Bio-Inspired Aggregation Control of Carbon Nanotubes for Ultra-Strong Composites

PubMed Central

Han, Yue; Zhang, Xiaohua; Yu, Xueping; Zhao, Jingna; Li, Shan; Liu, Feng; Gao, Peng; Zhang, Yongyi; Zhao, Tong; Li, Qingwen

2015-01-01

High performance nanocomposites require well dispersion and high alignment of the nanometer-sized components, at a high mass or volume fraction as well. However, the road towards such composite structure is severely hindered due to the easy aggregation of these nanometer-sized components. Here we demonstrate a big step to approach the ideal composite structure for carbon nanotube (CNT) where all the CNTs were highly packed, aligned, and unaggregated, with the impregnated polymers acting as interfacial adhesions and mortars to build up the composite structure. The strategy was based on a bio-inspired aggregation control to limit the CNT aggregation to be sub 20–50 nm, a dimension determined by the CNT growth. After being stretched with full structural relaxation in a multi-step way, the CNT/polymer (bismaleimide) composite yielded super-high tensile strengths up to 6.27–6.94 GPa, more than 100% higher than those of carbon fiber/epoxy composites, and toughnesses up to 117–192 MPa. We anticipate that the present study can be generalized for developing multifunctional and smart nanocomposites where all the surfaces of nanometer-sized components can take part in shear transfer of mechanical, thermal, and electrical signals. PMID:26098627

Micro- and nanostructured electro-active polymer actuators as smart muscles for incontinence treatment

NASA Astrophysics Data System (ADS)

Osmani, Bekim; Töpper, Tino; Deschenaux, Christian; Nohava, Jiri; Weiss, Florian M.; Leung, Vanessa; Müller, Bert

2015-02-01

Treatments of severe incontinence are currently based on purely mechanical systems that generally result in revision after three to five years. Our goal is to develop a prototype acting in a natural-analogue manner as artificial muscle, which is based on electro-active polymers. Dielectric actuators have outstanding performances including millisecond response times, mechanical strains of more than 10 % and power to mass densities similar to natural muscles. They basically consist of polymer films sandwiched between two compliant electrodes. The incompressible but elastic polymer film transduces the electrical energy into mechanical work according to the Maxwell pressure. Available polymer films are micrometers thick and voltages as large as kV are necessary to obtain 10 % strain. For medical implants, polymer films should be nanometer thin to realize actuation below 48 V. The metallic electrodes have to be stretchable to follow the strain of 10 % and remain conductive. Recent results on the stress/strain behavior of anisotropic EAP-cantilevers have shown dependencies on metal electrode preparation. We have investigated tunable anisotropic micro- and nanostructures for metallic electrodes. They show a preferred actuation direction with improved stress-strain behavior. The bending of the cantilever has been characterized by the laser beam deflection method. The impact of the electrode on the effective Young's Modulus is measured using an Ultra Nanoindentation Tester with an integrated reference system for soft polymer surfaces. Once ten thousand layers of nanometer-thin EAP actuators are available, devices beyond the envisioned application will flood the market.

An Analytical Model of Nanometer Scale Viscoelastic Properties of Polymer Surfaces Measured Using an Atomic Force Microscope

DTIC Science & Technology

2011-03-01

efficient partially buoyant cargo airlifters, fuel-efficient hybrid wing- body aircraft, and hyperprecision low-collateral damage munitions [17]. In order to...between the tip and the surface, or between the tip and the small layer of condensed water on the surface [78]. The third method is a continuum model...crystal near the ringing conditions. The second is by applying an alternating voltage to the piezo crystal in the z-direction. The third method is to

Enhanced endothelial cell density on NiTi surfaces with sub-micron to nanometer roughness

PubMed Central

Samaroo, Harry D; Lu, Jing; Webster, Thomas J

2008-01-01

The shape memory effect and superelastic properties of NiTi (or Nitinol, a nickel-titanium alloy) have already attracted much attention for various biomedical applications (such as vascular stents, orthodontic wires, orthopedic implants, etc). However, for vascular stents, conventional approaches have required coating NiTi with anti-thrombogenic or anti-inflammatory drug-eluting polymers which as of late have proven problematic for healing atherosclerotic blood vessels. Instead of focusing on the use of drug-eluting anti-thrombogenic or anti-inflammatory proteins, this study focused on promoting the formation of a natural anti-thrombogenic and anti-inflammatory surface on metallic stents: the endothelium. In this study, we synthesized various NiTi substrates with different micron to nanometer surface roughness by using dissimilar dimensions of constituent NiTi powder. Endothelial cell adhesion on these compacts was compared with conventional commercially pure (cp) titanium (Ti) samples. The results after 5 hrs showed that endothelial cells adhered much better on fine grain (<60 μm) compared with coarse grain NiTi compacts (<100 μm). Coarse grain NiTi compacts and conventional Ti promoted similar levels of endothelial cell adhesion. In addition, cells proliferated more after 5 days on NiTi with greater sub-micron and nanoscale surface roughness compared with coarse grain NiTi. In this manner, this study emphasized the positive pole that NiTi with sub-micron to nanometer surface features can play in promoting a natural anti-thrombogenic and anti-inflammatory surface (the endothelium) on a vascular stent and, thus, suggests that more studies should be conducted on NiTi with sub-micron to nanometer surface features. PMID:18488418

Polymer Layered Silicate Nanocomposites: A Review

PubMed Central

Mittal, Vikas

2009-01-01

This review aims to present recent advances in the synthesis and structure characterization as well as the properties of polymer layered silicate nanocomposites. The advent of polymer layered silicate nanocomposites has revolutionized research into polymer composite materials. Nanocomposites are organic-inorganic hybrid materials in which at least one dimension of the filler is less than 100 nm. A number of synthesis routes have been developed in the recent years to prepare these materials, which include intercalation of polymers or pre-polymers from solution, in-situ polymerization, melt intercalation etc. The nanocomposites where the filler platelets can be dispersed in the polymer at the nanometer scale owing to the specific filler surface modifications, exhibit significant improvement in the composite properties, which include enhanced mechanical strength, gas barrier, thermal stability, flame retardancy etc. Only a small amount of filler is generally required for the enhancement in the properties, which helps the composite materials retain transparency and low density.

Micro- and nanostructured electro-active polymer actuators as smart muscles for incontinence treatment

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

Osmani, Bekim, E-mail: bekim.osmani@unibas.ch, E-mail: tino.toepper@unibas.ch; Töpper, Tino, E-mail: bekim.osmani@unibas.ch, E-mail: tino.toepper@unibas.ch; Weiss, Florian M., E-mail: vanessa.leung@unibas.ch, E-mail: bert.mueller@unibas.ch

2015-02-17

Treatments of severe incontinence are currently based on purely mechanical systems that generally result in revision after three to five years. Our goal is to develop a prototype acting in a natural-analogue manner as artificial muscle, which is based on electro-active polymers. Dielectric actuators have outstanding performances including millisecond response times, mechanical strains of more than 10 % and power to mass densities similar to natural muscles. They basically consist of polymer films sandwiched between two compliant electrodes. The incompressible but elastic polymer film transduces the electrical energy into mechanical work according to the Maxwell pressure. Available polymer films aremore » micrometers thick and voltages as large as kV are necessary to obtain 10 % strain. For medical implants, polymer films should be nanometer thin to realize actuation below 48 V. The metallic electrodes have to be stretchable to follow the strain of 10 % and remain conductive. Recent results on the stress/strain behavior of anisotropic EAP-cantilevers have shown dependencies on metal electrode preparation. We have investigated tunable anisotropic micro- and nanostructures for metallic electrodes. They show a preferred actuation direction with improved stress-strain behavior. The bending of the cantilever has been characterized by the laser beam deflection method. The impact of the electrode on the effective Young's Modulus is measured using an Ultra Nanoindentation Tester with an integrated reference system for soft polymer surfaces. Once ten thousand layers of nanometer-thin EAP actuators are available, devices beyond the envisioned application will flood the market.« less

Direct observation and analysis of york-shell materials using low-voltage high-resolution scanning electron microscopy: Nanometal-particles encapsulated in metal-oxide, carbon, and polymer

NASA Astrophysics Data System (ADS)

Asahina, Shunsuke; Suga, Mitsuo; Takahashi, Hideyuki; Young Jeong, Hu; Galeano, Carolina; Schüth, Ferdi; Terasaki, Osamu

2014-11-01

Nanometal particles show characteristic features in chemical and physical properties depending on their sizes and shapes. For keeping and further enhancing their features, the particles should be protected from coalescence or degradation. One approach is to encapsulate the nanometal particles inside pores with chemically inert or functional materials, such as carbon, polymer, and metal oxides, which contain mesopores to allow permeation of only chemicals not the nanometal particles. Recently developed low-voltage high-resolution scanning electron microscopy was applied to the study of structural, chemical, and electron state of both nanometal particles and encapsulating materials in yolk-shell materials of Au@C, Ru/Pt@C, Au@TiO2, and Pt@Polymer. Progresses in the following categories were shown for the yolk-shell materials: (i) resolution of topographic image contrast by secondary electrons, of atomic-number contrast by back-scattered electrons, and of elemental mapping by X-ray energy dispersive spectroscopy; (ii) sample preparation for observing internal structures; and (iii) X-ray spectroscopy such as soft X-ray emission spectroscopy. Transmission electron microscopy was also used for characterization of Au@C.

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

NASA Astrophysics Data System (ADS)

Müller-Buschbaum, P.; Stamm, M.

1998-06-01

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

Stages of polymer transformation during remote plasma oxidation (RPO) at atmospheric pressure

NASA Astrophysics Data System (ADS)

Luan, P.; Oehrlein, G. S.

2018-04-01

The interaction of cold temperature plasma sources with materials can be separated into two types: ‘direct’ and ‘remote’ treatments. Compared to the ‘direct’ treatment which involves energetic charged species along with short-lived, strongly oxidative neutral species, ‘remote’ treatment by the long-lived weakly oxidative species is less invasive and better for producing uniformly treated surfaces. In this paper, we examine the prototypical case of remote plasma oxidation (RPO) of polymer materials by employing a surface micro-discharge (in a N2/O2 mixture environment) treatment on polystyrene. Using material characterization techniques including real-time ellipsometry, x-ray photoelectron spectroscopy, and Fourier-transform infrared spectroscopy, the time evolution of polymer film thickness, refractive index, surface, and bulk chemical composition were evaluated. These measurements revealed three consecutive stages of polymer transformation, i.e. surface adsorption and oxidation, bulk film permeation and thickness expansion followed by the material removal as a result of RPO. By correlating the observed film thickness changes with simultaneously obtained chemical information, we found that the three stages were due to the three effects of weakly oxidative species on polymers: (1) surface oxidation and nitrate (R-ONO2) chemisorption, (2) bulk oxidation, and (3) etching. Our results demonstrate that surface adsorption and oxidation, bulk oxidation, and etching can all happen during one continuous plasma treatment. We show that surface nitrate is only adsorbed on the top few nanometers of the polymer surface. The polymer film expansion also provided evidence for the diffusion and reaction of long-lived plasma species in the polymer bulk. Besides, we found that the remote plasma etched surface was relatively rich in O-C=O (ester or carboxylic acid). These findings clarify the roles of long-lived weakly oxidative plasma species on polymers and advance the understanding of plasma-polymer interactions on a molecular scale.

Reflectance spectra characteristics from an SPR grating fabricated by nano-imprint lithography technique for biochemical nanosensor applications

NASA Astrophysics Data System (ADS)

Setiya Pradana, Jalu; Hidayat, Rahmat

2018-04-01

In this paper, we report our research work on developing a Surface Plasmon Resonance (SPR) element with sub-micron (hundreds of nanometers) periodicity grating structure. This grating structure was fabricated by using a simple nano-imprint lithography technique from an organically siloxane polymers, which was then covered by nanometer thin gold layer. The formed grating structure was a very well defined square-shaped periodic structure. The measured reflectance spectra indicate the SPR wave excitation on this grating structure. For comparison, the simulations of reflectance spectra have been also carried out by using Rigorous Coupled-Wave Analysis (RCWA) method. The experimental results are in very good agreement with the simulation results.

AFM and SFG studies of pHEMA-based hydrogel contact lens surfaces in saline solution: adhesion, friction, and the presence of non-crosslinked polymer chains at the surface.

PubMed

Kim, Seong Han; Opdahl, Aric; Marmo, Chris; Somorjai, Gabor A

2002-04-01

The surfaces of two types of soft contact lenses neutral and ionic hydrogels--were characterized by atomic force microscopy (AFM) and sum-frequency-generation (SFG) vibrational spectroscopy. AFM measurements in saline solution showed that the presence of ionic functional groups at the surface lowered the friction and adhesion to a hydrophobic polystyrene tip. This was attributed to the specific interactions of water and the molecular orientation of hydrogel chains at the surface. Friction and adhesion behavior also revealed the presence of domains of non-crosslinked polymer chains at the lens surface. SFG showed that the lens surface became partially dehydrated upon exposure to air. On this partially dehydrated lens surface, the non-crosslinked domains exhibited low friction and adhesion in AFM. Fully hydrated in saline solution, the non-crosslinked domains extended more than tens of nanometers into solution and were mobile.

Bactericidal effects of plasma-modified surface chemistry of silicon nanograss

NASA Astrophysics Data System (ADS)

Ostrikov, Kola; Macgregor-Ramiasa, Melanie; Cavallaro, Alex; (Ken Ostrikov, Kostya; Vasilev, Krasimir

2016-08-01

The surface chemistry and topography of biomaterials regulate the adhesion and growth of microorganisms in ways that are still poorly understood. Silicon nanograss structures prepared via inductively coupled plasma etching were coated with plasma deposited nanometer-thin polymeric films to produce substrates with controlled topography and defined surface chemistry. The influence of surface properties on Staphylococcus aureus proliferation is demonstrated and explained in terms of nanograss substrate wetting behaviour. With the combination of the nanograss topography; hydrophilic plasma polymer coatings enhanced antimicrobial activity while hydrophobic coatings reduced it. This study advances the understanding of the effects of surface wettability on the bactericidal properties of reactive nano-engineered surfaces.

Three-dimensional single-molecule localization with nanometer accuracy using Metal-Induced Energy Transfer (MIET) imaging

NASA Astrophysics Data System (ADS)

Karedla, Narain; Chizhik, Anna M.; Stein, Simon C.; Ruhlandt, Daja; Gregor, Ingo; Chizhik, Alexey I.; Enderlein, Jörg

2018-05-01

Our paper presents the first theoretical and experimental study using single-molecule Metal-Induced Energy Transfer (smMIET) for localizing single fluorescent molecules in three dimensions. Metal-Induced Energy Transfer describes the resonant energy transfer from the excited state of a fluorescent emitter to surface plasmons in a metal nanostructure. This energy transfer is strongly distance-dependent and can be used to localize an emitter along one dimension. We have used Metal-Induced Energy Transfer in the past for localizing fluorescent emitters with nanometer accuracy along the optical axis of a microscope. The combination of smMIET with single-molecule localization based super-resolution microscopy that provides nanometer lateral localization accuracy offers the prospect of achieving isotropic nanometer localization accuracy in all three spatial dimensions. We give a thorough theoretical explanation and analysis of smMIET, describe its experimental requirements, also in its combination with lateral single-molecule localization techniques, and present first proof-of-principle experiments using dye molecules immobilized on top of a silica spacer, and of dye molecules embedded in thin polymer films.

Microscale patterning of thermoplastic polymer surfaces by selective solvent swelling.

PubMed

Rahmanian, Omid; Chen, Chien-Fu; DeVoe, Don L

2012-09-04

A new method for the fabrication of microscale features in thermoplastic substrates is presented. Unlike traditional thermoplastic microfabrication techniques, in which bulk polymer is displaced from the substrate by machining or embossing, a unique process termed orogenic microfabrication has been developed in which selected regions of a thermoplastic surface are raised from the substrate by an irreversible solvent swelling mechanism. The orogenic technique allows thermoplastic surfaces to be patterned using a variety of masking methods, resulting in three-dimensional features that would be difficult to achieve through traditional microfabrication methods. Using cyclic olefin copolymer as a model thermoplastic material, several variations of this process are described to realize growth heights ranging from several nanometers to tens of micrometers, with patterning techniques include direct photoresist masking, patterned UV/ozone surface passivation, elastomeric stamping, and noncontact spotting. Orogenic microfabrication is also demonstrated by direct inkjet printing as a facile photolithography-free masking method for rapid desktop thermoplastic microfabrication.

Gold-implanted shallow conducting layers in polymethylmethacrylate

NASA Astrophysics Data System (ADS)

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

2009-03-01

PMMA (polymethylmethacrylate) was ion implanted with gold at very low energy and over a range of different doses using a filtered cathodic arc metal plasma system. A nanometer scale conducting layer was formed, fully buried below the polymer surface at low implantation dose, and evolving to include a gold surface layer as the dose was increased. Depth profiles of the implanted material were calculated using the Dynamic TRIM computer simulation program. The electrical conductivity of the gold-implanted PMMA was measured in situ as a function of dose. Samples formed at a number of different doses were subsequently characterized by Rutherford backscattering spectrometry, and test patterns were formed on the polymer by electron beam lithography. Lithographic patterns were imaged by atomic force microscopy and demonstrated that the contrast properties of the lithography were well maintained in the surface-modified PMMA.

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.

Massive Fabrication of Polymer Microdiscs by Phase Separation and Freestanding Process.

PubMed

Zhang, Hong; Fujii, Mao; Okamura, Yosuke; Zhang, Li; Takeoka, Shinji

2016-06-29

We present a facile method to fabricate polymer thin films with tens of nanometers thickness and several micrometers size (also called "microdiscs" herein) by applying phase separation of polymer blend. A water-soluble supporting layer is employed to obtain a freestanding microdisc suspension. Owing to their miniaturized size, microdiscs can be injected through a syringe needle. Herein, poly(d,l-lactic acid) microdiscs were fabricated with various thicknesses and sizes, in the range from ca. 10 to 60 nm and from ca. 1.0 to 10.0 μm, respectively. Magnetic nanoparticles were deposited on polymer microdiscs with a surface coating method. The magnetic manipulation of microdiscs in a liquid environment under an external magnetic field was achieved with controllable velocity by adjusting the microdisc dimensions and the loading amount of magnetic components. Such biocompatible polymer microdiscs are expected to serve as injectable vehicles for targeted drug delivery.

Induced Infiltration of Hole-Transporting Polymer into Photocatalyst for Staunch Polymer-Metal Oxide Hybrid Solar Cells.

PubMed

Park, Jong Hwan; Jung, Youngsuk; Yang, Yooseong; Shin, Hyun Suk; Kwon, Soonchul

2016-10-05

For efficient solar cells based on organic semiconductors, a good mixture of photoactive materials in the bulk heterojunction on the length scale of several tens of nanometers is an important requirement to prevent exciton recombination. Herein, we demonstrate that nanoporous titanium dioxide inverse opal structures fabricated using a self-assembled monolayer method and with enhanced infiltration of electron-donating polymers is an efficient electron-extracting layer, which enhances the photovoltaic performance. A calcination process generates an inverse opal structure of titanium dioxide (<70 nm of pore diameters) providing three-dimensional (3D) electron transport pathways. Hole-transporting polymers was successfully infiltrated into the pores of the surface-modified titanium dioxide under vacuum conditions at 200 °C. The resulting geometry expands the interfacial area between hole- and electron-transport materials, increasing the thickness of the active layer. The controlled polymer-coating process over titanium dioxide materials enhanced photocurrent of the solar cell device. Density functional theory calculations show improved interfacial adhesion between the self-assembled monolayer-modified surface and polymer molecules, supporting the experimental result of enhanced polymer infiltration into the voids. These results suggest that the 3D inverse opal structure of the surface-modified titanium dioxide can serve as a favorable electron-extracting layer in further enhancing optoelectronic performance based on organic or organic-inorganic hybrid solar cell.

Laser-assisted immobilization of colloid silver nanoparticles on polyethyleneterephthalate

NASA Astrophysics Data System (ADS)

Siegel, Jakub; Lyutakov, Oleksiy; Polívková, Markéta; Staszek, Marek; Hubáček, Tomáš; Švorčík, Václav

2017-10-01

Immobilization of nanoobjects on the surface of underlying material belongs to current issues of material science. Such altered materials exhibits completely exceptional properties exploitable in a broad spectrum of industrially important applications ranging from catalysts up to health-care industry. Here we present unique approach for immobilization of electrochemically synthesized silver nanoparticles on polyethyleneterephthalate (PET) foil whose essence lies in physical incorporation of particles into thin polymer surface layer induced by polarized excimer laser light. Changes in chemical composition and surface structure of polymer after particle immobilization were recorded by wide range of analytical techniques such as ARXPS, EDX, RBS, AAS, Raman, ICP-MS, DLS, UV-vis, SEM, TEM, and AFM. Thorough analysis of both nanoparticles entering the immobilization step as well as modified PET surface allowed revealing the mechanism of immobilization process itself. Silver nanoparticles were physically embedded into a thin surface layer of polymer reaching several nanometers beneath the surface rather than chemically bonded to PET macromolecules. Laser-implanted nanoparticles open up new possibilities especially in the development of the next generation cell-conform antimicrobial coatings of polymeric materials, namely due to the considerable immobilization strength which is strong enough to prevent particle release into the surrounding environment.

Polyimide-Clay Composite Materials for Space Application

NASA Technical Reports Server (NTRS)

Orwoll, Robert A.; Connell, John W. (Technical Monitor)

2005-01-01

The introduction of nanometer-sized clay particles into a polyimide matrix has been shown to enhance the physical properties of specific polymer systems. The clay comprises large stacked platelets of the oxides of aluminum and silicon. These sheets have long dimensions on the order of tenths of a micrometer and thicknesses of several nanometers. Homogeneous dispersion of the clay platelets in the polymer matrix is necessary to achieve those enhancements in polymer properties. Natural montmorillonite with the empirical formula Na0.33Mg0.33Al1.67(OH)2(Si4O10) contains exchangeable inorganic cations. The clay lamellae stack together with the positive sodium ions situated between the surfaces of the individual sheets to balance negatively charged oxygen atoms that are on the surfaces of the sheets. These surface charges contribute to strong electrostatic forces which hold the sheets together tightly. Exfoliation can be accomplished only with unusual measures. In preparing clay nanocomposites, we have taken two steps to try to reduce these interlamellar forces in order to promote the separation (exfoliation) of the sheets and the dispersion of the individual clay particles throughout the organic polymer matrix. In the first step, some of the surface Na(+) ions are replaced with Li(+) ions. Unlike sodium cations, the lithium cations migrate into the interior of the lamellae when the system is heated. Their departure from the surface reduces the surface charge and therefore the attractive forces between the sheets. The loss of alkali metal cations from the surface can be measured as the cation exchange capacity (CEC) of the clay. For example, we found that the CEC of montmorillonite clay was reduced by almost two thirds by treating it with lithium ions and heating to 250 C for 24 hr. Lesser heating has a smaller effect on the CEC. X-ray diffraction measurements show that the d-spacing decreased from ca. 1.34 to 0.97 nm, apparently a consequence of a collapse of the clay layers. We observed that the d-spacing can be varied by altering the heat treatment. In the second part of our effort to reduce the interlamellar forces, the remaining inorganic surface cations were replaced by the trimethylphenylammonium ion (TMPA), the biphenyltrimethylammonium ion (BTMA), or the tetraphenylphosphonium ion (TPP).

SPM investigation of local aging effects in glassy polymers

NASA Astrophysics Data System (ADS)

Crider, Philip

2005-03-01

We investigate the cooperative and heterogeneous nature of glassy dynamics by nanometer-scale probing in a glassy polymer, Polyvinyl-Actetate (PVAc), with a Scanning Force Microscope (SFM). Using ultra-high-vacuum (UHV) Scanning Capacitive Force Microscopy techniques, nanometer-scale capacitive responses are probed. Dielectric relaxation near the glass transition is investigated, and scanning capabilities are utilized to analyze spatial response on a nanometer scale. The results of these studies may yield insight into the understanding of temperature-dependent cooperative length scales, local aging properties, and energy landscape properties of evolving dipole clusters on a mesoscopic scale. Results are used to test the validity and relevance of current models of glassy dynamics.

Novel adhesive properties of poly(ethylene-oxide) adsorbed nanolayers

NASA Astrophysics Data System (ADS)

Zeng, Wenduo

Solid-polymer interfaces play crucial roles in the multidisciplinary field of nanotechnology and are the confluence of physics, chemistry, biology, and engineering. There is now growing evidence that polymer chains irreversibly adsorb even onto weakly attractive solid surfaces, forming a nanometer-thick adsorbed polymer layer ("adsorbed polymer nanolayers"). It has also been reported that the adsorbed layers greatly impact on local structures and properties of supported polymer thin films. In this thesis, I aim to clarify adhesive and tribological properties of adsorbed poly(ethylene-oxide) (PEO) nanolayers onto silicon (Si) substrates, which remain unsolved so far. The adsorbed nanolayers were prepared by the established protocol: one has to equilibrate the melt or dense solution against a solid surface; the unadsorbed chains can be then removed by a good solvent, while the adsorbed chains are assumed to maintain the same conformation due to the irreversible freezing through many physical solid-segment contacts. I firstly characterized the formation process and the surface/film structures of the adsorbed nanolayers by using X-ray reflectivity, grazing incidence X-ray diffraction, and atomic force microscopy. Secondly, to compare the surface energy of the adsorbed layers with the bulk, static contact angle measurements with two liquids (water and glycerol) were carried out using a optical contact angle meter equipped with a video camera. Thirdly, I designed and constructed a custom-built adhesion-testing device to quantify the adhesive property. The experimental results provide new insight into the microscopic structure - macroscopic property relationship at the solid-polymer interface.

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

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

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

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

Review paper: progress in the field of conducting polymers for tissue engineering applications.

PubMed

Bendrea, Anca-Dana; Cianga, Luminita; Cianga, Ioan

2011-07-01

This review focuses on one of the most exciting applications area of conjugated conducting polymers, which is tissue engineering. Strategies used for the biocompatibility improvement of this class of polymers (including biomolecules' entrapment or covalent grafting) and also the integrated novel technologies for smart scaffolds generation such as micropatterning, electrospinning, self-assembling are emphasized. These processing alternatives afford the electroconducting polymers nanostructures, the most appropriate forms of the materials that closely mimic the critical features of the natural extracellular matrix. Due to their capability to electronically control a range of physical and chemical properties, conducting polymers such as polyaniline, polypyrrole, and polythiophene and/or their derivatives and composites provide compatible substrates which promote cell growth, adhesion, and proliferation at the polymer-tissue interface through electrical stimulation. The activities of different types of cells on these materials are also presented in detail. Specific cell responses depend on polymers surface characteristics like roughness, surface free energy, topography, chemistry, charge, and other properties as electrical conductivity or mechanical actuation, which depend on the employed synthesis conditions. The biological functions of cells can be dramatically enhanced by biomaterials with controlled organizations at the nanometer scale and in the case of conducting polymers, by the electrical stimulation. The advantages of using biocompatible nanostructures of conducting polymers (nanofibers, nanotubes, nanoparticles, and nanofilaments) in tissue engineering are also highlighted.

New Insights on Subsurface Imaging of Carbon Nanotubes in Polymer Composites via Scanning Electron Microscopy

NASA Technical Reports Server (NTRS)

Zhao, Minhua; Ming, Bin; Kim, Jae-Woo; Gibbons, Luke J.; Gu, Xiaohong; Nguyen, Tinh; Park, Cheol; Lillehei, Peter T.; Villarrubia, J. S.; Vladar, Andras E.;

Optical and Morphological Properties of P3HT and P3HT: PCBM Thin Films Used in Photovoltaic Applications

NASA Astrophysics Data System (ADS)

Hrostea, L.; Girtan, M.; Mallet, R.; Leontie, L.

2018-06-01

This work is focused on the study of some physical properties of poly(3-hexylthiophene-2,5-diyl) (P3HT) and poly(e-hexylthiophene-2,5-diyl): Methanolfullerene Phenyl-C61-Butyric-Accid-Methyl-Ester (PCBM) blend thin films. Knowing the polymer advantages, such as ease of processing, high thermal stability, strong interaction with light, its properties have captured the attention regarding the changes that can occur in a polymer:fullerene blend in term of them. Polymer and polymer:fullerene blend (1:0.1, 1:0.2, 1:0.4 and 1:0.8 ratios) were deposited by spin coating on glass and SnO2:F (FTO) coated glass. The optical properties were emphasized using spectrophotometry (300 – 2200 nm wavelength range) and spectroscopic ellipsometry models, to obtain the refractive index, extinction coefficient and the transmission (found higher than 80%). According to X-ray diffraction analysis, as-obtained films are amorphous. Investigation of the surface morphology of thin-film samples using Atomic Force Microscopy revealed a crystallite-like surface morphology with crystallite size in the nanometer range.

Novel SERS materials for multiplex biomolecular detection via controlled nanoparticle linking and polymer encapsulation

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

Braun, G B; Lee, S J; Laurence, T

2008-07-21

Over the past decade the emphasis on single-molecule sensitivity of surface-enhanced Raman spectroscopy (SERS) has brought to prominence the special role played by so-called SERS 'hot spots', oftentimes nanometer-scale junctions between nanostructures. In this report, optimally SERS enhancing silver clusters were synthesized using bifunctional linkers and polymer and/or protein encapsulation. The synthesis, which results in stable clusters even when stored for months or dried and re-dissolved, is scalable to large quantities. Using a sacrificial linker approach we also employ a permeable polymer/protein shell for general small molecule sensing. Finally, we utilize these nanomaterials by tagging specific epitopes on cancer cellsmore » and show that SERS signals from single clusters can be measured routinely.« less

In Situ Infrared Ellipsometry for Protein Adsorption Studies on Ultrathin Smart Polymer Brushes in Aqueous Environment

DOE PAGES

Kroning, Annika; Furchner, Andreas; Aulich, Dennis; ...

2015-02-10

The protein-adsorbing and -repelling properties of various smart nanometer-thin polymer brushes with high potential for biosensing and biomedical applications are studied by in-situ infrared-spectroscopic ellipsometry (IRSE). IRSE as a highly sensitive non-destructive technique allows us to investigate protein adsorption on polymer brushes in aqueous environment in dependence of external stimuli like temperature and pH. These stimuli are, for instance, relevant in switchable mixed brushes containing poly(N-isopropyl acrylamide) and poly(acrylic acid), respectively. We use such brushes as model surfaces for controlling protein adsorption of human serum albumin and human fibrinogen. IRSE can distinguish between polymer-specific vibrational bands, which yield insights intomore » the hydration state of the brushes, and changes in the protein-specific amide bands, which are related to changes of the protein secondary structure.« less

Nanometer-sized extracellular matrix coating on polymer-based scaffold for tissue engineering applications.

PubMed

Uchida, Noriyuki; Sivaraman, Srikanth; Amoroso, Nicholas J; Wagner, William R; Nishiguchi, Akihiro; Matsusaki, Michiya; Akashi, Mitsuru; Nagatomi, Jiro

2016-01-01

Surface modification can play a crucial role in enhancing cell adhesion to synthetic polymer-based scaffolds in tissue engineering applications. Here, we report a novel approach for layer-by-layer (LbL) fabrication of nanometer-size fibronectin and gelatin (FN-G) layers on electrospun fibrous poly(carbonate urethane)urea (PCUU) scaffolds. Alternate immersions into the solutions of fibronectin and gelatin provided thickness-controlled FN-G nano-layers (PCUU(FN-G) ) which maintained the scaffold's 3D structure and width of fibrous bundle of PCUU as evidenced by scanning electron miscroscopy. The PCUU(FN-G) scaffold improved cell adhesion and proliferation of bladder smooth muscles (BSMCs) when compared to uncoated PCUU. The high affinity of PCUU(FN-G) for cells was further demonstrated by migration of adherent BSMCs from culture plates to the scaffold. Moreover, the culture of UROtsa cells, human urothelium-derived cell line, on PCUU(FN-G) resulted in an 11-15 μm thick multilayered cell structure with cell-to-cell contacts although many UROtsa cells died without forming cell connections on PCUU. Together these results indicate that this approach will aid in advancing the technology for engineering bladder tissues in vitro. Because FN-G nano-layers formation is based on nonspecific physical adsorption of fibronectin onto polymer and its subsequent interactions with gelatin, this technique may be applicable to other polymer-based scaffold systems for various tissue engineering/regenerative medicine applications. © 2015 Wiley Periodicals, Inc.

GREENER PRODUCTION OF NOBLE METAL NANOSTRUCTURES AND NANOCOMPOSITES: RISK REDUCTION AND APPLICATIONS

EPA Science Inventory

The synthesis of nanometal/nano metal oxide/nanostructured polymer and their stabilization (through dispersant, biodegradable polymer) involves the use of natural renewable resources such plant material extract, biodegradable polymers, sugars, vitamins and finally efficient and s...

Microscale Patterning of Thermoplastic Polymer Surfaces by Selective Solvent Swelling

PubMed Central

Rahmanian, Omid; Chen, Chien-Fu; DeVoe, Don L.

2012-01-01

A new method for the fabrication of microscale features in thermoplastic substrates is presented. Unlike traditional thermoplastic microfabrication techniques, in which bulk polymer is displaced from the substrate by machining or embossing, a unique process termed orogenic microfabrication has been developed in which selected regions of a thermoplastic surface are raised from the substrate by an irreversible solvent swelling mechanism. The orogenic technique allows thermoplastic surfaces to be patterned using a variety of masking methods, resulting in three-dimensional features that would be difficult to achieve through traditional microfabrication methods. Using cyclic olefin copolymer as a model thermoplastic material, several variations of this process are described to realize growth heights ranging from several nanometers to tens of microns, with patterning techniques include direct photoresist masking, patterned UV/ozone surface passivation, elastomeric stamping, and noncontact spotting. Orogenic microfabrication is also demonstrated by direct inkjet printing as a facile photolithography-free masking method for rapid desktop thermoplastic microfabrication. PMID:22900539

Semi-Interpenetrating Polymer Networks for Enhanced Supercapacitor Electrodes.

PubMed

Fong, Kara D; Wang, Tiesheng; Kim, Hyun-Kyung; Kumar, R Vasant; Smoukov, Stoyan K

2017-09-08

Conducting polymers show great promise as supercapacitor materials due to their high theoretical specific capacitance, low cost, toughness, and flexibility. Poor ion mobility, however, can render active material more than a few tens of nanometers from the surface inaccessible for charge storage, limiting performance. Here, we use semi-interpenetrating networks (sIPNs) of a pseudocapacitive polymer in an ionically conductive polymer matrix to decrease ion diffusion length scales and make virtually all of the active material accessible for charge storage. Our freestanding poly(3,4-ethylenedioxythiophene)/poly(ethylene oxide) (PEDOT/PEO) sIPN films yield simultaneous improvements in three crucial elements of supercapacitor performance: specific capacitance (182 F/g, a 70% increase over that of neat PEDOT), cycling stability (97.5% capacitance retention after 3000 cycles), and flexibility (the electrodes bend to a <200 μm radius of curvature without breaking). Our simple and controllable sIPN fabrication process presents a framework to develop a range of polymer-based interpenetrated materials for high-performance energy storage technologies.

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.

Unidirectional Spin-Wave-Propagation-Induced Seebeck Voltage in a PEDOT:PSS/YIG Bilayer

NASA Astrophysics Data System (ADS)

Wang, P.; Zhou, L. F.; Jiang, S. W.; Luan, Z. Z.; Shu, D. J.; Ding, H. F.; Wu, D.

2018-01-01

We clarify the physical origin of the dc voltage generation in a bilayer of a conducting polymer film and a micrometer-thick magnetic insulator Y3Fe5O12 (YIG) film under ferromagnetic resonance and/or spin wave excitation conditions. The previous attributed mechanism, the inverse spin Hall effect in the polymer [Nat. Mater. 12, 622 (2013), 10.1038/nmat3634], is excluded by two control experiments. We find an in-plane temperature gradient in YIG which has the same angular dependence with the generated voltage. Both vanish when the YIG thickness is reduced to a few nanometers. Thus, we argue that the dc voltage is governed by the Seebeck effect in the polymer, where the temperature gradient is created by the nonreciprocal magnetostatic surface spin wave propagation in YIG.

Insight into the Broad Field of Polymer Nanocomposites: From Carbon Nanotubes to Clay Nanoplatelets, via Metal Nanoparticles

PubMed Central

Stefanescu, Eduard A.; Daranga, Codrin; Stefanescu, Cristina

2009-01-01

Highly ordered polymer nanocomposites are complex materials that display a rich morphological behavior owing to variations in composition, structure, and properties on a nanometer length scale. Metal-polymer nanocomposite materials are becoming more popular for applications requiring low cost, high metal surface areas. Catalytic systems seem to be the most prevalent application for a wide range of metals used in polymer nanocomposites, particularly for metals like Pt, Ni, Co, and Au, with known catalytic activities. On the other hand, among the most frequently utilized techniques to prepare polymer/CNT and/or polymer/clay nanocomposites are approaches like melt mixing, solution casting, electrospinning and solid-state shear pulverization. Additionally, some of the current and potential applications of polymer/CNT and/or polymer/clay nanocomposites include photovoltaic devices, optical switches, electromagnetic interference (EMI) shielding, aerospace and automotive materials, packaging, adhesives and coatings. This extensive review covers a broad range of articles, typically from high impact-factor journals, on most of the polymer-nanocomposites known to date: polymer/carbon nanotubes, polymer/metal nanospheres, and polymer/clay nanoplatelets composites. The various types of nanocomposites are described form the preparation stages to performance and applications. Comparisons of the various types of nanocomposites are conducted and conclusions are formulated.

Control and characterization of textured, hydrophobic ionomer surfaces

NASA Astrophysics Data System (ADS)

Wang, Xueyuan

Polymer thin films are of increasing interest in many industrial and technological applications. Superhydrophobic, self-cleaning surfaces have attracted a lot of attention for their application in self-cleaning, anti-sticking coatings, stain resistance, or anti-contamination surfaces in diverse technologies, including medical, transportation, textiles, electronics and paints. This thesis focuses on the preparation of nanometer to micrometer-size particle textured surfaces which are desirable for super water repellency. Textured surfaces consisting of nanometer to micrometer-sized lightly sulfonated polystyrene ionomer (SPS) particles were prepared by rapid evaporation of the solvent from a dilute polymer solution cast onto silica. The effect of the solvent used to spin coat the film, the molecular weight of the ionomer, and the rate of solvent evaporation were investigated. The nano-particle or micron-particle textured ionomer surfaces were prepared by either spin coating or solution casting ionomer solutions at controlled evaporation rates. The surface morphologies were consistent with a spinodal decomposition mechanism where the surface first existed as a percolated-like structure and then ripened into droplets if molecular mobility was retained for sufficient time. The SPS particles or particle aggregates were robust and resisted deformation even after annealing at 120°C for one week. The water contact angles on as-prepared surfaces were relatively low, ~ 90° since the polar groups in ionomer reduce the surface hydrophobicity. After chemical vapor deposition of 1H,1H,2H,2H-perfluorooctyltrichlorosilane, the surface contact angles increased to ~ 109° on smooth surfaces and ~140° on the textured surfaces. Water droplets stuck to these surfaces even when tilted 90 degrees. Superhydrophobic surfaces were prepared by spraying coating ionomer solutions and Chemical Vapor Deposition (CVD) of 1H,1H,2H,2H-perfluorooctyltrichlorosilane onto textured surfaces. The surfaces after CVD of silane exhibited water contact angle of 152° and the water droplet stuck to the surfaces without falling even when tilted upside down. This kind of sticky superhydrophobic surface would have potential applications in no-loss transport of liquid, and cleaning robots.

Self organized striping in ultra thin polymer films near melt: An investigation using Monte Carlo simulation

NASA Astrophysics Data System (ADS)

Singh, Satya Pal

2018-05-01

This paper work presents the results of Monte Carlo simulation performed for ultra thin short chained polymer films near melt, under strong confinement. Thin polymer films get ruptured when annealed above their glass transition temperatures. The pattern formations are generally explained on the basis of spinodal mechanism, if the thickness of the film is of the order of few tens of nanometers i.e. <100 nm. In this case, the film seems to tear apart in strips. The free end segments of the chains are more dynamic and coalescence into one another. This process seems to dominate over the spinodal waves resulting into a different type of dynamics. Polymer chains with 30 monomers are taken. 160, 200 and 240 chains are taken for three different cases of the studies. The three cases correspond to three different thickness of the films with 8, 10 and 12 layers of chains along direction perpendicular to the confining substrates. The bottom surface has affinity to monomers, whereas the upper surface has hard wall interaction with the monomers. Different time micrographs of the films are plotted along with density distributions of the monomers to explore the process.

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

Laser Micro and Nano Processing of Metals , Ceramics , and Polymers

NASA Astrophysics Data System (ADS)

Pfleging, Wilhelm; Kohler, Robert; Südmeyer, Isabelle; Rohde, Magnus

Laser -based material processing is well investigated for structuring , modification , and bonding of metals , ceramics , glasses, and polymers . Especially for material processing on micrometer, and nanometer scale laser-assisted processes will very likely become more prevalent as lasers offer more cost-effective solutions for advanced material research, and application. Laser ablation , and surface modification are suitable for direct patterning of materials and their surface properties. Lasers allow rapid prototyping and small-batch manufacturing . They can also be used to pattern moving substrates, permitting fly-processing of large areas at reasonable speed. Different types of laser processes such as ablation, modification, and welding can be successfully combined in order to enable a high grade of bulk and surface functionality. Ultraviolet lasers favored for precise and debris-free patterns can be generated without the need for masks, resist materials, or chemicals. Machining of materials, for faster operation, thermally driven laser processes using NIR and IR laser radiation, could be increasingly attractive for a real rapid manufacturing.

Characterization of ultraviolet light cured polydimethylsiloxane films for low-voltage, dielectric elastomer actuators

NASA Astrophysics Data System (ADS)

Töpper, Tino; Wohlfender, Fabian; Weiss, Florian; Osmani, Bekim; Müller, Bert

2016-04-01

The reduction the operation voltage has been the key challenge to realize of dielectric elastomer actuators (DEA) for many years - especially for the application fields of robotics, lens systems, haptics and future medical implants. Contrary to the approach of manipulating the dielectric properties of the electrically activated polymer (EAP), we intend to realize low-voltage operation by reducing the polymer thickness to the range of a few hundred nanometers. A study recently published presents molecular beam deposition to reliably grow nanometer-thick polydimethylsiloxane (PDMS) films. The curing of PDMS is realized using ultraviolet (UV) radiation with wavelengths from 180 to 400 nm radicalizing the functional side and end groups. The understanding of the mechanical properties of sub-micrometer-thin PDMS films is crucial to optimize DEAs actuation efficiency. The elastic modulus of UV-cured spin-coated films is measured by nano-indentation using an atomic force microscope (AFM) according to the Hertzian contact mechanics model. These investigations show a reduced elastic modulus with increased indentation depth. A model with a skin-like SiO2 surface with corresponding elastic modulus of (2.29 +/- 0.31) MPa and a bulk modulus of cross-linked PDMS with corresponding elastic modulus of (87 +/- 7) kPa is proposed. The surface morphology is observed with AFM and 3D laser microscopy. Wrinkled surface microstructures on UV-cured PDMS films occur for film thicknesses above (510 +/- 30) nm with an UV-irradiation density of 7.2 10-4 J cm-2 nm-1 at a wavelength of 190 nm.

Helium Ion Microscope: A New Tool for Sub-nanometer Imaging of Soft Materials

NASA Astrophysics Data System (ADS)

Shutthanandan, V.; Arey, B.; Smallwood, C. R.; Evans, J. E.

2017-12-01

High-resolution inspection of surface details is needed in many biological and environmental researches to understand the Soil organic material (SOM)-mineral interactions along with identifying microbial communities and their interactions. SOM shares many imaging characteristics with biological samples and getting true surface details from these materials are challenging since they consist of low atomic number materials. FE-SEM imaging is the main imagining technique used to image these materials in the past. These SEM images often show loss of resolution and increase noise due to beam damage and charging issues. Newly developed Helium Ion Microscope (HIM), on the other hand can overcome these difficulties and give very fine details. HIM is very similar to scanning electron microscopy (SEM) but instead of using electrons as a probe beam, HIM uses helium ions with energy ranges from 5 to 40 keV. HIM offers a series of advantages compared to SEM such as nanometer and sub-nanometer image resolutions (about 0.35 nm), detailed surface topography, high surface sensitivity, low Z material imaging (especially for polymers and biological samples), high image contrast, and large depth of field. In addition, HIM also has the ability to image insulating materials without any conductive coatings so that surface details are not modified. In this presentation, several scientific applications across biology and geochemistry will be presented to highlight the effectiveness of this powerful microscope. Acknowledgements: Research was performed using the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at PNNL. Work was supported by DOE-BER Mesoscale to Molecules Bioimaging Project FWP# 66382.

Polyelectrolyte multilayer capsules as vehicles with tunable permeability.

PubMed

Antipov, Alexei A; Sukhorukov, Gleb B

2004-11-29

This review is devoted to a novel type of polymer micro- and nanocapsules. The shell of the capsule is fabricated by alternate adsorption of oppositely charged polyelectrolytes (PEs) onto the surface of colloidal particles. Cores of different nature (organic or inorganic) with size varied from 0.1 to 10 mum can be used for templating such PE capsules. The shell thickness can be tuned in nanometer range by assembling of defined number of PE layers. The permeability of capsules depends on the pH, ionic strength, solvent, polymer composition, and shell thickness; it can be controlled and varied over wide range of substances regarding their molecular weight and charge. Including functional polymers into capsule wall, such as weak PEs or thermosensitive polymers, makes the capsule permeability sensitive to correspondent external stimuli. Permeability of the capsules is of essential interest in diverse areas related to exploitation of systems with controlled and sustained release properties. The envisaged applications of such capsules/vesicles cover biotechnology, medicine, catalysis, food industry, etc.

Magnetic field gradient driven self-assembly of superparamagnetic nanoparticles using programmable magnetically-recorded templates

NASA Astrophysics Data System (ADS)

Ye, L.; Qi, B.; Lawton, T. G.; Mefford, O. T.; Rinaldi, C.; Garzon, S.; Crawford, T. M.

2013-03-01

Using the enormous magnetic field gradients (100 MT/m @ z =20 nm) present near the surface of magnetic recording media, we demonstrate the fabrication of diffraction gratings with lines consisting entirely of magnetic nanoparticles assembled from a colloidal fluid onto a disk drive medium, followed by transfer to a flexible and transparent polymer thin film. These nanomanufactured gratings have line spacings programmed with commercial magnetic recording and are inherently concave with radii of curvature controlled by varying the polymer film thickness. The diffracted intensity increases non-monotonically with the length of time the colloidal fluid remains on the disk surface. In addition to comparing longitudinal and perpendicular magnetic recording, a combination of spectral diffraction efficiency measurements, magnetometry, scanning electron microscopy and inductively coupled plasma atomic emmission spectroscopy of these gratings are employed to understand colloidal nanoparticle dynamics in this extreme gradient limit. Such experiments are necessary to optimize nanoparticle assembly and obtain uniform patterned features. This low-cost and sustainable approach to nanomanufacturing could enable low-cost, high-quality diffraction gratings as well as more complex polymer nanocomposite materials assembled with single-nanometer precision.

[Application of electrostatic spinning technology in nano-structured polymer scaffold].

PubMed

Chen, Denglong; Li, Min; Fang, Qian

2007-04-01

To review the latest development in the research on the application of the electrostatic spinning technology in preparation of the nanometer high polymer scaffold. The related articles published at home and abroad during the recent years were extensively reviewed and comprehensively analyzed. Micro/nano-structure and space topology on the surfaces of the scaffold materials, especially the weaving structure, were considered to have an important effect on the cell adhesion, proliferation, directional growth, and biological activation. The electrospun scaffold was reported to have a resemblance to the structure of the extracellular matrix and could be used as a promising scaffold for the tissue engineering application. The electrospun scaffolds were applied to the cartilage, bone, blood vessel, heart, and nerve tissue engineering fields. The nano-structured polymer scaffold can support the cell adhesion, proliferation, location, and differentiation, and this kind of scaffold has a considerable value in the tissue engineering field.

Reversible modulation of the redox activity in conducting polymer nanofilms induced by hydrophobic collapse of a surface-grafted polyelectrolyte.

PubMed

Fenoy, Gonzalo E; Giussi, Juan M; von Bilderling, Catalina; Maza, Eliana M; Pietrasanta, Lía I; Knoll, Wolfgang; Marmisollé, Waldemar A; Azzaroni, Omar

2018-05-15

We present the covalent modification of a Pani-like conducting polymer (polyaminobenzylamine, PABA) by grafting of a polyelectrolyte brush (poly [2-(methacryloyloxy)-ethyl-trimethylammonium chloride], PMETAC). As PABA has extra pendant amino moieties, the grafting procedure does not affect the backbone nitrogen atoms that are implicated in the electronic structure of the conducting polymers. Moreover, perchlorate anions interact very strongly with the quaternary ammonium pendant groups of PMETAC through ion pairing. Therefore, the grafting does not only keep the electroactivity of PABA in aqueous solutions but it adds the ion-actuation properties of the PMETAC brush to the modified electrode as demonstrated by contact angle measurements and electrochemical methods. In this way, the conjugation of the electron transfer properties of the conducting polymer with the anion responsiveness of the integrated brush renders perchlorate actuation of the electrochemical response. These results constitute a rational integration of nanometer-sized polymer building blocks that yields synergism of functionalities and illustrate the potentialities of nanoarchitectonics for pushing the limits of soft material science into the nanoworld. Copyright © 2018 Elsevier Inc. All rights reserved.

Direct laser interference patterning of metallic sleeves for roll-to-roll hot embossing

NASA Astrophysics Data System (ADS)

Lang, Valentin; Rank, Andreas; Lasagni, Andrés. F.

2017-03-01

Surfaces equipped with periodic patterns with feature sizes in the micrometer, submicrometer and nanometer range present outstanding surface properties. Many of these surfaces can be found on different plants and animals. However, there are few methods capable to produce such patterns in a one-step process on relevant technological materials. Direct laser interference patterning (DLIP) provides both high resolution as well as high throughput. Recently, fabrication rates up to 1 m2·min-1 could be achieved. However, resolution was limited to a few micrometers due to typical thermal effects that arise when nanosecond pulsed laser systems are used. Therefore, this study introduces an alternative to ns-DLIP for the fabrication of multi-scaled micrometer and submicrometer structures on nickel surfaces using picosecond pulses (10 ps at a wavelength of 1064 nm). Due to the nature of the interaction process of the metallic surfaces with the ultrashort laser pulses, it was not only possible to directly transfer the shape of the interference pattern intensity distribution to the material (with spatial periods ranging from 1.5 μm to 5.7 μm), but also to selectively obtain laser induce periodic surface structures with feature sizes in the submicrometer and nanometer range. Finally, the structured nickel sleeves are utilized in a roll-to-roll hot embossing unit for structuring of polymer foils. Processing speeds up to 25 m·min-1 are reported.

Functionalizing the Surface of Lithium-Metal Anodes

DOE PAGES

Buonaiuto, Megan; Neuhold, Susanna; Schroeder, David J.; ...

2014-09-03

Metal-air batteries are an important aspect of many beyond lithium ion research efforts. However, as our understanding of how molecular oxygen can act as a rechargeable cathode has progressed; the problems associated with how these materials at various states of charge interact with the lithium metal anode are only beginning to come to the surface. In this study we have devised a method to coat the surface a lithium with a functional group to act as either an anchor for further derivation studies or be polymerized to create a nanometer thick polymer coating attached to the surface by silane groups.more » These stable films, formed by polymerization of vinyl substituents, lower cell impedance at the electrode and over the first 50 cycles, increase cycling efficiency and demonstrate lower capacity fade.« less

Engineering polyelectrolyte multilayer structure at the nanometer length scale by tuning polymer solution conformation.

NASA Astrophysics Data System (ADS)

Boddohi, Soheil; Killingsworth, Christopher; Kipper, Matt

2008-03-01

Chitosan (a weak polycation) and heparin (a strong polyanion) are used to make polyelectrolyte multilayers (PEM). PEM thickness and composition are determined as a function of solution pH (4.6 to 5.8) and ionic strength (0.1 to 0.5 M). Over this range, increasing pH increases the PEM thickness; however, the sensitivity to changes in pH is a strong function of ionic strength. The PEM thickness data are correlated to the polymer conformation in solution. Polyelectrolyte conformation in solution is characterized by gel permeation chromatography (GPC). The highest sensitivity of PEM structure to pH is obtained at intermediate ionic strength. Different interactions govern the conformation and adsorption phenomena at low and high ionic strength, leading to reduced sensitivity to solution pH at extreme ionic strengths. The correspondence between PEM thickness and polymer solution conformation offers opportunities to tune polymer thin film structure at the nanometer length scale by controlling simple, reproducible processing conditions.

Strain-dependent characterization of electrode and polymer network of electrically activated polymer actuators

NASA Astrophysics Data System (ADS)

Töpper, Tino; Osmani, Bekim; Weiss, Florian M.; Winterhalter, Carla; Wohlfender, Fabian; Leung, Vanessa; Müller, Bert

2015-04-01

Fecal incontinence describes the involuntary loss of bowel content and affects about 45 % of retirement home residents and overall more than 12 % of the adult population. Artificial sphincter implants for treating incontinence are currently based on mechanical systems with failure rates resulting in revision after three to five years. To overcome this drawback, artificial muscle sphincters based on bio-mimetic electro-active polymer (EAP) actuators are under development. Such implants require polymer films that are nanometer-thin, allowing actuation below 24 V, and electrodes that are stretchable, remaining conductive at strains of about 10 %. Strain-dependent resistivity measurements reveal an enhanced conductivity of 10 nm compared to 30 nm sputtered Au on silicone for strains higher than 5 %. Thus, strain-dependent morphology characterization with optical microscopy and atomic force microscopy could demonstrate these phenomena. Cantilever bending measurements are utilized to determine elastic/viscoelastic properties of the EAP films as well as their long-term actuation behavior. Controlling these properties enables the adjustment of growth parameters of nanometer-thin EAP actuators.

Prediction of Material Properties of Nanostructured Polymer Composites Using Atomistic Simulations

NASA Technical Reports Server (NTRS)

Hinkley, J.A.; Clancy, T.C.; Frankland, S.J.V.

2009-01-01

Atomistic models of epoxy polymers were built in order to assess the effect of structure at the nanometer scale on the resulting bulk properties such as elastic modulus and thermal conductivity. Atomistic models of both bulk polymer and carbon nanotube polymer composites were built. For the bulk models, the effect of moisture content and temperature on the resulting elastic constants was calculated. A relatively consistent decrease in modulus was seen with increasing temperature. The dependence of modulus on moisture content was less consistent. This behavior was seen for two different epoxy systems, one containing a difunctional epoxy molecule and the other a tetrafunctional epoxy molecule. Both epoxy structures were crosslinked with diamine curing agents. Multifunctional properties were calculated with the nanocomposite models. Molecular dynamics simulation was used to estimate the interfacial thermal (Kapitza) resistance between the carbon nanotube and the surrounding epoxy matrix. These estimated values were used in a multiscale model in order to predict the thermal conductivity of a nanocomposite as a function of the nanometer scaled molecular structure.

TOPICAL REVIEW: Surface modification and characterization for dispersion stability of inorganic nanometer-scaled particles in liquid media

NASA Astrophysics Data System (ADS)

Kamiya, Hidehiro; Iijima, Motoyuki

2010-08-01

Inorganic nanoparticles are indispensable for science and technology as materials, pigments and cosmetics products. Improving the dispersion stability of nanoparticles in various liquids is essential for those applications. In this review, we discuss why it is difficult to control the stability of nanoparticles in liquids. We also overview the role of surface interaction between nanoparticles in their dispersion and characterization, e.g. by colloid probe atomic force microscopy (CP-AFM). Two types of surface modification concepts, post-synthesis and in situ modification, were investigated in many previous studies. Here, we focus on post-synthesis modification using adsorption of various kinds of polymer dispersants and surfactants on the particle surface, as well as surface chemical reactions of silane coupling agents. We discuss CP-AFM as a technique to analyze the surface interaction between nanoparticles and the effect of surface modification on the nanoparticle dispersion in liquids.

Nanoscale molecularly imprinted polymers and method thereof

DOEpatents

Hart, Bradley R [Brentwood, CA; Talley, Chad E [Brentwood, CA

2008-06-10

Nanoscale molecularly imprinted polymers (MIP) having polymer features wherein the size, shape and position are predetermined can be fabricated using an xy piezo stage mounted on an inverted microscope and a laser. Using an AMF controller, a solution containing polymer precursors and a photo initiator are positioned on the xy piezo and hit with a laser beam. The thickness of the polymeric features can be varied from a few nanometers to over a micron.

Strong adsorption of random heteropolymers on protein surfaces

NASA Astrophysics Data System (ADS)

Nguyen, Trung; Qiao, Baofu; Panganiban, Brian; Delre, Christopher; Xu, Ting; Olvera de La Cruz, Monica

Rational design of copolymers for stablizing proteins' functionalities in unfavorable solvents and delivering nanoparticles through organic membranes demands a thorough understanding of how the proteins and colloids are encapsulated by a given type of copolymers. Random heteropolymers (RHPs), a special family of copolymers with random segment order, have long been recognized as a promising coating materials due to their biomimetic behaviors while allowing for much flexibility in the synthesis procedure. Of practical importance is the ability to predict the conditions under which a given family of random heteropolymers would provide optimal encapsulatio. Here we investigate the key factors that govern the adsorption of RHPs on the surface of a model protein. Using coarse-grained molecular simulation we identify the conditions under which the model protein is fully covered by the polymers. We have examined the nanometer-level details of the adsorbed polymer chains and found a clear connection between the surface coverage and adsorption strength, solvent selectivity and the volume fraction of adsorbing monomers. The results in this work set the stage for further investigation on engineering biomimetic RHPs for stabilizing and delivering functional proteins across multiple media.

Polymeric materials in Space

NASA Astrophysics Data System (ADS)

Skurat, Vladimir

Paper of short review type. It is the continuation of and addition to previous review papers "V. E. Skurat. Polymers in Space. In: Encyclopedia of aerospace engineering, vol. 4, Wiley and sons, 2010; Ibid., 2012 (on line)". Following topics are considered: (1) Destruction of polymers by solar radiation with various wavelengths in different spectral regions (visible-UV, vacuum UV (VUV), deep UV, soft and hard X-rays) are discussed. In difference with common polymer photochemistry induced by UV radiation, directions of various routs of polymer phototransformations and their relative yields are greatly dependent on wavelength of light (photon energy) during illuminations in VUV, deep UV and X-ray regions. During last twenty years, intensive spacecraft investigations of solar spectrum show great periodic and spontaneous variations of radiation intensities in short-wavelengths regions - up to one - two decimal orders of magnitude for X-rays. As a result, during solar flares the absorbed dose on the polymer surfaces from X-rays can be compared with absorbed dose from VUV radiation. (2) Some new approaches to predictions of reaction efficiencies of fast orbital atomic oxygen in their interaction with polymeric materials are considered. (3) Some aspects of photocatalitic destruction of polymers in vacuum conditions by full-spectrum solar radiation are discussed. This process can take place in enamels containing semiconducting particles (TiO2, ZnO) as pigments. (4) Contamination of spacecraft surfaces from intrinsic outer atmosphere play important role not only from the point of view of deterioration of optical and thermophysical properties. Layers of SiO2 contaminations with nanometer thicknesses can greatly diminish mass losses from perfluorinated polymers under VUV irradiation.

Nanoscale patterning of colloidal quantum dots on transparent and metallic planar surfaces.

PubMed

Park, Yeonsang; Roh, Young-Geun; Kim, Un Jeong; Chung, Dae-Young; Suh, Hwansoo; Kim, Jineun; Cheon, Sangmo; Lee, Jaesoong; Kim, Tae-Ho; Cho, Kyung-Sang; Lee, Chang-Won

2012-09-07

The patterning of colloidal quantum dots with nanometer resolution is essential for their application in photonics and plasmonics. Several patterning approaches, such as the use of polymer composites, molecular lock-and-key methods, inkjet printing and microcontact printing of quantum dots have been recently developed. Herein, we present a simple method of patterning colloidal quantum dots for photonic nanostructures such as straight lines, rings and dot patterns either on transparent or metallic substrates. Sub-10 nm width of the patterned line could be achieved with a well-defined sidewall profile. Using this method, we demonstrate a surface plasmon launcher from a quantum dot cluster in the visible spectrum.

Nanostructured polymer brushes.

PubMed

Schmelmer, Ursula; Paul, Anne; Küller, Alexander; Steenackers, Marin; Ulman, Abraham; Grunze, Michael; Gölzhäuser, Armin; Jordan, Rainer

2007-03-01

Nanopatterned polymer brushes with sub-50-nm resolution were prepared by a combination of electron-beam chemical lithography (EBCL) of self-assembled monolayers (SAMs) and surface-initiated photopolymerization (SIPP). As a further development of our previous work, selective EBCL was performed with a highly focused electron beam and not via a mask, to region-selectively convert a SAM of 4'-nitro-1,1'-biphenyl-4-thiol to defined areas of crosslinked 4'-amino-1,1'-biphenyl-4-thiol. These "written" structures were then used to prepare surface-bonded, asymmetric, azo initiator sites of 4'-azomethylmalonodinitrile-1,1'-biphenyl-4-thiol. In the presence of bulk styrene, SIPP amplified the primary structures of line widths from 500 to 10 nm to polystyrene structures of line widths 530 nm down to approximately 45 nm at a brush height of 10 or 7 nm, respectively, as measured by scanning electron microscopy and atomic force microscopy (AFM). The relative position of individual structures was within a tolerance of a few nanometers, as verified by AFM. At line-to-line spacings down to 50-70 nm, individual polymer brush structures are still observable. Below this threshold, neighboring structures merge due to chain overlap.

High-density regular arrays of nanometer-scale rods formed on silicon surfaces via femtosecond laser irradiation in water.

PubMed

Shen, Mengyan; Carey, James E; Crouch, Catherine H; Kandyla, Maria; Stone, Howard A; Mazur, Eric

2008-07-01

We report on the formation of high-density regular arrays of nanometer-scale rods using femtosecond laser irradiation of a silicon surface immersed in water. The resulting surface exhibits both micrometer-scale and nanometer-scale structures. The micrometer-scale structure consists of spikes of 5-10 mum width, which are entirely covered by nanometer-scale rods that are roughly 50 nm wide and normal to the surface of the micrometer-scale spikes. The formation of the nanometer-scale rods involves several processes: refraction of laser light in highly excited silicon, interference of scattered and refracted light, rapid cooling in water, roughness-enhanced optical absorptance, and capillary instabilities.

Impact of Interfacial Roughness on the Sorption Properties of Nanocast Polymers

DOE PAGES

Sridhar, Manasa; Gunugunuri, Krishna R.; Hu, Naiping; ...

2016-03-16

Nanocasting is an emerging method to prepare organic polymers with regular, nanometer pores using inorganic templates. This report assesses the impact of imperfect template replication on the sorption properties of such polymer castings. Existing X-ray diffraction data show that substantial diffuse scattering exists in the small-angle region even though TEM images show near perfect lattices of uniform pores. To assess the origin of the diffuse scattering, the morphology of the phenol - formaldehyde foams (PFF) was investigated by small-angle X-ray scattering (SAXS). The observed diffuse scattering is attributed to interfacial roughness due to fractal structures. Such roughness has a profoundmore » impact on the sorption properties. Conventional pore- filling models, for example, overestimate protein sorption capacity. A mathematical framework is presented to calculate sorption properties based on observed morphological parameters. The formalism uses the surface fractal dimension determined by SAXS in conjunction with nitrogen adsorption isotherms to predict lysozyme sorption. The results are consistent with measured lysozyme loading.« less

Photosensitizing effects of nanometer TiO2 on chlorothalonil photodegradation in aqueous solution and on the surface of pepper.

PubMed

Tan, Yong Qiang; Xiong, Hai Xia; Shi, Tao Zhong; Hua, Ri Mao; Wu, Xiang Wei; Cao, Hai Qun; Li, Xue De; Tang, Jun

2013-05-29

The present study examined the effects of anatase nanometer TiO2 on photochemical degradation of chlorothalonil in aqueous solution and on the plant surface. Results showed that nanometer TiO2 exhibited a strong photosensitizing effect on the degradation of chlorothalonil both in aqueous solution and on the surface of green pepper. The photosensitization rate was the highest in the sunlight compared to illumination under high-pressure mercury and UV lamps. Use of distinct hydroxyl radical scavengers indicated that nanometer TiO2 acted by producing hydroxyl radicals with strong oxidizing capacity. Notably, nanometer TiO2 facilitated complete photodegradation of chlorothalonil with no detectable accumulation of the intermediate chlorothalonil-4-hydroxy. Nanometer TiO2 was also active on the surface of green pepper under natural sunlight both inside and outside of plastic greenhouse. These results together suggest that nanometer TiO2 can be used as a photosensitizer to accelerate degradation of the pesticides under greenhouse conditions.

Graphene-doped polymer nanofibers for low-threshold nonlinear optical waveguiding

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

Meng, Chao; Yu, Shao-Liang; Wang, Hong -Qing

Graphene-doped polymer nanofibers are fabricated by taper drawing of solvated polyvinyl alcohol doped with liquid-phase exfoliated graphene flakes. Nanofibers drawn this way typically have diameters measured in hundreds of nanometers and lengths in tens of millimeters; they show excellent uniformity and surface smoothness for optical waveguiding. Owing to their tightly confined waveguiding behavior, light–matter interaction in these subwavelength-diameter nanofibers is significantly enhanced. Using approximately 1350-nm-wavelength femto-second pulses, we demonstrate saturable absorption behavior in these nanofibers with a saturation threshold down to 0.25 pJ pulse -1 (peak power ~1.3 W). Additionally, using 1064-nm-wavelength nanosecond pulses as switching light, we show all-opticalmore » modulation of a 1550-nm-wavelength signal light guided along a single nanofiber with a switching peak power of ~3.2 W.« less

Graphene-doped polymer nanofibers for low-threshold nonlinear optical waveguiding

DOE PAGES

Meng, Chao; Yu, Shao-Liang; Wang, Hong -Qing; ...

2015-11-06

Graphene-doped polymer nanofibers are fabricated by taper drawing of solvated polyvinyl alcohol doped with liquid-phase exfoliated graphene flakes. Nanofibers drawn this way typically have diameters measured in hundreds of nanometers and lengths in tens of millimeters; they show excellent uniformity and surface smoothness for optical waveguiding. Owing to their tightly confined waveguiding behavior, light–matter interaction in these subwavelength-diameter nanofibers is significantly enhanced. Using approximately 1350-nm-wavelength femto-second pulses, we demonstrate saturable absorption behavior in these nanofibers with a saturation threshold down to 0.25 pJ pulse -1 (peak power ~1.3 W). Additionally, using 1064-nm-wavelength nanosecond pulses as switching light, we show all-opticalmore » modulation of a 1550-nm-wavelength signal light guided along a single nanofiber with a switching peak power of ~3.2 W.« less

Geometry in Biomimetic Network: Double Gyroid to Pseudo-Single Gyroid in Nanohybrid Materials

NASA Astrophysics Data System (ADS)

Hsueh, Han-Yu; Ho, Rong-Ming; Hung, Yu-Chueh; Ling, Yi-Chun; Hasegawa, Hirokazu

2013-03-01

Biological systems have developed delicately arranged micro- and architectures to produce striking optical effects since millions of years ago. Inspired by the textures of butterfly wings with single gyroid (SG) structure, herein, we aim to fabricate biocompatible and robust materials with SG-like structure in nanometer size so as to give new materials with unprecedented optical properties for applications. Biommicking from the biological photonic structures of butterfly wings, a double gyroid (DG) structure in nanometer size is obtained from the self-assembly of polystyrene-b-poly(L-lactide) (PS-PLLA). To acquire robust backbone networks, inorganic networks in polymer matrix are fabricated by using the hydrolyzed PS-PLLA with DG structure as a template for sol-gel reaction. Owing to the soft polymer matrix, two co-continuous inorganic networks embedded in the polymer matrix can be rearranged by thermal annealing at temperature above the glass transition of the polymer. Consequently, the rearrangement of these inorganic networks leads the formation of SG-like structure possessing unique nanohybrids with ordered texture. This unique nanomaterials with SG-like structure is referred as a pseudo-SG (p-SG) nanohybrids.

Molecular threading: mechanical extraction, stretching and placement of DNA molecules from a liquid-air interface.

PubMed

Payne, Andrew C; Andregg, Michael; Kemmish, Kent; Hamalainen, Mark; Bowell, Charlotte; Bleloch, Andrew; Klejwa, Nathan; Lehrach, Wolfgang; Schatz, Ken; Stark, Heather; Marblestone, Adam; Church, George; Own, Christopher S; Andregg, William

2013-01-01

We present "molecular threading", a surface independent tip-based method for stretching and depositing single and double-stranded DNA molecules. DNA is stretched into air at a liquid-air interface, and can be subsequently deposited onto a dry substrate isolated from solution. The design of an apparatus used for molecular threading is presented, and fluorescence and electron microscopies are used to characterize the angular distribution, straightness, and reproducibility of stretched DNA deposited in arrays onto elastomeric surfaces and thin membranes. Molecular threading demonstrates high straightness and uniformity over length scales from nanometers to micrometers, and represents an alternative to existing DNA deposition and linearization methods. These results point towards scalable and high-throughput precision manipulation of single-molecule polymers.

Development and characterization of amorphous acrylate networks for use as switchable adhesives inspired from shapememory behavior

NASA Astrophysics Data System (ADS)

Lakhera, Nishant

Several types of insects and animals such as spiders and geckos are inherently able to climb along vertical walls and ceilings. This remarkable switchable adhesive behavior has been attributed to the fibrillar structures on their feet, with size ranging from few nanometers to a few micrometers depending on the species. Several studies have attempted to create synthetic micro-patterned surfaces trying to imitate this adhesive behavior seen in nature. The experimental procedures are scattered, with sole purpose of trying to increase adhesion, thereby making direct comparison between studies very difficult. There is a lack of fundamental understanding on adhesion of patterned surfaces. The influence of critical parameters like material modulus, glass transition temperature, viscoelastic effects, temperature and water absorption on adhesion is not fully explored and characterized. These parameters are expected to have a decisive influence on adhesion behavior of the polymer. Previous studies have utilized conventional "off-the-shelf" materials like epoxy, polyurethanes etc. It is however, impossible to change the material modulus, glass transition temperature etc. of these polymer systems without changing the base constituents itself, thereby explaining the gaps in the current research landscape. The purpose of this study was to use acrylate shape-memory polymers (SMPs) for their ability to be tailored to specific mechanical properties by control of polymer chemistry, without changing the base constituents. Polymer networks with tailorable glass transition, material modulus, water absorption etc. were developed and adhesion studies were performed to investigate the influence of temperature, viscoelastic effects, material modulus on the adhesion behavior of flat acrylate polymer surfaces. The knowledge base gained from these studies was utilized to better understand the fundamental mechanisms associated with adhesion behavior of patterned acrylate surfaces. Thermally induced switchable adhesion and water induced switchable adhesion of patterned acrylate surfaces was investigated. The viscoelastic energy dissipation occurring during the detachment phase was shown to dramatically increase adhesion under both thermally induced and water induced conditions. This effect was most pre-dominant at the glass transition temperature of the material. Increase in pre-load force and unloading velocity were also shown to increase the adhesive capability of the patterned acrylate SMPs.

In situ creation of reactive polymer nanoparticles and resulting polymer layers formed at the interfaces of liquid crystals (Conference Presentation)

NASA Astrophysics Data System (ADS)

Kang, Shin-Woong; Kundu, Sudarshan; Park, Heung-Shik; Oh, Keun Chan; Lyu, Jae Jin

2017-02-01

We report the in situ creation of reactive polymer nanoparticles and resulting polymer networks formed at the interfaces of liquid crystals. It is known that polymerization-induced phase separation proceeds in two distinct regimes depending on the concentration of monomer. For a high monomer concentration, phase separation occurs mainly through the spinodal decomposition process, consequently resulting in interpenetrating polymer networks. For a dilute system, however, the phase separation mainly proceeds and completes in the binodal decomposition regime. The system resembles the aggregation process of colloidal particle. In this case, the reaction kinetics is limited by the reaction between in situ created polymer aggregates and hence the network morphologies are greatly influenced by the diffusion of reactive polymer particles. The thin polymer layers localized at the surface of substrate are inevitably observed and can be comprehended by the interfacial adsorption and further cross-linking reaction of reactive polymer aggregates at the interface. This process provides a direct perception on understanding polymer stabilized liquid crystals accomplished by the interfacial polymer layer. The detailed study has been performed for an extremely dilute condition (below 0.5 wt%) by employing systematic experimental approaches. Creation and growth of polymer nanoparticles have been measured by particle size analyzer. The interfacial localization of polymer aggregates and resulting interfacial layer formation with a tens of nanometer scale have been exploited at various interfaces such as liquid-solid, liquid-liquid, and liquid-gas interfaces. The resulting interfacial layers have been characterized by using fuorescent confocal microscope and field emission scanning electron microscope. The detailed processes of the polymer stabilized vertically aligned liquid crystals will be discussed in support of the reported study.

Parallel array of nanochannels grafted with polymer-brushes-stabilized Au nanoparticles for flow-through catalysis.

PubMed

Liu, Jianxi; Ma, Shuanhong; Wei, Qiangbing; Jia, Lei; Yu, Bo; Wang, Daoai; Zhou, Feng

2013-12-07

Smart systems on the nanometer scale for continuous flow-through reaction present fascinating advantages in heterogeneous catalysis, in which a parallel array of straight nanochannels offers a platform with high surface area for assembling and stabilizing metallic nanoparticles working as catalysts. Herein we demonstrate a method for finely modifying the nanoporous anodic aluminum oxide (AAO), and further integration of nanoreactors. By using atomic transfer radical polymerization (ATRP), polymer brushes were successfully grafted on the inner wall of the nanochannels of the AAO membrane, followed by exchanging counter ions with a precursor for nanoparticles (NPs), and used as the template for deposition of well-defined Au NPs. The membrane was used as a functional nanochannel for novel flow-through catalysis. High catalytic performance and instantaneous separation of products from the reaction system was achieved in reduction of 4-nitrophenol.

Parallel array of nanochannels grafted with polymer-brushes-stabilized Au nanoparticles for flow-through catalysis

NASA Astrophysics Data System (ADS)

Liu, Jianxi; Ma, Shuanhong; Wei, Qiangbing; Jia, Lei; Yu, Bo; Wang, Daoai; Zhou, Feng

2013-11-01

Smart systems on the nanometer scale for continuous flow-through reaction present fascinating advantages in heterogeneous catalysis, in which a parallel array of straight nanochannels offers a platform with high surface area for assembling and stabilizing metallic nanoparticles working as catalysts. Herein we demonstrate a method for finely modifying the nanoporous anodic aluminum oxide (AAO), and further integration of nanoreactors. By using atomic transfer radical polymerization (ATRP), polymer brushes were successfully grafted on the inner wall of the nanochannels of the AAO membrane, followed by exchanging counter ions with a precursor for nanoparticles (NPs), and used as the template for deposition of well-defined Au NPs. The membrane was used as a functional nanochannel for novel flow-through catalysis. High catalytic performance and instantaneous separation of products from the reaction system was achieved in reduction of 4-nitrophenol.

Electrochemical Analysis of Conducting Polymer Thin Films

PubMed Central

Vyas, Ritesh N.; Wang, Bin

2010-01-01

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

Fabrication of Defined Polydopamine Nanostructures by DNA Origami-Templated Polymerization.

PubMed

Tokura, Yu; Harvey, Sean; Chen, Chaojian; Wu, Yuzhou; Ng, David Y W; Weil, Tanja

2018-02-05

A versatile, bottom-up approach allows the controlled fabrication of polydopamine (PD) nanostructures on DNA origami. PD is a biosynthetic polymer that has been investigated as an adhesive and promising surface coating material. However, the control of dopamine polymerization is challenged by the multistage-mediated reaction mechanism and diverse chemical structures in PD. DNA origami decorated with multiple horseradish peroxidase-mimicking DNAzyme motifs was used to control the shape and size of PD formation with nanometer resolution. These fabricated PD nanostructures can serve as "supramolecular glue" for controlling DNA origami conformations. Facile liberation of the PD nanostructures from the DNA origami templates has been achieved in acidic medium. This presented DNA origami-controlled polymerization of a highly crosslinked polymer provides a unique access towards anisotropic PD architectures with distinct shapes that were retained even in the absence of the DNA origami template. © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

[Synthesis and Study on Adsorption Property of Congo Red Molecularly Imprinted Polymer Nanospheres].

PubMed

Chang, Zi-qiang; Chen, Fu-bin; Zhang, Yu; Shi, Zuo-long; Yang, Chun-yan; Zhang, Zhu-jun

2015-07-01

Molecularly imprinted polymer nanospheres (MIP) were prepared with Congo red as the template, methacrylic acid (MAA) as a functional monomer, ethylene glycol dimethacrylate (EGDMA) as the cross linker, azodiisobutyronitrile (AIBN) as an initiator, and acetonitrile as the porogen by precipitation polymerization. The morphology of MIP was characterized by SEM and TEM which showed that the diameter of MIP was nanometer grade (90 nm) and the shape was homogeneous. The specific surface area and pore volumes of MIP and NIP were examined through Brunauer-Emett-Teller method of nitrogen adsorption experiments. Then, the adsorption and selective recognition ability of MIPs were evaluated using the equilibrium rebinding experiments. The results indicated that the prepared MIP showed a good selectivity recognition ability to its template. It concluded that MIP could be employed as an effective material for removing Congo red from waste water.

Advanced Materials through Assembly of Nanocelluloses.

PubMed

Kontturi, Eero; Laaksonen, Päivi; Linder, Markus B; Nonappa; Gröschel, André H; Rojas, Orlando J; Ikkala, Olli

2018-06-01

There is an emerging quest for lightweight materials with excellent mechanical properties and economic production, while still being sustainable and functionalizable. They could form the basis of the future bioeconomy for energy and material efficiency. Cellulose has long been recognized as an abundant polymer. Modified celluloses were, in fact, among the first polymers used in technical applications; however, they were later replaced by petroleum-based synthetic polymers. Currently, there is a resurgence of interest to utilize renewable resources, where cellulose is foreseen to make again a major impact, this time in the development of advanced materials. This is because of its availability and properties, as well as economic and sustainable production. Among cellulose-based structures, cellulose nanofibrils and nanocrystals display nanoscale lateral dimensions and lengths ranging from nanometers to micrometers. Their excellent mechanical properties are, in part, due to their crystalline assembly via hydrogen bonds. Owing to their abundant surface hydroxyl groups, they can be easily modified with nanoparticles, (bio)polymers, inorganics, or nanocarbons to form functional fibers, films, bulk matter, and porous aerogels and foams. Here, some of the recent progress in the development of advanced materials within this rapidly growing field is reviewed. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly sensitive and selective hyphenated technique (molecularly imprinted polymer solid-phase microextraction-molecularly imprinted polymer sensor) for ultra trace analysis of aspartic acid enantiomers.

PubMed

Prasad, Bhim Bali; Srivastava, Amrita; Tiwari, Mahavir Prasad

2013-03-29

The present work is related to combination of molecularly imprinted solid-phase microextraction and complementary molecularly imprinted polymer-sensor. The molecularly imprinted polymer grafted on titanium dioxide modified silica fiber was used for microextraction, while the same polymer immobilized on multiwalled carbon nanotubes/titanium dioxide modified pencil graphite electrode served as a detection tool. In both cases, the surface initiated polymerization was found to be advantageous to obtain a nanometer thin imprinted film. The modified silica fiber exhibited high adsorption capacity and enantioselective diffusion of aspartic acid isomers into respective molecular cavities. This combination enabled double preconcentrations of d- and l-aspartic acid that helped sensing both isomers in real samples, without any cross-selectivity and matrix complications. Taking into account 6×10(4)-fold dilution of serum and 2×10(3)-fold dilution of cerebrospinal fluid required by the proposed method, the limit of detection for l-aspartic acid is 0.031ngmL(-1). Also, taking into account 50-fold dilution required by the proposed method, the limit of detection for d-aspartic acid is 0.031ngmL(-1) in cerebrospinal fluid. Copyright © 2013 Elsevier B.V. All rights reserved.

Visualization of Hierarchical Nanodomains in Polymer/Fullerene Bulk Heterojunction Solar Cells

DOE PAGES

Wen, Jianguo; Miller, Dean J.; Chen, Wei; ...

2014-06-20

Here, traditional electron microscopy techniques such as bright-field imaging provide poor contrast for organic films and identification of structures in amorphous material can be problematic, particularly in high-performance organic solar cells. By combining energy-filtered corrected transmission electron microscopy, together with electron energy loss and X-ray energy-dispersive hyperspectral imaging, we have imaged PTB7/ PC 61BM blended polymer optical photovoltaic films, and were able to identify domains ranging in size from several hundred nanometers to several nanometers in extent. This work verifies that microstructural domains exist in bulk heterojunctions in PTB7/PC 61BM polymeric solar cells at multiple length scales and expands ourmore » understanding of optimal device performance providing insight for the design of even higher performance cells.« less

Artificial submicron or nanometer speckle fabricating technique and electron microscope speckle photography

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

Liu Zhanwei; Xie Huimin; Fang Daining

2007-03-15

In this article, a novel artificial submicro- or nanometer speckle fabricating technique is proposed by taking advantage of submicro or nanometer particles. In the technique, submicron or nanometer particles were adhered to an object surface by using ultrasonic dispersing technique. The particles on the object surface can be regarded as submicro or nanometer speckle by using a scanning electronic microscope at a special magnification. In addition, an electron microscope speckle photography (EMSP) method is developed to measure in-plane submicron or nanometer deformation of the object coated with the artificial submicro or nanometer speckles. The principle of artificial submicro or nanometermore » speckle fabricating technique and the EMSP method are discussed in detail in this article. Some typical applications of this method are offered. The experimental results verified that the artificial submicro or nanometer speckle fabricating technique and EMSP method is feasible.« less

High throughput, high resolution enzymatic lithography process: effect of crystallite size, moisture, and enzyme concentration.

PubMed

Mao, Zhantong; Ganesh, Manoj; Bucaro, Michael; Smolianski, Igor; Gross, Richard A; Lyons, Alan M

2014-12-08

By bringing enzymes into contact with predefined regions of a surface, a polymer film can be selectively degraded to form desired patterns that find a variety of applications in biotechnology and electronics. This so-called "enzymatic lithography" is an environmentally friendly process as it does not require actinic radiation or synthetic chemicals to develop the patterns. A significant challenge to using enzymatic lithography has been the need to restrict the mobility of the enzyme in order to maintain control of feature sizes. Previous approaches have resulted in low throughput and were limited to polymer films only a few nanometers thick. In this paper, we demonstrate an enzymatic lithography system based on Candida antartica lipase B (CALB) and poly(ε-caprolactone) (PCL) that can resolve fine-scale features, (<1 μm across) in thick (0.1-2.0 μm) polymer films. A Polymer Pen Lithography (PPL) tool was developed to deposit an aqueous solution of CALB onto a spin-cast PCL film. Immobilization of the enzyme on the polymer surface was monitored using fluorescence microscopy by labeling CALB with FITC. The crystallite size in the PCL films was systematically varied; small crystallites resulted in significantly faster etch rates (20 nm/min) and the ability to resolve smaller features (as fine as 1 μm). The effect of printing conditions and relative humidity during incubation is also presented. Patterns formed in the PCL film were transferred to an underlying copper foil demonstrating a "Green" approach to the fabrication of printed circuit boards.

Modification of conductive polyaniline with carbon nanomaterials

NASA Astrophysics Data System (ADS)

Sedaghat, Sajjad; Alavijeh, Mahdi Soleimani

2014-08-01

The synthesis of polyaniline/single-wall nanotube, polyaniline/multi-wall nanotube and polyaniline/single-wall nanotube/graphen nanosheets nanocomposites by in situ polymerization are reported in this study. The substrates were treated with a mixture of concentrated sulfuric acid and concentrated nitric acid before usage to functionalize with carboxylic and hydroxyl groups. Aniline monomers are adsorbed and polymerized on the surface of these fillers. Structural analysis using scanning electron microscopy showed that nanomaterials dispersed into polymer matrix and made tubular structures with diameters several tens to hundreds nanometers depending on the polyaniline content. These nanocomposites can be used for production of excellent electrode materials applications in high-performance supercapacitors.

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.

Positron Annihilation Spectroscopy as a Novel Interfacial Probe for Thin Polymeric Films and Nano-Composites

NASA Astrophysics Data System (ADS)

Awad, Somia; Chen, Hongmin; Maina, Grace; Lee, L. James; Gu, Xiaohong; Jean, Y. C.

2010-03-01

Positron annihilation spectroscopy (PAS) has been developed as a novel probe to characterize the sub-nanometer defect, free volume, profile from the surface, interfaces, and to the bulk in polymeric materials when a variable mono-energy slow positron beam is used. Free-volume hole sizes, fractions, and distributions are measurable as a function of depth at the high precision. PAS has been successfully used to study the interfacial properties of polymeric nanocomposites at different chemical bonding. In nano-scale thin polymeric films, such as in PS/SiO2, and PU/ZnO, significant variations of Tg as a function of depth and of wt% oxide are observed. Variations of Tg are dependent on strong or weak interactions between polymers and nano-scale oxides surfaces.

Through the eye of the needle: recent advances in understanding biopolymer translocation.

PubMed

Panja, Debabrata; Barkema, Gerard T; Kolomeisky, Anatoly B

2013-10-16

In recent years polymer translocation, i.e., transport of polymeric molecules through nanometer-sized pores and channels embedded in membranes, has witnessed strong advances. It is now possible to observe single-molecule polymer dynamics during the motion through channels with unprecedented spatial and temporal resolution. These striking experimental studies have stimulated many theoretical developments. In this short theory-experiment review, we discuss recent progress in this field with a strong focus on non-equilibrium aspects of polymer dynamics during the translocation process.

Application of Solid-State NMR Relaxometry for Characterization and Formulation Optimization of Grinding-Induced Drug Nanoparticle.

PubMed

Ueda, Keisuke; Higashi, Kenjirou; Moribe, Kunikazu

2016-03-07

The formation mechanism of drug nanoparticles was investigated using solid-state nuclear magnetic resonance (NMR) techniques for the efficient discovery of an optimized nanoparticle formulation. The cogrinding of nifedipine (NIF) with polymers, including hydroxypropyl methylcellulose (HPMC) and polyvinylpyrrolidone (PVP), and sodium dodecyl sulfate (SDS) was performed to prepare the NIF nanoparticle formulations. Then, solid-state NMR relaxometry was used for the nanometer-order characterization of NIF in the polymer matrix. Solid-state NMR measurements revealed that the crystal size of NIF was reduced to several tens of nanometers with amorphization of NIF by cogrinding with HPMC and SDS for 100 min. Similarly, the size of the NIF crystal was reduced to less than 90 nm in the 40 min ground mixture of NIF/PVP/SDS. Furthermore, 100 min grinding of NIF/PVP/SDS induced amorphization of almost all the NIF crystals followed by nanosizing. The hydrogen bond between NIF and PVP led to the efficient amorphization of NIF in the NIF/PVP/SDS system compared with NIF/HPMC/SDS system. The efficient nanosizing of the NIF crystal in the solid state, revealed by the solid-state NMR relaxation time measurements, enabled the formation of large amounts of NIF nanoparticles in water followed by the polymer dissolution. In contrast, excess amorphization of the NIF crystals failed to efficiently prepare the NIF nanoparticles. The solid-state characterization of the crystalline NIF revealed good correlation with the NIF nanoparticles formation during aqueous dispersion. Furthermore, the solid-state NMR measurements including relaxometry successfully elucidated the nanometer-order dispersion state of NIF in polymer matrix, leading to the discovery of optimized conditions for the preparation of suitable drug nanoparticles.

Flexible composite radiation detector

DOEpatents

Cooke, D Wayne [Santa Fe, NM; Bennett, Bryan L [Los Alamos, NM; Muenchausen, Ross E [Los Alamos, NM; Wrobleski, Debra A [Los Alamos, NM; Orler, Edward B [Los Alamos, NM

2006-12-05

A flexible composite scintillator was prepared by mixing fast, bright, dense rare-earth doped powdered oxyorthosilicate (such as LSO:Ce, LSO:Sm, and GSO:Ce) scintillator with a polymer binder. The binder is transparent to the scintillator emission. The composite is seamless and can be made large and in a wide variety of shapes. Importantly, the composite can be tailored to emit light in a spectral region that matches the optimum response of photomultipliers (about 400 nanometers) or photodiodes (about 600 nanometers), which maximizes the overall detector efficiency.

Functionality in Electrospun Nanofibrous Membranes Based on Fiber's Size, Surface Area, and Molecular Orientation

PubMed Central

Matsumoto, Hidetoshi; Tanioka, Akihiko

2011-01-01

Electrospinning is a versatile method for forming continuous thin fibers based on an electrohydrodynamic process. This method has the following advantages: (i) the ability to produce thin fibers with diameters in the micrometer and nanometer ranges; (ii) one-step forming of the two- or three-dimensional nanofiber network assemblies (nanofibrous membranes); and (iii) applicability for a broad spectrum of molecules, such as synthetic and biological polymers and polymerless sol-gel systems. Electrospun nanofibrous membranes have received significant attention in terms of their practical applications. The major advantages of nanofibers or nanofibrous membranes are the functionalities based on their nanoscaled-size, highly specific surface area, and highly molecular orientation. These functionalities of the nanofibrous membranes can be controlled by their fiber diameter, surface chemistry and topology, and internal structure of the nanofibers. This report focuses on our studies and describes fundamental aspects and applications of electrospun nanofibrous membranes. PMID:24957735

Bio-inspired direct patterning functional nanothin microlines: controllable liquid transfer.

PubMed

Wang, Qianbin; Meng, Qingan; Wang, Pengwei; Liu, Huan; Jiang, Lei

2015-04-28

Developing a general and low-cost strategy that enables direct patterning of microlines with nanometer thickness from versatile liquid-phase functional materials and precise positioning of them on various substrates remains a challenge. Herein, with inspiration from the oriental wisdom to control ink transfer by Chinese brushes, we developed a facile and general writing strategy to directly pattern various functional microlines with homogeneous distribution and nanometer-scale thickness. It is demonstrated that the width and thickness of the microlines could be well-controlled by tuning the writing method, providing guidance for the adaptation of this technique to various systems. It is also shown that various functional liquid-phase materials, such as quantum dots, small molecules, polymers, and suspensions of nanoparticles, could directly write on the substrates with intrinsic physicochemical properties well-preserved. Moreover, this technique enabled direct patterning of liquid-phase materials on certain microdomains, even in multiple layered style, thus a microdomain localized chemical reaction and the patterned surface chemical modification were enabled. This bio-inspired direct writing device will shed light on the template-free printing of various functional micropatterns, as well as the integrated functional microdevices.

Flame Retardant Effect of Aerogel and Nanosilica on Engineered Polymers

NASA Technical Reports Server (NTRS)

Williams, Martha K.; Smith, Trent M.; Roberson, Luke B.; Yang, Feng; Nelson, Gordon L.

2010-01-01

Aerogels are typically manufactured vIa high temperature and pressure-critical-point drying of a colloidal metal oxide gel filled with solvents. Aerogel materials derived from silica materials represent a structural morphology (amorphous, open-celled nanofoams) rather than a particular chemical constituency. Aerogel is not like conventional foams in that it is a porous material with extreme microporosity and composed of individual features only a few nanometers in length with a highly porous dendriticlike structure. This unique substance has unusual properties such as low thermal conductivity, refractive index and sound suppression; in addition to its exceptional ability to capture fast moving dust. The highly porous nature of the aerogel's structure provides large amounts of surface area per unit weight. For instance, a silica aerogel material with a density of 100 kilograms per cubic meters can have surface areas of around 800 to 1500 square meters per gram depending on the precursors and process utilized to produce it. To take advantage of the unique properties of silica aerogels, especially the ultra light weight and low thermal conductivity, their composites with various engineering polymers were prepared and their flammability was investigated by Cone Calorimetry. The flammability of various polystyrene/silica aerogel nanocomposites were measured. The combination of these nanocomposites with a NASA patented flame retardant SINK were also studied. The results were compared with the base polymer to show the differences between composites with different forms of silica.

ToF-SIMS and Laser-SNMS Imaging of Heterogeneous Topographically Complex Polymer Systems.

PubMed

Pelster, Andreas; Körsgen, Martin; Kurosawa, Takako; Morita, Hiromi; Arlinghaus, Heinrich F

2016-10-04

Heterogeneous polymer coatings, such as those used in organic electronics and medical devices, are of increasing industrial importance. In order to advance the development of these types of systems, analytical techniques are required which are able to determine the elemental and molecular spatial distributions, on a nanometer scale, with very high detection efficiency and sensitivity. The goal of this study was to investigate the suitability of laser postionization secondary neutral mass spectrometry (Laser-SNMS) with a 157 nm postionization laser beam to image structured polymer mixtures and compare the results with time-of-flight secondary ion mass spectrometry (ToF-SIMS) measurements using Bi 3 + primary ions. The results showed that Laser-SNMS is better suited than ToF-SIMS for unambiguous detection and submicrometer imaging of the wide range of polymers investigated. The data also showed that Laser-SNMS has the advantage of being much more sensitive (in general higher by more than an order of magnitude and peaking at up to 3 orders of magnitude) than ToF-SIMS while also showing superior performance on topographically complex structured insulating surfaces, due to significantly reduced field effects and a higher dynamic range as compared to ToF-SIMS. It is concluded that Laser-SNMS is a powerful complementary technique to ToF-SIMS for the analysis of heterogeneous polymers and other complex structured organic mixtures, providing submicrometer resolution and high sensitivity.

Nanocellular thermoplastic foam and process for making the same

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

Zhu, Lingbo; Costeux, Stephane; Patankar, Kshitish A.

Prepare a thermoplastic polymer foam having a porosity of 70% or more and at least one of: (i) an average cell size of 200 nanometers or less; and (ii) a nucleation density of at least 1.times.1015 effective nucleation sites per cubic centimeter of foamable polymer composition not including blowing agent using a foamable polymer composition containing a thermoplastic polymer selected from styrenic polymer and (meth)acrylic polymers, a blowing agent comprising at least 20 mole-percent carbon dioxide based on moles of blowing agent and an additive having a Total Hansen Solubility Parameter that differs from that of carbon dioxide by lessmore » than 2 and that is present at a concentration of 0.01 to 1.5 weight parts per hundred weight parts thermoplastic polymer.« less

Exploring the effects of electrospinning processing protocols on fiber surface morphology and polymer chain conformation

NASA Astrophysics Data System (ADS)

Stephens, Jean S.

Electrospinning is a fiber formation technique that uses electrostatic forces to create continuous, nanometer diameter fibers. The work presented here focuses on the continuing efforts to build a stronger fundamental understanding of electrospinning by exploring structure/property/process relationships by investigating the effects of process protocols on fiber surface morphology and polymer chain conformation. By varying the processing parameters it has been possible to produce fibers with unique surface features, microtextured/nanoporous fibers and nanowebs. In the microtextured/nanoporous fiber studies, changing the solution concentration, solvent volatility, and relative humidity was found to alter the size, shape, and distribution of pores on the fiber surface. The mechanisms that can explain the pore formation and texturing on the surface of the fibers are phase separation (aggregation into polymer rich and polymer lean regions) and breath figures (evaporative cooling and vapor condensation). Through a judicious choice of the electrospinning processing parameters we have also been able to create "web" like structures of nanofibers (5--25 nm) from collagen, dragline silk analog, nylon, and denatured collagen. Electrostatic repulsion and thin film dewetting are thought to be responsible for the formation of the nanowebs. These unique structures were characterized using FESEM, TEM, OM, and AFM. Raman spectroscopy, initially developed as a "real time" characterization technique to study electrospun fiber formation, has also been used to investigate the effect of electrospinning on the chain conformation of bioinspired polymers. Comparing the spectrum of the bulk material to that of the electrospun material identified conformational changes in nylon 6 and dragline silk analog. The conformational change in nylon 6 (alpha-form to gamma-form) results from the stresses induced on the electrospinning jet during fiber formation, whereas the conformational change in the silk analog (beta-sheet to alpha-helical) result from electric field assembling of the charged a-helical segments of the protein polymer in solution. The investigations described here have allowed us to build a virtual database of the processing conditions needed to create materials for tissue engineering constructs. Electrospun collagen membranes have been used in preliminary cell attachment studies. From the trials it was observed that the cells migrated into the membranes indicating that the membranes are suitable for tissue engineering scaffolds.

Nanoporous Polymers Based on Liquid Crystals

PubMed Central

Mulder, Dirk Jan; Sijbesma, Rint; Schenning, Albert

2018-01-01

In the present review, we discuss recent advances in the field of nanoporous networks based on polymerisable liquid crystals. The field has matured in the last decade, yielding polymers having 1D, 2D, and 3D channels with pore sizes on the nanometer scale. Next to the current progress, some of the future challenges are presented, with the integration of nanoporous membranes in functional devices considered as the biggest challenge. PMID:29324669

Precision-Trimming 2D Inverse-Opal Lattice on Elastomer to Ordered Nanostructures with Variable Size and Morphology.

PubMed

Zhan, Haoran; Chen, Yanqiu; Liu, Yu; Lau, Woonming; Bao, Chao; Li, Minggan; Lu, Yunlong; Mei, Jun; Hui, David

2017-05-23

A low-cost and scalable method is developed for producing large-area elastomer surfaces having ordered nanostructures with a variety of lattice features controllable to nanometer precision. The method adopts the known technique of molding a PDMS precursor film with a close-packed monolayer of monodisperse submicron polystyrene beads on water to form an inverse-opal dimple lattice with the dimple size controlled by the bead selection and the dimple depth by the molding condition. The subsequent novel precision engineering of the inverse-opal lattice comprises trimming the PDMS precursor by a combination of polymer curing temperature/time and polymer dissolution parameters. The resultant ordered surface nanostructures, fabricated with an increasing degree of trimming, include (a) submicron hemispherical dimples with nanothin interdimple rims and walls; (b) nanocones with variable degrees of tip-sharpness by trimming off the top part of the nanothin interdimple walls; and (c) soup-plate-like submicron shallow dimples with interdimple rims and walls by anisotropically trimming off the nanocones and forming close-packed shallow dimples. As exemplars of industrial relevance of these lattice features, tunable Young's modulus and wettability are demonstrated.

Graphite Nanoreinforcements for Aerospace Nanocomposites

NASA Technical Reports Server (NTRS)

Drzal, Lawrence T.

2005-01-01

New advances in the reinforcement of polymer matrix composite materials are critical for advancement of the aerospace industry. Reinforcements are required to have good mechanical and thermal properties, large aspect ratio, excellent adhesion to the matrix, and cost effectiveness. To fulfill the requirements, nanocomposites in which the matrix is filled with nanoscopic reinforcing phases having dimensions typically in the range of 1nm to 100 nm show considerably higher strength and modulus with far lower reinforcement content than their conventional counterparts. Graphite is a layered material whose layers have dimensions in the nanometer range and are held together by weak Van der Waals forces. Once these layers are exfoliated and dispersed in a polymer matrix as nano platelets, they have large aspect ratios. Graphite has an elastic modulus that is equal to the stiffest carbon fiber and 10-15 times that of other inorganic reinforcements, and it is also electrically and thermally conductive. If the appropriate surface treatment can be found for graphite, its exfoliation and dispersion in a polymer matrix will result in a composite with excellent mechanical properties, superior thermal stability, and very good electrical and thermal properties at very low reinforcement loadings.

Composite CD-MOF nanocrystals-containing microspheres for sustained drug delivery.

PubMed

Li, Haiyan; Lv, Nana; Li, Xue; Liu, Botao; Feng, Jing; Ren, Xiaohong; Guo, Tao; Chen, Dawei; Fraser Stoddart, J; Gref, Ruxandra; Zhang, Jiwen

2017-06-08

Metal-organic frameworks (MOFs), which are typically embedded in polymer matrices as composites, are emerging as a new class of carriers for sustained drug delivery. Most of the MOFs and the polymers used so far in these composites, however, are not pharmaceutically acceptable. In the investigation reported herein, composites of γ-cyclodextrin (γ-CD)-based MOFs (CD-MOFs) and polyacrylic acid (PAA) were prepared by a solid in oil-in-oil (s/o/o) emulsifying solvent evaporation method. A modified hydrothermal protocol has been established which produces efficiently at 50 °C in 6 h micron (5-10 μm) and nanometer (500-700 nm) diameter CD-MOF particles of uniform size with smooth surfaces and powder X-ray diffraction patterns that are identical with those reported in the literature. Ibuprofen (IBU) and Lansoprazole (LPZ), both insoluble in water and lacking in stability, were entrapped with high drug loading in nanometer-sized CD-MOFs by co-crystallisation (that is more effective than impregnation) without causing MOF crystal degradation during the loading process. On account of the good dispersion of drug-loaded CD-MOF nanocrystals inside polyacrylic acid (PAA) matrices and the homogeneous distribution of the drug molecules within these crystals, the composite microspheres exhibit not only spherical shapes and sustained drug release over a prolonged period of time, but they also demonstrate reduced cell toxicity. The cumulative release rate for IBU (and LPZ) follows the trend: IBU-γ-CD complex microspheres (ca. 80% in 2 h) > IBU microspheres > IBU-CD-MOF/PAA composite microspheres (ca. 50% in 24 h). Importantly, no burst release of IBU (and LPZ) was observed from the CD-MOF/PAA composite microspheres, suggesting an even distribution of the drug as well as strong drug carrier interactions inside the CD-MOF. In summary, these composite microspheres, composed of CD-MOF nanocrystals embedded in a biocompatible polymer (PAA) matrix, constitute an efficient and pharmaceutically acceptable MOF-based carrier for sustained drug release.

Diffuse polymer interfaces in lobed nanoemulsions preserved in aqueous media.

PubMed

Kim, Ginam; Sousa, Alioscka; Meyers, Deborah; Shope, Marilyn; Libera, Matthew

2006-05-24

Using valence electron energy loss spectroscopy (EELS) in the cryo-scanning transmission electron microscopy (STEM), we found that the polymer-polymer interface in two-phase nanocolloids of polydimethyl siloxane (PDMS) and copolymer (methyl acrylate (MA)-methyl methacrylate (MMA)-vinyl acetate (VA)) preserved in water was diffuse despite the fact that equilibrium thermodynamics indicates it should only be on the order of a few nanometers. The diffuse interface is a result of the kinetic trapping of the copolymer within the PDMS phase, and this finding suggests new nonequilibrium pathways to control interfaces during the synthesis of multicomponent polymeric nanostructures.

Basic analytical investigation of plasma-chemically modified carbon fibers1

NASA Astrophysics Data System (ADS)

Bubert, H.; Ai, X.; Haiber, S.; Heintze, M.; Brüser, V.; Pasch, E.; Brandl, W.; Marginean, G.

2002-10-01

The background of the present investigation is to enhance the overall adherence of vapor grown carbon fibers (VGCF) to the surrounding polymer matrix in different applications by forming polar groups at their surfaces and by modifying the surface morphology. This has been done by plasma treatments using a low-pressure plasma with different gases, flow rates, pressures and powers. Two different types of carbon fibers were investigated: carbon microfibers and carbon nanofibers. The characterization of fiber surfaces was achieved by photoelectron spectroscopy (XPS), contact angle measurements and titration. These investigations were accompanied by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The oxygen plasma treatment of the fibers changes the surfaces by forming a layer with a thickness of the order of one nanometer mainly consisting of functional groups like hydroxyl, carbonyl and carboxyl. After functionalization of the complete surface, a further plasma treatment does not enhance the superficial oxygen content but changes slightly the portions of the functional groups. A comparison of the methods applied provides a largely consistent image of the effect of plasma treatment.

Photonics walking up a human hair

NASA Astrophysics Data System (ADS)

Zeng, Hao; Parmeggiani, Camilla; Martella, Daniele; Wasylczyk, Piotr; Burresi, Matteo; Wiersma, Diederik S.

2016-03-01

While animals have access to sugars as energy source, this option is generally not available to artificial machines and robots. Energy delivery is thus the bottleneck for creating independent robots and machines, especially on micro- and nano- meter length scales. We have found a way to produce polymeric nano-structures with local control over the molecular alignment, which allowed us to solve the above issue. By using a combination of polymers, of which part is optically sensitive, we can create complex functional structures with nanometer accuracy, responsive to light. In particular, this allowed us to realize a structure that can move autonomously over surfaces (it can "walk") using the environmental light as its energy source. The robot is only 60 μm in total length, thereby smaller than any known terrestrial walking species, and it is capable of random, directional walking and rotating on different dry surfaces.

Mechanism of cyanoacetylene photochemistry at 185 and 254 nm

NASA Technical Reports Server (NTRS)

Clarke, D. W.; Ferris, J. P.

1996-01-01

The role of cyanoacetylene (HC3N) in the atmospheric photochemistry of Titan and its relevance to polymer formation are discussed. Investigation of the relative light absorption of HC3N, acetylene (C2H2), and diacetylene (C4H2) revealed that HC3N is an important absorber of UV light in the 205- to 225-nanometer wavelength region in Titan's polar regions. Laboratory studies established that photolysis of C2H2 initiates the polymerization of HC3N even though the HC3N is not absorbing the UV light. Quantum yield measurements establish that HC3N is 2-5 times as reactive as C2H2 for polymer formation. Photolysis of HC3N with 185-nanometer light in the presence of N2, H2, Ar, or CF4 results in a decrease in the yield of 1,3,5-tricyanobenzene (1,3,5-tcb), while photolysis in the presence of CH4, C2H6, or n-C4H10 results in an increase in 1,3,5-tcb. The rate of loss of HC3N is increased by all gases except H2, where it is unchanged. It was not possible to detect 1,3,5-tcb as a photoproduct when the partial pressure of HC3N was decreased to 1 torr. Photolysis of HC3N with 254-nanometer light in the presence of H2 or N2 results in the formation of 1,2,4-tcb, while photolysis in the presence of CH4, C2H6, or n-C4H10 results in the formation of increasing amounts of 1,3,5-tcb. Mechanisms for the formation of polymers are presented.

Rubber friction: The contribution from the area of real contact.

PubMed

Tiwari, A; Miyashita, N; Espallargas, N; Persson, B N J

2018-06-14

There are two contributions to the friction force when a rubber block is sliding on a hard and rough substrate surface, namely, a contribution F ad = τ f A from the area of real contact A and a viscoelastic contribution F visc from the pulsating forces exerted by the substrate asperities on the rubber block. Here we present experimental results obtained at different sliding speeds and temperatures, and we show that the temperature dependency of the shear stress τ f , for temperatures above the rubber glass transition temperature T g , is weaker than that of the bulk viscoelastic modulus. The physical origin of τ f for T > T g is discussed, and we propose that its temperature dependency is determined by the rubber molecule segment mobility at the sliding interface, which is higher than in the bulk because of increased free-volume effect due to the short-wavelength surface roughness. This is consistent with the often observed reduction in the glass transition temperature in nanometer-thick surface layers of glassy polymers. For temperatures T < T g , the shear stress τ f is nearly velocity independent and of similar magnitude as observed for glassy polymers such as PMMA or polyethylene. In this case, the rubber undergoes plastic deformations in the asperity contact regions and the contact area is determined by the rubber penetration hardness. For this case, we propose that the frictional shear stress is due to slip at the interface between the rubber and a transfer film adsorbed on the concrete surface.

Rubber friction: The contribution from the area of real contact

NASA Astrophysics Data System (ADS)

Tiwari, A.; Miyashita, N.; Espallargas, N.; Persson, B. N. J.

2018-06-01

There are two contributions to the friction force when a rubber block is sliding on a hard and rough substrate surface, namely, a contribution Fad = τf A from the area of real contact A and a viscoelastic contribution Fvisc from the pulsating forces exerted by the substrate asperities on the rubber block. Here we present experimental results obtained at different sliding speeds and temperatures, and we show that the temperature dependency of the shear stress τf, for temperatures above the rubber glass transition temperature Tg, is weaker than that of the bulk viscoelastic modulus. The physical origin of τf for T > Tg is discussed, and we propose that its temperature dependency is determined by the rubber molecule segment mobility at the sliding interface, which is higher than in the bulk because of increased free-volume effect due to the short-wavelength surface roughness. This is consistent with the often observed reduction in the glass transition temperature in nanometer-thick surface layers of glassy polymers. For temperatures T < Tg, the shear stress τf is nearly velocity independent and of similar magnitude as observed for glassy polymers such as PMMA or polyethylene. In this case, the rubber undergoes plastic deformations in the asperity contact regions and the contact area is determined by the rubber penetration hardness. For this case, we propose that the frictional shear stress is due to slip at the interface between the rubber and a transfer film adsorbed on the concrete surface.

Effect of Processing Parameters on the Morphology of PVDF Electrospun Nanofiber

NASA Astrophysics Data System (ADS)

Zulfikar, M. A.; Afrianingsih, I.; Nasir, M.; Alni, A.

2018-03-01

Electrospinning is a process that produces continuous polymer fibers with diameters in the submicron range through the action of an external electric field imposed on a polymer solution or melt. Because of the tiny diameter in several hundreds of nanometers and the high porosity, electrospun membranes show potential applications in extensive areas such as filtration systems, biomedical tissue templates, drug delivery membranes, and so on. In the electrospinning process, some parameters such as polymer concentration, feeding rate of the polymer solution, additives, humidity, viscosity, surface tension, applied voltage, and nozzle-to ground collector distance will affect the fiber diameter and morphology. In this work, we have evaluated the effects of two processing parameters including the flow rate of the polymer solution and nozzle-to ground collector distance, on the morphology of the fibers formed. The solutions used in the electrospinning experiments were prepared using Poly(vinylidene fluoride) (PVDF). This material was dissolved in N,N-dimethylformamide (DMF) to make solutions with concentrations of 20 wt%. These solutions was electrospun using a 5 mL plastic syringe with an 8 gauge stainless needle at an applied voltage of 20.0 kV, a flow rate of 0.02-0.04 mL/min and nozzle-to ground collector distance of 12 and 15 cm. Electrospinning of PVDF polymer solution was performed in horizontal alignment having a grounded aluminum foil which serves as a collector. The nanofibers obtained were characterized by polarizing optical microscope. We find that the low flow rate of the polymer solution and nozzle-to ground collector distance are strongly correlated with the formation of bead defects in the fibers.

Nanostructure formation and regulation during low-energy ion beam sputtering of fused silica surfaces

NASA Astrophysics Data System (ADS)

Liao, Wenlin; Dai, Yi-Fan; Nie, Xutao; Nie, Xuqing; Xu, Mingjin

2017-12-01

Ion beam sputtering (IBS) possesses strong surface nanostructuring behaviors, where dual microscopic phenomenon can be aroused to induce the formation of ultrasmooth surfaces or regular nanostructures. Low-energy IBS of fused silica surfaces is investigated to discuss the formation mechanism and the regulation of the IBS-induced nanostructures. The research results indicate that these microscopic phenomena can be attributed to the interaction of the IBS-induced surface roughening and smoothing effects, and the interaction process strongly depends on the sputtering conditions. Alternatively, ultrasmooth surface or regular nanostructure can be selectively generated through the regulation of the nanostructuring process, and the features of the generated nanostructures, such as amplitude and period, also can be regulated. Consequently, two different technology aims of nanofabrication, including nanometer-scale and nanometer-precision fabrication, can be realized, respectively. These dual microscopic mechanisms distinguish IBS as a promising nanometer manufacturing technology for the optical surfaces.

Depositing nanometer-sized particles of metals onto carbon allotropes

NASA Technical Reports Server (NTRS)

Delozier, Donavon M. (Inventor); Fallbach, Michael J. (Inventor); Smith, Joseph G. (Inventor); Watson, Kent A. (Inventor); Ghose, Sayata (Inventor); Connell, John W. (Inventor)

2010-01-01

A process for depositing nanometer-sized metal particles onto a substrate in the absence of aqueous solvents, organic solvents, and reducing agents, and without any required pre-treatment of the substrate, includes preparing an admixture of a metal compound and a substrate by dry mixing a chosen amount of the metal compound with a chosen amount of the substrate; and supplying energy to the admixture in an amount sufficient to deposit zero valance metal particles onto the substrate. This process gives rise to a number of deposited metallic particle sizes which may be controlled. The compositions prepared by this process are used to produce polymer composites by combining them with readily available commodity and engineering plastics. The polymer composites are used as coatings, or they are used to fabricate articles, such as free-standing films, fibers, fabrics, foams, molded and laminated articles, tubes, adhesives, and fiber reinforced articles. These articles are well-suited for many applications requiring thermal conductivity, electrical conductivity, antibacterial activity, catalytic activity, and combinations thereof.

Recent advances in material science for developing enzyme electrodes.

PubMed

Sarma, Anil Kumar; Vatsyayan, Preety; Goswami, Pranab; Minteer, Shelley D

2009-04-15

The enzyme-modified electrode is the fundamental component of amperometric biosensors and biofuel cells. The selection of appropriate combinations of materials, such as: enzyme, electron transport mediator, binding and encapsulation materials, conductive support matrix and solid support, for construction of enzyme-modified electrodes governs the efficiency of the electrodes in terms of electron transfer kinetics, mass transport, stability, and reproducibility. This review investigates the varieties of materials that can be used for these purposes. Recent innovation in conductive electro-active polymers, functionalized polymers, biocompatible composite materials, composites of transition metal-based complexes and organometallic compounds, sol-gel and hydro-gel materials, nanomaterials, other nano-metal composites, and nano-metal oxides are reviewed and discussed here. In addition, the critical issues related to the construction of enzyme electrodes and their application for biosensor and biofuel cell applications are also highlighted in this article. Effort has been made to cover the recent literature on the advancement of materials sciences to develop enzyme electrodes and their potential applications for the construction of biosensors and biofuel cells.

Method of synthesizing tungsten nanoparticles

DOEpatents

Thoma, Steven G; Anderson, Travis M

2013-02-12

A method to synthesize tungsten nanoparticles has been developed that enables synthesis of nanometer-scale, monodisperse particles that can be stabilized only by tetrahydrofuran. The method can be used at room temperature, is scalable, and the product concentrated by standard means. Since no additives or stabilizing surfactants are required, this method is particularly well suited for producing tungsten nanoparticles for dispersion in polymers. If complete dispersion is achieved due to the size of the nanoparticles, then the optical properties of the polymer can be largely maintained.

Selective Nanoscale Mass Transport across Atomically Thin Single Crystalline Graphene Membranes.

PubMed

Kidambi, Piran R; Boutilier, Michael S H; Wang, Luda; Jang, Doojoon; Kim, Jeehwan; Karnik, Rohit

2017-05-01

Atomically thin single crystals, without grain boundaries and associated defect clusters, represent ideal systems to study and understand intrinsic defects in materials, but probing them collectively over large area remains nontrivial. In this study, the authors probe nanoscale mass transport across large-area (≈0.2 cm 2 ) single-crystalline graphene membranes. A novel, polymer-free picture frame assisted technique, coupled with a stress-inducing nickel layer is used to transfer single crystalline graphene grown on silicon carbide substrates to flexible polycarbonate track etched supports with well-defined cylindrical ≈200 nm pores. Diffusion-driven flow shows selective transport of ≈0.66 nm hydrated K + and Cl - ions over ≈1 nm sized small molecules, indicating the presence of selective sub-nanometer to nanometer sized defects. This work presents a framework to test the barrier properties and intrinsic quality of atomically thin materials at the sub-nanometer to nanometer scale over technologically relevant large areas, and suggests the potential use of intrinsic defects in atomically thin materials for molecular separations or desalting. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Highly ordered nanocomposites via a monomer self-assembly in situ condensation approach

DOEpatents

Gin, D.L.; Fischer, W.M.; Gray, D.H.; Smith, R.C.

1998-12-15

A method for synthesizing composites with architectural control on the nanometer scale is described. A polymerizable lyotropic liquid-crystalline monomer is used to form an inverse hexagonal phase in the presence of a second polymer precursor solution. The monomer system acts as an organic template, providing the underlying matrix and order of the composite system. Polymerization of the template in the presence of an optional cross-linking agent with retention of the liquid-crystalline order is carried out followed by a second polymerization of the second polymer precursor within the channels of the polymer template to provide an ordered nanocomposite material. 13 figs.

Preparation, characterization and properties of polymer-layered silicate nanocomposites

NASA Astrophysics Data System (ADS)

Fonseca, Claudia Alencar

Nanocomposites are a relatively new class of composites, that in the polymer area typically consist of particle-filled polymers where at least one dimension of the dispersed particles is in the nanometer range. Amongst all potential nanocomposite precursors, those based on clay and layered silicates have been more widely investigated. These nanocomposites exhibit markedly improved mechanical, thermal, optical and physico-chemical properties when compared to conventional (microscale) composites. In the present work, properties of nanocomposites of Ethylene Methacrylic Acid copolymers and organically modified Montmorillonite formed from the melt was investigated. Nanocomposites of Poly(vinyl alcohol) and Montmorillonite formed from solution was also studied.

Highly ordered nanocomposites via a monomer self-assembly in situ condensation approach

DOEpatents

Gin, Douglas L.; Fischer, Walter M.; Gray, David H.; Smith, Ryan C.

1998-01-01

A method for synthesizing composites with architectural control on the nanometer scale is described. A polymerizable lyotropic liquid-crystalline monomer is used to form an inverse hexagonal phase in the presence of a second polymer precursor solution. The monomer system acts as an organic template, providing the underlying matrix and order of the composite system. Polymerization of the template in the presence of an optional cross-linking agent with retention of the liquid-crystalline order is carried out followed by a second polymerization of the second polymer precursor within the channels of the polymer template to provide an ordered nanocomposite material.

Microsecond MD Simulations of Nano-patterned Polymer Brushes on Self-Assembled Monolayers

NASA Astrophysics Data System (ADS)

Buie, Creighton; Qiu, Liming; Cheng, Kwan; Park, Soyeun

2010-03-01

Nano-patterned polymer brushes end-grafted onto self-assembled monolayers have gained increasing research interests due to their unique thermodynamic properties and their chemical and biomedical applications in colloids, biosensing and tissue engineering. So far, the interactions between the polymer brushes with the surrounding environments such as the floor and solvent at the nanometer length scale and microsecond time scale are still difficult to obtained experimentally and computationally. Using a Coarse-Grained MD approach, polymer brushes of different monomeric lengths, grafting density and hydrophobicity of the monomers grafted on self-assembled monolayers and in explicit solvent were studied. Molecular level information, such as lateral diffusion, transverse height and volume contour of the brushes, were calculated from our microsecond-MD simulations. Our results demonstrated the significance of the hydration of the polymer in controlling the conformational arrangement of the polymer brushes.

Mixing of immiscible polymers using nanoporous coordination templates

NASA Astrophysics Data System (ADS)

Uemura, Takashi; Kaseda, Tetsuya; Sasaki, Yotaro; Inukai, Munehiro; Toriyama, Takaaki; Takahara, Atsushi; Jinnai, Hiroshi; Kitagawa, Susumu

2015-07-01

The establishment of methodologies for the mixing of immiscible substances is highly desirable to facilitate the development of fundamental science and materials technology. Herein we describe a new protocol for the compatibilization of immiscible polymers at the molecular level using porous coordination polymers (PCPs) as removable templates. In this process, the typical immiscible polymer pair of polystyrene (PSt) and poly(methyl methacrylate) (PMMA) was prepared via the successive homopolymerizations of their monomers in a PCP to distribute the polymers inside the PCP particles. Subsequent dissolution of the PCP frameworks in a chelator solution affords a PSt/PMMA blend that is homogeneous in the range of several nanometers. Due to the unusual compatibilization, the thermal properties of the polymer blend are remarkably improved compared with the conventional solvent-cast blend. This method is also applicable to the compatibilization of PSt and polyacrylonitrile, which have very different solubility parameters.

Accelerated cell-surface interlocking on plasma polymer-modified porous ceramics.

PubMed

Rebl, Henrike; Finke, Birgit; Schmidt, Jürgen; Mohamad, Heba S; Ihrke, Roland; Helm, Christiane A; Nebe, J Barbara

2016-12-01

Excellent osseointegration of permanent implants is crucial for the long lasting success of the implantation. To improve the osseointegrative potential, bio-inert titanium alloy surfaces (Ti6Al4V) are modified by plasma chemical oxidation (PCO®) of the titanium-oxide layer to a non-stoichiometric, amorphous calcium phosphate layer. The native titanium-oxide film measuring only a few nanometers is converted by PCO® to a thick porous calcium phosphate layer of about 10μm. In a second step the PCO surface is combined with a cell adhesive plasma-polymerized allylamine (PPAAm) nano film (5 and 50nm). Independent of the PPAAm coating homogeneity, the human osteoblast-like MG-63 cells show a remarkable increase in cell size and well-developed filopodia. Analyses of the actin cytoskeleton reveal that the cells mold to the pore shape of the PPAAm-covered PCO, thereby establishing a strong attachment to the surface. Interestingly, we could demonstrate that even though our untreated PCO shows excellent hydrophilicity, this alone is not sufficient to facilitate fast cell spreading, but the positive surface charges mediated by PPAAm. This multilayer composite material guarantees enhanced interlocking of the cells with the porous surface. Copyright © 2016 Elsevier B.V. All rights reserved.

Fibrous mini-collagens in hydra nematocysts.

PubMed

Holstein, T W; Benoit, M; Herder, G V; David, C N; Wanner, G; Gaub, H E

1994-07-15

Nematocysts (cnidocysts) are exocytotic organelles found in all cnidarians. Here, atomic force microscopy and field emission scanning electron microscopy reveal the structure of the nematocyst capsule wall. The outer wall consists of globular proteins of unknown function. The inner wall consists of bundles of collagen-like fibrils having a spacing of 50 to 100 nanometers and cross-striations at intervals of 32 nanometers. The fibrils consist of polymers of "mini-collagens," which are abundant in the nematocysts of Hydra. The distinct pattern of mini-collagen fibers in the inner wall can provide the tensile strength necessary to withstand the high osmotic pressure (15 megapascals) in the capsules.

Nanometer-sized materials for solid-phase extraction of trace elements.

PubMed

Hu, Bin; He, Man; Chen, Beibei

2015-04-01

This review presents a comprehensive update on the state-of-the-art of nanometer-sized materials in solid-phase extraction (SPE) of trace elements followed by atomic-spectrometry detection. Zero-dimensional nanomaterials (fullerene), one-dimensional nanomaterials (carbon nanotubes, inorganic nanotubes, and nanowires), two-dimensional nanomaterials (nanofibers), and three-dimensional nanomaterials (nanoparticles, mesoporous nanoparticles, magnetic nanoparticles, and dendrimers) for SPE are discussed, with their application for trace-element analysis and their speciation in different matrices. A variety of other novel SPE sorbents, including restricted-access sorbents, ion-imprinted polymers, and metal-organic frameworks, are also discussed, although their applications in trace-element analysis are relatively scarce so far.

Characterization of proton exchange membrane materials for fuel cells by solid state nuclear magnetic resonance

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

Kong, Zueqian

2010-01-01

Solid-state nuclear magnetic resonance (NMR) has been used to explore the nanometer-scale structure of Nafion, the widely used fuel cell membrane, and its composites. We have shown that solid-state NMR can characterize chemical structure and composition, domain size and morphology, internuclear distances, molecular dynamics, etc. The newly-developed water channel model of Nafion has been confirmed, and important characteristic length-scales established. Nafion-based organic and inorganic composites with special properties have also been characterized and their structures elucidated. The morphology of Nafion varies with hydration level, and is reflected in the changes in surface-to-volume (S/V) ratio of the polymer obtained by small-anglemore » X-ray scattering (SAXS). The S/V ratios of different Nafion models have been evaluated numerically. It has been found that only the water channel model gives the measured S/V ratios in the normal hydration range of a working fuel cell, while dispersed water molecules and polymer ribbons account for the structures at low and high hydration levels, respectively.« less

Luminescence study of ZnSe/PVA (polyvinyl alcohol) composite film

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

Lahariya, Vikas

The ZnSe nanocrystals have been prepared into poly vinyl alcohol(PVA) polymer matrix on glass using ZnCl2 and Na2SeSO3 as zinc and selenium source respectively. Poly vinyl Alcohol (PVA) used as polymer matrix cum capping agent due to their high viscosity and water solubility. It is transparent for visible region and prevents Se- ions to photo oxidation. The ZnSe/PVA composite film was deposited on glass substrate. The film was characterized by X Ray Diffraction (XRD) and UV-Visible absorption Spectroscopy and Photoluminescence. The X Ray Diffraction (XRD) study confirms the nanometer size (10 nm) particle formation within PVA matrix with cubic zinc blendmore » crystal structure. The UV-Visible Absorption spectrum of ZnSe/PVA composite film shown blue shift in absorption edge indicating increased band gap due to quantum confinement. The calculated energy band gap from the absorption edge using Tauc relation is 3.4 eV. From the Photoluminescence study a broad peak at 435 nm has been observed in violet blue region due to recombination of surface states.« less

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

PubMed

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

2015-01-01

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

Exfoliation of Layered Magnesium Aluminum Silicate Platelets in Polymer Hosts Enabled by Cation Chemistry and Temperature

DTIC Science & Technology

2010-10-21

Preprints. 14. ABSTRACT Montmorillonite -smectite clay consists of anisotropic clay platelets, generally a nanometer in thickness by hundreds of...Cation Chemistry and Temperature GregO!)’ R. Yandek, Palrick N. RUlh. Joseph M. Mabry Montmorillonite -smedite clay consists 01 anisotropic clay

Biochemical evolution. I. Polymerization on internal, organophilic silica surfaces of dealuminated zeolites and feldspars

PubMed Central

Smith, Joseph V.

1998-01-01

Catalysis at mineral surfaces might generate replicating biopolymers from simple chemicals supplied by meteorites, volcanic gases, and photochemical gas reactions. Many ideas are implausible in detail because the proposed mineral surfaces strongly prefer water and other ionic species to organic ones. The molecular sieve silicalite (Union Carbide; = Al-free Mobil ZSM-5 zeolite) has a three-dimensional, 10-ring channel system whose electrically neutral Si-O surface strongly adsorbs organic species over water. Three -O-Si tetrahedral bonds lie in the surface, and the fourth Si-O points inwards. In contrast, the outward Si-OH of simple quartz and feldspar crystals generates their ionic organophobicity. The ZSM-5-type zeolite mutinaite occurs in Antarctica with boggsite and tschernichite (Al-analog of Mobil Beta). Archean mutinaite might have become de-aluminated toward silicalite during hot/cold/wet/dry cycles. Catalytic activity of silicalite increases linearly with Al-OH substitution for Si, and Al atoms tend to avoid each other. Adjacent organophilic and catalytic Al-OH regions in nanometer channels might have scavenged organic species for catalytic assembly into specific polymers protected from prompt photochemical destruction. Polymer migration along weathered silicic surfaces of micrometer-wide channels of feldspars might have led to assembly of replicating catalytic biomolecules and perhaps primitive cellular organisms. Silica-rich volcanic glasses should have been abundant on the early Earth, ready for crystallization into zeolites and feldspars, as in present continental basins. Abundant chert from weakly metamorphosed Archaean rocks might retain microscopic clues to the proposed mineral adsorbent/catalysts. Other framework silicas are possible, including ones with laevo/dextro one-dimensional channels. Organic molecules, transition-metal ions, and P occur inside modern feldspars. PMID:9520372

Biochemical evolution. I. Polymerization On internal, organophilic silica surfaces of dealuminated zeolites and feldspars.

PubMed

Smith, J V

1998-03-31

Catalysis at mineral surfaces might generate replicating biopolymers from simple chemicals supplied by meteorites, volcanic gases, and photochemical gas reactions. Many ideas are implausible in detail because the proposed mineral surfaces strongly prefer water and other ionic species to organic ones. The molecular sieve silicalite (Union Carbide; = Al-free Mobil ZSM-5 zeolite) has a three-dimensional, 10-ring channel system whose electrically neutral Si-O surface strongly adsorbs organic species over water. Three -O-Si tetrahedral bonds lie in the surface, and the fourth Si-O points inwards. In contrast, the outward Si-OH of simple quartz and feldspar crystals generates their ionic organophobicity. The ZSM-5-type zeolite mutinaite occurs in Antarctica with boggsite and tschernichite (Al-analog of Mobil Beta). Archean mutinaite might have become de-aluminated toward silicalite during hot/cold/wet/dry cycles. Catalytic activity of silicalite increases linearly with Al-OH substitution for Si, and Al atoms tend to avoid each other. Adjacent organophilic and catalytic Al-OH regions in nanometer channels might have scavenged organic species for catalytic assembly into specific polymers protected from prompt photochemical destruction. Polymer migration along weathered silicic surfaces of micrometer-wide channels of feldspars might have led to assembly of replicating catalytic biomolecules and perhaps primitive cellular organisms. Silica-rich volcanic glasses should have been abundant on the early Earth, ready for crystallization into zeolites and feldspars, as in present continental basins. Abundant chert from weakly metamorphosed Archaean rocks might retain microscopic clues to the proposed mineral adsorbent/catalysts. Other framework silicas are possible, including ones with laevo/dextro one-dimensional channels. Organic molecules, transition-metal ions, and P occur inside modern feldspars.

Building superlattices from individual nanoparticles via template-confined DNA-mediated assembly

NASA Astrophysics Data System (ADS)

Lin, Qing-Yuan; Mason, Jarad A.; Li, Zhongyang; Zhou, Wenjie; O’Brien, Matthew N.; Brown, Keith A.; Jones, Matthew R.; Butun, Serkan; Lee, Byeongdu; Dravid, Vinayak P.; Aydin, Koray; Mirkin, Chad A.

2018-02-01

DNA programmable assembly has been combined with top-down lithography to construct superlattices of discrete, reconfigurable nanoparticle architectures on a gold surface over large areas. Specifically, the assembly of individual colloidal plasmonic nanoparticles with different shapes and sizes is controlled by oligonucleotides containing “locked” nucleic acids and confined environments provided by polymer pores to yield oriented architectures that feature tunable arrangements and independently controllable distances at both nanometer- and micrometer-length scales. These structures, which would be difficult to construct by other common assembly methods, provide a platform to systematically study and control light-matter interactions in nanoparticle-based optical materials. The generality and potential of this approach are explored by identifying a broadband absorber with a solvent polarity response that allows dynamic tuning of visible light absorption.

Building superlattices from individual nanoparticles via template-confined DNA-mediated assembly

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

Lin, Qing-Yuan; Mason, Jarad A.; Li, Zhongyang

DNA programmable assembly has been combined with top-down lithography to construct superlattices of discrete, reconfigurable nanoparticle architectures on a gold surface over large areas. Specifically, individual colloidal plasmonic nanoparticles with different shapes and sizes are assembled with ‘locked” nucleic acids in polymer pores into oriented architectures that feature tunable arrangements and independently controllable distances at both nanometer and micrometer length scales. These structures, which would be difficult to construct via other common assembly methods, provide a platform to systematically study and control light-matter interactions in nanoparticle-based optical materials. The generality and potential of this approach is explored by identifying amore » broadband absorber with a solvent polarity response that allows dynamic tuning of the wavelength response and amplitude of visible light absorption.« less

Ultra-Light Precision Membrane Optics

NASA Technical Reports Server (NTRS)

Moore, Jim; Gunter, Kent; Patrick, Brian; Marty, Dave; Bates, Kevin; Gatlin, Romona; Clayton, Bill; Rood, Bob; Brantley, Whitt (Technical Monitor)

2001-01-01

SRS Technologies and NASA Marshall Space Flight Center have conducted a research effort to explore the possibility of developing ultra-lightweight membrane optics for future imaging applications. High precision optical flats and spherical mirrors were produced under this research effort. The thin film mirrors were manufactured using surface replication casting of CPI(Trademark), a polyimide material developed specifically for UV hardness and thermal stability. In the course of this program, numerous polyimide films were cast with surface finishes better than 1.5 nanometers rms and thickness variation of less than 63 nanometers. Precision membrane optical flats were manufactured demonstrating better than 1/13 wave figure error when measured at 633 nanometers. The aerial density of these films is 0.037 kilograms per square meter. Several 0.5-meter spherical mirrors were also manufactured. These mirrors had excellent surface finish (1.5 nanometers rms) and figure error on the order of tens of microns. This places their figure error within the demonstrated correctability of advanced wavefront correction technologies such as real time holography.

Monolayers and multilayers of conjugated polymers as nanosized electronic components.

PubMed

Zotti, Gianni; Vercelli, Barbara; Berlin, Anna

2008-09-01

Conjugated polymers (CPs) are interesting materials for preparing devices based on nanoscopic molecular architectures because they exhibit electrical, electronic, magnetic, and optical properties similar to those of metals or semiconductors while maintaining the flexibility and ease of processing of polymers. The production of well-defined mono- and multilayers of CPs on electrodes with nanometer-scale, one-dimensional resolution remains, however, an important challenge. In this Account, we describe the preparation and conductive properties of nanometer-sized CP molecular structures formed on electrode surfaces--namely, self-assembled monolayer (SAM), brush-type, and self-assembled multilayer CPs--and in combination with gold nanoparticles (AuNPs). We have electrochemically polymerized SAMs of carboxyalkyl-functionalized terthiophenes aligned either perpendicular or parallel to the electrode surface. Anodic coupling of various pyrrole- and thiophene-based monomers in solution with the oligothiophene-based SAMs produced brush-like films. Microcontact printing of these SAMs produced patterns that, after heterocoupling, exhibited large height enhancements, as measured using atomic force microscopy (AFM). We have employed layer-by-layer self-assembly of water-soluble polythiophene-based polyelectrolytes to form self-assembled multilayers. The combination of isostructural polycationic and polyanionic polythiophenes produced layers of chains aligned parallel to the substrate plane. These stable, robust, and dense layers formed with high regularity on the preformed monolayers, with minimal interchain penetration. Infrared reflection/adsorption spectroscopy and X-ray diffraction analyses revealed unprecedented degrees of order. Deposition of soluble polypyrroles produced molecular layers that, when analyzed using a gold-coated AFM tip, formed gold-polymer-gold junctions that were either ohmic or rectifying, depending of the layer sequence. We also describe the electronic conduction of model alpha,omega-capped sexithiophenes featuring a range of electron donor/acceptor units and lengths of additional conjugation. The sexithiophene cores exhibit redox-type conductivity, developing at the neutral/cation and cation/dication levels with values depending the nature of the substitution and the redox system. Extending the conjugation beyond the sexithiophene frame introduces further oxidation processes displaying enhanced conductivity. Finally, we discuss the ability of CP-based monolayers to coordinate AuNPs. Although thiophene- and pyrrole-based oligomers aggregate toluene-soluble AuNPs, alkyl substitution inhibits the aggregation process through steric restraint. Consequently, we investigated the interactions between AuNPs and polypyrrole or polythiophene monolayers, including those formed from star-shaped molecules. The hindered aggregation provided by alkyl substituents allowed us to adsorb thiol-functionalized oligothiophenes and oligopyrroles directly onto preformed AuNPs. Novel materials incorporating AuNPs of the same size but bearing different conjugated ends or bridges have great promise for applications in electrocatalysis, electroanalysis, and organic electronics.

Unexpected behavior of ultra-thin films of blends of polystyrene/poly(vinyl methyl ether) studied by specific heat spectroscopy

NASA Astrophysics Data System (ADS)

Madkour, Sherif; Szymoniak, Paulina; Schick, Christoph; Schönhals, Andreas

2017-05-01

Specific heat spectroscopy (SHS) employing AC nanochip calorimetry was used to investigate the glassy dynamics of ultra-thin films (thicknesses: 10 nm-340 nm) of a polymer blend, which is miscible in the bulk. In detail, a Poly(vinyl methyl ether) (PVME)/Polystyrene (PS) blend with the composition of 25/75 wt. % was studied. The film thickness was controlled by ellipsometry while the film topography was checked by atomic force microscopy. The results are discussed in the framework of the balance between an adsorbed and a free surface layer on the glassy dynamics. By a self-assembling process, a layer with a reduced mobility is irreversibly adsorbed at the polymer/substrate interface. This layer is discussed employing two different scenarios. In the first approach, it is assumed that a PS-rich layer is adsorbed at the substrate. Whereas in the second approach, a PVME-rich layer is suggested to be formed at the SiO2 substrate. Further, due to the lower surface tension of PVME, with respect to air, a nanometer thick PVME-rich surface layer, with higher molecular mobility, is formed at the polymer/air interface. By measuring the glassy dynamics of the thin films of PVME/PS in dependence on the film thickness, it was shown that down to 30 nm thicknesses, the dynamic Tg of the whole film was strongly influenced by the adsorbed layer yielding a systematic increase in the dynamic Tg with decreasing the film thickness. However, at a thickness of ca. 30 nm, the influence of the mobile surface layer becomes more pronounced. This results in a systematic decrease in Tg with the further decrease of the film thickness, below 30 nm. These results were discussed with respect to thin films of PVME/PS blend with a composition of 50/50 wt. % as well as literature results.

Measurement of nanoscale molten polymer droplet spreading using atomic force microscopy

NASA Astrophysics Data System (ADS)

Soleymaniha, Mohammadreza; Felts, Jonathan R.

2018-03-01

We present a technique for measuring molten polymer spreading dynamics with nanometer scale spatial resolution at elevated temperatures using atomic force microscopy (AFM). The experimental setup is used to measure the spreading dynamics of polystyrene droplets with 2 μm diameters at 115-175 °C on sapphire, silicon oxide, and mica. Custom image processing algorithms determine the droplet height, radius, volume, and contact angle of each AFM image over time to calculate the droplet spreading dynamics. The contact angle evolution follows a power law with time with experimentally determined values of -0.29 ± 0.01, -0.08 ± 0.02, and -0.21 ± 0.01 for sapphire, silicon oxide, and mica, respectively. The non-zero steady state contact angles result in a slower evolution of contact angle with time consistent with theories combining molecular kinetic and hydrodynamic models. Monitoring the cantilever phase provides additional information about the local mechanics of the droplet surface. We observe local crystallinity on the molten droplet surface, where crystalline structures appear to nucleate at the contact line and migrate toward the top of the droplet. Increasing the temperature from 115 °C to 175 °C reduced surface crystallinity from 35% to 12%, consistent with increasingly energetically favorable amorphous phase as the temperature approaches the melting temperature. This platform provides a way to measure spreading dynamics of extremely small volumes of heterogeneously complex fluids not possible through other means.

Study on the neotype zirconia's implant coated nanometer hydroxyapatite ceramics

NASA Astrophysics Data System (ADS)

Zhu, J. W.; Yang, D. W.

2007-07-01

In recent years, biologic ceramics is a popular material of implants and bioactive surface modification of dental implant became a research emphasis, which aims to improve bioactivity of implants materials and acquire firmer implants-bone interface. The zirconia ceramic has excellent mechanical properties and nanometer HA ceramics is a bioceramic well known for its bioactivity, therefore, nanometer HA ceramics coating on zirconia, allows combining the excellent mechanical properties of zirconia substrates with its bioactivity. This paper shows a new method for implant shape design and bioactive modification of dental implants surface. Zirconia's implant substrate was prepared by sintered method, central and lateral tunnels were drilled in the zirconia hollow porous cylindrical implants by laser processing. The HA powders and needle-like HA crystals were made by a wet precipitation and calcining method. Its surface was coated with nanometer HA ceramics which was used brush HA slurry and vacuum sintering. Mechanical testing results revealed that the attachment strength of nanometer HA ceramics coated zirconia samples is high. SEM and interface observation after inserted experiment indicated that calcium and phosphor content increased and symmetrically around coated implant-bone tissue interface. A significantly higher affinity index was demonstrated in vivo by histomorphometric evaluation in coated versus uncoated implants. SEM analysis demonstrated better bone adhesion to the material in coated implant at any situation. In addition, the hollow porous cylindrical implant coated with nanometer HA ceramics increase the interaction of bone and implant, the new bone induced into the surface of hollow porous cylindrical implant and through the most tunnels filled into central hole. The branch-like structure makes the implant and bone a body, which increased the contact area and decreased elastic ratio. Therefore, the macroscopical and microcosmic nested structure of implant coated nanometer HA ceramics had increased biocompatibility and improved the osteointegration. It endows the implants with new vital activity.

Variation of the transmittance spectrum of a polymer cladding optical fibre for the influence of hydrocarbons and changes in temperature

NASA Astrophysics Data System (ADS)

Santoyo, A. T.; Shlyagin, M. G.; Mendieta, F. J.; Spirin, V.; de Rivera, L. N.

2005-12-01

We develop an analysis of the behavior of an evanescent field fiber optic sensor under different conditions for its optimization. This paper presents results of an experimental study of the spectral characteristics of a polymer cladding optical fiber exposed to different analytes. The measurements were performed in the spectral interval from 1100 to 1800 nanometers in a temperature range from 5 to 50 degrees C. Influence of ambient temperature on the optical fiber transmittance was found to be strongly dependent on wavelength.

Profiling of patterned metal layers by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS)

NASA Astrophysics Data System (ADS)

Bi, Melody; Ruiz, Antonio M.; Gornushkin, Igor; Smith, Ben W.; Winefordner, James D.

2000-02-01

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used for profiling patterned thin metal layers on a polymer/silicon substrate. The parameters of the laser and ICP-MS operating conditions have been studied and optimized for this purpose. A new laser ablation chamber was designed and built to achieve the best spatial resolution. The results of the profiling by LA-ICP-MS were compared to those obtained from a laser ablation optical emission spectrometry (LA-OES) instrument, which measured the emission of the plasma at the sample surface, and thus, eliminated the time delay caused by the sample transport into the ICP-MS system. Emission spectra gave better spatial resolution than mass spectra. However, LA-ICP-MS provided much better sensitivity and was able to profile thin metal layers (on the order of a few nanometers) on the silicon surface. A lateral spatial resolution of 45 μm was achieved.

Solution-Based 3D Printing of Polymers of Intrinsic Microporosity.

PubMed

Zhang, Fengyi; Ma, Yao; Liao, Jianshan; Breedveld, Victor; Lively, Ryan P

2018-05-28

Current additive manufacturing methods have significant limitations in the classes of compatible polymers. Many polymers of significant technological interest cannot currently be 3D printed. Here, a generalizable method for 3D printing of viscous tenary polymer solutions (polymer/solvent/nonsolvent) is applied to both "intrinsically porous" (a polymer of intrinsic microporosity, PIM-1) and "intrinsically nonporous" (cellulose acetate) polymers. Successful ternary ink formulations require balancing of solution thermodynamics (phase separation), mass transfer (solvent evaporation), and rheology. As a demonstration, a microporous polymer (PIM-1) incompatible with current additive manufacturing technologies is 3D printed into a high-efficiency mass transfer contactor exhibiting hierarchical porosity ranging from sub-nanometer to millimeter pores. Short contactors (1.27 cm) can fully purify (<1 ppm) toluene vapor (1000 ppm) in N 2 gas for 1.7 h, which is six times longer than PIM-1 in traditional structures, and more than 4000 times the residence time of gas in the contactor. This solution-based additive manufacturing approach greatly extends the range of 3D-printable materials. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of Irreversible Adsorption on the Glass Transition Temperature of Polymer Thin Films as Measured by Fluorescence

NASA Astrophysics Data System (ADS)

Burroughs, Mary; Priestley, Rodney

2014-03-01

Polymers confined to the nanometer length scale have been shown to exhibit deviations in the glass transition temperature (Tg) from the bulk. With the increasing use of confined polymers in nanotechnology, understanding and predicting this behavior is extremely relevant to industries ranging from pharmaceuticals to organic electronics. Recent work (Napolitano, Wübbenhorst, Nature Communications, 2, 260 (2011)) has connected deviations in Tg under confinement with irreversible physical adsorption of polymer chains at substrate interfaces. Here we investigate the influence of irreversibly adsorbed layers on the Tg of polystyrene (PS) thin films supported on silica via fluorescence. We examine the Tg of the brushes as a function of annealing time and irreversibly adsorbed layer thickness. By incorporating fluorescently labeled polymer layers into multilayered films of unlabeled polymer, we will examine the influence of brushes on adjacent layers dynamics. Finally, we will compare the results on PS with those of poly(methyl methacrylate).

Hints at Ceres Composition from Color

NASA Image and Video Library

2015-09-30

This map-projected view of Ceres was created from images taken by NASA's Dawn spacecraft during its high-altitude mapping orbit, in August and September, 2015. Images taken using infrared (920 nanometers), red (750 nanometers) and blue (440 nanometers) spectral filters were combined to create this false-color view. Redder colors indicate places on Ceres' surface that reflect light strongly in the infrared, while bluish colors indicate enhanced reflectivity at short (bluer) wavelengths; green indicates places where albedo, or overall brightness, is strongly enhanced. Scientists use this technique in order to highlight subtle color differences across Ceres, which would appear fairly uniform in natural color. This can provide valuable insights into the mineral composition of the surface, as well as the relative ages of surface features. http://photojournal.jpl.nasa.gov/catalog/PIA19977

Spirit Beholds Bumpy Boulder

NASA Technical Reports Server (NTRS)

2006-01-01

As NASA's Mars Exploration Rover Spirit began collecting images for a 360-degree panorama of new terrain, the rover captured this view of a dark boulder with an interesting surface texture. The boulder sits about 40 centimeters (16 inches) tall on Martian sand about 5 meters (16 feet) away from Spirit. It is one of many dark, volcanic rock fragments -- many pocked with rounded holes called vesicles -- littering the slope of 'Low Ridge.' The rock surface facing the rover is similar in appearance to the surface texture on the outside of lava flows on Earth.

Spirit took this approximately true-color image with the panoramic camera on the rover's 810th sol, or Martian day, of exploring Mars (April 13, 2006), using the camera's 753-nanometer, 535-nanometer, and 432-nanometer filters.

Impact of electrode preparation on the bending of asymmetric planar electro-active polymer microstructures

NASA Astrophysics Data System (ADS)

Weiss, Florian M.; Töpper, Tino; Osmani, Bekim; Winterhalter, Carla; Müller, Bert

2014-03-01

Compliant electrodes of microstructures have been a research topic for many years because of the increasing interest in consumer electronics, robotics, and medical applications. This interest includes electrically activated polymers (EAP), mainly applied in robotics, lens systems, haptics and foreseen in a variety of medical devices. Here, the electrodes consist of metals such as gold, graphite, conductive polymers or certain composites. The common metal electrodes have been magnetron sputtered, thermally evaporated or prepared using ion implantation. In order to compare the functionality of planar metal electrodes in EAP microstructures, we have investigated the mechanical properties of magnetron sputtered and thermally evaporated electrodes taking advantage of cantilever bending of the asymmetric, rectangular microstructures. We demonstrate that the deflection of the sputtered electrodes is up to 39 % larger than that of thermally evaporated nanometer-thin film on a single silicone film. This difference has even more impact on nanometer-thin, multi-stack, low-voltage EAP actuators. The stiffening effect of many metallic electrode layers is expected to be one of the greatest drawbacks in the multi-stack approaches, which will be even more pronounced if the elastomer layer thickness will be in the sub-micrometer range. Additionally, an improvement in voltage and strain resolution is presented, which is as low as 2 V or 5 × 10-5 above 10 V applied.

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

Catauro, Michelina; Bollino, Flavia; Gloria, Antonio

The objective of the present study was to synthesize and to characterize Silica/polyethylene glycol (SiO{sub 2}/PEG) organic-inorganic hybrid materials containing a high polymer amount (60 and 70 wt%) for biomedical applications. Scanning electron microscopy (SEM) showed that the samples are homogeneous on the nanometer scale, confirming that they are nanocomposites. Fourier transform infrared spectroscopy (FT-IR) proved that the materials are class I hybrids because the two phases (SiO{sub 2} and PEG) interact by hydrogen bonds. To evaluate the possibility of using them in the biomedical field, the bioactivity and biocompatibility of the synthesized hybrids have been ascertained. The formation ofmore » a hydroxyapatite layer was observed on the hybrid surface by SEM/EDX and FTIR after soaking in simulated body fluid (SBF). Moreover, their biocompatibility was assessed by performing WST-8 cytotoxicity assay in vitro.« less

When beauty is only skin deep; optimizing the sensitivity of specular neutron reflectivity for probing structure beneath the surface of thin filmsa)

NASA Astrophysics Data System (ADS)

Majkrzak, Charles F.; Carpenter, Elisabeth; Heinrich, Frank; Berk, Norman F.

2011-11-01

Specular neutron reflectometry has become an established probe of the nanometer scale structure of materials in thin film and multilayered form. It has contributed especially to our understanding of soft condensed matter of interest in polymer science, organic chemistry, and biology and of magnetic hard condensed matter systems. In this paper we examine a number of key factors which have emerged that can limit the sensitivity of neutron reflection as such a probe. Among these is loss of phase information, and we discuss how knowledge about material surrounding a film of interest can be applied to help resolve the problem. In this context we also consider what role the quantum phenomenon of interaction-free measurement might play in enhancing the statistical efficiency for obtaining reflectivity or transmission data.

Importing super-resolution imaging into nanoscale puzzles of materials dynamics

NASA Astrophysics Data System (ADS)

King, John; Tsang, Chi Hang Boyce; Wilson, William; Granick, Steve

2014-03-01

A limitation of the exciting recent advances in sub-diffraction microscopy is that they focus on imaging rather than dynamical changes. We are engaged in extending this technique beyond the usual biological applications to address materials problems instead. To this end, we employ stimulated emission depletion (STED) microscopy, which relies on selectively turning off fluorescence emitters through stimulated emission, allowing only a small subset of emitters to be detected, such that the excitation spot size can be downsized to tens of nanometers. By coupling the STED excitation scheme to fluorescence correlation spectroscopy (FCS), diffusive processes are studied with nanoscale resolution. Here, we demonstrate the benefits of such experimental capabilities in a diverse range of complex systems, ranging from the diffusion of nano-objects in crowded 3D environments to the study of polymer diffusion on 2D surfaces.

Fabrication of complex nanoscale structures on various substrates

NASA Astrophysics Data System (ADS)

Han, Kang-Soo; Hong, Sung-Hoon; Lee, Heon

2007-09-01

Polymer based complex nanoscale structures were fabricated and transferred to various substrates using reverse nanoimprint lithography. To facilitate the fabrication and transference of the large area of the nanostructured layer to the substrates, a water-soluble polyvinyl alcohol mold was used. After generation and transference of the nanostructured layer, the polyvinyl alcohol mold was removed by dissolving in water. A residue-free, UV-curable, glue layer was formulated and used to bond the nanostructured layer onto the substrates. As a result, nanometer scale patterned polymer layers were bonded to various substrates and three-dimensional nanostructures were also fabricated by stacking of the layers.

Spirit Beholds Bumpy Boulder (False Color)

NASA Technical Reports Server (NTRS)

2006-01-01

As NASA's Mars Exploration Rover Spirit began collecting images for a 360-degree panorama of new terrain, the rover captured this view of a dark boulder with an interesting surface texture. The boulder sits about 40 centimeters (16 inches) tall on Martian sand about 5 meters (16 feet) away from Spirit. It is one of many dark, volcanic rock fragments -- many pocked with rounded holes called vesicles -- littering the slope of 'Low Ridge.' The rock surface facing the rover is similar in appearance to the surface texture on the outside of lava flows on Earth.

Spirit took this false-color image with the panoramic camera on the rover's 810th sol, or Martian day, of exploring Mars (April 13, 2006). This image is a false-color rendering using camera's 753-nanometer, 535-nanometer, and 432-nanometer filters.

Nanometer-scale modification and welding of silicon and metallic nanowires with a high-intensity electron beam.

PubMed

Xu, Shengyong; Tian, Mingliang; Wang, Jinguo; Xu, Jian; Redwing, Joan M; Chan, Moses H W

2005-12-01

We demonstrate that a high-intensity electron beam can be applied to create holes, gaps, and other patterns of atomic and nanometer dimensions on a single nanowire, to weld individual nanowires to form metal-metal or metal-semiconductor junctions, and to remove the oxide shell from a crystalline nanowire. In single-crystalline Si nanowires, the beam induces instant local vaporization and local amorphization. In metallic Au, Ag, Cu, and Sn nanowires, the beam induces rapid local surface melting and enhanced surface diffusion, in addition to local vaporization. These studies open up a novel approach for patterning and connecting nanomaterials in devices and circuits at the nanometer scale.

Effect of TiO, nanoparticles on the interface in the PET-rubber composites.

PubMed

Vladuta, Cristina; Andronic, Luminita; Duta, Anca

2010-04-01

Usually, ceramic powders (SiO2, ZnO) are used as fillers for enhancing rubber mechanical strength. Poly-ethylene terephthalate (PET)-rubber nanocomposites were prepared by compression molding using titanium oxide (TiO2) nanoparticles as low content fillers (<2% wt). The interface properties of PET-rubber nanocomposites were studied before and after keeping the samples under UV-radiation for a week. UV-radiation has interesting potential for the photochemical modification of polymers and TiO2. The influence of UV radiation on the properties of the interface polymer-TiO2 nanoparticles was evaluated. The impact of nanoparticle aggregates on the nanometer to micrometer organization of PET-rubber composites was studied with Atomic Force Microscopy (AFM). The interface properties were explained by measuring the contact angles and surface tensions. The interactions between components of nanocomposites were investigated with Fourier Transform-Infrared (FTIR) and the effects of TiO2 nanoparticle on the interfaces and composites crystalline structure were evaluated by X-ray diffraction (XRD). The results proved that the TiO2 nanoparticles, in different weight percentages, did not alter the nanocomposites crystallinity or the average crystallites size, but improve the interface properties.

Properties of antibacterial polypropylene/nanometal composite fibers

USDA-ARS?s Scientific Manuscript database

Melt spinning of polypropylene fibers containing silver and zinc nanoparticles was investigated. The nanometals were generally uniformly dispersed in polypropylene, but aggregation of these materials was observed on fiber surface and in fiber cross-sections. The mechanical properties of the resulted...

Flexible and conductive MXene films and nanocomposites with high capacitance

DOE PAGES

Ling, Zheng; Ren, Chang E.; Zhao, Meng-Qiang; ...

2014-11-11

MXenes, a new family of 2D materials, combine hydrophilic surfaces with metallic conductivity. Delamination of MXene produces single-layer nanosheets with thickness of about a nanometer and lateral size of the order of micrometers. The high aspect ratio of delaminated MXene renders it promising nanofiller in multifunctional polymer nanocomposites. In this study, Ti 3C 2T x MXene was mixed with either a charged polydiallyldimethylammonium chloride (PDDA) or an electrically neutral polyvinyl alcohol (PVA) to produce Ti 3C 2T x/polymer composites. The as-fabricated composites are flexible and have electrical conductivities as high as 2.2 × 10 4 S/m in the case ofmore » the Ti 3C 2T x/PVA composite film and 2.4 × 10 5 S/m for pure Ti 3C 2T x films. The tensile strength of the Ti 3C 2T x/PVA composites was significantly enhanced compared with pure Ti 3C 2T x or PVA films. The intercalation and confinement of the polymer between the MXene flakes not only increased flexibility but also enhanced cationic intercalation, offering an impressive volumetric capacitance of ~530 F/cm 3 for MXene/PVA-KOH composite film at 2 mV/s. Finally, to our knowledge, this study is a first, but crucial, step in exploring the potential of using MXenes in polymer-based multifunctional nanocomposites for a host of applications, such as structural components, energy storage devices, wearable electronics, electrochemical actuators, and radiofrequency shielding, to name a few.« less

Design and synthesis of guest-host nanostructures to enhance ionic conductivity across nanocomposite membranes

DOEpatents

Hu, Michael Z [Knoxville, TN; Kosacki, Igor [Oak Ridge, TN

2010-01-05

An ion conducting membrane has a matrix including an ordered array of hollow channels and a nanocrystalline electrolyte contained within at least some or all of the channels. The channels have opposed open ends, and a channel width of 1000 nanometers or less, preferably 60 nanometers or less, and most preferably 10 nanometers or less. The channels may be aligned perpendicular to the matrix surface, and the length of the channels may be 10 nanometers to 1000 micrometers. The electrolyte has grain sizes of 100 nanometers or less, and preferably grain sizes of 1 to 50 nanometers. The electrolyte may include grains with a part of the grain boundaries aligned with inner walls of the channels to form a straight oriented grain-wall interface or the electrolyte may be a single crystal. In one form, the electrolyte conducts oxygen ions, the matrix is silica, and the electrolyte is yttrium doped zirconia.

Hydrophobic thiol-ene surfaces fabricated via plasma activation and photo polymerization

NASA Astrophysics Data System (ADS)

Champathet, P.; Ervithayasuporn, V.; Osotchan, T.; Dangtip, S.

2017-09-01

Alumina, such as glazed alumina for electrical insulator, operated in an open field subjects to a very harsh condition; resulting in lifetime shortening. Coating hydrophobic layer on alumina surface can help prolonging its lifetime. In this study, 25 ×25 mm alumina sheets were used as substrates. The hydrophobic composite polymers were prepared from (3-mercaptopropyl)trimethoxysilane(MPTMS), 2,4,6,8-tetramethyl-2,4,6,8tetravinylcyclotetra siloxane(TMTVSi), pentaerythritoltetra(3-mercaptopropionate)(PETMP), 2,2-dimethoxy-2-phe nylaceto phenone(photoinitiator) and heptadecafluorodecylmethacrylate(HEFDMA) via the thiol-ene reaction. The alumina sheets were first activated by dielectric-barrier discharge plasma to improve its adhesion. All the polymers were found to optimize at the ratio of (MPTMS:TMTVSi:PETMP:HDFDMA) to 4:2:1:2 for coating on the alumina substrate. To enhance polymerization, 2,2-dimethoxy-2-phenylaceto phenome was also used as a photoinitiator A proper mixing sequence in the thiol-ene reaction results in film with excellent surface retention after prolong soaking in solvent such as acetone. FTIR shows that S-H and C=C functional groups have significantly changed after photopolymerization and thermally cured. The static contact angle increase from mere 53.0°±1.5° of the uncoated substrate to 120.0°±1.2° after coating. SEM shows the film with clear appearance of a few-micron thick. Under AFM, the coated surface roughness was about 9.3 nm with evenly distributed spikes of a few nanometer in height. The cross-cut test also confirmed the film was very smooth and none of the square of the films detached.

Universal Method for Creating Hierarchical Wrinkles on Thin-Film Surfaces.

PubMed

Jung, Woo-Bin; Cho, Kyeong Min; Lee, Won-Kyu; Odom, Teri W; Jung, Hee-Tae

2018-01-10

One of the most interesting topics in physical science and materials science is the creation of complex wrinkled structures on thin-film surfaces because of their several advantages of high surface area, localized strain, and stress tolerance. In this study, a significant step was taken toward solving limitations imposed by the fabrication of previous artificial wrinkles. A universal method for preparing hierarchical three-dimensional wrinkle structures of thin films on a multiple scale (e.g., nanometers to micrometers) by sequential wrinkling with different skin layers was developed. Notably, this method was not limited to specific materials, and it was applicable to fabricating hierarchical wrinkles on all of the thin-film surfaces tested thus far, including those of metals, two-dimensional and one-dimensional materials, and polymers. The hierarchical wrinkles with multiscale structures were prepared by sequential wrinkling, in which a sacrificial layer was used as the additional skin layer between sequences. For example, a hierarchical MoS 2 wrinkle exhibited highly enhanced catalytic behavior because of the superaerophobicity and effective surface area, which are related to topological effects. As the developed method can be adopted to a majority of thin films, it is thought to be a universal method for enhancing the physical properties of various materials.

Activating Aluminum Reactivity with Fluoropolymer Coatings for Improved Energetic Composite Combustion.

PubMed

McCollum, Jena; Pantoya, Michelle L; Iacono, Scott T

2015-08-26

Aluminum (Al) particles are passivated by an aluminum oxide (Al2O3) shell. Energetic blends of nanometer-sized Al particles with liquid perfluorocarbon-based oxidizers such as perfluoropolyethers (PFPE) excite surface exothermic reaction between fluorine and the Al2O3 shell. The surface reaction promotes Al particle reactivity. Many Al-fueled composites use solid oxidizers that induce no Al2O3 surface exothermicity, such as molybdenum trioxide (MoO3) or copper oxide (CuO). This study investigates a perfluorinated polymer additive, PFPE, incorporated to activate Al reactivity in Al-CuO and Al-MoO3. Flame speeds, differential scanning calorimetry (DSC), and quadrupole mass spectrometry (QMS) were performed for varying percentages of PFPE blended with Al/MoO3 or Al/CuO to examine reaction kinetics and combustion performance. X-ray photoelectron spectroscopy (XPS) was performed to identify product species. Results show that the performance of the thermite-PFPE blends is highly dependent on the bond dissociation energy of the metal oxide. Fluorine-Al-based surface reaction with MoO3 produces an increase in reactivity, whereas the blends with CuO show a decline when the PFPE concentration is increased. These results provide new evidence that optimizing Al combustion can be achieved through activating exothermic Al surface reactions.

Dynamics of polyelectrolyte adsorption on surfaces: Applications in the detection of iron in water

NASA Astrophysics Data System (ADS)

Gammana, Madhira N.

Layer by layer (LbL) self assembly is a simple multilayer thin (nanometer scale) film fabricating technique. The mechanism of film growth remains a topic of much controversy. For example, several models have been proposed to explain the origin of linear and exponential film growth that are attributed to differences in the dynamic processes that occur at the molecular level during film formation. The problem is that there are no methods that directly measure the dynamics of polymer formation during LbL film formation. In this thesis, I describe the essential elements of an ATR-IR spectroscopic method that was developed to enable measurement of the dynamics of the mass adsorbed and polyelectrolyte conformation during the formation of PEM's. In particular, I followed the sequential adsorption of Sodium polyacrylate (NaPA) and Poly (diallyldimethylammonium) chloride (PDADMAC) from deionized (DI) water and as a function of ionic strength to show that polymer diffusion occurs between layers when adsorbed from DI water. In contrast, a denser layer occurs with no polymer interdiffusion for deposition from 0.02M ionic strength solutions of NaPA and PDADMAC. While the mass deposited increased with ionic strength, linear multilayer growth in films were observed in all cases. This finding disputes a common viewpoint that interdiffusion of polymer layers is a key feature of exponential film growth. The theme of polymer layer adsorption was used in the detection of Fe 3+ in seawater. A new approach, developed previously in Tripp's group, utilized "vertical amplification" in which a block copolymer assembled on membranes provided multiple anchoring points extending from the surface for attaching a siderophore, desferrioxamine B (DFB). The Fe3+ chelates with the siderophore producing a red color that can be quantified by visible spectroscopy. However, the rate of Fe3+ uptake was found to be dependent on flow rate. The origin of this flow rate dependence was identified by the work presented in this thesis. It was found that the amount and rate of Fe3+ uptake was dependent on the relative size of each block in the polymer and the degree of reaction of DFB with the adsorbed layer. In particular, higher amounts and higher rates were obtained when the density of DFB was lowered. This shows that the DFB was sterically hindered from forming a hexacoordinate complex with Fe3+ by the presence of neighboring DFB molecules. This is a key factor that needs to be considered in developing Fe3+ detection systems based on siderophores anchored to surfaces.

Mechanism of nanoparticle actuation by responsive polymer brushes: from reconfigurable composite surfaces to plasmonic effects.

PubMed

Roiter, Yuri; Minko, Iryna; Nykypanchuk, Dmytro; Tokarev, Ihor; Minko, Sergiy

2012-01-07

The mechanism of nanoparticle actuation by stimuli-responsive polymer brushes triggered by changes in the solution pH was discovered and investigated in detail in this study. The finding explains the high spectral sensitivity of the composite ultrathin film composed of a poly(2-vinylpyridine) (P2VP) brush that tunes the spacing between two kinds of nanoparticles-gold nanoislands immobilized on a transparent support and gold colloidal particles adsorbed on the brush. The optical response of the film relies on the phenomenon of localized surface plasmon resonances in the noble metal nanoparticles, giving rise to an extinction band in visible spectra, and a plasmon coupling between the particles and the islands that has a strong effect on the band position and intensity. Since the coupling is controlled by the interparticle spacing, the pH-triggered swelling-shrinking transition in the P2VP brush leads to pronounced changes in the transmission spectra of the hybrid film. It was not established in the previous publications how the actuation of gold nanoparticles within a 10-15 nm interparticle distance could result in the 50-60 nm shift in the absorbance maximum in contrast to the model experiments and theoretical estimations of several nanometer shifts. In this work, the extinction band was deconvoluted into four spectrally separated and overlapping contributions that were attributed to different modes of interactions between the particles and the islands. These modes came into existence due to variations in the thickness of the grafted polymeric layer on the profiled surface of the islands. In situ atomic force microscopy measurements allowed us to explore the behavior of the Au particles as the P2VP brush switched between the swollen and collapsed states. In particular, we identified an interesting, previously unanticipated regime when a particle position in a polymer brush was switched between two distinct states: the particle exposed to the surface of the collapsed layer and the particle engulfed by the swollen brush. On average, the characteristic distance between the particles and the islands increased upon the brush swelling. The observed behavior was a result of the anchoring of the particles to polymeric chains that limited the particles' vertical motion range. The experimental findings will be used to design highly sensitive optical nanosensors based on a polymer-brush-modulated interparticle plasmon coupling.

Nanostructures and nanosecond dynamics at the polymer/filler interface

NASA Astrophysics Data System (ADS)

Koga, Tad; Barkley, Deborah; Endoh, Maya; Masui, Tomomi; Kishimoto, Hiroyuki; Nagao, Michihiro; Taniguchi, Takashi

We report in-situ nanostructures and nanosecond dynamics of polybutadiene (PB) chains bound to carbon black (CB) fillers (the so-called ``bound polymer layer (BPL)'') in polymer solutions (from dilute to concentrated solutions). The BPL on the CB fillers were extracted by solvent leaching of a CB-filled PB compound and subsequently dispersed in deuterated toluene (a good solvent) to label the BPL for ``contrast-matching'' small-angle neutron scattering (SANS) and neutron spin echo (NSE) techniques. The SANS results demonstrate that the BPL is composed of two regions regardless of molecular weights of PB: the inner unswollen region of 0.5 nm thick and outer swollen region where the polymer chains display a parabolic profile with a diffuse tail. In addition, the NSE results show that the dynamics of the swollen bound chains in the polymer solutions can be explained by the collective dynamics, the so-called ``breathing mode''. Intriguingly, it was also indicative that the collective dynamics is independent of the polymer concentrations and is much faster than that predicted from the solution viscosity. We will discuss the mechanism at the bound polymer-free polymer interface at the nanometer scale. T.K. acknowledges the financial support from NSF Grant (CMMI-1332499).

Characteristic length of glass transition

NASA Astrophysics Data System (ADS)

Donth, E.

1996-03-01

The characteristic length of the glass transition (ξ _α ) is based on the concept of cooperatively rearranging regions (CRR's) by Adam & Gibbs (1965): ξ _α is the diameter of one CRR. In the theoretical part of the talk a formula is derived how this length can be calculated from calorimetric data of the transformation interval. The approach is based on fluctuations in natural functional subsystems. The corresponding thermodynamics is represented e.g. in a book of the author (E. Donth, Relaxation and Thermodynamics in Polymers. Glass Transition, Akademie-Verlag, Berlin 1992). A typical value for this length is 3 nanometers. In the experimental part several examples are reported to enlarge the experimental evidence for such a length: Squeezing the glass transition in the amorphous layers of partially crystallized PET (C. Schick, Rostock), glass transition of small-molecule glass formers in a series of nanoscaled pores of porous glasses (F. Kremer, Leipzig), comparison with a concentration fluctuation model in homogeneous polymer mixtures (E.W. Fischer, Mainz), and, from our laboratory, backscaling to ξ _α across the main transition from the entanglement spacing in several amorphous polymers such as PVAC, PS, NR, and some polymer networks. Rouse backscaling was possible in the α β splitting region of several poly(n alkyl methacrylates) resulting in small characteristic lengths of order 1 nanometer near the onset of α cooperativity. In a speculative outlook a dynamic density pattern is presented, having a cellular structure with higher density and lower mobility of the cell walls. It will be explained, with the aid of different thermal expansion of wall and clusters, how the clusters within the cells maintain a certain mobility far below the glass temperature.

Mechanical and electrical properties of low density polyethylene filled with carbon nanotubes

NASA Astrophysics Data System (ADS)

Sabet, Maziyar; Soleimani, Hassan

2014-08-01

Carbon nanotubes (CNTs) reveal outstanding electrical and mechanical properties in addition to nanometer scale diameter and high aspect ratio, consequently, making it an ideal reinforcing agent for high strength polymer composites. Low density polyethylene (LDPE)/CNT composites were prepared via melt compounding. Mechanical and electrical properties of (LDPE)/CNT composites with different CNT contents were studied in this research.

Catalytic membranes for CO oxidation in fuel cells

DOEpatents

Sandi-Tapia, Giselle; Carrado Gregar, Kathleen; Kizilel, Riza

2010-06-08

A hydrogen permeable membrane, which includes a polymer stable at temperatures of about 200 C having clay impregnated with Pt or Au or Ru or Pd particles or mixtures thereof with average diameters of less than about 10 nanometers (nms) is disclosed. The membranes are useful in fuel cells or any device which requires hydrogen to be separated from carbon monoxide.

3D Structural Model of High-Performance Non-Fullerene Polymer Solar Cells as Revealed by High-Resolution AFM.

PubMed

Shi, Shaowei; Chen, Xiaofeng; Liu, Xubo; Wu, Xuefei; Liu, Feng; Zhang, Zhi-Guo; Li, Yongfang; Russell, Thomas P; Wang, Dong

2017-07-26

Rapid improvements in nonfullerene polymer solar cells (PSCs) have brought power conversion efficiencies to greater than 12%. To further improve device performance, a fundamental understanding of the correlations between structure and performance is essential. In this paper, based on a typical high-performance system consisting of J61(one donor-acceptor (D-A) copolymer of benzodithiophene and fluorine substituted benzotriazole) and ITIC (3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone)-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']-dithiophene), a 3D structural model is directly imaged by employing high-resolution atomic force microscopy (AFM). Hierarchical morphologies ranging from fiberlike crystallites, several nanometers in size, to a bicontinuous morphology, having domains tens of nanometers in size, are observed. A fibrillar interpenetrating networks of J61-rich domains embedded in a matrix comprised of a J61/ITIC is seen, reflecting the partial miscibility of J61 with ITIC. These hierarchical nanostructural characteristics are coupled to significantly enhanced exciton dissociation, and further contribute to photocurrent and final device performance.

Mechanical Properties of Nanostructured Materials Determined Through Molecular Modeling Techniques

NASA Technical Reports Server (NTRS)

Clancy, Thomas C.; Gates, Thomas S.

2005-01-01

The potential for gains in material properties over conventional materials has motivated an effort to develop novel nanostructured materials for aerospace applications. These novel materials typically consist of a polymer matrix reinforced with particles on the nanometer length scale. In this study, molecular modeling is used to construct fully atomistic models of a carbon nanotube embedded in an epoxy polymer matrix. Functionalization of the nanotube which consists of the introduction of direct chemical bonding between the polymer matrix and the nanotube, hence providing a load transfer mechanism, is systematically varied. The relative effectiveness of functionalization in a nanostructured material may depend on a variety of factors related to the details of the chemical bonding and the polymer structure at the nanotube-polymer interface. The objective of this modeling is to determine what influence the details of functionalization of the carbon nanotube with the polymer matrix has on the resulting mechanical properties. By considering a range of degree of functionalization, the structure-property relationships of these materials is examined and mechanical properties of these models are calculated using standard techniques.

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.

Chemical synthesis of chiral conducting polymers

DOEpatents

Wang, Hsing-Lin [Los Alamos, NM; Li, Wenguang [Los Alamos, NM

2009-01-13

An process of forming a chiral conducting polymer, e.g., polyaniline, is provided including reacting a monomer, e.g., an aniline monomer, in the presence of a chiral dopant acid to produce a first reaction mixture by addition of a solution including a first portion of an oxidizing agent, the first portion of oxidizing agent characterized as insufficient to allow complete reaction of the monomer, and further reacting the first reaction mixture in the presence of the chiral dopant acid by addition of a solution including a second portion of the oxidizing agent, the second portion of oxidizing agent characterized as insufficient to allow complete reaction of the monomer, and repeating the reaction by addition of further portions of the oxidizing agent until the monomer reaction is complete to produce a chiral conducting polymer, e.g., polyaniline. A preferred process includes addition of a catalyst during the reaction, the catalyst selected from among the group consisting of phenylene diamine, aniline oligomers and amino-capped aniline oligomers and metal salts.The processes of the present invention further provide a resultant polyaniline product having a chirality level defined by a molar ellipticity of from about 40.times.10.sup.3 degree-cm.sup.2/decimole to about 700.times.10.sup.3 degree-cm.sup.2/decimole. The processes of the present invention further provide a resultant polyaniline product having a nanofiber structure with a diameter of from about 30 nanometers to about 120 nanometers and from about 1 micron to about 5 microns in length.

Nano-Gap Embedded Plasmonic Gratings for Surface Plasmon Enhanced Fluorescence

NASA Astrophysics Data System (ADS)

Bhatnagar, Kunal; Bok, Sangho; Korampally, Venumadhav; Gangopadhyay, Shubhra

2012-02-01

Plasmonic nanostructures have been extensively used in the past few decades for applications in sub-wavelength optics, data storage, optoelectronic circuits, microscopy and bio-photonics. The enhanced electromagnetic field produced at the metal/dielectric interface by the excitation of surface plasmons via incident radiation can be used for signal enhancement in fluorescence and surface enhanced Raman scattering studies. Novel plasmonic structures on the sub wavelength scale have been shown to provide very efficient and extreme light concentration at the nano-scale. The enhanced electric field produced within a few hundred nanometers of these structures can be used to excite fluorophores in the surrounding environment. Fluorescence based bio-detection and bio-imaging are two of the most important tools in the life sciences. Improving the qualities and capabilities of fluorescence based detectors and imaging equipment has been a big challenge to the industry manufacturers. We report the novel fabrication of nano-gap embedded periodic grating substrates on the nanoscale using micro-contact printing and polymethylsilsesquioxane (PMSSQ) polymer. Fluorescence enhancement of up to 118 times was observed with these silver nanostructures in conjugation with Rhodamine-590 fluorescent dye. These substrates are ideal candidates for low-level fluorescence detection and single molecule imaging.

Sol-gel silica-based nanocomposites containing a high PEG amount: Chemical characterization and study of biological properties

NASA Astrophysics Data System (ADS)

Catauro, Michelina; Bollino, Flavia; Gloria, Antonio

2016-05-01

The objective of the present study was to synthesize and to characterize Silica/polyethylene glycol (SiO2/PEG) organic-inorganic hybrid materials containing a high polymer amount (60 and 70 wt%) for biomedical applications. Scanning electron microscopy (SEM) showed that the samples are homogeneous on the nanometer scale, confirming that they are nanocomposites. Fourier transform infrared spectroscopy (FT-IR) proved that the materials are class I hybrids because the two phases (SiO2 and PEG) interact by hydrogen bonds. To evaluate the possibility of using them in the biomedical field, the bioactivity and biocompatibility of the synthesized hybrids have been ascertained. The formation of a hydroxyapatite layer was observed on the hybrid surface by SEM/EDX and FTIR after soaking in simulated body fluid (SBF). Moreover, their biocompatibility was assessed by performing WST-8 cytotoxicity assay in vitro.

Self-assembly of nematic liquid crystal elastomer filaments

NASA Astrophysics Data System (ADS)

Wei, Wei-Shao; Xia, Yu; Yang, Shu; Yodh, A. G.

In this work we investigate the self-assembly of nematic liquid crystal polymer (NLCP) filaments and their corresponding cross-linked elastomer structures. Specifically, by fine-tuning surfactant concentration, prepolymer chain length, and temperature within a background aqueous phase we can generate filaments composed of oligomerized LC monomers. Filaments with narrowly dispersed diameters ranging from one hundred nanometers to a few micrometers can be obtained. Using polarization optical microscopy, we show that the nematic LCs within the filaments have an escaped radial structure. After photo-cross-linking, nematic liquid crystal elastomer filaments are obtained with well-maintained directors and smooth surface structure. Since these materials are elastomers, the size and mechanical and optical response of the filaments can be ''tuned'' near the nematic to isotropic phase transition temperature. This work is supported by NSF DMR16-07378, PENN MRSEC Grant DMR11-20901, and NASA Grant NNX08AO0G.

Advanced functional materials in solid phase extraction for ICP-MS determination of trace elements and their species - A review.

PubMed

He, Man; Huang, Lijin; Zhao, Bingshan; Chen, Beibei; Hu, Bin

2017-06-22

For the determination of trace elements and their species in various real samples by inductively coupled plasma mass spectrometry (ICP-MS), solid phase extraction (SPE) is a commonly used sample pretreatment technique to remove complex matrix, pre-concentrate target analytes and make the samples suitable for subsequent sample introduction and measurements. The sensitivity, selectivity/anti-interference ability, sample throughput and application potential of the methodology of SPE-ICP-MS are greatly dependent on SPE adsorbents. This article presents a general overview of the use of advanced functional materials (AFMs) in SPE for ICP-MS determination of trace elements and their species in the past decade. Herein the AFMs refer to the materials featuring with high adsorption capacity, good selectivity, fast adsorption/desorption dynamics and satisfying special requirements in real sample analysis, including nanometer-sized materials, porous materials, ion imprinting polymers, restricted access materials and magnetic materials. Carbon/silica/metal/metal oxide nanometer-sized adsorbents with high surface area and plenty of adsorption sites exhibit high adsorption capacity, and porous adsorbents would provide more adsorption sites and faster adsorption dynamics. The selectivity of the materials for target elements/species can be improved by using physical/chemical modification, ion imprinting and restricted accessed technique. Magnetic adsorbents in conventional batch operation offer unique magnetic response and high surface area-volume ratio which provide a very easy phase separation, greater extraction capacity and efficiency over conventional adsorbents, and chip-based magnetic SPE provides a versatile platform for special requirement (e.g. cell analysis). The performance of these adsorbents for the determination of trace elements and their species in different matrices by ICP-MS is discussed in detail, along with perspectives and possible challenges in the future development. Copyright © 2017 Elsevier B.V. All rights reserved.

Grinding model and material removal mechanism of medical nanometer zirconia ceramics.

PubMed

Zhang, Dongkun; Li, Changhe; Jia, Dongzhou; Wang, Sheng; Li, Runze; Qi, Xiaoxiao

2014-01-01

Many patents have been devoted to developing medical nanometer zirconia ceramic grinding techniques that can significantly improve both workpiece surface integrity and grinding quality. Among these patents is a process for preparing ceramic dental implants with a surface for improving osseo-integration by sand abrasive finishing under a jet pressure of 1.5 bar to 8.0 bar and with a grain size of 30 µm to 250 µm. Compared with other materials, nano-zirconia ceramics exhibit unmatched biomedical performance and excellent mechanical properties as medical bone tissue and dentures. The removal mechanism of nano-zirconia materials includes brittle fracture and plastic removal. Brittle fracture involves crack formation, extension, peeling, and chipping to completely remove debris. Plastic removal is similar to chip formation in metal grinding, including rubbing, ploughing, and the formation of grinding debris. The materials are removed in shearing and chipping. During brittle fracture, the grinding-led transverse and radial extension of cracks further generate local peeling of blocks of the material. In material peeling and removal, the mechanical strength and surface quality of the workpiece are also greatly reduced because of crack extension. When grinding occurs in the plastic region, plastic removal is performed, and surface grinding does not generate grinding fissures and surface fracture, producing clinically satisfactory grinding quality. With certain grinding conditions, medical nanometer zirconia ceramics can be removed through plastic flow in ductile regime. In this study, we analyzed the critical conditions for the transfer of brittle and plastic removal in nano-zirconia ceramic grinding as well as the high-quality surface grinding of medical nanometer zirconia ceramics by ELID grinding.

Hierarchical Nanomorphologies Promote Exciton Dissociation in Polymer: Fullerene Bulk Heterojunction Solar Cells

NASA Astrophysics Data System (ADS)

Chen, Wei; Darling, Seth

2012-02-01

In the last fifteen years, research efforts have led to organic photovoltaic (OPV) devices with power conversion efficiencies (PCEs) up to ˜8%, but these values are still insufficient for the devices to become widely marketable. To further improve solar cell performance a thorough understanding of the complex structure-property relationships in the OPV devices is required. In this work, we demonstrated that the OPV active layer of PTB7:fullerene bulk heterojunction (BHJ) solar cells, which set a historic record of PCE (7.4%), involves hierarchical nanomorphologies ranging from several nanometers of crystallites to tens of nanometers of nanocrystallite aggregates in PTB7-rich and fullerene-rich domains, themselves hundreds of nanometers in size. These hierarchical nanomorphologies with optimum crystallinity and intermixing of PTB7 with fullerenes are coupled to significantly enhanced exciton dissociation, which consequently contribute to photocurrent, leading to the superior performance of PTB7:fullerene BHJ solar cells. New insights of performance-related structures afforded by the current study should aid in the rational design of even higher performance polymeric solar cells.

Atomic Layer Deposition for the Modification and Creation of Nanomaterials

NASA Astrophysics Data System (ADS)

Needham, Erinn Christine

Atomic layer deposition (ALD) is a vapor-phase technique for the conformal deposition of material with sub-nanometer precision, making it an ideal process for modifying and even creating nanomaterials. The focus of this dissertation is the study of how ALD precursors interact with organic materials, namely polymers, to create selectively deposited nano-scale patterns and how ALD coatings modify biological responses to nanomaterials, namely carbon nanotubes (CNT), after inhalation. Nanoscale patterning is vital to the semiconductor industry. With features becoming smaller and more complex with each passing year, new techniques are required to meet the needs of the industry. The ability to selectively pattern a material onto a wafer is of particular interest for the replacement of costly etching steps. In the first half of this dissertation, a method for the selective deposition of nano-scale patterns is presented. Patterned polymers were used as sacrificial sponges to soak up ALD precursors for the creation of metal-oxide features. Meanwhile, deposition in areas without polymer was limited to the monolayer regime. Following infiltration, the saturated polymer was burned away and the precursor oxidized to form a metal oxide reproduction of the polymer pattern. Determining the reaction between the ALD precursor, trimethylaluminum, and polymer, poly(methyl methacrylate), helped to achieve patterning by informing the proper selection of reactor temperature as well as exposure and purge times. Using this technique, features from tens of nanometers to tens of microns were patterned uniformly and simultaneously across a 150 mm wafer. Finally, this technique was extended to pattern two different materials using only one patterned polymer layer. ALD was first used to deposit a metal oxide were there was no polymer. By selecting ALD precursors that do not react within or on top of the polymer, selective deposition of the first material was achieved. Following this, the polymer was infiltrated as before to selectively deposit the second material. By patterning two materials from one patterned polymer, no pattern alignment between materials is necessary. The reaction mechanism determined for this system can be applied and expanded to other vapor-phase metal-organic interactions with polymers. The ability to make and align nanoscale features is critically important for manufacturing improved semiconductor devices. The second half of this dissertation focuses on how modification of CNT affects biological response in a material-dependent manner. CNT have unique physical and chemical properties that lead to applications in many areas including: electronics, high-strength materials, filtration and drug delivery. By surface-modifying these materials, a whole new realm of applications appears. Despite the benefits these coatings may provide (e.g., photocatalytic properties and increased conductivity) they can also alter the toxicological response to MWCNT. In rodent models, the inhalation of MWCNT can lead to inflammation and fibrosis. Here, we observed that ZnO coatings on MWCNT led to an acute inflammatory response but did not change the fibrotic response in mice following inhalation. The contribution of ZnO coating dissolution was still unknown following the in vivo study with mice. Alumina, ZnO and aluminum-doped ZnO (AZO) coatings on MWCNT were studied in vitro using various cell lines to determine the contribution of ions to toxicity. AZO is less soluble than ZnO and composed only of previously-characterized materials. We discovered that the concentration of Zn2+ in solution correlated with levels of cytotoxicity in vitro and differences in dissolution between AZO and ZnO coatings led to differences in pro-inflammatory cytokine release. This knowledge can assist with the toxicological assessment of other pure and composite nanomaterials and lead to the creation of safer nanomaterials.

Template-directed control of crystal morphologies.

PubMed

Meldrum, Fiona C; Ludwigs, Sabine

2007-02-12

Biominerals are characterised by unique morphologies, and it is a long-term synthetic goal to reproduce these synthetically. We here apply a range of templating routes to investigate whether a fascinating category of biominerals, the single crystals with complex forms, can be produced using simple synthetic methods. Macroporous crystals with sponge-like morphologies identical to that of sea urchin skeletal plates were produced on templating with a sponge-like polymer membrane. Similarly, patterning of individual crystal faces was achieved from the micrometer to nanometer scale through crystallisation on colloidal particle monolayers and patterned polymer thin films. These experiments demonstrate the versatility of a templating approach to producing single crystals with unique morphologies.

Dispersion of cellulose nanofibers in biopolymer based nanocomposites

NASA Astrophysics Data System (ADS)

Wang, Bei

The focus of this work was to understand the fundamental dispersion mechanism of cellulose based nanofibers in bionanocomposites. The cellulose nanofibers were extracted from soybean pod and hemp fibers by chemo-mechanical treatments. These are bundles of cellulose nanofibers with a diameter ranging between 50 to 100 nm and lengths of thousands of nanometers which results in very high aspect ratio. In combination with a suitable matrix polymer, cellulose nanofiber networks show considerable potential as an effective reinforcement for high quality specialty applications of bio-based nanocomposites. Cellulose fibrils have a high density of --OH groups on the surface, which have a tendency to form hydrogen bonds with adjacent fibrils, reducing interaction with the surrounding matrix. The use of nanofibers has been mostly restricted to water soluble polymers. This thesis is focused on synthesizing the nanocomposite using a solid phase matrix polypropylene (PP) or polyethylene (PE) by hot compression and poly (vinyl alcohol) (PVA) in an aqueous phase by film casting. The mechanical properties of nanofiber reinforced PVA film demonstrated a 4-5 fold increase in tensile strength, as compared to the untreated fiber-blend-PVA film. It is necessary to reduce the entanglement of the fibrils and improve their dispersion in the matrix by surface modification of fibers without deteriorating their reinforcing capability. Inverse gas chromatography (IGC) was used to explore how various surface treatments would change the dispersion component of surface energy and acid-base character of cellulose nanofibers and the effect of the incorporation of these modified nanofibers into a biopolymer matrix on the properties of their nano-composites. Poly (lactic acid) (PLA) and polyhydroxybutyrate (PHB) based nanocomposites using cellulose nanofibers were prepared by extrusion, injection molding and hot compression. The IGC results indicated that styrene maleic anhydride coated and ethylene-acrylic acid coated fibers improved their potential to interact with both acidic and basic resins. From transmission electron micrograph, it was shown that the nanofibers were partially dispersed in the polymer matrix. The mechanical properties of the nanocomposites were lower than those predicted by theoretical calculations for both nanofiber reinforced biopolymers.

Long-range exciton transport in conjugated polymer nanofibers prepared by seeded growth

NASA Astrophysics Data System (ADS)

Jin, Xu-Hui; Price, Michael B.; Finnegan, John R.; Boott, Charlotte E.; Richter, Johannes M.; Rao, Akshay; Menke, S. Matthew; Friend, Richard H.; Whittell, George R.; Manners, Ian

2018-05-01

Easily processed materials with the ability to transport excitons over length scales of more than 100 nanometers are highly desirable for a range of light-harvesting and optoelectronic devices. We describe the preparation of organic semiconducting nanofibers comprising a crystalline poly(di-n-hexylfluorene) core and a solvated, segmented corona consisting of polyethylene glycol in the center and polythiophene at the ends. These nanofibers exhibit exciton transfer from the core to the lower-energy polythiophene coronas in the end blocks, which occurs in the direction of the interchain π-π stacking with very long diffusion lengths (>200 nanometers) and a large diffusion coefficient (0.5 square centimeters per second). This is made possible by the uniform exciton energetic landscape created by the well-ordered, crystalline nanofiber core.

Synthesis of polymer nanostructures via the use of surfactant surface aggregates as templates

NASA Astrophysics Data System (ADS)

Marquez, Maricel

The subject of this work is the synthesis of polymer nanostructures via the use of surfactant surface aggregates as templates, also termed Template Assisted Admicellar Polymerization (TAAP). The first chapter reviews some of the most current nanopatterning techniques (including both top-down and bottom-up approaches), with particular emphasis on the fabrication of organic and inorganic patterned nanostructures via particle lithography. In chapter 2, highly ordered hexagonal arrays of latex spheres were prepared on highly ordered pyrolytic graphite (HOPG) from a variation of the Langmuir Blodgett technique, using an anionic surfactant (SDS), and a low molecular weight (ca. 10000) polyacrylamide as spreading agents. When a nonionic polyethoxylated (EO = 9) surfactant was used as the spreading agent, no ordered arrays were observed. Based on the correlation found between the surface tension in the presence of the latex particles and the critical concentration at which hexagonal arrangements of latex spheres occurs; a model was proposed to explain the role of the spreading agent in forming stable monolayers at the air/liquid interface, which in turn are necessary for the formation of well-ordered monolayers on a solid substrate from the LB technique. According to this model, solid-like regions of small numbers of latex spheres form at the liquid-air interface, which are then transferred to the substrate. These ordered regions then act as nuclei for the formation of 2D arrays of latex spheres on the surface upon water evaporation. The role of other factors such as relative humidity, substrate and solvent choice, and pulling vs. compression speed were also found to affect the quality of the monolayers formed. Finally, a simple, easy to automate, yet effective surface tension method was proposed to predict the optimal conditions for the formation of ordered monolayers using a variation of the LB deposition method from any monodisperse set of spheres. In chapter 3, a novel method for the formation of nanometer-scale polymer structures on solid surfaces via template assisted admicellar polymerization (TAAP) is described. Admicellar polymerization uses a surfactant layer adsorbed on a surface to localize monomer to the surface prior to polymerization of the monomer. TAAP refers to nanostructures that form by restricting adsorption to the uncovered sites of an already-templated surface. In this case, the interstitial sites between adsorbed latex spheres were used as the template. Unlike most other process that form polymer nanostructures, polymer dimensions can be significantly smaller than the interstitial size because of sphere-surfactant-monomer interactions. As a proof of concept, nanostructures formed via TAAP were compared to structures prepared by others via adsorption of three different proteins (Bovine serum albumin, fibrinogen, and anti-mouse IgG) in the interstitial sites of colloidal monolayers. The size and shape of the nanostructures formed (honeycomb vs. pillars) was dependent upon the size of the spheres utilized and the method of polymer deposition (i.e. admicellar polymerization vs. polymer adsorption). Thinner honeycomb walls, and larger separation distances between the template and the nanostructures were consistently found for TAAP. In chapter 4, an in-depth study of the factors affecting TAAP is presented for three different monomers: aniline, pyrrole and methyl methacrylate; and three different surfaces: highly ordered pyrolytic graphite (HOPG), gold, and SiO2. Among the parameters discussed are the effect of monomer and surfactant concentration, surfactant chain length, polymerization time and temperature, solution ionic strength, substrate choice and surface treatment. Control over these parameters allowed the synthesis of polymer nanopillars, nanorings, honeycombs, and "honeytubes." Experimental results showed that the nanostructures' morphology can be effectively modified by changing the length of the hydrophobic chain of the surfactant. Nanostructures with fewer defects were found for surfactants with the longest hydrophobic tails (i.e. 12 carbon atoms). The hydrophobic nature of the monomer also seemed to affect the morphology of the nanostructure; poly(methyl methacrylate) (PMMA) honeycombs showed thicker walls compared to polyaniline (PANI) and polypyrrole (Ppy). In general, HOPG seems to be a better choice of substrate for TAAP compared to gold-coated glass and SiO2 wafers. Preliminary results on the formation of layered polymer nanostructures via multiple TAAP sequences were also presented.

Preparation and electrochemical characterization of gel polymer electrolyte based on electrospun polyacrylonitrile nonwoven membranes for lithium batteries

NASA Astrophysics Data System (ADS)

Raghavan, Prasanth; Manuel, James; Zhao, Xiaohui; Kim, Dul-Sun; Ahn, Jou-Hyeon; Nah, Changwoon

Electrospun membranes of polyacrylonitrile are prepared, and the electrospinning parameters are optimized to get fibrous membranes with uniform bead-free morphology. The polymer solution of 16 wt.% in N, N-dimethylformamide at an applied voltage of 20 kV results in the nanofibrous membrane with average fiber diameter of 350 nm and narrow fiber diameter distribution. Gel polymer electrolytes are prepared by activating the nonwoven membranes with different liquid electrolytes. The nanometer level fiber diameter and fully interconnected pore structure of the host polymer membranes facilitate easy penetration of the liquid electrolyte. The gel polymer electrolytes show high electrolyte uptake (>390%) and high ionic conductivity (>2 × 10 -3 S cm -1). The cell fabricated with the gel polymer electrolytes shows good interfacial stability and oxidation stability >4.7 V. Prototype coin cells with gel polymer electrolytes based on a membrane activated with 1 M LiPF 6 in ethylene carbonate/dimethyl carbonate or propylene carbonate are evaluated for discharge capacity and cycle property in Li/LiFePO 4 cells at room temperature. The cells show remarkably good cycle performance with high initial discharge properties and low capacity fade under continuous cycling.

Metal substrates with nanometer scale surface roughness for flexible electronics

NASA Astrophysics Data System (ADS)

Lee, Jong-Lam; Kim, Kisoo

2012-09-01

In this work, we present a novel way in fabricating a metal substrate with nanometer scale in surface roughness (Ra < 1 nm) using a surface roughness transfer method without any polishing or planarization process. Ag film (8 inch, Ra = 0.57 nm) and an INVAR (Invariable alloy) one (20 cm × 20 cm, Ra = 1.40 nm) were demonstrated. The INVAR film was used as a substrate for fabricating organic light emitting diodes (OLED) and organic photovoltaic (OPV). The optical and electrical characteristics of OLEDs and OPVs using the INVAR were comparable to those using a conventional ITO glass substrate.

Cyanate ester-nanoparticle composites as multifunctional structural capacitors

NASA Astrophysics Data System (ADS)

De Leon, J. Eliseo

An important goal of engineering is to increase the energy density of electrical energy storage devices used to deliver power onboard mobile platforms. Equally important is the goal to reduce the overall mass of the vehicles transporting these devices to achieve increased fuel and cost efficiency. One approach to meeting both these objectives is to develop multifunctional systems that serve as both energy storage and load bearing structural devices. Multifunctional devices consist of constituents that individually perform a subset of the overall desired functions. However, the synergy achieved by the combination of each constituent's characteristics allows for system-level benefits that cannot be achieved by simply optimizing the separate subsystems. We investigated multifunctional systems consisting of light weight polymer matrix and high dielectric constant fillers to achieve these objectives. The monomer of bisphenol E cyanate ester exhibited excellent processing ability because of its low room temperature viscosity. Additionally, the fully cured thermoset demonstrated excellent thermal stability, specific strength and stiffness. Fillers, including multi-walled carbon nanotubes, nanometer scale barium titanate and nanometer scale calcium copper titanate, offer high dielectric constants that raised the effective dielectric constant of the polymer matrix composite. The combination of high epsilon'and high dielectric strength produce high energy density components exhibiting increased electrical energy storage. Mechanical (load bearing) improvements of the PMCs were attributed to covalently bonded nanometer and micrometer sized filler particles, as well as the continuous glass fiber, integrated into the resin systems which increased the structural characteristics of the cured composites. Breakdown voltage tests and dynamic mechanical analysis were employed to demonstrate that precise combinations of these constituents, under the proper processing conditions, can satisfy the needs presented by the aerospace industry and military forces.

Synthesis of nanostructured/macroscopic low-density copper foams based on metal-coated polymer core–shell particles [Templated synthesis of nanowalled low-density copper foams

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

Kim, Sung Ho; Bazin, Nick; Shaw, Jessica I.

A robust, millimeter-sized low-density Cu foam with ~90% (v/v) porosity, ~30 nm thick walls, and ~1 μm diameter spherical pores is prepared by the slip-casting of metal-coated polymer core–shell particles followed by a thermal removal of the polymer. In this paper, we report our key findings that enable the development of the low-density Cu foams. First, we need to synthesize polystyrene (PS) particles coated with a very thin Cu layer (in the range of tens of nanometers). A simple reduction in the amount of Cu deposited onto the PS was not sufficient to form such a low-density Cu foams duemore » to issues related to foam collapse and densification upon the subsequent polymer removal step. Precise control over the morphology of the Cu coating on the particles is essential for the synthesis of a lower density of foams. Second, improving the dispersion of PS–Cu particles in a suspension used for the casting as well as careful optimization of a baking condition minimize the formation of irregular large voids, leading to Cu foams with a more uniform packing and a better connectivity of neighboring Cu hollow shells. Finally, we analyzed mechanical properties of the Cu foams with a depth-sensing indentation test. The uniform Cu foams show a significant improvement in mechanical properties (~1.5× modulus and ~3× hardness) compared to those of uncontrolled foam samples with a similar foam density but irregular large voids. As a result, higher surface areas and a good electric conductivity of the Cu foams present a great potential to future applications.« less

Synthesis of nanostructured/macroscopic low-density copper foams based on metal-coated polymer core–shell particles [Templated synthesis of nanowalled low-density copper foams

DOE PAGES

Kim, Sung Ho; Bazin, Nick; Shaw, Jessica I.; ...

2016-12-06

A robust, millimeter-sized low-density Cu foam with ~90% (v/v) porosity, ~30 nm thick walls, and ~1 μm diameter spherical pores is prepared by the slip-casting of metal-coated polymer core–shell particles followed by a thermal removal of the polymer. In this paper, we report our key findings that enable the development of the low-density Cu foams. First, we need to synthesize polystyrene (PS) particles coated with a very thin Cu layer (in the range of tens of nanometers). A simple reduction in the amount of Cu deposited onto the PS was not sufficient to form such a low-density Cu foams duemore » to issues related to foam collapse and densification upon the subsequent polymer removal step. Precise control over the morphology of the Cu coating on the particles is essential for the synthesis of a lower density of foams. Second, improving the dispersion of PS–Cu particles in a suspension used for the casting as well as careful optimization of a baking condition minimize the formation of irregular large voids, leading to Cu foams with a more uniform packing and a better connectivity of neighboring Cu hollow shells. Finally, we analyzed mechanical properties of the Cu foams with a depth-sensing indentation test. The uniform Cu foams show a significant improvement in mechanical properties (~1.5× modulus and ~3× hardness) compared to those of uncontrolled foam samples with a similar foam density but irregular large voids. As a result, higher surface areas and a good electric conductivity of the Cu foams present a great potential to future applications.« less

Vibration analysis of a new polymer quartz piezoelectric crystal sensor for detecting characteristic materials of volatility liquid

NASA Astrophysics Data System (ADS)

Gu, Yu; Li, Qiang; Xu, Bao-Jun; Zhao, Zhe

2014-01-01

We present a new polymer quartz piezoelectric crystal sensor that takes a quartz piezoelectric crystal as the basal material and a nanometer nonmetallic polymer thin film as the surface coating based on the principle of quartz crystal microbalance (QCM). The new sensor can be used to detect the characteristic materials of a volatile liquid. A mechanical model of the new sensor was built, whose structure was a thin circle plate composing of polytef/quartz piezoelectric/polytef. The mechanical model had a diameter of 8 mm and a thickness of 170 μm. The vibration state of the model was simulated by software ANSYS after the physical parameters and the boundary condition of the new sensor were set. According to the results of experiments, we set up a frequency range from 9.995850 MHz to 9.997225 MHz, 17 kinds of frequencies and modes of vibration were obtained within this range. We found a special frequency fsp of 9.996358 MHz. When the resonant frequency of the new sensor's mechanical model reached the special frequency, a special phenomenon occurred. In this case, the amplitude of the center point O on the mechanical model reached the maximum value. At the same time, the minimum absolute difference between the simulated frequency based on the ANSYS software and the experimental measured stable frequency was reached. The research showed that the design of the new polymer quartz piezoelectric crystal sensor perfectly conforms to the principle of QCM. A special frequency value fsp was found and subsequently became one of the most important parameters in the new sensor design.

Modeling Anisotropic Self-Assembly of Isotropic Objects: from Hairy Nanoparticles to Methylcellulose Fibrils

NASA Astrophysics Data System (ADS)

Ginzburg, Valeriy

Spontaneous symmetry breaking and formation of anisotropic structures from apparently isotropic building blocks is an exciting and not fully understood topic. I will discuss two examples of such self-assembly. The first example is related to the assembly of ``hairy'' nanoparticles in homopolymer matrices. The particles can assemble into long strings (they can also form other morphologies, as well) even though the shape of each particle and the distribution of ligands on the particle surface is spherically symmetric. Using the approach developed by Thompson, Ginzburg, Matsen, and Balazs, we show that presence of other particles can re-distribute the ligands and effectively ``polarize'' the particle-particle interaction, giving rise to the formation of 1d particle strings. In the second example, we consider aqueous solutions of methylcellulose (MC) polymers. It has been shown recently that at high temperature, the polymers form high-aspect ratio ``fibrils'' with diameter ~15 nm and length in the hundreds on nanometers. Using coarse-grained Molecular Dynamics (CG-MD), we propose that the ``fibrils'' are result of one-dimensional self-assembly of single molecule ``rings''. Each MC polymer chain is forced into a ring because of the balance between internal chain rigidity (favoring more expanded configuration) and unfavorable polymer-water interactions (favoring more collapsed conformation). We also develop a theory predicting rheology and phase behavior of aqueous MC, and validate it against experimental data. Both examples show that anisotropic self-assembly can show up in unexpected places, and various theoretical tools are needed to successfully model it. Funded by The Dow Chemical Company through Grant 223278AF. Collaborators: R. L. Sammler (Dow), W. Huang and R. Larson (U. of Michigan).

Contact resonance atomic force microscopy for viscoelastic characterization of polymer-based nanocomposites at variable temperature

NASA Astrophysics Data System (ADS)

Natali, Marco; Passeri, Daniele; Reggente, Melania; Tamburri, Emanuela; Terranova, Maria Letizia; Rossi, Marco

2016-06-01

Characterization of mechanical properties at the nanometer scale at variable temperature is one of the main challenges in the development of polymer-based nanocomposites for application in high temperature environments. Contact resonance atomic force microscopy (CR-AFM) is a powerful technique to characterize viscoelastic properties of materials at the nanoscale. In this work, we demonstrate the capability of CR-AFM of characterizing viscoelastic properties (i.e., storage and loss moduli, as well as loss tangent) of polymer-based nanocomposites at variable temperature. CR-AFM is first illustrated on two polymeric reference samples, i.e., low-density polyethylene (LDPE) and polycarbonate (PC). Then, temperature-dependent viscoelastic properties (in terms of loss tangent) of a nanocomposite sample constituted by a epoxy resin reinforced with single-wall carbon nanotubes (SWCNTs) are investigated.

Nanostructured bio-functional polymer brushes.

PubMed

Padeste, Celestino; Farquet, Patrick; Potzner, Christian; Solak, Harun H

2006-01-01

Structured poly(glycidyl methracrylate) (poly-GMA) brushes have been grafted onto flexible fluoro-polymer films using a radiation grafting process. The reactive epoxide of poly-GMA provides the basis for a versatile biofunctionalization of the grafted brushes. Structure definition by extreme ultraviolet (EUV) exposure allowed nanometer-scale resolution of periodic patterns. By variation of the exposure dose the height of the grafted structures can be adapted in a wide range. Derivatization of the grafted brushes included reaction with various amines with different side chains, hydrolysis of the epoxide to diols to increase protein resistance and introduction of ionic groups to yield poly-electrolytes. As an example for biofunctionalization, biotin was linked to the grafted brush and biofunctionality was demonstrated in a competitive biotin-streptavidin assay. In this article we also present a brief review of other approaches to obtain structured biofunctional polymer brushes.

Kinetics and Mechanism of in situ Simultaneous Formation of Metal Nanoparticles in Stabilizing Polymer Matrix

NASA Astrophysics Data System (ADS)

Pomogailo, Anatolii D.; Dzhardimalieva, Gulzhian I.; Rozenberg, Aleksander S.; Muraviev, Dmitri N.

2003-12-01

The kinetic peculiarities of the thermal transformations of unsaturated metal carboxylates (transition metal acrylates and maleates as well as their cocrystallites) and properties of metal-polymer nanocomposites formed have been studied. The composition and structure of metal-containing precursors and the products of the thermolysis were identified by X-ray analysis, optical and electron microscopy, magnetic measurements, EXAFS, IR and mass spectroscopy. The thermal transformations of metal-containing monomers studied are the complex process including dehydration, solid phase polymerization, and thermolysis process which proceed at varied temperature ranges. At 200-300°C the rate of thermal decay can be described by first-order equations. The products of decompositions are nanometer-sized particles of metal or its oxides with a narrow size distribution (the mean particle diameter of 5-10nm) stabilized by the polymer matrix.

“Nanofiltration” Enabled by Super-Absorbent Polymer Beads for Concentrating Microorganisms in Water Samples

NASA Astrophysics Data System (ADS)

Xie, Xing; Bahnemann, Janina; Wang, Siwen; Yang, Yang; Hoffmann, Michael R.

2016-02-01

Detection and quantification of pathogens in water is critical for the protection of human health and for drinking water safety and security. When the pathogen concentrations are low, large sample volumes (several liters) are needed to achieve reliable quantitative results. However, most microbial identification methods utilize relatively small sample volumes. As a consequence, a concentration step is often required to detect pathogens in natural waters. Herein, we introduce a novel water sample concentration method based on superabsorbent polymer (SAP) beads. When SAP beads swell with water, small molecules can be sorbed within the beads, but larger particles are excluded and, thus, concentrated in the residual non-sorbed water. To illustrate this approach, millimeter-sized poly(acrylamide-co-itaconic acid) (P(AM-co-IA)) beads are synthesized and successfully applied to concentrate water samples containing two model microorganisms: Escherichia coli and bacteriophage MS2. Experimental results indicate that the size of the water channel within water swollen P(AM-co-IA) hydrogel beads is on the order of several nanometers. The millimeter size coupled with a negative surface charge of the beads are shown to be critical in order to achieve high levels of concentration. This new concentration procedure is very fast, effective, scalable, and low-cost with no need for complex instrumentation.

"Nanofiltration" Enabled by Super-Absorbent Polymer Beads for Concentrating Microorganisms in Water Samples.

PubMed

Xie, Xing; Bahnemann, Janina; Wang, Siwen; Yang, Yang; Hoffmann, Michael R

2016-02-15

Detection and quantification of pathogens in water is critical for the protection of human health and for drinking water safety and security. When the pathogen concentrations are low, large sample volumes (several liters) are needed to achieve reliable quantitative results. However, most microbial identification methods utilize relatively small sample volumes. As a consequence, a concentration step is often required to detect pathogens in natural waters. Herein, we introduce a novel water sample concentration method based on superabsorbent polymer (SAP) beads. When SAP beads swell with water, small molecules can be sorbed within the beads, but larger particles are excluded and, thus, concentrated in the residual non-sorbed water. To illustrate this approach, millimeter-sized poly(acrylamide-co-itaconic acid) (P(AM-co-IA)) beads are synthesized and successfully applied to concentrate water samples containing two model microorganisms: Escherichia coli and bacteriophage MS2. Experimental results indicate that the size of the water channel within water swollen P(AM-co-IA) hydrogel beads is on the order of several nanometers. The millimeter size coupled with a negative surface charge of the beads are shown to be critical in order to achieve high levels of concentration. This new concentration procedure is very fast, effective, scalable, and low-cost with no need for complex instrumentation.

“Nanofiltration” Enabled by Super-Absorbent Polymer Beads for Concentrating Microorganisms in Water Samples

PubMed Central

Xie, Xing; Bahnemann, Janina; Wang, Siwen; Yang, Yang; Hoffmann, Michael R.

2016-01-01

Detection and quantification of pathogens in water is critical for the protection of human health and for drinking water safety and security. When the pathogen concentrations are low, large sample volumes (several liters) are needed to achieve reliable quantitative results. However, most microbial identification methods utilize relatively small sample volumes. As a consequence, a concentration step is often required to detect pathogens in natural waters. Herein, we introduce a novel water sample concentration method based on superabsorbent polymer (SAP) beads. When SAP beads swell with water, small molecules can be sorbed within the beads, but larger particles are excluded and, thus, concentrated in the residual non-sorbed water. To illustrate this approach, millimeter-sized poly(acrylamide-co-itaconic acid) (P(AM-co-IA)) beads are synthesized and successfully applied to concentrate water samples containing two model microorganisms: Escherichia coli and bacteriophage MS2. Experimental results indicate that the size of the water channel within water swollen P(AM-co-IA) hydrogel beads is on the order of several nanometers. The millimeter size coupled with a negative surface charge of the beads are shown to be critical in order to achieve high levels of concentration. This new concentration procedure is very fast, effective, scalable, and low-cost with no need for complex instrumentation. PMID:26876979

Fabrication of semiconductor-polymer compound nonlinear photonic crystal slab with highly uniform infiltration based on nano-imprint lithography technique.

PubMed

Qin, Fei; Meng, Zi-Ming; Zhong, Xiao-Lan; Liu, Ye; Li, Zhi-Yuan

2012-06-04

We present a versatile technique based on nano-imprint lithography to fabricate high-quality semiconductor-polymer compound nonlinear photonic crystal (NPC) slabs. The approach allows one to infiltrate uniformly polystyrene materials that possess large Kerr nonlinearity and ultrafast nonlinear response into the cylindrical air holes with diameter of hundred nanometers that are perforated in silicon membranes. Both the structural characterization via the cross-sectional scanning electron microscopy images and the optical characterization via the transmission spectrum measurement undoubtedly show that the fabricated compound NPC samples have uniform and dense polymer infiltration and are of high quality in optical properties. The compound NPC samples exhibit sharp transmission band edges and nondegraded high quality factor of microcavities compared with those in the bare silicon PC. The versatile method can be expanded to make general semiconductor-polymer hybrid optical nanostructures, and thus it may pave the way for reliable and efficient fabrication of ultrafast and ultralow power all-optical tunable integrated photonic devices and circuits.

The Synergistic Effect of Leukocyte Platelet-Rich Fibrin and Micrometer/Nanometer Surface Texturing on Bone Healing around Immediately Placed Implants: An Experimental Study in Dogs

PubMed Central

Neiva, Rodrigo F.; Gil, Luiz Fernando; Tovar, Nick; Janal, Malvin N.; Marao, Heloisa Fonseca; Pinto, Nelson; Coelho, Paulo G.

2016-01-01

Aims. This study evaluated the effects of L-PRF presence and implant surface texture on bone healing around immediately placed implants. Methods. The first mandibular molars of 8 beagle dogs were bilaterally extracted, and implants (Blossom™, Intra-Lock International, Boca Raton, FL) were placed in the mesial or distal extraction sockets in an interpolated fashion per animal. Two implant surfaces were distributed per sockets: (1) dual acid-etched (DAE, micrometer scale textured) and (2) micrometer/nanometer scale textured (Ossean™ surface). L-PRF (Intraspin system, Intra-Lock International) was placed in a split-mouth design to fill the macrogap between implant and socket walls on one side of the mandible. The contralateral side received implants without L-PRF. A mixed-model ANOVA (at α = 0.05) evaluated the effect of implant surface, presence of L-PRF, and socket position (mesial or distal), individually or in combination on bone area fraction occupancy (BAFO). Results. BAFO values were significantly higher for the Ossean relative to the DAE surface on the larger mesial socket. The presence of L-PRF resulted in higher BAFO. The Ossean surface and L-PRF presence resulted in significantly higher BAFO. Conclusion. L-PRF and the micro-/nanometer scale textured surface resulted in increased bone formation around immediately placed implants. PMID:28042577

Chemical synthesis of chiral conducting polymers

DOEpatents

Wang, Hsing-Lin; Li, Wenguang

2006-07-11

An process of forming a chiral conducting polymer, e.g., polyaniline, is provided including reacting a monomer, e.g., an aniline monomer, in the presence of a chiral dopant acid to produce a first reaction mixture by addition of a solution including a first portion of an oxidizing agent, the first portion of oxidizing agent characterized as insufficient to allow complete reaction of the monomer, and further reacting the first reaction mixture in the presence of the chiral dopant acid by addition of a solution including a second portion of the oxidizing agent, the second portion of oxidizing agent characterized as insufficient to allow complete reaction of the monomer, and repeating the reaction by addition of further portions of the oxidizing agent until the monomer reaction is complete to produce a chiral conducting polymer, e.g., polyaniline. A preferred process includes addition of a catalyst during the reaction, the catalyst selected from among the group consisting of phenylene diamine, aniline oligomers and amino-capped aniline oligomers and metal salts. The processes of the present invention further provide a resultant polyaniline product having a chirality level defined by a molar ellipticity of from about 40.times.10³ degree-cm²/decimole to about 700.times.10³ degree-cm²/decimole. The processes of the present invention further provide a resultant polyaniline product having a nanofiber structure with a diameter of from about 30 nanometers to about 120 nanometers and from about 1 micron to about 5 microns in length.

Multiscale Micromechanical Modeling of Polymer/Clay Nanocomposites and the Effective Clay Particle

NASA Astrophysics Data System (ADS)

Sheng, Nuo; Boyce, Mary C.; Parks, David M.; Manovitch, Oleg; Rutledge, Gregory C.; Lee, Hojun; McKinley, Gareth H.

2003-03-01

Polymer/clay nanocomposites have been observed to exhibit enhanced mechanical properties at low weight fractions (Wp) of clay. Continuum-based composite modeling reveals that the enhanced properties are strongly dependent on particular features of the second-phase ¡°particles¡+/-; in particular, the particle volume fraction (fp), the particle aspect ratio (L/t), and the ratio of particle mechanical properties to those of the matrix. However, these important aspects of as-processed nanoclay composites have yet to be consistently and accurately defined. A multiscale modeling strategy was developed to account for the hierarchical morphology of the nanocomposite: at a lengthscale of thousands of microns, the structure is one of high aspect ratio particles within a matrix; at the lengthscale of microns, the clay particle structure is either (a) exfoliated clay sheets of nanometer level thickness or (b) stacks of parallel clay sheets separated from one another by interlayer galleries of nanometer level height. Here, quantitative structural parameters extracted from XRD patterns and TEM micrographs are used to determine geometric features of the as-processed clay ¡°particles¡+/-, including L/t and the ratio of fp to Wp. These geometric features, together with estimates of silicate lamina stiffness obtained from molecular dynamics simulations, provide a basis for modeling effective mechanical properties of the clay particle. The structure-based predictions of the macroscopic elastic modulus of the nanocomposite as a function of clay weight fraction are in excellent agreement with experimental data. The adopted methodology offers promise for study of related properties in polymer/clay nanocomposites.

Supramolecular polymerization of a prebiotic nucleoside provides insights into the creation of sequence-controlled polymers.

PubMed

Wang, Jun; Bonnesen, Peter V; Rangel, E; Vallejo, E; Sanchez-Castillo, Ariadna; James Cleaves Ii, H; Baddorf, Arthur P; Sumpter, Bobby G; Pan, Minghu; Maksymovych, Petro; Fuentes-Cabrera, Miguel

2016-01-04

Self-assembly of a nucleoside on Au(111) was studied to ascertain whether polymerization on well-defined substrates constitutes a promising approach for making sequence-controlled polymers. Scanning tunneling microscopy and density functional theory were used to investigate the self-assembly on Au(111) of (RS)-N(9)-(2,3-dihydroxypropyl)adenine (DHPA), a plausibly prebiotic nucleoside analog of adenosine. It is found that DHPA molecules self-assemble into a hydrogen-bonded polymer that grows almost exclusively along the herringbone reconstruction pattern, has a two component sequence that is repeated over hundreds of nanometers, and is erasable with electron-induced excitation. Although the sequence is simple, more complicated ones are envisioned if two or more nucleoside types are combined. Because polymerization occurs on a substrate in a dry environment, the success of each combination can be gauged with high-resolution imaging and accurate modeling techniques. These characteristics make nucleoside self-assembly on a substrate an attractive approach for designing sequence-controlled polymers. Further, by choosing plausibly prebiotic nucleosides, insights may be provided into how nature created the first sequence-controlled polymers capable of storing information. Such insights, in turn, can inspire new ways of synthesizing sequence-controlled polymers.

Well-defined protein-polymer conjugates--synthesis and potential applications.

PubMed

Thordarson, Pall; Le Droumaguet, Benjamin; Velonia, Kelly

2006-11-01

During the last decades, numerous studies have focused on combining the unique catalytic/functional properties and structural characteristics of proteins and enzymes with those of synthetic molecules and macromolecules. The aim of such multidisciplinary studies is to improve the properties of the natural component, combine them with those of the synthetic, and create novel biomaterials in the nanometer scale. The specific coupling of polymers onto the protein structures has proved to be one of the most straightforward and applicable approaches in that sense. In this article, we focus on the synthetic pathways that have or can be utilized to specifically couple proteins to polymers. The different categories of well-defined protein-polymer conjugates and the effect of the polymer on the protein function are discussed. Studies have shown that the specific conjugation of a synthetic polymer to a protein conveys its physico-chemical properties and, therefore, modifies the biodistribution and solubility of the protein, making it in certain cases soluble and active in organic solvents. An overview of the applications derived from such bioconjugates in the pharmaceutical industry, biocatalysis, and supramolecular nanobiotechnology is presented at the final part of the article.

Vapor Grown Carbon Fiber/Hybrid Organic-Inorganic Matrix Composites. Nanometer-sized Silsesquiozane Phase Chemically Bound in a Matrix

DTIC Science & Technology

2006-04-28

for this work included: (1) Polyhedral oligomeric silsesquioxane chemicals (POSS macromers) of three types: those with no polymerizable group, those...Polyhedral oligomeric silsesquioxane chemicals (POSS macromers) of three types: those with no polymerizable group, those with one reactive function and...atoms and ions. Polyhedral Oligomeric Silsesquioxane/Organic Matrix Nanocomposites Major reviews of POSS polymer and copolymer chemistry. The first

Breakdown Voltage of Thermoplastics with Clay Nanometer-Sized Fillers (Postprint)

DTIC Science & Technology

2008-12-01

of clay nanofillers. Low density polyethylene ( LDPE ) is a mechanically tough, inexpensive polymer used heavily in industry. Numerous studies have...A blend of LDPE grafted with maleic anhydride ( LDPE -g- MA) is tested in this work for improved electrical properties with clay addition. The...LLDPE) copolymer with octene. LLDPE improves over regular LDPE in a number of mechanical properties, though it has a higher production cost. A

Nanometals for Solar-to-Chemical Energy Conversion: From Semiconductor-Based Photocatalysis to Plasmon-Mediated Photocatalysis and Photo-Thermocatalysis.

PubMed

Meng, Xianguang; Liu, Lequan; Ouyang, Shuxin; Xu, Hua; Wang, Defa; Zhao, Naiqin; Ye, Jinhua

2016-08-01

Nanometal materials play very important roles in solar-to-chemical energy conversion due to their unique catalytic and optical characteristics. They have found wide applications from semiconductor photocatalysis to rapidly growing surface plasmon-mediated heterogeneous catalysis. The recent research achievements of nanometals are reviewed here, with regard to applications in semiconductor photocatalysis, plasmonic photocatalysis, and plasmonic photo-thermocatalysis. As the first important topic discussed here, the latest progress in the design of nanometal cocatalysts and their applications in semiconductor photocatalysis are introduced. Then, plasmonic photocatalysis and plasmonic photo-thermocatalysis are discussed. A better understanding of electron-driven and temperature-driven catalytic behaviors over plasmonic nanometals is helpful to bridge the present gap between the communities of photocatalysis and conventional catalysis controlled by temperature. The objective here is to provide instructive information on how to take the advantages of the unique functions of nanometals in different types of catalytic processes to improve the efficiency of solar-energy utilization for more practical artificial photosynthesis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

SUN: A fully automated interferometric test bench aimed at measuring photolithographic grade lenses with a sub nanometer accuracy

NASA Astrophysics Data System (ADS)

Bourgois, R.; Hamy, A. L.; Pourcelot, P.

2017-10-01

SUN is a test bench developed by Safran Reosc to measure spherical or aspherical surface errors of litho-grade lenses with sub-nanometer accuracy. SUN provides full aperture high resolution interferometric measurements. Measurements are performed at the center of curvature using high precision transmission sphere (TS), and Computer Generated Holograms (CGH) for aspheres, in order to light the surface at normal incidence. SUN can measure lenses with diameter up to 350mm and a radius of curvature varying from 60 to 3000 mm.

Characterization of MreB polymers in E. coli and their correlations to cell shape

NASA Astrophysics Data System (ADS)

Nguyen, Jeffrey; Ouzonov, Nikolay; Gitai, Zemer; Shaevitz, Joshua

2015-03-01

Shape influences all facets of how bacteria interact with their environment. The size of E. coli is determined by the peptidoglycan cell wall and internal turgor pressure. The cell wall is patterned by MreB, an actin homolog that forms short polymers on the cytoplasmic membrane. MreB coordinates the breaking of old material and the insertion of new material for growth, but it is currently unknown what mechanism sets the absolute diameter of the cell. Using new techniques in fluorescence microscopy and image processing, we are able to quantify cell shape in 3- dimensions and access previously unattainable data on the conformation of MreB polymers. To study how MreB affects the diameter of bacteria, we analyzed the shapes and polymers of cells that have had MreB perturbed by one of two methods. We first treated cells with the MreB polymerization-inhibiting drug A22. Secondly, we created point mutants in MreB that change MreB polymer conformation and the cell shape. By analyzing the correlations between different shape and polymer metrics, we find that under both treatments, the average helical pitch angle of the polymers correlates strongly with the cell diameter. This observation links the micron scale shape of the cell to the nanometer scale MreB cytoskeleton.

Sub-nanometer surface chemistry and orbital hybridization in lanthanum-doped ceria nano-catalysts revealed by 3D electron microscopy.

PubMed

Collins, Sean M; Fernandez-Garcia, Susana; Calvino, José J; Midgley, Paul A

2017-07-14

Surface chemical composition, electronic structure, and bonding characteristics determine catalytic activity but are not resolved for individual catalyst particles by conventional spectroscopy. In particular, the nano-scale three-dimensional distribution of aliovalent lanthanide dopants in ceria catalysts and their effect on the surface electronic structure remains unclear. Here, we reveal the surface segregation of dopant cations and oxygen vacancies and observe bonding changes in lanthanum-doped ceria catalyst particle aggregates with sub-nanometer precision using a new model-based spectroscopic tomography approach. These findings refine our understanding of the spatially varying electronic structure and bonding in ceria-based nanoparticle aggregates with aliovalent cation concentrations and identify new strategies for advancing high efficiency doped ceria nano-catalysts.

Formation and composition of adsorbates on hydrophobic carbon surfaces from aqueous laccase-maltodextrin mixture suspension

NASA Astrophysics Data System (ADS)

Corrales Ureña, Yendry Regina; Lisboa-Filho, Paulo Noronha; Szardenings, Michael; Gätjen, Linda; Noeske, Paul-Ludwig Michael; Rischka, Klaus

2016-11-01

A robust procedure for the surface bio-functionalization of carbon surfaces was developed. It consists on the modification of carbon materials in contact with an aqueous suspension of the enzyme laccase from Trametes versicolor and the lyophilization agent maltodextrin, with the pH value adjusted close to the isoelectric point of the enzyme. We report in-situ investigations applying Quartz Crystal Microbalance with Dissipation (QCM-D) for carbon-coated sensor surfaces and, moreover, ex-situ measurements with static contact angle measurements, X-ray Photoelectron Spectroscopy (XPS) and Scanning Force Microscopy (SFM) for smooth Highly Oriented Pyrolytic Graphite (HOPG) substrates, for contact times between the enzyme formulation and the carbon material surface ranging from 20 s to 24 h. QCM-D studies reveals the formation of rigid layer of biomaterial, a few nanometers thin, which shows a strongly improved wettability of the substrate surface upon contact angle measurements. Following spectroscopic characterization, these layers are composed of mixtures of laccase and maltodextrin. The formation of these adsorbates is attributed to attractive interactions between laccase, the maltodextrin-based lyophilization agent and the hydrophobic carbon surfaces; a short-term contact between the aqueous laccase mixture suspension and HOPG surfaces is shown to merely result in de-wetting patterns influencing the results of contact angle measurements. The new enzyme-based surface modification of carbon-based materials is suggested to be applicable for the improvement of not only the wettability of low energy substrate surfaces with fluid formulations like coatings or adhesives, but also their adhesion in contact with hardened polymers.

Nanogeochemistry: Size-dependent mineral-fluid interface chemistry

NASA Astrophysics Data System (ADS)

Wang, Y.

2012-12-01

Nanostructures and nanometer mineral phases, both widely present in geologic materials, can potentially affect many geochemical processes. It is known that at nanometer scales a material tends to exhibit chemical properties distinct from the corresponding bulk phase. Understanding of this size-dependent property change will help us to bridge the existing knowledge gap between the molecular level understanding and the macro-scale laboratory/field observations of a geochemical process. In this presentation, I will review of the recent progresses in nanoscience and provide a perspective on how these progresses can potentially impact geochemical studies. My presentation will be focused the following areas: (1) the characterization of nanostructures in natural systems, (2) the study of fluids and chemical species in nanoconfinement, (3) the effects of nanopores on geochemical reaction and mass transfers, and (4) the use nanostructured materials for environmental management. I will demonstrate that the nanopore confinement can significantly modify geochemical reactions in porous geologic media. As the pore size is reduced to a few nanometers, the difference between surface acidity constants of a mineral (pK2 - pK1) decreases, giving rise to a higher surface charge density on a nanopore surface than that on an unconfined mineral-water interface. The change in surface acidity constants results in a shift of ion sorption edges and enhances ion sorption on nanopore surfaces. This effect causes preferential enrichment of trace elements in nanopores. I will then discuss the implications of this emergent nanometer-scale property to radionuclide transport and carbon dioxide storage in geologic media. This work was performed at Sandia National Laboratories, which is a multiprogram laboratory operated by Sandia Corporation, a Lockheed-Martin Company, for the DOE under contract DE-AC04-94AL8500.

Mercury's Weather-Beaten Surface: Understanding Mercury in the Context of Lunar and Asteroidal Space Weathering Studies

NASA Technical Reports Server (NTRS)

Domingue, Deborah L.; Chapman, Clark. R.; Killen, Rosemary M.; Zurbuchen, Thomas H.; Gilbert, Jason A.; Sarantos, Menelaos; Benna, Mehdi; Slavin, James A.; Schriver, David; Travnicek, Pavel M.;

Copper-assisted, anti-reflection etching of silicon surfaces

DOEpatents

Toor, Fatima; Branz, Howard

2014-08-26

A method (300) for etching a silicon surface (116) to reduce reflectivity. The method (300) includes electroless deposition of copper nanoparticles about 20 nanometers in size on the silicon surface (116), with a particle-to-particle spacing of 3 to 8 nanometers. The method (300) includes positioning (310) the substrate (112) with a silicon surface (116) into a vessel (122). The vessel (122) is filled (340) with a volume of an etching solution (124) so as to cover the silicon surface (116). The etching solution (124) includes an oxidant-etchant solution (146), e.g., an aqueous solution of hydrofluoric acid and hydrogen peroxide. The silicon surface (116) is etched (350) by agitating the etching solution (124) with, for example, ultrasonic agitation, and the etching may include heating (360) the etching solution (124) and directing light (365) onto the silicon surface (116). During the etching, copper nanoparticles enhance or drive the etching process.

The nanofluidic confinement apparatus: studying confinement-dependent nanoparticle behavior and diffusion

PubMed Central

Fringes, Stefan; Holzner, Felix

2018-01-01

The behavior of nanoparticles under nanofluidic confinement depends strongly on their distance to the confining walls; however, a measurement in which the gap distance is varied is challenging. Here, we present a versatile setup for investigating the behavior of nanoparticles as a function of the gap distance, which is controlled to the nanometer. The setup is designed as an open system that operates with a small amount of dispersion of ≈20 μL, permits the use of coated and patterned samples and allows high-numerical-aperture microscopy access. Using the tool, we measure the vertical position (termed height) and the lateral diffusion of 60 nm, charged, Au nanospheres as a function of confinement between a glass surface and a polymer surface. Interferometric scattering detection provides an effective particle illumination time of less than 30 μs, which results in lateral and vertical position detection accuracy ≈10 nm for diffusing particles. We found the height of the particles to be consistently above that of the gap center, corresponding to a higher charge on the polymer substrate. In terms of diffusion, we found a strong monotonic decay of the diffusion constant with decreasing gap distance. This result cannot be explained by hydrodynamic effects, including the asymmetric vertical position of the particles in the gap. Instead we attribute it to an electroviscous effect. For strong confinement of less than 120 nm gap distance, we detect the onset of subdiffusion, which can be correlated to the motion of the particles along high-gap-distance paths. PMID:29441273

Universal method for creating optically active nanostructures on layered materials

NASA Astrophysics Data System (ADS)

Kidd, Tim; He, Rui; Stollenwerk, Andrew; Oshea, Aaron; Beck, Ben; Spurgeon, Kyle; Gu, Genda

2014-03-01

We report a new method for the creating of nanostructures using a scanning electron microscope. Residual organic molecules on the surface of layered materials can be excited by electron beam radiation to burrow into the open spaces between the layers of these materials, and then are broken down further to form photoluminescent carbon nanoclusters. Surface characterization by atomic force microscopy shows the surface is nearly undamaged at the molecular level by this process, and a lack of nanostructure formation in non-layered materials confirms that the structures are created by sub-surface incorporation. The presence of carbon nanoclusters was determined by Raman Spectroscopy and photoluminescence in the visible light range. The nanostructures are react strongly to visible light, making them readily apparent using an optical microscope even for features measuring only a few nanometers tall. This technique can be used on apparently any layered material, with successful results on dichalcogenides, topological insulators, graphite, and high temperature copper oxide superconductors. This technique can create patterned nanostructures with vertical resolution at the nanometer scale and lateral resolution of tens of nanometers depending on beam spot size. This work is funded by University of Northern Iowa, NSF #DMR-1206530, and DOE #DE-AC02-98CH10886.

Molecular simulation of dispersion and mechanical stability of organically modified layered silicates in polymer matrices

NASA Astrophysics Data System (ADS)

Fu, Yao-Tsung

The experimental analysis of nanometer-scale separation processes and mechanical properties at buried interfaces in nanocomposites has remained difficult. We have employed molecular dynamics simulation in relation to available experimental data to alleviate such limitations and gain insight into the dispersion and mechanical stability of organically modified layered silicates in hydrophobic polymer matrices. We analyzed cleavage energies of various organically modified silicates as a function of the cation exchange capacity, surfactant head group chemistry, and chain length using MD simulations with the PCFF-PHYLLOSILICATE force field. The range of the cleavage energy is between 25 and 210 mJ/m2 upon the molecular structures and packing of surfactants. As a function of chain length, the cleavage energy indicates local minima for interlayer structures comprised of loosely packed layers of alkyl chains and local maxima for interlayer structures comprised of densely packed layers of alkyl chains between the layers. In addition, the distribution of cationic head groups between the layers in the equilibrium state determines whether large increases in cleavage energy due to Coulomb attraction. We have also examined mechanical bending and failure mechanisms of layered silicates on the nanometer scale using molecular dynamics simulation in comparison to a library of TEM data of polymer nanocomposites. We investigated the energy of single clay lamellae as a function of bending radius and different cation density. The layer energy increases particularly for bending radii below 20 nm and is largely independent of cation exchange capacity. The analysis of TEM images of agglomerated and exfoliated aluminosilicates of different CEC in polymer matrices at small volume fractions showed bending radii in excess of 100 nm due to free volumes in the polymer matrix. At a volume fraction >5%, however, bent clay layers were found with bending radii <20 nm and kinks as a failure mechanism in good agreement with simulation results. We have examined thermal conductivity of organically modified layered silicates using molecular dynamics simulation in comparison to experimental results by laser measurement. The thermal conductivity slightly increased from 0.08 to 0.14 Wm-1K-1 with increasing chain length, related to the gallery spacing and interlayer density of the organic material.

Dendronized Polymers: Synthesis, Characterization, Assembly at Interfaces, and Manipulation.

PubMed

Schlüter; Rabe

2000-03-01

Dendrimers are presently one of the most intensely studied classes of compounds because of their unusual structure. They can be described as a jungle of entangled branches traversed by winding trails which lead to sweet fruits and bright blossoms. On these trails one can reach the thicket's interior as well as find a way out. Expressed less lyrically, this thicket stands for regularly branched, densely packed structures, and the trails represent voids and channels not filled by bent back branches but by solvent. The fruit and blossoms are photochemically, electrochemically, or synthetically addressable units, catalytically active sites, etc., and the back and forth on the trails stands for transport processes. In a mathematical sense dendrimers are enveloped by an interface, which defines what is either in or out. This interface is shaped like a sphere if the trails are filled to bursting. Otherwise dendrimers are more flattened like amoeba, especially if in contact with a surface. The high density of the functional groups, the expansion of these compounds to a range of several nanometers, the existence of usable "surface" and transport possibilities in and with them have made dendrimers interesting candidates for many applications. This review describes how dendrimer construction and polymer synthesis were combined and used to move from fully or flattened spherical shapes to cylindrical ones. The shape-inducing influence of dendritic substituents can be driven to create nanoobjects with a cylindrical shape, which not only considerably widens the range of applications for the dendrimer class but also opens up new perspectives for supramolecular and polymer chemistry. Because of the sheer size of the described objects and complexity of shape-related properties, research in this area must necessarily be interdisciplinary. This article tries to mirror this by giving special attention not only to synthesis but also the characterization and behavior of these compounds in bulk and at interfaces. Furthermore, potential application fields are described.

Surface characterization and free thyroid hormones response of chemically modified poly(ethylene terephthalate) blood collection tubes

NASA Astrophysics Data System (ADS)

Jalali Dil, Ebrahim; Kim, Samuel C.; Saffar, Amir; Ajji, Abdellah; Zare, Richard N.; Sattayapiwat, Annie; Esguerra, Vanessa; Bowen, Raffick A. R.

2018-06-01

The surface chemistry and surface energy of chemically modified polyethylene terephthalate (PET) blood collection tubes (BCTs) were studied and the results showed a significant increase in hydrophilicity and polarity of modified PET surface. The surface modification created nanometer-sized, needle-like asperities through molecular segregation at the surface. The surface dynamics of the modified PET was examined by tracking its surface properties over a 280-day period. The results showed surface rearrangement toward a surface with lower surface energy and fewer nanometer-sized asperities. Thromboelastography (TEG) was used to evaluate and compare the thrombogenicity of the inner walls of various types of BCTs. The TEG tracings and data from various types of BCTs demonstrated differences in the reactionand coagulation times but not in clot strength. The performance of the modified tubes in free triiodothyronine (FT3) and free thyroxine (FT4) hormone tests was examined, and it was found that the interference of modified PET tubes was negligible compared to that of commercially available PET BCTs.

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

Hu, Michael Z.; Engtrakul, Chaiwat; Bischoff, Brian L.

A new class of inorganic-based membranes, i.e., High-Performance Architectured Surface Selective (HiPAS) membranes, is introduced to provide high perm-selective flux by exploiting unique separation mechanisms induced by superhydrophobic or superhydrophilic surface interactions and confined capillary condensation in enlarged membrane pores (~8 nm). The super-hydro-tunable HiPAS membranes were originally developed for the purpose of bio-oil/biofuel processing to achieve selective separations at higher flux relative to size selective porous membranes (e.g., inorganic zeolite-based membranes) and better high-temperature tolerance than polymer membranes (>250 C) for hot vapor processing. Due to surface-enhanced separation selectivity, HiPAS membranes can thus possibly enable larger pores to facilitatemore » large-flux separations by increasing from sub-nanometer pores to mesopores (2-50 nm) for vapor phase or micron-scale pores for liquid phase separations. In this paper, we describe an innovative membrane concept and a materials synthesis strategy to fabricate HiPAS membranes, and demonstrate selective permeation in both vapor- and liquid-phase applications. High permeability and selectivity were demonstrated using surrogate mixtures, such as ethanol-water, toluene-water, and toluene-phenol-water. The overall membrane evaluation results show promise for the future processing of biomass pyrolysis and upgraded product vapors and condensed liquid bio-oil intermediates.« less

Preparation of high-strength nanometer scale twinned coating and foil

DOEpatents

Zhang, Xinghang [Los Alamos, NM; Misra, Amit [Los Alamos, NM; Nastasi, Michael A [Santa Fe, NM; Hoagland, Richard G [Santa Fe, NM

2006-07-18

Very high strength single phase stainless steel coating has been prepared by magnetron sputtering onto a substrate. The coating has a unique microstructure of nanometer spaced twins that are parallel to each other and to the substrate surface. For cases where the coating and substrate do not bind strongly, the coating can be peeled off to provide foil.

Substrate comprising a nanometer-scale projection array

DOEpatents

Cui, Yi; Zhu, Jia; Hsu, Ching-Mei; Connor, Stephen T; Yu, Zongfu; Fan, Shanhui; Burkhard, George

2012-11-27

A method for forming a substrate comprising nanometer-scale pillars or cones that project from the surface of the substrate is disclosed. The method enables control over physical characteristics of the projections including diameter, sidewall angle, and tip shape. The method further enables control over the arrangement of the projections including characteristics such as center-to-center spacing and separation distance.

The composition of phobos: evidence for carbonaceous chondrite surface from spectral analysis.

PubMed

Pang, K D; Pollack, J B; Veverka, J; Lane, A L; Ajello, J M

1978-01-06

A reflectance spectrum of Phobos (from 200 to 1100 nanometers) has been compiled from the Mariner 9 ultraviolet spectrometer, Viking lander imaging, and ground-based photometric data. The reflectance of the martian satellite is approximately constant at 5 percent from 1100 to 400 nanometers but drops sharply below 400 nanometers, reaching a value of 1 percent at 200 nanometers. The spectral albedo of Phobos bears a striking resemblance to that of asteroids (1) Ceres and (2) Pallas. Comparison of the reflectance spectra of asteroids with those of meteorites has shown that the spectral signature of Ceres is indicative of a carbonaceous chondritic composition. A physical explanation of how the compositional information is imposed on the reflectance spectrum is given. On the basis of a good match between the reflectance spectra of Phobos and Ceres and the extensive research that has been done to infer the composition of Ceres, it seems reasonable to believe that the surface composition of Phobos is similar to that of carbonaceous chondrites. This suggestion is consistent with the recently determined low density of Mars's inner satellite. Our result and recent Viking noble gas measurements suggest different modes of origin for Mars and Phobos.

An investigation of the effect of processing conditions on the lamellar and spherulitic morphology of polyhydroxyalkanoates

NASA Astrophysics Data System (ADS)

Xie, Yuping; Akpalu, Yvonne A.

2007-03-01

Polyhydroxyalkanoates (PHAs) have recently attracted much interest because of their biodegradability and biocompatibility. Since the ultimate properties of polymers can be controlled by processing conditions, particularly cooling rates, the systematic and thorough understanding of the effects of cooling rates on the final morphology and the resulting mechanical properties of PHAs is necessary and important. In this presentation, the lamellar (tens of nanometers), fibrillar (several hundred nanometers) and spherulitic (˜μm) morphologies of poly (3-hydroxybutyric acid) (PHB) and the copolymer poly (3-hydroxybutyric acid-co-3-hydroxyvaleric acid) (PHBV) crystallized under different cooling rates were studied using small angle X-ray scattering, ultra small angle X-ray scattering, and polarized optical microscopy, respectively. The morphology was observed to depend strongly on cooling rate. The influence of cooling rate on the morphology and mechanical properties such as toughness, tensile strength and overall stress-strain behavior will be discussed.

Superhydrophobic and superhydrophilic surface-enhanced separation performance of porous inorganic membranes for biomass-to-biofuel conversion applications

DOE PAGES

Hu, Michael Z.; Engtrakul, Chaiwat; Bischoff, Brian L.; ...

2016-11-14

A new class of inorganic-based membranes, i.e., High-Performance Architectured Surface Selective (HiPAS) membranes, is introduced to provide high perm-selective flux by exploiting unique separation mechanisms induced by superhydrophobic or superhydrophilic surface interactions and confined capillary condensation in enlarged membrane pores (~8 nm). The super-hydro-tunable HiPAS membranes were originally developed for the purpose of bio-oil/biofuel processing to achieve selective separations at higher flux relative to size selective porous membranes (e.g., inorganic zeolite-based membranes) and better high-temperature tolerance than polymer membranes (>250 C) for hot vapor processing. Due to surface-enhanced separation selectivity, HiPAS membranes can thus possibly enable larger pores to facilitatemore » large-flux separations by increasing from sub-nanometer pores to mesopores (2-50 nm) for vapor phase or micron-scale pores for liquid phase separations. In this paper, we describe an innovative membrane concept and a materials synthesis strategy to fabricate HiPAS membranes, and demonstrate selective permeation in both vapor- and liquid-phase applications. High permeability and selectivity were demonstrated using surrogate mixtures, such as ethanol-water, toluene-water, and toluene-phenol-water. The overall membrane evaluation results show promise for the future processing of biomass pyrolysis and upgraded product vapors and condensed liquid bio-oil intermediates.« 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

Nanomaterials in Space: is the Future Granted?

NASA Astrophysics Data System (ADS)

Mircea, Chipara

The quantum effects of this confinement resulted in new or modified physical properties. Actually, these studies are extended from confined and patterned materials at the nanometer scale, to metamaterials (a new class of engineered nanocomposites) in which the role of interfaces, at nanometer scale, has a particular relevance. These researches resulted not only in new materials, but also in new devices and technologies. Smaller, lighter, better, and more efficient, are the blueprints of these new devices and technologies. Such features are of particular importance for space applications. patterned at nanometer scale and metamaterials) in space environments, by identifying several groups of problems: a). Dosimetry. The models for the range and deposited energy in a target assume that the target is infinite. The effect of the confinement at the nanometer scale is not considered. Accordingly, microdosimetry concepts have to be developed and tested at such scales. Physicists faced analogous problems at the transition from macroscopic to microscopic properties, as for example in the case of magnetic calculations. The usual macroscopic approaches failed to give an accurate representation of magnetic properties in the case of nanowires, magnetic nanoclusters, ultrathin films and multilayers, and patterned magnetic materials at nanometer scale, resulting in the development of a new theoretical approach (micromagnetic calculations and modeling [1, 2]). The linear approximation (single event), frequently used to explain and model the effect of ionizing radiation on materials would become obsolete. There are several factors that would enhance the contribution of higher order effects. The first is due to the fact that the energy released by the incident particle within the target is delocalised over an area of 102 to 104 nm2. This is actually the size of the latent track within the target. For a nanopatterned structure this area is larger than the size of the feature. As a result, the energy deposited by the incident particle may be spreaded over several features, resulting in a cooperative irradiation effect. Analogous effects including significant departures from linearity were noticed in the degradation of polymers [3]. b). Radiation induced defects in nanomaterials. The effects of ionizing radiation on nanometer sized crystalline structures may be dramatic. This behavior is extremely simple taking into account that the incident particle may displace the target's nuclei, by producing lattice defects. For a macroscopic crystal consisting of a huge number of nuclei, such defects have usually a reduced weight and accordingly the structure of the target is not significantly affected. At nanometer scale, the number of nuclei is fairly low 102 to 106 and the relative weight of these processes in dramatically enhanced. It is possible to speculate that in space, the future nanomaterial is not a nanocrystal but rather a nano amorphous structure. In metamaterials or nanocomposites the nanometer sized interface is affected by several contributions as the displacement of the atoms from one side of the interface into the other side of the interface, the enhancement of the diffusion process within the interface due to the energy released as heat in the nanointerface by the incident particle, and even the appearance of new interfaces represented by cooperative nanometer sized defects, induced by the impinging particle. Such effects have been already reported in the case of irradiated copolymers and block copolymers [3]. c). Competition between several degradation processes. The space environment is not only a cocktail of ionizing particles. Several factors as temperature, thermal cycling, pressure, presence of atomic oxygen, UV-Vis or IR radiation compete with the ionizing radiation. A proper understanding of their effect as well as a detailed analysis of possible couplings between such processes is important. develop and test a new theory for the effects of radiation on solid targets, at the nanometer scale, to extend previous calculations in order to include higher order effects, and finally to understand and if it is possible to protect these nanometer sized structures or to design nanometer sized structures that are less significantly affected by the space environment. As a final warning, a recent paper [4] mentioned that the under the effect of ion beam bombardment the nanocrystalline zirconia has been transformed in an amorphous material. References: [1]. A. Aharoni, Introduction to the Theory of Ferromagnetism, Oxford University Press, Oxford, 1996. [2]. M. Chipara, R. Skomski, D. J. Sellmyer, J. Magn. Magn. Mat. to appear. [3]. Irradiation of Polymers: Fundamentals and Technological Applications, Edited by Roger L. Clough, S. W. Shalaby, [4] A. Meldrum, L. A. Boatner, R. C. Ewing, Phys. Rev. Lett, 88, 025503-1 (2002).

Patterned layers of adsorbed extracellular matrix proteins: influence on mammalian cell adhesion.

PubMed

Dupont-Gillain, C C; Alaerts, J A; Dewez, J L; Rouxhet, P G

2004-01-01

Three patterned systems aiming at the control of mammalian cell behavior are presented. The determinant feature common to these systems is the spatial distribution of extracellular matrix (ECM) proteins (mainly collagen) on polymer substrates. This distribution differs from one system to another with respect to the scale at which it is affected, from the supracellular to the supramolecular scale, and with respect to the way it is produced. In the first system, the surface of polystyrene was oxidized selectively to form micrometer-scale patterns, using photolithography. Adsorption of ECM proteins in presence of a competitor was enhanced on the oxidized domains, allowing selective cell adhesion to be achieved. In the second system, electron beam lithography was used to engrave grooves (depth and width approximately 1 microm) on a poly(methyl methacrylate) (PMMA) substratum. No modification of the surface chemistry associated to the created topography could be detected. Cell orientation along the grooves was only observed when collagen was preadsorbed on the substratum. In the third system, collagen adsorbed on PMMA was dried in conditions ensuring the formation of a nanometer-scale pattern. Cell adhesion was enhanced on such patterned collagen layers compared to smooth collagen layers.

Micro/Nanofibre Optical Sensors: Challenges and Prospects

PubMed Central

Tong, Limin

2018-01-01

Micro/nanofibres (MNFs) are optical fibres with diameters close to or below the vacuum wavelength of visible or near-infrared light. Due to its wavelength- or sub-wavelength scale diameter and relatively large index contrast between the core and cladding, an MNF can offer engineerable waveguiding properties including optical confinement, fractional evanescent fields and surface intensity, which is very attractive to optical sensing on the micro and nanometer scale. In particular, the waveguided low-loss tightly confined large fractional evanescent fields, enabled by atomic level surface roughness and extraordinary geometric and material uniformity in a glass MNF, is one of its most prominent merits in realizing optical sensing with high sensitivity and great versatility. Meanwhile, the mesoporous matrix and small diameter of a polymer MNF, make it an excellent host fibre for functional materials for fast-response optical sensing. In this tutorial, we first introduce the basics of MNF optics and MNF optical sensors, and review the progress and current status of this field. Then, we discuss challenges and prospects of MNF sensors to some extent, with several clues for future studies. Finally, we conclude with a brief outlook for MNF optical sensors.

The quintuple-shape memory effect in electrospun nanofiber membranes

NASA Astrophysics Data System (ADS)

Zhang, Fenghua; Zhang, Zhichun; Liu, Yanju; Lu, Haibao; Leng, Jinsong

2013-08-01

Shape memory fibrous membranes (SMFMs) are an emerging class of active polymers, which are capable of switching from a temporary shape to their permanent shape upon appropriate stimulation. Quintuple-shape memory membranes based on the thermoplastic polymer Nafion, with a stable fibrous structure, are achieved via electrospinning technology, and possess a broad transition temperature. The recovery of multiple temporary shapes of electrospun membranes can be triggered by heat in a single triple-, quadruple-, quintuple-shape memory cycle, respectively. The fiber morphology and nanometer size provide unprecedented design flexibility for the adjustable morphing effect. SMFMs enable complex deformations at need, having a wide potential application field including smart textiles, artificial intelligence robots, bio-medical engineering, aerospace technologies, etc in the future.

Deep ultraviolet scanning near-field optical microscopy for the structural analysis of organic and biological materials

NASA Astrophysics Data System (ADS)

Aoki, Hiroyuki; Hamamatsu, Toyohiro; Ito, Shinzaburo

2004-01-01

Scanning near-field optical microscopy (SNOM) using a deep ultraviolet (DUV) light source was developed for in situ imaging of a variety of chemical species without staining. Numerous kinds of chemical species have a carbon-carbon double bond or aromatic group in their chemical structure, which can be excited at the wavelength below 300 nm. In this study, the wavelength range available for SNOM imaging was extended to the DUV region. DUV-SNOM allowed the direct imaging of polymer thin films with high detection sensitivity and spatial resolution of several tens of nanometers. In addition to the polymer materials, we demonstrated the near-field imaging of a cell without using a fluorescence label.

Visualizing Chemical Interaction Dynamics of Confined DNA Molecules

NASA Astrophysics Data System (ADS)

Henkin, Gilead; Berard, Daniel; Stabile, Frank; Leslie, Sabrina

We present a novel nanofluidic approach to controllably introducing reagent molecules to interact with confined biopolymers and visualizing the reaction dynamics in real time. By dynamically deforming a flow cell using CLiC (Convex Lens-induced Confinement) microscopy, we are able to tune reaction chamber dimensions from micrometer to nanometer scales. We apply this gentle deformation to load and extend DNA polymers within embedded nanotopographies and visualize their interactions with other molecules in solution. Quantifying the change in configuration of polymers within embedded nanotopographies in response to binding/unbinding of reagent molecules provides new insights into their consequent change in physical properties. CLiC technology enables an ultra sensitive, massively parallel biochemical analysis platform which can acces a broader range of interaction parameters than existing devices.

How to Build a Bacterial Cell: MreB as the Foreman of E. coli Construction.

PubMed

Shi, Handuo; Bratton, Benjamin P; Gitai, Zemer; Huang, Kerwyn Casey

2018-03-08

Cell shape matters across the kingdoms of life, and cells have the remarkable capacity to define and maintain specific shapes and sizes. But how are the shapes of micron-sized cells determined from the coordinated activities of nanometer-sized proteins? Here, we review general principles that have surfaced through the study of rod-shaped bacterial growth. Imaging approaches have revealed that polymers of the actin homolog MreB play a central role. MreB both senses and changes cell shape, thereby generating a self-organizing feedback system for shape maintenance. At the molecular level, structural and computational studies indicate that MreB filaments exhibit tunable mechanical properties that explain their preference for certain geometries and orientations along the cylindrical cell body. We illustrate the regulatory landscape of rod-shape formation and the connectivity between cell shape, cell growth, and other aspects of cell physiology. These discoveries provide a framework for future investigations into the architecture and construction of microbes. Copyright © 2018 Elsevier Inc. All rights reserved.

Nanoscale analysis of degradation processes of cellulose fibers.

PubMed

Teodonio, Lorenzo; Missori, Mauro; Pawcenis, Dominika; Łojewska, Joanna; Valle, Francesco

2016-12-01

Mapping the morphological and nano-mechanical properties of cellulose fibers within paper sheets or textile products at the nano-scale level by using atomic force microscopy is a challenging task due to the huge surface level variation of these materials. However this task is fundamental for applications in forensic or cultural heritage sciences and for the industrial characterization of materials. In order to correlate between nano-mechanical properties and local nanometer scale morphology of different layers of cellulose fibers, a new strategy to prepare samples of isolated cellulose fibers was designed. This approach is based on immobilizing isolated fibers onto glass slides chemically pretreated so as to promote cellulose adhesion. The experiments presented here aim at the nano-scale characterization of fibers in paper samples aged under different external agents (relative humidity, temperature) in such a way as to promote hydrolysis and oxidation of polymers. The observed variability of local mechanical properties of paper fibers was related to varying degrees of cellulose polymerization induced by artificial aging. Copyright © 2016 Elsevier Ltd. All rights reserved.

Supramolecular polymerization of a prebiotic nucleoside provides insights into the creation of sequence-controlled polymers

DOE PAGES

Wang, Jun; Bonnesen, Peter V; Rangel, E.; ...

2016-01-04

The self-assembly of a nucleoside on Au(111) was studied to ascertain whether polymerization on well-defined substrates constitutes a promising approach for making sequence-controlled polymers. Scanning tunneling microscopy and density functional theory were used to investigate the self-assembly on Au(111) of (RS)-N9-(2,3-dihydroxypropyl)adenine (DHPA), a plausibly prebiotic nucleoside analog of adenosine. It is found that DHPA molecules self-assemble into a hydrogen-bonded polymer that grows almost exclusively along the herringbone reconstruction pattern, has a two component sequence that is repeated over hundreds of nanometers, and is erasable with electron-induced excitation. Although the sequence is simple, more complicated ones are envisioned if two ormore » more nucleoside types are combined. Because polymerization occurs on a substrate in a dry environment, the success of each combination can be gauged with high-resolution imaging and accurate modeling techniques. The resulting characteristics make nucleoside self-assembly on a substrate an attractive approach for designing sequence-controlled polymers. Moreover, by choosing plausibly prebiotic nucleosides, insights may be provided into how nature created the first sequence-controlled polymers capable of storing information. Such insights, in turn, can inspire new ways of synthesizing sequence-controlled polymers.« less

Supramolecular polymerization of a prebiotic nucleoside provides insights into the creation of sequence-controlled polymers

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

Wang, Jun; Bonnesen, Peter V; Rangel, E.

The self-assembly of a nucleoside on Au(111) was studied to ascertain whether polymerization on well-defined substrates constitutes a promising approach for making sequence-controlled polymers. Scanning tunneling microscopy and density functional theory were used to investigate the self-assembly on Au(111) of (RS)-N9-(2,3-dihydroxypropyl)adenine (DHPA), a plausibly prebiotic nucleoside analog of adenosine. It is found that DHPA molecules self-assemble into a hydrogen-bonded polymer that grows almost exclusively along the herringbone reconstruction pattern, has a two component sequence that is repeated over hundreds of nanometers, and is erasable with electron-induced excitation. Although the sequence is simple, more complicated ones are envisioned if two ormore » more nucleoside types are combined. Because polymerization occurs on a substrate in a dry environment, the success of each combination can be gauged with high-resolution imaging and accurate modeling techniques. The resulting characteristics make nucleoside self-assembly on a substrate an attractive approach for designing sequence-controlled polymers. Moreover, by choosing plausibly prebiotic nucleosides, insights may be provided into how nature created the first sequence-controlled polymers capable of storing information. Such insights, in turn, can inspire new ways of synthesizing sequence-controlled polymers.« less

Nanostructure enhanced ionic transport in fullerene reinforced solid polymer electrolytes.

PubMed

Sun, Che-Nan; Zawodzinski, Thomas A; Tenhaeff, Wyatt E; Ren, Fei; Keum, Jong Kahk; Bi, Sheng; Li, Dawen; Ahn, Suk-Kyun; Hong, Kunlun; Rondinone, Adam J; Carrillo, Jan-Michael Y; Do, Changwoo; Sumpter, Bobby G; Chen, Jihua

2015-03-28

Solid polymer electrolytes, such as polyethylene oxide (PEO) based systems, have the potential to replace liquid electrolytes in secondary lithium batteries with flexible, safe, and mechanically robust designs. Previously reported PEO nanocomposite electrolytes routinely use metal oxide nanoparticles that are often 5-10 nm in diameter or larger. The mechanism of those oxide particle-based polymer nanocomposite electrolytes is under debate and the ion transport performance of these systems is still to be improved. Herein we report a 6-fold ion conductivity enhancement in PEO/lithium bis(trifluoromethanesulfonyl) imide (LiTFSI)-based solid electrolytes upon the addition of fullerene derivatives. The observed conductivity improvement correlates with nanometer-scale fullerene crystallite formation, reduced crystallinities of both the (PEO)6:LiTFSI phase and pure PEO, as well as a significantly larger PEO free volume. This improved performance is further interpreted by enhanced decoupling between ion transport and polymer segmental motion, as well as optimized permittivity and conductivity in bulk and grain boundaries. This study suggests that nanoparticle induced morphological changes, in a system with fullerene nanoparticles and no Lewis acidic sites, play critical roles in their ion conductivity enhancement. The marriage of fullerene derivatives and solid polymer electrolytes opens up significant opportunities in designing next-generation solid polymer electrolytes with improved performance.

Tailor-Made Electrospun Multilayer Composite Polymer Electrolytes for High-Performance Lithium Polymer Batteries.

PubMed

Lim, Du-Hyun; Haridas, Anupriya K; Figerez, Stelbin Peter; Raghavan, Prasanth; Matic, Aleksandar; Ahn, Jou-Hyeon

2018-09-01

A novel tailor-made multilayer composite polymer electrolyte, consisting of two outer layers of electrospun polyacrylonitrile (PAN) and one inner layer of poly(vinyl acetate) (PVAc)/poly(methyl methacrylate) (PMMA)/poly(ethylene oxide) (PEO) fibrous membrane, was prepared using continuous electrospinning. These membranes, which are made up of fibers with diameters in the nanometer range, were stacked in layers to produce interconnected pores that result in a high porosity. Gel polymer electrolytes (GPEs) were prepared by entrapping a liquid electrolyte (1 M LiPF6 in ethylene carbonate/dimethyl carbonate) in the membranes. The composite membranes exhibited a high electrolyte uptake of 450-510%, coupled with an improved room temperature ionic conductivity of up to 4.72 mS cm-1 and a high electrochemical stability of 4.6 V versus Li/Li+. Electrochemical investigations of a composite membrane of PAN-PVAc-PAN, with a LiFePO4 cathode synthesized in-house, showed a high initial discharge capacity of 145 mAh g-1, which corresponds to 85% utilization of the active material, and displayed stable cycle performance.

Rind-Like Features at a Meridiani Outcrop

NASA Technical Reports Server (NTRS)

2005-01-01

After months spent roving across a sea of rippled sands, Opportunity reached an outcrop in August 2005 and began investigating exposures of sedimentary rocks, intriguing rind-like features that appear to cap the rocks, and cobbles that dot the martian surface locally. Opportunity spent several sols analyzing a feature called 'Lemon Rind,' a thin surface layer covering portions of outcrop rocks poking through the sand north of 'Erebus Crater.' In images from the panoramic camera, Lemon Rind appears slightly different in color than surrounding rocks. It also appears to be slightly more resistant to wind erosion than the outcrop's interior. To obtain information on how this surface layer (or weathering rind) may have formed and how it compares to previously analyzed outcrops, Opportunity is using the microscopic imager, alpha particle X-ray spectrometer and Moessbauer spectrometer to analyze surfaces that have been brushed and ground with the rock abrasion tool. Scientists will compare these measurements with similar measurements made on the underlying rock material.

This is a false-color composite generated by draping enhanced red-green-blue color from the panoramic camera's 753-nanometer, 535-nanometer and 482-nanometer filters over a high-fidelity violet, 432-nanometer-filter image. The image was acquired on martian day, or sol 552 (Aug. 13, 2005) around 11:55 a.m. local true solar time. In this representation, bright sulfur-bearing sedimentary rocks appear light tan to brown, depending on their degree of dust contamination, and small dark 'blueberries' and other much less dusty rock fragments appear as different shades of blue. Draping the color derived from the blue to near-infrared filters over the violet filter image results in a false color view with the sharpest color and morphology contrasts.

Cleanability evaluation of ceramic glazes with nanometer far-infrared materials using contact angle measurement.

PubMed

Wang, Lijuan; Liang, Jinsheng; Di, Xingfu; Tang, Qingguo

2014-05-01

The cleanability of easy-to-clean ceramic glazes doped with nanometer far-infrared materials was compared with that of some high-quality household ceramic glazes from the market. The cleanability was evaluated by the contact angle measurement using a sessile drop method with a Dataphysics OCA-30 contact angle analyzer. The results showed that the difference of contact angles of water on the glazes before soiling and after cleaning could be used as a parameter for evaluating the cleanability of the glazes. The relationship between cleanability and surface properties, such as surface free energy and surface topography, was investigated. The surface free energy of the samples and their components were calculated using van Oss acid-base approach. By measuring advancing and receding contact angles, the contact angle hysteresis of the ceramic glazes due to the surface topography was investigated. It was shown that the cleanability of ceramic glazes containing nanometer far-infrared materials (NFIM) is better than that of household ceramic glazes from market, due to a higher ratio of electron-acceptor parameter to electron-donor parameter, which led to the effect of water hydration as well as better hydrophilic property and increased smoothness. The contact angle measurement not only accurately evaluates the cleanability of the ceramic glazes, but also has a contribution to the study of cleanability theory. Moreover, this method is simple, convenient and less sample-consumption.

Growth of delta-doped layers on silicon CCD/S for enhanced ultraviolet response

NASA Technical Reports Server (NTRS)

Hoenk, Michael E. (Inventor); Grunthaner, Paula J. (Inventor); Grunthaner, Frank J. (Inventor); Terhune, Robert W. (Inventor); Hecht, Michael H. (Inventor)

1994-01-01

The backside surface potential well of a backside-illuminated CCD is confined to within about half a nanometer of the surface by using molecular beam epitaxy (MBE) to grow a delta-doped silicon layer on the back surface. Delta-doping in an MBE process is achieved by temporarily interrupting the evaporated silicon source during MBE growth without interrupting the evaporated p+ dopant source (e.g., boron). This produces an extremely sharp dopant profile in which the dopant is confined to only a few atomic layers, creating an electric field high enough to confine the backside surface potential well to within half a nanometer of the surface. Because the probability of UV-generated electrons being trapped by such a narrow potential well is low, the internal quantum efficiency of the CCD is nearly 100% throughout the UV wavelength range. Furthermore, the quantum efficiency is quite stable.

Spin coating and plasma process for 2.5D and hybrid 3D micro-resonators on multilayer polymers

NASA Astrophysics Data System (ADS)

Bêche, B.; Gaviot, E.; Godet, C.; Zebda, A.; Potel, A.; Barbe, J.; Camberlein, L.; Vié, V.; Panizza, P.; Loas, G.; Hamel, C.; Zyss, J.; Huby, N.

2009-05-01

We have designed and realized three integrated photonic families of micro-resonators (MR) on multilayer organic materials. Such so-called 2.5D-MR and 3D-MR structures show off radius values ranging from 40 to 200μm. Both first and second families are especially designed on organic multilayer materials and shaped as ring- and disk-MR organics structures arranged upon (and coupled with) a pair of SU8-organic waveguides. The third family is related to hybrid 3D-MR structures composed of spherical glass-MR coupled to organic waveguides by a Langmuir-Blodgett lipid film about three nanometers in thickness. At first, polymer spin coating, surface plasma treatment and selective UV-lithography processes have been developed to realize 2.5D photonic micro-resonators. Secondly, we have designed and characterized photonic-quadripoles made of 3D-glass-MR arranged upon a pair of SU8 waveguides. Such structures are defined by a 4-ports or 4-waveguides coupled by the spherical glass-MR. We have achieved an evanescent photonic coupling between the 3D-MR and the 4-ports structure. Spectral resonances have been measured for 4-whispering gallery-modes (WGM) into such 3D-structures respectively characterized by a 0.97 nm free spectral range (FSR) and a high quality Q-factor up to 4.104.

Effect of Surface Hydration on Antifouling Properties of Mixed Charged Polymers.

PubMed

Leng, Chuan; Huang, Hao; Zhang, Kexin; Hung, Hsiang-Chieh; Xu, Yao; Li, Yaoxin; Jiang, Shaoyi; Chen, Zhan

2018-05-07

Interfacial water structure on a polymer surface in water (or surface hydration) is related to the antifouling activity of the polymer. Zwitterionic polymer materials exhibit excellent antifouling activity due to their strong surface hydration. It was proposed to replace zwitterionic polymers using mixed charged polymers because it is much easier to prepare mixed charged polymer samples with much lower costs. In this study, using sum frequency generation (SFG) vibrational spectroscopy, we investigated interfacial water structures on mixed charged polymer surfaces in water, and how such structures change while exposing to salt solutions and protein solutions. The 1:1 mixed charged polymer exhibits excellent antifouling property while other mixed charged polymers with different ratios of the positive/negative charges do not. It was found that on the 1:1 mixed charged polymer surface, SFG water signal is dominated by the contribution of the strongly hydrogen bonded water molecules, indicating strong hydration of the polymer surface. The responses of the 1:1 mixed charged polymer surface to salt solutions are similar to those of zwitterionic polymers. Interestingly, exposure to high concentrations of salt solutions leads to stronger hydration of the 1:1 mixed charged polymer surface after replacing the salt solution with water. Protein molecules do not substantially perturb the interfacial water structure on the 1:1 mixed charged polymer surface and do not adsorb to the surface, showing that this mixed charged polymer is an excellent antifouling material.

Highly crystallized nanometer-sized zeolite a with large Cs adsorption capability for the decontamination of water.

PubMed

Torad, Nagy L; Naito, Masanobu; Tatami, Junichi; Endo, Akira; Leo, Sin-Yen; Ishihara, Shinsuke; Wu, Kevin C-W; Wakihara, Toru; Yamauchi, Yusuke

2014-03-01

Nanometer-sized zeolite A with a large cesium (Cs) uptake capability is prepared through a simple post-milling recrystallization method. This method is suitable for producing nanometer-sized zeolite in large scale, as additional organic compounds are not needed to control zeolite nucleation and crystal growth. Herein, we perform a quartz crystal microbalance (QCM) study to evaluate the uptake ability of Cs ions by zeolite, to the best of our knowledge, for the first time. In comparison to micrometer-sized zeolite A, nanometer-sized zeolite A can rapidly accommodate a larger amount of Cs ions into the zeolite crystal structure, owing to its high external surface area. Nanometer-sized zeolite is a promising candidate for the removal of radioactive Cs ions from polluted water. Our QCM study on Cs adsorption uptake behavior provides the information of adsorption kinetics (e.g., adsorption amounts and rates). This technique is applicable to other zeolites, which will be highly valuable for further consideration of radioactive Cs removal in the future. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Superhydrophilic TiO2 thin film by nanometer scale surface roughness and dangling bonds

NASA Astrophysics Data System (ADS)

Bharti, Bandna; Kumar, Santosh; Kumar, Rajesh

2016-02-01

A remarkable enhancement in the hydrophilic nature of titanium dioxide (TiO2) films is obtained by surface modification in DC-glow discharge plasma. Thin transparent TiO2 films were coated on glass substrate by sol-gel dip coating method, and exposed in DC-glow discharge plasma. The plasma exposed TiO2 film exhibited a significant change in its wetting property contact angle, which is a representative of wetting property, has reduced to considerable limits 3.02° and 1.85° from its initial value 54.40° and 48.82° for deionized water and ethylene glycol, respectively. It is elucidated that the hydrophilic property of plasma exposed TiO2 films dependent mainly upon nanometer scale surface roughness. Variation, from 4.6 nm to 19.8 nm, in the film surface roughness with exposure time was observed by atomic force microscopy (AFM). Analysis of variation in the values of contact angle and surface roughness with increasing plasma exposure time reveal that the surface roughness is the main factor which makes the modified TiO2 film superhydrophilic. However, a contribution of change in the surface states, to the hydrophilic property, is also observed for small values of the plasma exposure time. Based upon nanometer scale surface roughness and dangling bonds, a variation in the surface energy of TiO2 film from 49.38 to 88.92 mJ/m2 is also observed. X-ray photoelectron spectroscopy (XPS) results show change in the surface states of titanium and oxygen. The observed antifogging properties are the direct results of the development of the superhydrophilic wetting characteristics to TiO2 films.

Measuring the bending of asymmetric planar EAP structures

NASA Astrophysics Data System (ADS)

Weiss, Florian M.; Zhao, Xue; Thalmann, Peter; Deyhle, Hans; Urwyler, Prabitha; Kovacs, Gabor; Müller, Bert

2013-04-01

The geometric characterization of low-voltage dielectric electro-active polymer (EAP) structures, comprised of nanometer thickness but areas of square centimeters, for applications such as artificial sphincters requires methods with nanometer precision. Direct optical detection is usually restricted to sub-micrometer resolution because of the wavelength of the light applied. Therefore, we propose to take advantage of the cantilever bending system with optical readout revealing a sub-micrometer resolution at the deflection of the free end. It is demonstrated that this approach allows us to detect bending of rather conventional planar asymmetric, dielectric EAP-structures applying voltages well below 10 V. For this purpose, we built 100 μm-thin silicone films between 50 nm-thin silver layers on a 25 μm-thin polyetheretherketone (PEEK) substrate. The increase of the applied voltage in steps of 50 V until 1 kV resulted in a cantilever bending that exhibits only in restricted ranges the expected square dependence. The mean laser beam displacement on the detector corresponded to 6 nm per volt. The apparatus will therefore become a powerful mean to analyze and thereby improve low-voltage dielectric EAP-structures to realize nanometer-thin layers for stack actuators to be incorporated into artificial sphincter systems for treating severe urinary and fecal incontinence.

SnTe microcrystals: Surface cleaning of a topological crystalline insulator

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

Saghir, M., E-mail: M.Saghir@warwick.ac.uk, E-mail: G.Balakrishnan@warwick.ac.uk; Walker, M.; McConville, C. F.

Investigating nanometer and micron sized materials thought to exhibit topological surface properties that can present a challenge, as clean surfaces are a pre-requisite for band structure measurements when using nano-ARPES or laser-ARPES in ultra-high vacuum. This issue is exacerbated when dealing with nanometer or micron sized materials, which have been prepared ex-situ and so have been exposed to atmosphere. We present the findings of an XPS study where various cleaning methods have been employed to reduce the surface contamination and preserve the surface quality for surface sensitive measurements. Microcrystals of the topological crystalline insulator SnTe were grown ex-situ and transferredmore » into ultra high vacuum (UHV) before being treated with either atomic hydrogen, argon sputtering, annealing, or a combination of treatments. The samples were also characterised using the scanning electron microscopy, both before and after treatment. It was found that atomic hydrogen cleaning with an anneal cycle (200 °C) gave the best clean surface results.« less

Anodization: a promising nano-modification technique of titanium implants for orthopedic applications.

PubMed

Yao, Chang; Webster, Thomas J

2006-01-01

Anodization is a well-established surface modification technique that produces protective oxide layers on valve metals such as titanium. Many studies have used anodization to produce micro-porous titanium oxide films on implant surfaces for orthopedic applications. An additional hydrothermal treatment has also been used in conjunction with anodization to deposit hydroxyapatite on titanium surfaces; this is in contrast to using traditional plasma spray deposition techniques. Recently, the ability to create nanometer surface structures (e.g., nano-tubular) via anodization of titanium implants in fluorine solutions have intrigued investigators to fabricate nano-scale surface features that mimic the natural bone environment. This paper will present an overview of anodization techniques used to produce micro-porous titanium oxide structures and nano-tubular oxide structures, subsequent properties of these anodized titanium surfaces, and ultimately their in vitro as well as in vivo biological responses pertinent for orthopedic applications. Lastly, this review will emphasize why anodized titanium structures that have nanometer surface features enhance bone forming cell functions.

Influence of nanophase titania topography on bacterial attachment and metabolism

PubMed Central

Park, Margaret R; Banks, Michelle K; Applegate, Bruce; Webster, Thomas J

2008-01-01

Surfaces with nanophase compared to conventional (or nanometer smooth) topographies are known to have different properties of area, charge, and reactivity. Previously published research indicates that the attachment of certain bacteria (such as Pseudomonas fluorescens 5RL) is higher on surfaces with nanophase compared to conventional topographies, however, their effect on bacterial metabolism is unclear. Results presented here show that the adhesion of Pseudomonas fluorescens 5RL and Pseudomonas putida TVA8 was higher on nanophase than conventional titania. Importantly, in terms of metabolism, bacteria attached to the nanophase surfaces had higher bioluminescence rates than on the conventional surfaces under all nutrient conditions. Thus, the results from this study show greater select bacterial metabolism on nanometer than conventional topographies, critical results with strong consequences for the design of improved biosensors for bacteria detection. PMID:19337418

Remote optical sensing on the nanometer scale with a bowtie aperture nano-antenna on a fiber tip of scanning near-field optical microscopy

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

Atie, Elie M.; Xie, Zhihua; El Eter, Ali

2015-04-13

Plasmonic nano-antennas have proven the outstanding ability of sensing chemical and physical processes down to the nanometer scale. Sensing is usually achieved within the highly confined optical fields generated resonantly by the nano-antennas, i.e., in contact to the nanostructures. In this paper, we demonstrate the sensing capability of nano-antennas to their larger scale environment, well beyond their plasmonic confinement volume, leading to the concept of “remote” (non contact) sensing on the nanometer scale. On the basis of a bowtie-aperture nano-antenna (BNA) integrated at the apex of a SNOM (Scanning Near-field Optical Microscopy) fiber tip, we introduce an ultra-compact, moveable, andmore » background-free optical nanosensor for the remote sensing of a silicon surface (up to distance of 300 nm). Sensitivity of the BNA to its large scale environment is high enough to expect the monitoring and control of the spacing between the nano-antenna and a silicon surface with sub-nanometer accuracy. This work paves the way towards an alternative class of nanopositioning techniques, based on the monitoring of diffraction-free plasmon resonance, that are alternative to nanomechanical and diffraction-limited optical interference-based devices.« less

Surface Plasmon Damping Quantified with an Electron Nanoprobe

PubMed Central

Bosman, Michel; Ye, Enyi; Tan, Shu Fen; Nijhuis, Christian A.; Yang, Joel K. W.; Marty, Renaud; Mlayah, Adnen; Arbouet, Arnaud; Girard, Christian; Han, Ming-Yong

2013-01-01

Fabrication and synthesis of plasmonic structures is rapidly moving towards sub-nanometer accuracy in control over shape and inter-particle distance. This holds the promise for developing device components based on novel, non-classical electro-optical effects. Monochromated electron energy-loss spectroscopy (EELS) has in recent years demonstrated its value as a qualitative experimental technique in nano-optics and plasmonic due to its unprecedented spatial resolution. Here, we demonstrate that EELS can also be used quantitatively, to probe surface plasmon kinetics and damping in single nanostructures. Using this approach, we present from a large (>50) series of individual gold nanoparticles the plasmon Quality factors and the plasmon Dephasing times, as a function of energy/frequency. It is shown that the measured general trend applies to regular particle shapes (rods, spheres) as well as irregular shapes (dendritic, branched morphologies). The combination of direct sub-nanometer imaging with EELS-based plasmon damping analysis launches quantitative nanoplasmonics research into the sub-nanometer realm. PMID:23425921

The 4-meter lunar engineering telescope

NASA Technical Reports Server (NTRS)

Peacock, Keith; Giannini, Judith A.; Kilgus, Charles C.; Bely, Pierre Y.; May, B. Scott; Cooper, Shannon A.; Schlimm, Gerard H.; Sounder, Charles; Ormond, Karen; Cheek, Eric

1991-01-01

The 16-meter diffraction limited lunar telescope incorporates a primary mirror with 312 one-meter segments; 3 nanometer active optics surface control with laser metrology and hexapod positioners; a space frame structure with one-millimeter stability; and a hexapod mount for pointing. The design data needed to limit risk in this development can be obtained by building a smaller engineering telescope on the moon with all of the features of the 16-meter design. This paper presents a 4.33-meter engineering telescope concept developed by the Summer 1990 Student Program of the NASA/JHU Space Grant Consortium Lunar Telescope Project. The primary mirror, made up of 18 one-meter hexagonal segments, is sized to provide interesting science as well as engineering data. The optics are configured as a Ritchey-Chretien with a coude relay to the focal plane beneath the surface. The optical path is continuously monitored with 3-nanometer precision interferometrically. An active optics processor and piezoelectric actuators operate to maintain the end-to-end optical configuration established by wave front sensing using a guide star. The mirror segments, consisting of a one-centimeter thick faceplate on 30-cm deep ribs, maintain the surface figure to a few nanometers under lunar gravity and thermal environment.

Understanding batteries on the micro- and nanometer scale

ScienceCinema

None

2018-01-16

In order to understand performance limitations and failure mechanisms of batteries, one has to investigate processes on the micro- and nanometer scale. A typical failure mechanism in lithium metal batteries is dendritic growth. During discharge, lithium is stripped of the anode surface and migrates to the cathode. During charge, lithium is deposited back on the anode. Repeated cycling can result in stripping and re-deposition that roughens the surface. The roughening of the surface changes the electric field and draws more metal to spikes that are beginning to grow. These can grow with tremendous mechanical force, puncture the separator, and directly connect the anode with the cathode which can create an internal short circuit. This can lead to an uncontrolled discharge reaction, which heats the cell and causes additional exothermic reactions leading to what is called thermal runaway. ORNL has developed a new technology called liquid electron microscopy. In a specially designed sample holder micro-chamber with electron-transparent windows, researchers can hold a liquid and take images of structures and particles at nanometer size. It's the first microscope holder of its kind used to investigate the inside of a battery while cycled.

Paved Path for Opportunity

NASA Technical Reports Server (NTRS)

2006-01-01

As NASA's Mars Exploration Rover Opportunity continues a southward trek from 'Erebus Crater' toward 'Victoria Crater,' the terrain consists of large sand ripples and patches of flat-lying rock outcrops, as shown in this image. Whenever possible, rover planners keep Opportunity on the 'pavement' for best mobility.

This false-color image mosaic was assembled using images acquired by the panoramic camera on Opportunity's 784th sol (April 8, 2006) at about 11:45 a.m. local solar time. The camera used its 753-nanometer, 535-nanometer and 432-nanometer filters. This view shows a portion of the outcrop named 'Bosque,' including rover wheel tracks, fractured and finely-layered outcrop rocks and smaller, dark cobbles littered across the surface.

Accounting for nanometer-thick adventitious carbon contamination in X-ray absorption spectra of carbon-based materials.

PubMed

Mangolini, Filippo; McClimon, J Brandon; Rose, Franck; Carpick, Robert W

2014-12-16

Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy is a powerful technique for characterizing the composition and bonding state of nanoscale materials and the top few nanometers of bulk and thin film specimens. When coupled with imaging methods like photoemission electron microscopy, it enables chemical imaging of materials with nanometer-scale lateral spatial resolution. However, analysis of NEXAFS spectra is often performed under the assumption of structural and compositional homogeneity within the nanometer-scale depth probed by this technique. This assumption can introduce large errors when analyzing the vast majority of solid surfaces due to the presence of complex surface and near-surface structures such as oxides and contamination layers. An analytical methodology is presented for removing the contribution of these nanoscale overlayers from NEXAFS spectra of two-layered systems to provide a corrected photoabsorption spectrum of the substrate. This method relies on the subtraction of the NEXAFS spectrum of the overlayer adsorbed on a reference surface from the spectrum of the two-layer system under investigation, where the thickness of the overlayer is independently determined by X-ray photoelectron spectroscopy (XPS). This approach is applied to NEXAFS data acquired for one of the most challenging cases: air-exposed hard carbon-based materials with adventitious carbon contamination from ambient exposure. The contribution of the adventitious carbon was removed from the as-acquired spectra of ultrananocrystalline diamond (UNCD) and hydrogenated amorphous carbon (a-C:H) to determine the intrinsic photoabsorption NEXAFS spectra of these materials. The method alters the calculated fraction of sp(2)-hybridized carbon from 5 to 20% and reveals that the adventitious contamination can be described as a layer containing carbon and oxygen ([O]/[C] = 0.11 ± 0.02) with a thickness of 0.6 ± 0.2 nm and a fraction of sp(2)-bonded carbon of 0.19 ± 0.03. This method can be generally applied to the characterization of surfaces and interfaces in several research fields and technological applications.

A Solid-State Intrinsically Stretchable Polymer Solar Cell.

PubMed

Li, Lu; Liang, Jiajie; Gao, Huier; Li, Ying; Niu, Xiaofan; Zhu, Xiaodan; Xiong, Yan; Pei, Qibing

2017-11-22

An organic solar cell based on a bulk heterojunction of a conjugated polymer and a methanofullerene PC 61 BM or PC 71 BM exhibits a complex morphology that controls both its photovoltaic and mechanical compliance (flexibility and stretchability). Here, the donor-acceptor blend of poly(thieno[3,4-b]-thiophene/benzodithiophene) (PTB7) and PC 71 BM containing a small amount of diiodooctane (DIO) in the spin-casting solution is reported to exhibit elastic deformability. The blend comprises nanometer-size, nanocrystalline grains that are relatively uniformly distributed. Large external deformation is accommodated by relative sliding between the grains. Reorientation of the nanocrystallites and the global reorientation of the PTB7 polymer chain were observed along the stretching direction up to 100% strain, which was reversible as the blend was allowed to relax to 0% strain. The polymer solar cell based on PTB7:PC 71 BM:DIO with such reversible morphological changes exhibited a rubbery elasticity at room temperature. The device could be stretched up to 100% strain, and the power-conversion efficiency shows a slight increase up to 30% strain and a global increase of power generation as the photoactive area increases with strain. Solar cells were fabricated employing a layer of the PTB7:PC 71 BM:DIO blend sandwiched between a pair of stretchable transparent electrodes, each comprising a stack of a silver nanowire percolation network and a single-wall carbon nanotube network embedded in the surface of a poly(urethane acylate) elastomer film. The solar cells were semitransparent and could be stretched like a rubbery film by as much as 100% strain. The measured power-conversion efficiency was 3.48%, which was increased to 3.67% after one cycle of stretching to 50% strain and lowered to 2.99% after 100 stretching cycles. The total power generation from the cells was significantly increased, thanks to the expanded active area as the cells were stretched.

Nanotip Carpets as Antireflection Surfaces

NASA Technical Reports Server (NTRS)

Bae, Youngsam; Mobasser, Sohrab; Manohara, Harish; Lee, Choonsup

2008-01-01

Carpet-like random arrays of metal-coated silicon nanotips have been shown to be effective as antireflection surfaces. Now undergoing development for incorporation into Sun sensors that would provide guidance for robotic exploratory vehicles on Mars, nanotip carpets of this type could also have many uses on Earth as antireflection surfaces in instruments that handle or detect ultraviolet, visible, or infrared light. In the original Sun-sensor application, what is required is an array of 50-micron-diameter apertures on what is otherwise an opaque, minimally reflective surface, as needed to implement a miniature multiple-pinhole camera. The process for fabrication of an antireflection nanotip carpet for this application (see Figure 1) includes, and goes somewhat beyond, the process described in A New Process for Fabricating Random Silicon Nanotips (NPO-40123), NASA Tech Briefs, Vol. 28, No. 1 (November 2004), page 62. In the first step, which is not part of the previously reported process, photolithography is performed to deposit etch masks to define the 50-micron apertures on a silicon substrate. In the second step, which is part of the previously reported process, the non-masked silicon area between the apertures is subjected to reactive ion etching (RIE) under a special combination of conditions that results in the growth of fluorine-based compounds in randomly distributed formations, known in the art as "polymer RIE grass," that have dimensions of the order of microns. The polymer RIE grass formations serve as microscopic etch masks during the next step, in which deep reactive ion etching (DRIE) is performed. What remains after DRIE is the carpet of nano - tips, which are high-aspect-ratio peaks, the tips of which have radii of the order of nanometers. Next, the nanotip array is evaporatively coated with Cr/Au to enhance the absorption of light (more specifically, infrared light in the Sun-sensor application). The photoresist etch masks protecting the apertures are then removed by dipping the substrate into acetone. Finally, for the Sun-sensor application, the back surface of the substrate is coated with a 57-nm-thick layer of Cr for attenuation of sunlight.

One-pot biosynthesis of polymer-inorganic nanocomposites

NASA Astrophysics Data System (ADS)

Geng, Jiaqing; Yang, Dong; Zhu, Yong; Cao, Lichao; Jiang, Zhongyi; Sun, Yan

2011-06-01

A biological method is demonstrated to fabricate the polymer-inorganic nanocomposites (PINCs) utilizing bacterium as an efficient and versatile biofactory. Gluconacetobacter xylinum that can produce bacterial cellulose is incubated in the culture medium containing titanium or silica precursor. The PINCs can be acquired under the elaborate control of the culturing condition of G. xylinum, in which the formation of inorganic nanoparticles about several tens of nanometers in size synchronizes the fabrication of reticulated bacterial cellulose membrane composed of dense and finely branched nanofibers about 60-120 nm in diameter. The composition and chemical states, morphology, thermal stability of the inorganic nanoparticles, and nanocomposites were extensively characterized. A tentative mechanism for the formation of PINCs is proposed. It is hoped that this study may establish a generic platform toward facile and green synthesis of nanocomposite materials.

Nanopore detection of DNA molecules in crowded neutral polymer solutions

NASA Astrophysics Data System (ADS)

Sharma, Rajesh Kumar; Dai, Liang; Doyle, Patrick; Garaj, Slaven

Nanopore sensing is a precise technique for analysis of the structure and dynamics of individual biomolecules in different environments, and has even become a prominent technique for next-gen DNA sequencing. In the nanopore sensor, an individual DNA molecule is electrophoretically translocated through a single, nanometer-scaled pore in a solid-state membrane separating two chambers filled with electrolyte. The conformation of the molecule is deduced from modulations in the ionic current through the pore during the translocation event. Using nanopores, we investigated the dynamics of the DNA molecules in a crowded solution of neutral polymers of different sizes and concentrations. The translocation dynamics depends significantly on the size and concentration of the polymers, as different contributions to the electrophoretic and entropic forces on the DNA molecules come into play. This setup offers an excellent, tuneable model-system for probing biologically relevant questions regarding the behaviour of DNA molecules in highly confined and crowded environments. Singapore-MIT Alliance for Research and Technology.

Metal-organic framework nanosheets in polymer composite materials for gas separation

PubMed Central

Seoane, Beatriz; Miro, Hozanna; Corma, Avelino; Kapteijn, Freek; Llabrés i Xamena, Francesc X.; Gascon, Jorge

2014-01-01

Composites incorporating two-dimensional nanostructures within polymeric matrices hold potential as functional components for several technologies, including gas separation. Prospectively, employing metal-organic-frameworks (MOFs) as versatile nanofillers would notably broaden the scope of functionalities. However, synthesizing MOFs in the form of free standing nanosheets has proven challenging. We present a bottom-up synthesis strategy for dispersible copper 1,4-benzenedicarboxylate MOF lamellae of micrometer lateral dimensions and nanometer thickness. Incorporating MOF nanosheets into polymer matrices endows the resultant composites with outstanding CO2 separation performance from CO2/CH4 gas mixtures, together with an unusual and highly desired increment in the separation selectivity with pressure. As revealed by tomographic focused-ion-beam scanning-electron-microscopy, the unique separation behaviour stems from a superior occupation of the membrane cross-section by the MOF nanosheets as compared to isotropic crystals, which improves the efficiency of molecular discrimination and eliminates unselective permeation pathways. This approach opens the door to ultrathin MOF-polymer composites for various applications. PMID:25362353

Quadratic Electro-Optic Effect and Electroabsorption in a Novel Nano-Optical Material based on the Nonconjugated Conductive Polymer, Poly(ethylenepyrrolediyl) Derivative

NASA Astrophysics Data System (ADS)

Swamy, R.; Vippa, P.; Rajagopalan, H.; Titus, J.; Thakur, M.; Sen, A.

2005-03-01

We report quadratic electro-optic effect and electroabsorption measurements in a novel nano-optical material based on the nonconjugated conductive polymer, iodine-doped poly(ethylenepyrrolediyl) derivative. Such effect has been recently reported in doped polyisoprene [1]. The measurement was made at 633 nm using field-induced birefringence. A modulation of 0.1% was observed for a field of 0.66 V/micron (film thickness 0.3 micron). The change in refractive index, δn, is 3.35x10-4 and the Kerr constant is 1.2x10-9 m/V^2 which is about 125 times that of nitrobenzene. Modulation due to electroabsorption was 0.05%. The exceptionally large electro-optic effect is most likely due to the specific structure and quantum confinement within a nanometer volume. In contrast, nonlinearity in a conjugated polymer is known to decrease upon iodine doping. [1] Thakur, Swamy and Titus, Macromolecules, Vol.37, 2677, (2004).

Quadratic Electro-optic Effect in a Novel Nano-optical Polymer (iodine-doped polyisoprene)

NASA Astrophysics Data System (ADS)

Swamy, Rajendra; Titus, Jitto; Thakur, Mrinal

2004-03-01

In this report, exceptionally large quadratic electro-optic effect in a novel nano-optical polymer will be discussed. The material involved is cis-1,4-polyisoprene or natural rubber which is a nonconjugated conductive polymer[1,2].Upon doping with an acceptor such as iodine, an electron is transferred from its isolated double bond to the dopant leading to a charge-transfer complex. The positive charge (hole) thus created is localized around the double-bond site, within a nanometer dimension - thus, forming a nano-optical material. The quadratic electro-optic measurement on the doped polyisoprene film was made using field-induced birefringence method. The measured Kerr coefficient is about sixty six times that of nitrobenzene at 632 nm. Significant electroabsorption was also observed in this material at 632 nm. 1. M. Thakur, J. Macromol. Sci. - PAC, 2001, A38(12), 1337. 2. M. Thakur, S. Khatavkar and E.J. Parish, J. Macromol. Sci. - PAC, 2003, A40 (12), 1397.

Cellulose nanowhiskers and nanofibers from biomass for composite applications

NASA Astrophysics Data System (ADS)

Wang, Tao

2011-12-01

Biological nanocomposites such as plant cell wall exhibit high mechanical properties at a light weight. The secret of the rigidity and strength of the cell wall lies in its main structural component -- cellulose. Native cellulose exists as highly-ordered microfibrils, which are just a few nanometers wide and have been found to be stiffer than many synthetic fibers. In the quest for sustainable development around the world, using cellulose microfibrils from plant materials as renewable alternatives to conventional reinforcement materials such as glass fibers and carbon fibers is generating particular interest. In this research, by mechanical disintegration and by controlled chemical hydrolysis, both cellulose nanofibers and nanowhiskers were extracted from the cell wall of an agricultural waste, wheat straw. The reinforcement performances of the two nanofillers were then studied and compared using the water-soluble polyvinyl alcohol (PVOH) as a matrix material. It was found that while both of these nanofillers could impart higher stiffness to the polymer, the nanofibers from biomass were more effective in composite reinforcement than the cellulose crystals thanks to their large aspect ratio and their ability to form interconnected network structures through hydrogen bonding. One of the biggest challenges in the development of cellulose nanocomposites is achieving good dispersion. Because of the high density of hydroxyl groups on the surface of cellulose, it remains a difficult task to disperse cellulose nanofibers in many commonly used polymer matrices. The present work addresses this issue by developing a water-based route taking advantage of polymer colloidal suspensions. Combining cellulose nanofibers with one of the most important biopolymers, poly(lactic acid) (PLA), we have prepared nanocomposites with excellent fiber dispersion and improved modulus and strength. The bio-based nanocomposites have a great potential to serve as light-weight structural materials for automotive, medical, and other applications.

Comparison of roll-to-roll replication approaches for microfluidic and optical functions in lab-on-a-chip diagnostic devices

NASA Astrophysics Data System (ADS)

Brecher, Christian; Baum, Christoph; Bastuck, Thomas

2015-03-01

Economically advantageous microfabrication technologies for lab-on-a-chip diagnostic devices substituting commonly used glass etching or injection molding processes are one of the key enablers for the emerging market of microfluidic devices. On-site detection in fields of life sciences, point of care diagnostics and environmental analysis requires compact, disposable and highly functionalized systems. Roll-to-roll production as a high volume process has become the emerging fabrication technology for integrated, complex high technology products within recent years (e.g. fuel cells). Differently functionalized polymer films enable researchers to create a new generation of lab-on-a-chip devices by combining electronic, microfluidic and optical functions in multilayer architecture. For replication of microfluidic and optical functions via roll-to-roll production process competitive approaches are available. One of them is to imprint fluidic channels and optical structures of micro- or nanometer scale from embossing rollers into ultraviolet (UV) curable lacquers on polymer substrates. Depending on dimension, shape and quantity of those structures there are alternative manufacturing technologies for the embossing roller. Ultra-precise diamond turning, electroforming or casting polymer materials are used either for direct structuring or manufacturing of roller sleeves. Mastering methods are selected for application considering replication quality required and structure complexity. Criteria for the replication quality are surface roughness and contour accuracy. Structure complexity is evaluated by shapes producible (e.g. linear, circular) and aspect ratio. Costs for the mastering process and structure lifetime are major cost factors. The alternative replication approaches are introduced and analyzed corresponding to the criteria presented. Advantages and drawbacks of each technology are discussed and exemplary applications are presented.

Corona plasma modification of polyamide 66 for the design of textile delivery systems for cosmetic therapy

NASA Astrophysics Data System (ADS)

Labay, C.; Canal, J. M.; Navarro, A.; Canal, C.

2014-10-01

Cosmetic and medical applications of technical textiles are a research expanding field. One of the added values of these new materials would be that they are suitable to contain and release active ingredients in a controlled manner. The influence of the initial state of the surface of polyamide 6.6 (PA66) fibers on the wetting properties of the fibers as well as on the incorporation of caffeine on the fibers and on its release kinetics from the fibers has been investigated. Comparison between industrially-finished PA66 fabrics and laboratory washed fabrics has been done to carry out this study. Furthermore, surface modification of the PA66 fibers by low temperature plasma has been studied regarding the modification of the physical, chemical and topographical properties of the textile fibers. Corona plasma treatment has been investigated to achieve surface modification in the first nanometers of polymer fibers surface in order to modulate the incorporation and the release of caffeine. It has been demonstrated that both initial state of the PA66 surface and prior plasma treatment of the PA66 fibers before the active principle incorporation condition caffeine release kinetics from the textile fibers. The final release percentage increases linearly with the C-O and Cdbnd O functional groups incorporated by plasma on the surface. It has also been established that the release amounts of caffeine achieved after 8 h from the PA66 fabric are in the same order of magnitude than topical doses of commercial gel-based formulations.

Lithography-free glass surface modification by self-masking during dry etching

NASA Astrophysics Data System (ADS)

Hein, Eric; Fox, Dennis; Fouckhardt, Henning

2011-01-01

Glass surface morphologies with defined shapes and roughness are realized by a two-step lithography-free process: deposition of an ~10-nm-thin lithographically unstructured metallic layer onto the surface and reactive ion etching in an Ar/CF4 high-density plasma. Because of nucleation or coalescence, the metallic layer is laterally structured during its deposition. Its morphology exhibits islands with dimensions of several tens of nanometers. These metal spots cause a locally varying etch velocity of the glass substrate, which results in surface structuring. The glass surface gets increasingly rougher with further etching. The mechanism of self-masking results in the formation of surface structures with typical heights and lateral dimensions of several hundred nanometers. Several metals, such as Ag, Al, Au, Cu, In, and Ni, can be employed as the sacrificial layer in this technology. Choice of the process parameters allows for a multitude of different glass roughness morphologies with individual defined and dosed optical scattering.

Melting behavior of nanometer sized gold isomers

NASA Astrophysics Data System (ADS)

Liu, H. B.; Ascencio, J. A.; Perez-Alvarez, M.; Yacaman, M. J.

2001-09-01

In the present work, the melting behavior of nanometer sized gold isomers was studied using a tight-binding potential with a second momentum approximation. The cases of cuboctahedra, icosahedra, Bagley decahedra, Marks decahedra and star-like decahedra were considered. We calculated the temperature dependence of the total energy and volume during melting and the melting point for different types and sizes of clusters. In addition, the structural evolutions of the nanosized clusters during the melting transition were monitored and revealed. It is found that the melting process has three characteristic time periods for the intermediate nanosized clusters. The whole process includes surface disordering and reordering, followed by surface melting and a final rapid overall melting. This is a new observation, which it is in contrast with previous reports where surface melting is the dominant step.

Microscopy of Analogs for Martian Dust and Soil

NASA Technical Reports Server (NTRS)

Anderson, M. A.; Pike, W. T.; Weitz, C. M.

1999-01-01

The upcoming Mars 2001 lander will carry an atomic force microscope (AFM) as part of the Mars Environmental Compatibility Assessment (MECA) payload. By operating in a tapping mode, the AFM is capable of sub-nanometer resolution in three dimensions and can distinguish between substances of different compositions by employing phase-contrast imaging. Phase imaging is an extension of tapping-mode AFM that provides nanometer-scale information about surface composition not revealed in the topography. Phase imaging maps the phase of the cantilever oscillation during the tapping mode scan, hence detecting variations in composition, adhesion, friction, and viscoelasticity. Because phase imaging highlights edges and is not affected by large-scale height differences, it provides for clearer observation of fine features, such as grain edges, which can be obscured by rough topography. To prepare for the Mars 01 mission, we are testing the AFM on a lunar soil and terrestrial basaltic glasses to determine the AFMOs ability to define particle shapes and sizes and grain-surface textures. The test materials include the Apollo 17 soil 79221, which is a mixture of agglutinates, impact and volcanic beads, and mare and highland rock and mineral fragments. The majority of the lunar soil particles are less than 100 microns in size, comparable to the sizes estimated for Martian dust. The terrestrial samples are millimeter size basaltic glasses collected on Black Pointe at Mono Lake, just north of the Long Valley caldera in California. The basaltic glass formed by a phreatomagmatic eruption 13,000 years ago beneath a glacier that covered the Mono Lake region. Because basaltic glass formed by reworking of pyroclastic deposits may represent a likely source for Martian dunes, these basaltic glass samples represent plausible analogs to the types of particles that may be studied in sand dunes by the 01 lander and rover. We have used the AFM to examine several different soil particles at various resolutions. The instrument has demonstrated the ability to identify parallel ridges characteristic of twinning on a 150-micron plagioclase feldspar particle. Extremely small (10-100 nanometer) adhering particles are visible on the surface of the feldspar grain, and appear elongate with smooth surfaces. Phase contrast imaging of the nanometer particles shows several compositions to be present. When the AFM was applied to a 100-micron glass spherule, it was possible to define an extremely smooth surface.E Also visible on the surface of the glass spherule were chains of 100-nanometer- and-smaller impact melt droplets. Additional information is contained in the original extended abstract.

Electrochemical depositing rGO-Ti-rGO heterogeneous substrates with higher thermal conductivity and heat transfer performance compared to pure Ti.

PubMed

Wang, Jing; Wang, Huatao; Zhang, Wenying; Yang, Xinyi; Wen, Guangwu; Wang, Yijie; Zhou, Weiwei

2017-02-17

Titanium (Ti) and its alloys are widely applied in many high strength, light weight applications, but their thermal conductivity is lower compared to that of other metals, which limits their further applications. In this paper, we demonstrated experimentally that rGO-Ti-rGO heterogeneous substrates with higher thermal conductivity, up to ∼38.8% higher than Ti, could be fabricated by electrochemical depositing rGO on their surface. The rGO layers are grown on the surface of Ti substrates, with appearance of bedclothes on the beds. The thickness of rGO layers is around 300-500 nm and around 600-1000 nm when deposited for 5 cycles and 10 cycles, respectively. According to the cooling experiment results, as-prepared Ti + rGO substrates can present excellent thermal conduction performance, and reduce the chip temperature close to 3.2 °C-13.1 °C lower than Ti alloy substrates with the heat flow density of 0.4-3.6 W cm -2 . Finally, the approach to electro-chemically deposit hundreds of nanometer rGO layers on the surface of Ti substrates can improve their thermal conductivity and heat transfer performance, which may have further application in the increasing thermal conduction of other metal-alloys, ceramics and polymers.

Temperature dependence of the structural relaxation time in equilibrium below the nominal T(g): results from freestanding polymer films.

PubMed

Ngai, K L; Capaccioli, Simone; Paluch, Marian; Prevosto, Daniele

2014-05-22

When the thickness is reduced to nanometer scale, freestanding high molecular weight polymer thin films undergo large reduction of degree of cooperativity and coupling parameter n in the Coupling Model (CM). The finite-size effect together with the surfaces with high mobility make the α-relaxation time of the polymer in nanoconfinement, τ(α)(nano)(T), much shorter than τ(α)(bulk)(T) in the bulk. The consequence is avoidance of vitrification at and below the bulk glass transition temperature, T(g)(bulk), on cooling, and the freestanding polymer thin film remains at thermodynamic equilibrium at temperatures below T(g)(bulk). Molecular dynamics simulations have shown that the specific volume of the freestanding film is the same as the bulk glass-former at equilibrium at the same temperatures. Extreme nanoconfinement renders total or almost total removal of cooperativity of the α-relaxation, and τ(α)(nano)(T) becomes the same or almost the same as the JG β-relaxation time τ(β)(bulk)(T) of the bulk glass-former at equilibrium and at temperatures below T(g)(bulk). Taking advantage of being able to obtain τ(β)(bulk)(T) at equilibrium density below T(g)(bulk) by extreme nanoconfinement of the freestanding films, and using the CM relation between τ(α)(bulk)(T) and τ(β)(bulk)(T), we conclude that the Vogel-Fulcher-Tammann-Hesse (VFTH) dependence of τ(α)(bulk)(T) cannot hold for glass-formers in equilibrium at temperatures significantly below T(g)(bulk). In addition, τ(α)(bulk)(T) does not diverge at the Vogel temperature, T₀, as suggested by the VFTH-dependence and predicted by some theories of glass transition. Instead, τ(α)(bulk)(T) of the glass-former at equilibrium has a much weaker temperature dependence than the VFTH-dependence at temperature below T(g)(bulk) and even below T₀. This conclusion from our analysis is consistent with the temperature dependence of τ(α)(bulk)(T) found experimentally in polymers aged long enough time to attain the equilibrium state at various temperatures below T(g)(bulk).

Helium Ion Microscopy (HIM) for the imaging of biological samples at sub-nanometer resolution

NASA Astrophysics Data System (ADS)

Joens, Matthew S.; Huynh, Chuong; Kasuboski, James M.; Ferranti, David; Sigal, Yury J.; Zeitvogel, Fabian; Obst, Martin; Burkhardt, Claus J.; Curran, Kevin P.; Chalasani, Sreekanth H.; Stern, Lewis A.; Goetze, Bernhard; Fitzpatrick, James A. J.

2013-12-01

Scanning Electron Microscopy (SEM) has long been the standard in imaging the sub-micrometer surface ultrastructure of both hard and soft materials. In the case of biological samples, it has provided great insights into their physical architecture. However, three of the fundamental challenges in the SEM imaging of soft materials are that of limited imaging resolution at high magnification, charging caused by the insulating properties of most biological samples and the loss of subtle surface features by heavy metal coating. These challenges have recently been overcome with the development of the Helium Ion Microscope (HIM), which boasts advances in charge reduction, minimized sample damage, high surface contrast without the need for metal coating, increased depth of field, and 5 angstrom imaging resolution. We demonstrate the advantages of HIM for imaging biological surfaces as well as compare and contrast the effects of sample preparation techniques and their consequences on sub-nanometer ultrastructure.

Helium Ion Microscopy (HIM) for the imaging of biological samples at sub-nanometer resolution.

PubMed

Joens, Matthew S; Huynh, Chuong; Kasuboski, James M; Ferranti, David; Sigal, Yury J; Zeitvogel, Fabian; Obst, Martin; Burkhardt, Claus J; Curran, Kevin P; Chalasani, Sreekanth H; Stern, Lewis A; Goetze, Bernhard; Fitzpatrick, James A J

2013-12-17

Scanning Electron Microscopy (SEM) has long been the standard in imaging the sub-micrometer surface ultrastructure of both hard and soft materials. In the case of biological samples, it has provided great insights into their physical architecture. However, three of the fundamental challenges in the SEM imaging of soft materials are that of limited imaging resolution at high magnification, charging caused by the insulating properties of most biological samples and the loss of subtle surface features by heavy metal coating. These challenges have recently been overcome with the development of the Helium Ion Microscope (HIM), which boasts advances in charge reduction, minimized sample damage, high surface contrast without the need for metal coating, increased depth of field, and 5 angstrom imaging resolution. We demonstrate the advantages of HIM for imaging biological surfaces as well as compare and contrast the effects of sample preparation techniques and their consequences on sub-nanometer ultrastructure.

Fluorescent Polymer-Single-Walled Carbon Nanotube Complexes with Charged and Noncharged Dendronized Perylene Bisimides for Bioimaging Studies.

PubMed

Huth, Katharina; Glaeske, Mareen; Achazi, Katharina; Gordeev, Georgy; Kumar, Shiv; Arenal, Raúl; Sharma, Sunil K; Adeli, Mohsen; Setaro, Antonio; Reich, Stephanie; Haag, Rainer

2018-06-05

Fluorescent nanomaterials are expected to revolutionize medical diagnostic, imaging, and therapeutic tools due to their superior optical and structural properties. Their inefficient water solubility, cell permeability, biodistribution, and high toxicity, however, limit the full potential of their application. To overcome these obstacles, a water-soluble, fluorescent, cytocompatible polymer-single-walled carbon nanotube (SWNT) complex is introduced for bioimaging applications. The supramolecular complex consists of an alkylated polymer conjugated with neutral hydroxylated or charged sulfated dendronized perylene bisimides (PBIs) and SWNTs as a general immobilization platform. The polymer backbone solubilizes the SWNTs, decorates them with fluorescent PBIs, and strongly improves their cytocompatibility by wrapping around the SWNT scaffold. In photophysical measurements and biological in vitro studies, sulfated complexes exhibit superior optical properties, cellular uptake, and intracellular staining over their hydroxylated analogs. A toxicity assay confirms the highly improved cytocompatibility of the polymer-wrapped SWNTs toward surfactant-solubilized SWNTs. In microscopy studies the complexes allow for the direct imaging of the SWNTs' cellular uptake via the PBI and SWNT emission using the 1st and 2nd optical window for bioimaging. These findings render the polymer-SWNT complexes with nanometer size, dual fluorescence, multiple charges, and high cytocompatibility as valuable systems for a broad range of fluorescence bioimaging studies. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Release of engineered nanomaterials from polymer nanocomposites: diffusion, dissolution, and desorption.

PubMed

Duncan, Timothy V; Pillai, Karthik

2015-01-14

Polymer nanocomposites-polymer-based materials that incorporate filler elements possessing at least one dimension in the nanometer range-are increasingly being developed for commercial applications ranging from building infrastructure to food packaging to biomedical devices and implants. Despite a wide range of intended applications, it is also important to understand the potential for exposure to these nanofillers, which could be released during routine use or abuse of these materials, so it can be determined whether they pose a risk to human health or the environment. This article is the first in a series of two that review the state of the science regarding the release of engineered nanomaterials (ENMs) from polymer nanocomposites. Two ENM release paradigms are considered in this series: the release of ENMs via passive diffusion, desorption, and dissolution into external liquid media and release of ENMs assisted by matrix degradation. The present article focuses primarily on the first paradigm and includes (1) an overview of basic interactions between polymers and liquid environments and a brief summary of diffusion physics as they apply to polymeric materials; (2) a summary of both experimental and theoretical methods to assess contaminant release (including ENMs) from polymers by diffusion, dissolution, and desorption; and (3) a thorough, critical review of the associated body of peer-reviewed literature on ENM release by these mechanisms. A short outlook section on knowledge gaps and future research needs is also provided.

SFG and AFM Studies of Polymer Surface Monolayers

NASA Astrophysics Data System (ADS)

Somorjai, Gabor A.

2003-03-01

Sum frequency generation vibrational spectroscopy and atomic force microscopy techniques were utilized to study the structure and composition of polymer surfaces ranging from polyethylene and polypropylene to copolymers of polyurethane and polystyrene. The surface methyl groups aligned perpendicular to the surface above the glass transition temperature of polypropylene. Large side groups such as the phenyl group on polystyrene is also near the surface normal at the polymer-air interface. At the air interface hydrophobic groups are dominant on the polymer surface while at solid-water interface hydrophilic groups segregate to the surface. Minimizing surface energy is the cause of readjusting the surface composition at polymer-water interfaces as compared to polymer-air interfaces. Upon stretching the soft component of two-component polymer systems segregates to the surface and both the surface structure and the surface composition undergo reversible or irreversible changes depending on the magnitude of the stretch. Since the heart beat forces bio-polymers to stretch over 40 million times a year the molecular behavior due to stretching has important physiological consequences.

Synthesis and applications of titania nanotubes: Drug delivery and ionomer composites

NASA Astrophysics Data System (ADS)

Kulkarni, Harsha Prabhakar

In this dissertation, the potential of a tubular form of titania (titanium dioxide) has been explored for two diverse applications, in the field of targeted drug delivery for medical applications and in the field of composite materials for structural applications. We introduce the tubular form of titania, a material well known for its catalytic properties. The tubes are synthesized by hydrothermal procedure and are nanometers in dimension, with an inside diameter of 5-6 nm, outside diameter of 10-12, and an aspect ratio of ˜100:1 (l:d), structures both chemically and thermally stable. Biocompatible titania nanotubes with large catalytic surface area are used as vehicles for carrying Doxorubicin, an anticancer chemotherapeutic drug, to explore its potential in targeted drug delivery. Optical properties of Doxorubicin are used to study adsorption and release of the drug molecule from the nanotube surface. Pilot experiments show strong adsorption of 4 wt% of doxorubicin on the nanotube surface characterized by the quenching of its absorption centered at 490 nm. Quinone and protonated amino groups on the drug molecule, involved in protonation and deprotonation with the surface hydroxyls and molecular water on the nanotube surface, are responsible for adsorption. Doxorubicin adsorbed on the nanotube surface show pH specific release, with 40% release at a physiological pH of 7.4 as compared to 4% and 10% at pH values of 3.4 and 5.7 respectively under sink conditions. In vitro cytotoxicity experiments, used to characterize the anticancer potential of the nanotube-drug conjugate, shows comparable toxicity for the conjugates as the free drug. Nanotubes with strong adsorption of doxorubicin, large surface area, pH controlled release, and effective toxicity, demonstrate its potential as a vehicle for targeted drug delivery. If nanotube-drug conjugates with reversible bonds between them, and a pH controlled release in an aqueous solution are promising for medical applications, nanotube-polymer conjugates with nanotubes as reinforcing structures in a polymer matrix with improved mechanical properties are equally promising for structural applications. Nanotubes are used as reinforcing structures in Surlyn, a polyethylene-co-methacrylic acid polymer containing ions. When cooled from the melt, Surlyn shows strong aging effects on mechanical properties over periods of several days to months. Structures in the matrix of the polymer which form with time are responsible for these aging effects on mechanical properties. Aging at short times after cooling from the melt reveal subtle contributions from these structures not fully formed and mechanical properties not fully recovered. Nanotubes are used as reinforcing structures to improve the mechanical properties at short aging times, a property desired for high temperature applications demanding a quick recovery of mechanical properties. A unique Atomic Force Microscope (AFM) based Local Thermal Analysis (LTA) probe is used to study the mechanical properties of Surlyn and Nanotube-Surlyn composite. Nanotube-Surlyn composites show superior mechanical properties at both short and long aging times after cooling from the melt, as the structures in the matrix continue to form at long aging times.

Driven polymer translocation in good and bad solvent: Effects of hydrodynamics and tension propagation.

PubMed

Moisio, J E; Piili, J; Linna, R P

2016-08-01

We investigate the driven polymer translocation through a nanometer-scale pore in the presence and absence of hydrodynamics both in good and bad solvent. We present our results on tension propagating along the polymer segment on the cis side that is measured for the first time using our method that works also in the presence of hydrodynamics. For simulations we use stochastic rotation dynamics, also called multiparticle collision dynamics. We find that in the good solvent the tension propagates very similarly whether hydrodynamics is included or not. Only the tensed segment is by a constant factor shorter in the presence of hydrodynamics. The shorter tensed segment and the hydrodynamic interactions contribute to a smaller friction for the translocating polymer when hydrodynamics is included, which shows as smaller waiting times and a smaller exponent in the scaling of the translocation time with the polymer length. In the bad solvent hydrodynamics has a minimal effect on polymer translocation, in contrast to the good solvent, where it speeds up translocation. We find that under bad-solvent conditions tension does not spread appreciably along the polymer. Consequently, translocation time does not scale with the polymer length. By measuring the effective friction in a setup where a polymer in free solvent is pulled by a constant force at the end, we find that hydrodynamics does speed up collective polymer motion in the bad solvent even more effectively than in the good solvent. However, hydrodynamics has a negligible effect on the motion of individual monomers within the highly correlated globular conformation on the cis side and hence on the entire driven translocation under bad-solvent conditions.

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.

Flow and evaporation in single micrometer and nanometer scale pipes

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

Velasco, A. E.; Yang, C.; Siwy, Z. S.

2014-07-21

We report measurements of pressure driven flow of fluids entering vacuum through a single pipe of micrometer or nanometer scale diameter. Nanopores were fabricated by etching a single ion track in polymer or mica foils. A calibrated mass spectrometer was used to measure the flow rates of nitrogen and helium through pipes with diameter ranging from 10 μm to 31 nm. The flow of gaseous and liquid nitrogen was studied near 77 K, while the flow of helium was studied from the lambda point (2.18 K) to above the critical point (5.2 K). Flow rates were controlled by changing the pressure drop across the pipemore » in the range 0–31 atm. When the pressure in the pipe reached the saturated vapor pressure, an abrupt flow transition was observed. A simple viscous flow model is used to determine the position of the liquid/vapor interface in the pipe. The observed mass flow rates are consistent with no slip boundary conditions.« less

A scanning tunneling microscope with a scanning range from hundreds of micrometers down to nanometer resolution.

PubMed

Kalkan, Fatih; Zaum, Christopher; Morgenstern, Karina

2012-10-01

A beetle type stage and a flexure scanning stage are combined to form a two stages scanning tunneling microscope (STM). It operates at room temperature in ultrahigh vacuum and is capable of scanning areas up to 300 μm × 450 μm down to resolution on the nanometer scale. This multi-scale STM has been designed and constructed in order to investigate prestructured metallic or semiconducting micro- and nano-structures in real space from atomic-sized structures up to the large-scale environment. The principle of the instrument is demonstrated on two different systems. Gallium nitride based micropillars demonstrate scan areas up to hundreds of micrometers; a Au(111) surface demonstrates nanometer resolution.

Mapping the layer count of few-layer hexagonal boron nitride at high lateral spatial resolutions

NASA Astrophysics Data System (ADS)

Mohsin, Ali; Cross, Nicholas G.; Liu, Lei; Watanabe, Kenji; Taniguchi, Takashi; Duscher, Gerd; Gu, Gong

2018-01-01

Layer count control and uniformity of two dimensional (2D) layered materials are critical to the investigation of their properties and to their electronic device applications, but methods to map 2D material layer count at nanometer-level lateral spatial resolutions have been lacking. Here, we demonstrate a method based on two complementary techniques widely available in transmission electron microscopes (TEMs) to map the layer count of multilayer hexagonal boron nitride (h-BN) films. The mass-thickness contrast in high-angle annular dark-field (HAADF) imaging in the scanning transmission electron microscope (STEM) mode allows for thickness determination in atomically clean regions with high spatial resolution (sub-nanometer), but is limited by surface contamination. To complement, another technique based on the boron K ionization edge in the electron energy loss spectroscopy spectrum (EELS) of h-BN is developed to quantify the layer count so that surface contamination does not cause an overestimate, albeit at a lower spatial resolution (nanometers). The two techniques agree remarkably well in atomically clean regions with discrepancies within  ±1 layer. For the first time, the layer count uniformity on the scale of nanometers is quantified for a 2D material. The methodology is applicable to layer count mapping of other 2D layered materials, paving the way toward the synthesis of multilayer 2D materials with homogeneous layer count.

Electronic transport properties of nano-scale Si films: an ab initio study

NASA Astrophysics Data System (ADS)

Maassen, Jesse; Ke, Youqi; Zahid, Ferdows; Guo, Hong

2010-03-01

Using a recently developed first principles transport package, we study the electronic transport properties of Si films contacted to heavily doped n-type Si leads. The quantum transport analysis is carried out using density functional theory (DFT) combined with nonequilibrium Green's functions (NEGF). This particular combination of NEGF-DFT allows the investigation of Si films with thicknesses in the range of a few nanometers and lengths up to tens of nanometers. We calculate the conductance, the momentum resolved transmission, the potential profile and the screening length as a function of length, thickness, orientation and surface structure. Moreover, we compare the properties of Si films with and without a top surface passivation by hydrogen.

Controllable surface-plasmon resonance in engineered nanometer epitaxial silicide particles embedded in silicon

NASA Technical Reports Server (NTRS)

Fathauer, R. W.; Ksendzov, A.; Iannelli, J. M.; George, T.

1991-01-01

Epitaxial CoSi2 particles in a single-crystal silicon matrix are grown by molecular-beam epitaxy using a technique that allows nanometer control over particle size in three dimensions. These composite layers exhibit resonant absorption predicted by effective-medium theory. Selection of the height and diameter of disklike particles through a choice of growth conditions allows tailoring of the depolarization factor and hence of the surface-plasmon resonance energy. Resonant absorption from 0.49 to 1.04 eV (2.5 to 1.2 micron) is demonstrated and shown to agree well with values predicted by the Garnett (1904, 1906) theory using the bulk dielectric constants for CoSi2 and Si.

Theory for polymer analysis using nanopore-based single-molecule mass spectrometry

PubMed Central

Reiner, Joseph E.; Kasianowicz, John J.; Nablo, Brian J.; Robertson, Joseph W. F.

2010-01-01

Nanometer-scale pores have demonstrated potential for the electrical detection, quantification, and characterization of molecules for biomedical applications and the chemical analysis of polymers. Despite extensive research in the nanopore sensing field, there is a paucity of theoretical models that incorporate the interactions between chemicals (i.e., solute, solvent, analyte, and nanopore). Here, we develop a model that simultaneously describes both the current blockade depth and residence times caused by individual poly(ethylene glycol) (PEG) molecules in a single α-hemolysin ion channel. Modeling polymer-cation binding leads to a description of two significant effects: a reduction in the mobile cation concentration inside the pore and an increase in the affinity between the polymer and the pore. The model was used to estimate the free energy of formation for K+-PEG inside the nanopore (≈-49.7 meV) and the free energy of PEG partitioning into the nanopore (≈0.76 meV per ethylene glycol monomer). The results suggest that rational, physical models for the analysis of analyte-nanopore interactions will develop the full potential of nanopore-based sensing for chemical and biological applications. PMID:20566890

Sensitive SERS detection at the single-particle level based on nanometer-separated mushroom-shaped plasmonic dimers

NASA Astrophysics Data System (ADS)

Xiang, Quan; Li, Zhiqin; Zheng, Mengjie; Liu, Qing; Chen, Yiqin; Yang, Lan; Jiang, Tian; Duan, Huigao

2018-03-01

Elevated metallic nanostructures with nanogaps (<10 nm) possess advantages for surface enhanced Raman scattering (SERS) via the synergic effects of nanogaps and efficient decoupling from the substrate through an elevated three-dimensional (3D) design. In this work, we demonstrate a pattern-transfer-free process to reliably define elevated nanometer-separated mushroom-shaped dimers directly from 3D resist patterns based on the gap-narrowing effect during the metallic film deposition. By controlling the initial size of nanogaps in resist structures and the following deposited film thickness, metallic nanogaps could be tuned at the sub-10 nm scale with single-digit nanometer precision. Both experimental and simulated results revealed that gold dimer on mushroom-shaped pillars have the capability to achieve higher SERS enhancement factor comparing to those plasmonic dimers on cylindrical pillars or on a common SiO2/Si substrate, implying that the nanometer-gapped elevated dimer is an ideal platform to achieve the highest possible field enhancement for various plasmonic applications.

Farewell to Iapetus

NASA Image and Video Library

2017-09-18

Cassini bids farewell to Saturn's yin-and-yang moon, Iapetus. This image is from the last set of observations Cassini made of this world of striking contrasts. The spacecraft helped scientists better understand Iapetus, solving a centuries-old mystery of why it should be bright on one side and dark on the other. Cassini observations of Iapetus (914 mile or 1471 kilometers across) support the prevailing theory that led to the understanding that the dichotomy of the surface is due to a combination of infalling dust from outside of the moon followed by a migration of water ice from the darker (therefore warmer) areas to the cold, brighter surfaces. See PIA11690 for more details. This false-color view is a composite of individual frames obtained using filters sensitive to ultraviolet (centered at 338 nanometers), green (centered at 568 nanometers) and infrared light (centered at 930 nanometers). The view has been enhanced to accentuate subtle color differences and fine-scale surface features. This view looks toward the Saturn-facing hemisphere of Iapetus. North on Iapetus is up and rotated 12 degrees to the left. The view was acquired on May 30, 2017, at a distance of approximately 1.5 million miles (2.5 million kilometers) from Iapetus. Image scale is 9 miles (15 kilometers) per pixel. https://photojournal.jpl.nasa.gov/catalog/PIA21347

Thickness and surface roughness study of co-sputtered nanostructured alumina/tungsten (Al2O3/W) thin films

NASA Astrophysics Data System (ADS)

Naveen, A.; Krishnamurthy, L.; Shridhar, T. N.

2018-04-01

Tungsten (W) and Alumina (Al2O3) thin films have been developed using co-sputtering technique on SS304, Copper (Cu) and Glass slides using Direct Current magnetron sputtering (DC) and Radio Frequency (RF) magnetron sputtering methods respectively. Central Composite Design (CCD) method approach has been adopted to determine the number of experimental plans for deposition and DC power, RF power and Argon gas flow rate have been input parameters, each at 5 levels for development of thin films. In this research paper, study has been carried out determine the optimized condition of deposition parameters for thickness and surface roughness of the thin films. Thickness and average Surface roughness in terms of nanometer (nm) have been characterized by thickness profilometer and atomic force microscopy respectively. The maximum and minimum average thickness observed to be 445 nm and 130 respectively. The optimum deposition condition for W/Al2O3 thin film growth was determined to be at 1000 watts of DC power and 800 watts of RF power, 20 minutes of deposition time, and almost 300 Standard Cubic Centimeter(SCCM) of Argon gas flow. It was observed that average roughness difference found to be less than one nanometer on SS substrate and one nanometer on copper approximately.

Understanding the effect of size and shape of gold nanomaterials on nanometal surface energy transfer.

PubMed

Rakshit, Soumyadipta; Moulik, Satya Priya; Bhattacharya, Subhash Chandra

2017-04-01

Gold Nanomaterials (GNMs) interact with fluorophores via electromagnetic coupling under excitation. In this particular work we carried out (to the best of our knowledge for the first time) a comprehensive study of systematic quenching of a blue emitter 2-Anthracene Sulfonate (2-AS) in the presence of gold nanoparticles of different size and shape. We synthesized gold nanomaterials of four different dimensions [nanoparticle (0D), nanorod (1D), nanotriangle (2D) and nanobipyramids (3D)] and realized the underlying effect on the emitting dipole in terms of steady and time resolved fluorescence. Nanometal Surface Energy Transfer (NSET) has already been proved to be the best long range spectroscopic ruler so far. Many attempts have been made to understand the interaction between a fluorescent molecule and gold nanomaterials. But not a single model can interpret alone the interaction phenomena. We have opted three different models to compare the experimental and theoretical data. Due to the presence of size dependent absorptivity and dielectric function, modified CPS-Kuhn model was proved to be the worthiest to comprehend variance of behavior of an emitting dipole in close proximity to nanometal surface by coupling with the image dipole of gold nanomaterials. Copyright © 2016 Elsevier Inc. All rights reserved.

Observing Optical Plasmons on a Single Nanometer Scale

PubMed Central

Cohen, Moshik; Shavit, Reuven; Zalevsky, Zeev

2014-01-01

The exceptional capability of plasmonic structures to confine light into deep subwavelength volumes has fashioned rapid expansion of interest from both fundamental and applicative perspectives. Surface plasmon nanophotonics enables to investigate light - matter interaction in deep nanoscale and harness electromagnetic and quantum properties of materials, thus opening pathways for tremendous potential applications. However, imaging optical plasmonic waves on a single nanometer scale is yet a substantial challenge mainly due to size and energy considerations. Here, for the first time, we use Kelvin Probe Force Microscopy (KPFM) under optical illumination to image and characterize plasmonic modes. We experimentally demonstrate unprecedented spatial resolution and measurement sensitivity both on the order of a single nanometer. By comparing experimentally obtained images with theoretical calculation results, we show that KPFM maps may provide valuable information on the phase of the optical near field. Additionally, we propose a theoretical model for the relation between surface plasmons and the material workfunction measured by KPFM. Our findings provide the path for using KPFM for high resolution measurements of optical plasmons, prompting the scientific frontier towards quantum plasmonic imaging on submolecular scales. PMID:24556874

Electrospraying and ultraviolet light curing of nanometer-thin polydimethylsiloxane membranes for low-voltage dielectric elastomer transducers

NASA Astrophysics Data System (ADS)

Osmani, Bekim; Töpper, Tino; Siketanc, Matej; Kovacs, Gabor M.; Müller, Bert

2017-04-01

Dielectric elastomer transducers (DETs) have attracted interest as actuators, sensors, and even as self-sensing actuators for applications in medicine, soft robotics, and microfluidics. To reach strains of more than 10 %, they currently require operating voltages of several hundred volts. In medical applications for artificial muscles, however, their operation is limited to a very few tens of volts, which implies high permittivity materials and thin-film structures. Such micro- or nanostructures can be prepared using electro-spraying, a cost-effective technique that allows upscaling using multiple nozzles for the fabrication of silicone films down to nanometer thickness. Deposition rates of several micrometers per hour have already been reached. It has been recently demonstrated that such membranes can be fabricated by electro-spraying and subsequent ultraviolet light irradiation. Herein, we introduce a relatively fast deposition of a dimethyl silicone copolymer fluid that contains mercaptopropyl side chains in addition to the methyl groups. Its elastic modulus was tuned with the irradiation dose of the 200 W Hg-Xe lamp. We also investigated the formation of elastomer films, using polymer concentrations in ethyl acetate of 1, 2, 5 and 10 vol%. After curing, the surface roughness was measured by means of atomic force microscopy. This instrument also enabled us to determine the average elastic modulus out of, for example, 400 nanoindentation measurements, using a spherical tip with a radius of 500 nm. The elastomer films were cured for a period of less than one minute, a speed that makes it feasible to combine electro-spraying and in situ curing in a single process step for fabricating low-voltage, multilayer DETs.

Fractography of glass at the nanometer scale

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

Guilloteau, E.; Arribart, H.; Creuzet, F.

1996-12-01

The authors present a nanometer scale description of the fracture surface of soda-lime glass. This is achieved by the use of Atomic Force Microscopy. The mirror zone is shown to be built with elementary entities, the density of which increases continuously while the mist and hackle zones are approached. Moreover, the overall picture leads to some kind of self-similarity, in the sense that small regions of the hackle zone exhibit the full set of mirror, mist and hackle areas.

pH-induced vesicle-to-micelle transition in amphiphilic diblock copolymer: investigation by energy transfer between in situ formed polymer embedded gold nanoparticles and fluorescent dye.

PubMed

Maiti, Chiranjit; Banerjee, Rakesh; Maiti, Saikat; Dhara, Dibakar

2015-01-01

The ability to regulate the formation of nanostructures through self-assembly of amphiphilic block copolymers is of immense significance in the field of biology and medicine. In this work, a new block copolymer synthesized by using reversible addition-fragmentation chain transfer (RAFT) polymerization technique from poly(ethylene glycol) monomethyl ether acrylate (PEGMA) and Boc-l-tryptophan acryloyloxyethyl ester (Boc-l-trp-HEA) was found to spontaneously form pH-responsive water-soluble nanostructures after removal of the Boc group. While polymer vesicles or polymerosomes were formed at physiological pH, the micelles were formed at acidic pH (< 5.2), and this facilitated a pH-induced reversible vesicle-to-micelle transition. Formation of these nanostructures was confirmed by different characterization techniques, viz. transmission electron microscopy, dynamic light scattering, and steady-state fluorescence measurements. Further, these vesicles were successfully utilized to reduce HAuCl4 and stabilize the resulting gold nanoparticles (AuNPs). These AuNPs, confined within the hydrophobic shell of the vesicles, could participate in energy transfer process with fluorescent dye molecules encapsulated in the core of the vesicles, thus forming a nanometal surface energy transfer (NSET) pair. Subsequently, following the efficiency of energy transfer between this pair, it was possible to monitor the process of transition from vesicles to micelles. Thus, in this work, we have successfully demonstrated that NSET can be used to follow the transition between nanostructures formed by amphiphilic block copolymers.

Polyurethane Ionophore-Based Thin Layer Membranes for Voltammetric Ion Activity Sensing.

PubMed

Cuartero, Maria; Crespo, Gaston A; Bakker, Eric

2016-06-07

We report on a plasticized polyurethane ionophore-based thin film material (of hundreds of nanometer thickness) for simultaneous voltammetric multianalyte ion activity detection triggered by the oxidation/reduction of an underlying poly(3-octylthiophene) film. This material provides excellent mechanical, physical, and chemical robustness compared to other polymers. Polyurethane films did not exhibit leaching of lipophilic additives after rinsing with a direct water jet and exhibited resistance to detachment from the underlying electrode surface, resulting in a voltammetric current response with less than <1.5% RSD variation (n = 50). In contrast, plasticized poly(vinyl chloride), polystyrene, and poly(acrylate) ionophore-based membranes of the same thickness and composition exhibited a significant deterioration of the signal after identical treatment. While previously reported works emphasized fundamental advancement of multi-ion detection with multi-ionophore-based thin films, polyurethane thin membranes allow one to achieve real world measurements without sacrificing analytical performance. Indeed, polyurethane membranes are demonstrated to be useful for the simultaneous determination of potassium and lithium in undiluted human serum and blood with attractive precision.

Magnetic assembly of nonmagnetic particles into photonic crystal structures.

PubMed

He, Le; Hu, Yongxing; Kim, Hyoki; Ge, Jianping; Kwon, Sunghoon; Yin, Yadong

2010-11-10

We report the rapid formation of photonic crystal structures by assembly of uniform nonmagnetic colloidal particles in ferrofluids using external magnetic fields. Magnetic manipulation of nonmagnetic particles with size down to a few hundred nanometers, suitable building blocks for producing photonic crystals with band gaps located in the visible regime, has been difficult due to their weak magnetic dipole moment. Increasing the dipole moment of magnetic holes has been limited by the instability of ferrofluids toward aggregation at high concentration or under strong magnetic field. By taking advantage of the superior stability of highly surface-charged magnetite nanocrystal-based ferrofluids, in this paper we have been able to successfully assemble 185 nm nonmagnetic polymer beads into photonic crystal structures, from 1D chains to 3D assemblies as determined by the interplay of magnetic dipole force and packing force. In a strong magnetic field with large field gradient, 3D photonic crystals with high reflectance (83%) in the visible range can be rapidly produced within several minutes, making this general strategy promising for fast creation of large-area photonic crystals using nonmagnetic particles as building blocks.

Functional Nanostructured Materials Based on Polymerized Surfactant Liquid Crystal Assemblies Liquid Crystal Assemblies

NASA Astrophysics Data System (ADS)

Gin, Douglas

2003-03-01

The development of materials with controlled nanostructures is one of the most important new areas of scientific research in chemistry and engineering. Our research group has developed a novel approach for making nanostructured polymer materials with unique functional properties using liquid crystals as starting materials. In this approach, we design polymerizable organic building blocks based on lyotropic liquid crystals (LLCs) (i.e., amphiphiles or surfactants) that carry, or can accommodate, a functional property of general interest. Through appropriate molecular design, these monomers self-assemble in the presence of water into fluid, yet ordered phase-separated, water-hydrocarbon assemblies with predictable nanoscale geometries. The architectures of these LLC phases can range from stacked two-dimensional lamellae to hexagonally ordered cylindrical channels with uniform feature sizes in the 1-10 nm range. These LLC phases are then photopolymerized into robust polymer networks with preservation of their small-scale structures. This approach allows us to investigate the effect of nanometer-scale architecture on important bulk properties, as well as to engineer chemical environments on the nanometer-scale for several areas of application. In this talk, new functional materials based on the polymerization of the lyotropic inverted hexagonal phase will be presented as one example of our general approach. Issues in the design and photopolymerization of functional amphiphilic monomers that adopt this LC architecture will be discussed. More importantly, the use of the resulting nanostructured polymer networks in three areas of application will be presented: (1) as templates for the synthesis of functional nanocomposites; (2) as tunable heterogeneous catalysts, and (3) as nanoporous membrane and separation media. In particular, issues pertaining to the contribution of nanoscale architecture to the performance of these systems will be highlighted. Opportunities for tailoring the nanoscale chemical environment and architecture of these materials through molecular design will be presented. Finally, the development of methods for controlling macroscopic orientation through processing will also be discussed.

Plasmon Surface Polariton Dispersion by Direct Optical Observation.

ERIC Educational Resources Information Center

Swalen, J. D.; And Others

1980-01-01

Describes several simple experiments that can be used to observe directly the dispersion curve of plasmon surface polaritons (PSP) on flat metal surfaces. A method is described of observing the increonental change in the wave vector of the PSP due to coatings that differ in thickness by a few nanometers. (Author/CS)

Detection of submicron scale cracks and other surface anomalies using positron emission tomography

DOEpatents

Cowan, Thomas E.; Howell, Richard H.; Colmenares, Carlos A.

2004-02-17

Detection of submicron scale cracks and other mechanical and chemical surface anomalies using PET. This surface technique has sufficient sensitivity to detect single voids or pits of sub-millimeter size and single cracks or fissures of millimeter size; and single cracks or fissures of millimeter-scale length, micrometer-scale depth, and nanometer-scale length, micrometer-scale depth, and nanometer-scale width. This technique can also be applied to detect surface regions of differing chemical reactivity. It may be utilized in a scanning or survey mode to simultaneously detect such mechanical or chemical features over large interior or exterior surface areas of parts as large as about 50 cm in diameter. The technique involves exposing a surface to short-lived radioactive gas for a time period, removing the excess gas to leave a partial monolayer, determining the location and shape of the cracks, voids, porous regions, etc., and calculating the width, depth, and length thereof. Detection of 0.01 mm deep cracks using a 3 mm detector resolution has been accomplished using this technique.

Lignin nanoparticle synthesis

DOEpatents

Dirk, Shawn M.; Cicotte, Kirsten Nicole; Wheeler, David R.; Benko, David A.

2015-08-11

A method including reducing a particle size of lignin particles to an average particle size less than 40 nanometers; after reducing the particle size, combining the lignin particles with a polymeric material; and forming a structure of the combination. A method including exposing lignin to a diazonium precursor including a functional group; modifying the lignin by introducing the functional group to the lignin; and combining the modified lignin with a polymeric material to form a composite. An apparatus including a composite of a polymer and lignin wherein the lignin has an average particle size less than 100 micrometers.

Polymer-Based Surfaces Designed to Reduce Biofilm Formation: From Antimicrobial Polymers to Strategies for Long-Term Applications.

PubMed

Riga, Esther K; Vöhringer, Maria; Widyaya, Vania Tanda; Lienkamp, Karen

2017-10-01

Contact-active antimicrobial polymer surfaces bear cationic charges and kill or deactivate bacteria by interaction with the negatively charged parts of their cell envelope (lipopolysaccharides, peptidoglycan, and membrane lipids). The exact mechanism of this interaction is still under debate. While cationic antimicrobial polymer surfaces can be very useful for short-term applications, they lose their activity once they are contaminated by a sufficiently thick layer of adhering biomolecules or bacterial cell debris. This layer shields incoming bacteria from the antimicrobially active cationic surface moieties. Besides discussing antimicrobial surfaces, this feature article focuses on recent strategies that were developed to overcome the contamination problem. This includes bifunctional materials with simultaneously presented antimicrobial and protein-repellent moieties; polymer surfaces that can be switched from an antimicrobial, cell-attractive to a cell-repellent state; polymer surfaces that can be regenerated by enzyme action; degradable antimicrobial polymers; and antimicrobial polymer surfaces with removable top layers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Linear alkane polymerization on a gold surface.

PubMed

Zhong, Dingyong; Franke, Jörn-Holger; Podiyanachari, Santhosh Kumar; Blömker, Tobias; Zhang, Haiming; Kehr, Gerald; Erker, Gerhard; Fuchs, Harald; Chi, Lifeng

2011-10-14

In contrast to the many methods of selectively coupling olefins, few protocols catenate saturated hydrocarbons in a predictable manner. We report here the highly selective carbon-hydrogen (C-H) activation and subsequent dehydrogenative C-C coupling reaction of long-chain (>C(20)) linear alkanes on an anisotropic gold(110) surface, which undergoes an appropriate reconstruction by adsorption of the molecules and subsequent mild annealing, resulting in nanometer-sized channels (1.22 nanometers in width). Owing to the orientational constraint of the reactant molecules in these one-dimensional channels, the reaction takes place exclusively at specific sites (terminal CH(3) or penultimate CH(2) groups) in the chains at intermediate temperatures (420 to 470 kelvin) and selects for aliphatic over aromatic C-H activation.

Frequency-doubled vertical-external-cavity surface-emitting laser

DOEpatents

Raymond, Thomas D.; Alford, William J.; Crawford, Mary H.; Allerman, Andrew A.

2002-01-01

A frequency-doubled semiconductor vertical-external-cavity surface-emitting laser (VECSEL) is disclosed for generating light at a wavelength in the range of 300-550 nanometers. The VECSEL includes a semiconductor multi-quantum-well active region that is electrically or optically pumped to generate lasing at a fundamental wavelength in the range of 600-1100 nanometers. An intracavity nonlinear frequency-doubling crystal then converts the fundamental lasing into a second-harmonic output beam. With optical pumping with 330 milliWatts from a semiconductor diode pump laser, about 5 milliWatts or more of blue light can be generated at 490 nm. The device has applications for high-density optical data storage and retrieval, laser printing, optical image projection, chemical-sensing, materials processing and optical metrology.

Influence of nanometer scale particulate fillers on some properties of microfilled composite resin.

PubMed

Garoushi, Sufyan; Lassila, Lippo V J; Vallittu, Pekka K

2011-07-01

The aim of this study was to evaluate the effect of different weight fractions of nanometer sized particulate filler on properties of microfilled composite resin. Composite resin was prepared by mixing 33 wt% of resin matrix to the 67 wt% of silane treated microfine silica particulate fillers with various fractions of nanometer sized fillers (0, 10, 15, 20, 30 wt%) using a high speed mixing machine. Test specimens made of the composites were tested with a three-point bending test with a speed of 1.0 mm/min until fracture. Surface microhardess (Vicker's microhardness) was also determined. The volumetric shrinkage in percent was calculated as a buoyancy change in distilled water by means of the Archimedes principle. The degree of monomer conversion (DC%) of the experimental composites containing different nanofiller fractions was measured using FTIR spectroscopy. Surface roughness (Ra) was determined using a surface profilometer. Nanowear measurements were carried out using a nanoindentation device. The water uptake of specimens was also measured. Parameters were statistically analysed by ANOVA (P < 0.05). The group without nanofillers showed the highest flexural strength and modulus, DC% and Ra value. The group with 30% nanofillers had the highest water uptake and volumetric shrinkage. No significant difference was found in Vicker's microhardness and the nanowear of the composites. The plain microfilled composite demonstrated superior properties compared to the composites loaded with nanofillers with the exception of surface roughness.

Surface segregation and surface tension of polydisperse polymer melts.

PubMed

Minnikanti, Venkatachala S; Qian, Zhenyu; Archer, Lynden A

2007-04-14

The effect of polydispersity on surface segregation of a lower molecular weight polymer component in a higher molecular weight linear polymer melt host is investigated theoretically. We show that the integrated surface excess zM of a polymer component of molecular weight M satisfies a simple relation zM=2Ue(M/Mw-1)phiM, where Mw is the weight averaged molecular weight, phiM is the polymer volume fraction, and Ue is the attraction of polymer chain ends to the surface. Ue is principally of entropic origin, but also reflects any energetic preference of chain ends to the surface. We further show that the surface tension gammaM of a polydisperse melt of high molar mass components depends on the number average degree of polymerization Mn as, gammaM=gammainfinity+2UerhobRT/Mn. The parameter gammainfinity is the asymptotic surface tension of an infinitely long polymer of the same chemistry, rhob is the bulk density of the polymer, R is the universal gas constant, and T is the temperature. The predicted gammaM compare favorably with surface tension values obtained from self-consistent field theory simulations that include equation of state effects, which account for changes in polymer density with molecular weight. We also compare the predicted surface tension with available experimental data.

Non-contact XUV metrology of Ru/B4C multilayer optics by means of Hartmann wavefront analysis.

PubMed

Ruiz-Lopez, Mabel; Dacasa, Hugo; Mahieu, Benoit; Lozano, Magali; Li, Lu; Zeitoun, Philippe; Bleiner, Davide

2018-02-20

Short-wavelength imaging, spectroscopy, and lithography scale down the characteristic length-scale to nanometers. This poses tight constraints on the optics finishing tolerances, which is often difficult to characterize. Indeed, even a tiny surface defect degrades the reflectivity and spatial projection of such optics. In this study, we demonstrate experimentally that a Hartmann wavefront sensor for extreme ultraviolet (XUV) wavelengths is an effective non-contact analytical method for inspecting the surface of multilayer optics. The experiment was carried out in a tabletop laboratory using a high-order harmonic generation as an XUV source. The wavefront sensor was used to measure the wavefront errors after the reflection of the XUV beam on a spherical Ru/B 4 C multilayer mirror, scanning a large surface of approximately 40 mm in diameter. The results showed that the technique detects the aberrations in the nanometer range.

Accurate formula for dissipative interaction in frequency modulation atomic force microscopy

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

Suzuki, Kazuhiro; Matsushige, Kazumi; Yamada, Hirofumi

2014-12-08

Much interest has recently focused on the viscosity of nano-confined liquids. Frequency modulation atomic force microscopy (FM-AFM) is a powerful technique that can detect variations in the conservative and dissipative forces between a nanometer-scale tip and a sample surface. We now present an accurate formula to convert the dissipation power of the cantilever measured during the experiment to damping of the tip-sample system. We demonstrated the conversion of the dissipation power versus tip-sample separation curve measured using a colloidal probe cantilever on a mica surface in water to the damping curve, which showed a good agreement with the theoretical curve.more » Moreover, we obtained the damping curve from the dissipation power curve measured on the hydration layers on the mica surface using a nanometer-scale tip, demonstrating that the formula allows us to quantitatively measure the viscosity of a nano-confined liquid using FM-AFM.« less

Adhesion properties in systems of laminated pigmented polymers, carbon-graphite fiber composite framework and titanium surfaces in implant suprastructures.

PubMed

Segerström, Susanna; Ruyter, I Eystein

2009-09-01

For long-term stability the adhering interfaces of an implant-retained supraconstruction of titanium/carbon-graphite fiber-reinforced (CGFR) polymer/opaquer layer/denture base polymer/denture teeth must function as a unity. The aim was to evaluate adhesion of CGFR polymer to a titanium surface or CGFR polymer to two different opaquer layers/with two denture base polymers. Titanium plates were surface-treated and silanized and combined with a bolt of CGFR polymer or denture base polymer (Probase Hot). Heat-polymerized plates of CGFR polymer (47 wt% fiber) based on poly(methyl methacrylate) and a copolymer matrix were treated with an opaquer (Sinfony or Ropak) before a denture base polymer bolt was attached (Probase Hot or Lucitone 199). All specimens were heat-polymerized, water saturated (200 days) and thermally cycled (5000 cycles, 5/55 degrees C) before shear bond testing. Silicatized titanium surfaces gave higher bond strength to CGFR polymer (16.2+/-2.34 and 18.6+/-1.32) MPa and cohesive fracture than a sandblasted surface (5.9+/-2.11) MPa where the fracture was adhesive. The opaquer Sinfony gave higher adhesion values and mainly cohesive fractures than the opaquer Ropak. Different surface treatments (roughened or polished) of the CGFR polymer had no effect on bond strength. The fracture surfaces of silicatized titanium/CGFR polymer/opaquer layer (Sinfony)/denture base polymers were mainly cohesive. A combination of these materials in an implant-retained supraconstruction is promising for in vivo evaluation.

Metal-assisted exfoliation (MAE): green process for transferring graphene to flexible substrates and templating of sub-nanometer plasmonic gaps (Presentation Recording)

NASA Astrophysics Data System (ADS)

Zaretski, Aliaksandr V.; Marin, Brandon C.; Moetazedi, Herad; Dill, Tyler J.; Jibril, Liban; Kong, Casey; Tao, Andrea R.; Lipomi, Darren J.

2015-09-01

This paper describes a new technique, termed "metal-assisted exfoliation," for the scalable transfer of graphene from catalytic copper foils to flexible polymeric supports. The process is amenable to roll-to-roll manufacturing, and the copper substrate can be recycled. We then demonstrate the use of single-layer graphene as a template for the formation of sub-nanometer plasmonic gaps using a scalable fabrication process called "nanoskiving." These gaps are formed between parallel gold nanowires in a process that first produces three-layer thin films with the architecture gold/single-layer graphene/gold, and then sections the composite films with an ultramicrotome. The structures produced can be treated as two gold nanowires separated along their entire lengths by an atomically thin graphene nanoribbon. Oxygen plasma etches the sandwiched graphene to a finite depth; this action produces a sub-nanometer gap near the top surface of the junction between the wires that is capable of supporting highly confined optical fields. The confinement of light is confirmed by surface-enhanced Raman spectroscopy measurements, which indicate that the enhancement of the electric field arises from the junction between the gold nanowires. These experiments demonstrate nanoskiving as a unique and easy-to-implement fabrication technique that is capable of forming sub-nanometer plasmonic gaps between parallel metallic nanostructures over long, macroscopic distances. These structures could be valuable for fundamental investigations as well as applications in plasmonics and molecular electronics.

Study on surface roughness evolvement of Nd-doped phosphate glass after IBF

NASA Astrophysics Data System (ADS)

Li, Furen; Xie, Xuhui; Zhou, Lin; Tie, Guipeng; Hu, Hao

2016-10-01

Nd doped phosphate glass is widely used as gain media in high power laser system. It is traditionally polished with the annular polishing technology. The edge effect is inevitable in annular polishing process and it results in the low manufacturing efficiency. Ion Beam Figuring (IBF) is a highly deterministic, non-contact method for the ultra-precision optics fabrication. So the edge effect is avoided. Nanometer and sub-nanometer precision is realizable in IBF. In this paper, Nd doped phosphate glass was polished with IBF, and the evolvement of surface roughness was emphasized. The roughness of surface polished with ion beam at normal and oblique incidence was researched. The oblique incident angle was 45°. The surface roughness was measured with the white light interferometer. No evident change was observed. This means that the pre-finish roughness can be preserved in IBF. The results denote that IBF is a feasible method to correct the contour errors of Nd doped phosphate glass, and the roughness will not be coarsened.

Hydrophilization and hydrophobic recovery in polymers obtained by casting of polymer solutions on water surface.

PubMed

Bormashenko, Edward; Chaniel, Gilad; Gendelman, Oleg

2014-12-01

We demonstrate the possibility of hydrophilization of polymer films in situ under the process of their preparation. The polymer surface is hydrophilized when the polymer solution is spread on the water surface and the solvent is evaporated. Essential hydrophilization of the polymer surface is achieved under this process. We relate the observed hydrophilization of polymer films to the dipole-dipole interaction of the polar moieties of polymer chains with highly polar water molecules. The dipole-dipole interaction between water molecules and polar groups of polymer chains, orienting the polar groups of a polymer, may prevail over the London dispersion forces. The process, reported in the paper, allows to manufacture the films in which the hydrophilic moieties of the polymer molecule are oriented toward the polymer/air interface. It is demonstrated that even such traditionally extremely hydrophobic polymers as polydimethylsiloxane can be markedly hydrophilized. This hydrophilization, however, does not persist forever. After removal from the water surface, hydrophobic recovery was observed, i.e. polymer films restored their hydrophobicity with time. The characteristic time of the hydrophobic recovery is on the order of magnitude of hours. Copyright © 2014 Elsevier Inc. All rights reserved.

Structure and Dynamics of Solvated Polymers near a Silica Surface: On the Different Roles Played by Solvent.

PubMed

Perrin, Elsa; Schoen, Martin; Coudert, François-Xavier; Boutin, Anne

2018-04-26

Whereas it is experimentally known that the inclusion of nanoparticles in hydrogels can lead to a mechanical reinforcement, a detailed molecular understanding of the adhesion mechanism is still lacking. Here we use coarse-grained molecular dynamics simulations to investigate the nature of the interface between silica surfaces and solvated polymers. We show how differences in the nature of the polymer and the polymer-solvent interactions can lead to drastically different behavior of the polymer-surface adhesion. Comparing explicit and implicit solvent models, we conclude that this effect cannot be fully described in an implicit solvent. We highlight the crucial role of polymer solvation for the adsorption of the polymer chain on the silica surface, the significant dynamics of polymer chains on the surface, and details of the modifications in the structure solvated polymer close to the interface.

Scanning transmission electron microscopy and its application to the study of nanoparticles and nanoparticle systems.

PubMed

Liu, Jingyue

2005-06-01

Scanning transmission electron microscopy (STEM) techniques can provide imaging, diffraction and spectroscopic information, either simultaneously or in a serial manner, of the specimen with an atomic or a sub-nanometer spatial resolution. High-resolution STEM imaging, when combined with nanodiffraction, atomic resolution electron energy-loss spectroscopy and nanometer resolution X-ray energy dispersive spectroscopy techniques, is critical to the fundamental studies of importance to nanoscience and nanotechnology. The availability of sub-nanometer or sub-angstrom electron probes in a STEM instrument, due to the use of a field emission gun and aberration correctors, ensures the greatest capabilities for studies of sizes, shapes, defects, crystal and surface structures, and compositions and electronic states of nanometer-size regions of thin films, nanoparticles and nanoparticle systems. The various imaging, diffraction and spectroscopy modes available in a dedicated STEM or a field emission TEM/STEM instrument are reviewed and the application of these techniques to the study of nanoparticles and nanostructured catalysts is used as an example to illustrate the critical role of the various STEM techniques in nanotechnology and nanoscience research.

Scanning tunneling microscope nanoetching method

DOEpatents

Li, Yun-Zhong; Reifenberger, Ronald G.; Andres, Ronald P.

1990-01-01

A method is described for forming uniform nanometer sized depressions on the surface of a conducting substrate. A tunneling tip is used to apply tunneling current density sufficient to vaporize a localized area of the substrate surface. The resulting depressions or craters in the substrate surface can be formed in information encoding patterns readable with a scanning tunneling microscope.

Corrosion-resistant metal surfaces

DOEpatents

Sugama, Toshifumi [Wading River, NY

2009-03-24

The present invention relates to metal surfaces having thereon an ultrathin (e.g., less than ten nanometer thickness) corrosion-resistant film, thereby rendering the metal surfaces corrosion-resistant. The corrosion-resistant film includes an at least partially crosslinked amido-functionalized silanol component in combination with rare-earth metal oxide nanoparticles. The invention also relates to methods for producing such corrosion-resistant films.

Controlled reflectance surfaces with film-coupled colloidal nanoantennas

PubMed Central

Moreau, Antoine; Ciraci, Cristian; Mock, Jack J.; Hill, Ryan T.; Wang, Qiang; Wiley, Benjamin J.; Chilkoti, Ashutosh; Smith, David R.

2013-01-01

Efficient and tunable absorption is essential for a variety of applications, such as the design of controlled emissivity surfaces for thermophotovoltaic devices1; tailoring of the infrared spectrum for controlled thermal dissipation2; and detector elements for imaging3. Metamaterials based on metallic elements are particularly efficient as absorbing media, because both the electrical and the magnetic properties of a metamaterial can be tuned by structured design4. To date, metamaterial absorbers in the infrared or visible range have been fabricated using lithographically patterned metallic structures2,5–9, making them inherently difficult to produce over large areas and hence reducing their applicability. We demonstrate here an extraordinarily simple method to create a metamaterial absorber by randomly adsorbing chemically synthesized silver nanocubes onto a nanoscale thick polymer spacer layer on a gold film –making no effort to control the spatial arrangement of the cubes on the film– and show that the film-coupled nanocubes provide a reflectance spectrum that can be tailored by varying the geometry. Each nanocube is the optical analog of the well-known grounded patch antenna, with a nearly identical local field structure that is modified by the plasmonic response of the metal dielectric function, and with an anomalously large absorption efficiency that can be partly attributed to an interferometric effect10. The absorptivity of large surface areas can be controlled using this method, at scales out of reach of lithographic approaches like e-beam lithography otherwise required to manipulate matter at the nanometer scale. PMID:23222613

Live-cell imaging of neurofilament transport in cultured neurons.

PubMed

Uchida, Atsuko; Monsma, Paula C; Fenn, J Daniel; Brown, Anthony

2016-01-01

Neurofilaments, which are the intermediate filaments of nerve cells, are space-filling cytoskeletal polymers that contribute to the growth of axonal caliber. In addition to their structural role, neurofilaments are cargos of axonal transport that move along microtubule tracks in a rapid, intermittent, and bidirectional manner. Though they measure just 10nm in diameter, which is well below the diffraction limit of optical microscopes, these polymers can reach 100 μm or more in length and are often packed densely, just tens of nanometers apart. These properties of neurofilaments present unique challenges for studies on their movement. In this article, we describe several live-cell fluorescence imaging strategies that we have developed to image neurofilament transport in axons of cultured neurons on short and long timescales. Together, these methods form a powerful set of complementary tools with which to study the axonal transport of these unique intracellular cargos. Copyright © 2016 Elsevier Inc. All rights reserved.

Fabrication routes for one-dimensional nanostructures via block copolymers

NASA Astrophysics Data System (ADS)

Tharmavaram, Maithri; Rawtani, Deepak; Pandey, Gaurav

2017-05-01

Nanotechnology is the field which deals with fabrication of materials with dimensions in the nanometer range by manipulating atoms and molecules. Various synthesis routes exist for the one, two and three dimensional nanostructures. Recent advancements in nanotechnology have enabled the usage of block copolymers for the synthesis of such nanostructures. Block copolymers are versatile polymers with unique properties and come in many types and shapes. Their properties are highly dependent on the blocks of the copolymers, thus allowing easy tunability of its properties. This review briefly focusses on the use of block copolymers for synthesizing one-dimensional nanostructures especially nanowires, nanorods, nanoribbons and nanofibers. Template based, lithographic, and solution based approaches are common approaches in the synthesis of nanowires, nanorods, nanoribbons, and nanofibers. Synthesis of metal, metal oxides, metal oxalates, polymer, and graphene one dimensional nanostructures using block copolymers have been discussed as well.

Novel and simple alternative to create nanofibrillar matrices of interest for tissue engineering.

PubMed

Sohier, Jérôme; Corre, Pierre; Perret, Christophe; Pilet, Paul; Weiss, Pierre

2014-04-01

Synthetic analogs to natural extracellular matrix (ECM) at the nanometer level are of great potential for regenerative medicine. This study introduces a novel and simple method to produce polymer nanofibers and evaluates the properties of the resulting structures, as well as their suitability to support cells and their potential interest for bone and vascular applications. The devised approach diffracts a polymer solution by means of a spraying apparatus and of an airstream as sole driving force. The resulting nanofibers were produced in an effective fashion and a factorial design allowed isolating the processing parameters that control nanofiber size and distribution. The nanofibrillar matrices revealed to be of very high porosity and were effectively colonized by human bone marrow mesenchymal cells, while allowing ECM production and osteoblastic differentiation. In vivo, the matrices provided support for new bone formation and provided a good patency as small diameter vessel grafts.

Breath-Figure Self-Assembly, a Versatile Method of Manufacturing Membranes and Porous Structures: Physical, Chemical and Technological Aspects

PubMed Central

2017-01-01

The review is devoted to the physical, chemical, and technological aspects of the breath-figure self-assembly process. The main stages of the process and impact of the polymer architecture and physical parameters of breath-figure self-assembly on the eventual pattern are covered. The review is focused on the hierarchy of spatial and temporal scales inherent to breath-figure self-assembly. Multi-scale patterns arising from the process are addressed. The characteristic spatial lateral scales of patterns vary from nanometers to dozens of micrometers. The temporal scale of the process spans from microseconds to seconds. The qualitative analysis performed in the paper demonstrates that the process is mainly governed by interfacial phenomena, whereas the impact of inertia and gravity are negligible. Characterization and applications of polymer films manufactured with breath-figure self-assembly are discussed. PMID:28813026

Photoinitiated grafting of porous polymer monoliths and thermoplastic polymers for microfluidic devices

DOEpatents

Frechet, Jean M. J. [Oakland, CA; Svec, Frantisek [Alameda, CA; Rohr, Thomas [Leiden, NL

2008-10-07

A microfluidic device preferably made of a thermoplastic polymer that includes a channel or a multiplicity of channels whose surfaces are modified by photografting. The device further includes a porous polymer monolith prepared via UV initiated polymerization within the channel, and functionalization of the pore surface of the monolith using photografting. Processes for making such surface modifications of thermoplastic polymers and porous polymer monoliths are set forth.

Three-Dimensional Structures Self-Assembled from DNA Bricks

PubMed Central

Ke, Yonggang; Ong, Luvena L.; Shih, William M.; Yin, Peng

2013-01-01

We describe a simple and robust method to construct complex three-dimensional (3D) structures using short synthetic DNA strands that we call “DNA bricks”. In one-step annealing reactions, bricks with hundreds of distinct sequences self-assemble into prescribed 3D shapes. Each 32-nucleotide brick is a modular component; it binds to four local neighbors and can be removed or added independently. Each 8-base-pair interaction between bricks defines a voxel with dimensions 2.5 nanometers by 2.5 nanometers by 2.7 nanometers, and a master brick collection defines a “molecular canvas” with dimensions of 10 by 10 by 10 voxels. By selecting subsets of bricks from this canvas, we constructed a panel of 102 distinct shapes exhibiting sophisticated surface features as well as intricate interior cavities and tunnels. PMID:23197527

Direct observation of terahertz surface modes in nanometer-sized liquid water pools.

PubMed

Boyd, J E; Briskman, A; Colvin, V L; Mittleman, D M

2001-10-01

The far-infrared absorption spectrum of nanometer-sized water pools at the core of AOT micelles exhibits a pronounced resonance which is absent in bulk water. The amplitude and spectral position of this resonance are sensitive to the size of the confined water core. This resonance results from size-dependent modifications in the vibrational density of states, and thus has far-reaching implications for chemical processes which involve water sequestered within small cavities. These data represent the first study of the terahertz dielectric properties of confined liquids.

Synthesis of Highly Active Sub-Nanometer Pt@Rh Core-Shell Nanocatalyst via a Photochemical Route: Porous Titania Nanoplates as a Superior Photoactive Support.

PubMed

Zhan, Wen-Wen; Zhu, Qi-Long; Dang, Song; Liu, Zheng; Kitta, Mitsunori; Suenaga, Kazutomo; Zheng, Lan-Sun; Xu, Qiang

2017-04-01

Sub-nanometer Pt@Rh nanoparticles highly dispersed on MIL-125-derived porous TiO 2 nanoplates are successfully prepared for the first time by a photochemical route, where the porous TiO 2 nanoplates with a relatively high specific surface area play a dual role as both effective photoreductant and catalyst support. The resulting Pt@Rh/p-TiO 2 can be utilized as a highly active catalyst. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly Sensitive, Uniform, and Reproducible Surface-Enhanced Raman Spectroscopy Substrate with Nanometer-Scale Quasi-periodic Nanostructures.

PubMed

Jin, Yuanhao; Wang, Yingcheng; Chen, Mo; Xiao, Xiaoyang; Zhang, Tianfu; Wang, Jiaping; Jiang, Kaili; Fan, Shoushan; Li, Qunqing

2017-09-20

We introduce a simple and cost-effective approach for fabrication of effective surface-enhanced Raman spectroscopy (SERS) substrates. It is shown that the as-fabricated substrates show excellent SERS effects in various probe molecules with high sensitivity, that is, picomolar level detection, and also good reliability. With a SERS enhancement factor beyond 10 8 and excellent reproducibility (deviation less than 5%) of signal intensity, the fabrication of the SERS substrate is realized on a four-inch wafer and proven to be effective in pesticide residue detection. The SERS substrate is realized first through the fabrication of quasi-periodic nanostructured silicon with dimension features in tens of nanometers using superaligned carbon nanotubes networks as an etching mask, after which a large amount of hot spots with nanometer gaps are formed through deposition of a gold film. With rigorous nanostructure design, the enhanced performance of electromagnetic field distribution for nanostructures is optimized. With the advantage of cost-effective large-area preparation, it is believed that the as-fabricated SERS substrate could be used in a wide variety of actual applications where detection of trace amounts is necessary.

Wrapping conformations of a polymer on a curved surface

NASA Astrophysics Data System (ADS)

Lin, Cheng-Hsiao; Tsai, Yan-Chr; Hu, Chin-Kun

2007-03-01

The conformation of a polymer on a curved surface is high on the agenda for polymer science. We assume that the free energy of the system is the sum of bending energy of the polymer and the electrostatic attraction between the polymer and surface. As is also assumed, the polymer is very stiff with an invariant length for each segment so that we can neglect its tensile energy and view its length as a constant. Based on the principle of minimization of free energy, we apply a variation method with a locally undetermined Lagrange multiplier to obtain a set of equations for the polymer conformation in terms of local geometrical quantities. We have obtained some numerical solutions for the conformations of the polymer chain on cylindrical and ellipsoidal surfaces. With some boundary conditions, we find that the free energy profiles of polymer chains behave differently and depend on the geometry of the surface for both cases. In the former case, the free energy of each segment distributes within a narrower range and its value per unit length oscillates almost periodically in the azimuthal angle. However, in the latter case the free energy distributes in a wider range with larger value at both ends and smaller value in the middle of the chain. The structure of a polymer wrapping around an ellipsoidal surface is apt to dewrap a polymer from the endpoints. The dependence of threshold lengths for a polymer on the initially anchored positions is also investigated. With initial conditions, the threshold wrapping length is found to increase with the electrostatic attraction strength for the ellipsoidal surface case. When a polymer wraps around a sphere surface, the threshold length increases monotonically with the radius without the self-intersection configuration for a polymer. We also discuss potential applications of the present theory to DNA/protein complex and further researches on DNA on the curved surface.

On the use of SPM to probe the interplay between polymer surface chemistry and polymer surface mechanics

NASA Astrophysics Data System (ADS)

Brogly, Maurice; Noel, Olivier; Awada, Houssein; Castelein, Gilles

2007-03-01

Adhesive properties of a polymer surface results from the complex contribution of surface chemistry and activation of sliding and dissipating mechanisms within the polymer surface layer. The purpose of this study is to dissociate the different contributions (chemical and mechanical) included in an AFM force-distance curve in order to establish relationships between the surface viscoelastic properties of the polymer, the surface chemistry of functionalized polymer surfaces and the adhesive forces, as determined by C-AFM experiments. Indeed we are interested in the measurements of local attractive or adhesive forces in AFM contact mode, of controlled chemical and mechanical model substrates. In order to investigate the interplay between mechanical or viscoelastic mechanisms and surface chemistry during the tip - polymer contact, we achieved force measurements on model PDMS polymer networks, whose surfaces are chemically controlled with the same functional groups as before (silicon substrates). On the basis of AFM nano-indentation experiments, surface Young moduli have been determined. The results show that the viscoelastic contribution is dominating in the adhesion force measurement. We propose an original model, which express the local adhesion force to the energy dissipated within the contact and the surface properties of the material (thermodynamic work of adhesion). Moreover we show that the dissipation function is related to Mc, the mass between crosslinks of the network.

MC3T3-E1 Cells on Titanium Surfaces with Nanometer Smoothness and Fibronectin Immobilization

PubMed Central

Hayakawa, Tohru; Yoshida, Eiji; Yoshimura, Yoshitaka; Uo, Motohiro; Yoshinari, Masao

2012-01-01

The present study was aimed to evaluate the viability and total protein contents of osteoblast-like cells on the titanium surface with different surface mechanical treatment, namely, nanometer smoothing (Ra: approximately 2.0 nm) and sandblasting (Ra: approximately 1.0 μm), and biochemical treatment, namely, with or without fibronectin immobilization. Fibronectin could be easily immobilized by tresyl chloride-activation technique. MC3T3-E1 cells were seeded on the different titanium surfaces. Cell viability was determined by MTT assay. At 1 day of cell culture, there were no significant differences in cell viability among four different titanium surfaces. At 11 days, sandblasted titanium surface with fibronectin immobilization showed the significantly highest cell viability than other titanium surface. No significant differences existed for total protein contents among four different titanium surfaces at 11 days of cell culture. Scanning electron microscopy observation revealed that smoothness of titanium surface produced more spread cell morphologies, but that fibronectin immobilization did not cause any changes of the morphologies of attached cells. Fibronectin immobilization provided greater amount of the number of attached cells and better arrangement of attached cells. In conclusion, the combination of sandblasting and fibronectin immobilization enhanced the cell viability and fibronectin immobilization providing better arrangements of attached cells. PMID:22675359

Polymer brush covalently attached to OH-functionalized mica surface via surface-initiated ATRP: control of grafting density and polymer chain length.

PubMed

Lego, Béatrice; François, Marion; Skene, W G; Giasson, Suzanne

2009-05-05

The controlled grafting density of poly(tert-butyl acrylate) was studied on OH-activated mica substrates via surface-initiated atom-transfer radical polymerization (ATRP). By properly adjusting parameters such as the immobilization reaction time and the concentration of an ATRP initiator, a wide range of initiator surface coverages and hence polymer densities on mica were possible. The covalently immobilized initiator successfully promoted the polymerization of tert-butyl acrylate on mica surfaces. The resulting polymer layer thickness was measured by AFM using a step-height method. Linear relationships of the polymer thickness with respect to the molecular weight of the free polymer and with respect to the monomer conversion were observed, suggesting that ATRP is well controlled and relatively densely end-grafted layers were obtained. The polymer grafting density controlled by adjusting the initiator surface coverage was confirmed by the polymer layer swelling capacity and film thickness measurements.

The relationship between surface tension and the industrial performance of water-soluble polymers prepared from acid hydrolysis lignin, a saccharification by-product from woody materials.

PubMed

Matsushita, Yasuyuki; Imai, Masanori; Iwatsuki, Ayuko; Fukushima, Kazuhiko

2008-05-01

In this study, water-soluble anionic and cationic polymers were prepared from sulfuric acid lignin (SAL), an acid hydrolysis lignin, and the relationship between the surface tension of these polymers and industrial performance was examined. The SAL was phenolized (P-SAL) to enhance its solubility and reactivity. Sulfonation and the Mannich reaction with aminocarboxylic acids produced water-soluble anionic polymers and high-dispersibility gypsum paste. The dispersing efficiency increased as the surface tension decreased, suggesting that the fluidity of the gypsum paste increased with the polymer adsorption on the gypsum particle surface. Water-soluble cationic polymers were prepared using the Mannich reaction with dimethylamine. The cationic polymers showed high sizing efficiency under neutral papermaking conditions; the sizing efficiency increased with the surface tension. This suggests that the polymer with high hydrophilicity spread in the water and readily adhered to the pulp surface and the rosin, showing good retention.

Panoramic View of Electrochemical Pseudocapacitor and Organic Solar Cell Research in Molecularly Engineered Energy Materials (MEEM)

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

Aguirre, Jordan C.; Ferreira, Amy; Ding, Hong

2014-07-09

Our program on capacitive energy storage is a comprehensive one that combines experimental and computational components to achieve a fundamental understanding of charge storage processes in redox-based materials, specifically transition metal oxides. Some of the highlights of this program are the identification of intercalation pseudocapacitance in Nb2O5, which enables high energy density to be achieved at high rates, and the development of a new route for synthesizing mesoporous films in which preformed nanocrystal building blocks are used in combination with polymer templating. The resulting material architectures have large surface areas and enable electrolyte access to the redox active pore walls,more » while the interconnected mesoporous film provides good electronic conductivity. Select first-principles density-functional theory studies of prototypical pseudocapacitor materials are reviewed, providing insight into the key physical and chemical features involved in charge transfer and ion diffusion. Rigorous multiscale physical models and numerical tools have been developed and used to reproduce electrochemical properties of carbon-based electrochemical capacitors with the ultimate objective of facilitating the optimization of electrode design. For the organic photovoltaic (OPV) program, our focus has been ongoing beyond the trial-and-error Edisonian approaches that have been responsible for the increase in power conversion efficiency of blend-cast (BC) bulk heterojunction blends of polymers and fullerenes. Our first approach has been to use molecular self-assembly to create the ideal nanometer-scale architecture using thermodynamics rather than relying on the kinetics of spontaneous phase segregation. We have created fullerenes that self-assemble into one-dimensional stacks and have shown that use of these self-assembled fullerenes lead to dramatically enhanced OPV performance relative to fullerenes that do not assemble. We also have created self-assembling conjugated polymers that form gels based on electrically continuous cross-linked micelles in solution, opening the possibility for water-processable “green” production of OPVs based on these materials. Our second approach has been to avoid kinetic control over phase separation by using a sequential processing (SqP) technique to deposit the polymer and fullerene materials in separate deposition steps. The polymer layer is deposited first, using solvents and deposition conditions that optimize the polymer crystallinity for swelling and hole mobility. The fullerene layer is then deposited in a second step from a solvent that swells the polymer but does not dissolve it, allowing the fullerene to penetrate into the polymer underlayer to the desired degree. Careful comparison of composition- and thickness-matched BC and SqP devices shows that SqP not only produces more efficient devices but also leads to devices that behave more consistently.« less

Performance of Topological Insulator Interconnects

NASA Astrophysics Data System (ADS)

Philip, Timothy M.; Hirsbrunner, Mark R.; Park, Moon Jip; Gilbert, Matthew J.

2017-01-01

The poor performance of copper interconnects at the nanometer scale calls for new material solutions for continued scaling of integrated circuits. We propose the use of three dimensional time-reversal-invariant topological insulators (TIs), which host backscattering-protected surface states, for this purpose. Using semiclassical methods, we demonstrate that nanoscale TI interconnects have a resistance 1-3 orders of magnitude lower than copper interconnects and graphene nanoribbons at the nanometer scale. We use the nonequilibrium Green function (NEGF) formalism to measure the change in conductance of nanoscale TI and metal interconnects caused by the presence of impurity disorder. We show that metal interconnects suffer a resistance increase, relative to the clean limit, in excess of 500% due to disorder while the TI's surface states increase less than 35% in the same regime.

Atomic Origins of the Self-Healing Function in Cement–Polymer Composites

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

Nguyen, Manh-Thuong; Wang, Zheming; Rod, Kenton A.

Motivated by recent advances in self-healing cement and epoxy polymer composites, we present a combined ab initio molecular dynamics and sum frequency generation (SFG) spectroscopy study of a calcium-silicate-hydrate/polymer interface. On stable, low-defect surfaces, the polymer only weakly adheres through coordination and hydrogen bonding interactions and can be easily mobilized towards defected surfaces. Conversely, on fractured surfaces, the polymer strongly anchors through ionic Ca-O bonds resulting from the deprotonation of polymer hydroxyl groups. In addition, polymer S-S groups are turned away from the cement/polymer interface, allowing for the self-healing function within the polymer. The overall elasticity and healing properties ofmore » these composites stem from a flexible hydrogen bonding network that can readily adapt to surface morphology. The theoretical vibrational signals associated with the proposed cement-polymer interfacial chemistry were confirmed experimentally by SFG spectroscopy.« less

Atomic Origins of the Self-Healing Function in Cement-Polymer Composites.

PubMed

Nguyen, Manh-Thuong; Wang, Zheming; Rod, Kenton A; Childers, M Ian; Fernandez, Carlos; Koech, Phillip K; Bennett, Wendy D; Rousseau, Roger; Glezakou, Vassiliki-Alexandra

2018-01-24

Motivated by recent advances in self-healing cement and epoxy polymer composites, we present a combined ab initio molecular dynamics and sum frequency generation (SFG) vibrational spectroscopy study of a calcium-silicate-hydrate/polymer interface. On stable, low-defect surfaces, the polymer only weakly adheres through coordination and hydrogen bonding interactions and can be easily mobilized toward defected surfaces. Conversely, on fractured surfaces, the polymer strongly anchors through ionic Ca-O bonds resulting from the deprotonation of polymer hydroxyl groups. In addition, polymer S-S groups are turned away from the cement-polymer interface, allowing for the self-healing function within the polymer. The overall elasticity and healing properties of these composites stem from a flexible hydrogen bonding network that can readily adapt to surface morphology. The theoretical vibrational signals associated with the proposed cement-polymer interfacial chemistry were confirmed experimentally by SFG vibrational spectroscopy.

Comblike poly(ethylene oxide)/hydrophobic C6 branched chitosan surfactant polymers as anti-infection surface modifying agents.

PubMed

Mai-ngam, Katanchalee

2006-05-01

A series of structurally well-defined poly(ethylene oxide)/hydrophobic C6 branched chitosan surfactant polymers that undergo surface induced self assembly on hydrophobic biomaterial surfaces were synthesized and characterized. The surfactant polymers consist of low molecular weight (Mw) chitosan backbone with hydrophilic poly(ethylene oxide) (PEO) and hydrophobic hexyl pendant groups. Chitosan was depolymerized by nitrous acid deaminative cleavage. Hexanal and aldehyde-terminated PEO chains were simultaneously attached to low Mw chitosan hydrochloride via reductive amination. The surfactant polymers were prepared with various ratios of the two side chains. The molecular composition of the surfactant polymers was determined by FT-IR and 1H NMR. Surface active properties at the air-water interface were determined by Langmuir film balance measurements. The surfactant polymers with PEO/hexyl ratios of 1:3.0 and 1:14.4 were used as surface modifying agents to investigate their anti-infection properties. E. coli adhesion on Silastic surface was decreased significantly by the surfactant polymer with PEO/hexyl 1:3.0. Surface growth of adherent E. coli was effectively suppressed by both tested surfactant polymers.

Polymer poling characterization using second harmonic generation (SHG)

NASA Astrophysics Data System (ADS)

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

2006-04-01

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

FS laser processing of bio-polymer thin films for studying cell-to-substrate specific response

NASA Astrophysics Data System (ADS)

Daskalova, A.; Nathala, Chandra S. R.; Kavatzikidou, P.; Ranella, A.; Szoszkiewicz, R.; Husinsky, W.; Fotakis, C.

2016-09-01

The use of ultra-short pulses for nanoengineering of biomaterials opens up possibilities for biological, medical and tissue engineering applications. Structuring the surface of a biomaterial into arrays with micro- and nanoscale features and architectures, defines new roadmaps to innovative engineering of materials. Thin films of novel collagen/elastin composite and gelatin were irradiated by Ti:sapphire fs laser in air at central wavelength 800 nm, with pulse durations in the range of 30 fs. The size and shape as well as morphological forms occurring in the resulted areas of interaction were analyzed as a function of irradiation fluence and number of pulses by atomic force microscopy (AFM). The fs interaction regime allows generation of well defined micro porous surface arrays. In this study we examined a novel composite consisting of collagen and elastin in order to create a biodegradable matrix to serve as a biomimetic surface for cell attachment. Confocal microscopy images of modified zones reveal formation of surface fringe patterns with orientation direction alongside the area of interaction. Outside the crater rim a wave-like topography pattern is observed. Structured, on a nanometer scale, surface array is employed for cell-culture experiments for testing cell's responses to substrate morphology. Mice fibroblasts migration was monitored after 3 days cultivation period using FESEM. We found that fibroblasts cells tend to migrate and adhere along the laser modified zones. The performed study proved that the immobilized collagen based biofilms suite as a template for successful fibroblasts cell guidance and orientation. Fs laser induced morphological modification of biomimetic materials exhibit direct control over fibroblasts behaviour due to induced change in their wettability state.

Nanogap embedded silver gratings for surface plasmon enhanced fluorescence

NASA Astrophysics Data System (ADS)

Bhatnagar, Kunal

Plasmonic nanostructures have been extensively used in the past few decades for applications in sub-wavelength optics, data storage, optoelectronic circuits, microscopy and bio-photonics. The enhanced electromagnetic field produced at the metal and dielectric interface by the excitation of surface plasmons via incident radiation can be used for signal enhancement in fluorescence and surface enhanced Raman scattering studies. Novel plasmonic structures have shown to provide very efficient and extreme light concentration at the nano-scale in recent years. The enhanced electric field produced within a few hundred nanometers of these surfaces can be used to excite fluorophores in the surrounding environment. Fluorescence based bio-detection and bio-imaging are two of the most important tools in the life sciences and improving the qualities and capabilities of fluorescence based detectors and imaging equipment remains a big challenge for industry manufacturers. We report a novel fabrication technique for producing nano-gap embedded periodic grating substrates on the nanoscale using a store bought HD-DVD and conventional soft lithography procedures. Polymethylsilsesquioxane (PMSSQ) polymer is used as the ink for the micro-contact printing process with PDMS stamps obtained from the inexpensive HD-DVDs as master molds. Fluorescence enhancement factors of up to 118 times were observed with these silver nanostructures in conjugation with Rhodamine-590 fluorescent dye. These substrates are ideal candidates for a robust and inexpensive optical system with applications such as low-level fluorescence based analyte detection, single molecule imaging, and surface enhanced Raman studies. Preliminary results in single molecule experiments have also been obtained by imaging individual 3 nm and 20 nm dye-doped nanoparticles attached to the silver plasmonic gratings using epi-fluorescence microscopy.

Living Nanocrystals: Synthesis of Precisely Defined Metal Oxide Nanocrystals Through a Continuous Growth Process

NASA Astrophysics Data System (ADS)

Jansons, Adam Wayne

Colloidal nanocrystals offer new and improved performance in applications as well as less environmental impact when compared to traditional device fabrication methods. The important properties that enable improved applications are a direct result of nanocrystal structure. While there have been many great advances in the production of colloidal nanocrystals over the past three decades, precise, atomic-level control of the size, composition, and structure of the inorganic core remains challenging. Rather than dictate these material aspects through traditional synthetic routes, this dissertation details the development and exploitation of a colloidal nanocrystal synthetic method inspired by polymerization reactions. Living polymerization reactions offer precise control of polymer size and structure and have tremendously advanced polymer science, allowing the intuitive production of polymers and block co-polymers of well-defined molecular weights. Similarly, living nanocrystal synthetic methods allow an enhanced level of structural control, granting the synthesis of binary, doped, and core/shell nanocrystals of well-defined size, composition, and structure. This improved control in turn grants enhanced nanocrystal property performance and deepens our understanding of structure/property relationships. This dissertation defines living nanocrystal growth and demonstrates the potential of the living methods in the colloidal production of oxide nanocrystals. After a brief introduction, living growth is defined and discussed in the context of synthetic prerequisites, attributes, and outcomes. Living growth is also compared to more traditional colloidal nanocrystal synthetic methods. The following chapters then demonstrate the precise control living approaches offer in three separate studies; the first highlights sub-nanometer control of nanocrystal size from 2-22+ nm in diameter. Next the improvement in nanocrystal composition is illustrated using several transition metal dopants into an oxide nanocrystal matrix at near thermodynamically allowed compositions. Additionally, precise radial dopant placement is demonstrated, which has striking implications for material properties. The radial position of tin in tin-doped indium oxide nanocrystals and the resulting differences on the localized surface plasmon resonance are discussed. Finally, future opportunities are reviewed. This dissertation includes previously published co-authored material.

Origin of change in molecular-weight dependence for polymer surface tension.

PubMed

Thompson, R B; Macdonald, J R; Chen, P

2008-09-01

Self-consistent-field theory is used to reproduce the behavior of polymer surface tension with molecular-weight for both lower and higher molecular-weight polymers. The change in behavior of the surface tension between these two regimes is shown to be due to the almost total exclusion of polymer from the nonpolymer bulk phase. The predicted two regime surface tension behavior with molecular-weight and the exclusion explanation are shown to be valid for a range of different polymer compressibilities.

Cell adhesion pattern created by OSTE polymers.

PubMed

Liu, Wenjia; Li, Yiyang; Ding, Xianting

2017-04-24

Engineering surfaces with functional polymers is a crucial issue in the field of micro/nanofabrication and cell-material interface studies. For many applications of surface patterning, it does not need cells to attach on the whole surface. Herein, we introduce a novel polymer fabrication protocol of off-stoichiometry thiol-ene (OSTE) polymers to create heterogeneity on the surface by utilizing 3D printing and soft-lithography. By choosing two OSTE polymers with different functional groups, we create a pattern where only parts of the surface can facilitate cell adhesion. We also study the hydrophilic property of OSTE polymers by mixing poly(ethylene glycol) (PEG) directly with pre-polymers and plasma treatments afterwards. Moreover, we investigate the effect of functional groups' excess ratio and hydrophilic property on the cell adhesion ability of OSTE polymers. The results show that the cell adhesion ability of OSTE materials can be tuned within a wide range by the coupling effect of functional groups' excess ratio and hydrophilic property. Meanwhile, by mixing PEG with pre-polymers and undergoing oxygen plasma treatment afterward can significantly improve the hydrophilic property of OSTE polymers.

Carbon fiber CVD coating by carbon nanostructured for space materials protection against atomic oxygen

NASA Astrophysics Data System (ADS)

Pastore, Roberto; Bueno Morles, Ramon; Micheli, Davide

2016-07-01

In recent years, the emphasis in space research has been shifting from space exploration to commercialization of space. In order to utilize space for commercial purposes it is necessary to understand the low earth orbit (LEO) space environment where most of the activities will be carried out. The studies on the LEO environment are mainly focused towards understanding the effect of atomic oxygen (AO) on spacecraft materials. In the first few shuttle flights, materials looked frosty because they were actually being eroded and textured: AO reacts with organic materials on spacecraft exteriors, gradually damaging them. When a spacecraft travel in LEO (where crewed vehicles and the International Space Station fly), the AO formed from the residual atmosphere can react with the spacecraft surfaces, causing damage to the vehicle. Polymers are widely used in space vehicles and systems as structural materials, thermal blankets, thermal control coatings, conformal coatings, adhesives, lubricants, etc. Exposure of polymers and composites to the space environment may result in different detrimental effects via modification of their chemical, electrical, thermal, optical and mechanical properties as well as surface erosion. The major degradation effects in polymers are due to their exposure to atomic oxygen, vacuum ultraviolet and synergistic effects, which result in different damaging effects by modification of the polymer's chemical properties. In hydrocarbon containing polymers the main AO effect is the surface erosion via chemical reactions and the release of volatile reaction products associated with the mass loss. The application of a thin protective coating to the base materials is one of the most commonly used methods of preventing AO degradation. The purpose is to provide a barrier between base material and AO environment or, in some cases, to alter AO reactions to inhibit its diffusion. The effectiveness of a coating depends on its continuity, porosity, degree of adhesion and durability in the environment. Though these coatings are efficient in protecting polymer composites, their application imposes severe constraints. Their thermal expansion coefficients may differ markedly from those of polymer composite substrates: as a result, cracks develop in the coatings on thermal cycling and AO can penetrate through them to the substrate. In addition to the technicalities of forming an effective barrier, such factors as cost, convenience of application and ease of repair are important considerations in the selection of a coating for a particular application. The latter issues drive the aerospace research toward the development of novel light composite materials, like the so called polymer nanocomposites, which are materials with a polymer matrix and a filler with at least one dimension less than 100 nanometers. Current interest in nanocomposites has been generated and maintained because nanoparticle-filled polymers exhibit unique combinations of properties not achievable with traditional composites. These combinations of properties can be achieved because of the small size of the fillers, the large surface area the fillers provide, and in many cases the unique properties of the fillers themselves. In particular, the carbon fiber-based polymeric composite materials are the basic point of interest: the aim of the present study is to find new solution to produce carbon fiber-based composites with even more upgraded performances. One intriguing strategy to tackle such an issue has been picked out in the coupling between the carbon fibers and the carbon nanostructures. That for two main reasons: first, carbon nanostructures have shown fancy potentialities for any kind of technological applications since their discovery, second, the chemical affinity between fiber and nanostructure (made of the same element) should be a likely route to approach the typical problems due to thermo-mechanical compatibility. This work is joined in such framework, by the purpose to integrate the carbon nanostructures in the carbon fibers by means of chemical vapor deposition (CVD) method, in order to develop the basic substrate of advanced carbon-based nanocomposite for atomic oxygen protection. The nanostructures grown onto the carbon fibers can be used to create multiscale hybrid carbon nanotube/carbon fiber composites where individual carbon fibers, which are several microns in diameter, are surrounded by nanotubes. The present objective is the setting-up of the CVD parameters for a reliable growth of carbon nanostructures on carbon fiber surface; after that, the results of a preliminary characterization related to atomic oxygen effects testing by means of a ground LEO simulation facility are reported and discussed.

Estimation of polymer-surface interfacial interaction strength by a contact AFM technique.

PubMed

Dvir, H; Jopp, J; Gottlieb, M

2006-12-01

Atomic force microscopy (AFM) measurements were employed to assess polymer-surface interfacial interaction strength. The main feature of the measurement is the use of contact-mode AFM as a tool to scratch off the polymer monolayer adsorbed on the solid surface. Tapping-mode AFM was used to determine the depth of the scraped recess. Independent determination of the layer thickness obtained from optical phase interference microscopy (OPIM) confirmed the depth of the AFM scratch. The force required for the complete removal of the polymer layer with no apparent damage to the substrate surface was determined. Polypropylene (PP), low-density polyethylene (PE), and PP-grafted-maleic anhydride (PP-g-ma) were scraped off silane-treated glass slabs, and the strength of surface interaction of the polymer layer was determined. In all cases it was determined that the magnitude of surface interaction force is of the order of van der Waals (VDW) interactions. The interaction strength is influenced either by polymer ability to wet the surface (hydrophobic or hydrophilic interactions) or by hydrogen bonding between the polymer and the surface treatment.

AFM Studies of Lunar Soils and Application to the Mars 2001 Mission

NASA Technical Reports Server (NTRS)

Weitz, C. M.; Anderson, M. S.; Marshall, J.

1999-01-01

The upcoming Mars 01 mission will carry an Atomic Force Microscope (AFM) as part of the Mars Environmental Compatibility Assessment (MECA) instrument. By operating in a tapping mode, the AFM is capable of sub-nanometer resolution in three dimensions and can distinguish between substances of different compositions by employing phase contrast imaging. To prepare for the Mars 01 mission, we are testing the AFM on a lunar soil to determine its ability to define particle shapes and sizes and grain-surface textures. The test materials are from the Apollo 17 soil 79221, which is a mixture of agglutinates, impact and volcanic beads, and mare and highland rock and mineral fragments. The majority of the lunar soil particles are less than 100 microns in size, comparable to the sizes estimated for martian dust. We have used the AFM to examine several different soil particles at various resolutions. The instrument has demonstrated the ability to identify parallel ridges characteristic of twinning on a 150 micron plagioclase feldspar particle. Extremely small (10-100 nanometer) adhering particles are visible on the surface of the feldspar grain, and they appear elongate with smooth surfaces. Phase contrast imaging of the nanometer particles shows several compositions to be present. When the AFM was applied to a 100 micron glass spherule, it was possible to define an extremely smooth surface; this is in clear contrast to results from a basalt fragment which exhibited a rough surface texture. Also visible on the surface of the glass spherule were chains of 100 nanometer and smaller impact melt droplets. For the '01 Mars mission, the AFM is intended to define the size and shape distributions of soil particles, in combination with the NMCA optical microscope system and images from the Robot Arm Camera (RAC). These three data sets will provide a means of assessing potentially hazardous soil and dust properties. The study that we have conducted on the lunar soils now suggests that the NMCA experiment will be able to define grain transport and weathering processes. For example, it should be possible to determine if Martian grains have been subjected to aeolian or water transport, volcanic activity, impact melting processes, in-situ weathering, and a host of other processes. Additionally, textural maturity could be assessed (via freshness and form of fracture patterns and grain shapes). Thus, the AFM has the potential to shed new light on Martian surface processes by adding the submicroscopic dimension to planetary investigations.

Nanometer Scale Titanium Surface Texturing Are Detected by Signaling Pathways Involving Transient FAK and Src Activations

PubMed Central

Zambuzzi, Willian F.; Bonfante, Estevam A.; Jimbo, Ryo; Hayashi, Mariko; Andersson, Martin; Alves, Gutemberg; Takamori, Esther R.; Beltrão, Paulo J.; Coelho, Paulo G.; Granjeiro, José M.

2014-01-01

Background It is known that physico/chemical alterations on biomaterial surfaces have the capability to modulate cellular behavior, affecting early tissue repair. Such surface modifications are aimed to improve early healing response and, clinically, offer the possibility to shorten the time from implant placement to functional loading. Since FAK and Src are intracellular proteins able to predict the quality of osteoblast adhesion, this study evaluated the osteoblast behavior in response to nanometer scale titanium surface texturing by monitoring FAK and Src phosphorylations. Methodology Four engineered titanium surfaces were used for the study: machined (M), dual acid-etched (DAA), resorbable media microblasted and acid-etched (MBAA), and acid-etch microblasted (AAMB). Surfaces were characterized by scanning electron microscopy, interferometry, atomic force microscopy, x-ray photoelectron spectroscopy and energy dispersive X-ray spectroscopy. Thereafter, those 4 samples were used to evaluate their cytotoxicity and interference on FAK and Src phosphorylations. Both Src and FAK were investigated by using specific antibody against specific phosphorylation sites. Principal Findings The results showed that both FAK and Src activations were differently modulated as a function of titanium surfaces physico/chemical configuration and protein adsorption. Conclusions It can be suggested that signaling pathways involving both FAK and Src could provide biomarkers to predict osteoblast adhesion onto different surfaces. PMID:24999733

The effect of polymer surface modification on polymer-protein interaction via interfacial polymerization and hydrophilic polymer grafting

USDA-ARS?s Scientific Manuscript database

Protein membrane separation is prone to fouling on the membrane surface resulting from protein adsorption onto the surface. Surface modification of synthetic membranes is one way to reduce fouling. We investigated surface modification of polyethersulfone (PES) as a way of improving hydrophilicity ...

Kinetically driven self-assembly of a binary solute mixture with controlled phase separation via electro-hydrodynamic flow of corona discharge.

PubMed

Jung, Hee Joon; Huh, June; Park, Cheolmin

2012-10-21

This feature article describes a new and facile process to fabricate a variety of thin films of non-volatile binary solute mixtures suitable for high performance organic electronic devices via electro-hydrodynamic flow of conventional corona discharge. Both Corona Discharge Coating (CDC) and a modified version of CDC, Scanning Corona Discharge Coating (SCDC), are based on utilizing directional electric flow, known as corona wind, of the charged uni-polar particles generated by corona discharge between a metallic needle and a bottom plate under a high electric field (5-10 kV cm(-1)). The electric flow rapidly spreads out the binary mixture solution on the bottom plate and subsequently forms a smooth and flat thin film in a large area within a few seconds. In the case of SCDC, the static movement of the bottom electrode on which a binary mixture solution is placed provides further control of thin film formation, giving rise to a film highly uniform over a large area. Interesting phase separation behaviors were observed including nanometer scale phase separation of a polymer-polymer binary mixture and vertical phase separation of a polymer-organic semiconductor mixture. Core-shell type phase separation of either polymer-polymer or polymer-colloidal nanoparticle binary mixtures was also developed with a periodically patterned microstructure when the relative location of the corona wind was controlled to a binary solution droplet on a substrate. We also demonstrate potential applications of thin functional films with controlled microstructures by corona coating to various organic electronic devices such as electroluminescent diodes, field effect transistors and non-volatile polymer memories.

Kinetically driven self-assembly of a binary solute mixture with controlled phase separation via electro-hydrodynamic flow of corona discharge

NASA Astrophysics Data System (ADS)

Jung, Hee Joon; Huh, June; Park, Cheolmin

2012-09-01

This feature article describes a new and facile process to fabricate a variety of thin films of non-volatile binary solute mixtures suitable for high performance organic electronic devices via electro-hydrodynamic flow of conventional corona discharge. Both Corona Discharge Coating (CDC) and a modified version of CDC, Scanning Corona Discharge Coating (SCDC), are based on utilizing directional electric flow, known as corona wind, of the charged uni-polar particles generated by corona discharge between a metallic needle and a bottom plate under a high electric field (5-10 kV cm-1). The electric flow rapidly spreads out the binary mixture solution on the bottom plate and subsequently forms a smooth and flat thin film in a large area within a few seconds. In the case of SCDC, the static movement of the bottom electrode on which a binary mixture solution is placed provides further control of thin film formation, giving rise to a film highly uniform over a large area. Interesting phase separation behaviors were observed including nanometer scale phase separation of a polymer-polymer binary mixture and vertical phase separation of a polymer-organic semiconductor mixture. Core-shell type phase separation of either polymer-polymer or polymer-colloidal nanoparticle binary mixtures was also developed with a periodically patterned microstructure when the relative location of the corona wind was controlled to a binary solution droplet on a substrate. We also demonstrate potential applications of thin functional films with controlled microstructures by corona coating to various organic electronic devices such as electroluminescent diodes, field effect transistors and non-volatile polymer memories.

Materials and methods for stabilizing nanoparticles in salt solutions

DOEpatents

Robinson, David Bruce; Zuckermann, Ronald; Buffleben, George M.

2013-06-11

Sequence-specific polymers are proving to be a powerful approach to assembly and manipulation of matter on the nanometer scale. Ligands that are peptoids, or sequence-specific N-functional glycine oligomers, allow precise and flexible control over the arrangement of binding groups, steric spacers, charge, and other functionality. We have synthesized short peptoids that can prevent the aggregation of gold nanoparticles in high-salt environments including divalent salt, and allow co-adsorption of a single DNA molecule. This degree of precision and versatility is likely to prove essential in bottom-up assembly of nanostructures and in biomedical applications of nanomaterials.

Experimental elaboration and analysis of dye-sensitized TiO2 solar cells (DSSC) dyed by natural dyes and conductive polymers

NASA Astrophysics Data System (ADS)

KałuŻyński, P.; Maciak, E.; Herzog, T.; Wójcik, M.

2016-09-01

In this paper we propose low cost and easy in development fully working dye-sensitized solar cell module made with use of a different sensitizing dyes (various anthocyanins and P3HT) for increasing the absorption spectrum, transparent conducting substrates (vaccum spattered chromium and gold), nanometer sized TiO2 film, iodide and methyl viologen dichloride based electrolyte, and a counter electrode (vaccum spattered platinum or carbon). Moreover, some of the different technologies and optimization manufacturing processes were elaborated for energy efficiency increase and were presented in this paper.

A general microchip surface modification approach using a spin-coated polymer resist film doped with hydroxypropyl cellulose.

PubMed

Sun, Xiuhua; Yang, Weichun; Geng, Yanli; Woolley, Adam T

2009-04-07

We have developed a simple and effective method for surface modification of polymer microchips by entrapping hydroxypropyl cellulose (HPC) in a spin-coated thin film on the surface. Poly(methyl methacrylate-8.5-methacrylic acid), a widely available commercial resist formulation, was utilized as a matrix for dissolving HPC and providing adherence to native polymer surfaces. Various amounts of HPC (0.1-2.0%) dissolved in the copolymer and spun on polymer surfaces were evaluated. The modified surfaces were characterized by contact angle measurement, X-ray photoelectron spectroscopy and atomic force microscopy. The developed method was applied on both poly(methyl methacrylate) and cyclic olefin copolymer microchips. A fluorescently labeled myoglobin digest, binary protein mixture, and human serum sample were all separated in these surface-modified polymer microdevices. Our work exhibits an easy and reliable way to achieve favorable biomolecular separation performance in polymer microchips.

A general microchip surface modification approach using a spin-coated polymer resist film doped with hydroxypropyl cellulose

PubMed Central

Sun, Xiuhua; Yang, Weichun; Geng, Yanli; Woolley, Adam T.

2009-01-01

We have developed a simple and effective method for surface modification of polymer microchips by entrapping hydroxypropyl cellulose (HPC) in a spin-coated thin film on the surface. Poly(methyl methacrylate-8.5-methacrylic acid), a widely available commercial resist formulation, was utilized as a matrix for dissolving HPC and providing adherence to native polymer surfaces. Various amounts of HPC (0.1–2.0%) dissolved in the copolymer and spun on polymer surfaces were evaluated. The modified surfaces were characterized by contact angle measurement, X-ray photoelectron spectroscopy and atomic force microscopy. The developed method was applied on both poly(methyl methacrylate) and cyclic olefin copolymer microchips. A fluorescently labeled myoglobin digest, binary protein mixture, and human serum sample were all separated in these surface-modified polymer microdevices. Our work exhibits an easy and reliable way to achieve favorable biomolecular separation performance in polymer microchips. PMID:19294306

Affinity study on bovine serum albumin's peptides to amphiphilic gold nanoparticles: A test of epitopes and non-epitopes

NASA Astrophysics Data System (ADS)

Yuan, Ming; Li, Wanrong; Yang, Mingming; Huang, Xiufeng; Bai, Zhijun; Liu, Yushuang; Cai, Weijun; Wang, Yuqin; Zhang, Feng

2017-09-01

It is an inevitable event that nanoparticles (NPs) will encounter proteins/peptides in nano-medicine, so it has been significant to know their interaction mechanism before in vivo applications. Previously, a 105-amino-acid sequence had been reported as the binding site between bovine serum albumin (BSA) and amphiphilic polymer coated gold nanoparticles (AP-AuNPs) along with a mortise-tenon joint hypothesis. This article tested the affinity difference between two epitope peptide sequences such as: LGEYGFQNALIVR (S1), DAFLGSFLYEYSR (S2) and one non-epitope peptide sequence as: FDEHVKLVNELTEF (S3). With the photoluminescent amino acid residues, the fluorescence quenching method based on the nanometal surface energy transfer (NSET) principle was able to study the thermodynamics of the current binding system. The binding constants (Ka) were determined and followed the order as: Ka-S1 > Ka-S2 >> Ka-S3. Moreover, Hill constants indicated that cooperativity only presented in the interactions of AP-AuNP with either S1 or S2, but not for S3. Moreover, gel electrophoresis, surface plasmon resonance, atomic force microscopy and three dimensional fluorescence microscopy were all also used to comprehensively analyse the binding interaction mechanism. These results further provided useful information to better understand the mortise-tenon joint, which might find applications to nanofabrication and biomedicine.

Structure of Cellulose Microfibrils in Primary Cell Walls from Collenchyma1[C][W][OA

PubMed Central

Thomas, Lynne H.; Forsyth, V. Trevor; Šturcová, Adriana; Kennedy, Craig J.; May, Roland P.; Altaner, Clemens M.; Apperley, David C.; Wess, Timothy J.; Jarvis, Michael C.

2013-01-01

In the primary walls of growing plant cells, the glucose polymer cellulose is assembled into long microfibrils a few nanometers in diameter. The rigidity and orientation of these microfibrils control cell expansion; therefore, cellulose synthesis is a key factor in the growth and morphogenesis of plants. Celery (Apium graveolens) collenchyma is a useful model system for the study of primary wall microfibril structure because its microfibrils are oriented with unusual uniformity, facilitating spectroscopic and diffraction experiments. Using a combination of x-ray and neutron scattering methods with vibrational and nuclear magnetic resonance spectroscopy, we show that celery collenchyma microfibrils were 2.9 to 3.0 nm in mean diameter, with a most probable structure containing 24 chains in cross section, arranged in eight hydrogen-bonded sheets of three chains, with extensive disorder in lateral packing, conformation, and hydrogen bonding. A similar 18-chain structure, and 24-chain structures of different shape, fitted the data less well. Conformational disorder was largely restricted to the surface chains, but disorder in chain packing was not. That is, in position and orientation, the surface chains conformed to the disordered lattice constituting the core of each microfibril. There was evidence that adjacent microfibrils were noncovalently aggregated together over part of their length, suggesting that the need to disrupt these aggregates might be a constraining factor in growth and in the hydrolysis of cellulose for biofuel production. PMID:23175754

Structure of cellulose microfibrils in primary cell walls from collenchyma.

PubMed

Thomas, Lynne H; Forsyth, V Trevor; Sturcová, Adriana; Kennedy, Craig J; May, Roland P; Altaner, Clemens M; Apperley, David C; Wess, Timothy J; Jarvis, Michael C

2013-01-01

In the primary walls of growing plant cells, the glucose polymer cellulose is assembled into long microfibrils a few nanometers in diameter. The rigidity and orientation of these microfibrils control cell expansion; therefore, cellulose synthesis is a key factor in the growth and morphogenesis of plants. Celery (Apium graveolens) collenchyma is a useful model system for the study of primary wall microfibril structure because its microfibrils are oriented with unusual uniformity, facilitating spectroscopic and diffraction experiments. Using a combination of x-ray and neutron scattering methods with vibrational and nuclear magnetic resonance spectroscopy, we show that celery collenchyma microfibrils were 2.9 to 3.0 nm in mean diameter, with a most probable structure containing 24 chains in cross section, arranged in eight hydrogen-bonded sheets of three chains, with extensive disorder in lateral packing, conformation, and hydrogen bonding. A similar 18-chain structure, and 24-chain structures of different shape, fitted the data less well. Conformational disorder was largely restricted to the surface chains, but disorder in chain packing was not. That is, in position and orientation, the surface chains conformed to the disordered lattice constituting the core of each microfibril. There was evidence that adjacent microfibrils were noncovalently aggregated together over part of their length, suggesting that the need to disrupt these aggregates might be a constraining factor in growth and in the hydrolysis of cellulose for biofuel production.

Ordered quasi-two-dimensional structure of nanoparticles in semiflexible ring polymer brushes under compression

NASA Astrophysics Data System (ADS)

Hua, Yunfeng; Deng, Zhenyu; Jiang, Yangwei; Zhang, Linxi

2017-06-01

Molecular dynamics simulations of a coarse-grained bead-spring model of ring polymer brushes under compression are presented. Flexible polymer brushes are always disordered during compression, whereas semiflexible polymer brushes tend to be ordered under sufficiently strong compression. Further, the polymer monomer density of the semiflexible polymer brush is very high near the brush surface, inducing a peak value of the free energy near the surface. Therefore, when nanoparticles are compressed in semiflexible ring polymer brushes, they tend to exhibit a closely packed single-layer structure between the brush surface and the impenetrable wall, and a quasi-two-dimensional ordered structure near the brush surface is formed under strong compression. These findings provide a new approach to designing responsive applications.

Process for hardening the surface of polymers

DOEpatents

Mansur, Louis K.; Lee, Eal H.

1992-01-01

Hard surfaced polymers and the method for making them is generally described. Polymers are subjected to simultaneous multiple ion beam bombardment, that results in a hardening of the surface and improved wear resistance.

Graphene and silver-nanoprism dispersion for printing optically-transparent electrodes

NASA Astrophysics Data System (ADS)

Sinar, Dogan; Knopf, George K.; Nikumb, Suwas

2017-02-01

Optically transparent electrodes (OTEs) are used for bioelectronics, touch screens, visual displays, and photovoltaic cells. Although the conductive coating for these electrodes is often composed of indium tin oxide (ITO), indium is a very expensive material and thin ITO films are relatively brittle compared to conductive polymer or graphene thin films. An alternative highly conductive optically transparent thin film based on a graphene (G) and silver-nanoprism (AgNP) dispersion is introduced in this paper. The aqueous G ink is first synthesized using carboxymethyl cellulose (CMC) as a stabilizing agent. Silver (Ag) nanoprisms are then prepared separately by a simple thermal process which involves the reduction of silver nitrate by sodium borohydride. These Ag nanoprisms are only a few nanometers thick but have relatively large surface areas (>1000 nm2). As a consequence, the nanoprisms provide more efficient injection of free carriers to the G layer. The concentrated G-AgNP dispersions are then deposited on optically transparent glass and polyimide substrates using an inkjet printer with a HP6602A print head. After printing, these optically thin films can be thermally treated to further increase electrical conductivity. Thermal treatment decomposes CMC which frees elemental carbon from polymer chain and, simultaneously, causes the film to become hydrophobic. Preliminary experiments demonstrate that the G-AgNP films on glass substrates exhibit high conductivity at 70% transparency (550 nm). Additional tests on the Gr-AgNP thin films printed on polymide substrates show mechanical stability under bending with minimal reduction in electrical conductivity or optical transparency.

Relaxation processes and glass transition of confined polymer melts: A molecular dynamics simulation of 1,4-polybutadiene between graphite walls.

PubMed

Solar, M; Binder, K; Paul, W

2017-05-28

Molecular dynamics simulations of a chemically realistic model for 1,4-polybutadiene in a thin film geometry confined by two graphite walls are presented. Previous work on melts in the bulk has shown that the model faithfully reproduces static and dynamic properties of the real material over a wide temperature range. The present work studies how these properties change due to nano-confinement. The focus is on orientational correlations observable in nuclear magnetic resonance experiments and on the local intermediate incoherent neutron scattering function, F s (q z , z, t), for distances z from the graphite walls in the range of a few nanometers. Temperatures from about 2T g down to about 1.15T g , where T g is the glass transition temperature in the bulk, are studied. It is shown that weakly attractive forces between the wall atoms and the monomers suffice to effectively bind a polymer coil that is near the wall. For a wide regime of temperatures, the Arrhenius-like adsorption/desorption kinetics of the monomers is the slowest process, while very close to T g the Vogel-Fulcher-Tammann-like α-relaxation takes over. The α-process is modified only for z≤1.2 nm due to the density changes near the walls, less than expected from studies of coarse-grained (bead-spring-type) models. The weakness of the surface effects on the glass transition in this case is attributed to the interplay of density changes near the wall with the torsional potential. A brief discussion of pertinent experiments is given.

Poly(ethylene oxide) surfactant polymers.

PubMed

Vacheethasanee, Katanchalee; Wang, Shuwu; Qiu, Yongxing; Marchant, Roger E

2004-01-01

We report on a series of structurally well-defined surfactant polymers that undergo surface-induced self-assembly on hydrophobic biomaterial surfaces. The surfactant polymers consist of a poly(vinyl amine) backbone with poly(ethylene oxide) and hexanal pendant groups. The poly(vinyl amine) (PVAm) was synthesized by hydrolysis of poly(N-vinyl formamide) following free radical polymerization of N-vinyl formamide. Hexanal and aldehyde-terminated poly(ethylene oxide) (PEO) were simultaneously attached to PVAm via reductive amination. Surfactant polymers with different PEO:hexanal ratios and hydrophilic/hydrophobic balances were prepared, and characterized by FT-IR, 1H-NMR and XPS spectroscopies. Surface active properties at the air/water interface were determined by surface tension measurements. Surface activity at a solid surface/water interface was demonstrated by atomic force microscopy, showing epitaxially molecular alignment for surfactant polymers adsorbed on highly oriented pyrolytic graphite. The surfactant polymers described in this report can be adapted for simple non-covalent surface modification of biomaterials and hydrophobic surfaces to provide highly hydrated interfaces.

Atomic Oxygen Erosion Yield Dependence Upon Texture Development in Polymers

NASA Technical Reports Server (NTRS)

Banks, Bruce A.; Loftus, Ryan J.; Miller, Sharon K.

2016-01-01

The atomic oxygen erosion yield (volume of a polymer that is lost due to oxidation per incident atom) of polymers is typically assumed to be reasonably constant with increasing fluence. However polymers containing ash or inorganic pigments, tend to have erosion yields that decrease with fluence due to an increasing presence of protective particles on the polymer surface. This paper investigates two additional possible causes for erosion yields of polymers that are dependent upon atomic oxygen. These are the development of surface texture which can cause the erosion yield to change with fluence due to changes in the aspect ratio of the surface texture that develops and polymer specific atomic oxygen interaction parameters. The surface texture development under directed hyperthermal attack produces higher aspect ratio surface texture than isotropic thermal energy atomic oxygen attack. The fluence dependence of erosion yields is documented for low Kapton H (DuPont, Wilmington, DE) effective fluences for a variety of polymers under directed hyperthermal and isotropic thermal energy attack.

Metal Oxide Nanoparticles in Electrospun Polymers and Their Fate in Aqueous Waste Streams

NASA Astrophysics Data System (ADS)

Hoogesteijn von Reitzenstein, Natalia

Nanotechnology is becoming increasingly present in our environment. Engineered nanoparticles (ENPs), defined as objects that measure less than 100 nanometers in at least one dimension, are being integrated into commercial products because of their small size, increased surface area, and quantum effects. These special properties have made ENPs antimicrobial agents in clothing and plastics, among other applications in industries such as pharmaceuticals, renewable energy, and prosthetics. This thesis incorporates investigations into both application of nanoparticles into polymers as well as implications of nanoparticle release into the environment. First, the integration of ENPs into polymer fibers via electrospinning was explored. Electrospinning uses an external electric field applied to a polymer solution to produce continuous fibers with large surface area and small volume, a quality which makes the fibers ideal for water and air purification purposes. Indium oxide and titanium dioxide nanoparticles were embedded in polyvinylpyrrolidone and polystyrene. Viscosity, critical voltage, and diameter of electrospun fibers were analyzed in order to determine the effects of nanoparticle integration into the polymers. Critical voltage and viscosity of solution increased at 5 wt% ENP concentration. Fiber morphology was not found to change significantly as a direct effect of ENP addition, but as an effect of increased viscosity and surface tension. These results indicate the possibility for seamless integration of ENPs into electrospun polymers. Implications of ENP release were investigated using phase distribution functional assays of nanoscale silver and silver sulfide, as well as photolysis experiments of nanoscale titanium dioxide to quantify hydroxyl radical production. Functional assays are a means of screening the relevant importance of multiple processes in the environmental fate and transport of ENPs. Four functional assays---water-soil, water-octanol, water-wastewater sludge and water-surfactant---were used to compare concentrations of silver sulfide ENPs (Ag2S-NP) and silver ENPs (AgNP) capped by four different coatings. The functional assays resulted in reproducible experiments which clearly showed variations between nanoparticle phase distributions; the findings may be a product of the effects of the different coatings of the ENPs used. In addition to phase distribution experiments, the production of hydroxyl radical (HO˙) by nanoscale titanium dioxide (TiO2) under simulated solar irradiation was investigated. Hydroxyl radical are a short-lived, highly reactive species produced by solar radiation in aquatic environments that affect ecosystem function and degrades pollutants. HO˙ is produced by photolysis of TiO2 and nitrate (NO3-); these two species were used in photolysis experiments to compare the relative loads of hydroxyl radical which nanoscale TiO2 may add upon release to natural waters. Para-chlorobenzoic acid (pCBA) was used as a probe. Measured rates of pCBA oxidation in the presence of various concentrations of TiO2 nanoparticles and NO3 - were utilized to calculate pseudo first order rate constants. Results indicate that, on a mass concentration basis in water, TiO2 produces hydroxyl radical steady state concentrations at 1.3 times more than the equivalent amount of NO3-; however, TiO 2 concentrations are generally less than one order of magnitude lower than concentrations of NO3-. This has implications for natural waterways as the amount of nanoscale TiO2 released from consumer products into natural waterways increases in proportion to its use.

Nature's Mechanisms for Tough, Self-healing Polymers and Polymer Adhesives

NASA Astrophysics Data System (ADS)

Hansma, Paul

2007-03-01

Spider silk^2 and the natural polymer adhesives in abalone shells^3 and bone^4,5 can give us insights into nature's mechanisms for tough, self-healing polymers and polymer adhesives. The natural polymer adhesives in biomaterials have been optimized by evolution. An optimized polymer adhesive has five characteristics. 1) It holds together the strong elements of the composite. 2) It yields just before the strong elements would otherwise break. 3) It dissipates large amounts of energy as it yields. 4) It self heals after it yields. 5) It takes just a few percent by weight. Both natural polymer adhesives and silk rely on sacrificial bonds and hidden length for toughness and self-healing.^6 A relatively large energy, of order 100eV, is required to stretch a polymer molecule after a weak bond, a sacrificial bond, breaks and liberates hidden length, which was previously hidden, typically in a loop or folded domain, from whatever was stretching the polymer. The bond is called sacrificial if it breaks at forces well below the forces that could otherwise break the polymer backbone, typically greater than 1nN. In many biological cases, the breaking of sacrificial bonds has been found to be reversible, thereby also providing a ``self-healing'' property to the material.^2-4 Individual polymer adhesive molecules based on sacrificial bonds and hidden length can supply forces of order 300pN over distances of 100s of nanometers. Model calculations show that a few percent by weight of adhesives based on these principles could be optimized adhesives for high performance composite materials including nanotube and graphene sheet composites. ^2N. Becker, E. Oroudjev, S. Mutz et al., Nature Materials 2 (4), 278 (2003). ^3B. L. Smith, T. E. Schaffer, M. Viani et al., Nature 399 (6738), 761 (1999). ^4J. B. Thompson, J. H. Kindt, B. Drake et al., Nature 414 (6865), 773 (2001). ^5G. E. Fantner, T. Hassenkam, J. H. Kindt et al., Nature Materials 4, 612 (2005). ^6G. E. Fantner, E. Oroudjev, G. Schitter et al., Biophysical Journal 90 (4), 1411 (2006).

Fabrication of a nanometer thick nitrogen delta doped layer at the sub-surface region of (100) diamond

NASA Astrophysics Data System (ADS)

Chandran, Maneesh; Michaelson, Shaul; Saguy, Cecile; Hoffman, Alon

2016-11-01

In this letter, we report on the proof of a concept of an innovative delta doping technique to fabricate an ensemble of nitrogen vacancy centers at shallow depths in (100) diamond. A nitrogen delta doped layer with a concentration of ˜1.8 × 1020 cm-3 and a thickness of a few nanometers was produced using this method. Nitrogen delta doping was realized by producing a stable nitrogen terminated (N-terminated) diamond surface using the RF nitridation process and subsequently depositing a thin layer of diamond on the N-terminated diamond surface. The concentration of nitrogen on the N-terminated diamond surface and its stability upon exposure to chemical vapor deposition conditions are determined by x-ray photoelectron spectroscopy analysis. The SIMS profile exhibits a positive concentration gradient of 1.9 nm/decade and a negative gradient of 4.2 nm/decade. The proposed method offers a finer control on the thickness of the delta doped layer than the currently used ion implantation and delta doping techniques.

Process for hardening the surface of polymers

DOEpatents

Mansur, L.K.; Lee, E.H.

1992-07-14

Hard surfaced polymers and the method for making them is generally described. Polymers are subjected to simultaneous multiple ion beam bombardment, that results in a hardening of the surface and improved wear resistance. 1 figure.

Method of making a coating of a microtextured surface

DOEpatents

Affinito, John D [Tucson, AZ; Graff, Gordon L [West Richland, WA; Martin, Peter M [Kennewick, WA; Gross, Mark E [Pasco, WA; Burrows, Paul E [Kennewick, WA; Sapochak, Linda S [Henderson, NV

2004-11-02

A method for conformally coating a microtextured surface. The method includes flash evaporating a polymer precursor forming an evaporate, passing the evaporate to a glow discharge electrode creating a glow discharge polymer precursor plasma from the evaporate, cryocondensing the glow discharge polymer precursor plasma on the microtextured surface and crosslinking the glow discharge polymer precursor plasma thereon, wherein the crosslinking resulting from radicals created in the glow discharge polymer precursor plasma.

Laser-induced asymmetric faceting and growth of a nano-protrusion on a tungsten tip

NASA Astrophysics Data System (ADS)

Yanagisawa, Hirofumi; Zadin, Vahur; Kunze, Karsten; Hafner, Christian; Aabloo, Alvo; Kim, Dong Eon; Kling, Matthias F.; Djurabekova, Flyura; Osterwalder, Jürg; Wuensch, Walter

2016-12-01

Irradiation of a sharp tungsten tip by a femtosecond laser and exposed to a strong DC electric field led to reproducible surface modifications. By a combination of field emission microscopy and scanning electron microscopy, we observed asymmetric surface faceting with sub-ten nanometer high steps. The presence of faceted features mainly on the laser-exposed side implies that the surface modification was driven by a laser-induced transient temperature rise on a scale of a couple of picoseconds in the tungsten tip apex. Moreover, we identified the formation of a nano-tip a few nanometers high located at one of the corners of a faceted plateau. The results of simulations emulating the experimental conditions are consistent with the experimental observations. The presented technique would be a new method to fabricate a nano-tip especially for generating coherent electron pulses. The features may also help to explain the origin of enhanced field emission, which leads to vacuum arcs, in high electric field devices such as radio-frequency particle accelerators.

Instability of confined water films between elastic surfaces.

PubMed

de Beer, Sissi; 't Mannetje, Dieter; Zantema, Sietske; Mugele, Frieder

2010-03-02

We investigated the dynamics of nanometer thin water films at controlled ambient humidity adsorbed onto two atomically smooth mica sheets upon rapidly bringing the surfaces into contact. Using a surface forces apparatus (SFA) in imaging mode, we found that the water films break up into a distribution of drops with a typical thickness of a few nanometers and a characteristic lateral size and spacing of several micrometers. Whereas the characteristic length is found to be independent of the ambient humidity, the characteristic time of the breakup decreases from approximately 1 to 0.01 s with increasing humidity. The existence of characteristic length and time scales shows that this breakup is controlled by an instability rather than a conventional nucleation and growth mechanism for SFA experiments. These findings cannot be explained by a dispersion-driven instability mechanism. In contrast, a model involving the elastic energies for the deformation of both the mica sheets and the underlying glue layer correctly reproduces the scaling of the characteristic length and time with humidity.

Polymer surface treatment with particle beams

DOEpatents

Stinnett, Regan W.; VanDevender, J. Pace

1999-01-01

A polymer surface and near surface treatment process produced by irradiation with high energy particle beams. The process is preferably implemented with pulsed ion beams. The process alters the chemical and mechanical properties of the polymer surface in a manner useful for a wide range of commercial applications.

Birefringence and anisotropic optical absorption in porous silicon

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

Efimova, A. I., E-mail: efimova@vega.phys.msu.ru; Krutkova, E. Yu.; Golovan', L. A.

2007-10-15

The refractive indices and the coefficients of optical absorption by free charge carriers and local vibrations in porous silicon (por-Si) films, comprising nanometer-sized silicon residues (nanocrystals) separated by nanometer-sized pores (nanopores) formed in the course of electrochemical etching of the initial single crystal silicon, have been studied by polarization-resolved IR absorption spectroscopy techniques. It is shown that the birefringence observed in por-Si is related to the anisotropic shapes of nanocrystals and nanopores, while the anisotropy (dichroism) of absorption by the local vibrational modes is determined predominantly by the microrelief of the surface of nanocrystals. It is demonstrated that silicon-hydrogen surfacemore » bonds in nanocrystals can be restored by means of selective hydrogen thermodesorption with the formation of a considerable number of H-terminated surface Si-Si dimers.« less

Solar cell comprising a plasmonic back reflector and method therefor

DOEpatents

Ding, I-Kang; Zhu, Jia; Cui, Yi; McGehee, Michael David

2014-11-25

A method for forming a solar cell having a plasmonic back reflector is disclosed. The method includes the formation of a nanoimprinted surface on which a metal electrode is conformally disposed. The surface structure of the nanoimprinted surface gives rise to a two-dimensional pattern of nanometer-scale features in the metal electrode enabling these features to collectively form the plasmonic back reflector.

Nano-scale topography of bearing surface in advanced alumina/zirconia hip joint before and after severe exposure in water vapor environment.

PubMed

Pezzotti, Giuseppe; Saito, Takuma; Padeletti, Giuseppina; Cossari, Pierluigi; Yamamoto, Kengo

2010-06-01

The aim of this study was to perform a surface morphology assessment with nanometer scale resolution on femoral heads made of an advanced zirconia toughened alumina (ZTA) composite. Femoral heads were characterized to a degree of statistical accuracy in the as-received state and after exposures up to 100 h in severe vapor-moist environment. Surface screening was made using an atomic force microscope (AFM). Scanning was systematically repeated on portions of surface as large as several tens of micrometers, randomly selected on the head surface, to achieve sufficient statistical reliability without lowering the nanometer-scale spatial resolution of the roughness measurement. No significant difference was found in the recorded values of surface roughness after environmental exposure (at 134 degrees C, under 2 bar), which was always comparable to that of the as-received head. Surface roughness safely lay <10 nm after environmental exposures up to 100 h, which corresponded to an exposure time in vivo of several human lifetimes (i.e., according to an experimentally derived thermal activation energy). In addition, the roughness results were significantly (about one order of magnitude) lower as compared to those recorded on femoral heads made of monolithic zirconia tested under the same conditions. (c) 2010 Orthopaedic Research Society. Published by Wiley Periodicals, Inc.

Laser Pulse Bidirectional Reflectance from CALIPSO Mission

NASA Technical Reports Server (NTRS)

Lu, Xiaomei; Hu, Yongxiang; Yang, Yuekui; Liu, Zhaoyan; Vaughan, Mark; Lucker, Patricia; Trepte, Charles

2017-01-01

In this Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation (CALIPSO) study, we present a simple way of determining laser pulse bidirectional reflectance over snow/ice surface using the Cloud-Aerosol LIdar with Orthogonal Polarization (CALIOP) 532 nanometer polarization channels' measurements. The saturated laser pulse returns from snow and ice surfaces are recovered based on surface tail information. The method overview and initial assessment of the method performance will be presented. The retrieved snow surface bidirectional reflectance is compared with reflectance from both CALIOP cloud cover regions and Moderate Resolution Imaging Spectroradiometer (Earth Observing System (EOS)) (MODIS) Bi-directional Reflectance Distribution Function (BRDF) / Albedo model parameters. The comparisons show that the snow surface bidirectional reflectance over Antarctica for saturation region are generally reliable with a mean value of about 0.90 plus or minus 0.10, while the mean surface reflectance from cloud cover region is about 0.84 plus or minus 0.13 and the calculated MODIS reflectance at 555 nanometers from the BRDF / Albedo model with near nadir illumination and viewing angles is about 0.96 plus or minus 0.04. The comparisons here demonstrate that the snow surface reflectance underneath the cloud with cloud optical depth of about 1 is significantly lower than that for a clear sky condition.

Study of first electronic transition and hydrogen bonding state of ultra-thin water layer of nanometer thickness on an α-alumina surface by far-ultraviolet spectroscopy

NASA Astrophysics Data System (ADS)

Goto, Takeyoshi; Kinugasa, Tomoya

2018-05-01

The first electronic transition (A˜ ← X˜) and the hydrogen bonding state of an ultra-thin water layer of nanometer thickness between two α-alumina surfaces (0.5-20 nm) were studied using far-ultraviolet (FUV) spectroscopy in the wavelength range 140-180 nm. The ultra-thin water layer of nanometer thickness was prepared by squeezing a water droplet ( 1 μL) between a highly polished α-alumina prism and an α-alumina plate using a high pressure clamp ( 4.7 MPa), and the FUV spectra of the water layer at different thicknesses were measured using the attenuated total reflection method. As the water layer became thinner, the A˜ ← X˜ bands were gradually shifted to higher or lower energy relative to that of bulk water; at thicknesses smaller than 4 nm, these shifts were substantial (0.1-0.2 eV) in either case. The FUV spectra of the water layer with thickness < 4 nm indicate the formation of structured ice-like hydrogen bond (H-bond) layers for the higher energy shifts or the formation of slightly weaker H-bond layers as compared to those in the bulk liquid state for lower energy shifts. In either case, the H-bond structure of bulk liquid water is nearly lost at thicknesses below 4 nm, because of steric hydration forces between the α-alumina surfaces.

The electrostatic fluidic trap: a new approach to the spatial control and manipulation of matter at the nanometer scale (presentation video)

NASA Astrophysics Data System (ADS)

Krishnan, Madhavi

2014-09-01

I will describe a new technique to trap matter at the nanometer scale in fluids. Rather than apply external fields to the object of interest, our approach relies on spatial tailoring of the interaction between an object and its neighbouring surfaces in order to create spatial potential minima in three dimensions. We demonstrate how the strong and long-ranged electrostatic interaction can be modulated by tailoring substrate geometry to achieve stable spatial trapping of charged objects, as small as single proteins in solution.

Ellipsometric Analysis of Contaminant Layer on Optical Witness Samples from MISSE

NASA Technical Reports Server (NTRS)

Norwood, Joseph K.

2007-01-01

Several optical witness samples included in the Materials for International Space Station Experiment (MISSE) trays have been analyzed with a variable angle spectroscopic ellipsometer or VASE. Witness samples of gold or platinum mirrors are extremely useful as collectors of space-borne contamination, due to the relative inertness of these noble metals in the atomic oxygen-rich environment of LEO. Highly accurate thickness measurements, typically at the sub-nanometer scale, may be achieved with this method, which uses polarized light in a spectral range of 300 to 1300 nanometers at several angles of incidence to the sample surface.

Molecular Level Investigations of Interfacial Friction of Polymer Brush Surfaces

NASA Astrophysics Data System (ADS)

Perry, Scott

2005-03-01

The development of synthetic polymer lubricants to mimic joint lubrication within the human body will be presented. Unlike most industrial applications involving oils and greases, lubrication of these joints is accomplished in an aqueous environment. Fundamentally, water is a poor lubricant in most settings due to the weak pressure dependence of its viscosity, yet the contacting surfaces of skeletal joints function with low friction throughout a lifetime. Motivated by the molecular structure of materials making up joint surfaces, interfacial friction between polymer brush surfaces under aqueous environments has been probed with an array of molecularly sensitive surface analytical techniques including atomic force microscopy. The brush surfaces, comprised of poly(L-lysine)-g-poly(ethylene glycol) (PLL-g-PEG), have been generated through the spontaneous adsorption of polymer from solution onto oxide substrates and sodium borosilicate surfaces (AFM tip). The character of the polymer films has been investigated in-situ with the quartz crystal microbalance (QCM) and atomic force microscope (AFM) and ex-situ with ellipsometry and X-ray photoelectron spectroscopy (XPS). The interfacial friction measurements have been carried out on polymer-coated substrates with bare or polymer-coated, microsphere-attached tips in over a range of solution conditions. It was found that the adsorption of polymer on oxides strikingly reduced the interfacial friction, resulting in ultra-low friction under certain conditions. By using a series of PLL-g-PEG polymers differing from each other in PEG side-chain length and grafting ratio, we observed that frictional properties of polymer-coated interfaces strongly depend on the architecture of PLL-g-PEG. Polymer-film formation and the influence of polymer architecture will be reviewed while the role of solvent and manifestation of ultra-low friction will be discussed in detail.

Nanotechnology: MEMS and NEMS and their applications to smart systems and devices

NASA Astrophysics Data System (ADS)

Varadan, Vijay K.

2003-10-01

The microelectronics industry has seen explosive growth during the last thirty years. Extremely large markets for logic and memory devices have driven the development of new materials, and technologies for the fabrication of even more complex devices with features sizes now down at the sub micron and nanometer level. Recent interest has arisen in employing these materials, tools and technologies for the fabrication of miniature sensors and actuators and their integration with electronic circuits to produce smart devices and systems. This effort offers the promise of: (1) increasing the performance and manufacturability of both sensors and actuators by exploiting new batch fabrication processes developed including micro stereo lithographic and micro molding techniques; (2) developing novel classes of materials and mechanical structures not possible previously, such as diamond like carbon, silicon carbide and carbon nanotubes, micro-turbines and micro-engines; (3) development of technologies for the system level and wafer level integration of micro components at the nanometer precision, such as self-assembly techniques and robotic manipulation; (4) development of control and communication systems for MEMS devices, such as optical and RF wireless, and power delivery systems, etc. A novel composite structure can be tailored by functionalizing carbon nano tubes and chemically bonding them with the polymer matrix e.g. block or graft copolymer, or even cross-linked copolymer, to impart exceptional structural, electronic and surface properties. Bio- and Mechanical-MEMS devices derived from this hybrid composite provide a new avenue for future smart systems. The integration of NEMS (NanoElectroMechanical Systems), MEMS, IDTs (Interdigital Transducers) and required microelectronics and conformal antenna in the multifunctional smart materials and composites results in a smart system suitable for sending and control of a variety functions in automobile, aerospace, marine and civil strutures and food and medical industries. This unique combination of technologies also results in novel conformal sensors that can be remotely sensed by an antenna system with the advantage of no power requirements at the sensor site. This paper provides a brief review of MEMS and NEMS based smart systems for various applications mentioned above. Carbon Nano Tubes (CNT) with their unique structure, have already proven to be valuable in their application as tips for scanning probe microscopy, field emission devices, nanoelectronics, H2-storage, electromagnetic absorbers, ESD, EMI films and coatings and structural composites. For many of these applications, highly purified and functionalized CNT which are compatible with many host polymers are needed. A novel microwave CVD processing technique to meet these requirements has been developed at Penn State Center for the Engineering of Electronic and Acoustic Materials and Devices (CEEAMD). This method enables the production of highly purified carbon nano tubes with variable size (from 5 - 40 nm) at low cost (per gram) and high yield. Whereas, carbon nano tubes synthesized using the laser ablation or arc discharge evaporation method always include impurity due to catalyst or catalyst support. The Penn State research is based on the use of zeolites over other metal/metal oxides in the microwave field for a high production and uniformity of the product. An extended coventional purification method has been employed to purify our products in order to remove left over impurity. A novel composite structure can be tailored by functionalizing carbon nano tubes and chemically bonding them with the polymer matrix e.g. block or graft copolymer, or even cross-linked copolymer, to impart exceptional structural, electronic and surface properties. Bio- and Mechanical-MEMS devices derived from this hybrid composites will be presented.

MEMS- and NEMS-based smart devices and systems

NASA Astrophysics Data System (ADS)

Varadan, Vijay K.

2001-11-01

The microelectronics industry has seen explosive growth during the last thirty years. Extremely large markets for logic and memory devices have driven the development of new materials, and technologies for the fabrication of even more complex devices with features sized now don at the sub micron and nanometer level. Recent interest has arisen in employing these materials, tools and technologies for the fabrication of miniature sensors and actuators and their integration with electronic circuits to produce smart devices and systems. This effort offers the promise of: 1) increasing the performance and manufacturability of both sensors and actuators by exploiting new batch fabrication processes developed including micro stereo lithographic an micro molding techniques; 2) developing novel classes of materials and mechanical structures not possible previously, such as diamond like carbon, silicon carbide and carbon nanotubes, micro-turbines and micro-engines; 3) development of technologies for the system level and wafer level integration of micro components at the nanometer precision, such as self-assembly techniques and robotic manipulation; 4) development of control and communication systems for MEMS devices, such as optical and RF wireless, and power delivery systems, etc. A novel composite structure can be tailored by functionalizing carbon nano tubes and chemically bonding them with the polymer matrix e.g. block or graft copolymer, or even cross-linked copolymer, to impart exceptional structural, electronic and surface properties. Bio- and Mechanical-MEMS devices derived from this hybrid composite provide a new avenue for future smart systems. The integration of NEMS (NanoElectroMechanical Systems), MEMS, IDTs (Interdigital Transducers) and required microelectronics and conformal antenna in the multifunctional smart materials and composites results in a smart system suitable for sensing and control of a variety functions in automobile, aerospace, marine and civil structures and food and medical industries. This unique combination of technologies also results in novel conformal sensors that can be remotely sensed by an antenna system with the advantage of no power requirements at the sensor site. This paper provides a brief review of MEMS and NEMS based smart systems for various applications mentioned above. Carbon Nano Tubes (CNT) with their unique structure, have already proven to be valuable in their application as tips for scanning probe microscopy, field emission devices, nanoelectronics, H2-storage, electromagnetic absorbers, ESD, EMI films and coatings and structural composites. For many of these applications, highly purified and functionalized CNT which are compatible with many host polymers are needed. A novel microwave CVD processing technique to meet these requirements has been developed at Penn State Center for the engineering of Electronic and Acoustic Materials and Devices (CEEAMD). This method enables the production of highly purified carbon nano tubes with variable size (from 5-40 nm) at low cost (per gram) and high yield. Whereas, carbon nano tubes synthesized using the laser ablation or arc discharge evaporation method always include impurity due to catalyst or catalyst support. The Penn State research is based on the use of zeolites over other metal/metal oxides in the microwave field for a high production and uniformity of the product. An extended conventional purification method has been employed to purify our products in order to remove left over impurity. A novel composite structure can be tailored by functionalizing carbon nano tubes and chemically bonding them with the polymer matrix e.g. block or graft copolymer, or even cross- linked copolymer, to impart exceptional structural, electronic and surface properties. Bio- and Mechanical-MEMS devices derived from this hybrid composites will be presented.

Experimental studies of contact angle hysteresis phenomena on polymer surfaces – Toward the understanding and control of wettability for different applications.

PubMed

Grundke, K; Pöschel, K; Synytska, A; Frenzel, R; Drechsler, A; Nitschke, M; Cordeiro, A L; Uhlmann, P; Welzel, P B

2015-08-01

Contact angle hysteresis phenomena on polymer surfaces have been studied by contact angle measurements using sessile liquid droplets and captive air bubbles in conjunction with a drop shape method known as Axisymmetric Drop Shape Analysis - Profile (ADSA-P). In addition, commercially available sessile drop goniometer techniques were used. The polymer surfaces were characterized with respect to their surface structure (morphology, roughness, swelling) and surface chemistry (elemental surface composition, acid-base characteristics) by scanning electron microscopy (SEM), scanning force microscopy (SFM), ellipsometry, X-ray photoelectron spectroscopy (XPS) and streaming potential measurements. Heterogeneous polymer surfaces with controlled roughness and chemical composition were prepared by different routes using plasma etching and subsequent dip coating or grafting of polymer brushes, anodic oxidation of aluminium substrates coated with thin polymer films, deposition techniques to create regular patterned and rough fractal surfaces from core-shell particles, and block copolymers. To reveal the effects of swelling and reorientation at the solid/liquid interface contact angle hysteresis phenomena on polyimide surfaces, cellulose membranes, and thermo-responsive hydrogels have been studied. The effect of different solutes in the liquid (electrolytes, surfactants) and their impact on contact angle hysteresis were characterized for solid polymers without and with ionizable functional surface groups in aqueous electrolyte solutions of different ion concentrations and pH and for photoresist surfaces in cationic aqueous surfactant solutions. The work is an attempt toward the understanding of contact angle hysteresis phenomena on polymer surfaces aimed at the control of wettability for different applications. Copyright © 2014 Elsevier B.V. All rights reserved.

Interaction Mechanisms between Air Bubble and Molybdenite Surface: Impact of Solution Salinity and Polymer Adsorption.

PubMed

Xie, Lei; Wang, Jingyi; Yuan, Duowei; Shi, Chen; Cui, Xin; Zhang, Hao; Liu, Qi; Liu, Qingxia; Zeng, Hongbo

2017-03-07

The surface characteristics of molybdenite (MoS 2 ) such as wettability and surface interactions have attracted much research interest in a wide range of engineering applications, such as froth flotation. In this work, a bubble probe atomic force microscope (AFM) technique was employed to directly measure the interaction forces between an air bubble and molybdenite mineral surface before/after polymer (i.e., guar gum) adsorption treatment. The AFM imaging showed that the polymer coverage on the surface of molybdenite could achieve ∼5.6, ∼44.5, and ∼100% after conditioning in 1, 5, and 10 ppm polymer solution, respectively, which coincided with the polymer coverage results based on contact angle measurements. The electrolyte concentration and surface treatment by polymer adsorption were found to significantly affect bubble-mineral interaction and attachment. The experimental force results on bubble-molybdenite (without polymer treatment) agreed well with the calculations using a theoretical model based on the Reynolds lubrication theory and augmented Young-Laplace equation including the effect of disjoining pressure. The overall surface repulsion was enhanced when the NaCl concentration decreased from 100 to 1 mM, which inhibited the bubble-molybdenite attachment. After conditioning the molybdenite surface in 1 ppm polymer solution, it was more difficult for air bubbles to attach to the molybdenite surface due to the weakened hydrophobic interaction with a shorter decay length. Increasing the polymer concentration to 5 ppm effectively inhibited bubble attachment on mineral surface, which was mainly due to the much reduced hydrophobic interaction as well as the additional steric repulsion between the extended polymer chains and bubble surface. The results provide quantitative information on the interaction mechanism between air bubbles and molybdenite mineral surfaces on the nanoscale, with useful implications for the development of effective polymer depressants and fundamental understanding of bubble-solid interactions in mineral flotation. The methodologies used in this work can be readily extended to studying similar interfacial interactions in many other engineering applications such as froth flotation deinking and bitumen extraction in oil sands industry.

Surface Characterization of an Organized Titanium Dioxide Layer

NASA Astrophysics Data System (ADS)

Curtis, Travis

Soft lithographic printing techniques can be used to control the surface morphology of titanium dioxide layers on length scales of several hundred nanometers. Controlling surface morphology and volumetric organization of titanium dioxide electrodes can potentially be used in dye-sensitized solar cell devices. This thesis explores how layer-by-layer replication can lead to well defined, dimensionally controlled volumes and details how these control mechanisms influence surface characteristics of the semiconducting oxide.

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.

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.

Determination of mechanical behavior of nanoscale materials using molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Heo, Seongjun

It is important to understand the mechanical properties of nanometer-scale materials for use in such applications as microelectromechanical systems (MEMS) and nanoelectromechanical systems (NEMS). These properties are difficult to measure directly using experimental methods due to their small sizes. Computational simulations provide important insights that complement experimental data and lead to improved understanding of the mechanical properties of nanometer-scale systems. Molecular dynamics (MD) simulations, which are used to investigate the properties of materials at the atomic scale, is used in my research to determine (1) best thermostat managing way for acceptable mechanical behavior of nanoscale systems; (2) filling effect on the bending and compressive properties of carbon nanotubes (CNTs); (3) vibrational behavior of bridged and cantilevered CNT bombarded by external fluid atoms; (4) frictional behavior of filled CNT bundles and the effect of external molecules on friction; (5) effect of sliding orientations on the tribological properties of polyethylene (PE). In all the simulations the reactive empirical bond-order (REBO) potential combined with the Lennard Jones potential is applied to control inter-atomic interactions. During the MD simulations, thermostats are used to maintain the system temperature at a constant value. Tests indicate that the simulations describe the mechanical behavior of CNTs differently depending on the type of thermostat used, and the relative fraction of the system to which the thermostat is applied. The results indicate that Langevin and velocity rescaling thermostats are more reliable for temperature control than the Nose-Hoover thermostat. In examining CNT bending and compression, the simulations predict filled CNTs are more resistant to external bending and compressive forces than hollow CNTs. The mechanical properties deteriorate with increases in temperature and number of CNT wall defects. MD simulations of the vibrational behavior of bridged and cantilevered CNTs are found to match the results of continuum mechanics calculations. The principal vibration frequency of the CNT is predicted to decrease with increasing nanotube length, gas pressure, and the atomic mass of the external fluid. In studies of CNT tribology, simulations show that two layers of filled CNTs are more resistant to compressive forces and exhibit lower friction coefficients during sliding than unfilled CNTs. The friction coefficient increases with the thickness of the CNT layer due to the increase in effective friction interface. The addition of an external, molecular fluid of benzene molecules is predicted to reduce the friction coefficient of CNTs because of the lubricity of the molecules. Lastly, simulation results illustrate the effect of relative orientation on the tribological properties of polyethylene (PE) sliding surfaces. The friction coefficient of perpendicular sliding is much higher than that of parallel sliding based on the polymer chain orientation. The PE exhibits stick-slip motion during sliding regardless of the sliding orientation. In addition, the PE shows no surface morphology change due to the higher strength of the PE bonds, which is in contrast to the behavior of other polymers, such as polytetrafluoroethylene (PTFE), which exhibits bond breaking and realignment of surface chains along the sliding direction in the less favorable orientation.

Polymer surface treatment with particle beams

DOEpatents

Stinnett, R.W.; VanDevender, J.P.

1999-05-04

A polymer surface and near surface treatment process produced by irradiation with high energy particle beams is disclosed. The process is preferably implemented with pulsed ion beams. The process alters the chemical and mechanical properties of the polymer surface in a manner useful for a wide range of commercial applications. 16 figs.

Optical monitoring of proteins at solid interfaces

NASA Astrophysics Data System (ADS)

Dunne, G.; McDonnell, L.; Miller, R.; McMillan, N. D.; O'Rourke, B.; Mitchell, C. I.

2005-06-01

The adsorption properties of polymers are of great importance for implant studies. A better understanding of these properties can lead to improved implant materials. In this study the surface energy of different polymers was derived from contact angle measurements taken using profile analysis tensiometry (PAT) of sessile drops of water. The contact angles were measured for advancing and receding water drops on polished polymer surfaces and also on polymer surfaces modified by adsorbing protein to the surface prior to analysis of the sessile drop. The protein used was bovine serum albumin (BSA) and the surfaces were poly-methylmethacrylate (PMMA), poly-ether-ether-ketone (PEEK) and stainless steel. The polymer surfaces were also studied using atomic force microscopy (AFM). Images of the surfaces were taken in different states: rough, smooth and with albumin adsorbed. As a method to identify the proteins on the surface easier, anti-albumin antibodies with 30nm nano gold particles attached were adsorbed to the albumin on the surfaces. Using nano gold particles made the imaging more straightforward and thus made identification of the protein on the surface easier. The results from this work show the differing hydrophobicities of polymer surfaces under different conditions and a new nanotechnological method of protein identification.

Polyelectrolyte-Mediated Transport of Doxorubicin Through the Bilayer Lipid Membrane

NASA Astrophysics Data System (ADS)

Yaroslavov, Alexander A.; Kitaeva, Marina V.; Melik-Nubarov, Nikolay S.; Menger, Frederic M.

A model is developed for the effect of ionic polymers on the transport of doxorubicin, an antitumor drug, through a bilayer membrane. Accordingly, a protonated (cationic) form of doxorubicin binds to an anionic polymer, poly(acrylic acid), the resulting complex being several hundred nanometers in size. Nevertheless, large complex species associate with neutral egg lecithin liposomes by means of hydrophobic attraction between the doxorubicin and the liposome bilayer. Then, the doxorubicin enters the liposome interior which has been imparted with an acidic buffer to protonate the doxorubicin. The rate of transmembrane Dox permeation decreases when elevating the polyacid-to-doxorubicin ratio. A cationic polymer, polylysine, being coupled with liposomes containing the negative lipid cardiolipin, accelerates membrane transport of doxorubicin with the maximum rate at a complete neutralization of the membrane charge by an interacting polycation. The effect of a polycation on doxorubicin transport becomes more pronounced as small negative liposomes (60-80 nm in diameter) are changed to larger ones (approx. 600 nm in diameter). An opportunity thus opens up for the manipulation of the kinetics of drug uptake by cells and, ultimately, the control of the pharmaceutical action of drugs.

Polymer Dynamics from Synthetic to Biological Macromolecules

NASA Astrophysics Data System (ADS)

Richter, D.; Niedzwiedz, K.; Monkenbusch, M.; Wischnewski, A.; Biehl, R.; Hoffmann, B.; Merkel, R.

2008-02-01

High resolution neutron scattering together with a meticulous choice of the contrast conditions allows to access the large scale dynamics of soft materials including biological molecules in space and time. In this contribution we present two examples. One from the world of synthetic polymers, the other from biomolecules. First, we will address the peculiar dynamics of miscible polymer blends with very different component glass transition temperatures. Polymethylmetacrylate (PMMA), polyethyleneoxide (PEO) are perfectly miscible but exhibit a difference in the glass transition temperature by 200 K. We present quasielastic neutron scattering investigations on the dynamics of the fast component in the range from angströms to nanometers over a time frame of five orders of magnitude. All data may be consistently described in terms of a Rouse model with random friction, reflecting the random environment imposed by the nearly frozen PMMA matrix on the fast mobile PEO. In the second part we touch on some new developments relating to large scale internal dynamics of proteins by neutron spin echo. We will report results of some pioneering studies which show the feasibility of such experiments on large scale protein motion which will most likely initiate further studies in the future.

One-step synthesis and patterning of aligned polymer nanowires on a substrate

DOEpatents

Wang, Zhong L [Marietta, GA; Wang, Xudong [Atlanta, GA; Morber, Jenny R [Atlanta, GA; Liu, Jin [Danbury, CT

2011-11-08

In a method of making a polymer structure on a substrate a layer of a first polymer, having a horizontal top surface, is applied to a surface of the substrate. An area of the top surface of the polymer is manipulated to create an uneven feature that is plasma etched to remove a first portion from the layer of the first polymer thereby leaving the polymer structure extending therefrom. A light emitting structure includes a conductive substrate from which an elongated nanostructure of a first polymer extends. A second polymer coating is disposed about the nanostructure and includes a second polymer, which includes a material such that a band gap exists between the second polymer coating and the elongated nanostructure. A conductive material coats the second polymer coating. The light emitting structure emits light when a voltage is applied between the conductive substrate and the conductive coating.

Surface Lewis acid-base properties of polymers measured by inverse gas chromatography.

PubMed

Shi, Baoli; Zhang, Qianru; Jia, Lina; Liu, Yang; Li, Bin

2007-05-18

Surface Lewis acid-base properties are significant for polymers materials. The acid constant, K(a) and base constant, K(b) of many polymers were characterized by some researchers with inverse gas chromatography (IGC) in recent years. In this paper, the surface acid-base constants, K(a) and K(b) of 20 kinds of polymers measured by IGC in recent years are summarized and discussed, including seven polymers characterized in this work. After plotting K(b) versus K(a), it is found that the polymers can be encircled by a triangle. They scatter in two regions of the triangle. Four polymers exist in region I. K(b)/K(a) of the polymers in region I are 1.4-2.1. The other polymers exist in region II. Most of the polymers are relative basic materials.

Chemical anchoring of organic conducting polymers to semiconducting surfaces

DOEpatents

Frank, A.J.; Honda, K.

1984-01-01

According to the present invention, an improved method of coating electrodes with conductive polymer films and/or preselected catalysts is provided. The charge conductive polymer is covalently or coordinatively attached to the electrode surface to strengthen the adhesion characteristics of the polymer to the electrode surface or to improve charge conductive properties between the conductive polymer and the electrode surface. Covalent or coordinative attachment is achieved by a number of alternative methods including covalently or coordinatively attaching the desired monomer to the electrode by means of a suitable coupling reagent and, thereafter, electrochemically polymerizing the monomer in situ.

Chemical anchoring of organic conducting polymers to semiconducting surfaces

DOEpatents

Frank, Arthur J.; Honda, Kenji

1984-01-01

According to the present invention, an improved method of coating electrodes with conductive polymer films and/or preselected catalysts is provided. The charge-conductive polymer is covalently or coordinatively attached to the electrode surface to strengthen the adhesion characteristics of the polymer to the electrode surface or to improve charge-conductive properties between the conductive polymer and the electrode surface. Covalent or coordinative attachment is achieved by a number of alternative methods including covalently or coordinatively attaching the desired monomer to the electrode by means of a suitable coupling reagent and, thereafter, electrochemically polymerizing the monomer in situ.

Solvothermal synthesis of nanoporous polymer chalk for painting superhydrophobic surfaces.

PubMed

Zhang, Yong-Lai; Wang, Jian-Nan; He, Yan; He, Yinyan; Xu, Bin-Bin; Wei, Shu; Xiao, Feng-Shou

2011-10-18

Reported here is a facile synthesis of nanoporous polymer chalk for painting superhydrophobic surfaces. Taking this nanoporous polymer as a media, superhydrophobicity is rapidly imparted onto three typical kinds of substrates, including paper, transparent polydimethylsiloxane (PDMS), and finger skin. Quantitative characterization showed that the adhesion between the water droplet and polymer-coated substrates decreased significantly compared to that on the original surface, further indicating the effective wetting mode transformation. The nanoporous polymer coating would open a new door for facile, rapid, safe, and larger scale fabrication of superhydrophobic surfaces on general substrates. © 2011 American Chemical Society

Chemical Patterning by Mechanical Removal of Aqueous Polymers

NASA Astrophysics Data System (ADS)

Barnett, Katherine; Knoebel, Jodi; Davis, Robert C.

2006-10-01

We are developing a new method for micro and nanoscale patterning of lipids and proteins on solid surfaces. A layer of polyethylene glycol (PEG) teminated polyallyl amine (PAA) was initially applied to a mica surface. The PEG surface is a low adhesion surface for proteins. Following polymer deposition an Atomic Force Microscope (AFM) tip was used to remove the polymer layer in desired regions. AFM imaging of the surface after mechanical polymer removal shows squares of exposed MICA surrounded by the PEG surface. The clean mica regions are now available for specific adsorption of lipid or protein layers.

Nano Scale Mechanical Analysis of Biomaterials Using Atomic Force Microscopy

NASA Astrophysics Data System (ADS)

Dutta, Diganta

The atomic force microscope (AFM) is a probe-based microscope that uses nanoscale and structural imaging where high resolution is desired. AFM has also been used in mechanical, electrical, and thermal engineering applications. This unique technique provides vital local material properties like the modulus of elasticity, hardness, surface potential, Hamaker constant, and the surface charge density from force versus displacement curve. Therefore, AFM was used to measure both the diameter and mechanical properties of the collagen nanostraws in human costal cartilage. Human costal cartilage forms a bridge between the sternum and bony ribs. The chest wall of some humans is deformed due to defective costal cartilage. However, costal cartilage is less studied compared to load bearing cartilage. Results show that there is a difference between chemical fixation and non-chemical fixation treatments. Our findings imply that the patients' chest wall is mechanically weak and protein deposition is abnormal. This may impact the nanostraws' ability to facilitate fluid flow between the ribs and the sternum. At present, AFM is the only tool for imaging cells' ultra-structure at the nanometer scale because cells are not homogeneous. The first layer of the cell is called the cell membrane, and the layer under it is made of the cytoskeleton. Cancerous cells are different from normal cells in term of cell growth, mechanical properties, and ultra-structure. Here, force is measured with very high sensitivity and this is accomplished with highly sensitive probes such as a nano-probe. We performed experiments to determine ultra-structural differences that emerge when such cancerous cells are subject to treatments such as with drugs and electric pulses. Jurkat cells are cancerous cells. These cells were pulsed at different conditions. Pulsed and non-pulsed Jurkat cell ultra-structures were investigated at the nano meter scale using AFM. Jurkat cell mechanical properties were measured under different conditions. In addition, AFM was used to measure the charge density of cell surface in physiological conditions. We found that the treatments changed the cancer cells' ultra-structural and mechanical properties at the nanometer scale. Finally, we used AFM to characterize many non-biological materials with relevance to biomedical science. Various metals, polymers, and semi-conducting materials were characterized in air and multiple liquid media through AFM - techniques from which a plethora of industries can benefit. This applies especially to the fledging solar industry which has found much promise in nanoscopic insights. Independent of the material being examined, a reliable method to measure the surface force between a nano probe and a sample surface in a variety of ionic concentrations was also found in the process of procuring these measurements. The key findings were that the charge density increases with the increase of the medium's ionic concentration.

Surface Characterization of Polymer Blends by XPS and ToF-SIMS

PubMed Central

Chan, Chi Ming; Weng, Lu-Tao

2016-01-01

The surface properties of polymer blends are important for many industrial applications. The physical and chemical properties at the surface of polymer blends can be drastically different from those in the bulk due to the surface segregation of the low surface energy component. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary mass spectrometry (ToF-SIMS) have been widely used to characterize surface and bulk properties. This review provides a brief introduction to the principles of XPS and ToF-SIMS and their application to the study of the surface physical and chemical properties of polymer blends. PMID:28773777

Chemical-state-selective mapping at nanometer scale using synchrotron radiation and photoelectron emission microscopy.

PubMed

Hirao, Norie; Baba, Yuji; Sekiguchi, Tetsuhiro; Shimoyama, Iwao; Honda, Mitsunori

2010-01-01

For surface analyses of semiconductor devices and various functional materials, it has become indispensable to analyze valence states at nanometer scale due to the rapid developments of nanotechnology. Since a method for microscopic mapping dependent on the chemical bond states has not been established so far, we have developed a photoelectron emission microscopy (PEEM) system combined with synchrotron soft X-ray excitation. The samples investigated were Si/SiO(x) micro-patterns prepared by O(2)(+) ion implantation in Si(001) wafer using a mask. PEEM images excited by various photon energies around the Si K-edge were observed. The lateral spatial resolution of the system was about 41 nm. The brightness of each spot in PEEM images changed depending on the photon energy, due to the X-ray absorption intensity of the respective chemical state. Since the surface of this sample was topographically flat, it has been demonstrated that the present method can be applied to observations of the microscopic pattern, depending not on the morphology, but only on the valence states of silicon. We have also in-situ measured the changes of the PEEM images upon annealing, and elucidated the mechanism of the lateral diffusion of oxygen and valence states of silicon at the nanometer scale.

Multiple Ion Implantation Effects on Wear and Wet Ability of Polyethylene Based Polymers

NASA Astrophysics Data System (ADS)

Torrisi, L.; Visco, A. M.; Campo, N.

2004-10-01

Polyethylene based polymers were ion implanted with multiple irradiations of different ions (N+, Ar+ and Kr+) at energies between 30 keV and 300 keV and doses ranging between 1013 and 1016 ions/cm2. The ion implantation dehydrogenises the polyethylene inducing cross-link effects in the residual polymer carbons. At high doses the irradiated surface show properties similar to graphite surfaces. The depth of the modified layers depends on the ion range in polyethylene at the incident ion energy. The chemical modification depends on the implanted doses and on the specie of the incident ions. A "pin-on-disc" machine was employed to measure the polymer wear against AISI-316 L stainless steel. A "contact-angle-test" machine was employed to measure the wet ability of the polymer surface for 1 μl pure water drop. Measurements demonstrate that the multiple ion implantation treatments decrease the surface wear and the surface wetting and produce a more resistant polymer surface. The properties of the treated surfaces improves the polymer functionality for many bio-medical applications, such as those relative to the polyethylene friction discs employed in knee and hip prosthesis joints. The possibility to use multiply ion implantations of polymers with traditional ion implanters and with laser ion sources producing plasmas is investigated.

Electrostatic Assembly of Nanomaterials for Hybrid Electrodes and Supercapacitors

NASA Astrophysics Data System (ADS)

Hammond, Paula

2015-03-01

Electrostatic assembly methods have been used to generate a range of new materials systems of interest for electrochemical energy and storage applications. Over the past several years, it has been demonstrated that carbon nanotubes, metals, metal oxides, polymeric nanomaterials, and biotemplated materials systems can be incorporated into ultrathin films to generate supercapacitors and battery electrodes that illustrate significant energy density and power. The unique ability to control the incorporation of such a broad range of materials at the nanometer length scale allows tailoring of the final properties of these unique composite systems, as well as the capability of creating complex micron-scale to nanoporous morphologies based on the scale of the nanomaterial that is absorbed within the structure, or the conditions of self-assembly. Recently we have expanded these capabilities to achieve new electrodes that are templated atop electrospun polmer fiber scaffolds, in which the polymer can be selectively removed to achieve highly porous materials. Spray-layer-by-layer and filtration methods of functionalized multiwall carbon nanotubes and polyaniline nanofibers enable the generation of electrode systems with unusually high surface. Incorporation of psuedocapacitive nanoparticles can enhance capacitive properties, and other catalytic or metallic nanoparticles can be implemented to enhance electrochemical or catalytic function.

Biogenic formation and growth of uraninite (UO₂).

PubMed

Lee, Seung Yeop; Baik, Min Hoon; Choi, Jong Won

2010-11-15

Biogenic UO₂ (uraninite) nanocrystals may be formed as a product of a microbial reduction process in uranium-enriched environments near the Earth's surface. We investigated the size, nanometer-scale structure, and aggregation state of UO₂ formed by iron-reducing bacterium, Shewanella putrefaciens CN32, from a uranium-rich solution. Characterization of biogenic UO₂ precipitates by high-resolution transmission electron microscopy (HRTEM) revealed that the UO₂ nanoparticles formed were highly aggregated by organic polymers. Nearly all of the nanocrystals were networked in more or less 100 nm diameter spherical aggregates that displayed some concentric UO₂ accumulation with heterogeneity. Interestingly, pure UO₂ nanocrystals were piled on one another at several positions via UO₂-UO₂ interactions, which seem to be intimately related to a specific step in the process of growing large single crystals. In the process, calcium that was easily complexed with aqueous uranium(VI) appeared not to be combined with bioreduced uranium(IV), probably due to its lower binding energy. However, when phosphate was added to the system, calcium was found to be easily associated with uranium(IV), forming a new uranium phase, ningyoite. These results will extend the limited knowledge of microbial uraniferous mineralization and may provide new insights into the fate of aqueous uranium complexes.

Radiative Enhancement of Linear and Third-Order Vibrational Excitations by an Array of Infrared Plasmonic Antennas.

PubMed

Gandman, Andrey; Mackin, Robert T; Cohn, Bar; Rubtsov, Igor V; Chuntonov, Lev

2018-05-22

Infrared gold antennas localize enhanced near fields close to the metal surface, when excited at the frequency of their plasmon resonance, and amplify vibrational signals from the nearby molecules. We study the dependence of the signal enhancement on the thickness of a polymer film containing vibrational chromophores, deposited on the antenna array, using linear (FTIR) and third-order femtosecond vibrational spectroscopy (transient absorption and 2DIR). Our results show that for a film thickness beyond only a few nanometers the near-field interaction is not sufficient to account for the magnitude of the observed signal, which nevertheless has a clear Fano line shape, suggesting a radiative origin of the molecule-plasmon interaction. The mutual radiative damping of plasmonic and molecular transitions leads to the spectroscopic signal of a molecular vibrational excitation to be enhanced by up to a factor of 50 in the case of linear spectroscopy and over 2000 in the case of third-order spectroscopy. A qualitative explanation for the observed effect is given by the extended coupled oscillators model, which takes into account both near-field and radiative interactions between the plasmonic and molecular transitions.

UV light induced surface modification of HDPE films with bioactive compounds

NASA Astrophysics Data System (ADS)

Daniloska, Vesna; Blazevska-Gilev, Jadranka; Dimova, Vesna; Fajgar, Radek; Tomovska, Radmila

2010-01-01

The development of different techniques for surface modification of polymers becomes popular in a last decade. These techniques preserve useful bulk polymer properties unchanged, while the activation of the polymer surface offers more possibilities for polymer applications. In this work, a new, one-step method for bio-activation of HDPE (high density polyethylene) surface by UV irradiation is presented. HDPE films coupled with selected active compound and a photoinitiator was treated by UV lamp, emitting light at 254 nm. For surface functionalization of HDPE films, the following compounds were employed: 2-aminopyridine (AP), N 1-(2-pyridylaminomethyl)-1,2,4-triazole (TA) and benzocaine (BC). The influence of irradiation time on the extent of surface changes was investigated. The modified polymer surfaces were investigated by Fourier transformed infrared (FTIR) and Raman spectroscopy, scanning electron microscopy (SEM) and contact angle measurements, demonstrating successful functionalization of HDPE surface.

Interference techniques in fluorescence microscopy

NASA Astrophysics Data System (ADS)

Dogan, Mehmet

We developed a set of interference-based optical microscopy techniques to study biological structures through nanometer-scale axial localization of fluorescent biomarkers. Spectral self-interference fluorescence microscopy (SSFM) utilizes interference of direct and reflected waves emitted from fluorescent molecules in the vicinity of planar reflectors to reveal the axial position of the molecules. A comprehensive calculation algorithm based on Green's function formalism is presented to verify the validity of approximations used in a far-field approach that describes the emission of fluorescent markers near interfaces. Using the validated model, theoretical limits of axial localization were determined with emphasis given to numerical aperture (NA) dependence of localization uncertainty. SSFM was experimentally demonstrated in conformational analysis of nucleoproteins. In particular, interaction between surface-tethered 75-mer double strand DNA and integration host factor (IHF) protein was probed on Si-SiO2 substrates by determining the axial position of fluorescent labels attached to the free ends of DNA molecules. Despite its sub-nanometer precision axial localization capability, SSFM lacks high lateral resolution due to the low-NA requirement for planar reflectors. We developed a second technique, 4Pi-SSFM, which improves the lateral resolution of a conventional SSFM system by an order of magnitude while achieving nanometer-scale axial localization precision. Using two opposing high-NA objectives, fluorescence signal is interferometrically collected and spectral interference pattern is recorded. Axial position of emitters is found from analysis of the spectra. The 4Pi-SSFM technique was experimentally demonstrated by determining the surface profiles of fabricated glass surfaces and outer membranes of Shigella, a type of Gram-negative bacteria. A further discussion is presented to localize surface O antigen, which is an important oligosaccharide structure in the virulence mechanism of the Gram-negative bacteria, including E. coli and Shigella.

Smart tool holder

DOEpatents

Day, Robert Dean; Foreman, Larry R.; Hatch, Douglas J.; Meadows, Mark S.

1998-01-01

There is provided an apparatus for machining surfaces to accuracies within the nanometer range by use of electrical current flow through the contact of the cutting tool with the workpiece as a feedback signal to control depth of cut.

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

Martinez, Andre P.; Carrillo, Jan-Michael Y.; Dobrynin, Andrey V.

The molecular weight and polydispersity of the chains in a polymer brush are critical parameters determining the brush properties. However, the characterization of polymer brushes is hindered by the vanishingly small mass of polymer present in brush layers. In this study, in order to obtain sufficient quantities of polymer for analysis, polymer brushes were grown from high surface area fibrous nylon membranes by ATRP. We synthesized the brushes with varying surface initiator densities, polymerization times, and amounts of sacrificial initiator, then cleaved from the substrate, and analyzed by GPC and NMR. Characterization showed that the surface-grown polymer chains were moremore » polydisperse and had lower average molecular weight compared to solution-grown polymers synthesized concurrently. Furthermore, the molecular weight distribution of the polymer brushes was observed to be bimodal, with a low molecular weight population of chains representing a significant mass fraction of the polymer chains at high surface initiator densities. Moreover, the origin of this low MW polymer fraction is proposed to be the termination of growing chains by recombination during the early stages of polymerization, a mechanism confirmed by molecular dynamics simulations of brush polymerization.« less

Durable polymer-aerogel based superhydrophobic coatings, a composite material

DOEpatents

Kissel, David J; Brinker, Charles Jeffrey

2014-03-04

Provided are polymer-aerogel composite coatings, devices and articles including polymer-aerogel composite coatings, and methods for preparing the polymer-aerogel composite. The exemplary article can include a surface, wherein the surface includes at least one region and a polymer-aerogel composite coating disposed over the at least one region, wherein the polymer-aerogel composite coating has a water contact angle of at least about 140.degree. and a contact angle hysteresis of less than about 1.degree.. The polymer-aerogel composite coating can include a polymer and an ultra high water content catalyzed polysilicate aerogel, the polysilicate aerogel including a three dimensional network of silica particles having surface functional groups derivatized with a silylating agent and a plurality of pores.

Durable polymer-aerogel based superhydrophobic coatings: a composite material

DOEpatents

Kissel, David J.; Brinker, Charles Jeffrey

2016-02-02

Provided are polymer-aerogel composite coatings, devices and articles including polymer-aerogel composite coatings, and methods for preparing the polymer-aerogel composite. The exemplary article can include a surface, wherein the surface includes at least one region and a polymer-aerogel composite coating disposed over the at least one region, wherein the polymer-aerogel composite coating has a water contact angle of at least about 140.degree. and a contact angle hysteresis of less than about 1.degree.. The polymer-aerogel composite coating can include a polymer and an ultra high water content catalyzed polysilicate aerogel, the polysilicate aerogel including a three dimensional network of silica particles having surface functional groups derivatized with a silylating agent and a plurality of pores.

Hydrophobically-associating cationic polymers as micro-bubble surface modifiers in dissolved air flotation for cyanobacteria cell separation.

PubMed

Yap, R K L; Whittaker, M; Diao, M; Stuetz, R M; Jefferson, B; Bulmus, V; Peirson, W L; Nguyen, A V; Henderson, R K

2014-09-15

Dissolved air flotation (DAF), an effective treatment method for clarifying algae/cyanobacteria-laden water, is highly dependent on coagulation-flocculation. Treatment of algae can be problematic due to unpredictable coagulant demand during blooms. To eliminate the need for coagulation-flocculation, the use of commercial polymers or surfactants to alter bubble charge in DAF has shown potential, termed the PosiDAF process. When using surfactants, poor removal was obtained but good bubble adherence was observed. Conversely, when using polymers, effective cell removal was obtained, attributed to polymer bridging, but polymers did not adhere well to the bubble surface, resulting in a cationic clarified effluent that was indicative of high polymer concentrations. In order to combine the attributes of both polymers (bridging ability) and surfactants (hydrophobicity), in this study, a commercially-available cationic polymer, poly(dimethylaminoethyl methacrylate) (polyDMAEMA), was functionalised with hydrophobic pendant groups of various carbon chain lengths to improve adherence of polymer to a bubble surface. Its performance in PosiDAF was contrasted against commercially-available poly(diallyl dimethyl ammonium chloride) (polyDADMAC). All synthesised polymers used for bubble surface modification were found to produce positively charged bubbles. When applying these cationic micro-bubbles in PosiDAF, in the absence of coagulation-flocculation, cell removals in excess of 90% were obtained, reaching a maximum of 99% cell removal and thus demonstrating process viability. Of the synthesised polymers, the polymer containing the largest hydrophobic functionality resulted in highly anionic treated effluent, suggesting stronger adherence of polymers to bubble surfaces and reduced residual polymer concentrations. Copyright © 2014 Elsevier Ltd. All rights reserved.

Ion implantation method for preparing polymers having oxygen erosion resistant surfaces

DOEpatents

Lee, Eal H.; Mansur, Louis K.; Heatherly, Jr., Lee

1995-01-01

Hard surfaced polymers and the method for making them are generally described. Polymers are subjected to simultaneous multiple ion beam bombardment, that results in a hardening of the surface, improved wear resistance, and improved oxygen erosion resistance.

Designing of silk and ZnO based antibacterial and noncytotoxic bionanocomposite films and study of their mechanical and UV absorption behavior.

PubMed

Kiro, Anamika; Bajpai, Jaya; Bajpai, A K

2017-01-01

Bionanocomposites of sericin and polyvinyl alcohol (PVA) were prepared by solution casting method and zinc oxide nanoparticles were impregnated within the polymer blend matrix through homogenous phase reaction between zinc chloride and sodium hydroxide at high temperature following an ex-situ co-precipitation method. The prepared bionanocomposites were characterized using Fourier Transform Infrared Spectroscopy, X-ray diffraction, Field Emission Scanning Electron Microscopy, Transmission Electron Microscopy and Atomic Force Microscopy techniques. The presence of characteristic groups of sericin and ZnO nanoparticles was ascertained by the FTIR spectra. XRD analysis confirmed the impregnation of ZnO nanoparticles and sericin within the PVA matrix. XRD and FESEM of the bionanocomposites provided information about their semicrystalline nature, crystallite size of the particles, and irregular rough surfaces. The TEM confirmed the size of ZnO particles to be in the nanometer range. AFM confirmed the platykurtic nature of the surface while the negative surface skewness shows the predominance of valleys over peaks suggesting for the planar nature of the surface of the bionanocomposites. UV absorption properties of bionanocomposite films were determined by UV absorption spectroscopy. UV absorption increased with increasing amount of ZnO nanoparticles in the nanocomposites. Sericin was found to absorb UV-C radiations between 200-290nm which is mainly due to aromatic amino acids like tryptophan, tyrosine and phenylalanine. The ZnO nanoparticles and sericin protein showed antimicrobial properties as evident from the inhibition zones obtained against Staphylococcus aureus and Escherichia coli. The bionanocomposite was found to be noncytotoxic which was proved by in vitro cytotoxicity test. Microhardness of bionanocomposite films increased with increase in the amount of ZnO nanoparticles in the sericin and PVA matrix. Copyright © 2016 Elsevier Ltd. All rights reserved.

Polymer Brushes Containing Sulfonated Sugar Repeat Units: Synthesis, Characterization and In Vitro Testing of Blood Coagulation Activation

PubMed Central

Ayres, N.; Holt, D. J.; Jones, C.F.; Corum, L. E.; Grainger, D. W.

2009-01-01

A new polymer brush chemistry containing sulfonated carbohydrate repeat units has been synthesized from silicon substrates using ATRP methods and characterized both in bulk and using surface analysis. The polymer brush was designed to act as a mimic for the naturally occurring sulfonated glycosaminoglycan, heparin, commonly used for modifying blood-contacting surfaces both in vitro and in vivo. Surface analysis showed conversion of brush saccharide precursor chemistry to the desired sulfonated polymer product. The sulfonated polymer brush surface was further analyzed using three conventional in vitro tests for blood compatibility -- plasma recalcification times, complement activation, and thrombin generation. The sulfonated polymer brush films on silicon oxide wafers exhibited better assay performance in these blood component assays than the unsulfonated sugar functionalized polymer brush in all tests performed. PMID:19859552

Micromechanics of Amorphous Metal/Polymer Hybrid Structures with 3D Cellular Architectures: Size Effects, Buckling Behavior, and Energy Absorption Capability.

PubMed

Mieszala, Maxime; Hasegawa, Madoka; Guillonneau, Gaylord; Bauer, Jens; Raghavan, Rejin; Frantz, Cédric; Kraft, Oliver; Mischler, Stefano; Michler, Johann; Philippe, Laetitia

2017-02-01

By designing advantageous cellular geometries and combining the material size effects at the nanometer scale, lightweight hybrid microarchitectured materials with tailored structural properties are achieved. Prior studies reported the mechanical properties of high strength cellular ceramic composites, obtained by atomic layer deposition. However, few studies have examined the properties of similar structures with metal coatings. To determine the mechanical performance of polymer cellular structures reinforced with a metal coating, 3D laser lithography and electroless deposition of an amorphous layer of nickel-boron (NiB) is used for the first time to produce metal/polymer hybrid structures. In this work, the mechanical response of microarchitectured structures is investigated with an emphasis on the effects of the architecture and the amorphous NiB thickness on their deformation mechanisms and energy absorption capability. Microcompression experiments show an enhancement of the mechanical properties with the NiB thickness, suggesting that the deformation mechanism and the buckling behavior are controlled by the brittle-to-ductile transition in the NiB layer. In addition, the energy absorption properties demonstrate the possibility of tuning the energy absorption efficiency with adequate designs. These findings suggest that microarchitectured metal/polymer hybrid structures are effective in producing materials with unique property combinations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Jet blown PTFE for control of biocompatibility

NASA Astrophysics Data System (ADS)

Leibner, Evan Scott

The development of fully hemocompatible cardiovascular biomaterials will have a major impact on the practice of modern medicine. Current artificial surfaces, unlike native vascular surfaces, are not able to control clot and thrombus formation. Protein interactions are an important component in hemocompatibility and can result in decreased patency due to thrombus formation or surface passivation which can improve endothelization. It is believed that controlling these properties, specifically the nanometer sizes of the fibers on the material's surface, will allow for better control of biological responses. The biocompatibility of Teflon, a widely used polymer for vascular grafts, would be improved with nanostructured control of surface features. Due to the difficultly in processing polytetrafluoroethylene (PTFE), it has not been possible to create nanofibrous PTFE surfaces. The novel technique of Jet Blowing allows for the formation of nanostructured PTFE (nPTFE). A systematic investigation into controlling polymer properties by varying the processing conditions of temperature, pressure, and gas used in the Jet Blowing allows for an increased understanding of the effects of plasticization on the material's properties. This fundamental understanding of the material science behind the Jet Blowing process has enabled control of the micro and nanoscale structure of nPTFE. While protein adsorption, a key component of biocompatibility, has been widely studied, it is not fully understood. Major problems in the field of biomaterials include a lack of standard protocols to measure biocompatibility, and inconstant literature on protein adsorption. A reproducible protocol for measuring protein adsorption onto superhydrophobic surfaces (ePTFE and nPTFE) has been developed. Both degassing of PBS buffer solutions and evacuation of the air around the expanded PTFE (ePTFE) prior to contact with protein solutions are essential. Protein adsorption experiments show a four-fold difference in the measure of proteins adsorbed using radiometry (I-125 labeled human serum albumin (HSA)) and electrophoresis (unlabeled HSA). This provides evidence that the standard method of radiolabeled protein for measuring adsorption does not fully account for changes to the HSA molecules due to labeling. The differences between measured protein values can be attributed to the radiolabel affecting the HSA hydrophobicity resulting in a change in the protein's interactions with the hydrophobic surface. Additionally, our work has provided repeatable results showing that the amount of protein adsorbed onto the polymer surface, after washing, accounted for only 65% of the amount of protein that was removed from solution based on depletion analysis. This implies that measurement of the amount of strongly bound protein on the material significantly underestimates the actual amount of protein adsorbing into the surface region of the material interface. HSA adsorption isotherms demonstrate an increase in protein adsorption capacity on the nPTFE surface compared to adsorption on the same surface area of ePTFE. Preliminary cell work shows that the nPTFE surfaces had a larger number of cells growing on the surface of the material when compared to ePTFE surfaces. The research also shows that while most endothelial cells were not viable on the ePTFE surface after 96 hours, they remained alive on the nPTFE surface during that same time period. Surface functionalization using ammonia plasma has been performed. X-ray photoelectron spectroscopy (XPS) analysis revealed the presence of amine groups on the nPTFE surface. The amine groups can be used to couple polypeptides onto the PTFE surface in the future. The selection of different peptides will allow for selective control of cell adhesion. This research shows that nPTFE has potential for improved biocompatibility over standard ePTFE, based on increased protein adsorption capacity, increased viability of endothelial cells, and the ability to plasma modify the PTFE surface.

Polymer Brushes: Synthesis, Characterization, Applications

NASA Astrophysics Data System (ADS)

Advincula, Rigoberto C.; Brittain, William J.; Caster, Kenneth C.; Rühe, Jürgen

2004-09-01

Materials scientists, polymer chemists, surface physicists and materials engineers will find this book a complete and detailed treatise on the field of polymer brushes, their synthesis, characterization and manifold applications. In a first section, the various synthetic pathways and different surface materials are introduced and explained, followed by a second section covering important aspects of characterization and analysis in both flat surfaces and particles. These specific surface initiated polymerization (SIP) systems such as linear polymers, homopolymers, block copolymers, and hyperbranched polymers are unique compared to previously reported systems by chemisorption or physisorption. They have found their way in both large-scale and miniature applications of polymer brushes, which is covered in the last section. Such 'hairy' surfaces offer fascinating opportunities for addressing numerous problems of both academic and, in particular, industrial interest: high-quality, functional or protective coatings, composite materials, surface engineered particles, metal-organic interfaces, biological applications, micro-patterning, colloids, nanoparticles, functional devices, and many more. It is the desire of the authors that this book will be of benefit to readers who want to "brush-up on polymers".

Influence of Polymers on the Crystal Growth Rate of Felodipine: Correlating Adsorbed Polymer Surface Coverage to Solution Crystal Growth Inhibition.

PubMed

Schram, Caitlin J; Taylor, Lynne S; Beaudoin, Stephen P

2015-10-20

The bioavailability of orally administered drugs that exhibit poor aqueous solubility can be enhanced with the use of supersaturating dosage forms. Stabilization of these forms by preventing or inhibiting crystallization in solution is an important area of study. Polymers can be used to stabilize supersaturated systems; however, the properties that impact their effectiveness as crystal growth rate inhibitors are not yet fully understood. In this study, the impact of various polymers on the crystal growth rate of felodipine and the conformation of these polymers adsorbed to crystalline felodipine was investigated in order to gain a mechanistic understanding of crystal growth inhibition. It was determined that polymer hydrophobicity impacted polymer adsorption as well as adsorbed polymer conformation. Polymer conformation impacts its surface coverage, which was shown to directly correlate to the polymer's effectiveness as a growth rate inhibitor. By modeling this correlation, it is possible to predict polymer effectiveness given the surface coverage of the polymer.

Surface preparation of substances for continuous convective assembly of fine particles

DOEpatents

Rossi, Robert

2003-01-01

A method for producing periodic nanometer-scale arrays of metal or semiconductor junctions on a clean semiconductor substrate surface is provided comprising the steps of: etching the substrate surface to make it hydrophilic, forming, under an inert atmosphere, a crystalline colloid layer on the substrate surface, depositing a metal or semiconductor material through the colloid layer onto the surface of the substrate, and removing the colloid from the substrate surface. The colloid layer is grown on the clean semiconductor surface by withdrawing the semiconductor substrate from a sol of colloid particles.

Development of Multifunctional Nanoparticles for Targeted Drug Delivery and Non-invasive Imaging of Therapeutic Effect

PubMed Central

Sajja, Hari Krishna; East, Michael P.; Mao, Hui; Wang, Andrew Y.; Nie, Shuming; Yang, Lily

2011-01-01

Nanotechnology is a multidisciplinary scientific field undergoing explosive development. Nanometer-sized particles offer novel structural, optical and electronic properties that are not attainable with individual molecules or bulk solids. Advances in nanomedicine can be made by engineering biodegradable nanoparticles such as magnetic iron oxide nanoparticles, polymers, dendrimers and liposomes that are capable of targeted delivery of both imaging agents and anticancer drugs. This leads toward the concept and possibility of personalized medicine for the potential of early detection of cancer lesions, determination of molecular signatures of the tumor by non-invasive imaging and, most importantly, molecular targeted cancer therapy. Increasing evidence suggests that the nanoparticles, whose surface contains a targeting molecule that binds to receptors highly expressed in tumor cells, can serve as cancer image contrast agents to increase sensitivity and specificity in tumor detection. In comparison with other small molecule contrast agents, the advantage of using nanoparticles is their large surface area and the possibility of surface modifications for further conjugation or encapsulation of large amounts of therapeutic agents. Targeted nanoparticles ferry large doses of therapeutic agents into malignant cells while sparing the normal healthy cells. Such multifunctional nanodevices hold the promise of significant improvement of current clinical management of cancer patients. This review explores the development of nanoparticles for enabling and improving the targeted delivery of therapeutic agents, the potential of nanomedicine, and the development of novel and more effective diagnostic and screening techniques to extend the limits of molecular diagnostics providing point-of-care diagnosis and more personalized medicine. PMID:19275541

Mesoporous-silica films, fibers, and powders by evaporation

DOEpatents

Bruinsma, Paul J.; Baskaran, Suresh; Bontha, Jagannadha R.; Liu, Jun

2008-05-06

This invention pertains to surfactant-templated nanometer-scale porosity of a silica precursor solution and forming a mesoporous material by first forming the silica precursor solution into a preform having a high surface area to volume ratio, then rapid drying or evaporating a solvent from the silica precursor solution. The mesoporous material may be in any geometric form, but is preferably in the form of a film, fiber, powder or combinations thereof. The rapid drying or evaporation of solvent from the solution is accomplished by layer thinning, for example spin casting, liquid drawing, and liquid spraying respectively. Production of a film is by layer thinning, wherein a layer of the silica precursor solution is formed on a surface followed by removal of an amount of the silica precursor solution and leaving a geometrically thinner layer of the silica precursor solution from which the solvent quickly escapes via evaporation. Layer thinning may be by any method including but not limited to squeegeeing and/or spin casting. In powder formation by spray drying, the same conditions of fast drying exists as in spin-casting (as well as in fiber spinning) because of the high surface-area to volume ratio of the product. When a powder is produced by liquid spraying, the particles or micro-bubbles within the powder are hollow spheres with walls composed of mesoporous silica. Mesoporous fiber formation starts with a similar silica precursor solution but with an added pre-polymer making a pituitous mixture that is drawn into a thin strand from which solvent is evaporated leaving the mesoporous fiber(s).

Mesoporous-silica films, fibers, and powders by evaporation

DOEpatents

Bruinsma, Paul J.; Baskaran, Suresh; Bontha, Jagannadha R.; Liu, Jun

1999-01-01

This invention pertains to surfactant-templated nanometer-scale porosity of a silica precursor solution and forming a mesoporous material by first forming the silica precursor solution into a preform having a high surface area to volume ratio, then rapid drying or evaporating a solvent from the silica precursor solution. The mesoporous material may be in any geometric form, but is preferably in the form of a film, fiber, powder or combinations thereof. The rapid drying or evaporation of solvent from the solution is accomplished by layer thinning, for example spin casting, liquid drawing, and liquid spraying respectively. Production of a film is by layer thinning, wherein a layer of the silica precursor solution is formed on a surface followed by removal of an amount of the silica precursor solution and leaving a geometrically thinner layer of the silica precursor solution from which the solvent quickly escapes via evaporation. Layer thinning may be by any method including but not limited to squeegeeing and/or spin casting. In powder formation by spray drying, the same conditions of fast drying exists as in spin-casting (as well as in fiber spinning) because of the high surface-area to volume ratio of the product. When a powder is produced by liquid spraying, the particles or micro-bubbles within the powder are hollow spheres with walls composed of mesoporous silica. Mesoporous fiber formation starts with a similar silica precursor solution but with an added pre-polymer making a pituitous mixture that is drawn into a thin strand from which solvent is evaporated leaving the mesoporous fiber(s).

Mesoporous-silica films, fibers, and powders by evaporation

DOEpatents

Bruinsma, P.J.; Baskaran, S.; Bontha, J.R.; Liu, J.

1999-07-13

This invention pertains to surfactant-templated nanometer-scale porosity of a silica precursor solution and forming a mesoporous material by first forming the silica precursor solution into a preform having a high surface area to volume ratio, then rapid drying or evaporating a solvent from the silica precursor solution. The mesoporous material may be in any geometric form, but is preferably in the form of a film, fiber, powder or combinations thereof. The rapid drying or evaporation of solvent from the solution is accomplished by layer thinning, for example spin casting, liquid drawing, and liquid spraying respectively. Production of a film is by layer thinning, wherein a layer of the silica precursor solution is formed on a surface followed by removal of an amount of the silica precursor solution and leaving a geometrically thinner layer of the silica precursor solution from which the solvent quickly escapes via evaporation. Layer thinning may be by any method including but not limited to squeegeeing and/or spin casting. In powder formation by spray drying, the same conditions of fast drying exists as in spin-casting (as well as in fiber spinning) because of the high surface-area to volume ratio of the product. When a powder is produced by liquid spraying, the particles or micro-bubbles within the powder are hollow spheres with walls composed of mesoporous silica. Mesoporous fiber formation starts with a similar silica precursor solution but with an added pre-polymer making a pituitous mixture that is drawn into a thin strand from which solvent is evaporated leaving the mesoporous fiber(s). 24 figs.

Distribution of Chains in Polymer Brushes Produced by a “Grafting From” Mechanism

DOE PAGES

Martinez, Andre P.; Carrillo, Jan-Michael Y.; Dobrynin, Andrey V.; ...

2016-01-11

The molecular weight and polydispersity of the chains in a polymer brush are critical parameters determining the brush properties. However, the characterization of polymer brushes is hindered by the vanishingly small mass of polymer present in brush layers. In this study, in order to obtain sufficient quantities of polymer for analysis, polymer brushes were grown from high surface area fibrous nylon membranes by ATRP. We synthesized the brushes with varying surface initiator densities, polymerization times, and amounts of sacrificial initiator, then cleaved from the substrate, and analyzed by GPC and NMR. Characterization showed that the surface-grown polymer chains were moremore » polydisperse and had lower average molecular weight compared to solution-grown polymers synthesized concurrently. Furthermore, the molecular weight distribution of the polymer brushes was observed to be bimodal, with a low molecular weight population of chains representing a significant mass fraction of the polymer chains at high surface initiator densities. Moreover, the origin of this low MW polymer fraction is proposed to be the termination of growing chains by recombination during the early stages of polymerization, a mechanism confirmed by molecular dynamics simulations of brush polymerization.« less

Polymer diffusion in the interphase between surface and solution.

PubMed

Weger, Lukas; Weidmann, Monika; Ali, Wael; Hildebrandt, Marcus; Gutmann, Jochen Stefan; Hoffmann-Jacobsen, Kerstin

2018-05-22

Total internal reflection fluorescence correlation spectroscopy (TIR-FCS) is applied to study the self-diffusion of polyethylene glycol solutions in the presence of weakly attractive interfaces. Glass coverslips modified with aminopropyl- and propyl-terminated silanes are used to study the influence of solid surfaces on polymer diffusion. A model of three phases of polymer diffusion allows to describe the experimental fluorescence autocorrelation functions. Besides the two-dimensional diffusion of adsorbed polymer on the substrate and three-dimensional free diffusion in bulk solution, a third diffusion time scale is observed with intermediate diffusion times. This retarded three-dimensional diffusion in solution is assigned to long range effects of solid surfaces on diffusional dynamics of polymers. The respective diffusion constants show Rouse scaling (D~N -1 ) indicating a screening of hydrodynamic interactions by the presence of the surface. Hence, the presented TIR-FCS method proves to be a valuable tool to investigate the effect of surfaces on polymer diffusion beyond the first adsorbed polymer layer on the 100 nm length scale.

Ion implantation method for preparing polymers having oxygen erosion resistant surfaces

DOEpatents

Lee, E.H.; Mansur, L.K.; Heatherly, L. Jr.

1995-04-18

Hard surfaced polymers and the method for making them are generally described. Polymers are subjected to simultaneous multiple ion beam bombardment, that results in a hardening of the surface, improved wear resistance, and improved oxygen erosion resistance. 8 figs.

Engineering live cell surfaces with functional polymers via cytocompatible controlled radical polymerization

NASA Astrophysics Data System (ADS)

Niu, Jia; Lunn, David J.; Pusuluri, Anusha; Yoo, Justin I.; O'Malley, Michelle A.; Mitragotri, Samir; Soh, H. Tom; Hawker, Craig J.

2017-06-01

The capability to graft synthetic polymers onto the surfaces of live cells offers the potential to manipulate and control their phenotype and underlying cellular processes. Conventional grafting-to strategies for conjugating preformed polymers to cell surfaces are limited by low polymer grafting efficiency. Here we report an alternative grafting-from strategy for directly engineering the surfaces of live yeast and mammalian cells through cell surface-initiated controlled radical polymerization. By developing cytocompatible PET-RAFT (photoinduced electron transfer-reversible addition-fragmentation chain-transfer polymerization), synthetic polymers with narrow polydispersity (Mw/Mn < 1.3) could be obtained at room temperature in 5 minutes. This polymerization strategy enables chain growth to be initiated directly from chain-transfer agents anchored on the surface of live cells using either covalent attachment or non-covalent insertion, while maintaining high cell viability. Compared with conventional grafting-to approaches, these methods significantly improve the efficiency of grafting polymer chains and enable the active manipulation of cellular phenotypes.

Smart tool holder

DOEpatents

Day, R.D.; Foreman, L.R.; Hatch, D.J.; Meadows, M.S.

1998-09-08

There is provided an apparatus for machining surfaces to accuracies within the nanometer range by use of electrical current flow through the contact of the cutting tool with the workpiece as a feedback signal to control depth of cut. 3 figs.

Silica powders for powder evacuated thermal insulating panel and method

DOEpatents

Harris, Michael T.; Basaran, Osman A.; Kollie, Thomas G.; Weaver, Fred J.

1996-01-01

A powder evacuated thermal insulating panel using generally spherical and porous silica particles of a median size less than about 100 nanometers in diameter, a pour packing density of about 0.4 to 0.6 g/cm.sup.3 and an external surface area in the range of about 90 to 600 m.sup.2/ g is described. The silica powders are prepared by reacting a tetraakyl silicate with ammonia and water in an alcohol solvent, distilling the solution after the reaction to remove the ammonia and recover the alcohol. The resulting aqueous slurry was dried, ball-milled, and dried again to provide the silica particles with defined internal and external porosity. The nanometer size and the large external surface area of the silica particles along with the internal and external porosity of the silica particles provide powder evacuated thermal insulating panels with significantly higher R-values than obtainable using previously known silica powders.

Silica powders for powder evacuated thermal insulating panel and method

DOEpatents

Harris, Michael T.; Basaran, Osman A.; Kollie, Thomas G.; Weaver, Fred J.

1994-01-01

A powder evacuated thermal insulating panel using generally spherical and porous silica particles of a median size less than about 100 nanometers in diameter, a pour packing density of about 0.4 to 0.6 g/cm.sup.3 and an external surface area in the range of about 90 to 600 m.sup.2 /g is described. The silica powders are prepared by reacting a tetraakyl silicate with ammonia and water in an alcohol solvent, distilling the solution after the reaction to remove the ammonia and recover the alcohol. The resulting aqueous slurry was dried, ball-milled, and dried again to provide the silica particles with defined internal and external porosity. The nanometer size and the large external surface area of the silica particles along with the internal and external porosity of the silica particles provide powder evacuated thermal insulating panels with significantly higher R-values than obtainable using previously known silica powders.

Silica powders for powder evacuated thermal insulating panel and method

DOEpatents

Harris, Michael T.; Basaran, Osman A.; Kollie, Thomas G.; Weaver, Fred J.

1995-01-01

A powder evacuated thermal insulating panel using generally spherical and porous silica particles of a median size less than about 100 nanometers in diameter, a pour packing density of about 0.4 to 0.6 g/cm.sup.3 and an external surface area in the range of about 90 to 600 m.sup.2/ g is described. The silica powders are prepared by reacting a tetraakyl silicate with ammonia and water in an alcohol solvent, distilling the solution after the reaction to remove the ammonia and recover the alcohol. The resulting aqueous slurry was dried, ball-milled, and dried again to provide the silica particles with defined internal and external porosity. The nanometer size and the large external surface area of the silica particles along with the internal and external porosity of the silica particles provide powder evacuated thermal insulating panels with significantly higher R-values than obtainable using previously known silica powders.

Silica powders for powder evacuated thermal insulating panel and method

DOEpatents

Harris, M.T.; Basaran, O.A.; Kollie, T.G.; Weaver, F.J.

1996-01-02

A powder evacuated thermal insulating panel using generally spherical and porous silica particles of a median size less than about 100 nanometers in diameter, a pour packing density of about 0.4 to 0.6 g/cm{sup 3} and an external surface area in the range of about 90 to 600 m{sup 2}/g is described. The silica powders are prepared by reacting a tetraalkyl silicate with ammonia and water in an alcohol solvent, distilling the solution after the reaction to remove the ammonia and recover the alcohol. The resulting aqueous slurry was dried, ball-milled, and dried again to provide the silica particles with defined internal and external porosity. The nanometer size and the large external surface area of the silica particles along with the internal and external porosity of the silica particles provide powder evacuated thermal insulating panels with significantly higher R-values than obtainable using previously known silica powders. 2 figs.

The Art and Science of Polymer Brushes: Recent Developments in Patterning and Characterization Approaches.

PubMed

Panzarasa, Guido

2017-06-28

Polymer brushes are dense arrays of macromolecular chains tethered by one end at a surface. They are at the cutting edge of polymer nanotechnology since the dawn of controlled surface-initiated polymerization techniques unlocked new prospects for the synthesis of polymer brushes with tailorable properties. More recently, thanks to the growing interest in the use of brushes for the generation of functional surfaces, the need for advanced patterning and characterization approaches rapidly increased. Meeting these needs requires the contribution of experts from different disciplines: polymer chemistry, surface science, electrochemistry and particle physics. The focus of this review is to highlight recent developments in the field of polymer brushes, specifically the application of photocatalytic lithography as a versatile patterning strategy, the study of grafted-from polymer brushes by electrochemical methods and, most importantly, the introduction of positron annihilation spectroscopy as a powerful technique for the investigation of the structure of polymer brushes and of their composites with nanoparticles.

Utilization of star-shaped polymer architecture in the creation of high-density polymer brush coatings for the prevention of platelet and bacteria adhesion

PubMed Central

Totani, Masayasu; Terada, Kayo; Terashima, Takaya; Kim, Ill Yong; Ohtsuki, Chikara; Xi, Chuanwu; Tanihara, Masao

2014-01-01

We demonstrate utilization of star-shaped polymers as high-density polymer brush coatings and their effectiveness to inhibit the adhesion of platelets and bacteria. Star polymers consisting of poly(2-hydroxyethyl methacrylate) (PHEMA) and/or poly(methyl methacrylate) (PMMA), were synthesized using living radical polymerization with a ruthenium catalyst. The polymer coatings were prepared by simple drop casting of the polymer solution onto poly(ethylene terephthalate) (PET) surfaces and then dried. Among the star polymers prepared in this study, the PHEMA star polymer (star-PHEMA) and the PHEMA/PMMA (mol. ratio of 71/29) heteroarm star polymer (star-H71M29) coatings showed the highest percentage of inhibition against platelet adhesion (78–88% relative to noncoated PET surface) and Escherichia coli (94–97%). These coatings also showed anti-adhesion activity against platelets after incubation in Dulbecco's phosphate buffered saline or surfactant solution for 7 days. In addition, the PMMA component of the star polymers increased the scratch resistance of the coating. These results indicate that the star-polymer architecture provides high polymer chain density on PET surfaces to prevent adhesion of platelets and bacteria, as well as coating stability and physical durability to prevent exposure of bare PET surfaces. The star polymers provide a simple and effective approach to preparing anti-adhesion polymer coatings on biomedical materials against the adhesion of platelets and bacteria. PMID:25485105

In-line characterization of nanostructured mass-produced polymer components using scatterometry

NASA Astrophysics Data System (ADS)

Skovlund Madsen, Jonas; Højlund Thamdrup, Lasse; Czolkos, Ilja; Hansen, Poul Erik; Johansson, Alicia; Garnaes, Jørgen; Nygård, Jesper; Hannibal Madsen, Morten

2017-08-01

Scatterometry is used as an in-line metrology solution for injection molded nanostructures to evaluate the pattern replication fidelity. The method is used to give direct feedback to an operator when testing new molding parameters and for continuous quality control. A compact scatterometer has been built and tested at a fabrication facility. The scatterometry measurements, including data analysis and handling of the samples, are much faster than the injection molding cycle time, and thus, characterization does not slow down the production rate. Fabrication and characterization of 160 plastic parts with line gratings are presented here, and the optimal molding temperatures for replication of nanostructures are found for two polymers. Scatterometry results are compared to state of the art metrology solutions: atomic force and scanning electron microscopy. It is demonstrated that the scatterometer can determine the structural parameters of the samples with an accuracy of a few nanometers in less than a second, thereby enabling in-line characterization.

Natural biopolymer-based nanocomposite films for packaging applications.

PubMed

Rhim, Jong-Whan; Ng, Perry K W

2007-01-01

Concerns on environmental waste problems caused by non-biodegradable petrochemical-based plastic packaging materials as well as the consumer's demand for high quality food products has caused an increasing interest in developing biodegradable packaging materials using annually renewable natural biopolymers such as polysaccharides and proteins. Inherent shortcomings of natural polymer-based packaging materials such as low mechanical properties and low water resistance can be recovered by applying a nanocomposite technology. Polymer nanocomposites, especially natural biopolymer-layered silicate nanocomposites, exhibit markedly improved packaging properties due to their nanometer size dispersion. These improvements include increased modulus and strength, decreased gas permeability, and increased water resistance. Additionally, biologically active ingredients can be added to impart the desired functional properties to the resulting packaging materials. Consequently, natural biopolymer-based nanocomposite packaging materials with bio-functional properties have a huge potential for application in the active food packaging industry. In this review, recent advances in the preparation of natural biopolymer-based films and their nanocomposites, and their potential use in packaging applications are addressed.

Quadratic Electro-optic Effect in a Novel Nonconjugated Conductive Polymer, iodine-doped Polynorbornene

NASA Astrophysics Data System (ADS)

Narayanan, Ananthakrishnan; Thakur, Mrinal

2009-03-01

Quadratic electro-optic effect in a novel nonconjugated conductive polymer, iodine-doped polynorbornene has been measured using field-induced birefringence at 633 nm. The electrical conductivity^1 of polynorbornene increases by twelve orders of magnitude to about 0.01 S/cm upon doping with iodine. The electro-optic measurement has been made in a film doped at the medium doping-level. The electro-optic modulation signal was recorded using a lock-in amplifier for various applied ac voltages (4 kHz) and the quadratic dependence of the modulation on the applied voltage was observed. A modulation of about 0.01% was observed for an applied electric field of 3 V/micron for a 100 nm thick film The Kerr coefficient as determined is about 1.77x10-11m/V^2. This exceptionally large quadratic electro-optic effect has been attributed to the confinement of this charge-transfer system within a sub-nanometer dimension. 1. A. Narayanan, A. Palthi and M. Thakur, J. Macromol. Sci. -- PAC, accepted.

Methods of nanoassembly of a fractal polymer and materials formed thereby

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

Newkome, George R; Moorefield, Charles N

2012-07-24

The invention relates to the formation of synthesized fractal constructs and the methods of chemical self-assembly for the preparation of a non-dendritic, nano-scale, fractal constructs or molecules. More particularly, the invention relates to fractal constructs formed by molecular self-assembly, to create synthetic, nanometer-scale fractal shapes. In an embodiment, a nanoscale Sierpinski hexagonal gasket is formed. This non-dendritic, perfectly self-similar fractal macromolecule is comprised of bisterpyridine building blocks that are bound together by coordination to 36 Ru and 6 Fe ions to form a nearly planar array of increasingly larger hexagons around a hollow center.

Methods of nanoassembly of a fractal polymer and materials formed thereby

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

Newkome, George R; Moorefield, Charles N

2014-09-23

The invention relates to the formation of synthesized fractal constructs and the methods of chemical self-assembly for the preparation of a non-dendritic, nano-scale, fractal constructs or molecules. More particularly, the invention relates to fractal constructs formed by molecular self-assembly, to create synthetic, nanometer-scale fractal shapes. In an embodiment, a nanoscale Sierpinski hexagonal gasket is formed. This non-dendritic, perfectly self-similar fractal macromolecule is comprised of bisterpyridine building blocks that are bound together by coordination to (36) Ru and (6) Fe ions to form a nearly planar array of increasingly larger hexagons around a hollow center.

Influence of the type of electric discharge on the properties of the produced aluminium nanoparticles

NASA Astrophysics Data System (ADS)

Shiyan, L. N.; Yavorovskii, N. A.; Pustovalov, A. V.; Gryaznova, E. N.

2015-04-01

The effect of the method of aluminum nanopowder production on the aluminum products with water reaction is described. It has been established that the interaction of aluminum nanopowder prepared by the electric wire explosion, the phase composition of the reaction products mainly consists of boehmite (AlOOH) and has a fibrous structure. Therefore, that boehmite (AlOOH) can be used for modification of polymer membranes. The modified membranes can be used as water treatment from the impurity of formed true solutions according to adsorptive mechanism, and from colloidal nanometer and micron particles according to the mechanism of mechanical separation of particles depending on sizes.

Enhancement of electrical transport modulation in epitaxial VO2 nanowire field-effect transistor

NASA Astrophysics Data System (ADS)

Tanaka, Hidekazu; Chikanari, Masashi; Kanki, Teruo

Strongly correlated system vanadium dioxide VO2 has attracted widespread concerns from researchers as an exciting electronic material, due to the many intriguing features, especially metal-insulator transition (MIT) in vicinity of room temperature. In this work, we report a diverse geometry for high sensitivity in the transport modulation. By taking advantage of nanometer scale channel, instead of thin film channels, we demonstrated the enhancement of resistance modulation by applying gate voltage. Also we designed the insulating gate, consisting of high-k material Ta2O5/organic polymer parylene-C hybrid insulator. Such as this hybrid gate dielectric would effectively reduce interface deterioration of active channel oxide and provide sufficient carrier density. Moreover, benefited from the nanometer scale channel, the VO2 nanowire-based transistor could deliver a resistance modulation ratio over 8.5%, which are about 10 folds higher than that of the film case. Furthermore, this result is explained that in spite of the stronger field distribution in the edge parts of VO2 nanowire channel yielded little carrier density, the generated mobility modulation would biquadratic increase according to Brinkman-Rice picture as new finding.

Aberration-Corrected Electron Beam Lithography at the One Nanometer Length Scale

DOE PAGES

Manfrinato, Vitor R.; Stein, Aaron; Zhang, Lihua; ...

2017-04-18

Patterning materials efficiently at the smallest length scales has been a longstanding challenge in nanotechnology. Electron-beam lithography (EBL) is the primary method for patterning arbitrary features, but EBL has not reliably provided sub-4 nm patterns. The few competing techniques that have achieved this resolution are orders of magnitude slower than EBL. In this work, we employed an aberration-corrected scanning transmission electron microscope for lithography to achieve unprecedented resolution. Here we show aberration-corrected EBL at the one nanometer length scale using poly(methyl methacrylate) (PMMA) and have produced both the smallest isolated feature in any conventional resist (1.7 ± 0.5 nm) andmore » the highest density patterns in PMMA (10.7 nm pitch for negative-tone and 17.5 nm pitch for positive-tone PMMA). We also demonstrate pattern transfer from the resist to semiconductor and metallic materials at the sub-5 nm scale. These results indicate that polymer-based nanofabrication can achieve feature sizes comparable to the Kuhn length of PMMA and ten times smaller than its radius of gyration. Use of aberration-corrected EBL will increase the resolution, speed, and complexity in nanomaterial fabrication.« less

Surface properties of functional polymer systems

NASA Astrophysics Data System (ADS)

Wong, Derek

Polymer surface modification typically involves blending with other polymers or chemical modification of the parent polymer. Such strategies inevitably result in polymer systems that are spatially and chemically heterogeneous, and which exhibit the phenomenon of surface segregation. This work investigates the effects of chain architecture on the surface segregation behavior of such functionally modified polymers using a series of end- and center-fluorinated poly(D,L-lactide). Surface segregation of the fluorinated functional groups was observed in both chain architectures via AMPS and water contact angle. Higher surface segregation was noted for functional groups located at the chain end as opposed to those in the middle of the chain. A self-consistent mean-field lattice theory was used to model the composition depth profiles of functional groups and excellent agreement was found between the model predictions and the experimental AMPS data in both chain architectures. Polymer properties are also in general dependent on both time and temperature, and exhibit a range of relaxation times in response to environmental stimuli. This behavior arises from the characteristic frequencies of molecular motions of the polymer chain and the interrelationship between time and temperature has been widely established for polymer bulk properties. There is evidence that surface properties also respond in a manner that is time and temperature dependent and that this dependence may not be the same as that observed for bulk properties. AMPS and water contact angle experiments were used to investigate the surface reorganization behavior of functional groups using a series of anionically synthesized end-fluorinated and end-carboxylated poly(styrene). It was found that both types of functional end-groups reorganized upon a change in the polarity of the surface environment in order to minimize the surface free energy. ADXPS and contact angle results suggest that the reorganization depth was confined to the top 2--3 nm of the surface. Contact angle results showed also that the reorganization process proceeded as a function of (time) 1/2, indicating that it is likely diffusion controlled. The magnitudes of the activation energies determined from the experimental data according to the Arhenius equation, suggest that the process is possibly correlated with known bulk beta and gamma relaxations in the polymer.

Tip-enhanced near-field optical microscopy

PubMed Central

Mauser, Nina; Hartschuh, Achim

2013-01-01

Tip-enhanced near-field optical microscopy (TENOM) is a scanning probe technique capable of providing a broad range of spectroscopic information on single objects and structured surfaces at nanometer spatial resolution and with highest detection sensitivity. In this review, we first illustrate the physical principle of TENOM that utilizes the antenna function of a sharp probe to efficiently couple light to excitations on nanometer length scales. We then discuss the antenna-induced enhancement of different optical sample responses including Raman scattering, fluorescence, generation of photocurrent and electroluminescence. Different experimental realizations are presented and several recent examples that demonstrate the capabilities of the technique are reviewed. PMID:24100541

Optical depth localization of nitrogen-vacancy centers in diamond with nanometer accuracy.

PubMed

Häußler, Andreas J; Heller, Pascal; McGuinness, Liam P; Naydenov, Boris; Jelezko, Fedor

2014-12-01

Precise positioning of nitrogen-vacancy (NV) centers is crucial for their application in sensing and quantum information. Here we present a new purely optical technique enabling determination of the NV position with nanometer resolution. We use a confocal microscope to determine the position of individual emitters along the optical axis. Using two separate detection channels, it is possible to simultaneously measure reflected light from the diamond surface and fluorescent light from the NV center and statistically evaluate both signals. An accuracy of 2.6 nm for shallow NV centers was achieved and is consistent with other techniques for depth determination.

Morphological Properties of Siloxane-Hydrogel Contact Lens Surfaces.

PubMed

Stach, Sebastian; Ţălu, Ştefan; Trabattoni, Silvia; Tavazzi, Silvia; Głuchaczka, Alicja; Siek, Patrycja; Zając, Joanna; Giovanzana, Stefano

2017-04-01

The aim of this study was to quantitatively characterize the micromorphology of contact lens (CL) surfaces using atomic force microscopy (AFM) and multifractal analysis. AFM and multifractal analysis were used to characterize the topography of new and worn siloxane-hydrogel CLs made of Filcon V (I FDA group). CL surface roughness was studied by AFM in intermittent-contact mode, in air, on square areas of 25 and 100 μm 2 , by using a Nanoscope V MultiMode (Bruker). Detailed surface characterization of the surface topography was obtained using statistical parameters of 3-D (three-dimensional) surface roughness, in accordance with ISO 25178-2: 2012. Before wear, the surface was found to be characterized by out-of-plane and sharp structures, whilst after a wear of 8 h, two typical morphologies were observed. One morphology (sharp type) has a similar aspect as the unworn CLs and the other morphology (smooth type) is characterized by troughs and bumpy structures. The analysis of the AFM images revealed a multifractal geometry. The generalized dimension D q and the singularity spectrum f(α) provided quantitative values that characterize the local scale properties of CL surface geometry at nanometer scale. Surface statistical parameters deduced by multifractal analysis can be used to assess the CL micromorphology and can be used by manufacturers in developing CLs with improved surface characteristics. These parameters can also be used in understanding the tribological interactions of the back surface of the CL with the corneal surface and the front surface of the CL with the under-surface of the eyelid (friction, wear, and micro-elastohydrodynamic lubrication at a nanometer scale).

Smoothing Polymer Surfaces by Solvent-Vapor Exposure

NASA Astrophysics Data System (ADS)

Anthamatten, Mitchell

2003-03-01

Ultra-smooth polymer surfaces are of great importance in a large body of technical applications such as optical coatings, supermirrors, waveguides, paints, and fusion targets. We are investigating a simple approach to controlling surface roughness: by temporarily swelling the polymer with solvent molecules. As the solvent penetrates into the polymer, its viscosity is lowered, and surface tension forces drive surface flattening. To investigate sorption kinetics and surface-smoothing phenomena, a series of vapor-deposited poly(amic acid) films were exposed to dimethyl sulfoxide vapors. During solvent exposure, the surface topology was continuously monitored using light interference microscopy. The resulting power spectra indicate that high-frequency defects smooth faster than low-frequency defects. This frequency dependence was studied by depositing polymer films onto a series of 2D sinusoidal surfaces and performing smoothing experiments. Results show that the amplitudes of the sinusoidal surfaces decay exponentially with solvent exposure time, and the exponential decay constants are proportional to surface frequency. This work was performed under the auspices of the U.S. Department of Energy by the University of California Lawrence Livermore National Laboratory under contract No. W-7405-Eng-48.

Nanometer resolution optical coherence tomography using broad bandwidth XUV and soft x-ray radiation

DOE PAGES

Fuchs, Silvio; Rödel, Christian; Blinne, Alexander; ...

2016-02-10

Optical coherence tomography (OCT) is a non-invasive technique for cross-sectional imaging. It is particularly advantageous for applications where conventional microscopy is not able to image deeper layers of samples in a reasonable time, e.g. in fast moving, deeper lying structures. However, at infrared and optical wavelengths, which are commonly used, the axial resolution of OCT is limited to about 1 μm, even if the bandwidth of the light covers a wide spectral range. Here, we present extreme ultraviolet coherence tomography (XCT) and thus introduce a new technique for non-invasive cross-sectional imaging of nanometer structures. XCT exploits the nanometerscale coherence lengthsmore » corresponding to the spectral transmission windows of, e.g., silicon samples. The axial resolution of coherence tomography is thus improved from micrometers to a few nanometers. Tomographic imaging with an axial resolution better than 18 nm is demonstrated for layer-type nanostructures buried in a silicon substrate. Using wavelengths in the water transmission window, nanometer-scale layers of platinum are retrieved with a resolution better than 8 nm. As a result, XCT as a nondestructive method for sub-surface tomographic imaging holds promise for several applications in semiconductor metrology and imaging in the water window.« less

Multiscale Modeling at Nanointerfaces: Polymer Thin Film Materials Discovery via Thermomechanically Consistent Coarse Graining

NASA Astrophysics Data System (ADS)

Hsu, David D.

Due to high nanointerfacial area to volume ratio, the properties of "nanoconfined" polymer thin films, blends, and composites become highly altered compared to their bulk homopolymer analogues. Understanding the structure-property mechanisms underlying this effect is an active area of research. However, despite extensive work, a fundamental framework for predicting the local and system-averaged thermomechanical properties as a function of configuration and polymer species has yet to be established. Towards bridging this gap, here, we present a novel, systematic coarse-graining (CG) method which is able to capture quantitatively, the thermomechanical properties of real polymer systems in bulk and in nanoconfined geometries. This method, which we call thermomechanically consistent coarse-graining (TCCG), is a two-bead-per-monomer CG hybrid approach through which bonded interactions are optimized to match the atomistic structure via the Iterative Boltzmann Inversion method (IBI), and nonbonded interactions are tuned to macroscopic targets through parametric studies. We validate the TCCG method by systematically developing coarse-grain models for a group of five specialized methacrylate-based polymers including poly(methyl methacrylate) (PMMA). Good correlation with bulk all-atom (AA) simulations and experiments is found for the temperature-dependent glass transition temperature (Tg) Flory-Fox scaling relationships, self-diffusion coefficients of liquid monomers, and modulus of elasticity. We apply this TCCG method also to bulk polystyrene (PS) using a comparable coarse-grain CG bead mapping strategy. The model demonstrates chain stiffness commensurate with experiments, and we utilize a density-correction term to improve the transferability of the elastic modulus over a 500 K range. Additionally, PS and PMMA models capture the unexplained, characteristically dissimilar scaling of Tg with the thickness of free-standing films as seen in experiments. Using vibrational density of states (VDOS) analysis, we discover that increasing backbone to sidechain mass ratio in CG models increases the amplitude of sidechain fluctuations associated with flexibility, and suppresses the free-surface Tg-nanoconfinement effect. This uncovers that intrinsic mass distribution and sidechain flexibility differences in the PS and PMMA chemical structure are central to explaining the dissimilarities in their free surface response. PS and PMMA models are subsequently combined in the supported bilayer film configuration to explore the local Tg-nanoconfinement effect associated with different interface types at nanometer resolution. We find that Tg gradients in the interphase regions where chain mobility deviates from the bulk are independent of the film thickness above a critical thickness and add by the principle of superposition below the critical thickness to good approximation. The analytical expressions describing the interphase regions and their interactions demonstrate geometric universality and can be used to derive accurate local and global Tg estimations for complex nanophase blends and nanocomposite configurations. Our studies ascertain the significance of molecular characteristics on nanoconfinement, and highlight the ability for chemistry-specific CG models to explore and predict thermomechanical property modification accompanying interfacial nanoconfinement.

Effects of Alternating Hydrogenated and Protonated Segments in polymers on their Wettability.

NASA Astrophysics Data System (ADS)

Smith, Dennis; Traiphol, Rakchart; Cheng, Gang; Perahia, Dvora

2003-03-01

Polymers consisting of alternating hydrogenated and fluorinated segments exhibit unique interfacial characteristics governed by the components that dominate the interface. Presence of fluorine reduces the interfacial energy and is expected to decrease the adhesion to the polymer surface. Thin liquid crystalline (LC) layers of 4,4?-octyl-cyanobiphenyl, cast on top of a polymeric layer consisting of alternating methylstylbine protonated segments bridged by a fluorinated group was used as a mechanistic tool to study of interfacial effects on three parameters: wetting, interfacial alignment and surface induces structures. The liquid crystal cast on a low interfacial energy fluorinated polymeric film exhibits bulk homeotropic alignment as expected. However it fully wetted the polymer surface despite the incompatibility of the protonated LC and mainly fluorinated polymer interface. Further more, it was found to stabilize the interfacial Semitic layers to a higher temperature and induce different surface ordering that was not observed at the same temperature neither in the bulk nor at the interfaces with silicon or glass surface. These results indicate that the interfacial interactions of polymers with liquid crystals are a complex function of both surface energies and the interfacial structure of the polymer.

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.

Periodic surface instabilities in stressed polymer solids

NASA Astrophysics Data System (ADS)

Tsukruk, Vladimir V.; Reneker, Darrell H.

1995-03-01

The surface morphology of isothermally grown polymer single crystals of polypropylene is observed by atomic force microscopy. The distinguishing features of the polymer single crystals studied are periodic undulations and transverse fractures (cracks) across the single crystal laths. Up to 20 wrinkles are observed near the edges of the cracks. The periodicity of these surface perturbations is 400+/-100 nm and the amplitude is 6+/-3 nm. The formation of the periodic modulations and transverse fractures is attributed to surface stress relief caused by the uniaxial thermal contraction of polymer solids.

Polyphosphazine-based polymer materials

DOEpatents

Fox, Robert V.; Avci, Recep; Groenewold, Gary S.

2010-05-25

Methods of removing contaminant matter from porous materials include applying a polymer material to a contaminated surface, irradiating the contaminated surface to cause redistribution of contaminant matter, and removing at least a portion of the polymer material from the surface. Systems for decontaminating a contaminated structure comprising porous material include a radiation device configured to emit electromagnetic radiation toward a surface of a structure, and at least one spray device configured to apply a capture material onto the surface of the structure. Polymer materials that can be used in such methods and systems include polyphosphazine-based polymer materials having polyphosphazine backbone segments and side chain groups that include selected functional groups. The selected functional groups may include iminos, oximes, carboxylates, sulfonates, .beta.-diketones, phosphine sulfides, phosphates, phosphites, phosphonates, phosphinates, phosphine oxides, monothio phosphinic acids, and dithio phosphinic acids.

Subnanometer and nanometer catalysts, method for preparing size-selected catalysts

DOEpatents

Vajda, Stefan , Pellin, Michael J.; Elam, Jeffrey W [Elmhurst, IL; Marshall, Christopher L [Naperville, IL; Winans, Randall A [Downers Grove, IL; Meiwes-Broer, Karl-Heinz [Roggentin, GR

2012-04-03

Highly uniform cluster based nanocatalysts supported on technologically relevant supports were synthesized for reactions of top industrial relevance. The Pt-cluster based catalysts outperformed the very best reported ODHP catalyst in both activity (by up to two orders of magnitude higher turn-over frequencies) and in selectivity. The results clearly demonstrate that highly dispersed ultra-small Pt clusters precisely localized on high-surface area supports can lead to affordable new catalysts for highly efficient and economic propene production, including considerably simplified separation of the final product. The combined GISAXS-mass spectrometry provides an excellent tool to monitor the evolution of size and shape of nanocatalyst at action under realistic conditions. Also provided are sub-nanometer gold and sub-nanometer to few nm size-selected silver catalysts which possess size dependent tunable catalytic properties in the epoxidation of alkenes. Invented size-selected cluster deposition provides a unique tool to tune material properties by atom-by-atom fashion, which can be stabilized by protective overcoats.

Subnanometer and nanometer catalysts, method for preparing size-selected catalysts

DOEpatents

Vajda, Stefan [Lisle, IL; Pellin, Michael J [Naperville, IL; Elam, Jeffrey W [Elmhurst, IL; Marshall, Christopher L [Naperville, IL; Winans, Randall A [Downers Grove, IL; Meiwes-Broer, Karl-Heinz [Roggentin, GR

2012-03-27

Highly uniform cluster based nanocatalysts supported on technologically relevant supports were synthesized for reactions of top industrial relevance. The Pt-cluster based catalysts outperformed the very best reported ODHP catalyst in both activity (by up to two orders of magnitude higher turn-over frequencies) and in selectivity. The results clearly demonstrate that highly dispersed ultra-small Pt clusters precisely localized on high-surface area supports can lead to affordable new catalysts for highly efficient and economic propene production, including considerably simplified separation of the final product. The combined GISAXS-mass spectrometry provides an excellent tool to monitor the evolution of size and shape of nanocatalyst at action under realistic conditions. Also provided are sub-nanometer gold and sub-nanometer to few nm size-selected silver catalysts which possess size dependent tunable catalytic properties in the epoxidation of alkenes. Invented size-selected cluster deposition provides a unique tool to tune material properties by atom-by-atom fashion, which can be stabilized by protective overcoats.

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.

The atomic nature of polymer-metal interactions in adhesion, friction and wear

NASA Technical Reports Server (NTRS)

Buckley, D. H.; Brainard, W. A.

1973-01-01

Adhesion experiments with polytetra-fluoroethylene (PTFE) and polyimide contacting tungsten indicate that the polymers bond chemically to the clean metal surface. Polymer chain fragments which transfer to the surface of tungsten in field ion microscopy adhesion studies are highly oriented. Auger emission spectroscopy of PTFE transfer films to various metal surfaces indicates that the PTFE is bonded to the metal surface via the carbon atom. With PTFE in sliding contact with different orientations of aluminum, metal orientation is found to influence surfaces in sliding. The lowest friction and least amount of surface damage is detected on the highest atomic density (111) plane. The friction process itself can initiate polymer film formation from simple organic molecules.

The Hydrophobicity and Adhesion of Heterogeneous Surfaces of Dual Nanometer and Micron Scale Structures

DTIC Science & Technology

2011-04-11

scale post geometry. superhydrophobic , surface modification, adhesion, contact angle, Cassie, Wenzel, PDMS, CYTOP, Teflon AF, roll-off angle U U U U SAR...width > 1, the micro-scale features dominated the wetting state regardless of the nano-scale post geometry., KEYWORDS superhydrophobic , surface... superhydrophobicity can be routinely found in nature. Fo~ example, many plant leaves1.2, bird feathers3, insect wings and insect legs4 take advantage of

DATA FROM A SOLAR ULTRAVIOLET MONITORING NETWORK

EPA Science Inventory

The U.S. Environmental Protection Agency, in conjunction with the National Park Service, operates a network of 21 spectrophotometers, measuring spectrally-resolved, surface UV radiation of wavelengths 290-363 nanometers. Fourteen of the measurement sites are in National Parks,...

Probing the surface profile and friction behavior of heterogeneous polymers: a molecular dynamics study

NASA Astrophysics Data System (ADS)

Dai, L.; Sorkin, V.; Zhang, Y. W.

2017-04-01

We perform molecular dynamics simulations to investigate molecular structure alternation and friction behavior of heterogeneous polymer (perfluoropolyether) surfaces using a nanoscale probing tip (tetrahedral amorphous carbon). It is found that depending on the magnitude of the applied normal force, three regimes exist: the shallow depth-sensing (SDS), deep depth-sensing (DDS), and transitional depth-sensing (TDS) regimes; TDS is between SDS and DDS. In SDS, the tip is floating on the polymer surface and there is insignificant permanent alternation in the polymer structure due to largely recoverable atomic deformations, and the surface roughness profile can be accurately measured. In DDS, the tip is plowing through the polymer surface and there is significant permanent alternation in the molecular structure. In this regime, the lateral friction force rises sharply and fluctuates violently when overcoming surface pile-ups. In SDS, the friction can be described by a modified Amonton’s law including the adhesion effect; meanwhile, in DDS, the adhesion effect is negligible but the friction coefficient is significantly higher. The underlying reason for the difference in these regimes rests upon different contributions by the repulsion and attraction forces between the tip and polymer surfaces to the friction force. Our findings here reveal important insights into lateral depth-sensing on heterogeneous polymer surfaces and may help improve the precision of depth-sensing devices.

Impact of surface porosity and topography on the mechanical behavior of high strength biomedical polymers.

PubMed

Evans, Nathan T; Irvin, Cameron W; Safranski, David L; Gall, Ken

2016-06-01

The ability to control the surface topography of orthopedic implant materials is desired to improve osseointegration but is often at the expense of mechanical performance in load bearing environments. Here we investigate the effects of surface modifications, roughness and porosity, on the mechanical properties of a set of polymers with diverse chemistry and structure. Both roughness and surface porosity resulted in samples with lower strength, failure strain and fatigue life due to stress concentrations at the surface; however, the decrease in ductility and fatigue strength were greater than the decrease in monotonic strength. The fatigue properties of the injection molded polymers did not correlate with yield strength as would be traditionally observed in metals. Rather, the fatigue properties and the capacity to maintain properties with the introduction of surface porosity correlated with the fracture toughness of the polymers. Polymer structure impacted the materials relative capacity to maintain monotonic and cyclic properties in the face of surface texture and porosity. Generally, amorphous polymers with large ratios of upper to lower yield points demonstrated a more significant drop in ductility and fatigue strength with the introduction of porosity compared to crystalline polymers with smaller ratios in their upper to lower yield strength. The latter materials have more effective dissipation mechanisms to minimize the impact of surface porosity on both monotonic and cyclic damage. Copyright © 2016 Elsevier Ltd. All rights reserved.

Metal Catalyzed Fusion: Nuclear Active Environment vs. Process

NASA Astrophysics Data System (ADS)

Chubb, Talbot

2009-03-01

To achieve radiationless dd fusion and/or other LENR reactions via chemistry: some focus on environment of interior or altered near-surface volume of bulk metal; some on environment inside metal nanocrystals or on their surface; some on the interface between nanometal crystals and ionic crystals; some on a momentum shock-stimulation reaction process. Experiment says there is also a spontaneous reaction process.

Friction between Polymer Brushes

NASA Astrophysics Data System (ADS)

Sokoloff, Jeffrey

2006-03-01

A polymer brush consists of a surface with a fairly concentrated coating of polymer chains, each one of which has one of its ends tightly bound to the surface. They serve as extremely effective lubricant, producing friction coefficients as low as 0.001 or less! Polymer brushes are a promising way to reduce friction to extremely low values. They have the disadvantage, however, that they must be immersed in a liquid solvent in order to function as a lubricant. The presence of a solvent is believed to result in osmotic pressure which partially supports the load. The density profile of a polymer brush (i.e., the density of monomers as a function of distance from the surface to which the polymers are attached) is well established. What is not understood is how the interaction of polymer brush coated surfaces in contact with each other is able to account for the details of the observed low friction. For example, molecular dynamics studies generally do not predict static friction, whereas surface force apparatus measurements due to Tadmor, et. al., find that there is static friction. This is the topic of the present presentation.

Photocatalytic activity of PANI loaded coordination polymer composite materials: Photoresponse region extension and quantum yields enhancement via the loading of PANI nanofibers on surface of coordination polymer

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

Cui, Zhongping; Qi, Ji; Xu, Xinxin, E-mail: xuxx@mail.neu.edu.cn

2013-09-15

To enhance photocatalytic property of coordination polymer in visible light region, polyaniline (PANI) loaded coordination polymer photocatalyst was synthesized through in-situ chemical oxidation of aniline on the surface of coordination polymer. The photocatalytic activity of PANI loaded coordination polymer composite material for degradation of Rhodamine B (RhB) was investigated. Compared with pure coordination polymer photocatalyst, which can decompose RhB merely under UV light irradiation, PANI loaded coordination polymer photocatalyst displays more excellent photocatalytic activity in visible light region. Furthermore, PANI loaded coordination polymer photocatalyst exhibits outstanding stability during the degradation of RhB. - Graphical abstract: PANI loaded coordination polymer compositemore » material, which displays excellent photocatalytic activity under visible light was firstly synthesized through in-situ chemical oxidation of aniline on surface of coordination polymer. Display Omitted - Highlights: • This PANI loaded coordination polymer composite material represents the first conductive polymer loaded coordination polymer composite material. • PANI/coordination polymer composite material displays more excellent photocatalytic activity for the degradation of MO in visible light region. • The “combination” of coordination polymer and PANI will enable us to design high-activity, high-stability and visible light driven photocatalyst in the future.« less

Solution Exchange Lithography: A Versatile Tool for Sequential Surface Engineering

NASA Astrophysics Data System (ADS)

Pester, Christian; Mattson, Kaila; Bothman, David; Klinger, Daniel; Lee, Kenneth; Discekici, Emre; Narupai, Benjaporn; Hawker, Craig

The covalent attachment of polymers has emerged as a viable strategy for the preparation of multi-functional surfaces. Patterned, surface-grafted polymer brushes provide spatial control over wetting, mechanical, biological or electronic properties, and allow fabrication of `intelligent' substrates which selectively adapt to their environment. However, the route towards patterned polymer brush surfaces often remains challenging, creating a demand for more efficient and less complicated fabrication strategies. We describe the design and application of a novel experimental setup to combine light-mediated and flow chemistry for the fabrication of hierarchical surface-grafted polymer brushes. Using light-mediated, surface initiated controlled radical polymerization and post-functionalization via well-established, and highly efficient chemistries, polymer brush films of previously unimaginable complexity are now shown to be accessible. This methodology allows full flexibility to exchange both lithographic photomasks and chemical environments in-situ, readily affording multidimensional thin film architectures, all from uniformly functionalized substrates.

Molecular Velcro constructed from polymer loop brushes showing enhanced adhesion force

NASA Astrophysics Data System (ADS)

Zhou, Tian; Han, Biao; Han, Lin; Li, Christopher; Department of Materials Science; Engineering Team; School of Biomedical Engineering, Science; Health Systems Team

2015-03-01

Molecular Velcro is commonly seen in biological systems as the formation of strong physical entanglement at molecular scale could induce strong adhesion, which is crucial to many biological processes. To mimic this structure, we designed, and fabricated polymer loop brushes using polymer single crystals with desired surface functionality and controlled chain folding. Compared with reported loop brushes fabricated using triblock copolymers, the present loop bushes have precise loop sizes, loop grafting density, and well controlled tethering locations on the solid surface. Atomic force microscopy-based force spectroscopy measurements using a polymer chain coated probe reveal that the adhesion force are significantly enhanced on the loop brush surface as compared with its single-strand counterpart. This study directly shows the effect of polymer brush conformation on their properties, and suggests a promising strategy for advanced polymer surface design.

Understanding the origins of metal-organic framework/polymer compatibility.

PubMed

Semino, R; Moreton, J C; Ramsahye, N A; Cohen, S M; Maurin, G

2018-01-14

The microscopic interfacial structures for a series of metal-organic framework/polymer composites consisting of the Zr-based UiO-66 coupled with different polymers are systematically explored by applying a computational methodology that integrates density functional theory calculations and force field-based molecular dynamics simulations. These predictions are correlated with experimental findings to unravel the structure-compatibility relationship of the MOF/polymer pairs. The relative contributions of the intermolecular MOF/polymer interactions and the flexibility/rigidity of the polymer with respect to the microscopic structure of the interface are rationalized, and their impact on the compatibility of the two components in the resulting composite is discussed. The most compatible pairs among those investigated involve more flexible polymers, i.e. polyvinylidene fluoride (PVDF) and polyethylene glycol (PEG). These polymers exhibit an enhanced contact surface, due to a better adaptation of their configuration to the MOF surface. In these cases, the irregularities at the MOF surface are filled by the polymer, and even some penetration of the terminal groups of the polymer into the pores of the MOF can be observed. As a result, the affinity between the MOF and the polymer is very high; however, the pores of the MOF may be sterically blocked due to the strong MOF/polymer interactions, as evidenced by UiO-66/PEG composites. In contrast, composites involving polymers that exhibit higher rigidity, such as the polymer of intrinsic microporosity-1 (PIM-1) or polystyrene (PS), present interfacial microvoids that contribute to a decrease in the contact surface between the two components, thus reducing the MOF/polymer affinity.

Formation and properties of surface-anchored polymer assemblies with tunable physico-chemical characteristics

NASA Astrophysics Data System (ADS)

Wu, Tao

We describe two new methodologies leading to the formation of novel surface-anchored polymer assemblies on solid substrates. While the main goal is to understand the fundamentals pertaining to the preparation and properties of the surface-bound polymer assemblies (including neutral and chargeable polymers), several examples also are mentioned throughout the Thesis that point out to practical applications of such structures. The first method is based on generating assemblies comprising anchored polymers with a gradual variation of grafting densities on solid substrates. These structures are prepared by first covering the substrate with a molecular gradient of the polymerization initiator, followed by polymerization from these substrate-bound initiator centers ("grafting from"). We apply this technique to prepare grafting density gradients of poly(acryl amide) (PAAm) and poly(acrylic acid) (PAA) on silica-covered substrates. We show that using the grafting density gradient geometry, the characteristics of surface-anchored polymers in both the low grafting density ("mushroom") regime as well as the high grafting density ("brush") regime can be accessed conveniently on a single sample. We use a battery of experimental methods, including Fourier transform infrared spectroscopy (FTIR), Near-edge absorption fine structure spectroscopy (NEXAFS), contact angle, ellipsometry, to study the characteristics of the surface-bound polymer layers. We also probe the scaling laws of neutral polymer as a function of grafting density, and for weak polyelectrolyte, in addition to the grafting density, we study the affect of solution ionic strength and pH values. In the second novel method, which we coined as "mechanically assisted polymer assembly" (MAPA), we form surface anchored polymers by "grafting from" polymerization initiators deposited on elastic surfaces that have been previously extended uniaxially by a certain length increment, Deltax. Upon releasing the strain in the substrate after completion of polymerization, we show the grafting density of the polymers grafted to flexible substrates can be tuned as a function of Deltax.

Study of adhesion and friction properties on a nanoparticle gradient surface: transition from JKR to DMT contact mechanics.

PubMed

Ramakrishna, Shivaprakash N; Nalam, Prathima C; Clasohm, Lucy Y; Spencer, Nicholas D

2013-01-08

We have previously investigated the dependence of adhesion on nanometer-scale surface roughness by employing a roughness gradient. In this study, we correlate the obtained adhesion forces on nanometer-scale rough surfaces to their frictional properties. A roughness gradient with varying silica particle (diameter ≈ 12 nm) density was prepared, and adhesion and frictional forces were measured across the gradient surface in perfluorodecalin by means of atomic force microscopy with a polyethylene colloidal probe. Similarly to the pull-off measurements, the frictional forces initially showed a reduction with decreasing particle density and later an abrupt increase as the colloidal sphere began to touch the flat substrate beneath, at very low particle densities. The friction-load relation is found to depend on the real contact area (A(real)) between the colloid probe and the underlying particles. At high particle density, the colloidal sphere undergoes large deformations over several nanoparticles, and the contact adhesion (JKR type) dominates the frictional response. However, at low particle density (before the colloidal probe is in contact with the underlying surface), the colloidal sphere is suspended by a few particles only, resulting in local deformations of the colloid sphere, with the frictional response to the applied load being dominated by long-range, noncontact (DMT-type) interactions with the substrate beneath.

Characterizing Spatial Organization of Cell Surface Receptors in Human Breast Cancer with STORM

NASA Astrophysics Data System (ADS)

Lyall, Evan; Chapman, Matthew R.; Sohn, Lydia L.

2012-02-01

Regulation and control of complex biological functions are dependent upon spatial organization of biological structures at many different length scales. For instance Eph receptors and their ephrin ligands bind when opposing cells come into contact during development, resulting in spatial organizational changes on the nanometer scale that lead to changes on the macro scale, in a process known as organ morphogenesis. One technique able to probe this important spatial organization at both the nanometer and micrometer length scales, including at cell-cell junctions, is stochastic optical reconstruction microscopy (STORM). STORM is a technique that localizes individual fluorophores based on the centroids of their point spread functions and then reconstructs a composite image to produce super resolved structure. We have applied STORM to study spatial organization of the cell surface of human breast cancer cells, specifically the organization of tyrosine kinase receptors and chemokine receptors. A better characterization of spatial organization of breast cancer cell surface proteins is necessary to fully understand the tumorigenisis pathways in the most common malignancy in United States women.

Single-molecule height measurements on microsomal cytochrome P450 in nanometer-scale phospholipid bilayer disks

NASA Astrophysics Data System (ADS)

Bayburt, Timothy H.; Sligar, Stephen G.

2002-05-01

The architecture of membrane proteins in their native environment of the phospholipid bilayer is critical for understanding physiological function, but has been difficult to realize experimentally. In this communication we describe the incorporation of a membrane-anchored protein into a supported phospholipid bilayer. Cytochrome P450 2B4 solubilized and purified from the hepatic endoplasmic reticulum was incorporated into phospholipid bilayer nanostructures and oriented on a surface for visualization by atomic force microscopy. Individual P450 molecules were observed protruding from the bilayer surface. Problems associated with deformation of the protein by the atomic force microscopy probe were avoided by analyzing force-dependent height measurements to quantitate the height of the protein above the bilayer surface. Measurements of the atomic force microscopy cantilever deflection as a function of probe-sample separation reveal that the top of the P450 opposite the N-terminal membrane anchor region sits 3.5 nanometers above the phospholipid-water boundary. Models of the orientation of the enzyme are presented and discussed in relation to membrane interactions and interaction with cytochrome P450 reductase.

Can single molecule localization microscopy be used to map closely spaced RGD nanodomains?

PubMed Central

Nicovich, Philip R.; Soeriyadi, Alexander; Nieves, Daniel J.; Gooding, J. Justin; Gaus, Katharina

2017-01-01

Cells sense and respond to nanoscale variations in the distribution of ligands to adhesion receptors. This makes single molecule localization microscopy (SMLM) an attractive tool to map the distribution of ligands on nanopatterned surfaces. We explore the use of SMLM spatial cluster analysis to detect nanodomains of the cell adhesion-stimulating tripeptide arginine-glycine-aspartic acid (RGD). These domains were formed by the phase separation of block copolymers with controllable spacing on the scale of tens of nanometers. We first determined the topology of the block copolymer with atomic force microscopy (AFM) and then imaged the localization of individual RGD peptides with direct stochastic optical reconstruction microscopy (dSTORM). To compare the data, we analyzed the dSTORM data with DBSCAN (density-based spatial clustering application with noise). The ligand distribution and polymer topology are not necessary identical since peptides may attach to the polymer outside the nanodomains and/or coupling and detection of peptides within the nanodomains is incomplete. We therefore performed simulations to explore the extent to which nanodomains could be mapped with dSTORM. We found that successful detection of nanodomains by dSTORM was influenced by the inter-domain spacing and the localization precision of individual fluorophores, and less by non-specific absorption of ligands to the substratum. For example, under our imaging conditions, DBSCAN identification of nanodomains spaced further than 50 nm apart was largely independent of background localisations, while nanodomains spaced closer than 50 nm required a localization precision of ~11 nm to correctly estimate the modal nearest neighbor distance (NDD) between nanodomains. We therefore conclude that SMLM is a promising technique to directly map the distribution and nanoscale organization of ligands and would benefit from an improved localization precision. PMID:28723958

The Role of Interfaces in Polyethylene/Metal-Oxide Nanocomposites for Ultrahigh-Voltage Insulating Materials.

PubMed

Pourrahimi, Amir Masoud; Olsson, Richard T; Hedenqvist, Mikael S

2018-01-01

Recent progress in the development of polyethylene/metal-oxide nanocomposites for extruded high-voltage direct-current (HVDC) cables with ultrahigh electric insulation properties is presented. This is a promising technology with the potential of raising the upper voltage limit in today's underground/submarine cables, based on pristine polyethylene, to levels where the loss of energy during electric power transmission becomes low enough to ensure intercontinental electric power transmission. The development of HVDC insulating materials together with the impact of the interface between the particles and the polymer on the nanocomposites electric properties are shown. Important parameters from the atomic to the microlevel, such as interfacial chemistry, interfacial area, and degree of particle dispersion/aggregation, are discussed. This work is placed in perspective with important work by others, and suggested mechanisms for improved insulation using nanoparticles, such as increased charge trap density, adsorption of impurities/ions, and induced particle dipole moments are considered. The effects of the nanoparticles and of their interfacial structures on the mechanical properties and the implications of cavitation on the electric properties are also discussed. Although the main interest in improving the properties of insulating polymers has been on the use of nanoparticles, leading to nanodielectrics, it is pointed out here that larger microscopic hierarchical metal-oxide particles with high surface porosity also impart good insulation properties. The impact of the type of particle and its inherent properties (purity and conductivity) on the nanocomposite dielectric and insulating properties are also discussed based on data obtained by a newly developed technique to directly observe the charge distribution on a nanometer scale in the nanocomposite. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Shen, Yong; Desseaux, Solenne; Aden, Bethany

We report that surface-grafting thermoresponsive polymers allows the preparation of thin polymer brush coatings with surface properties that can be manipulated by variation of temperature. In most instances, thermoresponsive polymer brushes are produced using polymers that dehydrate and collapse above a certain temperature. This report presents the preparation and properties of polymer brushes that show thermoresponsive surface properties, yet are shape-persistent in that they do not undergo main chain collapse. The polymer brushes presented here are obtained via vapor deposition surface-initiated ring-opening polymerization (SI-ROP) of γ-di- or tri(ethylene glycol)-modified glutamic acid N-carboxyanhydrides. Vapor deposition SI-ROP of γ-di- or tri(ethylene glycol)-modifiedmore » L- or D-glutamic acid N-carboxyanhydrides affords helical surface-tethered polymer chains that do not show any changes in secondary structure between 10 and 70 °C. QCM-D experiments, however, revealed significant dehydration of poly(γ-(2-(2-methoxyethoxy)ethyl)-l-glutamate) (poly(L-EG 2-Glu)) brushes upon heating from 10 to 40 °C. At the same time, AFM and ellipsometry studies did not reveal significant variations in film thickness over this temperature range, which is consistent with the shape-persistent nature of these polypeptide brushes and indicates that the thermoresponsiveness of the films is primarily due to hydration and dehydration of the oligo(ethylene glycol) side chains. The results we present here illustrate the potential of surface-initiated NCA ring-opening polymerization to generate densely grafted assemblies of polymer chains that possess well-defined secondary structures and tunable surface properties. These polypeptide brushes complement their conformationally unordered counterparts that can be generated via surface-initiated polymerization of vinyl-type monomers and represent another step forward to biomimetic surfaces and interfaces.« less

Submicron Surface-Patterned Fibers and Textiles

DTIC Science & Technology

2016-11-04

These authors contributed equally Keywords: grating, fiber, polymer , patterning, textile Distribution A: approved for public release...requirements. Second, textile materials are primarily polymer -based, while most surface-patterning techniques have been developed for silicon...Alternative substrates, especially flexible polymers , remain challenging to pattern [25,26] due to the highly specific surface chemistry of different

Tea stains-inspired initiator primer for surface grafting of antifouling and antimicrobial polymer brush coatings.

PubMed

Pranantyo, Dicky; Xu, Li Qun; Neoh, Koon-Gee; Kang, En-Tang; Ng, Ying Xian; Teo, Serena Lay-Ming

2015-03-09

Inspired by tea stains, plant polyphenolic tannic acid (TA) was beneficially employed as the primer anchor for functional polymer brushes. The brominated TA (TABr) initiator primer was synthesized by partial modification of TA with alkyl bromide functionalities. TABr with trihydroxyphenyl moieties can readily anchor on a wide range of substrates, including metal, metal oxide, polymer, glass, and silicon. Concomitantly, the alkyl bromide terminals serve as initiation sites for atom transfer radical polymerization (ATRP). Cationic [2-(methacryloyloxy)ethyl]trimethylammonium chloride (META) and zwitterionic 2-methacryloyloxyethyl phosphorylcholine (MPC) and N-(3-sulfopropyl)-N-(methacryloxyethyl)-N,N-dimethylammonium betaine (SBMA) were graft-polymerized from the TABr-anchored stainless steel (SS) surface. The cationic polymer brushes on the modified surfaces are bactericidal, while the zwitterionic coatings exhibit resistance against bacterial adhesion. In addition, microalgal attachment (microfouling) and barnacle cyprid settlement (macrofouling) on the functional polymer-grafted surfaces were significantly reduced, in comparison to the pristine SS surface. Thus, the bifunctional TABr initiator primer provides a unique surface anchor for the preparation of functional polymer brushes for inhibiting both microfouling and macrofouling.

Entropic (de)stabilization of surface-bound peptides conjugated with polymers

NASA Astrophysics Data System (ADS)

Carmichael, Scott P.; Shell, M. Scott

2015-12-01

In many emerging biotechnologies, functional proteins must maintain their native structures on or near interfaces (e.g., tethered peptide arrays, protein coated nanoparticles, and amphiphilic peptide micelles). Because the presence of a surface is known to dramatically alter the thermostability of tethered proteins, strategies to stabilize surface-bound proteins are highly sought. Here, we show that polymer conjugation allows for significant control over the secondary structure and thermostability of a model surface-tethered peptide. We use molecular dynamics simulations to examine the folding behavior of a coarse-grained helical peptide that is conjugated to polymers of various lengths and at various conjugation sites. These polymer variations reveal surprisingly diverse behavior, with some stabilizing and some destabilizing the native helical fold. We show that ideal-chain polymer entropies explain these varied effects and can quantitatively predict shifts in folding temperature. We then develop a generic theoretical model, based on ideal-chain entropies, that predicts critical lengths for conjugated polymers to effect changes in the folding of a surface-bound protein. These results may inform new design strategies for the stabilization of surface-associated proteins important for a range technological applications.

Triboelectric energy harvesting with surface-charge-fixed polymer based on ionic liquid

PubMed Central

Sano, Chikako; Mitsuya, Hiroyuki; Ono, Shimpei; Miwa, Kazumoto; Toshiyoshi, Hiroshi; Fujita, Hiroyuki

2018-01-01

Abstract A novel triboelectric energy harvester has been developed using an ionic liquid polymer with cations fixed at the surface. In this report, the fabrication of the device and the characterization of its energy harvesting performance are detailed. An electrical double layer was induced in the ionic liquid polymer precursor to attract the cations to the surface where they are immobilized using a UV-based crosslinking reaction. The finalized polymer is capable of generating an electrical current when contacted by a metal electrode. Using this property, energy harvesting experiments were conducted by cyclically contacting a gold-surface electrode with the charge fixed surface of the polymer. Control experiments verified the effect of immobilizing the cations at the surface. By synthesizing a polymer with the optimal composition ratio of ionic liquid to macromonomer, an output of 77 nW/cm2 was obtained with a load resistance of 1 MΩ at 1 Hz. This tuneable power supply with a μA level current output may contribute to Internet of Things networks requiring numerous sensor nodes at remote places in the environment. PMID:29707070

Entropic (de)stabilization of surface-bound peptides conjugated with polymers.

PubMed

Carmichael, Scott P; Shell, M Scott

2015-12-28

In many emerging biotechnologies, functional proteins must maintain their native structures on or near interfaces (e.g., tethered peptide arrays, protein coated nanoparticles, and amphiphilic peptide micelles). Because the presence of a surface is known to dramatically alter the thermostability of tethered proteins, strategies to stabilize surface-bound proteins are highly sought. Here, we show that polymer conjugation allows for significant control over the secondary structure and thermostability of a model surface-tethered peptide. We use molecular dynamics simulations to examine the folding behavior of a coarse-grained helical peptide that is conjugated to polymers of various lengths and at various conjugation sites. These polymer variations reveal surprisingly diverse behavior, with some stabilizing and some destabilizing the native helical fold. We show that ideal-chain polymer entropies explain these varied effects and can quantitatively predict shifts in folding temperature. We then develop a generic theoretical model, based on ideal-chain entropies, that predicts critical lengths for conjugated polymers to effect changes in the folding of a surface-bound protein. These results may inform new design strategies for the stabilization of surface-associated proteins important for a range technological applications.

Sampling the Uppermost Surface of Airless Bodies

NASA Technical Reports Server (NTRS)

Noble, S. K.; Keller, L. P.; Christoffersen, R.

2011-01-01

The uppermost surface of an airless body is a critical source of ground-truth information for the various remote sensing techniques that only penetrate nanometers to micrometers into the surface. Such samples will also be vital for understanding conditions at the surface and acquiring information about how the body interacts with its environment, including solar wind interaction, grain charging and levitation [1]. Sampling the uppermost surface while preserving its structure (e.g. porosity, grain-to-grain contacts) however, is a daunting task that has not been achieved on any sample return mission to date.

Interfacial pattern changes of imprinted multilayered material in milli- and microscales

NASA Astrophysics Data System (ADS)

Yonekura, Kazuhiro; Tokumaru, Kazuki; Tsumori, Fujio

2018-06-01

Nanoimprint lithography (NIL) is a technique that transfers a mold pattern of nanometer order to the surface of a resist material by heating and pressing. NIL is an excellent technology in terms of high productivity, accuracy, and resolution. Recently, NIL has been applied to the processing of different multilayered materials, in which it is possible to process multiple materials simultaneously. In this processing of multilayered materials, it is possible to form an interfacial pattern between the upper layer and the lower layer simultaneously with patterning on the mold surface. This interface pattern can be controlled by the deformation characteristics, initial thickness, and so forth. In this research, we compared the interfacial pattern changes of imprinted multilayered materials in milli- and microscales. For multilayered imprint using multiple materials, it is important to know the flow of the resist and its dependence on the scale. If there is similarity in the relationship produced by the scale on the imprinted samples, a process design with a number of feedbacks could be realized. It also becomes easier to treat structures in the millimeter scale for the experiment. In this study, we employed micropowder imprint (µPI) for multilayered material imprint. A compound sheet of alumina powder and polymer binder was used for imprint. Two similar experiments in different scales, micro- and millimeter scales, were carried out. Results indicate that the interfacial patterns of micro- and millimeter-scale-imprinted samples are similar.

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

Ultrafast third-harmonic spectroscopy of single nanoantennas fabricated using helium-ion beam lithography

NASA Astrophysics Data System (ADS)

Kollmann, H.; Esmann, M.; Becker, S. F.; Piao, X.; Huynh, C.; Kautschor, L.-O.; Bösker, G.; Vieker, H.; Beyer, A.; Gölzhäuser, A.; Park, N.; Silies, M.; Lienau, C.

2016-03-01

Metallic nanoantennas are able to spatially localize far-field electromagnetic waves on a few nanometer length scale in the form of surface plasmon excitations 1-3. Standard tools for fabricating bowtie and rod antennas with sub-20 nm feature sizes are Electron Beam Lithography or Ga-based Focused Ion Beam (FIB) Milling. These structures, however, often suffer from surface roughness and hence show only a limited optical polarization contrast and therefore a limited electric field localization. Here, we combine Ga- and He-ion based milling (HIM) for the fabrication of gold bowtie and rod antennas with gap sizes of less than 6 nm combined with a high aspect ratio. Using polarization-sensitive Third-Harmonic (TH) spectroscopy, we compare the nonlinear optical properties of single HIM-antennas with sub-6-nm gaps with those produced by standard Ga-based FIB. We find a pronounced enhancement of the total TH intensity of more than three in comparison to Ga-FIB antennas and a highly improved polarization contrast of the TH intensity of 250:1 for Heion produced antennas 4. These findings combined with Finite-Element Method calculations demonstrate a field enhancement of up to one hundred in the few-nanometer gap of the antenna. This makes He-ion beam milling a highly attractive and promising new tool for the fabrication of plasmonic nanoantennas with few-nanometer feature sizes.

Modeling and analysis of sub-surface leakage current in nano-MOSFET under cutoff regime

NASA Astrophysics Data System (ADS)

Swami, Yashu; Rai, Sanjeev

2017-02-01

The high leakage current in nano-meter regimes is becoming a significant portion of power dissipation in nano-MOSFET circuits as threshold voltage, channel length, and gate oxide thickness are scaled down to nano-meter range. Precise leakage current valuation and meticulous modeling of the same at nano-meter technology scale is an increasingly a critical work in designing the low power nano-MOSFET circuits. We present a specific compact model for sub-threshold regime leakage current in bulk driven nano-MOSFETs. The proposed logical model is instigated and executed into the latest updated PTM bulk nano-MOSFET model and is found to be in decent accord with technology-CAD simulation data. This paper also reviews various transistor intrinsic leakage mechanisms for nano-MOSFET exclusively in weak inversion, like drain-induced barricade lowering (DIBL), gate-induced drain leakage (GIDL), gate oxide tunneling (GOT) leakage etc. The root cause of the sub-surface leakage current is mainly due to the nano-scale short channel length causing source-drain coupling even in sub-threshold domain. Consequences leading to carriers triumphing the barricade between the source and drain. The enhanced model effectively considers the following parameter dependence in the account for better-quality value-added results like drain-to-source bias (VDS), gate-to-source bias (VGS), channel length (LG), source/drain junction depth (Xj), bulk doping concentration (NBULK), and operating temperature (Top).

Decoupling Mechanical and Ion Transport Properties in Polymer Electrolyte Membranes

NASA Astrophysics Data System (ADS)

McIntosh, Lucas D.

Polymer electrolytes are mixtures of a polar polymer and salt, in which the polymer replaces small molecule solvents and provides a dielectric medium so that ions can dissociate and migrate under the influence of an external electric field. Beginning in the 1970s, research in polymer electrolytes has been primarily motivated by their promise to advance electrochemical energy storage and conversion devices, such as lithium ion batteries, flexible organic solar cells, and anhydrous fuel cells. In particular, polymer electrolyte membranes (PEMs) can improve both safety and energy density by eliminating small molecule, volatile solvents and enabling an all-solid-state design of electrochemical cells. The outstanding challenge in the field of polymer electrolytes is to maximize ionic conductivity while simultaneously addressing orthogonal mechanical properties, such as modulus, fracture toughness, or high temperature creep resistance. The crux of the challenge is that flexible, polar polymers best-suited for polymer electrolytes (e.g., poly(ethylene oxide)) offer little in the way of mechanical robustness. Similarly, polymers typically associated with superior mechanical performance (e.g., poly(methyl methacrylate)) slow ion transport due to their glassy polymer matrix. The design strategy is therefore to employ structured electrolytes that exhibit distinct conducting and mechanically robust phases on length scales of tens of nanometers. This thesis reports a remarkably simple, yet versatile synthetic strategy---termed polymerization-induced phase separation, or PIPS---to prepare PEMs exhibiting an unprecedented combination of both high conductivity and high modulus. This performance is enabled by co-continuous, isotropic networks of poly(ethylene oxide)/ionic liquid and highly crosslinked polystyrene. A suite of in situ, time-resolved experiments were performed to investigate the mechanism by which this network morphology forms, and it appears to be tied to the disordered structure observed in diblock polymer melts near the order-disorder transition. In the resulting solid PEMs, the conductivity and modulus are both high, exceeding the 1 mS/cm and approaching the 1 GPa metrics, respectively, often cited for lithium-metal batteries. In the final chapter, an alternative synthetic route to generate nanostructured PEMs is presented. This strategy relies on the formation of a thermodynamically stable network morphology exhibited by a triblock terpolymer prepared with crosslinking moieties along the backbone. Although the mechanical properties of the resulting PEM are excellent, the conductivity is found to be somewhat limited by network defects that result from the solvent-casting procedure.

Catechol-Functionalized Synthetic Polymer as a Dental Adhesive to Contaminated Dentin Surface for a Composite Restoration.

PubMed

Lee, Sang-Bae; González-Cabezas, Carlos; Kim, Kwang-Mahn; Kim, Kyoung-Nam; Kuroda, Kenichi

2015-08-10

This study reports a synthetic polymer functionalized with catechol groups as dental adhesives. We hypothesize that a catechol-functionalized polymer functions as a dental adhesive for wet dentin surfaces, potentially eliminating the complications associated with saliva contamination. We prepared a random copolymer containing catechol and methoxyethyl groups in the side chains. The mechanical and adhesive properties of the polymer to dentin surface in the presence of water and salivary components were determined. It was found that the new polymer combined with an Fe(3+) additive improved bond strength of a commercial dental adhesive to artificial saliva contaminated dentin surface as compared to a control sample without the polymer. Histological analysis of the bonding structures showed no leakage pattern, probably due to the formation of Fe-catechol complexes, which reinforce the bonding structures. Cytotoxicity test showed that the polymers did not inhibit human gingival fibroblast cells proliferation. Results from this study suggest a potential to reduce failure of dental restorations due to saliva contamination using catechol-functionalized polymers as dental adhesives.

Catechol-Functionalized Synthetic Polymer as a Dental Adhesive to Contaminated Dentin Surface for a Composite Restoration

PubMed Central

2015-01-01

This study reports a synthetic polymer functionalized with catechol groups as dental adhesives. We hypothesize that a catechol-functionalized polymer functions as a dental adhesive for wet dentin surfaces, potentially eliminating the complications associated with saliva contamination. We prepared a random copolymer containing catechol and methoxyethyl groups in the side chains. The mechanical and adhesive properties of the polymer to dentin surface in the presence of water and salivary components were determined. It was found that the new polymer combined with an Fe3+ additive improved bond strength of a commercial dental adhesive to artificial saliva contaminated dentin surface as compared to a control sample without the polymer. Histological analysis of the bonding structures showed no leakage pattern, probably due to the formation of Fe–catechol complexes, which reinforce the bonding structures. Cytotoxicity test showed that the polymers did not inhibit human gingival fibroblast cells proliferation. Results from this study suggest a potential to reduce failure of dental restorations due to saliva contamination using catechol-functionalized polymers as dental adhesives. PMID:26176305

Piezoelectric biosensor with a ladder polymer substrate coating

DOEpatents

Renschler, Clifford L.; White, Christine A.; Carter, Robert M.

1998-01-01

A piezoelectric biosensor substrate useful for immobilizing biomolecules in an oriented manner on the surface of a piezoelectric sensor has a ladder polymer of polyacrylonitrile. To make the substrate, a solution of an organic polymer, preferably polyacrylonitrile, is applied to the surface of a piezoelectric sensor. The organic polymer is modifying by heating the polymer in a controlled fashion in air such that a ladder polymer is produced which, in turn, forms the attachment point for the biomolecules comprising the piezoelectric biosensor.

Piezoelectric biosensor with a ladder polymer substrate coating

DOEpatents

Renschler, C.L.; White, C.A.; Carter, R.M.

1998-09-29

A piezoelectric biosensor substrate useful for immobilizing biomolecules in an oriented manner on the surface of a piezoelectric sensor has a ladder polymer of polyacrylonitrile. To make the substrate, a solution of an organic polymer, preferably polyacrylonitrile, is applied to the surface of a piezoelectric sensor. The organic polymer is modifying by heating the polymer in a controlled fashion in air such that a ladder polymer is produced which, in turn, forms the attachment point for the biomolecules comprising the piezoelectric biosensor. 3 figs.

Synthesis of surface-anchored DNA-polymer bioconjugates using reversible addition-fragmentation chain transfer polymerization.

PubMed

He, Peng; He, Lin

2009-07-13

We report here an approach to grafting DNA-polymer bioconjugates on a planar solid support using reversible addition-fragmentation chain transfer (RAFT) polymerization. In particular, a trithiocarbonate compound as the RAFT chain transfer agent (CTA) is attached to the distal point of a surface-immobilized oligonucleotide. Initiation of RAFT polymerization leads to controlled growth of polymers atop DNA molecules on the surface. Growth kinetics of poly(monomethoxy-capped oligo(ethylene glycol) methacrylate) atop DNA molecules is investigated by monitoring the change of polymer film thickness as a function of reaction time. The reaction conditions, including the polymerization temperature, the initiator concentration, the CTA surface density, and the selection of monomers, are varied to examine their impacts on the grafting efficiency of DNA-polymer conjugates. Comparing to polymer growth atop small molecules, the experimental results suggest that DNA molecules significantly accelerate polymer growth, which is speculated as a result of the presence of highly charged DNA backbones and purine/pyrimidine moieties surrounding the reaction sites.

Polymer-Based Protein Engineering: Synthesis and Characterization of Armored, High Graft Density Polymer-Protein Conjugates.

PubMed

Carmali, Sheiliza; Murata, Hironobu; Cummings, Chad; Matyjaszewski, Krzysztof; Russell, Alan J

2017-01-01

Atom transfer radical polymerization (ATRP) from the surface of a protein can generate remarkably dense polymer shells that serve as armor and rationally tune protein function. Using straightforward chemistry, it is possible to covalently couple or display multiple small molecule initiators onto a protein surface. The chemistry is fine-tuned to be sequence specific (if one desires a single targeted site) at controlled density. Once the initiator is anchored on the protein surface, ATRP is used to grow polymers on protein surface, in situ. The technique is so powerful that a single-protein polymer conjugate molecule can contain more than 90% polymer coating by weight. If desired, stimuli-responsive polymers can be "grown" from the initiated sites to prepare enzyme conjugates that respond to external triggers such as temperature or pH, while still maintaining enzyme activity and stability. Herein, we focus mainly on the synthesis of chymotrypsin-polymer conjugates. Control of the number of covalently coupled initiator sites by changing the stoichiometric ratio between enzyme and the initiator during the synthesis of protein-initiator complexes allowed fine-tuning of the grafting density. For example, very high grafting density chymotrypsin conjugates were prepared from protein-initiator complexes to grow the temperature-responsive polymers, poly(N-isopropylacrylamide), and poly[N,N'-dimethyl(methacryloyloxyethyl) ammonium propane sulfonate]. Controlled growth of polymers from protein surfaces enables one to predictably manipulate enzyme kinetics and stability without the need for molecular biology-dependent mutagenesis. © 2017 Elsevier Inc. All rights reserved.

Sub-micron elastic property characterization of materials using a near-field scanning optical microscope

NASA Astrophysics Data System (ADS)

Blodgett, David W.; Spicer, James B.

2001-12-01

The ability to characterize the sub-surface mechanical properties of a bulk or thin film material at the sub-micron level has applications in the microelectronics and thin film industries. In the microelectronics industry, with the decrease of line widths and the increase of component densities, sub-surface voids have become increasingly detrimental. Any voids along an integrated circuit (IC) line can lead to improper electrical connections between components and can cause failure of the device. In the thin film industry, the detection of impurities is also important. Any impurities can detract from the film's desired optical, electrical, or mechanical properties. Just as important as the detection of voids and impurities, is the measurement of the elastic properties of a material on the nanometer scale. These elastic measurements provide insight into the microstructural properties of the material. We have been investigating a technique that couples the high-resolution surface imaging capabilities of the apertureless near-field scanning optical microscope (ANSOM) with the sub-surface characterization strengths of high-frequency ultrasound. As an ultrasonic wave propagates, the amplitude decreases due to geometrical spreading, attenuation from absorption, and scattering from discontinuities. Measurement of wave speeds and attenuation provides the information needed to quantify the bulk or surface properties of a material. The arrival of an ultrasonic wave at or along the surface of a material is accompanied with a small surface displacement. Conventional methods for the ultrasound detection rely on either a contact transducer or optical technique (interferometric, beam deflection, etc.). However, each of these methods is limited by the spatial resolution dictated by the detection footprint. As the footprint size increases, variations across the ultrasonic wavefront are effectively averaged, masking the presence of any nanometer-scale sub-surface or surface mechanical property variations. The use of an ANSOM for sensing ultrasonic wave arrivals reduces the detection footprint allowing any nanometer scale variations in the microstructure of a material to be detected. In an ANSOM, the ultrasonic displacement is manifested as perturbations on the near-field signal due to the small variations in the tip-sample caused by the wave arrival. Due to the linear dependence of the near-field signal on tip-sample separation, these perturbations can be interpreted using methods identical to those for conventional ultrasonic techniques. In this paper, we report results using both contact transducer (5 MHz) and laser-generated ultrasound.

Functional patterned coatings by thin polymer film dewetting.

PubMed

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

2017-12-01

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

ELECTROSTATIC CHARGE STIMULATES OXIDATIVE STRESS IN CNS MICROGLIA.

EPA Science Inventory

Nanometer size particles carry free radical activity on their surface and can create oxidative stress (OS)-mediated inflammatory changes upon impact. The oxidative burst signals the activation of phage-lineage cells such as peripheral macrophages, Kupffer cells and CNS microgl...

Building a road map for tailoring multilayer polyelectrolyte films

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

Ankner, John Francis; Bardoel, Agatha A; Sukishvili, Svetlana

2012-01-01

Researchers are moving a step closer to a definite road map for building layer-by-layer (LbL) assembled polyelectrolyte films, with the assistance of the Liquids Reflectometer at Oak Ridge National Laboratory's Spallation Neutron Source, in Oak Ridge, Tennessee. Scientists using the liquids reflectometer have successfully taken snapshots in close to real time of these multilayered structures for different applications when they modify the structure and function parameters. Polyelecrolytes are polymers that carry charge in aqueous solutions. They contain chemical groups that dissociate in water, making such polymers charged. Most polyelectrolytes are water soluble. They are important components in foods, soaps, shampoos,more » and cosmetics products. They show promise for such environmental work as oil recovery and water treatment. Polyelectrolytes are compelling because researchers can chemically modify how they interact with water for multiple applications. When two types of polyelectrolytes of opposite charge are assembled at a surface in a sequential way using the LbL assembly technique, 'the result is the forming of surface films, useful for coatings, biomedical implants and devices, controlling adhesion of biological molecules, and controlling delivery of therapeutic molecules from surfaces,' said Svetlana Sukhishvili of the Stevens Institute of Technology in New Jersey, the lead chemist on the collaboration. 'Medical doctors often prefer to deliver multiple therapeutic compounds from the coatings in a time-resolved manner,' Sukhishvili said. 'To assist them, material scientists need to learn how to build coatings in which polymer layering will not be compromised when exposed to normal physiological conditions.' 'Being able to control these properties, understanding how what you do to the materials affects their properties, this allows you to apply them to situations where interacting with an environment is very helpful, whether in a biological context or any other kind of water soluble context,' said John Ankner, lead instrument scientist for the Liquids Reflectometer. Ankner said that when several parameters are systematically altered, that allows researchers to map out the whole range of structures in the polymer. 'This work really sets a road map for how to get started with synthesizing polyelectrolyte materials for specific applications. Then, one can say, ok, this methylated material, the one that is 30% charged, is going to be what we want to use for a particular application.' The ORNL collaboration with the Stevens Institute has been conducting a series of experiments at the SNS to study layered film stratification in these polymers. Researchers stitch the polyelectrolyte chains in the LbL films together through what is called ionic pairing and arrange them within fuzzy, ultrathin layers that lie parallel to a solid surface substrate. Exposure of these films to aqueous solutions that contain salt (i.e., conditions that imitate real life) can compromise this film layering, as the salt ions act to weaken the ionic pairing that binds such layers together. So salt solutions are of key interest in studying how to make such layers for use in human applications. In the first research, Ankner, Sukhishvili and her student Li Xu looked at the effects of the layering of two types of LbL films of changing the charge density with a salt solution, and of blocking access to a charged site by nearby groups. The films were composed of positively charged variants of PDMA, a methyl polymer, and PDEA, an ethyl polymer. The other component of both systems is the ion exchanger polystyrene sulfonate (PSS) which features a fixed negative charge. First, a silicon substrate was dipped into solutions of PDMA and PDEA in dilute sodium chloride for a fixed time. Depending on the deposition time and the concentration of the solution, a nanometer-thick monolayer of the polymer adsorbs to the silicon surface. The film buildup is then continued by depositing a layer of PSS, and the cycle is repeated. The PDMA (methyl)/PSS and PDEA (ethyl)/PSS films were then annealed in varying concentrations of aqueous salt solutions. The chemists wanted to know if in these multi-layer cake-like assemblies, the structure can be systematically altered by varying the salt concentration, time in solution, and ultimately other environmental parameters, such as temperature or pH. Neutron reflectivity of the layered films exhibits the quality of the layering, in particular the concentration of the layers and how intermixed they are with adjacent layers. In this research, neutron reflectivity data from films built from 10%, 40%, and 100% charged PDMA or PDEA polyelectrolytes and 100% charged PSS were quantitatively compared to predicted, layered arrangements until the models produced reflectivity patterns matching those of the data.« less

Interactions of polymer surfaces and thin films

NASA Astrophysics Data System (ADS)

Zeng, Hongbo

2007-12-01

Characterization of the adhesion, tribological properties and dynamics of polymer surfaces has been of great interest for many years since polymers are commonly used as adhesive and lubricant coatings to produce both high and low adhesion or friction. Improving our fundamental understanding of the interactions of polymer surfaces at the molecular level is needed to develop further techniques in materials science and chemical engineering. The objectives of my research were to correlate the nano- and micro-scale properties of various polymer thin film and surface phenomena: adhesion, adhesion hysteresis, friction, lubrication, surface deformations, coalescence, spreading, and wear, and identify the fundamental physical forces and mechanisms at the molecular and micro-scales. I studied the adhesion of polymer films at temperatures ranging from below to above the glass transition temperature, Tg. The adhesion hysteresis was found to peak somewhere around Tg, but to also depend on the load, contact time and detachment rate. The results revealed some new scaling relations for the dynamic (rate-dependent) adhesion forces and effective surface energies of polymers. I studied the way polymer surfaces deform during adhesion (coalescence), spreading (wetting) and separation (detachment, rupture, fracture and failure) processes, and characterized the differences (and transition) between liquid-like and solid-like behavior during these processes, e.g., the transition from liquid-to-viscoelastic-to-ductile-to-brittle behavior. Complex and novel transient (dynamic) surface shape changes were found to occur during transitions that involved highly-ordered or disordered fingers, ripples, waves or cracks. A full picture has emerged for the transition from viscous liquid-like to brittle solid-like behavior of adhering and detaching interfaces. Finally, I developed a new experiment technique whereby an electric field can be applied across the two surfaces in a Surface Force Apparatus for the first time, and two types of experiments were performed to measure the normal and/or lateral forces between two surfaces under an E-field.

Effect of polymer surface modification on polymer-protein interaction via hydrophilic polymer grafting.

PubMed

Liu, S X; Kim, J-T; Kim, S

2008-04-01

Surface modification of flat sheet ultrafiltration membranes, polyethersulfone (PES), was investigated to improve the hydrophilicity of the membrane surface thereby reducing adsorption of the proteins onto the membrane. Grafting of hydrophilic polymers onto UV/ozone-treated PES was used to improve the hydrophilicity of the commercial PES membranes. Hydrophilic polymers, that is, poly(vinyl alcohol) (PVA), polyethylene glycol (PEG), and chitosan, were employed to graft onto PES membrane surfaces because of their excellent hydrophilic property. The surfaces of modified PES membranes were characterized by contact angle measurement, FTIR, and AFM. The FTIR spectra indicated that PES membranes were successfully modified by grafting of the hydrophilic polymers. The modified PES membranes showed 20% to 50% reduction in contact angle measurements in comparison with those of the virgin PES membrane. The tapping mode AFM technique was employed to investigate the changes of surface topography, cross-section, and root mean square roughness of the modified PES membrane surfaces. The modified PES membranes showed elevated roughness (ranging from 7.0 to 25.7 nm) compared with that of the virgin PES membrane (2.1 nm). It is concluded that grafting of PVA, PEG, or chitosan onto UV/ozone-treated PES membranes increases hydrophilicity and lowers protein adsorption by 20% to 60% compared to the virgin PES membrane. Among the 3 hydrophilic polymers studied, PEG showed the most favorable result in terms of contact angle and protein adsorption.

Surface structure of coherently strained ceria ultrathin films

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

Shi, Yezhou; Stone, Kevin H.; Guan, Zixuan

2016-11-14

Cerium oxide, or ceria, is an important material for solid oxide fuel cells and water splitting devices. Although the ceria surface is active in catalytic and electrochemical reactions, how its catalytic properties are affected by the surface structure under operating conditions is far from understood. We investigate the structure of the coherently strained CeO 2 ultrathin films on yttria-stabilized zirconia (001) single crystals by specular synchrotron x-ray diffraction (XRD) under oxidizing conditions as a first step to study the surface structure in situ. An excellent agreement between the experiment data and the model is achieved by using a “stacks andmore » islands” model that has a two-component roughness. One component is due to the tiny clusters of nanometer scale in lateral dimensions on each terrace, while the other component is due to slightly different CeO 2 thickness that span over hundreds of nanometers on neighboring terraces. We attribute the nonuniform thickness to step depairing during the thin film deposition that is supported by the surface morphology results on the microscopic level. Importantly, our model also shows that the polarity of the ceria surface is removed by a half monolayer surface coverage of oxygen. In conclusion, the successful resolution of the ceria surface structure using in situ specular synchrotron XRD paves the way to study the structural evolution of ceria as a fuel cell electrode under catalytically relevant temperatures and gas pressures.« less

Studies of Surface Charging of Polymers by Indirect Triboelectrification

NASA Astrophysics Data System (ADS)

Mantovani, James; Calle, Carlos; Groop, Ellen; Buehler, Martin

2001-03-01

Charge is known to develop on the surface of an insulating polymer by frictional charging through direct physical contact with another material. We will present results of recent triboelectrification studies of polymer surfaces that utilized an indirect method of frictional charging. This method first involves placing a grounded thin metal foil in stationary contact over the polymer surface. The exposed metal foil is then rubbed with the surface of the material that generates the triboelectric charge. Data is presented for five types of polymers: fiberglass/epoxy, polycarbonate (Lexan), polytetraflouroethylene (Teflon), Rulon J, and polymethylmethacrylate (PMMA, Lucite). The amount of charge that develops on an insulator's surface is measured using the MECA Electrometer, which was developed jointly by NASA Kennedy Space Center and the Jet Propulsion Laboratory to study the electrostatic properties of soil on the surface of Mars. Even though the insulator's surface is electrically shielded from the rubbing material by the grounded metal foil, charge measurements obtained by the MECA Electrometer after the metal foil is separated from the insulator's surface reveal that the insulator's surface does accumulate charge by indirect frictional charging. A possible explanation of the observations will be presented based on a simple contact barrier model.

Enhancing the chroma of pigmented polymers using antireflective surface structures.

PubMed

Clausen, Jeppe S; Christiansen, Alexander B; Kristensen, Anders; Mortensen, N Asger

2013-11-10

In this paper we investigate how the color of a pigmented polymer is affected by reduction of the reflectance at the air-polymer interface. Both theoretical and experimental investigations show modified diffuse-direct reflectance spectra when the reflectance of the surface is lowered. Specifically it is found that the color change is manifested as an increase in chroma, leading to a clearer color experience. The experimental implementation is done using random tapered surface structures replicated in polymer from silicon masters using hot embossing.

Surface modification of cellulose using silane coupling agent.

PubMed

Thakur, Manju Kumari; Gupta, Raju Kumar; Thakur, Vijay Kumar

2014-10-13

Recently there has been a growing interest in substituting traditional synthetic polymers with natural polymers for different applications. However, natural polymers such as cellulose suffer from few drawbacks. To become viable potential alternatives of synthetic polymers, cellulosic polymers must have comparable physico-chemical properties to that of synthetic polymers. So in the present work, cellulose polymer has been modified by a series of mercerization and silane functionalization to optimize the reaction conditions. Structural, thermal and morphological characterization of the cellulose has been done using FTIR, TGA and SEM, techniques. Surface modified cellulose polymers were further subjected to evaluation of their properties like swelling and chemical resistance behavior. Published by Elsevier Ltd.

Application of scanning angle Raman spectroscopy for determining the location of buried polymer interfaces with tens of nanometer precision

DOE PAGES

Damin, Craig A.; Nguyen, Vy H. T.; Niyibizi, Auguste S.; ...

2015-02-11

In this study, near-infrared scanning angle (SA) Raman spectroscopy was utilized to determine the interface location in bilayer films (a stack of two polymer layers) of polystyrene (PS) and polycarbonate (PC). Finite-difference-time-domain (FDTD) calculations of the sum square electric field (SSEF) for films with total bilayer thicknesses of 1200–3600 nm were used to construct models for simultaneously measuring the film thickness and the location of the buried interface between the PS and PC layers. Samples with total thicknesses of 1320, 1890, 2300, and 2750 nm and varying PS/PC interface locations were analyzed using SA Raman spectroscopy. Comparing SA Raman spectroscopymore » and optical profilometry measurements, the average percent difference in the total bilayer thickness was 2.0% for films less than ~2300 nm thick. The average percent difference in the thickness of the PS layer, which reflects the interface location, was 2.5% when the PS layer was less than ~1800 nm. SA Raman spectroscopy has been shown to be a viable, non-destructive method capable of determining the total bilayer thickness and buried interface location for bilayer samples consisting of thin polymer films with comparable indices of refraction.« less