Cells through Chlorinated Thieno[3,4-b]thiophene Polymer Donor

DOE PAGES

Wang, Huan; Chao, Pengjie; Chen, Hui; ...

2017-08-01

Here, the chlorinated polymer, PBTCl, have been found to be an efficient donor in non-fullerene PSCs, which showed a blue-shifted absorbance compared to that of its fluorine analog (PTB7-th), and resulted in a more complementary light absorption with non-fullerene acceptor, such as ITIC. Meanwhile, chlorine substitution lowered the HOMO level of PBTCl, which increased the open-circuit voltage of the corresponding polymer-based devices. The 2D GIWAXS analysis illustrated that the PBTCl/ITIC blend film exhibited a “face-on” orientation and scattering features of both PBTCl and ITIC, suggesting that the blend of PBTCl and ITIC was phase separated and formed individual crystalline domainsmore » of the donor and acceptor, which promoted charge transfer in the bi-continuous film and eventually elevated the solar energy conversion efficiency. The PBTCl-based non-fullerene PSC exhibited a maximum PCE of 7.57% with a Voc of 0.91 V, which was an approximately 13% increasing in the PCE compared to the fluorine-analog-based device.« less

Simultaneous Increase in Open-Circuit Voltage and Efficiency of Fullerene-Free Solar Cells through Chlorinated Thieno[3,4-b]thiophene Polymer Donor

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

Wang, Huan; Chao, Pengjie; Chen, Hui

Here, the chlorinated polymer, PBTCl, have been found to be an efficient donor in non-fullerene PSCs, which showed a blue-shifted absorbance compared to that of its fluorine analog (PTB7-th), and resulted in a more complementary light absorption with non-fullerene acceptor, such as ITIC. Meanwhile, chlorine substitution lowered the HOMO level of PBTCl, which increased the open-circuit voltage of the corresponding polymer-based devices. The 2D GIWAXS analysis illustrated that the PBTCl/ITIC blend film exhibited a “face-on” orientation and scattering features of both PBTCl and ITIC, suggesting that the blend of PBTCl and ITIC was phase separated and formed individual crystalline domainsmore » of the donor and acceptor, which promoted charge transfer in the bi-continuous film and eventually elevated the solar energy conversion efficiency. The PBTCl-based non-fullerene PSC exhibited a maximum PCE of 7.57% with a Voc of 0.91 V, which was an approximately 13% increasing in the PCE compared to the fluorine-analog-based device.« less

Solid particle erosion of polymers and composites

NASA Astrophysics Data System (ADS)

Friedrich, K.; Almajid, A. A.

2014-05-01

After a general introduction to the subject of solid particle erosion of polymers and composites, the presentation focusses more specifically on the behavior of unidirectional carbon fiber (CF) reinforced polyetheretherketone (PEEK) composites under such loadings, using different impact conditions and erodents. The data were analyzed on the basis of a newly defined specific erosive wear rate, allowing a better comparison of erosion data achieved under various testing conditions. Characteristic wear mechanisms of the CF/PEEK composites consisted of fiber fracture, matrix cutting and plastic matrix deformation, the relative contribution of which depended on the impingement angles and the CF orientation. The highest wear rates were measured for impingement angles between 45 and 60°. Using abrasion resistant neat polymer films (in this case PEEK or thermoplastic polyurethane (TPU) ones) on the surface of a harder substrate (e.g. a CF/PEEK composite plate) resulted in much lower specific erosive wear rates. The use of such polymeric films can be considered as a possible method to protect composite surfaces from damage caused by minor impacts and erosion. In fact, they are nowadays already successfully applied as protections for wind energy rotor blades.

Achieving a Collapsible, Strong, and Highly Thermally Conductive Film Based on Oriented Functionalized Boron Nitride Nanosheets and Cellulose Nanofiber.

PubMed

Wu, Kai; Fang, Jinchao; Ma, Jinrui; Huang, Rui; Chai, Songgang; Chen, Feng; Fu, Qiang

2017-09-06

Boron nitride nanosheet (BNNS) films receive wide attention in both academia and industry because of their high thermal conductivity (TC) and good electrical insulation capability. However, the brittleness and low strength of the BNNS film largely limit its application. Herein, functionalized BNNSs (f-BNNSs) with a well-maintained in-plane crystalline structure were first prepared utilizing urea in the aqueous solution via ball-milling for the purpose of improving their stability in water and enhancing the interaction with the polymer matrix. Then, a biodegradable and highly thermally conductive film with an orderly oriented structure based on cellulose nanofibers (CNFs) and f-BNNSs was prepared just by simple vacuum-assisted filtration. The modification of the BNNS and the introduction of the CNF result in a better orientation of the f-BNNS, sufficient connection between f-BNNS themselves, and strong interaction between f-BNNS and CNF, which not only make the prepared composite film strong and tough but also possess higher in-plane TC. An increase of 70% in-plane TC, 63.2% tensile strength, and 77.8% elongation could be achieved for CNF/f-BNNS films, compared with that for CNF/BNNS films at the filler content of 70%. Although at such a high f-BNNS content, this composite film can be bended and folded. It is even more interesting to find that the in-plane TC could be greatly enhanced with the decrease of the thickness of the film, and a value of 30.25 W/m K can be achieved at the thickness of ∼30 μm for the film containing 70 wt % f-BNNS. We believe that this highly thermally conductive film with good strength and toughness could have potential applications in next-generation highly powerful and collapsible electronic devices.

Aggregation control in natural brush-printed conjugated polymer films and implications for enhancing charge transport

PubMed Central

Wang, Gang; Huang, Wei; Eastham, Nicholas D.; Fabiano, Simone; Manley, Eric F.; Zeng, Li; Wang, Binghao; Zhang, Xinan; Chen, Zhihua; Li, Ran; Chang, Robert P. H.; Chen, Lin X.; Bedzyk, Michael J.; Melkonyan, Ferdinand S.; Facchetti, Antonio; Marks, Tobin J.

2017-01-01

Shear-printing is a promising processing technique in organic electronics for microstructure/charge transport modification and large-area film fabrication. Nevertheless, the mechanism by which shear-printing can enhance charge transport is not well-understood. In this study, a printing method using natural brushes is adopted as an informative tool to realize direct aggregation control of conjugated polymers and to investigate the interplay between printing parameters, macromolecule backbone alignment and aggregation, and charge transport anisotropy in a conjugated polymer series differing in architecture and electronic structure. This series includes (i) semicrystalline hole-transporting P3HT, (ii) semicrystalline electron-transporting N2200, (iii) low-crystallinity hole-transporting PBDTT-FTTE, and (iv) low-crystallinity conducting PEDOT:PSS. The (semi-)conducting films are characterized by a battery of morphology and microstructure analysis techniques and by charge transport measurements. We report that remarkably enhanced mobilities/conductivities, as high as 5.7×/3.9×, are achieved by controlled growth of nanofibril aggregates and by backbone alignment, with the adjusted R2 (R2adj) correlation between aggregation and charge transport as high as 95%. However, while shear-induced aggregation is important for enhancing charge transport, backbone alignment alone does not guarantee charge transport anisotropy. The correlations between efficient charge transport and aggregation are clearly shown, while mobility and degree of orientation are not always well-correlated. These observations provide insights into macroscopic charge transport mechanisms in conjugated polymers and suggest guidelines for optimization. PMID:29109282

Characterization, performance and optimization of PVDF as a piezoelectric film for advanced space mirror concepts.

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

Jones, Gary D.; Assink, Roger Alan; Dargaville, Tim Richard

2005-11-01

Piezoelectric polymers based on polyvinylidene fluoride (PVDF) are of interest for large aperture space-based telescopes as adaptive or smart materials. Dimensional adjustments of adaptive polymer films depend on controlled charge deposition. Predicting their long-term performance requires a detailed understanding of the piezoelectric material features, expected to suffer due to space environmental degradation. Hence, the degradation and performance of PVDF and its copolymers under various stress environments expected in low Earth orbit has been reviewed and investigated. Various experiments were conducted to expose these polymers to elevated temperature, vacuum UV, {gamma}-radiation and atomic oxygen. The resulting degradative processes were evaluated. Themore » overall materials performance is governed by a combination of chemical and physical degradation processes. Molecular changes are primarily induced via radiative damage, and physical damage from temperature and atomic oxygen exposure is evident as depoling, loss of orientation and surface erosion. The effects of combined vacuum UV radiation and atomic oxygen resulted in expected surface erosion and pitting rates that determine the lifetime of thin films. Interestingly, the piezo responsiveness in the underlying bulk material remained largely unchanged. This study has delivered a comprehensive framework for material properties and degradation sensitivities with variations in individual polymer performances clearly apparent. The results provide guidance for material selection, qualification, optimization strategies, feedback for manufacturing and processing, or alternative materials. Further material qualification should be conducted via experiments under actual space conditions.« less

In Situ Self Assembly of Nanocomposites: Competition of Chaotic Advection and Interfacial Effects as Observed by X-Ray Diffreaction

PubMed Central

Ratnaweera, Dilru R.; Mahesha, Chaitra; Zumbrunnen, David A.; Perahia, Dvora

2015-01-01

The effects of chaotic advection on the in situ assembly of a hierarchal nanocomposite of Poly Amide 6, (nylon 6 or PA6) and platelet shape nanoparticles (NPs) were studied. The assemblies were formed by chaotic advection, where melts of pristine PA6 and a mixture of PA6 with NPs were segregated into discrete layers and extruded into film in a continuous process. The process assembles the nanocomposite into alternating pristine-polymer and oriented NP/polymer layers. The structure of these hierarchal assemblies was probed by X-rays as a processing parameter, N, was varied. This parameter provides a measure of the extent of in situ structuring by chaotic advection. We found that all assemblies are semi-crystalline at room temperature. Increasing N impacts the ratio of α to γ crystalline forms. The effects of the chaotic advection vary with the concentration of the NPs. For nanocomposites with lower NP concentrations the amount of the γ crystalline form increased with N. However, at higher NP concentrations, interfacial effects of the NP play a significant role in determining the structure, where the NPs oriented along the melt flow direction and the polymer chains oriented perpendicular to the NP surfaces. PMID:28347015

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.

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.

Photoluminescence and solid state properties of rigid pi- conjugated polymers with applications to LED: Alkyl- substituted p-phenyleneethynylene polymers and triblock copolymers

NASA Astrophysics Data System (ADS)

Huang, Wen-Yao

A series of substituted poly(p-phenyleneethynylene)s, PPE, were synthesized by alkyne metathesis. The substituents dibutyl (a), dioctyl (b), ditetradecyl (c), di-2-ethylhexyl (d) and di-2-cyclohexylethyl; (e)were placed on the 2,5 positions of the phenyl rings. X-ray diffraction studies indicated that the main chains of each polymer were arranged in regular, layered arrays. Liquid crystalline structures were observed by polarized optical microscopy in PPE 4b, 4c and 4d. The temperatures of isotropization of the liquid crystalline structures coincided with the disordering temperatures determined by differential scanning calorimetry. The UV absorption spectra showed a gradual blue shift of the λmax for all these polymers, suggesting a decrease in the electronic delocalization along the chain as the size and geometry of the side group changed. The photoluminescence spectra in dilute toluene solutions are consistent with vibronic coupling and emission from localized excited states. The emission spectra of thin films show characteristics typical of excimer or aggregate formation in the solid state. Lastly, an improved method of molecular weight determination by end group analysis was devised. Molecular organization and orientation in thin films (~100 nm) of a triblock copolymer, PPEPEG, was studied. The morphology of the thin film can be visualized as consisting of PMMA as the major phase in which domains of vertically oriented triblock copolymers are dispersed with PEG groups facing the air-film interface. The molecular and supramolecular structure of a series of well-defined fully conjugated poly(2,5- diakyl-p-phenyleneethynylene)s, PPE, in toluene has been studied in the sol state and in the gel state by surface tension and photoluminescence measurements. Poly (2,6[4- phenyl quinoline]), I, and poly (2,6[p-phenylene] 4- phenyl quinoline), II, were synthesized by the self- condensation of 5-acetyl-2-aminobezophenone and 4-amino- 4 '-acetyl-3-benzoyl biphenyl, respectively. They were soluble in acidic solvents. The fluorescent properties of I and II were investigated as a function of concentration in HCOOH, CCl2HCOOH, and CH 3SO3H solutions. Silica sol was used as nanoscale glue to prepare composite gels. (Abstract shortened by UMI.)

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.

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.

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.

Rotated grating coupled surface plasmon resonance on wavelength-scaled shallow rectangular gratings

NASA Astrophysics Data System (ADS)

Szalai, A.; Szekeres, G.; Balázs, J.; Somogyi, A.; Csete, Maria

2013-09-01

Theoretical investigation of rotated grating coupling phenomenon was performed on a multilayer comprising 416-nmperiodic shallow rectangular polymer grating on bimetal film made of gold and silver layers. During the multilayer illumination by 532 nm wavelength p-polarized light the polar and azimuthal angles were varied. In presence of 0-35 nm, 0-50 nm and 15-50 nm thick polymer-layers at the valleys and hills splitting was observed on the dual-angle dependent reflectance in two regions: (i) close to 0° azimuthal angle corresponding to incidence plane parallel to the periodic pattern (P-orientation); and (ii) around ~33.5°/29°/30° azimuthal angle (C-orientation), in agreement with our previous experimental studies. The near-field study revealed that in P-orientation the E-field is enhanced at the glass side with p/2 periodicity at the first minimum appearing at 49°/50°/52° polar angles, and comprises maxima below both the valleys and hills; while E-field enhancement is observable both at the glass and polymer side with p-periodicity at the second minimum developing at 55°/63/64° tilting, comprising maxima intermittently below the valleys or above the hills. In Corientation coupled plasmonic modes are observable, involving modes propagating along the valleys at the secondary maxima appearing at ~35°/32°/32° azimuthal and ~49°/51°/56° polar angles, while modes confined along the polymer hills are observable at the primary minima, which are coupled most strongly at the ~31.5°/25°/28° azimuthal and ~55°/63°/66° polar angles. The secondary peak observable in C-orientation is proposed for biosensing applications, since the supported modes are confined along the valleys, where biomolecules prefer to attach.

In situ SHG monitoring of dipolar orientation and relaxation in Disperse Red type/derivative urethane-urea copolymer

NASA Astrophysics Data System (ADS)

Samoc, A.; Holland, A.; Tsuchimori, M.; Watanabe, O.; Samoc, M.; Luther-Davies, B.; Kolev, V. Z.

2005-09-01

We investigated linear optical and second-order nonlinear optical (NLO) properties of films of urethane-urea copolymer (UU2) functionalised with a high concentration of an azobenzene chromophore. The polymer films on ITO-coated substrate were corona poled to induce a noncentrosymmetric organization of chromophore dipoles and data on the second harmonic generated with the laser beam (the fundamental wavelength 1053 nm, 6 ps/pulse, 20 Hz repetition rate) was acquired as a function of time and temperature. Second harmonic generation (SHG) was used to monitor in situ the polar alignment and relaxation of orientation of the side-chain Disperse Red-like chromophore molecules in the films poled at room temperature and high above the glass transition temperature (Tg 140-150oC). The deff coefficient was determined from the Maker-fringe method and corrected for absorption. A strong second harmonic effect with a fast relaxation was observed in "cold" (room temperature) poling experiments. A large second-order resonantly enhanced optical nonlinearity (d33 of the order of 200 pm/V) was obtained in high temperature poling. A strong and stable nonlinearity has persisted for years after the films were high-temperature poled.

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.

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.

Investigation of PTFE transfer films by infrared emission spectroscopy and phase-locked ellipsometry

NASA Technical Reports Server (NTRS)

Lauer, James L.; Bunting, Bruce G.; Jones, William R., Jr.

1987-01-01

When a PTFE sheet was rubbed unidirectionally over a smooth surface of stainless steel an essentially monomolecular transfer film was formed. By ellipsometric and emission infrared spectroscopic techniques it was shown that the film was 10 to 15 A thick and birefringent. From the intensity differences of infrared bands obtained with a polarizer passing radiation polarized in mutually perpendicular planes, it was possible to deduce transfer film orientation with the direction of rubbing. After standing in air for several weeks the transfer films apparently increased in thickness by as much as threefold. At the same time both the index of refraction and the absorption index decreased. Examination of the surfaces by optical and electron microscopies showed that the films had become porous and flaky. These observations were consistent with previous tribological measurements. The coefficients of friction decreased with the formation of the transfer film but increased again as the film developed breaks. The applicability of the ellipsometric and polarized infrared emission techniques to the identification of monomolecular tribological transfer films of polymers such as PTFE has been demonstrated.

Changes of the optical characteristics of radiochromic films in the transition from EBT3 to EBT-XD films.

PubMed

Schoenfeld, Andreas A; Wieker, Soeren; Harder, Dietrich; Poppe, Bjoern

2016-07-01

A new type of radiochromic film, the EBT-XD film, has been introduced with the aim to reduce the orientation effect and the lateral response artifact occurring in the use of radiochromic films together with flatbed scanners. The task of the present study is to quantify the changes of optical characteristics involved with the transition from the well-known EBT3 films to the new EBT-XD films, using the optical bench arrangement already applied by Schoenfeld et al (2014 Phys. Med. Biol. 59 3575-97). Largely reduced polarization effects and the almost complete loss of the anisotropy of the scattered light produced in a radiation-exposed film have been observed. The Rayleigh-Debye-Gans theory is used to understand these optical changes as arising from the reduced length-to-width ratio of the LiPCDA polymer crystals in the active layer of the EBT-XD film. The effect of these changes on the flatbed scanning artifacts will be shortly addressed, but treated in more detail in a further paper.

Changes of the optical characteristics of radiochromic films in the transition from EBT3 to EBT-XD films

NASA Astrophysics Data System (ADS)

Schoenfeld, Andreas A.; Wieker, Soeren; Harder, Dietrich; Poppe, Bjoern

2016-07-01

A new type of radiochromic film, the EBT-XD film, has been introduced with the aim to reduce the orientation effect and the lateral response artifact occurring in the use of radiochromic films together with flatbed scanners. The task of the present study is to quantify the changes of optical characteristics involved with the transition from the well-known EBT3 films to the new EBT-XD films, using the optical bench arrangement already applied by Schoenfeld et al (2014 Phys. Med. Biol. 59 3575-97). Largely reduced polarization effects and the almost complete loss of the anisotropy of the scattered light produced in a radiation-exposed film have been observed. The Rayleigh-Debye-Gans theory is used to understand these optical changes as arising from the reduced length-to-width ratio of the LiPCDA polymer crystals in the active layer of the EBT-XD film. The effect of these changes on the flatbed scanning artifacts will be shortly addressed, but treated in more detail in a further paper.

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.

Molecular characterization of organic electronic films.

PubMed

DeLongchamp, Dean M; Kline, R Joseph; Fischer, Daniel A; Richter, Lee J; Toney, Michael F

2011-01-18

Organic electronics have emerged as a viable competitor to amorphous silicon for the active layer in low-cost electronics. The critical performance of organic electronic materials is closely related to their morphology and molecular packing. Unlike their inorganic counterparts, polymers combine complex repeat unit structure and crystalline disorder. This combination prevents any single technique from being able to uniquely solve the packing arrangement of the molecules. Here, a general methodology for combining multiple, complementary techniques that provide accurate unit cell dimensions and molecular orientation is described. The combination of measurements results in a nearly complete picture of the organic film morphology. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

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.

SPM analysis of fibrinogen adsorption on solid surfaces

NASA Astrophysics Data System (ADS)

Choukourov, A.; Grinevich, A.; Saito, N.; Takai, O.

2007-09-01

The adsorption kinetics, adhesion and orientation of human fibrinogen on solid surfaces have been studied by surface probe microscopy (SPM) and quartz crystal microbalance techniques (QCM). CF 3-, NH 2-terminated organo-silane self-assembled monolayers (SAM) and OH-terminated silicon dioxide have been used as model surfaces. Furthermore, the interaction of fibrinogen with nanocomposite Ti/hydrocarbon plasma polymer films (Ti/ppCH) deposited by dc magnetron sputtering has also been studied.

Exploring Alkyl Chains in Benzobisthiazole-Naphthobisthiadiazole Polymers: Impact on Solar-Cell Performance, Crystalline Structures, and Optoelectronics.

PubMed

Al-Naamani, Eman; Gopal, Anesh; Ide, Marina; Osaka, Itaru; Saeki, Akinori

2017-11-01

The shapes and lengths of the alkyl chains of conjugated polymers greatly affect the efficiencies of organic photovoltaic devices. This often results in a trade-off between solubility and self-organizing behavior; however, each material has specific optimal chains. Here we report on the effect of alkyl side chains on the film morphologies, crystallinities, and optoelectronic properties of new benzobisthiazole-naphthobisthiadiazole (PBBT-NTz) polymers. The power conversion efficiencies (PCEs) of linear-branched and all-branched polymers range from 2.5% to 6.6%; the variations in these PCEs are investigated by atomic force microscopy, two-dimensional X-ray diffraction (2D-GIXRD), and transient photoconductivity techniques. The best-performing linear-branched polymer, bearing dodecyl and decyltetradecyl chains (C12-DT), exhibits nanometer-scale fibers along with the highest crystallinity, comprising predominant edge-on and partial face-on orientations. This morphology leads to the highest photoconductivity and the longest carrier lifetime. These results highlight the importance of long alkyl chains for inducing intermolecular stacking, which is in contrast to observations made for analogous previously reported polymers.

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.

Enhanced efficiency of hybrid amorphous silicon solar cells based on single-walled carbon nanotubes/polymer composite thin film.

PubMed

Rajanna, Pramod Mulbagal; Gilshteyn, Evgenia; Yagafarov, Timur; Alekseeva, Alena; Anisimov, Anton; Sergeev, Oleg; Neumueller, Alex; Bereznev, Sergei; Maricheva, Jelena; Nasibulin, Albert

2018-01-09

We report a simple approach to fabricate hybrid solar cells (HSCs) based on a single-walled carbon nanotube (SWCNT) film and a thin film hydrogenated amorphous silicon (a-Si:H). Randomly oriented high quality SWCNTs with an enhanced conductivity by means of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate are used as a window layer and a front electrode. A series of HSCs are fabricated in ambient conditions with different SWCNT film thicknesses. The polymethylmethacrylate layer drop-casted on fabricated HSCs reduces the reflection fourfold and enhances the short-circuit Jsc, open-circuit Voc, and efficiency by nearly 10%. A state-of-the-art J-V performance is shown for SWCNT/a-Si HSC with an open-circuit voltage of 900 mV and efficiency of 3.4% under simulated one-sun AM 1.5G direct illumination. © 2018 IOP Publishing Ltd.

Enhanced efficiency of hybrid amorphous silicon solar cells based on single-walled carbon nanotubes and polymer composite thin film.

PubMed

Rajanna, Pramod M; Gilshteyn, Evgenia P; Yagafarov, Timur; Aleekseeva, Alena K; Anisimov, Anton S; Neumüller, Alex; Sergeev, Oleg; Bereznev, Sergei; Maricheva, Jelena; Nasibulin, Albert G

2018-01-31

We report a simple approach to fabricate hybrid solar cells (HSCs) based on a single-walled carbon nanotube (SWCNT) film and thin film hydrogenated amorphous silicon (a-Si:H). Randomly oriented high-quality SWCNTs with conductivity enhanced by means of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate are used as a window layer and a front electrode. A series of HSCs are fabricated in ambient conditions with varying SWCNT film thicknesses. The polymethylmethacrylate layer drop-casted on fabricated HSCs reduces the reflection fourfold and enhances the short-circuit J sc , open-circuit V oc , and efficiency by nearly 10%. A state-of-the-art J-V performance is shown for SWCNT/a-Si HSC with an open-circuit voltage of 900 mV and an efficiency of 3.4% under simulated one-sun AM 1.5 G direct illumination.

Enhanced efficiency of hybrid amorphous silicon solar cells based on single-walled carbon nanotubes and polymer composite thin film

NASA Astrophysics Data System (ADS)

Rajanna, Pramod M.; Gilshteyn, Evgenia P.; Yagafarov, Timur; Aleekseeva, Alena K.; Anisimov, Anton S.; Neumüller, Alex; Sergeev, Oleg; Bereznev, Sergei; Maricheva, Jelena; Nasibulin, Albert G.

2018-03-01

We report a simple approach to fabricate hybrid solar cells (HSCs) based on a single-walled carbon nanotube (SWCNT) film and thin film hydrogenated amorphous silicon (a-Si:H). Randomly oriented high-quality SWCNTs with conductivity enhanced by means of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate are used as a window layer and a front electrode. A series of HSCs are fabricated in ambient conditions with varying SWCNT film thicknesses. The polymethylmethacrylate layer drop-casted on fabricated HSCs reduces the reflection fourfold and enhances the short-circuit J sc , open-circuit V oc , and efficiency by nearly 10%. A state-of-the-art J-V performance is shown for SWCNT/a-Si HSC with an open-circuit voltage of 900 mV and an efficiency of 3.4% under simulated one-sun AM 1.5 G direct illumination.

Thin Films Formed from Conjugated Polymers with Ionic, Water-Soluble Backbones.

PubMed

Voortman, Thomas P; Chiechi, Ryan C

2015-12-30

This paper compares the morphologies of films of conjugated polymers in which the backbone (main chain) and pendant groups are varied between ionic/hydrophilic and aliphatic/hydrophobic. We observe that conjugated polymers in which the pendant groups and backbone are matched, either ionic-ionic or hydrophobic-hydrophobic, form smooth, structured, homogeneous films from water (ionic) or tetrahydrofuran (hydrophobic). Mismatched conjugated polymers, by contrast, form inhomogeneous films with rough topologies. The polymers with ionic backbone chains are conjugated polyions (conjugated polymers with closed-shell charges in the backbone), which are semiconducting materials with tunable bad-gaps, not unlike uncharged conjugated polymers.

Morphology design of porous coordination polymer crystals by coordination modulation.

PubMed

Umemura, Ayako; Diring, Stéphane; Furukawa, Shuhei; Uehara, Hiromitsu; Tsuruoka, Takaaki; Kitagawa, Susumu

2011-10-05

The design of crystal morphology, or exposed crystal facets, has enabled the development (e.g., catalytic activities, material attributes, and oriented film formation) of porous coordination polymers (PCPs) without changing material compositions. However, because crystal growth mechanisms are not fully understood, control of crystal morphology still remains challenging. Herein, we report the morphology design of [Cu(3)(btc)(2)](n) (btc = benzene-1,3,5-tricarboxylate) by the coordination modulation method (modulator = n-dodecanoic acid or lauric acid). A morphological transition (octahedron-cuboctahedron-cube) in the [Cu(3)(btc)(2)](n) crystal was observed with an increase in concentration of the modulator. By suitably defining a coarse-grained standard unit of [Cu(3)(btc)(2)](n) as its cuboctahedron main pore and determining its attachment energy on crystal surfaces, Monte Carlo coarse-grain modeling revealed the population and orientation of carboxylates and elucidated an important role of the modulator in determining the <100>- and <111>-growth throughout the crystal growth process. This comprehension, in fact, successfully led to designed crystal morphologies with oriented growth on bare substrates. Because selective crystal orientations on the bare substrates were governed by crystal morphology, this contribution also casts a new light on the unexplored issue of the significance of morphology design of PCPs.

Modeling out-of-plane actuation in thin-film nematic polymer networks: From chiral ribbons to auto-origami boxes via twist and topology

PubMed Central

Gimenez-Pinto, Vianney; Ye, Fangfu; Mbanga, Badel; Selinger, Jonathan V.; Selinger, Robin L. B.

2017-01-01

Various experimental and theoretical studies demonstrate that complex stimulus-responsive out-of-plane distortions such as twist of different chirality, emergence of cones, simple and anticlastic bending can be engineered and pre-programmed in a liquid crystalline rubbery material given a well-controlled director microstructure. Via 3-d finite element simulation studies, we demonstrate director-encoded chiral shape actuation in thin-film nematic polymer networks under external stimulus. Furthermore, we design two complex director fields with twisted nematic domains and nematic disclinations that encode a pattern of folds for an auto-origami box. This actuator will be flat at a reference nematic state and form four well-controlled bend distortions as orientational order changes. Device fabrication is applicable via current experimental techniques. These results are in qualitative agreement with theoretical predictions, provide insight into experimental observations, and demonstrate the value of finite element methods at the continuum level for designing and engineering liquid crystal polymeric devices. PMID:28349949

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

Unified description of the slip phenomena in sheared polymer films: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Priezjev, Nikolai

2010-03-01

The dynamic behavior of the slip length in shear flow of polymer melts past atomically smooth surfaces is investigated using MD simulations. The polymer melt was modeled as a collection of FENE-LJ bead-spring chains. We consider shear flow conditions at low pressures and weak wall-fluid interaction energy so that fluid velocity profiles are linear throughout the channel at all shear rates examined. In agreement with earlier studies we confirm that for shear- thinning fluids the slip length passes through a local minimum at low shear rates and then increases rapidly at higher shear rates. We found that the rate dependence of the slip length depends on the lattice orientation at high shear rates. The MD results show that the ratio of slip length to viscosity follows a master curve when plotted as a function of a single variable that depends on the structure factor, contact density and temperature of the first fluid layer near the solid wall. The universal dependence of the slip length holds for a number of parameters of the interface: fluid density and structure (chain length), wall-fluid interaction energy, wall density, lattice orientation, thermal or solid walls.

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

Infrared vibrational nanocrystallography and nanoimaging

PubMed Central

Muller, Eric A.; Pollard, Benjamin; Bechtel, Hans A.; van Blerkom, Peter; Raschke, Markus B.

2016-01-01

Molecular solids and polymers can form low-symmetry crystal structures that exhibit anisotropic electron and ion mobility in engineered devices or biological systems. The distribution of molecular orientation and disorder then controls the macroscopic material response, yet it is difficult to image with conventional techniques on the nanoscale. We demonstrated a new form of optical nanocrystallography that combines scattering-type scanning near-field optical microscopy with both optical antenna and tip-selective infrared vibrational spectroscopy. From the symmetry-selective probing of molecular bond orientation with nanometer spatial resolution, we determined crystalline phases and orientation in aggregates and films of the organic electronic material perylenetetracarboxylic dianhydride. Mapping disorder within and between individual nanoscale domains, the correlative hybrid imaging of nanoscale heterogeneity provides insight into defect formation and propagation during growth in functional molecular solids. PMID:27730212

Enhancing Performance of Large-Area Organic Solar Cells with Thick Film via Ternary Strategy.

PubMed

Zhang, Jianqi; Zhao, Yifan; Fang, Jin; Yuan, Liu; Xia, Benzheng; Wang, Guodong; Wang, Zaiyu; Zhang, Yajie; Ma, Wei; Yan, Wei; Su, Wenming; Wei, Zhixiang

2017-06-01

Large-scale fabrication of organic solar cells requires an active layer with high thickness tolerability and the use of environment-friendly solvents. Thick films with high-performance can be achieved via a ternary strategy studied herein. The ternary system consists of one polymer donor, one small molecule donor, and one fullerene acceptor. The small molecule enhances the crystallinity and face-on orientation of the active layer, leading to improved thickness tolerability compared with that of a polymer-fullerene binary system. An active layer with 270 nm thickness exhibits an average power conversion efficiency (PCE) of 10.78%, while the PCE is less than 8% with such thick film for binary system. Furthermore, large-area devices are successfully fabricated using polyethylene terephthalate (PET)/Silver gride or indium tin oxide (ITO)-based transparent flexible substrates. The product shows a high PCE of 8.28% with an area of 1.25 cm 2 for a single cell and 5.18% for a 20 cm 2 module. This study demonstrates that ternary organic solar cells exhibit great potential for large-scale fabrication and future applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Substrate-dependent structural and CO sensing properties of LaCoO3 epitaxial films

NASA Astrophysics Data System (ADS)

Liu, Haifeng; Sun, Hongjuan; Xie, Ruishi; Zhang, Xingquan; Zheng, Kui; Peng, Tongjiang; Wu, Xiaoyu; Zhang, Yanping

2018-06-01

LaCoO3 thin films were grown on different (0 0 1) oriented LaAlO3, SrTiO3 and (LaAlO3)0.3(Sr2AlTaO6)0.7 by the polymer assisted deposition method, respectively. All the LaCoO3 thin films are in epitaxial growth on these substrates, with tetragonal distortion of CoO6 octahedrons. Due to different in-plane lattice mismatch, the LaCoO3 film on LaAlO3 has the largest tetragonal distortion of CoO6 octahedrons while the film grown on (LaAlO3)0.3(Sr2AlTaO6)0.7 has the smallest tetragonal distortion. The relative contents of the surface absorbed oxygen species are found to increase for the LaCoO3 epitaxial films grown on (0 0 1) oriented (LaAlO3)0.3(Sr2AlTaO6)0.7, SrTiO3 and LaAlO3 substrates, sequentially. The film sensors exhibit good CO sensing properties at 150 °C, and the LaCoO3 film on LaAlO3 shows the highest response but the film on (LaAlO3)0.3(Sr2AlTaO6)0.7 shows the lowest. It reveals that the larger degree of Jahn-Teller-like tetragonal distortion of CoO6 octahedrons may greatly improve the surface absorbing and catalytic abilities, corresponding to more excellent CO sensing performance. The present study suggests that the formation of epitaxial films is an efficient methodology for controlling the octahedral distortion and thereby improving the gas sensing performance of perovskite transition metal oxides.

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.

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.

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.

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.

Dielectric Properties of PMMA and its Composites with ZrO2

NASA Astrophysics Data System (ADS)

Sannakki, Basavaraja; Anita

The polymer films of PMMA with different thickness and its composites with ZrO2 at various weight percentages but of same thickness have been studied. The determination of its dielectric properties, dielectric loss, a.conductivity and dielectric modulus were carried out using capacitance measurements of the above samples as a function of frequency, over the range 50 Hz - 5 MHz at room temperature. The films of PMMA and its composites have been characterized using X-Ray Diffractometer. The dielectric permittivity of films of PMMA behaves nonlinearly as frequency increases over the range 50-300 Hz, where as above 300 Hz the values of dielectric constant remains constant. But it is observed that the dielectric constant of PMMA increases as thickness of the film increases. In case of composite films of PMMA with ZrO2 the values of dielectric permittivity decreases gradually up to frequency of around 1 KHz and at higher frequencies it remains constant for all the weight percentages of ZrO2. The complex form of dielectric modulus of PMMA is obtained from the experimentally measured data of dielectric constant and dielectric loss values. The relaxation time of the orientation of dipoles is obtained from the peak value of angular frequency through the plots of imaginary part of electrical modulus as function of frequency. The impedance of PMMA polymer increases as thickness of the films increases. The a c conductivity of PMMA film remains constant up to frequency of 1 MHz and above. It shows a nonlinear phenomenon with peak values at frequency 4 MHz. Shape and size of the nanoparticles of composite film of PMMA with ZrO2 was analyzed by Field Emission Scanning Electron Microscope (FESEM).

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.

Simulation of bipolar charge transport in nanocomposite polymer films

NASA Astrophysics Data System (ADS)

Lean, Meng H.; Chu, Wei-Ping L.

2015-03-01

This paper describes 3D particle-in-cell simulation of bipolar charge injection and transport through nanocomposite film comprised of ferroelectric ceramic nanofillers in an amorphous polymer matrix. The classical electrical double layer (EDL) model for a monopolar core is extended (eEDL) to represent the nanofiller by replacing it with a dipolar core. Charge injection at the electrodes assumes metal-polymer Schottky emission at low to moderate fields and Fowler-Nordheim tunneling at high fields. Injected particles migrate via field-dependent Poole-Frenkel mobility and recombine with Monte Carlo selection. The simulation algorithm uses a boundary integral equation method for solution of the Poisson equation coupled with a second-order predictor-corrector scheme for robust time integration of the equations of motion. The stability criterion of the explicit algorithm conforms to the Courant-Friedrichs-Levy limit assuring robust and rapid convergence. The model is capable of simulating a wide dynamic range spanning leakage current to pre-breakdown. Simulation results for BaTiO3 nanofiller in amorphous polymer matrix indicate that charge transport behavior depend on nanoparticle polarization with anti-parallel orientation showing the highest leakage conduction and therefore lowest level of charge trapping in the interaction zone. Charge recombination is also highest, at the cost of reduced leakage conduction charge. The eEDL model predicts the meandering pathways of charge particle trajectories.

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.

The Relationship Between Chemical Structure and Dielectric Properties of Plasma-Enhanced Chemical Vapor Deposited Polymer Thin Films (Postprint)

DTIC Science & Technology

2007-01-01

C6H6, Aldrich Co., liquid , high performance liquid chromatography (HPLC) grade with a purity of 99.9%) and octafluorocyclobutane (C4F8, OFCB...attributed to the lack of molecular mobility (confined by the crosslinking) and low ionic polarization of the molecular structures [6]. The frequency...in dielectric constant at low frequencies can be traced to orientational polarizations of trapped free radicals, unpaired electron sites, oligomeric

Interface properties between a low band gap conjugated polymer and a calcium metal electrode.

PubMed

Zhang, Wei; Pan, Xiao; Feng, Xuefei; Wang, Chia-Hsin; Yang, Yaw-Wen; Ju, Huanxin; Zhu, Junfa

2016-04-14

Interfaces between metal electrodes and π-conjugated polymers play an important role in the organic optoelectronic devices. In this paper, the molecular orientation of the pristine poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (APFO3) films, chemical reactions and the electronic structure during the interface formation of Ca/APFO3 have been investigated in detail using synchrotron radiation photoemission spectroscopy (SRPES), X-ray photoemission spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. It is shown that the APFO3 film has a high degree of orientational ordering with its aromatic ring tilted at an angle of 43° from the substrate, and the 9,9-dioctyl fluorene unit (F8) is almost in the same plane as the benzothiazole unit (BT). Upon vapor-deposition of Ca onto APFO3 at room temperature, Ca dopes electrons into APFO3 and induces the downward band bending of APFO3. Moreover, Ca can diffuse into the APFO3 subsurface and react with N, S and C atoms of APFO3. Finally, the barrier of electron injection at the Ca/APFO3 interface is derived by the energy level alignment diagram. These results enable us to gain comprehensive insights into APFO3 and will facilitate the reasonable design of high performance devices based on APFO3.

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.

Phosphorene-directed self-assembly of asymmetric PS-b-PMMA block copolymer for perpendicularly-oriented sub-10 nm PS nanopore arrays

NASA Astrophysics Data System (ADS)

Zhang, Ziming; Zheng, Lu; Khurram, Muhammad; Yan, Qingfeng

2017-10-01

Few-layer black phosphorus, also known as phosphorene, is a new two-dimensional material which is of enormous interest for applications, mainly in electronics and optoelectronics. Herein, we for the first time employ phosphorene for directing the self-assembly of asymmetric polystyrene-block-polymethylmethacrylate (PS-b-PMMA) block copolymer (BCP) thin film to form the perpendicular orientation of sub-10 nm PS nanopore arrays in a hexagonal fashion normal to the interface. We experimentally demonstrate that none of the PS and PMMA blocks exhibit preferential affinity to the phosphorene-modified surface. Furthermore, the perpendicularly-oriented PS nanostructures almost stay unchanged with the variation of number of layers of few-layer phosphorene nanoflakes between 15-30 layers. Differing from the neutral polymer brushes which are widely used for chemical modification of the silicon substrate, phosphorene provides a novel physical way to control the interfacial interactions between the asymmetric PS-b-PMMA BCP thin film and the silicon substrate. Based on our results, it is possible to build a new scheme for producing sub-10 nm PS nanopore arrays oriented perpendicularly to the few-layer phosphorene nanoflakes. Furthermore, the nanostructural microdomains could serve as a promising nanolithography template for surface patterning of phosphorene nanoflakes.

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 ...

Orientation Control in Thin Films of a High-χ Block Copolymer with a Surface Active Embedded Neutral Layer.

PubMed

Zhang, Jieqian; Clark, Michael B; Wu, Chunyi; Li, Mingqi; Trefonas, Peter; Hustad, Phillip D

2016-01-13

Directed self-assembly (DSA) of block copolymers (BCPs) is an attractive advanced patterning technology being considered for future integrated circuit manufacturing. By controlling interfacial interactions, self-assembled microdomains in thin films of polystyrene-block-poly(methyl methacrylate), PS-b-PMMA, can be oriented perpendicular to surfaces to form line/space or hole patterns. However, its relatively weak Flory interaction parameter, χ, limits its capability to pattern sub-10 nm features. Many BCPs with higher interaction parameters are capable of forming smaller features, but these "high-χ" BCPs typically have an imbalance in surface energy between the respective blocks that make it difficult to achieve the required perpendicular orientation. To address this challenge, we devised a polymeric surface active additive mixed into the BCP solution, referred to as an embedded neutral layer (ENL), which segregates to the top of the BCP film during casting and annealing and balances the surface tensions at the top of the thin film. The additive comprises a second BCP with a "neutral block" designed to provide matched surface tensions with the respective polymers of the main BCP and a "surface anchoring block" with very low surface energy that drives the material to the air interface during spin-casting and annealing. The surface anchoring block allows the film to be annealed above the glass transition temperature of the two materials without intermixing of the two components. DSA was also demonstrated with this embedded neutral top layer formulation on a chemical patterned template using a single step coat and simple thermal annealing. This ENL technology holds promise to enable the use of high-χ BCPs in advanced patterning applications.

Epitaxial Growth of Thin Ferroelectric Polymer Films on Graphene Layer for Fully Transparent and Flexible Nonvolatile Memory.

PubMed

Kim, Kang Lib; Lee, Wonho; Hwang, Sun Kak; Joo, Se Hun; Cho, Suk Man; Song, Giyoung; Cho, Sung Hwan; Jeong, Beomjin; Hwang, Ihn; Ahn, Jong-Hyun; Yu, Young-Jun; Shin, Tae Joo; Kwak, Sang Kyu; Kang, Seok Ju; Park, Cheolmin

2016-01-13

Enhancing the device performance of organic memory devices while providing high optical transparency and mechanical flexibility requires an optimized combination of functional materials and smart device architecture design. However, it remains a great challenge to realize fully functional transparent and mechanically durable nonvolatile memory because of the limitations of conventional rigid, opaque metal electrodes. Here, we demonstrate ferroelectric nonvolatile memory devices that use graphene electrodes as the epitaxial growth substrate for crystalline poly(vinylidene fluoride-trifluoroethylene) (PVDF-TrFE) polymer. The strong crystallographic interaction between PVDF-TrFE and graphene results in the orientation of the crystals with distinct symmetry, which is favorable for polarization switching upon the electric field. The epitaxial growth of PVDF-TrFE on a graphene layer thus provides excellent ferroelectric performance with high remnant polarization in metal/ferroelectric polymer/metal devices. Furthermore, a fully transparent and flexible array of ferroelectric field effect transistors was successfully realized by adopting transparent poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] semiconducting polymer.

Polymer compositions, polymer films and methods and precursors for forming same

DOEpatents

Klaehn, John R; Peterson, Eric S; Orme, Christopher J

2013-09-24

Stable, high performance polymer compositions including polybenzimidazole (PBI) and a melamine-formaldehyde polymer, such as methylated, poly(melamine-co-formaldehyde), for forming structures such as films, fibers and bulky structures. The polymer compositions may be formed by combining polybenzimidazole with the melamine-formaldehyde polymer to form a precursor. The polybenzimidazole may be reacted and/or intertwined with the melamine-formaldehyde polymer to form the polymer composition. For example, a stable, free-standing film having a thickness of, for example, between about 5 .mu.m and about 30 .mu.m may be formed from the polymer composition. Such films may be used as gas separation membranes and may be submerged into water for extended periods without crazing and cracking. The polymer composition may also be used as a coating on substrates, such as metal and ceramics, or may be used for spinning fibers. Precursors for forming such polymer compositions are also disclosed.

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.

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.

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.

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.

Tailoring uniform gold nanoparticle arrays and nanoporous films for next-generation optoelectronic devices

NASA Astrophysics Data System (ADS)

Farid, Sidra; Kuljic, Rade; Poduri, Shripriya; Dutta, Mitra; Darling, Seth B.

2018-06-01

High-density arrays of gold nanodots and nanoholes on indium tin oxide (ITO)-coated glass surfaces are fabricated using a nanoporous template fabricated by the self-assembly of diblock copolymers of poly (styrene-block-methyl methacrylate) (PS-b-PMMA) structures. By balancing the interfacial interactions between the polymer blocks and the substrate using random copolymer, cylindrical block copolymer microdomains oriented perpendicular to the plane of the substrate have been obtained. Nanoporous PS films are created by selectively etching PMMA cylinders, a straightforward route to form highly ordered nanoscale porous films. Deposition of gold on the template followed by lift off and sonication leaves a highly dense array of gold nanodots. These materials can serve as templates for the vapor-liquid-solid (VLS) growth of semiconductor nanorod arrays for next generation hybrid optoelectronic applications.

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.

Structure-Property Relationships of Semiconducting Polymers for Flexible and Durable Polymer Field-Effect Transistors.

PubMed

Kim, Min Je; Jung, A-Ra; Lee, Myeongjae; Kim, Dongjin; Ro, Suhee; Jin, Seon-Mi; Nguyen, Hieu Dinh; Yang, Jeehye; Lee, Kyung-Koo; Lee, Eunji; Kang, Moon Sung; Kim, Hyunjung; Choi, Jong-Ho; Kim, BongSoo; Cho, Jeong Ho

2017-11-22

We report high-performance top-gate bottom-contact flexible polymer field-effect transistors (FETs) fabricated by flow-coating diketopyrrolopyrrole (DPP)-based and naphthalene diimide (NDI)-based polymers (P(DPP2DT-T2), P(DPP2DT-TT), P(DPP2DT-DTT), P(NDI2OD-T2), P(NDI2OD-F2T2), and P(NDI2OD-Se2)) as semiconducting channel materials. All of the polymers displayed good FET characteristics with on/off current ratios exceeding 10 7 . The highest hole mobility of 1.51 cm 2 V -1 s -1 and the highest electron mobility of 0.85 cm 2 V -1 s -1 were obtained from the P(DPP2DT-T2) and P(NDI2OD-Se2) polymer FETs, respectively. The impacts of the polymer structures on the FET performance are well-explained by the interplay between the crystallinity, the tendency of the polymer backbone to adopt an edge-on orientation, and the interconnectivity of polymer fibrils in the film state. Additionally, we demonstrated that all of the flexible polymer-based FETs were highly resistant to tensile stress, with negligible changes in their carrier mobilities and on/off ratios after a bending test. Conclusively, these high-performance, flexible, and durable FETs demonstrate the potential of semiconducting conjugated polymers for use in flexible electronic applications.

Natural-Synthetic Hybrid Polymers Developed via Electrospinning: The Effect of PET in Chitosan/Starch System

PubMed Central

Espíndola-González, Adolfo; Martínez-Hernández, Ana Laura; Fernández-Escobar, Francisco; Castaño, Victor Manuel; Brostow, Witold; Datashvili, Tea; Velasco-Santos, Carlos

2011-01-01

Chitosan is an amino polysaccharide found in nature, which is biodegradable, nontoxic and biocompatible. It has versatile features and can be used in a variety of applications including films, packaging, and also in medical surgery. Recently a possibility to diversify chitosan properties has emerged by combining it with synthetic materials to produce novel natural-synthetic hybrid polymers. We have studied structural and thermophysical properties of chitosan + starch + poly(ethylene terephthalate) (Ch + S + PET) fibers developed via electrospinning. Properties of these hybrids polymers are compared with extant chitosan containing hybrids synthesized by electrospinning. Molecular interactions and orientation in the fibers are analyzed by infrared and Raman spectroscopies respectively, morphology by scanning electron microscopy and thermophysical properties by thermogravimetric analysis and differential scanning calorimetry. Addition of PET to Ch + S systems results in improved thermal stability at elevated temperatures. PMID:21673930

Structural features of the adsorption layer of pentacene on the graphite surface and the PMMA/graphite hybrid surface

NASA Astrophysics Data System (ADS)

Fadeeva, A. I.; Gorbunov, V. A.; Litunenko, T. A.

2017-08-01

Using the molecular dynamics and the Monte Carlo methods, we have studied the structural features and growth mechanism of the pentacene film on graphite and polymethylmethacrylate /graphite surfaces. Monolayer capacity and molecular area, optimal angles between the pentacene molecules and graphite and PMMA/graphite surfaces as well as the characteristic angles between the neighboring pentacene molecules in the adsorption layer were estimated. It is shown that the orientation of the pentacene molecules in the film is determined by a number of factors, including the surface concentration of the molecules, relief of the surface, presence or absence of the polymer layer and its thickness. The pentacene molecules adsorbed on the graphite surface keep a horizontal position relative to the long axis at any surface coverage/thickness of the film. In the presence of the PMMA layer on the graphite, the increase of the number of pentacene molecules as well as the thickness of the PMMA layer induce the change of molecular orientation from predominantly horizontal to vertical one. The reason for such behavior is supposed to be the roughness of the PMMA surface.

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...

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.

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.

Laser patterning of transparent polymers assisted by plasmon excitation.

PubMed

Elashnikov, R; Trelin, A; Otta, J; Fitl, P; Mares, D; Jerabek, V; Svorcik, V; Lyutakov, O

2018-06-13

Plasmon-assisted lithography of thin transparent polymer films, based on polymer mass-redistribution under plasmon excitation, is presented. The plasmon-supported structures were prepared by thermal annealing of thin Ag films sputtered on glass or glass/graphene substrates. Thin films of polymethylmethacrylate, polystyrene and polylactic acid were then spin-coated on the created plasmon-supported structures. Subsequent laser beam writing, at the wavelength corresponding to the position of plasmon absorption, leads to mass redistribution and patterning of the thin polymer films. The prepared structures were characterized using UV-Vis spectroscopy and confocal and AFM microscopy. The shape of the prepared structures was found to be strongly dependent on the substrate type. The mechanism leading to polymer patterning was examined and attributed to the plasmon-heating. The proposed method makes it possible to create different patterns in polymer films without the need for wet technological stages, powerful light sources or a change in the polymer optical properties.

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.

Morphology of poly-p-xylylene crystallized during polymerization.

NASA Technical Reports Server (NTRS)

Kubo, S.; Wunderlich, B.

1971-01-01

The morphology of as-polymerized poly-p-xylylene grown between -17 and 30 C is found to consist of lame llar alpha crystals oriented with the (010) plane parallel to the support surface. The crystallinity decreases with decreasing polymerization temperature. Spherulitic and nonspherulitic portions of the polymer film consist of folded chain lamellas with the chain axis parallel to the support surface. The results were obtained by small- and wide-angle X-ray measurements, electron and optical microscopy, and differential thermal analysis.

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.

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...

Fabrication and performance of efficient thin circular polarization gratings with Bragg properties using bulk photo-alignment of a liquid crystalline polymer

NASA Astrophysics Data System (ADS)

Sakhno, Oksana; Gritsai, Yuri; Sahm, Hagen; Stumpe, Joachim

2018-03-01

Thin circular polarization gratings, characterized by high diffraction efficiency and large, up to 42°, diffraction angles were created by polarization holography for the first time. The high efficiency of the gratings is the result of the specific properties of a photo-crosslinkable liquid crystalline polymer and a two-step photochemical/thermal processing procedure. A diffraction efficiency of up to 98% at 532 nm has been achieved for gratings with periods of 700 nm. In contrast to polarization gratings with larger periods these gratings exhibit Bragg properties. So one beam is either transmitted or diffracted depending on the direction of the circular polarization of the incident light, whereas the maximal diffraction efficiency is achieved only at the proper incident angle. The fabrication procedure consists of holographic exposure of the film at room temperature which provides the photo-selective cycloaddition of cinnamic ester groups. Upon subsequent thermal annealing above T g bulk photo-alignment of the LC polymer film occurs enhancing the optical anisotropy within the grating. The holographic patterning provides high spatial resolution, the arbitrary orientation of the LC director as well as high optical quality, thermal and chemical stability of the final gratings. Highly efficient symmetric and slanted circular polarization gratings were fabricated with the proposed technique.

Enhancing the value of commodity polymers: Part 1. Structure-property relationships in composite materials based on maleated polypropylene/inorganic phosphate glasses. Part 2. New value-added applications for polyesters

NASA Astrophysics Data System (ADS)

Gupta, Mohit

The first part of the thesis (Chapters 2 & 3) describes a new class of organic polymer/inorganic glass composite materials with property improvements that are impossible to achieve with classical polymer blends or composites. These materials exhibit good processability, superior mechanical performance, good thermal stability, and have excellent gas barrier properties. Low glass transition temperature phosphate glasses (Pglass) are used as inorganic fillers and slightly maleated polypropylene is used as the organic polymer matrix. The Pglass, which was dispersed as spherical droplets in the unoriented composites can be elongated into high aspect ratio platelets during the biaxial stretching process. Biaxially oriented films exhibited a brick wall type microstructure with highly aligned inorganic platelets in a ductile organic matrix and the oxygen barrier properties are significantly improved due to presence of Pglass platelets as impermeable inclusions. Mechanical properties of the biaxially oriented films showed significant improvements compared to neat polymer due to uniform dispersion of the Pglass platelets. Properly dispersed and aligned platelets have proven to be very effective for increasing the composite modulus. These developed materials therefore show promise to help fulfill the ever increasing demand for new advanced materials for a wide variety of advanced packaging applications because of their gas barrier properties, flexibility, transparency, mechanical strength and performance under humid conditions. The second part of the thesis (Chapters 4 & 5) describes new value-added applications for polyesters. Chapter 4 reports a novel process for the decolorization of green and blue colored PET bottle flakes using hydrogen peroxide. The decolorized flakes were characterized for color, intrinsic viscosity values. Decolorized flakes exhibited color values similar to those of colorless recycled PET and even though IV values decreased, bleached flakes still exhibit useful molecular weight. The consumption of H2O2 during the bleaching process was quantified by titrating the residual peroxide using a standard solution of potassium permanganate. Chapter 5 reports synthesis of ductile amorphous polymers which change their color as a function of mechanical deformation. Cyano--OPV moieties were covalently incorporated into the backbone of amorphous polyester PETG. The materials exhibit a significant color change upon compression consistent with efficient breakup of the dye aggregates upon deformation and therefore can be useful for technological applications that require smart coatings with integrated scratch detectors.

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.

An Examination of Radiation Induced Tensile Failure of Stressed and Unstressed Polymer Films Flown on MISSE-6

NASA Technical Reports Server (NTRS)

Miller, Sharon K.; Sechkar, Edward A.

2012-01-01

Thin film polymers are used in many spacecraft applications for thermal control (multilayer insulation and sunshields), as lightweight structural members (solar array blankets, inflatable/deployable structures) and have been proposed for propulsion (solar sails). Polymers in these applications are often under a tensile load and are directly exposed to the space environment, therefore it is important to understand the effect of stress in combination with the environment on the durability of these polymer films. The purpose of the Polymer Film Tensile Experiment, flown as part of Materials International Space Station Experiment 6 (MISSE 6), was to expose a variety of polymer films to the low Earth orbital environment under both relaxed and tension conditions. This paper describes the results of post flight tensile testing of these samples.

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

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.

Orientation-adjusted anomalous insulator-metal transition in NdNiO3/LaMnO3 bilayers

NASA Astrophysics Data System (ADS)

Pan, S. Y.; Shi, L.; Zhao, J. Y.; Zhou, S. M.; Xu, X. M.

2018-04-01

NdNiO3/LaMnO3 (NNO/LMO) bilayers were epitaxially grown on SrTiO3 (STO) substrates with different orientations by the polymer-assisted deposition technique. A well crystallization quality of the bilayers is confirmed by X-ray diffraction. Two consecutive transitions, an anomalous insulator-metal transition at ˜100 K followed by the typical metal-insulator transition at ˜171 K, are observed in the (001)-oriented NNO/LMO/STO bilayer. The anomalous insulator-metal transition temperature increases to 142 K for the (111)-oriented NNO/LMO/STO bilayer. Meanwhile, the magnetic properties of the NNO/LMO bilayers show an obvious difference with [100] and [111] orientations. Considering the different strain directions and the related oxygen octahedral distortion/rotation, it is suggested that the magnetic changes and the low-temperature anomalous insulator-metal transition in the NNO/LMO bilayers are attributed to the strong interlayer exchange coupling and charge transfer adjusted by the substrate orientation, which can be an effective technique to tune the properties of transition-metal oxide films.

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.

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.

SFG analysis of the molecular structures at the surfaces and buried interfaces of PECVD ultralow-dielectric constant pSiCOH: Reactive ion etching and dielectric recovery

NASA Astrophysics Data System (ADS)

Myers, John N.; Zhang, Xiaoxian; Huang, Huai; Shobha, Hosadurga; Grill, Alfred; Chen, Zhan

2017-05-01

Molecular structures at the surface and buried interface of an amorphous ultralow-k pSiCOH dielectric film were quantitatively characterized before and after reactive ion etching (RIE) and subsequent dielectric repair using sum frequency generation (SFG) vibrational spectroscopy and Auger electron spectroscopy. SFG results indicated that RIE treatment of the pSiCOH film resulted in a depletion of ˜66% of the surface methyl groups and changed the orientation of surface methyl groups from ˜47° to ˜40°. After a dielectric recovery process that followed the RIE treatment, the surface molecular structure was dominated by methyl groups with an orientation of ˜55° and the methyl surface coverage at the repaired surface was 271% relative to the pristine surface. Auger depth profiling indicated that the RIE treatment altered the top ˜25 nm of the film and that the dielectric recovery treatment repaired the top ˜9 nm of the film. Both SFG and Auger profiling results indicated that the buried SiCNH/pSiCOH interface was not affected by the RIE or the dielectric recovery process. Beyond characterizing low-k materials, the developed methodology is general and can be used to distinguish and characterize different molecular structures and elemental compositions at the surface, in the bulk, and at the buried interface of many different polymer or organic thin films.

Orientation dependence of phase diagrams and physical properties in epitaxial Ba0.6Sr0.4TiO3 films

NASA Astrophysics Data System (ADS)

Qiu, J. H.; Zhao, T. X.; Chen, Z. H.; Yuan, N. Y.; Ding, J. N.

2018-04-01

Orientation dependence of phase diagrams and physical properties of Ba0.6Sr0.4TiO3 films are investigated by using a phenomenological Landau-Devonshire theory. New ferroelectric phases, such as the tetragonal a1 phase and the orthorhombic a2 c phase in (110) oriented film and the monoclinic MA phase in (111) oriented film, appear in the "misfit strain-temperature" phase diagrams as compared with (001) oriented film. Moreover, the phase diagrams of (110) and (111) oriented films are more complex than that of (001) oriented film due to the nonlinear coupling terms appeared in the thermodynamic potential. The dielectric and piezoelectric properties largely depend on the misfit strain and orientation. (111) oriented film has the better piezoelectric property than (110) oriented film. Furthermore, the compressive misfit strain is prone to induce the larger piezoelectric property than tensile misfit strain.

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.

Structure-Processing Relationships in Solution Processable Polymer Thin Film Transistors and Small Molecule Bulk Heterojunction Solar Cells

NASA Astrophysics Data System (ADS)

Perez, Louis A.

A regio-regular (RR) conjugated copolymer based on cyclopenta[2,1-b:3,4- b]dithiophene (CDT) and pyridal[2,1,3]thiadiazole (PT) structural units was prepared by using polymerization reactions involving reactants specifically designed to avoid random orientation of the asymmetric PT heterocycle. Compared to its regio-irregular (RI) counterpart, the RR polymer exhibits a two orders of magnitude increase in hole mobility from 0.005 to 0.6 cm2V -1s-1. To probe the reason for this difference in mobility, we examined the crystalline structure and its orientation in thin films of both copolymers as a function of depth via grazing incidence wide angle X-ray scattering (GIWAXS). In the RI film, the pi-pi stacking direction of the crystallites is mainly perpendicular to the substrate normal (edge-on orientation) while in the RR film the crystallites adopt a mixed pi-pi stacking orientation in the center of the film as well as near the interface between the polymer and the dielectric layer. These results demonstrate that control of backbone regularity is another important design criterion to consider in the synthesis and optimization of new conjugated copolymers with asymmetric structural units. Solution processed organic photovoltaic devices (OPVs) have emerged as a promising sustainable energy technology due to their ease of fabrication, potential to enable low-cost manufacturing, and ability to be incorporated onto light-weight flexible substrates. To date, the most efficacious OPV device architecture, the bulk heterojunction (BHJ), consists of a blend of a light-harvesting conjugated organic electron donating molecule and a strong electron-accepting compound (usually a soluble fullerene derivative e.g. [6,6]-phenyl C71 butyric acid methyl ester (PC71BM). BHJ layer morphology, which has been shown to be highly dependent on processing, has a significant effect on OPV performance. It is postulated that optimal BHJ morphologies consist of discrete bicontinuous nanoscale domains of each moiety, on the order of the exciton diffusion length, which extend vertically from each electrode, thereby increasing the surface area of the domains and forming continuous conducting pathways for efficient charge extraction and transfer. An optimal morphology, however, is seldom achieved during film formation; therefore, a number of processing techniques, such as thermal and sol vent annealing, and the addition of solvent additives to the casting solution have been explored to control the morphology in order to attain the multiple structural requirements. Solvent additive processing, a technique that is used in most record performing polymer:fullerene BHJ solar cell devices, involves the addition of small volumes of a high boiling point liquid to the BHJ casting solu- tion. Solvent additive processing, with 1,8-diiodooctane (DIO) as the additive, has recently been employed in solution processable small molecule (SPSM) BHJ systems, showing similar drastic effects on several device metrics and ultimately the power conversion efficiency (PCE). A recent SPSM study delineates how the volume of solvent additive used affects device performance: when 0.4 v/v% of DIO was used, the PCE increased from 1.8 to 7%, while a deterioration in the PCE to less than 1% occurred when only 1 v/v% of DIO was used. Several structural characterization techniques, such as grazing incidence wide and small-angle X-ray scattering (GIWAXS and GISAXS), and energy filtered transmission electron microscopy (EF-TEM), were used to investigate structure-processing-property relationships in additive-treated SPSM BHJ films and were correlated to device performance. Scattering experiments showed that the use of additives had several effects on the structure of the BHJ at multiple length scales: e.g. the number and orientation of SPSM crystallites, different pi-pi stacking distances, and the nano-scale domain size. Additionally, EF-TEM further verified the effect of additives on the domain size and was complemented with tomographic reconstructions to provide a 3D representation of the BHJ morphology due to solvent additive processing. Finally, in situ GIWAXS was also performed to investigate the kinetics of crystallite formation during and shortly after spin-casting. The additive was shown to induce a complex structural evolution effect on the microstructure of SPSMs by inciting the formation of a metastable polymorph and enhanced crystalline quality of the SPSM during and shortly after casting, whereas the non-additive treated SPSM structure was static after initial crystallite formation. The results from this study have important implications for future optimization and design of solvent additive processed SPSM BHJ blends for OPV devices.

Pulsed-Laser Crystallization of Ferroelectric/Piezoelectric Oxide Thin Films

NASA Astrophysics Data System (ADS)

Rajashekhar, Adarsh

Integration of ferroelectric/piezoelectric thin films, such as those of lead zirconate titanate (PZT), with temperature sensitive substrates (complementary metal oxide semiconductors (CMOS), or polymers) would benefit from growth at substrate temperatures below 400°C. However, high temperatures are usually required for obtaining good quality PZT films via conventional routes like rapid thermal processing (>550°C). Those conditions are not compatible either with polymer substrates or completed CMOS circuits and dictate exploration of alternative methods to realize integration with such substrates. In part of this work, factors influencing KrF excimer laser induced crystallization of amorphous sputtered Pb(Zr0.30Ti0.70)O3 thin films at substrate temperatures < 215°C were investigated. (111) Pt/Si substrates were utilized to understand the process window. Laser energy densities studied were in the range 35 - 85 mJ/cm2. The Pb content in the films was varied via the Ar gas pressure (in the range 5 mTorr - 9 mTorr) during sputtering of amorphous films. It was seen that a higher Pb content in the asdeposited films aided nucleation of the perovskite phase. Ozone-containing ambients (10% O3/90% O2) during the annealing promoted the formation of the metastable Pb-rich pyrochlore/fluorite phase, while annealing in pure oxygen produced the perovskite phase at relatively lower annealing laser energy densities. Heterogeneous nucleation from the substrate is favored on utilizing a layer-by-layer growth and crystallization process. Films were also grown on polymers using this method. Ferroelectric switching was demonstrated, but extensive process optimization would be needed to reduce leakage and porosity. Real time laser annealing during growth allows for scaling of the layer-by-layer growth process. A pulsed laser deposition system with in situ laser annealing was thus designed, built, and utilized to grow Pb(Zr 0.52Ti0.48)O3 thin films on a laser crystallized Pb(Zr0.20Ti0.80)O3 seed layer, at a temperature of 370°C. Polycrystalline 1.1 microm thick films exhibited columnar grains with small grain sizes ( 30 nm). The films showed well-saturated hysteresis loops (with a remanent polarization of 25 microC/cm2, and a coercive field of 50 kV/cm) and exhibited loss tangents <2.5% with a permittivity of 730. Film orientation could be controlled via the substrate choice; {111} Pb(Zr0.52Ti0.48)O3 films were grown on oriented (111) Pb(Zr0.30Ti0.70)O3 sol-gel seed layers, while epitaxial {001} films were prepared on (100) SrTiO 3 single crystals. In order to study the microstructure evolution in these films, in situ pulsed-laser annealing was used to grow crystalline lead zirconate titanate (PbZr0.52Ti0.48O3) thin films at a substrate temperature of 370°C on PbZr0.30Ti 0.70O3-buffered platinized silicon substrates. Transmission electron microscopy (TEM) analysis indicated that the films were well crystallized into columnar grains, but with pores segregated at the grain boundaries. Lateral densification of the grain columns was significantly improved by reducing the partial pressure of oxygen from 120 mTorr to 50 mTorr, presumably due to enhanced adatom mobility at the surface accompanying increased bombardment. It was found that varying the fractional annealing duration with respect to the deposition duration produced little effect on lateral grain growth. However, increasing the fractional annealing duration led to shift of 111 PZT X-ray diffraction peaks to higher 2theta values, suggesting residual in-plane tensile stresses in the films. Thermal simulations were used to understand the annealing process. Evolution of the film microstructure is described in terms of transient heating from the pulsed laser determining the nucleation events, while the energy of the arriving species dictates grain growth/coarsening.

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.

Hierarchically Ordered Nanopatterns for Spatial Control of Biomolecules

PubMed Central

2015-01-01

The development and study of a benchtop, high-throughput, and inexpensive fabrication strategy to obtain hierarchical patterns of biomolecules with sub-50 nm resolution is presented. A diblock copolymer of polystyrene-b-poly(ethylene oxide), PS-b-PEO, is synthesized with biotin capping the PEO block and 4-bromostyrene copolymerized within the polystyrene block at 5 wt %. These two handles allow thin films of the block copolymer to be postfunctionalized with biotinylated biomolecules of interest and to obtain micropatterns of nanoscale-ordered films via photolithography. The design of this single polymer further allows access to two distinct superficial nanopatterns (lines and dots), where the PEO cylinders are oriented parallel or perpendicular to the substrate. Moreover, we present a strategy to obtain hierarchical mixed morphologies: a thin-film coating of cylinders both parallel and perpendicular to the substrate can be obtained by tuning the solvent annealing and irradiation conditions. PMID:25363506

Direct monolithic integration of vertical single crystalline octahedral molecular sieve nanowires on silicon

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

Carretero-Genevrier, Adrian; Oro-Sole, Judith; Gazquez, Jaume

2013-12-13

We developed an original strategy to produce vertical epitaxial single crystalline manganese oxide octahedral molecular sieve (OMS) nanowires with tunable pore sizes and compositions on silicon substrates by using a chemical solution deposition approach. The nanowire growth mechanism involves the use of track-etched nanoporous polymer templates combined with the controlled growth of quartz thin films at the silicon surface, which allowed OMS nanowires to stabilize and crystallize. α-quartz thin films were obtained after thermal activated crystallization of the native amorphous silica surface layer assisted by Sr 2+- or Ba 2+-mediated heterogeneous catalysis in the air at 800 °C. These α-quartzmore » thin films work as a selective template for the epitaxial growth of randomly oriented vertical OMS nanowires. Furthermore, the combination of soft chemistry and epitaxial growth opens new opportunities for the effective integration of novel technological functional tunneled complex oxides nanomaterials on Si substrates.« less

Investigation of Aromatic/Aliphatic Polyimides as Dispersants for Single Wall Carbon Nanotubes

NASA Technical Reports Server (NTRS)

Delozier, Donavon M.; Watson, Kent A.; Smith, Joseph G., Jr.; Clancy, Thomas C.; Connell, John W.

2006-01-01

Novel aromatic/aliphatic polyimides were prepared from 2,7-diamino-9,9'- dioctylfluorene (AFDA) and aromatic dianhydrides. Upon investigating the effectiveness of these polyimides for dispersing single wall carbon nanotubes (SWNTs) in solution, three were discovered to disperse SWNTs in N,N-dimethylacetamide (DMAc). Two of these polyimides, one from 3,3',4,4'-oxydiphthalic anhydride (ODPA) and one from symmetric 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA), were used to prepare nanocomposites. Homogeneous polyimide/SWNT suspensions from both polymers were used in the preparation of films and fibers containing up to 1 wt% SWNTs. The samples were thermally treated to remove residual solvent and the films were characterized for SWNT dispersion by optical and high resolution scanning electron microscopy (HRSEM). Electrical and mechanical properties of the films were also determined. Electrospun fibers were examined by HRSEM to characterize SWNT alignment and orientation.

Chromophore Poling in Thin Films of Organic Glasses. 2. Two-Electrode Corona Discharge Setup

NASA Astrophysics Data System (ADS)

Vilitis, O.; Muzikante, I.; Rutkis, M.; Vembris, A.

2012-01-01

In Part 1 of the article we provided description of the corona discharge physics and overview of the methods used for corona poling in thin organic films. Subsequent sections describe comparatively simple technical methods for poling the organic nonlinear optical polymers using a two-electrode (point-to-plate or wire-to-plate) technique. The polarization build-up was studied by the DC positive corona method for poling the nonlinear optical (NLO) polymers. The experimental setup provides the corona discharge current from 0.5 μA up to 3 μA by applying 3 kV - 12 kV voltage to the corona electrode and makes possible selection among the types of corona electrodes (needle, multi-needle, wire, etc.). The results of experimental testing of the poling setup show that at fixed optimal operational parameters of poling - the sample orientation temperature and the discharge current - the corona charging of polymeric materials can successfully be performed applying the two-electrode technique. To study the dynamics of both poling and charge transport processes the three-electrode charging system - a corona triode - should be applied.

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.

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

Ferroelectric and piezoelectric responses of (110) and (001)-oriented epitaxial Pb(Zr{sub 0.52}Ti{sub 0.48})O{sub 3} thin films on all-oxide layers buffered silicon

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

Vu, Hien Thu; Nguyen, Minh Duc, E-mail: minh.nguyen@itims.edu.vn; Inorganic Materials Science

2015-12-15

Graphical abstract: The cross sections show a very dense structure in the (001)-oriented films (c,d), while an open columnar growth structure is observed in the case of the (110)-oriented films (a,b). The (110)-oriented PZT films show a significantly larger longitudinal piezoelectric coefficient (d33{sub ,f}), but smaller transverse piezoelectric coefficient (d31{sub ,f}) than the (001) oriented films. - Highlights: • We fabricate all-oxide, epitaxial piezoelectric PZT thin films on Si. • The orientation of the films can be controlled by changing the buffer layer stack. • The coherence of the in-plane orientation of the grains and grain boundaries affects the ferroelectricmore » properties. • Good cycling stability of the ferroelectric properties of (001)-oriented PZT thin films. The (110)-oriented PZT thin films show a larger d33{sub ,f} but smaller d31{sub ,f} than the (001)-oriented films. - Abstract: Epitaxial ferroelectric Pb(Zr{sub 0.52}Ti{sub 0.48})O{sub 3} (PZT) thin films were fabricated on silicon substrates using pulsed laser deposition. Depending on the buffer layers and perovskite oxide electrodes, epitaxial films with different orientations were grown. (110)-oriented PZT/SrRuO{sub 3} (and PZT/LaNiO{sub 3}) films were obtained on YSZ-buffered Si substrates, while (001)-oriented PZT/SrRuO{sub 3} (and PZT/LaNiO{sub 3}) were fabricated with an extra CeO{sub 2} buffer layer (CeO{sub 2}/YSZ/Si). There is no effect of the electrode material on the properties of the films. The initial remnant polarizations in the (001)-oriented films are higher than those of (110)-oriented films, but it increases to the value of the (001) films upon cycling. The longitudinal piezoelectric d33{sub ,f} coefficients of the (110) films are larger than those of the (001) films, whereas the transverse piezoelectric d31{sub ,f} coefficients in the (110)-films are less than those in the (001)-oriented films. The difference is ascribed to the lower density (connectivity between grains) of the former films.« 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.

Organic Photovoltaic Devices Based on Oriented n-Type Molecular Films Deposited on Oriented Polythiophene Films.

PubMed

Mizokuro, Toshiko; Tanigaki, Nobutaka; Miyadera, Tetsuhiko; Shibata, Yousei; Koganezawa, Tomoyuki

2018-04-01

The molecular orientation of π-conjugated molecules has been reported to significantly affect the performance of organic photovoltaic devices (OPVs) based on molecular films. Hence, the control of molecular orientation is a key issue toward the improvement of OPV performance. In this research, oriented thin films of an n-type molecule, 3,4,9,10-Perylenetetracarboxylic Bisbenzimida-zole (PTCBI), were formed by deposition on in-plane oriented polythiophene (PT) films. Orientation of the PTCBI films was evaluated by polarized UV-vis spectroscopy and 2D-Grazing incidence X-ray diffraction. Results indicated that PTCBI molecules on PT film exhibit nearly edge-on and in-plane orientation (with molecular long axis along the substrate), whereas PTCBI molecules without PT film exhibit neither. OPVs composed of PTCBI molecular film with and without PT were fabricated and evaluated for correlation of orientation with performance. The OPVs composed of PTCBI film with PT showed higher power conversion efficiency (PCE) than that of film without PT. The experiment indicated that in-plane orientation of PTCBI molecules absorbs incident light more efficiently, leading to increase in PCE.

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.

Selective Photophysical Modification on Light-Emitting Polymer Films for Micro- and Nano-Patterning

PubMed Central

Zhang, Xinping; Liu, Feifei; Li, Hongwei

2016-01-01

Laser-induced cross-linking in polymeric semiconductors was utilized to achieve micro- and nano-structuring in thin films. Single- and two-photon cross-linking processes led to the reduction in both the refractive index and thickness of the polymer films. The resultant photonic structures combine the features of both relief- and phase-gratings. Selective cross-linking in polymer blend films based on different optical response of different molecular phases enabled “solidification” of the phase-separation scheme, providing a stable template for further photonic structuring. Dielectric and metallic structures are demonstrated for the fabrication methods using cross-linking in polymer films. Selective cross-linking enables direct patterning into polymer films without introducing additional fabrication procedures or additional materials. The diffraction processes of the emission of the patterned polymeric semiconductors may provide enhanced output coupling for light-emitting diodes or distributed feedback for lasers. PMID:28773248

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.

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.

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.

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

Electrochemical and scanning probe microscopic characterization of spontaneously adsorbed organothiolate monolayers at gold

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

Wong, Sze-Shun Season

1999-12-10

This dissertation presented several results which add to the general knowledge base regarding organothiolates monolayer spontaneously adsorbed at gold films. Common to the body of this work is the use of voltammetric reductive resorption and variants of scanning probe microscopy to gain insight into the nature of the monolayer formation process as well as the resulting interface. The most significant result from this work is the success of using friction force microscopy to discriminate the end group orientation of monolayer chemisorbed at smooth gold surfaces with micrometer resolution (Chapter 4). The ability to detect the differences in the orientational dispositionmore » is demonstrated by the use PDMS polymer stamp to microcontact print an adlayer of n-alkanethiolate of length n in a predefine pattern onto a gold surface, followed by the solution deposition of a n-alkanethiol of n ± 1 to fill in the areas on the gold surface intentionally not coated by the stamping process. These two-component monolayers can be discriminated by using friction force microscopy which detects differences in friction contributed by the differences in the orientation of the terminal groups at surfaces. This success has recently led to the detection of the orientation differences at nanometer scale. Although the substrates examined in this work consisted entirely of smooth gold films, the same test can be performed on other smooth substrates and monolayer materials.« less

Multi-Scale Responses of Liquid Crystals Triggered by Interfacial Assemblies of Cleavable Homopolymers.

PubMed

Kim, Young-Ki; Huang, Yuran; Tsuei, Michael; Wang, Xin; Gianneschi, Nathan C; Abbott, Nicholas L

2018-04-22

Liquid crystals (LCs) offer the basis of stimuli-responsive materials that can amplify targeted molecular events into macroscopic outputs. However, general and versatile design principles are needed to realize the full potential of these materials. To this end, we report the synthesis of two homopolymers with mesogenic side chains that can be cleaved upon exposure to either H 2 O 2 (polymer P1) or UV light (polymer P2). Optical measurements reveal that the polymers dissolve in bulk LC and spontaneously assemble at nematic LC-aqueous interfaces to impose a perpendicular orientation on the LCs. Subsequent addition of H 2 O 2 to the aqueous phase or exposure of the LC to UV was shown to trigger a surface-driven ordering transition to a planar orientation and an accompanying macroscopic optical output. Differences in the dynamics of the response to each stimulus are consistent with sequential processing of P1 at the LC-aqueous interface (H 2 O 2 ) and simultaneous transformation of P2 within the LC (UV). The versatility of the approach is demonstrated by creating stimuli-responsive LCs as films or microdroplets, and by dissolving mixtures of P1 and P2 into LCs to create LC materials that respond to two stimuli. Overall, our results validate a simple and generalizable approach to the rational design of polymers that can be used to program stimuli-responsiveness into LC materials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Improving polymer/nanocrystal hybrid solar cell performance via tuning ligand orientation at CdSe quantum dot surface.

PubMed

Fu, Weifei; Wang, Ling; Zhang, Yanfang; Ma, Ruisong; Zuo, Lijian; Mai, Jiangquan; Lau, Tsz-Ki; Du, Shixuan; Lu, Xinhui; Shi, Minmin; Li, Hanying; Chen, Hongzheng

2014-11-12

Achieving superior solar cell performance based on the colloidal nanocrystals remains challenging due to their complex surface composition. Much attention has been devoted to the development of effective surface modification strategies to enhance electronic coupling between the nanocrystals to promote charge carrier transport. Herein, we aim to attach benzenedithiol ligands onto the surface of CdSe nanocrystals in the "face-on" geometry to minimize the nanocrystal-nanocrystal or polymer-nanocrystal distance. Furthermore, the "electroactive" π-orbitals of the benzenedithiol are expected to further enhance the electronic coupling, which facilitates charge carrier dissociation and transport. The electron mobility of CdSe QD films was improved 20 times by tuning the ligand orientation, and high performance 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):CdSe nanocrystal hybrid solar cells were also achieved, showing a highest power conversion efficiency of 4.18%. This research could open up a new pathway to improve further the performance of colloidal nanocrystal based solar cells.

Viscoelasticity of thin biomolecular films: a case study on nucleoporin phenylalanine-glycine repeats grafted to a histidine-tag capturing QCM-D sensor.

PubMed

Eisele, Nico B; Andersson, Fredrik I; Frey, Steffen; Richter, Ralf P

2012-08-13

Immobilization of proteins onto surfaces is useful for the controlled generation of biomolecular assemblies that can be readily characterized with in situ label-free surface-sensitive techniques. Here we analyze the performance of a quartz crystal microbalance with dissipation monitoring (QCM-D) sensor surface that enables the selective and oriented immobilization of histidine-tagged molecules for morphological and interaction studies. More specifically, we characterize monolayers of natively unfolded nucleoporin domains that are rich in phenylalanine-glycine repeats (FGRDs). An FGRD meshwork is thought to be responsible for the selectivity of macromolecular transport across the nuclear pore complex between the cytosol and the nucleus of living cells. We demonstrate that nucleoporin FGRD films can be formed on His-tag Capturing Sensors with properties comparable to a previously reported immobilization platform based on supported lipid bilayers (SLB). Approaches to extract the film thickness and viscoelastic properties in a time-resolved manner from the QCM-D response are described, with particular emphasis on the practical implementation of viscoelastic modeling and a detailed analysis of the quality and reliability of the fit. By comparing the results with theoretical predictions for the viscoelastic properties of polymer solutions and gels, and experimental data from an atomic force microscopy indentation assay, we demonstrate that detailed analysis can provide novel insight into the morphology and dynamics of FG repeat domain films. The immobilization approach is simple and versatile, and can be easily extended to other His-tagged biomolecules. The data analysis procedure should be useful for the characterization of other ultrathin biomolecular and polymer films.

Origin of vertical orientation in two-dimensional metal halide perovskites and its effect on photovoltaic performance.

PubMed

Chen, Alexander Z; Shiu, Michelle; Ma, Jennifer H; Alpert, Matthew R; Zhang, Depei; Foley, Benjamin J; Smilgies, Detlef-M; Lee, Seung-Hun; Choi, Joshua J

2018-04-06

Thin films based on two-dimensional metal halide perovskites have achieved exceptional performance and stability in numerous optoelectronic device applications. Simple solution processing of the 2D perovskite provides opportunities for manufacturing devices at drastically lower cost compared to current commercial technologies. A key to high device performance is to align the 2D perovskite layers, during the solution processing, vertical to the electrodes to achieve efficient charge transport. However, it is yet to be understood how the counter-intuitive vertical orientations of 2D perovskite layers on substrates can be obtained. Here we report a formation mechanism of such vertically orientated 2D perovskite in which the nucleation and growth arise from the liquid-air interface. As a consequence, choice of substrates can be liberal from polymers to metal oxides depending on targeted application. We also demonstrate control over the degree of preferential orientation of the 2D perovskite layers and its drastic impact on device performance.

Chemically modified graphene/polyimide composite films based on utilization of covalent bonding and oriented distribution.

PubMed

Huang, Ting; Lu, Renguo; Su, Chao; Wang, Hongna; Guo, Zheng; Liu, Pei; Huang, Zhongyuan; Chen, Haiming; Li, Tongsheng

2012-05-01

Herein, we have developed a rather simple composite fabrication approach to achieving molecular-level dispersion and planar orientation of chemically modified graphene (CMG) in the thermosetting polyimide (PI) matrix as well as realizing strong adhesion at the interfacial regions between reinforcing filler and matrix. The covalent adhesion of CMG to PI matrix and oriented distribution of CMG were carefully confirmed and analyzed by detailed investigations. Combination of covalent bonding and oriented distribution could enlarge the effectiveness of CMG in the matrix. Efficient stress transfer was found at the CMG/PI interfaces. Significant improvements in the mechanical performances, thermal stability, electrical conductivity, and hydrophobic behavior were achieved by addition of only a small amount of CMG. Furthermore, it is noteworthy that the hydrophilic-to-hydrophobic transition and the electrical percolation were observed at only 0.2 wt % CMG in this composite system. This facile methodology is believed to afford broad application potential in graphene-based polymer nanocomposites, especially other types of high-performance thermosetting systems.

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

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.

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

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.

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

Molecular Design for Preparation of Hexagonal-Ordered Porous Films Based on Side-chain Type Liquid-Crystalline Star Polymer.

PubMed

Naka, Yumiko; Takayama, Hiromu; Koyama, Teruhisa; Le, Khoa V; Sasaki, Takeo

2018-05-02

Fabrication of regularly porous films by the breath-figure method has attracted much attention. The simple, low-cost technique uses the condensation of water droplets to produce these structures, but the phenomenon itself is complex, requiring control over many interacting parameters that change throughout the process. Developing a unified understanding for the molecular design of polymers to prepare ordered porous films is challenging, but required for further advancements. In this article, the effects of the chemical structure of polymers in the breath-figure technique were systematically explored using side-chain type liquid-crystalline (LC) star polymers. The formation of porous films was affected by the structure of the polymers. Although the entire film surface of poly(11-[4-(4-cyanobiphenyl)oxy]undecyl methacrylate) (P11CB) had a hexagonal ordered porous structure over a certain Mn value, regularly arranged holes did not easily form in poly(methyl methacrylate) (PMMA), even though the main chain of PMMA is similar to that of P11CB. Comparing P11CB and poly(11-[(1,1'-biphenyl)-4-yloxy]undecyl methacrylate) (P11B) (P11CB without cyano groups) showed that the local polar groups in hydrophobic polymers promoted the formation of ordered porous films. No holes formed in poly(4-cyanobiphenyl methacrylate) (P0CB) (P11CB without alkyl spacers) films due to its hydrophilicity. The introduction of alkyl chains in P0CB allowed the preparation of honeycomb-structured films by increasing the internal tension. However, alkyl chains in the side chain alone did not result in a porous structure, as in the case of poly(11-[(1,1'-biphenyl)-4-yloxy]undecyl methacrylate) (P11). Aromatic rings are also required to increase the Tg and improve film formability. In the present study, suitable molecular designs of polymers were found, specifically hydrophobic polymers with local polar groups, to form a regularly porous structure. Development of clear guidelines for the molecular design of polymers is the subject of our current research, which will enable the fabrication of porous films using various functional polymers.

High conversion efficiency distributed feedback laser from a dye-doped holographic transmission grating

NASA Astrophysics Data System (ADS)

Liu, Lijuan; Zhang, Guiyang; Kong, Xiaobo; Liu, Yonggang; Xuan, Li

2018-01-01

A high conversion efficiency distributed feedback (DFB) laser from a dye-doped holographic polymer dispersed liquid crystal (HPDLC) transmission grating structure was reported. The alignment polyimide (PI) films were used to control the orientation of the phase separated liquid crystals (LCs) to increase the refractive index difference between the LC and the polymer, so it can provide better light feedback. The lasing wavelength located at 645.8 nm near the maximum of the amplified spontaneous emission (ASE) spectrum with the lowest threshold 0.97 μ J/pulse and the highest conversion efficiency 1.6% was obtained. The laser performance under electric field were also investigated and illustrated. The simple configuration, one-step fabrication organic dye laser shows the potential to realize ultra-low cost plastic lasers.

Experimental study of the polymer powder film thickness uniformity produced by the corona discharge

NASA Astrophysics Data System (ADS)

Fazlyyyakhmatov, Marsel

2017-01-01

The results of an experimental study of the polymer powder film thickness uniformity are presented. Polymer powder films are produced by the electrostatic field of corona discharge. Epoxy and epoxy-polyester powder films with thickness in the range of 30-120 microns are studied. Experimentally confirmed possibility of using these coatings as protective matching layer of piezoceramic transducers at frequencies of 0.5-15 MHz.

Direct Printing of Graphene onto Plastic Substrates.

NASA Astrophysics Data System (ADS)

Hines, Daniel; Lock, Evgeniya; Walton, Scott; Baraket, Mira; Laskoski, Matthew; Mulvaney, Shawn; Sheehan, Paul; Lee, Woo; Robinson, Jeremy

2011-03-01

Graphene films have been synthesized on metal foils using CVD growth and have the potential to be compatible with roll-to-roll printing. To be usable in electronic devices, these films need to be removed from the metallic substrate. Currently this is accomplished by spin coating a polymer film over the graphene and chemically etching away the metal substrate. We have developed a direct printing method that allows graphene films to be printed off the metal substrate onto a polymer substrate. This printing process does not generate chemical waste, is compatible with roll-to-toll processing and renders the metal foil reusable. Adhesion of the graphene film to the polymer substrate is established by attaching perfluorophenylazides (PFPA) azide linker molecules to a plasma activated polymer surface. The transfer printing was performed by placing the PFPA treated polymer surface in contact with a graphene covered Cu foil and heating under pressure. Graphene films successfully printed onto a polystyrene substrate have been characterized by Raman spectroscopy and electrical measurements revealed the presence of Gr on the polymer surface. Details of the printing process along with characteristics of the graphene film after printing will be presented.

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.

Characterization of Homopolymer and Polymer Blend Films by Phase Sensitive Acoustic Microscopy

NASA Astrophysics Data System (ADS)

Ngwa, Wilfred; Wannemacher, Reinhold; Grill, Wolfgang

2003-03-01

CHARACTERIZATION OF HOMOPOLYMER AND POLYMER BLEND FILMS BY PHASE SENSITIVE ACOUSTIC MICROSCOPY W Ngwa, R Wannemacher, W Grill Institute of Experimental Physics II, University of Leipzig, 04103 Leipzig, Germany Abstract We have used phase sensitive acoustic microscopy (PSAM) to study homopolymer thin films of polystyrene (PS) and poly (methyl methacrylate) (PMMA), as well as PS/PMMA blend films. We show from our results that PSAM can be used as a complementary and highly valuable technique for elucidating the three-dimensional (3D) morphology and micromechanical properties of thin films. Three-dimensional image acquisition with vector contrast provides the basis for: complex V(z) analysis (per image pixel), 3D image processing, height profiling, and subsurface image analysis of the polymer films. Results show good agreement with previous studies. In addition, important new information on the three dimensional structure and properties of polymer films is obtained. Homopolymer film structure analysis reveals (pseudo-) dewetting by retraction of droplets, resulting in a morphology that can serve as a starting point for the analysis of polymer blend thin films. The outcome of confocal laser scanning microscopy studies, performed on the same samples are correlated with the obtained results. Advantages and limitations of PSAM are discussed.

Heterogeneous nucleation of polymorphs on polymer surfaces: polymer-molecule interactions using a heterogeneous dielectric solvation model.

PubMed

Wahlberg, Nanna; Madsen, Anders Ø; Mikkelsen, Kurt V

2018-06-09

We have investigated the mechanism of the nucleation of acetaminophen on poly(methyl-methacrylate) and poly(vinyl-acetate) utilizing a combination of quantum mechanical computations and electrostatic models. We have used a heterogeneous dielectric solvation model to determine the stability of different orientations of acetaminophen on polymer surfaces. We find that for the nucleation of acetaminophen on the polymer surfaces in vacuum, the most stable orientation is a flat orientation. For the nucleation process in solution where acetaminophen and the polymer surface are surrounded by a solvent, we find that the heterogeneous dielectric solvation model predicts that a sideways orientation is the most stable orientation.

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

Modeling electrical response of polymer-coated SAW resonators by equivalent circuit representation.

PubMed

Kshetrimayum, Roshan; Yadava, R D S; Tandon, R P

2011-07-01

The paper presents an equivalent circuit model of the polymer coated surface acoustic wave (SAW) resonators by combining coupling-of-mode (COM) description of SAW resonators and perturbation calculation of SAW propagation under polymer loading. An expression for the motional load produced by polymer coating is deduced in terms of COM parameters and polymer characteristics. In addition, expressions for the shifts in resonance frequency and attenuation due to polymer loading are obtained. Simulation results are presented for one-port and two-port resonator devices coated with viscoelastic thin polymer film. The influence of polymer film on resonator response is studied with regard to variations in film thickness and shear modulus. The model simplifies understanding of polymer-coated SAW sensors. Copyright © 2010 Elsevier B.V. All rights reserved.

Piezoresistivity of mechanically drawn single-walled carbon nanotube (SWCNT) thin films-: mechanism and optimizing principle

NASA Astrophysics Data System (ADS)

Obitayo, Waris

The individual carbon nanotube (CNT) based strain sensors have been found to have excellent piezoresistive properties with a reported gauge factor (GF) of up to 3000. This GF on the other hand, has been shown to be structurally dependent on the nanotubes. In contrast, to individual CNT based strain sensors, the ensemble CNT based strain sensors have very low GFs e.g. for a single walled carbon nanotube (SWCNT) thin film strain sensor, GF is ~1. As a result, studies which are mostly numerical/analytical have revealed the dependence of piezoresistivity on key parameters like concentration, orientation, length and diameter, aspect ratio, energy barrier height and Poisson ratio of polymer matrix. The fundamental understanding of the piezoresistive mechanism in an ensemble CNT based strain sensor still remains unclear, largely due to discrepancies in the outcomes of these numerical studies. Besides, there have been little or no experimental confirmation of these studies. The goal of my PhD is to study the mechanism and the optimizing principle of a SWCNT thin film strain sensor and provide experimental validation of the numerical/analytical investigations. The dependence of the piezoresistivity on key parameters like orientation, network density, bundle diameter (effective tunneling area), and length is studied, and how one can effectively optimize the piezoresistive behavior of a SWCNT thin film strain sensors. To reach this goal, my first research accomplishment involves the study of orientation of SWCNTs and its effect on the piezoresistivity of mechanically drawn SWCNT thin film based piezoresistive sensors. Using polarized Raman spectroscopy analysis and coupled electrical-mechanical test, a quantitative relationship between the strain sensitivity and SWCNT alignment order parameter was established. As compared to randomly oriented SWCNT thin films, the one with draw ratio of 3.2 exhibited ~6x increase on the GF. My second accomplishment involves studying the influence of the network density on the piezoresistivity of mechanically drawn SWCNT thin films. Mechanically drawn SWCNT thin films with different layer (or thickness) e.g. 1-layer, 3-layer, 10-layer and 20-layer SWCNT thin films were prepared to understand the variation of SWCNT network density as well as the alignment of SWCNTs on the strain sensitivity. The less entangled SWCNT bundles observed in the sparse network density (1- layer and 3-layer SWCNT thin films) allows for easy alignment and the best gauge factors. As compared to the randomly oriented SWCNT thin films, the one with draw ratio of 3.2 exhibited ~8x increase on the GF for the 1-layer SWCNT thin films while the 20-layer SWCNT thin films exhibited ~3x increase in the GF. My third accomplishment examines the effect of SWCNT bundles with different diameters on the piezoresistive behavior of mechanically drawn SWCNT thin films. SWCNT thin film network of sparse morphology (1-layer) with different bundle sizes were prepared by varying the sonication duration e.g. S0.5hr, S4hr, S10hr and S20hr and using spraying coating. The GF increased by a factor of ~10 when the randomly oriented SWCNT thin film was stretched to a draw ratio of 3.2 for the S0.5hr SWCNT thin films and by a factor of ~2 for the S20hr SWCNT thin films. Three main mechanisms were attributed to this behavior e.g. effect of concentration of exfoliated nanotubes, bundle reduction due to mechanical stretching, and influence of bundle length on the alignment of SWCNTs. Furthermore, information about the average length and length distribution is very essential when investigating the influence of individual nanotube length on the strain sensitivity. With that in mind, we would use our previously developed preparative ultracentrifuge method (PUM), and our newly developed gel electrophoresis and simultaneous Raman and photoluminescence spectroscopy (GEP-SRSPL) to characterize the average length and length distribution of individual SWCNTs respectively.

Preliminary biocompatibility experiment of polymer films for laser-assisted tissue welding.

PubMed

Sorg, Brian S; Welch, Ashley J

2003-01-01

The purpose of this study was to examine the impact of a polymer film for liquid solder strength reinforcement on the short term healing of a wound closed by laser-tissue soldering. Full thickness incisions created on the dorsum of Sprague-Dawley rats were closed by laser-tissue soldering: albumin solder with Indocyanine Green (ICG) dye was inserted between the incision edges and photothermally coagulated with a diode laser. A poly(DL-lactic-co-glycolic acid) (PLGA) polymer film was implanted subcutaneously in the bottom of the incision (controls had no film). Specimens were harvested at 0, 3, 7, and 14 days for breaking strength testing and histological analysis. Breaking strengths of the controls at 0 and 14 days were statistically stronger than the specimens with the implanted films (t-test, P < 0.05). A slight difficulty in apposing the wound edges due to the film presence may have contributed to the low acute strengths. Interference with the wound contraction process by the films possibly contributed to the lower breaking strength at 14 days. Wound histology indicated a mild foreign body reaction to the polymer film material. The polymer film was well tolerated by the tissue, and the tissue response to the material was consistent with that seen in the literature. The breaking strength differences between control and film-implanted specimens at 0 and 14 days were probably the result of mechanical complications (tissue apposition and wound contraction) due to the presence of the film, and not due to the film material itself. The use of polymer film patches for liquid solder reinforcement and breaking strength enhancement may have certain application specific issues that need to be addressed. Strategies to account for these issues require further research. Copyright 2003 Wiley-Liss, Inc.

In situ synthesis of metal nanoparticles in polymer matrix and their optical limiting applications.

PubMed

Porel, S; Venkatram, N; Rao, D Narayana; Radhakrishnan, T P

2007-06-01

We present an overview of the simple and environmentally benign protocol we have developed recently, for the in situ generation of metal nanoparticles inside polymer films by mild thermal annealing, leading to free-standing as well as supported thin films of nanoparticle-embedded polymer. The fabrication chemistry is discussed and spectroscopic/microscopic characterizations of silver and gold nanoparticles in poly(vinyl alcohol) film are presented. Optical limiting characteristics of the silver-polymer system are investigated in detail and preliminary results for the gold-polymer system are reported.

Study of Polymer Crystallization by Physical Vapor Deposition

NASA Astrophysics Data System (ADS)

Jeong, Hyuncheol

When a polymer is confined under the submicron length scale, confinement size and interfaces can significantly impact the crystallization kinetics and resulting morphology. The ability to tune the morphology of confined polymer systems is of critical importance for the development of high-performance polymer microelectronics. The wisdom from the research on confined crystallization suggests that it would be beneficial to have a processing route in which the crystallization of polymers is driven by interface and temperature effects at a nanometer-scale confinement. In practice, for atomic and small-molecular systems, physical vapor deposition (PVD) has been recognized as the most successful processing route for the precise control of the film structure at surface utilizing confinement effects. While standard PVD technologies are not generally applicable to the deposition of the chemically fragile macromolecules, the development of matrix-assisted pulsed laser evaporation (MAPLE) now enables the non-destructive PVD of high-molecular weight polymers. In this thesis work, we investigated the use of MAPLE for the precise control of the crystallization of polymer films at a molecular level. We also sought to decipher the rules governing the crystallization of confined polymers, by using MAPLE as a tool to form confined polymer systems onto substrates with a controlled temperature. We first explored the early stages of film growth and crystallization of poly(ethylene oxide) (PEO) at the substrate surface formed by MAPLE. The unique mechanism of film formation in MAPLE, the deposition of submicron-sized polymer droplets, allowed for the manifestation of confinement and substrate effects in the crystallization of MAPLE-deposited PEO. Furthermore, we also focused on the property of the amorphous PEO film formed by MAPLE, showing the dependence of polymer crystallization kinetics on the thermal history of the amorphous phase. Lastly, we probed how MAPLE processing affected the semi-crystalline structure in MAPLE-deposited polyethylene (PE) films. Depositing PE at various temperatures remarkably allowed for the tunability of the melting temperature and crystallinity of the PE films, thus manipulating the semi-crystalline structure. By comparing the structure of PE formed by different processing routes, i.e., MAPLE and melt-crystallization, we discussed how processing routes affect the development of semi-crystalline phase in polymer films.

Photoelectrochemical electrodes

NASA Technical Reports Server (NTRS)

Williams, R. M.; Rembaum, A. (Inventor)

1983-01-01

The surface of a moderate band gap semiconductor such as p-type molybdenum sulfide is modified to contain an adherent film of charge mediating ionene polymer containing an electroactive unit such as bipyridimium. Electron transport between the electrode and the mediator film is favorable and photocorrosion and recombination processes are suppressed. Incorporation of particles of catalyst such as platinum within the film provides a reduction in overvoltage. The polymer film is readily deposited on the electrode surface and can be rendered stable by ionic or addition crosslinking. Catalyst can be predispersed in the polymer film or a salt can be impregnated into the film and reduced therein.

Controlled Release of Antimicrobial ClO2 Gas from a Two-Layer Polymeric Film System.

PubMed

Bai, Zhifeng; Cristancho, Diego E; Rachford, Aaron A; Reder, Amy L; Williamson, Alexander; Grzesiak, Adam L

2016-11-16

We report a two-component label system comprising a chlorite-containing polymer film and an acid-containing polymer film that can release antimicrobial ClO 2 gas upon adhering the two films together to enable a reaction of the chlorite and acid under moisture exposure. The chlorite-containing film comprises a commercial acrylate-based pressure-sensitive adhesive polymer impregnated with sodium chlorite. The acid-containing film comprises a commercial poly(vinyl alcohol) polymer loaded with tartaric acid. Both of the films were prepared on low ClO 2 -absorbing substrate films from stable aqueous systems of the polymers with high reagent loading. Rapid and sustained releases of significant amounts of ClO 2 gas from the label system were observed in an in situ quantification system using UV-vis spectroscopy. It was found that the ClO 2 release is slower at a lower temperature and can be accelerated by moisture in the atmosphere and the films. Controlled release of ClO 2 gas from the label system was demonstrated by tailoring film composition and thickness. A model was developed to extract release kinetics and revealed good conversions of the label system. This two-component system can potentially be applied as a two-part label without premature release for applications in food packaging.

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

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.

One-step preparation of antimicrobial silver nanoparticles in polymer matrix

NASA Astrophysics Data System (ADS)

Lyutakov, O.; Kalachyova, Y.; Solovyev, A.; Vytykacova, S.; Svanda, J.; Siegel, J.; Ulbrich, P.; Svorcik, V.

2015-03-01

Simple one-step procedure for in situ preparation of silver nanoparticles (AgNPs) in the polymer thin films is described. Nanoparticles (NPs) were prepared by reaction of N-methyl pyrrolidone with silver salt in semi-dry polymer film and characterized by transmission electron microscopy, XPS, and UV-Vis spectroscopy techniques. Direct synthesis of NPs in polymer has several advantages; even though it avoids time-consuming NPs mixing with polymer matrix, uniform silver distribution in polymethylmethacrylate (PMMA) films is achieved without necessity of additional stabilization. The influence of the silver concentration, reaction temperature and time on reaction conversion rate, and the size and size-distribution of the AgNPs was investigated. Polymer films doped with AgNPs were tested for their antibacterial activity on Gram-negative bacteria. Antimicrobial properties of AgNPs/PMMA films were found to be depended on NPs concentration, their size and distribution. Proposed one-step synthesis of functional polymer containing AgNPs is environmentally friendly, experimentally simple and extremely quick. It opens up new possibilities in development of antimicrobial coatings with medical and sanitation applications.

Organometallic Polymeric Conductors

NASA Technical Reports Server (NTRS)

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. The highest conductivities reported (approximately 4/Scm) were achieved with polythiophene in a polystyrene host polymer. The best films using a polyamide as base polymer were four orders of magnitude less conductive than the polystyrene films. The authors suggested that this was because polyimides were unable to swell sufficiently for infiltration of monomer as in the polystyrene. It was not clear, however, if the different conductivities obtained were merely the result of differing oxidation conditions. Oxidation time, temperature and oxidant concentration varied widely among the studies.

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.

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.

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.

Sub-10-nm patterning via directed self-assembly of block copolymer films with a vapour-phase deposited topcoat

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

Suh, Hyo Seon; Kim, Do Han; Moni, Priya

2017-03-27

Directed self-assembly (DSA) of the domain structure in block copolymer (BCP) thin films is a promising approach for sub-10-nm surface patterning. DSA requires the control of interfacial properties on both interfaces of a BCP film to induce the formation of domains that traverse the entire film with a perpendicular orientation. Here we show a methodology to control the interfacial properties of BCP films that uses a polymer topcoat deposited by initiated chemical vapour deposition (iCVD). The iCVD topcoat forms a crosslinked network that grafts to and immobilizes BCP chains to create an interface that is equally attractive to both blocksmore » of the underlying copolymer. The topcoat, in conjunction with a chemically patterned substrate, directs the assembly of the grating structures in BCP films with a half-pitch dimension of 9.3 nm. As the iCVD topcoat can be as thin as 7 nm, it is amenable to pattern transfer without removal. As a result, the ease of vapour-phase deposition, applicability to high-resolution BCP systems and integration with pattern-transfer schemes are attractive properties of iCVD topcoats for industrial applications.« less

Effect of hydrated salts on the microstructure and phase transformation of poly(vinylidenefluoride-hexafluoropropylene) composites

NASA Astrophysics Data System (ADS)

Yuennan, Jureeporn; Sukwisute, Pisan; Muensit, Nantakan

2018-05-01

The present work has investigated a means of fabricating porous, β phase P(VDF-HFP) film by adding two kinds of hydrated metal salts. Without the use of mechanical stretching or electrical poling treatments, MgCl2 · 6H2O and AlCl3 · 6H2O are found to induce the formation of β phase crystals in porous film derived from the solution casting method. Trivalent Al ions have been found to effectively promote the self-oriented β phase of the P(VDF-HFP) film greater than divalent Mg ions. The overall β content is achieved about 38% and 42% for adding 0.25 wt% Mg- and Al-salts, respectively. The average pore sizes and surface roughness of porous P(VDF-HFP) films are increased with increasing salt concentration. The dielectric constant of about 5 for pure P(VDF-HFP) film (at 100 Hz) has been boosted up to 13–19 when adding the salts. In addition, the P(VDF-HFP) films filled with Al-salt exhibit the largest piezoelectric coefficient of 20 pC/N. Thus, the modified polymers are one of candidate materials for using in dielectric and piezoelectric applications.

Plastic Deformation as a Means to Achieve Stretchable Polymer Semiconductors

NASA Astrophysics Data System (ADS)

O'Connor, Brendan

Developing intrinsically stretchable semiconductors will seamlessly transition traditional devices into a stretchable platform. Polymer semiconductors are inherently soft materials due to the weak van der Waal intermolecular bonding allowing for flexible devices. However, these materials are not typically stretchable and when large strains are applied they either crack or plastically deform. Here, we study the use of repeated plastic deformation as a means of achieving stretchable films. In this talk, critical aspects of polymer semiconductor material selection, morphology and interface properties will be discussed that enable this approach of achieving stretchable films. We show that one can employ high performance donor-acceptor polymer semiconductors that are typically brittle through proper polymer blending to significantly increase ductility to achieve stretchable films. We demonstrate a polymer blend film that can be repeatedly deformed over 65%, while maintaining charge mobility consistently above 0.15 cm2/Vs. During the stretching process we show that the films follow a well-controlled repeated deformation pattern for over 100 stretching cycles.

Chlorination of Side Chains: A Strategy for Achieving a High Open Circuit Voltage Over 1.0 V in Benzo[1,2-b:4,5-b']dithiophene-Based Non-Fullerene Solar Cells

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

Chao, Pengjie; Mu, Zhao; Wang, Huan

Here, a benzo[1,2-b:4,5-b']dithiophene-based donor material with chlorine atoms substituted on its side chains, named PBClT, was designed and developed for application in non-fullerene solar cells to enhance the open-circuit voltage ( V oc) without decreasing charge carrier transfer in the corresponding blend films. The results demonstrated that the chlorinated PBClT polymer was an efficient donor in non-fullerene polymer solar cells (PSCs) and exhibited a blue-shifted absorbance, resulting in more complementary light absorption with non-fullerene acceptors, such as ITIC. In addition, the chlorine substitution decreased the HOMO level of PBClT, and as a result, the V oc of the corresponding solarmore » cell increased dramatically to 1.01 V, which is much higher than that of the non-chlorine analog, PTB7-Th, with a V oc of approximately 0.82 V. The 2D-GIWAX results illustrated that the PBClT/ITIC blend film exhibited a “face-on” orientation, which suggested that the chlorine substituents on the side chains favored π-π stacking in the direction perpendicular to the electron flow in photovoltaic devices. Furthermore, the PBClT/ITIC blend film showed a π-π stacking distance of 3.85 Å, which was very close to that of its non-chlorine analog blend film with a distance of approximately 3.74 Å. Based on this result, the introduction of multiple chlorine atoms on the conjugated side chains not only adjusted the energy level of the low-band-gap polymer through the electron withdrawing ability of the chlorine atoms but also subtly avoided obvious morphological changes that could result from strong steric hindrance in the main chain of the polymers. The PBClT/ITIC-based PSCs exhibited a maximum PCE of 8.46% with a V oc of 1.01 V, which is an increase in the PCE of approximately 22% compared to the PTB7-Th-based device based on our parallel experiments.« less

Chlorination of Side Chains: A Strategy for Achieving a High Open Circuit Voltage Over 1.0 V in Benzo[1,2-b:4,5-b']dithiophene-Based Non-Fullerene Solar Cells

DOE PAGES

Chao, Pengjie; Mu, Zhao; Wang, Huan; ...

2018-04-23

Here, a benzo[1,2-b:4,5-b']dithiophene-based donor material with chlorine atoms substituted on its side chains, named PBClT, was designed and developed for application in non-fullerene solar cells to enhance the open-circuit voltage ( V oc) without decreasing charge carrier transfer in the corresponding blend films. The results demonstrated that the chlorinated PBClT polymer was an efficient donor in non-fullerene polymer solar cells (PSCs) and exhibited a blue-shifted absorbance, resulting in more complementary light absorption with non-fullerene acceptors, such as ITIC. In addition, the chlorine substitution decreased the HOMO level of PBClT, and as a result, the V oc of the corresponding solarmore » cell increased dramatically to 1.01 V, which is much higher than that of the non-chlorine analog, PTB7-Th, with a V oc of approximately 0.82 V. The 2D-GIWAX results illustrated that the PBClT/ITIC blend film exhibited a “face-on” orientation, which suggested that the chlorine substituents on the side chains favored π-π stacking in the direction perpendicular to the electron flow in photovoltaic devices. Furthermore, the PBClT/ITIC blend film showed a π-π stacking distance of 3.85 Å, which was very close to that of its non-chlorine analog blend film with a distance of approximately 3.74 Å. Based on this result, the introduction of multiple chlorine atoms on the conjugated side chains not only adjusted the energy level of the low-band-gap polymer through the electron withdrawing ability of the chlorine atoms but also subtly avoided obvious morphological changes that could result from strong steric hindrance in the main chain of the polymers. The PBClT/ITIC-based PSCs exhibited a maximum PCE of 8.46% with a V oc of 1.01 V, which is an increase in the PCE of approximately 22% compared to the PTB7-Th-based device based on our parallel experiments.« less

Hidden Gratings in Holographic Liquid Crystal Polymer-Dispersed Liquid Crystal Films.

PubMed

De Sio, Luciano; Lloyd, Pamela F; Tabiryan, Nelson V; Bunning, Timothy J

2018-04-18

Dynamic diffraction gratings that are hidden in the field-off state are fabricated utilizing a room-temperature photocurable liquid crystal (LC) monomer and nematic LC (NLC) using holographic photopolymerization techniques. These holographic LC polymer-dispersed LCs (HLCPDLCs) are hidden because of the refractive index matching between the LC polymer and the NLC regions in the as-formed state (no E-field applied). Application of a moderate E-field (5 V/μm) generates a refractive index mismatch because of the NLC reorientation (along the E-field) generating high-diffraction efficiency transmission gratings. These dynamic gratings are characterized by morphological, optical, and electrooptical techniques. They exhibit a morphology made of oriented LC polymer regions (containing residual NLC) alternating with a two-phase region of an NLC and LC polymer. Unlike classic holographic polymer-dispersed LC gratings formed with a nonmesogenic monomer, there is index matching between the as-formed alternating regions of the grating. These HLCPDLCs exhibit broad band and high diffraction efficiency (≈90%) at the Bragg angle, are transparent to white light across the visible range because of the refractive index matching, and exhibit fast response times (1 ms). The ability of HLCPDLCs not to consume electrical power in the off state opens new possibilities for the realization of energy-efficient switchable photonic devices.

Effects of polymer-nanoparticle interactions on the viscosity of unentangled polymers under extreme nanoconfinement during capillary rise infiltration.

PubMed

Hor, Jyo Lyn; Wang, Haonan; Fakhraai, Zahra; Lee, Daeyeon

2018-03-28

We explore the effect of confinement and polymer-nanoparticle interactions on the viscosity of unentangled polymers undergoing capillary rise infiltration (CaRI) in dense packings of nanoparticles. In CaRI, a polymer is thermally induced to wick into the dense packings of nanoparticles, leading to the formation of polymer-infiltrated nanoparticle films, a new class of thin film nanocomposites with extremely high concentrations of nanoparticles. To understand the effect of this extreme nanoconfinement, as well as polymer-nanoparticle interactions on the polymer viscosity in CaRI films, we use two polymers that are known to have very different interactions with SiO2 nanoparticles. Using in situ spectroscopic ellipsometry, we monitor the polymer infiltration process, from which we infer the polymer viscosity based on the Lucas-Washburn model. Our results suggest that physical confinement increases the viscosity by approximately two orders of magnitude. Furthermore, confinement also increases the glass transition temperature of both polymers. Thus, under extreme nanoconfinement, the physical confinement has a more significant impact than the polymer-nanoparticle interactions on the viscosity of unentangled polymers, measured through infiltration dynamics, as well as the glass transition temperature. These findings will provide fundamental frameworks for designing processes to enable the fabrication of CaRI nanocomposite films with a wide range of nanoparticles and polymers.

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.

Conjugation of bioactive groups to poly(lactic acid) and poly[(lactic acid)-co-(glycolic acid)] films.

PubMed

Prime, Emma L; Cooper-White, Justin J; Qiao, Greg G

2007-12-06

A novel PLA-based polymer containing reactive pendent ketone or hydroxyl groups was synthesized by the copolymerization of L-lactide with epsilon-caprolactone-based monomers. The polymer was activated with NPC, resulting in an amine-reactive polymer which was then cast into thin polymeric films, either alone or as part of a blend with PLGA, before immersion into a solution of the cell adhesion peptide GRGDS in PBS buffer allowed for conjugation of GRGDS to the film surfaces. Subsequent 3T3 fibroblast cell adhesion studies demonstrated an increase in cellular adhesion and spreading over films cast from unmodified PLGA. Hence the new polymer can be used to obtain covalent linkage of amine-containing molecules to polymer surfaces.

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.

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.

Retention of Antibacterial Activity in Geranium Plasma Polymer Thin Films

PubMed Central

Al-Jumaili, Ahmed; Bazaka, Kateryna

2017-01-01

Bacterial colonisation of biomedical devices demands novel antibacterial coatings. Plasma-enabled treatment is an established technique for selective modification of physicochemical characteristics of the surface and deposition of polymer thin films. We investigated the retention of inherent antibacterial activity in geranium based plasma polymer thin films. Attachment and biofilm formation by Staphylococcus aureus, Pseudomonas aeruginosa, and Escherichia coli was significantly reduced on the surfaces of samples fabricated at 10 W radio frequency (RF) power, compared to that of control or films fabricated at higher input power. This was attributed to lower contact angle and retention of original chemical functionality in the polymer films fabricated under low input power conditions. The topography of all surfaces was uniform and smooth, with surface roughness of 0.18 and 0.69 nm for films fabricated at 10 W and 100 W, respectively. Hardness and elastic modules of films increased with input power. Independent of input power, films were optically transparent within the visible wavelength range, with the main absorption at ~290 nm and optical band gap of ~3.6 eV. These results suggest that geranium extract-derived polymers may potentially be used as antibacterial coatings for contact lenses. PMID:28902134

Potential of far-ultraviolet absorption spectroscopy as a highly sensitive qualitative and quantitative analysis method for polymer films, part I: classification of commercial food wrap films.

PubMed

Sato, Harumi; Higashi, Noboru; Ikehata, Akifumi; Koide, Noriko; Ozaki, Yukihiro

2007-07-01

The aim of the present study is to propose a totally new technique for the utilization of far-ultraviolet (UV) spectroscopy in polymer thin film analysis. Far-UV spectra in the 120-300 nm region have been measured in situ for six kinds of commercial polymer wrap films by use of a novel type of far-UV spectrometer that does not need vacuum evaporation. These films can be straightforwardly classified into three groups, polyethylene (PE) films, polyvinyl chloride (PVC) films, and polyvinylidene chloride (PVDC) films, by using the raw spectra. The differences in the wavelength of the absorption band due to the sigma-sigma* transition of the C-C bond have been used for the classification of the six kinds of films. Using this method, it was easy to distinguish the three kinds of PE films and to separate the two kinds of PVDC films. Compared with other spectroscopic methods, the advantages of this technique include nondestructive analysis, easy spectral measurement, high sensitivity, and simple spectral analysis. The present study has demonstrated that far-UV spectroscopy is a very promising technique for polymer film analysis.

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.

Precursor polymer compositions comprising polybenzimidazole

DOEpatents

Klaehn, John R.; Peterson, Eric S.; Orme, Christopher J.

2015-07-14

Stable, high performance polymer compositions including polybenzimidazole (PBI) and a melamine-formaldehyde polymer, such as methylated, poly(melamine-co-formaldehyde), for forming structures such as films, fibers and bulky structures. The polymer compositions may be formed by combining polybenzimidazole with the melamine-formaldehyde polymer to form a precursor. The polybenzimidazole may be reacted and/or intertwined with the melamine-formaldehyde polymer to form the polymer composition. For example, a stable, free-standing film having a thickness of, for example, between about 5 .mu.m and about 30 .mu.m may be formed from the polymer composition. Such films may be used as gas separation membranes and may be submerged into water for extended periods without crazing and cracking. The polymer composition may also be used as a coating on substrates, such as metal and ceramics, or may be used for spinning fibers. Precursors for forming such polymer compositions are also disclosed.

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.

Tuning relaxation dynamics and mechanical properties of polymer films of identical thickness

NASA Astrophysics Data System (ADS)

Kchaou, Marwa; Alcouffe, Pierre; Chandran, Sivasurender; Cassagnau, Philippe; Reiter, Günter; Al Akhrass, Samer

2018-03-01

Using dewetting as a characterization tool, we demonstrate that physical properties of thin polymer films can be regulated and tuned by employing variable processing conditions. For different molecular weights, the variable behavior of polystyrene films of identical thickness, prepared along systematically altered pathways, became predictable through a single parameter P , defined as the ratio of time required over time available for the equilibration of polymers. In particular, preparation-induced residual stresses, the corresponding relaxation times as well as the rupture probability of such films (of identical thickness) varied by orders of magnitude following scaling relations with P . Our experimental findings suggest that we can predictably enhance properties and hence maximize the performance of thin polymer films via appropriately chosen processing conditions.

Investigation of transition States in bulk and freestanding film polymer glasses.

PubMed

Jain, Tushar S; de Pablo, Juan J

2004-04-16

We have performed transition state searches on the potential energy landscape for bulk and freestanding film polymer glasses and identified connected minima. An analysis of the displacements between minima shows that the sites that undergo the greatest displacement are highly localized in space for both the bulk and the thin-film systems studied. In the case of the thin film, the clusters originate at the surface and penetrate into the center of the film thereby coupling the relaxation in the center of the film to the mobile surface layer. Furthermore, the energy barriers between minima are lower in the thin film than in the bulk system. These findings can rationalize the experimentally observed depression of the glass transition temperature in freestanding polymer films.

Semiconductor-nanocrystal/conjugated polymer thin films

DOEpatents

Alivisatos, A. Paul; Dittmer, Janke J.; Huynh, Wendy U.; Milliron, Delia

2014-06-17

The invention described herein provides for thin films and methods of making comprising inorganic semiconductor-nanocrystals dispersed in semiconducting-polymers in high loading amounts. The invention also describes photovoltaic devices incorporating the thin films.

Semiconductor-nanocrystal/conjugated polymer thin films

DOEpatents

Alivisatos, A. Paul; Dittmer, Janke J.; Huynh, Wendy U.; Milliron, Delia

2010-08-17

The invention described herein provides for thin films and methods of making comprising inorganic semiconductor-nanocrystals dispersed in semiconducting-polymers in high loading amounts. The invention also describes photovoltaic devices incorporating the thin films.

Influence of macromolecular architecture on necking in polymer extrusion film casting process

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

Pol, Harshawardhan; Banik, Sourya; Azad, Lal Busher

2015-05-22

Extrusion film casting (EFC) is an important polymer processing technique that is used to produce several thousand tons of polymer films/coatings on an industrial scale. In this research, we are interested in understanding quantitatively how macromolecular chain architecture (for example long chain branching (LCB) or molecular weight distribution (MWD or PDI)) influences the necking and thickness distribution of extrusion cast films. We have used different polymer resins of linear and branched molecular architecture to produce extrusion cast films under controlled experimental conditions. The necking profiles of the films were imaged and the velocity profiles during EFC were monitored using particlemore » tracking velocimetry (PTV) technique. Additionally, the temperature profiles were captured using an IR thermography and thickness profiles were calculated. The experimental results are compared with predictions of one-dimensional flow model of Silagy et al{sup 1} wherein the polymer resin rheology is modeled using molecular constitutive equations such as the Rolie-Poly (RP) and extended Pom Pom (XPP). We demonstrate that the 1-D flow model containing the molecular constitutive equations provides new insights into the role of macromolecular chain architecture on film necking.{sup 1}D. Silagy, Y. Demay, and J-F. Agassant, Polym. Eng. Sci., 36, 2614 (1996)« less

Strain and in-plane orientation effects on the ferroelectricity of (111)-oriented tetragonal Pb(Zr0.35Ti0.65)O3 thin films prepared by metal organic chemical vapor deposition

NASA Astrophysics Data System (ADS)

Kuwabara, Hiroki; Menou, Nicolas; Funakubo, Hiroshi

2007-05-01

The growth and characterization of epitaxial (111)-oriented Pb(Zr0.35Ti0.65)O3 films deposited by metal organic chemical vapor deposition on (100)-oriented silicon substrates [(111)SrRuO3‖(111)Pt ‖(100)yttria-stabilizedzirconia‖(100)Si] are reported. The orientation, microstructure, and electric properties of these films are compared to those of fiber-textured highly (111)-oriented lead zirconate titanate (PZT) films deposited on (111)SrRuO3/(111)Pt/TiOx/SiO2/(100)Si substrates and epitaxial (111)-oriented PZT films deposited on (111)SrRuO3‖(111)SrTiO3 substrates. The ferroelectric properties of these films are not drastically influenced by the in-plane orientation of the film and by the strain state imposed by the underlying substrate. These results support the use of fiber-textured highly (111)-oriented films in highly stable ferroelectric capacitors.

Effect of Polymer Electrode Morphology on Performance of a Lithium/Polypyrrole Battery. M.S. Thesis

NASA Technical Reports Server (NTRS)

Nicholson, Marjorie Anne

1991-01-01

A variety of conducting polymer batteries were described in the recent literature. In this work, a Li/Polypyrrole secondary battery is described. The effect of controlling the morphology of the polymer on enhancement of counterion diffusion in the polymer phase is explored. A method of preparing conducting polymers was developed which yields high surface area per unit volume of electrode material. A porous membrane is used as a template in which to electrochemically polymerize pyrrole, then the membrane is dissolved, leaving the polymer in a fibrillar form. Conventionally, the polymer is electrochemically polymerized as a dense polymer film on a smooth Pt disk electrode. Previous work has shown that when the polymer is electrochemically polymerized in fribrillar form, charge transport rates are faster and charge capacities are greater than for dense, conventionally grown films containing the same amount of polymer. The purpose is to expand previous work by further investigating the possibilities of the optimization of transport rates in polypyrrole films by controlling the morphology of the films. The utility of fibrillar polypyrrole as a cathode material in a lithium/polymer secondary battery is then assessed. The performance of the fibrillar battery is compared to the performance of an analogous battery which employed a conventionally grown polypyrrole film. The study includes a comparison of cyclic voltammetry, shape of charge/discharge curves, discharge time and voltage, cycle life, coulombic efficiencies, charge capacities, energy densities, and energy efficiencies.

Methods for Assessment of Biodegradability of Plastic Films in Soil †

PubMed Central

Yabannavar, Asha V.; Bartha, Richard

1994-01-01

Traditional and novel techniques were tested and compared for their usefulness in evaluating biodegrad-ability claims made for newly formulated “degradable” plastic film products. Photosensitized polyethylene (PE), starch-PE, extensively plasticized polyvinyl chloride (PVC), and polypropylene (PP) films were incorporated into aerobic soil. Biodegradation was measured for 3 months under generally favorable conditions. Carbon dioxide evolution, residual weight recovery, and loss of tensile strength measurements were supplemented, for some films, by gas chromatographic measurements of plasticizer loss and gel permeation chromatographic (GPC) measurement of polymer molecular size distribution. Six- and 12-week sunlight exposures of photosensitized PE films resulted in extensive photochemical damage that failed to promote subsequent mineralization in soil. An 8% starch-PE film and the plasticized PVC film evolved significant amounts of CO2 in biodegradation tests and lost residual weight and tensile strength, but GPC measurements demonstrated that all these changes were confined to the additives and the PE and PVC polymers were not degraded. Carbon dioxide evolution was found to be a useful screening tool for plastic film biodegradation, but for films with additives, polymer biodegradation needs to be confirmed by GPC. Photochemical cross-linking of polymer strands reduces solubility and may interfere with GPC measurements of polymer degradation. PMID:16349408

Multi-Stimuli-Responsive Polymer Materials: Particles, Films, and Bulk Gels.

PubMed

Cao, Zi-Quan; Wang, Guo-Jie

2016-06-01

Stimuli-responsive polymers have received tremendous attention from scientists and engineers for several decades due to the wide applications of these smart materials in biotechnology and nanotechnology. Driven by the complex functions of living systems, multi-stimuli-responsive polymer materials have been designed and developed in recent years. Compared with conventional single- or dual-stimuli-based polymer materials, multi-stimuli-responsive polymer materials would be more intriguing since more functions and finer modulations can be achieved through more parameters. This critical review highlights the recent advances in this area and focuses on three types of multi-stimuli-responsive polymer materials, namely, multi-stimuli-responsive particles (micelles, micro/nanogels, vesicles, and hybrid particles), multi-stimuli-responsive films (polymer brushes, layer-by-layer polymer films, and porous membranes), and multi-stimuli-responsive bulk gels (hydrogels, organogels, and metallogels) from recent publications. Various stimuli, such as light, temperature, pH, reduction/oxidation, enzymes, ions, glucose, ultrasound, magnetic fields, mechanical stress, solvent, voltage, and electrochemistry, have been combined to switch the functions of polymers. The polymer design, preparation, and function of multi-stimuli-responsive particles, films, and bulk gels are comprehensively discussed here. © 2016 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rationalising polymer selection for supersaturated film forming systems produced by an aerosol spray for the transdermal delivery of methylphenidate.

PubMed

Edwards, A; Qi, S; Liu, F; Brown, M B; McAuley, W J

2017-05-01

Film forming systems offer a number of advantages for topical and transdermal drug delivery, in particular enabling production of a supersaturated state which can greatly improve drug absorption and bioavailability. However the suitability of individual film forming polymers to stabilise the supersaturated state and optimise delivery of drugs is not well understood. This study reports the use of differential scanning calorimetry (DSC) to measure the solubility of methylphenidate both as the free base and as the hydrochloride salt in two polymethacrylate copolymers, Eudragit RS (EuRS) and Eudragit E (EuE) and relates this to the ability of films formed using these polymers to deliver methylphenidate across a model membrane. EuRS provided greater methylphenidate delivery when the drug was formulated as the free base in comparison EuE because the lower solubility of the drug in EuRS provided a higher degree of drug saturation in the polymeric film. In contrast EuE provided greater delivery of methylphenidate hydrochloride as EuRS could not prevent its crystallisation from a supersaturated state. Methylphenidate flux across the membrane could be directly related to degree of saturation of the drug in the film formulation as estimated by the drug solubility in the individual polymers demonstrating the importance of drug solubility in the polymer included in film forming systems for topical/transdermal drug delivery. In addition DSC has been demonstrated to be a useful tool for determining the solubility of drugs in polymers used in film forming systems and the approaches outlined here are likely to be useful for predicting the suitability of polymers for particular drugs in film forming transdermal drug delivery systems. Copyright © 2017. Published by Elsevier B.V.

Orientation filtering for crystalline films

DOEpatents

Smith, Henry I.; Atwater, Harry A.; Thompson, Carl V.; Geis, Michael W.

1986-12-30

A substrate is coated with a film to be recrystallized. A pattern of crystallization barriers is created in the film, for example, by etching voids in the film. An encapsulation layer is generally applied to protect the film, fill the voids and otherwise enhance a recrystallization process. Recrystallization is carried out such that certain orientations pass preferentially through the barrier, generally as a result of growth-velocity anisotropy. The result is a film of a specific predetermined crystallographic orientation, a range of orientations or a set of discrete orientations.

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.

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

Surface energy characteristics of zeolite embedded PVDF nanofiber films with electrospinning process

NASA Astrophysics Data System (ADS)

Kang, Dong Hee; Kang, Hyun Wook

2016-11-01

Electrospinning is a nano-scale fiber production method with various polymer materials. This technique allows simple fiber diameters control by changing the physical conditions such as applied voltage and polymer solution viscosity during the fabrication process. The electrospun polymer fibers form a thin porous film with high surface area to volume ratio. Due to these unique characteristics, it is widely used for many application fields such as photocatalyst, electric sensor, and antibacterial scaffold for tissue engineering. Filtration is one of the main applications of electrospun polymer fibers for specific application of filtering out dust particles and dehumidification. Most polymers which are commonly used in electrospinning are hard to perform the filtering and dehumidification simultaneously because of their low hygroscopic property. To overcome this obstacle, the desiccant polymers are developed such as polyacrylic acid and polysulfobetaine methacrylate. However, the desiccant polymers are generally expensive and need special solvent for electrospinning. An alternating way to solve these problems is mixing desiccant material like zeolite in polymer solution during an electrospinning process. In this study, the free surface energy characteristics of electrospun polyvinylidene fluoride (PVDF) film with various zeolite concentrations are investigated to control the hygroscopic property of general polymers. Fundamental physical property of wettability with PVDF shows hydrophobicity. The electrospun PVDF film with small weight ratio with higher than 0.1% of zeolite powder shows diminished contact angles that certifying the wettability of PVDF can be controlled using desiccant material in electrospinning process. To quantify the surface energy of electrospun PVDF films, sessile water droplets are introduced on the electrospun PVDF film surface and the contact angles are measured. The contact angles of PVDF film are 140° for without zeolite and 80° for with 5 wt% of zeolite respectively. As a result, the surface energy of PVDF film can be controlled by embedding zeolite particles in electrospinning process and applied to filtration application of dust filtering and dehumidification simultaneously with low manufacturing cost.

Characterization of ethyl cellulose polymer.

PubMed

Mahnaj, Tazin; Ahmed, Salah U; Plakogiannis, Fotios M

2013-01-01

Ethyl cellulose (EC) polymer was characterized for its property before considering the interactions with the plasicizer. Ethocel Std.10 FP Premium from Dow chemical company USA was tested for its solubility, morphology and thermal properties. Seven percentage of EC solution in ethanol was found to be the right viscosity used to prepare the film. The EC polymer and EC film without any plasticizers showed almost identical thermal behavior, but in X-ray diffraction showed different arrangements of crystallites and amorphous region. Dynamic mechanical analysis of film showed that without a plasticizer, EC film was not flexible and had very low elongation with high applied force. The aim of the work was to avoid using the commercially available EC dispersions Surelease® and Aquacoat®; both already have additives on it. Instead, Ethocel EC polymer (powder) was characterized in our laboratory in order to find out the properties of polymer before considering the interactions of the polymer with various plasticizers.

The Fabrication of Nanoimprinted P3HT Nanograting by Patterned ETFE Mold at Room Temperature and Its Application for Solar Cell

NASA Astrophysics Data System (ADS)

Ding, Guangzhu; Wang, Kaixuan; Li, Xiaohui; Chen, Qing; Hu, Zhijun; Liu, Jieping

2016-05-01

Nanoimprinting lithography (NIL) is investigated as a promising method to define nanostructure; however, finding a practical method to achieve large area patterning of conjugated polymer remains a challenge. We demonstrate here that a simple and cost-effective technique is proposed to fabricate the nanoimprinted P3HT nanograting by solvent-assisted room temperature NIL (SART-NIL) method with patterned ETFE film as mold. The patterned ETFE template is produced by embossing ETFE film into a patterned silicon master and is used as template to transfer nanogratings during the SART-NIL process. It indicates that highly reproducible and well-controlled P3HT nanograting film is obtained successfully with feature size of nanogratings ranging from 130 to 700 nm, due to the flexibility, stiffness, and low surface energy of ETFE mold. Moreover, the SART-NIL method using ETFE mold is able to fabricate nanogratings but not to induce the change of molecular orientation within conjugated polymer. The conducting ability of P3HT nanograting in the vertical direction is also not damaged after patterning. Finally, we further apply P3HT nanograting for the fabrication of active layer of OBHJ solar cell device, to investigate the morphology role presented by ETFE mold in device performance. The device performance of OBHJ solar cell is preferential to that of PBHJ device obviously.

The Fabrication of Nanoimprinted P3HT Nanograting by Patterned ETFE Mold at Room Temperature and Its Application for Solar Cell.

PubMed

Ding, Guangzhu; Wang, Kaixuan; Li, Xiaohui; Chen, Qing; Hu, Zhijun; Liu, Jieping

2016-12-01

Nanoimprinting lithography (NIL) is investigated as a promising method to define nanostructure; however, finding a practical method to achieve large area patterning of conjugated polymer remains a challenge. We demonstrate here that a simple and cost-effective technique is proposed to fabricate the nanoimprinted P3HT nanograting by solvent-assisted room temperature NIL (SART-NIL) method with patterned ETFE film as mold. The patterned ETFE template is produced by embossing ETFE film into a patterned silicon master and is used as template to transfer nanogratings during the SART-NIL process. It indicates that highly reproducible and well-controlled P3HT nanograting film is obtained successfully with feature size of nanogratings ranging from 130 to 700 nm, due to the flexibility, stiffness, and low surface energy of ETFE mold. Moreover, the SART-NIL method using ETFE mold is able to fabricate nanogratings but not to induce the change of molecular orientation within conjugated polymer. The conducting ability of P3HT nanograting in the vertical direction is also not damaged after patterning. Finally, we further apply P3HT nanograting for the fabrication of active layer of OBHJ solar cell device, to investigate the morphology role presented by ETFE mold in device performance. The device performance of OBHJ solar cell is preferential to that of PBHJ device obviously.

Features of microbiological behavior and biocide properties of electrosynthesized polymethylolacrylamide films

NASA Astrophysics Data System (ADS)

Kolzunova, Lidia G.

2016-05-01

The biocide properties of an electrosynthesized of acrylamide, N,N'-methylene-bis-acrylamide and formaldehyde copolymer films against the Staphylococcus aureus and bacterial association extracted from seawater (marine biological organisms) were investigated. Copolymer films were stable in organic solvents, acids and alkali and insoluble in water, though capable to swelling ability. Besides, the polymer is thermally stable up to 237°C. It was established that the anti-bacterial effect of the films started to be expressed after two days and was maintained from 2 up to 45 days. It was established that the degree of polymer films toxicity depended on the polymer synthesis conditions, pre-treatment method and duration of the biological object exposure to the effect. It was shown that antiseptic properties of the polymer material under study were imparted by formaldehyde both as sorbed by the polymer and as included into the copolymer composition. The toxicological effect of the polymethylolacrylamide films under study on microorganisms can be applied as in medicine (antiseptic materials and implants) as for equipment protection from bio-fouling and bio-corrosion. Microbiological stability and sterilizing effect of electrosynthesized polymethylolacrylamide ultrafiltration membranes enables one not only to prolong the operation time of film membranes, but also to provide partial sterilization of organic solutions to be filtered. It was established that polymer waste can be utilized by means of microbial destruction. It was found that the washed out polymer induced a specific bacteria behavior consisting of a complex of reactions directed to search, capture and consume nutrients.

Neutron Reflectivity Measurement for Polymer Dynamics near Graphene Oxide Monolayers

NASA Astrophysics Data System (ADS)

Koo, Jaseung

We investigated the diffusion dynamics of polymer chains confined between graphene oxide layers using neutron reflectivity (NR). The bilayers of polymethylmetacrylate (PMMA)/ deuterated PMMA (d-PMMA) films and polystyrene (PS)/d-PS films with various film thickness sandwiched between Langmuir-Blodgett (LB) monolayers of graphene oxide (GO) were prepared. From the NR results, we found that PMMA diffusion dynamics was reduced near the GO surface while the PS diffusion was not significantly changed. This is due to the different strength of GO-polymer interaction. In this talk, these diffusion results will be compared with dewetting dynamics of polymer thin films on the GO monolayers. This has given us the basis for development of graphene-based nanoelectronics with high efficiency, such as heterojunction devices for polymer photovoltaic (OPV) applications.

Anomalous Drag Reduction and Hydrodynamic Interactions of Nanoparticles in Polymer Nanocomposite Thin Films

NASA Astrophysics Data System (ADS)

Basu, Jaydeep; Begam, Nafisa; Chandran, Sivasurender; Sprung, Michael

2015-03-01

One of the central dogma of fluid physics is the no-slip boundary condition whose validity has come under intense scrutiny, especially in the fields of micro and nanofluidics. Although various studies show the violation of the no-slip condition its effect on flow of colloidal particles in viscous media has been rarely explored. Here we report unusually large reduction of effective drag experienced by polymer grafted nanoparticles moving through a highly viscous film of polymer, well above its glass transition temperature. The extent of drag reduction increases with decreasing temperature and polymer film thickness. We also observe apparent divergence of the wave vector dependent hydrodynamic interaction function of these nanoparticles with an anomalous power law exponent of ~ 2 at the lowest temperatures and film thickness. Such strong hydrodynamic interactions are not expected in polymer melts where these interactions are known to be screened to molecular dimensions. We provide evidence for the presence of large hydrodynamic slip at the nanoparticle-polymer interface and demonstrate its tunability with temperature and confinement. Our study suggests novel physics emerging in dynamics nanoparticles due to confinement and interface wettability in thin films of polymer nanocomposites.

Effect of size and moisture on the mechanical behavior of SU-8 thin films

NASA Astrophysics Data System (ADS)

Robin, C. J.; Jonnalagadda, K. N.

2016-02-01

The mechanical properties of SU-8 were investigated in conjunction with size effect, mechanical anisotropy and moisture absorption. Uniaxial tensile experiments were conducted on SU-8 films of 500 nm and 2 μm thickness. A spin coating process was used to fabricate the films with one set from a single coat (single layer) and the others containing multiple coats (multilayer) with pre-baking in between. The stress versus strain response was obtained from in situ optical experiments and a digital image correlation method. Compared to single layer films, the multilayer films showed a significant increase in mechanical properties as well as in-plane anisotropy. This anisotropy was confirmed using Fourier transform infrared spectroscopy and attributed to the spin coating process, which resulted in higher crosslinking density in the film, and molecular orientation in the radial direction. Moisture absorption studies revealed that the mechanical properties were affected by water, which exists in both the free and bonded form in the polymer and acts as a plasticizer. The effect of moisture was similar in both the single and multilayer films, but was higher for the latter due to multiple processing steps as well as the existence of higher percentage of epoxy polar groups.

Impact of polymer film thickness and cavity size on polymer flow during embossing : towards process design rules for nanoimprint lithography.

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

Schunk, Peter Randall; King, William P.; Sun, Amy Cha-Tien

2006-08-01

This paper presents continuum simulations of polymer flow during nanoimprint lithography (NIL). The simulations capture the underlying physics of polymer flow from the nanometer to millimeter length scale and examine geometry and thermophysical process quantities affecting cavity filling. Variations in embossing tool geometry and polymer film thickness during viscous flow distinguish different flow driving mechanisms. Three parameters can predict polymer deformation mode: cavity width to polymer thickness ratio, polymer supply ratio, and Capillary number. The ratio of cavity width to initial polymer film thickness determines vertically or laterally dominant deformation. The ratio of indenter width to residual film thickness measuresmore » polymer supply beneath the indenter which determines Stokes or squeeze flow. The local geometry ratios can predict a fill time based on laminar flow between plates, Stokes flow, or squeeze flow. Characteristic NIL capillary number based on geometry-dependent fill time distinguishes between capillary or viscous driven flows. The three parameters predict filling modes observed in published studies of NIL deformation over nanometer to millimeter length scales. The work seeks to establish process design rules for NIL and to provide tools for the rational design of NIL master templates, resist polymers, and process parameters.« less

Enhanced energy density and thermal conductivity in poly(fluorovinylidene-co-hexafluoropropylene) nanocomposites incorporated with boron nitride nanosheets exfoliated under assistance of hyperbranched polyethylene.

PubMed

Ye, Huijian; Lu, Tiemei; Xu, Chunfeng; Zhong, Mingqiang; Xu, Lixin

2018-03-02

Polymer dielectric film with a large dielectric constant, high energy density and enhanced thermal conductivity are of significance for the development of impulse capacitors. However, the fabrication of polymer dielectrics combining high energy density and thermal conductivity is still a challenge at the moment. Here we demonstrate the facile exfoliation of hexagonal boron nitride nanosheets (BNNSs) in common organic solvents under sonication with the assistance of hyperbranched polyethylene (HBPE). The noncovalent CH-π interactions between the nanosheets and HBPE ensure the dispersion of BNNSs in organic solvents with high concentrations, because of the highly branched chain structure of HBPE. Subsequently, the resultant BNNSs with a few defects are distributed uniformly in the poly(fluorovinylidene-co-hexafluoropropylene) (P(VDF-HFP)) nanocomposite films prepared via simple solution casting. The BNNS/P(VDF-HFP) nanocomposite exhibits outstanding dielectric properties, high energy density and high thermal conductivity. The dielectric constant of the 0.5 wt% nanocomposite film is 35.5 at 100 Hz with an energy density of 5.6 J cm -3 at 325 MV m -1 and a high charge-discharge efficiency of 79% due to the depression of the charge injection and chemical species ionization in a high field. Moreover, a thermal conductivity of 1.0 wt% nanocomposite film reaches 0.91 W·m -1  · K -1 , which is 3.13 times higher than that of the fluoropolymer matrix. With dipole accumulation and orientation in the interfacial zone, lightweight, flexible BNNS/P(VDF-HFP) nanocomposite films with high charge-discharge performance and thermal conductivity, exhibit promising applications in relatively high-temperature electronics and energy storage devices.

Enhanced energy density and thermal conductivity in poly(fluorovinylidene-co-hexafluoropropylene) nanocomposites incorporated with boron nitride nanosheets exfoliated under assistance of hyperbranched polyethylene

NASA Astrophysics Data System (ADS)

Ye, Huijian; Lu, Tiemei; Xu, Chunfeng; Zhong, Mingqiang; Xu, Lixin

2018-03-01

Polymer dielectric film with a large dielectric constant, high energy density and enhanced thermal conductivity are of significance for the development of impulse capacitors. However, the fabrication of polymer dielectrics combining high energy density and thermal conductivity is still a challenge at the moment. Here we demonstrate the facile exfoliation of hexagonal boron nitride nanosheets (BNNSs) in common organic solvents under sonication with the assistance of hyperbranched polyethylene (HBPE). The noncovalent CH-π interactions between the nanosheets and HBPE ensure the dispersion of BNNSs in organic solvents with high concentrations, because of the highly branched chain structure of HBPE. Subsequently, the resultant BNNSs with a few defects are distributed uniformly in the poly(fluorovinylidene-co-hexafluoropropylene) (P(VDF-HFP)) nanocomposite films prepared via simple solution casting. The BNNS/P(VDF-HFP) nanocomposite exhibits outstanding dielectric properties, high energy density and high thermal conductivity. The dielectric constant of the 0.5 wt% nanocomposite film is 35.5 at 100 Hz with an energy density of 5.6 J cm-3 at 325 MV m-1 and a high charge-discharge efficiency of 79% due to the depression of the charge injection and chemical species ionization in a high field. Moreover, a thermal conductivity of 1.0 wt% nanocomposite film reaches 0.91 W·m-1 · K-1, which is 3.13 times higher than that of the fluoropolymer matrix. With dipole accumulation and orientation in the interfacial zone, lightweight, flexible BNNS/P(VDF-HFP) nanocomposite films with high charge-discharge performance and thermal conductivity, exhibit promising applications in relatively high-temperature electronics and energy storage devices.

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.

Surface Polarity and Self-Structured Nanogrooves Collaboratively Oriented Molecular Packing for High Crystallinity toward Efficient Charge Transport.

PubMed

Ji, Deyang; Xu, Xiaomin; Jiang, Longfeng; Amirjalayer, Saeed; Jiang, Lang; Zhen, Yonggang; Zou, Ye; Yao, Yifan; Dong, Huanli; Yu, Junsheng; Fuchs, Harald; Hu, Wenping

2017-02-22

Efficient charge transport in organic semiconductors is essential for construction of high performance optoelectronic devices. Herein, for the first time, we demonstrate that poly(amic acid) (PAA), a facilely deposited and annealing-free dielectric layer, can tailor the growth of organic semiconductor films with large area and high crystallinity toward efficient charge transport and high mobility in their thin film transistors. Pentacene is used as a model system to demonstrate the concept with mobility up to 30.6 cm 2 V -1 s -1 , comparable to its high quality single crystal devices. The structure of PAA has corrugations with OH groups pointing out of the surface, and the presence of an amide bond further allows adjacent polymer strands to interact via hydrogen bonding, leading to a self-rippled surface perpendicular to the corrugation. On the other hand, the strong polar groups (-COOH/-CONH) of PAA could provide repulsive forces between PAA and pentacene, which results in the vertical orientation of pentacene on the dielectric surface. Indeed, in comparison with its imidized counterpart polyimide (PI), PAA dielectric significantly enhances the film crystallinity, drastically increases the domain size, and decreases the interface trap density, giving rise to superior device performance with high mobility. This concept can be extended to more organic semiconducting systems, e.g., 2,6-diphenylanthracene (DPA), tetracene, copper phthalocyanine (CuPc), and copper hexadecafluorophthalocyanine (F 16 CuPc), demonstrating the general applicability. The results show the importance of combining surface nanogrooves with the strong polarity in orienting the molecular arrangement for high crystallinity toward efficient charge transport in organic semiconductors.

Phase equilibria in polymer-blend thin films

NASA Astrophysics Data System (ADS)

Clarke, Nigel; Souche, Mireille

2010-03-01

To describe equilibrium concentration profiles in thin films of polymer mixtures, we propose a Hamiltonian formulation of the Flory-Huggins-de Gennes theory describing a polymer blend thin film. We first focus on the case of 50:50 polymer blends confined between anti-symmetric walls. The different phases of the system and the transitions between them, including finite size effects, are systematically studied through their relation with the geometry of the Hamiltonian flow in phase space. This method provides an easy and efficient way, with strong graphical insight, to infer the qualitative physical behavior of polymer blend thin films. The addition of a further degree of freedom in the system, namely a solvent, may result in a chaotic behavior of the system, characterized by the existence of solutions with exponential sensitivity to initial conditions. Such solutions and there subsequent contribution to the out-of-equilibrium dynamics of the system are well described in Hamiltonian formalism. A fully consistent treatment of the Flory-Huggins-de Gennes theory of thin film polymer blend solutions, in the spirit of the Hamiltonian approach will be presented. 1. M. Souche and N. Clarke, J. Chem. Phys., submitted.

Durability of ITO-MgF2 Films for Space-Inflatable Polymer Structures

NASA Technical Reports Server (NTRS)

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

2003-01-01

This paper presents results from ITO-MgF2 film durability evaluations that included tape peel, fold, thermal cycle, and AO exposure testing. Polymer coupon preparation is described as well as ITO-MgF2 film deposition equipment, procedures and film characterization. Durability testing methods are also described. The pre- and post-test condition of the films is assessed visually, microscopically, and electrically. Results show that at 500 ITO - 9 vol% MgF2 film is suitable to protect polymer surfaces, such as those used in space-inflatable structures of the PowerSphere microsatellite concept, during a 1-year Earth orbiting mission. Future plans for ground-based and orbital testing of this film are also discussed.

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

Optical Input/Electrical Output Memory Elements based on a Liquid Crystalline Azobenzene Polymer.

PubMed

Mosciatti, Thomas; Bonacchi, Sara; Gobbi, Marco; Ferlauto, Laura; Liscio, Fabiola; Giorgini, Loris; Orgiu, Emanuele; Samorì, Paolo

2016-03-01

Responsive polymer materials can change their properties when subjected to external stimuli. In this work, thin films of thermotropic poly(metha)acrylate/azobenzene polymers are explored as active layer in light-programmable, electrically readable memories. The memory effect is based on the reversible modifications of the film morphology induced by the photoisomerization of azobenzene mesogenic groups. When the film is in the liquid crystalline phase, the trans → cis isomerization induces a major surface reorganization on the mesoscopic scale that is characterized by a reduction in the effective thickness of the film. The film conductivity is measured in vertical two-terminal devices in which the polymer is sandwiched between a Au contact and a liquid compliant E-GaIn drop. We demonstrate that the trans → cis isomerization is accompanied by a reversible 100-fold change in the film conductance. In this way, the device can be set in a high- or low-resistance state by light irradiation at different wavelengths. This result paves the way toward the potential use of poly(metha)acrylate/azobenzene polymer films as active layer for optical input/electrical output memory elements.

Orientation filtering for crystalline films

DOEpatents

Smith, H.I.; Atwater, H.A.; Thompson, C.V.; Geis, M.W.

1986-12-30

A substrate is coated with a film to be recrystallized. A pattern of crystallization barriers is created in the film, for example, by etching voids in the film. An encapsulation layer is generally applied to protect the film, fill the voids and otherwise enhance a recrystallization process. Recrystallization is carried out such that certain orientations pass preferentially through the barrier, generally as a result of growth-velocity anisotropy. The result is a film of a specific predetermined crystallographic orientation, a range of orientations or a set of discrete orientations. 7 figs.

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.

Local variation of fragility and glass transition temperature of ultra-thin supported polymer films.

PubMed

Hanakata, Paul Z; Douglas, Jack F; Starr, Francis W

2012-12-28

Despite extensive efforts, a definitive picture of the glass transition of ultra-thin polymer films has yet to emerge. The effect of film thickness h on the glass transition temperature T(g) has been widely examined, but this characterization does not account for the fragility of glass-formation, which quantifies how rapidly relaxation times vary with temperature T. Accordingly, we simulate supported polymer films of a bead-spring model and determine both T(g) and fragility, both as a function of h and film depth. We contrast changes in the relaxation dynamics with density ρ and demonstrate the limitations of the commonly invoked free-volume layer model. As opposed to bulk polymer materials, we find that the fragility and T(g) do not generally vary proportionately. Consequently, the determination of the fragility profile--both locally and for the film as a whole--is essential for the characterization of changes in film dynamics with confinement.

Structure and properties of small molecule-polymer blend semiconductors for organic thin film transistors.

PubMed

Kang, Jihoon; Shin, Nayool; Jang, Do Young; Prabhu, Vivek M; Yoon, Do Y

2008-09-17

A comprehensive structural and electrical characterization of solution-processed blend films of 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-pentacene) semiconductor and poly(alpha-methylstyrene) (PalphaMS) insulator was performed to understand and optimize the blend semiconductor films, which are very attractive as the active layer in solution-processed organic thin-film transistors (OTFTs). Our study, based on careful measurements of specular neutron reflectivity and grazing-incidence X-ray diffraction, showed that the blends with a low molecular-mass PalphaMS exhibited a strong segregation of TIPS-pentacene only at the air interface, but surprisingly the blends with a high molecular-mass PalphaMS showed a strong segregation of TIPS-pentacene at both air and bottom substrate interfaces with high crystallinity and desired orientation. This finding led to the preparation of a TIPS-pentacene/PalphaMS blend active layer with superior performance characteristics (field-effect mobility, on/off ratio, and threshold voltage) over those of neat TIPS-pentacene, as well as the solution-processability of technologically attractive bottom-gate/bottom-contact OTFT devices.

Fabrication of nanostructured ZnO film as a hole-conducting layer of organic photovoltaic cell

PubMed Central

2013-01-01

We have investigated the effect of fibrous nanostructured ZnO film as a hole-conducting layer on the performance of polymer photovoltaic cells. By increasing the concentration of zinc acetate dihydrate, the changes of performance characteristics were evaluated. Fibrous nanostructured ZnO film was prepared by sol-gel process and annealed on a hot plate. As the concentration of zinc acetate dihydrate increased, ZnO fibrous nanostructure grew from 300 to 600 nm. The obtained ZnO nanostructured fibrous films have taken the shape of a maze-like structure and were characterized by UV-visible absorption, scanning electron microscopy, and X-ray diffraction techniques. The intensity of absorption bands in the ultraviolet region was increased with increasing precursor concentration. The X-ray diffraction studies show that the ZnO fibrous nanostructures became strongly (002)-oriented with increasing concentration of precursor. The bulk heterojunction photovoltaic cells were fabricated using poly(3-hexylthiophene-2,5-diyl) and indene-C60 bisadduct as active layer, and their electrical properties were investigated. The external quantum efficiency of the fabricated device increased with increasing precursor concentration. PMID:23680100

Fabrication of nanostructured ZnO film as a hole-conducting layer of organic photovoltaic cell

NASA Astrophysics Data System (ADS)

Kim, Hyomin; Kwon, Yiseul; Choe, Youngson

2013-05-01

We have investigated the effect of fibrous nanostructured ZnO film as a hole-conducting layer on the performance of polymer photovoltaic cells. By increasing the concentration of zinc acetate dihydrate, the changes of performance characteristics were evaluated. Fibrous nanostructured ZnO film was prepared by sol-gel process and annealed on a hot plate. As the concentration of zinc acetate dihydrate increased, ZnO fibrous nanostructure grew from 300 to 600 nm. The obtained ZnO nanostructured fibrous films have taken the shape of a maze-like structure and were characterized by UV-visible absorption, scanning electron microscopy, and X-ray diffraction techniques. The intensity of absorption bands in the ultraviolet region was increased with increasing precursor concentration. The X-ray diffraction studies show that the ZnO fibrous nanostructures became strongly (002)-oriented with increasing concentration of precursor. The bulk heterojunction photovoltaic cells were fabricated using poly(3-hexylthiophene-2,5-diyl) and indene-C60 bisadduct as active layer, and their electrical properties were investigated. The external quantum efficiency of the fabricated device increased with increasing precursor concentration.

Plasmonic extinction in gold nanoparticle-polymer films as film thickness and nanoparticle separation decrease below resonant wavelength

NASA Astrophysics Data System (ADS)

Dunklin, Jeremy R.; Bodinger, Carter; Forcherio, Gregory T.; Keith Roper, D.

2017-01-01

Plasmonic nanoparticles embedded in polymer films enhance optoelectronic properties of photovoltaics, sensors, and interconnects. This work examined optical extinction of polymer films containing randomly dispersed gold nanoparticles (AuNP) with negligible Rayleigh scattering cross-sections at particle separations and film thicknesses less than (sub-) to greater than (super-) the localized surface plasmon resonant (LSPR) wavelength, λLSPR. Optical extinction followed opposite trends in sub- and superwavelength films on a per nanoparticle basis. In ˜70-nm-thick polyvinylpyrrolidone films containing 16 nm AuNP, measured resonant extinction per particle decreased as particle separation decreased from ˜130 to 76 nm, consistent with trends from Maxwell Garnett effective medium theory and coupled dipole approximation. In ˜1-mm-thick polydimethylsiloxane films containing 16-nm AuNP, resonant extinction per particle plateaued at particle separations ≥λLSPR, then increased as particle separation radius decreased from ˜514 to 408 nm. Contributions from isolated particles, interparticle interactions and heterogeneities in sub- and super-λLSPR films containing AuNP at sub-λLSPR separations were examined. Characterizing optoplasmonics of thin polymer films embedded with plasmonic NP supports rational development of optoelectronic, biomedical, and catalytic activity using these nanocomposites.

A flexible tactile-feedback touch screen using transparent ferroelectric polymer film vibrators

NASA Astrophysics Data System (ADS)

Ju, Woo-Eon; Moon, Yong-Ju; Park, Cheon-Ho; Choi, Seung Tae

2014-07-01

To provide tactile feedback on flexible touch screens, transparent relaxor ferroelectric polymer film vibrators were designed and fabricated in this study. The film vibrator can be integrated underneath a transparent cover film or glass, and can also produce acoustic waves that cause a tactile sensation on human fingertips. Poly(vinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene) [P(VDF-TrFE-CTFE)] polymer was used as the relaxor ferroelectric polymer because it produces a large strain under applied electric fields, shows a fast response, and has excellent optical transparency. The natural frequency of this tactile-feedback touch screen was designed to be around 200-240 Hz, at which the haptic perception of human fingertips is the most sensitive; therefore, the resonance of the touch screen at its natural frequency provides maximum haptic sensation. A multilayered relaxor ferroelectric polymer film vibrator was also demonstrated to provide the same vibration power at reduced voltage. The flexible P(VDF-TrFE-CTFE) film vibrators developed in this study are expected to provide tactile sensation not only in large-area flat panel displays, but also in flexible displays and touch screens.

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.

The theory and design of piezoelectric/pyroelectric polymer film sensors for biomedical engineering applications.

PubMed

Brown, L F

1989-01-01

The unique properties of piezoelectric/pyroelectric polymers offer many new opportunities for biomedical engineering sensor applications. Since their discovery nearly 20 years ago, the polymer films have been used for many novel switching and sensor applications. Despite the prodigious exposure from many recent publications describing piezo film applications, methods of sensor fabrication and circuit interfacing still elude most engineers. This paper is presented as a tutorial guide to applying piezo polymers to biomedical engineering applications. A review of the fundamentals of piezoelectricity/pyroelectricity in piezo polymers is first presented. Their material properties are contrasted with piezoelectric ceramic materials. Some advantages and disadvantages of the films for biomedical sensors are discussed. Specific details on the fabrication of piezo film sensors are presented. Methods are described for forming, cutting, and mounting film sensors, and making lead connections. A brief discussion of equivalent circuit models for the design and simulation of piezoelectric/pyroelectric sensors is included, as well as common circuit interface techniques. Finally, several sources are recommended for further information on a variety of biomedical sensor applications.

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.

Dewetting acrylic polymer films with water/propylene carbonate/surfactant mixtures - implications for cultural heritage conservation.

PubMed

Baglioni, M; Montis, C; Brandi, F; Guaragnone, T; Meazzini, I; Baglioni, P; Berti, D

2017-09-13

The removal of hydrophobic polymer films from surfaces is one of the top priorities of modern conservation science. Nanostructured fluids containing water, good solvents for polymers, either immiscible or partially miscible with water, and surfactants have been used in the last decade to achieve controlled removal. The dewetting of the polymer film is often an essential step to achieve efficient removal; however, the role of the surfactant throughout the process is yet to be fully understood. We report on the dewetting of a methacrylate/acrylate copolymer film induced by a ternary mixture of water, propylene carbonate (PC) and C 9-11 E 6 , a nonionic alcohol ethoxylate surfactant. The fluid microstructure was characterised through small angle X-ray scattering and the interactions between the film and water, water/PC and water/PC/C 9-11 E 6 , were monitored through confocal laser-scanning microscopy (CLSM) and analised both from a thermodynamic and a kinetic point of view. The presence of a surfactant is a prerequisite to induce dewetting of μm-thick films at room temperature, but it is not a thermodynamic driver. The amphiphile lowers the interfacial energy between the phases and favors the loss of adhesion of the polymer on glass, decreasing, in turn, the activation energy barrier, which can be overcome by the thermal fluctuations of polymer film stability, initiating the dewetting process.

Dynamic studies of nano-confined polymer thin films

NASA Astrophysics Data System (ADS)

Geng, Kun

Polymer thin films with the film thickness (h0 ) below 100 nm often exhibit physical properties different from the bulk counterparts. In order to make the best use of polymer thin films in applications, it is important to understand the physical origins of these deviations. In this dissertation, I will investigate how different factors influence dynamic properties of polymer thin films upon nano-confinement, including glass transition temperature (Tg), effective viscosity (etaeff) and self-diffusion coefficient (D ). The first part of this dissertation concerns the impacts of the molecular weight (MW) and tacticity on the Tg's of nano-confined polymer films. Previous experiments showed that the Tg of polymer films could be depressed or increased as h0 decreases. While these observations are usually attributed to the effects of the interfaces, some experiments suggested that MW's and tacticities might also play a role. To understand the effects of these factors, the Tg's of silica-based poly(alpha-methyl styrene) (PalphaMS/SiOx) and poly(methyl methacrylate) (PMMA/SiOx) thin films were studied, and the results suggested that MW's and tacticities influence Tg in nontrivial ways. The second part concerns an effort to resolve the long-standing controversy about the correlation between different dynamics of polymer thin films upon nano-confinement. Firstly, I discuss the experimental results of Tg, D and etaeff of poly(isobutyl methacrylate) films supported by silica (PiBMA/SiOx). Both T g and D were found to be independent of h 0, but etaeff decreased with decreasing h 0. Since both D and etaeff describe transport phenomena known to depend on the local friction coefficient or equivalently the local viscosity, it is questionable why D and etaeff displayed seemingly inconsistent h 0 dependencies. We envisage the different h0 dependencies to be caused by Tg, D and etaeff being different functions of the local T g's (Tg,i) or viscosities (eta i). By assuming a three-layer model, we were able to account for the experimental data and resolve the inconsistency. By extending the same ideas to the analogous data of silica-based polystyrene films (PS/SiOx), we found a resolution to the inconsistency regarding the effects of nano-confinement on the dynamics of polymer thin films.

Development of textured magnesium oxide templates and bicrystals using ion beam assisted deposition

NASA Astrophysics Data System (ADS)

Vallejo, Ronald N.

Recently, there has been an increased research effort in the deposition of near-single-crystal thin films on substrates that do not provide a template for epitaxial crystalline film growth. Ion beam assisted deposition (IBAD) has been demonstrated as one of the most promising methods to artificially control the texture in thin films. Biaxially textured MgO templates of 10 nm thickness were successfully fabricated on glass and silicon substrates without any buffer layers using IBAD. This work has shed insights on several issues. First, surface morphology ˜ 1 nm or better is only a necessary condition for textured IBAD-MgO, but not a sufficient condition. Additional surface preparation must be provided for nucleation and subsequent formation of the textured IBAD-MgO templates. Second, the role of buffer layer on IBAD-MgO texturing. It was found that the ion beam pre-exposure of the substrates prior to IBAD processing provided a sufficient condition for the nucleation and subsequent texture formation of the IBAD grown films. The ion pre-exposure replaced the need for buffer layers in silicon and glass substrates. Finally, by pre-exposing the substrates to Ar + ions, it was found that the ion beam modified the surface and improved the surface roughness of the glass substrates. Textured MgO epi templates were demonstrated for the first time on polymer based substrates (polyimide). This is a crucial step in the realization of epitaxial suspended devices. To achieve an epitaxial film on a sacrificial layer, an epitaxial template film must first be grown prior to subsequent film growth. The role of ion pre-exposure and buffer layer on texture formation was investigated in this part of the work. This thesis also presents groundbreaking results on the fabrication of bicrystal MgO films and bicrystal networks using ion beam assisted deposition. Highly oriented bicrystals, with a common (100) out-of-plane orientation and (110) in-plane orientations having a tilt angle of 45° and 20° have been successfully fabricated. This method has also been used to fabricate two dimensional bicrystal MgO networks in the micrometer scale. The same strategy can be applied to generate nanometer scale bicrystal networks of desired patterns.

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.

Phase equilibria in polymer blend thin films: A Hamiltonian approach

NASA Astrophysics Data System (ADS)

Souche, M.; Clarke, N.

2009-12-01

We propose a Hamiltonian formulation of the Flory-Huggins-de Gennes theory describing a polymer blend thin film. We then focus on the case of 50:50 polymer blends confined between antisymmetric walls. The different phases of the system and the transitions between them, including finite-size effects, are systematically studied through their relation with the geometry of the Hamiltonian flow in phase space. This method provides an easy and efficient way, with strong graphical insight, to infer the qualitative physical behavior of polymer blend thin films.

Morphology in electrochemically grown conducting polymer films

DOEpatents

Rubinstein, Israel; Gottesfeld, Shimshon; Sabatani, Eyal

1992-01-01

A conducting polymer film with an improved space filling is formed on a metal electrode surface. A self-assembling monolayer is formed directly on the metal surface where the monolayer has a first functional group that binds to the metal surface and a second chemical group that forms a chemical bonding site for molecules forming the conducting polymer. The conducting polymer is then conventioonally deposited by electrochemical deposition. In one example, a conducting film of polyaniline is formed on a gold electrode surface with an intermediate monolayer of p-aminothiophenol.

Morphology in electrochemically grown conducting polymer films

DOEpatents

Rubinstein, I.; Gottesfeld, S.; Sabatani, E.

1992-04-28

A conducting polymer film with an improved space filling is formed on a metal electrode surface. A self-assembling monolayer is formed directly on the metal surface where the monolayer has a first functional group that binds to the metal surface and a second chemical group that forms a chemical bonding site for molecules forming the conducting polymer. The conducting polymer is then conventionally deposited by electrochemical deposition. In one example, a conducting film of polyaniline is formed on a gold electrode surface with an intermediate monolayer of p-aminothiophenol. 2 figs.

Polymeric matrix materials for infrared metamaterials

DOEpatents

Dirk, Shawn M; Rasberry, Roger D; Rahimian, Kamyar

2014-04-22

A polymeric matrix material exhibits low loss at optical frequencies and facilitates the fabrication of all-dielectric metamaterials. The low-loss polymeric matrix material can be synthesized by providing an unsaturated polymer, comprising double or triple bonds; partially hydrogenating the unsaturated polymer; depositing a film of the partially hydrogenated polymer and a crosslinker on a substrate; and photopatterning the film by exposing the film to ultraviolet light through a patterning mask, thereby cross-linking at least some of the remaining unsaturated groups of the partially hydrogenated polymer in the exposed portions.

Optical properties of BaTiO3 nanoparticles and silver nanoprisms in polymer host matrices

NASA Astrophysics Data System (ADS)

Requena, Sebastian

Nanocomposites are materials comprised of a host matrix, such as glass or polymer, with embedded nanoparticles. Embedding nanoparticles into the host makes it possible to create materials with properties that are distinctly unique from those of their host and nanoparticle constituents. Nanocomposites can have superior mechanical, thermal, and optical properties compared to their host materials. We characterized the photoluminescent properties of BaTiO3 polymer nanocomposites and the effects of chemically modifying the nanoparticles surface on said properties. BaTiO3 nanopowders of average grain sizes 50 nm and 100 nm were functionalized by (3-aminopropyl)triethoxysilane (3APTS) and mixed with poly(methyl methacrylate)/toluene solution. The nanocomposites films morphology and chemical structure were studied via AFM and FTIR. The photoluminescence spectrum of the pure nanoparticles was composed of an emission at ˜3.0 eV and multiple bands centered at ˜2.5 eV. Surface functionalization of the BaTiO3 nanoparticles via 3APTS increased overall luminescence at room temperature while only enhancing the ˜3.0 eV emission at low-temperature. On the other hand, polymer coating of the functionalized nanoparticles significantly enhances ˜3.0 eV emissions while decreasing emissions associated with near-surface lattice distortions at ˜2.5 eV. Chemical modification of the surface with 3APTS and PMMA presents a pathway to tune and control the photoluminescent properties of BTO nanoparticles. We also present optical studies of two different size distributions of silver triangular nanoprisms, one with a dipole resonance at ˜520 nm and the other with a dipole resonance at ˜650 nm, placed in different media. The silver nanoprisms were embedded in a polyvinyl alcohol (PVA) polymer matrix and oriented by stretching the polymer/nanoprism nanocomposite films. We observe significantly increased linear dichroism in the region associated with the plasmonic in-plane dipole mode upon stretching. Additionally, there is a weaker linear dichroism in the region associated with out-of-plane modes, which vanish in the extinction spectrum of the stretched nanocomposite film. Our results show that these silver nanoprisms are promising as key components in wavelength-specific depolarizers and depolarization-based assays.

Highly Enhanced Raman Scattering on Carbonized Polymer Films.

PubMed

Yoon, Jong-Chul; Hwang, Jongha; Thiyagarajan, Pradheep; Ruoff, Rodney S; Jang, Ji-Hyun

2017-06-28

We have discovered a carbonized polymer film to be a reliable and durable carbon-based substrate for carbon enhanced Raman scattering (CERS). Commercially available SU8 was spin coated and carbonized (c-SU8) to yield a film optimized to have a favorable Fermi level position for efficient charge transfer, which results in a significant Raman scattering enhancement under mild measurement conditions. A highly sensitive CERS (detection limit of 10 -8 M) that was uniform over a large area was achieved on a patterned c-SU8 film and the Raman signal intensity has remained constant for 2 years. This approach works not only for the CMOS-compatible c-SU8 film but for any carbonized film with the correct composition and Fermi level, as demonstrated with carbonized-PVA (poly(vinyl alcohol)) and carbonized-PVP (polyvinylpyrollidone) films. Our study certainly expands the rather narrow range of Raman-active material platforms to include robust carbon-based films readily obtained from polymer precursors. As it uses broadly applicable and cheap polymers, it could offer great advantages in the development of practical devices for chemical/bio analysis and sensors.

Core-Shell Double Gyroid Structure Formed by Linear ABC Terpolymer Thin Films.

PubMed

Antoine, Ségolène; Aissou, Karim; Mumtaz, Muhammad; Telitel, Siham; Pécastaings, Gilles; Wirotius, Anne-Laure; Brochon, Cyril; Cloutet, Eric; Fleury, Guillaume; Hadziioannou, Georges

2018-05-01

The synthesis and self-assembly in thin-film configuration of linear ABC triblock terpolymer chains consisting of polystyrene (PS), poly(2-vinylpyridine) (P2VP), and polyisoprene (PI) are described. For that purpose, a hydroxyl-terminated PS-b-P2VP (45 kg mol -1 ) building block and a carboxyl-terminated PI (9 kg mol -1 ) are first separately prepared by anionic polymerization, and then are coupled via a Steglich esterification reaction. This quantitative and metal-free catalyst synthesis route reveals to be very interesting since functionalization and purification steps are straightforward, and well-defined terpolymers are produced. A solvent vapor annealing (SVA) process is used to promote the self-assembly of frustrated PS-b-P2VP-b-PI chains into a thin-film core-shell double gyroid (Q 230 , space group: Ia3¯d) structure. As terraces are formed within PS-b-P2VP-b-PI thin films during the SVA process under a CHCl 3 vapor, different plane orientations of the Q 230 structure ((211), (110), (111), and (100)) are observed at the polymer-air interface depending on the film thickness. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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

Johnson, Kyle J.; Glynos, Emmanouil; Maroulas, Serafeim-Dionysios

Incorporating nanoparticles (NPs) within a polymer host to create polymer nanocomposites (PNCs) while having the effect of increasing the functionality (e.g., sensing, energy conversion) of these materials influences other properties. One challenge is to understand the effects of nanoparticles on the viscosity of nanoscale thick polymer films. A new mechanism that contributes to an enhancement of the viscosity of nanoscale thick polymer/nanoparticle films is identified. We show that while the viscosities of neat homopolymer poly(2-vinylpyridine) (P2VP) films as thin as 50 nm remained the same as the bulk, polymer/nanoparticle films containing P2VP brush-coated gold NPs, spaced 50 nm apart, exhibitedmore » unprecedented increases in viscosities of over an order of magnitude. For thicker films or more widely separated NPs, the chain dynamics and viscosities were comparable to the bulk values. These results - NP proximities and suppression of their dynamics - suggest a new mechanism by which the viscosities of polymeric liquids could be controlled for nanoscale applications.« less

Spectral and time-resolved properties of photoinduced hydroxyquinolines doped thin polymer films

NASA Astrophysics Data System (ADS)

Mehata, Mohan Singh

2018-01-01

Quinoline and its derivatives have a wide range of biological and pharmacological activities. Quinoline ring is used to design functional materials (quinoline derivatives) for OLEDs and field-induce electrooptics. It possesses antibacterial, antifungal, antimalarial, cardiotonic, anthelmintic, anti-inflammatory, anticonvulsant and analgesic activity. Here, we have examined photoexcitation dynamics of 6-hydroxyquinoline (6-HQ) doped in polymer films of polymethyl methacrylate (PMMA), polyvinyl alcohol (PVA) and cellulose acetate (CA) at atmospheric conditions. The absorption maximum of 6-HQ in polymer films was observed at 333 ± 1 nm, whereas fluorescence (FL) maximum fell in the range of 365-371 nm. In PVA film, in addition to the typical FL, a band maximum at 432 nm appeared as a result of an excited-state intermolecular proton transfer (ESIPT) reaction facilitated in the hydrogen-bonded complex formed in the ground state between 6-HQ:PVA. The multi-exponential decay behavior of 6-HQ in all the three polymer films indicates a nanoscale heterogeneity of the polymer environments.

Influence of ordering change on the optical and thermal properties of inflation polyethylene films

NASA Astrophysics Data System (ADS)

Morikawa, Junko; Orie, Akihiro; Hikima, Yuta; Hashimoto, Toshimasa; Juodkazis, Saulius

2011-04-01

Changes of thermal diffusivity inside femtosecond laser-structured volumes as small as few percent were reliably determined (with standard deviation less than 1%) with miniaturized sensors. An increase of thermal diffusivity of a crystalline high-density polyethylene (HDPE) inflation films by 10-20% from the measured (1.16 ± 0.01) × 10 -7 m 2 s -1 value in regions not structured by femtosecond laser pulses is considerably larger than that of non-crystalline polymers, 0-3%. The origin of the change of thermal diffusivity are interplay between the laser induced disordering, voids' formation, compaction, and changes in molecular orientation. It is shown that laser structuring can be used to modify thermal and optical properties. The birefringence and infrared spectroscopy with thermal imaging of CH 2 vibrations are confirming inter-relation between structural, optical, and thermal properties of the laser-structured crystalline HDPE inflation films. Birefringence modulation as high as Δ n ˜ ± 1 × 10 -3 is achieved with grating structures.

Comparison of solution-mixed and sequentially processed P3HT: F4TCNQ films: effect of doping-induced aggregation on film morphology

DOE PAGES

Jacobs, Ian E.; Aasen, Erik W.; Oliveira, Julia L.; ...

2016-03-23

Doping polymeric semiconductors often drastically reduces the solubility of the polymer, leading to difficulties in processing doped films. Here, we compare optical, electrical, and morphological properties of P3HT films doped with F4TCNQ, both from mixed solutions and using sequential solution processing with orthogonal solvents. We demonstrate that sequential doping occurs rapidly (<1 s), and that the film doping level can be precisely controlled by varying the concentration of the doping solution. Furthermore, the choice of sequential doping solvent controls whether dopant anions are included or excluded from polymer crystallites. Atomic force microscopy (AFM) reveals that sequential doping produces significantly moremore » uniform films on the nanoscale than the mixed-solution method. In addition, we show that mixed-solution doping induces the formation of aggregates even at low doping levels, resulting in drastic changes to film morphology. Sequentially coated films show 3–15 times higher conductivities at a given doping level than solution-doped films, with sequentially doped films processed to exclude dopant anions from polymer crystallites showing the highest conductivities. In conclusion, we propose a mechanism for doping induced aggregation in which the shift of the polymer HOMO level upon aggregation couples ionization and solvation energies. To show that the methodology is widely applicable, we demonstrate that several different polymer:dopant systems can be prepared by sequential doping.« less

Comparison of solution-mixed and sequentially processed P3HT: F4TCNQ films: effect of doping-induced aggregation on film morphology

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

Jacobs, Ian E.; Aasen, Erik W.; Oliveira, Julia L.

Doping polymeric semiconductors often drastically reduces the solubility of the polymer, leading to difficulties in processing doped films. Here, we compare optical, electrical, and morphological properties of P3HT films doped with F4TCNQ, both from mixed solutions and using sequential solution processing with orthogonal solvents. We demonstrate that sequential doping occurs rapidly (<1 s), and that the film doping level can be precisely controlled by varying the concentration of the doping solution. Furthermore, the choice of sequential doping solvent controls whether dopant anions are included or excluded from polymer crystallites. Atomic force microscopy (AFM) reveals that sequential doping produces significantly moremore » uniform films on the nanoscale than the mixed-solution method. In addition, we show that mixed-solution doping induces the formation of aggregates even at low doping levels, resulting in drastic changes to film morphology. Sequentially coated films show 3–15 times higher conductivities at a given doping level than solution-doped films, with sequentially doped films processed to exclude dopant anions from polymer crystallites showing the highest conductivities. In conclusion, we propose a mechanism for doping induced aggregation in which the shift of the polymer HOMO level upon aggregation couples ionization and solvation energies. To show that the methodology is widely applicable, we demonstrate that several different polymer:dopant systems can be prepared by sequential doping.« less

Robust Polymer Films: Nanoscale Stiffening as a Route to Strong Materials

DTIC Science & Technology

2011-10-20

Rheological Methods," Drexel University, Philadelphia, PA, March 4, 2011. S.Xu, "Geometry and molecular architecture effects in nanobubble inflation...2007. G.B. McKenna, "The viscoelastic properties of ultrathin polymer films as measured with a novel nanobubble inflation technique.” March Meeting of...mechanical response of ultrathin polymer films using the Texas Tech nanobubble inflation technique as the means to determine the viscoelastic

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

The effects of incidence angle on film dosimetry and their consequences in IMRT dose verification.

PubMed

Srivastava, R P; De Wagter, C

2012-10-01

The dosimetric accuracy of EDR2 radiographic film has been rigorously assessed in regular and intensity modulated beams for various incidence angles, including the parallel and perpendicular orientation. There clearly exists confusion in literature regarding the effect of film orientation. The primary aim is to clarify potential sources of the confusion and to gain physical insight into the film orientation effect with a link to radiochromic film as well. An inverse pyramid IMRT field, consisting of six regular and elongated 3 × 20 cm(2) field segments, was studied in perpendicular and parallel orientation. Assessment of film self-perturbation and intrinsic directional sensitivity were also included in the experiments. Finally, the authors investigated the orientational effect in composite beams in the two extreme orientations, i.e., perpendicular and parallel. The study of an inverse pyramid dose profile revealed good agreement between the perpendicular film and the diamond detector within 0.5% in the low-scatter regions for both 6 and 18 MV. The parallel oriented film demonstrated a 3% under-response at 5-cm (6 MV) depth against the perpendicular orientation, but both orientations over responded equally in the central region, which received only scattered dose, at both 5- and 20-cm depths. In a regular 6-MV 5 × 5 cm(2) field, a 4.1% lower film response was observed in the parallel orientation compared to perpendicular orientation. The under response gradually increased to 6% when reducing the field size to 0.5 × 5 cm(2). On the other hand, the film showed a 1.7% lower response in parallel orientation for the large field size of 20 × 20 cm(2) at 5-cm depth but the difference disappeared at 10 cm. At 18 MV, similar but somewhat lower differences were found between the two orientations. The directional sensitivity of the film diminishes with increasing field size and depth. Surprisingly a composite IMRT beam consisting of 20 adjacent strip segments also produced a significant orientational dependence of film response, notwithstanding the large total field size of 20 × 20 cm(2). This analysis allowed the development of a hypothesis about the physics behind the orientational dependence of film response in general and to formulate precautions when using film dosimetry in the dosimetric verification of multibeam treatments.

Three-Dimensional Microphase Separation and Synergistic Permeability in Stacked Lipid–Polymer Hybrid Membranes

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

Kang, Minjee; Lee, Byeongdu; Leal, Cecilia

Here, we present new structures of soft-material thin films that augment the functionality of substrate-mediated delivery systems. A hybrid material composed of phospholipids and block copolymers adopts a multilayered membrane structure supported on a solid surface. The hybrid films comprise intentional intramembrane heterogeneities that register across multilayers. These stacked domains convey unprecedented enhancement and control of permeability of solutes across micrometer-thick films. Using grazing incidence X-ray scattering, phase contrast atomic force microscopy, and confocal microscopy, we observed that in each lamella, lipid and polymers partition unevenly within the membrane plane segregating into lipid- or polymer-rich domains. Interestingly, we found evidencemore » that like-domains align in registry across multilayers, thereby making phase separation three-dimensional. Phase boundaries exist over extended length scales to compensate the height mismatch between lipid and polymer molecules. We show that microphase separation in hybrid films can be exploited to augment the capability of drug-eluting substrates. Lipid–polymer hybrid films loaded with paclitaxel show synergistic permeability of drug compared to single-component counterparts. We present a thorough structural study of stacked lipid–polymer hybrid membranes and propose that the presence of registered domains and domain boundaries impart enhanced drug release functionality. This work offers new perspectives in designing thin films for controlled delivery applications« less

Three-Dimensional Microphase Separation and Synergistic Permeability in Stacked Lipid–Polymer Hybrid Membranes

DOE PAGES

Kang, Minjee; Lee, Byeongdu; Leal, Cecilia

2017-10-20

Here, we present new structures of soft-material thin films that augment the functionality of substrate-mediated delivery systems. A hybrid material composed of phospholipids and block copolymers adopts a multilayered membrane structure supported on a solid surface. The hybrid films comprise intentional intramembrane heterogeneities that register across multilayers. These stacked domains convey unprecedented enhancement and control of permeability of solutes across micrometer-thick films. Using grazing incidence X-ray scattering, phase contrast atomic force microscopy, and confocal microscopy, we observed that in each lamella, lipid and polymers partition unevenly within the membrane plane segregating into lipid- or polymer-rich domains. Interestingly, we found evidencemore » that like-domains align in registry across multilayers, thereby making phase separation three-dimensional. Phase boundaries exist over extended length scales to compensate the height mismatch between lipid and polymer molecules. We show that microphase separation in hybrid films can be exploited to augment the capability of drug-eluting substrates. Lipid–polymer hybrid films loaded with paclitaxel show synergistic permeability of drug compared to single-component counterparts. We present a thorough structural study of stacked lipid–polymer hybrid membranes and propose that the presence of registered domains and domain boundaries impart enhanced drug release functionality. This work offers new perspectives in designing thin films for controlled delivery applications« less

Ibuprofen-loaded poly(lactic-co-glycolic acid) films for controlled drug release.

PubMed

Pang, Jianmei; Luan, Yuxia; Li, Feifei; Cai, Xiaoqing; Du, Jimin; Li, Zhonghao

2011-01-01

Ibuprofen- (IBU) loaded biocompatible poly(lactic-co-glycolic acid) (PLGA) films were prepared by spreading polymer/ibuprofen solution on the nonsolvent surface. By controlling the weight ratio of drug and polymer, different drug loading polymer films can be obtained. The synthesized ibuprofen-loaded PLGA films were characterized with scanning electron microscopy, powder X-ray diffraction, and differential scanning calorimetry. The drug release behavior of the as-prepared IBU-loaded PLGA films was studied to reveal their potential application in drug delivery systems. The results show the feasibility of the as-obtained films for controlling drug release. Furthermore, the drug release rate of the film could be controlled by the drug loading content and the release medium. The development of a biodegradable ibuprofen system, based on films, should be of great interest in drug delivery systems.

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

Luo, Sijun, E-mail: sluo1@tulane.edu; Riggs, Brian C.; Shipman, Joshua T.

Direct integration of proton conductor films on Pt-coated substrates opens the way to film-based proton transport devices. Columnar SrZr{sub 0.95}Y{sub 0.05}O{sub 3−δ} (SZY) films with dense microstructure were deposited on Pt-coated MgO(100) substrates at 830 °C by pulsed laser deposition. The optimal window of ambient O{sub 2} pressure for good crystallinity of SZY films is from 400 to 600 mTorr. The ambient O{sub 2} compresses the plasma plume of SZY and increases the deposition rate. The 10 nm thick Ti adhesion layer on MgO(100) greatly affects the orientation of the sputtered Pt layers. Pt deposited directly on MgO shows a highly (111)-preferredmore » orientation and leads to preferentially oriented SZY films while the addition of a Ti adhesion layer makes Pt show a less preferential orientation that leads to randomly oriented SZY films. The RMS surface roughness of preferentially oriented SZY films is larger than that of randomly oriented SZY films deposited under the same ambient O{sub 2} pressure. As the O{sub 2} pressure increased, the RMS surface roughness of preferentially oriented SZY films increased, reaching 45.7 nm (2.61% of film thickness) at 600 mTorr. This study revealed the ambient O{sub 2} pressure and orientation dependent surface roughness of SZY films grown on Pt-coated MgO substrates, which provides the potential to control the surface microstructure of SZY films for electrochemical applications in film-based hydrogen devices.« less

Special Polymer/Carbon Composite Films for Detecting SO2

NASA Technical Reports Server (NTRS)

Homer, Margie; Ryan, Margaret; Yen, Shiao-Pin; Kisor, Adam; Jewell, April; Shevade, Abhijit; Manatt, Kenneth; Taylor, Charles; Blanco, Mario; Goddard, William

2008-01-01

A family of polymer/carbon films has been developed for use as sensory films in electronic noses for detecting SO2 gas at concentrations as low as 1 part per million (ppm). Most previously reported SO2 sensors cannot detect SO2 at concentrations below tens of ppm; only a few can detect SO2 at 1 ppm. Most of the sensory materials used in those sensors (especially inorganic ones that include solid oxide electrolytes, metal oxides, and cadmium sulfide) must be used under relatively harsh conditions that include operation and regeneration at temperatures greater than 100 C. In contrast, the present films can be used to detect 1 ppm of SO2 at typical opening temperatures between 28 and 32 C and can be regenerated at temperatures between 36 and 40 C. The basic concept of making sensing films from polymer/carbon composites is not new. The novelty of the present family of polymer/carbon composites lies in formulating the polymer components of these composites specifically to optimize their properties for detecting SO2. First-principles quantum-mechanical calculations of the energies of binding of SO2 molecules to various polymer functionalities are used as a guide for selecting polymers and understanding the role of polymer functionalities in sensing. The polymer used in the polymer-carbon composite is a copolymer of styrene derivative units with vinyl pyridine or substituted vinyl pyridine derivative units. To make a substituted vinyl pyridine for use in synthesizing such a polymer, poly(2-vinyl pyridine) that has been dissolved in methanol is reacted with 3-chloropropylamine that has been dissolved in a solution of methanol. The methanol is then removed to obtain the copolymer. Later, the copolymer can be dissolved in an appropriate solvent with a suspension of carbon black to obtain a mixture that can be cast and then dried to obtain a sensory film.

Convective polymer assembly for the deposition of nanostructures and polymer thin films on immobilized particles.

PubMed

Richardson, Joseph J; Björnmalm, Mattias; Gunawan, Sylvia T; Guo, Junling; Liang, Kang; Tardy, Blaise; Sekiguchi, Shota; Noi, Ka Fung; Cui, Jiwei; Ejima, Hirotaka; Caruso, Frank

2014-11-21

We report the preparation of polymer particles via convective polymer assembly (CPA). Convection is used to move polymer solutions and cargo through an agarose gel that contains immobilized template particles. This method both coats and washes the particles in a process that is amenable to automation, and does not depend on passive diffusion or electrical currents, thus facilitating incorporation of fragile and nanoscale objects, such as liposomes and gold nanoparticles, into the thin polymer films. Template dissolution leads to the formation of stable polymer particles and capsules.

Nanoparticles of conjugated polymers prepared from phase-separated films of phospholipids and polymers for biomedical applications.

PubMed

Yoon, Jungju; Kwag, Jungheon; Shin, Tae Joo; Park, Joonhyuck; Lee, Yong Man; Lee, Yebin; Park, Jonghyup; Heo, Jung; Joo, Chulmin; Park, Tae Jung; Yoo, Pil J; Kim, Sungjee; Park, Juhyun

2014-07-09

Phase separation in films of phospholipids and conjugated polymers results in nanoassemblies because of a difference in the physicochemical properties between the hydrophobic polymers and the polar lipid heads, together with the comparable polymer side-chain lengths to lipid tail lengths, thus producing nanoparticles of conjugated polymers upon disassembly in aqueous media by the penetration of water into polar regions of the lipid heads. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microstructured Polymer Blend Surfaces Produced by Spraying Functional Copolymers and Their Blends

PubMed Central

Vargas-Alfredo, Nelson; Rodríguez Hernández, Juan

2016-01-01

We described the fabrication of functional and microstructured surfaces from polymer blends by spray deposition. This simple technique offers the possibility to simultaneously finely tune the microstructure as well as the surface chemical composition. Whereas at lower polymer concentration, randomly distributed surface micropatterns were observed, an increase of the concentration leads to significant changes on these structures. On the one hand, using pure homopolystyrene fiber-like structures were observed when the polymer concentration exceeded 30 mg/mL. Interestingly, the incorporation of 2,3,4,5,6-pentafluorostyrene changed the morphology, and, instead of fibers, micrometer size particles were identified at the surface. These fluorinated microparticles provide superhydrophobic properties leading to surfaces with contact angles above 165°. Equally, in addition to the microstructures provided by the spray deposition, the use of thermoresponsive polymers to fabricate interfaces with responsive properties is also described. Contact angle measurements revealed variations on the surface wettability upon heating when blends of polystyrene and polystyrene-b-poly(dimethylaminoethyl methacrylate) are employed. Finally, the use of spraying techniques to fabricate gradient surfaces is proposed. Maintaining a constant orientation, the surface topography and thus the contact angle varies gradually from the center to the edge of the film depending on the spray angle. PMID:28773555

High through-plane thermal conduction of graphene nanoflake filled polymer composites melt-processed in an L-shape kinked tube.

PubMed

Jung, Haejong; Yu, Seunggun; Bae, Nam-Seok; Cho, Suk Man; Kim, Richard Hahnkee; Cho, Sung Hwan; Hwang, Ihn; Jeong, Beomjin; Ryu, Ji Su; Hwang, Junyeon; Hong, Soon Man; Koo, Chong Min; Park, Cheolmin

2015-07-22

Design of materials to be heat-conductive in a preferred direction is a crucial issue for efficient heat dissipation in systems using stacked devices. Here, we demonstrate a facile route to fabricate polymer composites with directional thermal conduction. Our method is based on control of the orientation of fillers with anisotropic heat conduction. Melt-compression of solution-cast poly(vinylidene fluoride) (PVDF) and graphene nanoflake (GNF) films in an L-shape kinked tube yielded a lightweight polymer composite with the surface normal of GNF preferentially aligned perpendicular to the melt-flow direction, giving rise to a directional thermal conductivity of approximately 10 W/mK at 25 vol % with an anisotropic thermal conduction ratio greater than six. The high directional thermal conduction was attributed to the two-dimensional planar shape of GNFs readily adaptable to the molten polymer flow, compared with highly entangled carbon nanotubes and three-dimensional graphite fillers. Furthermore, our composite with its density of approximately 1.5 g/cm(3) was mechanically stable, and its thermal performance was successfully preserved above 100 °C even after multiple heating and cooling cycles. The results indicate that the methodology using an L-shape kinked tube is a new way to achieve polymer composites with highly anisotropic thermal conduction.

Effects of excipients on the tensile strength, surface properties and free volume of Klucel® free films of pharmaceutical importance

NASA Astrophysics Data System (ADS)

Gottnek, Mihály; Süvegh, Károly; Pintye-Hódi, Klára; Regdon, Géza

2013-08-01

The physicochemical properties of polymers planned to be applied as mucoadhesive films were studied. Two types of Klucel® hydroxypropylcellulose (LF and MF) were used as film-forming polymers. Hydroxypropylcellulose was incorporated in 2 w/w% with glycerol and xylitol as excipients and lidocaine base as an active ingredient at 5, 10 or 15 w/w% of the mass of the film-forming polymer. The free volume changes of the films were investigated by positron annihilation lifetime spectroscopy, the mechanical properties of the samples were measured with a tensile strength tester and contact angles were determined to assess the surface properties of the films. It was found that the Klucel® MF films had better physicochemical properties than those of the LF films. Klucel® MF as a film-forming polymer with lidocaine base and both excipients at 5 w/w% exhibited physicochemical properties and good workability. The excipients proved to exert strong effects on the physicochemical properties of the tested systems and it is very important to study them intensively in preformulation studies in the pharmaceutical technology in order to utilise their benefits and to avoid any disadvantageous effects.

Elements of adaptive optics based on metallized polymer films

NASA Astrophysics Data System (ADS)

Voliak, T. B.; Krasiuk, I. K.; Pashinin, P. P.

Results of an experimental study of the stability of metallized polymer films exposed to laser radiation at wavelengths of 1.06 and 10.6 microns are reported, and methods for fabricating variable-curvature mirrors from these films are discussed. Formulas are presented for calculating the shape of film mirrors as a function of the pressure acting on the film, mounting contour, and film properties. The performance of film mirrors is investigated experimentally in a pulsed CO2 laser with stable and unstable resonators.

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.

High-Performance Photovoltaic Behavior of Oriented Purple Membrane Polymer Composite Films

PubMed Central

Zhang, Liangmin; Zeng, Tingying; Cooper, Kristie; Claus, Richard O.

2003-01-01

The photovoltaic behavior of films in which bacteriorhodopsin molecules are embedded in a polyvinyl alcohol matrix has been investigated by using both pulsed laser excitation and regular light illumination. Response times as short as milliseconds, photocurrents as great as 120 μA/cm2, and photovoltages as large as 3.8 V have been obtained. A theoretical model has been developed and used to extract several physical parameters and fit the experimental results. Some important intrinsic parameters have been obtained. Theoretical results indicate that the average displacement of the excited protons is on the order of several tens of microns. Other curve fits show that photocurrent and photovoltage increase linearly with external field, but increase exponentially with flash power. These theoretical models and results can be extended to other kinds of photoactive polymeric materials. PMID:12668458

Polymers for electronics and spintronics.

PubMed

Bujak, Piotr; Kulszewicz-Bajer, Irena; Zagorska, Malgorzata; Maurel, Vincent; Wielgus, Ireneusz; Pron, Adam

2013-12-07

This critical review is devoted to semiconducting and high spin polymers which are of great scientific interest in view of further development of the organic electronics and the emerging organic spintronic fields. Diversified synthetic strategies are discussed in detail leading to high molecular mass compounds showing appropriate redox (ionization potential (IP), electron affinity (EA)), electronic (charge carrier mobility, conductivity), optoelectronic (electroluminescence, photoconductivity) and magnetic (magnetization, ferromagnetic spin interactions) properties and used as active components of devices such as n- and p-channel field effect transistors, ambipolar light emitting transistors, light emitting diodes, photovoltaic cells, photodiodes, magnetic photoswitches, etc. Solution processing procedures developed with the goal of depositing highly ordered and oriented films of these polymers are also described. This is completed by the description of principal methods that are used for characterizing these macromolecular compounds both in solution and in the solid state. These involve various spectroscopic methods (UV-vis-NIR, UPS, pulse EPR), electrochemistry and spectroelectrochemistry, magnetic measurements (SQUID), and structural and morphological investigations (X-ray diffraction, STM, AFM). Finally, four classes of polymers are discussed in detail with special emphasis on the results obtained in the past three years: (i) high IP, (ii) high |EA|, (iii) low band gap and (iv) high spin ones.

Preparation of redox polymer cathodes for thin film rechargeable batteries

DOEpatents

Skotheim, T.A.; Lee, H.S.; Okamoto, Yoshiyuki.

1994-11-08

The present invention relates to the manufacture of thin film solid state electrochemical devices using composite cathodes comprising a redox polymer capable of undergoing oxidation and reduction, a polymer solid electrolyte and conducting carbon. The polymeric cathode material is formed as a composite of radiation crosslinked polymer electrolytes and radiation crosslinked redox polymers based on polysiloxane backbones with attached organosulfur side groups capable of forming sulfur-sulfur bonds during electrochemical oxidation.

Constitutive Modeling of Nanotube/Polymer Composites with Various Nanotube Orientations

NASA Technical Reports Server (NTRS)

Odegard, Gregory M.; Gates, Thomas S.

2002-01-01

In this study, a technique has been proposed for developing constitutive models for polymer composite systems reinforced with single-walled carbon nanotubes (SWNT) with various orientations with respect to the bulk material coordinates. A nanotube, the local polymer adjacent to the nanotube, and the nanotube/polymer interface have been modeled as an equivalent-continuum fiber by using an equivalent-continuum modeling method. The equivalent-continuum fiber accounts for the local molecular structure and bonding information and serves as a means for incorporating micromechanical analyses for the prediction of bulk mechanical properties of SWNT/polymer composite. As an example, the proposed approach is used for the constitutive modeling of a SWNT/LaRC-SI (with a PmPV interface) composite system, with aligned nanotubes, three-dimensionally randomly oriented nanotubes, and nanotubes oriented with varying degrees of axisymmetry. It is shown that the Young s modulus is highly dependent on the SWNT orientation distribution.

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

Routh, Prahlad K.; Nykypanchuk, Dmytro; Venkatesh, T. A.

Large area, device relevant sized microporous thin films are formed with commercially available polythiophenes by the breath figure technique, a water-assisted micro patterning method, with such semitransparent thin films exhibiting periodicity and uniformity dictated by the length of the polymer side chain. Compared to drop casted thin films, the microporous thin films exhibit increased crystallinity due to stronger packing of the polymer inside the honeycomb frame.

Characterization of polymer, DNA-based, and silk thin film resistivities and of DNA-based films prepared for enhanced electrical conductivity

NASA Astrophysics Data System (ADS)

Yaney, Perry P.; Ouchen, Fahima; Grote, James G.

2009-08-01

DC resistivity studies were carried out on biopolymer films of DNA-CTMA and silk fibroin, and on selected traditional polymer films, including PMMA and APC. Films of DNA-CTMA versus molecular weight and with conductive dopants PCBM, BAYTRON P and ammonium tetrachloroplatinate are reported. The films were spin coated on glass slides configured for measurements of volume dc resistance. The measurements used the alternating polarity method to record the applied voltage-dependent current independent of charging and background currents. The Arrhenius equation plus a constant was fitted to the conductivity versus temperature data of the polymers and the non-doped DNA-based biopolymers with activation energies ranging from 0.8 to 1.4 eV.

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.

Oxygen and hydrogen evolution reaction on oriented single crystals of ruthenium dioxide

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

Berger, L I; Pollak, F H; Canivez, Y

1979-01-01

A novel design for water electrolysis using a solid polymer electrolyte is being developed by General Electric. Ruthenium is one of the best electrocatalysts for the oxygen evolution reaction. There are problems connected with the significant loss in electrocatalytic activity with time. This performance degradation is presumably due to the gradual formation of an RuO/sub 2/ film. We have performed electrochemical measurements on (100), (110) and (111) oriented single crystals of RuO/sub 2/ in order to elucidate the mechanism of the electrocatalytic process. Large single crystals were grown by the vapor transport method. Our investigation has revealed several interesting differencesmore » for the various orientations. This study indicates that RuO/sub 3/ may be an important intermediate species prior to oxygen evolution and that the formation of the RuO/sub 3/ is the rate limiting process. Similar results were previously obtained for IrO/sub 2/.« less

Highly Flexible and Planar Supercapacitors Using Graphite Flakes/Polypyrrole in Polymer Lapping Film.

PubMed

Raj, C Justin; Kim, Byung Chul; Cho, Won-Je; Lee, Won-gil; Jung, Sang-Don; Kim, Yong Hee; Park, Sang Yeop; Yu, Kook Hyun

2015-06-24

Flexible supercapacitor electrodes have been fabricated by simple fabrication technique using graphite nanoflakes on polymer lapping films as flexible substrate. An additional thin layer of conducting polymer polypyrrole over the electrode improved the surface conductivity and exhibited excellent electrochemical performances. Such capacitor films showed better energy density and power density with a maximum capacitance value of 37 mF cm(-2) in a half cell configuration using 1 M H2SO4 electrolyte, 23 mF cm(-2) in full cell, and 6 mF cm(-2) as planar cell configuration using poly(vinyl alcohol) (PVA)/phosphoric acid (H3PO4) solid state electrolyte. Moreover, the graphite nanoflakes/polypyrrole over polymer lapping film demonstrated good flexibility and cyclic stability.

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.

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.

Gas Permeation in Thin Glassy Polymer Films

NASA Astrophysics Data System (ADS)

Paul, Donald

2011-03-01

The development of asymmetric and composite membranes with very thin dense ``skins'' needed to achieve high gas fluxes enabled the commercial use of membranes for molecular level separations. It has been generally assumed that these thin skins, with thicknesses of the order of 100 nm, have the same permeation characteristics as films with thicknesses of 25 microns or more. Thick films are easily made in the laboratory and have been used extensively for measuring permeation characteristics to evaluate the potential of new polymers for membrane applications. There is now evidence that this assumption can be in very significant error, and use of thick film data to select membrane materials or predict performance should be done with caution. This presentation will summarize our work on preparing films of glassy polymers as thin as 20 nm and characterizing their behavior by gas permeation, ellipsometry and positron annihilation lifetime spectroscopy. Some of the most important polymers used commercially as gas separation membranes, i.e., Matrimid polyimide, polysulfone (PSF) and poly(2,6-dimethyl-1,4-phenylene oxide) (PPO), have been made into well-defined thin films in our laboratories by spin casting techniques and their properties studied using the techniques we have developed. These thin films densify (or physically age) much faster than thicker films, and, as result, the permeability decreases, sometimes by several-fold over weeks or months for thin films. This means that the properties of these thin films can be very different from bulk films. The techniques, interpretations and implications of these observations will be discussed. In a broader sense, gas permeation measurements can be a powerful way of developing a better understanding of the effects of polymer chain confinement and/or surface mobility on the behavior of thin films.

Dynamic mechanical thermal analysis of hypromellose 2910 free films.

PubMed

Cespi, Marco; Bonacucina, Giulia; Mencarelli, Giovanna; Casettari, Luca; Palmieri, Giovanni Filippo

2011-10-01

It is common practice to coat oral solid dosage forms with polymeric materials for controlled release purposes or for practical and aesthetic reasons. Good knowledge of thermo-mechanical film properties or their variation as a function of polymer grade, type and amount of additives or preparation method is of prime importance in developing solid dosage forms. This work focused on the dynamic mechanical thermal characteristics of free films of hypromellose 2910 (also known as HPMC), prepared using three grades of this polymer from two different manufacturers, in order to assess whether polymer chain length or origin affects the mechanical or thermo-mechanical properties of the final films. Hypromellose free films were obtained by casting their aqueous solutions prepared at a specific concentrations in order to obtain the same viscosity for each. The films were stored at room temperature until dried and then examined using a dynamic mechanical analyser. The results of the frequency scans showed no significant differences in the mechanical moduli E' and E″ of the different samples when analysed at room temperature; however, the grade of the polymer affected material transitions during the heating process. Glass transition temperature, apparent activation energy and fragility parameters depended on polymer chain length, while the material brand showed little impact on film performance. Copyright © 2011 Elsevier B.V. All rights reserved.

Porous structures of polymer films prepared by spin coating with mixed solvents under humid condition.

PubMed

Park, Min Soo; Joo, Wonchul; Kim, Jin Kon

2006-05-09

We investigate the effects of interfacial energy between water and solvent as well as polymer concentration on the formation of porous structures of polymer films prepared by spin coating of cellulose acetate butyrate (CAB) in mixed solvent of tetrahydrofuran (THF) and chloroform under humid condition. The interfacial energy between water and the solvent was gradually changed by the addition of chloroform to the solvent. At a high polymer concentration (0.15 g/cm3 in THF), porous structures were limited only at the top surfaces of CAB films, regardless of interfacial energies, due to the high viscosity of the solution. At a medium concentration (approximately 0.08 g/cm3 in THF), CAB film had relatively uniform pores at the top surface and very small pores inside the film because of the mixing of the water droplets with THF solution. When chloroform was added to THF, pores at the inner CAB film had a comparable size with those at the top surface because of the reduced degree of the mixing between the water droplets and the mixed solvent. A further decrease in polymer concentration (0.05 g/cm3 in THF) caused the final films to have a two-layer porous structure, and the size of pores at each layer was almost the same.

Influence of substrate and film thickness on polymer LIPSS formation

NASA Astrophysics Data System (ADS)

Cui, Jing; Nogales, Aurora; Ezquerra, Tiberio A.; Rebollar, Esther

2017-02-01

Here we focus on the influence of both, substrate and film thickness on polymer Laser Induced Periodic Surface Structures (LIPSS) formation in polymer films. For this aim a morphological description of ripples structures generated on spin-coated polystyrene (PS) films by a linearly polarized laser beam with a wavelength of 266 nm is presented. The influence of different parameters on the quality and characteristics of the formed laser-induced periodic surface structures (LIPSS) was investigated. We found that well-ordered LIPSS are formed either on PS films thinner than 200 nm or thicker than 400 nm supported on silicon substrates as well as on thicker free standing films. However less-ordered ripples are formed on silicon supported films with intermediate thicknesses in the range of 200-380 nm. The effect of the thermal and optical properties of the substrate on the quality of LIPSS was analyzed. Differences observed in the fluence and number of pulses needed for the onset of surface morphological modifications is explained considering two main effects which are: (1) The temperature increase on polymer surface induced by the action of cumulative laser irradiation and (2) The differences in thermal conductivity between the polymer and the substrate which strongly affect the heat dissipation generated by irradiation.

Measuring Exciton Diffusion in Conjugated Polymer Films with Super-resolution Microscopy

NASA Astrophysics Data System (ADS)

Penwell, Samuel; Ginsberg, Lucas; Noriega Manez, Rodrigo; Ginsberg, Naomi

2015-03-01

Conjugated polymers are highly tunable organic semiconductors, which can be solution processed to form thin films, making them prime candidates for organic photovoltaic devices. One of the most important parameters in a conjugated polymer solar cell is the exciton diffusion length, which depends on intermolecular couplings, and is typically on the order of 10 nm. This mean exciton migration can vary dramatically between films and within a single film due to heterogeneities in morphology on length scales of 10's to 100's nm. To study the variability of exciton diffusion and morphology within individual conjugated polymer films, we are adapting stimulated emission depletion microscopy. STED is typically used in biology with well-engineered fluorescent labels or on NV-centers in diamond. I will, however, describe how we have demonstrated STED in conjugated polymer films of MEH-PPV and CN-PPV by taking care to first understand the film's photophysical properties. This new approach provides a way to study exciton diffusion by utilizing subdiffraction optical excitation volumes. In this way, we will obtain a spatiotemporal map of exciton distributions that will help to correlate the energetic landscape to film morphology at the nanoscale. This research is supported in part by the Department of Energy Office of Science Graduate Fellowship Program (DOE SCGF), made possible in part by the American Recovery and Reinvestment Act of 2009, administered by ORISE-ORAU under Contract No. DE-AC05-06.

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.

Polymer Ni-MH battery based on PEO-PVA-KOH polymer electrolyte

NASA Astrophysics Data System (ADS)

Yang, Chun-Chen

An alkaline polymer electrolyte film has been prepared by a solvent-casting method. Poly(vinyl alcohol), PVA is added to improve the ionic conductivity of the electrolyte. The ionic conductivity increases from 10 -7 to 10 -2 S cm -1 at room temperature when the weight percent ratio of poly(ethylene oxide), PEO to PVA is increased from 10:0 to 5:5. The activation energy of the ionic conductivity for the PEO-PVA-KOH polymer electrolyte is 3-8 kJ mol -1. The properties of the electrolyte film are characterized by a wide variety of techniques and it is found that the film exhibits good mechanical stability and high ionic conductivity at room temperature. The application of such electrolyte films to nickel-metal-hydride (Ni-MH) batteries is examined and the electrochemical characteristics of a polymer Ni-MH battery are obtained.

Capillary levelling as a probe of rheology in polymer thin films

NASA Astrophysics Data System (ADS)

McGraw, Joshua D.; Jago, Nick M.; Dalnoki-Veress, Kari

2011-03-01

While measuring the rheology of bulk polymer systems is routine, when the size of a system becomes comparable to the molecular size, flow properties are poorly understood and hard to measure. Here, we present the results of experiments that are easily performed and can probe the rheological properties of polymer films that are mere tens of nanometres in thickness. We prepare glassy bilayer polymer films with height profiles well approximated by a step function. Upon annealing above the glass transition, broadening of the height profiles due to gradients in the Laplace pressure is observed. By validating the technique as a probe of the rheology with a range of molecular weights, we will show that this robust technique can be used to investigate the effects of confinement and interfaces on the rheology of ultrathin polymer films. Financial support from NSERC of Canada is gratefully acknowledged.

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

Orientation of Zn3P2 films via phosphidation of Zn precursors

NASA Astrophysics Data System (ADS)

Katsube, Ryoji; Nose, Yoshitaro

2017-02-01

Orientation of solar absorber is an important factor to achieve high efficiency of thin film solar cells. In the case of Zn3P2 which is a promising absorber of low-cost and high-efficiency solar cells, (110)/(001) orientation was only reported in previous studies. We have successfully prepared (101)-oriented Zn3P2 films by phosphidation of (0001)-oriented Zn films at 350 °C. The phosphidation mechanism of Zn is discussed through STEM observations on the partially-reacted sample and the consideration of the relationship between the crystal structures of Zn and Zn3P2 . We revealed that (0001)-oriented Zn led to nucleation of (101)-oriented Zn3P2 due to the similarity in atomic arrangement between Zn and Zn3P2 . The electrical resistivity of the (101)-oriented Zn3P2 film was lower than those of (110)/(001)-oriented films, which is an advantage of the phosphidation technique to the growth processes in previous works. The results in this study demonstrated that well-conductive Zn3P2 films could be obtained by controlling orientations of crystal grains, and provide a guiding principle for microstructure control in absorber materials.

Novel "breath figure"-based synthetic PLGA matrices for in vitro modeling of mammary morphogenesis and assessing chemotherapeutic response.

PubMed

Ponnusamy, Thiruselvam; Chakravarty, Geetika; Mondal, Debasis; John, Vijay T

2014-05-01

Biodegradable poly(lactic-co-glycolic acid) (PLGA) porous films are developed to support mammary cell growth and function. Such porous polymer matrices of PLGA are generated using the easily implemented water-templating "breath-figure" technique that allows water droplets to penetrate the nascent polymer films to create a rough porous polymer film. Such breath figure-based micropatterned porous films show higher epithelial differentiation and growth than the corresponding flat 2D films, and represent the first instance of using them for tissue culture. Specifically, the breath figure morphology supports robust acinar growth with almost double the number of lobular-alveolar units compared to the 2D cultures. Gene profile analysis indicates that the cells grown on porous polymer films show enhanced expressions of mammary differentiation genes (GATA3, EMA, and INTEGB4) but lower the expression of mesenchymal gene (CALLA). Hormonal stimulation of these cultures dramatically increases expression of progenitor marker gene Notch1. Importantly, cells grown on porous PLGA films exhibit an enhanced resistance to doxorubicin treatment in comparison to 2D cultures. Breath-figure PLGA films show promise in mimicking in vivo mammary functions and can potentially be used to screen chemotherapeutic drugs. The simplicity and ease of fabrication of these polymer films is especially appealing to the development of effective biomaterials to support cell culture and differentiation. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Method for forming thin composite solid electrolyte film for lithium batteries

NASA Technical Reports Server (NTRS)

Attia, Alan I. (Inventor); Nagasubramanian, Ganesan (Inventor)

1997-01-01

A composite solid electrolyte film is formed by dissolving a lithium salt such as lithium iodide in a mixture of a first solvent which is a cosolvent for the lithium salt and a binder polymer such as polyethylene oxide and a second solvent which is a solvent for the binder polymer and has poor solubility for the lithium salt. Reinforcing filler such as alumina particles are then added to form a suspension followed by the slow addition of binder polymer. The binder polymer does not agglomerate the alumina particles. The suspension is cast into a uniform film.

Method for forming thin composite solid electrolyte film for lithium batteries

NASA Technical Reports Server (NTRS)

Nagasubramanian, Ganesan (Inventor); Attia, Alan I. (Inventor)

1994-01-01

A composite solid electrolyte film is formed by dissolving a lithium salt such as lithium iodide in a mixture of a first solvent which is a co-solvent for the lithium salt and a binder polymer such as polyethylene oxide and a second solvent which is a solvent for the binder polymer and has poor solubility for the lithium salt. Reinforcing filler such as alumina particles are then added to form a suspension followed by the slow addition of binder polymer. The binder polymer does not agglomerate the alumina particles. The suspension is cast into a uniform film.

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.

Scanning Angle Raman spectroscopy in polymer thin film characterization

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

Nguyen, Vy H.T.

The focus of this thesis is the application of Raman spectroscopy for the characterization of thin polymer films. Chapter 1 provides background information and motivation, including the fundamentals of Raman spectroscopy for chemical analysis, scanning angle Raman scattering and scanning angle Raman scattering for applications in thin polymer film characterization. Chapter 2 represents a published manuscript that focuses on the application of scanning angle Raman spectroscopy for the analysis of submicron thin films with a description of methodology for measuring the film thickness and location of an interface between two polymer layers. Chapter 3 provides an outlook and future directionsmore » for the work outlined in this thesis. Appendix A, contains a published manuscript that outlines the use of Raman spectroscopy to aid in the synthesis of heterogeneous catalytic systems. Appendix B and C contain published manuscripts that set a foundation for the work presented in Chapter 2.« less

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.

Composite membranes from photochemical synthesis of ultrathin polymer films

NASA Astrophysics Data System (ADS)

Liu, Chao; Martin, Charles R.

1991-07-01

THERE has recently been a resurgence of interest in synthetic membranes and membrane-based processes1-12. This is motivated by a wide variety of technological applications, such as chemical separations1-7, bioreactors and sensors8,9, energy conversion10,11 and drug-delivery systems12. Many of these technologies require the ability to prepare extremely thin, defect-free synthetic (generally polymeric) films, which are supported on microporous supports to form composite membranes. Here we describe a method for producing composite membranes of this sort that incorporate high-quality polymer films less than 50-nm thick. The method involves interfacial photopolymerization of a thin polymer film on the surface of the microporous substrate. We have been able to use this technique to synthesize a variety of functionalized ultrathin films based on electroactive, photoactive and ion-exchange polymers. We demonstrate the method here with composite membranes that show exceptional gas-transport properties.

Structure of disordered gold-polymer thin films using small angle x-ray scattering

NASA Astrophysics Data System (ADS)

Teixeira, F. S.; Salvadori, M. C.; Cattani, M.; Brown, I. G.

2010-11-01

We have investigated the structure of disordered gold-polymer thin films using small angle x-ray scattering and compared the results with the predictions of a theoretical model based on two approaches—a structure form factor approach and the generalized Porod law. The films are formed of polymer-embedded gold nanoclusters and were fabricated by very low energy gold ion implantation into polymethylmethacrylate (PMMA). The composite films span (with dose variation) the transition from electrically insulating to electrically conducting regimes, a range of interest fundamentally and technologically. We find excellent agreement with theory and show that the PMMA-Au films have monodispersive or polydispersive characteristics depending on the implanted ion dose.

Bottom Extreme-Ultraviolet-Sensitive Coating for Evaluation of the Absorption Coefficient of Ultrathin Film

NASA Astrophysics Data System (ADS)

Hijikata, Hayato; Kozawa, Takahiro; Tagawa, Seiichi; Takei, Satoshi

2009-06-01

A bottom extreme-ultraviolet-sensitive coating (BESC) for evaluation of the absorption coefficients of ultrathin films such as extreme ultraviolet (EUV) resists was developed. This coating consists of a polymer, crosslinker, acid generator, and acid-responsive chromic dye and is formed by a conventional spin-coating method. By heating the film after spin-coating, a crosslinking reaction is induced and the coating becomes insoluble. A typical resist solution can be spin-coated on a substrate covered with the coating film. The evaluation of the linear absorption coefficients of polymer films was demonstrated by measuring the EUV absorption of BESC substrates on which various polymers were spin-coated.

Surface analysis monitoring of polyelectrolyte deposition on Ba 0.5Sr 0.5TiO 3 thin films

NASA Astrophysics Data System (ADS)

Morales-Cruz, Angel L.; Fachini, Estevão R.; Miranda, Félix A.; Cabrera, Carlos R.

2007-09-01

Thin films are currently gaining interest in many areas such as integrated optics, sensors, friction, reducing coatings, surface orientation layers, and general industrial applications. Recently, molecular self-assembling techniques have been applied for thin film deposition of electrically conducting polymers, conjugated polymers for light-emitting devices, nanoparticles, and noncentrosymmetric-ordered second order nonlinear optical (NOL) devices. Polyelectrolytes self-assemblies have been used to prepare thin films. The alternate immersion of a charged surface in polyannion and a polycation solution leads usually to the formation of films known as polyelectrolyte multilayers. These polyanion and polycation structures are not neutral. However, charge compensation appears on the surface. This constitutes the building driving force of the polyelectrolyte multilayer films. The present approach consists of two parts: (a) the chemisorption of 11-mercaptoundecylamine (MUA) to construct a self-assembled monolayer with the consequent protonation of the amine, and (b) the deposition of opposite charged polyelectrolytes in a sandwich fashion. The approach has the advantage that ionic attraction between opposite charges is the driving force for the multilayer buildup. For our purposes, the multilayer of polyelectrolytes depends on the quality of the surface needed for the application. In many cases, this approach will be used in a way that the roughness factor defects will be diminished. The polyelectrolytes selected for the study were: polystyrene sulfonate sodium salt (PSS), poly vinylsulfate potassium salt (PVS), and polyallylamine hydrochloride (PAH), as shown in Fig. 1. The deposition of polyelectrolytes was carried out by a dipping procedure with the corresponding polyelectrolyte. Monitoring of the alternate deposition of polyelectrolyte bilayers was done by surface analysis techniques such as X-ray photoelectron spectroscopy (XPS), specular reflectance infrared (IR), and atomic force microscopy (AFM). The surface analysis results are presented through the adsorption steps of the polyelectrolytes layer by layer.

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.

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.

Stability of self-assembled polymer films investigated by optical laser reflectometry.

PubMed

Dejeu, Jérôme; Diziain, Séverine; Dange, Catherine; Membrey, François; Charraut, Daniel; Foissy, Alain

2008-04-01

We studied the influence of post-treatment rinsing after the formation of self-assembled polyelectrolyte films made with the weak base poly(allylamine hydrochloride) (PAH) and the strong acid poly(styrene sulfonate) (PSS). The stability of the film was studied using optical fixed-angle laser reflectometry to measure the release of polymeric material and AFM experiments to reveal the change of morphology and thickness. We found that the polymer films were stable upon rinsing when the pH was the same in the solution as that used in the buildup (pH 9). The films released most of the polymeric material when rinsed at higher pH values, but a layer remained that corresponded to a PAH monolayer directly bound with the silica surface. Films containing at least four bilayers were stable upon rinsing at lower pH values, but the stability of thinner films depended on the type of the last polymer deposited. They were stable in the case of PSS as an outermost deposit, but they released a large part of their material in the case of PAH. The stability results were determined using a simple model of the step-by-step assembly of the polymer film described formerly.

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.

Multi-pin chemiresistors for microchemical sensors

DOEpatents

Ho, Clifford K [Albuquerque, NM

2007-02-20

A multi-pin chemiresistor for use in microchemical sensors. A pair of free-standing, bare wires is supported by an electrically insulating support, and are oriented parallel to each other and spaced closely together. A free-standing film of a chemically sensitive polymer that swells when exposed to vapors of a volatile chemical is formed in-between the pair of closely-spaced wires by capillary action. Similar in construction to a thermocouple, this "chemicouple" is relatively inexpensive and easy to fabricate by dipping the pair of bare wires into a bath of well-mixed chemiresistor ink. Also, a chemiresistor "stick" is formed by dipping an electrically insulating rod with two or more linear or spiral-wrapped electrical traces into the bath of well-mixed chemiresistor ink, which deposits a uniform coating of the chemically sensitive polymer on the rod and the electrical traces. These "sticks" can be easily removed and replaced from a multi-chemiresistor plug.

Annihilation of photochemical reactivity of photo-alignment layer.

PubMed

Hong, S H; Hwang, Y J; Lee, S G; Shin, D M

2008-09-01

The gas-polymer and liquid-polymer interfacial reactions of photosensitive polyimide can annihilate photo-reactive carbon-carbon double bonds, which remain after photo-alignment process. The annihilation processes dramatically affect voltage holding ratio and reorientation of photo-active functional groups. Photochemical dimerizations were identified using UV-visible and FT-IR spectroscopy. Polyimide films containing cinnamate groups were irradiated by linear polarized ultra violet (LPUV) light. Schadt et al. claims that the photo-alignment results from the anisotropy depletion of the cinnamate side chains as a consequence of the (2+2) cycloaddition reactions. The photo-aligned polyimide induces the orientation of nematic liquid crystals perpendicular to the polarization axis. However, the un-reacted photo-sensitive functional groups generate problems such as image sticking and reduced contrast ratio. Voltage holding ratio and photo-fading observed from photo-alignment layer can be dramatically improved by annihilation process of remnant photoreactive groups.

Display technologies; Proceedings of the Meeting, National Chiao Tung Univ., Hsinchu, Taiwan, Dec. 17, 18, 1992

NASA Astrophysics Data System (ADS)

Chen, Shu-Hsia; Wu, Shin-Tson

1992-10-01

A broad range of interdisciplinary subjects related to display technologies is addressed, with emphasis on high-definition displays, CRTs, projection displays, materials for display application, flat-panel displays, display modeling, and polymer-dispersed liquid crystals. Particular attention is given to a CRT approach to high-definition television display, a superhigh-resolution electron gun for color display CRT, a review of active-matrix liquid-crystal displays, color design for LCD parameters in projection and direct-view applications, annealing effects on ZnS:TbF3 electroluminescent devices prepared by RF sputtering, polycrystalline silicon thin film transistors with low-temperature gate dielectrics, refractive index dispersions of liquid crystals, a new rapid-response polymer-dispersed liquid-crystal material, and improved liquid crystals for active-matrix displays using high-tilt-orientation layers. (No individual items are abstracted in this volume)

Polymeric membrane systems of potential use for battery separators

NASA Technical Reports Server (NTRS)

Philipp, W. H.

1977-01-01

Two membrane systems were investigated that may have potential use as alkaline battery separators. One system comprises two miscible polymers: a support polymer (e.g., polyvinyl formal) and an ion conductor such as polyacrylic acid. The other system involves a film composed of two immiscible polymers: a conducting polymer (e.g., calcium polyacrylate) suspended in an inert polymer support matrix, polyphenylene oxide. Resistivities in 45-percent potassium hydroxide and qualitative mechanical properties are presented for films comprising various proportions of conducting and support polymers. In terms of these parameters, the results are encouraging for optimum ratios of conducting to support polymers.

{001} Oriented piezoelectric films prepared by chemical solution deposition on Ni foils

NASA Astrophysics Data System (ADS)

Yeo, Hong Goo; Trolier-McKinstry, Susan

2014-07-01

Flexible metal foil substrates are useful in some microelectromechanical systems applications including wearable piezoelectric sensors or energy harvesters based on Pb(Zr,Ti)O3 (PZT) thin films. Full utilization of the potential of piezoelectrics on metal foils requires control of the film crystallographic texture. In this study, {001} oriented PZT thin films were grown by chemical solution deposition (CSD) on Ni foil and Si substrates. Ni foils were passivated using HfO2 grown by atomic layer deposition in order to suppress substrate oxidation during subsequent thermal treatment. To obtain the desired orientation of PZT film, strongly (100) oriented LaNiO3 films were integrated by CSD on the HfO2 coated substrates. A high level of {001} LaNiO3 and PZT film orientation were confirmed by X-ray diffraction patterns. Before poling, the low field dielectric permittivity and loss tangents of (001) oriented PZT films on Ni are near 780 and 0.04 at 1 kHz; the permittivity drops significantly on poling due to in-plane to out-of-plane domain switching. (001) oriented PZT film on Ni displayed a well-saturated hysteresis loop with a large remanent polarization ˜36 μC/cm2, while (100) oriented PZT on Si showed slanted P-E hysteresis loops with much lower remanent polarizations. The |e31,f| piezoelectric coefficient was around 10.6 C/m2 for hot-poled (001) oriented PZT film on Ni.

Emulsion-Based RIR-MAPLE Deposition of Conjugated Polymers: Primary Solvent Effect and Its Implications on Organic Solar Cell Performance.

PubMed

Ge, Wangyao; Li, Nan K; McCormick, Ryan D; Lichtenberg, Eli; Yingling, Yaroslava G; Stiff-Roberts, Adrienne D

2016-08-03

Emulsion-based, resonant infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE) has been demonstrated as an alternative technique to deposit conjugated polymer films for photovoltaic applications; yet, a fundamental understanding of how the emulsion target characteristics translate into film properties and solar cell performance is unclear. Such understanding is crucial to enable the rational improvement of organic solar cell (OSC) efficiency and to realize the expected advantages of emulsion-based RIR-MAPLE for OSC fabrication. In this paper, the effect of the primary solvent used in the emulsion target is studied, both experimentally and theoretically, and it is found to determine the conjugated polymer cluster size in the emulsion as well as surface roughness and internal morphology of resulting polymer films. By using a primary solvent with low solubility-in-water and low vapor pressure, the surface roughness of deposited P3HT and PCPDTBT polymer films was reduced to 10 nm, and the efficiency of P3HT:PC61BM OSCs was increased to 3.2% (∼100 times higher compared to the first MAPLE OSC demonstration [ Caricato , A. P. ; Appl. Phys. Lett. 2012 , 100 , 073306 ]). This work unveils the mechanism of polymer film formation using emulsion-based RIR-MAPLE and provides insight and direction to determine the best ways to take advantage of the emulsion target approach to control film properties for different applications.

Lattice cluster theory for dense, thin polymer films.

PubMed

Freed, Karl F

2015-04-07

While the application of the lattice cluster theory (LCT) to study the miscibility of polymer blends has greatly expanded our understanding of the monomer scale molecular details influencing miscibility, the corresponding theory for inhomogeneous systems has not yet emerged because of considerable technical difficulties and much greater complexity. Here, we present a general formulation enabling the extension of the LCT to describe the thermodynamic properties of dense, thin polymer films using a high dimension, high temperature expansion. Whereas the leading order of the LCT for bulk polymer systems is essentially simple Flory-Huggins theory, the highly non-trivial leading order inhomogeneous LCT (ILCT) for a film with L layers already involves the numerical solution of 3(L - 1) coupled, highly nonlinear equations for the various density profiles in the film. The new theory incorporates the essential "transport" constraints of Helfand and focuses on the strict imposition of excluded volume constraints, appropriate to dense polymer systems, rather than the maintenance of chain connectivity as appropriate for lower densities and as implemented in self-consistent theories of polymer adsorption at interfaces. The ILCT is illustrated by presenting examples of the computed profiles of the density, the parallel and perpendicular bonds, and the chain ends for free standing and supported films as a function of average film density, chain length, temperature, interaction with support, and chain stiffness. The results generally agree with expected general trends.

Scanning angle Raman spectroscopy: A nondestructive method for simultaneously determining mixed polymer fractional composition and film thickness

DOE PAGES

Bobbitt, Jonathan M.; Mendivelso-Pérez, Deyny; Smith, Emily A.

2016-11-03

A scanning angle (SA) Raman spectroscopy method was developed to simultaneously measure the chemical composition and thickness of waveguide mixed polymer films with varying fractional compositions. In order to test the method, six films of polystyrene-block-poly(methyl methacrylate), some mixed with poly(methyl methacrylate) homopolymer (PS-b-PMMA:PMMA), and two films of poly(2-vinylnapthalene)-block-poly(methyl methacrylate) (P2VN-b-PMMA) were prepared. The film thickness ranged from 495 to 971 nm. The chemical composition and thickness of PS-b-PMMA:PMMA films was varied by the addition of the PMMA homopolymer and annealing the films in toluene. SA Raman peak amplitude ratios (1001 cm -1 for PS, 812 cm -1 for PMMA,more » and 1388 cm -1 for P2VN) were used to calculate the refractive index of the polymer film, an input parameter in calculations of the sum square electric field (SSEF). The film thickness was determined by SSEF models of the experimental Raman amplitudes versus the incident angle of light. The average film thickness determined by the developed SA Raman spectroscopy method was within 5% of the value determined by optical profilometry. In conclusion, SA Raman spectroscopy will be useful for in situ label-free analyses of mixed polymer waveguide films.« less

Self-lubricating polymer composites and polymer transfer film lubrication for space applications

NASA Technical Reports Server (NTRS)

Fusaro, Robert L.

1990-01-01

The use of self-lubricating polymers and polymer composites in space is somewhat limited today. In general, they are only used when other methods are inadequate. There is potential, however, for these materials to make a significant impact on future space missions if properly utilized. Some of the different polymers and fillers used to make self-lubricating composites are surveyed. The mechanisms of composite lubrication and wear, the theory behind transfer film lubricating mechanisms, and some factors which affect polymer composite wear and transfer are examined. In addition, some of the current space tribology application areas for self-lubricating polymer composites and polymer transfer are mentioned.

Tuning polymorphism and orientation in organic semiconductor thin films via post-deposition processing.

PubMed

Hiszpanski, Anna M; Baur, Robin M; Kim, Bumjung; Tremblay, Noah J; Nuckolls, Colin; Woll, Arthur R; Loo, Yueh-Lin

2014-11-05

Though both the crystal structure and molecular orientation of organic semiconductors are known to impact charge transport in thin-film devices, separately accessing different polymorphs and varying the out-of-plane molecular orientation is challenging, typically requiring stringent control over film deposition conditions, film thickness, and substrate chemistry. Here we demonstrate independent tuning of the crystalline polymorph and molecular orientation in thin films of contorted hexabenzocoronene, c-HBC, during post-deposition processing without the need to adjust deposition conditions. Three polymorphs are observed, two of which have not been previously reported. Using our ability to independently tune the crystal structure and out-of-plane molecular orientation in thin films of c-HBC, we have decoupled and evaluated the effects that molecular packing and orientation have on device performance in thin-film transistors (TFTs). In the case of TFTs comprising c-HBC, polymorphism and molecular orientation are equally important; independently changing either one affects the field-effect mobility by an order of magnitude.

Semitransparent conductive carbon films synthesized by sintering spin-coated sp3-based network polymer

NASA Astrophysics Data System (ADS)

Yanase, Takashi; Uwabe, Hiroaki; Hasegawa, Koki; Nagahama, Taro; Yamaguchi, Makoto; Shimada, Toshihiro

2018-03-01

We synthesized semitransparent conducting thin films of amorphous carbon from sp3-rich network polymer. The films showed a reasonable optical transparency (58-73% transmission in the wavelength range of 380-2200 nm), a low electric resistivity (6.7 × 10-3 Ω cm), and durability against corrosive chemical reagents. The sintering of the amorphous films results in the formation of a carbon honeycomb lattice in the films.

Modeling solvent evaporation during thin film formation in phase separating polymer mixtures

DOE PAGES

Cummings, John; Lowengrub, John S.; Sumpter, Bobby G.; ...

2018-02-09

Preparation of thin films by dissolving polymers in a common solvent followed by evaporation of the solvent has become a routine processing procedure. However, modeling of thin film formation in an evaporating solvent has been challenging due to a need to simulate processes at multiple length and time scales. In this paper, we present a methodology based on the principles of linear non-equilibrium thermodynamics, which allows systematic study of various effects such as the changes in the solvent properties due to phase transformation from liquid to vapor and polymer thermodynamics resulting from such solvent transformations. The methodology allows for themore » derivation of evaporative flux and boundary conditions near each surface for simulations of systems close to the equilibrium. We apply it to study thin film microstructural evolution in phase segregating polymer blends dissolved in a common volatile solvent and deposited on a planar substrate. Finally, effects of the evaporation rates, interactions of the polymers with the underlying substrate and concentration dependent mobilities on the kinetics of thin film formation are studied.« less

Modeling solvent evaporation during thin film formation in phase separating polymer mixtures

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

Cummings, John; Lowengrub, John S.; Sumpter, Bobby G.

Preparation of thin films by dissolving polymers in a common solvent followed by evaporation of the solvent has become a routine processing procedure. However, modeling of thin film formation in an evaporating solvent has been challenging due to a need to simulate processes at multiple length and time scales. In this paper, we present a methodology based on the principles of linear non-equilibrium thermodynamics, which allows systematic study of various effects such as the changes in the solvent properties due to phase transformation from liquid to vapor and polymer thermodynamics resulting from such solvent transformations. The methodology allows for themore » derivation of evaporative flux and boundary conditions near each surface for simulations of systems close to the equilibrium. We apply it to study thin film microstructural evolution in phase segregating polymer blends dissolved in a common volatile solvent and deposited on a planar substrate. Finally, effects of the evaporation rates, interactions of the polymers with the underlying substrate and concentration dependent mobilities on the kinetics of thin film formation are studied.« less

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.

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.

Film Sensor Device Fabricated by a Piezoelectric Poly(L-lactic acid) Film

NASA Astrophysics Data System (ADS)

Ando, Masamichi; Kawamura, Hideki; Kageyama, Keisuke; Tajitsu, Yoshiro

2012-09-01

Synthetic piezoelectric polymer films produced from petroleum feedstock have long been used as thin-film sensors and actuators. However, the fossil fuel requirements for synthetic polymer production and carbon dioxide emission from its combustion have raised concern about the environmental impact of its continued use. Eco-friendly biomass polymers, such as poly(L-lactic acid) (PLLA), are made from plant-based (vegetable starch) plastics and, thus, have a much smaller carbon footprint. Additionally, PLLA does not exhibit pyroelectricity or unnecessary poling. This suggests the usefulness of PLLA films for the human-machine interface (HMI). As an example of a new HMI, we have produced a TV remote control using a PLLA film. The intuitive operation provided by this PLLA device suggests that it is useful for the elderly or handicapped.

Ferro- and piezoelectric properties of polar-axis-oriented CaBi4Ti4O15 films

NASA Astrophysics Data System (ADS)

Kato, Kazumi; Fu, Desheng; Suzuki, Kazuyuki; Tanaka, Kiyotaka; Nishizawa, Kaori; Miki, Takeshi

2004-05-01

Polar-axis-oriented CaBi4Ti4O15 (CBTi144) films were fabricated on Pt foils using a complex metal alkoxide solution. The 500-nm-thick film showed the columnar structure and consisted of well-developed grains. The a/b-axis orientation of the ferroelectric films is considered to be associated with the preferred orientation of Pt foil. The film showed good ferro- and piezoelectric properties. The Pr and Ec were 25 μC/cm2 and 306 kV/cm, respectively, at an applied voltage of 115 V. The d33 was characterized as 30 pm/V by piezoresponse force microscopy. The values were twice as large as those of the CBTi144 thin film with random orientation. The polar-axis-oriented CBTi144 films would open up possibilities for devices as Pb-free piezoelectric materials.

Quercetin as natural stabilizing agent for bio-polymer

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

Morici, Elisabetta; Arrigo, Rossella; Dintcheva, Nadka Tzankova

The introduction of antioxidants in polymers is the main way to prevent or delay the degradation process. In particular natural antioxidants receive attention in the food industry also because of their presumed safety. In this work bio-polymers, i.e. a commercial starch-based polymer (Mater-Bi®) and a bio-polyester (PLA), and a bio-polyether (PEO) were additivated with quercetin, a natural flavonoid antioxidants, in order to formulate bio-based films for ecosustainable packaging and outdoor applications. The photo-oxidation behavior of unstabilized and quercetin stabilized films was analyzed and compared with the behavior of films additivated with a commercial synthetic light stabilizer. The quercetin is ablemore » to slow down the photo-degradation rate of all bio-polymeric films investigated in similar way to the synthetic stabilizer.« less

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.

Quercetin as natural stabilizing agent for bio-polymer

NASA Astrophysics Data System (ADS)

Morici, Elisabetta; Arrigo, Rossella; Dintcheva, Nadka Tzankova

2014-05-01

The introduction of antioxidants in polymers is the main way to prevent or delay the degradation process. In particular natural antioxidants receive attention in the food industry also because of their presumed safety. In this work bio-polymers, i.e. a commercial starch-based polymer (Mater-Bi®) and a bio-polyester (PLA), and a bio-polyether (PEO) were additivated with quercetin, a natural flavonoid antioxidants, in order to formulate bio-based films for ecosustainable packaging and outdoor applications. The photo-oxidation behavior of unstabilized and quercetin stabilized films was analyzed and compared with the behavior of films additivated with a commercial synthetic light stabilizer. The quercetin is able to slow down the photo-degradation rate of all bio-polymeric films investigated in similar way to the synthetic stabilizer.

Dry-film polymer waveguide for silicon photonics chip packaging.

PubMed

Hsu, Hsiang-Han; Nakagawa, Shigeru

2014-09-22

Polymer waveguide made by dry film process is demonstrated for silicon photonics chip packaging. With 8 μm × 11.5 μm core waveguide, little penalty is observed up to 25 Gbps before or after the light propagate through a 10-km long single-mode fiber (SMF). Coupling loss to SMF is 0.24 dB and 1.31 dB at the polymer waveguide input and output ends, respectively. Alignment tolerance for 0.5 dB loss increase is +/- 1.0 μm along both vertical and horizontal directions for the coupling from the polymer waveguide to SMF. The dry-film polymer waveguide demonstrates promising performance for silicon photonics chip packaging used in next generation optical multi-chip module.

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.

Cellulose Fibre-Reinforced Biofoam for Structural Applications

PubMed Central

Obradovic, Jasmina; Voutilainen, Mikko; Virtanen, Pasi; Lassila, Lippo; Fardim, Pedro

2017-01-01

Traditionally, polymers and macromolecular components used in the foam industry are mostly derived from petroleum. The current transition to a bio-economy creates demand for the use of more renewable feedstocks. Soybean oil is a vegetable oil, composed mainly of triglycerides, that is suitable material for foam production. In this study, acrylated epoxidized soybean oil and variable amounts of cellulose fibres were used in the production of bio-based foam. The developed macroporous bio-based architectures were characterised by several techniques, including porosity measurements, nanoindentation testing, scanning electron microscopy, and thermogravimetric analysis. It was found that the introduction of cellulose fibres during the foaming process was necessary to create the three-dimensional polymer foams. Using cellulose fibres has potential as a foam stabiliser because it obstructs the drainage of liquid from the film region in these gas-oil interfaces while simultaneously acting as a reinforcing agent in the polymer foam. The resulting foams possessed a porosity of approximately 56%, and the incorporation of cellulose fibres did not affect thermal behaviour. Scanning electron micrographs showed randomly oriented pores with irregular shapes and non-uniform pore size throughout the samples. PMID:28772981

Positive and negative ZnO micropatterning on functionalized polymer surfaces.

PubMed

Yang, Peng; Zou, Shengli; Yang, Wantai

2008-09-01

Patterned ZnO deposition on substrates has received increasing attention because of its great potential in photocatalysis, energy conversion, and electro-optical techniques. Chemical solution growth is especially promising for organic substrates due to its very mild reaction conditions. Here this method is used on functionality-patterned polymer surfaces in order to fabricate positive and negative ZnO micropatterns. A ZnO film made of arrayed rods, typically 500-750 nm in diameter and 2.5 microm in length, is selectively obtained on sulfated and hydroxylated regions of biaxially oriented poly(propylene), giving rise to positive patterns. For reactive polyesters such as poly(ethylene terephthalate), the ZnO rods selectively remain on the unmodified original regions, creating negative patterns. Unlike complex photolithography procedures, the irradiation and patterning processes do not require the use of positive or negative photoresists, and possible damage from acidic solutions on the underlying substrate during the chemical etching process is avoided. The process thus proves to be a simple, creditable, and low-cost method, which could be easily applied on a variety of inert and reactive polymer surfaces.

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.

Highly oriented diamond films on Si: growth, characterization, and devices

NASA Astrophysics Data System (ADS)

Stoner, Brian R.; Malta, D. M.; Tessmer, A. J.; Holmes, J.; Dreifus, David L.; Glass, R. C.; Sowers, A.; Nemanich, Robert J.

1994-04-01

Highly oriented, (100) textured diamond films have been grown on single-crystal Si substrates via microwave plasma enhanced chemical vapor deposition. A multistep deposition process including bias-enhanced nucleation and textured growth was used to obtain smooth films consisting of epitaxial grains with only low-angle grain boundaries. Boron-doped layers were selectively deposited onto the surface of these oriented films and temperature-dependent Hall effect measurements indicated a 3 to 5 times improvement in hole mobility over polycrystalline films grown under similar conditions. Room temperature hole mobilities between 135 and 278 cm2/V-s were measured for the highly oriented samples as compared to 2 to 50 cm2/V-s for typical polycrystalline films. Grain size effects and a comparison between the transport properties of polycrystalline, highly oriented and homoepitaxial films will be discussed. Metal-oxide- semiconductor field-effect transistors were then fabricated on the highly oriented films and exhibited saturation and pinch-off of the channel current.

Effects of Convection During the Photodeposition of Polydiacetylene Thin Films

NASA Technical Reports Server (NTRS)

Frazier, D. O.; Hung, R. J.; Paley, M. S.; Long, Y. T.

1997-01-01

In this work, we describe a preliminary investigation of buoyancy-driven heat transfer during the growth of thin films from solution following exposure to ultraviolet (UV) light. Irradiation of the growth cell occurs at various directions relative to gravitational acceleration. Through numerical computations, the steady-state flow and temperature profiles are simulated during the course of light exposure. Light-induced polymerization accompanies a heat transfer process through a fairly complicated recirculating flow pattern. A scaling analysis shows that buoyancy-driven velocities only reduce by a factor of 10 for gravity levels as low as 10(exp -2)g(sub 0). Paley et al. observe what appears to be gravitationally sensitive particle development and inclusion in thin films using a photodeposition process. From this study it is clear that production of homogeneous thin films would have to occur in the environment of a complicated flow pattern of recirculation with a nonuniform temperature distribution. Indeed, even when irradiation occurs from the top of the cell, the most stable stratified cell orientation, defects remain in our films due to the persistence of buoyancy-driven convection. To achieve homogeneity, minimal scattering centers, and possible molecular order, photodeposition of polymer films by UV light exposure must proceed in a reduced-convection environment. Fluid mechanics simulations are useful for establishing gravitational sensitivity to this recently discovered process (patent # 5,451,433) for preparing thin films having quite promising nonlinear optical characteristics.

Effects of Convection during the Photodeposition of Polydiacetylene Thin Films

NASA Technical Reports Server (NTRS)

Frazier, D. O.; Hung, R. J.; Paley, M. S.; Long, Y. T.

1997-01-01

In this work, we describe a preliminary investigation of buoyancy-driven heat transfer during the growth of thin films from solution following exposure to ultraviolet (UV) light. Irradiation of the growth cell occurs at various directions relative to gravitational acceleration. Through numerical computations, the steady-state flow and temperature profiles are simulated during the course of light exposure. Light-induced polymerization accompanies a heat transfer process through a fairly complicated recirculating flow pattern. A scaling analysis shows that buoyancy-driven velocities only reduce by a factor of 10 for gravity levels as low as 10(exp -2) g(sub 0). Paley et al. observe what appears to be gravitationally sensitive particle development and inclusion in thin films using a photodeposition process. From this study, it is clear that production of homogeneous thin films would have to occur in the environment of a complicated flow pattern of recirculation with a nonuniform temperature distribution. Indeed, even when irradiation occurs from the top of the cell, the most stable stratified cell orientation, defects remain in our films due to the persistence of buoyancy-driven convection. To achieve homogeneity, minimal scattering centers, and possible molecular order, photodeposition of polymer films by UV light exposure must proceed in a reduced-convection environment. Fluid mechanics simulations are useful for establishing gravitational sensitivity to this recently discovered process (patent # 5,451,433) for preparing thin films having quite promising nonlinear optical characteristics.

High Performances of Artificial Nacre-Like Graphene Oxide-Carrageenan Bio-Nanocomposite Films.

PubMed

Zhu, Wenkun; Chen, Tao; Li, Yi; Lei, Jia; Chen, Xin; Yao, Weitang; Duan, Tao

2017-05-16

This study was inspired by the unique multi-scale and multi-level 'brick-and-mortar' (B&M) structure of nacre layers. We prepared the B&M, environmentally-friendly graphene oxide-carrageenan (GO-Car) nanocomposite films using the following steps. A natural polyhydroxy polymer, carrageenan, was absorbed on the surface of monolayer GO nanosheets through hydrogen-bond interactions. Following this, a GO-Car hybridized film was produced through a natural drying process. We conducted structural characterization in addition to analyzing mechanical properties and cytotoxicity of the films. Scanning electron microscope (SEM) and X-ray diffraction (XRD) analyses showed that the nanocomposite films had a similar morphology and structure to nacre. Furthermore, the results from Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and Thermogravimetric (TG/DTG) were used to explain the GO-Car interaction. Analysis from static mechanical testers showed that GO-Car had enhanced Young's modulus, maximum tensile strength and breaking elongation compared to pure GO. The GO-Car nanocomposite films, containing 5% wt. of Car, was able to reach a tensile strength of 117 MPa. The biocompatibility was demonstrated using a RAW264.7 cell test, with no significant alteration found in cellular morphology and cytotoxicity. The preparation process for GO-Car films is simple and requires little time, with GO-Car films also having favorable biocompatibility and mechanical properties. These advantages make GO-Car nanocomposite films promising materials in replacing traditional petroleum-based plastics and tissue engineering-oriented support materials.

High Performances of Artificial Nacre-Like Graphene Oxide-Carrageenan Bio-Nanocomposite Films

PubMed Central

Zhu, Wenkun; Chen, Tao; Li, Yi; Lei, Jia; Chen, Xin; Yao, Weitang; Duan, Tao

2017-01-01

This study was inspired by the unique multi-scale and multi-level ‘brick-and-mortar’ (B&M) structure of nacre layers. We prepared the B&M, environmentally-friendly graphene oxide-carrageenan (GO-Car) nanocomposite films using the following steps. A natural polyhydroxy polymer, carrageenan, was absorbed on the surface of monolayer GO nanosheets through hydrogen-bond interactions. Following this, a GO-Car hybridized film was produced through a natural drying process. We conducted structural characterization in addition to analyzing mechanical properties and cytotoxicity of the films. Scanning electron microscope (SEM) and X-ray diffraction (XRD) analyses showed that the nanocomposite films had a similar morphology and structure to nacre. Furthermore, the results from Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and Thermogravimetric (TG/DTG) were used to explain the GO-Car interaction. Analysis from static mechanical testers showed that GO-Car had enhanced Young’s modulus, maximum tensile strength and breaking elongation compared to pure GO. The GO-Car nanocomposite films, containing 5% wt. of Car, was able to reach a tensile strength of 117 MPa. The biocompatibility was demonstrated using a RAW264.7 cell test, with no significant alteration found in cellular morphology and cytotoxicity. The preparation process for GO-Car films is simple and requires little time, with GO-Car films also having favorable biocompatibility and mechanical properties. These advantages make GO-Car nanocomposite films promising materials in replacing traditional petroleum-based plastics and tissue engineering-oriented support materials. PMID:28772897

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.

The development of chiral nematic mesoporous materials.

PubMed

Kelly, Joel A; Giese, Michael; Shopsowitz, Kevin E; Hamad, Wadood Y; MacLachlan, Mark J

2014-04-15

Cellulose nanocrystals (CNCs) are obtained from the sulfuric acid-catalyzed hydrolysis of bulk cellulose. The nanocrystals have diameters of ~5-15 nm and lengths of ~100-300 nm (depending on the cellulose source and hydrolysis conditions). This lightweight material has mostly been investigated to reinforce composites and polymers because it has remarkable strength that rivals carbon nanotubes. But CNCs have an additional, less explored property: they organize into a chiral nematic (historically referred to as cholesteric) liquid crystal in water. When dried into a thin solid film, the CNCs retain the helicoidal chiral nematic order and assemble into a layered structure where the CNCs have aligned orientation within each layer, and their orientation rotates through the stack with a characteristic pitch (repeating distance). The cholesteric ordering can act as a 1-D photonic structure, selectively reflecting circularly polarized light that has a wavelength nearly matching the pitch. During CNC self-assembly, it is possible to add sol-gel precursors, such as Si(OMe)4, that undergo hydrolysis and condensation as the solvent evaporates, leading to a chiral nematic silica/CNC composite material. Calcination of the material in air destroys the cellulose template, leaving a high surface area mesoporous silica film that has pore diameters of ~3-10 nm. Importantly, the silica is brilliantly iridescent because the pores in its interior replicate the chiral nematic structure. These films may be useful as optical filters, reflectors, and membranes. In this Account, we describe our recent research into mesoporous films with chiral nematic order. Taking advantage of the chiral nematic order and nanoscale of the CNC templates, new functional materials can be prepared. For example, heating the silica/CNC composites under an inert atmosphere followed by removal of the silica leaves highly ordered, mesoporous carbon films that can be used as supercapacitor electrodes. The composition of the mesoporous films can be varied by using assorted organosilica precursors. After removal of the cellulose by acid-catalyzed hydrolysis, highly porous, iridescent organosilica films are obtained. These materials are flexible and offer the ability to tune the chemical and mechanical properties through variation of the organic spacer. Chiral nematic mesoporous silica and organosilica materials, obtainable as centimeter-scale freestanding films, are interesting hosts for nanomaterials. When noble metal nanoparticles are incorporated into the pores, they show strong circular dichroism signals associated with their surface plasmon resonances that arise from dipolar coupling of the particles within the chiral nematic host. Fluorescent conjugated polymers show induced circular dichroism spectra when encapsulated in the chiral nematic host. The porosity, film structure, and optical properties of these materials could enable their use in sensors. We describe the development of chiral nematic mesoporous silica and organosilica, demonstrate different avenues of host-guest chemistry, and identify future directions that exploit the unique combination of properties present in these materials. The examples covered in this Account demonstrate that there is a rich diversity of composite materials accessible using CNC templating.

Synthesis and Characterization of Thin Film Lithium-Ion Batteries Using Polymer Electrolytes

NASA Technical Reports Server (NTRS)

Maranchi, Jeffrey P.; Kumta, Prashant N.; Hepp, Aloysius F.; Raffaelle, Ryne P.

2002-01-01

The present paper describes the integration of thin film electrodes with polymer electrolytes to form a complete thin film lithium-ion battery. Thin film batteries of the type, LiCoO2 [PAN, EC, PC, LiN(CF3SO2)2] SnO2 have been fabricated. The results of the synthesis and characterization studies will be presented and discussed.

Forming giant-sized polymersomes using gel-assisted rehydration

DOE PAGES

Greene, Adrienne C.; Sasaki, Darryl Y.; Bachand, George D.

2016-05-26

Here, we present a protocol to rapidly form giant polymer vesicles ( pGVs). Briefly, polymer solutions are dehydrated on dried agarose films adhered to coverslips. Rehydration of the polymer films results in rapid formation of pGVs. This method greatly advances the preparation of synthetic giant vesicles for direct applications in biomimetic studies.

Determining heat loss from the surface of polymer films via modeling of experimental fluorescence thermometry

NASA Astrophysics Data System (ADS)

Firestone, Gabriel; Bochinski, Jason; Meth, Jeffrey; Clarke, Laura

Understanding of the heat transfer characteristics of a polymer during processing is critical to predicting and controlling the resulting properties and has been studied extensively in injection molding. As new methodologies for polymer processing are developed, such as photothermal heating, it is important to build an understanding of how heat transfer properties change under these novel conditions. By combining theoretical and experimental approaches, the thermal properties of photothermally heated polymer films were measured. The key idea is that by measuring the steady state temperature profile of a spot heated polymer film via a fluorescence probe (the temperature versus distance from the heated region) and fitting to a theoretical model, heat transfer coefficients can be extracted. We apply this approach to three different polymer systems, crosslinked epoxy, poly(methyl methacrylate) and poly(ethylene oxide) thin films with a range of thicknesses, under different heating laser intensities and with different resultant temperatures. We will discuss the resultant trends and extension of the model beyond a simple spot heating configuration. Support from National Science Foundation CMMI-1069108 and CMMI-1462966.

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.

The rheology, degradation, processing, and characterization of renewable resource polymers

NASA Astrophysics Data System (ADS)

Conrad, Jason David

Renewable resource polymers have become an increasingly popular alternative to conventional fossil fuel based polymers over the past couple decades. The push by the government as well as both industrial and consumer markets to go "green" has provided the drive for companies to research and develop new materials that are more environmentally friendly and which are derived from renewable materials. Two polymers that are currently being produced commercially are poly-lactic acid (PLA) and polyhydroxyalkanoate (PHA) copolymers, both of which can be derived from renewable feedstocks and have shown to exhibit similar properties to conventional materials such as polypropylene, polyethylene, polystyrene, and PET. PLA and PHA are being used in many applications including food packaging, disposable cups, grocery bags, and biomedical applications. In this work, we report on the rheological properties of blends of PLA and PHA copolymers. The specific materials used in the study include Natureworks RTM 7000D grade PLA and PHA copolymers of poly(3-hydroxybutyrate-co-3-hydroxyvalerate). Blends ranging from 10 to 50 percent PHA by weight are also examined. Shear and extensional experiments are performed to characterize the flow behavior of the materials in different flow fields. Transient experiments are performed to study the shear rheology over time in order to determine how the viscoelastic properties change under typical processing conditions and understand the thermal degradation behavior of the materials. For the blends, it is determined that increasing the PHA concentration in the blend results in a decrease in viscosity and increase in degradation. Models are fit to the viscosity of the blends using the pure material viscosities in order to be able to predict the behavior at a given blend composition. We also investigate the processability of these materials into films and examine the resultant properties of the cast films. The mechanical and thermal properties of the films are studied as a function of the blend composition. With increasing PHA content in the blends, the films show increases in the crystallinity and the percent elongation versus the pure materials, but decreases in both the modulus and the tensile strength. The 10% PHA blend is found to be the optimum concentration since the toughness is significantly improved without sacrificing the strength of the material. A post-processing uniaxial orientation step is also studied, and an improvement in the mechanical properties and crystallinity of the films is discovered with the largest effects observed by varying the stretch ratio. Increasing the stretch ratio resulted in an improvement in percent elongation and greater modulus, strength, and crystallinity versus the unstretched samples. Therefore, by varying the blend composition and film processing parameters, we are able to systematically manipulate the properties of the final product and therefore tailor the materials for specific applications depending on the desired properties.

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.

Improvement of PET surface hydrophilicity and roughness through blending

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

Kolahchi, Ahmad Rezaei; Ajji, Abdellah; Carreau, Pierre J.

Controlling the adhesion of the polymer surface is a key issue in surface science, since polymers have been a commonly used material for many years. The surface modification in this study includes two different aspects. One is to enhance the hydrophilicity and the other is to create the roughness on the PET film surface. In this study we developed a novel and simple approach to modify polyethylene terephthalate (PET) film surface through polymer blending in twin-screw extruder. One example described in the study uses polyethylene glycol (PEG) in polyethylene terephthalate (PET) host to modify a PET film surface. Low contentmore » of polystyrene (PS) as a third component was used in the system to increase the rate of migration of PEG to the surface of the film. Surface enrichment of PEG was observed at the polymer/air interface of the polymer film containing PET-PEG-PS whereas for the PET-PEG binary blend more PEG was distributed within the bulk of the sample. Furthermore, a novel method to create roughness at the PET film surface was proposed. In order to roughen the surface of PET film, a small amount of PKHH phenoxy resin to change PS/PET interfacial tension was used. The compatibility effect of PKHH causes the formation of smaller PS droplets, which were able to migrate more easily through PET matrix. Consequently, resulting in a locally elevated concentration of PS near the surface of the film. The local concentration of PS eventually reached a level where a co-continuous morphology occurred, resulting in theinstabilities on the surface of the film.« less

Synthesis, Characterization, and Electrochemical Properties of Polyaniline Thin Films

NASA Astrophysics Data System (ADS)

Rami, Soukaina

Conjugated polymers have been used in various applications (battery, supercapacitor, electromagnetic shielding, chemical sensor, biosensor, nanocomposite, light-emitting-diode, electrochromic display etc.) due to their excellent conductivity, electrochemical and optical properties, and low cost. Polyaniline has attracted the researchers from all disciplines of science, engineering, and industry due to its redox properties, environmental stability, conductivity, and optical properties. Moreover, it is a polymer with fast electroactive switching and reversible properties displayed at low potential, which is an important feature in many applications. The thin oriented polyaniline films have been fabricated using self-assembly, Langmuir-Blodgett, in-situ self-assembly, layer-by-layer, and electrochemical technique. The focus of this thesis is to synthesize and characterize polyaniline thin films with and without dyes. Also, the purpose of this thesis is to find the fastest electroactive switching PANI electrode in different electrolytic medium by studying their electrochemical properties. These films were fabricated using two deposition techniques: in-situ self-assembly and electrochemical deposition. The characterization of these films was done using techniques such as Fourier Transform Infrared Spectroscopy (FTIR), UV-spectroscopy, Scanning Electron Microscope (SEM), and X-Ray Diffraction (XRD). FTIR and UV-spectroscopy showed similar results in the structure of the polyaniline films. However, for the dye incorporated films, since there was an addition in the synthesis of the material, peak locations shifted, and new peaks corresponding to these materials appeared. The 1 layer PANI showed compact film morphology, comparing to other PANI films, which displayed a fiber-like structure. Finally, the electrochemical properties of these thin films were studied using cyclic voltammetry (CV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS) in different scenarios. These scenarios included the study in different acid based electrolytes and different gel based electrolytes. The ultra-thin self-assembled PANI films were shown to have a faster switching time, especially for the 1 layer PANI, whereas the color contrast could be observed for the film containing the dye molecule. Also, HCl based electrolyte gave the best electrochemical reversibility compared to other acids used. For the gelatin and PVA based electrolytes, having the same concentration, the results were similar. Hence, the change in the electrolyte consistencies, from liquid to semi-solid, did not change the electrochemical properties of the films. Finally, in the EIS, it was shown that these PANI thin films exhibit a pseudo-capacitance behavior, and as the film thickness grew, the capacitance increased.

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

A molecular design principle of lyotropic liquid-crystalline conjugated polymers with directed alignment capability for plastic electronics

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

Kim, Bong-Gi; Jeong, Eun Jeong; Chung, Jong Won

Conjugated polymers with a one-dimensional p-orbital overlap exhibit optoelectronic anisotropy. Their unique anisotropic properties can be fully realized in device applications only when the conjugated chains are aligned. Here, we report a molecular design principle of conjugated polymers to achieve concentration-regulated chain planarization, self-assembly, liquid-crystal-like good mobility and non-interdigitated side chains. As a consequence of these intra- and intermolecular attributes, chain alignment along an applied flow field occurs. This liquid-crystalline conjugated polymer was realized by incorporating intramolecular sulphur–fluorine interactions and bulky side chains linked to a tetrahedral carbon having a large form factor. By optimizing the polymer concentration and themore » flow field, we could achieve a high dichroic ratio of 16.67 in emission from conducting conjugated polymer films. Two-dimensional grazing-incidence X-ray diffraction was performed to analyse a well-defined conjugated polymer alignment. Thin-film transistors built on highly aligned conjugated polymer films showed more than three orders of magnitude faster carrier mobility along the conjugated polymer alignment direction than the perpendicular direction.« less

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.

Extracting interface locations in multilayer polymer waveguide films using scanning angle Raman spectroscopy

DOE PAGES

Bobbitt, Jonathan M.; Smith, Emily A.

2017-11-09

There is an increasing demand for nondestructive in situ techniques that measure chemical content, total thickness, and interface locations for multilayer polymer films, and SA Raman spectroscopy in combination with appropriate data models can provide this information. A scanning angle (SA) Raman spectroscopy method was developed to measure the chemical composition of multilayer polymer waveguide films and to extract the location of buried interfaces between polymer layers with 7–80-nm axial spatial resolution. The SA Raman method measures Raman spectra as the incident angle of light upon a prism-coupled thin film is scanned. Six multilayer films consisting of poly(methyl methacrylate)/polystyrene ormore » poly(methyl methacrylate)/polystyrene/poly(methyl methacrylate) were prepared with total thicknesses ranging from 330-1260 nm. The interface locations were varied by altering the individual layer thicknesses between 140-680 nm. The Raman amplitude ratio of the 1605 cm -1 peak for PS and 812 cm -1 peak for PMMA was used in calculations of the electric field intensity within the polymer layers to model the SA Raman data and extract the total thickness and interface locations. There is an average 8% and 7% difference in the measured thickness between the SA Raman and profilometry measurements for bilayer and trilayer films, respectively.« less

Extracting interface locations in multilayer polymer waveguide films using scanning angle Raman spectroscopy

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

Bobbitt, Jonathan M.; Smith, Emily A.

There is an increasing demand for nondestructive in situ techniques that measure chemical content, total thickness, and interface locations for multilayer polymer films, and SA Raman spectroscopy in combination with appropriate data models can provide this information. A scanning angle (SA) Raman spectroscopy method was developed to measure the chemical composition of multilayer polymer waveguide films and to extract the location of buried interfaces between polymer layers with 7–80-nm axial spatial resolution. The SA Raman method measures Raman spectra as the incident angle of light upon a prism-coupled thin film is scanned. Six multilayer films consisting of poly(methyl methacrylate)/polystyrene ormore » poly(methyl methacrylate)/polystyrene/poly(methyl methacrylate) were prepared with total thicknesses ranging from 330-1260 nm. The interface locations were varied by altering the individual layer thicknesses between 140-680 nm. The Raman amplitude ratio of the 1605 cm -1 peak for PS and 812 cm -1 peak for PMMA was used in calculations of the electric field intensity within the polymer layers to model the SA Raman data and extract the total thickness and interface locations. There is an average 8% and 7% difference in the measured thickness between the SA Raman and profilometry measurements for bilayer and trilayer films, respectively.« less