Plasma assisted surface coating/modification processes - An emerging technology

NASA Technical Reports Server (NTRS)

Spalvins, T.

1987-01-01

A broad understanding of the numerous ion or plasma assisted surface coating/modification processes is sought. An awareness of the principles of these processes is needed before discussing in detail the ion nitriding technology. On the basis of surface modifications arising from ion or plasma energizing and interactions, it can be broadly classified as deposition of distinct overlay coatings (sputtering-dc, radio frequency, magnetron, reactive; ion plating-diode, triode) and surface property modification without forming a discrete coating (ion implantation, ion beam mixing, laser beam irradiation, ion nitriding, ion carburizing, plasma oxidation. These techniques offer a great flexibility and are capable in tailoring desirable chemical and structural surface properties independent of the bulk properties.

Plasma assisted surface coating/modification processes: An emerging technology

NASA Technical Reports Server (NTRS)

Spalvins, T.

1986-01-01

A broad understanding of the numerous ion or plasma assisted surface coating/modification processes is sought. An awareness of the principles of these processes is needed before discussing in detail the ion nitriding technology. On the basis of surface modifications arising from ion or plasma energizing and interactions, it can be broadly classified as deposition of distinct overlay coatings (sputtering-dc, radio frequency, magnetron, reactive; ion plating-diode, triode) and surface property modification without forming a discrete coating (ion implantation, ion beam mixing, laser beam irradiation, ion nitriding, ion carburizing, plasma oxidation). These techniques offer a great flexibility and are capable in tailoring desirable chemical and structural surface properties independent of the bulk properties.

Atomic Mechanism of Hybridization-Dependent Surface Reconstruction with Tailored Functionality in Hexagonal Multiferroics.

PubMed

Deng, Shiqing; Cheng, Shaobo; Xu, Changsong; Ge, Binghui; Sun, Xuefeng; Yu, Rong; Duan, Wenhui; Zhu, Jing

2017-08-16

The broken symmetry along with anomalous defect structures and charging conditions at multiferroics surface can alter both crystal structures and electronic configurations, bringing in emergent physical properties. Extraordinary surface states are induced into original mutually coupled order parameters in such strongly correlated oxides, which flourish in diverse properties but remain less explored. Here, we report the peculiar surface ferroelectric states and reconfigurable functionalities driven by the relaxation of surface and consequent changes in O 2p and Y 4d orbital (p-d) hybridization within a representative hexagonal multiferroics, YMnO 3 . An unprecedented surface reconstruction is achieved by tailored p-d hybridization coupling with in-plane oxygen vacancies, which is atomically revealed on the basis of the advantages of state-of-the-art aberration-corrected (scanning) transmission electron microscopy. Further ab initio density functional theory calculations verify the key roles of in-plane oxygen vacancies in modulating polarization properties and electronic structure, which should be regarded as the atomic multiferroic element. This surface configuration is found to induce tunable functionalities, such as surface ferromagnetism and conductivity. Meanwhile, the controversial origin of improper ferroelectricity that is unexpectedly free from critical size has also been atomically unraveled. Our findings provide new insights into the design and implementation of surface chemistry devices by simply controlling the oxygen stoichiometry, greatly advance our understandings of surface science in strongly correlated oxides, and enable exciting innovations and new technological functionality paradigms.

Synthesis of visible light driven cobalt tailored Ag{sub 2}O/TiON nanophotocatalyst by reverse micelle processing for degradation of Eriochrome Black T

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

Hussain, Syed Tajammul, E-mail: dr_tajammul@yahoo.ca; Rashid; Department of Chemistry, Quaid-i-Azam University, Islamabad

2013-02-15

Graphical abstract: Cobalt tailored Ag{sub 2}O/TiON nanophotocatalyst is synthesized using reverse micelle technique and it showed extraordinary photocatalytic activity. Display Omitted Highlights: ► TiON/Ag{sub 2}O/Co nanophotocatalyst is synthesized using microemulsion technique. ► Low temperature anatase phase and outstanding photocatlytic activity is observed. ► Effect of temperature and inert atmosphere on materials phase is investigated. ► Homogeneous dopants distribution and oxygen vacancies are examined. ► Enhancement in surface area, quantum efficiency and optical properties is observed. -- Abstract: An ultra efficient cobalt tailored silver and nitrogen co-doped titania (TiON/Ag{sub 2}O/Co) visible nanophotocatalyst is successfully synthesized using modified reverse micelle processing. Composition,more » phase, distribution of dopants, functional group analysis, optical properties and morphology of synthesized materials are investigated by means of X-ray diffraction (XRD), transmission electron microscopy (TEM) based techniques and others. Charge states of titanium (Ti) and silver are explored through core-loss electron energy loss spectroscopy (EELS) analysis and X ray photoelectron spectroscopy (XPS). Our characterization results showed that the synthesized nanophotocatalyst consisted of anatase phased qausispherical nanoparticles that exhibited homogeneous distribution of dopants, large surface area, high quantum efficiency and enhanced optical properties. At lower content of doped Co ions, the TiON/Ag{sub 2}O responded with extraordinary photocatalytic properties. The cobalt tailored nanophotocatalyst showed remarkable activity against Eriochrome Black T (EBT). Moreover, comparative degradation behavior of EBT with TiON, Ag{sub 2}O/TiON and Co/Ag{sub 2}O/TiON is also investigated.« less

Sol-gel Technology and Advanced Electrochemical Energy Storage Materials

NASA Technical Reports Server (NTRS)

Chu, Chung-tse; Zheng, Haixing

1996-01-01

Advanced materials play an important role in the development of electrochemical energy devices such as batteries, fuel cells, and electrochemical capacitors. The sol-gel process is a versatile solution for use in the fabrication of ceramic materials with tailored stoichiometry, microstructure, and properties. This processing technique is particularly useful in producing porous materials with high surface area and low density, two of the most desirable characteristics for electrode materials. In addition,the porous surface of gels can be modified chemically to create tailored surface properties, and inorganic/organic micro-composites can be prepared for improved material performance device fabrication. Applications of several sol-gel derived electrode materials in different energy storage devices are illustrated in this paper. V2O5 gels are shown to be a promising cathode material for solid state lithium batteries. Carbon aerogels, amorphous RuO2 gels and sol-gel derived hafnium compounds have been studied as electrode materials for high energy density and high power density electrochemical capacitors.

Tailoring the surface properties of polypropylene films through cold atmospheric pressure plasma (CAPP) assisted polymerization and immobilization of biomolecules for enhancement of anti-coagulation activity

NASA Astrophysics Data System (ADS)

Navaneetha Pandiyaraj, K.; Ram Kumar, M. C.; Arun Kumar, A.; Padmanabhan, P. V. A.; Deshmukh, R. R.; Bah, M.; Ismat Shah, S.; Su, Pi-Guey; Halleluyah, M.; Halim, A. S.

2016-05-01

Enhancement of anti-thrombogenic properties of polypropylene (PP) to avert the adsorption of plasma proteins (fibrinogen and albumin), adhesion and activation of the platelets are very important for vast biomedical applications. The cold atmospheric pressure plasma (CAPP) assisted polymerization has potential to create the specific functional groups such as Osbnd Cdbnd O, Cdbnd O, Csbnd N and Ssbnd S. on the surface of polymeric films using selective precursor in vapour phase to enhance anti-thrombogenic properties. Such functionalized polymeric surfaces would be suitable for various biomedical applications especially to improve the blood compatibility. The eventual aspiration of the present investigation is to develop the biofunctional coating onto the surface of PP films using acrylic acid (AAc) and polyethylene glycol (PEG) as a precursor in a vapour phase by incorporating specific functional groups for immobilization of biomolecules such as heparin (HEP), chitosan (CHI) and insulin (INS) on the surface of plasma modified PP films. The surface properties such as hydrophilicity, chemical composition, surface topography of the surface modified PP films were analyzed by contact angle (CA), Fourier transform infrared spectroscopy (FTIR), X-ray photo electron spectroscopy (XPS) and atomic force microscopy (AFM). Furthermore the anti-thrombogenic properties of the surface modified PP films were studied by in vitro tests which include platelet adhesion and protein adsorption analysis. It was found that the anti-thrombogenic properties of the PP films are effectively controlled by the CAPP grafting of AAc and PEG followed by immobilization of biomolecules of heparin, chitosan and insulin. The grafting and immobilization was confirmed by FTIR and XPS through the recognition of specific functional groups such as COOH, Csbnd O, Ssbnd S and Csbnd N. on the surface of PP film. Furthermore, the surface morphology and hydrophilic nature of the PP films also tailored significantly by the successful grafting and immobilization which is confirmed by AFM and CA analysis. Owing to the physico-chemical changes on the surface of PP films induced by CAPP assisted polymerization, the anti-thrombogenic properties of PP films were enhanced as confirmed by in vitro analysis.

Effect of surface etching and electrodeposition of copper on nitinol

NASA Astrophysics Data System (ADS)

Ramos-Moore, E.; Rosenkranz, A.; Matamala, L. F.; Videla, A.; Durán, A.; Ramos-Grez, J.

2017-10-01

Nitinol-based materials are very promising for medical and dental applications since those materials can combine shape memory, corrosion resistance, biocompatibility and antibacterial properties. In particular, surface modifications and coating deposition can be used to tailor and to unify those properties. We report preliminary results on the study of the effect of surface etching and electrodeposition of Copper on Nitinol using optical, chemical and thermal techniques. The results show that surface etching enhances the surface roughness of Nitinol, induces the formation of Copper-based compounds at the Nitinol-Copper interface, reduces the austenitic-martensitic transformations enthalpies and reduces the Copper coating roughness. Further studies are needed in order to highlight the influence of the electrodeposited Copper on the memory shape properties of NiTi.

Surface tailored single walled carbon nanotubes as catalyst support for direct methanol fuel cell

NASA Astrophysics Data System (ADS)

Kireeti, Kota V. M. K.; Jha, Neetu

2017-10-01

A strategy for tuning the surface property of Single Walled Carbon Nanotubes (SWNTs) for enhanced methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) along with methanol tolerance is presented. The surface functionality is tailored using controlled acid and base treatment. Acid treatment leads to the attachment of carboxylic carbon (CC) fragments to SWNT making it hydrophilic (P3-SWNT). Base treatment of P3-SWNT with 0.05 M NaOH reduces the CCs and makes it hydrophobic (P33-SWNT). Pt catalyst supported on the P3-SWNT possesses enhanced MOR whereas that supported on P33-SWNT not only enhances ORR kinetics but also possess good tolerance towards methanol oxidation as verified by the electrochemical technique.

Methods and apparatus for altering material using ion beams

DOEpatents

Bloomquist, Douglas D.; Buchheit, Rudy; Greenly, John B.; McIntyre, Dale C.; Neau, Eugene L.; Stinnett, Regan W.

1996-01-01

A method and apparatus for treating material surfaces using a repetitively pulsed ion beam. In particular, a method of treating magnetic material surfaces in order to reduce surface defects, and produce amorphous fine grained magnetic material with properties that can be tailored by adjusting treatment parameters of a pulsed ion beam. In addition to a method of surface treating materials for wear and corrosion resistance using pulsed particle ion beams.

Tailoring Interfacial Properties by Controlling Carbon Nanotube Coating Thickness on Glass Fibers Using Electrophoretic Deposition.

PubMed

Tamrakar, Sandeep; An, Qi; Thostenson, Erik T; Rider, Andrew N; Haque, Bazle Z Gama; Gillespie, John W

2016-01-20

The electrophoretic deposition (EPD) method was used to deposit polyethylenimine (PEI) functionalized multiwall carbon nanotube (CNT) films onto the surface of individual S-2 glass fibers. By varying the processing parameters of EPD following Hamaker's equation, the thickness of the CNT film was controlled over a wide range from 200 nm to 2 μm. The films exhibited low electrical resistance, providing evidence of coating uniformity and consolidation. The effect of the CNT coating on fiber matrix interfacial properties was investigated through microdroplet experiments. Changes in interfacial properties due to application of CNT coatings onto the fiber surface with and without a CNT-modified matrix were studied. A glass fiber with a 2 μm thick CNT coating and the unmodified epoxy matrix showed the highest increase (58%) in interfacial shear strength (IFSS) compared to the baseline. The increase in the IFSS was proportional to CNT film thickness. Failure analysis of the microdroplet specimens indicated higher IFSS was related to fracture morphologies with higher levels of surface roughness. EPD enables the thickness of the CNT coating to be adjusted, facilitating control of fiber/matrix interfacial resistivity. The electrical sensitivity provides the opportunity to fabricate a new class of sizing with tailored interfacial properties and the ability to detect damage initiation.

Gd{sup 3+} incorporated ZnO nanoparticles: A versatile material

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

Kumar, Surender, E-mail: surender40@gmail.com; Sahare, P.D.

Graphical abstract: - Highlights: • Chemically synthesized Gd{sup 3+} doped ZnO nanoparticles. • The broad visible emission of the ZnO is dependent on the surface defects and can be tailored by Gd{sup 3+} doing. • PL and magnetic properties are modified by Gd{sup 3+} doping. • Photocatalysis experiment reveals that the ZnO: Gd{sup 3+} degrades the Rh B dye faster than the undoped ZnO. - Abstract: Gd{sup 3+} doped ZnO nanoparticles are synthesized by wet chemical route method and investigated through structural, optical, magnetic and photocatalytic properties. Transmission Electron Microscopy technique has been performed on undoped and Gd{sup 3+} dopedmore » ZnO nanoparticles. X-ray diffraction, X-ray photoelectron spectroscopy and Raman analyses are carried out in order to examine the desired phase formation and substitution of Gd{sup 3+} in the ZnO matrix. Gd{sup 3+} doped ZnO nanoparticles show enhanced photoluminescent and ferromagnetic properties as compared to undoped ZnO. The broad visible emission of ZnO is found to be largely dependent on the surface defects and these surface defects can be tailored by Gd{sup 3+} doping concentration. Furthermore, Gd{sup 3+} doped ZnO nanoparticles also show improved photocatalytic properties as compared with undoped ZnO nanoparticles under ultraviolet irradiation.« less

Shaping electrocatalysis through tailored nanomaterials

DOE PAGES

Kang, Yijin; Yang, Peidong; Markovic, Nenad M.; ...

2016-09-21

Electrocatalysis is a subclass of heterogeneous catalysis that is aimed towards increase of the electrochemical reaction rates that are taking place at the surface of electrodes. Real-world electrocatalysts are usually based on precious metals in the form of nanoparticles due to their high surface-to-volume ratio, which enables better utilization of employed materials. Ability to tailor nanostructure of an electrocatalyst is critical in order to tune their electrocatalytic properties. Over the last decade, that has mainly been achieved through implementation of fundamental studies performed on well-defined extended surfaces with distinct single crystalline and polycrystalline structures. Based on these studies, it hasmore » been demonstrated that performance of an electrocatalyst could be significantly changed through the control of size, composition, morphology and architecture of employed nanomaterials. Here, this review outlines the following steps in the process of rational development of an efficient electrocatalyst: 1) electrochemical properties of well-defined surfaces, 2) synthesis and characterization of different classes of electrocatalysts, and 3) correlation between physical properties (size, shape, composition and morphology) and electrochemical behavior (adsorption, electrocatalytic activity and durability) of electrocatalyst. In addition, this is a brief summary of the novel research platforms in the development of functional nano materials for energy conversion and storage applications such as fuel cells electrolyzers and batteries.« less

Protein adsorption on tailored substrates: long-range forces and conformational changes

NASA Astrophysics Data System (ADS)

Bellion, M.; Santen, L.; Mantz, H.; Hähl, H.; Quinn, A.; Nagel, A.; Gilow, C.; Weitenberg, C.; Schmitt, Y.; Jacobs, K.

2008-10-01

Adsorption of proteins onto solid surfaces is an everyday phenomenon that is not yet fully understood. To further the current understanding, we have performed in situ ellipsometry studies to reveal the adsorption kinetics of three different proteins, lysozyme, α-amylase and bovine serum albumin. As substrates we offer Si wafers with a controlled Si oxide layer thickness and a hydrophilic or hydrophobic surface functionalization, allowing the tailoring of the influence of short- and long-range interactions. Our studies show that not only the surface chemistry determines the properties of an adsorbed protein layer but also the van der Waals contributions of a composite substrate. We compare the experimental findings to results of a colloidal Monte Carlo approach that includes conformational changes of the adsorbed proteins induced by density fluctuations.

Mesoscopic modeling of structural and thermodynamic properties of fluids confined by rough surfaces.

PubMed

Terrón-Mejía, Ketzasmin A; López-Rendón, Roberto; Gama Goicochea, Armando

2015-10-21

The interfacial and structural properties of fluids confined by surfaces of different geometries are studied at the mesoscopic scale using dissipative particle dynamics simulations in the grand canonical ensemble. The structure of the surfaces is modeled by a simple function, which allows us to simulate readily different types of surfaces through the choice of three parameters only. The fluids we have modeled are confined either by two smooth surfaces or by symmetrically and asymmetrically structured walls. We calculate structural and thermodynamic properties such as the density, temperature and pressure profiles, as well as the interfacial tension profiles for each case and find that a structural order-disorder phase transition occurs as the degree of surface roughness increases. However, the magnitude of the interfacial tension is insensitive to the structuring of the surfaces and depends solely on the magnitude of the solid-fluid interaction. These results are important for modern nanotechnology applications, such as in the enhanced recovery of oil, and in the design of porous materials with specifically tailored properties.

Reconfigurable modified surface layers using plasma capillaries around the neutral inclusion regime

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

Varault, S.; Universite Paul Sabatier—CNRS-Laplace 118, Route de Narbonne, F-31062 Toulouse Cedex 9; Gabard, B.

We show both theoretically and experimentally reconfigurable properties achieved by plasma inclusions placed in modified surface layers generally used to tailor the transmission and beaming properties of electromagnetic bandgap based waveguiding structures. A proper parametrization of the plasma capillaries allows to reach the neutral inclusion regime, where the inclusions appear to be electromagnetically transparent, letting the surface mode characteristics unaltered. Varying the electron density of the plasma inclusions provoques small perturbations around this peculiar regime, and we observe significant modifications of the transmission/beaming properties. This offers a way to dynamically select the enhanced transmission frequency or to modify the radiationmore » pattern of the structure, depending on whether the modified surface layer is placed at the entrance/exit of the waveguide.« less

Evaluating polymeric biomaterial–environment interfaces by Langmuir monolayer techniques

PubMed Central

Schöne, Anne-Christin; Roch, Toralf; Schulz, Burkhard

2017-01-01

Polymeric biomaterials are of specific relevance in medical and pharmaceutical applications due to their wide range of tailorable properties and functionalities. The knowledge about interactions of biomaterials with their biological environment is of crucial importance for developing highly sophisticated medical devices. To achieve optimal in vivo performance, a description at the molecular level is required to gain better understanding about the surface of synthetic materials for tailoring their properties. This is still challenging and requires the comprehensive characterization of morphological structures, polymer chain arrangements and degradation behaviour. The review discusses selected aspects for evaluating polymeric biomaterial–environment interfaces by Langmuir monolayer methods as powerful techniques for studying interfacial properties, such as morphological and degradation processes. The combination of spectroscopic, microscopic and scattering methods with the Langmuir techniques adapted to polymers can substantially improve the understanding of their in vivo behaviour. PMID:28468918

Tailoring plasmonic properties of nanobeam composites by the sliding disorder

NASA Astrophysics Data System (ADS)

Gric, Tatjana; Hess, Ortwin

2017-11-01

Nanobeam composites are important for designing sensing, nonlinear, and emission functionalities. Here, we describe a method for tuning the plasmonic properties of a silver nanobeam-based metamaterial. Such metamaterials open the wide avenues for a variety of applications in the fields of bio- and chemical sensing, nonlinearity enhancement, and fluorescence control. Specifically, we present the boundary between two nanobeam composites stacked together and exhibiting the sliding disorder. The modes are tunable. We simulated the solutions of surface plasmon polaritons (SPP) modes and their propagations. The configuration proposed here makes a breakthrough of the conventional configuration allowing for optimizations of SPP properties and making SPP application more flexible in practices. The wide plasmonic tuning range of nanobeam composites makes them promising in metamaterial-based optoelectronic devices. The plasma frequency is found to be tailored by the sliding disorder.

Composites reinforced via mechanical interlocking of surface-roughened microplatelets within ductile and brittle matrices.

PubMed

Libanori, R; Carnelli, D; Rothfuchs, N; Binelli, M R; Zanini, M; Nicoleau, L; Feichtenschlager, B; Albrecht, G; Studart, A R

2016-04-12

Load-bearing reinforcing elements in a continuous matrix allow for improved mechanical properties and can reduce the weight of structural composites. As the mechanical performance of composite systems are heavily affected by the interfacial properties, tailoring the interactions between matrices and reinforcing elements is a crucial problem. Recently, several studies using bio-inspired model systems suggested that interfacial mechanical interlocking is an efficient mechanism for energy dissipation in platelet-reinforced composites. While cheap and effective solutions are available at the macroscale, the modification of surface topography in micron-sized reinforcing elements still represents a challenging task. Here, we report a simple method to create nanoasperities with tailored sizes and densities on the surface of alumina platelets and investigate their micromechanical effect on the energy dissipation mechanisms of nacre-like materials. Composites reinforced with roughened platelets exhibit improved mechanical properties for both organic ductile epoxy and inorganic brittle cement matrices. Mechanical interlocking increases the modulus of toughness (area under the stress-strain curve) by 110% and 56% in epoxy and cement matrices, respectively, as compared to those reinforced with flat platelets. This interlocking mechanism can potentially lead to a significant reduction in the weight of mechanical components while retaining the structural performance required in the application field.

Tailored nanoporous coatings fabricated on conformable polymer substrates.

PubMed

Poxson, David J; Mont, Frank W; Cho, Jaehee; Schubert, E Fred; Siegel, Richard W

2012-11-01

Nanoporous coatings have become the subject of intense investigation, in part because they have been shown to have unique and tailorable physical properties that can depart greatly from their dense or macroscopic counterparts. Nanoporous coatings are frequently fabricated utilizing oblique-angle or glancing-angle physical vapor-phase deposition techniques. However, a significant limitation for such coatings exists; they are almost always deposited on smooth and rigid planar substrates, such as silicon and glass. This limitation greatly constrains the applicability, tailorability, functionality and even the economic viability, of such nanoporous coatings. Here, we report our findings on nanoporous/polymer composite systems (NPCS) fabricated by utilizing oblique-angle electron-beam methodology. These unique composite systems exhibit several favorable characteristics, namely, (i) fine-tuned control over coating nanoporosity and thickness, (ii) excellent adhesion between the nanoporous coating and polymer substrate, (iii) the ability to withstand significant and repeated bending, and (iv) the ability to be molded conformably on two and three-dimensional surfaces while closely retaining the composite system's designed nanoporous film structure and, hence, properties.

A facile strategy to design zeolite L crystals with tunable morphology and surface architecture.

PubMed

Lupulescu, Alexandra I; Kumar, Manjesh; Rimer, Jeffrey D

2013-05-01

Tailoring the anisotropic growth rates of materials to achieve desired structural outcomes is a pervasive challenge in synthetic crystallization. Here we discuss a method to selectively control the growth of zeolite crystals, which are used extensively in a wide range of industrial applications. This facile method cooperatively tunes crystal properties, such as morphology and surface architecture, through the use of inexpensive, commercially available chemicals with specificity for binding to crystallographic surfaces and mediating anisotropic growth. We examined over 30 molecules as potential zeolite growth modifiers (ZGMs) of zeolite L (LTL type) crystallization. ZGM efficacy was quantified through a combination of macroscopic (bulk) and microscopic (surface) investigations that identified modifiers capable of dramatically altering the cylindrical morphology of LTL crystals. We demonstrate an ability to tailor properties critical to zeolite performance, such as external porous surface area, crystal shape, and pore length, which can enhance sorbate accessibility to LTL pores, tune the supramolecular organization of guest-host composites, and minimize the diffusion path length, respectively. We report that a synergistic combination of ZGMs and the judicious adjustment of synthesis parameters produce LTL crystals with unique surface features, and a range of length-to-diameter aspect ratios spanning 3 orders of magnitude. A systematic examination of different ZGM structures and molecular compositions (i.e., hydrophobicity and binding moieties) reveal interesting physicochemical properties governing their efficacy and specificity. Results of this study suggest this versatile strategy may prove applicable for a host of framework types to produce unrivaled materials that have eluded more conventional techniques.

Co-delivery of antigen and a lipophilic anti-inflammatory drug to cells via a tailorable nanocarrier emulsion.

PubMed

Chuan, Yap Pang; Zeng, Bi Yun; O'Sullivan, Brendan; Thomas, Ranjeny; Middelberg, Anton P J

2012-02-15

Nanotechnology promises new drug carriers that can be tailored to specific applications. Here we report a new approach to drug delivery based on tailorable nanocarrier emulsions (TNEs), motivated by a need to co-deliver a protein antigen and a lipophilic drug for specific inhibition of nuclear factor kappa B (NF-κB) in antigen presenting cells (APCs). Co-delivery for NF-κB inhibition holds promise as a strategy for the treatment of rheumatoid arthritis. We used a highly surface-active peptide (SAP) to prepare a nanosized emulsion having defined surface properties predictable from the SAP sequence. Incorporating the lipophilic drug into the oil phase at the time of emulsion formation enabled its facile packaging. The SAP is depleted from bulk during emulsification, allowing simple subsequent addition of the drug-loaded oil-in-water emulsion to a solution of protein antigen. Decoration of emulsion surface with antigen was achieved via electrostatic deposition. In vitro data showed that the TNE prepared this way was internalized and well-tolerated by model APCs, and that good suppression of NF-κB expression was achieved. This work reports a new type of nanotechnology-based carrier, a TNE, which can potentially be tailored for co-delivery of multiple therapeutic components, and can be made using simple methods using only biocompatible materials. Copyright © 2011 Elsevier Inc. All rights reserved.

Derivatizing weak polyelectrolytes--solution properties, self-aggregation, and association with anionic surfaces of hydrophobically modified poly(ethylene imine).

PubMed

Griffiths, Peter C; Paul, Alison; Fallis, Ian A; Wellappili, Champa; Murphy, Damien M; Jenkins, Robert; Waters, Sarah J; Nilmini, Renuka; Heenan, Richard K; King, Stephen M

2007-10-15

The physical properties of weak polyelectrolytes may be tailored via hydrophobic modification to exhibit useful properties under appropriate pH and ionic strength conditions as a consequence of the often inherently competing effects of electrostatics and hydrophobicity. Pulsed-gradient spin-echo NMR (PGSE-NMR), electron paramagnetic resonance (EPR), small-angle neutron scattering (SANS) surface tension, fluorescence, and pH titration have been used to examine the solution conformation and aggregation behavior of a series of hydrophobically modified hyperbranched poly(ethylene imine) (PEI) polymers in aqueous solution, and their interaction with sodium dodecylsulfate (SDS). PGSE-NMR gave a particularly insightful picture of the apparent molecular weight distribution. The presence of the hydrophobes led to a lower effective charge on the polymer at any given pH, compared to the (parent) nonmodified samples. Analysis of the SANS data showed that the propensity to form highly elliptical or rod-like aggregates at higher pHs, reflecting both the changes in protonation behavior induced by the hydrophobic modification and an hydrophobic interaction, but that these structures were disrupted with decreasing pH (increasing charge). The parent samples were not surface active yet the hydrophobically modified samples show pronounced surface activity and the presence of small hydrophobic domains. The surface activity increased with an increase in the degree of modification. On addition of SDS, the onset of the formation of polymer/surfactant complexes was insensitive to the degree of modification with the resultant PEI/SDS complexes resembling the size and shape of simple SDS micelles. Indeed, the presence of the SDS effectively nullifies the effects of the hydrophobe. Hydrophobic modification is therefore a viable option to tailor pH dependent properties, whose effects may be removed by the presence of surfactant.

Laser surface structuring of AZ31 Mg alloy for controlled wettability.

PubMed

Gökhan Demir, Ali; Furlan, Valentina; Lecis, Nora; Previtali, Barbara

2014-06-01

Structured surfaces exhibit functional properties that can enhance the performance of a bioimplant in terms of biocompatibility, adhesion, or corrosion behavior. In order to tailor the surface property, chemical and physical methods can be used in a sequence of many steps. On the other hand, laser surface processing can provide a single step solution to achieve the designated surface function with the use of simpler equipment and high repeatability. This work provides the details on the surface structuring of AZ31, a biocompatible and biodegradable Mg alloy, by a single-step laser surface structuring based on remelting. The surfaces are characterized in terms of topography, chemistry, and physical integrity, as well as the effective change in the surface wetting behavior is demonstrated. The results imply a great potential in local or complete surface structuring of medical implants for functionalization by the flexible positioning of the laser beam.

Plasma assisted surface treatments of biomaterials.

PubMed

Minati, L; Migliaresi, C; Lunelli, L; Viero, G; Dalla Serra, M; Speranza, G

2017-10-01

The biocompatibility of an implant depends upon the material it is composed of, in addition to the prosthetic device's morphology, mechanical and surface properties. Properties as porosity and pore size should allow, when required, cells penetration and proliferation. Stiffness and strength, that depend on the bulk characteristics of the material, should match the mechanical requirements of the prosthetic applications. Surface properties should allow integration in the surrounding tissues by activating proper communication pathways with the surrounding cells. Bulk and surface properties are not interconnected, and for instance a bone prosthesis could possess the necessary stiffness and strength for the application omitting out prerequisite surface properties essential for the osteointegration. In this case, surface treatment is mandatory and can be accomplished using various techniques such as applying coatings to the prosthesis, ion beams, chemical grafting or modification, low temperature plasma, or a combination of the aforementioned. Low temperature plasma-based techniques have gained increasing consensus for the surface modification of biomaterials for being effective and competitive compared to other ways to introduce surface functionalities. In this paper we review plasma processing techniques and describe potentialities and applications of plasma to tailor the interface of biomaterials. Copyright © 2017 Elsevier B.V. All rights reserved.

Quantitative characterization of surface topography using spectral analysis

NASA Astrophysics Data System (ADS)

Jacobs, Tevis D. B.; Junge, Till; Pastewka, Lars

2017-03-01

Roughness determines many functional properties of surfaces, such as adhesion, friction, and (thermal and electrical) contact conductance. Recent analytical models and simulations enable quantitative prediction of these properties from knowledge of the power spectral density (PSD) of the surface topography. The utility of the PSD is that it contains statistical information that is unbiased by the particular scan size and pixel resolution chosen by the researcher. In this article, we first review the mathematical definition of the PSD, including the one- and two-dimensional cases, and common variations of each. We then discuss strategies for reconstructing an accurate PSD of a surface using topography measurements at different size scales. Finally, we discuss detecting and mitigating artifacts at the smallest scales, and computing upper/lower bounds on functional properties obtained from models. We accompany our discussion with virtual measurements on computer-generated surfaces. This discussion summarizes how to analyze topography measurements to reconstruct a reliable PSD. Analytical models demonstrate the potential for tuning functional properties by rationally tailoring surface topography—however, this potential can only be achieved through the accurate, quantitative reconstruction of the PSDs of real-world surfaces.

Surface Termination of the Metal-Organic Framework HKUST-1: A Theoretical Investigation.

PubMed

Amirjalayer, Saeed; Tafipolsky, Maxim; Schmid, Rochus

2014-09-18

The surface morphology and termination of metal-organic frameworks (MOF) is of critical importance in many applications, but the surface properties of these soft materials are conceptually different from those of other materials like metal or oxide surfaces. Up to now, experimental investigations are scarce and theoretical simulations have focused on the bulk properties. The possible surface structure of the archetypal MOF HKUST-1 is investigated by a first-principles derived force field in combination with DFT calculations of model systems. The computed surface energies correctly predict the [111] surface to be most stable and allow us to obtain an unprecedented atomistic picture of the surface termination. Entropic factors are identified to determine the preferred surface termination and to be the driving force for the MOF growth. On the basis of this, reported strategies like employing "modulators" during the synthesis to tailor the crystal morphology are discussed.

Biomimicry 1: PC.

PubMed

Cumberland, D C; Gunn, J; Malik, N; Holt, C M

1998-01-01

The surface properties of stents can be modified by coating them, for example with a polymer. Phosphorylcoline (PC) is the major component of the outer layer of the cell membrane. The haemo- and biocompatibility of a PC-containing polymer is thus based on biomimicry, and has been confirmed by several experiments showing much reduced thrombogenicity of PC-coated surfaces, and porcine coronary artery implants showing no sign of adverse effect. Clinical experience with the PC-coated BiodivYsio appears favourable. The PC coating can be tailored for take up and controlled elution of various drugs for stent-based local delivery, a property which is being actively explored.

The influence of size and charge of chitosan/polyglutamic acid hollow spheres on cellular internalization, viability and blood compatibility.

PubMed

Dash, Biraja C; Réthoré, Gildas; Monaghan, Michael; Fitzgerald, Kathleen; Gallagher, William; Pandit, Abhay

2010-11-01

Polymeric hollow spheres can be tailored as efficient carriers of various therapeutic molecules due to their tunable properties. However, the entry of these synthetic vehicles into cells, their cell viability and blood compatibility depend on their physical and chemical properties e.g. size, surface charge. Herein, we report the effect of size and surface charge on cell viability and cellular internalization behaviour and their effect on various blood components using chitosan/polyglutamic acid hollow spheres as a model system. Negatively charged chitosan/polyglutamic acid hollow spheres of various sizes 100, 300, 500 and 1000 nm were fabricated using a template based method and covalently surface modified using linear polyethylene glycol and methoxyethanol amine to create a gradient of surface charge from negative to neutrally charged spheres respectively. The results here suggest that both size and surface charge have a significant influence on the sphere's behaviour, most prominently on haemolysis, platelet activation, plasma recalcification time, cell viability and internalization over time. Additionally, cellular internalization behaviour and viability was found to vary with different cell types. These results are in agreement with those of inorganic spheres and liposomes, and can serve as guidelines for tailoring polymeric solid spheres for specific desired applications in biological and pharmaceutical fields, including the design of nanometer to submicron-sized delivery vehicles. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Adsorption of organic molecules on mineral surfaces studied by first-principle calculations: A review.

PubMed

Zhao, Hongxia; Yang, Yong; Shu, Xin; Wang, Yanwei; Ran, Qianping

2018-04-09

First-principle calculations, especially by the density functional theory (DFT) methods, are becoming a power technique to study molecular structure and properties of organic/inorganic interfaces. This review introduces some recent examples on the study of adsorption models of organic molecules or oligomers on mineral surfaces and interfacial properties obtained from first-principles calculations. The aim of this contribution is to inspire scientists to benefit from first-principle calculations and to apply the similar strategies when studying and tailoring interfacial properties at the atomistic scale, especially for those interested in the design and development of new molecules and new products. Copyright © 2017. Published by Elsevier B.V.

Tailored Mesoporous Silicas: From Confinement Effects to Catalysis

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

Buchanan III, A C; Kidder, Michelle

2010-01-01

Ordered mesoporous silicas continue to find widespread use as supports for diverse applications such as catalysis, separations, and sensors. They provide a versatile platform for these studies because of their high surface area and the ability to control pore size, topology, and surface properties over wide ranges. Furthermore, there is a diverse array of synthetic methodologies for tailoring the pore surface with organic, organometallic, and inorganic functional groups. In this paper, we will discuss two examples of tailored mesoporous silicas and the resultant impact on chemical reactivity. First, we explore the impact of pore confinement on the thermochemical reactivity ofmore » phenethyl phenyl ether (PhCH2CH2OPh, PPE), which is a model of the dominant {beta}-aryl ether linkage present in lignin derived from woody biomass. The influence of PPE surface immobilization, grafting density, silica pore diameter, and presence of a second surface-grafted inert 'spacer' molecule on the product selectivity has been examined. We will show that the product selectivity can be substantially altered compared with the inherent gas-phase selectivity. Second, we have recently initiated an investigation of mesoporous silica supported, heterobimetallic oxide materials for photocatalytic conversion of carbon dioxide. Through surface organometallic chemistry, isolated M-O-M species can be generated on mesoporous silicas that, upon irradiation, form metal to metal charge transfer bands capable of converting CO{sub 2} into CO. Initial results from studies of Ti(IV)-O-Sn(II) on SBA-15 will be presented.« less

Fractal characterization and wettability of ion treated silicon surfaces

NASA Astrophysics Data System (ADS)

Yadav, R. P.; Kumar, Tanuj; Baranwal, V.; Vandana, Kumar, Manvendra; Priya, P. K.; Pandey, S. N.; Mittal, A. K.

2017-02-01

Fractal characterization of surface morphology can be useful as a tool for tailoring the wetting properties of solid surfaces. In this work, rippled surfaces of Si (100) are grown using 200 keV Ar+ ion beam irradiation at different ion doses. Relationship between fractal and wetting properties of these surfaces are explored. The height-height correlation function extracted from atomic force microscopic images, demonstrates an increase in roughness exponent with an increase in ion doses. A steep variation in contact angle values is found for low fractal dimensions. Roughness exponent and fractal dimensions are found correlated with the static water contact angle measurement. It is observed that after a crossover of the roughness exponent, the surface morphology has a rippled structure. Larger values of interface width indicate the larger ripples on the surface. The contact angle of water drops on such surfaces is observed to be lowest. Autocorrelation function is used for the measurement of ripple wavelength.

Flush Mounting Of Thin-Film Sensors

NASA Technical Reports Server (NTRS)

Moore, Thomas C., Sr.

1992-01-01

Technique developed for mounting thin-film sensors flush with surfaces like aerodynamic surfaces of aircraft, which often have compound curvatures. Sensor mounted in recess by use of vacuum pad and materials selected for specific application. Technique involves use of materials tailored to thermal properties of substrate in which sensor mounted. Together with customized materials, enables flush mounting of thin-film sensors in most situations in which recesses for sensors provided. Useful in both aircraft and automotive industries.

Tailoring the nature and strength of electron-phonon interactions in the SrTiO3(001) 2D electron liquid

NASA Astrophysics Data System (ADS)

Wang, Z.; McKeown Walker, S.; Tamai, A.; Wang, Y.; Ristic, Z.; Bruno, F. Y.; de la Torre, A.; Riccò, S.; Plumb, N. C.; Shi, M.; Hlawenka, P.; Sánchez-Barriga, J.; Varykhalov, A.; Kim, T. K.; Hoesch, M.; King, P. D. C.; Meevasana, W.; Diebold, U.; Mesot, J.; Moritz, B.; Devereaux, T. P.; Radovic, M.; Baumberger, F.

2016-08-01

Surfaces and interfaces offer new possibilities for tailoring the many-body interactions that dominate the electrical and thermal properties of transition metal oxides. Here, we use the prototypical two-dimensional electron liquid (2DEL) at the SrTiO3(001) surface to reveal a remarkably complex evolution of electron-phonon coupling with the tunable carrier density of this system. At low density, where superconductivity is found in the analogous 2DEL at the LaAlO3/SrTiO3 interface, our angle-resolved photoemission data show replica bands separated by 100 meV from the main bands. This is a hallmark of a coherent polaronic liquid and implies long-range coupling to a single longitudinal optical phonon branch. In the overdoped regime the preferential coupling to this branch decreases and the 2DEL undergoes a crossover to a more conventional metallic state with weaker short-range electron-phonon interaction. These results place constraints on the theoretical description of superconductivity and allow a unified understanding of the transport properties in SrTiO3-based 2DELs.

Dry particle coating of polymer particles for tailor-made product properties

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

Blümel, C., E-mail: karl-ernst.wirth@fau.de; Schmidt, J., E-mail: karl-ernst.wirth@fau.de; Dielesen, A., E-mail: karl-ernst.wirth@fau.de

2014-05-15

Disperse polymer powders with tailor-made particle properties are of increasing interest in industrial applications such as Selective Laser Beam Melting processes (SLM). This study focuses on dry particle coating processes to improve the conductivity of the insulating polymer powder in order to assemble conductive devices. Therefore PP particles were coated with Carbon Black nanoparticles in a dry particle coating process. This process was investigated in dependence of process time and mass fraction of Carbon Black. The conductivity of the functionalized powders was measured by impedance spectroscopy. It was found that there is a dependence of process time, respectively coating ratiomore » and conductivity. The powder shows higher conductivities with increasing number of guest particles per host particle surface area, i.e. there is a correlation between surface functionalization density and conductivity. The assembled composite particles open new possibilities for processing distinct polymers such as PP in SLM process. The fundamentals of the dry particle coating process of PP host particles with Carbon Black guest particles as well as the influence on the electrical conductivity will be discussed.« less

Capacitance, charge dynamics, and electrolyte-surface interactions in functionalized carbide-derived carbon electrodes

DOE PAGES

Dyatkin, Boris; Mamontov, Eugene; Cook, Kevin M.; ...

2015-12-24

Our study analyzed the dynamics of ionic liquid electrolyte inside of defunctionalized, hydrogenated, and aminated pores of carbide-derived carbon supercapacitor electrodes. The approach tailors surface functionalities and tunes nanoporous structures to decouple the influence of pore wall composition on capacitance, ionic resistance, and long-term cyclability. Moreover, quasi-elastic neutron scattering probes the self-diffusion properties and electrode-ion interactions of electrolyte molecules confined in functionalized pores. Room-temperature ionic liquid interactions in confined pores are strongest when the hydrogen-containing groups are present on the surface. This property translates into higher capacitance and greater ion transport through pores during electrochemical cycling. Aminated pores, unlike hydrogenatedmore » pores, do not favorably interact with ionic liquid ions and, subsequently, are outperformed by defunctionalized surfaces.« less

Tailoring of Microstructure and Properties of Titanium Parts with Local Rapid Heat Treatment

DTIC Science & Technology

2010-07-19

an approximate approach. Specifically, the temperature at the surface was measured using a two-color pyrometer (IMPAC IGA100) having a 0.2 μs...with pyrometer are shown in Fig. 34. It is necessary to underline, that due to very small diameter of spot measured by pyrometer every temperature...special surface vibro- acoustic treatment (of shot peening type) [19]. So, application of LRHT, from one hand – forming small-grained beta-transformed

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

Zorn, Gilad, E-mail: zorn@ge.com; Castner, David G.; Tyagi, Anuradha

Perfluorophenylazide (PFPA) chemistry is a novel method for tailoring the surface properties of solid surfaces and nanoparticles. It is general and versatile, and has proven to be an efficient way to immobilize graphene, proteins, carbohydrates, and synthetic polymers. The main thrust of this work is to provide a detailed investigation on the chemical composition and surface density of the PFPA tailored surface. Specifically, gold surfaces were treated with PFPA-derivatized (11-mercaptoundecyl)tetra(ethylene glycol) (PFPA-MUTEG) mixed with 2-[2-(2-mercaptoethoxy)ethoxy]ethanol (MDEG) at varying solution mole ratios. Complementary analytical techniques were employed to characterize the resulting films including Fourier transform infrared spectroscopy to detect fingerprints ofmore » the PFPA group, x-ray photoelectron spectroscopy and ellipsometry to study the homogeneity and uniformity of the films, and near edge x-ray absorption fine structures to study the electronic and chemical structure of the PFPA groups. Results from these studies show that the films prepared from 90:10 and 80:20 PFPA-MUTEG/MDEG mixed solutions exhibited the highest surface density of PFPA and the most homogeneous coverage on the surface. A functional assay using surface plasmon resonance with carbohydrates covalently immobilized onto the PFPA-modified surfaces showed the highest binding affinity for lectin on the PFPA-MUTEG/MDEG film prepared from a 90:10 solution.« less

Bulk and Thin film Properties of Nanoparticle-based Ionic Materials

NASA Astrophysics Data System (ADS)

Fang, Jason

2008-03-01

Nanoparticle-based ionic materials (NIMS) offer exciting opportunities for research at the forefront of science and engineering. NIMS are hybrid particles comprised of a charged oligomeric corona attached to hard, inorganic nanoparticle cores. Because of their hybrid nature, physical properties --rheological, optical, electrical, thermal - of NIMS can be tailored over an unusually wide range by varying geometric and chemical characteristics of the core and canopy and thermodynamic variables such as temperature and volume fraction. On one end of the spectrum are materials with a high core content, which display properties similar to crystalline solids, stiff waxes, and gels. At the opposite extreme are systems that spontaneously form particle-based fluids characterized by transport properties remarkably similar to simple liquids. In this poster I will present our efforts to synthesize NIMS and discuss their bulk and surface properties. In particular I will discuss our work on preparing smart surfaces using NIMS.

Texturing of polypropylene (PP) with nanosecond lasers

NASA Astrophysics Data System (ADS)

Riveiro, A.; Soto, R.; del Val, J.; Comesaña, R.; Boutinguiza, M.; Quintero, F.; Lusquiños, F.; Pou, J.

2016-06-01

Polypropylene (PP) is a biocompatible and biostable polymer, showing good mechanical properties that has been recently introduced in the biomedical field for bone repairing applications; however, its poor surface properties due to its low surface energy limit their use in biomedical applications. In this work, we have studied the topographical modification of polypropylene (PP) laser textured with Nd:YVO4 nanosecond lasers emitting at λ = 1064 nm, 532 nm, and 355 nm. First, optical response of this material under these laser wavelengths was determined. The application of an absorbing coating was also studied. The influence of the laser processing parameters on the surface modification of PP was investigated by means of statistically designed experiments. Processing maps to tailor the roughness, and wettability, the main parameters affecting cell adhesion characteristics of implants, were also determined. Microhardness measurements were performed to discern the impact of laser treatment on the final mechanical properties of PP.

Influence of surface charge on the potential toxicity of PLGA nanoparticles towards Calu-3 cells

PubMed Central

Mura, Simona; Hillaireau, Herve; Nicolas, Julien; Le Droumaguet, Benjamin; Gueutin, Claire; Zanna, Sandrine; Tsapis, Nicolas; Fattal, Elias

2011-01-01

Background Because of the described hazards related to inhalation of manufactured nanoparticles, we investigated the lung toxicity of biodegradable poly (lactide-co-glycolide) (PLGA) nanoparticles displaying various surface properties on human bronchial Calu-3 cells. Methods Positively and negatively charged as well as neutral nanoparticles were tailored by coating their surface with chitosan, Poloxamer, or poly (vinyl alcohol), respectively. Nanoparticles were characterized in terms of size, zeta potential, and surface chemical composition, confirming modifications provided by hydrophilic polymers. Results Although nanoparticle internalization by lung cells was clearly demonstrated, the cytotoxicity of the nanoparticles was very limited, with an absence of inflammatory response, regardless of the surface properties of the PLGA nanoparticles. Conclusion These in vitro results highlight the safety of biodegradable PLGA nanoparticles in the bronchial epithelium and provide initial data on their potential effects and the risks associated with their use as nanomedicines. PMID:22114491

Reversible Tailoring of Mechanical Properties of Carbon Nanotube Forests by Immersing in Solvents

DTIC Science & Technology

2014-12-07

quantify the strength of vdW interactions between CNTs, Hamaker constant of CNTs in vacuum, Av ¼ V 12pD 2 G , was evaluated where ‘V’ is the vdW...effectively do not interact with each other. Therefore, we assumed curved surface–surface vdW interaction between two CNTs to evaluate the Hamaker ...of the vdW forces are directly proportional to Hamaker constant, which depends on the macroscopic properties of the interacting objects and the

Tailoring structure and technological properties of plant proteins using high hydrostatic pressure.

PubMed

Queirós, Rui P; Saraiva, Jorge A; da Silva, José A Lopes

2018-06-13

The demand for proteins is rising and alternatives to meat proteins are necessary since animal husbandry is expensive and intensive to the environment. Plant proteins appear as an alternative; however, their techno-functional properties need improvement. High-pressure processing (HPP) is a non-thermal technology that has several applications including the modification of proteins. The application of pressure allows modifying proteins' structure hence allowing to change several of their properties, such as hydration, hydrophobicity, and hydrophilicity. These properties may influence the solubility of proteins and their ability to stabilize emulsions or foams, create aggregates or gels, and their general role in stability and texture of food commodities. Commonly HPP decreases the proteins' solubility yet increasing their surface hydrophobicity exposing sulfhydryl groups, which promotes aggregation or gelation or enhance their ability to stabilize emulsions/foams. However, these effects are not verifiable for all the proteins and are immensely dependent on the type and concentration of the protein, environmental conditions (pH, ionic strength, and co-solutes), and HPP conditions. This review collects and critically discusses the available information on how HPP affects the structure of plant proteins and how their techno-functional properties can be tailored using this approach.

Robustness of an artificially tailored fisheye imaging system with a curvilinear image surface

NASA Astrophysics Data System (ADS)

Lee, Gil Ju; Nam, Won Il; Song, Young Min

2017-11-01

Curved image sensors inspired by animal and insect eyes have provided a new development direction in next-generation digital cameras. It is known that natural fish eyes afford an extremely wide field of view (FOV) imaging due to the geometrical properties of the spherical lens and hemispherical retina. However, its inherent drawbacks, such as the low off-axis illumination and the fabrication difficulty of a 'dome-like' hemispherical imager, limit the development of bio-inspired wide FOV cameras. Here, a new type of fisheye imaging system is introduced that has simple lens configurations with a curvilinear image surface, while maintaining high off-axis illumination and a wide FOV. Moreover, through comparisons with commercial conventional fisheye designs, it is determined that the volume and required number of optical elements of the proposed design is practical while capturing the fundamental optical performances. Detailed design guidelines for tailoring the proposed optic system are also discussed.

Advances and directions of ion nitriding/carburizing

NASA Technical Reports Server (NTRS)

Spalvins, Talivaldis

1989-01-01

Ion nitriding and carburizing are plasma activated thermodynamic processes for the production of case hardened surface layers not only for ferrous materials, but also for an increasing number of nonferrous metals. When the treatment variables are properly controlled, the use of nitrogenous or carbonaceous glow discharge medium offers great flexibility in tailoring surface/near-surface properties independently of the bulk properties. The ion nitriding process has reached a high level of maturity and has gained wide industrial acceptance, while the more recently introduced ion carburizing process is rapidly gaining industrial acceptance. The current status of plasma mass transfer mechanisms into the surface regarding the formation of compound and diffusion layers in ion nitriding and carbon build-up ion carburizing is reviewed. In addition, the recent developments in design and construction of advanced equipment for obtaining optimized and controlled case/core properties is summarized. Also, new developments and trends such as duplex plasma treatments and alternatives to dc diode nitriding are highlighted.

Surface charge control for zwitterionic polymer brushes: Tailoring surface properties to antifouling applications.

PubMed

Guo, Shanshan; Jańczewski, Dominik; Zhu, Xiaoying; Quintana, Robert; He, Tao; Neoh, Koon Gee

2015-08-15

Electrostatic interactions play an important role in adhesion phenomena particularly for biomacromolecules and microorganisms. Zero charge valence of zwitterions has been claimed as the key to their antifouling properties. However, due to the differences in the relative strength of their acid and base components, zwitterionic materials may not be charge neutral in aqueous environments. Thus, their charge on surfaces should be further adjusted for a specific pH environment, e.g. physiological pH typical in biomedical applications. Surface zeta potential for thin polymeric films composed of polysulfobetaine methacrylate (pSBMA) brushes is controlled through copolymerizing zwitterionic SBMA and cationic methacryloyloxyethyltrimethyl ammonium chloride (METAC) via surface-initiated atom transfer polymerization. Surface properties including zeta potential, roughness, free energy and thickness are measured and the antifouling performance of these surfaces is assessed. The zeta potential of pSBMA brushes is -40 mV across a broad pH range. By adding 2% METAC, the zeta potential of pSBMA can be tuned to zero at physiological pH while minimally affecting other physicochemical properties including dry brush thickness, surface free energy and surface roughness. Surfaces with zero and negative zeta potential best resist fouling by bovine serum albumin, Escherichia coli and Staphylococcus aureus. Surfaces with zero zeta potential also reduce fouling by lysozyme more effectively than surfaces with negative and positive zeta potential. Copyright © 2015 Elsevier Inc. All rights reserved.

Analysis of a two row hydrostatic journal bearing with variable properties, inertia effects and surface roughness

NASA Technical Reports Server (NTRS)

Braun, M. J.; Adams, M. L.; Mullen, R. L.

1985-01-01

A computer algorithm for simulation of hydrostatic journal bearing pressure-flow behavior has been generated. The effects taken into account are inertia, cavitation, variable properties (isothermal bearing) and roughness. The program has been specifically tailored for simulation of the hybrid bearing of the cryogenic turbopumps of the main shuttle engine. Due to the high pressure (515 psia) of the supply line no cavitation has been found. The influence of the roughness effects have been found to become important only when the surface-roughness order of magnitude is comparable with that of the bearing clearance itself. Pocket edge inertia and variable properties have been found to have quite an important influence upon the pocket pressure, field pressure distribution and lubricant mass flow.

Gas Metal Arc Welding Parameters Effect on Properties of Tailored Orbital Weld of SS304 and BS1387

NASA Astrophysics Data System (ADS)

Ayof, M. N.; Hussein, N. I. S.; Noh, M. Z. Mohd

2017-09-01

Dissimilar material pipes in a power plant boiler water piping system are used to transmit water at various temperatures, either in extremely high temperature water or room temperature water. In this study, tailored orbital welding of dissimilar material of Stainless Steel (SS) 304 and British Steel (BS) 1387 were performed by Gas Metal Arc Welding (GMAW) with automated fixed nozzle-rotational jig. This study focused on GMAW parameters variation effects on mechanical properties of SS304 and BS1387 dissimilar material tailored orbital welding. The weldment quality was tested by performing non-destructive dye penetrant test. The tensile strength and microhardness were studied to verify the influence of welding parameters variations. Design of Experiment (DOE) was employed to generate process parameter using Response Surface Methodology (RSM) method. Welding parameters that were arc current, arc voltage and travel speed as input response, whilst, tensile strength and microhardness as output response. Results from non-destructive test showed no major defect occurred. The tensile strength and microhardness increased when arc current and voltage increased and travel speed decreased. Microhardness at weldment was higher than base material.

Analysis of the surface density and reactivity of perfluorophenylazide and the impact on ligand immobilization.

PubMed

Zorn, Gilad; Castner, David G; Tyagi, Anuradha; Wang, Xin; Wang, Hui; Yan, Mingdi

2015-03-01

Perfluorophenylazide (PFPA) chemistry is a novel method for tailoring the surface properties of solid surfaces and nanoparticles. It is general and versatile, and has proven to be an efficient way to immobilize graphene, proteins, carbohydrates, and synthetic polymers. The main thrust of this work is to provide a detailed investigation on the chemical composition and surface density of the PFPA tailored surface. Specifically, gold surfaces were treated with PFPA-derivatized (11-mercaptoundecyl)tetra(ethylene glycol) (PFPA-MUTEG) mixed with 2-[2-(2-mercaptoethoxy)ethoxy]ethanol (MDEG) at varying solution mole ratios. Complementary analytical techniques were employed to characterize the resulting films including Fourier transform infrared spectroscopy to detect fingerprints of the PFPA group, x-ray photoelectron spectroscopy and ellipsometry to study the homogeneity and uniformity of the films, and near edge x-ray absorption fine structures to study the electronic and chemical structure of the PFPA groups. Results from these studies show that the films prepared from 90:10 and 80:20 PFPA-MUTEG/MDEG mixed solutions exhibited the highest surface density of PFPA and the most homogeneous coverage on the surface. A functional assay using surface plasmon resonance with carbohydrates covalently immobilized onto the PFPA-modified surfaces showed the highest binding affinity for lectin on the PFPA-MUTEG/MDEG film prepared from a 90:10 solution.

Sapphire substrate-induced effects in VO2 thin films grown by oxygen plasma-assisted pulsed laser deposition

NASA Astrophysics Data System (ADS)

Skuza, J. R.; Scott, D. W.; Pradhan, A. K.

2015-11-01

We investigate the structural and electronic properties of VO2 thin films on c-plane sapphire substrates with three different surface morphologies to control the strain at the substrate-film interface. Only non-annealed substrates with no discernible surface features (terraces) provided a suitable template for VO2 film growth with a semiconductor-metal transition (SMT), which was much lower than the bulk transition temperature. In addition to strain, oxygen vacancy concentration also affects the properties of VO2, which can be controlled through deposition conditions. Oxygen plasma-assisted pulsed laser deposition allows favorable conditions for VO2 film growth with SMTs that can be easily tailored for device applications.

Method for selective immobilization of macromolecules on self assembled monolayer surfaces

DOEpatents

Laskin, Julia [Richland, WA; Wang, Peng [Billerica, MA

2011-11-29

Disclosed is a method for selective chemical binding and immobilization of macromolecules on solid supports in conjunction with self-assembled monolayer (SAM) surfaces. Immobilization involves selective binding of peptides and other macromolecules to SAM surfaces using reactive landing (RL) of mass-selected, gas phase ions. SAM surfaces provide a simple and convenient platform for tailoring chemical properties of a variety of substrates. The invention finds applications in biochemistry ranging from characterization of molecular recognition events at the amino acid level and identification of biologically active motifs in proteins, to development of novel biosensors and substrates for stimulated protein and cell adhesion.

Synthesis and surface engineering of nanomaterials by atmospheric-pressure microplasmas

NASA Astrophysics Data System (ADS)

McKenna, J.; Patel, J.; Mitra, S.; Soin, N.; Švrček, V.; Maguire, P.; Mariotti, D.

2011-11-01

Two different atmospheric pressure microplasma systems are discussed and used for the synthesis and surface engineering of a range of nanomaterials. Specifically a gas-phase approach from vaporized tetramethylsilane has been used to synthesize silicon carbide nanoparticles with diameters below 10 nm. A different microplasma system that interfaces with a liquid solution has then been used for the synthesis of surfactant-free electrically stabilized gold nanoparticles with varying size. A similar microplasma-liquid system has been finally successfully used to tailor surface properties of silicon nanoparticles and to reduce graphene oxide into graphene. The synthesis and surface engineering mechanisms are also discussed.

Towards an in vitro model mimicking the foreign body response: tailoring the surface properties of biomaterials to modulate extracellular matrix.

PubMed

Damanik, Febriyani F R; Rothuizen, Tonia C; van Blitterswijk, Clemens; Rotmans, Joris I; Moroni, Lorenzo

2014-09-19

Despite various studies to minimize host reaction following a biomaterial implantation, an appealing strategy in regenerative medicine is to actively use such an immune response to trigger and control tissue regeneration. We have developed an in vitro model to modulate the host response by tuning biomaterials' surface properties through surface modifications techniques as a new strategy for tissue regeneration applications. Results showed tunable surface topography, roughness, wettability, and chemistry by varying treatment type and exposure, allowing for the first time to correlate the effect of these surface properties on cell attachment, morphology, strength and proliferation, as well as proinflammatory (IL-1β, IL-6) and antiinflammatory cytokines (TGF-β1, IL-10) secreted in medium, and protein expression of collagen and elastin. Surface microstructuring, derived from chloroform partial etching, increased surface roughness and oxygen content. This resulted in enhanced cell adhesion, strength and proliferation as well as a balance of soluble factors for optimum collagen and elastin synthesis for tissue regeneration. By linking surface parameters to cell activity, we could determine the fate of the regenerated tissue to create successful soft tissue-engineered replacement.

Towards an in vitro model mimicking the foreign body response: tailoring the surface properties of biomaterials to modulate extracellular matrix

NASA Astrophysics Data System (ADS)

Damanik, Febriyani F. R.; Rothuizen, Tonia C.; van Blitterswijk, Clemens; Rotmans, Joris I.; Moroni, Lorenzo

2014-09-01

Despite various studies to minimize host reaction following a biomaterial implantation, an appealing strategy in regenerative medicine is to actively use such an immune response to trigger and control tissue regeneration. We have developed an in vitro model to modulate the host response by tuning biomaterials' surface properties through surface modifications techniques as a new strategy for tissue regeneration applications. Results showed tunable surface topography, roughness, wettability, and chemistry by varying treatment type and exposure, allowing for the first time to correlate the effect of these surface properties on cell attachment, morphology, strength and proliferation, as well as proinflammatory (IL-1β, IL-6) and antiflammatory cytokines (TGF-β1, IL-10) secreted in medium, and protein expression of collagen and elastin. Surface microstructuring, derived from chloroform partial etching, increased surface roughness and oxygen content. This resulted in enhanced cell adhesion, strength and proliferation as well as a balance of soluble factors for optimum collagen and elastin synthesis for tissue regeneration. By linking surface parameters to cell activity, we could determine the fate of the regenerated tissue to create successful soft tissue-engineered replacement.

On the organization and thermal behavior of functional groups on Ti3C2 MXene surfaces in vacuum

NASA Astrophysics Data System (ADS)

Persson, Ingemar; Näslund, Lars-Åke; Halim, Joseph; Barsoum, Michel W.; Darakchieva, Vanya; Palisaitis, Justinas; Rosen, Johanna; Persson, Per O. Å.

2018-03-01

The two-dimensional (2D) MXene Ti3C2T x is functionalized by surface groups (T x ) that determine its surface properties for, e.g. electrochemical applications. The coordination and thermal properties of these surface groups has, to date, not been investigated at the atomic level, despite strong variations in the MXene properties that are predicted from different coordinations and from the identity of the functional groups. To alleviate this deficiency, and to characterize the functionalized surfaces of single MXene sheets, the present investigation combines atomically resolved in situ heating in a scanning transmission electron microscope (STEM) and STEM simulations with temperature-programmed x-ray photoelectron spectroscopy (TP-XPS) in the room temperature to 750 °C range. Using these techniques, we follow the surface group coordination at the atomic level. It is concluded that the F and O atoms compete for the DFT-predicted thermodynamically preferred site and that at room temperature that site is mostly occupied by F. At higher temperatures, F desorbs and is replaced by O. Depending on the O/F ratio, the surface bare MXene is exposed as F desorbs, which enables a route for tailored surface functionalization.

Improved spatial resolution for spot sampling in thermal desorption atomic force microscopy – mass spectrometry via rapid heating functions

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

Somnath, Suhas; Jesse, Stephen; Van Berkel, Gary J.

The key to advancing materials is to understand and control their structure and chemistry. However, thorough chemical characterization is challenging since existing techniques characterize only a few properties of the specimen, thereby necessitating multiple measurement platforms to acquire the necessary information. The multimodal combination of atomic force microscopy (AFM) and mass spectrometry (MS) transcends existing analytical capabilities for nanometer scale spatially resolved correlation of the chemical and physical properties of a sample surface. One such hybrid system employs heated AFM cantilevers for thermal desorption (TD) sampling of molecules from a surface and subsequent gas phase ionization and detection of themore » liberated species by MS. Here in this paper, we report on the use of voltage pulse trains to tailor cantilever heating such that spot sampling size was reduced and mass spectral signal was improved compared to constant voltage, static heating of the cantilever. Desorption efficiency (DE), defined as the quotient of the mass spectral signal intensity and the volume of the desorption crater, was used to judge the effectiveness of a particular tailored heating function. To guide the development and optimization of the heating functions and aid in interpreting experimental results, a 1D finite element model was developed that predicted the cantilever response to different heating functions. Three tailored heating functions that used different combinations, magnitudes, and durations of rectangular voltage pulses, were used for surface spot sampling. The resultant sampling spot size and DE were compared to the same metrics obtained with the conventional method that uses a single voltage pulse. Using a model system composed of a thin film of ink containing pigment yellow 74 as a model system, desorption craters shrunk from 2 μm, using the conventional approach, to 310 nm using the optimum tailored heating function. This same pulsed heating function produced a 381× improvement in the DE and an 8× improvement in spatial resolution compared to the conventional heating approach showing that signal/amount of material sampled was improved significantly by this new cantilever heating strategy.« less

Improved spatial resolution for spot sampling in thermal desorption atomic force microscopy – mass spectrometry via rapid heating functions

DOE PAGES

Somnath, Suhas; Jesse, Stephen; Van Berkel, Gary J.; ...

2017-04-17

The key to advancing materials is to understand and control their structure and chemistry. However, thorough chemical characterization is challenging since existing techniques characterize only a few properties of the specimen, thereby necessitating multiple measurement platforms to acquire the necessary information. The multimodal combination of atomic force microscopy (AFM) and mass spectrometry (MS) transcends existing analytical capabilities for nanometer scale spatially resolved correlation of the chemical and physical properties of a sample surface. One such hybrid system employs heated AFM cantilevers for thermal desorption (TD) sampling of molecules from a surface and subsequent gas phase ionization and detection of themore » liberated species by MS. Here in this paper, we report on the use of voltage pulse trains to tailor cantilever heating such that spot sampling size was reduced and mass spectral signal was improved compared to constant voltage, static heating of the cantilever. Desorption efficiency (DE), defined as the quotient of the mass spectral signal intensity and the volume of the desorption crater, was used to judge the effectiveness of a particular tailored heating function. To guide the development and optimization of the heating functions and aid in interpreting experimental results, a 1D finite element model was developed that predicted the cantilever response to different heating functions. Three tailored heating functions that used different combinations, magnitudes, and durations of rectangular voltage pulses, were used for surface spot sampling. The resultant sampling spot size and DE were compared to the same metrics obtained with the conventional method that uses a single voltage pulse. Using a model system composed of a thin film of ink containing pigment yellow 74 as a model system, desorption craters shrunk from 2 μm, using the conventional approach, to 310 nm using the optimum tailored heating function. This same pulsed heating function produced a 381× improvement in the DE and an 8× improvement in spatial resolution compared to the conventional heating approach showing that signal/amount of material sampled was improved significantly by this new cantilever heating strategy.« less

Plexcitonics: Coupled and Plasmon-Exciton Systems with Tailorable Properties

DTIC Science & Technology

2013-11-14

demonstrated efficient steam generation from aqueous nanoparticles solutions without heating the bulk volume of the liquid. Application in ethanol ...solutions without heating the bulk volume of the liquid. Applications in ethanol distillation and sanitation have been demonstrated. Key Accomplishments...nanoparticle surface. This state-selective population of adsorbate resonances could be exploited to prepare reactants in specific states on nanoparticle

Molecular self-assembly approaches for supramolecular electronic and organic electronic devices

NASA Astrophysics Data System (ADS)

Yip, Hin-Lap

Molecular self-assembly represents an efficient bottom-up strategy to generate structurally well-defined aggregates of semiconducting pi-conjugated materials. The capability of tuning the chemical structures, intermolecular interactions and nanostructures through molecular engineering and novel materials processing renders it possible to tailor a large number of unprecedented properties such as charge transport, energy transfer and light harvesting. This approach does not only benefit traditional electronic devices based on bulk materials, but also generate a new research area so called "supramolecular electronics" in which electronic devices are built up with individual supramolecular nanostructures with size in the sub-hundred nanometers range. My work combined molecular self-assembly together with several novel materials processing techniques to control the nucleation and growth of organic semiconducting nanostructures from different type of pi-conjugated materials. By tailoring the interactions between the molecules using hydrogen bonds and pi-pi stacking, semiconducting nanoplatelets and nanowires with tunable sizes can be fabricated in solution. These supramolecular nanostructures were further patterned and aligned on solid substrates through printing and chemical templating methods. The capability to control the different hierarchies of organization on surface provides an important platform to study their structural-induced electronic properties. In addition to using molecular self-assembly to create different organic nanostructures, functional self-assembled monolayer (SAM) formed by spontaneous chemisorption on surfaces was used to tune the interfacial property in organic solar cells. Devices showed dramatically improved performance when appropriate SAMs were applied to optimize the contact property for efficiency charge collection.

The hydrophilic-to-hydrophobic transition in glassy silica is driven by the atomic topology of its surface

NASA Astrophysics Data System (ADS)

Yu, Yingtian; Krishnan, N. M. Anoop; Smedskjaer, Morten M.; Sant, Gaurav; Bauchy, Mathieu

2018-02-01

The surface reactivity and hydrophilicity of silicate materials are key properties for various industrial applications. However, the structural origin of their affinity for water remains unclear. Here, based on reactive molecular dynamics simulations of a series of artificial glassy silica surfaces annealed at various temperatures and subsequently exposed to water, we show that silica exhibits a hydrophilic-to-hydrophobic transition driven by its silanol surface density. By applying topological constraint theory, we show that the surface reactivity and hydrophilic/hydrophobic character of silica are controlled by the atomic topology of its surface. This suggests that novel silicate materials with tailored reactivity and hydrophilicity could be developed through the topological nanoengineering of their surface.

Applications of laser-induced periodic surface structures (LIPSS)

NASA Astrophysics Data System (ADS)

Bonse, Jörn; Kirner, Sabrina V.; Höhm, Sandra; Epperlein, Nadja; Spaltmann, Dirk; Rosenfeld, Arkadi; Krüger, Jörg

2017-02-01

Laser-induced periodic surface structures (LIPSS, ripples) are a universal phenomenon that can be observed on almost any material after the irradiation by linearly polarized laser beams, particularly when using ultrashort laser pulses with durations in the picosecond to femtosecond range. During the past few years significantly increasing research activities have been reported in the field of LIPSS, since their generation in a single-step process provides a simple way of nanostructuring and surface functionalization towards the control of optical, mechanical or chemical properties. In this contribution current applications of LIPSS are reviewed, including the colorization of technical surfaces, the control of surface wetting, the tailoring of surface colonization by bacterial biofilms, and the improvement of the tribological performance of nanostructured metal surfaces.

41 CFR 101-29.212 - Tailoring.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 41 Public Contracts and Property Management 2 2010-07-01 2010-07-01 true Tailoring. 101-29.212 Section 101-29.212 Public Contracts and Property Management Federal Property Management Regulations System FEDERAL PROPERTY MANAGEMENT REGULATIONS SUPPLY AND PROCUREMENT 29-FEDERAL PRODUCT DESCRIPTIONS 29.2...

Laser Tailoring the Surface Chemistry and Morphology for Wear, Scale and Corrosion Resistant Superhydrophobic Coatings.

PubMed

Boinovich, Ludmila B; Emelyanenko, Kirill A; Domantovsky, Alexander G; Emelyanenko, Alexandre M

2018-06-04

A strategy, combining laser chemical modification with laser texturing, followed by chemisorption of the fluorinated hydrophobic agent was used to fabricate the series of superhydrophobic coatings on an aluminum alloy with varied chemical compositions and parameters of texture. It was shown that high content of aluminum oxynitride and aluminum oxide formed in the surface layer upon laser treatment allows solving the problem of enhancement of superhydrophobic coating resistance to abrasive loads. Besides, the multimodal structure of highly porous surface layer leads to self-healing ability of fabricated coatings. Long-term behavior of designed coatings in "hard" hot water with an essential content of calcium carbonate demonstrated high antiscaling resistance with self-cleaning potential against solid deposits onto the superhydrophobic surfaces. Study of corrosion protection properties and the behavior of coatings at long-term contact with 0.5 M NaCl solution indicated extremely high chemical stability and remarkable anticorrosion properties.

PCL-based Shape Memory Polymers with Variable PDMS Soft Segment Lengths

PubMed Central

Zhang, Dawei; Giese, Melissa L.; Prukop, Stacy L.; Grunlan, Melissa A.

2012-01-01

Thermoresponsive shape memory polymers (SMPs) are stimuli-responsive materials that return to their permanent shape from a temporary shape in response to heating. The design of new SMPs which obtain a broader range of properties including mechanical behavior is critical to realize their potential in biomedical as well as industrial and aerospace applications. To tailor the properties of SMPs, “AB networks” comprised of two distinct polymer components have been investigated but are overwhelmingly limited to those in which both components are organic. In this present work, we prepared inorganic-organic SMPs comprised of inorganic polydimethyl-siloxane (PDMS) segments of varying lengths and organic poly(ε-caprolactone) (PCL) segments. PDMS has a particularly low Tg (−125 °C) which makes it a particularly effective soft segment to tailor the mechanical properties of PCL-based SMPs. The SMPs were prepared via the rapid photocure of solutions of diacrylated PCL40-block-PDMSm-block-PCL40 macromers (m = 20, 37, 66 and 130). The resulting inorganic-organic SMP networks exhibited excellent shape fixity and recovery. By changing the PDMS segment length, the thermal, mechanical, and surface properties were systematically altered. PMID:22904597

Innovative Sol-Gel Routes for the Bottom-up Preparation of Heterogeneous Catalysts.

PubMed

Debecker, Damien P

2017-12-11

Heterogeneous catalysts can be prepared by different methods offering various levels of control on the final properties of the solid. In this account, we exemplify bottom-up preparation routes that are based on the sol-gel chemistry and allow to tailor some decisive properties of solid catalysts. First, an emulsion templating strategy is shown to lead to macrocellular self-standing monoliths with a macroscopic 3D structure. The latter can be used as catalyst or catalyst supports in flow chemistry, without requiring any subsequent shaping step. Second, the aerosol-assisted sol-gel process allows for the one-step and continuous production of porous mixed oxides. Tailored textural properties can be obtained together with an excellent control on composition and homogeneity. Third, the application of non-hydrolytic sol-gel routes, in the absence of water, leads to mixed oxides with outstanding textural properties and with peculiar surface chemistry. In all cases, the resulting catalytic performance can be correlated with the specificities of the preparation routes presented. This is exemplified in catalytic reactions in the fields of biomass conversion, petro chemistry, enantioselective organic synthesis, and air pollution mitigation. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoporous Monolithic Microsphere Arrays Have Anti-Adhesive Properties Independent of Humidity

PubMed Central

Eichler-Volf, Anna; Xue, Longjian; Kovalev, Alexander; Gorb, Elena V.; Gorb, Stanislav N.; Steinhart, Martin

2016-01-01

Bioinspired artificial surfaces with tailored adhesive properties have attracted significant interest. While fibrillar adhesive pads mimicking gecko feet are optimized for strong reversible adhesion, monolithic microsphere arrays mimicking the slippery zone of the pitchers of carnivorous plants of the genus Nepenthes show anti-adhesive properties even against tacky counterpart surfaces. In contrast to the influence of topography, the influence of relative humidity (RH) on adhesion has been widely neglected. Some previous works deal with the influence of RH on the adhesive performance of fibrillar adhesive pads. Commonly, humidity-induced softening of the fibrils enhances adhesion. However, little is known on the influence of RH on solid anti-adhesive surfaces. We prepared polymeric nanoporous monolithic microsphere arrays (NMMAs) with microsphere diameters of a few 10 µm to test their anti-adhesive properties at RHs of 2% and 90%. Despite the presence of continuous nanopore systems through which the inner nanopore walls were accessible to humid air, the topography-induced anti-adhesive properties of NMMAs on tacky counterpart surfaces were retained even at RH = 90%. This RH-independent robustness of the anti-adhesive properties of NMMAs significantly contrasts the adhesion enhancement by humidity-induced softening on nanoporous fibrillar adhesive pads made of the same material. PMID:28773497

Laser interference patterning methods: Possibilities for high-throughput fabrication of periodic surface patterns

NASA Astrophysics Data System (ADS)

Lasagni, Andrés Fabián

2017-06-01

Fabrication of two- and three-dimensional (2D and 3D) structures in the micro- and nano-range allows a new degree of freedom to the design of materials by tailoring desired material properties and, thus, obtaining a superior functionality. Such complex designs are only possible using novel fabrication techniques with high resolution, even in the nanoscale range. Starting from a simple concept, transferring the shape of an interference pattern directly to the surface of a material, laser interferometric processing methods have been continuously developed. These methods enable the fabrication of repetitive periodic arrays and microstructures by irradiation of the sample surface with coherent beams of light. This article describes the capabilities of laser interference lithographic methods for the treatment of both photoresists and solid materials. Theoretical calculations are used to calculate the intensity distributions of patterns that can be realized by changing the number of interfering laser beams, their polarization, intensity and phase. Finally, different processing systems and configurations are described and, thus, demonstrating the possibility for the fast and precise tailoring of material surface microstructures and topographies on industrial relevant scales as well as several application cases for both methods.

Casimir quantum levitation tuned by means of material properties and geometries

NASA Astrophysics Data System (ADS)

Dou, Maofeng; Lou, Fei; Boström, Mathias; Brevik, Iver; Persson, Clas

2014-05-01

The Casimir force between two surfaces is attractive in most cases. Although stable suspension of nano-objects has been achieved, the sophisticated geometries make them difficult to be merged with well-established thin film processes. We find that by introducing thin film surface coating on porous substrates, a repulsive to attractive force transition is achieved when the separations are increased in planar geometries, resulting in a stable suspension of two surfaces near the force transition separation. Both the magnitude of the force and the transition distance can be flexibly tailored though modifying the properties of the considered materials, that is, thin film thickness, doping concentration, and porosity. This stable suspension can be used to design new nanodevices with ultralow friction. Moreover, it might be convenient to merge this thin film coating approach with micro- and nanofabrication processes in the future.

Semiconductor-Based Nanotechnology Applications

DTIC Science & Technology

2012-11-07

Nanotechnology Organization Conference, November 4-6, 2012 at the Hilton Arlington, VA 4. Selective toxicity of zinc oxide nanoparticles to cancer...surface structure of oxide nanoparticles , we have recently shown that both magnetic and photoluminescence properties can be tailored. ZnO nanoparticles ...as SnO2, ZnO , and CeO2, reported in 40 refereed research papers. In this ARO project, studies on ultra small particles of these oxides with

Tailored interphase structure for improved strength and energy absorption of composites

NASA Astrophysics Data System (ADS)

Gao, Xiao

Fiber reinforced polymeric composites are lightweight, high-strength and high impact-resistant materials used widely for various applications. It has been shown that the mechanical performance of composites are dependent on the interphase, a three-dimensional region of nanometer size in the vicinity of the fiber-matrix boundary that possesses properties different from those of either the fiber reinforcement or the matrix resin and governs the load transfer from matrix to fiber. This research conducts a systematic study on glass fiber-epoxy interphase structure by tailoring adhesion between constituents and the creation of textures to control strength and energy absorption through mechanical interlocking between glass fiber and epoxy matrix. Our objective is to establish the foundation for microstructural design and optimization of the composite's structural and impact performance. Two ways of roughening the glass fiber surface have been studied to create the mechanical interlocking between fiber and resin; the first technique involves forming in-situ islands on the glass fiber surface by using silane blends of Glycidoxypropyltrimethoxy silane (GPS) and Tetraethoxy silane (TEOS); the second technique applies a silane coupling agents based sizing with the incorporation of silica nanoparticles (Ludox TMA, 22 nm) onto the fiber surface. The microdroplet test was selected to characterize the influence of adhesion and mechanical interlocking effects on interphase properties of different sizing sized glass fiber reinforced epoxy systems. A suitable data reduction scheme enables the strength and specified energy absorbed due to debonding, dynamic sliding, and quasi-static sliding to be quantified. In order to validate the effect of tailored interphase structure, which is induced by creating mechanical interlocking between fiber and resin, on macroscopic composite properties, composite panels were made from these four different sizing sized glass fibers and tested using the punch shear test. The composite panel made from the hybrid sizing sized glass fiber exhibited improved strength and energy absorption consistent with the trends in micromechanical measurements. Through all failure stages under macromechanical testing, hybrid sizing sized glass fiber/epoxyamine composite panel shows an increase in the strength and total energy absorption by 13% and 26%, respectively, compared to the compatible sizing sized baseline. Both micromechanical and macromechanical tests demonstrate the significant influence of tailoring the interphase structure on improving the impact performance of the composites. The hybrid sizing with the incorporation of nanoparticles, in particular, can greatly improve the impact resistance (i.e. energy absorption) of composites without sacrificing its structural performance (i.e. strength).

Tailored Emission Properties of ZnTe/ZnTe:O/ZnO Core-Shell Nanowires Coupled with an Al Plasmonic Bowtie Antenna Array.

PubMed

Nie, Kui-Ying; Tu, Xuecou; Li, Jing; Chen, Xuanhu; Ren, Fang-Fang; Zhang, Guo-Gang; Kang, Lin; Gu, Shulin; Zhang, Rong; Wu, Peiheng; Zheng, Youdou; Tan, Hark Hoe; Jagadish, Chennupati; Ye, Jiandong

2018-06-14

The ability to manipulate light-matter interaction in semiconducting nanostructures is fascinating for implementing functionalities in advanced optoelectronic devices. Here, we report the tailoring of radiative emissions in a ZnTe/ZnTe:O/ZnO core-shell single nanowire coupled with a one-dimensional aluminum bowtie antenna array. The plasmonic antenna enables changes in the excitation and emission processes, leading to an obvious enhancement of near band edge emission (2.2 eV) and subgap excitonic emission (1.7 eV) bound to intermediate band states in a ZnTe/ZnTe:O/ZnO core-shell nanowire as well as surface-enhanced Raman scattering at room temperature. The increase of emission decay rate in the nanowire/antenna system, probed by time-resolved photoluminescence spectroscopy, yields an observable enhancement of quantum efficiency induced by local surface plasmon resonance. Electromagnetic simulations agree well with the experimental observations, revealing a combined effect of enhanced electric near-field intensity and the improvement of quantum efficiency in the ZnTe/ZnTe:O/ZnO nanowire/antenna system. The capability of tailoring light-matter interaction in low-efficient emitters may provide an alternative platform for designing advanced optoelectronic and sensing devices with precisely controlled response.

Design, characterization, and aerosol dispersion performance modeling of advanced spray-dried microparticulate/nanoparticulate mannitol powders for targeted pulmonary delivery as dry powder inhalers.

PubMed

Li, Xiaojian; Vogt, Frederick G; Hayes, Don; Mansour, Heidi M

2014-04-01

The purpose was to design and characterize inhalable microparticulate/nanoparticulate dry powders of mannitol with essential particle properties for targeted dry powder delivery for cystic fibrosis mucolytic treatment by dilute organic solution spray drying, and, in addition, to tailor and correlate aerosol dispersion performance delivered as dry powder inhalers based on spray-drying conditions and solid-state physicochemical properties. Organic solution advanced spray drying from dilute solution followed by comprehensive solid-state physicochemical characterization and in vitro dry powder aerosolization were used. The particle size distribution of the spray-dried (SD) powders was narrow, unimodal, and in the range of ∼500 nm to 2.0 μm. The particles possessed spherical particle morphology, relatively smooth surface morphology, low water content and vapor sorption (crystallization occurred at exposure above 65% relative humidity), and retention of crystallinity by polymorphic interconversion. The emitted dose, fine particle fraction (FPF), and respirable fraction (RF) were all relatively high. The mass median aerodynamic diameters were below 4 μm for all SD mannitol aerosols. The in vitro aerosol deposition stage patterns could be tailored based on spray-drying pump rate. Positive linear correlation was observed between both FPF and RF values with spray-drying pump rates. The interplay between various spray-drying conditions, particle physicochemical properties, and aerosol dispersion performance was observed and examined, which enabled tailoring and modeling of high aerosol deposition patterns.

Design, Characterization, and Aerosol Dispersion Performance Modeling of Advanced Spray-Dried Microparticulate/Nanoparticulate Mannitol Powders for Targeted Pulmonary Delivery as Dry Powder Inhalers

PubMed Central

Li, Xiaojian; Vogt, Frederick G.; Hayes, Don

2014-01-01

Abstract Background: The purpose was to design and characterize inhalable microparticulate/nanoparticulate dry powders of mannitol with essential particle properties for targeted dry powder delivery for cystic fibrosis mucolytic treatment by dilute organic solution spray drying, and, in addition, to tailor and correlate aerosol dispersion performance delivered as dry powder inhalers based on spray-drying conditions and solid-state physicochemical properties. Methods: Organic solution advanced spray drying from dilute solution followed by comprehensive solid-state physicochemical characterization and in vitro dry powder aerosolization were used. Results: The particle size distribution of the spray-dried (SD) powders was narrow, unimodal, and in the range of ∼500 nm to 2.0 μm. The particles possessed spherical particle morphology, relatively smooth surface morphology, low water content and vapor sorption (crystallization occurred at exposure above 65% relative humidity), and retention of crystallinity by polymorphic interconversion. The emitted dose, fine particle fraction (FPF), and respirable fraction (RF) were all relatively high. The mass median aerodynamic diameters were below 4 μm for all SD mannitol aerosols. Conclusion: The in vitro aerosol deposition stage patterns could be tailored based on spray-drying pump rate. Positive linear correlation was observed between both FPF and RF values with spray-drying pump rates. The interplay between various spray-drying conditions, particle physicochemical properties, and aerosol dispersion performance was observed and examined, which enabled tailoring and modeling of high aerosol deposition patterns. PMID:24502451

Fabrication of microlens array with controllable high NA and tailored optical characteristics using confined ink-jetting

NASA Astrophysics Data System (ADS)

Wang, Li; Luo, Yu; Liu, ZengZeng; Feng, Xueming; Lu, Bingheng

2018-06-01

This work presents an economic and controllable fabricating method of high numerical aperture (NA) polymer microlens array (MLA) based on ink-jetting technology. The MLAs are ink-jetted to align on micro platforms patterned flexible PDMS substrate. The shape of a sole lens is constructed by the ink-jetted pre-cured polymer volume confined on a micro platform. In this way, MLAs with targeted geometries-as well as tailored optical characteristics-can be printed, leading to freely designed optical properties. High NA from 0.446 to 0.885 and focal lengths between 99.26 μm and 39.45 μm are demonstrated, confirming theoretical predictions. Particularly, both the simulations and experimental measurements in optical properties are carried out, demonstrating that microlenses with shapes beyond a hemisphere (CA > 90°) exhibits higher light utilization efficiency and wider viewing angle. Meanwhile, the MLAs are fabricated on flexible PDMS substrates and can be attached to other curved surfaces for wider field of view imaging and higher sensitivity.

Hierarchical tailoring of strut architecture to control permeability of additive manufactured titanium implants.

PubMed

Zhang, Z; Jones, D; Yue, S; Lee, P D; Jones, J R; Sutcliffe, C J; Jones, E

2013-10-01

Porous titanium implants are a common choice for bone augmentation. Implants for spinal fusion and repair of non-union fractures must encourage blood flow after implantation so that there is sufficient cell migration, nutrient and growth factor transport to stimulate bone ingrowth. Additive manufacturing techniques allow a large number of pore network designs. This study investigates how the design factors offered by selective laser melting technique can be used to alter the implant architecture on multiple length scales to control and even tailor the flow. Permeability is a convenient parameter that characterises flow, correlating to structure openness (interconnectivity and pore window size), tortuosity and hence flow shear rates. Using experimentally validated computational simulations, we demonstrate how additive manufacturing can be used to tailor implant properties by controlling surface roughness at a microstructual level (microns), and by altering the strut ordering and density at a mesoscopic level (millimetre). Copyright © 2013 The Authors. Published by Elsevier B.V. All rights reserved.

Nano interface potential influences in CdTe quantum dots and biolabeling

NASA Astrophysics Data System (ADS)

Kanagasubbulakshmi, S.; Kadirvelu, K.

2018-05-01

Nano interface influences in physiochemical properties of quantum dots (QDs) are the challenging approach to tailor its surface functionalities. In this study, a set of polar and non-polar solvents were selected to analyze the influences in solvent-based dynamic radius and surface potential of QDs. From the nano interface chemistry of polar and non-polar solvents, an appropriate mechanism of precipitation and hydrophobic ligand exchange strategy were elucidated by correlating Henry's equation. Further, the in vitro cytotoxic potential and antimicrobial activity of QDs were assessed to perform biolabeling. From the observations, an appropriate dosage of QDs was fixed to label the animal ((RAW 264.7 cell lines) and bacterial cells (Escherichia coli) for effective cell attachment. Biolabeling was achieved by tailoring nano interface chemistry of QDs without additional support of biomolecules. Bacterial cell wall-based interaction of QDs was evaluated using SEM and EDAX analysis. Thus, provided clear insights into the nano interface chemistry in the development of highly photostable QDs will be helpful in biomedical applications.

Plasma-assisted interface engineering of boron nitride nanostructure films.

PubMed

Pakdel, Amir; Bando, Yoshio; Golberg, Dmitri

2014-10-28

Today many aspects of science and technology are progressing into the nanoscale realm where surfaces and interfaces are intrinsically important in determining properties and performances of materials and devices. One familiar phenomenon in which interfacial interactions play a major role is the wetting of solids. In this work we use a facile one-step plasma method to control the wettability of boron nitride (BN) nanostructure films via covalent chemical functionalization, while their surface morphology remains intact. By tailoring the concentration of grafted hydroxyl groups, superhydrophilic, hydrophilic, and hydrophobic patterns are created on the initially superhydrophobic BN nanosheet and nanotube films. Moreover, by introducing a gradient of the functional groups, directional liquid spreading toward increasing [OH] content is achieved on the films. The resulting insights are meant to illustrate great potentials of this method to tailor wettability of ceramic films, control liquid flow patterns for engineering applications such as microfluidics and biosensing, and improve the interfacial contact and adhesion in nanocomposite materials.

Processing and property evaluation of tungsten-based mixed oxides for photovoltaics and optoelectronics

NASA Astrophysics Data System (ADS)

Vargas, Mirella

Tungsten Oxide (WO3) films and low-dimensional structures have proven to be promising candidates in the fields of photonics and electronics. WO3 is a well-established n-type semiconductor characterized by unique electrochromic behavior, an ideal optical band gap that permits transparency over a wide spectral range, and high chemical integrity. The plethora of diverse properties endow WO3 to be highly effective in applications related to electrochromism, gas sensing, and deriving economical energy. Compared to the bulk films, a materials system involving WO3 and a related species (elements or metal oxides) offer the opportunity to tailor the electrochromic response, and an overall enhancement of the physio-chemical and optical properties. In the present case, WO3 and TiO2 composite films have been fabricated by reactive magnetron sputtering employing W/Ti alloy targets, and individual W and Ti targets for co-sputtering. Composite WO3-TiO2 films were fabricated with variable chemical composition and the effect of variable bulk chemistry on film structure, surface/interface chemistry and chemical valence state of the W and Ti cations was investigated in detail. The process-property relationships between composition and physical properties for the films deposited by using W/Ti alloy targets of variable Ti content are associated with decreases in the deposition rate of the WO3-TiO2 films due to the lower sputter yield of the strongly bonded TiO2 formed on the target surface. Additionally, for the co-sputtered films using variable tungsten power, the optical properties demonstrate unique optical modulation. The changes associated with the physical color of the films demonstrate the potential to tailor the optical behavior for the design and fabrication of multilayer photovoltaic and catalytic devices. The process-structure-property correlation derived in this work will provide a road-map to optimize and produce W-Ti-O thin films with desired properties for a given technological application.

Efficient and Tunable Three-Dimensional Functionalization of Fully Zwitterionic Antifouling Surface Coatings.

PubMed

Lange, Stefanie C; van Andel, Esther; Smulders, Maarten M J; Zuilhof, Han

2016-10-11

To enhance the sensitivity and selectivity of surface-based (bio)sensors, it is of crucial importance to diminish background signals that arise from the nonspecific binding of biomolecules, so-called biofouling. Zwitterionic polymer brushes have been shown to be excellent antifouling materials. However, for sensing purposes, antifouling does not suffice but needs to be combined with the possibility to efficiently modify the brush with recognition units. So far this has been achieved only at the expense of either antifouling properties or binding capacity. Herein we present a conceptually new approach by integrating both characteristics into a single tailor-made monomer: a novel sulfobetaine-based zwitterionic monomer equipped with a clickable azide moiety. Copolymerization of this monomer with a well-established standard sulfobetaine monomer results in highly antifouling surface coatings with a large yet tunable number of clickable groups present throughout the entire brush. Subsequent functionalization of the azido brushes via widely used strain-promoted alkyne azide click reactions yields fully zwitterionic 3D-functionalized coatings with a recognition unit of choice that can be tailored for any specific application. Here we show a proof of principle with biotin-functionalized brushes on Si 3 N 4 that combine excellent antifouling properties with specific avidin binding from a protein mixture. The signal-to-noise ratio is significantly improved over that of traditional chain-end modification of sulfobetaine polymer brushes, even if the azide content is lowered to 1%. This therefore offers a viable approach to the development of biosensors with greatly enhanced performance on any surface.

Feasibility of Department of Defense Used Lubricating Oil Re-refining.

DTIC Science & Technology

1983-12-01

greater product selectivity (increasing cost effec- tiveness by tailoring the process to meet market demand ). In addition most processes have high yields...However, several issues were surfaced. The question of who in DLA is responsible for the administra- tion of a re-refining program must be resolved...Both the Property Disposal and Supply groups have a role. The Disposal group now has responsibility for .1%- iv -. d

Spatial and directional control of self-assembled wrinkle patterns by UV light absorption

NASA Astrophysics Data System (ADS)

Kortz, C.; Oesterschulze, E.

2017-12-01

Wrinkle formation on surfaces is a phenomenon that is observed in layered systems with a compressed elastic thin capping layer residing on a viscoelastic film. So far, the properties of the viscoelastic material could only be changed replacing it by another material. Here, we propose to use a photosensitive material whose viscoelastic properties, Young's modulus, and glass transition temperature can easily be adjusted by the absorption of UV light. Employing UV lithography masks during the exposure, we gain additionally spatial and directional control of the self-assembled wrinkle pattern formation that relies on a spinodal decomposition process. Inspired by the results on surface wrinkling and its dependence on the intrinsic stress, we also derive a method to avoid wrinkling locally by tailoring the mechanical stress distribution in the layered system choosing UV masks with convex patterns. This is of particular interest in technical applications where the buckling of surfaces is undesirable.

Self-organized molecular films with long-range quasiperiodic order.

PubMed

Fournée, Vincent; Gaudry, Émilie; Ledieu, Julian; de Weerd, Marie-Cécile; Wu, Dongmei; Lograsso, Thomas

2014-04-22

Self-organized molecular films with long-range quasiperiodic order have been grown by using the complex potential energy landscape of quasicrystalline surfaces as templates. The long-range order arises from a specific subset of quasilattice sites acting as preferred adsorption sites for the molecules, thus enforcing a quasiperiodic structure in the film. These adsorption sites exhibit a local 5-fold symmetry resulting from the cut by the surface plane through the cluster units identified in the bulk solid. Symmetry matching between the C60 fullerene and the substrate leads to a preferred adsorption configuration of the molecules with a pentagonal face down, a feature unique to quasicrystalline surfaces, enabling efficient chemical bonding at the molecule-substrate interface. This finding offers opportunities to investigate the physical properties of model 2D quasiperiodic systems, as the molecules can be functionalized to yield architectures with tailor-made properties.

Tailoring pore properties of MCM-48 silica for selective adsorption of CO2.

PubMed

Kim, Sangil; Ida, Junichi; Guliants, Vadim V; Lin, Jerry Y S

2005-04-07

Four different types of amine-attached MCM-48 silicas were prepared and investigated for CO(2) separation from N(2). Monomeric and polymeric hindered and unhindered amines were attached to the pore surface of the MCM-48 silica and characterized with respect to their CO(2) sorption properties. The pore structures and amino group content in these modified silicas were investigated by XRD, FT-IR, TGA, N(2) adsorption/desorption at 77 K and CHN/Si analysis, which confirmed that in all cases the amino groups were attached to the pore surface of MCM-48 at 1.5-5.2 mmol/g. The N(2) adsorption/desorption analysis showed a considerable decrease of the pore volume and surface area for the MCM-48 silica containing a polymeric amine (e.g., polyethyleneimine). The CO(2) adsorption rates and capacities of the amine-attached MCM-48 samples were studied employing a sorption microbalance. The results obtained indicated that in addition to the concentration of surface-attached amino groups, specific interactions between CO(2) and the surface amino groups, and the resultant pore structure after amine group attachment have a significant impact on CO(2) adsorption properties of these promising adsorbent materials.

Microwave plasma induced surface modification of diamond-like carbon films

NASA Astrophysics Data System (ADS)

Rao Polaki, Shyamala; Kumar, Niranjan; Gopala Krishna, Nanda; Madapu, Kishore; Kamruddin, Mohamed; Dash, Sitaram; Tyagi, Ashok Kumar

2017-12-01

Tailoring the surface of diamond-like carbon (DLC) film is technically relevant for altering the physical and chemical properties, desirable for useful applications. A physically smooth and sp3 dominated DLC film with tetrahedral coordination was prepared by plasma-enhanced chemical vapor deposition technique. The surface of the DLC film was exposed to hydrogen, oxygen and nitrogen plasma for physical and chemical modifications. The surface modification was based on the concept of adsorption-desorption of plasma species and surface entities of films. Energetic chemical species of microwave plasma are adsorbed, leading to desorbtion of the surface carbon atoms due to energy and momentum exchange. The interaction of such reactive species with DLC films enhanced the roughness, surface defects and dangling bonds of carbon atoms. Adsorbed hydrogen, oxygen and nitrogen formed a covalent network while saturating the dangling carbon bonds around the tetrahedral sp3 valency. The modified surface chemical affinity depends upon the charge carriers and electron covalency of the adsorbed atoms. The contact angle of chemically reconstructed surface increases when a water droplet interacts either through hydrogen or van dear Waals bonding. These weak interactions influenced the wetting property of the DLC surface to a great extent.

The mechanical behavior of GLARE laminates for aircraft structures

NASA Astrophysics Data System (ADS)

Wu, Guocai; Yang, J.-M.

2005-01-01

GLARE (glass-reinforced aluminum laminate) is a new class of fiber metal laminates for advanced aerospace structural applications. It consists of thin aluminum sheets bonded together with unidirectional or biaxially reinforced adhesive prepreg of high-strength glass fibers. GLARE laminates offer a unique combination of properties such as outstanding fatigue resistance, high specific static properties, excellent impact resistance, good residual and blunt notch strength, flame resistance and corrosion properties, and ease of manufacture and repair. GLARE laminates can be tailored to suit a wide variety of applications by varying the fiber/resin system, the alloy type and thickness, stacking sequence, fiber orientation, surface pretreatment technique, etc. This article presents a comprehensive overview of the mechanical properties of various GLARE laminates under different loading conditions.

Unravelling Some of the Structure-Property Relationships in Graphene Oxide at Low Degree of Oxidation.

PubMed

Savazzi, Filippo; Risplendi, Francesca; Mallia, Giuseppe; Harrison, Nicholas M; Cicero, Giancarlo

2018-04-05

Graphene oxide (GO) is a versatile 2D material whose properties can be tuned by changing the type and concentration of oxygen-containing functional groups attached to its surface. However, a detailed knowledge of the dependence of the chemo/physical features of this material on its chemical composition is largely unknown. We combine classical molecular dynamics and density functional theory simulations to predict the structural and electronic properties of GO at low degree of oxidation and suggest a revision of the Lerf-Klinowski model. We find that layer deformation is larger for samples containing high concentrations of epoxy groups and that correspondingly the band gap increases. Targeted chemical modification of the GO surface appears to be an effective route to tailor the electronic properties of the monolayer for given applications. Our simulations also show that the chemical shift of the C-1s XPS peak allows one to unambiguously characterize GO composition, resolving the peak attribution  uncertainty often encountered in experiments.

Sapphire substrate-induced effects in VO{sub 2} thin films grown by oxygen plasma-assisted pulsed laser deposition

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

Skuza, J. R., E-mail: jrskuza@nsu.edu, E-mail: apradhan@nsu.edu; Scott, D. W.; Pradhan, A. K., E-mail: jrskuza@nsu.edu, E-mail: apradhan@nsu.edu

2015-11-21

We investigate the structural and electronic properties of VO{sub 2} thin films on c-plane sapphire substrates with three different surface morphologies to control the strain at the substrate-film interface. Only non-annealed substrates with no discernible surface features (terraces) provided a suitable template for VO{sub 2} film growth with a semiconductor-metal transition (SMT), which was much lower than the bulk transition temperature. In addition to strain, oxygen vacancy concentration also affects the properties of VO{sub 2}, which can be controlled through deposition conditions. Oxygen plasma-assisted pulsed laser deposition allows favorable conditions for VO{sub 2} film growth with SMTs that can bemore » easily tailored for device applications.« less

Tailoring nanostructured, graded, and particle-reinforced Al laminates by accumulative roll bonding.

PubMed

Göken, Mathias; Höppel, Heinz Werner

2011-06-17

Accumulative roll bonding (ARB) is a very attractive process for processing large sheets to achieve ultrafine-grained microstructure and high strength. Commercial purity Al and many Al alloys from the 5xxx and the precipitation strengthened 6xxx alloy series have been successfully processed by the ARB process into an ultrafine-grained state and superior ductility have been achieved for some materials like technical purity Al. It has also been shown that the ARB process can be successfully used to produce multi-component materials with tailored properties by reinforcement or grading, respectively. This allows optimizing the properties based on two or more materials/alloys. For example, to achieve high corrosion resistance and good visual surface properties it is interesting to produce a composite of two different Al alloys, where for example a high strength alloy of the 5xxx series is used as the core material and a 6xxx series alloy as the clad material. It has been shown that such a composite achieves more or less the same strength as the core material although 50% of the composite consists of the significant softer clad alloy. Furthermore, it has been found, that the serrated yielding which typically appears in 5xxx series alloys and limits applications as outer skin materials completely disappears. Moreover, the ARB process allows many other attractive ways to design new composites and graded material structures with unique properties by the introduction of particles, fibres and sheets. Strengthening with nanoparticles for example is a very attractive way to improve the properties and accelerate the grain refining used in the severe plastic deformation process. With an addition of only 0.1 vol.-% Al2O3 nanoparticles a significantly accelerated grain refinement has been found which reduces the number of ARB passes necessary to achieve the maximum in strength. The paper provides a short review on recent developments in the field of ARB processing for producing multicomponent ultrafine-grained sheet materials with tailored properties.

Restoring the magnetism of ultrathin LaMn O3 films by surface symmetry engineering

NASA Astrophysics Data System (ADS)

Peng, J. J.; Song, C.; Li, F.; Gu, Y. D.; Wang, G. Y.; Pan, F.

2016-12-01

The frustration of magnetization and conductivity properties of ultrathin manganite is detrimental to their device performance, preventing their scaling down process. Here we demonstrate that the magnetism of ultrathin LaMn O3 films can be restored by a SrTi O3 capping layer, which engineers the surface from a symmetry breaking induced out-of-plane orbital occupancy to the recovered in-plane orbital occupancy. The stabilized in-plane orbital occupancy would strengthen the intralayer double exchange and thus recovers the robust magnetism. This method is proved to be effective for films as thin as 2 unit cells, greatly shrinking the critical thickness of 6 unit cells for ferromagnetic LaMn O3 as demonstrated previously [Wang et al., Science 349, 716 (2015), 10.1126/science.aaa5198]. The achievement made in this work opens up new perspectives to an active control of surface states and thereby tailors the surface functional properties of transition metal oxides.

Optically transparent, mechanically durable, nanostructured superhydrophobic surfaces enabled by spinodally phase-separated glass thin films

NASA Astrophysics Data System (ADS)

Aytug, Tolga; Simpson, John T.; Lupini, Andrew R.; Trejo, Rosa M.; Jellison, Gerald E.; Ivanov, Ilia N.; Pennycook, Stephen J.; Hillesheim, Daniel A.; Winter, Kyle O.; Christen, David K.; Hunter, Scott R.; Haynes, J. Allen

2013-08-01

We describe the formation and properties of atomically bonded, optical quality, nanostructured thin glass film coatings on glass plates, utilizing phase separation by spinodal decomposition in a sodium borosilicate glass system. Following deposition via magnetron sputtering, thermal processing and differential etching, these coatings are structurally superhydrophilic (i.e., display anti-fogging functionality) and demonstrate robust mechanical properties and superior abrasion resistance. After appropriate chemical surface modification, the surfaces display a stable, non-wetting Cassie-Baxter state and exhibit exceptional superhydrophobic performance, with water droplet contact angles as large as 172°. As an added benefit, in both superhydrophobic and superhydrophilic states these nanostructured surfaces can block ultraviolet radiation and can be engineered to be anti-reflective with broadband and omnidirectional transparency. Thus, the present approach could be tailored toward distinct coatings for numerous markets, such as residential windows, windshields, specialty optics, goggles, electronic and photovoltaic cover glasses, and optical components used throughout the US military.

Optically transparent, mechanically durable, nanostructured superhydrophobic surfaces enabled by spinodally phase-separated glass thin films.

PubMed

Aytug, Tolga; Simpson, John T; Lupini, Andrew R; Trejo, Rosa M; Jellison, Gerald E; Ivanov, Ilia N; Pennycook, Stephen J; Hillesheim, Daniel A; Winter, Kyle O; Christen, David K; Hunter, Scott R; Haynes, J Allen

2013-08-09

We describe the formation and properties of atomically bonded, optical quality, nanostructured thin glass film coatings on glass plates, utilizing phase separation by spinodal decomposition in a sodium borosilicate glass system. Following deposition via magnetron sputtering, thermal processing and differential etching, these coatings are structurally superhydrophilic (i.e., display anti-fogging functionality) and demonstrate robust mechanical properties and superior abrasion resistance. After appropriate chemical surface modification, the surfaces display a stable, non-wetting Cassie-Baxter state and exhibit exceptional superhydrophobic performance, with water droplet contact angles as large as 172°. As an added benefit, in both superhydrophobic and superhydrophilic states these nanostructured surfaces can block ultraviolet radiation and can be engineered to be anti-reflective with broadband and omnidirectional transparency. Thus, the present approach could be tailored toward distinct coatings for numerous markets, such as residential windows, windshields, specialty optics, goggles, electronic and photovoltaic cover glasses, and optical components used throughout the US military.

Tailoring density and optical and thermal behavior of gold surfaces and nanoparticles exploiting aromatic dithiols.

PubMed

Bruno, Giovanni; Babudri, Francesco; Operamolla, Alessandra; Bianco, Giuseppe V; Losurdo, Maria; Giangregorio, Maria M; Hassan Omar, Omar; Mavelli, Fabio; Farinola, Gianluca M; Capezzuto, Pio; Naso, Francesco

2010-06-01

Self-assembled monolayers (SAMs) derived of 4-methoxy-terphenyl-3'',5''-dimethanethiol (TPDMT) and 4-methoxyterphenyl-4''-methanethiol (TPMT) have been prepared by chemisorption from solution onto gold thin films and nanoparticles. The SAMs have been characterized by spectroscopic ellipsometry, Raman spectroscopy and atomic force microscopy to determine their optical properties, namely the refractive index and extinction coefficient, in an extended spectral range of 0.75-6.5 eV. From the analysis of the optical data, information on SAMs structural organization has been inferred. Comparison of SAMs generated from the above aromatic thiols to well-known SAMs generated from the alkanethiol dodecanethiol revealed that the former aromatic SAMs are densely packed and highly vertically oriented, with a slightly higher packing density and a absence of molecular inclination in TPMT/Au. The thermal behavior of SAMs has also been monitored using ellipsometry in the temperature range 25-500 degrees C. Gold nanoparticles functionalized by the same aromatic thiols have also been discussed for surface enhanced Raman spectroscopy applications. This study represents a step forward tailoring the optical and thermal behavior of surfaces as well as nanoparticles.

Tailoring surface and photocatalytic properties of ZnO and nitrogen-doped ZnO nanostructures using microwave-assisted facile hydrothermal synthesis

NASA Astrophysics Data System (ADS)

Rangel, R.; Cedeño, V.; Ramos-Corona, A.; Gutiérrez, R.; Alvarado-Gil, J. J.; Ares, O.; Bartolo-Pérez, P.; Quintana, P.

2017-08-01

Microwave hydrothermal synthesis, using an experimental 23 factorial design, was used to produce tunable ZnO nano- and microstructures, and their potential as photocatalysts was explored. Photocatalytic reactions were conducted in a microreactor batch system under UV and visible light irradiation, while monitoring methylene blue degradation, as a model system. The variables considered in the microwave reactor to produce ZnO nano- or microstructures, were time, NaOH concentration and synthesis temperature. It was found that, specific surface area and volume/surface area ratio were affected as a consequence of the synthesis conditions. In the second stage, the samples were plasma treated in a nitrogen atmosphere, with the purpose of introducing nitrogen into the ZnO crystalline structure. The central idea is to induce changes in the material structure as well as in its optical absorption, to make the plasma-treated material useful as photocatalyst in the visible region of the electromagnetic spectrum. Pristine ZnO and nitrogen-doped ZnO compounds were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), specific surface area (BET), XPS, and UV-Vis diffuse reflectance spectroscopy. The results show that the methodology presented in this work is effective in tailoring the specific surface area of the ZnO compounds and incorporation of nitrogen into their structure, factors which in turn, affect its photocatalytic behavior.

Effects of Dopant Ionic Radius on Cerium Reduction in Epitaxial Cerium Oxide Thin Films

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

Yang, Nan; Orgiani, Pasquale; Di Bartolomeo, Elisabetta

The role of trivalent rare-earth dopants in ceria epitaxial films on surface ion exchange reactivity and ion conductivity has been systematically studied. Single-crystal epitaxial films with unique crystal orientation and micro-structure nature have allowed us to rule out the influence of structural defects on both transport and surface ion exchange properties. The films conductivities were larger than those reported in literature for both polycrystalline ceramic pellets and crystalline films. An increase in oxygen vacancies and Ce 3+ concentration while decreasing the dopant ionic radius from La 3+ to Yb 3+ was observed, thus explaining the measured increased activation energy andmore » enhanced surface reactivity. The more significant ability of smaller dopant ionic radius in releasing the stress strength induced by the larger Ce 3+ ionic radius allows promoting the formation of oxygen vacancies and Ce 3+, which are two precious species in determining the efficiency of ion transport and surface ion exchange processes. This can open new perspectives in designing ceria-based materials in tailoring functional properties, either ion migration or surface reactivity, by rational cation substitutions.« less

Effects of Dopant Ionic Radius on Cerium Reduction in Epitaxial Cerium Oxide Thin Films

DOE PAGES

Yang, Nan; Orgiani, Pasquale; Di Bartolomeo, Elisabetta; ...

2017-04-17

The role of trivalent rare-earth dopants in ceria epitaxial films on surface ion exchange reactivity and ion conductivity has been systematically studied. Single-crystal epitaxial films with unique crystal orientation and micro-structure nature have allowed us to rule out the influence of structural defects on both transport and surface ion exchange properties. The films conductivities were larger than those reported in literature for both polycrystalline ceramic pellets and crystalline films. An increase in oxygen vacancies and Ce 3+ concentration while decreasing the dopant ionic radius from La 3+ to Yb 3+ was observed, thus explaining the measured increased activation energy andmore » enhanced surface reactivity. The more significant ability of smaller dopant ionic radius in releasing the stress strength induced by the larger Ce 3+ ionic radius allows promoting the formation of oxygen vacancies and Ce 3+, which are two precious species in determining the efficiency of ion transport and surface ion exchange processes. This can open new perspectives in designing ceria-based materials in tailoring functional properties, either ion migration or surface reactivity, by rational cation substitutions.« less

A review of the biomaterials technologies for infection-resistant surfaces.

PubMed

Campoccia, Davide; Montanaro, Lucio; Arciola, Carla Renata

2013-11-01

Anti-infective biomaterials need to be tailored according to the specific clinical application. All their properties have to be tuned to achieve the best anti-infective performance together with safe biocompatibility and appropriate tissue interactions. Innovative technologies are developing new biomaterials and surfaces endowed with anti-infective properties, relying either on antifouling, or bactericidal, or antibiofilm activities. This review aims at thoroughly surveying the numerous classes of antibacterial biomaterials and the underlying strategies behind them. Bacteria repelling and antiadhesive surfaces, materials with intrinsic antibacterial properties, antibacterial coatings, nanostructured materials, and molecules interfering with bacterial biofilm are considered. Among the new strategies, the use of phages or of antisense peptide nucleic acids are discussed, as well as the possibility to modulate the local immune response by active cytokines. Overall, there is a wealth of technical solutions to contrast the establishment of an implant infection. Many of them exhibit a great potential in preclinical models. The lack of well-structured prospective multicenter clinical trials hinders the achievement of conclusive data on the efficacy and comparative performance of anti-infective biomaterials. © 2013 Elsevier Ltd. All rights reserved.

Surface-Enhanced Separation of Water from Hydrocarbons: Potential Dewatering Membranes for the Catalytic Fast Pyrolysis of Pine Biomass

DOE PAGES

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

2016-01-01

The impact of surface-selective coatings on water permeation through a membrane when exposed to catalytic fast pyrolysis (CFP) vapor products was studied by tailoring the surface properties of the membrane coating from superhydrophilic to superhydrophobic. Our approach utilized high-performance architectured surface-selective (HiPAS) membranes that were inserted after a CFP reactor. At this insertion point, the inner wall surface of a tubular membrane was exposed to a mixture of water and upgraded product vapors, including light gases and deoxygenated hydrocarbons. Under proper membrane operating conditions, a high selectivity for water over 1-ring upgraded biomass pyrolysis hydrocarbons was observed due to amore » surface-enhanced capillary condensation process. Owing to this surface-enhanced effect, HiPAS membranes have the potential to enable high flux separations suggesting that water can be selectively removed from the CFP product vapors.« less

Surface-Enhanced Separation of Water from Hydrocarbons: Potential Dewatering Membranes for the Catalytic Fast Pyrolysis of Pine Biomass

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

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

2016-10-20

The impact of surface-selective coatings on water permeation through a membrane when exposed to catalytic fast pyrolysis (CFP) vapor products was studied by tailoring the surface properties of the membrane coating from superhydrophilic to superhydrophobic. Our approach used high-performance architectured surface-selective (HiPAS) membranes that were inserted after a CFP reactor. At this insertion point, the inner wall surface of a tubular membrane was exposed to a mixture of water and upgraded product vapors, including light gases and deoxygenated hydrocarbons. Under proper membrane operating conditions, a high selectivity for water over one-ring upgraded biomass pyrolysis hydrocarbons was observed as a resultmore » of a surface-enhanced capillary condensation process. Owing to this surface-enhanced effect, HiPAS membranes have the potential to enable high flux separations, suggesting that water can be selectively removed from the CFP product vapors.« less

Hydrothermally tailor-made chitosan fiber for micro-solid phase extraction of petroleum acids in crude oils.

PubMed

Zhu, Gang-Tian; Hu, Xiao-Li; He, Sheng; He, Xiao-Mei; Zhu, Shu-Kui; Feng, Yu-Qi

2018-06-05

Tailor-made chitosan fiber was prepared via hydrothermal treatment to serve as a micro-solid phase extraction (micro-SPE) sorbent for the analysis of petroleum acids (PAs) in crude oils. Chitosan fiber, which is commercial and cheap, has a diameter of about 10 μm and a length of a few centimeters. The fibrous property of the sorbent enables the micro-SPE to deal with viscous crude oil samples because of the low back-pressure during extraction, while the abundant hydroxyl groups and amino groups on the surface of chitosan fiber can provide high density of specific sites for adsorption of PAs. Moreover, it was found that hydrothermal treatment at certain conditions could tune the surface properties of chitosan fiber, leading to significant improvement of the capacity of the fiber in adsorption of PAs. Using hydrothermally treated chitosan fiber as sorbent, the micro-SPE was applied to the determination of PAs in crude oils, with the advantages of easy-operation, rapidness and high sensitivity (the limits of detection range from 0.7 ng/g to 5.4 ng/g). Furthermore, coupled with comprehensive two dimensional gas chromatography-mass spectrometry (GC × GCMS), the treated chitosan fiber packed micro-SPE method showed a great potential for comprehensive profiling of PAs in crude oils. Copyright © 2018 Elsevier B.V. All rights reserved.

Building devices from colloidal quantum dots.

PubMed

Kagan, Cherie R; Lifshitz, Efrat; Sargent, Edward H; Talapin, Dmitri V

2016-08-26

The continued growth of mobile and interactive computing requires devices manufactured with low-cost processes, compatible with large-area and flexible form factors, and with additional functionality. We review recent advances in the design of electronic and optoelectronic devices that use colloidal semiconductor quantum dots (QDs). The properties of materials assembled of QDs may be tailored not only by the atomic composition but also by the size, shape, and surface functionalization of the individual QDs and by the communication among these QDs. The chemical and physical properties of QD surfaces and the interfaces in QD devices are of particular importance, and these enable the solution-based fabrication of low-cost, large-area, flexible, and functional devices. We discuss challenges that must be addressed in the move to solution-processed functional optoelectronic nanomaterials. Copyright © 2016, American Association for the Advancement of Science.

Manufacturing of tailored tubes with a process integrated heat treatment

NASA Astrophysics Data System (ADS)

Hordych, Illia; Boiarkin, Viacheslav; Rodman, Dmytro; Nürnberger, Florian

2017-10-01

The usage of work-pieces with tailored properties allows for reducing costs and materials. One example are tailored tubes that can be used as end parts e.g. in the automotive industry or in domestic applications as well as semi-finished products for subsequent controlled deformation processes. An innovative technology to manufacture tubes is roll forming with a subsequent inductive heating and adapted quenching to obtain tailored properties in the longitudinal direction. This processing offers a great potential for the production of tubes with a wide range of properties, although this novel approach still requires a suited process design. Based on experimental data, a process simulation is being developed. The simulation shall be suitable for a virtual design of the tubes and allows for gaining a deeper understanding of the required processing. The model proposed shall predict microstructural and mechanical tube properties by considering process parameters, different geometries, batch-related influences etc. A validation is carried out using experimental data of tubes manufactured from various steel grades.

Multipole and field uniformity tailoring of a 750 MHz rf dipole

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

Delayen, Jean R.; Castillo, Alejandro

2014-12-01

In recent years great interest has been shown in developing rf structures for beam separation, correction of geometrical degradation on luminosity, and diagnostic applications in both lepton and hadron machines. The rf dipole being a very promising one among all of them. The rf dipole has been tested and proven to have attractive properties that include high shunt impedance, low and balance surface fields, absence of lower order modes and far-spaced higher order modes that simplify their damping scheme. As well as to be a compact and versatile design in a considerable range of frequencies, its fairly simple geometry dependencymore » is suitable both for fabrication and surface treatment. The rf dipole geometry can also be optimized for lowering multipacting risk and multipole tailoring to meet machine specific field uniformity tolerances. In the present work a survey of field uniformities, and multipole contents for a set of 750 MHz rf dipole designs is presented as both a qualitative and quantitative analysis of the inherent flexibility of the structure and its limitations.« less

Microstructure and mechanical properties of diamond films on titanium-aluminum-vanadium alloy

NASA Astrophysics Data System (ADS)

Catledge, Shane Aaron

The primary focus of this dissertation is the investigation of the processing-structure-property relationships of diamond films deposited on Ti-6Al-4V alloy by microwave plasma chemical vapor deposition (MPCVD). By depositing a well-adhered protective layer of diamond on an alloy component, its hardness, wear-resistance, performance, and overall lifetime could be significantly increased. However, due to the large thermal expansion mismatch between the diamond film and metal (and the corresponding residual stress induced in the film), film adhesion is typically unsatisfactory and often results in immediate delamination after processing. Therefore, it is a major goal of this research to improve adhesion of the diamond film to the alloy substrate. Through the use of innovative processing techniques involving MPCVD deposition conditions and methane (CH4), nitrogen (N2), and hydrogen (H2) chemistry, we have achieved diamond films which consistently adhere to the alloy substrate. In addition, we have discovered that, with the appropriate choice of deposition conditions, the film structure can be tailored to range from highly crystalline, well-faceted diamond to nanocrystalline diamond with extremely low surface roughness (as low as 27 nm). The relationship between processing and structure was studied using in-situ optical emission spectroscopy, micro-Raman spectroscopy, surface profilometry, glancing-angle x-ray diffraction, and scanning electron microscopy. We observe that when nitrogen is added to the H2/CH4 feedgas mixture, a carbon-nitrogen (CN) emission band arises and its relative abundance to the carbon dimer (C2) gas species is shown to have a pronounced influence on the diamond film structure. By appropriate choice of deposition chemistry and conditions, we can tailor the diamond film structure and its corresponding properties. The mechanical properties of interest in this thesis are those relating to the integrity of the film/substrate interface, as well as the hardness, wear resistance, residual stress, and elastic modulus of the film. The mechanical properties of the diamond coatings were characterized by indentation and wear testing instruments. Finally, we developed a model based on fundamental thermodynamic and optical principles for extracting the time dependence of film thickness and surface roughness using optical pyrometry for the case of an absorbing substrate. This model provides a convenient way to determine film thickness during growth in CVD systems as well as a reliable estimate of surface roughness.

Effective Heat and Mass Transport Properties of Anisotropic Porous Ceria for Solar Thermochemical Fuel Generation

PubMed Central

Haussener, Sophia; Steinfeld, Aldo

2012-01-01

High-resolution X-ray computed tomography is employed to obtain the exact 3D geometrical configuration of porous anisotropic ceria applied in solar-driven thermochemical cycles for splitting H2O and CO2. The tomography data are, in turn, used in direct pore-level numerical simulations for determining the morphological and effective heat/mass transport properties of porous ceria, namely: porosity, specific surface area, pore size distribution, extinction coefficient, thermal conductivity, convective heat transfer coefficient, permeability, Dupuit-Forchheimer coefficient, and tortuosity and residence time distributions. Tailored foam designs for enhanced transport properties are examined by means of adjusting morphologies of artificial ceria samples composed of bimodal distributed overlapping transparent spheres in an opaque medium. PMID:28817039

Ullmann-like reactions for the synthesis of complex two-dimensional materials

NASA Astrophysics Data System (ADS)

Quardokus, Rebecca C.; Tewary, V. K.; DelRio, Frank W.

2016-11-01

Engineering two-dimensional materials through surface-confined synthetic techniques is a promising avenue for designing new materials with tailored properties. Developing and understanding reaction mechanisms for surface-confined synthesis of two-dimensional materials requires atomic-level characterization and chemical analysis. Beggan et al (2015 Nanotechnology 26 365602) used scanning tunneling microscopy and x-ray photoelectron spectroscopy to elucidate the formation mechanism of surface-confined Ullmann-like coupling of thiophene substituted porphyrins on Ag(111). Upon surface deposition, bromine is dissociated and the porphyrins couple with surface adatoms to create linear strands and hexagonally packed molecules. Annealing the sample results in covalently-bonded networks of thienylporphyrin derivatives. A deeper understanding of surface-confined Ullmann-like coupling has the potential to lead to precision-engineered nano-structures through synthetic techniques. Contribution of the National Institute of Standards and Technology, not subject to copyright in the United States of America.

Structural transformation in monolayer materials: a 2D to 1D transformation.

PubMed

Momeni, Kasra; Attariani, Hamed; LeSar, Richard A

2016-07-20

Reducing the dimensions of materials to atomic scales results in a large portion of atoms being at or near the surface, with lower bond order and thus higher energy. At such scales, reduction of the surface energy and surface stresses can be the driving force for the formation of new low-dimensional nanostructures, and may be exhibited through surface relaxation and/or surface reconstruction, which can be utilized for tailoring the properties and phase transformation of nanomaterials without applying any external load. Here we used atomistic simulations and revealed an intrinsic structural transformation in monolayer materials that lowers their dimension from 2D nanosheets to 1D nanostructures to reduce their surface and elastic energies. Experimental evidence of such transformation has also been revealed for one of the predicted nanostructures. Such transformation plays an important role in bi-/multi-layer 2D materials.

High Pressure Laminates with Antimicrobial Properties

PubMed Central

Magina, Sandra; Santos, Mauro D.; Ferra, João; Cruz, Paulo; Portugal, Inês; Evtuguin, Dmitry

2016-01-01

High-pressure laminates (HPLs) are durable, resistant to environmental effects and good cost-benefit decorative surface composite materials with special properties tailored to meet market demand. In the present work, polyhexamethylene biguanide (PHMB) was incorporated for the first time into melamine-formaldehyde resin (MF) matrix on the outer layer of HPLs to provide them antimicrobial properties. Chemical binding of PHMB to resin matrix was detected on the surface of produced HPLs by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR). Antimicrobial evaluation tests were carried out on the ensuing HPLs doped with PHMB against gram-positive Listeria innocua and gram-negative Escherichia coli bacteria. The results revealed that laminates prepared with 1.0 wt % PHMB in MF resin were bacteriostatic (i.e., inhibited the growth of microorganisms), whereas those prepared with 2.4 wt % PHMB in MF resin exhibited bactericidal activity (i.e., inactivated the inoculated microorganisms). The results herein reported disclose a promising strategy for the production of HPLs with antimicrobial activity without affecting basic intrinsic quality parameters of composite material. PMID:28787897

High Pressure Laminates with Antimicrobial Properties.

PubMed

Magina, Sandra; Santos, Mauro D; Ferra, João; Cruz, Paulo; Portugal, Inês; Evtuguin, Dmitry

2016-02-06

High-pressure laminates (HPLs) are durable, resistant to environmental effects and good cost-benefit decorative surface composite materials with special properties tailored to meet market demand. In the present work, polyhexamethylene biguanide (PHMB) was incorporated for the first time into melamine-formaldehyde resin (MF) matrix on the outer layer of HPLs to provide them antimicrobial properties. Chemical binding of PHMB to resin matrix was detected on the surface of produced HPLs by attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR). Antimicrobial evaluation tests were carried out on the ensuing HPLs doped with PHMB against gram-positive Listeria innocua and gram-negative Escherichia coli bacteria. The results revealed that laminates prepared with 1.0 wt % PHMB in MF resin were bacteriostatic ( i.e. , inhibited the growth of microorganisms), whereas those prepared with 2.4 wt % PHMB in MF resin exhibited bactericidal activity ( i.e. , inactivated the inoculated microorganisms). The results herein reported disclose a promising strategy for the production of HPLs with antimicrobial activity without affecting basic intrinsic quality parameters of composite material.

Chemically-Tailored Surfaces of Silica Gel and Alumina Examined Using Color

ERIC Educational Resources Information Center

Taralp, Alpay; Buyukbayram, Gulen; Armagan, Onsel; Yalcin, Ender

2004-01-01

Color is used for studying the chemically-tailored surfaces of silica gel and alumina. When this technique of using color was applied by the students, they were able to grasp the principles of surface engineering and acquire an appreciation of its merits and at the same time they were able to learn the fundamentals of aldehyde chemistry,…

Ternary composite scaffolds with tailorable degradation rate and highly improved colonization by human bone marrow stromal cells.

PubMed

Idaszek, J; Bruinink, A; Święszkowski, W

2015-07-01

Poly(ε-caprolactone), PCL, is of great interest for fabrication of biodegradable scaffolds due to its high compatibility with various manufacturing techniques, especially Fused Deposition Modeling (FDM). However, slow degradation and low strength make application of PCL limited only to longer-term bioresorbable and non-load bearing implants. To overcome latter drawbacks, ternary PCL-based composite fibrous scaffolds consisting of 70-95 wt % PCL, 5 wt % Tricalcium Phosphate (TCP) and 0-25 wt % poly(lactide-co-glycolide) (PLGA) were fabricated using FDM. In the present study, the effect of composition of the scaffolds on their mechanical properties, degradation kinetics, and surface properties (wettability, surface energy, and roughness) was investigated and correlated with response of human bone marrow mesenchymal stromal cells (HBMC). The presence of PLGA increased degradation kinetics, surface roughness and significantly improved scaffold colonization. Of the evaluated surface properties only the wettability was correlated with the surface area colonized by HBMC. This study demonstrates that introduction of PLGA into PCL-TCP binary composite could largely abolish the disadvantages of the PCL matrix and improve biocompatibility by increasing wettability and polar interactions rather than surface roughness. Additionally, we showed great potential of multicellular spheroids as a sensitive in vitro tool for detection of differences in chemistry of 3D scaffolds. © 2014 Wiley Periodicals, Inc.

Tailoring the properties of a zero-valent iron-based composite by mechanochemistry for nitrophenols degradation in wastewaters.

PubMed

Cagnetta, Giovanni; Huang, Jun; Lomovskiy, Igor O; Yu, Gang

2017-11-01

Zero-valent iron (ZVI) is a valuable material for environmental remediation, because of its safeness, large availability, and inexpensiveness. Moreover, its reactivity can be improved by addition of (nano-) particles of other elements such as noble metals. However, common preparation methods for this kind of iron-based composites involve wet precipitation of noble metal salt precursors, so they are often expensive and not green. Mechanochemical procedures can provide a solvent-free alternative, even at a large scale. The present study demonstrates that it is possible to tailor functional properties of ZVI-based materials, utilizing high-energy ball milling. All main preparation parameters are investigated and discussed. Specifically, a copper-carbon-iron ternary composite was prepared for fast degradation of 4-nitrophenol (utilized as model pollutant) to 4-aminophenol and other phenolic compounds. Copper and carbon are purposely chosen to insert specific properties to the composite: Copper acts as efficient nano-cathode that enhances electron transfer from iron to 4-nitrophenol, while carbon protects the iron surface from fast oxidation in open air. In this way, the reactive material can rapidly reduce high concentration of nitrophenols in water, it does not require acid washing to be activated, and can be stored in open air for one week without any significant activity loss.

Tailoring surface plasmon resonance and dipole cavity plasmon modes of scattering cross section spectra on the single solid-gold/gold-shell nanorod

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

Chou Chau, Yuan-Fong, E-mail: chou.fong@ubd.edu.bn; Lim, Chee Ming; Kumara, N. T. R. N.

Tunable surface plasmon resonance (SPR) and dipole cavity plasmon modes of the scattering cross section (SCS) spectra on the single solid-gold/gold-shell nanorod have been numerically investigated by using the finite element method. Various effects, such as the influence of SCS spectra under x- and y-polarizations on the surface of the single solid-gold/gold-shell nanorod, are discussed in detail. With the single gold-shell nanorod, one can independently tune the relative SCS spectrum width by controlling the rod length and rod diameter, and the surface scattering by varying the shell thickness and polarization direction, as well as the dipole peak energy. These behaviorsmore » are consistent with the properties of localized SPRs and offer a way to optically control and produce selected emission wavelengths from the single solid-gold/gold-shell nanorod. The electric field and magnetic distributions provide us a qualitative idea of the geometrical properties of the single solid-gold/gold-shell nanorod on plasmon resonance.« less

Tailoring surface plasmon resonance and dipole cavity plasmon modes of scattering cross section spectra on the single solid-gold/gold-shell nanorod

NASA Astrophysics Data System (ADS)

Chou Chau, Yuan-Fong; Lim, Chee Ming; Lee, Chuanyo; Huang, Hung Ji; Lin, Chun-Ting; Kumara, N. T. R. N.; Yoong, Voo Nyuk; Chiang, Hai-Pang

2016-09-01

Tunable surface plasmon resonance (SPR) and dipole cavity plasmon modes of the scattering cross section (SCS) spectra on the single solid-gold/gold-shell nanorod have been numerically investigated by using the finite element method. Various effects, such as the influence of SCS spectra under x- and y-polarizations on the surface of the single solid-gold/gold-shell nanorod, are discussed in detail. With the single gold-shell nanorod, one can independently tune the relative SCS spectrum width by controlling the rod length and rod diameter, and the surface scattering by varying the shell thickness and polarization direction, as well as the dipole peak energy. These behaviors are consistent with the properties of localized SPRs and offer a way to optically control and produce selected emission wavelengths from the single solid-gold/gold-shell nanorod. The electric field and magnetic distributions provide us a qualitative idea of the geometrical properties of the single solid-gold/gold-shell nanorod on plasmon resonance.

Hierarchically engineered fibrous scaffolds for bone regeneration

PubMed Central

Sachot, Nadège; Castaño, Oscar; Mateos-Timoneda, Miguel A.; Engel, Elisabeth; Planell, Josep A.

2013-01-01

Surface properties of biomaterials play a major role in the governing of cell functionalities. It is well known that mechanical, chemical and nanotopographic cues, for example, influence cell proliferation and differentiation. Here, we present a novel coating protocol to produce hierarchically engineered fibrous scaffolds with tailorable surface characteristics, which mimic bone extracellular matrix. Based on the sol–gel method and a succession of surface treatments, hollow electrospun polylactic acid fibres were coated with a silicon–calcium–phosphate bioactive organic–inorganic glass. Compared with pure polymeric fibres that showed a completely smooth surface, the coated fibres exhibited a nanostructured topography and greater roughness. They also showed improved hydrophilic properties and a Young's modulus sixfold higher than non-coated ones, while remaining fully flexible and easy to handle. Rat mesenchymal stem cells cultured on these fibres showed great cellular spreading and interactions with the material. This protocol can be transferred to other structures and glasses, allowing the fabrication of various materials with well-defined features. This novel approach represents therefore a valuable improvement in the production of artificial matrices able to direct stem cell fate through physical and chemical interactions. PMID:23985738

Stability of Phosphonic Self Assembled Monolayers (SAMs) on Cobalt Chromium (Co-Cr) Alloy under Oxidative conditions

PubMed Central

Bhure, Rahul; Abdel-Fattah, Tarek M.; Bonner, Carl; Hall, Felicia; Mahapatro, Anil

2011-01-01

Cobalt Chromium (Co-Cr) alloys has been widely used in the biomedical arena for cardiovascular, orthopedic and dental applications. Surface modification of the alloy allows us to tailor the interfacial properties to address critical challenges of Co-Cr alloy in medical applications. Self assembled monolayers (SAMs) of Octadecylphosphonic acid (ODPA) have been used to form thin films on the oxide layer of the Co-Cr alloy surface by solution deposition technique. The SAMs formed were investigated for their stability to oxidative conditions of ambient laboratory environment over periods of 1, 3, 7 and 14 days. The samples were then characterized for their stability using X-ray Photoelectron Spectroscopy (XPS), Atomic Force Microscopy (AFM) and Contact Angle Measurements. Detailed high energy XPS elemental scans confirmed the presence of the phosphonic monolayer after oxidative exposure which suggested that the SAMs were firmly attached to the oxide layer of Co-Cr alloy. AFM images gave topographical data of the surface and showed islands of SAMs on Co-Cr alloy surface, before and after SAM formation and also over the duration of the oxidative exposure. Contact angle measurements confirmed the hydrophobicity of the surface over 14 days. Thus the SAMs were found to be stable for the duration of the study. These SAMs could be subsequently tailored by modifying the terminal functional groups and could be used for various potential biomedical applications such as drug delivery, biocompatibility and tissue integration PMID:21603056

Fabrication of Porous Ceramic-Geopolymer Based Material to Improve Water Absorption and Retention in Construction Materials: A Review

NASA Astrophysics Data System (ADS)

Jamil, N. H.; Ibrahim, W. M. A. W.; Abdullah, M. M. A. B.; Sandu, A. V.; Tahir, M. F. M.

2017-06-01

Porous ceramic nowadays has been investigated for a variety of its application such as filters, lightweight structural component and others due to their specific properties such as high surface area, stability and permeability. Besides, it has the properties of low thermal conductivity. Various formation techniques making these porous ceramic properties can be tailored or further fine-tuned to obtain the optimum characteristic. Porous materials also one of the good candidate for absorption properties. Conventional construction materials are not design to have good water absorption and retention that lead to the poor performance on these criteria. Temperature is a major driving force for moisture movement and influences sorption characteristics of many constructions materials. The effect of elevated temperatures on the water absorption coefficient and retention remain as critical issue that need to be investigated. Therefore, this paper will review the process parameters in fabricating porous ceramic for absorption properties.

Development of Tailorable Electrically Conductive Thermal Control Material Systems

NASA Technical Reports Server (NTRS)

Deshpande, M. S.; Harada, Y.

1998-01-01

The optical characteristics of surfaces on spacecraft are fundamental parameters in controlling its temperature. Passive thermal control coatings with designed solar absorptance and infrared emittance properties have been developed and been in use for some time. In this total space environment, the coating must be stable and maintain its desired optical properties for the course of the mission lifetime. The mission lifetimes are increasing and in our quest to save weight, newer substrates are being integrated which limit electrical grounding schemes. All of this has already added to the existing concerns about spacecraft charging and related spacecraft failures or operational failures. The concern is even greater for thermal control surfaces that are very large. One way of alleviating such concerns is to design new thermal control material systems (TCMS) that can help to mitigate charging via providing charge leakage paths. The object of this program was to develop two types of passive electrically conductive TCMS.

Highly selective covalent organic functionalization of epitaxial graphene

NASA Astrophysics Data System (ADS)

Bueno, Rebeca A.; Martínez, José I.; Luccas, Roberto F.; Del Árbol, Nerea Ruiz; Munuera, Carmen; Palacio, Irene; Palomares, Francisco J.; Lauwaet, Koen; Thakur, Sangeeta; Baranowski, Jacek M.; Strupinski, Wlodek; López, María F.; Mompean, Federico; García-Hernández, Mar; Martín-Gago, José A.

2017-05-01

Graphene functionalization with organics is expected to be an important step for the development of graphene-based materials with tailored electronic properties. However, its high chemical inertness makes difficult a controlled and selective covalent functionalization, and most of the works performed up to the date report electrostatic molecular adsorption or unruly functionalization. We show hereafter a mechanism for promoting highly specific covalent bonding of any amino-terminated molecule and a description of the operating processes. We show, by different experimental techniques and theoretical methods, that the excess of charge at carbon dangling-bonds formed on single-atomic vacancies at the graphene surface induces enhanced reactivity towards a selective oxidation of the amino group and subsequent integration of the nitrogen within the graphene network. Remarkably, functionalized surfaces retain the electronic properties of pristine graphene. This study opens the door for development of graphene-based interfaces, as nano-bio-hybrid composites, fabrication of dielectrics, plasmonics or spintronics.

Synthesis and Biomedical Applications of Poly((meth)acrylic acid) Brushes.

PubMed

Qu, Zhenyuan; Xu, Hong; Gu, Hongchen

2015-07-15

Poly((meth)acrylic acid) (P(M)AA) brushes possess a number of distinctive properties that are particularly attractive for biomedical applications. This minireview summarizes recent advances in the synthesis and biomedical applications of P(M)AA brushes and brushes containing P(M)AA segments. First, we review different surface-initiated polymerization (SIP) methods, with a focus on recent progress in the surface-initiated controlled/living radical polymerization (SI-CLRP) techniques used to generate P(M)AA brushes with a tailored structure. Next, we discuss biomolecule immobilization methods for P(M)AA brushes, including physical adsorption, covalent binding, and affinity interactions. Finally, typical biomedical applications of P(M)AA brushes are reviewed, and their performance is discussed based on their unique properties. We conclude that P(M)AA brushes are promising biomaterials, and more potential biomedical applications are expected to emerge with the further development of synthetic techniques and increased understanding of their interactions with biological systems.

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

Paskiewicz, Deborah M.; Sichel-Tissot, Rebecca; Karapetrova, Evguenia

The field of oxide electronics has benefited from the wide spectrum of functionalities available to the ABO 3 perovskites, and researchers are now employing defect engineering in single crystalline heterostructures to tailor properties. However, bulk oxide single crystals are not conducive to many types of applications, particularly those requiring mechanical flexibility. Here, we demonstrate the realization of an all-oxide, single-crystalline nanomembrane heterostructure. With a surface-to-volume ratio of 2 × 10 7 , the nanomembranes are fully flexible and can be readily transferred to other materials for handling purposes or for new materials integration schemes. Using in situ synchrotron X-ray scattering,more » we find that the nanomembranes can bond to other host substrates near room temperature and demonstrate coupling between surface reactivity and electromechanical properties in ferroelectric nanomembrane systems. Finally, the synthesis technique described here represents a significant advancement in materials integration and provides a new platform for the development of flexible oxide electronics.« less

Bile salts at the air-water interface: adsorption and desorption.

PubMed

Maldonado-Valderrama, J; Muros-Cobos, J L; Holgado-Terriza, J A; Cabrerizo-Vílchez, M A

2014-08-01

Bile salts (BS) are bio-surfactants which constitute a vital component in the process of fat digestion. Despite the importance of the interfacial properties in their biological role, these have been scarcely studied in the literature. In this work, we present the adsorption-desorption profiles of two BS (NaTC and NaGDC) including dilatational rheology. Findings from this study reveal very different surface properties of NaTC and NaGDC which originate from different complexation properties relevant to the digestion process. Dynamic adsorption curves show higher adsorption rates for NaTC and suggest the existence of various conformational regimes in contrast to NaGDC which presents only one conformational regime. This is corroborated by analysis of the adsorption isotherms and more in detail by the rheological behaviour. Accordingly, the dilatational response at 1Hz displays two maxima of the dilatational modulus for NaTC as a function of bulk concentration, in contrast to NaGDC which displays only one maximum. The desorption profiles reveal that NaTC adopts an irreversibly adsorbed form at high surface coverage whereas NaGDC fully desorbs from the surface within the whole range of concentrations used. Analysis of the adsorption-desorption profiles provides new insight into the surface properties of BS, suggesting a surface complexation of NaTC. This knowledge can be useful since through interfacial engineering we might control the extent of lipolysis providing the basis for the rational design of food products with tailored digestibility. Copyright © 2014 Elsevier B.V. All rights reserved.

Property Control of (Perfluorinated Ionomer)/(Inorganic Oxide) Composites by Tailoring the Nanoscale Morphology

DTIC Science & Technology

1994-06-10

RPeport PROPERTY CONTROL OF ( PERFLUORINATED IONOMER)/(INORGANIC OXIDE) COMPOSITES BY TAILORING THE NANOSCALE MORPHOLOGY Kenneth A. Mauritz and Robert...Concept ......................................... 45 B. [Si0 2 -TiO2 (mixed)]/Nafion Nanocomposites: Sorption of Pre-Mixed Alkoxides...Nanocomposites: Sorption of Pre- Mixed Alkoxides ......................................... 49 A. Experimental Procedure ............................. 49 B

FE Simulation Models for Hot Stamping an Automobile Component with Tailor-Welded High-Strength Steels

NASA Astrophysics Data System (ADS)

Tang, Bingtao; Wang, Qiaoling; Wei, Zhaohui; Meng, Xianju; Yuan, Zhengjun

2016-05-01

Ultra-high-strength in sheet metal parts can be achieved with hot stamping process. To improve the crash performance and save vehicle weight, it is necessary to produce components with tailored properties. The use of tailor-welded high-strength steel is a relatively new hot stamping process for saving weight and obtaining desired local stiffness and crash performance. The simulation of hot stamping boron steel, especially tailor-welded blanks (TWBs) stamping, is more complex and challenging. Information about thermal/mechanical properties of tools and sheet materials, heat transfer, and friction between the deforming material and the tools is required in detail. In this study, the boron-manganese steel B1500HS and high-strength low-alloy steel B340LA are tailor welded and hot stamped. In order to precisely simulate the hot stamping process, modeling and simulation of hot stamping tailor-welded high-strength steels, including phase transformation modeling, thermal modeling, and thermal-mechanical modeling, is investigated. Meanwhile, the welding zone of tailor-welded blanks should be sufficiently accurate to describe thermal, mechanical, and metallurgical parameters. FE simulation model using TWBs with the thickness combination of 1.6 mm boron steel and 1.2 mm low-alloy steel is established. In order to evaluate the mechanical properties of the hot stamped automotive component (mini b-pillar), hardness and microstructure at each region are investigated. The comparisons between simulated results and experimental observations show the reliability of thermo-mechanical and metallurgical modeling strategies of TWBs hot stamping process.

Inducing electric polarization in ultrathin insulating layers

NASA Astrophysics Data System (ADS)

Martinez-Castro, Jose; Piantek, Marten; Persson, Mats; Serrate, David; Hirjibehedin, Cyrus F.

Studies of ultrathin polar oxide films have attracted the interest of researchers for a long time due to their different properties compared to bulk materials. However they present several challenges such as the difficulty in the stabilization of the polar surfaces and the limited success in tailoring their properties. Moreover, recently developed Van der Waals materials have shown that the stacking of 2D-layers trigger new collective states thanks to the interaction between layers. Similarly, interface phenomena emerge in polar oxides, like induced ferroelectricity. This represents a promising way for the creation of new materials with customized properties that differ from those of the isolated layers. Here we present a new approach for the fabrication and study of atomically thin insulating films. We show that the properties of insulating polar layers of sodium chloride (NaCl) can be engineered when they are placed on top of a charge modulated template of copper nitride (Cu2N). STM studies carried out in ultra-high vacuum and at low temperatures over NaCl/Cu2N/Cu(001) show that we are able to build up and stabilize interfaces of polar surface at the limit of one atomic layer showing new properties not present before at the atomic scale.

Aminopropyl-modified magnesium-phyllosilicates: layered solids with tailored interlayer access and reactivity.

PubMed

Ferreira, Ricardo B; da Silva, César R; Pastore, Heloise O

2008-12-16

Despite its wide application, the synthesis of aminopropyl-modified magnesium-phyllosilicates was known only in the case where every silicon atom bore an organic pending group. This paper shows the preparation of aminopropyl-modified talc where tailored amounts of silicon atoms are bound to an aminopropyl group. The decrease in the concentration of the organoamino group leaves a proportional concentration of interlayer SiOH groups that can be used to react with other silylation agents. The amino group reacts with CO2, forming a carbamate functionality; it seems that the presence of this group avoids delamination in water as performed for the parent compound. Bearing in mind that the aminopropyl group can be changed by other groups, the present synthesis strategy demonstrates ways to produce solids with controlled surface properties with interlayer amino and SiOH groups in variable concentrations, allowing formation of several other interlayer functionalities.

Tuning the acid/base properties of nanocarbons by functionalization via amination.

PubMed

Arrigo, Rosa; Hävecker, Michael; Wrabetz, Sabine; Blume, Raoul; Lerch, Martin; McGregor, James; Parrott, Edward P J; Zeitler, J Axel; Gladden, Lynn F; Knop-Gericke, Axel; Schlögl, Robert; Su, Dang Sheng

2010-07-21

The surface chemical properties and the electronic properties of vapor grown carbon nanofibers (VGCNFs) have been modified by treatment of the oxidized CNFs with NH(3). The effect of treatment temperature on the types of nitrogen functionalities introduced was evaluated by synchrotron based X-ray photoelectron spectroscopy (XPS), while the impact of the preparation methods on the surface acid-base properties was investigated by potentiometric titration, microcalorimetry, and zeta potential measurements. The impact of the N-functionalization on the electronic properties was measured by THz-Time Domain spectroscopy. The samples functionalized via amination are characterized by the coexistence of acidic and basic O and N sites. The population of O and N species is temperature dependent. In particular, at 873 K nitrogen is stabilized in substitutional positions within the graphitic structure, as heterocyclic-like moieties. The surface presents heterogeneously distributed and energetically different basic sites. A small amount of strong basic sites gives rise to a differential heat of CO(2) adsorption of 150 kJ mol(-1). However, when functionalization is carried out at 473 K, nitrogen moieties with basic character are introduced and the maximum heat of adsorption is significantly lower, at approximately 90 kJ mol(-1). In the latter sample, energetically different basic sites coexist with acidic oxygen groups introduced during the oxidative step. Under these conditions, a bifunctional acidic and basic surface is obtained with high hydrophilic character. N-functionalization carried out at higher temperature changes the electronic properties of the CNFs as evaluated by THz-TDS. The functionalization procedure presented in this work allows high versatility and flexibility in tailoring the surface chemistry of nanocarbon material to specific needs. This work shows the potential of the N-containing nanocarbon materials obtained via amination in catalysis as well as electronic device materials.

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

Laskin, Julia; Johnson, Grant E.; Prabhakaran, Venkateshkumar

Immobilization of complex molecules and clusters on supports plays an important role in a variety of disciplines including materials science, catalysis and biochemistry. In particular, deposition of clusters on surfaces has attracted considerable attention due to their non-scalable, highly size-dependent properties. The ability to precisely control the composition and morphology of clusters and small nanoparticles on surfaces is crucial for the development of next generation materials with rationally tailored properties. Soft- and reactive landing of ions onto solid or liquid surfaces introduces unprecedented selectivity into surface modification by completely eliminating the effect of solvent and sample contamination on the qualitymore » of the film. The ability to select the mass-to-charge ratio of the precursor ion, its kinetic energy and charge state along with precise control of the size, shape and position of the ion beam on the deposition target makes soft-landing an attractive approach for surface modification. High-purity uniform thin films on surfaces generated using mass-selected ion deposition facilitate understanding of critical interfacial phenomena relevant to catalysis, energy generation and storage, and materials science. Our efforts have been directed toward understanding charge retention by soft-landed metal and metal-oxide cluster ions, which may affect both their structure and reactivity. Specifically, we have examined the effect of the surface on charge retention by both positively and negatively charged cluster ions. We found that the electronic properties of the surface play an important role in charge retention by cluster cations. Meanwhile, the electron binding energy is a key factor determining charge retention by cluster anions. These findings provide the scientific foundation for the rational design of interfaces for advanced catalysts and energy storage devices. Further optimization of electrode-electrolyte interfaces for applications in energy storage and electrocatalysis may be achieved by understanding and controlling the properties of soft-landed cluster ions.« less

Point Defects in Oxides: Tailoring Materials Through Defect Engineering

NASA Astrophysics Data System (ADS)

Tuller, Harry L.; Bishop, Sean R.

2011-08-01

Optimization of electrical, optical, mechanical, and other properties of many advanced, functional materials today relies on precise control of point defects. This article illustrates the progress that has been made in elucidating the often complex equilibria exhibited by many materials by examining two recently well-characterized model systems, TlBr for radiation detection and PrxCe1-xO2-δ, of potential interest in solid-oxide fuel cells. The interplay between material composition, electrical conductivity, and mechanical properties (electrochemomechanics) is discussed, and implications in these relations, for example, enhancing electrical properties through large mechanical strains, are described. The impact of space charge and strain fields at interfaces, particularly important in nanostructure materials, is also emphasized. Key experimental techniques useful in characterizing bulk and surface defects are summarized and reviewed.

Surface functionalization of nanobiomaterials for application in stem cell culture, tissue engineering, and regenerative medicine.

PubMed

Rana, Deepti; Ramasamy, Keerthana; Leena, Maria; Jiménez, Constanza; Campos, Javier; Ibarra, Paula; Haidar, Ziyad S; Ramalingam, Murugan

2016-05-01

Stem cell-based approaches offer great application potential in tissue engineering and regenerative medicine owing to their ability of sensing the microenvironment and respond accordingly (dynamic behavior). Recently, the combination of nanobiomaterials with stem cells has paved a great way for further exploration. Nanobiomaterials with engineered surfaces could mimic the native microenvironment to which the seeded stem cells could adhere and migrate. Surface functionalized nanobiomaterial-based scaffolds could then be used to regulate or control the cellular functions to culture stem cells and regenerate damaged tissues or organs. Therefore, controlling the interactions between nanobiomaterials and stem cells is a critical factor. However, surface functionalization or modification techniques has provided an alternative approach for tailoring the nanobiomaterials surface in accordance to the physiological surrounding of a living cells; thereby, enhancing the structural and functional properties of the engineered tissues and organs. Currently, there are a variety of methods and technologies available to modify the surface of biomaterials according to the specific cell or tissue properties to be regenerated. This review highlights the trends in surface modification techniques for nanobiomaterials and the biological relevance in stem cell-based tissue engineering and regenerative medicine. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:554-567, 2016. © 2016 American Institute of Chemical Engineers.

Impact of Surface Functionalization on the Quantum Coherence of Nitrogen-Vacancy Centers in Nanodiamonds.

PubMed

Ryan, Robert G; Stacey, Alastair; O'Donnell, Kane M; Ohshima, Takeshi; Johnson, Brett C; Hollenberg, Lloyd C L; Mulvaney, Paul; Simpson, David A

2018-04-18

Nanoscale quantum probes such as the nitrogen-vacancy (NV) center in diamonds have demonstrated remarkable sensing capabilities over the past decade as control over fabrication and manipulation of these systems has evolved. The biocompatibility and rich surface chemistry of diamonds has added to the utility of these probes but, as the size of these nanoscale systems is reduced, the surface chemistry of diamond begins to impact the quantum properties of the NV center. In this work, we systematically study the effect of the diamond surface chemistry on the quantum coherence of the NV center in nanodiamonds (NDs) 50 nm in size. Our results show that a borane-reduced diamond surface can on average double the spin relaxation time of individual NV centers in nanodiamonds when compared to thermally oxidized surfaces. Using a combination of infrared and X-ray absorption spectroscopy techniques, we correlate the changes in quantum relaxation rates with the conversion of sp 2 carbon to C-O and C-H bonds on the diamond surface. These findings implicate double-bonded carbon species as a dominant source of spin noise for near surface NV centers. The link between the surface chemistry and quantum coherence indicates that through tailored engineering of the surface, the quantum properties and magnetic sensitivity of these nanoscale systems may approach that observed in bulk diamond.

Fabrication of phosphonic acid films on nitinol nanoparticles by dynamic covalent assembly

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

Quinones, Rosalynn; Garretson, Samantha; Behnke, Grayce

Nitinol (NiTi) nanoparticles are a valuable metal alloy due to many unique properties that allow for medical applications. NiTi nanoparticles have the potential to form nanofluids, which can advance the thermal conductivity of fluids by controlling the surface functionalization through chemical attachment of organic acids to the surface to form self-assembled alkylphosphonate films. In this study, phosphonic functional head groups such as 16-phosphonohexadecanoic acid, octadecylphosphonic acid, and 12-aminododecylphosphonic acid were used to form an ordered and strongly chemically bounded film on the NiTi nanopowder. The surface of the NiTi nanoparticles was modified in order to tailor the chemical and physicalmore » properties to the desired application. The modified NiTi nanoparticles were characterized using infrared spectroscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, and 31P solid-state nuclear magnetic resonance. The interfacial bonding was identified by spectroscopic data suggesting the phosphonic head group adsorbs in a mixed bidentate/monodentate binding motif on the NiTi nanoparticles. Dynamic light scattering and scanning electron microscopy-energy dispersive X-ray spectroscopy revealed the particle sizes. Differential scanning calorimetry was used to examine the phase transitions. Zeta potential determination as a function of pH was examined to investigate the surface properties of charged nanoparticles. In conclusion, the influence of environmental stability of the surface modifications was also assessed.« less

Gelation And Mechanical Response of Patchy Rods

NASA Astrophysics Data System (ADS)

Kazem, Navid; Majidi, Carmel; Maloney, Craig

We perform Brownian Dynamics simulations to study the gelation of suspensions of attractive, rod-like particles. We show that details of the particle-particle interactions can dramatically affect the dynamics of gelation and the structure and mechanics of the networks that form. If the attraction between the rods is perfectly smooth along their length, they will collapse into compact bundles. If the attraction is sufficiently corrugated or patchy, over time, a rigid space spanning network forms. We study the structure and mechanical properties of the networks that form as a function of the fraction of the surface that is allowed to bind. Surprisingly, the structural and mechanical properties are non-monotonic in the surface coverage. At low coverage, there are not a sufficient number of cross-linking sites to form networks. At high coverage, rods bundle and form disconnected clusters. At intermediate coverage, robust networks form. The elastic modulus and yield stress are both non-monotonic in the surface coverage. The stiffest and strongest networks show an essentially homogeneous deformation under strain with rods re-orienting along the extensional axis. Weaker, clumpy networks at high surface coverage exhibit relatively little re-orienting with strong non-affine deformation. These results suggest design strategies for tailoring surface interactions between rods to yield rigid networks with optimal properties. National Science Foundation and the Air Force Office of Scientific Research.

Fabrication of phosphonic acid films on nitinol nanoparticles by dynamic covalent assembly

DOE PAGES

Quinones, Rosalynn; Garretson, Samantha; Behnke, Grayce; ...

2017-09-25

Nitinol (NiTi) nanoparticles are a valuable metal alloy due to many unique properties that allow for medical applications. NiTi nanoparticles have the potential to form nanofluids, which can advance the thermal conductivity of fluids by controlling the surface functionalization through chemical attachment of organic acids to the surface to form self-assembled alkylphosphonate films. In this study, phosphonic functional head groups such as 16-phosphonohexadecanoic acid, octadecylphosphonic acid, and 12-aminododecylphosphonic acid were used to form an ordered and strongly chemically bounded film on the NiTi nanopowder. The surface of the NiTi nanoparticles was modified in order to tailor the chemical and physicalmore » properties to the desired application. The modified NiTi nanoparticles were characterized using infrared spectroscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, and 31P solid-state nuclear magnetic resonance. The interfacial bonding was identified by spectroscopic data suggesting the phosphonic head group adsorbs in a mixed bidentate/monodentate binding motif on the NiTi nanoparticles. Dynamic light scattering and scanning electron microscopy-energy dispersive X-ray spectroscopy revealed the particle sizes. Differential scanning calorimetry was used to examine the phase transitions. Zeta potential determination as a function of pH was examined to investigate the surface properties of charged nanoparticles. In conclusion, the influence of environmental stability of the surface modifications was also assessed.« less

Bioinspired, roughness-induced, water and oil super-philic and super-phobic coatings prepared by adaptable layer-by-layer technique

PubMed Central

Brown, Philip S.; Bhushan, Bharat

2015-01-01

Coatings with specific surface wetting properties are of interest for anti-fouling, anti-fogging, anti-icing, self-cleaning, anti-smudge, and oil-water separation applications. Many previous bioinspired surfaces are of limited use due to a lack of mechanical durability. Here, a layer-by-layer technique is utilized to create coatings with four combinations of water and oil repellency and affinity. An adapted layer-by-layer approach is tailored to yield specific surface properties, resulting in a durable, functional coating. This technique provides necessary flexibility to improve substrate adhesion combined with desirable surface chemistry. Polyelectrolyte binder, SiO2 nanoparticles, and silane or fluorosurfactant layers are deposited, combining surface roughness and necessary chemistry to result in four different coatings: superhydrophilic/superoleophilic, superhydrophobic/superoleophilic, superhydrophobic/superoleophobic, and superhydrophilic/superoleophobic. The superoleophobic coatings display hexadecane contact angles >150° with tilt angles <5°, whilst the superhydrophobic coatings display water contact angles >160° with tilt angles <2°. One coating combines both oleophobic and hydrophobic properties, whilst others mix and match oil and water repellency and affinity. Coating durability was examined through the use of micro/macrowear experiments. These coatings display transparency acceptable for some applications. Fabrication via this novel combination of techniques results in durable, functional coatings displaying improved performance compared to existing work where either durability or functionality is compromised. PMID:26353971

Direct synthesis of antimicrobial coatings based on tailored bi-elemental nanoparticles

NASA Astrophysics Data System (ADS)

Benetti, Giulio; Cavaliere, Emanuele; Canteri, Adalberto; Landini, Giulia; Rossolini, Gian Maria; Pallecchi, Lucia; Chiodi, Mirco; Van Bael, Margriet J.; Winckelmans, Naomi; Bals, Sara; Gavioli, Luca

2017-03-01

Ultrathin coatings based on bi-elemental nanoparticles (NPs) are very promising to limit the surface-related spread of bacterial pathogens, particularly in nosocomial environments. However, tailoring the synthesis, composition, adhesion to substrate, and antimicrobial spectrum of the coating is an open challenge. Herein, we report on a radically new nanostructured coating, obtained by a one-step gas-phase deposition technique, and composed of bi-elemental Janus type Ag/Ti NPs. The NPs are characterized by a cluster-in-cluster mixing phase with metallic Ag nano-crystals embedded in amorphous TiO2 and present a promising antimicrobial activity including also multidrug resistant strains. We demonstrate the flexibility of the method to tune the embedded Ag nano-crystals dimension, the total relative composition of the coating, and the substrate type, opening the possibility of tailoring the dimension, composition, antimicrobial spectrum, and other physical/chemical properties of such multi-elemental systems. This work is expected to significantly spread the range of applications of NPs coatings, not only as an effective tool in the prevention of healthcare-associated infections but also in other technologically relevant fields like sensors or nano-/micro joining.

Structural characteristics of surface-functionalized nitrogen-doped diamond-like carbon films and effective adjustment to cell attachment

NASA Astrophysics Data System (ADS)

Liu, Ai-Ping; Liu, Min; Yu, Jian-Can; Qian, Guo-Dong; Tang, Wei-Hua

2015-05-01

Nitrogen-doped diamond-like carbon (DLC:N) films prepared by the filtered cathodic vacuum arc technology are functionalized with various chemical molecules including dopamine (DA), 3-Aminobenzeneboronic acid (APBA), and adenosine triphosphate (ATP), and the impacts of surface functionalities on the surface morphologies, compositions, microstructures, and cell compatibility of the DLC:N films are systematically investigated. We demonstrate that the surface groups of DLC:N have a significant effect on the surface and structural properties of the film. The activity of PC12 cells depends on the particular type of surface functional groups of DLC:N films regardless of surface roughness and wettability. Our research offers a novel way for designing functionalized carbon films as tailorable substrates for biosensors and biomedical engineering applications. Project supported by the National Natural Science Foundation of China (Grant Nos. 51272237, 51272231, and 51010002) and the China Postdoctoral Science Foundation (Grant Nos. 2012M520063, 2013T60587, and Bsh1201016).

Graded metascreens to enable a new degree of nanoscale light management

PubMed Central

Mohammadi Estakhri, Nasim; Argyropoulos, Christos; Alù, Andrea

2015-01-01

Optical metasurfaces, typically referred to as two-dimensional metamaterials, are arrays of engineered subwavelength inclusions suitably designed to tailor the light properties, including amplitude, phase and polarization state, over deeply subwavelength scales. By exploiting anomalous localized interactions of surface elements with optical waves, metasurfaces can go beyond the functionalities offered by conventional diffractive optical gratings. The innate simplicity of implementation and the distinct underlying physics of their wave–matter interaction distinguish metasurfaces from three-dimensional metamaterials and provide a valuable means of moulding optical waves in the desired manner. Here, we introduce a general approach based on the electromagnetic equivalence principle to develop and synthesize graded, non-periodic metasurfaces to generate arbitrarily prescribed distributions of electromagnetic waves. Graded metasurfaces are realized with a single layer of spatially modulated, electrically polarizable nanoparticles, tailoring the scattering response of the surface with nanoscale resolutions. We discuss promising applications based on the proposed local wave management technique, including the design of ultrathin optical carpet cloaks, alignment-free polarization beam splitters and a novel approach to enable broadband light absorption enhancement in thin-film solar cells. This concept opens up a practical route towards efficient planarized optical structures with potential impact on the integrated nanophotonic technology. PMID:26217059

Surface Coating of Oxide Powders: A New Synthesis Method to Process Biomedical Grade Nano-Composites

PubMed Central

Palmero, Paola; Montanaro, Laura; Reveron, Helen; Chevalier, Jérôme

2014-01-01

Composite and nanocomposite ceramics have achieved special interest in recent years when used for biomedical applications. They have demonstrated, in some cases, increased performance, reliability, and stability in vivo, with respect to pure monolithic ceramics. Current research aims at developing new compositions and architectures to further increase their properties. However, the ability to tailor the microstructure requires the careful control of all steps of manufacturing, from the synthesis of composite nanopowders, to their processing and sintering. This review aims at deepening understanding of the critical issues associated with the manufacturing of nanocomposite ceramics, focusing on the key role of the synthesis methods to develop homogeneous and tailored microstructures. In this frame, the authors have developed an innovative method, named “surface-coating process”, in which matrix oxide powders are coated with inorganic precursors of the second phase. The method is illustrated into two case studies; the former, on Zirconia Toughened Alumina (ZTA) materials for orthopedic applications, and the latter, on Zirconia-based composites for dental implants, discussing the advances and the potential of the method, which can become a valuable alternative to the current synthesis process already used at a clinical and industrial scale. PMID:28788117

Substrate-insensitive atomic layer deposition of plasmonic titanium nitride films

DOE PAGES

Yu, Ing-Song; Cheng, Hsyi-En; Chang, Chun-Chieh; ...

2017-02-06

The plasmonic properties of titanium nitride (TiN) films depend on the type of substrate when using typical deposition methods such as sputtering. We show atomic layer deposition (ALD) of TiN films with very weak dependence of plasmonic properties on the substrate, which also suggests the prediction and evaluation of plasmonic performance of TiN nanostructures on arbitrary substrates under a given deposition condition. Our results also observe that substrates with more nitrogen-terminated (N-terminated) surfaces will have significant impact on the deposition rate as well as the film plasmonic properties. Furthermore, we illustrate that the plasmonic properties of ALD TiN films canmore » be tailored by simply adjusting the deposition and/or post-deposition annealing temperatures. These characteristics and the capability of conformal coating make ALD TiN films on templates ideal for applications that require the fabrication of complex 3D plasmonic nanostructures.« less

Carbon-based sputtered coatings for enhanced chitosan-based films properties

NASA Astrophysics Data System (ADS)

Fernandes, C.; Calderon V., S.; Ballesteros, Lina F.; Cerqueira, Miguel A.; Pastrana, L. M.; Teixeira, José A.; Ferreira, P. J.; Carvalho, S.

2018-03-01

In order to make bio-based packaging materials competitive in comparison to petroleum-based one, some of their properties need to be improved, among which gas permeability is of crucial importance. Thus, in this work, carbon-based coatings were applied on chitosan-based films by radiofrequency reactive magnetron sputtering aiming to improve their barrier properties. Chemical and morphological properties were evaluated in order to determine the effect of the coatings on the chemical structure, surface hydrophobicity and barrier properties of the system. Chemical analysis, performed by electron energy loss spectroscopy and Fourier transform infrared spectroscopy, suggests similar chemical characteristics among all coatings although higher incorporation of hydrogen as the acetylene flux increases was observed. On the other hand, scanning transmission electron microscopy revealed that the porosity of the carbon layer can be tailored by the acetylene flux. More importantly, the chitosan oxygen permeability showed a monotonic reduction as a function of the acetylene flux. This study opens up new opportunities to apply nanostructured coatings on bio-based polymer for enhanced oxygen barrier properties.

Exploring routes to tailor the physical and chemical properties of oxides via doping: an STM study

NASA Astrophysics Data System (ADS)

Nilius, Niklas

2015-08-01

Doping opens fascinating possibilities for tailoring the electronic, optical, magnetic, and chemical properties of oxides. The dopants perturb the intrinsic behavior of the material by generating charge centers for electron transfer into adsorbates, by inducing new energy levels for electronic and optical excitations, and by altering the surface morphology and hence the adsorption and reactivity pattern. Despite a vivid scientific interest, knowledge on doped oxides is limited when compared to semiconductors, which reflects the higher complexity and the insulating nature of many oxides. In fact, atomic-scale studies, aiming at a mechanistic understanding of dopant-related processes, are still scarce. In this article, we review our scanning tunneling microscopy (STM) experiments on thin, crystalline oxide films with a defined doping level. We demonstrate how the impurities alter the surface morphology and produce cationic/anionic vacancies in order to keep the system charge neutral. We discuss how individual dopants can be visualized in the lattice, even if they reside in subsurface layers. By means of STM-conductance and x-ray photoelectron spectroscopy, we determine the electronic impact of dopants, including the energies of their eigen states and local band-bending effects in the host oxide. Electronic transitions between dopant-induced gap states give rise to new optical modes, as detected with STM luminescence spectroscopy. From a chemical perspective, dopants are introduced to improve the redox potential of oxide materials. Electron transfer from Mo-donors, for example, alters the growth behavior of gold and activates O2 molecules on a wide-gap CaO surface. Such results demonstrate the enormous potential of doped oxides in heterogeneous catalysis. Our experiments address the issue of doping from a fundamental viewpoint, posing questions on the lattice position, charge state, and electron-transfer potential of the impurity ions. Whether doped oxides are suitable to catalyze surface reactions needs to be explored in more applied studies in the future.

Curing of Composites: An Integrated Multiscale Process Description Toward Tailored Structures and Properties

DTIC Science & Technology

2004-11-01

surface prox- Experimental studies𔃼-l4 have shown that the ad- imity of the fiber changes the structure of the resin in sorption of an epoxy system... sorption layer to the ith bulk layer, and RdE(i + 1, The adsorbed state exchanges mass with the bulk i) is the rate term of the desorption of epoxy mole...thickness from -y = 0 to a ;5 nonzero value was primarily due to the shift in the 7 contribution to the interphase gradient from that of ad- 40 sorption

The effect of nanoparticle size on in vivo pharmacokinetics and cellular interaction

PubMed Central

Hoshyar, Nazanin; Gray, Samantha; Han, Hongbin; Bao, Gang

2016-01-01

Nanoparticle-based technologies offer exciting new approaches to disease diagnostics and therapeutics. To take advantage of unique properties of nanoscale materials and structures, the size, shape and/or surface chemistry of nanoparticles need to be optimized, allowing their functionalities to be tailored for different biomedical applications. Here we review the effects of nanoparticle size on cellular interaction and in vivo pharmacokinetics, including cellular uptake, biodistribution and circulation half-life of nanoparticles. Important features of nanoparticle probes for molecular imaging and modeling of nanoparticle size effects are also discussed. PMID:27003448

Redox control of ferrocene-based complexes with systematically extended π-conjugated connectors: switchable and tailorable second order nonlinear optics.

PubMed

Wang, Wen-Yong; Ma, Na-Na; Sun, Shi-Ling; Qiu, Yong-Qing

2014-03-14

The studies of geometrical structures, thermal stabilities, redox properties, nonlinear responses and optoelectronic properties have been carried out on a series of novel ferrocenyl (Fc) chromophores with the view of assessing their switchable and tailorable second order nonlinear optics (NLO). The use of a constant Fc donor and a 4,4'-bipyridinium acceptor and varied conjugated bridges makes it possible to systematically determine the contribution of organic connectors to chromophore nonlinear optical activities. The structures reveal that both the reduction reactions and organic connectors have a significant influence on 4,4'-bipyridinium. The potential energy surface maps along with plots of reduced density gradient mirror the thermal stabilities of the Fc-based chromophores. The first and second reductions take place preferentially at the 4,4'-bipyridinium moieties. Significantly, the reduction processes result in the molecular switches with large NLO contrast varying from zero or very small to a large value. Moreover, time-dependent density functional theory results indicate that the absorption peaks are mainly attributed to Fc to 4,4'-bipyridinium charge transfer and the mixture of intramolecular charge transfer within the two respective 4,4'-bipyridinium moieties coupled with interlayer charge transfer between the two 4,4'-bipyridinium moieties. This provides us with comprehensive information on the effect of organic connectors on the NLO properties.

Status and directions of modified tribological surfaces by ion processes

NASA Technical Reports Server (NTRS)

Spalvins, Talivaldis

1988-01-01

An overview is presented of recent advances in modifying contacting surfaces in motion by the various ion assisted surface coating/modification processes to reduce and control tribological failures. The ion assisted coating processes and the surface modification processes offer the greatest potential to custom tailor and optimize the tribological performance. Hard, wear resistant and low shear coatings deposited by the ion assisted processes are discussed. Primarily the recent advances of sputtered MoS2 ion plated Au, Ag, Pb lubricating films and sputtered and ion plated hard, wear resistant TiN, HfN, TiC films are described in terms of structural property performance interrelationships which lead to improved adhesion, cohesion, nucleation, morphological growth, density, film thickness as determined by structural and chemical characterization and frictional and wear behavior. Also, the recent tribological advances using the surface modification processes such as ion implantation, ion beam mixing is discussed with emphasis on the development of lubricous high temperature ceramic surfaces.

Tailoring Mater-Bi properties by the use of a biowaste-derived additive

NASA Astrophysics Data System (ADS)

Cerruti, Pierfrancesco; Santagata, Gabriella; Gomez d'Ayala, Giovanna; Malinconico, Mario; Ambrogi, Veronica; Carfagna, Cosimo; Persico, Paola

2010-06-01

In this work, a polyphenol-containing extract from winery bio-waste (EP) has been used as additive to tailor Mater-Bi properties. EP was able to efficiently modulate both polymer processing and mechanical, thermal and biodegradation properties. EP decreased the melt viscosity, behaved as a Mater-Bi plasticizer and delayed the Mater-Bi crosslinking process occurring upon thermal aging. Finally, the biodisintegration rate of doped Mater-Bi decreased, thus indicating that EP interfered with the microbial digestion of the polymer films.

PPV-Based Conjugated Polymer Nanoparticles as a Versatile Bioimaging Probe: A Closer Look at the Inherent Optical Properties and Nanoparticle-Cell Interactions.

PubMed

Peters, Martijn; Zaquen, Neomy; D'Olieslaeger, Lien; Bové, Hannelore; Vanderzande, Dirk; Hellings, Niels; Junkers, Thomas; Ethirajan, Anitha

2016-08-08

Conjugated polymers have attracted significant interest in the bioimaging field due to their excellent optical properties and biocompatibility. Tailor-made poly(p-phenylenevinylene) (PPV) conjugated polymer nanoparticles (NPs) are in here described. Two different nanoparticle systems using poly[2-methoxy-5-(3',7'-dimethoxyoctyloxy)-1,4-phenylenevinylene] (MDMO-PPV) and a functional statistical copolymer 2-(5'-methoxycarbonylpentyloxy)-5-methoxy-1,4-phenylenevinylene (CPM-MDMO-PPV), containing ester groups on the alkoxy side chains, were synthesized by combining miniemulsion and solvent evaporation processes. The hydrolysis of ester groups into carboxylic acid groups on the CPM-MDMO-PPV NPs surface allows for biomolecule conjugation. The NPs exhibited excellent optical properties with a high fluorescent brightness and photostability. The NPs were in vitro tested as potential fluorescent nanoprobes for studying cell populations within the central nervous system. The cell studies demonstrated biocompatibility and surface charge dependent cellular uptake of the NPs. This study highlights that PPV-derivative based particles are a promising bioimaging probe and can cater potential applications in the field of nanomedicine.

Designed cellulose nanocrystal surface properties for improving barrier properties in polylactide nanocomposites.

PubMed

Espino-Pérez, Etzael; Bras, Julien; Almeida, Giana; Plessis, Cédric; Belgacem, Naceur; Perré, Patrick; Domenek, Sandra

2018-03-01

Nanocomposites are an opportunity to increase the performance of polymer membranes by fine-tuning their morphology. In particular, the understanding of the contribution of the polymer matrix/nanofiller interface to the overall transport properties is key to design membranes with tailored selective and adsorptive properties. In that aim, cellulose nanocrystals (CNC)/polylactide (PLA) nanocomposites were fabricated with chemically designed interfaces, which were ensuring the compatibility between the constituents and impacting the mass transport mechanism. A detailed analysis of the mass transport behaviour of different permeants in CNC/PLA nanocomposites was carried out as a function of their chemical affinity to grafted CNC surfaces. Penetrants (O 2 and cyclohexane), which were found to slightly interact with the constituents of the nanocomposites, provided information on the small tortuosity effect of CNC on diffusive mass transport. The mass transport of water (highly interacting with CNC) and anisole (interacting only with designed CNC surfaces) exhibited non-Fickian, Case II behaviour. The water vapour caused significant swelling of the CNC, which created a preferential pathway for mass transport. CNC surface grafting could attenuate this phenomenon and decrease the water transport rate. Anisole, an aromatic organic vapour, became reversibly trapped at the specifically designed CNC/PLA interface, but without any swelling or creation of an accelerated pathway. This caused the decrease of the overall mass transport rate. The latter finding could open a way to the creation of materials with specifically designed barrier properties by designing nanocomposites interfaces with specific interactions towards permeants. Copyright © 2017 Elsevier Ltd. All rights reserved.

Giant Ferroelectric Polarization in Ultrathin Ferroelectrics via Boundary-Condition Engineering.

PubMed

Xie, Lin; Li, Linze; Heikes, Colin A; Zhang, Yi; Hong, Zijian; Gao, Peng; Nelson, Christopher T; Xue, Fei; Kioupakis, Emmanouil; Chen, Longqing; Schlom, Darrel G; Wang, Peng; Pan, Xiaoqing

2017-08-01

Tailoring and enhancing the functional properties of materials at reduced dimension is critical for continuous advancement of modern electronic devices. Here, the discovery of local surface induced giant spontaneous polarization in ultrathin BiFeO 3 ferroelectric films is reported. Using aberration-corrected scanning transmission electron microscopy, it is found that the spontaneous polarization in a 2 nm-thick ultrathin BiFeO 3 film is abnormally increased up to ≈90-100 µC cm -2 in the out-of-plane direction and a peculiar rumpled nanodomain structure with very large variation in c/a ratios, which is analogous to morphotropic phase boundaries (MPBs), is formed. By a combination of density functional theory and phase-field calculations, it is shown that it is the unique single atomic Bi 2 O 3 - x layer at the surface that leads to the enhanced polarization and appearance of the MPB-like nanodomain structure. This finding clearly demonstrates a novel route to the enhanced functional properties in the material system with reduced dimension via engineering the surface boundary conditions. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cell surface engineering with polyelectrolyte multilayer thin films.

PubMed

Wilson, John T; Cui, Wanxing; Kozlovskaya, Veronika; Kharlampieva, Eugenia; Pan, Di; Qu, Zheng; Krishnamurthy, Venkata R; Mets, Joseph; Kumar, Vivek; Wen, Jing; Song, Yuhua; Tsukruk, Vladimir V; Chaikof, Elliot L

2011-05-11

Layer-by-layer assembly of polyelectrolyte multilayer (PEM) films represents a bottom-up approach for re-engineering the molecular landscape of cell surfaces with spatially continuous and molecularly uniform ultrathin films. However, fabricating PEMs on viable cells has proven challenging owing to the high cytotoxicity of polycations. Here, we report the rational engineering of a new class of PEMs with modular biological functionality and tunable physicochemical properties which have been engineered to abrogate cytotoxicity. Specifically, we have discovered a subset of cationic copolymers that undergoes a conformational change, which mitigates membrane disruption and facilitates the deposition of PEMs on cell surfaces that are tailorable in composition, reactivity, thickness, and mechanical properties. Furthermore, we demonstrate the first successful in vivo application of PEM-engineered cells, which maintained viability and function upon transplantation and were used as carriers for in vivo delivery of PEMs containing biomolecular payloads. This new class of polymeric film and the design strategies developed herein establish an enabling technology for cell transplantation and other therapies based on engineered cells. © 2011 American Chemical Society

Characterization Of Graphene-Ferroelectric Superlattice Hybrid Devices

NASA Astrophysics Data System (ADS)

Yusuf, Mohammed; Du, Xu; Dawber, Matthew

2013-03-01

Ferroelectric materials possess a spontaneous electrical polarization, which can be controlled by an electric field. A good interface between ferroelectric surface and graphene sheets can introduce a new generation of multifunctional devices, in which the ferroelectric material can be used to control the properties of graphene. In our approach, problems encountered in previous efforts to combine ferroelectric/carbon systems are overcome by the use of artificially layered superlattice materials grown in the form of epitaxial thin films. In these materials the phase transition temperature and dielectric response of the material can be tailored, allowing us to avoid polarization screening by surface absorbates, whilst maintaining an atomically smooth surface and optimal charge doping properties. Using ferroelectric PbTiO3/SrTiO3 superlattices, we have shown ultra-low-voltage operation of graphene field effect devices within +/- 1 V at room temperature. The switching of the graphene field effect transistors is characterized by pronounced resistance hysteresis, suitable for ultra-fast non-volatile electronics. Low temperature characterization confirmed that the coercive field required for the ferroelectric domain switching increases significantly with decreasing temperatures. National Science Foundation (NSF) (grant number 1105202)

Improved antifouling properties and selective biofunctionalization of stainless steel by employing heterobifunctional silane-polyethylene glycol overlayers and avidin-biotin technology

PubMed Central

Hynninen, Ville; Vuori, Leena; Hannula, Markku; Tapio, Kosti; Lahtonen, Kimmo; Isoniemi, Tommi; Lehtonen, Elina; Hirsimäki, Mika; Toppari, J. Jussi; Valden, Mika; Hytönen, Vesa P.

2016-01-01

A straightforward solution-based method to modify the biofunctionality of stainless steel (SS) using heterobifunctional silane-polyethylene glycol (silane-PEG) overlayers is reported. Reduced nonspecific biofouling of both proteins and bacteria onto SS and further selective biofunctionalization of the modified surface were achieved. According to photoelectron spectroscopy analyses, the silane-PEGs formed less than 10 Å thick overlayers with close to 90% surface coverage and reproducible chemical compositions. Consequently, the surfaces also became more hydrophilic, and the observed non-specific biofouling of proteins was reduced by approximately 70%. In addition, the attachment of E. coli was reduced by more than 65%. Moreover, the potential of the overlayer to be further modified was demonstrated by successfully coupling biotinylated alkaline phosphatase (bAP) to a silane-PEG-biotin overlayer via avidin-biotin bridges. The activity of the immobilized enzyme was shown to be well preserved without compromising the achieved antifouling properties. Overall, the simple solution-based approach enables the tailoring of SS to enhance its activity for biomedical and biotechnological applications. PMID:27381834

Improved antifouling properties and selective biofunctionalization of stainless steel by employing heterobifunctional silane-polyethylene glycol overlayers and avidin-biotin technology

NASA Astrophysics Data System (ADS)

Hynninen, Ville; Vuori, Leena; Hannula, Markku; Tapio, Kosti; Lahtonen, Kimmo; Isoniemi, Tommi; Lehtonen, Elina; Hirsimäki, Mika; Toppari, J. Jussi; Valden, Mika; Hytönen, Vesa P.

2016-07-01

A straightforward solution-based method to modify the biofunctionality of stainless steel (SS) using heterobifunctional silane-polyethylene glycol (silane-PEG) overlayers is reported. Reduced nonspecific biofouling of both proteins and bacteria onto SS and further selective biofunctionalization of the modified surface were achieved. According to photoelectron spectroscopy analyses, the silane-PEGs formed less than 10 Å thick overlayers with close to 90% surface coverage and reproducible chemical compositions. Consequently, the surfaces also became more hydrophilic, and the observed non-specific biofouling of proteins was reduced by approximately 70%. In addition, the attachment of E. coli was reduced by more than 65%. Moreover, the potential of the overlayer to be further modified was demonstrated by successfully coupling biotinylated alkaline phosphatase (bAP) to a silane-PEG-biotin overlayer via avidin-biotin bridges. The activity of the immobilized enzyme was shown to be well preserved without compromising the achieved antifouling properties. Overall, the simple solution-based approach enables the tailoring of SS to enhance its activity for biomedical and biotechnological applications.

Formation and Properties of Laser-Induced Periodic Surface Structures on Different Glasses.

PubMed

Gräf, Stephan; Kunz, Clemens; Müller, Frank A

2017-08-10

The formation and properties of laser-induced periodic surface structures (LIPSS) was investigated on different technically relevant glasses including fused silica, borosilicate glass, and soda-lime-silicate glass under irradiation of fs-laser pulses characterized by a pulse duration τ = 300 fs and a laser wavelength λ = 1025 nm. For this purpose, LIPSS were fabricated in an air environment at normal incidence with different laser peak fluence, pulse number, and repetition frequency. The generated structures were characterized by using optical microscopy, scanning electron microscopy, focused ion beam preparation and Fast-Fourier transformation. The results reveal the formation of LIPSS on all investigated glasses. LIPSS formation on soda-lime-silicate glass is determined by remarkable melt-formation as an intra-pulse effect. Differences between the different glasses concerning the appearing structures, their spatial period and their morphology were discussed based on the non-linear absorption behavior and the temperature-dependent viscosity. The findings facilitate the fabrication of tailored LIPSS-based surface structures on different technically relevant glasses that could be of particular interest for various applications.

Formation and Properties of Laser-Induced Periodic Surface Structures on Different Glasses

PubMed Central

Kunz, Clemens; Müller, Frank A.

2017-01-01

The formation and properties of laser-induced periodic surface structures (LIPSS) was investigated on different technically relevant glasses including fused silica, borosilicate glass, and soda-lime-silicate glass under irradiation of fs-laser pulses characterized by a pulse duration τ = 300 fs and a laser wavelength λ = 1025 nm. For this purpose, LIPSS were fabricated in an air environment at normal incidence with different laser peak fluence, pulse number, and repetition frequency. The generated structures were characterized by using optical microscopy, scanning electron microscopy, focused ion beam preparation and Fast-Fourier transformation. The results reveal the formation of LIPSS on all investigated glasses. LIPSS formation on soda-lime-silicate glass is determined by remarkable melt-formation as an intra-pulse effect. Differences between the different glasses concerning the appearing structures, their spatial period and their morphology were discussed based on the non-linear absorption behavior and the temperature-dependent viscosity. The findings facilitate the fabrication of tailored LIPSS-based surface structures on different technically relevant glasses that could be of particular interest for various applications. PMID:28796180

Bioorthogonal layer-by-layer encapsulation of pancreatic islets via hyperbranched polymers

PubMed Central

Gattás-Asfura, Kerim M.; Stabler, Cherie L.

2013-01-01

The encapsulation of viable tissues via layer-by-layer polymer assembly provides a versatile platform for cell surface engineering, with nanoscale control over capsule properties. Herein, we report the development of a hyperbranched polymer-based, ultrathin capsule architecture expressing bioorthogonal functionality and tailored physiochemical properties. Random carbodiimide-based condensation of 3,5-dicarboxyphenyl glycineamide on alginate yielded a highly branched polysaccharide with multiple, spatially restricted, and readily functionalizable terminal carboxylate moieties. Poly(ethylene glycol) (PEG) was utilized to link azido end groups to the structured alginate. Together with phosphine functionalized poly(amido amine) (PAMAM) dendrimer, nanoscale layer-by-layer coatings, covalently stabilized via Staudinger ligation, were assembled onto solid surfaces and pancreatic islets. The effects of electrostatic and/or bioorthogonal covalent interlayer interactions on the resulting coating efficiency and stability, as well as pancreatic islet viability and function, were studied. These hyperbranched polymers provide a flexible platform for the formation of covalently stabilized ultrathin coatings on viable cells and tissues. In addition, the hyperbranched nature of the polymers presents a highly functionalized surface capable of bioorthogonal conjugation of additional bioactive or labeling motifs. PMID:24063764

Tailored Voltage Waveforms in an SF6 /O2 discharge: slope asymmetry and its effect on surface nanotexturing of silicon

NASA Astrophysics Data System (ADS)

Fischer, G.; Drahi, E.; Poulain, G.; Bruneau, B.; Johnson, E. V.

2016-09-01

The nanotexturing of the surface of a crystalline silicon (c-Si) wafer for improved photovoltaic performance can be achieved through the use of a SF6 /O2 capacitively coupled reactive ion etching plasma. In this study, we attempt to modify the texturing conditions by taking advantage of slope asymmetries of Tailored Voltage Waveform (TVW) excitation. We show that TVW shapes resembling ``sawtooths'', presenting a large slope asymmetry, induce high ionization asymmetries in the discharge, and that the dominance of this effect strongly depends on both gas mixture and pressure. These asymmetries have been previously observed in other electronegative gas and are due to differing plasma sheath dynamics at powered and grounded electrode in a discharge operating in drift-ambipolar mode. The texturing of c-Si in SF6 /O2 occurs through competing mechanisms, including etching by fluorine radicals and in-situ deposition of micro-masking species. The relative fluxes of etching and passivating species are expected to be strongly varied due to the plasma asymmetry. Morphological and optical characterization of textured c-Si surfaces will give more insight into both the plasma properties and the mechanisms involved in dry nanotexturing. This project has been supported by the French Government in the frame of the program of investment for the future (Programme d'Investissement d'Avenir - ANR-IEED-002-01).

Ultrasonic cavitation erosion-corrosion behavior of friction stir processed stainless steel.

PubMed

Selvam, Karthikeyan; Mandal, Priya; Grewal, Harpreet Singh; Arora, Harpreet Singh

2018-06-01

Cavitation erosion remains the primary cause of material degradation in fluid machinery components operating at high speed. Micro-jets/shock waves caused by implosion of bubbles on material surface results in significant material loss and premature failure of the components. The presence of corrosive medium further exuberates this effect, causing rapid degradation. Here, we demonstrate a novel pathway to control cavitation erosion-corrosion by tailoring the surface properties using submerged friction stir processing (FSP), a severe plastic deformation process. FSP parameters were varied over wide range of strain-rates to generate tailored microstructures. High strain-rate processing resulted in nearly single phase fine grained structure while low strain-rate processing resulted in phase transformation in addition to grain refinement. As-received and processed samples were subjected to ultrasonic cavitation in distilled water as well as in corrosive environment of 3.5% NaCl solution. Individual roles of cavitation erosion, corrosion and their synergistic effects were analyzed. Depending on the microstructure, processed samples showed nearly 4-6 times higher cavitation erosion resistance compared to as-received alloy. Superior cavitation erosion-corrosion resistance of processed samples was attributed to surface strengthening, higher strain-hardening ability and quick passivation kinetics. The results of current study could be potentially transformative in designing robust materials for hydro-dynamic applications. Copyright © 2018 Elsevier B.V. All rights reserved.

Modeling of silicon in femtosecond laser-induced modification regimes: accounting for ambipolar diffusion

NASA Astrophysics Data System (ADS)

Derrien, Thibault J.-Y.; Bulgakova, Nadezhda M.

2017-05-01

During the last decades, femtosecond laser irradiation of materials has led to the emergence of various applications based on functionalization of surfaces at the nano- and microscale. Via inducing a periodic modification on material surfaces (band gap modification, nanostructure formation, crystallization or amorphization), optical and mechanical properties can be tailored, thus turning femtosecond laser to a key technology for development of nanophotonics, bionanoengineering, and nanomechanics. Although modification of semiconductor surfaces with femtosecond laser pulses has been studied for more than two decades, the dynamics of coupling of intense laser light with excited matter remains incompletely understood. In particular, swift formation of a transient overdense electron-hole plasma dynamically modifies optical properties in the material surface layer and induces large gradients of hot charge carriers, resulting in ultrafast charge-transport phenomena. In this work, the dynamics of ultrafast laser excitation of a semiconductor material is studied theoretically on the example of silicon. A special attention is paid to the electron-hole pair dynamics, taking into account ambipolar diffusion effects. The results are compared with previously developed simulation models, and a discussion of the role of charge-carrier dynamics in localization of material modification is provided.

Controlling wetting and self-assembly dynamics by tailored hydrophobic and oleophobic surfaces.

PubMed

Miele, Ermanno; Malerba, Mario; Dipalo, Michele; Rondanina, Eliana; Toma, Andrea; De Angelis, Francesco

2014-06-25

Tailored hydrophobic and oleophobic surfaces are exploited for controlling the wetting behaviour and evaporation process of solution dropped on them. This enables molecules and nano-objects that are dissolved in water or organic solvents to be delivered and arranged in a well-defined 2D layout. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biomedical imaging and therapy with physically and physiologically tailored magnetic nanoparticles

NASA Astrophysics Data System (ADS)

Khandhar, Amit Praful

Magnetic particle imaging (MPI) and magnetic fluid hyperthermia (MFH) are emerging imaging and therapy approaches that have the potential to improve diagnostic safety and disease management of heart disease and cancer - the number 1 and 2 leading causes of deaths in the United States. MPI promises real-time, tomographic and quantitative imaging of superparamagnetic iron oxide nanoparticle (SPION) tracers distributed in vivo, and is targeted to offer a safer angiography alternative for its first clinical application. MFH uses ac-fields to dissipate heat from SPIONs that can be delivered locally to promote hyperthermia therapy (~42°C) in cancer cells. Both technologies use safe radiofrequency magnetic fields to exploit the fundamental magnetic relaxation properties of superparamagnetic iron oxide nanoparticles (SPIONs), which must be tailored for optimal imaging in the case of MPI, and maximum hyperthermia potency in the case of MFH. Furthermore, the magnetic core and shell of SPIONs are both central to the optimization process; the shell, in particular, bridges the translational gap between the optimized core and its safe and effective use in the physiological environment. Unfortunately, existing SPIONs that were originally designed as MRI contrast agents lack the basic physical properties that enable the clinical translation of MPI and MFH. In this work, the core and shell of monodisperse SPIONs were optimized in concert to accomplish two equally important objectives: (1) biocompatibility, and (2) MPI and MFH efficacy of SPIONs in physiological environments. Critically, it was found that the physical and physiological responses of SPIONs are coupled, and impacting one can have consequences on the other. It was shown that the poly(ethylene glycol) (PEG)-based shell when properly optimized reduced protein adsorption to SPION surface and phagocytic uptake in macrophages - both prerequisites for designing long-circulating SPIONs. In MPI, tailoring the surface coating reduced protein adsorption and improved colloidal stability, which were critical in retaining the magnetization relaxation properties of the SPIONs. The improvements in surface coatings enabled the use of larger SPION cores (> 20 nm core diameter), which were used to demonstrate benchmark-imaging performance in some of the world's first MPI scanners at Philips Medical Imaging and University of California, Berkeley. In MFH, it was shown for the first time that optimization of heat loss from SPIONs (W/g) is possible by tailoring the core size and size distribution for the given ac-field conditions. Biodistribution and blood circulation studies in mice showed that SPIONs accumulated primarily in the liver and spleen with minimal renal involvement, and demonstrated gradual clearance. Circulation time was evaluated using the MPI signal detected over time in blood, which offered insight on the relevant circulation time for angiography applications. In comparison with carboxy-dextran coated ResovistRTM SPIONs, the PEG-coated SPIONs developed in this work circulated substantially longer; furthermore, reducing the hydrodynamic diameter showed a 4.5x improvement in blood half-life. The work presented in this thesis demonstrates that the combined effort in optimizing the core and shell properties of SPIONs enhances biocompatibility and efficacy, with the in vivo studies providing critical feedback on the success (or failure) of the optimization process. Future work will entail designing functionalized SPIONs for targeting specific disease sites, which will further enable the molecular level diagnosis and therapy of diseases.

Supercapacitor Electrode Materials from Highly Porous Carbon Nanofibers with Tailored Pore Distributions

NASA Astrophysics Data System (ADS)

Chathurika Abeykoon, Nimali

Environmental and human health risks associated with the traditional methods of energy production (e.g., oil and gas) and intermittency and uncertainty of renewable sources (e.g., solar and wind) have led to exploring effective and alternative energy sources to meet the growing energy demands. Electricity based on energy storage devices are the most promising solutions for realization of these objectives. Among the energy storage devices, electrochemical double layer capacitors (EDLCs) or supercapacitors have become an attractive research interest due to their outstanding performance, especially high power densities, long cycle life and rapid charge and discharge times, which enables them to utilize in many applications including consumer electronics and transportation, where high power is needed. However, low energy density of supercapacitors is a major obstacle to compete with the commercially existing high energy density energy storage device such as batteries. The fabrication of advanced electrodes materials with very high surface area from novel precursors and utilization of electrolytes with higher operating voltages are essential to enhance energy density of supercapacitors. In this work, carbon nanofibers (CNFs) from different polymer precursors with new fabrication techniques are explored to develop highly porous carbon with tailored pore distributions to match with employed ionic liquid electrolytes (which possess high working voltages), to realize high energy storage capability. Novel electrode materials derived from electrospun immiscible polymer blends and synthesized copolymers and terpolymers were described. Pore distributions of CNFs were tailored by varying the composition of polymers in immiscible blends or varying the monomer ratios of copolymer or terpolymers. Chapter 1 gives the detailed introduction of supercapacitors including history and storage principle of EDLCs, fabrication of carbon nanofiber based electrodes and electrolytes employed for EDLCs. It also explains the necessity and the advantages of tailored high surface area nanofibers as an electrode materials for supercapacitors. Chapter 2 describes the preparation of high surface area carbon nanofibers using polymer blends containing PAN and PMMA and introduces an effective and simple strategy to improve the surface area of CNFs by using a sacrificial polymer, PMMA. Chapter 3 describes blending of high fractional free volume polymer, 6FDA-DAM: DABA (3:2) into PBI to increase surface area and by using the higher etch rate of 6FDA-DAM: DABA in the blend to optimize pore distribution of CNFs. Chapter 4 introduces a novel approach to increase surface area of CNFs without any physical or chemical activation by using an in situ porogen containing copolymer P(AN-co-IA). The concept developed here avoids unnecessary and complex extra activation steps when fabricating carbon nanofibers which leads to lower char yield and uncontrollable pore sizes. Chapter 5 describes enhancement of surface area by using terpolymer P(AN-VIM-IA) to develop a new precursor. This approach is further advantageous since terpolymer can combine superior electrochemical properties of homopolymer, PAN and P(AN- co-IA) and P(AN-co-VIM). Chapter 6 describes the use of commercially available small molecule compatibilizer 2-MI to tailor pore architecture of carbon fiber derived from the immiscible blend of PBI/6FDD to match with the ion sizes of ionic liquid electrolytes thereby increasing the surface area of the CNFs that is accessible to electrolytes.

Hydroxide-catalyzed bonding

NASA Technical Reports Server (NTRS)

Gwo, Dz-Hung (Inventor)

2003-01-01

A method of bonding substrates by hydroxide-catalyzed hydration/dehydration involves applying a bonding material to at least one surface to be bonded, and placing the at least one surface sufficiently close to another surface such that a bonding interface is formed between them. A bonding material of the invention comprises a source of hydroxide ions, and may optionally include a silicate component, a particulate filling material, and a property-modifying component. Bonding methods of the invention reliably and reproducibly provide bonds which are strong and precise, and which may be tailored according to a wide range of possible applications. Possible applications for bonding materials of the invention include: forming composite materials, coating substrates, forming laminate structures, assembly of precision optical components, and preparing objects of defined geometry and composition. Bonding materials and methods of preparing the same are also disclosed.

Temperature and Microstructural Effects on the Superconducting Properties of Niobium Thin Films

DOE PAGES

Beebe, Melissa R.; Valente-Feliciano, Anne -Marie; Beringer, Douglas B.; ...

2016-11-23

Here, superconducting thin films have a wide range of dc and RF applications, from detectors to superconducting radio frequency. Amongst the most used materials, niobium (Nb) has the highest critical temperature (TC) and highest lower critical field (HC1) of the elemental superconductors and can be deposited on a variety of substrates, making Nb thin films very appealing for such applications. Here, we present temperature-dependent dc studies on the critical temperature and critical fields of Nb thin films grown on copper and r-plane sapphire surfaces. Additionally, we correlate the dc superconducting properties of these films with their microstructure, which allows formore » the possibility of tailoring future films for a specific application.« less

Surface modification of NiTi by plasma based ion implantation for application in harsh environments

NASA Astrophysics Data System (ADS)

Oliveira, R. M.; Fernandes, B. B.; Carreri, F. C.; Gonçalves, J. A. N.; Ueda, M.; Silva, M. M. N. F.; Silva, M. M.; Pichon, L.; Camargo, E. N.; Otubo, J.

2012-12-01

The substitution of conventional components for NiTi in distinct devices such as actuators, valves, connectors, stents, orthodontic arc-wires, e.g., usually demands some kind of treatment to be performed on the surface of the alloy. A typical case is of biomaterials made of NiTi, in which the main drawback is the Ni out-diffusion, an issue that has been satisfactorily addressed by plasma based ion implantation (PBII). Even though PBII can tailor selective surface properties of diverse materials, usually, only thin modified layers are attained. When NiTi alloys are to be used in the harsh space environment, as is the case of devices designed to remotely release the solar panels and antenna arrays of satellites, e.g., superior mechanical and tribological properties are demanded. For this case the thickness of the modified layer must be larger than the one commonly achieved by conventional PBII. In this paper, new nitrogen PBII set up was used to treat samples of NiTi in moderate temperature of 450 °C, with negative voltage pulses of 7 kV/250 Hz/20 μs, in a process lasting 1 h. A rich nitrogen atomic concentration of 85 at.% was achieved on the near surface and nitrogen diffused at least for 11 μm depth. Tribological properties as well as corrosion resistance were evaluated.

Current Approach in Surface Plasmons for Thin Film and Wire Array Solar Cell Applications

PubMed Central

Zhou, Keya; Guo, Zhongyi; Liu, Shutian; Lee, Jung-Ho

2015-01-01

Surface plasmons, which exist along the interface of a metal and a dielectric, have been proposed as an efficient alternative method for light trapping in solar cells during the past ten years. With unique properties such as superior light scattering, optical trapping, guide mode coupling, near field concentration, and hot-electron generation, metallic nanoparticles or nanostructures can be tailored to a certain geometric design to enhance solar cell conversion efficiency and to reduce the material costs. In this article, we review current approaches on different kinds of solar cells, such as crystalline silicon (c-Si) and amorphous silicon (a-Si) thin film solar cells, organic solar cells, nanowire array solar cells, and single nanowire solar cells. PMID:28793457

Tailoring of the Perpendicular Magnetization Component in Ferromagnetic Films on a Vicinal Substrate

NASA Astrophysics Data System (ADS)

Stupakiewicz, A.; Maziewski, A.; Matlak, K.; Spiridis, N.; Ślęzak, M.; Ślęzak, T.; Zajac, M.; Korecki, J.

2008-11-01

We have engineered the magnetic properties of 1 8 nm Co films epitaxially grown on an Au-buffered bifacial W(110)/W(540) single crystal. The surface of Au/W(110) was atomically flat, whereas the Au/W(540) followed the morphology of the vicinal W surface, showing a regular array of monoatomic steps. For Co grown on Au/W(540), the existence of the out-of-plane magnetization component extended strongly to a thickness d of about 8 nm, which was accompanied by an anomalous increase of the out-of-plane switching field with increasing d. In addition, the process of up-down magnetization switching could be realized with both a perpendicular and in-plane external magnetic field.

Tuning the morphology of silver nanostructures photochemically coated on glass substrates: an effective approach to large-scale functional surfaces

NASA Astrophysics Data System (ADS)

Zaier, Mohamed; Vidal, Loic; Hajjar-Garreau, Samar; Bubendorff, Jean-Luc; Balan, Lavinia

2017-03-01

This paper reports on a simple and environmentally friendly photochemical process capable of generating nano-layers (8-22 nm) of silver nanostructures directly onto glass surfaces. This approach opens the way to large-scale functionalized surfaces with plasmonic properties through a single light-induced processing. Thus, Ag nanostructures top-coated were obtained through photo-reduction, at room temperature, of a photosensitive formulation containing a metal precursor, free from extra toxic stabilizers or reducing agents. The reactive formulation was confined between two glass slides and exposed to a continuous near-UV source. In this way, stable silver nano-layers can be generated directly on the substrate with a very good control of the morphology of as-synthesized nanostructures that allows tailoring the optical properties of the coated layers. The position and width of the corresponding surface plasmon resonance bands can be adjusted over a broad spectral window. By extension, this low-cost and easy-to-apply process can also be used to coat ultra thin layers of metal nanostructures on a variety of substrates. The possibility of controlling of nanostructures shape should achieve valuable developments in many fields, as diverse as plasmonics, surface enhanced Raman scattering, nano-electronic circuitry, or medical devices.

Confinement properties of 2D porous molecular networks on metal surfaces

NASA Astrophysics Data System (ADS)

Müller, Kathrin; Enache, Mihaela; Stöhr, Meike

2016-04-01

Quantum effects that arise from confinement of electronic states have been extensively studied for the surface states of noble metals. Utilizing small artificial structures for confinement allows tailoring of the surface properties and offers unique opportunities for applications. So far, examples of surface state confinement include thin films, artificial nanoscale structures, vacancy and adatom islands, self-assembled 1D chains, vicinal surfaces, quantum dots and quantum corrals. In this review we summarize recent achievements in changing the electronic structure of surfaces by adsorption of nanoporous networks whose design principles are based on the concepts of supramolecular chemistry. Already in 1993, it was shown that quantum corrals made from Fe atoms on a Cu(1 1 1) surface using single atom manipulation with a scanning tunnelling microscope confine the Shockley surface state. However, since the atom manipulation technique for the construction of corral structures is a relatively time consuming process, the fabrication of periodic two-dimensional (2D) corral structures is practically impossible. On the other side, by using molecular self-assembly extended 2D porous structures can be achieved in a parallel process, i.e. all pores are formed at the same time. The molecular building blocks are usually held together by non-covalent interactions like hydrogen bonding, metal coordination or dipolar coupling. Due to the reversibility of the bond formation defect-free and long-range ordered networks can be achieved. However, recently also examples of porous networks formed by covalent coupling on the surface have been reported. By the choice of the molecular building blocks, the dimensions of the network (pore size and pore to pore distance) can be controlled. In this way, the confinement properties of the individual pores can be tuned. In addition, the effect of the confined state on the hosting properties of the pores will be discussed in this review article.

Confinement properties of 2D porous molecular networks on metal surfaces.

PubMed

Müller, Kathrin; Enache, Mihaela; Stöhr, Meike

2016-04-20

Quantum effects that arise from confinement of electronic states have been extensively studied for the surface states of noble metals. Utilizing small artificial structures for confinement allows tailoring of the surface properties and offers unique opportunities for applications. So far, examples of surface state confinement include thin films, artificial nanoscale structures, vacancy and adatom islands, self-assembled 1D chains, vicinal surfaces, quantum dots and quantum corrals. In this review we summarize recent achievements in changing the electronic structure of surfaces by adsorption of nanoporous networks whose design principles are based on the concepts of supramolecular chemistry. Already in 1993, it was shown that quantum corrals made from Fe atoms on a Cu(1 1 1) surface using single atom manipulation with a scanning tunnelling microscope confine the Shockley surface state. However, since the atom manipulation technique for the construction of corral structures is a relatively time consuming process, the fabrication of periodic two-dimensional (2D) corral structures is practically impossible. On the other side, by using molecular self-assembly extended 2D porous structures can be achieved in a parallel process, i.e. all pores are formed at the same time. The molecular building blocks are usually held together by non-covalent interactions like hydrogen bonding, metal coordination or dipolar coupling. Due to the reversibility of the bond formation defect-free and long-range ordered networks can be achieved. However, recently also examples of porous networks formed by covalent coupling on the surface have been reported. By the choice of the molecular building blocks, the dimensions of the network (pore size and pore to pore distance) can be controlled. In this way, the confinement properties of the individual pores can be tuned. In addition, the effect of the confined state on the hosting properties of the pores will be discussed in this review article.

The microflow behavior and interphase characterization of fiber-reinforced polymer composites

NASA Astrophysics Data System (ADS)

Foley, Maureen Elizabeth

There is typically a trade off that takes place when designing a composite part for ballistic purposes. Structural strength requirements typically call for less than 1% voids with strong adhesion between the fiber and matrix whereas for ballistic applications, such as spall plates for body armor where energy absorbing properties are paramount, the composites are usually resin lean and have weaker fiber matrix interphases. The energy absorbing properties of a composite can be tailored through the sizings applied to the fiber or through control of the resin infiltration of the composite part. The goal of this research was two pronged. The first was to develop a transverse microflow model that could be used to predict the microflow within a tow assuming it is completely surrounded by resin. The models developed consider the capillary pressure on the flow front, which is typically ignored by literature models, as the main driving force for transverse flow into the fiber bundles. This capillary pressure is a function of the surface properties of the resin and fiber and by tailoring these properties one can control the microflow of the resin. The dynamic model, which takes into account the fiber radius, fiber volume fraction, fiber count, resin contact angle with the fiber and the resin surface tension, was used to study the effects of tow count, fiber volume fraction and contact angle on the infiltration time. The second goal of this research was the development of an interphase characterization methodology that can be used to evaluate the interphase properties, using the Dynamic Interphase Loading Apparatus (DILA), once the fiber preforms are infiltrated. The DILA is a unique piece of equipment that allows one to pushout a fiber from a thin composite slice while recording the resulting force and displacement. The interphase characterization process includes indenter selection, sample and test configuration design, test parameters, post test validation and data reduction. This process was used to evaluate glass fiber reinforced epoxy and vinyl ester systems under quasi-static and cyclic loading as examples of the DILA capabilities.

Metal segregation in hierarchically structured cathode materials for high-energy lithium batteries

DOE PAGES

Lin, Feng; Xin, Huolin L.; Nordlund, Dennis; ...

2016-01-11

Controlling surface and interfacial properties of battery materials is key to improving performance in rechargeable Li-ion devices. Surface reconstruction from a layered to a rock salt structure in metal oxide cathode materials is commonly observed and results in poor high-voltage cycling performance, impeding attempts to improve energy density. Hierarchically structured LiNi 0.4Mn 0.4Co 0.2O 2 (NMC-442) spherical powders, made by spray pyrolysis, exhibit local elemental distribution gradients that deviate from the global NMC-442 composition; specifically, they are Ni-rich and Mn-poor at particle surfaces. These materials demonstrate improved Coulombic efficiencies, discharge capacities, and high-voltage capacity retention in lithium half-cell configurations. Themore » subject powders show superior resistance against surface reconstruction due to the tailored surface chemistry, compared to conventional NMC-442 materials. This paves the way towards the development of a new generation of robust and stable high-energy NMC cathodes for Li-ion batteries.« less

Measuring binding kinetics of aromatic thiolated molecules with nanoparticles via surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Devetter, Brent M.; Mukherjee, Prabuddha; Murphy, Catherine J.; Bhargava, Rohit

2015-05-01

Colloidal plasmonic nanomaterials, consisting of metals such as gold and silver, are excellent candidates for advanced optical probes and devices, but precise control over surface chemistry is essential for realizing their full potential. Coupling thiolated (R-SH) molecules to nanoprobe surfaces is a convenient and established route to tailor surface properties. The ability to dynamically probe and monitor the surface chemistry of nanoparticles in solution is essential for rapidly manufacturing spectroscopically tunable nanoparticles. In this study, we report the development of surface-enhanced Raman spectroscopy (SERS) as a method to monitor the kinetics of gold-thiolate bond formation on colloidal gold nanoparticles. A theoretical model combining SERS enhancement with the Beer-Lambert law is proposed to explain ensemble scattering and absorption effects in colloids during chemisorption. In order to maximize biological relevance and signal reproducibility, experiments used to validate the model focused on maintaining nanoparticle stability after the addition of water-soluble aromatic thiolated molecules. Our results indicate that ligand exchange on gold nanoparticles follow a first-order Langmuir adsorption model with rate constants on the order of 0.01 min-1. This study demonstrates an experimental spectroscopic method and theoretical model for monitoring binding kinetics that may prove useful for designing novel probes.Colloidal plasmonic nanomaterials, consisting of metals such as gold and silver, are excellent candidates for advanced optical probes and devices, but precise control over surface chemistry is essential for realizing their full potential. Coupling thiolated (R-SH) molecules to nanoprobe surfaces is a convenient and established route to tailor surface properties. The ability to dynamically probe and monitor the surface chemistry of nanoparticles in solution is essential for rapidly manufacturing spectroscopically tunable nanoparticles. In this study, we report the development of surface-enhanced Raman spectroscopy (SERS) as a method to monitor the kinetics of gold-thiolate bond formation on colloidal gold nanoparticles. A theoretical model combining SERS enhancement with the Beer-Lambert law is proposed to explain ensemble scattering and absorption effects in colloids during chemisorption. In order to maximize biological relevance and signal reproducibility, experiments used to validate the model focused on maintaining nanoparticle stability after the addition of water-soluble aromatic thiolated molecules. Our results indicate that ligand exchange on gold nanoparticles follow a first-order Langmuir adsorption model with rate constants on the order of 0.01 min-1. This study demonstrates an experimental spectroscopic method and theoretical model for monitoring binding kinetics that may prove useful for designing novel probes. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr01006c

Possible alternatives to critical elements in coatings for extreme applications

NASA Astrophysics Data System (ADS)

Grilli, Maria Luisa; Valerini, Daniele; Piticescu, Radu Robert; Bellezze, Tiziano; Yilmaz, Mehmet; Rinaldi, Antonio; Cuesta-López, Santiago; Rizzo, Antonella

2018-03-01

Surface functionalisation and protection have been used since a long time for improving specific properties of materials such as lubrication, water repellence, brightness, and for increasing durability of objects and tools. Among the different kinds of surface treatments used to achieve the required properties, the use of coatings is fundamental to guarantee substrate durability in harsh environments. Extreme working conditions of temperature, pressure, irradiation, wear and corrosion occur in several applications, thus very often requiring bulk material protection by means of coatings. In this study, three main classes of coatings used in extreme conditions are considered: i) hard and superhard coatings for application in machining tools, ii) coatings for high temperatures (thermal barrier coatings), and iii) coatings against corrosion. The presence of critical elements in such coatings (Cr, Y, W, Co, etc.) is analysed and the possibility to use CRMs-free substitutes is reviewed. The role of multilayers and nanocomposites in tailoring coating performances is also discussed for thermal barrier and superhard coatings.

Fabrication of near-net shape graphite/magnesium composites for large mirrors

NASA Astrophysics Data System (ADS)

Wendt, Robert; Misra, Mohan

1990-10-01

Successful development of space-based surveillance and laser systems will require large precision mirrors which are dimensionally stable under thermal, static, and dynamic (i.e., structural vibrations and retargeting) loading conditions. Among the advanced composites under consideration for large space mirrors, graphite fiber reinforced magnesium (Gr/Mg) is an ideal candidate material that can be tailored to obtain an optimum combination of properties, including a high modulus of elasticity, zero coefficient of thermal expansion, low density, and high thermal conductivity. In addition, an innovative technique, combining conventional filament winding and vacuum casting has been developed to produce near-net shape Gr/Mg composites. This approach can significantly reduce the cost of fabricating large mirrors by decreasing required machining. However, since Gr/Mg cannot be polished to a reflective surface, plating is required. This paper will review research at Martin Marietta Astronautics Group on Gr/Mg mirror blank fabrication and measured mechanical and thermal properties. Also, copper plating and polishing methods, and optical surface characteristics will be presented.

New Perspectives on Biomedical Applications of Iron Oxide Nanoparticles.

PubMed

Magro, Massimiliano; Baratella, Davide; Bonaiuto, Emanuela; de A Roger, Jessica; Vianello, Fabio

2018-02-12

Iron oxide nanomaterials are considered promising tools for improved therapeutic efficacy and diagnostic applications in biomedicine. Accordingly, engineered iron oxide nanomaterials are increasingly proposed in biomedicine, and the interdisciplinary researches involving physics, chemistry, biology (nanotechnology) and medicine have led to exciting developments in the last decades. The progresses of the development of magnetic nanoparticles with tailored physico-chemical and surface properties produced a variety of clinically relevant applications, spanning from magnetic resonance imaging (MRI), drug delivery, magnetic hyperthermia, to in vitro diagnostics. Notwithstanding the wellknown conventional synthetic procedures and their wide use, along with recent advances in the synthetic methods open the door to new generations of naked iron oxide nanoparticles possessing peculiar surface chemistries, suitable for other competitive biomedical applications. New abilities to rationally manipulate iron oxides and their physical, chemical, and biological properties, allow the emersion of additional possibilities for designing novel nanomaterials for theranostic applications. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Single-Crystalline SrRuO 3 Nanomembranes: A Platform for Flexible Oxide Electronics

DOE PAGES

Paskiewicz, Deborah M.; Sichel-Tissot, Rebecca; Karapetrova, Evguenia; ...

2016-12-11

The field of oxide electronics has benefited from the wide spectrum of functionalities available to the ABO 3 perovskites, and researchers are now employing defect engineering in single crystalline heterostructures to tailor properties. However, bulk oxide single crystals are not conducive to many types of applications, particularly those requiring mechanical flexibility. Here, we demonstrate the realization of an all-oxide, single-crystalline nanomembrane heterostructure. With a surface-to-volume ratio of 2 × 10 7 , the nanomembranes are fully flexible and can be readily transferred to other materials for handling purposes or for new materials integration schemes. Using in situ synchrotron X-ray scattering,more » we find that the nanomembranes can bond to other host substrates near room temperature and demonstrate coupling between surface reactivity and electromechanical properties in ferroelectric nanomembrane systems. Finally, the synthesis technique described here represents a significant advancement in materials integration and provides a new platform for the development of flexible oxide electronics.« less

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

Elimelech, Orian; Liu, Jing; Plonka, Anna M.

Doping of nanocrystals (NCs) is a key, yet underexplored, approach for tuning of the electronic properties of semiconductors. An important route for doping of NCs is by vacancy formation. The size and concentration dependence of doping was studied in copper(I) sulfide (Cu2S) NCs through a redox reaction with iodine molecules (I2), which formed vacancies accompanied by a localized surface plasmon response. X-ray spectroscopy and diffraction reveal transformation from Cu2S to Cu-depleted phases, along with CuI formation. Greater reaction efficiency was observed for larger NCs. This behavior is attributed to interplay of the vacancy formation energy, which decreases for smaller sizedmore » NCs, and the growth of CuI on the NC surface, which is favored on well-defined facets of larger NCs. This doping process allows tuning of the plasmonic properties of a semiconductor across a wide range of plasmonic frequencies by varying the size of NCs and the concentration of iodine. Controlled vacancy doping of NCs may be used to tune and tailor semiconductors for use in optoelectronic applications.« less

LPWA using supersonic gas jet with tailored density profile

NASA Astrophysics Data System (ADS)

Kononenko, O.; Bohlen, S.; Dale, J.; D'Arcy, R.; Dinter, M.; Erbe, J. H.; Indorf, G.; di Lucchio, L.; Goldberg, L.; Gruse, J. N.; Karstensen, S.; Libov, V.; Ludwig, K.; Martinez de La Ossa, A.; Marutzky, F.; Niroula, A.; Osterhoff, J.; Quast, M.; Schaper, L.; Schwinkendorf, J.-P.; Streeter, M.; Tauscher, G.; Weichert, S.; Palmer, C.; Horbatiuk, Taras

2016-10-01

Laser driven plasma wakefield accelerators have been explored as a potential compact, reproducible source of relativistic electron bunches, utilising an electric field of many GV/m. Control over injection of electrons into the wakefield is of crucial importance in producing stable, mono-energetic electron bunches. Density tailoring of the target, to control the acceleration process, can also be used to improve the quality of the bunch. By using gas jets to provide tailored targets it is possible to provide good access for plasma diagnostics while also producing sharp density gradients for density down-ramp injection. OpenFOAM hydrodynamic simulations were used to investigate the possibility of producing tailored density targets in a supersonic gas jet. Particle-in-cell simulations of the resulting density profiles modelled the effect of the tailored density on the properties of the accelerated electron bunch. Here, we present the simulation results together with preliminary experimental measurements of electron and x-ray properties from LPWA experiments using gas jet targets and a 25 TW, 25 fs Ti:Sa laser system at DESY.

FWP executive summaries, Basic Energy Sciences Materials Sciences Programs (SNL/NM)

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

Samara, G.A.

1997-05-01

The BES Materials Sciences Program has the central theme of Scientifically Tailored Materials. The major objective of this program is to combine Sandia`s expertise and capabilities in the areas of solid state sciences, advanced atomic-level diagnostics and materials synthesis and processing science to produce new classes of tailored materials as well as to enhance the properties of existing materials for US energy applications and for critical defense needs. Current core research in this program includes the physics and chemistry of ceramics synthesis and processing, the use of energetic particles for the synthesis and study of materials, tailored surfaces and interfacesmore » for materials applications, chemical vapor deposition sciences, artificially-structured semiconductor materials science, advanced growth techniques for improved semiconductor structures, transport in unconventional solids, atomic-level science of interfacial adhesion, high-temperature superconductors, and the synthesis and processing of nano-size clusters for energy applications. In addition, the program includes the following three smaller efforts initiated in the past two years: (1) Wetting and Flow of Liquid Metals and Amorphous Ceramics at Solid Interfaces, (2) Field-Structured Anisotropic Composites, and (3) Composition-Modulated Semiconductor Structures for Photovoltaic and Optical Technologies. The latter is a joint effort with the National Renewable Energy Laboratory. Separate summaries are given of individual research areas.« less

A multifunctional biphasic water splitting catalyst tailored for integration with high-performance semiconductor photoanodes

NASA Astrophysics Data System (ADS)

Yang, Jinhui; Cooper, Jason K.; Toma, Francesca M.; Walczak, Karl A.; Favaro, Marco; Beeman, Jeffrey W.; Hess, Lucas H.; Wang, Cheng; Zhu, Chenhui; Gul, Sheraz; Yano, Junko; Kisielowski, Christian; Schwartzberg, Adam; Sharp, Ian D.

2017-03-01

Artificial photosystems are advanced by the development of conformal catalytic materials that promote desired chemical transformations, while also maintaining stability and minimizing parasitic light absorption for integration on surfaces of semiconductor light absorbers. Here, we demonstrate that multifunctional, nanoscale catalysts that enable high-performance photoelectrochemical energy conversion can be engineered by plasma-enhanced atomic layer deposition. The collective properties of tailored Co3O4/Co(OH)2 thin films simultaneously provide high activity for water splitting, permit efficient interfacial charge transport from semiconductor substrates, and enhance durability of chemically sensitive interfaces. These films comprise compact and continuous nanocrystalline Co3O4 spinel that is impervious to phase transformation and impermeable to ions, thereby providing effective protection of the underlying substrate. Moreover, a secondary phase of structurally disordered and chemically labile Co(OH)2 is introduced to ensure a high concentration of catalytically active sites. Application of this coating to photovoltaic p+n-Si junctions yields best reported performance characteristics for crystalline Si photoanodes.

Adsorption Properties of Lignin-derived Activated Carbon Fibers (LACF)

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

Contescu, Cristian I.; Gallego, Nidia C.; Thibaud-Erkey, Catherine

The object of this CRADA project between Oak Ridge National Laboratory (ORNL) and United Technologies Research Center (UTRC) is the characterization of lignin-derived activated carbon fibers (LACF) and determination of their adsorption properties for volatile organic compounds (VOC). Carbon fibers from lignin raw materials were manufactured at Oak Ridge National Laboratory (ORNL) using the technology previously developed at ORNL. These fibers were physically activated at ORNL using various activation conditions, and their surface area and pore-size distribution were characterized by gas adsorption. Based on these properties, ORNL did down-select five differently activated LACF materials that were delivered to UTRC formore » measurement of VOC adsorption properties. UTRC used standard techniques based on breakthrough curves to measure and determine the adsorption properties of indoor air pollutants (IAP) - namely formaldehyde and carbon dioxide - and to verify the extent of saturated fiber regenerability by thermal treatments. The results are summarized as follows: (1) ORNL demonstrated that physical activation of lignin-derived carbon fibers can be tailored to obtain LACF with surface areas and pore size distributions matching the properties of activated carbon fibers obtained from more expensive, fossil-fuel precursors; (2) UTRC investigated the LACF potential for use in air cleaning applications currently pursued by UTRC, such as building ventilation, and demonstrated their regenerability for CO2 and formaldehyde, (3) Both partners agree that LACF have potential for possible use in air cleaning applications.« less

Warming up human body by nanoporous metallized polyethylene textile.

PubMed

Cai, Lili; Song, Alex Y; Wu, Peilin; Hsu, Po-Chun; Peng, Yucan; Chen, Jun; Liu, Chong; Catrysse, Peter B; Liu, Yayuan; Yang, Ankun; Zhou, Chenxing; Zhou, Chenyu; Fan, Shanhui; Cui, Yi

2017-09-19

Space heating accounts for the largest energy end-use of buildings that imposes significant burden on the society. The energy wasted for heating the empty space of the entire building can be saved by passively heating the immediate environment around the human body. Here, we demonstrate a nanophotonic structure textile with tailored infrared (IR) property for passive personal heating using nanoporous metallized polyethylene. By constructing an IR-reflective layer on an IR-transparent layer with embedded nanopores, the nanoporous metallized polyethylene textile achieves a minimal IR emissivity (10.1%) on the outer surface that effectively suppresses heat radiation loss without sacrificing wearing comfort. This enables 7.1 °C decrease of the set-point compared to normal textile, greatly outperforming other radiative heating textiles by more than 3 °C. This large set-point expansion can save more than 35% of building heating energy in a cost-effective way, and ultimately contribute to the relief of global energy and climate issues.Energy wasted for heating the empty space of the entire building can be saved by passively heating the immediate environment around the human body. Here, the authors show a nanophotonic structure textile with tailored infrared property for passive personal heating using nanoporous metallized polyethylene.

Applications of functional polymer brushes for nanoparticle uptake and prevention of protein adsorption

NASA Astrophysics Data System (ADS)

Arifuzzaman, Shafi M.

The central theme of this Ph.D. dissertation is to develop novel multifunctional polymer coatings for understanding partition of proteins and nanoparticles on polymers grafted to flat surfaces (so-called brushes). Systematic investigation of the adsorption phenomena is accomplished by utilizing surface-anchored assemblies comprising grafted polymers with variation in physical properties (i.e., length or/and grafting density) and chemical functionality. The chemical composition of the brush is tailored by either "chemical coloring" of a parent homopolymer brush with selective chemical moieties or by sequential growth of two chemically dissimilar polymer blocks. We present preparation of two types of tailor-made, surface-grafted copolymers: (1) those composed of hydrophilic and hydrophobic blocks (so-called amphiphilic polymer brushes), and (2) those comprising of anionic and cationic polymer segments (so-called polyampholyte brushes). We describe the organization of functionality in the grafted polymer brushes and the partitioning of proteins and nanoparticles using a battery of complementary analytical probes. Specifically, we address how varying the molecular weight, grafting density, and chemical composition of the brush affects adsorbtion and desorbtion of model proteins and gold nanoparticles. Our observations indicate densely-populated responsive amphiphilic polymers are very efficient in suppressing protein adsorption. In addition, we have established that the length of poly(ethylene glycol) spacers attached to a parent homopolymer brush is a key factor governing uptake of gold nanoparticles. Both grafting density and molecular weight of the coating are important in controlling the kinetics and thermodynamics of protein adsorption on surfaces. Our findings and methodologies can lead to the development of next generation environmentally friendly antifouling surfaces and will find application in medical devices, antifouling coatings and anti reflection finishes.

R6G molecule induced modulation of the optical properties of reduced graphene oxide nanosheets for use in ultrasensitive SPR sensing

PubMed Central

Xue, Tianyu; Yu, Shansheng; Zhang, Xiaoming; Zhang, Xinzheng; Wang, Lei; Bao, Qiaoliang; Chen, Caiyun; Zheng, Weitao; Cui, Xiaoqiang

2016-01-01

A proper understanding of the role that molecular doping plays is essential to research on the modulation of the optical and electronic properties of graphene. The adsorption of R6G molecules onto defect-rich reduced graphene oxide nanosheets results in a shift of the Fermi energy and, consequently, a variation in the optical constants. This optical variation in the graphene nanosheets is used to develop an ultrasensitive surface plasmon resonance biosensor with a detection limit of 10−17 M (0.01 fM) at the molecular level. A density functional theory calculation shows that covalent bonds were formed between the R6G molecules and the defect sites on the graphene nanosheets. Our study reveals the important role that defects play in tailoring the properties and sensor device applications of graphene materials. PMID:26887525

Towards in vivo focal cortical dysplasia phenotyping using quantitative MRI.

PubMed

Adler, Sophie; Lorio, Sara; Jacques, Thomas S; Benova, Barbora; Gunny, Roxana; Cross, J Helen; Baldeweg, Torsten; Carmichael, David W

2017-01-01

Focal cortical dysplasias (FCDs) are a range of malformations of cortical development each with specific histopathological features. Conventional radiological assessment of standard structural MRI is useful for the localization of lesions but is unable to accurately predict the histopathological features. Quantitative MRI offers the possibility to probe tissue biophysical properties in vivo and may bridge the gap between radiological assessment and ex-vivo histology. This review will cover histological, genetic and radiological features of FCD following the ILAE classification and will explain how quantitative voxel- and surface-based techniques can characterise these features. We will provide an overview of the quantitative MRI measures available, their link with biophysical properties and finally the potential application of quantitative MRI to the problem of FCD subtyping. Future research linking quantitative MRI to FCD histological properties should improve clinical protocols, allow better characterisation of lesions in vivo and tailored surgical planning to the individual.

Towards scalable nano-engineering of graphene

PubMed Central

Martínez-Galera, A. J.; Brihuega, I.; Gutiérrez-Rubio, A.; Stauber, T.; Gómez-Rodríguez, J. M.

2014-01-01

By merging bottom-up and top-down strategies we tailor graphene's electronic properties within nanometer accuracy, which opens up the possibility to design optical and plasmonic circuitries at will. In a first step, graphene electronic properties are macroscopically modified exploiting the periodic potential generated by the self assembly of metal cluster superlattices on a graphene/Ir(111) surface. We then demonstrate that individual metal clusters can be selectively removed by a STM tip with perfect reproducibility and that the structures so created are stable even at room temperature. This enables one to nanopattern circuits down to the 2.5 nm only limited by the periodicity of the Moiré-pattern, i.e., by the distance between neighbouring clusters, and different electronic and optical properties should prevail in the covered and uncovered regions. The method can be carried out on micro-meter-sized regions with clusters of different materials permitting to tune the strength of the periodic potential. PMID:25472802

Porous silicon in drug delivery devices and materials☆

PubMed Central

Anglin, Emily J.; Cheng, Lingyun; Freeman, William R.; Sailor, Michael J.

2009-01-01

Porous Si exhibits a number of properties that make it an attractive material for controlled drug delivery applications: The electrochemical synthesis allows construction of tailored pore sizes and volumes that are controllable from the scale of microns to nanometers; a number of convenient chemistries exist for the modification of porous Si surfaces that can be used to control the amount, identity, and in vivo release rate of drug payloads and the resorption rate of the porous host matrix; the material can be used as a template for organic and biopolymers, to prepare composites with a designed nanostructure; and finally, the optical properties of photonic structures prepared from this material provide a self-reporting feature that can be monitored in vivo. This paper reviews the preparation, chemistry, and properties of electrochemically prepared porous Si or SiO2 hosts relevant to drug delivery applications. PMID:18508154

Superhydrophobic Silicon Nanocrystal-Silica Aerogel Hybrid Materials: Synthesis, Properties, and Sensing Application.

PubMed

Kehrle, Julian; Purkait, Tapas K; Kaiser, Simon; Raftopoulos, Konstantinos N; Winnacker, Malte; Ludwig, Theresa; Aghajamali, Maryam; Hanzlik, Marianne; Rodewald, Katia; Helbich, Tobias; Papadakis, Christine M; Veinot, Jonathan G C; Rieger, Bernhard

2018-04-24

Silicon nanocrystals (SiNCs) are abundant and exhibit exquisitely tailorable optoelectronic properties. The incorporation of SiNCs into highly porous and lightweight substrates such as aerogels leads to hybrid materials possessing the attractive features of both materials. This study describes the covalent deposition of SiNCs on and intercalation into silica aerogels, explores the properties, and demonstrates a prototype sensing application of the composite material. SiNCs of different sizes were functionalized with triethoxyvinylsilane (TEVS) via a radical grafting approach and subsequently used for the synthesis of photoluminescent silica hybrids. The resulting SiNC-containing aerogels possess high porosities, SiNC-based size-dependent photoluminescence, transparency, and a superhydrophobic macroscopic surface. The materials were used to examine the photoluminescence response toward low concentrations of 3-nitrotoluene (270 μM), demonstrating their potential as a sensing platform for high-energy materials.

Tailoring the structures and photonic properties of low-dimensional organic materials by crystal engineering.

PubMed

Li, Qing; Jin, Wang; Chu, Manman; Zhang, Wei; Gu, Jianmin; Shahid, Bilal; Chen, Aibing; Yu, Yifeng; Qiao, Shanlin; Zhao, Yong Sheng

2018-03-08

Low-dimensional organic materials have given rise to tremendous interest in optoelectronic applications, owing to their controllable photonic properties. However, the controlled-synthesis approaches for organic nano-/micro-architectures are very difficult to attain, because the weak interaction (van der Waals force) between the organic molecules cannot dominate the kinetic process of crystal growth. We report a simple method, which involves selective adhesion to the organic crystal plane by hydrogen-bonding interaction for modulating the crystal growth process, which leads either to the self-assembly of one organic molecule into two-dimensional (2D) microsheets with an obvious asymmetric light propagation or one-dimensional (1D) microrods with low propagation loss. The method of tailoring the structures and photonic properties for fabricating different micro-structures would provide enlightenment for the development of tailor-made mini-sized devices for photonic integrated circuits.

Tailoring of quantum dot emission efficiency by localized surface plasmon polaritons in self-organized mesoscopic rings.

PubMed

Margapoti, Emanuela; Gentili, Denis; Amelia, Matteo; Credi, Alberto; Morandi, Vittorio; Cavallini, Massimiliano

2014-01-21

We report on the tailoring of quantum dot (QD) emission efficiency by localized surface plasmon polaritons in self-organized mesoscopic rings. Ag nanoparticles (NPs) with CdSe QDs embedded in a polymeric matrix are spatially organised in mesoscopic rings and coupled in a tuneable fashion by breath figure formation. The mean distance between NPs and QDs and consequently the intensity of QD photoluminescence, which is enhanced by the coupling of surface plasmons and excitons, are tuned by acting on the NP concentration.

Study of magnetic nanoparticles and overcoatings for biological applications including a sensor device

NASA Astrophysics Data System (ADS)

Grancharov, Stephanie G.

I. A general introduction to the field of nanomaterials is presented, highlighting their special attributes and characteristics. Nanoparticles in general are discussed with respect to their structure, form and properties. Magnetic particles in particular are highlighted, especially the iron oxides. The importance and interest of integrating these materials with biological media is discussed, with emphasis on transferring particles from one medium to another, and subsequent modification of surfaces with different types of materials. II. A general route to making magnetic iron oxide nanoparticles is explained, both as maghemite and magnetite, including properties of the particles and characterization. A novel method of producing magnetite particles without a ligand is then presented, with subsequent characterization and properties described. III. Attempts to coat iron oxide nanoparticles with a view to creating biofunctional magnetic nanoparticles are presented, using a gold overcoating method. Methods of synthesis and characterization are examined, with unique problems to core-shell structures analyzed. IV. Solubility of nanoparticles in both aqueous and organic media is discussed and examined. The subsequent functionalization of the surface of maghemite and magnetite nanoparticles with a variety of biomaterials including block copolypeptides, phospholipids and carboxydextran is then presented. These methods are integral to the use of magnetic nanoparticles in biological applications, and therefore their properties are examined once tailored with these molecules. V. A new type of magnetic nanoparticle sensor-type device is described. This device integrates bio-and DNA-functionalized nanoparticles with conjugate functionalized silicon dioxide surfaces. These techniques to pattern particles to a surface are then incorporated into a device with a magnetic tunnel junction, which measures magnetoresistance in the presence of an external magnetic field. This configuration thereby introduces a new way to detect magnetic nanoparticles via their magnetic properties after conjugation via biological entities.

Nanoscale Insight and Control of Structural and Electronic Properties of Organic Semiconductor / Metal Interfaces

NASA Astrophysics Data System (ADS)

Maughan, Bret

Organic semiconductor interfaces are promising materials for use in next-generation electronic and optoelectronic devices. Current models for metal-organic interfacial electronic structure and dynamics are inadequate for strongly hybridized systems. This work aims to address this issue by identifying the factors most important for understanding chemisorbed interfaces with an eye towards tuning the interfacial properties. Here, I present the results of my research on chemisorbed interfaces formed between thin-films of phthalocyanine molecules grown on monocrystalline Cu(110). Using atomically-resolved nanoscale imaging in combination with surface-sensitive photoemission techniques, I show that single-molecule level interactions control the structural and electronic properties of the interface. I then demonstrate that surface modifications aimed at controlling interfacial interactions are an effective way to tailor the physical and electronic structure of the interface. This dissertation details a systematic investigation of the effect of molecular and surface functionalization on interfacial interactions. To understand the role of molecular structure, two types of phthalocyanine (Pc) molecules are studied: non-planar, dipolar molecules (TiOPc), and planar, non-polar molecules (H2Pc and CuPc). Multiple adsorption configurations for TiOPc lead to configuration-dependent self-assembly, Kondo screening, and electronic energy-level alignment. To understand the role of surface structure, the Cu(110) surface is textured and passivated by oxygen chemisorption prior to molecular deposition, which gives control over thin-film growth and interfacial electronic structure in H2Pc and CuPc films. Overall, the work presented here demonstrates a method for understanding interfacial electronic structure of strongly hybridized interfaces, an important first step towards developing more robust models for metal-organic interfaces, and reliable, predictive tuning of interfacial properties.

Proof-of-concept switchable hydrophobic/hydrophilic patterned surfaces from thermo-mechanically tailored acrylate systems

NASA Astrophysics Data System (ADS)

Laursen, Christopher M.

A novel, proof-of-concept, switchable hydrophobic/hydrophilic structured surface targeted to assist in antifouling of materials in aqueous environments was created through the development of a multi-tiered platform. The understructure consists of a thermo-mechanically tailored acrylate based polymer patterned in a pillared array, which was then overlaid with spatially tailored hydrophobic/hydrophilic surface chemistry treatments. Development focused on the synthesis of a ternary acrylate system displaying proper thermo-mechanical behavior in submerged conditions for the understructure, creation of a sufficient soft molding technique, and methods to chemically alter water-surface wetting interactions. The final acrylate based polymer constituents were chosen based on expected low-toxicity and the ability to be photopolymerized, while the final system displayed appropriate mechanical toughness, water absorption, and material stiffness over a select temperature window. This was important as alteration in wettability characteristics relied upon a stark transition in the polymeric materials stiffness within a narrow temperature range. The material qualitatively displayed a more hydrophobic state with the pillared surface structures erect, and a more hydrophilic state with the pillars bent over.

Positrons in surface physics

NASA Astrophysics Data System (ADS)

Hugenschmidt, Christoph

2016-12-01

Within the last decade powerful methods have been developed to study surfaces using bright low-energy positron beams. These novel analysis tools exploit the unique properties of positron interaction with surfaces, which comprise the absence of exchange interaction, repulsive crystal potential and positron trapping in delocalized surface states at low energies. By applying reflection high-energy positron diffraction (RHEPD) one can benefit from the phenomenon of total reflection below a critical angle that is not present in electron surface diffraction. Therefore, RHEPD allows the determination of the atom positions of (reconstructed) surfaces with outstanding accuracy. The main advantages of positron annihilation induced Auger-electron spectroscopy (PAES) are the missing secondary electron background in the energy region of Auger-transitions and its topmost layer sensitivity for elemental analysis. In order to enable the investigation of the electron polarization at surfaces low-energy spin-polarized positrons are used to probe the outermost electrons of the surface. Furthermore, in fundamental research the preparation of well defined surfaces tailored for the production of bound leptonic systems plays an outstanding role. In this report, it is envisaged to cover both the fundamental aspects of positron surface interaction and the present status of surface studies using modern positron beam techniques.

Tailoring the Crystal Structure Toward Optimal Super Conductors

DTIC Science & Technology

2016-06-23

AFRL-AFOSR-VA-TR-2016-0210 TAILORING THE CRYSTAL STRUCTURE TOWARD OPTIMAL SUPERCONDUCTORS Emilia Morosan WILLIAM MARSH RICE UNIV HOUSTON TX Final...TAILORING THE CRYSTAL STRUCTURE TOWARD OPTIMAL SUPERCONDUCTORS 5a. CONTRACT NUMBER FA9550-11-1-0023 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6...studied the properties of layered transition metal compounds in search of unconventional superconductors . The aim is to identify ground states competing

Sequence-Dependent Structure/Function Relationships of Catalytic Peptide-Enabled Gold Nanoparticles Generated under Ambient Synthetic Conditions.

PubMed

Bedford, Nicholas M; Hughes, Zak E; Tang, Zhenghua; Li, Yue; Briggs, Beverly D; Ren, Yang; Swihart, Mark T; Petkov, Valeri G; Naik, Rajesh R; Knecht, Marc R; Walsh, Tiffany R

2016-01-20

Peptide-enabled nanoparticle (NP) synthesis routes can create and/or assemble functional nanomaterials under environmentally friendly conditions, with properties dictated by complex interactions at the biotic/abiotic interface. Manipulation of this interface through sequence modification can provide the capability for material properties to be tailored to create enhanced materials for energy, catalysis, and sensing applications. Fully realizing the potential of these materials requires a comprehensive understanding of sequence-dependent structure/function relationships that is presently lacking. In this work, the atomic-scale structures of a series of peptide-capped Au NPs are determined using a combination of atomic pair distribution function analysis of high-energy X-ray diffraction data and advanced molecular dynamics (MD) simulations. The Au NPs produced with different peptide sequences exhibit varying degrees of catalytic activity for the exemplar reaction 4-nitrophenol reduction. The experimentally derived atomic-scale NP configurations reveal sequence-dependent differences in structural order at the NP surface. Replica exchange with solute-tempering MD simulations are then used to predict the morphology of the peptide overlayer on these Au NPs and identify factors determining the structure/catalytic properties relationship. We show that the amount of exposed Au surface, the underlying surface structural disorder, and the interaction strength of the peptide with the Au surface all influence catalytic performance. A simplified computational prediction of catalytic performance is developed that can potentially serve as a screening tool for future studies. Our approach provides a platform for broadening the analysis of catalytic peptide-enabled metallic NP systems, potentially allowing for the development of rational design rules for property enhancement.

Ultra lightweight PMMA-based composite plates with robust super-hydrophobic surfaces.

PubMed

Pareo, Paola; De Gregorio, Gian Luca; Manca, Michele; Pianesi, Maria Savina; De Marco, Luisa; Cavallaro, Francesco; Mari, Margherita; Pappadà, Silvio; Ciccarella, Giuseppe; Gigli, Giuseppe

2011-11-15

Extremely lightweight plates made of an engineered PMMA-based composite material loaded with hollow glass micro-sized spheres, nano-sized silica particles and aluminum hydroxide prismatic micro-flakes were realized by cast molding. Their interesting bulk mechanical properties were combined to properly tailored surface topography compatible with the achievement of a superhydrophobic behavior after the deposition of a specifically designed hydrophobic coating. With this aim, we synthesized two different species of fluoromethacrylic polymers functionalized with methoxysilane anchoring groups to be covalently grafted onto the surface protruding inorganic fillers. By modulating the feed composition of the reacting monomers, it was possible to combine the hydrophobic character of the polymer with an high adhesion strength to the substrate and hence to maximize both the water contact angle (up to 157°) and the durability of the easy-to-clean effect (up to 2000 h long outdoor exposure). Copyright © 2011 Elsevier Inc. All rights reserved.

Effect of tethering on the surface dynamics of a thin polymer melt layer

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

Uğur, Gökçe; Akgun, Bulent; Jiang, Zhang

The surface height fluctuations of a layer of low molecular weight (2.2k) untethered perdeuterated polystyrene (dPS) chains adjacent to a densely grafted polystyrene brush are slowed dramatically. Due to the interpenetration of the brush with the layer of “untethered chains” a hydrodynamic continuum theory can only describe the fluctuations when the effective thickness of the film is taken to be that which remains above the swollen brush. Furthermore, the portion of the film of initially untethered chains that interpenetrates with the brush becomes so viscous as to effectively play the role of a rigid substrate. They provide a route formore » tailoring polymer layer surface properties such as wetting, adhesion and friction, since these hybrid samples contain a covalently tethered layer at the bottom, does not readily dewet, and are more robust than thin layers of untethered short chains on rigid substrates.« less

Control of the plasmonic near-field in metallic nanohelices.

PubMed

Caridad, José M; Winters, Sinéad; McCloskey, David; Duesberg, Georg S; Donegan, John F; Krstić, Vojislav

2018-08-10

The optical response of metallic nanohelices is mainly governed by a longitudinal localised surface plasmon resonance (LSPR) which arises due to the helical anisotropy of the system. Up to now, experimental studies have predominantly addressed the far-field response, despite the fact that the LSPR being of broad interest for converting incoming light into strongly enhanced (chiral) optical near-fields. Here, we demonstrate the control and spatial reproducibility of the plasmon-induced electromagnetic near-field around metallic nanohelices via surface-enhanced Raman scattering. We discuss how the near-field intensity of these nanostructures can be custom-tailored through both the nanoscaled helical structure and the electronic properties of the constituting metals. Our experiments, which employ graphene as an accurate probing material, are in quantitative agreement with corresponding numerical simulations. The findings demonstrate metallic nanohelices as reference nanostructured surfaces able to provide and fine-tune optical fields for fundamental studies as well as sensing or (chiro-optical) imaging applications.

Biological Activation of Inert Ceramics: Recent Advances Using Tailored Self-Assembled Monolayers on Implant Ceramic Surfaces

PubMed Central

Böke, Frederik; Schickle, Karolina; Fischer, Horst

2014-01-01

High-strength ceramics as materials for medical implants have a long, research-intensive history. Yet, especially on applications where the ceramic components are in direct contact with the surrounding tissue, an unresolved issue is its inherent property of biological inertness. To combat this, several strategies have been investigated over the last couple of years. One promising approach investigates the technique of Self-Assembled Monolayers (SAM) and subsequent chemical functionalization to create a biologically active tissue-facing surface layer. Implementation of this would have a beneficial impact on several fields in modern implant medicine such as hip and knee arthroplasty, dental applications and related fields. This review aims to give a summarizing overview of the latest advances in this recently emerging field, along with thorough introductions of the underlying mechanism of SAMs and surface cell attachment mechanics on the cell side. PMID:28788687

Effect of tethering on the surface dynamics of a thin polymer melt layer

DOE PAGES

Uğur, Gökçe; Akgun, Bulent; Jiang, Zhang; ...

2016-05-13

The surface height fluctuations of a layer of low molecular weight (2.2k) untethered perdeuterated polystyrene (dPS) chains adjacent to a densely grafted polystyrene brush are slowed dramatically. Due to the interpenetration of the brush with the layer of “untethered chains” a hydrodynamic continuum theory can only describe the fluctuations when the effective thickness of the film is taken to be that which remains above the swollen brush. Furthermore, the portion of the film of initially untethered chains that interpenetrates with the brush becomes so viscous as to effectively play the role of a rigid substrate. They provide a route formore » tailoring polymer layer surface properties such as wetting, adhesion and friction, since these hybrid samples contain a covalently tethered layer at the bottom, does not readily dewet, and are more robust than thin layers of untethered short chains on rigid substrates.« less

Dynamic tailoring of surface plasmon polaritons through incident angle modulation.

PubMed

Qiu, Peizhen; Zhang, Dawei; Jing, Ming; Lu, Taiguo; Yu, Binbin; Zhan, Qiwen; Zhuang, Songlin

2018-04-16

Dynamic tailoring of the propagating surface plasmon polaritons (SPPs) through incident angle modulation is proposed and numerically demonstrated. The generation and tailoring mechanism of the SPPs are discussed. The relationship formula between the incident angle and the generated SPP wave vector direction is theoretically derived. The correctness of the formula is verified with three different approaches using finite difference time domain method. Using this formula, the generated SPP wave vector direction can be precisely modulated by changing the incident angle. The precise modulation results of two dimensional Bessel-like SPP beam and SPP bottle beam array are given. The results can deepen the understanding of the generation and modulation mechanism of the SPPs.

Investigation of fatigue strength of tool steels in sheet-bulk metal forming

NASA Astrophysics Data System (ADS)

Pilz, F.; Gröbel, D.; Merklein, M.

2018-05-01

To encounter trends regarding an efficient production of complex functional components in forming technology, the process class of sheet-bulk metal forming (SBMF) can be applied. SBMF is characterized by the application of bulk forming operations on sheet metal, often in combination with sheet forming operations [1]. The combination of these conventional process classes leads to locally varying load conditions. The resulting load conditions cause high tool loads, which lead to a reduced tool life, and an uncontrolled material flow. Several studies have shown that locally modified tool surfaces, so-called tailored surfaces, have the potential to control the material flow and thus to increase the die filling of functional elements [2]. A combination of these modified tool surfaces and high tool loads in SBMF is furthermore critical for the tool life and leads to fatigue. Tool fatigue is hardly predictable and due to a lack of data [3], a challenge in tool design. Thus, it is necessary to provide such data for tool steels used in SBMF. The aim of this study is the investigation of the influence of tailored surfaces on the fatigue strength of the powder metallurgical tool steel ASP2023 (1.3344, AISI M3:2), which is typically used in cold forging applications, with a hardness 60 HRC ± 1 HRC. To conduct this investigation, the rotating bending test is chosen. As tailored surfaces, a DLC-coating and a surface manufactured by a high-feed-milling process are chosen. As reference a polished surface which is typical for cold forging tools is used. Before the rotating bending test, the surface integrity is characterized by measuring topography and residual stresses. After testing, the determined values of the surface integrity are correlated with the reached fracture load cycle to derive functional relations. Based on the gained results the investigated tailored surfaces are evaluated regarding their feasibility to modify tool surfaces within SBMF.

Experimental verification of the rainbow trapping effect in adiabatic plasmonic gratings

PubMed Central

Gan, Qiaoqiang; Gao, Yongkang; Wagner, Kyle; Vezenov, Dmitri; Ding, Yujie J.; Bartoli, Filbert J.

2011-01-01

We report the experimental observation of a trapped rainbow in adiabatically graded metallic gratings, designed to validate theoretical predictions for this unique plasmonic structure. One-dimensional graded nanogratings were fabricated and their surface dispersion properties tailored by varying the grating groove depth, whose dimensions were confirmed by atomic force microscopy. Tunable plasmonic bandgaps were observed experimentally, and direct optical measurements on graded grating structures show that light of different wavelengths in the 500–700-nm region is “trapped” at different positions along the grating, consistent with computer simulations, thus verifying the “rainbow” trapping effect. PMID:21402936

Biomimetic microstructures for photonic and fluidic synergies

NASA Astrophysics Data System (ADS)

Vasileiou, Maria; Mpatzaka, Theodora; Alexandropoulos, Dimitris; Vainos, Nikolaos A.

2017-08-01

Nature-inspired micro- and nano-structures offer a unique platform for the development of novel synergetic systems combining photonic and microfluidic functionalities. In this context, we examine the paradigm of butterfly Vanessa cardui and develop artificial diffractive microstructures inspired by its natural designs. Softlithographic and nanoimprint protocols are developed to replicate surfaces of natural specimens. Further to their optical behavior, interphases tailored by such microstructures exhibit enhanced hydrophobic properties, as compared to their planar counterparts made of the same materials. Such synergies exploited by new design approaches pave the way to prospective optofluidic, lab-on-chip and sensing applications.

Potential of direct metal deposition technology for manufacturing thick functionally graded coatings and parts for reactors components

NASA Astrophysics Data System (ADS)

Thivillon, L.; Bertrand, Ph.; Laget, B.; Smurov, I.

2009-03-01

Direct metal deposition (DMD) is an automated 3D deposition process arising from laser cladding technology with co-axial powder injection to refine or refurbish parts. Recently DMD has been extended to manufacture large-size near-net-shape components. When applied for manufacturing new parts (or their refinement), DMD can provide tailored thermal properties, high corrosion resistance, tailored tribology, multifunctional performance and cost savings due to smart material combinations. In repair (refurbishment) operations, DMD can be applied for parts with a wide variety of geometries and sizes. In contrast to the current tool repair techniques such as tungsten inert gas (TIG), metal inert gas (MIG) and plasma welding, laser cladding technology by DMD offers a well-controlled heat-treated zone due to the high energy density of the laser beam. In addition, this technology may be used for preventative maintenance and design changes/up-grading. One of the advantages of DMD is the possibility to build functionally graded coatings (from 1 mm thickness and higher) and 3D multi-material objects (for example, 100 mm-sized monolithic rectangular) in a single-step manufacturing cycle by using up to 4-channel powder feeder. Approved materials are: Fe (including stainless steel), Ni and Co alloys, (Cu,Ni 10%), WC compounds, TiC compounds. The developed coatings/parts are characterized by low porosity (<1%), fine microstructure, and their microhardness is close to the benchmark value of wrought alloys after thermal treatment (Co-based alloy Stellite, Inox 316L, stainless steel 17-4PH). The intended applications concern cooling elements with complex geometry, friction joints under high temperature and load, light-weight mechanical support structures, hermetic joints, tubes with complex geometry, and tailored inside and outside surface properties, etc.

Chimeric Peptides as Implant Functionalization Agents for Titanium Alloy Implants with Antimicrobial Properties

NASA Astrophysics Data System (ADS)

Yucesoy, Deniz T.; Hnilova, Marketa; Boone, Kyle; Arnold, Paul M.; Snead, Malcolm L.; Tamerler, Candan

2015-04-01

Implant-associated infections can have severe effects on the longevity of implant devices and they also represent a major cause of implant failures. Treating these infections associated with implants by antibiotics is not always an effective strategy due to poor penetration rates of antibiotics into biofilms. Additionally, emerging antibiotic resistance poses serious concerns. There is an urge to develop effective antibacterial surfaces that prevent bacterial adhesion and proliferation. A novel class of bacterial therapeutic agents, known as antimicrobial peptides (AMPs), are receiving increasing attention as an unconventional option to treat septic infection, partly due to their capacity to stimulate innate immune responses and for the difficulty of microorganisms to develop resistance towards them. While host and bacterial cells compete in determining the ultimate fate of the implant, functionalization of implant surfaces with AMPs can shift the balance and prevent implant infections. In the present study, we developed a novel chimeric peptide to functionalize the implant material surface. The chimeric peptide simultaneously presents two functionalities, with one domain binding to a titanium alloy implant surface through a titanium-binding domain while the other domain displays an antimicrobial property. This approach gains strength through control over the bio-material interfaces, a property built upon molecular recognition and self-assembly through a titanium alloy binding domain in the chimeric peptide. The efficiency of chimeric peptide both in-solution and absorbed onto titanium alloy surface was evaluated in vitro against three common human host infectious bacteria, Streptococcus mutans, Staphylococcus epidermidis, and Escherichia coli. In biological interactions such as occur on implants, it is the surface and the interface that dictate the ultimate outcome. Controlling the implant surface by creating an interface composed chimeric peptides may therefore open up new possibilities to modify the implant site and tailor it to a desirable bioactivity.

Morphological and physical - chemical issues of metal nanostructures used in medical field

NASA Astrophysics Data System (ADS)

Duceac, L. D.; Velenciuc, N.; Dobre, E. C.

2016-06-01

In recent years applications of nanotechnology integrated into nanomedicine and bio-nanotechnology have attracted the attention of many researchers from different fields. Processes from chemical engineering especially nanostructured materials play an important role in medical and pharmaceutical development. Fundamental researches focused on finding simple, easily accomplished synthesis methods, morphological aspects and physico-chemical advanced characterization of nanomaterials. More over, by controlling synthesis conditions textural characteristics and physicochemical properties such as particle size, shape, surface, porosity, aggregation degree and composition can be tailored. Low cytotoxicity and antimicrobial effects of these nanostructured materials makes them be applied in medicine field. The major advantage of metal based nanoparticles is the use either for their antimicrobial properties or as drug-carriers having the potential to be active at low concentrations against infectious agents.

Structure-Property Relationship of Phenylene-Based Self-Assembled-Monolayers for Record Low Work Function of Indium Tin Oxide.

PubMed

Benneckendorf, Frank S; Hillebrandt, Sabina; Ullrich, Florian; Rohnacher, Valentina; Hietzschold, Sebastian; Jänsch, Daniel; Freudenberg, Jan; Beck, Sebastian; Mankel, Eric; Jaegermann, Wolfram; Pucci, Annemarie; Bunz, Uwe H F; Müllen, Klaus

2018-06-20

Studying the structure-property relations of tailored dipolar phenyl and biphenylphosphonic acids we report self-assembled monolayers with a significant decrease of the work function (WF) of indium-tin oxide (ITO) electrodes. While the strengths of the dipoles are varied through the different molecular lengths and the introduction of electron-withdrawing fluorine atoms, the surface energy is kept constant through the electron-donating N,N dimethylamine head groups. The self-assembled monolayer formation and its modification of the electrodes are investigated via infrared reflection absorption spectroscopy, contact angle measurements, and photoelectron spectroscopy. The WF decrease of ITO correlates with increasing molecular dipoles. The lowest ever recorded WF of 3.7 eV is achieved with the fluorinated biphenylphosphonic acid.

Natural and synthetic polymers in fabric and home care applications

NASA Astrophysics Data System (ADS)

Paderes, Monissa; Ahirwal, Deepak; Fernández Prieto, Susana

2017-07-01

Polymers can be tailored to provide different benefits in Fabric & Home Care formulations depending on the monomers and modifications used, such as avoiding dye transfer inhibition in the wash, modifying the surface of tiles or increasing the viscosity and providing suspension properties to consumer products. Specifically, the rheology modification properties of synthetic and natural polymers are discussed in this chapter. The choice of a polymeric rheology modifier will depend on the formulation ingredients (charges, functional groups), the type and the amount of surfactants, the pH and the desired rheology modification. Natural polymeric rheology modifiers have been traditionally used in the food industry, being xanthan gum one of the most well-known ones. On the contrary, synthetic rheology modifiers are preferably used in paints & coats, textile printing and cleaning products.

Engineered Nanomaterials: Their Physicochemical Characteristics and How to Measure Them.

PubMed

Atluri, Rambabu; Jensen, Keld Alstrup

2017-01-01

Numerous types of engineered nanomaterials (ENMs) are commercially available and developments move towards producing more advanced nanomaterials with tailored properties. Such advanced nanomaterials may include chemically doped or modified derivatives with specific surface chemistries; also called higher generation or multiconstituent nanomaterials. To fully enjoy the benefits of nanomaterials, appropriate characterisation of ENMs is necessary for many aspects of their production, use, testing and reporting to regulatory bodies. This chapter introduces both structural and textural properties of nanomaterials with a focus on demonstrating the information that can be achieved by analysis of primary physicochemical characteristics and how such information is critical to understand or assess the possible toxicity of engineered nanomaterials. Many of characterization methods are very specific to obtain particular characteristics and therefore the most widely used techniques are explained and demonstrated.

Photonic and phononic surface and edge modes in three-dimensional phoxonic crystals

NASA Astrophysics Data System (ADS)

Ma, Tian-Xue; Wang, Yue-Sheng; Zhang, Chuanzeng

2018-04-01

We investigate the photonic and phononic surface and edge modes in finite-size three-dimensional phoxonic crystals. By appropriately terminating the phoxonic crystals, the photons and phonons can be simultaneously guided at the two-dimensional surface and/or the one-dimensional edge of the terminated crystals. The Bloch surface and edge modes show that the electromagnetic and acoustic waves are highly localized near the surface and edge, respectively. The surface and edge geometries play important roles in tailoring the dispersion relations of the surface and edge modes, and dual band gaps for the surface or edge modes can be simultaneously achieved by changing the geometrical configurations. Furthermore, as the band gaps for the bulk modes are the essential prerequisites for the realization of dual surface and edge modes, the photonic and phononic bulk-mode band gap properties of three different types of phoxonic crystals with six-connected networks are revealed. It is found that the geometrical characteristic of the crystals with six-connected networks leads to dual large bulk-mode band gaps. Compared with the conventional bulk modes, the surface and edge modes provide a new approach for the photon and phonon manipulation and show great potential for phoxonic crystal devices and optomechanics.

Controlled-reflectance surfaces with film-coupled colloidal nanoantennas.

PubMed

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

2012-12-06

Efficient and tunable absorption is essential for a variety of applications, such as designing controlled-emissivity surfaces for thermophotovoltaic devices, tailoring an infrared spectrum for controlled thermal dissipation and producing detector elements for imaging. 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 design. So far, metamaterial absorbers in the infrared or visible range have been fabricated using lithographically patterned metallic structures, making them inherently difficult to produce over large areas and hence reducing their applicability. Here we demonstrate a 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. We show that the film-coupled nanocubes provide a reflectance spectrum that can be tailored by varying the geometry (the size of the cubes and/or the thickness of the spacer). Each nanocube is the optical analogue of a grounded patch antenna, with a nearly identical local field structure that is modified by the plasmonic response of the metal's dielectric function, and with an anomalously large absorption efficiency that can be partly attributed to an interferometric effect. The absorptivity of large surface areas can be controlled using this method, at scales out of reach of lithographic approaches (such as electron-beam lithography) that are otherwise required to manipulate matter on the nanoscale.

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

Tuning the characteristics of surface plasmon polariton nanolasers by tailoring the dispersion relation

NASA Astrophysics Data System (ADS)

Lu, Tien-Chang; Chou, Yu-Hsun; Hong, Kuo-Bin; Chung, Yi-Cheng; Lin, Tzy-Rong; Arakelian, S. M.; Alodjants, A. P.

2017-08-01

Nanolasers with ultra-compact footprint are able to provide high intensity coherent light, which have various potential applications in high capacity signal processing, biosensing, and sub-wavelength imaging. Among various nanolasers, those lasers with cavities surrounded with metals have shown to have superior light emission properties due to the surface plasmon effect providing better field confinement capability and allowing exotic light-matter interaction. In this talk, we report robust ultraviolet ZnO nanolaser by using silver (Ag) [1] and aluminum (Al) [2] to strongly shrink the mode volume. The nanolasers operated at room temperature and even high temperature (353K) shows several distinct features including an extremely small mode volume, large Purcell factor and group index. Comparison of characteristics between Ag- and Al-based will also be made.

Blueprinting macromolecular electronics.

PubMed

Palma, Carlos-Andres; Samorì, Paolo

2011-06-01

Recently, by mastering either top-down or bottom-up approaches, tailor-made macromolecular nano-objects with semiconducting properties have been fabricated. These engineered nanostructures for organic electronics are based on conjugated systems predominantly made up of sp²-hybridized carbon, such as graphene nanoribbons. Here, we describe developments in a selection of these nanofabrication techniques, which include graphene carving, stimulus-induced synthesis of conjugated polymers and surface-assisted synthesis. We also assess their potential to reproduce chemically and spatially precise molecular arrangements, that is, molecular blueprints. In a broad context, the engineering of a molecular blueprint represents the fabrication of an integrated all-organic macromolecular electronic circuit. In this Perspective, we suggest chemical routes, as well as convergent on-surface synthesis and microfabrication approaches, for the ultimate goal of bringing the field closer to technology.

Recent Prospects in the Inline Monitoring of Nanocomposites and Nanocoatings by Optical Technologies.

PubMed

Bugnicourt, Elodie; Kehoe, Timothy; Latorre, Marcos; Serrano, Cristina; Philippe, Séverine; Schmid, Markus

2016-08-19

Nanostructured materials have emerged as a key research field in order to confer materials with unique or enhanced properties. The performance of nanocomposites depends on a number of parameters, but the suitable dispersion of nanoparticles remains the key in order to obtain the full nanocomposites' potential in terms of, e.g., flame retardance, mechanical, barrier, thermal properties, etc. Likewise, the performance of nanocoatings to obtain, for example, tailored surface affinity with selected liquids (e.g., for self-cleaning ability or anti-fog properties), protective effects against flame propagation, ultra violet (UV) radiation or gas permeation, is highly dependent on the nanocoating's thickness and homogeneity. In terms of recent advances in the monitoring of nanocomposites and nanocoatings, this review discusses commonly-used offline characterization approaches, as well as promising inline systems. All in all, having good control over both the dispersion and thickness of these materials would help with reaching optimal and consistent properties to allow nanocomposites to extend their use.

Recent Prospects in the Inline Monitoring of Nanocomposites and Nanocoatings by Optical Technologies

PubMed Central

Bugnicourt, Elodie; Kehoe, Timothy; Latorre, Marcos; Serrano, Cristina; Philippe, Séverine; Schmid, Markus

2016-01-01

Nanostructured materials have emerged as a key research field in order to confer materials with unique or enhanced properties. The performance of nanocomposites depends on a number of parameters, but the suitable dispersion of nanoparticles remains the key in order to obtain the full nanocomposites’ potential in terms of, e.g., flame retardance, mechanical, barrier, thermal properties, etc. Likewise, the performance of nanocoatings to obtain, for example, tailored surface affinity with selected liquids (e.g., for self-cleaning ability or anti-fog properties), protective effects against flame propagation, ultra violet (UV) radiation or gas permeation, is highly dependent on the nanocoating’s thickness and homogeneity. In terms of recent advances in the monitoring of nanocomposites and nanocoatings, this review discusses commonly-used offline characterization approaches, as well as promising inline systems. All in all, having good control over both the dispersion and thickness of these materials would help with reaching optimal and consistent properties to allow nanocomposites to extend their use. PMID:28335278

Metamaterial Receivers for High Efficiency Concentrated Solar Energy Conversion

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

Yellowhair, Julius E.; Kwon, Hoyeong; Alu, Andrea

Operation of concentrated solar power receivers at higher temperatures (>700°C) would enable supercritical carbon dioxide (sCO 2) power cycles for improved power cycle efficiencies (>50%) and cost-effective solar thermal power. Unfortunately, radiative losses at higher temperatures in conventional receivers can negatively impact the system efficiency gains. One approach to improve receiver thermal efficiency is to utilize selective coatings that enhance absorption across the visible solar spectrum while minimizing emission in the infrared to reduce radiative losses. Existing coatings, however, tend to degrade rapidly at elevated temperatures. In this report, we report on the initial designs and fabrication of spectrally selectivemore » metamaterial-based absorbers for high-temperature, high-thermal flux environments important for solarized sCO 2 power cycles. Metamaterials are structured media whose optical properties are determined by sub-wavelength structural features instead of bulk material properties, providing unique solutions by decoupling the optical absorption spectrum from thermal stability requirements. The key enabling innovative concept proposed is the use of structured surfaces with spectral responses that can be tailored to optimize the absorption and retention of solar energy for a given temperature range. In this initial study through the Academic Alliance partnership with University of Texas at Austin, we use Tungsten for its stability in expected harsh environments, compatibility with microfabrication techniques, and required optical performance. Our goal is to tailor the optical properties for high (near unity) absorptivity across the majority of the solar spectrum and over a broad range of incidence angles, and at the same time achieve negligible absorptivity in the near infrared to optimize the energy absorbed and retained. To this goal, we apply the recently developed concept of plasmonic Brewster angle to suitably designed nanostructured Tungsten surfaces. We predict that this will improve the receiver thermal efficiencies by at least 10% over current solar receivers.« less

Improving Dielectric Properties of PVDF Composites by Employing Surface Modified Strong Polarized BaTiO₃ Particles Derived by Molten Salt Method.

PubMed

Fu, Jing; Hou, Yudong; Zheng, Mupeng; Wei, Qiaoyi; Zhu, Mankang; Yan, Hui

2015-11-11

BaTiO3/polyvinylidene fluoride (BT/PVDF) is the extensive reported composite material for application in modern electric devices. However, there still exists some obstacles prohibiting the further improvement of dielectric performance, such as poor interfacial compatibility and low dielectric constant. Therefore, in depth study of the size dependent polarization and surface modification of BT particle is of technological importance in developing high performance BT/PVDF composites. Here, a facile molten-salt synthetic method has been applied to prepare different grain sized BT particles through tailoring the calcination temperature. The size dependent spontaneous polarizationof BT particle was thoroughly investigated by theoretical calculation based on powder X-ray diffraction Rietveld refinement data. The results revealed that 600 nm sized BT particles possess the strong polarization, ascribing to the ferroelectric size effect. Furthermore, the surface of optimal BT particles has been modified by water-soluble polyvinylprrolidone (PVP) agent, and the coated particles exhibited fine core-shell structure and homogeneous dispersion in the PVDF matrix. The dielectric constant of the resulted composites increased significantly, especially, the prepared composite with 40 vol % BT loading exhibited the largest dielectric constant (65, 25 °C, 1 kHz) compared with the literature values of BT/PVDF at the same concentration of filler. Moreover, the energy storage density of the composites with tailored structure was largely enhanced at the low electric field, showing promising application as dielectric material in energy storage device. Our work suggested that introduction of strong polarized ferroelectric particles with optimal size and construction of core-shell structured coated fillers by PVP in the PVDF matrix are efficacious in improving dielectric performance of composites. The demonstrated approach can also be applied to the design and preparation of other polymers-based nanocomposites filled with ferroelectric particles to achieve desirable dielectric properties.

Manipulating topological-insulator properties using quantum confinement

NASA Astrophysics Data System (ADS)

Kotulla, M.; Zülicke, U.

2017-07-01

Recent discoveries have spurred the theoretical prediction and experimental realization of novel materials that have topological properties arising from band inversion. Such topological insulators are insulating in the bulk but have conductive surface or edge states. Topological materials show various unusual physical properties and are surmised to enable the creation of exotic Majorana-fermion quasiparticles. How the signatures of topological behavior evolve when the system size is reduced is interesting from both a fundamental and an application-oriented point of view, as such understanding may form the basis for tailoring systems to be in specific topological phases. This work considers the specific case of quantum-well confinement defining two-dimensional layers. Based on the effective-Hamiltonian description of bulk topological insulators, and using a harmonic-oscillator potential as an example for a softer-than-hard-wall confinement, we have studied the interplay of band inversion and size quantization. Our model system provides a useful platform for systematic study of the transition between the normal and topological phases, including the development of band inversion and the formation of massless-Dirac-fermion surface states. The effects of bare size quantization, two-dimensional-subband mixing, and electron-hole asymmetry are disentangled and their respective physical consequences elucidated.

Applications of nanomaterials as vaccine adjuvants

PubMed Central

Zhu, Motao; Wang, Rongfu; Nie, Guangjun

2014-01-01

Vaccine adjuvants are applied to amplify the recipient's specific immune responses against pathogen infection or malignancy. A new generation of adjuvants is being developed to meet the demands for more potent antigen-specific responses, specific types of immune responses, and a high margin of safety. Nanotechnology provides a multifunctional stage for the integration of desired adjuvant activities performed by the building blocks of tailor-designed nanoparticles. Using nanomaterials for antigen delivery can provide high bioavailability, sustained and controlled release profiles, and targeting and imaging properties resulting from manipulation of the nanomaterials’ physicochemical properties. Moreover, the inherent immune-regulating activity of particular nanomaterials can further promote and shape the cellular and humoral immune responses toward desired types. The combination of both the delivery function and immunomodulatory effect of nanomaterials as adjuvants is thought to largely benefit the immune outcomes of vaccination. In this review, we will address the current achievements of nanotechnology in the development of novel adjuvants. The potential mechanisms by which nanomaterials impact the immune responses to a vaccine and how physicochemical properties, including size, surface charge and surface modification, impact their resulting immunological outcomes will be discussed. This review aims to provide concentrated information to promote new insights for the development of novel vaccine adjuvants. PMID:25483497

Influence of matrix and filler fraction on biofilm formation on the surface of experimental resin-based composites.

PubMed

Ionescu, Andrei; Brambilla, Eugenio; Wastl, Daniel S; Giessibl, Franz J; Cazzaniga, Gloria; Schneider-Feyrer, Sibylle; Hahnel, Sebastian

2015-01-01

The aim of this study was to investigate the impact of resin matrix chemistry and filler fraction on biofilm formation on the surface of experimental resin-based composites (RBCs). Specimens were prepared from eight experimental RBC formulations differing in resin matrix blend (BisGMA/TEGDMA in a 7:3 wt% ratio or UDMA/aliphatic dimethacrylate in a 1:1 wt% ratio) and filler fraction (no fillers; 65 wt% dental glass with an average diameter of 7 or 0.7 µm or 65 wt% SiO2 with an average diameter of 20 nm). Surface roughness, surface free energy, and chemical surface composition were determined; surface topography was visualized using atomic force microscopy. Biofilm formation was simulated under continuous flow conditions for a 48 h period using a monospecies Streptococcus mutans and a multispecies biofilm model. In the monospecies biofilm model, the impact of the filler fraction overruled the influence of the resin matrix, indicating lowest biofilm formation on RBCs with nano-scaled filler particles and those manufactured from the neat resin blends. The multispecies model suggested a more pronounced effect of the resin matrix blend, as significantly higher biofilm formation was identified on RBCs with a UDMA/dimethacrylate matrix blend than on those including a BisGMA/TEGDMA matrix blend but analogous filler fractions. Although significant differences in surface properties between the various materials were identified, correlations between the surface properties and biofilm formation were poor, which highlights the relevance of surface topography and chemistry. These results may help to tailor novel RBC formulations which feature reduced biofilm formation on their surface.

Porous NiTi for bone implants: a review.

PubMed

Bansiddhi, A; Sargeant, T D; Stupp, S I; Dunand, D C

2008-07-01

NiTi foams are unique among biocompatible porous metals because of their high recovery strain (due to the shape-memory or superelastic effects) and their low stiffness facilitating integration with bone structures. To optimize NiTi foams for bone implant applications, two key areas are under active study: synthesis of foams with optimal architectures, microstructure and mechanical properties; and tailoring of biological interactions through modifications of pore surfaces. This article reviews recent research on NiTi foams for bone replacement, focusing on three specific topics: (i) surface modifications designed to create bio-inert porous NiTi surfaces with low Ni release and corrosion, as well as bioactive surfaces to enhance and accelerate biological activity; (ii) in vitro and in vivo biocompatibility studies to confirm the long-term safety of porous NiTi implants; and (iii) biological evaluations for specific applications, such as in intervertebral fusion devices and bone tissue scaffolds. Possible future directions for bio-performance and processing studies are discussed that could lead to optimized porous NiTi implants.

Porous NiTi for bone implants: A review

PubMed Central

Bansiddhi, A.; Sargeant, T.D.; Stupp, S.I.; Dunand, D.C.

2011-01-01

NiTi foams are unique among biocompatible porous metals because of their high recovery strain (due to the shape-memory or superelastic effects) and their low stiffness facilitating integration with bone structures. To optimize NiTi foams for bone implant applications, two key areas are under active study: synthesis of foams with optimal architectures, microstructure and mechanical properties; and tailoring of biological interactions through modifications of pore surfaces. This article reviews recent research on NiTi foams for bone replacement, focusing on three specific topics: (i) surface modifications designed to create bio-inert porous NiTi surfaces with low Ni release and corrosion, as well as bioactive surfaces to enhance and accelerate biological activity; (ii) In vitro and in vivo biocompatibility studies to confirm the long-term safety of porous NiTi implants; and (iii) biological evaluations for specific applications, such as in intervertebral fusion devices and bone tissue scaffolds. Possible future directions for bio-performance and processing studies are discussed that could lead to optimized porous NiTi implants. PMID:18348912

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.

Phonon Surface Scattering and Thermal Energy Distribution in Superlattices.

PubMed

Kothari, Kartik; Maldovan, Martin

2017-07-17

Thermal transport at small length scales has attracted significant attention in recent years and various experimental and theoretical methods have been developed to establish the reduced thermal conductivity. The fundamental understanding of how phonons move and the physical mechanisms behind nanoscale thermal transport, however, remains poorly understood. Here we move beyond thermal conductivity calculations and provide a rigorous and comprehensive physical description of thermal phonon transport in superlattices by solving the Boltzmann transport equation and using the Beckman-Kirchhoff surface scattering theory with shadowing to precisely describe phonon-surface interactions. We show that thermal transport in superlattices can be divided in two different heat transport modes having different physical properties at small length scales: layer-restricted and extended heat modes. We study how interface conditions, periodicity, and composition can be used to manipulate the distribution of thermal energy flow among such layer-restricted and extended heat modes. From predicted frequency and mean free path spectra of superlattices, we also investigate the existence of wave effects. The results and insights in this paper advance the fundamental understanding of heat transport in superlattices and the prospects of rationally designing thermal systems with tailored phonon transport properties.

What does nitric acid really do to carbon nanofibers? [What nitric acid really does to carbon nanofibers

DOE PAGES

Sainio, S.; Nordlund, D.; Gandhiraman, R.; ...

2016-09-15

Understanding the chemical nature of the surface of carbon nanofibers (CNF) is critical in assessing their fundamental properties and tailoring them for the right application. To gain such knowledge, we present here a detailed X-ray adsorption spectroscopy (XAS) study accompanied by high resolution transmission electron microscopy (TEM) micrographs of two morphologically different CNF pairs (tetrahedral amorphous carbon (ta-C) grown “open structured” fibers and traditional bamboo-like “closed structured” fibers), where the surface chemical properties and structural features of the fibers are investigated in depth and the effects of nitric acid treatment on the fibers are revealed. The morphology of the fibermore » and/or the original seed- and adhesion layers markedly affect the response of the fibers to the acid treatment. Results also show that the nitric acid treatment increases the observed sp 2 intensity and modifies the two types of fibers to become more-alike both structurally and with respect to their oxygen functionalities. Furthermore, the XAS and HRTEM results confirm that a short nitric acid treatment does not remove the Ni catalyst particle but, instead, oxidizes their surfaces, especially in the case of ta-C grown fibers.« less

A mini-review on rare earth metal-doped TiO2 for photocatalytic remediation of wastewater.

PubMed

Saqib, Najm Us; Adnan, Rohana; Shah, Irfan

2016-08-01

Titanium dioxide (TiO2) has been considered a useful material for the treatment of wastewater due to its non-toxic character, chemical stability and excellent electrical and optical properties which contribute in its wide range of applications, particularly in environmental remediation technology. However, the wide band gap of TiO2 photocatalyst (anatase phase, 3.20 eV) limits its photocatalytic activity to the ultraviolet region of light. Besides that, the electron-hole pair recombination has been found to reduce the efficiency of the photocatalyst. To overcome these problems, tailoring of TiO2 surface with rare earth metals to improve its surface, optical and photocatalytic properties has been investigated by many researchers. The surface modifications with rare earth metals proved to enhance the efficiency of TiO2 photocatalyts by way of reducing the band gap by shifting the working wavelength to the visible region and inhibiting the anatase-to-rutile phase transformations. This review paper summarises the attempts on modification of TiO2 using rare earth metals describing their effect on the photocatalytic activities of the modified TiO2 photocatalyst.

What does nitric acid really do to carbon nanofibers? [What nitric acid really does to carbon nanofibers

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

Sainio, S.; Nordlund, D.; Gandhiraman, R.

Understanding the chemical nature of the surface of carbon nanofibers (CNF) is critical in assessing their fundamental properties and tailoring them for the right application. To gain such knowledge, we present here a detailed X-ray adsorption spectroscopy (XAS) study accompanied by high resolution transmission electron microscopy (TEM) micrographs of two morphologically different CNF pairs (tetrahedral amorphous carbon (ta-C) grown “open structured” fibers and traditional bamboo-like “closed structured” fibers), where the surface chemical properties and structural features of the fibers are investigated in depth and the effects of nitric acid treatment on the fibers are revealed. The morphology of the fibermore » and/or the original seed- and adhesion layers markedly affect the response of the fibers to the acid treatment. Results also show that the nitric acid treatment increases the observed sp 2 intensity and modifies the two types of fibers to become more-alike both structurally and with respect to their oxygen functionalities. Furthermore, the XAS and HRTEM results confirm that a short nitric acid treatment does not remove the Ni catalyst particle but, instead, oxidizes their surfaces, especially in the case of ta-C grown fibers.« less

Structure-Property Relationships of Polymer Brushes in Restricted Geometries and their Utilization as Ultra-Low Lubricants

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

Kuhl, Tonya Lynn; Faller, Roland

2015-09-28

Though polymer films are widely used to modify or tailor the physical, chemical and mechanical properties of interfaces in both solid and liquid systems, the rational design of interface- or surface-active polymer modifiers has been hampered by a lack of information about the behavior and structure-property relationships of this class of molecules. This is especially true for systems in which the role of the polymer is to modify the interaction between two solid surfaces in intimate contact and under load, to cause them to be mechanically coupled (e.g. to promote adhesion and wetting) or to minimize their interaction (e.g. lubrication,more » colloidal stabilization, etc.). Detailed structural information on these systems has largely been precluded by the many difficulties and challenges associated with direct experimental measurements of polymer structure in these geometries. As a result, many practitioners have been forced to employ indirect measurements or rely wholly on theoretical modeling. This has resulted in an incomplete understanding of the structure-property relationships, which are relied upon for the rational design of improved polymer modifiers. Over the course of this current research program, we made direct measurements of the structure of polymers at the interface between two solid surfaces under confinement and elucidated the fundamental physics behind these phenomena using atomistic and coarse grained simulations. The research has potential to lead to new lubricants and wear reducing agents to improve efficiency.« less

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

Gotman, Irena, E-mail: gotman@technion.ac.il; Gutmanas, Elazar Y., E-mail: gutmanas@technion.ac.il; Tomsk Polytechnic University, Tomsk, 634050

Continuous research activities in the field of nanomedicine in the past decade have, to a great extent, been focused on nanoparticle technologies for cancer therapy. Gold and iron oxide nanoparticles (NP) are two of the most studied inorganic nanomaterials due to their unique optical and magnetic properties. Both types of NPs are emerging as promising systems for anti-tumor drug delivery and for nanoparticle-mediated thermal therapy of cancer. In thermal therapy, localized heating inside tumors or in proximity of tumor cells can be induced, for example, with Au NPs by radiofrequency ablation heating or conversion of photon energy (photothermal therapy) andmore » in iron oxide magnetic NPs by heat generation through relaxation in an alternating magnetic field (magnetic hyperthermia). Furthermore, the superparamagnetic properties of iron oxide nanoparticles have led to their use as potent MRI (magnetic resonance imaging) contrast agents. Surface modification/coating can produce NPs with tailored and desired properties, such as enhanced blood circulation time, stability, biocompatibility and water solubility. To target nanoparticles to specific tumor cells, NPs should be conjugated with targeting moieties on the surface which bind to receptors or other molecular structures on the cell surface. The article presents several approaches to enhancing the specificity of Au and iron oxide nanoparticles for tumor tissue by appropriate surface modification/functionalization, as well as the effect of these treatments on the saturation magnetization value of iron oxide NPs. The use of other nanoparticles and nanostructures in cancer treatment is also briefly reviewed.« less

Iron oxide and gold nanoparticles in cancer therapy

NASA Astrophysics Data System (ADS)

Gotman, Irena; Psakhie, Sergey G.; Lozhkomoev, Aleksandr S.; Gutmanas, Elazar Y.

2016-08-01

Continuous research activities in the field of nanomedicine in the past decade have, to a great extent, been focused on nanoparticle technologies for cancer therapy. Gold and iron oxide nanoparticles (NP) are two of the most studied inorganic nanomaterials due to their unique optical and magnetic properties. Both types of NPs are emerging as promising systems for anti-tumor drug delivery and for nanoparticle-mediated thermal therapy of cancer. In thermal therapy, localized heating inside tumors or in proximity of tumor cells can be induced, for example, with Au NPs by radiofrequency ablation heating or conversion of photon energy (photothermal therapy) and in iron oxide magnetic NPs by heat generation through relaxation in an alternating magnetic field (magnetic hyperthermia). Furthermore, the superparamagnetic properties of iron oxide nanoparticles have led to their use as potent MRI (magnetic resonance imaging) contrast agents. Surface modification/coating can produce NPs with tailored and desired properties, such as enhanced blood circulation time, stability, biocompatibility and water solubility. To target nanoparticles to specific tumor cells, NPs should be conjugated with targeting moieties on the surface which bind to receptors or other molecular structures on the cell surface. The article presents several approaches to enhancing the specificity of Au and iron oxide nanoparticles for tumor tissue by appropriate surface modification/functionalization, as well as the effect of these treatments on the saturation magnetization value of iron oxide NPs. The use of other nanoparticles and nanostructures in cancer treatment is also briefly reviewed.

The Role of Water in Mediating Interfacial Adhesion and Shear Strength in Graphene Oxide.

PubMed

Soler-Crespo, Rafael A; Gao, Wei; Mao, Lily; Nguyen, Hoang T; Roenbeck, Michael R; Paci, Jeffrey T; Huang, Jiaxing; Nguyen, SonBinh T; Espinosa, Horacio D

2018-06-12

Graphene oxide (GO), whose highly tunable surface chemistry enables the formation of strong interfacial hydrogen-bond networks, has garnered increasing interest in the design of devices that operate in the presence of water. For instance, previous studies have suggested that controlling GO's surface chemistry leads to enhancements in interfacial shear strength, allowing engineers to manage deformation pathways and control failure mechanisms. However, these previous reports have not explored the role of ambient humidity and only offer extensive chemical modifications to GO's surface as the main pathway to control GO's interfacial properties. Herein, through atomic force microscopy experiments on GO-GO interfaces, the adhesion energy and interfacial shear strength of GO were measured as a function of ambient humidity. Experimental evidence shows that adhesion energy and interfacial shear strength can be improved by a factor of 2-3 when GO is exposed to moderate (∼30% water weight) water content. Furthermore, complementary molecular dynamics simulations uncovered the mechanisms by which these nanomaterial interfaces achieve their properties. They reveal that the strengthening mechanism arises from the formation of strongly interacting hydrogen-bond networks, driven by the chemistry of the GO basal plane and intercalated water molecules between two GO surfaces. In summary, the methodology and findings here reported provide pathways to simultaneously optimize GO's interfacial and in-plane mechanical properties, by tailoring the chemistry of GO and accounting for water content, in engineering applications such as sensors, filtration membranes, wearable electronics, and structural materials.

Probing Interfacial Electronic States in CdSe Quantum Dots using Second Harmonic Generation Spectroscopy

DOE PAGES

Doughty, Benjamin L.; Ma, Yingzhong; Shaw, Robert W

2015-01-07

Understanding and rationally controlling the properties of nanomaterial surfaces is a rapidly expanding field of research due to the dramatic role they play on the optical and electronic properties vital to light harvesting, emitting and detection technologies. This information is essential to the continued development of synthetic approaches designed to tailor interfaces for optimal nanomaterial based device performance. In this work, closely spaced electronic excited states in model CdSe quantum dots (QDs) are resolved using second harmonic generation (SHG) spectroscopy, and the corresponding contributions from surface species to these states are assessed. Two distinct spectral features are observed in themore » SHG spectra, which are not readily identified in linear absorption and photoluminescence excitation spectra. These features include a weak band at 395 6 nm, which coincides with transitions to the 2S1/2 1Se state, and a much more pronounced band at 423 4 nm arising from electronic transitions to the 1P3/2 1Pe state. Chemical modification of the QD surfaces through oxidation resulted in disappearance of the SHG band corresponding to the 1P3/2 1Pe state, indicating prominent surface contributions. Signatures of deep trap states localized on the surfaces of the QDs are also observed. We further find that the SHG signal intensities depend strongly on the electronic states being probed and their relative surface contributions, thereby offering additional insight into the surface specificity of SHG signals from QDs.« less

Durable anti-fogging effect and adhesion improvement on polymer surfaces

NASA Astrophysics Data System (ADS)

Moser, E. M.; Gilliéron, D.; Henrion, G.

2010-01-01

The hydrophobic properties of polymeric surfaces may cause fogging in transparent packaging and poor adhesion to printing colours and coatings. Novel plasma processes for durable functionalization of polypropylene and polyethylene terephthalate substrates were developed and analysed using optical emission spectroscopy. A worm-like nano pattern was created on the polypropylene surface prior to the deposition of thin polar plasma polymerised layers. For both substrates, highly polar surfaces exhibiting a surface tension of up to 69 mN/m and a water contact angle of about 10° were produced - providing the anti-fogging effect. The deposition of thin plasma polymerised layers protects the increased surface areas and enables to tailoring the surface energy of the substrate in a wide range. Wetting characteristics were determined by dynamic contact angle measurements. Investigations of the chemical composition of several layers using X-ray photoelectron spectroscopy and FT-infrared spectroscopy were correlated with functional testing. The surface topography was investigated using atomic force microscopy. The weldability and peeling-off characteristics of the plasma treated polymer films could be adjusted by varying the process parameters. Global and specific migration analyses were undertaken in order to ensure the manufacturing of plasma treated polymer surfaces for direct food contact purposes.

Magnesium coated phosphate glass fibers for unidirectional reinforcement of polycaprolactone composites.

PubMed

Liu, Xiaoling; Grant, David M; Palmer, Graham; Parsons, Andrew J; Rudd, Chris D; Ahmed, Ifty

2015-10-01

Bioresorbable composites have shown much potential for bone repair applications, as they have the ability to degrade completely over time and their degradation and mechanical properties can be tailored to suit the end application. In this study, phosphate glass fiber (from the system 45% P2 O5-16% CaO-24% MgO-11% Na2 O-4% Fe2 O3 (given in mol%)) were used to reinforce polycaprolactone (PCL) with approximately 20% fiber volume fraction. The glass fiber surfaces were coated with magnesium (Mg) through magnetron sputtering to improve the fiber-matrix interfacial properties. The Mg coating provided a rough fiber surface (roughness (Ra) of about 44nm). Both noncoated and Mg-coated fiber-reinforced composites were assessed. The water uptake and mass loss properties for the composites were assessed in phosphate-buffered saline (PBS) at 37°C for up to 28 days, and ion release profiles were also investigated in both water and PBS media. Inhibition of media influx was observed for the Mg-coated composites. The composite mechanical properties were characterized on the basis of both tensile and flexural tests and their retention in PBS media at 37°C was also investigated. A higher retention of the mechanical properties was observed for the Mg-coated composites over the 28 days degradation period. © 2014 Wiley Periodicals, Inc.

Aeroelastic Tailoring of Transport Aircraft Wings: State-of-the-Art and Potential Enabling Technologies

NASA Technical Reports Server (NTRS)

Jutte, Christine; Stanford, Bret K.

2014-01-01

This paper provides a brief overview of the state-of-the-art for aeroelastic tailoring of subsonic transport aircraft and offers additional resources on related research efforts. Emphasis is placed on aircraft having straight or aft swept wings. The literature covers computational synthesis tools developed for aeroelastic tailoring and numerous design studies focused on discovering new methods for passive aeroelastic control. Several new structural and material technologies are presented as potential enablers of aeroelastic tailoring, including selectively reinforced materials, functionally graded materials, fiber tow steered composite laminates, and various nonconventional structural designs. In addition, smart materials and structures whose properties or configurations change in response to external stimuli are presented as potential active approaches to aeroelastic tailoring.

Impact of surface strain on the spin dynamics of deposited Co nanowires

NASA Astrophysics Data System (ADS)

Polyakov, O. P.; Korobova, J. G.; Stepanyuk, O. V.; Bazhanov, D. I.

2017-01-01

Tailoring the magnetic properties at atomic-scale is essential in the engineering of modern spintronics devices. One of the main concerns in the novel nanostructured materials design is the decrease of the paid energy in the way of functioning, but allowing to switch between different magnetic states with a relative low-cost energy at the same time. Magnetic anisotropy (MA) energy defines the stability of a spin in the preferred direction and is a fundamental variable in magnetization switching processes. Transition-metal wires are known to develop large, stable spin and orbital magnetic moments together with MA energies that are orders of magnitude larger than in the corresponding solids. Different ways of controlling the MA have been exploited such as alloying, surface charging, and external electrical fields. Here we investigate from a first-principle approach together with dynamic calculations, the surface strain driven mechanism to tune the magnetic properties of deposited nanowires. We consider as a prototype system, the monoatomic Co wires deposited on strained Pt(111) and Au(111) surfaces. Our first-principles calculations reveal a monotonic increase/decrease of MA energy under compressive/tensile strain in supported Co wire. Moreover, the spin dynamics studies based on solving the Landau-Lifshitz-Gilbert equation show that the induced surface-strain leads to a substantial decrease of the required external magnetic field magnitude for magnetization switching in Co wire.

Modification of silicone elastomer with zwitterionic silane for durable antifouling properties.

PubMed

Yeh, Shiou-Bang; Chen, Chien-Sheng; Chen, Wen-Yih; Huang, Chun-Jen

2014-09-30

Biofouling on medical devices generally causes adverse complications, such as thrombosis, infection, and pathogenic calcification. Silicone is a widely used material for medical applications. Its surface modification typically encounters undesirable "hydrophobic recovery", leading to deterioration of surface engineering. In this study, we developed a stable superhydrophilic zwitterionic interface on polydimethylsiloxane (PDMS) elastomer by covalent silanization of sulfobetaine silane (SBSi) to resist nonspecific adsorption of bacteria, proteins, and lipids. SBSi is a zwitterionic organosilane assembly, enabling resisting surface reconstruction by forming a cross-linked network and polar segregation. Surface elemental composition was confirmed by X-ray photoelectron spectroscopy (XPS), and the long-term stability of modification was accessed using a contact angle goniometer. The biofouling tests were carried out by exposing substrates to bacterial, protein, and lipid solutions, revealing the excellent bioinertness of SBSi-tailored PDMS, even after 30 day storage in ambient. For the real-world application, we modified commercially available silicone hydrogel contact lenses with developed zwitterionic silane, presenting its antibacterial adhesion property. Moreover, the cytotoxicity of SBSi was accessed with NIH-3T3 fibroblast by the MTT assay, showing negligible cytotoxicity up to a concentration of 5 mM. Consequently, the strategy of surface engineering in this work can effectively retard the "hydrophobic recovery" occurrence and can be applied to other silicone-based medical devices in a facile way.

Facile modulation of cell adhesion to a poly(ethylene glycol) diacrylate film with incorporation of polystyrene nano-spheres.

PubMed

Yang, Wenguang; Yu, Haibo; Li, Gongxin; Wang, Yuechao; Liu, Lianqing

2016-12-01

Poly(ethylene glycol) diacrylate (PEGDA) is a common hydrogel that has been actively investigated for various tissue engineering applications owing to its biocompatibility and excellent mechanical properties. However, the native PEGDA films are known for their bio-inertness which can hinder cell adhesion, thereby limiting their applications in tissue engineering and biomedicine. Recently, nano composite technology has become a particularly hot topic, and has led to the development of new methods for delivering desired properties to nanomaterials. In this study, we added polystyrene nano-spheres (PS) into a PEGDA solution to synthesize a nano-composite film and evaluated its characteristics. The experimental results showed that addition of the nanospheres to the PEGDA film not only resulted in modification of the mechanical properties and surface morphology but further improved the adhesion of cells on the film. The tensile modulus showed clear dependence on the addition of PS, which enhanced the mechanical properties of the PEGDA-PS film. We attribute the high stiffness of the hybrid hydrogel to the formation of additional cross-links between polymeric chains and the nano-sphere surface in the network. The effect of PS on cell adhesion and proliferation was evaluated in L929 mouse fibroblast cells that were seeded on the surface of various PEGDA-PS films. Cells density increased with a larger PS concentration, and the cells displayed a spreading morphology on the hybrid films, which promoted cell proliferation. Impressively, cellular stiffness could also be modulated simply by tuning the concentration of nano-spheres. Our results indicate that the addition of PS can effectively tailor the physical and biological properties of PEGDA as well as the mechanical properties of cells, with benefits for biomedical and biotechnological applications.

Bridging Nano- and Microtribology in Mechanical and Biomolecular Layers

NASA Astrophysics Data System (ADS)

Tomala, Agnieszka; Göçerler, Hakan; Gebeshuber, Ille C.

The physical and chemical composition of surfaces determine various important properties of solids such as corrosion rates, adhesive properties, frictional properties, catalytic activity, wettability, contact potential and - finally and most importantly - failure mechanisms. Very thin, weak layers (of man-made and biological origin) on much harder substrates that reduce friction are the focus of the micro- and nanotribological investigations presented in this chapter.Biomolecular layers fulfil various functions in organs of the human body. Examples comprise the skin that provides a protective physical barrier between the body and the environment, preventing unwanted inward and outward passage of water and electrolytes, reducing penetration by destructive chemicals, arresting the penetration of microorganisms and external antigens and absorbing radiation from the sun, or the epithelium of the cornea that blocks the passage of foreign material, such as dust, water and bacteria, into the eye and that contributes to the lubrication layer that ensures smooth movement of the eyelids over the eyeballs.Monomolecular thin films, additive-derived reaction layers and hard coatings are widely used to tailor tribological properties of surfaces. Nanotribological investigations on these substrates can reveal novel properties regarding the orientation of chemisorbed additive layers, development of rubbing films with time and the relation of frictional properties to surface characteristics in diamond coatings.Depending on the questions to be answered with the tribological research, various micro- and nanotribological measurement methods are applied, including scanning probe microscopy (AFM, FFM), scanning electron microscopy, microtribometer investigations, angle-resolved photoelectron spectroscopy and optical microscopy. Thoughts on the feasibility of a unified approach to energy-dissipating systems and how it might be reached (touching upon new ways of scientific publishing, dealing with over-information regarding the literature and the importance of specialists as well as generalists in tribology) conclude this chapter.

Control of the interparticle spacing in superparamagnetic iron oxide nanoparticle clusters by surface ligand engineering

NASA Astrophysics Data System (ADS)

Dan, Wang; Bingbing, Lin; Taipeng, Shen; Jun, Wu; Fuhua, Hao; Chunchao, Xia; Qiyong, Gong; Huiru, Tang; Bin, Song; Hua, Ai

2016-07-01

Polymer-mediated self-assembly of superparamagnetic iron oxide (SPIO) nanoparticles allows modulation of the structure of SPIO nanocrystal cluster and their magnetic properties. In this study, dopamine-functionalized polyesters (DA-polyester) were used to directly control the magnetic nanoparticle spacing and its effect on magnetic resonance relaxation properties of these clusters was investigated. Monodisperse SPIO nanocrystals with different surface coating materials (poly(ɛ-caprolactone), poly(lactic acid)) of different molecular weights containing dopamine (DA) structure (DA-PCL2k, DA-PCL1k, DA-PLA1k)) were prepared via ligand exchange reaction, and these nanocrystals were encapsulated inside amphiphilic polymer micelles to modulate the SPIO nanocrystal interparticle spacing. Small-angle x-ray scattering (SAXS) was applied to quantify the interparticle spacing of SPIO clusters. The results demonstrated that the tailored magnetic nanoparticle clusters featured controllable interparticle spacing providing directly by the different surface coating of SPIO nanocrystals. Systematic modulation of SPIO nanocrystal interparticle spacing can regulate the saturation magnetization (M s) and T 2 relaxation of the aggregation, and lead to increased magnetic resonance (MR) relaxation properties with decreased interparticle spacing. Project supported by the National Key Basic Research Program of China (Grant No. 2013CB933903), the National Key Technology R&D Program of China (Grant No. 2012BAI23B08), and the National Natural Science Foundation of China (Grant Nos. 20974065, 51173117, and 50830107).

Photocatalytic oxide films in the built environment

NASA Astrophysics Data System (ADS)

Österlund, Lars; Topalian, Zareh

2014-11-01

The possibility to increase human comfort in buildings is a powerful driving force for the introduction of new technology. Among other things our sense of comfort depends on air quality, temperature, lighting level, and the possibility of having visual contact between indoors and outdoors. Indeed there is an intimate connection between energy, comfort, and health issues in the built environment, leading to a need for intelligent building materials and green architecture. Photocatalytic materials can be applied as coatings, filters, and be embedded in building materials to provide self-cleaning, antibacterial, air cleaning, deodorizing, and water cleaning functions utilizing either solar light or artificial illumination sources - either already present in buildings, or by purposefully designed luminaries. Huge improvements in indoor comfort can thus be made, and also alleviate negative health effects associated with buildings, such as the sick-house syndrome. At the same time huge cost savings can be made by reducing maintenance costs. Photocatalytic oxides can be chemically modified by changing their acid-base surface properties, which can be used to overcome deactivation problems commonly encountered for TiO2 in air cleaning applications. In addition, the wetting properties of oxides can be tailored by surface chemical modifications and thus be made e.g. oleophobic and water repellent. Here we show results of surface acid modified TiO2 coatings on various substrates by means of photo-fixation of surface sulfate species by a method invented in our group. In particular, we show that such surface treatments of photocatalytic concrete made by mixing TiO2 nanoparticles in reactive concrete powders result in concrete surfaces with beneficial self-cleaning properties. We propose that such approaches are feasible for a number of applications in the built environment, including glass, tiles, sheet metals, plastics, etc.

Ligand-tailored single-site silica supported titanium catalysts: Synthesis, characterization and towards cyanosilylation reaction

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

Xu, Wei; Li, Yani; Yu, Bo

2015-01-15

A successive anchoring of Ti(NMe{sub 2}){sub 4}, cyclopentadiene and a O-donor ligand, 1-hydroxyethylbenzene (PEA), 1,1′-bi-2-naphthol (Binol) or 2,3-dihydroxybutanedioic acid diethyl ester (Tartrate), on silica was conducted by SOMC strategy in moderate conditions. The silica, monitored by in-situ Fourier transform infrared spectroscopy (in-situ FT-IR), was pretreated at different temperatures (200, 500 and 800 °C). The ligand tailored silica-supported titanium complexes were characterized by in-situ FT-IR, {sup 13}C CP MAS-NMR, X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge structure (XANES) and elemental analysis in detail, verifying that the surface titanium species are single sited. The catalytic activity of the ligand tailored single-sitemore » silica supported titanium complexes was evaluated by a cyanosilylation of benzaldehyde. The results showed that the catalytic activity is dependent strongly on the dehydroxylation temperatures of silica and the configuration of the ligands. - Graphical abstract: The ligand-tailored silica supported “single site” titanium complexes were synthesized by SOMC strategy and fully characterized. Their catalytic activity were evaluated by benzaldehyde silylcyanation. - Highlights: • Single-site silica supported Ti active species was prepared by SOMC technique. • O-donor ligand tailored Ti surface species was synthesized. • The surface species was characterized by XPS, {sup 13}C CP-MAS NMR, XANES etc. • Catalytic activity of the Ti active species in silylcyanation reaction was evaluated.« less

Uncovering the Design Principle of Amino Acid-Derived Photoluminescent Biodots with Tailor-Made Structure-Properties and Applications for Cellular Bioimaging.

PubMed

Xu, Hesheng Victor; Zheng, Xin Ting; Zhao, Yanli; Tan, Yen Nee

2018-06-13

Natural amino acids possess side chains with different functional groups (R groups), which make them excellent precursors for programmable synthesis of biomolecule-derived nanodots (biodots) with desired properties. Herein, we report the first systematic study to uncover the material design rules of biodot synthesis from 20 natural α-amino acids via a green hydrothermal approach. The as-synthesized amino acid biodots (AA dots) are comprehensively characterized to establish a structure-property relationship between the amino acid precursors and the corresponding photoluminescent properties of AA dots. It was found that the amino acids with reactive R groups, including amine, hydroxyl, and carboxyl functional groups form unique C-O-C/C-OH and N-H bonds in the AA dots which stabilize the surface defects, giving rise to brightly luminescent AA dots. Furthermore, the AA dots were found to be amorphous and the length of the R group was observed to affect the final morphology (e.g., disclike nanostructure, nanowire, or nanomesh) of the AA dots, which in turn influence their photoluminescent properties. It is noteworthy to highlight that the hydroxyl-containing amino acids, that is, Ser and Thr, form the brightest AA dots with a quantum yield of 30.44% and 23.07%, respectively, and possess high photostability with negligible photobleaching upon continuous UV exposure for 3 h. Intriguingly, by selective mixing of Ser or Thr with another amino acid precursor, the resulting mixed AA dots could inherit unique properties such as improved photostability and significant red shift in their emission wavelength, producing enhanced green and red fluorescent intensity. Moreover, our cellular studies demonstrate that the as-synthesized AA dots display outstanding biocompatibility and excellent intracellular uptake, which are highly desirable for imaging applications. We envision that the material design rules discovered in this study will be broadly applicable for the rational selection of amino acid precursors in the tailored synthesis of biodots.

Tailored porous silicon microparticles: fabrication and properties

PubMed Central

Chiappini, Ciro; Tasciotti, Ennio; Fakhoury, Jean R.; Fine, Daniel; Pullan, Lee; Wang, Young-Chung; Fu, Lianfeng

2010-01-01

The use of mesoporous silicon particles for drug delivery has been widely explored thanks to their biodegradability and biocompatibility. The ability to tailor the physicochemical properties of porous silicon at the micro and nano scale confers versatility to this material. We present a method for the fabrication of highly reproducible, monodisperse mesoporous silicon particles with controlled physical characteristics through electrochemical etch of patterned silicon trenches. We tailored particle size in the micrometer range and pore size in the nanometer range, shape from tubular to discoidal to hemispherical, and porosity from 46% to over 80%. In addition, we correlated the properties of the porous matrix with the loading of model nanoparticles (Q-dots) and observed their three-dimensional arrangement within the matrix by transmission electron microscopy tomography. The methods developed in this study provide effective means to fabricate mesoporous silicon particles according to the principles of rational design for therapeutic vectors and to characterize the distribution of nanoparticles within the porous matrix PMID:20162656

Advancements in tailored hot stamping simulations: Cooling channel and distortion analyses

NASA Astrophysics Data System (ADS)

Billur, Eren; Wang, Chao; Bloor, Colin; Holecek, Martin; Porzner, Harald; Altan, Taylan

2013-12-01

Hot stamped components have been widely used in the automotive industry in the last decade where ultra high strength is required. These parts, however, may not provide sufficient toughness to absorb crash energy. Therefore, these components are "tailored" by controlling the microstructure at various locations. Simulation of tailored hot stamped components requires more detailed analysis of microstructural changes. Furthermore, since the part is not uniformly quenched, severe distortion can be observed. CPF, together with ESI have developed a number of techniques to predict the final properties of a tailored part. This paper discusses the recent improvements in modeling distortion and die design with cooling channels.

Tailoring Silica-alumina Supported Pt-Pd As Poison Tolerant Catalyst For Aromatics Hydrogenation

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

Yu, Yanzhe; Gutierrez, Oliver Y.; Haller, Gary L.

2013-08-01

The tailoring of the physicochemical and catalytic properties of mono- and bimetallic Pt-Pd catalysts supported on amorphous silica-alumina is studied. Electron energy loss spectroscopy and extended X-ray absorption fine structure analyses indicated that bimetallic Pt-Pd and relatively large monometallic Pd particles were formed, whereas the X-ray absorption near edge structure provided direct evidence for the electronic deficiency of the Pt atoms. The heterogeneous distribution of metal particles was also shown by high resolution transmission electron microscopy. The average structure of the bimetallic particles (Pt-rich core and Pd-rich shell) and the presence of Pd particles led to surface Pd enrichment, whichmore » was independently shown by IR spectra of adsorbed CO. The specific metal distribution, average size, and surface composition of the Pt-Pd particles depend to a large extent on the metal precursors. In the presence of NH3 ligands, Pt-Pd particles with a fairly homogeneous bulk and surface metal distribution were formed. Also high Lewis acid site concentration of the carrier leads to more homogeneous bimetallic particles. All catalysts were active for the hydrogenation of tetralin in the absence and presence of quinoline and dibenzothiophene (DBT). Monometallic Pt catalysts had the highest hydrogenation activity in poison-free and quinoline-containing feed. When DBT was present, bimetallic Pt-Pd catalysts with the most homogenous metal distribution showed the highest activity. The higher resistance of bimetallic catalysts towards sulfur poisoning compared to their monometallic Pt counterparts results from the weakened metal-sulfur bond on the electron deficient Pt atoms. Thus, increasing the fraction of electron deficient Pt on the surface of the bimetallic particles increases the efficiency of the catalyst in the presence of sulfur.« less

Free surfaces recast superconductivity in few-monolayer MgB2: Combined first-principles and ARPES demonstration.

PubMed

Bekaert, J; Bignardi, L; Aperis, A; van Abswoude, P; Mattevi, C; Gorovikov, S; Petaccia, L; Goldoni, A; Partoens, B; Oppeneer, P M; Peeters, F M; Milošević, M V; Rudolf, P; Cepek, C

2017-10-31

Two-dimensional materials are known to harbour properties very different from those of their bulk counterparts. Recent years have seen the rise of atomically thin superconductors, with a caveat that superconductivity is strongly depleted unless enhanced by specific substrates, intercalants or adatoms. Surprisingly, the role in superconductivity of electronic states originating from simple free surfaces of two-dimensional materials has remained elusive to date. Here, based on first-principles calculations, anisotropic Eliashberg theory, and angle-resolved photoemission spectroscopy (ARPES), we show that surface states in few-monolayer MgB 2 make a major contribution to the superconducting gap spectrum and density of states, clearly distinct from the widely known, bulk-like σ- and π-gaps. As a proof of principle, we predict and measure the gap opening on the magnesium-based surface band up to a critical temperature as high as ~30 K for merely six monolayers thick MgB 2 . These findings establish free surfaces as an unavoidable ingredient in understanding and further tailoring of superconductivity in atomically thin materials.

Surface Patterning Using Diazonium Ink Filled Nanopipette.

PubMed

Zhou, Min; Yu, Yun; Blanchard, Pierre-Yves; Mirkin, Michael V

2015-11-03

Molecular grafting of diazonium is a widely employed surface modification technique. Local electrografting of this species is a promising approach to surface doping and related properties tailoring. The instability of diazonium cation complicates this process, so that this species was generated in situ in many reported studies. In this Article, we report the egress transfer of aryl diazonium cation across the liquid/liquid interface supported at the nanopipette tip that can be used for controlled delivery this species to the external aqueous phase for local substrate patterning. An aryl diazonium salt was prepared with weakly coordinating and lipophilic tetrakis(pentafluorophenyl)borate anion stable as a solid and soluble in low polarity media. The chemically stable solution of this salt in 1,2-dichloroethane can be used as "diazonium ink". The ink-filled nanopipette was employed as a tip in the scanning electrochemical microscope (SECM) for surface patterning with the spatial resolution controlled by the pipette orifice radius and a few nanometers film thickness. The submicrometer-size grafted spots produced on the HOPG surface were located and imaged with the atomic force microscope (AFM).

Dry powder inhaler performance of spray dried mannitol with tailored surface morphologies as carrier and salbutamol sulphate.

PubMed

Mönckedieck, M; Kamplade, J; Fakner, P; Urbanetz, N A; Walzel, P; Steckel, H; Scherließ, R

2017-05-30

Nowadays, dry powder inhalation as applied in the therapy of pulmonary diseases is known as a very effective route of drug delivery to the lungs. Here, the system of coarse carrier and fine drug particles attached to the carrier surface has successfully been applied to overcome the cohesiveness of small drug particles. Particle properties of both carrier and drug are known to affect drug dispersion as has widely been discussed for lactose monohydrate and various drugs. This study utilises particle-engineered mannitol as an alternative carrier to discover the effect of mannitol carrier particle properties like particle shape, surface roughness, flowability or particle size on aerodynamic performance during inhalation. Spray drying as a technique to accurately control those properties was chosen for the generation of carrier sizes between 50 and 80 μm and different morphologies and therefore various carrier flowabilities. A set of these carriers has then been blended with different spray dried and jet-milled qualities of salbutamol sulphate as model drug to examine the influence of carrier particle properties on aerodynamic behaviour and at the same time to cover the effect of drug particle properties on particle-particle interactions. This experimental setup allowed a general view on how drug and carrier properties affect the Fine Particle Fraction (FPF) as indicator for inhalation performance and gave the first study to distinguish between mannitol carrier particle shape and surface roughness. Further it was possible to relate carrier particle size and shape to drug accumulation and detachment mechanisms during inhalation as size and shape had the main influence on drug detachment. The addition of jet-milled mannitol fines provided an initial insight into the improving effect of ternary powder blends as has been intensively studied for lactose monohydrate but not for mannitol yet. Copyright © 2017 Elsevier B.V. All rights reserved.

Sequence-Dependent Structure/Function Relationships of Catalytic Peptide-Enabled Gold Nanoparticles Generated under Ambient Synthetic Conditions

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

Bedford, Nicholas M.; Hughes, Zak E.; Tang, Zhenghua

Peptide-enabled nanoparticle (NP) synthesis routes can create and/or assemble functional nanomaterials under environmentally friendly conditions, with properties dictated by complex interactions at the biotic/abiotic interface. Manipulation of this interface through sequence modification can provide the capability for material properties to be tailored to create enhanced materials for energy, catalysis, and sensing applications. Fully realizing the potential of these materials requires a comprehensive understanding of sequence-dependent structure/function relationships that is presently lacking. In this work, the atomic-scale structures of a series of peptide-capped Au NPs are determined using a combination of atomic pair distribution function analysis of high-energy X-ray diffraction datamore » and advanced molecular dynamics (MD) simulations. The Au NPs produced with different peptide sequences exhibit varying degrees of catalytic activity for the exemplar reaction 4-nitrophenol reduction. The experimentally derived atomic-scale NP configurations reveal sequence-dependent differences in structural order at the NP surface. Replica exchange with solute-tempering MD simulations are then used to predict the morphology of the peptide overlayer on these Au NPs and identify factors determining the structure/catalytic properties relationship. We show that the amount of exposed Au surface, the underlying surface structural disorder, and the interaction strength of the peptide with the Au surface all influence catalytic performance. A simplified computational prediction of catalytic performance is developed that can potentially serve as a screening tool for future studies. Our approach provides a platform for broadening the analysis of catalytic peptide-enabled metallic NP systems, potentially allowing for the development of rational design rules for property enhancement.« less

A chemical stability study of trimethylsilane plasma nanocoatings for coronary stents.

PubMed

Jones, John Eric; Yu, Qingsong; Chen, Meng

2017-01-01

Trimethylsilane (TMS) plasma nanocoatings were deposited onto stainless steel coupons in direct current (DC) and radio frequency (RF) glow discharges and additional NH 3 /O 2 plasma treatment to tailor the coating surface properties. The chemical stability of the nanocoatings were evaluated after 12 week storage under dry condition (25 °C) and immersion in simulated body fluid (SBF) at 37 °C. It was found that nanocoatings did not impact surface roughness of underlying stainless steel substrates. X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy were used to characterize surface chemistry and compositions. Both DC and RF nanocoatings had Si- and C-rich composition; and the O- and N-contents on the surfaces were substantially increased after NH 3 /O 2 plasma treatment. Contact angle measurements showed that DC-TMS nanocoating with NH 3 /O 2 treatment generated very hydrophilic surfaces. DC-TMS nanocoatings with NH 3 /O 2 treatment showed minimal surface chemistry change after 12 week immersion in SBF. However, nitrogen functionalities on RF-TMS coating with NH 3 /O 2 post treatment were not as stable as in DC case. Cell culture studies revealed that the surfaces with DC coating and NH 3 /O 2 post treatment demonstrated substantially improved proliferation of endothelial cells over the 12 week storage period at both dry and wet conditions, as compared to other coated surfaces. Therefore, DC nanocoatings with NH 3 /O 2 post treatment may be chemically stable for long-term properties, including shelf-life storage and exposure to the bloodstream for coronary stent applications.

Stem cell behavior on tailored porous oxide surface coatings.

PubMed

Lavenus, Sandrine; Poxson, David J; Ogievetsky, Nika; Dordick, Jonathan S; Siegel, Richard W

2015-07-01

Nanoscale surface topographies are known to have a profound influence on cell behavior, including cell guidance, migration, morphology, proliferation, and differentiation. In this study, we have observed the behavior of human mesenchymal stem cells cultured on a range of tailored porous SiO2 and TiO2 nanostructured surface coatings fabricated via glancing angle electron-beam deposition. By controlling the physical vapor deposition angle during fabrication, we could control systematically the deposited coating porosity, along with associated topographic features. Immunocytochemistry and image analysis quantitatively revealed the number of adherent cells, as well as their basic cellular morphology, on these surfaces. Signaling pathway studies showed that even with subtle changes in nanoscale surface structures, the behavior of mesenchymal stem cells was strongly influenced by the precise surface structures of these porous coatings. Copyright © 2015 Elsevier Ltd. All rights reserved.

ATRP-based synthesis and characterization of light-responsive coatings for transdermal delivery systems

PubMed Central

Pauly, Anja C; Schöller, Katrin; Baumann, Lukas; Rossi, René M; Dustmann, Kathrin; Ziener, Ulrich; de Courten, Damien; Wolf, Martin; Boesel, Luciano F; Scherer, Lukas J

2015-01-01

The grafting of poly(hydroxyethylmethacrylate) on polymeric porous membranes via atom transfer radical polymerization (ATRP) and subsequent modification with a photo-responsive spiropyran derivative is described. This method leads to photo-responsive membranes with desirable properties such as light-controlled permeability changes, exceptional photo-stability and repeatability of the photo-responsive switching. Conventional track etched polyester membranes were first treated with plasma polymer coating introducing anchoring groups, which allowed the attachment of ATRP-initiator molecules on the membrane surface. Surface initiated ARGET–ATRP of hydroxyethylmethacrylate (where ARGET stands for activator regenerated by electron transfer) leads to a membrane covered with a polymer layer, whereas the controlled polymerization procedure allows good control over the thickness of the polymer layer in respect to the polymerization conditions. Therefore, the final permeability of the membranes could be tailored by choice of pore diameter of the initial membranes, applied monomer concentration or polymerization time. Moreover a remarkable switch in permeability (more than 1000%) upon irradiation with UV-light could be achieved. These properties enable possible applications in the field of transdermal drug delivery, filtration, or sensing. PMID:27877791

Metamorphic quantum dots: Quite different nanostructures

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

Seravalli, L.; Frigeri, P.; Nasi, L.

In this work, we present a study of InAs quantum dots deposited on InGaAs metamorphic buffers by molecular beam epitaxy. By comparing morphological, structural, and optical properties of such nanostructures with those of InAs/GaAs quantum dot ones, we were able to evidence characteristics that are typical of metamorphic InAs/InGaAs structures. The more relevant are: the cross-hatched InGaAs surface overgrown by dots, the change in critical coverages for island nucleation and ripening, the nucleation of new defects in the capping layers, and the redshift in the emission energy. The discussion on experimental results allowed us to conclude that metamorphic InAs/InGaAs quantummore » dots are rather different nanostructures, where attention must be put to some issues not present in InAs/GaAs structures, namely, buffer-related defects, surface morphology, different dislocation mobility, and stacking fault energies. On the other hand, we show that metamorphic quantum dot nanostructures can provide new possibilities of tailoring various properties, such as dot positioning and emission energy, that could be very useful for innovative dot-based devices.« less

ATRP-based synthesis and characterization of light-responsive coatings for transdermal delivery systems

NASA Astrophysics Data System (ADS)

Pauly, Anja C.; Schöller, Katrin; Baumann, Lukas; Rossi, René M.; Dustmann, Kathrin; Ziener, Ulrich; de Courten, Damien; Wolf, Martin; Boesel, Luciano F.; Scherer, Lukas J.

2015-06-01

The grafting of poly(hydroxyethylmethacrylate) on polymeric porous membranes via atom transfer radical polymerization (ATRP) and subsequent modification with a photo-responsive spiropyran derivative is described. This method leads to photo-responsive membranes with desirable properties such as light-controlled permeability changes, exceptional photo-stability and repeatability of the photo-responsive switching. Conventional track etched polyester membranes were first treated with plasma polymer coating introducing anchoring groups, which allowed the attachment of ATRP-initiator molecules on the membrane surface. Surface initiated ARGET-ATRP of hydroxyethylmethacrylate (where ARGET stands for activator regenerated by electron transfer) leads to a membrane covered with a polymer layer, whereas the controlled polymerization procedure allows good control over the thickness of the polymer layer in respect to the polymerization conditions. Therefore, the final permeability of the membranes could be tailored by choice of pore diameter of the initial membranes, applied monomer concentration or polymerization time. Moreover a remarkable switch in permeability (more than 1000%) upon irradiation with UV-light could be achieved. These properties enable possible applications in the field of transdermal drug delivery, filtration, or sensing.

Size Dependence of Doping by a Vacancy Formation Reaction in Copper Sulfide Nanocrystals

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

Elimelech, Orian; Liu, Jing; Plonka, Anna M.

Doping of nanocrystals (NCs) is a key, yet underexplored, approach for tuning of the electronic properties of semiconductors. An important route for doping of NCs is by vacancy formation. The size and concentration dependence of doping was studied in copper(I) sulfide (Cu2S) NCs through a redox reaction with iodine molecules (I2), which formed vacancies accompanied by a localized surface plasmon response. X-ray spectroscopy and diffraction reveal transformation from Cu2S to Cu-depleted phases, along with CuI formation. Greater reaction efficiency was observed for larger NCs. This behavior is attributed to interplay of the vacancy formation energy, which decreases for smaller sizedmore » NCs, and the growth of CuI on the NC surface, which is favored on well-defined facets of larger NCs. This doping process allows tuning of the plasmonic properties of a semiconductor across a wide range of plasmonic frequencies by varying the size of NCs and the concentration of iodine. Controlled vacancy doping of NCs may be used to tune and tailor semiconductors for use in optoelectronic applications.« less

Freeze Tape Casting of Functionally Graded Porous Ceramics

NASA Technical Reports Server (NTRS)

Sofie, Stephen W.

2007-01-01

Freeze tape casting is a means of making preforms of ceramic sheets that, upon subsequent completion of fabrication processing, can have anisotropic and/or functionally graded properties that notably include aligned and graded porosity. Freeze tape casting was developed to enable optimization of the microstructures of porous ceramic components for use as solid oxide electrodes in fuel cells: Through alignment and grading of pores, one can tailor surface areas and diffusion channels for flows of gas and liquid species involved in fuel-cell reactions. Freeze tape casting offers similar benefits for fabrication of optimally porous ceramics for use as catalysts, gas sensors, and filters.

Gas-sensing enhancement methods for hydrothermal synthesized SnO2-based sensors

NASA Astrophysics Data System (ADS)

Zhao, Yalei; Zhang, Wenlong; Yang, Bin; Liu, Jingquan; Chen, Xiang; Wang, Xiaolin; Yang, Chunsheng

2017-11-01

Gas sensing for hydrothermal synthesized SnO2-based gas sensors can be enhanced in three ways: structural improvement, composition optimization, and processing improvement. There have been zero-dimensional, one-dimensional, and three-dimensional structures reported in the literature. Controllable synthesis of different structures has been deployed to increase specific surface area. Change of composition would intensively tailor the SnO2 structure, which affected the gas-sensing performance. Furthermore, doping and compounding methods have been adopted to promote gas-sensing performance by adjusting surface conditions of SnO2 crystals and constructing heterojunctions. As for processing area, it is very important to find the optimal reaction time and temperature. In this paper, a gas-solid reaction rate constant was proposed to evaluate gas-sensing properties and find an excellent hydrothermal synthesized SnO2-based gas sensor.

Double-tailored nonimaging reflector optics for maximum-performance solar concentration.

PubMed

Goldstein, Alex; Gordon, Jeffrey M

2010-09-01

A nonimaging strategy that tailors two mirror contours for concentration near the étendue limit is explored, prompted by solar applications where a sizable gap between the optic and absorber is required. Subtle limitations of this simultaneous multiple surface method approach are derived, rooted in the manner in which phase space boundaries can be tailored according to the edge-ray principle. The fundamental categories of double-tailored reflective optics are identified, only a minority of which can pragmatically offer maximum concentration at high collection efficiency. Illustrative examples confirm that acceptance half-angles as large as 30 mrad can be realized at a flux concentration of approximately 1000.

Modulation of Silica Nanoparticle Uptake into Human Osteoblast Cells by Variation of the Ratio of Amino and Sulfonate Surface Groups: Effects of Serum

PubMed Central

2015-01-01

To study the importance of the surface charge for cellular uptake of silica nanoparticles (NPs), we synthesized five different single- or multifunctionalized fluorescent silica NPs (FFSNPs) by introducing various ratios of amino and sulfonate groups into their surface. The zeta potential values of these FFSNPs were customized from highly positive to highly negative, while other physicochemical properties remained almost constant. Irrespective of the original surface charge, serum proteins adsorbed onto the surface, neutralized the zeta potential values, and prevented the aggregation of the tailor-made FFSNPs. Depending on the surface charge and on the absence or presence of serum, two opposite trends were found concerning the cellular uptake of FFSNPs. In the absence of serum, positively charged NPs were more strongly accumulated by human osteoblast (HOB) cells than negatively charged NPs. In contrast, in serum-containing medium, anionic FFSNPs were internalized by HOB cells more strongly, despite the similar size and surface charge of all types of protein-covered FFSNPs. Thus, at physiological condition, when the presence of proteins is inevitable, sulfonate-functionalized silica NPs are the favorite choice to achieve a desired high rate of NP internalization. PMID:26030456

Evolution and tailoring of plasmonic properties in Ag:ZrO2 nanocomposite films by swift heavy ion irradiation

NASA Astrophysics Data System (ADS)

Kumar, Manish; Kulriya, P. K.; Pivin, J. C.; Avasthi, D. K.

2011-02-01

Ag:ZrO2 nanocomposite films have been synthesized by a sol-gel dip coating process at room temperature, followed by irradiation using swift heavy ions. The effect of electronic energy loss and fluences on the evolution and consequently on the tailoring of plasmonic properties of films has been studied. The optical study exhibits that color of films converts from transparent in pristine form into shiny yellow when films are irradiated by 100 MeV Ag ions at a fluence of 3×1012 ions/cm2. However, irradiation by 120 MeV O ions up to the fluence of 1 × 1014 ions/cm2 does not induce any coloration in films. The coloration is attributed to the evolution of plasmonic feature resulting in a surface plasmon resonance (SPR) induced absorption peak in the visible region. Increase in fluence from 3 × 1012 to 6 × 1013 ions/cm2 of 100 MeV Ag ions induces a redshift in SPR induced peak position from 434 to 487 nm. Microstructural studies confirms the conversion of Ag2O3 (in pristine films) into cubic phase of metallic Ag and the increase of average size of particles with the increasing fluence up to 6 × 1013 ions/cm2. Further increase in fluence leads to the dissolution of Ag atoms in the ZrO2 matrix.

An oxygen pressure sensor using surface acoustic wave devices

NASA Technical Reports Server (NTRS)

Leighty, Bradley D.; Upchurch, Billy T.; Oglesby, Donald M.

1993-01-01

Surface acoustic wave (SAW) piezoelectric devices are finding widespread applications in many arenas, particularly in the area of chemical sensing. We have developed an oxygen pressure sensor based on coating a SAW device with an oxygen binding agent which can be tailored to provide variable sensitivity. The coating is prepared by dissolving an oxygen binding agent in a toluene solution of a copolymer which is then sprayed onto the surface of the SAW device. Experimental data shows the feasibility of tailoring sensors to measure the partial pressure of oxygen from 2.6 to 67 KPa (20 to 500 torr). Potential applications of this technology are discussed.

Concise Review: Fabrication, Customization, and Application of Cell Mimicking Microparticles in Stem Cell Science

PubMed Central

Labriola, Nicholas R.; Azagury, Aharon; Gutierrez, Robert; Mathiowitz, Edith

2018-01-01

Abstract Stem and non‐stem cell behavior is heavily influenced by the surrounding microenvironment, which includes other cells, matrix, and potentially biomaterials. Researchers have been successful in developing scaffolds and encapsulation techniques to provide stem cells with mechanical, topographical, and chemical cues to selectively direct them toward a desired differentiation pathway. However, most of these systems fail to present truly physiological replications of the in vivo microenvironments that stem cells are typically exposed to in tissues. Thus, cell mimicking microparticles (CMMPs) have been developed to more accurately recapitulate the properties of surrounding cells while still offering ways to tailor what stimuli are presented. This nascent field holds the promise of reducing, or even eliminating, the need for live cells in select, regenerative medicine therapies, and diagnostic applications. Recent, CMMP‐based studies show great promise for the technology, yet only reproduce a small subset of cellular characteristics from among those possible: size, morphology, topography, mechanical properties, surface molecules, and tailored chemical release to name the most prominent. This Review summarizes the strengths, weaknesses, and ideal applications of micro/nanoparticle fabrication and customization methods relevant to cell mimicking and provides an outlook on the future of this technology. Moving forward, researchers should seek to combine multiple techniques to yield CMMPs that replicate as many cellular characteristics as possible, with an emphasis on those that most strongly influence the desired therapeutic effects. The level of flexibility in customizing CMMP properties allows them to substitute for cells in a variety of regenerative medicine, drug delivery, and diagnostic systems. Stem Cells Translational Medicine 2018;7:232–240 PMID:29316362

Photoelectrochemistry by Design: Tailoring the Nanoscale Structure of Pt/NiO Composites Leads to Enhanced Photoelectrochemical Hydrogen Evolution Performance

PubMed Central

2017-01-01

Photoelectrochemical hydrogen evolution is a promising avenue to store the energy of sunlight in the form of chemical bonds. The recent rapid development of new synthetic approaches enables the nanoscale engineering of semiconductor photoelectrodes, thus tailoring their physicochemical properties toward efficient H2 formation. In this work, we carried out the parallel optimization of the morphological features of the semiconductor light absorber (NiO) and the cocatalyst (Pt). While nanoporous NiO films were obtained by electrochemical anodization, the monodisperse Pt nanoparticles were synthesized using wet chemical methods. The Pt/NiO nanocomposites were characterized by XRD, XPS, SEM, ED, TEM, cyclic voltammetry, photovoltammetry, EIS, etc. The relative enhancement of the photocurrent was demonstrated as a function of the nanoparticle size and loading. For mass-specific surface activity the smallest nanoparticles (2.0 and 4.8 nm) showed the best performance. After deconvoluting the trivial geometrical effects (stemming from the variation of Pt particle size and thus the electroactive surface area), however, the intermediate particle sizes (4.8 and 7.2 nm) were found to be optimal. Under optimized conditions, a 20-fold increase in the photocurrent (and thus the H2 evolution rates) was observed for the nanostructured Pt/NiO composite, compared to the benchmark nanoparticulate NiO film. PMID:28620447

Plasma-Enabled Carbon Nanostructures for Early Diagnosis of Neurodegenerative Diseases

PubMed Central

Pineda, Shafique; Han, Zhao Jun; Ostrikov, Kostya (Ken)

2014-01-01

Carbon nanostructures (CNs) are amongst the most promising biorecognition nanomaterials due to their unprecedented optical, electrical and structural properties. As such, CNs may be harnessed to tackle the detrimental public health and socio-economic adversities associated with neurodegenerative diseases (NDs). In particular, CNs may be tailored for a specific determination of biomarkers indicative of NDs. However, the realization of such a biosensor represents a significant technological challenge in the uniform fabrication of CNs with outstanding qualities in order to facilitate a highly-sensitive detection of biomarkers suspended in complex biological environments. Notably, the versatility of plasma-based techniques for the synthesis and surface modification of CNs may be embraced to optimize the biorecognition performance and capabilities. This review surveys the recent advances in CN-based biosensors, and highlights the benefits of plasma-processing techniques to enable, enhance, and tailor the performance and optimize the fabrication of CNs, towards the construction of biosensors with unparalleled performance for the early diagnosis of NDs, via a plethora of energy-efficient, environmentally-benign, and inexpensive approaches. PMID:28788112

A multifunctional biphasic water splitting catalyst tailored for integration with high-performance semiconductor photoanodes

DOE PAGES

Yang, Jinhui; Cooper, Jason K.; Toma, Francesca M.; ...

2016-11-07

Artificial photosystems are advanced by the development of conformal catalytic materials that promote desired chemical transformations, while also maintaining stability and minimizing parasitic light absorption for integration on surfaces of semiconductor light absorbers. We demonstrate that multifunctional, nanoscale catalysts that enable high-performance photoelectrochemical energy conversion can be engineered by plasma-enhanced atomic layer deposition. The collective properties of tailored Co 3 O 4 /Co(OH) 2 thin films simultaneously provide high activity for water splitting, permit efficient interfacial charge transport from semiconductor substrates, and enhance durability of chemically sensitive interfaces. Furthermore, these films comprise compact and continuous nanocrystalline Co 3 O 4more » spinel that is impervious to phase transformation and impermeable to ions, thereby providing effective protection of the underlying substrate. Moreover, a secondary phase of structurally disordered and chemically labile Co(OH) 2 is introduced to ensure a high concentration of catalytically active sites. Application of this coating to photovoltaic p + n-Si junctions yields best reported performance characteristics for crystalline Si photoanodes.« less

Immuno gold nanocages with tailored optical properties for targeted photothermal destruction of cancer cells.

PubMed

Chen, Jingyi; Wang, Danling; Xi, Jiefeng; Au, Leslie; Siekkinen, Andy; Warsen, Addie; Li, Zhi-Yuan; Zhang, Hui; Xia, Younan; Li, Xingde

2007-05-01

Gold nanocages with a relatively small size (e.g., approximately 45 nm in edge length) have been developed, and the structure of these nanocages was tailored to achieve strong absorption in the near-infrared (NIR) region for photothermal cancer treatment. Numerical calculations show that the nanocage has a large absorption cross section of 3.48 x 10(-14) m(2), facilitating conversion of NIR irradiation into heat. The gold nanocages were conjugated with monoclonal antibodies (anti-HER2) to target epidermal growth factor receptors (EGFR) that are overexpressed on the surface of breast cancer cells (SK-BR-3). Our preliminary photothermal results show that the nanocages strongly absorb light in the NIR region with an intensity threshold of 1.5 W/cm(2) to induce thermal destruction to the cancer cells. In the intensity range of 1.5-4.7 W/cm(2), the circular area of damaged cells increased linearly with the irradiation power density. These results suggest that this new class of bioconjugated gold nanostructures, immuno gold nanocages, can potentially serve as an effective photothermal therapeutic agent for cancer treatment.

“Click” Synthesis of Dextran Macrostructures for Combinatorial-Designed Self-Assembled Nanoparticles Encapsulating Diverse Anticancer Therapeutics

PubMed Central

Abeylath, Sampath C.; Amiji, Mansoor

2011-01-01

With the non-specific toxicity of anticancer drugs to healthy tissues upon systemic administration, formulations capable of enhanced selectivity in delivery to the tumor mass and cells are highly desirable. Based on the diversity of the drug payloads, we have investigated a combinatorial-designed strategy where the nano-sized formulations are tailored based on the physicochemical properties of the drug and the delivery needs. Individually functionalized C2 to C12 lipid-, thiol-, and poly(ethylene glycol) (PEG)-modified dextran derivatives were synthesized via “click” chemistry from O-pentynyl dextran and relevant azides. These functionalized dextrans in combination with anticancer drugs form nanoparticles by self-assembling in aqueous medium having PEG surface functionalization and intermolecular disulfide bonds. Using anticancer drugs with logP values ranging from −0.5 to 3.0, the optimized nanoparticles formulations were evaluated for preliminary cellular delivery and cytotoxic effects in SKOV3 human ovarian adenocarcinoma cells. The results show that with the appropriate selection of lipid-modified dextran, one can effectively tailor the self-assembled nano-formulation for intended therapeutic payload. PMID:21978947

Using a novel rigid-fluoride polymer to control the interfacial thickness of graphene and tailor the dielectric behavior of poly(vinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene) nanocomposites.

PubMed

Han, Xianghui; Chen, Sheng; Lv, Xuguang; Luo, Hang; Zhang, Dou; Bowen, Chris R

2018-01-24

Polymer nanocomposites based on conductive fillers for high performance dielectrics have attracted increasing attention in recent years. However, a number of physical issues are unclear, such as the effect of interfacial thickness on the dielectric properties of the polymer nanocomposites, which limits the enhancement of permittivity. In this research, two core-shell structured reduced graphene oxide (rGO)@rigid-fluoro-polymer conducting fillers with different shell thicknesses are prepared using a surface-initiated reversible-addition-fragmentation chain transfer polymerization method, which are denoted as rGO@PTFMS-1 with a thin shell and rGO@PTFMS-2 with a thick shell. A rigid liquid crystalline fluoride-polymer poly{5-bis[(4-trifluoro-methoxyphenyl)oxycarbonyl]styrene} (PTFMS) is chosen for the first time to tailor the shell thicknesses of rGO via tailoring the degree of polymerization. The effect of interfacial thickness on the dielectric behavior of the P(VDF-TrFE-CTFE) nanocomposites with rGO and modified rGO is studied in detail. The results demonstrate that the percolation threshold of the nanocomposites increased from 0.68 vol% to 1.69 vol% with an increase in shell thickness. Compared to the rGO@PTFMS-1/P(VDF-TrFE-CTFE) composites, the rGO@PTFMS-2/P(VDF-TrFE-CTFE) composites exhibited a higher breakdown strength and a lower dielectric constant, which can be interpreted by interfacial polarization and the micro-capacitor model, resulting from the insulating nature of the rigid-polymer shell and the change of rGO's morphology. The findings provide an innovative approach to tailor dielectric composites, and promote a deeper understanding of the influence of interfacial region thickness on the dielectric performance.

HiMAT structural development design methodology. [aeroelastic tailoring of the canard and wing box and distributed load tests

NASA Technical Reports Server (NTRS)

Price, M. A.

1979-01-01

In order to improve aerodynamic performance, a twist criterion was used to design the canard and wing lifting surfaces of two graphite-epoxy research aircraft. To meet that twist criterion, the lifting surfaces were tailored using graphite-epoxy tape. The outer surface of the aircraft is essentially constructed of 95 percent graphite epoxy materials. The analytical tools and methodology used to design those lifting surfaces are described. One aircraft was subjected to an 8g ground test in order to verify structural integrity and to determine how well the desired twist was achieved. Test results are presented and the reductions of both flight and ground strain test gages and their associated stresses are discussed.

Synthesis and photocatalytic properties of graphitic carbon nitride nanofibers using porous anodic alumina templates

NASA Astrophysics Data System (ADS)

Suchitra, S. M.; Udayashankar, N. K.

2017-12-01

In the present study, we describe an effective method for the synthesis of Graphitic carbon nitride (GCN) nanostructures using porous anodic alumina (AAO) membrane as template by simple thermal condensation of cyanamide. Synthesized nanostructure was fully analysed by various techniques to detect its crystalline nature, morphology, luminescent properties followed by the evaluation of its photocatalytic activity in the degradation of Methylene blue dye. Structural analysis of synthesized GCNNF was systematically carried out using x-ray powder diffraction (XRD) and scanning electron microscope (SEM), and. The results confirmed the growth of GCN inside the nanochannels of anodic alumina templates. Luminescent properties of GCNNF were studied using photoluminescence (PL) spectroscopy. PL analysis showed the presence of a strong emission peak in the wavelength range of 350-600 nm in blue region. GCNNF displays higher photocatalytic performance in the photodegradation of methylene blue compare to the bulk GCN. Highlights 1. In the present paper, we report the synthesis of graphitic carbon nitride nanofibers (GCNNF) using porous anodic aluminium oxide membranes as templates through thermal condensation of cyanamide at 500 °C. 2. The synthesis of Graphitic carbon nitride nanofibers using porous andic alumina template is the efficient approach for increasing crystallinity and surface area. 3. The high surface area of graphitic carbon nitride nanofibers has a good impact on novel optical and photocatalytic properties of the bulkGCN. 4. AAO templating of GCN is one of the versatile method to produce tailorable GCN nanostructures with higher surface area and less number of structural defects. 5. Towards photocatalytic degradation of dyes, the tuning of physical properties is very essential thing hence we are succeeded in achieving better catalytic performance of GCN nanostructures by making use of AAO templates.

Modulation of human multipotent and pluripotent stem cells using surface nanotopographies and surface-immobilised bioactive signals: A review.

PubMed

Wang, Peng-Yuan; Thissen, Helmut; Kingshott, Peter

2016-11-01

The ability to control the interactions of stem cells with synthetic surfaces is proving to be effective and essential for the quality of passaged stem cells and ultimately the success of regenerative medicine. The stem cell niche is crucial for stem cell self-renewal and differentiation. Thus, mimicking the stem cell niche, and here in particular the extracellular matrix (ECM), in vitro is an important goal for the expansion of stem cells and their applications. Here, surface nanotopographies and surface-immobilised biosignals have been identified as major factors that control stem cell responses. The development of tailored surfaces having an optimum nanotopography and displaying suitable biosignals is proposed to be essential for future stem cell culture, cell therapy and regenerative medicine applications. While early research in the field has been restricted by the limited availability of micro- and nanofabrication techniques, new approaches involving the use of advanced fabrication and surface immobilisation methods are starting to emerge. In addition, new cell types such as induced pluripotent stem cells (iPSCs) have become available in the last decade, but have not been fully understood. This review summarises significant advances in the area and focuses on the approaches that are aimed at controlling the behavior of human stem cells including maintenance of their self-renewal ability and improvement of their lineage commitment using nanotopographies and biosignals. More specifically, we discuss developments in biointerface science that are an important driving force for new biomedical materials and advances in bioengineering aiming at improving stem cell culture protocols and 3D scaffolds for clinical applications. Cellular responses revolve around the interplay between the surface properties of the cell culture substrate and the biomolecular composition of the cell culture medium. Determination of the precise role played by each factor, as well as the synergistic effects amongst the factors, all of which influence stem cell responses is essential for future developments. This review provides an overview of the current state-of-the-art in the design of complex material surfaces aimed at being the next generation of tools tailored for applications in cell culture and regenerative medicine. This review focuses on the effect of surface nanotopographies and surface-bound biosignals on human stem cells. Recently, stem cell research attracts much attention especially the induced pluripotent stem cells (iPSCs) and direct lineage reprogramming. The fast advance of stem cell research benefits disease treatment and cell therapy. On the other hand, surface property of cell adhered materials has been demonstrated very important for in vitro cell culture and regenerative medicine. Modulation of cell behavior using surfaces is costeffective and more defined. Thus, we summarise the recent progress of modulation of human stem cells using surface science. We believe that this review will capture a broad audience interested in topographical and chemical patterning aimed at understanding complex cellular responses to biomaterials. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Towards 4th generation biomaterials: a covalent hybrid polymer-ormoglass architecture

NASA Astrophysics Data System (ADS)

Sachot, N.; Mateos-Timoneda, M. A.; Planell, J. A.; Velders, A. H.; Lewandowska, M.; Engel, E.; Castaño, O.

2015-09-01

Hybrid materials are being extensively investigated with the aim of mimicking the ECM microenvironment to develop effective solutions for bone tissue engineering. However, the common drawbacks of a hybrid material are the lack of interactions between the scaffold's constituents and the masking of its bioactive phase. Conventional hybrids often degrade in a non-homogeneous manner and the biological response is far from optimal. We have developed a novel material with strong interactions between constituents. The bioactive phase is directly exposed on its surface mimicking the structure of the ECM of bone. Here, polylactic acid electrospun fibers have been successfully and reproducibly coated with a bioactive organically modified glass (ormoglass, Si-Ca-P2 system) covalently. In comparison with the pure polymeric mats, the fibers obtained showed improved hydrophilicity and mechanical properties, bioactive ion release, exhibited a nanoroughness and enabled good cell adhesion and spreading after just one day of culture (rMSCs and rEPCs). The fibers were coated with different ormoglass compositions to tailor their surface properties (roughness, stiffness, and morphology) by modifying the experimental parameters. Knowing that cells modulate their behavior according to the exposed physical and chemical signals, the development of this instructive material is a valuable advance in the design of functional regenerative biomaterials.Hybrid materials are being extensively investigated with the aim of mimicking the ECM microenvironment to develop effective solutions for bone tissue engineering. However, the common drawbacks of a hybrid material are the lack of interactions between the scaffold's constituents and the masking of its bioactive phase. Conventional hybrids often degrade in a non-homogeneous manner and the biological response is far from optimal. We have developed a novel material with strong interactions between constituents. The bioactive phase is directly exposed on its surface mimicking the structure of the ECM of bone. Here, polylactic acid electrospun fibers have been successfully and reproducibly coated with a bioactive organically modified glass (ormoglass, Si-Ca-P2 system) covalently. In comparison with the pure polymeric mats, the fibers obtained showed improved hydrophilicity and mechanical properties, bioactive ion release, exhibited a nanoroughness and enabled good cell adhesion and spreading after just one day of culture (rMSCs and rEPCs). The fibers were coated with different ormoglass compositions to tailor their surface properties (roughness, stiffness, and morphology) by modifying the experimental parameters. Knowing that cells modulate their behavior according to the exposed physical and chemical signals, the development of this instructive material is a valuable advance in the design of functional regenerative biomaterials. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr04275e

Traction-separation laws and stick-slip shear phenomenon of interfaces between cellulose nanocrystals

NASA Astrophysics Data System (ADS)

Sinko, Robert; Keten, Sinan

2015-05-01

Cellulose nanocrystals (CNCs) are one of nature's most abundant structural material building blocks and possess outstanding mechanical properties including a tensile modulus comparable to Kevlar. It remains challenging to upscale these properties in CNC neat films and nanocomposites due to the difficulty of characterizing interfacial bonding between CNCs that governs stress transfer under deformation. Here we present new analyses based on atomistic simulations of shear and tensile failure of the interfaces between Iβ CNCs, providing new insight into factors governing the mechanical behavior of hierarchical nanocellulose materials. We compare the two most relevant crystal interfaces and find that hydrogen bonded surfaces have greater tensile strength compared to the surfaces governed by weaker interactions. On the contrary, shearing simulations reveal that friction between the atomic interfaces depends not only on surface energy but also the energy landscape along the shear direction. While being a weaker interface, the intersheet plane exhibits greater energy barriers to shear. The molecular roughness of this interface, characterized by a greater energy barrier, exhibits stick-slip deformation behavior as opposed to a more continuous sliding and rebonding mechanism observed for the interfaces with hydrogen bonds. Analytical models to describe the energy landscapes are developed using energy scaling relations for van der Waals surfaces in combination with a modification of the Prandtl-Tomlinson model for atomic friction. Our simulations pave the way for tailoring hierarchical CNC materials by taking a similar approach to techniques employed for describing metals, where mechanical properties can be tuned through a deeper understanding of grain boundary physics and nanoscale interfaces.

Nanomechanics of Cells and Biomaterials Studied by Atomic Force Microscopy.

PubMed

Kilpatrick, Jason I; Revenko, Irène; Rodriguez, Brian J

2015-11-18

The behavior and mechanical properties of cells are strongly dependent on the biochemical and biomechanical properties of their microenvironment. Thus, understanding the mechanical properties of cells, extracellular matrices, and biomaterials is key to understanding cell function and to develop new materials with tailored mechanical properties for tissue engineering and regenerative medicine applications. Atomic force microscopy (AFM) has emerged as an indispensable technique for measuring the mechanical properties of biomaterials and cells with high spatial resolution and force sensitivity within physiologically relevant environments and timescales in the kPa to GPa elastic modulus range. The growing interest in this field of bionanomechanics has been accompanied by an expanding array of models to describe the complexity of indentation of hierarchical biological samples. Furthermore, the integration of AFM with optical microscopy techniques has further opened the door to a wide range of mechanotransduction studies. In recent years, new multidimensional and multiharmonic AFM approaches for mapping mechanical properties have been developed, which allow the rapid determination of, for example, cell elasticity. This Progress Report provides an introduction and practical guide to making AFM-based nanomechanical measurements of cells and surfaces for tissue engineering applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Deposition of Nanostructured Thin Film from Size-Classified Nanoparticles

NASA Technical Reports Server (NTRS)

Camata, Renato P.; Cunningham, Nicholas C.; Seol, Kwang Soo; Okada, Yoshiki; Takeuchi, Kazuo

2003-01-01

Materials comprising nanometer-sized grains (approximately 1_50 nm) exhibit properties dramatically different from those of their homogeneous and uniform counterparts. These properties vary with size, shape, and composition of nanoscale grains. Thus, nanoparticles may be used as building blocks to engineer tailor-made artificial materials with desired properties, such as non-linear optical absorption, tunable light emission, charge-storage behavior, selective catalytic activity, and countless other characteristics. This bottom-up engineering approach requires exquisite control over nanoparticle size, shape, and composition. We describe the design and characterization of an aerosol system conceived for the deposition of size classified nanoparticles whose performance is consistent with these strict demands. A nanoparticle aerosol is generated by laser ablation and sorted according to size using a differential mobility analyzer. Nanoparticles within a chosen window of sizes (e.g., (8.0 plus or minus 0.6) nm) are deposited electrostatically on a surface forming a film of the desired material. The system allows the assembly and engineering of thin films using size-classified nanoparticles as building blocks.

Polysulfone ultrafiltration membrane incorporated with Ag-SiO2 nanohybrid for effective fouling control.

PubMed

Wu, Huiqing; Huang, Jing; Liu, Yuejun

2017-06-01

An anti-fouling hybrid membrane was prepared by incorporating Ag-SiO 2 nanohybrid into a polysulfone (PSf) matrix. The addition of Ag-SiO 2 can significantly improve the hydrophilicity, separation property, anti-fouling ability, and especially anti-bacterial activity of hybrid membranes. The optimum performance of the Ag-SiO 2 /PSf hybrid membrane is achieved when the concentration of Ag-SiO 2 is as low as 0.45 wt%. Compared with PSf membrane and SiO 2 /PSf hybrid membrane, the Ag-SiO 2 /PSf hybrid membrane displays the best overall properties. The excellent performance of the Ag-SiO 2 /PSf hybrid membrane can be attributed to the well-tailored structure and unique property of Ag-SiO 2 nanohybrid, where nanosized Ag (∼5 nm) can densely and uniformly disperse on the surface of silica spheres. The obtained membrane could be a promising material for water treatment.

3D printing of optical materials: an investigation of the microscopic properties

NASA Astrophysics Data System (ADS)

Persano, Luana; Cardarelli, Francesco; Arinstein, Arkadii; Uttiya, Sureeporn; Zussman, Eyal; Pisignano, Dario; Camposeo, Andrea

2018-02-01

3D printing technologies are currently enabling the fabrication of objects with complex architectures and tailored properties. In such framework, the production of 3D optical structures, which are typically based on optical transparent matrices, optionally doped with active molecular compounds and nanoparticles, is still limited by the poor uniformity of the printed structures. Both bulk inhomogeneities and surface roughness of the printed structures can negatively affect the propagation of light in 3D printed optical components. Here we investigate photopolymerization-based printing processes by laser confocal microscopy. The experimental method we developed allows the printing process to be investigated in-situ, with microscale spatial resolution, and in real-time. The modelling of the photo-polymerization kinetics allows the different polymerization regimes to be investigated and the influence of process variables to be rationalized. In addition, the origin of the factors limiting light propagation in printed materials are rationalized, with the aim of envisaging effective experimental strategies to improve optical properties of printed materials.

Characterization of nanostructured surfaces generated by reconstitution of the porin MspA from Mycobacterium smegmatis.

PubMed

Wörner, Michael; Lioubashevski, Oleg; Basel, Matthew T; Niebler, Sandra; Gogritchiani, Eliso; Egner, Nicole; Heinz, Christian; Hoferer, Jürgen; Cipolloni, Michela; Janik, Katharine; Katz, Evgeny; Braun, Andre M; Willner, Itamar; Niederweis, Michael; Bossmann, Stefan H

2007-06-01

Nanostructures with long-term stability at the surface of gold electrodes are generated by reconstituting the porin MspA from Mycobacterium smegmatis into a specially designed monolayer of long-chain lipid surfactant on gold. Tailored surface coverage of gold electrodes with long-chain surfactants is achieved by electrochemically assisted deposition of organic thiosulfates (Bunte salts). The subsequent reconstitution of the octameric-pore MspA is guided by its extraordinary self-assembling properties. Importantly, electrochemical reduction of copper(II) yields copper nanoparticles within the MspA nanopores. Electrochemical impedance spectroscopy, reflection electron microscopy, and atomic force microscopy (AFM) show that: 1) the MspA pores within the self-assembled monolayer (SAM) are monodisperse and electrochemically active, 2) MspA reconstitutes in SAMs and with a 10-nm thickness, 3) AFM is a suitable method to detect pores within SAMs, and 4) the electrochemical reduction of Cu2+ to Cu0 under overpotential conditions starts within the MspA pores.

Nano-assembly of nanodiamonds by conjugation to actin filaments.

PubMed

Bradac, Carlo; Say, Jana M; Rastogi, Ishan D; Cordina, Nicole M; Volz, Thomas; Brown, Louise J

2016-03-01

Fluorescent nanodiamonds (NDs) are remarkable objects. They possess unique mechanical and optical properties combined with high surface areas and controllable surface reactivity. They are non-toxic and hence suited for use in biological environments. NDs are also readily available and commercially inexpensive. Here, the exceptional capability of controlling and tailoring their surface chemistry is demonstrated. Small, bright diamond nanocrystals (size ˜30 nm) are conjugated to protein filaments of actin (length ˜3-7 µm). The conjugation to actin filaments is extremely selective and highly target-specific. These unique features, together with the relative simplicity of the conjugation-targeting method, make functionalised nanodiamonds a powerful and versatile platform in biomedicine and quantum nanotechnologies. Applications ranging from using NDs as superior biological markers to, potentially, developing novel bottom-up approaches for the fabrication of hybrid quantum devices that would bridge across the bio/solid-state interface are presented and discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quantitative assessment of interfacial interactions with rough membrane surface and its implications for membrane selection and fabrication in a MBR.

PubMed

Chen, Jianrong; Mei, Rongwu; Shen, Liguo; Ding, Linxian; He, Yiming; Lin, Hongjun; Hong, Huachang

2015-03-01

The interfacial interactions between a foulant particle and rough membrane surface in a submerged membrane bioreactor (MBR) were quantitatively assessed by using a new-developed method. It was found that the profile of total interaction versus separation distance was complicated. There were an energy barrier and two negative energy ranges in the profile. Further analysis showed that roughness scale significantly affected the strength and properties of interfacial interactions. It was revealed that there existed a critical range of roughness scale within which the total energy in the separation distance ranged from 0 to several nanometers was continually repulsive. Decrease in foulant size would increase the strength of specific interaction energy, but did not change the existence of a critical roughness scale range. These findings suggested the possibility to "tailor" membrane surface morphology for membrane fouling mitigation, and thus gave significant implications for membrane selection and fabrication in MBRs. Copyright © 2014 Elsevier Ltd. All rights reserved.

Controlling Self-Assembly of Engineered Peptides on Graphite by Rational Mutation

PubMed Central

So, Christopher R.; Hayamizu, Yuhei; Yazici, Hilal; Gresswell, Carolyn; Khatayevich, Dmitriy; Tamerler, Candan; Sarikaya, Mehmet

2012-01-01

Self-assembly of proteins on surfaces is utilized in many fields to integrate intricate biological structures and diverse functions with engineered materials. Controlling proteins at bio-solid interfaces relies on establishing key correlations between their primary sequences and resulting spatial organizations on substrates. Protein self-assembly, however, remains an engineering challenge. As a novel approach, we demonstrate here that short dodecapeptides selected by phage display are capable of self-assembly on graphite and form long-range ordered biomolecular nanostructures. Using atomic force microscopy and contact angle studies, we identify three amino-acid domains along the primary sequence that steer peptide ordering and lead to nanostructures with uniformly displayed residues. The peptides are further engineered via simple mutations to control fundamental interfacial processes, including initial binding, surface aggregation and growth kinetics, and intermolecular interactions. Tailoring short peptides via their primary sequence offers versatile control over molecular self-assembly, resulting in well-defined surface properties essential in building engineered, chemically rich, bio-solid interfaces. PMID:22233341

Secondary electron emission yield dependence on the Fermi level in Silicon

NASA Astrophysics Data System (ADS)

Urrabazo, David; Goeckner, Matthew; Overzet, Lawrence

2013-09-01

Secondary Electron Emission (SEE) by ion bombardment plays a key role in determining the properties of many plasmas. As a result, significant efforts have been expended to control the SEE coefficient (increasing or decreasing it) by tailoring the electron work function of surfaces. A few recent publications point to the possibility of controlling the SEE coefficient of semiconductor surfaces in real time through controlling the numbers of electrons in the conduction band near the surface. Large control over the plasma was achieved by injecting electrons into the semiconductor just under the cathode surface via a subsurface PN junction. The hypothesis was that SEE is dependent on the numbers of electrons in the conduction band near the surface (which is related to the position of the Fermi level near the surface). We are testing the validity of this hypothesis. We have begun fundamental ion beam studies to explore this possible dependence of SEE on the Fermi energy level using Si. Various doping levels and dopants are being evaluated and the results of these tests will be presented. This work was supported in part by US Dept. of Energy. Acknowledgement to Dr. L. Raja at UT Austin.

Surface grafted antibodies: controlled architecture permits enhanced antigen detection.

PubMed

Sebra, Robert P; Masters, Kristyn S; Bowman, Christopher N; Anseth, Kristi S

2005-11-22

The attachment of antibodies to substrate surfaces is useful for achieving specific detection of antigens and toxins associated with clinical and field diagnostics. Here, acrylated whole antibodies were produced through conjugation chemistry, with the goal of covalently photografting these proteins from surfaces in a controlled fashion, to facilitate rapid and sensitive antigenic detection. A living radical photopolymerization chemistry was used to graft the acrylated whole antibodies on polymer surfaces at controlled densities and spatial locations by controlling the exposure time and area, respectively. Copolymer grafts containing these antibodies were synthesized to demonstrate two principles. First, PEG functionalities were introduced to prevent nonspecific protein interactions and improve the reaction kinetics by increasing solvation and mobility of the antibody-containing chains. Both of these properties lead to sensitive (pM) and rapid (<20 min) detection of antigens with this surface modification technique. Second, graft composition was tailored to include multiple antibodies on the same grafted chains, establishing a means for simultaneously detecting multiple antigens on one grafted surface area. Finally, the addition of PEG spacers between the acrylate functionality and the pendant detection antibodies was tuned to enhance the detection of a short-half-life molecule, glucagon, in a complex biological environment, plasma.

Manipulation of the Geometry and Modulation of the Optical Response of Surfactant-Free Gold Nanostars: A Systematic Bottom-Up Synthesis

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

De Silva Indrasekara, Agampodi S.; Johnson, Sean F.; Odion, Ren A.

Among plasmonic nanoparticles, surfactant-free branched gold nanoparticles have exhibited exceptional properties as a nanoplatform for a wide variety of applications ranging from surface-enhanced Raman scattering sensing and imaging applications to photothermal treatment and photoimmunotherapy for cancer treatments. The effectiveness and reliability of branched gold nanoparticles in biomedical applications strongly rely on the consistency and reproducibility of physical, chemical, optical, and therapeutic properties of nanoparticles, which are mainly governed by their morphological features. Herein, we present an optimized bottom-up synthesis that improves the reproducibility and homogeneity of the gold-branched nanoparticles with desired morphological features and optical properties. We identified that themore » order of reagent addition is crucial for improved homogeneity of the branched nature of nanoparticles that enable a high batch-to-batch reproducibility and reliability. In addition, a different combination of the synthesis parameters, in particular, additive halides and concentration ratios of reactive Au to Ag and Au to Au seeds, which yield branched nanoparticle of similar localized surface plasmon resonances but with distinguishable changes in the dimensions of the branches, was realized. Overall, our study introduces the design parameters for the purpose-tailored manufacturing of surfactant-free gold nanostars in a reliable manner.« less

Manipulation of the Geometry and Modulation of the Optical Response of Surfactant-Free Gold Nanostars: A Systematic Bottom-Up Synthesis

DOE PAGES

De Silva Indrasekara, Agampodi S.; Johnson, Sean F.; Odion, Ren A.; ...

2018-02-22

Among plasmonic nanoparticles, surfactant-free branched gold nanoparticles have exhibited exceptional properties as a nanoplatform for a wide variety of applications ranging from surface-enhanced Raman scattering sensing and imaging applications to photothermal treatment and photoimmunotherapy for cancer treatments. The effectiveness and reliability of branched gold nanoparticles in biomedical applications strongly rely on the consistency and reproducibility of physical, chemical, optical, and therapeutic properties of nanoparticles, which are mainly governed by their morphological features. Herein, we present an optimized bottom-up synthesis that improves the reproducibility and homogeneity of the gold-branched nanoparticles with desired morphological features and optical properties. We identified that themore » order of reagent addition is crucial for improved homogeneity of the branched nature of nanoparticles that enable a high batch-to-batch reproducibility and reliability. In addition, a different combination of the synthesis parameters, in particular, additive halides and concentration ratios of reactive Au to Ag and Au to Au seeds, which yield branched nanoparticle of similar localized surface plasmon resonances but with distinguishable changes in the dimensions of the branches, was realized. Overall, our study introduces the design parameters for the purpose-tailored manufacturing of surfactant-free gold nanostars in a reliable manner.« less

Zirconium tungstate/epoxy nanocomposites: effect of nanoparticle morphology and negative thermal expansivity.

PubMed

Wu, Hongchao; Rogalski, Mark; Kessler, Michael R

2013-10-09

The ability to tailor the coefficient of thermal expansion (CTE) of a polymer is essential for mitigating thermal residual stress and reducing microcracks caused by CTE mismatch of different components in electronic applications. This work studies the effect of morphology and thermal expansivity of zirconium tungstate nanoparticles on the rheological, thermo-mechanical, dynamic-mechanical, and dielectric properties of ZrW2O8/epoxy nanocomposites. Three types of ZrW2O8 nanoparticles were synthesized under different hydrothermal conditions and their distinct properties were characterized, including morphology, particle size, aspect ratio, surface area, and CTE. Nanoparticles with a smaller particle size and larger surface area led to a more significant reduction in gel-time and glass transition temperature of the epoxy nanocomposites, while a higher initial viscosity and significant shear thinning behavior was found in prepolymer suspensions containing ZrW2O8 with larger particle sizes and aspect ratios. The thermo- and dynamic-mechanical properties of epoxy-based nanocomposites improved with increasing loadings of the three types of ZrW2O8 nanoparticles. In addition, the introduced ZrW2O8 nanoparticles did not negatively affect the dielectric constant or the breakdown strength of the epoxy resin, suggesting potential applications of ZrW2O8/epoxy nanocomposites in the microelectronic insulation industry.

A structural model for composite rotor blades and lifting surfaces

NASA Technical Reports Server (NTRS)

Rehfield, Lawrence W.; Atilgan, Ali R.

1987-01-01

Composite material systems are currently candidates for aerospace structures, primarily for the design flexibiity they offer i.e., it is possible to tailor the material and manufacturing approach to the application. Two notable examples are the wing of the Grumman/USAF/DARPA X-29 and rotor blades under development by the U.S.A. Aerostructures Directorate (AVSCOM), Langley Research Center. A working definition of elastic or structural tailoring is the use of structural concept, fiber orientation, ply stacking sequence, and a blend of materials to achieve specific performance goals. In the design process, choices of materials and dimensions are made which produce specific response characteristics which permit the selected goals to be achieved. Common choices for tailoring goals are preventing instabilities or vibration resonances or enhancing damage tolerance. An essential, enabling factor in the design of tailored composite structures is structural modeling that accurately, but simply, characterizes response. The objective of this paper is to improve the single-cell beam model for composite rotor blades or lifting surfaces and to demonstrate its usefullness in applications.

A theoretical review on electronic, magnetic and optical properties of silicene.

PubMed

Chowdhury, Suman; Jana, Debnarayan

2016-12-01

Inspired by the success of graphene, various two dimensional (2D) structures in free standing (FS) (hypothetical) form and on different substrates have been proposed recently. Silicene, a silicon counterpart of graphene, is predicted to possess massless Dirac fermions and to exhibit an experimentally accessible quantum spin Hall effect. Since the effective spin-orbit interaction is quite significant compared to graphene, buckling in silicene opens a gap of 1.55 meV at the Dirac point. This band gap can be further tailored by applying in plane stress, an external electric field, chemical functionalization and defects. In this topical theoretical review, we would like to explore the electronic, magnetic and optical properties, including Raman spectroscopy of various important derivatives of monolayer and bilayer silicene (BLS) with different adatoms (doping). The magnetic properties can be tailored by chemical functionalization, such as hydrogenation and introducing vacancy into the pristine planar silicene. Apart from some universal features of optical absorption present in all these 2D materials, the study on reflectivity modulation with doping (Al and P) concentration in silicene has indicated the emergence of some strong peaks having the robust characteristic of a doped reflective surface for both polarizations of the electromagnetic (EM) field. Besides this, attempts will be made to understand the electronic properties of silicene from some simple tight-binding Hamiltonian. We also point out the importance of shape dependence and optical anisotropy properties in silicene nanodisks and establish that a zigzag trigonal possesses the maximum magnetic moment. We also suggest future directions to be explored to make the synthesis of silicene and its various derivatives viable for verification of theoretical predictions. Although this is a fairly new route, the results obtained so far from experimental and theoretical studies in understanding silicene have shown enough significant promising features to open a new direction in the silicon industry, silicon based nano-structures in spintronics and in opto-electronic devices.

General introduction: Liquid and solid (materials, main properties and applications …)

NASA Astrophysics Data System (ADS)

Zabler, Simon

2014-10-01

A general introduction about the diversity of foam structures is given with focus onto the structural, mechanical and dynamical properties at hand. Two classes of materials are addressed: liquid and semi-solid foams, on the one hand, solid foams, on the other hand. The latter can be subdivided into metallic, ceramic and organic foams, depending on the nature of the solid skeleton that supports the overall cell structure. Solid foams generally stem from the concept of mechanical light-weight structures, but they can just as well be employed for their large surface area as well as for their acoustic and thermal properties. Modern biomaterials use tailored ceramic or organo-ceramic foams as bone scaffolds, whereas hierarchically micro- and nanoporous structures are being used by chemistry to control catalytic reactions. Future materials design and development is going to rely increasingly on natural and synthetic foam structures and properties, be it food, thermal insulators or car frames, thus giving a promising outlook onto the foam research and development that is about to come. xml:lang="fr"

Tailoring the structural and optical properties of TiN thin films by Ag ion implantation

NASA Astrophysics Data System (ADS)

Popović, M.; Novaković, M.; Rakočević, Z.; Bibić, N.

2016-12-01

Titanium nitride (TiN) thin films thickness of ∼260 nm prepared by dc reactive sputtering were irradiated with 200 keV silver (Ag) ions to the fluences ranging from 5 × 1015 ions/cm2 to 20 × 1015 ions/cm2. After implantation TiN layers were annealed 2 h at 700 °C in a vacuum. Ion irradiation-induced microstructural changes were examined by using Rutherford backscattering spectrometry, X-ray diffraction and transmission electron microscopy, while the surface topography was observed using atomic force microscopy. Spectroscopic ellipsometry was employed to get insights on the optical and electronic properties of TiN films with respect to their microstructure. The results showed that the irradiations lead to deformation of the lattice, increasing disorder and formation of new Ag phase. The optical results demonstrate the contribution of surface plasmon resonace (SPR) of Ag particles. SPR position shifted in the range of 354.3-476.9 nm when Ag ion fluence varied from 5 × 1015 ions/cm2 to 20 × 1015 ions/cm2. Shift in peak wavelength shows dependence on Ag particles concentration, suggesting that interaction between Ag particles dominate the surface plasmon resonance effect. Presence of Ag as second metal in the layer leads to overall decrease of optical resistivity of TiN.

Tailoring the optical and hydrophobic property of zinc oxide nanorod by coating with amorphous graphene

NASA Astrophysics Data System (ADS)

Pahari, D.; Das, N. S.; Das, B.; Chattopadhyay, K. K.; Banerjee, D.

2016-09-01

Zinc oxide (ZnO) nanorods were synthesized at room temperature on potassium permanganate activated silicon and glass substrate by simple chemical method using zinc acetate as precursor. To modify the surface energy of the as prepared ZnO thin films the samples were coated with amorphous graphene (a-G) synthesized by un-zipping of chemically synthesized amorphous carbon nanotubes (a-CNTs). All the pure and coated samples were characterized by x-ray diffraction, field emission scanning electron microscope, Raman spectroscopy, and Fourier transformed infrared spectroscopy. The roughness analysis of the as prepared samples was done by atomic force microscopic analysis. The detail optical properties of all the samples were studied with the help of a UV-Visible spectrophotometer. The surface energy of the as prepared pure and coated samples was calculated by measuring the contact angle of two different liquids. It is seen that the water repellence of ZnO nanorods got increased after they are being coated with a-Gs. Also even after UV irradiation the contact angle remain same unlike the case for the uncoated sample where the contact angle gets decreased significantly after UV irradiation. Existing Cassie-Wenzel model has been employed along with the Owen's approach to determine the different components of surface energy.

Effect of Surface Chemistry on the Fluorescence of Detonation Nanodiamonds.

PubMed

Reineck, Philipp; Lau, Desmond W M; Wilson, Emma R; Fox, Kate; Field, Matthew R; Deeleepojananan, Cholaphan; Mochalin, Vadym N; Gibson, Brant C

2017-11-28

Detonation nanodiamonds (DNDs) have unique physical and chemical properties that make them invaluable in many applications. However, DNDs are generally assumed to show weak fluorescence, if any, unless chemically modified with organic molecules. We demonstrate that detonation nanodiamonds exhibit significant and excitation-wavelength-dependent fluorescence from the visible to the near-infrared spectral region above 800 nm, even without the engraftment of organic molecules to their surfaces. We show that this fluorescence depends on the surface functionality of the DND particles. The investigated functionalized DNDs, produced from the same purified DND as well as the as-received polyfunctional starting material, are hydrogen, hydroxyl, carboxyl, ethylenediamine, and octadecylamine-terminated. All DNDs are investigated in solution and on a silicon wafer substrate and compared to fluorescent high-pressure high-temperature nanodiamonds. The brightest fluorescence is observed from octadecylamine-functionalized particles and is more than 100 times brighter than the least fluorescent particles, carboxylated DNDs. The majority of photons emitted by all particle types likely originates from non-diamond carbon. However, we locally find bright and photostable fluorescence from nitrogen-vacancy centers in diamond in hydrogenated, hydroxylated, and carboxylated detonation nanodiamonds. Our results contribute to understanding the effects of surface chemistry on the fluorescence of DNDs and enable the exploration of the fluorescent properties of DNDs for applications in theranostics as nontoxic fluorescent labels, sensors, nanoscale tracers, and many others where chemically stable and brightly fluorescent nanoparticles with tailorable surface chemistry are needed.

Mechanical Characterization of Polydopamine-Assisted Silver Deposition on Polymer Substrates

NASA Astrophysics Data System (ADS)

Cordes, Amanda Laurence

Inspired by the adhesive proteins in marine mussels, polydopamine has become a popular adhesive ad-layer for surface functionalization of a variety of substrates. Based on the chemistry of the dopamine monomer, amine and thiol functional groups are hypothesized to increase adhesion between polymer substrates and polydopamine thin films. This hypothesis was the central motivation for development of a tailorable thiol-ene system in order to study the effects of substrate chemistry on polydopamine adhesion. While polydopamine-adhered silver has been studied on a variety of substrates, no in depth mechanical characterization has been performed and to date, no research has been published on thiol-enes coated in polydopamine-adhered silver. The purpose of this study was to characterize the mechanical durability and adhesion properties of a polydopamine-adhered silver film on commercial substrates and a tailorable thiol-ene system. Polydopamine and silver coatings were deposited on a variety of polymer substrates through a simple dip-coat process. The polydopamine forms a thin uniform adhesive layer and the silver deposits in a discontinuous manner with a nanoparticle sized base layer covering the full surface and micron-sized clusters adhered sporadically on top. Mechanical tensile testing was performed to characterize the durability of the silver coating on commercial polymers. Coated nylon and HDPE showed no signs of degradation or delamination of the polydopamine-adhered silver coating up to 30% strain although both substrates showed large plastic deformation. Peel tests were performed on both commercial polymers as well as a tailorable thiol-ene system. Results support the hypothesis that polydopamine adhesion is increased with the presence of functional groups. Parts of the HDPE sample were cleanly peeled, but silver patches were left sporadically across the surface pointing to weaker adhesion between polyethylene and polydopamine. A high adhesive strength tape was used on nylon and the thiol-ene polymers and removed some of the large clusters but was ineffective at removing the particle base layer. The silver base layer remained firmly attached on the surface after multiple rounds of peel testing. With the addition of functional groups in the polymer makeup, the adhesion strength of polydopamine-adhered silver coatings can be increased to create a mechanically durable and adhesively robust silver coating.

Computational design of surfaces, nanostructures and optoelectronic materials

NASA Astrophysics Data System (ADS)

Choudhary, Kamal

Properties of engineering materials are generally influenced by defects such as point defects (vacancies, interstitials, substitutional defects), line defects (dislocations), planar defects (grain boundaries, free surfaces/nanostructures, interfaces, stacking faults) and volume defects (voids). Classical physics based molecular dynamics and quantum physics based density functional theory can be useful in designing materials with controlled defect properties. In this thesis, empirical potential based molecular dynamics was used to study the surface modification of polymers due to energetic polyatomic ion, thermodynamics and mechanics of metal-ceramic interfaces and nanostructures, while density functional theory was used to screen substituents in optoelectronic materials. Firstly, polyatomic ion-beams were deposited on polymer surfaces and the resulting chemical modifications of the surface were examined. In particular, S, SC and SH were deposited on amorphous polystyrene (PS), and C2H, CH3, and C3H5 were deposited on amorphous poly (methyl methacrylate) (PMMA) using molecular dynamics simulations with classical reactive empirical many-body (REBO) potentials. The objective of this work was to elucidate the mechanisms by which the polymer surface modification took place. The results of the work could be used in tailoring the incident energy and/or constituents of ion beam for obtaining a particular chemistry inside the polymer surface. Secondly, a new Al-O-N empirical potential was developed within the charge optimized many body (COMB) formalism. This potential was then used to examine the thermodynamic stability of interfaces and mechanical properties of nanostructures composed of aluminum, its oxide and its nitride. The potentials were tested for these materials based on surface energies, defect energies, bulk phase stability, the mechanical properties of the most stable bulk phase, its phonon properties as well as with a genetic algorithm based evolution theory of the materials to ensure that no spurious phases had a lower cohesive energy. Thirdly, lanthanide doped and co-doped Y3Al5O 12 were examined using density functional theory (DFT) with semi-local and local functional. Theoretical results were compared and validated with experimental data and new co-doped materials with high efficiency were predicted. Finally, Transition element doped CH3NH3PbI3 were studied with DFT for validation of the model with experimental data and replacement materials for toxic Pb were predicted.

Femtosecond laser fabricated spike structures for selective control of cellular behavior.

PubMed

Schlie, Sabrina; Fadeeva, Elena; Koch, Jürgen; Ngezahayo, Anaclet; Chichkov, Boris N

2010-09-01

In this study we investigate the potential of femtosecond laser generated micrometer sized spike structures as functional surfaces for selective cell controlling. The spike dimensions as well as the average spike to spike distance can be easily tuned by varying the process parameters. Moreover, negative replications in soft materials such as silicone elastomer can be produced. This allows tailoring of wetting properties of the spike structures and their negative replicas representing a reduced surface contact area. Furthermore, we investigated material effects on cellular behavior. By comparing human fibroblasts and SH-SY5Y neuroblastoma cells we found that the influence of the material was cell specific. The cells not only changed their morphology, but also the cell growth was affected. Whereas, neuroblastoma cells proliferated at the same rate on the spike structures as on the control surfaces, the proliferation of fibroblasts was reduced by the spike structures. These effects can result from the cell specific adhesion patterns as shown in this work. These findings show a possibility to design defined surface microstructures, which could control cellular behavior in a cell specific manner.

Water-based adhesives with tailored hydrophobic association: dilution resistance and improved setting behavior.

PubMed

Dundua, Alexander; Landfester, Katharina; Taden, Andreas

2014-11-01

Hydrophobic association and stimuli-responsiveness is a powerful tool towards water-based adhesives with strongly improved properties, which is demonstrated based on the example of hydrophobically modified alkali-soluble latexes (HASE) with modulated association. Their rheological properties are highly tunable due to the hydrophobic domains that act as physical crosslinking sites of adjustable interaction strength. Ethanol, propanol, and butanol are used as water-soluble model additives with different hydrophobicity in order to specifically target the association sites and impact the viscoelastic properties and stimuli-responsiveness. The rheological and mechanical property response upon dilution with water can be tailored, and dilution-resistant or even dilution-thickening systems are obtained. The investigations are of high importance for water-based adhesives, as our findings provide insight into general structure-property relationships to improve their setting behavior, especially upon contact with wet substrates. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Identification of a process window for tailored carburization of sheet metals in hot stamping

NASA Astrophysics Data System (ADS)

Horn, Alexander; Merklein, Marion

2018-05-01

Due to governmental regulations concerning the reduction of CO2 emissions and increasing safety standards, hot stamping of high strength boron manganese steel sheets has evolved into a state of the art process for manufacturing structural car body parts. The combined forming and in-die quenching process enables the formation of a fully martensitic microstructure. Therefore, press hardened steels offer high strength, but low ductility. In order to further improve passenger safety, a tailored configuration of mechanical properties is desired. Besides state of the art methods, like the application of locally different heat treatment temperatures or varying quenching rates, the adjustment of mechanical properties of sheet metals by a tailored carburization is a novel approach. For the carburization process, the specimens are first coated with graphite and subsequently heat treated. Within this contribution, different coating strategies as well as heat treatment temperatures and dwell times are investigated. For the determination of a process window, mechanical properties such as tensile strength and microhardness will be analyzed and correlated with the resulting microstructure.

Tailoring of optical properties of fluorescein using green synthesized gold nanoparticles.

PubMed

John, Jisha; Thomas, Lincy; George, Nibu A; Kurian, Achamma; George, Sajan D

2015-06-28

Dye-nanoparticle mixtures hold great promise in biological as well as photonics applications due to their capability to tailor the emission behavior of dye by tuning the nanoparticles parameters. However, as compared to the well-defined dye-nanoparticle distance, studies lack the understanding of homogenous mixtures of dye and nanoparticles. In this work, we investigate the influence of shape and concentration of gold nanoparticles prepared via green synthesis on the optical properties of fluorescein dye in a dye-nanoparticle mixture. We have investigated the radiative path of deexcitation using steady state fluorescence and the non-radiative path is probed using a laser based dual-beam thermal lens technique. The energy transfer efficiency as well as dye-nanoparticle distance is studied using both techniques. Furthermore, we have explored the influence of nanoparticles parameters on the fluorescence quantum yield of fluorescein using the thermal lens technique. The studies indicate that spherical nanoparticles are efficient quenchers while star shaped nanoparticles can probe larger dye-NP distances. The tailoring of dye properties by tuning nanoparticle parameters can be utilized in diverse areas including bioimaging, solar cells, and sensors.

Preparation and characterization of polymeric nanocomposite films for application as protective coatings

NASA Astrophysics Data System (ADS)

Gagliardi, S.; Rondino, F.; D'Erme, C.; Persia, F.; Menchini, F.; Santarelli, M. L.; Paulke, B.-R.; Enayati, A. L.; Falconieri, M.

2017-08-01

Addiction of ceramic nanoparticles to acrylic polymers provides a simple and effective means to produce paints with important properties, such as mechanical resistance and tailored wettability, even though for optimal performances, an engineered nanoparticle distribution would be desirable. In this paper we report on the realization and on the morphological and functional characterization of nanocomposites where the nanophase is distributed on the surface of acrylic polymer films, in order to enhance the expression of surface-related properties. To this aim, commercial titanium oxide and silicon oxide nanopowders were dispersed in water and the suspensions were air-sprayed on polymeric films prepared by paint brushing, thus producing a nanostructured ceramic surface coating. Control of the pH of suspensions and acrylic acid functionalization of the surface of titania were used together with high power ultrasonic treatments in order to control dimension of the aggregates in the sprayed suspensions. Optical microscopy, mechanical profilometry, and atomic force microscopy were used to characterize the nanocomposite surface morphology and correlate it to the coating functional properties, evaluated through mechanical abrasion tests and contact angle measurements; also, colorimetry on coated stones was performed in order to test the impact of the coatings on the aesthetical appearance and their photostability under UV irradiation. Results show that the nanostructured ceramic layer slightly improves the resistance of coatings to mechanical abrasion in case of polymer films prepared from latexes. The nanocomposite surface layer does not affect the wettability of the polymer, which remained slightly hydrophilic; this behavior is likely due to inadequate distribution of the nanophase. On the other hand UV-induced superhydrophilicity was observed when the concentration of surface titania nanoparticles is about 0.6 mg/cm2. Colorimetric analysis on historical and Carrara marbles before and after coating evidenced the good transparency of the nanocomposites. Accelerated aging tests permitted to demonstrate that, on the historical marbles, the presence of the nanoparticles has a protective action against UV-induced damage of the underlying polymer film, preventing photodegradation.

Chimeric peptides as implant functionalization agents for titanium alloy implants with antimicrobial properties.

PubMed

Yucesoy, Deniz T; Hnilova, Marketa; Boone, Kyle; Arnold, Paul M; Snead, Malcolm L; Tamerler, Candan

2015-04-01

Implant-associated infections can have severe effects on the longevity of implant devices and they also represent a major cause of implant failures. Treating these infections associated with implants by antibiotics is not always an effective strategy due to poor penetration rates of antibiotics into biofilms. Additionally, emerging antibiotic resistance poses serious concerns. There is an urge to develop effective antibacterial surfaces that prevent bacterial adhesion and proliferation. A novel class of bacterial therapeutic agents, known as antimicrobial peptides (AMP's), are receiving increasing attention as an unconventional option to treat septic infection, partly due to their capacity to stimulate innate immune responses and for the difficulty of microorganisms to develop resistance towards them. While host- and bacterial- cells compete in determining the ultimate fate of the implant, functionalization of implant surfaces with antimicrobial peptides can shift the balance and prevent implant infections. In the present study, we developed a novel chimeric peptide to functionalize the implant material surface. The chimeric peptide simultaneously presents two functionalities, with one domain binding to a titanium alloy implant surface through a titanium-binding domain while the other domain displays an antimicrobial property. This approach gains strength through control over the bio-material interfaces, a property built upon molecular recognition and self-assembly through a titanium alloy binding domain in the chimeric peptide. The efficiency of chimeric peptide both in-solution and absorbed onto titanium alloy surface was evaluated in vitro against three common human host infectious bacteria, S. mutans, S. epidermidis , and E. coli . In biological interactions such as occurs on implants, it is the surface and the interface that dictate the ultimate outcome. Controlling the implant surface by creating an interface composed chimeric peptides may therefore open up new possibilities to cover the implant site and tailor it to a desirable bioactivity.

Porphyrins at interfaces

NASA Astrophysics Data System (ADS)

Auwärter, Willi; Écija, David; Klappenberger, Florian; Barth, Johannes V.

2015-02-01

Porphyrins and other tetrapyrrole macrocycles possess an impressive variety of functional properties that have been exploited in natural and artificial systems. Different metal centres incorporated within the tetradentate ligand are key for achieving and regulating vital processes, including reversible axial ligation of adducts, electron transfer, light-harvesting and catalytic transformations. Tailored substituents optimize their performance, dictating their arrangement in specific environments and mediating the assembly of molecular nanoarchitectures. Here we review the current understanding of these species at well-defined interfaces, disclosing exquisite insights into their structural and chemical properties, and also discussing methods by which to manipulate their intramolecular and organizational features. The distinct characteristics arising from the interfacial confinement offer intriguing prospects for molecular science and advanced materials. We assess the role of surface interactions with respect to electronic and physicochemical characteristics, and describe in situ metallation pathways, molecular magnetism, rotation and switching. The engineering of nanostructures, organized layers, interfacial hybrid and bio-inspired systems is also addressed.

Biodegradable polyester-based microcarriers with modified surface tailored for tissue engineering.

PubMed

Privalova, A; Markvicheva, E; Sevrin, Ch; Drozdova, M; Kottgen, C; Gilbert, B; Ortiz, M; Grandfils, Ch

2015-03-01

Microcarriers have been proposed in tissue engineering, namely for bone, cartilage, skin, vascular, and central nervous system. Although polyester-based microcarriers have been already used for this purpose, their surface properties should be improved to provide better cell growth. The goal of this study was to prepare microbeads based on poly(D,L-lactide) acid, poly(L-lactide) acid, and to study cell behavior (adhesion, spreading, growth, and proliferation) in function of microbead topography and surface chemistry. To improve L-929 fibroblasts adhesion, microbead surface has been modified with three polycations: chitosan, poly(2-dimethylamino ethylmethacrylate) (PDMAEMA), or chitosan-g-oligolactide copolymer (chit-g-OLA). Although modification of the microbead surface with chitosan and PDMAEMA was performed through physical adsorption on the previously prepared microbeads, chit-g-OLA copolymer was introduced directly during microbead processing. This simple approach (1) bypass the use of an emulsifier (polyvinyl alcohol, PVA); (2) avoid surface "contamination" with PVA molecules limiting a control of the surface characteristics. In vitro study of the growth of mouse fibroblasts on the microbeads showed that both surface topography and chemistry affected cell attachment, spreading, and proliferation. Cultivation of L-929 fibroblasts for 7 days resulted in the formation of a 3D cell-scaffold network. © 2014 Wiley Periodicals, Inc.

The Effect of Compositional Tailoring on the Thermal Expansion and Tribological Properties of PS300: A Solid Lubricant Composite Coating

NASA Technical Reports Server (NTRS)

DellaCorte, C.; Fellenstein, J. A.

1996-01-01

This paper describes a research program in which the goal is to alter the thermal expansion coefficient of a composite solid lubricant coating, PS300, by compositional tailoring. PS300 is a plasma sprayed coating consisting of chrome oxide, silver and barium fluoride/calcium fluoride eutectic in NiCr binder. By adjusting the composition, the thermal expansion coefficient can be altered, and hence chosen, to more closely match a selected substrate preventing coating spallation at extreme temperatures. Thermal expansion coefficients (CTE) for a variety of compositions were measured from 25 to 800 C using a commercial dilatometer. The CTE's ranged from 7.0 to 13 x lO(exp -6)/deg C depending on the binder content. Subsequent tribological testing of a modified composition indicated that friction and wear properties were relatively insensitive to compositional tailoring.

Surface modification technologies using concentrated solar radiation

NASA Astrophysics Data System (ADS)

Pitts, J. Roland; Stanley, J. T.; Tracy, Ed; Fields, C. L.

Research conducted at the Solar Energy Research Institute (SERI) during the past three years addressed a number of the critical areas and has explored the possibility of using highly concentrated solar radiation to induce beneficial surface transformation. The principal goal is to develop new coatings and processes that improve the performance and lifetime of materials at reduced processing costs. Highly concentrated radiant energy provides a controllable means of delivering large flux densities to solid surfaces, where the resulting thermal energy can cause phase changes, atomic migrations, and chemical reactions on a surface without greatly perturbing the bulk properties; alternatively, the photons may directly interact with species on the surface. These changes may result in improved properties of the materials by making the surface harder, more resistant to corrosion or wear, thermally resistant, or with lower coefficients of friction. In a solar furnace, this flux can be delivered in large quantities over large areas, or it can be tailored to match the demands of a particular process. Furthermore, this occurs without the environmental liability associated with providing power to more conventional light sources. Recent work at SERI has used fluxes in the range from 100 to 250 w/sq cm for inducing such beneficial surface transformations. Significant results have been obtained in the area of phase transformation hardening of steels and melting powders and preapplied coatings to form fully dense, well-bonded coatings on the surface. New directions in coating technology using highly concentrated solar beams to induce chemical vapor deposition processes are described. Application areas that have not been researched in detail but would appear to be good matches to the solar technology are also reviewed.

Tailoring of Boehmite-Derived Aluminosilicate Aerogel Structure and Properties: Influence of Ti Addition

NASA Technical Reports Server (NTRS)

Hurwitz, Frances I.; Guo, Haiquan; Sheets, Erik J.; Miller, Derek R.; Newlin, Katy N.

2010-01-01

Aluminosilicate aerogels offer potential for extremely low thermal conductivities at temperatures greater than 900 C, beyond where silica aerogels reach their upper temperature limits. Aerogels have been synthesized at various Al:Si ratios, including mullite compositions, using Boehmite (AlOOH) as the Al source, and tetraethoxy orthosilicate as the Si precursor. The Boehmite-derived aerogels are found to form by a self-assembly process of AlOOH crystallites, with Si-O groups on the surface of an alumina skeleton. Morphology, surface area and pore size varies with the crystallite size of the starting Boehmite powder, as well as with synthesis parameters. Ternary systems, including Al-Si-Ti aerogels incorporating a soluble Ti precursor, are possible with careful control of pH. The addition of Ti influences sol viscosity, gelation time pore structure and pore size distribution, as well as phase formation on heat treatment.

Conformal piezoelectric systems for clinical and experimental characterization of soft tissue biomechanics

NASA Astrophysics Data System (ADS)

Dagdeviren, Canan; Shi, Yan; Joe, Pauline; Ghaffari, Roozbeh; Balooch, Guive; Usgaonkar, Karan; Gur, Onur; Tran, Phat L.; Crosby, Jessi R.; Meyer, Marcin; Su, Yewang; Chad Webb, R.; Tedesco, Andrew S.; Slepian, Marvin J.; Huang, Yonggang; Rogers, John A.

2015-07-01

Mechanical assessment of soft biological tissues and organs has broad relevance in clinical diagnosis and treatment of disease. Existing characterization methods are invasive, lack microscale spatial resolution, and are tailored only for specific regions of the body under quasi-static conditions. Here, we develop conformal and piezoelectric devices that enable in vivo measurements of soft tissue viscoelasticity in the near-surface regions of the epidermis. These systems achieve conformal contact with the underlying complex topography and texture of the targeted skin, as well as other organ surfaces, under both quasi-static and dynamic conditions. Experimental and theoretical characterization of the responses of piezoelectric actuator-sensor pairs laminated on a variety of soft biological tissues and organ systems in animal models provide information on the operation of the devices. Studies on human subjects establish the clinical significance of these devices for rapid and non-invasive characterization of skin mechanical properties.

Dry Sintering Meets Wet Silver-Ion "Soldering": Charge-Transfer Plasmon Engineering of Solution-Assembled Gold Nanodimers From Visible to Near-Infrared I and II Regions.

PubMed

Fang, Lingling; Wang, Yueliang; Liu, Miao; Gong, Ming; Xu, An; Deng, Zhaoxiang

2016-11-07

Achieving highly tunable and localized surface plasmon resonance up to near infrared (NIR) regions is a key target in nanoplasmonics. In particular, a self-assembly process capable of producing highly uniform and solution-processable nanomaterials with tailor-made plasmonic properties is lacking. We herein address this problem through a conjunctive use of wet Ag + soldering and dry thermal sintering to produce nanodimer-derived structures with precisely engineered charge-transfer plasmon (CTP). The sintered dimers are water soluble, featuring gradually shifted CTP spanning an 800 nm wavelength range (up to NIR II). Upon silica removal, the products are grafted by DNA to offer surface functionality. This process is also adaptable to DNA-linked AuNP dimers toward plasmonic meta-materials via DNA-guided soldering and sintering. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Visible Quantum Nanophotonics.

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

Subramania, Ganapathi Subramanian; Wang, George T.; Fischer, Arthur J.

2017-09-01

The goal of this LDRD is to develop a quantum nanophotonics capability that will allow practical control over electron (hole) and photon confinement in more than one dimension. We plan to use quantum dots (QDs) to control electrons, and photonic crystals to control photons. InGaN QDs will be fabricated using quantum size control processes, and methods will be developed to add epitaxial layers for hole injection and surface passivation. We will also explore photonic crystal nanofabrication techniques using both additive and subtractive fabrication processes, which can tailor photonic crystal properties. These two efforts will be combined by incorporating the QDsmore » into photonic crystal surface emitting lasers (PCSELs). Modeling will be performed using finite-different time-domain and gain analysis to optimize QD-PCSEL designs that balance laser performance with the ability to nano-fabricate structures. Finally, we will develop design rules for QD-PCSEL architectures, to understand their performance possibilities and limits.« less

Fine-tuning the Wall Thickness of Ordered Mesoporous Graphene by Exploiting Ligand Exchange of Colloidal Nanocrystals

NASA Astrophysics Data System (ADS)

Han, Dandan; Yan, Yancui; Wei, Jishi; Wang, Biwei; Li, Tongtao; Guo, Guannan; Yang, Dong; Xie, Songhai; Dong, Angang

2017-12-01

Because of their unique physical properties, three-dimensional (3D) graphene has attracted enormous attention over the past years. However, it is still a challenge to precisely control the layer thickness of 3D graphene. Here, we report a novel strategy to rationally adjust the wall thickness of ordered mesoporous graphene (OMG). By taking advantage of ligand exchange capability of colloidal Fe3O4 nanocrystals, we are able to fine-tune the wall thickness of OMG from 2 to 6 layers of graphene by tailoring the hydrocarbon ligands attached to the nanocrystal surface. When evaluated as electrocatalyst for oxygen reduction reaction upon S and N doping, the 4-layer OMG is found to show better catalytic performance compared with its 2- and 6-layer counterparts, which we attribute to the enhanced exposure of active sites resulting from its ultrathin wall thickness and high surface area.

Tailored metal matrix composites for high-temperature performance

NASA Technical Reports Server (NTRS)

Morel, M. R.; Saravanos, D. A.; Chamis, C. C.

1992-01-01

A multi-objective tailoring methodology is presented to maximize stiffness and load carrying capacity of a metal matrix cross-ply laminated at elevated temperatures. The fabrication process and fiber volume ratio are used as the design variables. A unique feature is the concurrent effects from fabrication, residual stresses, material nonlinearity, and thermo-mechanical loading on the laminate properties at the post-fabrication phase. For a (0/90)(sub s) graphite/copper laminate, strong coupling was observed between the fabrication process, laminate characteristics, and thermo-mechanical loading. The multi-objective tailoring was found to be more effective than single objective tailoring. Results indicate the potential to increase laminate stiffness and load carrying capacity by controlling the critical parameters of the fabrication process and the laminate.

The switching behaviors induced by torsion angle in a diblock co-oligomer molecule with tailoring graphene nanoribbon electrodes

NASA Astrophysics Data System (ADS)

Yang, Aiyun; Xia, Caijuan; Zhang, Boqun; Wang, Jun; Su, Yaoheng; Tu, Zheyan

2018-02-01

By applying first-principles method based on density functional theory combined with nonequilibrium Green’s function, we investigate the effect of torsion angle on the electronic transport properties in dipyrimidinyl-diphenyl co-oligomer molecular device with tailoring graphene nanoribbon electrodes. The results show that the torsion angle plays an important role on the electronic transport properties of the molecular device. When the torsion angle rotates from 0∘ to 90∘, the molecular devices exhibit very different current-voltage characteristics which can realize the on and off states of the molecular switch.

Sensitized gelatin as a versatile biomaterial with tailored mechanical and optical properties

NASA Astrophysics Data System (ADS)

Muric, B.; Pantelic, D.; Vasiljevic, D.; Zarkov, B.; Jelenkovic, B.; Pantovic, S.; Rosic, M.

2013-11-01

We have found that gelatin doped with tot'hema (medication used for curing anemia) and eosin becomes elastic, while retaining good optical properties. The mechanical properties of tot'hema-eosin-sensitized gelatin films (TESG) have been investigated for various concentrations of tot'hema (ranging from 5 to 30% v/v). TESG specimens were prepared according to the ASTM standards for elastic materials. Tensile strength, strain at break and Young's modulus were measured. The results show that the extensibility of TESG film increases with increasing tot'hema concentration, while the Young's modulus and stress at break exponentially decrease. Mechanical properties can be tailored to suit various biomedical applications such as blood vessels, human lens capsules and biosensors based on microlenses. Tunable (strain responsive) TESG microlenses were produced and a mechanical model of blood vessels was prepared.

Improving the fiber coupling efficiency for DARWIN by loss-less shaping of the receive beams

NASA Astrophysics Data System (ADS)

Voland, Ch.; Weigel, Th.; Dreischer, Th.; Wallner, O.; Ergenzinger, K.; Ries, H.; Jetter, R.; Vosteen, A.

2017-11-01

For the DARWIN mission the extremely low planet signal levels require an optical instrument design with utmost efficiency to guarantee the required science performance. By shaping the transverse amplitude and phase distributions of the receive beams, the singlemode fibre coupling efficiency can be increased to almost 100%, thus allowing for a gain of more than 20% compared to conventional designs. We show that the use of "tailored freeform surfaces" for purpose of beam shaping dramatically reduces the coupling degradations, which otherwise result from mode mismatch between the Airy pattern of the image and the fibre mode, and therefore allows for achieving a performance close to the physical limitations. We present an application of tailored surfaces for building a beam shaping optics that shall enhance fibre coupling performance as core part of a space based interferometer in the future DARWIN mission and present performance predictions by wave-optical simulations. We assess the feasibility of manufacturing the corresponding tailored surfaces and describe the proof of concept demonstrator we use for experimental performance verification.

Silver nanoparticles as a key feature of a plasma polymer composite layer in mitigation of charge injection into polyethylene under dc stress

NASA Astrophysics Data System (ADS)

Milliere, L.; Maskasheva, K.; Laurent, C.; Despax, B.; Boudou, L.; Teyssedre, G.

2016-01-01

The aim of this work is to limit charge injection from a semi-conducting electrode into low density polyethylene (LDPE) under dc field by tailoring the polymer surface using a silver nanoparticles-containing layer. The layer is composed of a plane of silver nanoparticles embedded in a semi-insulating organosilicon matrix deposited on the polyethylene surface by a plasma process. Size, density and surface coverage of the nanoparticles are controlled through the plasma process. Space charge distribution in 300 μm thick LDPE samples is measured by the pulsed-electroacoustic technique following a short term (step-wise voltage increase up to 50 kV mm-1, 20 min in duration each, followed by a polarity inversion) and a longer term (up to 12 h under 40 kV mm-1) protocols for voltage application. A comparative study of space charge distribution between a reference polyethylene sample and the tailored samples is presented. It is shown that the barrier effect depends on the size distribution and the surface area covered by the nanoparticles: 15 nm (average size) silver nanoparticles with a high surface density but still not percolating form an efficient barrier layer that suppress charge injection. It is worthy to note that charge injection is detected for samples tailored with (i) percolating nanoparticles embedded in organosilicon layer; (ii) with organosilicon layer only, without nanoparticles and (iii) with smaller size silver particles (<10 nm) embedded in organosilicon layer. The amount of injected charges in the tailored samples increases gradually in the samples ranking given above. The mechanism of charge injection mitigation is discussed on the basis of complementary experiments carried out on the nanocomposite layer such as surface potential measurements. The ability of silver clusters to stabilize electrical charges close to the electrode thereby counterbalancing the applied field appears to be a key factor in explaining the charge injection mitigation effect.

Tailoring the morphology of raspberry-like carbon black/polystyrene composite microspheres for fabricating superhydrophobic surface

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

Bao, Yubin; Li, Qiuying, E-mail: liqy@ecust.edu.cn; Shanghai Key Laboratory Polymeric Materials

In our previous report, raspberry-like carbon black/polystyrene (CB/PS) composite microsphere was prepared through heterocoagulation process. Based on the previous study, in the present work, the morphology of raspberry-like CB/PS particle is tailored through adjusting the polarity and the concentration ratio of CB/PS colloidal suspension with the purpose to prepare particulate film for the fabrication of superhydrophobic surface. Scanning electron microscope (SEM) confirms the morphology of raspberry-like particle and the coverage of CB. Rough surfaces fabricated by raspberry-like particles with proper morphology are observed by SEM and clear evidence of superhydrophobic surface is shown. The structure of raspberry-like particle is analyzedmore » by atom force microscope. The proposed relationship between the hydrophobicity and the structure of CB aggregates on the surface of PS microsphere is discussed in details.« less

Targeting Strategies for Multifunctional Nanoparticles in Cancer Imaging and Therapy

PubMed Central

Yu, Mi Kyung; Park, Jinho; Jon, Sangyong

2012-01-01

Nanomaterials offer new opportunities for cancer diagnosis and treatment. Multifunctional nanoparticles harboring various functions including targeting, imaging, therapy, and etc have been intensively studied aiming to overcome limitations associated with conventional cancer diagnosis and therapy. Of various nanoparticles, magnetic iron oxide nanoparticles with superparamagnetic property have shown potential as multifunctional nanoparticles for clinical translation because they have been used asmagnetic resonance imaging (MRI) constrast agents in clinic and their features could be easily tailored by including targeting moieties, fluorescence dyes, or therapeutic agents. This review summarizes targeting strategies for construction of multifunctional nanoparticles including magnetic nanoparticles-based theranostic systems, and the various surface engineering strategies of nanoparticles for in vivo applications. PMID:22272217

Patterned titania nanostructures produced by electrochemical anodization of titanium sheet

NASA Astrophysics Data System (ADS)

Dong, Junzhe; Ariyanti, Dessy; Gao, Wei; Niu, Zhenjiang; Weil, Emeline

2017-07-01

A two-step anodization method has been used to produce patterned arrays of TiO2 on the surface of Ti sheet. Hexagonal ripples were created on Ti substrate after removing the TiO2 layer produced by first-step anodization. The shallow concaves were served as an ideal position for the subsequent step anodization due to their low electrical resistance, resulting in novel hierarchical nanostructures with small pits inside the original ripples. The mechanism of morphology evolution during patterned anodization was studied through changing the anodizing voltages and duration time. This work provides a new idea for controlling nanostructures and thus tailoring the photocatalytic property and wettability of anodic TiO2.

Peptide-Decorated Tunable-Fluorescence Graphene Quantum Dots.

PubMed

Sapkota, Bedanga; Benabbas, Abdelkrim; Lin, Hao-Yu Greg; Liang, Wentao; Champion, Paul; Wanunu, Meni

2017-03-22

We report here the synthesis of graphene quantum dots with tunable size, surface chemistry, and fluorescence properties. In the size regime 15-35 nm, these quantum dots maintain strong visible light fluorescence (mean quantum yield of 0.64) and a high two-photon absorption (TPA) cross section (6500 Göppert-Mayer units). Furthermore, through noncovalent tailoring of the chemistry of these quantum dots, we obtain water-stable quantum dots. For example, quantum dots with lysine groups bind strongly to DNA in solution and inhibit polymerase-based DNA strand synthesis. Finally, by virtue of their mesoscopic size, the quantum dots exhibit good cell permeability into living epithelial cells, but they do not enter the cell nucleus.

Tailoring the hydrophobicity of graphene for its use as nanopores for DNA translocation

NASA Astrophysics Data System (ADS)

Schneider, Grégory F.; Xu, Qiang; Hage, Susanne; Luik, Stephanie; Spoor, Johannes N. H.; Malladi, Sairam; Zandbergen, Henny; Dekker, Cees

2013-10-01

Graphene nanopores are potential successors to biological and silicon-based nanopores. For sensing applications, it is however crucial to understand and block the strong nonspecific hydrophobic interactions between DNA and graphene. Here we demonstrate a novel scheme to prevent DNA-graphene interactions, based on a tailored self-assembled monolayer. For bare graphene, we encounter a paradox: whereas contaminated graphene nanopores facilitated DNA translocation well, clean crystalline graphene pores very quickly exhibit clogging of the pore. We attribute this to strong interactions between DNA nucleotides and graphene, yielding sticking and irreversible pore closure. We develop a general strategy to noncovalently tailor the hydrophobic surface of graphene by designing a dedicated self-assembled monolayer of pyrene ethylene glycol, which renders the surface hydrophilic. We demonstrate that this prevents DNA to adsorb on graphene and show that single-stranded DNA can now be detected in graphene nanopores with excellent nanopore durability and reproducibility.

Unique properties of ceria nanoparticles supported on metals: novel inverse ceria/copper catalysts for CO oxidation and the water-gas shift reaction.

PubMed

Senanayake, Sanjaya D; Stacchiola, Dario; Rodriguez, Jose A

2013-08-20

Oxides play a central role in important industrial processes, including applications such as the production of renewable energy, remediation of environmental pollutants, and the synthesis of fine chemicals. They were originally used as catalyst supports and were thought to be chemically inert, but now they are used to build catalysts tailored toward improved selectivity and activity in chemical reactions. Many studies have compared the morphological, electronic, and chemical properties of oxide materials with those of unoxidized metals. Researchers know much less about the properties of oxides at the nanoscale, which display distinct behavior from their bulk counterparts. More is known about metal nanoparticles. Inverse-model catalysts, composed of oxide nanoparticles supported on metal or oxide substrates instead of the reverse (oxides supporting metal nanoparticles), are excellent tools for systematically testing the properties of novel catalytic oxide materials. Inverse models are prepared in situ and can be studied with a variety of surface science tools (e.g. scanning tunneling microscopy, X-ray photoemission spectroscopy, ultraviolet photoemission spectroscopy, low-energy electron microscopy) and theoretical tools (e.g. density functional theory). Meanwhile, their catalytic activity can be tested simultaneously in a reactor. This approach makes it possible to identify specific functions or structures that affect catalyst performance or reaction selectivity. Insights gained from these tests help to tailor powder systems, with the primary objective of rational design (experimental and theoretical) of catalysts for specific chemical reactions. This Account describes the properties of inverse catalysts composed of CeOx nanoparticles supported on Cu(111) or CuOx/Cu(111) as determined through the methods described above. Ceria is an important material for redox chemistry because of its interchangeable oxidation states (Ce⁴⁺ and Ce³⁺). Cu(111), meanwhile, is a standard catalyst for reactions such as CO oxidation and the water-gas shift (WGS). This metal serves as an ideal replacement for other noble metals that are neither abundant nor cost effective. To prepare the inverse system we deposited nanoparticles (2-20 nm) of cerium oxide onto the Cu(111) surface. During this process, the Cu(111) surface grows an oxide layer that is characteristic of Cu₂O (Cu¹⁺). This oxide can influence the growth of ceria nanoparticles. Evidence suggests triangular-shaped CeO₂(111) grows on Cu₂O(111) surfaces while rectangular CeO₂(100) grows on Cu₄O₃(111) surfaces. We used the CeOx/Cu₂O/Cu(111) inverse system to study two catalytic processes: the WGS (CO + H₂O → CO₂ + H₂) and CO oxidation (2CO + O₂ → 2CO₂). We discovered that the addition of small amounts of ceria nanoparticles can activate the Cu(111) surface and achieve remarkable enhancement of catalytic activity in the investigated reactions. In the case of the WGS, the CeOx nanoparticle facilitated this process by acting at the interface with Cu to dissociate water. In the CO oxidation case, an enhancement in the dissociation of O₂ by the nanoparticles was a key factor. The strong interaction between CeOx nanoparticles and Cu(111) when preoxidized and reduced in CO resulted in a massive surface reconstruction of the copper substrate with the introduction of microterraces that covered 25-35% of the surface. This constitutes a new mechanism for surface reconstruction not observed before. These microterraces helped to facilitate a further enhancement of activity towards the WGS by opening an additional channel for the dissociation of water. In summary, inverse catalysts of CeOx/Cu(111) and CeO₂/Cu₂O/Cu(111) demonstrate the versatility of a model system to obtain insightful knowledge of catalytic processes. These systems will continue to offer a unique opportunity to probe key catalytic components and elucidate the relationship between structure and reactivity of novel materials and reactions in the future.

Near-infrared photocatalysts of BiVO4/CaF2:Er3+, Tm3+, Yb3+ with enhanced upconversion properties

NASA Astrophysics Data System (ADS)

Huang, Shouqiang; Zhu, Nanwen; Lou, Ziyang; Gu, Lin; Miao, Chen; Yuan, Haiping; Shan, Aidang

2014-01-01

Upconversion photocatalysts have the potential to absorb the near-infrared (NIR) light in solar energy and improve the photocatalytic performance. A hierarchical upconversion photocatalyst of BiVO4 (BVO)/CaF2:Er3+, Tm3+, Yb3+ (CF) combined with the narrow-band semiconductor of BVO and the luminescence agent of CF to enhance upconversion properties was synthesized via the hydrothermal method. The CF particles were deposited homogeneously on the surface of the BVO/CF composite with regular dendritic structure, which led to efficient upconversion emissions. The upconversion emission intensity of the BVO/CF composite was 8 times higher than that of pure CF, through tailoring the crystal symmetry of lanthanide ions by Bi3+ ions. The upconverted ultraviolet (361 and 379 nm), violet (408 nm), and blue (485 nm) light was able to excite BVO for photocatalysis in BVO/CF under NIR irradiation, which improved the degradation rate of methyl orange (MO).Upconversion photocatalysts have the potential to absorb the near-infrared (NIR) light in solar energy and improve the photocatalytic performance. A hierarchical upconversion photocatalyst of BiVO4 (BVO)/CaF2:Er3+, Tm3+, Yb3+ (CF) combined with the narrow-band semiconductor of BVO and the luminescence agent of CF to enhance upconversion properties was synthesized via the hydrothermal method. The CF particles were deposited homogeneously on the surface of the BVO/CF composite with regular dendritic structure, which led to efficient upconversion emissions. The upconversion emission intensity of the BVO/CF composite was 8 times higher than that of pure CF, through tailoring the crystal symmetry of lanthanide ions by Bi3+ ions. The upconverted ultraviolet (361 and 379 nm), violet (408 nm), and blue (485 nm) light was able to excite BVO for photocatalysis in BVO/CF under NIR irradiation, which improved the degradation rate of methyl orange (MO). Electronic supplementary information (ESI) available: Additional tables and figures. See DOI: 10.1039/c3nr05266d

A review of combined experimental and computational procedures for assessing biopolymer structure–process–property relationships

PubMed Central

Gronau, Greta; Krishnaji, Sreevidhya T.; Kinahan, Michelle E.; Giesa, Tristan; Wong, Joyce Y.; Kaplan, David L.; Buehler, Markus J.

2013-01-01

Tailored biomaterials with tunable functional properties are desirable for many applications ranging from drug delivery to regenerative medicine. To improve the predictability of biopolymer materials functionality, multiple design parameters need to be considered, along with appropriate models. In this article we review the state of the art of synthesis and processing related to the design of biopolymers, with an emphasis on the integration of bottom-up computational modeling in the design process. We consider three prominent examples of well-studied biopolymer materials – elastin, silk, and collagen – and assess their hierarchical structure, intriguing functional properties and categorize existing approaches to study these materials. We find that an integrated design approach in which both experiments and computational modeling are used has rarely been applied for these materials due to difficulties in relating insights gained on different length- and time-scales. In this context, multiscale engineering offers a powerful means to accelerate the biomaterials design process for the development of tailored materials that suit the needs posed by the various applications. The combined use of experimental and computational tools has a very broad applicability not only in the field of biopolymers, but can be exploited to tailor the properties of other polymers and composite materials in general. PMID:22938765

A review of combined experimental and computational procedures for assessing biopolymer structure-process-property relationships.

PubMed

Gronau, Greta; Krishnaji, Sreevidhya T; Kinahan, Michelle E; Giesa, Tristan; Wong, Joyce Y; Kaplan, David L; Buehler, Markus J

2012-11-01

Tailored biomaterials with tunable functional properties are desirable for many applications ranging from drug delivery to regenerative medicine. To improve the predictability of biopolymer materials functionality, multiple design parameters need to be considered, along with appropriate models. In this article we review the state of the art of synthesis and processing related to the design of biopolymers, with an emphasis on the integration of bottom-up computational modeling in the design process. We consider three prominent examples of well-studied biopolymer materials - elastin, silk, and collagen - and assess their hierarchical structure, intriguing functional properties and categorize existing approaches to study these materials. We find that an integrated design approach in which both experiments and computational modeling are used has rarely been applied for these materials due to difficulties in relating insights gained on different length- and time-scales. In this context, multiscale engineering offers a powerful means to accelerate the biomaterials design process for the development of tailored materials that suit the needs posed by the various applications. The combined use of experimental and computational tools has a very broad applicability not only in the field of biopolymers, but can be exploited to tailor the properties of other polymers and composite materials in general. Copyright © 2012 Elsevier Ltd. All rights reserved.

Tailoring magnetic properties of Co nanocluster assembled films using hydrogen

NASA Astrophysics Data System (ADS)

Romero, C. P.; Volodin, A.; Paddubrouskaya, H.; Van Bael, M. J.; Van Haesendonck, C.; Lievens, P.

2018-07-01

Tailoring magnetic properties in nanocluster assembled cobalt (Co) thin films was achieved by admitting a small percentage of H2 gas (∼2%) into the Co gas phase cluster formation chamber prior to deposition. The oxygen content in the films is considerably reduced by the presence of hydrogen during the cluster formation, leading to enhanced magnetic interactions between clusters. Two sets of Co samples were fabricated, one without hydrogen gas and one with hydrogen gas. Magnetic properties of the non-hydrogenated and the hydrogen-treated Co nanocluster assembled films are comparatively studied using magnetic force microscopy and vibrating sample magnetometry. When comparing the two sets of samples the considerably larger coercive field of the H2-treated Co nanocluster film and the extended micrometer-sized magnetic domain structure confirm the enhancement of magnetic interactions between clusters. The thickness of the antiferromagnetic CoO layer is controlled with this procedure and modifies the exchange bias effect in these films. The exchange bias shift is lower for the H2-treated Co nanocluster film, which indicates that a thinner antiferromagnetic CoO reduces the coupling with the ferromagnetic Co. The hydrogen-treatment method can be used to tailor the oxidation levels thus controlling the magnetic properties of ferromagnetic cluster-assembled films.

Lithium aluminosilicate reinforced with carbon nanofiber and alumina for controlled-thermal-expansion materials

NASA Astrophysics Data System (ADS)

Borrell, Amparo; García-Moreno, Olga; Torrecillas, Ramón; García-Rocha, Victoria; Fernández, Adolfo

2012-02-01

Materials with a very low or tailored thermal expansion have many applications ranging from cookware to the aerospace industry. Among others, lithium aluminosilicates (LAS) are the most studied family with low and negative thermal expansion coefficients. However, LAS materials are electrical insulators and have poor mechanical properties. Nanocomposites using LAS as a matrix are promising in many applications where special properties are achieved by the addition of one or two more phases. The main scope of this work is to study the sinterability of carbon nanofiber (CNFs)/LAS and CNFs/alumina/LAS nanocomposites, and to adjust the ratio among components for obtaining a near-zero or tailored thermal expansion. Spark plasma sintering of nanocomposites, consisting of commercial CNFs and alumina powders and an ad hoc synthesized β-eucryptite phase, is proposed as a solution to improving mechanical and electrical properties compared with the LAS ceramics obtained under the same conditions. X-ray diffraction results on phase compositions and microstructure are discussed together with dilatometry data obtained in a wide temperature range (-150 to 450 °C). The use of a ceramic LAS phase makes it possible to design a nanocomposite with a very low or tailored thermal expansion coefficient and exceptional electrical and mechanical properties.

Tunable coating of gold nanostars: tailoring robust SERS labels for cell imaging

NASA Astrophysics Data System (ADS)

Bassi, B.; Taglietti, A.; Galinetto, P.; Marchesi, N.; Pascale, A.; Cabrini, E.; Pallavicini, P.; Dacarro, G.

2016-07-01

Surface modification of noble metal nanoparticles with mixed molecular monolayers is one of the most powerful tools in nanotechnology, and is used to impart and tune new complex surface properties. In imaging techniques based on surface enhanced Raman spectroscopy (SERS), precise and controllable surface modifications are needed to carefully design reproducible, robust and adjustable SERS nanoprobes. We report here the attainment of SERS labels based on gold nanostars (GNSs) coated with a mixed monolayer composed of a poly ethylene glycol (PEG) thiol (neutral or negatively charged) that ensure stability in biological environments, and of a signalling unit 7-Mercapto-4-methylcoumarin as a Raman reporter molecule. The composition of the coating mixture is precisely controlled using an original method, allowing the modulation of the SERS intensity and ensuring overall nanoprobe stability. The further addition of a positively charged layer of poly (allylamine hydrocloride) on the surface of negatively charged SERS labels does not change the SERS response, but it promotes the penetration of GNSs in SH-SY5Y neuroblastoma cells. As an example of an application of such an approach, we demonstrate here the internalization of these new labels by means of visualization of cell morphology obtained with SERS mapping.

Reactive polymer coatings: A robust platform towards sophisticated surface engineering for biotechnology

NASA Astrophysics Data System (ADS)

Chen, Hsien-Yeh

Functionalized poly(p-xylylenes) or so-called reactive polymers can be synthesized via chemical vapor deposition (CVD) polymerization. The resulting ultra-thin coatings are pinhole-free and can be conformally deposited to a wide range of substrates and materials. More importantly, the equipped functional groups can served as anchoring sites for tailoring the surface properties, making these reactive coatings a robust platform that can deal with sophisticated challenges faced in biointerfaces. In this work presented herein, surface coatings presenting various functional groups were prepared by CVD process. Such surfaces include aldehyde-functionalized coating to precisely immobilize saccharide molecules onto well-defined areas and alkyne-functionalized coating to click azide-modified molecules via Huisgen 1,3-dipolar cycloaddition reaction. Moreover, CVD copolymerization has been conducted to prepare multifunctional coatings and their specific functions were demonstrated by the immobilization of biotin and NHS-ester molecules. By using a photodefinable coating, polyethylene oxides were immobilized onto a wide range of substrates through photo-immobilization. Spatially controlled protein resistant properties were characterized by selective adsorption of fibrinogen and bovine serum albumin as model systems. Alternatively, surface initiator coatings were used for polymer graftings of polyethylene glycol) methyl ether methacrylate, and the resultant protein- and cell- resistant properties were characterized by adsorption of kinesin motor proteins, fibrinogen, and murine fibroblasts (NIH3T3). Accessibility of reactive coatings within confined microgeometries was systematically studied, and the preparation of homogeneous polymer thin films within the inner surface of microchannels was demonstrated. Moreover, these advanced coatings were applied to develop a dry adhesion process for microfluidic devices. This process provides (i) excellent bonding strength, (ii) extended storage time prior to bonding, and (iii) well-defined surface functionalities for subsequent surface modifications. Finally, we have also prepared surface microstructures and surface patterns using reactive coatings via photopatterning, projection lithography, supramolecular nanostamping (SuNS), and vapor-assisted micropatterning in replica structures (VAMPIR). These patterning techniques can be complimentarily used and provide access to precisely confined microenvironments on flat and curved geometries. Reactive coatings provide a technology platform that creates active, long-term control and may lead to improved mimicry of biological systems for effective bio-functional modifications.

Heterocyclic Salt Synthesis and Rational Properties Tailoring (PREPRINT)

DTIC Science & Technology

2009-06-23

performance behavior can be tailored in a controlled manner, defines the objective of a pertinent synthesis effort. Achieving this objective by...the structure of the anion. To illustrate this premise, four general synthesis methods to synthesize heterocyclic salts, including several new binary...manner, defines the objective of a pertinent synthesis effort. Achieving this objective by introducing structural alterations in a neutral covalent

Zero expansion glass ceramic ZERODUR® roadmap for advanced lithography

NASA Astrophysics Data System (ADS)

Westerhoff, Thomas; Jedamzik, Ralf; Hartmann, Peter

2013-04-01

The zero expansion glass ceramic ZERODUR® is a well-established material in microlithography in critical components as wafer- and reticle-stages, mirrors and frames in the stepper positioning and alignment system. The very low coefficient of thermal expansion (CTE) and its extremely high CTE homogeneity are key properties to achieve the tight overlay requirements of advanced lithography processes. SCHOTT is continuously improving critical material properties of ZERODUR® essential for microlithography applications according to a roadmap driven by the ever tighter material specifications broken down from the customer roadmaps. This paper will present the SCHOTT Roadmap for ZERODUR® material property development. In the recent years SCHOTT established a physical model based on structural relaxation to describe the coefficient of thermal expansion's temperature dependence. The model is successfully applied for the new expansion grade ZERODUR® TAILORED introduced to the market in 2012. ZERODUR® TAILORED delivers the lowest thermal expansion of ZERODUR® products at microlithography tool application temperature allowing for higher thermal stability for tighter overlay control in IC production. Data will be reported demonstrating the unique CTE homogeneity of ZERODUR® and its very high reproducibility, a necessary precondition for serial production for microlithography equipment components. New data on the bending strength of ZERODUR® proves its capability to withstand much higher mechanical loads than previously reported. Utilizing a three parameter Weibull distribution it is possible to derive minimum strength values for a given ZERODUR® surface treatment. Consequently the statistical uncertainties of the earlier approach based on a two parameter Weibull distribution have been eliminated. Mechanical fatigue due to stress corrosion was included in a straightforward way. The derived formulae allows calculating life time of ZERODUR® components for a given stress load or the allowable maximum stress for a minimum required life time.

Concise Review: Fabrication, Customization, and Application of Cell Mimicking Microparticles in Stem Cell Science.

PubMed

Labriola, Nicholas R; Azagury, Aharon; Gutierrez, Robert; Mathiowitz, Edith; Darling, Eric M

2018-02-01

Stem and non-stem cell behavior is heavily influenced by the surrounding microenvironment, which includes other cells, matrix, and potentially biomaterials. Researchers have been successful in developing scaffolds and encapsulation techniques to provide stem cells with mechanical, topographical, and chemical cues to selectively direct them toward a desired differentiation pathway. However, most of these systems fail to present truly physiological replications of the in vivo microenvironments that stem cells are typically exposed to in tissues. Thus, cell mimicking microparticles (CMMPs) have been developed to more accurately recapitulate the properties of surrounding cells while still offering ways to tailor what stimuli are presented. This nascent field holds the promise of reducing, or even eliminating, the need for live cells in select, regenerative medicine therapies, and diagnostic applications. Recent, CMMP-based studies show great promise for the technology, yet only reproduce a small subset of cellular characteristics from among those possible: size, morphology, topography, mechanical properties, surface molecules, and tailored chemical release to name the most prominent. This Review summarizes the strengths, weaknesses, and ideal applications of micro/nanoparticle fabrication and customization methods relevant to cell mimicking and provides an outlook on the future of this technology. Moving forward, researchers should seek to combine multiple techniques to yield CMMPs that replicate as many cellular characteristics as possible, with an emphasis on those that most strongly influence the desired therapeutic effects. The level of flexibility in customizing CMMP properties allows them to substitute for cells in a variety of regenerative medicine, drug delivery, and diagnostic systems. Stem Cells Translational Medicine 2018;7:232-240. © 2018 The Authors Stem Cells Translational Medicine published by Wiley Periodicals, Inc. on behalf of AlphaMed Press.

One-Pot synthesis of phosphorylated mesoporous carbon heterogeneous catalysts with tailored surface acidity

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

Fulvio, Pasquale F; Mahurin, Shannon Mark; Mayes, Richard T

2012-01-01

Soft-templated phosphorylated mesoporous carbons with homogeneous distributions of phosphate groups were prepared by a 'one-pot' synthesis method using mixtures of phosphoric acid with hydrochloric, or nitric acids in the presence of Pluronic F127 triblock copolymer. Adjusting the various ratios of phosphoric acid used in these mixtures resulted in carbons with distinct adsorption, structural and surface acidity properties. The pore size distributions (PSDs) from nitrogen adsorption at -196 C showed that mesoporous carbons exhibit specific surface areas as high as 551 m{sup 2}/g and mesopores as large as 13 nm. Both structural ordering of the mesopores and the final phosphate contentsmore » were strongly dependent on the ratios of H{sub 3}PO{sub 4} in the synthesis gels, as shown by transmission electron microscopy (TEM), X-ray photoelectron (XPS) and energy dispersive X-ray spectroscopy (EDS). The number of surface acid sites determined from temperature programmed desorption of ammonia (NH{sub 3}-TPD) were in the range of 0.3-1.5 mmol/g while the active surface areas are estimated to comprise 5-54% of the total surface areas. Finally, the conversion temperatures for the isopropanol dehydration were lowered by as much as 100 C by transitioning from the least acidic to the most acidic catalysts surface.« less

Tailor-made functional surfaces: potential elastomeric biomaterials I.

PubMed

Desai, Shrojal; Bodas, Dhananjay; Patil, K R; Patole, Milind; Singh, R P

2003-01-01

In the present investigation, different functional monomers, like hydroxyethyl methacrylate, acrylic acid, N-vinyl pyrrolidone and glycidyl methacrylate, have been grafted onto the surface of EPDM film (approx. 200 microm) using simultaneous photo-grafting (lambda > or = 290 nm) and cold plasma-grafting techniques, to alter the surface properties, such as hydrophilicity and, therefore, biocompatibility. Here, we have carried out simultaneous plasma-grafting, unlike the conventional post plasma-grafting. The effect of different surface grafting techniques on the degree of surface modification and resultant biocompatibility has been investigated. The chemical changes on the polymer backbone are followed from the results of attenuated total reflection Fourier transform infrared (ATR-FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS), which shows the peaks corresponding to the functional groups of the monomers grafted onto the film surface. The morphology of the modified surfaces was investigated using scanning electron microscopy (SEM) technique. The induced hydrophilicity and resultant cell compatibility were followed from the water contact angle measurements and in vitro human carcinoma cell adhesion/proliferation tests, respectively. All the grafted samples exhibited variable cell compatibilities depending upon the type of monomer and their degree of grafting; however, always better than the neat samples. Hydroxyethyl methacrylate and acrylic acid showed exceptionally high cell compatibility in terms of cell adhesion and proliferation.

Attachment dynamics of Photosystem I on nano-tailored surfaces for photovoltaic applications

NASA Astrophysics Data System (ADS)

Mukherjee, Dibyendu; Bruce, Barry D.; Khomami, Bamin

2010-03-01

Photosystem I (PSI), a biological photodiode, is a supra-molecular protein complex that charge separates upon exposure to light. Effective use of photo-electrochemical activities of PSI for hybrid photovoltaic (PV) device fabrications requires optimal encapsulation of these proteins onto organic/ inorganic substrates. Our results indicate that various experimental parameters alter the surface attachment dynamics of PSI deposited from colloidal aqueous buffer suspensions onto OH-terminated alkanethiolate/Au SAM substrates, thereby resulting in complex structural arrangements which affect the electron transfer and capture pathway of PSI. We present surface topographical, specific adsorption and polarization fluorescence characterizations of PSI/Au SAM substrates to elucidate the protein-surface interaction kinetics as well as the directional attachment dynamics of PSI. Our final goal is to enable site-specific homogeneous attachment of directionally aligned PSI onto chemically tailored nano-patterned substrates.

Influence of non-thermal TiCl4/Ar+O2 plasma-assisted TiOx based coatings on the surface of polypropylene (PP) films for the tailoring of surface properties and cytocompatibility.

PubMed

Pandiyaraj, K N; Kumar, A Arun; Ramkumar, M C; Sachdev, A; Gopinath, P; Cools, Pieter; De Geyter, N; Morent, R; Deshmukh, R R; Hegde, P; Han, C; Nadagouda, M N

2016-05-01

The superior bulk properties (corrosion resistance, high strength to weight ratio, relatively low cost and easy processing) of hydrocarbon based polymers such as polypropylene (PP) have contributed significantly to the development of new biomedical applications such as artificial organs and cell scaffolds. However, low cell affinity is one of the main draw backs for PP due to its poor surface properties. In tissue engineering, physico-chemical surface properties such as hydrophilicity, polar functional groups, surface charge and morphology play a crucial role to enrich the cell proliferation and adhesion. In this present investigation TiOx based biocompatible coatings were developed on the surface of PP films via DC excited glow discharge plasma, using TiCl4/Ar+O2 gas mixture as a precursor. Various TiOx-based coatings are deposited on the surface of PP films as a function of discharge power. The changes in hydrophilicity of the TiOx/PP film surfaces were studied using contact angle analysis and surface energy calculations by Fowke's approximation. X-ray photo-electron spectroscopy (XPS) was used to investigate the surface chemical composition of TiOx/PP films. The surface morphology of the obtained TiOx/PP films was investigated by scanning electron and transmission electron microscopy (SEM &TEM). Moreover, the surface topography of the material was analyzed by atomic force microscopy (AFM). The cytocompatibility of the TiOx/PP films was investigated via in vitro analysis (cell viability, adhesion and cytotoxicity) using NIH3T3 (mouse embryonic fibroblast) cells. Furthermore the antibacterial activities of TiOx/PP films were also evaluated against two distinct bacterial models namely Gram positive Staphylococcus aureus (S.aureus) and Gram negative Escherichia coli DH5α. (E.coli) bacteria. XPS results clearly indicate the successful incorporation of TiOx and oxygen containing polar functional groups on the surface of plasma treated PP films. Moreover the surface of modified PP films exhibited nano structured morphology, as confirmed by SEM, TEM and AFM. The physico-chemical changes have improved the hydrophilicity of the PP films. The in-vitro analysis clearly confirms that the TiOx coated PP films performs as good as the standard tissue culture plates and also are unlikely to impact the bacterial cell viability. Copyright © 2016 Elsevier B.V. All rights reserved.

Design and immunological evaluation of anti-CD205-tailored PLGA-based nanoparticulate cancer vaccine.

PubMed

Jahan, Sheikh Tasnim; Sadat, Sams Ma; Haddadi, Azita

2018-01-01

The aim of this research was to develop a targeted antigen-adjuvant assembled delivery system that will enable dendritic cells (DCs) to efficiently mature to recognize antigens released from tumor cells. It is important to target the DCs with greater efficiency to prime T cell immune responses. In brief, model antigen, ovalbumin (OV), and monophosphoryl lipid A adjuvant were encapsulated within the nanoparticle (NP) by double emulsification solvent evaporation method. Targeted NPs were obtained through ligand incorporation via physical adsorption or chemical conjugation process. Intracellular uptake of the NPs and the maturation of DCs were evaluated with flow cytometry. Remarkably, the developed delivery system had suitable physicochemical properties, such as particle size, surface charge, OV encapsulation efficiency, biphasic OV release pattern, and safety profile. The ligand modified formulations had higher targeting efficiency than the non-tailored NPs. This was also evident when the targeted formulations expressed comparatively higher fold increase in surface activation markers such as CD40, CD86, and major histocompatibility complex class II molecules. The maturation of DCs was further confirmed through secretion of extracellular cytokines compared to control cells in the DC microenvironment. Physicochemical characterization of NPs was performed based on the polymer end groups, their viscosities, and ligand-NP bonding type. In conclusion, the DC stimulatory response was integrated to develop a relationship between the NP structure and desired immune response. Therefore, the present study narrates a comparative evaluation of some selected parameters to choose a suitable formulation useful for in vivo cancer immunotherapy.

Fabrication of polyurethane and polyurethane based composite fibres by the electrospinning technique for soft tissue engineering of cardiovascular system.

PubMed

Kucinska-Lipka, J; Gubanska, I; Janik, H; Sienkiewicz, M

2015-01-01

Electrospinning is a unique technique, which provides forming of polymeric scaffolds for soft tissue engineering, which include tissue scaffolds for soft tissues of the cardiovascular system. Such artificial soft tissues of the cardiovascular system may possess mechanical properties comparable to native vascular tissues. Electrospinning technique gives the opportunity to form fibres with nm- to μm-scale in diameter. The arrangement of obtained fibres and their surface determine the biocompatibility of the scaffolds. Polyurethanes (PUs) are being commonly used as a prosthesis of cardiovascular soft tissues due to their excellent biocompatibility, non-toxicity, elasticity and mechanical properties. PUs also possess fine spinning properties. The combination of a variety of PU properties with an electrospinning technique, conducted at the well tailored conditions, gives unlimited possibilities of forming novel polyurethane materials suitable for soft tissue scaffolds applied in cardiovascular tissue engineering. This paper can help researches to gain more widespread and deeper understanding of designing electrospinable PU materials, which may be used as cardiovascular soft tissue scaffolds. In this paper we focus on reagents used in PU synthesis designed to increase PU biocompatibility (polyols) and biodegradability (isocyanates). We also describe suggested surface modifications of electrospun PUs, and the direct influence of surface wettability on providing enhanced biocompatibility of scaffolds. We indicate a great influence of electrospinning parameters (voltage, flow rate, working distance) and used solvents (mostly DMF, THF and HFIP) on fibre alignment and diameter - what impacts the biocompatibility and hemocompatibility of such electrospun PU scaffolds. Moreover, we present PU modifications with natural polymers with novel approach applied in electrospinning of PU scaffolds. This work may contribute with further developing of novel electrospun PUs, which may be applied as soft tissue scaffolds of the cardiovascular system. Copyright © 2014. Published by Elsevier B.V.

Tailoring optical properties of TiO2-Cr co-sputtered films using swift heavy ions

NASA Astrophysics Data System (ADS)

Gupta, Ratnesh; Sen, Sagar; Phase, D. M.; Avasthi, D. K.; Gupta, Ajay

2018-05-01

Effect of 100 MeV Au7+ ion irradiation on structure and optical properties of Cr-doped TiO2 films has been studied using X-ray photoelectron spectroscopy, soft X-ray absorption spectroscopy, UV-Visible spectroscopy, X-ray reflectivity, and atomic force microscopy. X-ray reflectivity measurement implied that film thickness reduces as a function of ion fluence while surface roughness increases. The variation in surface roughness is well correlated with AFM results. Ion irradiation decreases the band gap energy of the film. Swift heavy ion irradiation enhances the oxygen vacancies in the film, and the extra electrons in the vacancies act as donor-like states. In valence band spectrum, there is a shift in the Ti3d peak towards lower energies and the shift is equivalent to the band gap energy obtained from UV spectrum. Evidence for band bending is also provided by the corresponding Ti XPS peak which exhibits a shift towards lower energy due to the downward band bending. X-ray absorption studies on O Kand Cr L3,2 edges clearly indicate that swift heavy ion irradiation induces formation of Cr-clusters in TiO2 matrix.

Shape Effect of Magnetic Nanoparticles on Hyperthermia Applications

NASA Astrophysics Data System (ADS)

Mohapatra, Jeotikanta; Zeng, F.; Elkins, K.; Poudyal, N.; Gandha, K.; Liu, J. Ping

Magnetic Fe3O4 nanoparticles (NPs) are extensively studied for their applications in advanced technologies. Incorporation of different transition metal ions and control of their sizes from nanometre to submicron scale are the keys for the magnetic property manipulation. We have investigated an alternative approach to optimize the magnetic properties by tailoring the shape of the NPs based on the observation that anisotropy of the NPs plays a crucial role in defining the magnetic characteristics. To synthesize monodisperse Fe3O4 NPs we have modified the conventional thermal decomposition to a `solvent-less' synthesis approach where long chain amine/acid acts as reducing and surface functionalizing agent. Various shapes like spheres, rods, octahedrons and cubes are obtained through simple alteration in reaction conditions. Octahedral and cube shaped Fe3O4 NPs exhibit bulk magnetization (92 emu/g) value due to the reduced surface spin disorder. These anisotropic NPs serve better in hyperthermia applications compared to the conventional spherical NPs. The cube and octahedron NPs show significantly higher SAR value, making them a potential candidate for hyperthermia treatment. This work has been supported by the U.S. DoD/ARO under Grant W911NF-11-0507.

Implantation and growth of dendritic gold nanostructures on graphene derivatives: electrical property tailoring and Raman enhancement.

PubMed

Jasuja, Kabeer; Berry, Vikas

2009-08-25

Interfacing electron-rich metal nanoparticles with graphene derivatives can sensitively regulate the properties of the resultant hybrid with potential applications in metal-doped graphene field-effect transistors (FETs), surface-enhanced Raman spectroscopy, and catalysis. Here, we show that by controlling the rate of diffusion and catalytic reduction of gold ions on graphene oxide (GO), dendritic "snowflake-shaped" gold nanostructures (SFGNs) can be templated on graphene. The structural features of the SFGNs and their interfacing mechanism with GO were characterized by microscopic analysis and Raman-scattering. We demonstrate that (a) SFGNs grow on GO-surface via diffusion limited aggregation; (b) SFGN's morphology (dendritic to globular), size (diameter of 150-500 nm and a height of 45-55 nm), coverage density, and dispersion stability can be controlled by regulating the chemiophysical forces; (c) SFGNs enhance the Raman signal by 2.5 folds; and (d) SFGNs act as antireduction resist during GO-SFGN's chemical reduction. Further, the SFGNs interfacing with graphene reduces the apparent band gap (from 320 to 173 meV) and the Schottky barrier height (from 126 to 56 meV) of the corresponding FET.

Development of Tailorable Electrically Conductive Thermal Control Material Systems

NASA Technical Reports Server (NTRS)

Deshpande, M. S.; Harada, Y.

1997-01-01

The optical characteristics of surfaces on spacecraft are fundamental parameters in controlling its temperature. Passive thermal control coatings with designed solar absorptance and infrared emittance properties have been developed and have been in use for some time. In this total space environment, the coating must be stable and maintain its desired optical properties as well as mechanical properties for the course of the mission lifetime. The mission lifetimes are increasing and in our quest to save weight, newer substrates are being integrated which limit electrical grounding schemes. All of this has added to already existing concerns about spacecraft charging and related spacecraft failures or operational failures. The concern is even greater for thermal control surfaces that are very large. One way of alleviating such concerns is to design new thermal control material systems (TCMS) that can help to mitigate charging via providing charge leakage paths. The objective of this program was to develop two types of passive electrically conductive TCMS. The first was a highly absorbing/emitting black surface and the second was a low (alpha(sub s)/epsilon(sub N)) type white surface. The surface resistance goals for the black absorber was 10(exp 4) to 10(exp 9) Omega/square, and for the white surfaces it was 10(exp 6) to 10(exp 10) Omega/square. Several material system concepts were suggested and evaluated for space environment stability and electrical performance characterization. Our efforts in designing and evaluating these material systems have resulted in several developments. New concepts, pigments and binders have been developed to provide new engineering quality TCMS. Some of these have already found application on space hardware, some are waiting to be recognized by thermal designers, and some require further detailed studies to become state-of-the-art for future space hardware and space structures. Our studies on baseline state-of-the-art materials and conductive concepts have resulted in several important findings that are of interest to all thermal designers and systems integrators.

Cell-surface engineering by a conjugation-and-release approach based on the formation and cleavage of oxime linkages upon mild electrochemical oxidation and reduction.

PubMed

Pulsipher, Abigail; Dutta, Debjit; Luo, Wei; Yousaf, Muhammad N

2014-09-01

We report a strategy to rewire cell surfaces for the dynamic control of ligand composition on cell membranes and the modulation of cell-cell interactions to generate three-dimensional (3D) tissue structures applied to stem-cell differentiation, cell-surface tailoring, and tissue engineering. We tailored cell surfaces with bioorthogonal chemical groups on the basis of a liposome-fusion and -delivery method to create dynamic, electroactive, and switchable cell-tissue assemblies through chemistry involving chemoselective conjugation and release. Each step to modify the cell surface: activation, conjugation, release, and regeneration, can be monitored and modulated by noninvasive, label-free analytical techniques. We demonstrate the utility of this methodology by the conjugation and release of small molecules to and from cell surfaces and by the generation of 3D coculture spheroids and multilayered cell tissues that can be programmed to undergo assembly and disassembly on demand. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tailored optical vector fields for ultrashort-pulse laser induced complex surface plasmon structuring.

PubMed

Ouyang, J; Perrie, W; Allegre, O J; Heil, T; Jin, Y; Fearon, E; Eckford, D; Edwardson, S P; Dearden, G

2015-05-18

Precise tailoring of optical vector beams is demonstrated, shaping their focal electric fields and used to create complex laser micro-patterning on a metal surface. A Spatial Light Modulator (SLM) and a micro-structured S-waveplate were integrated with a picosecond laser system and employed to structure the vector fields into radial and azimuthal polarizations with and without a vortex phase wavefront as well as superposition states. Imprinting Laser Induced Periodic Surface Structures (LIPSS) elucidates the detailed vector fields around the focal region. In addition to clear azimuthal and radial plasmon surface structures, unique, variable logarithmic spiral micro-structures with a pitch Λ ∼1μm, not observed previously, were imprinted on the surface, confirming unambiguously the complex 2D focal electric fields. We show clearly also how the Orbital Angular Momentum(OAM) associated with a helical wavefront induces rotation of vector fields along the optic axis of a focusing lens and confirmed by the observed surface micro-structures.

A Study of the Surface Structure of Polymorphic Graphene and Other Two-Dimensional Materials for Use in Novel Electronics and Organic Photovoltaics

NASA Astrophysics Data System (ADS)

Grady, Maxwell

For some time there has been interest in the fundamental physical properties of low- dimensional material systems. The discovery of graphene as a stable two-dimensional form of solid carbon lead to an exponential increase in research in two-dimensional and other re- duced dimensional systems. It is now known that there is a wide range of materials which are stable in two-dimensional form. These materials span a large configuration space of struc- tural, mechanical, and electronic properties, which results in the potential to create novel electronic devices from nano-scale heterostructures with exactly tailored device properties. Understanding the material properties at the nanoscale level requires specialized tools to probe materials with atomic precision. Here I present the growth and analysis of a novel graphene-ruthenium system which exhibits unique polymorphism in its surface structure, hereby referred to as polymorphic graphene. Scanning Tunneling Microscopy (STM) investigations of the polymorphic graphene surface reveal a periodically rippled structure with a vast array of domains, each exhibiting xvia unique moire period. The majority of moire domains found in this polymorphic graphene system are previously unreported in past studies of the structure of graphene on ruthenium. To better understand many of the structural properties of this system, characterization methods beyond those available at the UNH surface science lab are employed. Further investigation using Low Energy Electron Microscopy (LEEM) has been carried out at Sandia National Laboratory's Center for Integrated Nanotechnology and the Brookhaven National Laboratory Center for Functional Nanomaterials. To aid in analysis of the LEEM data, I have developed an open source software package to automate extraction of electron reflectivity curves from real space and reciprocal space data sets. This software has been used in the study of numerous other two-dimensional materials beyond graphene. When combined with computational modeling, the analysis of electron I(V) curves presents a method to quantify structural parameters in a material with angstrom level precision. While many materials studied in this thesis offer unique electronic properties, my work focuses primarily on their structural aspects, as well as the instrumentation required to characterize the structure with ultra high resolution.

Reactive Processing of Environment Conscious, Biomorphic Ceramics: A Novel and Eco-friendly Route to Advanced Ceramic

NASA Technical Reports Server (NTRS)

Singh, M.

2002-01-01

Environment-conscious, biomorphic ceramics (Ecoceramics) are a new class of materials that can be produced with renewable resources (wood) and wood wastes (wood sawdust). These materials have tailorable properties with numerous potential applications. Silicon carbide-based ecoceramics have been fabricated by the infiltration of wood-derived carbonaceous preforms with oxide and silicon based materials. The wood-derived carbonaceous preforms have been shown to be quite useful in producing porous or dense materials with different microstructures and compositions. The microstructure and mechanical properties (flexural strength, fracture toughness, elastic modulus, and compressive strength) of a wide variety of Sic-based ecoceramics have been measured. Ecoceramics have tailorable properties and behave like ceramic materials manufactured by conventional approaches. In this presentation the fabrication approach, microstructure, and thermomechanical properties of a wide variety of Sic-based Ecoceramics will be reported.

Methods for providing ceramic matrix composite components with increased thermal capacity

NASA Technical Reports Server (NTRS)

Steibel, James Dale (Inventor); Utah, David Alan (Inventor)

2001-01-01

A method for enhancing the cooling capability of a turbine component made from a ceramic matrix composite. The method improves the thermal performance of the component by producing a surface having increased cooling capacity, thereby allowing the component to operate at a higher temperature. The method tailors the available surface area on the cooling surface of the composite component by depositing a particulate layer of coarse grained ceramic powders of preselected size onto the surface of the ceramic matrix composite component. The size of the particulate is selectively tailored to match the desired surface finish or surface roughness of the article. The article may be designed to have different surface finishes for different locations, so that the application of different sized powders can provide different cooling capabilities at different locations, if desired. The compositions of the particulates are chemically compatible with the ceramic material comprising the outer surface or portion of the ceramic matrix composite. The particulates are applied using a slurry and incorporated into the article by heating to an elevated temperature without melting the matrix, the particulates or the fiber reinforcement.

Comparison of modification strategies towards enhanced charge carrier separation and photocatalytic degradation activity of metal oxide semiconductors (TiO2, WO3 and ZnO)

NASA Astrophysics Data System (ADS)

Kumar, S. Girish; Rao, K. S. R. Koteswara

2017-01-01

Metal oxide semiconductors (TiO2, WO3 and ZnO) finds unparalleled opportunity in wastewater purification under UV/visible light, largely encouraged by their divergent admirable features like stability, non-toxicity, ease of preparation, suitable band edge positions and facile generation of active oxygen species in the aqueous medium. However, the perennial failings of these photocatalysts emanates from the stumbling blocks like rapid charge carrier recombination and meager visible light response. In this review, tailoring the surface-bulk electronic structure through the calibrated and veritable approaches such as impurity doping, deposition with noble metals, sensitizing with other compounds (dyes, polymers, inorganic complexes and simple chelating ligands), hydrogenation process (annealing under hydrogen atmosphere), electronic integration with other semiconductors, modifying with carbon nanostructures, designing with exposed facets and tailoring with hierarchical morphologies to overcome their critical drawbacks are summarized. Taking into account the materials intrinsic properties, the pros and cons together with similarities and striking differences for each strategy in specific to TiO2, WO3 & ZnO are highlighted. These subtlety enunciates the primacy for improving the structure-electronic properties of metal oxides and credence to its fore in the practical applications. Future research must focus on comparing the performances of ZnO, TiO2 and WO3 in parallel to get insight into their photocatalytic behaviors. Such comparisons not only reveal the changed surface-electronic structure upon various modifications, but also shed light on charge carrier dynamics, free radical generation, structural stability and compatibility for photocatalytic reactions. It is envisioned that these cardinal tactics have profound implications and can be replicated to other semiconductor photocatalysts like CeO2, In2O3, Bi2O3, Fe2O3, BiVO4, AgX, BiOX (X = Cl, Br & I), Bi2WO6, Bi2MoO6, etc., to improve their competence for various environmental applications.

Breakable mesoporous silica nanoparticles for targeted drug delivery

NASA Astrophysics Data System (ADS)

Maggini, Laura; Cabrera, Ingrid; Ruiz-Carretero, Amparo; Prasetyanto, Eko A.; Robinet, Eric; de Cola, Luisa

2016-03-01

``Pop goes the particle''. Here we report on the preparation of redox responsive mesoporous organo-silica nanoparticles containing disulfide (S-S) bridges (ss-NPs) that, even upon the exohedral grafting of targeting ligands, retained their ability to undergo structural degradation, and increase their local release activity when exposed to a reducing agent. This degradation could be observed also inside glioma C6 cancer cells. Moreover, when anticancer drug-loaded pristine and derivatized ss-NPs were fed to glioma C6 cells, the responsive hybrids were more effective in their cytotoxic action compared to non-breakable particles. The possibility of tailoring the surface functionalization of this hybrid, yet preserving its self-destructive behavior and enhanced drug delivery properties, paves the way for the development of effective biodegradable materials for in vivo targeted drug delivery.``Pop goes the particle''. Here we report on the preparation of redox responsive mesoporous organo-silica nanoparticles containing disulfide (S-S) bridges (ss-NPs) that, even upon the exohedral grafting of targeting ligands, retained their ability to undergo structural degradation, and increase their local release activity when exposed to a reducing agent. This degradation could be observed also inside glioma C6 cancer cells. Moreover, when anticancer drug-loaded pristine and derivatized ss-NPs were fed to glioma C6 cells, the responsive hybrids were more effective in their cytotoxic action compared to non-breakable particles. The possibility of tailoring the surface functionalization of this hybrid, yet preserving its self-destructive behavior and enhanced drug delivery properties, paves the way for the development of effective biodegradable materials for in vivo targeted drug delivery. Electronic supplementary information (ESI) available: Full experimental procedures, additional SEM and TEM images of particles, complete UV-Vis and PL-monitored characterization of the breakdown of the particles, SAXS, N2 adsorption, cytotoxicity assays. See DOI: 10.1039/c5nr09112h

Enhanced properties of tungsten thin films deposited with a novel HiPIMS approach

NASA Astrophysics Data System (ADS)

Velicu, Ioana-Laura; Tiron, Vasile; Porosnicu, Corneliu; Burducea, Ion; Lupu, Nicoleta; Stoian, George; Popa, Gheorghe; Munteanu, Daniel

2017-12-01

Despite the tremendous potential for industrial use of tungsten (W), very few studies have been reported so far on controlling and tailoring the properties of W thin films obtained by physical vapor deposition techniques and, even less, for those deposited by High Power Impulse Magnetron Sputtering (HiPIMS). This study presents results on the deposition process and properties characterization of nanocrystalline W thin films deposited on silicon and molybdenum substrates (100 W average sputtering power) by conventional dc magnetron sputtering (dcMS) and HiPIMS techniques. Topological, structural, mechanical and tribological properties of the deposited thin films were investigated. It was found that in HiPIMS, both deposition process and coatings properties may be optimized by using an appropriate magnetic field configuration and pulsing design. Compared to the other deposited samples, the W films grown in multi-pulse (5 × 3 μs) HiPIMS assisted by an additional magnetic field, created with a toroidal-shaped permanent magnet placed in front of the magnetron cathode, show significantly enhanced properties, such as: smoother surfaces, higher homogeneity and denser microstructure, higher hardness and Young's modulus values, better adhesion to the silicon substrate and lower coefficient of friction. Mechanical behaviour and structural changes are discussed based on plasma diagnostics results.

Solution and interfacial behavior of modified silicone polymers and their interactions with solid substrates

NASA Astrophysics Data System (ADS)

Purohit, Parag

Surface treatment is very important step in many applications such as fabric finishing, coatings, cosmetics and personal care. Silicone polymers are a class of organic/inorganic materials that show unique properties such as weak intermolecular forces and high flexibility enabling even a very high molecular weight chain to achieve optimal orientation on surfaces. Material properties such as softness, repellency, bounciness and friction can therefore be tailored by using appropriately modified silicone polymers. Despite wide applications, the underlying mechanisms of material modification are unknown and tailoring silicones for applications remains mostly empirical. Thus the objective of this research is to understand the solution and interfacial behavior of functionalized silicone polymers, which govern their performance in material modification. Modified silicones are simultaneously hydrophobic and oleophobic in nature and due to this nearly universal non-compatibility, the studies of these polymers present unusual challenges. Due to this incompatible nature, the functionalized silicone polymers were emulsified into O/W emulsions to study their solution and interfacial properties. The colloidal properties such as electrokinetic and droplet distribution of these emulsions are assumed to play an important role in the observed surface and physical properties of solid substrates (in present study, cellulosic substrates) as well the stability of emulsions itself. To understand the effects of modified silicones on cellulosic substrates a variety of techniques such as frictional analysis, scanning electron microscopy and atomic force microscopy that can probe from macro to nano level were used. It is hypothesized that the size distribution and charge of silicone emulsions as well as the physiochemical conditions such as pH, control silicone conformation which in turn affect the modification of the substrate properties. With bimodal droplet distribution of silicone emulsions, the nano-sized droplets can penetrate deeper into the substrate to provide bounciness, whereas macro-sized droplets can coat the top layer leading to friction reduction. It was observed that at pH 5.5 the silicone treatment resulted in charge reversal of fibers as opposed to treatment at pH 9.5. On a macroscopic scale 20% reduction in frictional coefficient of the fabric was observed after treatment with quaternized (cationically modified) silicones as compared to untreated fibers. It was also observed using AFM that the fibrils treated with quaternized silicones are uniform, well stacked and smoother than the untreated fibers. Spectroscopic analysis of treated fibers using Raman spectroscopy indicated a decrease in fiber stress as a function of modification of silicone polymer and the interaction pH. It is concluded that the protonated amine functional silicone (below pH 7) as well as the quaternized silicone interacts with the negatively charged cellulose fibers primarily through electrostatic interactions. It is proposed that this initial surface coating is a uniform thin film which allows further deposition of polymer from the emulsion. It was observed that at high pH the zetapotential of silicone emulsions decreases drastically and the nano emulsions turn turbid. It is proposed that the observed electrophoretic and nephelometric behavior at high pH is due to flocculation of nanosized droplets to micron size, which eventually leads to droplets coalescing and emulsion destabilization. It is also postulated that the nano emulsion possess a critical dilution concentration (CDC), above which dilution leads to rapid coalescence. This critical dilution phase was further confirmed through polarity parameter and excimer formation studies which show significantly different polymer and surfactant microstructures near the CDC. Hence it is concluded that the observed surface properties of the substrate obtained above the CDC are significantly different than those below the CDC. The results reveal the vital role of physiochemical parameters such as pH, droplet size, and concentration on the emulsion stability as well as the observed physical/chemical properties of the substrates.

Discrete tuning concept for fiber-integrated lasers based on tailored FBG arrays and a theta cavity layout.

PubMed

Tiess, Tobias; Becker, Martin; Rothhardt, Manfred; Bartelt, Hartmut; Jäger, Matthias

2017-03-15

We demonstrate a novel tuning concept for pulsed fiber-integrated lasers with a fiber Bragg grating (FBG) array as a discrete and tailored spectral filter, as well as a modified laser design. Based on a theta cavity layout, the structural delay lines originating from the FBG array are balanced, enabling a constant repetition rate and stable pulse properties over the full tuning range. The emission wavelength is electrically tuned with respect to the filter properties based on an adapted temporal gating scheme using an acousto-optic modulator. This concept has been investigated with an Yb-doped fiber laser, demonstrating excellent emission properties with high signal contrast (>35  dB) and narrow linewidth (<150  pm) over a tuning range of 25 nm.

Sputter-Coated Microparticle Additives for Tailored Optical Properties

DTIC Science & Technology

2016-09-01

hour at best). The microspheres coated in this work will be incorporated into a polymer matrix for composite and large-area coating applications...demonstrated, they will be incorporated into a polymer matrix for further testing. 15. SUBJECT TERMS fluidized bed, thin film, microparticles, coating...films of metals, ceramics , and multilayered materials.1 This is a practical method for the batch production of microparticles with tailored optical

Effects of self-assembled monolayer structural order, surface homogeneity and surface energy on pentacene morphology and thin film transistor device performance.

PubMed

Hutchins, Daniel Orrin; Weidner, Tobias; Baio, Joe; Polishak, Brent; Acton, Orb; Cernetic, Nathan; Ma, Hong; Jen, Alex K-Y

2013-01-04

A systematic study of six phosphonic acid (PA) self-assembled monolayers (SAMs) with tailored molecular structures is performed to evaluate their effectiveness as dielectric modifying layers in organic field-effect transistors (OFETs) and determine the relationship between SAM structural order, surface homogeneity, and surface energy in dictating device performance. SAM structures and surface properties are examined by near edge X-ray absorption fine structure (NEXAFS) spectroscopy, contact angle goniometry, and atomic force microscopy (AFM). Top-contact pentacene OFET devices are fabricated on SAM modified Si with a thermally grown oxide layer as a dielectric. For less ordered methyl- and phenyl-terminated alkyl ~(CH 2 ) 12 PA SAMs of varying surface energies, pentacene OFETs show high charge carrier mobilities up to 4.1 cm 2 V -1 s -1 . It is hypothesized that for these SAMs, mitigation of molecular scale roughness and subsequent control of surface homogeneity allow for large pentacene grain growth leading to high performance pentacene OFET devices. PA SAMs that contain bulky terminal groups or are highly crystalline in nature do not allow for a homogenous surface at a molecular level and result in charge carrier mobilities of 1.3 cm 2 V -1 s -1 or less. For all molecules used in this study, no causal relationship between SAM surface energy and charge carrier mobility in pentacene FET devices is observed.

Effects of self-assembled monolayer structural order, surface homogeneity and surface energy on pentacene morphology and thin film transistor device performance

PubMed Central

Hutchins, Daniel Orrin; Weidner, Tobias; Baio, Joe; Polishak, Brent; Acton, Orb; Cernetic, Nathan; Ma, Hong; Jen, Alex K.-Y.

2013-01-01

A systematic study of six phosphonic acid (PA) self-assembled monolayers (SAMs) with tailored molecular structures is performed to evaluate their effectiveness as dielectric modifying layers in organic field-effect transistors (OFETs) and determine the relationship between SAM structural order, surface homogeneity, and surface energy in dictating device performance. SAM structures and surface properties are examined by near edge X-ray absorption fine structure (NEXAFS) spectroscopy, contact angle goniometry, and atomic force microscopy (AFM). Top-contact pentacene OFET devices are fabricated on SAM modified Si with a thermally grown oxide layer as a dielectric. For less ordered methyl- and phenyl-terminated alkyl ~(CH2)12 PA SAMs of varying surface energies, pentacene OFETs show high charge carrier mobilities up to 4.1 cm2 V−1 s−1. It is hypothesized that for these SAMs, mitigation of molecular scale roughness and subsequent control of surface homogeneity allow for large pentacene grain growth leading to high performance pentacene OFET devices. PA SAMs that contain bulky terminal groups or are highly crystalline in nature do not allow for a homogenous surface at a molecular level and result in charge carrier mobilities of 1.3 cm2 V−1 s−1 or less. For all molecules used in this study, no causal relationship between SAM surface energy and charge carrier mobility in pentacene FET devices is observed. PMID:24086795

Self-Healing Natural Rubber with Tailorable Mechanical Properties Based on Ionic Supramolecular Hybrid Network.

PubMed

Xu, Chuanhui; Cao, Liming; Huang, Xunhui; Chen, Yukun; Lin, Baofeng; Fu, Lihua

2017-08-30

In most cases, the strength of self-healing supramolecular rubber based on noncovalent bonds is in the order of KPa, which is a challenge for their further applications. Incorporation of conventional fillers can effectively enhance the strength of rubbers, but usually accompanied by a sacrifice of self-healing capability due to that the filler system is independent of the reversible supramolecular network. In the present work, in situ reaction of methacrylic acid (MAA) and excess zinc oxide (ZnO) was realized in natural rubber (NR). Ionic cross-links in NR matrix were obtained by limiting the covalent cross-linking of NR molecules and allowing the in situ polymerization of MAA/ZnO. Because of the natural affinity between Zn 2+ ion-rich domains and ZnO, the residual nano ZnO participated in formation of a reversible ionic supramolecular hybrid network, thus having little obstructions on the reconstruction of ionic cross-links. Meanwhile, the well dispersed residual ZnO could tailor the mechanical properties of NR by changing the MAA/ZnO molar ratios. The present study thus provides a simple method to fabricate a new self-healing NR with tailorable mechanical properties that may have more potential applications.

Friction Stir Processing of Stainless Steel for Ascertaining Its Superlative Performance in Bioimplant Applications.

PubMed

Perumal, G; Ayyagari, A; Chakrabarti, A; Kannan, D; Pati, S; Grewal, H S; Mukherjee, S; Singh, S; Arora, H S

2017-10-25

Substrate-cell interactions for a bioimplant are driven by substrate's surface characteristics. In addition, the performance of an implant and resistance to degradation are primarily governed by its surface properties. A bioimplant typically degrades by wear and corrosion in the physiological environment, resulting in metallosis. Surface engineering strategies for limiting degradation of implants and enhancing their performance may reduce or eliminate the need for implant removal surgeries and the associated cost. In the current study, we tailored the surface properties of stainless steel using submerged friction stir processing (FSP), a severe plastic deformation technique. FSP resulted in significant microstructural refinement from 22 μm grain size for the as-received alloy to 0.8 μm grain size for the processed sample with increase in hardness by nearly 1.5 times. The wear and corrosion behavior of the processed alloy was evaluated in simulated body fluid. The processed sample demonstrated remarkable improvement in both wear and corrosion resistance, which is explained by surface strengthening and formation of a highly stable passive layer. The methylthiazol tetrazolium assay demonstrated that the processed sample is better in supporting cell attachment, proliferation with minimal toxicity, and hemolysis. The athrombogenic characteristic of the as-received and processed samples was evaluated by fibrinogen adsorption and platelet adhesion via the enzyme-linked immunosorbent assay and lactate dehydrogenase assay, respectively. The processed sample showed less platelet and fibrinogen adhesion compared with the as-received alloy, signifying its high thromboresistance. The current study suggests friction stir processing to be a versatile toolbox for enhancing the performance and reliability of currently used bioimplant materials.

Model Amphiphilic Block Copolymers with Tailored Molecular Weight and Composition in PDMS-Based Films to Limit Soft Biofouling

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

Wenning, Brandon M.; Martinelli, Elisa; Mieszkin, Sophie

A set of controlled surface composition films was produced utilizing amphiphilic block copolymers dispersed in a cross-linked poly(dimethylsiloxane) network. These block copolymers contained oligo(ethylene glycol) (PEGMA) and fluoroalkyl (AF6) side chains in selected ratios and molecular weights to control surface chemistry including antifouling and fouling-release performance. Such properties were assessed by carrying out assays using two algae, the green macroalga Ulva linza (favors attachment to polar surfaces) and the unicellular diatom Navicula incerta (favors attachment to nonpolar surfaces). All films performed well against U. linza and exhibited high removal of attached sporelings (young plants) under an applied shear stress, withmore » the lower molecular weight block copolymers being the best performing in the set. The composition ratios from 50:50 to 60:40 of the AF6/PEGMA side groups were shown to be more effective, with several films exhibiting spontaneous removal of the sporelings. The cells of N. incerta were also removed from several coating compositions. All films were characterized by surface techniques including captive bubble contact angle, atomic force microscopy, and near edge X-ray absorption fine structure spectroscopy to correlate surface chemistry and morphology with biological performance.« less

Measuring binding kinetics of aromatic thiolated molecules with nanoparticles via surface-enhanced Raman spectroscopy.

PubMed

DeVetter, Brent M; Mukherjee, Prabuddha; Murphy, Catherine J; Bhargava, Rohit

2015-05-21

Colloidal plasmonic nanomaterials, consisting of metals such as gold and silver, are excellent candidates for advanced optical probes and devices, but precise control over surface chemistry is essential for realizing their full potential. Coupling thiolated (R-SH) molecules to nanoprobe surfaces is a convenient and established route to tailor surface properties. The ability to dynamically probe and monitor the surface chemistry of nanoparticles in solution is essential for rapidly manufacturing spectroscopically tunable nanoparticles. In this study, we report the development of surface-enhanced Raman spectroscopy (SERS) as a method to monitor the kinetics of gold-thiolate bond formation on colloidal gold nanoparticles. A theoretical model combining SERS enhancement with the Beer-Lambert law is proposed to explain ensemble scattering and absorption effects in colloids during chemisorption. In order to maximize biological relevance and signal reproducibility, experiments used to validate the model focused on maintaining nanoparticle stability after the addition of water-soluble aromatic thiolated molecules. Our results indicate that ligand exchange on gold nanoparticles follow a first-order Langmuir adsorption model with rate constants on the order of 0.01 min(-1). This study demonstrates an experimental spectroscopic method and theoretical model for monitoring binding kinetics that may prove useful for designing novel probes.

Measuring binding kinetics of aromatic thiolated molecules with nanoparticles via surface-enhanced Raman spectroscopy

PubMed Central

DeVetter, Brent M.; Mukherjee, Prabuddha; Murphy, Catherine J.; Bhargava, Rohit

2015-01-01

Colloidal plasmonic nanomaterials, consisting of metals such as gold and silver, are excellent candidates for advanced optical probes and devices, but precise control over surface chemistry is essential for realizing their full potential. Coupling thiolated (R-SH) molecules to nanoprobe surfaces is a convenient and established route to tailor surface properties. The ability to dynamically probe and monitor the surface chemistry of nanoparticles in solution is essential for rapidly manufacturing spectroscopically tunable nanoparticles. In this study, we report the development of surface-enhanced Raman spectroscopy (SERS) as a method to monitor the kinetics of gold-thiolate bond formation on colloidal gold nanoparticles. A theoretical model combining SERS enhancement with the Beer-Lambert law is proposed to explain ensemble scattering and absorption effects in colloids during chemisorption. In order to maximize biological relevance and signal reproducibility, experiments used to validate the model focused on maintaining nanoparticle stability after the addition of water-soluble aromatic thiolated molecules. Our results indicate that ligand exchange on gold nanoparticles follow a first-order Langmuir adsorption model with rate constants on the order of 0.01 min 1. This study demonstrates an experimental spectroscopic method and theoretical model for monitoring binding kinetics that may prove useful for designing novel probes. PMID:25905515

Simultaneous tuning of chemical composition and topography of copolymer surfaces: micelles as building blocks.

PubMed

Zhao, Ning; Zhang, Xiaoyan; Zhang, Xiaoli; Xu, Jian

2007-05-14

A simple method is described for controlling the surface chemical composition and topography of the diblock copolymer poly(styrene)-b-poly(dimethylsiloxane)(PS-b-PDMS) by casting the copolymer solutions from solvents with different selectivities. The surface morphology and chemical composition were characterized by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), respectively, and the wetting behavior was studied by water contact angle (CA) and sliding angle (SA) and by CA hysteresis. Chemical composition and morphology of the surface depend on solvent properties, humidity of the air, solution concentration, and block lengths. If the copolymer is cast from a common solvent, the resultant surface is hydrophobic, with a flat morphology, and dominated by PDMS on the air side. From a PDMS-selective solvent, the surface topography depends on the morphology of the micelles. Starlike micelles give rise to a featureless surface nearly completely covered by PDMS, while crew-cut-like micelles lead to a rough surface with a hierarchical structure that consists partly of PDMS. From a PS-selective solvent, however, surface segregation of PDMS was restricted, and the surface morphology can be controlled by vapor-induced phase separation. On the basis of the tunable surface roughness and PDMS concentration on the air side, water repellency of the copolymer surface could be tailored from hydrophobic to superhydrophobic. In addition, reversible switching behavior between hydrophobic and superhydrophobic can be achieved by exposing the surface to solvents with different selectivities.

Bacteria-directed construction of hollow TiO2 micro/nanostructures with enhanced photocatalytic hydrogen evolution activity.

PubMed

Zhou, Han; Fan, Tongxiang; Ding, Jian; Zhang, Di; Guo, Qixin

2012-03-12

A general method has been developed for the synthesis of various hollow TiO2 micro/nanostructures with bacteria as templates to further study the structural effect on photocatalytic hydrogen evolution properties. TiO2 hollow spheres and hollow tubes, served as prototypes, are obtained via a surface sol-gel process using cocci and bacillus as biotemplates, respectively. The formation mechanisms are based on absorption of metal-alkoxide molecules from solution onto functional cell wall surfaces and subsequent hydrolysis to give nanometer-thick oxide layers. The UV-Vis absorption spectrum shows that the porous TiO2 hollow spheres have enhanced light harvesting property compared with the corresponding solid counterpart. This could be attributed to their unique hollow porous micro/nanostructures with microsized hollow cavities and nanovoids which could bring about multiple scattering and rayleigh scattering of light, respectively. The hollow TiO2 structures exhibit superior photocatalytic hydrogen evolution activities under UV and visible light irradiation in the presence of sacrificial reagents. The hydrogen evolution rate of hollow structures is about 3.6 times higher than the solid counterpart and 1.5 times higher than P25-TiO2. This work demonstrates the structural effect on enhancing the photocatalytic hydrogen evolution performance which would pave a new pathway to tailor and improve catalytic properties over a broad range.

Effect of silver ion-induced disorder on morphological, chemical and optical properties of poly (methyl methacrylate)

NASA Astrophysics Data System (ADS)

Arif, Shafaq; Saleemi, Farhat; Rafique, M. Shahid; Naab, Fabian; Toader, Ovidiu; Mahmood, Arshad; Aziz, Uzma

2016-11-01

Ion implantation is a versatile technique to tailor the surface properties of polymers in a controlled manner. In the present study, samples of poly (methyl methacrylate) (PMMA) have been implanted with 400 keV silver (Ag+) ion beam to various ion fluences ranging from 5 × 1013 to 5 × 1015 ions/cm2. The effect of Ag+ ion-induced disorder on morphological, chemical and optical properties of PMMA is analyzed using Atomic Force Microscope (AFM), Fourier transform infrared spectroscopy (FTIR) and ultraviolet-visible (UV-Vis) spectroscopy. Furthermore, the electrical conductivity of pristine and implanted PMMA is measured using four probe apparatus. The AFM images revealed the growth of nano-sized grainy structures and hillocks above the surface of implanted PMMA. The FTIR spectra confirmed the modifications in chemical structure of PMMA along with the formation of sbnd Cdbnd Csbnd carbon contents. The refractive index, extinction coefficient and photoconductivity of implanted PMMA have been found to increase as a function of ion fluence. Simultaneously, indirect optical band gap is reduced from 3.13 to 0.81 eV at a relatively high fluence (5 × 1015 ions/cm2). A linear correlation has been established between the band gap and Urbach energies. Moreover, the electrical conductivity of Ag+ implanted PMMA has increased from 2.14 × 10-10 (pristine) to 9.6 × 10-6 S/cm.

Membrane-targeted self-assembling cyclic peptide nanotubes.

PubMed

Rodríguez-Vázquez, Nuria; Ozores, H Lionel; Guerra, Arcadio; González-Freire, Eva; Fuertes, Alberto; Panciera, Michele; Priegue, Juan M; Outeiral, Juan; Montenegro, Javier; Garcia-Fandino, Rebeca; Amorin, Manuel; Granja, Juan R

2014-01-01

Peptide nanotubes are novel supramolecular nanobiomaterials that have a tubular structure. The stacking of cyclic components is one of the most promising strategies amongst the methods described in recent years for the preparation of nanotubes. This strategy allows precise control of the nanotube surface properties and the dimensions of the tube diameter. In addition, the incorporation of 3- aminocycloalkanecarboxylic acid residues in the nanotube-forming peptides allows control of the internal properties of the supramolecular tube. The research aimed at the application of membrane-interacting self-assembled cyclic peptide nanotubes (SCPNs) is summarized in this review. The cyclic peptides are designed to interact with phospholipid bilayers to induce nanotube formation. The properties and orientation of the nanotube can be tuned by tailoring the peptide sequence. Hydrophobic peptides form transmembrane pores with a hydrophilic orifice, the nature of which has been exploited to transport ions and small molecules efficiently. These synthetic ion channels are selective for alkali metal ions (Na(+), K(+) or Cs(+)) over divalent cations (Ca(2+)) or anions (Cl(-)). Unfortunately, selectivity was not achieved within the series of alkali metal ions, for which ion transport rates followed the diffusion rates in water. Amphipathic peptides form nanotubes that lie parallel to the membrane. Interestingly, nanotube formation takes place preferentially on the surface of bacterial membranes, thus making these materials suitable for the development of new antimicrobial agents.

Metal-Coated Cenospheres Obtained via Magnetron Sputter Coating: A New Precursor for Syntactic Foams

NASA Astrophysics Data System (ADS)

Shishkin, A.; Hussainova, I.; Kozlov, V.; Lisnanskis, M.; Leroy, P.; Lehmhus, D.

2018-05-01

Syntactic foams (SFs) and metal matrix syntactic foams (MMSFs) represent an advanced type of metal matrix composites (MMCs) based on hollow microspheres as particulate reinforcement. In general, SF and MMSFs allow tailoring of properties through choice of matrix, reinforcement, and volume fraction of the latter. A further handle for property adjustment is surface modification of the reinforcing particles. The present study introduces cenospheres for use as filler material in SF and MMSFs and as lightweight filler with electromagnetic interference shielding properties in civil engineering, which have been surface coated by means of physical vapor deposition, namely vibration-assisted sputter coating using a magnetron sputtering system. Altogether four types of such cenosphere-based composite powders (CPs) with an original particle size range of 50-125 µm (average particle size d50 75 µm) were studied. Surface films deposited on these were composed of Cu, stainless steel, Ti, and Ti-TiN double layers. For Cu coatings, the deposited metal film thickness was shown to be dependent on the sputtering energy. Scanning electron microscope backscattering images revealed nonporous films uniform in thickness directly after sputtering. Film thickness varied between 0.15 µm and 2.5 µm, depending on coating material and sputtering parameters. From these materials, samples were produced without addition of metal powders, exhibiting metal contents as low as 8-10 wt.% based on the coating alone. Obtained samples had an apparent density of 1.1-1.9 g/cm3 and compressive strengths ranging from 22 MPa to 135 MPa.

Thin-film metal hydrides.

PubMed

Remhof, Arndt; Borgschulte, Andreas

2008-12-01

The goal of the medieval alchemist, the chemical transformation of common metals into nobel metals, will forever be a dream. However, key characteristics of metals, such as their electronic band structure and, consequently, their electric, magnetic and optical properties, can be tailored by controlled hydrogen doping. Due to their morphology and well-defined geometry with flat, coplanar surfaces/interfaces, novel phenomena may be observed in thin films. Prominent examples are the eye-catching hydrogen switchable mirror effect, the visualization of solid-state diffusion and the formation of complex surface morphologies. Thin films do not suffer as much from embrittlement and/or decrepitation as bulk materials, allowing the study of cyclic absorption and desorption. Therefore, thin-metal hydride films are used as model systems to study metal-insulator transitions, for high throughput combinatorial research or they may be used as indicator layers to study hydrogen diffusion. They can be found in technological applications as hydrogen sensors, in electrochromic and thermochromic devices. In this review, we discuss the effect of hydrogen loading of thin niobium and yttrium films as archetypical examples of a transition metal and a rare earth metal, respectively. Our focus thereby lies on the hydrogen induced changes of the electronic structure and the morphology of the thin films, their optical properties, the visualization and the control of hydrogen diffusion and on the study of surface phenomena and catalysis.

Shape-Tailorable Graphene-Based Ultra-High-Rate Supercapacitor for Wearable Electronics.

PubMed

Xie, Binghe; Yang, Cheng; Zhang, Zhexu; Zou, Peichao; Lin, Ziyin; Shi, Gaoquan; Yang, Quanhong; Kang, Feiyu; Wong, Ching-Ping

2015-06-23

With the bloom of wearable electronics, it is becoming necessary to develop energy storage units, e.g., supercapacitors that can be arbitrarily tailored at the device level. Although gel electrolytes have been applied in supercapacitors for decades, no report has studied the shape-tailorable capability of a supercapacitor, for instance, where the device still works after being cut. Here we report a tailorable gel-based supercapacitor with symmetric electrodes prepared by combining electrochemically reduced graphene oxide deposited on a nickel nanocone array current collector with a unique packaging method. This supercapacitor with good flexibility and consistency showed excellent rate performance, cycling stability, and mechanical properties. As a demonstration, these tailorable supercapacitors connected in series can be used to drive small gadgets, e.g., a light-emitting diode (LED) and a minimotor propeller. As simple as it is (electrochemical deposition, stencil printing, etc.), this technique can be used in wearable electronics and miniaturized device applications that require arbitrarily shaped energy storage units.

Metal flow of a tailor-welded blank in deep drawing process

NASA Astrophysics Data System (ADS)

Yan, Qi; Guo, Ruiquan

2005-01-01

Tailor welded blanks were used in the automotive industry to consolidate parts, reduce weight, and increase safety. In recent years, this technology was developing rapidly in China. In Chinese car models, tailor welded blanks had been applied in a lot of automobile parts such as rail, door inner, bumper, floor panel, etc. Concerns on the properties of tailor welded blanks had become more and more important for automobile industry. A lot of research had shown that the strength of the welded seam was higher than that of the base metal, such that the weld failure in the aspect of strength was not a critical issue. However, formability of tailor welded blanks in the stamping process was complex. Among them, the metal flow of tailor welded blanks in the stamping process must be investigated thoroughly in order to reduce the scrap rate during the stamping process in automobile factories. In this paper, the behavior of metal flow for tailor welded blanks made by the laser welding process with two types of different thickness combinations were studied in the deep drawing process. Simulations and experiment verification of the movement of weld line for tailor welded blanks were discussed in detail. Results showed that the control on the movement of welded seam during stamping process by taking some measures in the aspect of blank holder was effective.

Bioactivity of Hybrid Polymeric Magnetic Nanoparticles and Their Applications in Drug Delivery.

PubMed

Mohammed, Leena; Ragab, Doaa; Gomaa, Hassan

2016-01-01

Engineered magnetic nanoparticles (MNPs) possess unique properties and hold great potential in biomedicine and clinical applications. With their magnetic properties and their ability to work at cellular and molecular level, MNP have been applied both in-vitro and in-vivo in targeted drug delivery and imaging. Focusing on Iron Oxide Superparamagnetic nanoparticles (SPIONs), this paper elaborates on the recent advances in development of hybrid polymeric-magnetic nanoparticles. Their main applications in drug delivery include Chemotherapeutics, Hyperthermia treatment, Radio-therapeutics, Gene delivary, and Biotheraputics. Physiochemical properties such as size, shape, surface and magnetic properties are key factors in determining their behavior. Additionally tailoring SPIONs surface is often vital for desired cell targetting and improved efficiency. Polymer coating is specifically reviewed with brief discussion of SPIONs administration routes. Commonly used drug release models for describing release mechanisms and the nanotoxicity aspects are also discussed. This review focus on superparamagnetic nanoparticles coated with different types of polymers starting with the key physiochemical features that dominate their behavior. The importance of surface modification is addressed. Subsequently, the major classes of polymer modified iron oxide nanoparticles is demonstrated according to their clinical use and application. Clinically approved nanoparticles are then addressed and the different routes of administration are mentioned. Lastly, mathematical models of drug release profile of the common used nanoparticles are addressed. MNPs emerging in recent medicine are remarkable for both imaging and therapeutics, particularly, as drug carriers for their great potential in targeted delivery and cancer treatment. Targeting ability and biocompatibility can be improved though surface coating which provides a mean to alter the surface features including physical characteristics and chemical functionality. The use of biocompatible polymers can prevent aggregation, increase colloidal stability, evades nanoparticles uptake by RES, and can provide a surface for conjugation of targeting ligands such as peptide and biomolecules with high affinity to target cells. Great efforts to bring MNPs from lab testing stage to clinic are needed to understand their physicochemical properties and how they behave in vivo, which resulted in few of them to exist in the market today. Although magnetic nanoparticles have not yet fully reached their optimal safety and efficiency due to the challenges they face in vivo, their shortcomings can be overcome through improvement of magnetictargeted carrier by pre-clinical trials and continuous studies.

Selective Laser Melting: a regular unit cell approach for the manufacture of porous, titanium, bone in-growth constructs, suitable for orthopedic applications.

PubMed

Mullen, Lewis; Stamp, Robin C; Brooks, Wesley K; Jones, Eric; Sutcliffe, Christopher J

2009-05-01

In this study, a novel porous titanium structure for the purpose of bone in-growth has been designed, manufactured and evaluated. The structure was produced by Selective Laser Melting (SLM); a rapid manufacturing process capable of producing highly intricate, functionally graded parts. The technique described utilizes an approach based on a defined regular unit cell to design and produce structures with a large range of both physical and mechanical properties. These properties can be tailored to suit specific requirements; in particular, functionally graded structures with bone in-growth surfaces exhibiting properties comparable to those of human bone have been manufactured. The structures were manufactured and characterized by unit cell size, strand diameter, porosity, and compression strength. They exhibited a porosity (10-95%) dependant compression strength (0.5-350 Mpa) comparable to the typical naturally occurring range. It is also demonstrated that optimized structures have been produced that possesses ideal qualities for bone in-growth applications and that these structures can be applied in the production of orthopedic devices. (c) 2008 Wiley Periodicals, Inc.

[The study of antimicrobial properties of silver nanoparticles in the form of a colloidal solution in the matrix of finely dispersed silica].

PubMed

Korchak, G I; Surmasheva, E V; Mikhienkova, A I; Nikonova, N A; Romanenko, L I; Oliĭnyk, Z A; Gorval', A K; Rosada, M A

2012-01-01

In the experimental study obtained with chemical method colloid solution of nanoparticles (NPs) of silver (Ag) and a composite on his base in the matrix of finely dispersed silica with particle size of 8-12 nm and NPs concentration in basic solution of 0,0016% (0,016 mg/cm3) were established to exhibit high antimicrobial activity against the test organisms: E. coli, P. aeruginosa, S. Aureus and C. Albicans, which depended on a set of factors. Antibacterial properties of tissue impregnated with Ag-NPs were studied. As stabilizing substances a mixture of surface-active substance sodium dodecyl sulfate and polymer polyvinylpyrrolidone was used Before the beginning of the study effective neutralizer was tailored. Times of preservation of antimicrobial activity of test samples have been established, and also their stability throughout long term of supervision (24 months) has been shown. Effect of organic pollution on antimicrobal activity of the samples has been studied. Based on obtained results the algorithm of the study of antimicrobial properties of nanopreparations has been elaborated.

Static and dynamic wetting behaviour of ionic liquids.

PubMed

Delcheva, Iliana; Ralston, John; Beattie, David A; Krasowska, Marta

2015-08-01

Ionic liquids (ILs) are a unique family of molecular liquids ('molten salts') that consist of a combination of bulky organic cations coupled to inorganic or organic anions. The net result of steric hindrance and strong hydrogen bonding between components results in a material that is liquid at room temperature. One can alter the properties of ionic liquids through chemical modification of anion and cation, thus tailoring the IL for a given application. One such property that can be controlled or selected is the wettability of an IL on a particular solid substrate. However, the study of wetting of ionic liquids is complicated by the care required for accurate and reproducible measurement, due to both the susceptibility of the IL properties to water content, as well as to the sensitivity of wettability measurements to the state of the solid surface. This review deals with wetting studies of ILs to date, including both static and dynamic wetting, as well as issues concerning line tension and the formation of precursor and wetting films. Copyright © 2014 Elsevier B.V. All rights reserved.

Engineering noble metal nanomaterials for environmental applications

NASA Astrophysics Data System (ADS)

Li, Jingguo; Zhao, Tingting; Chen, Tiankai; Liu, Yanbiao; Ong, Choon Nam; Xie, Jianping

2015-04-01

Besides being valuable assets in our daily lives, noble metals (namely, gold, silver, and platinum) also feature many intriguing physical and chemical properties when their sizes are reduced to the nano- or even subnano-scale; such assets may significantly increase the values of the noble metals as functional materials for tackling important societal issues related to human health and the environment. Among which, designing/engineering of noble metal nanomaterials (NMNs) to address challenging issues in the environment has attracted recent interest in the community. In general, the use of NMNs for environmental applications is highly dependent on the physical and chemical properties of NMNs. Such properties can be readily controlled by tailoring the attributes of NMNs, including their size, shape, composition, and surface. In this feature article, we discuss recent progress in the rational design and engineering of NMNs with particular focus on their applications in the field of environmental sensing and catalysis. The development of functional NMNs for environmental applications is highly interdisciplinary, which requires concerted efforts from the communities of materials science, chemistry, engineering, and environmental science.

Modification of electrical properties of silicon dioxide through intrinsic nano-patterns

NASA Astrophysics Data System (ADS)

Majee, Subimal; Barshilia, Devesh; Banerjee, Debashree; Kumar, Sanjeev; Mishra, Prabhash; Akhtar, Jamil

2018-05-01

The inherent network of nanopores and voids in silicon dioxide (SiO2) is generally undesirable for aspects of film quality, electrical insulation and dielectric performance. However, if we view these pores as natural nano-patterns embedded in a dielectric matrix then that opens up new vistas for exploration. The nano-pattern platform can be used to tailor electrical, optical, magnetic and mechanical properties of the carrier film. In this article we report the tunable electrical properties of thermal SiO2 thin-film achieved through utilization of the metal-nanopore network where the pores are filled with metallic Titanium (Ti). Without any intentional chemical doping, we have shown that the electrical resistivity of the oxide film can be controlled through physical filling up of the intrinsic oxide nanopores with Ti. The electrical resistivity of the composite film remains constant even after complete removal of the metal from the film surface except the pores. Careful morphological, electrical and structural analyses are carried out to establish that the presence of Ti in the nanopores play a crucial role in the observed conductive nature of the nanoporous film.

Engineering noble metal nanomaterials for environmental applications.

PubMed

Li, Jingguo; Zhao, Tingting; Chen, Tiankai; Liu, Yanbiao; Ong, Choon Nam; Xie, Jianping

2015-05-07

Besides being valuable assets in our daily lives, noble metals (namely, gold, silver, and platinum) also feature many intriguing physical and chemical properties when their sizes are reduced to the nano- or even subnano-scale; such assets may significantly increase the values of the noble metals as functional materials for tackling important societal issues related to human health and the environment. Among which, designing/engineering of noble metal nanomaterials (NMNs) to address challenging issues in the environment has attracted recent interest in the community. In general, the use of NMNs for environmental applications is highly dependent on the physical and chemical properties of NMNs. Such properties can be readily controlled by tailoring the attributes of NMNs, including their size, shape, composition, and surface. In this feature article, we discuss recent progress in the rational design and engineering of NMNs with particular focus on their applications in the field of environmental sensing and catalysis. The development of functional NMNs for environmental applications is highly interdisciplinary, which requires concerted efforts from the communities of materials science, chemistry, engineering, and environmental science.

Self-assembly and nanosphere lithography for large-area plasmonic patterns on graphene.

PubMed

Lotito, Valeria; Zambelli, Tomaso

2015-06-01

Plasmonic structures on graphene can tailor its optical properties, which is essential for sensing and optoelectronic applications, e.g. for the enhancement of photoresponsivity of graphene photodetectors. Control over their structural and, hence, spectral properties can be attained by using electron beam lithography, which is not a viable solution for the definition of patterns over large areas. For the fabrication of large-area plasmonic nanostructures, we propose to use self-assembled monolayers of nanospheres as a mask for metal evaporation and etching processes. An optimized approach based on self-assembly at air/water interface with a properly designed apparatus allows the attainment of monolayers of hexagonally closely packed patterns with high long-range order and large area coverage; special strategies are devised in order to protect graphene against damage resulting from surface treatment and further processing steps such as reactive ion etching, which could potentially impair graphene properties. Therefore we demonstrate that nanosphere lithography is a cost-effective solution to create plasmonic patterns on graphene. Copyright © 2014 Elsevier Inc. All rights reserved.

Direct Visualization of Conformation and Dense Packing of DNA-Based Soft Colloids

NASA Astrophysics Data System (ADS)

Zhang, Jing; Lettinga, Paul M.; Dhont, Jan K. G.; Stiakakis, Emmanuel

2014-12-01

Soft colloids—such as polymer-coated particles, star polymers, block-copolymer micelles, microgels—constitute a broad class of materials where microscopic properties such as deformability and penetrability of the particle play a key role in tailoring their macroscopic properties which is of interest in many technological areas. The ability to access these microscopic properties is not yet demonstrated despite its great importance. Here we introduce novel DNA-coated colloids with star-shaped architecture that allows accessing the above local structural information by directly visualizing their intramolecular monomer density profile and arm's free-end locations with confocal fluorescent microscopy. Compression experiments on a two-dimensional hexagonal lattice formed by these macromolecular assemblies reveal an exceptional resistance to mutual interpenetration of their charged corona at pressures approaching the MPa range. Furthermore, we find that this lattice, in a close packing configuration, is surprisingly tolerant to particle size variation. We anticipate that these stimuli-responsive materials could aid to get deeper insight in a wide range of problems in soft matter, including the study and design of biomimetic lubricated surfaces.

Chemical and Topographical Modification of Polycarbonate Surfaces through Diffusion/Photocuring Processes of Hydrogel Precursors Based on Vinylpyrrolidone.

PubMed

Gallardo, Alberto; Lujan, Noelia; Reinecke, Helmut; García, Carolina; Campo, Adolfo Del; Rodriguez-Hernandez, Juan

2017-02-21

Facile procedures capable of simultaneously conferring hydrophilicity and tailored topography to surfaces of hydrophobic supports, such as polycarbonate (PC), are very attractive but rare. In this work, we describe a simple methodology to wrinkle PC surfaces after a process of (a) contacting with a photopolymerizable vinylic solution, (b) UV curing of such solutions, and (c) detachment of the formed polymer network, upon swelling in ethanol. The influence of different parameters such as contact lag time between the PC surface and the polymerizable solution, the monomer concentration and type of solvents, as well as the cross-linking degree on the formation of wrinkles, has been studied. The dimensions of the wrinkles can be tailored to some extent by altering the different parameters. Surface chemistry has been analyzed by contact angle measurements and by confocal Raman microscopy. The results are consistent with a chemical alteration of the surface and the formation of an outer hydrogel layer, which is interpenetrated into the PC structure. A mechanism of monomer diffusion and PC swelling that produces surface instabilities and wrinkling is proposed.

A highly attenuating and frequency tailorable annular hole phononic crystal for surface acoustic waves.

PubMed

Ash, B J; Worsfold, S R; Vukusic, P; Nash, G R

2017-08-02

Surface acoustic wave (SAW) devices are widely used for signal processing, sensing and increasingly for lab-on-a-chip applications. Phononic crystals can control the propagation of SAW, analogous to photonic crystals, enabling components such as waveguides and cavities. Here we present an approach for the realisation of robust, tailorable SAW phononic crystals, based on annular holes patterned in a SAW substrate. Using simulations and experiments, we show that this geometry supports local resonances which create highly attenuating phononic bandgaps at frequencies with negligible coupling of SAWs into other modes, even for relatively shallow features. The enormous bandgap attenuation is up to an order-of-magnitude larger than that achieved with a pillar phononic crystal of the same size, enabling effective phononic crystals to be made up of smaller numbers of elements. This work transforms the ability to exploit phononic crystals for developing novel SAW device concepts, mirroring contemporary progress in photonic crystals.The control and manipulation of propagating sound waves on a surface has applications in on-chip signal processing and sensing. Here, Ash et al. deviate from standard designs and fabricate frequency tailorable phononic crystals with an order-of-magnitude increase in attenuation.

Validation of Spectral Unmixing Results from Informed Non-Negative Matrix Factorization (INMF) of Hyperspectral Imagery

NASA Astrophysics Data System (ADS)

Wright, L.; Coddington, O.; Pilewskie, P.

2017-12-01

Hyperspectral instruments are a growing class of Earth observing sensors designed to improve remote sensing capabilities beyond discrete multi-band sensors by providing tens to hundreds of continuous spectral channels. Improved spectral resolution, range and radiometric accuracy allow the collection of large amounts of spectral data, facilitating thorough characterization of both atmospheric and surface properties. We describe the development of an Informed Non-Negative Matrix Factorization (INMF) spectral unmixing method to exploit this spectral information and separate atmospheric and surface signals based on their physical sources. INMF offers marked benefits over other commonly employed techniques including non-negativity, which avoids physically impossible results; and adaptability, which tailors the method to hyperspectral source separation. The INMF algorithm is adapted to separate contributions from physically distinct sources using constraints on spectral and spatial variability, and library spectra to improve the initial guess. Using this INMF algorithm we decompose hyperspectral imagery from the NASA Hyperspectral Imager for the Coastal Ocean (HICO), with a focus on separating surface and atmospheric signal contributions. HICO's coastal ocean focus provides a dataset with a wide range of atmospheric and surface conditions. These include atmospheres with varying aerosol optical thicknesses and cloud cover. HICO images also provide a range of surface conditions including deep ocean regions, with only minor contributions from the ocean surfaces; and more complex shallow coastal regions with contributions from the seafloor or suspended sediments. We provide extensive comparison of INMF decomposition results against independent measurements of physical properties. These include comparison against traditional model-based retrievals of water-leaving, aerosol, and molecular scattering radiances and other satellite products, such as aerosol optical thickness from the Moderate Resolution Imaging Spectroradiometer (MODIS).

Comparison of multilayer formation between different cellulose nanofibrils and cationic polymers.

PubMed

Eronen, Paula; Laine, Janne; Ruokolainen, Janne; Osterberg, Monika

2012-05-01

The multilayer formation between polyelectrolytes of opposite charge offers possibility for creating new tailored materials. Exchanging one or both components for charged nanofibrillated cellulose (NFC) further increases the variety of achievable properties. We explored this by introducing unmodified, low charged NFC and high charged TEMPO-oxidized NFC. Systematic evaluation of the effect of both NFC charge and properties of cationic polyelectrolytes on the structure of the multilayers was performed. As the cationic component cationic NFC was compared with two different cationic polyelectrolytes, poly(dimethyldiallylammoniumchloride) and cationic starch. Quartz crystal microbalance with dissipation (QCM-D) was used to monitor the multilayer formation and AFM colloidal probe microscopy (CPM) was further applied to probe surface interactions in order to gain information about fundamental interactions and layer properties. Generally, the results verified the characteristic multilayer formation between NFC of different charge and how the properties of formed multilayers can be tuned. However, the strong nonelectrostatic affinity between cellulosic fibrils was observed. CPM measurements revealed monotonically repulsive forces, which were in good correspondence with the QCM-D observations. Significant increase in adhesive forces was detected between the swollen high charged NFC. Copyright © 2011 Elsevier Inc. All rights reserved.

Unraveling atomic-level self-organization at the plasma-material interface

NASA Astrophysics Data System (ADS)

Allain, J. P.; Shetty, A.

2017-07-01

The intrinsic dynamic interactions at the plasma-material interface and critical role of irradiation-driven mechanisms at the atomic scale during exposure to energetic particles require a priori the use of in situ surface characterization techniques. Characterization of ‘active’ surfaces during modification at atomic-scale levels is becoming more important as advances in processing modalities are limited by an understanding of the behavior of these surfaces under realistic environmental conditions. Self-organization from exposure to non-equilibrium and thermalized plasmas enable dramatic control of surface morphology, topography, composition, chemistry and structure yielding the ability to tune material properties with an unprecedented level of control. Deciphering self-organization mechanisms of nanoscale morphology (e.g. nanodots, ripples) and composition on a variety of materials including: compound semiconductors, semiconductors, ceramics, polymers and polycrystalline metals via low-energy ion-beam assisted plasma irradiation are critical to manipulate functionality in nanostructured systems. By operating at ultra-low energies near the damage threshold, irradiation-driven defect engineering can be optimized and surface-driven mechanisms controlled. Tunability of optical, electronic, magnetic and bioactive properties is realized by reaching metastable phases controlled by atomic-scale irradiation-driven mechanisms elucidated by novel in situ diagnosis coupled to atomistic-level computational tools. Emphasis will be made on tailored surface modification from plasma-enhanced environments on particle-surface interactions and their subsequent modification of hard and soft matter interfaces. In this review, we examine current trends towards in situ and in operando surface and sub-surface characterization to unravel atomic-scale mechanisms at the plasma-material interface. This work will emphasize on recent advances in the field of plasma and ion-induced nanopatterning and nanostructuring as well as ultra-thin film deposition. Future outlook will examine the critical role of complementary surface-sensitive techniques and trends towards advances in both in situ and in operando tooling.

Tailoring plasmonic properties of gold nanohole arrays for surface-enhanced Raman scattering

PubMed Central

Zheng, Peng; Cushing, Scott K.; Suri, Savan; Wu, Nianqiang

2015-01-01

The wide plasmonic tuning range of nanotriangle and nanohole array patterns fabricated by nanosphere lithography makes them promising in surface-enhanced Raman scattering (SERS) sensors. Unfortunately, it is challenging to optimize these patterns for SERS sensing because their optical response is a complex mixture of localized and propagating surface plasmons. In this paper, transmission and reflection measurements are combined with finite difference time domain simulations to identify and separate each plasmonic mode, discerning which resonance leads to the electromagnetic field enhancement. The SERS enhancement is found to be dominated by the absorption, which is shifted from the transmission and reflection dips usually used as tuning points, and by the ‘gap’ defects formed within the pattern. These effects have different spectral and geometric dependences, forming two optimization curves which can be used to predict the best performance for a given excitation wavelength. The developed model is verified with experimental SERS measurements for several nanohole sizes and periodicities, and then used to give optimal fabrication parameters for a range of measurement conditions. The results will promote the application of two-dimensional plasmonic nanoarrays in SERS sensors. PMID:25586930

Parallel nano-assembling of a multifunctional GO/HapNP coating on ultrahigh-purity magnesium for biodegradable implants

NASA Astrophysics Data System (ADS)

Santos, C.; Piedade, C.; Uggowitzer, P. J.; Montemor, M. F.; Carmezim, M. J.

2015-08-01

This work reports the one-step fabrication of a novel coating on ultra high purity magnesium using a parallel nano assembling process. The multifunctional biodegradable surface was obtained by adding hydroxyapatite nanoparticles (HapNP) plus graphene oxide (GO). The coating was characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffractometer (XRD), micro-Raman spectroscopy. The thin phosphate coating (thickness of 1 μm) reveals a uniform coverage with cypress like structures. The incorporation of HapNP and GO promotes the hydrophilic behavior of the coating surface. The results revealed that the proposed coating can be used to tailor the surface properties such as wettability by adjusting the contents of HapNP and GO. The in vitro degradation rate of the coated magnesium suggests that the presence of HapNP and GO/HapNP in the phosphate coating decreased the current density compared to the single phosphate coating and uncoated magnesium. This study also reveals the HapNP/GO/phosphate coating induces apatite formation, showing suitable degradability that makes it a promising coating candidate for enhanced bone regeneration.

Magnetic wire trap arrays for biomarker-based molecular detection

NASA Astrophysics Data System (ADS)

Vieira, Gregory; Mahajan, Kalpesh; Ruan, Gang; Winter, Jessica; Sooryakumar, R.

2012-02-01

Submicrometer-scale magnetic devices built on chip-based platforms have recently been shown to present opportunities for new particle trapping and manipulation technologies. Meanwhile, advances in nanoparticle fabrication allow for the building of custom-made particles with precise control of their size, composition, and other properties such as magnetism, fluorescence, and surface biomarker characteristics. In particular, carefully tailored surface biomarkers facilitate precise binding to targeted molecules, self-actuated construction of hybrid structures, and fluorescence-based detection schemes. Based on these progresses, we present an on-chip detection mechanism for molecules with known surface markers. Hybrid nanostructures consisting of micelle nanoparticles, fluorescent quantum dots, and superparamagnetic iron oxide nanoparticles are used to detect proteins or DNA molecules. The target is detected by the magnetic and fluorescent functionalities of the composite nanostructure, whereas in the absence of the target these signals are not present. Underlying this approach is the simultaneous manipulation via ferromagnetic zigzag nanowire arrays and imaging via quantum dot excitation. This chip-based detection technique could provide a powerful, low cost tool for ultrasensitive molecule detection with ramifications in healthcare diagnostics and small-scale chemical synthesis.

Coupling Solar Energy into Reactions: Materials Design for Surface Plasmon-Mediated Catalysis.

PubMed

Long, Ran; Li, Yu; Song, Li; Xiong, Yujie

2015-08-26

Enabled by surface plasmons, noble metal nanostructures can interact with and harvest incident light. As such, they may serve as unique media to generate heat, supply energetic electrons, and provide strong local electromagnetic fields for chemical reactions through different mechanisms. This solar-to-chemical pathway provides a new approach to solar energy utilization, alternative to conventional semiconductor-based photocatalysis. To provide readers with a clear picture of this newly recognized process, this review presents coupling solar energy into chemical reactions through plasmonic nanostructures. It starts with a brief introduction of surface plasmons in metallic nanostructures, followed by a demonstration of tuning plasmonic features by tailoring their physical parameters. Owing to their tunable plasmonic properties, metallic materials offer a platform to trigger and drive chemical reactions at the nanoscale, as systematically overviewed in this article. The design rules for plasmonic materials for catalytic applications are further outlined based on existing examples. At the end of this article, the challenges and opportunities for further development of plasmonic-mediated catalysis toward energy and environmental applications are discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Functionally Graded Designer Viscoelastic Materials Tailored to Perform Prescribed Tasks with Probabilistic Failures and Lifetimes

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

Hilton, Harry H.

Protocols are developed for formulating optimal viscoelastic designer functionally graded materials tailored to best respond to prescribed loading and boundary conditions. In essence, an inverse approach is adopted where material properties instead of structures per se are designed and then distributed throughout structural elements. The final measure of viscoelastic material efficacy is expressed in terms of failure probabilities vs. survival time000.

Polymeric Nanofibers in Tissue Engineering

PubMed Central

Dahlin, Rebecca L.; Kasper, F. Kurtis

2011-01-01

Polymeric nanofibers can be produced using methods such as electrospinning, phase separation, and self-assembly, and the fiber composition, diameter, alignment, degradation, and mechanical properties can be tailored to the intended application. Nanofibers possess unique advantages for tissue engineering. The small diameter closely matches that of extracellular matrix fibers, and the relatively large surface area is beneficial for cell attachment and bioactive factor loading. This review will update the reader on the aspects of nanofiber fabrication and characterization important to tissue engineering, including control of porous structure, cell infiltration, and fiber degradation. Bioactive factor loading will be discussed with specific relevance to tissue engineering. Finally, applications of polymeric nanofibers in the fields of bone, cartilage, ligament and tendon, cardiovascular, and neural tissue engineering will be reviewed. PMID:21699434

Impedance matched thin metamaterials make metals absorbing.

PubMed

Mattiucci, N; Bloemer, M J; Aközbek, N; D'Aguanno, G

2013-11-13

Metals are generally considered good reflectors over the entire electromagnetic spectrum up to their plasma frequency. Here we demonstrate an approach to tailor their absorbing characteristics based on the effective metamaterial properties of thin, periodic metallo-dielectric multilayers by exploiting a broadband, inherently non-resonant, surface impedance matching mechanism. Based on this mechanism, we design, fabricate and test omnidirectional, thin (<1 micron), polarization independent, extremely efficient absorbers (in principle being capable to reach A > 99%) over a frequency range spanning from the UV to the IR. Our approach opens new venues to design cost effective materials for many applications such as thermo-photovoltaic energy conversion devices, light harvesting for solar cells, flat panel display, infrared detectors, stray light reduction, stealth and others.

Plasma deposition and surface modification techniques for wear resistance

NASA Technical Reports Server (NTRS)

Spalvins, T.

1982-01-01

The ion-assisted or plasma coating technology is discussed as it applies to the deposition of hard, wear resistant refractory compound films. Of the many sputtering and ion plating modes and configurations the reactive magnetron sputtering and the reactive triode ion plating techniques are the preferred ones to deposit wear resistant coatings for tribological applications. Both of these techniques incorporate additional means to enhance the ionization efficiency and chemical reaction to precision tailor desirable tribological characteristics. Interrelationships between film formation, structure, and ribological properties are strictly controlled by the deposition parameters and the substrate condition. The enhanced ionization contributes to the excellent adherence and coherence, reduced internal stresses and improved structural growth to form dense, cohesive, equiaxed grain structure for improved wear resistance and control.

Light-induced covalent immobilization of monolayers of magnetic nanoparticles on hydrogen-terminated silicon.

PubMed

Leem, Gyu; Zhang, Shishan; Jamison, Andrew C; Galstyan, Eduard; Rusakova, Irene; Lorenz, Bernd; Litvinov, Dmitri; Lee, T Randall

2010-10-01

Specifically tailored ω-alkenyl-1-carboxylic acids were synthesized for use as surfactants in the single-step preparation of manganese ferrite (MnFe2O4) nanoparticles (NPs). Monodisperse manganese ferrite NPs terminated with ω-alkenyl moieties were prepared via a one-pot reaction at high temperature without the need of ligand exchange. Using this approach, simple adjustment of the rate of heating allowed precise tuning of the size of the nanoparticles, which were characterized in bulk form by transmission electron microscopy (TEM), Fourier-transform infrared (FT-IR) spectroscopy, and X-ray diffraction (XRD). These surfactant-coated magnetic nanoparticles were then deposited onto hydrogen-terminated silicon(111) wafers and covalently anchored to the surface by UV-initiated covalent bonding. Analysis by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) confirmed that the UV treatment led to covalent immobilization of the NPs on the silicon surface with a consistent packing density across the surface. The magnetic properties of the stable, surface-bound nanoparticle arrays were characterized using a superconducting quantum interference device (SQUID) magnetometer. The materials and methods described here are being developed for use in bit-patterned ultrahigh density magnetic recording media and nanoscale biomagnetic sensing.

Tunable Luminescent Carbon Nanospheres with Well-Defined Nanoscale Chemistry for Synchronized Imaging and Therapy.

PubMed

Mukherjee, Prabuddha; Misra, Santosh K; Gryka, Mark C; Chang, Huei-Huei; Tiwari, Saumya; Wilson, William L; Scott, John W; Bhargava, Rohit; Pan, Dipanjan

2015-09-01

In this work, we demonstrate the significance of defined surface chemistry in synthesizing luminescent carbon nanomaterials (LCN) with the capability to perform dual functions (i.e., diagnostic imaging and therapy). The surface chemistry of LCN has been tailored to achieve two different varieties: one that has a thermoresponsive polymer and aids in the controlled delivery of drugs, and the other that has fluorescence emission both in the visible and near-infrared (NIR) region and can be explored for advanced diagnostic modes. Although these particles are synthesized using simple, yet scalable hydrothermal methods, they exhibit remarkable stability, photoluminescence and biocompatibility. The photoluminescence properties of these materials are tunable through careful choice of surface-passivating agents and can be exploited for both visible and NIR imaging. Here the synthetic strategy demonstrates the possibility to incorporate a potent antimetastatic agent for inhibiting melanomas in vitro. Since both particles are Raman active, their dispersion on skin surface is reported with Raman imaging and utilizing photoluminescence, their depth penetration is analysed using fluorescence 3D imaging. Our results indicate a new generation of tunable carbon-based probes for diagnosis, therapy or both. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tribological coating of titanium alloys by laser processing

NASA Astrophysics Data System (ADS)

Pang, Wang

Titanium-based alloys have been used for aerospace materials for many years. Recently, these alloys are now being increasingly considered for automotive, industrial and consumer applications. Their excellent creep resistance, corrosion resistance and relative higher specific strength ratio are attractive for many applications. However, the main obstacle for the wide adoption of Ti alloys in various industries is their poor tribological properties. In slide wear, Ti deforms and adhesive wear readily occurs. Their poor tribological properties are mainly due to low hardness and absolute values of tensile and shear strength. Different surface modification techniques have been studied in order to improve the tribological characteristics of Ti alloys, i.e. PVD, nitrding, carburizing, boriding, plating etc. Coatings produced by these techniques have their own limitations such as thermal distortion and grain growth. A different approach is to introduce hard particles in the Ti alloy matrix to form a MMC coating, which has tailor-made hardness and wear resistance properties. Laser cladding or laser alloying techniques facilitate the fabrication of surface MMC on Ti alloys without thermal distortion to the substrate. In this project, the fabrication of hard and wear resistant layers of metal matrix composite on titanium alloys substrate by laser surface alloying was investigated. Powder mixtures of Mo and WC were used to form the MMC layer. By optimizing the processing parameters and pre-placed powder mixture compositions, surface MMC of different properties have been successfully fabricated on CP-Ti and Ti6A14V respectively. The structure and characteristics of the MMC surface were investigated by metallography, SEM, XRD, and E-DAX. It was found that the hardness of the laser alloyed Mo/WC MMC surface was 300% higher than that of the CP-Ti substrate Excellent metallurgical bonding with the MMC layer of the substrate has been achieved. The relative kinetic frictional tests were carried out and the results showed that the kinetic coefficient of friction of the laser fabricated Ti-Mo-WC MMC coatings was much lower than that of the CP-Ti and Ti6A14V substrate. The wear resistance of this Ti-Mo-WC MMC was found to be between 60 to 150 times better than those of CP-Ti. The experimental results also identified a key issue of mixing efficiency that the density of WC was much higher than that of Ti and Mo and this rendered poor mixing between the different constituents. This resulted in a relatively poor repeatability of the coating quality. To solve this issue, a lower density carbide phase, TiC, was used. The hardness and dry sliding wear resistance of the Ti-Mo-TiC MMC was found to be lower than those of Ti-Mo-WC MMC. The mixing efficiency of the TiC in the Ti-Mo-MMC was found to be better than the WC in Ti-Mo-WC MMC. This combination gave a harder and more wear resistant MMC with more uniform properties across the width and depth of the alloyed layer formed. A mathematical model for predicting the melt depth of the alloyed MMC layer was developed together with a heat transfer mechanism between layers of powders under the laser irradiation. The model facilitates the prediction of melt depth of the alloyed layer and the dilution ratio of the MMC layer. It thus enabled the composition of the MMC layer to be predicted and tailor made. The project results contribute significantly to the knowledge of improving the wear and frictional properties of one of the most important engineering metals for the automobile and aerospace industries.

Tailoring galvanic replacement reaction for the preparation of Pt/Ag bimetallic hollow nanostructures with controlled number of voids.

PubMed

Zhang, Weiqing; Yang, Jizheng; Lu, Xianmao

2012-08-28

Here we report the synthesis of Pt/Ag bimetallic nanostructures with controlled number of void spaces via a tailored galvanic replacement reaction (GRR). Ag nanocubes (NCs) were employed as the template to react with Pt ions in the presence of HCl. The use of HCl in the GRR caused rapid precipitation of AgCl, which grew on the surface of Ag NCs and acted as a removable secondary template for the deposition of Pt. The number of nucleation sites for AgCl was tailored by controlling the amount of HCl added to the Ag NCs or by introducing PVP to the reaction. This strategy led to the formation of Pt/Ag hollow nanoboxes, dimers, multimers, or popcorn-shaped nanostructures consisting of one, two, or multiple hollow domains. Due to the presence of large void space and porous walls, these nanostructures exhibited high surface area and improved catalytic activity for methanol oxidation reaction.

Comparing Laser Welding Technologies with Friction Stir Welding for Production of Aluminum Tailor-Welded Blanks

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

Hovanski, Yuri; Carsley, John; Carlson, Blair

2014-01-15

A comparison of welding techniques was performed to determine the most effective method for producing aluminum tailor-welded blanks for high volume automotive applications. Aluminum sheet was joined with an emphasis on post weld formability, surface quality and weld speed. Comparative results from several laser based welding techniques along with friction stir welding are presented. The results of this study demonstrate a quantitative comparison of weld methodologies in preparing tailor-welded aluminum stampings for high volume production in the automotive industry. Evaluation of nearly a dozen welding variations ultimately led to down selecting a single process based on post-weld quality and performance.

Oligonucleotide-Functionalized Anisotropic Gold Nanoparticles

NASA Astrophysics Data System (ADS)

Jones, Matthew Robert

In this thesis, we describe the properties of oligonucleotide-functionalized gold colloids under the unique set of conditions where the particles are geometrically anisotropic and have nanometer-scale dimensions. While nearly two decades of previous work elucidated numerous unexpected and emergent phenomena arising from the combination of inorganic nanoparticles with surface-bound DNA strands, virtually nothing was known about how these properties are altered when the shape of the nanoparticle core is chosen to be non-spherical. In particular, we are interested in understanding, and ultimately controlling, the ways in which these DNA-conjugated anisotropic nanostructures interact when their attraction is governed by programmable DNA hybridization events. Chapter 1 introduces the field of DNA-based materials assembly by discussing how nanoscale building blocks which present rigid, directional interactions can be thought of as possessing artificial versions of the familiar chemical principles of "bonds" and "valency". In chapter 2 we explore the fundamental interparticle binding thermodynamics of DNA-functionalized spherical and anisotropic nanoparticles, which reveals enormous preferences for collective ligand interactions occurring between flat surfaces over those that occur between curved surfaces. Using these insights, chapter 3 demonstrates that when syntheses produce mixtures of different nanoparticle shapes, the tailorable nature of DNA-mediated interparticle association can be used to selectively crystallize and purify the desired anisotropic nanostructure products, leaving spherical impurity particles behind. Chapter 4 leverages the principle that the flat facets of anisotropic particles generate directional DNA-based hybridization interactions to assemble a variety of tailorable nanoparticle superlattices whose symmetry and dimensionality are a direct consequence of the shape of the nanoparticle building block used in their construction. Chapter 5 explores a useful application of having thermally labile DNA duplexes bound to anisotropic nanoparticles -- the selective photothermal heating and release of hybridized oligonucleotides via a plasmon excitation-based mechanism. The final chapter presents a brief summary of the seminal findings of this thesis and provides an outlook covering future directions and remaining challenges for the field. A comprehensive review covering methods to synthesize and assemble noble metal nanostructures is included in the appendix as an additional resource. All experimental chapters are organized similarly; they begin with an abstract or introduction to motivate and contextualize the work, present the main results and discussion with brief experimental details, and conclude with more detailed, supplementary information for the interested reader. As a whole, this work establishes fundamental understanding and new experimental methods for exploiting nanoscale shape anisotropy to manipulate the chemical and physical properties of matter.

Tailoring barrier properties of thermoplastic corn starch-based films (TPCS) by means of a multilayer design.

PubMed

Fabra, María José; López-Rubio, Amparo; Cabedo, Luis; Lagaron, Jose M

2016-12-01

This work compares the effect of adding different biopolyester electrospun coatings made of polycaprolactone (PCL), polylactic acid (PLA) and polyhydroxybutyrate (PHB) on oxygen and water vapour barrier properties of a thermoplastic corn starch (TPCS) film. The morphology of the developed multilayer structures was also examined by Scanning Electron Microscopy (SEM). Results showed a positive linear relationship between the amount of the electrospun coatings deposited onto both sides of the TPCS film and the thickness of the coating. Interestingly, the addition of electrospun biopolyester coatings led to an exponential oxygen and water vapour permeability drop as the amount of the electrospun coating increased. This study demonstrated the versatility of the technology here proposed to tailor the barrier properties of food packaging materials according to the final intended use. Copyright © 2016 Elsevier Inc. All rights reserved.

Tailoring double Fano profiles with plasmon-assisted quantum interference in hybrid exciton-plasmon system

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

Zhao, Dongxing; Wu, Jiarui; Gu, Ying, E-mail: ygu@pku.edu.cn

2014-09-15

We propose tailoring of the double Fano profiles via plasmon-assisted quantum interference in a hybrid exciton-plasmon system. Tailoring is performed by the interference between two exciton channels interacting with a common localized surface plasmon. Using an applied field of low intensity, the absorption spectrum of the hybrid system reveals a double Fano lineshape with four peaks. For relatively large field intensity, a broad flat window in the absorption spectrum appears which results from the destructive interference between excitons. Because of strong constructive interference, this window vanishes as intensity is further increased. We have designed a nanometer bandpass optical filter formore » visible light based on tailoring of the optical spectrum. This study provides a platform for quantum interference that may have potential applications in ultracompact tunable quantum devices.« less

The relationships between deformation mechanisms and mechanical properties of additively manufactured porous biomaterials.

PubMed

Kadkhodapour, J; Montazerian, H; Darabi, A Ch; Zargarian, A; Schmauder, S

2017-06-01

Modulating deformation mechanism through manipulating morphological parameters of scaffold internal pore architecture provides potential to tailor the overall mechanical properties under physiological loadings. Whereas cells sense local strains, cell differentiation is also impressed by the elastic deformations. In this paper, structure-property relations were developed for Ti6-Al-4V scaffolds designed based on triply periodic minimal surfaces. 10mm cubic scaffolds composed of 5×5×5 unit cells formed of F-RD (bending dominated) and I-WP (stretching dominated) architectures were additively manufactured at different volume fractions and subjected to compressive tests. The first stages of deformation for stretching dominated structure, was accompanied by bilateral layer-by-layer failure of unit cells owing to the buckling of micro-struts, while for bending dominated structure, namely F-RD, global shearing bands appeared since the shearing failure of struts in the internal architecture. Promoted mechanical properties were found for stretching dominated structure since the global orientation of struts were parallel to loading direction while inclination of struts diminished specific properties for bending dominated structure. Moreover, elastic-plastic deformation was computationally studied by applying Johnson-Cook damage model to the voxel-based models in FE analysis. Scaling analysis was performed for mechanical properties with respect to the relative density thereby failure mechanism was correlated to the constants of power law describing mechanical properties. Copyright © 2016 Elsevier Ltd. All rights reserved.

Thermodynamic Stability of Molybdenum Oxycarbides Formed from Orthorhombic Mo 2 C in Oxygen-Rich Environments

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

Likith, S. R. J.; Farberow, C. A.; Manna, S.

Molybdenum carbide (Mo 2C) nanoparticles and thin films are particularly suitable catalysts for catalytic fast pyrolysis (CFP) as they are effective for deoxygenation and can catalyze certain reactions that typically occur on noble metals. Oxygen deposited during deoxygenation reactions may alter the carbide structure, leading to the formation of oxycarbides, which can determine changes in catalytic activity or selectivity. Despite emerging spectroscopic evidence of bulk oxycarbides, so far there have been no reports of their precise atomic structure or their relative stability with respect to orthorhombic Mo 2C. This knowledge is essential for assessing the catalytic properties of molybdenum (oxy)carbidesmore » for CFP. In this article, we use density functional theory (DFT) calculations to (a) describe the thermodynamic stability of surface and subsurface configurations of oxygen and carbon atoms for a commonly studied Mo-terminated surface of orthorhombic Mo 2C and (b) determine atomic structures for oxycarbides with a Mo:C ratio of 2:1. The surface calculations suggest that oxygen atoms are not stable under the top Mo layer of the Mo 2C(100) surface. Coupling DFT calculations with a polymorph sampling method, we determine (Mo 2C) xO y oxycarbide structures for a wide range of oxygen compositions. Oxycarbides with lower oxygen content (y/x = 2) adopt layered structures reminiscent of the parent carbide phase, with flat Mo layers separated by layers of oxygen and carbon; for higher oxygen content, our results suggest the formation of amorphous phases, as the atomic layers lose their planarity with increasing oxygen content. We characterize the oxidation states of Mo in the oxycarbide structures determined computationally, and simulate their X-ray diffraction (XRD) patterns in order to facilitate comparisons with experiments. Our study may provide a platform for large-scale investigations of the catalytic properties of oxycarbides and their surfaces and for tailoring the catalytic properties for different desired reactions.« less

Applications of Neutron Scattering in the Chemical Industry: Proton Dynamics of Highly Dispersed Materials, Characterization of Fuel Cell Catalysts, and Catalysts from Large-Scale Chemical Processes

NASA Astrophysics Data System (ADS)

Albers, Peter W.; Parker, Stewart F.

The attractiveness of neutron scattering techniques for the detailed characterization of materials of high degrees of dispersity and structural complexity as encountered in the chemical industry is discussed. Neutron scattering picks up where other analytical methods leave off because of the physico-chemical properties of finely divided products and materials whose absorption behavior toward electromagnetic radiation and electrical conductivity causes serious problems. This is demonstrated by presenting typical applications from large-scale production technology and industrial catalysis. These include the determination of the proton-related surface chemistry of advanced materials that are used as reinforcing fillers in the manufacture of tires, where interrelations between surface chemistry, rheological properties, improved safety, and significant reduction of fuel consumption are the focus of recent developments. Neutron scattering allows surface science studies of the dissociative adsorption of hydrogen on nanodispersed, supported precious metal particles of fuel cell catalysts under in situ loading at realistic gas pressures of about 1 bar. Insight into the occupation of catalytically relevant surface sites provides valuable information about the catalyst in the working state and supplies essential scientific input for tailoring better catalysts by technologists. The impact of deactivation phenomena on industrial catalysts by coke deposition, chemical transformation of carbonaceous deposits, and other processes in catalytic hydrogenation processes that result in significant shortening of the time of useful operation in large-scale plants can often be traced back in detail to surface or bulk properties of catalysts or materials of catalytic relevance. A better understanding of avoidable or unavoidable aspects of catalyst deactivation phenomena under certain in-process conditions and the development of effective means for reducing deactivation leads to more energy-efficient and, therefore, environmentally friendly processes and helps to save valuable resources. Even small or gradual improvements in all these fields are of considerable economic impact.

Thermodynamic Stability of Molybdenum Oxycarbides Formed from Orthorhombic Mo 2 C in Oxygen-Rich Environments

DOE PAGES

Likith, S. R. J.; Farberow, C. A.; Manna, S.; ...

2017-12-20

Molybdenum carbide (Mo 2C) nanoparticles and thin films are particularly suitable catalysts for catalytic fast pyrolysis (CFP) as they are effective for deoxygenation and can catalyze certain reactions that typically occur on noble metals. Oxygen deposited during deoxygenation reactions may alter the carbide structure, leading to the formation of oxycarbides, which can determine changes in catalytic activity or selectivity. Despite emerging spectroscopic evidence of bulk oxycarbides, so far there have been no reports of their precise atomic structure or their relative stability with respect to orthorhombic Mo 2C. This knowledge is essential for assessing the catalytic properties of molybdenum (oxy)carbidesmore » for CFP. In this article, we use density functional theory (DFT) calculations to (a) describe the thermodynamic stability of surface and subsurface configurations of oxygen and carbon atoms for a commonly studied Mo-terminated surface of orthorhombic Mo 2C and (b) determine atomic structures for oxycarbides with a Mo:C ratio of 2:1. The surface calculations suggest that oxygen atoms are not stable under the top Mo layer of the Mo 2C(100) surface. Coupling DFT calculations with a polymorph sampling method, we determine (Mo 2C) xO y oxycarbide structures for a wide range of oxygen compositions. Oxycarbides with lower oxygen content (y/x = 2) adopt layered structures reminiscent of the parent carbide phase, with flat Mo layers separated by layers of oxygen and carbon; for higher oxygen content, our results suggest the formation of amorphous phases, as the atomic layers lose their planarity with increasing oxygen content. We characterize the oxidation states of Mo in the oxycarbide structures determined computationally, and simulate their X-ray diffraction (XRD) patterns in order to facilitate comparisons with experiments. Our study may provide a platform for large-scale investigations of the catalytic properties of oxycarbides and their surfaces and for tailoring the catalytic properties for different desired reactions.« less

Band-structure tailoring and surface passivation for highly efficient near-infrared responsive PbS quantum dot photovoltaics

NASA Astrophysics Data System (ADS)

Zhou, Ru; Niu, Haihong; Ji, Fengwei; Wan, Lei; Mao, Xiaoli; Guo, Huier; Xu, Jinzhang; Cao, Guozhong

2016-11-01

PbS is a promising light harvester for near-infrared (NIR) responsive quantum dot (QD) photovoltaics due to its narrow bulk band gap (0.41 eV) and large exciton Bohr radius (18 nm). However, the relatively low conduction band (CB) and high-density surface defects of PbS as two major drawbacks for its use in solar cells severely hamper the photovoltaic performance enhancement. In this work, a modified solution-based successive ionic layer adsorption and reaction (SILAR) utilizing mixed cationic precursors of Pb2+ and Cd2+ is explored, and such a scheme offers two benefits, band-structure tailoring and surface passivation. In-situ deposited CdS suppresses the excessive growth of PbS in the mesopores, thereby facilitating the favorable electron injection from PbS to TiO2 in view of the up-shifted CB level of QDs; the intimate interpenetration of two sulfides with each other leads to superior passivation of trap state defects on PbS, which suppresses the interfacial charge recombination. With the construction of photovoltaics based on such a hybrid (Pb,Cd)S/CdS configuration, impressive power conversion efficiency up to 4.08% has been reached, outperforming that of the conventional PbS/CdS pattern (2.95%). This work highlights the great importance of band-structure tailoring and surface passivation for constructing highly efficient PbS QD photovoltaics.

Design & synthesis of silicone elastomer networks with tunable physico-chemical characteristics

NASA Astrophysics Data System (ADS)

Willoughby, Julie Ann-Crowe

2007-05-01

We have engineered functional surfaces via the manipulation of silicone elastomers (SEs). The most common silicone, poly(dimethylsiloxane) PDMS, can be both challenging and advantageous in the design of surfaces due to its inherent inertness and flexibility of the siloxane backbone. This unique polymer is approaching a $10 billion dollar market attributed to its formulation in a wide array of applications; from the personal care industry to the electronics industry. While it can be used for many applications, surface design with PDMS usually requires a chemical or physical modification of the polymeric network. In addition, surface characteristics are tailored for specific functions since there is not one surface that fits all end-uses. In studying the intrinsic behavior of engineered SEs, we asked questions regarding surface stability, environmental conformation and adaptability, and tuning physical features. We report on the formation of responsive surfaces with tailorable surface-reconstruction kinetics and switching hysteresis by thiol-ene radical addition of mercaptoalkanols with variable lengths to poly(vinylmethylsiloxane) networks. Exposing the modified surfaces to water led to a rearrangement of the hydrophilic alkanes at the surface. The rearrangement kinetics decreases with increasing number of the methylene spacers (n) in the mercaptoalkanol. The response kinetics is found to be very fast for n = 2 and 6. For instance, upon exposing to water, the water contact angle on 3-mercaptopropanol-based surfaces decreases by ≈35° at the rate of 2°/second. The high flexibility of the siloxane backbone endows these materials with switching longevity; the materials were able to switch their wettability over 10 cycles with minimum hysteresis. Increasing the number of methylene spacers to n = 11 decreases the surface reorganization dramatically. Formation of semi-crystalline regions in such materials (detected via IR) is responsible for initial "sluggish" kinetics and eventual surface "freezing". The effects of surface chemistry and topology on cellular adhesion and proliferation have been studied extensively in the past. However, little work exists that aims at probing the effects of surface morphology and elastic modulus on cell behavior. To achieve timely and comprehensive experimental design, there is need for the availability of novel substrata with tunable mechanical properties (or compliance) at the micro and meso-scale level ranging from individual cells to whole tissues. Despite expansive research that has targeted the understanding of cellular response to its host scaffold, the choice of material and extrapolation of findings from one cell/material system to another has proven difficult. Thus establishing general relationships between substrate compliance and cell behavior cannot be considered independent of the material and cell type. In our work, we have explored creating surfaces from SEs comprising gradients in stiffness (or elastic modulus), by controlling the degree of cross-linking. Network regions consisting of higher cross-linking demonstrate a greater elastic modulus. We present two methods to control the mechanical properties of silicone elastomers. The first technique utilizes interdiffusion of multiple SEs with varied molecular weights that are subsequently cross-linked into a network. The second method involves synthesizing a UV-curable SE. This method controls the degree of cross-linking by regulating the intensity of the UV light via a transparency with tunable transmittance placed on top of the SE film. Our results show that it is possible to generate compliance gradients through either route, enabling a large range of both gradient patterns and stiffness.

Cultural tailoring and feasibility assessment of a sexual health middle school curriculum: a pilot test in Puerto Rico.

PubMed

Escobar-Chaves, Soledad Liliana; Shegog, Ross; Moscoso-Alvarez, Margarita R; Markham, Christine; Tortolero-Luna, Guillermo; Peskin, Melissa; Tortolero, Susan

2011-08-01

To assess the need for cultural tailoring of an effective sexual health middle school curriculum, "It's Your Game: Keep It Real" (IYG), prior to implementation in Puerto Rican (PR) middle schools. Seventy-three seventh-grade bilingual students participated in IYG curriculum activities (both group-based and computer-based) in two 2-hour testing sessions in spring 2008. Rating scales of acceptability, understandability, credibility, ease of use, and motivational appeal and qualitative feedback via open-ended responses and group process provided insight into needed surface and deep structure cultural tailoring. Students rated IYG highly on cultural tailoring and motivational parameters and were highly engaged by the lesson content. School personnel rated IYG as a feasible strategy for use in PR middle schools. While surface cultural elements (eg, characters, attire, body language) were identified as important foci for adaptation, content related to deeper cultural elements such as core behaviors, risky situations, attitudes, and specific skills were considered as relevant to PR youth as to their US counterparts. Effective human immunodeficiency virus, sexually transmitted disease, and pregnancy skills training prevention programs such as IYG that are developed for minority US youth may offer a feasible option for international implementation when extensive cultural adaptation is not a viable option. © 2011, American School Health Association.

A controlled release of ibuprofen by systematically tailoring the morphology of mesoporous silica materials

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

Qu Fengyu; Chemistry and Pharmaceutical College, Jiamusi University, Jiamusi 154007; Zhu Guangshan

2006-07-15

A series of mesoporous silica materials with similar pore sizes, different morphologies and variable pore geometries were prepared systematically. In order to control drug release, ibuprofen was employed as a model drug and the influence of morphology and pore geometry of mesoporous silica on drug release profiles was extensively studied. The mesoporous silica and drug-loaded samples were characterized by X-ray diffraction, Fourier transform IR spectroscopy, N{sub 2} adsorption and desorption, scanning electron microscopy, and transmission electron microscopy. It was found that the drug-loading amount was directly correlated to the Brunauer-Emmett-Teller surface area, pore geometry, and pore volume; while the drugmore » release profiles could be controlled by tailoring the morphologies of mesoporous silica carriers. - Graphical abstract: The release of ibuprofen is controlled by tailoring the morphologies of mesoporous silica. The mesoporous silica and drug-loaded samples are characterized by powder X-ray diffraction, Fourier transform IR spectroscopy, N{sub 2} adsorption and desorption, scanning electron microscopy, and transmission electron microscopy. The drug-loading amount is directly correlated to the Brunauer-Emmett-Teller surface area, pore geometry, and pore volume; while the drug release profiles can be controlled by tailoring the morphologies of mesoporous silica carriers.« less

DNA-templated assembly of viral protein hydrogel

NASA Astrophysics Data System (ADS)

Xu, Xin; Tao, Ailin; Xu, Yun

2014-11-01

Hydrogels are a promising class of biomaterials that can be easily tailored to produce a native extracellular matrix that exhibits desirable mechanical and chemical properties. Here we report the construction of a hydrogel via the assembly of cucumber mosaic virus (CMV) capsid protein and Y-shaped and cross-shaped DNAs.Hydrogels are a promising class of biomaterials that can be easily tailored to produce a native extracellular matrix that exhibits desirable mechanical and chemical properties. Here we report the construction of a hydrogel via the assembly of cucumber mosaic virus (CMV) capsid protein and Y-shaped and cross-shaped DNAs. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr02414a

Tailored Rh surface facilitates, enhancement of Raman scattering in trimetallic AuPt core/Rh shell composites: Experimental and theoretical evidences

NASA Astrophysics Data System (ADS)

Loganathan, B.; Chandraboss, V. L.; Senthilvelan, S.; Karthikeyan, B.

2016-01-01

We present a detailed analysis of surface-enhanced Raman scattering of 7-azaindole and L-cysteine adsorbed on a tailored Rh surface by using experimental and density functional theoretical (DFT) calculations. DFT with the B3LYP/Lanl2DZ basis set was used for the optimization of the ground state geometries and simulation of the surface-enhanced Raman spectrum of probe molecules adsorbed on Rh6 cluster. 7-azaindole and L-cysteine adsorption at the shell interface was ascertained from first-principles. In addition, characterization of synthesized trimetallic AuPt core/Rh shell colloidal nanocomposites has been analyzed by UV-visible spectroscopy, high-resolution transmission and scanning electron microscopy, selected area electron diffraction pattern analysis, energy-dispersive X-ray spectroscopy, atomic force, confocal Raman microscopy, FT-Raman and surface-enhanced Raman spectroscopic analysis. This analysis serves as the first step in gaining an accurate understanding of specific interactions at the interface of organic and biomolecules and to gain knowledge on the surface composition of trimetallic Au/Pt/Rh colloidal nanocomposites.

In Vitro Characterization of the Two-Stage Non-Classical Reassembly Pathway of S-Layers

PubMed Central

Breitwieser, Andreas; Iturri, Jagoba; Toca-Herrera, Jose-Luis; Sleytr, Uwe B.; Pum, Dietmar

2017-01-01

The recombinant bacterial surface layer (S-layer) protein rSbpA of Lysinibacillus sphaericus CCM 2177 is an ideal model system to study non-classical nucleation and growth of protein crystals at surfaces since the recrystallization process may be separated into two distinct steps: (i) adsorption of S-layer protein monomers on silicon surfaces is completed within 5 min and the amount of bound S-layer protein sufficient for the subsequent formation of a closed crystalline monolayer; (ii) the recrystallization process is triggered—after washing away the unbound S-layer protein—by the addition of a CaCl2 containing buffer solution, and completed after approximately 2 h. The entire self-assembly process including the formation of amorphous clusters, the subsequent transformation into crystalline monomolecular arrays, and finally crystal growth into extended lattices was investigated by quartz crystal microbalance with dissipation (QCM-D) and atomic force microscopy (AFM). Moreover, contact angle measurements showed that the surface properties of S-layers change from hydrophilic to hydrophobic as the crystallization proceeds. This two-step approach is new in basic and application driven S-layer research and, most likely, will have advantages for functionalizing surfaces (e.g., by spray-coating) with tailor-made biological sensing layers. PMID:28216572

Behaviour of the surface hydroxide groups of exfoliated kaolinite in the gas phase and during water adsorption.

PubMed

Táborosi, Attila; Szilágyi, Róbert K

2016-02-14

The chemical and physical properties, and thus the reactivity of phylloaluminosilicates can be tailored by intercalation, delamination, and exfoliation processes. In going from the periodic crystalline to the molecular exfoliated phase, surface defects and modifications gain importance as each face of the phylloaluminosilicate comes in direct contact with the external chemical environment. In this work, we extend our earlier studies on the molecular cluster modelling of exfoliated kaolinite sheets by evaluating the positions and orientations of surface hydroxide groups and bridging oxide anions, as the sites of reactivity. The previous focus on the inner chemical environment of a single kaolinite layer is shifted to the surface exposed octahedral aluminium-hydroxide and tetrahedral silicon-oxide sheets. The combination of semi-empirical, ab initio wave function, and density functional calculations unanimously support the amphoteric nature of the surface hydroxide groups with respect to H-bonding donor/acceptor capabilities. To a lesser extent, we observe the same for the bridging oxide anions. This is in contrast to the crystalline phase, which manifests only donor orientation for maintaining an inter-layer H-bond network. These results suggest that both electrophilic and nucleophilic characteristics of the octahedral and tetrahedral sheets need to be considered during intercalation and concomitant exfoliation of the kaolinite sheets.

Fluidized Bed Sputtering for Particle and Powder Metallization

DTIC Science & Technology

2013-04-01

Introduction Small particles are often added to material systems to modify mechanical, dielectric, optical, or other properties . However, the particle...the poor mechanical properties of the wax degrade the bulk mechanical properties of the composite material . Thin metal coatings on the catalyst...to create precisely tailored optical properties . Alternating layers of ceramic and metal thin films can be designed to create optical filters that

Graph-based analysis of kinetics on multidimensional potential-energy surfaces.

PubMed

Okushima, T; Niiyama, T; Ikeda, K S; Shimizu, Y

2009-09-01

The aim of this paper is twofold: one is to give a detailed description of an alternative graph-based analysis method, which we call saddle connectivity graph, for analyzing the global topography and the dynamical properties of many-dimensional potential-energy landscapes and the other is to give examples of applications of this method in the analysis of the kinetics of realistic systems. A Dijkstra-type shortest path algorithm is proposed to extract dynamically dominant transition pathways by kinetically defining transition costs. The applicability of this approach is first confirmed by an illustrative example of a low-dimensional random potential. We then show that a coarse-graining procedure tailored for saddle connectivity graphs can be used to obtain the kinetic properties of 13- and 38-atom Lennard-Jones clusters. The coarse-graining method not only reduces the complexity of the graphs, but also, with iterative use, reveals a self-similar hierarchical structure in these clusters. We also propose that the self-similarity is common to many-atom Lennard-Jones clusters.

Tailoring transport properties of phase-separated manganite films with ordered magnetic nanostructures

DOE PAGES

Vlaminck, V.; Yanez, W.; Hoffman, J.; ...

2016-08-02

Here, the magnetotransport properties of thin manganite films (La 0.7Ca 0.3MnO 3) coupled with arrays of permalloy (Py) nanodots deposited on the surface of the film are studied as a function of temperature, magnetic field, and the size of the dots. In the presence of the magnetic dots, a reduction of the electrical resistivity is observed, especially at the insulator-to-metal transition, as well as a shift of the transition peak towards higher temperatures. This indicates that, due to local interface exchange coupling, highly conductive ferromagnetic domains are nucleated in the manganite film underneath the Py nanodots. The use of amore » simplified resistor network model allows us to estimate the size of the metallic regions induced by exchange coupling. At low temperatures, these regions extend ~70 nm beyond the edge of the nanodots, a length scale comparable to the correlation length of the ferromagnetic clusters in the phase-separated state of La 0.7Ca 0.3MnO 3.« less

Tailoring the morphology of electrodeposited ZnO and its photoluminescence properties

NASA Astrophysics Data System (ADS)

Cui, H.; Mollar, M.; Marí, B.

2011-01-01

High density ZnO columnar films with well-aligned and well-perpendicular to the surface of film were electrodeposited on ITO substrates by using an electrolyte consisting of a mix of water and organic solvent namely dimethylsulfoxide (DMSO). The effect of mixing ratio of water and DMSO on the growth of film has been examined critically. SEM images have shown that well-oriented ZnO quasi-nano columns were formed perpendicular to the substrate. At the same time we found there are three kinds of competitions for growth of ZnO crystalmorphology i.e. column, rod and needle like. The needle like morphology has high density with well-aligned structure. The reasons for the growth of films of different morphology and their photoluminescence (PL) properties have been presented and discussed. It has been found that the three-dimensional (3D) ordered ZnO structure exhibits high intensity PL band which may shift their position and intensity with the varying conditions of depositions.

Graphene growth from reduced graphene oxide by chemical vapour deposition: seeded growth accompanied by restoration

NASA Astrophysics Data System (ADS)

Chang, Sung-Jin; Hyun, Moon Seop; Myung, Sung; Kang, Min-A.; Yoo, Jung Ho; Lee, Kyoung G.; Choi, Bong Gill; Cho, Youngji; Lee, Gaehang; Park, Tae Jung

2016-03-01

Understanding the underlying mechanisms involved in graphene growth via chemical vapour deposition (CVD) is critical for precise control of the characteristics of graphene. Despite much effort, the actual processes behind graphene synthesis still remain to be elucidated in a large number of aspects. Herein, we report the evolution of graphene properties during in-plane growth of graphene from reduced graphene oxide (RGO) on copper (Cu) via methane CVD. While graphene is laterally grown from RGO flakes on Cu foils up to a few hundred nanometres during CVD process, it shows appreciable improvement in structural quality. The monotonous enhancement of the structural quality of the graphene with increasing length of the graphene growth from RGO suggests that seeded CVD growth of graphene from RGO on Cu surface is accompanied by the restoration of graphitic structure. The finding provides insight into graphene growth and defect reconstruction useful for the production of tailored carbon nanostructures with required properties.

Graphene growth from reduced graphene oxide by chemical vapour deposition: seeded growth accompanied by restoration.

PubMed

Chang, Sung-Jin; Hyun, Moon Seop; Myung, Sung; Kang, Min-A; Yoo, Jung Ho; Lee, Kyoung G; Choi, Bong Gill; Cho, Youngji; Lee, Gaehang; Park, Tae Jung

2016-03-10

Understanding the underlying mechanisms involved in graphene growth via chemical vapour deposition (CVD) is critical for precise control of the characteristics of graphene. Despite much effort, the actual processes behind graphene synthesis still remain to be elucidated in a large number of aspects. Herein, we report the evolution of graphene properties during in-plane growth of graphene from reduced graphene oxide (RGO) on copper (Cu) via methane CVD. While graphene is laterally grown from RGO flakes on Cu foils up to a few hundred nanometres during CVD process, it shows appreciable improvement in structural quality. The monotonous enhancement of the structural quality of the graphene with increasing length of the graphene growth from RGO suggests that seeded CVD growth of graphene from RGO on Cu surface is accompanied by the restoration of graphitic structure. The finding provides insight into graphene growth and defect reconstruction useful for the production of tailored carbon nanostructures with required properties.

Graphene growth from reduced graphene oxide by chemical vapour deposition: seeded growth accompanied by restoration

PubMed Central

Chang, Sung-Jin; Hyun, Moon Seop; Myung, Sung; Kang, Min-A; Yoo, Jung Ho; Lee, Kyoung G.; Choi, Bong Gill; Cho, Youngji; Lee, Gaehang; Park, Tae Jung

2016-01-01

Understanding the underlying mechanisms involved in graphene growth via chemical vapour deposition (CVD) is critical for precise control of the characteristics of graphene. Despite much effort, the actual processes behind graphene synthesis still remain to be elucidated in a large number of aspects. Herein, we report the evolution of graphene properties during in-plane growth of graphene from reduced graphene oxide (RGO) on copper (Cu) via methane CVD. While graphene is laterally grown from RGO flakes on Cu foils up to a few hundred nanometres during CVD process, it shows appreciable improvement in structural quality. The monotonous enhancement of the structural quality of the graphene with increasing length of the graphene growth from RGO suggests that seeded CVD growth of graphene from RGO on Cu surface is accompanied by the restoration of graphitic structure. The finding provides insight into graphene growth and defect reconstruction useful for the production of tailored carbon nanostructures with required properties. PMID:26961409

Active molecular plasmonics: tuning surface plasmon resonances by exploiting molecular dimensions

NASA Astrophysics Data System (ADS)

Chen, Kai; Leong, Eunice Sok Ping; Rukavina, Michael; Nagao, Tadaaki; Liu, Yan Jun; Zheng, Yuebing

2015-06-01

Molecular plasmonics explores and exploits the molecule-plasmon interactions on metal nanostructures to harness light at the nanoscale for nanophotonic spectroscopy and devices. With the functional molecules and polymers that change their structural, electrical, and/or optical properties in response to external stimuli such as electric fields and light, one can dynamically tune the plasmonic properties for enhanced or new applications, leading to a new research area known as active molecular plasmonics (AMP). Recent progress in molecular design, tailored synthesis, and self-assembly has enabled a variety of scenarios of plasmonic tuning for a broad range of AMP applications. Dimension (i.e., zero-, two-, and threedimensional) of the molecules on metal nanostructures has proved to be an effective indicator for defining the specific scenarios. In this review article, we focus on structuring the field of AMP based on the dimension of molecules and discussing the state of the art of AMP. Our perspective on the upcoming challenges and opportunities in the emerging field of AMP is also included.

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

Rani, R.; Kumar, N., E-mail: niranjan@igcar.gov.in; Lin, I-Nan

Nanostructured diamond films are having numerous unique properties including superior tribological behavior which is promising for enhancing energy efficiency and life time of the sliding devices. High wear resistance is the principal criterion for the smooth functioning of any sliding device. Such properties are achievable by tailoring the grain size and grain boundary volume fraction in nanodiamond film. Ultra-nanocrystalline diamond (UNCD) film was attainable using optimized gas plasma condition in a microwave plasma enhanced chemical vapor deposition (MPECVD) system. Crystalline phase of ultra-nanodiamond grains with matrix phase of amorphous carbon and short range ordered graphite are encapsulated in nanowire shapedmore » morphology. Film showed ultra-high wear resistance and frictional stability in micro-tribological contact conditions. The negligible wear of film at the beginning of the tribological contact was later transformed into the wearless regime for prolonged sliding cycles. Both surface roughness and high contact stress were the main reasons of wear at the beginning of sliding cycles. However, the interface gets smoothened due to continuous sliding, finally leaded to the wearless regime.« less

Biomaterials and Culture Technologies for Regenerative Therapy of Liver Tissue.

PubMed

Perez, Roman A; Jung, Cho-Rok; Kim, Hae-Won

2017-01-01

Regenerative approach has emerged to substitute the current extracorporeal technologies for the treatment of diseased and damaged liver tissue. This is based on the use of biomaterials that modulate the responses of hepatic cells through the unique matrix properties tuned to recapitulate regenerative functions. Cells in liver preserve their phenotype or differentiate through the interactions with extracellular matrix molecules. Therefore, the intrinsic properties of the engineered biomaterials, such as stiffness and surface topography, need to be tailored to induce appropriate cellular functions. The matrix physical stimuli can be combined with biochemical cues, such as immobilized functional groups or the delivered actions of signaling molecules. Furthermore, the external modulation of cells, through cocultures with nonparenchymal cells (e.g., endothelial cells) that can signal bioactive molecules, is another promising avenue to regenerate liver tissue. This review disseminates the recent approaches of regenerating liver tissue, with a focus on the development of biomaterials and the related culture technologies. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bimetallic Metal-Organic Frameworks for Controlled Catalytic Graphitization of Nanoporous Carbons

PubMed Central

Tang, Jing; Salunkhe, Rahul R.; Zhang, Huabin; Malgras, Victor; Ahamad, Tansir; Alshehri, Saad M.; Kobayashi, Naoya; Tominaka, Satoshi; Ide, Yusuke; Kim, Jung Ho; Yamauchi, Yusuke

2016-01-01

Single metal-organic frameworks (MOFs), constructed from the coordination between one-fold metal ions and organic linkers, show limited functionalities when used as precursors for nanoporous carbon materials. Herein, we propose to merge the advantages of zinc and cobalt metals ions into one single MOF crystal (i.e., bimetallic MOFs). The organic linkers that coordinate with cobalt ions tend to yield graphitic carbons after carbonization, unlike those bridging with zinc ions, due to the controlled catalytic graphitization by the cobalt nanoparticles. In this work, we demonstrate a feasible method to achieve nanoporous carbon materials with tailored properties, including specific surface area, pore size distribution, degree of graphitization, and content of heteroatoms. The bimetallic-MOF-derived nanoporous carbon are systematically characterized, highlighting the importance of precisely controlling the properties of the carbon materials. This can be done by finely tuning the components in the bimetallic MOF precursors, and thus designing optimal carbon materials for specific applications. PMID:27471193

Effects of morphology and chemical doping on electrochemical properties of metal hydroxides in pseudocapacitors.

PubMed

Lee, Gyeonghee; Varanasi, Chakrapani V; Liu, Jie

2015-02-21

It is well known that both the structural morphology and chemical doping are important factors that affect the properties of metal hydroxide materials in electrochemical energy storage devices. In this work, an effective method to tailor the morphology and chemical doping of metal hydroxides is developed. It is shown that the morphology and the degree of crystallinity of Ni(OH)2 can be changed by adding glucose in the ethanol-mediated solvothermal synthesis. Ni(OH)2 produced in this manner exhibited an increased specific capacitance, which is partially attributed to its increased surface area. Interestingly, the effect of morphology on cobalt doped-Ni(OH)2 is found to be more effective at low cobalt contents than at high cobalt contents in terms of improving the electrochemical performance. This result reveals the existence of competitive effects between chemical doping and morphology change. These findings will provide important insights to design effective materials for energy storage devices.

Localized conductive patterning via focused electron beam reduction of graphene oxide

NASA Astrophysics Data System (ADS)

Kim, Songkil; Kulkarni, Dhaval D.; Henry, Mathias; Zackowski, Paul; Jang, Seung Soon; Tsukruk, Vladimir V.; Fedorov, Andrei G.

2015-03-01

We report on a method for "direct-write" conductive patterning via reduction of graphene oxide (GO) sheets using focused electron beam induced deposition (FEBID) of carbon. FEBID treatment of the intrinsically dielectric graphene oxide between two metal terminals opens up the conduction channel, thus enabling a unique capability for nanoscale conductive domain patterning in GO. An increase in FEBID electron dose results in a significant increase of the domain electrical conductivity with improving linearity of drain-source current vs. voltage dependence, indicative of a change of graphene oxide electronic properties from insulating to semiconducting. Density functional theory calculations suggest a possible mechanism underlying this experimentally observed phenomenon, as localized reduction of graphene oxide layers via interactions with highly reactive intermediates of electron-beam-assisted dissociation of surface-adsorbed hydrocarbon molecules. These findings establish an unusual route for using FEBID as nanoscale lithography and patterning technique for engineering carbon-based nanomaterials and devices with locally tailored electronic properties.

An overview of poly(lactic-co-glycolic) acid (PLGA)-based biomaterials for bone tissue engineering.

PubMed

Gentile, Piergiorgio; Chiono, Valeria; Carmagnola, Irene; Hatton, Paul V

2014-02-28

Poly(lactic-co-glycolic) acid (PLGA) has attracted considerable interest as a base material for biomedical applications due to its: (i) biocompatibility; (ii) tailored biodegradation rate (depending on the molecular weight and copolymer ratio); (iii) approval for clinical use in humans by the U.S. Food and Drug Administration (FDA); (iv) potential to modify surface properties to provide better interaction with biological materials; and (v) suitability for export to countries and cultures where implantation of animal-derived products is unpopular. This paper critically reviews the scientific challenge of manufacturing PLGA-based materials with suitable properties and shapes for specific biomedical applications, with special emphasis on bone tissue engineering. The analysis of the state of the art in the field reveals the presence of current innovative techniques for scaffolds and material manufacturing that are currently opening the way to prepare biomimetic PLGA substrates able to modulate cell interaction for improved substitution, restoration, or enhancement of bone tissue function.

Tailoring thermal conductivity via three-dimensional porous alumina

PubMed Central

Abad, Begoña; Maiz, Jon; Ruiz-Clavijo, Alejandra; Caballero-Calero, Olga; Martin-Gonzalez, Marisol

2016-01-01

Three-dimensional anodic alumina templates (3D-AAO) are an astonishing framework with open highly ordered three-dimensional skeleton structures. Since these templates are architecturally different from conventional solids or porous templates, they teem with opportunities for engineering thermal properties. By establishing the mechanisms of heat transfer in these frameworks, we aim to create materials with tailored thermal properties. The effective thermal conductivity of an empty 3D-AAO membrane was measured. As the effective medium theory was not valid to extract the skeletal thermal conductivity of 3D-AAO, a simple 3D thermal conduction model was developed, based on a mixed series and parallel thermal resistor circuit, giving a skeletal thermal conductivity value of approximately 1.25 W·m−1·K−1, which matches the value of the ordinary AAO membranes prepared from the same acid solution. The effect of different filler materials as well as the variation of the number of transversal nanochannels and the length of the 3D-AAO membrane in the effective thermal conductivity of the composite was studied. Finally, the thermal conductivity of two 3D-AAO membranes filled with cobalt and bismuth telluride was also measured, which was in good agreement with the thermal model predictions. Therefore, this work proved this structure as a powerful approach to tailor thermal properties. PMID:27934930

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.

Silicon and germanium nanoparticles with tailored surface chemistry as novel inorganic fiber brightening agents.

PubMed

Deb-Choudhury, Santanu; Prabakar, Sujay; Krsinic, Gail; Dyer, Jolon M; Tilley, Richard D

2013-07-31

Low-molecular-weight organic molecules, such as coumarins and stilbenes, are used commercially as fluorescent whitening agents (FWAs) to mask photoyellowing and to brighten colors in fabrics. FWAs achieve this by radiating extra blue light, thus changing the hue and also adding to the brightness. However, organic FWAs can rapidly photodegrade in the presence of ultraviolet (UV) radiation, exacerbating the yellowing process through a reaction involving singlet oxygen species. Inorganic nanoparticles, on the other hand, can provide a similar brightening effect with the added advantage of photostability. We report a targeted approach in designing new inorganic silicon- and germanium-based nanoparticles, functionalized with hydrophilic (amine) surface terminations as novel inorganic FWAs. When applied on wool, by incorporation in a sol-gel Si matrix, the inorganic FWAs improved brightness properties, demonstrated enhanced photostability toward UV radiation, especially the germanium nanoparticles, and also generated considerably lower levels of reactive oxygen species compared to a commercial stilbene-based organic FWA, Uvitex NFW.

Surface plasmon-enhanced optical absorption in monolayer MoS2 with one-dimensional Au grating

NASA Astrophysics Data System (ADS)

Song, Jinlin; Lu, Lu; Cheng, Qiang; Luo, Zixue

2018-05-01

The optical absorption of a composite photonic structure, namely monolayer molybdenum disulfide (MoS2)-covered Au grating, is theoretically investigated using a rigorous coupled-wave analysis algorithm. The enhancement of localized electromagnetic field due to surface plasmon polaritons supported by Au grating can be utilized to enhance the absorption of MoS2. The remarkable enhancement of absorption due to exciton transition can also be realized. When the period of grating is 600 nm, the local absorption of the monolayer MoS2 on Au grating is nearly 7 times higher than the intrinsic absorption due to B exciton transition. A further study reveals that the absorption properties of Au grating can be tailored by altering number of MoS2 layers, changing to a MoS2 nanoribbon array, and inserting a hafnium dioxide (HfO2) spacer. This work will contribute to the design of MoS2-based optical and optoelectronic devices.

Functionalization of polymer powders for SLS-processes using an atmospheric plasma jet in a fluidized bed reactor

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

Sachs, Marius; Schmitt, Adeliene; Schmidt, Jochen

2015-05-22

Recently additive manufacturing processes such as selective laser sintering (SLS) of polymers have gained more importance for industrial applications [1]. Tailor-made modification of polymers is essential in order to make these processes more efficient and to cover the industrial demands. The so far used polymer materials show weak performance regarding the mechanical stability of processed parts. To overcome this limitation, a new route to functionalize the surface of commercially available polymer particles (PA12; PE-HD; PP) using an atmospheric plasma jet in combination with a fluidized bed reactor has been investigated. Consequently, an improvement of adhesion and wettability [2] of themore » polymer surface without restraining the bulk properties of the powder is achieved. The atmospheric plasma jet process can provide reactive species at moderate temperatures which are suitable for polymer material. The functionalization of the polymer powders improves the quality of the devices build in a SLS-process.« less

Cavity-excited Huygens' metasurface antennas for near-unity aperture illumination efficiency from arbitrarily large apertures

PubMed Central

Epstein, Ariel; Wong, Joseph P. S.; Eleftheriades, George V.

2016-01-01

One of the long-standing problems in antenna engineering is the realization of highly directive beams using low-profile devices. In this paper, we provide a solution to this problem by means of Huygens' metasurfaces (HMSs), based on the equivalence principle. This principle states that a given excitation can be transformed to a desirable aperture field by inducing suitable electric and (equivalent) magnetic surface currents. Building on this concept, we propose and demonstrate cavity-excited HMS antennas, where the single-source-fed cavity is designed to optimize aperture illumination, while the HMS facilitates the current distribution that ensures phase purity of aperture fields. The HMS breaks the coupling between the excitation and radiation spectra typical to standard partially reflecting surfaces, allowing tailoring of the aperture properties to produce a desirable radiation pattern, without incurring edge-taper losses. The proposed low-profile design yields near-unity aperture illumination efficiencies from arbitrarily large apertures, offering new capabilities for microwave, terahertz and optical radiators. PMID:26790605

Control and near-field detection of surface plasmon interference patterns.

PubMed

Dvořák, Petr; Neuman, Tomáš; Břínek, Lukáš; Šamořil, Tomáš; Kalousek, Radek; Dub, Petr; Varga, Peter; Šikola, Tomáš

2013-06-12

The tailoring of electromagnetic near-field properties is the central task in the field of nanophotonics. In addition to 2D optics for optical nanocircuits, confined and enhanced electric fields are utilized in detection and sensing, photovoltaics, spatially localized spectroscopy (nanoimaging), as well as in nanolithography and nanomanipulation. For practical purposes, it is necessary to develop easy-to-use methods for controlling the electromagnetic near-field distribution. By imaging optical near-fields using a scanning near-field optical microscope, we demonstrate that surface plasmon polaritons propagating from slits along the metal-dielectric interface form tunable interference patterns. We present a simple way how to control the resulting interference patterns both by variation of the angle between two slits and, for a fixed slit geometry, by a proper combination of laser beam polarization and inhomogeneous far-field illumination of the structure. Thus the modulation period of interference patterns has become adjustable and new variable patterns consisting of stripelike and dotlike motifs have been achieved, respectively.

Wood-Graphene Oxide Composite for Highly Efficient Solar Steam Generation and Desalination.

PubMed

Liu, Keng-Ku; Jiang, Qisheng; Tadepalli, Sirimuvva; Raliya, Ramesh; Biswas, Pratim; Naik, Rajesh R; Singamaneni, Srikanth

2017-03-01

Solar steam generation is a highly promising technology for harvesting solar energy, desalination and water purification. We introduce a novel bilayered structure composed of wood and graphene oxide (GO) for highly efficient solar steam generation. The GO layer deposited on the microporous wood provides broad optical absorption and high photothermal conversion resulting in rapid increase in the temperature at the liquid surface. On the other hand, wood serves as a thermal insulator to confine the photothermal heat to the evaporative surface and to facilitate the efficient transport of water from the bulk to the photothermally active space. Owing to the tailored bilayer structure and the optimal thermo-optical properties of the individual components, the wood-GO composite structure exhibited a solar thermal efficiency of ∼83% under simulated solar excitation at a power density of 12 kW/m 2 . The novel composite structure demonstrated here is highly scalable and cost-efficient, making it an attractive material for various applications involving large light absorption, photothermal conversion and heat localization.

Polysaccharide-derived mesoporous materials (Starbon®) for sustainable separation of complex mixtures.

PubMed

Zuin, Vânia G; Budarin, Vitaliy L; De Bruyn, Mario; Shuttleworth, Peter S; Hunt, Andrew J; Pluciennik, Camille; Borisova, Aleksandra; Dodson, Jennifer; Parker, Helen L; Clark, James H

2017-09-21

The recovery and separation of high value and low volume extractives are a considerable challenge for the commercial realisation of zero-waste biorefineries. Using solid-phase extractions (SPE) based on sustainable sorbents is a promising method to enable efficient, green and selective separation of these complex extractive mixtures. Mesoporous carbonaceous solids derived from renewable polysaccharides are ideal stationary phases due to their tuneable functionality and surface structure. In this study, the structure-separation relationships of thirteen polysaccharide-derived mesoporous materials and two modified types as sorbents for ten naturally-occurring bioactive phenolic compounds were investigated. For the first time, a comprehensive statistical analysis of the key molecular and surface properties influencing the recovery of these species was carried out. The obtained results show the possibility of developing tailored materials for purification, separation or extraction, depending on the molecular composition of the analyte. The wide versatility and application span of these polysaccharide-derived mesoporous materials offer new sustainable and inexpensive alternatives to traditional silica-based stationary phases.

Tailored protein encapsulation into a DNA host using geometrically organized supramolecular interactions

PubMed Central

Sprengel, Andreas; Lill, Pascal; Stegemann, Pierre; Bravo-Rodriguez, Kenny; Schöneweiß, Elisa-C.; Merdanovic, Melisa; Gudnason, Daniel; Aznauryan, Mikayel; Gamrad, Lisa; Barcikowski, Stephan; Sanchez-Garcia, Elsa; Birkedal, Victoria; Gatsogiannis, Christos; Ehrmann, Michael; Saccà, Barbara

2017-01-01

The self-organizational properties of DNA have been used to realize synthetic hosts for protein encapsulation. However, current strategies of DNA–protein conjugation still limit true emulation of natural host–guest systems, whose formation relies on non-covalent bonds between geometrically matching interfaces. Here we report one of the largest DNA–protein complexes of semisynthetic origin held in place exclusively by spatially defined supramolecular interactions. Our approach is based on the decoration of the inner surface of a DNA origami hollow structure with multiple ligands converging to their corresponding binding sites on the protein surface with programmable symmetry and range-of-action. Our results demonstrate specific host–guest recognition in a 1:1 stoichiometry and selectivity for the guest whose size guarantees sufficient molecular diffusion preserving short intermolecular distances. DNA nanocontainers can be thus rationally designed to trap single guest molecules in their native form, mimicking natural strategies of molecular recognition and anticipating a new method of protein caging. PMID:28205515

Gadolinium-modulated 19F signals from Perfluorocarbon Nanoparticles as a New Strategy for Molecular Imaging

PubMed Central

Neubauer, Anne M.; Myerson, Jacob; Caruthers, Shelton D.; Hockett, Franklin D.; Winter, Patrick M.; Chen, Junjie; Gaffney, Patrick J.; Robertson, J. David; Lanza, Gregory M.; Wickline, Samuel A.

2008-01-01

Recent advances in the design of fluorinated nanoparticles for magnetic resonance molecular imaging have enabled specific detection of 19F nuclei, providing unique and quantifiable spectral signatures. However, a pressing need for signal enhancement exists because the total 19F in imaging voxels is often limited. By directly incorporating a relaxation agent (gadolinium) into the lipid monolayer that surrounds the perfluorocarbon, a marked augmentation of the 19F signal from 200nm nanoparticles was achieved. This design increases the magnetic relaxation rate of the 19F nuclei 4-fold at 1.5 T and effects a 125% increase in signal, an effect which is maintained when they are targeted to human plasma clots. By varying the surface concentration of gadolinium, the relaxation effect can be quantitatively modulated to tailor particle properties. This novel strategy dramatically improves the sensitivity and range of 19F MRI/MRS and forms the basis for designing contrast agents capable of sensing their surface chemistry. PMID:18956457

Tailored protein encapsulation into a DNA host using geometrically organized supramolecular interactions

NASA Astrophysics Data System (ADS)

Sprengel, Andreas; Lill, Pascal; Stegemann, Pierre; Bravo-Rodriguez, Kenny; Schöneweiß, Elisa-C.; Merdanovic, Melisa; Gudnason, Daniel; Aznauryan, Mikayel; Gamrad, Lisa; Barcikowski, Stephan; Sanchez-Garcia, Elsa; Birkedal, Victoria; Gatsogiannis, Christos; Ehrmann, Michael; Saccà, Barbara

2017-02-01

The self-organizational properties of DNA have been used to realize synthetic hosts for protein encapsulation. However, current strategies of DNA-protein conjugation still limit true emulation of natural host-guest systems, whose formation relies on non-covalent bonds between geometrically matching interfaces. Here we report one of the largest DNA-protein complexes of semisynthetic origin held in place exclusively by spatially defined supramolecular interactions. Our approach is based on the decoration of the inner surface of a DNA origami hollow structure with multiple ligands converging to their corresponding binding sites on the protein surface with programmable symmetry and range-of-action. Our results demonstrate specific host-guest recognition in a 1:1 stoichiometry and selectivity for the guest whose size guarantees sufficient molecular diffusion preserving short intermolecular distances. DNA nanocontainers can be thus rationally designed to trap single guest molecules in their native form, mimicking natural strategies of molecular recognition and anticipating a new method of protein caging.

Flexible power fabrics made of carbon nanotubes for harvesting thermoelectricity.

PubMed

Kim, Suk Lae; Choi, Kyungwho; Tazebay, Abdullah; Yu, Choongho

2014-03-25

Thermoelectric energy conversion is very effective in capturing low-grade waste heat to supply electricity particularly to small devices such as sensors, wireless communication units, and wearable electronics. Conventional thermoelectric materials, however, are often inadequately brittle, expensive, toxic, and heavy. We developed both p- and n-type fabric-like flexible lightweight materials by functionalizing the large surfaces and junctions in carbon nanotube (CNT) mats. The poor thermopower and only p-type characteristics of typical CNTs have been converted into both p- and n-type with high thermopower. The changes in the electronic band diagrams of the CNTs were experimentally investigated, elucidating the carrier type and relatively large thermopower values. With our optimized device design to maximally utilize temperature gradients, an electrochromic glucose sensor was successfully operated without batteries or external power supplies, demonstrating self-powering capability. While our fundamental study provides a method of tailoring electronic transport properties, our device-level integration shows the feasibility of harvesting electrical energy by attaching the device to even curved surfaces like human bodies.

The adsorption of tetracycline and vancomycin onto nanodiamond with controlled release.

PubMed

Giammarco, James; Mochalin, Vadym N; Haeckel, James; Gogotsi, Yury

2016-04-15

The unique properties and tailorable surface of detonation nanodiamonds have given rise to an abundance of potential biomedical applications. Very little is known about the details of adsorption/desorption equilibria of drugs on/from nanodiamonds with different purity, surface chemistry, and agglomeration state. The studies presented here delve into the details of adsorption and desorption of tetracycline (TET) and vancomycin (VAN) on nanodiamond, which are critically important for the rational design of the nanodiamond drug delivery systems. The nanodiamonds studied in these experiments were as-received (ND), purified and carboxyl terminated (ND-COOH), and aminated (ND-NH2). The monolayer capacities of the drugs loaded onto the nanodiamonds are reported herein using Langmuir and Freundlich isotherm models. The results from the desorption studies demonstrate that, by changing the pH environment of drug loaded nanodiamond using buffers of pH 4.09, 7.45, 8.02, and a phosphate buffered saline (PBS) solution, the drug release can effectively be triggered. Copyright © 2016 Elsevier Inc. All rights reserved.

Characterization and electrochemical application of carbon materials based on poly(phenylene oxide)

NASA Astrophysics Data System (ADS)

Gray, Hunter

Carbon materials possess excellent electrical and surface properties for the next generation of energy storage devices. Polymers provide a carbon rich and tailorable precursor for the production of carbon materials. Therefore, activated carbons were prepared from poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) via a three step process: thermal oxidation, carbonization, and activation with KOH. The activated carbons are predominately microporous with BET specific surface areas up to 2638 m2/g. Impedance spectroscopy revealed these carbons possess electrical conductivities comparable to commercial carbon blacks and consequently were employed in thin-film composite electrodes in electrochemical double-layer capacitors. Cyclic voltammetry confirmed maximum specific capacitances of 13.23 F/g and 2.848 F/g for aqueous and organic electrolyte systems, respectively. Additionally, carbon nanotubes were synthesized from PPO and other polymers with a nickel catalyst via chemical vapor deposition as revealed by transmission electron microscopy. This is the first report of carbon nanotubes produced from PPO.

Cavity-excited Huygens' metasurface antennas for near-unity aperture illumination efficiency from arbitrarily large apertures.

PubMed

Epstein, Ariel; Wong, Joseph P S; Eleftheriades, George V

2016-01-21

One of the long-standing problems in antenna engineering is the realization of highly directive beams using low-profile devices. In this paper, we provide a solution to this problem by means of Huygens' metasurfaces (HMSs), based on the equivalence principle. This principle states that a given excitation can be transformed to a desirable aperture field by inducing suitable electric and (equivalent) magnetic surface currents. Building on this concept, we propose and demonstrate cavity-excited HMS antennas, where the single-source-fed cavity is designed to optimize aperture illumination, while the HMS facilitates the current distribution that ensures phase purity of aperture fields. The HMS breaks the coupling between the excitation and radiation spectra typical to standard partially reflecting surfaces, allowing tailoring of the aperture properties to produce a desirable radiation pattern, without incurring edge-taper losses. The proposed low-profile design yields near-unity aperture illumination efficiencies from arbitrarily large apertures, offering new capabilities for microwave, terahertz and optical radiators.

Electron beam irradiation impact on surface structure and wettability of ethylene-vinyl alcohol copolymer

NASA Astrophysics Data System (ADS)

El-Saftawy, A. A.; Ragheb, M. S.; Zakhary, S. G.

2018-06-01

In the present study, electron beam (EB) is utilized to tailor the surface structure and wetting behavior of ethylene-vinyl alcohol (EVOH) copolymer. The structural deformation is examined by x-ray diffractometer (XRD). The recorded patterns reveal the formation of disordered systems on the irradiated surface. Also, the surface crystallinity degree, crystallite size, and micro-strain are studied. The microstructure induced modifications of the irradiated samples are investigated by 1-dimensional proton nuclear magnetic resonance 1H NMR spectroscopic analysis. The recorded spectra showed that the hydroxyl group (O-H) absorption intensity, enhanced compared to that of methylene (-CH2) and methine (>C-H) groups. Likewise, the changes of the polymer surface chemistry are studied by Fourier transform infrared spectroscopy (FTIR) and showed that the surface polarity improved after irradiation. The contact angle method is used to prove the surface wettability improvements after irradiation. Additionally, the fucoidan-coated samples exhibit great enhancements in surface wettability and have a reduced recovery effect compared to the uncoated samples. The surface free energy and bonding adhesion are studied as well. The fucoidan-coated samples are found to have a larger adhesion strength than that of the EVOH samples (pristine and irradiated). Finally, surface morphology and roughness are traced by atomic force microscopy (AFM). The improvements in surface wettability and adhesion are attributed to the modified surface roughness and the increased surface polarity. To sum up, combining EB irradiation and fucoidan enhance the surface wettability of EVOH in a controlled way keeping the bulk properties unaffected.

Concurrent micromechanical tailoring and fabrication process optimization for metal-matrix composites

NASA Technical Reports Server (NTRS)

Morel, M.; Saravanos, D. A.; Chamis, Christos C.

1990-01-01

A method is presented to minimize the residual matrix stresses in metal matrix composites. Fabrication parameters such as temperature and consolidation pressure are optimized concurrently with the characteristics (i.e., modulus, coefficient of thermal expansion, strength, and interphase thickness) of a fiber-matrix interphase. By including the interphase properties in the fabrication process, lower residual stresses are achievable. Results for an ultra-high modulus graphite (P100)/copper composite show a reduction of 21 percent for the maximum matrix microstress when optimizing the fabrication process alone. Concurrent optimization of the fabrication process and interphase properties show a 41 percent decrease in the maximum microstress. Therefore, this optimization method demonstrates the capability of reducing residual microstresses by altering the temperature and consolidation pressure histories and tailoring the interphase properties for an improved composite material. In addition, the results indicate that the consolidation pressures are the most important fabrication parameters, and the coefficient of thermal expansion is the most critical interphase property.

Syringyl Methacrylate, a Hardwood Lignin-Based Monomer for High-Tg Polymeric Materials.

PubMed

Holmberg, Angela L; Reno, Kaleigh H; Nguyen, Ngoc A; Wool, Richard P; Epps, Thomas H

2016-05-17

As viable precursors to a diverse array of macromolecules, biomass-derived compounds must impart wide-ranging and precisely controllable properties to polymers. Herein, we report the synthesis and subsequent reversible addition-fragmentation chain-transfer polymerization of a new monomer, syringyl methacrylate (SM, 2,6-dimethoxyphenyl methacrylate), that can facilitate widespread property manipulations in macromolecules. Homopolymers and heteropolymers synthesized from SM and related monomers have broadly tunable and highly controllable glass transition temperatures ranging from 114 to 205 °C and zero-shear viscosities ranging from ∼0.2 kPa·s to ∼17,000 kPa·s at 220 °C, with consistent thermal stabilities. The tailorability of these properties is facilitated by the controlled polymerization kinetics of SM and the fact that one vs two o -methoxy groups negligibly affect monomer reactivity. Moreover, syringol, the precursor to SM, is an abundant component of depolymerized hardwood (e.g., oak) and graminaceous (e.g., switchgrass) lignins, making SM a potentially sustainable and low-cost candidate for tailoring macromolecular properties.

Comparative surface dynamics of amorphous and semicrystalline polymer films

PubMed Central

Becker, James S.; Brown, Ryan D.; Killelea, Daniel R.; Yuan, Hanqiu; Sibener, S. J.

2011-01-01

The surface dynamics of amorphous and semicrystalline polymer films have been measured using helium atom scattering. Time-of-flight data were collected to resolve the elastic and inelastic scattering components in the diffuse scattering of neutral helium atoms from the surface of a thin poly(ethylene terephthalate) film. Debye–Waller attenuation was observed for both the amorphous and semicrystalline phases of the polymer by recording the decay of elastically scattered helium atoms with increasing surface temperature. Thermal attenuation measurements in the specular scattering geometry yielded perpendicular mean-square displacements of 2.7•10-4 Å2 K-1 and 3.1•10-4 Å2 K-1 for the amorphous and semicrystalline surfaces, respectively. The semicrystalline surface was consistently ∼15% softer than the amorphous across a variety of perpendicular momentum transfers. The Debye–Waller factors were also measured at off-specular angles to characterize the parallel mean-square displacements, which were found to increase by an order of magnitude over the perpendicular mean-square displacements for both surfaces. In contrast to the perpendicular motion, the semicrystalline state was ∼25% stiffer than the amorphous phase in the surface plane. These results were uniquely accessed through low-energy neutral helium atom scattering due to the highly surface-sensitive and nonperturbative nature of these interactions. The goal of tailoring the chemical and physical properties of complex advanced materials requires an improved understanding of interfacial dynamics, information that is obtainable through atomic beam scattering methods. PMID:20713734

Tailoring the structure of metal oxide nanostructures towards enhanced sensing properties for environmental applications.

PubMed

Yang, Mingqing; He, Junhui

2012-02-15

The present article reviews recent works in our laboratory about the sensing properties to toxic gases using nanostructured WO(3), TiO(2), FTiO(2), and CuO functionalized quartz crystal microbalance (QCM) sensors. WO(3) and TiO(2) functionalized QCM sensors have much shorter response time than those functionalized by conventional hydrogen-bond acidic branched copolymers for detection of dimethyl methylphosphonate (DMMP). FTiO(2) functionalized QCM sensors can improve the gas sensing characteristics by shortening the response time but at the price of partial irreversibility. The sensing mechanism was examined by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Varied CuO nanostructures were synthesized by simple modulation of reaction conditions. All the as-prepared CuO was applied on QCM resonators and explored for HCN sensing. Surprisingly, responses of all the sensors to HCN were found to be in an opposite direction as compared with other common volatile substances, offering excellent selectivity for HCN detection. The sensitivity was very high, and the response and recovery were very fast. Comparison of the specific surface areas of CuO nanostructures showed that CuO of higher surface area is more sensitive than that of lower surface area, indicating that the specific surface area of these CuO nanostructures plays an important role in the sensitivity of related sensors. Based on experimental results, a sensing mechanism was proposed in which a surface redox reaction occurs between CuO and Cu(2)O on the CuO nanostructures reversibly upon contact with HCN and air, respectively. The CuO functionalized QCM sensors are considered to be a promising candidate for trace HCN gas detection in practical applications. Copyright © 2011 Elsevier Inc. All rights reserved.

Targeted ENO schemes with tailored resolution property for hyperbolic conservation laws

NASA Astrophysics Data System (ADS)

Fu, Lin; Hu, Xiangyu Y.; Adams, Nikolaus A.

2017-11-01

In this paper, we extend the range of targeted ENO (TENO) schemes (Fu et al. (2016) [18]) by proposing an eighth-order TENO8 scheme. A general formulation to construct the high-order undivided difference τK within the weighting strategy is proposed. With the underlying scale-separation strategy, sixth-order accuracy for τK in the smooth solution regions is designed for good performance and robustness. Furthermore, a unified framework to optimize independently the dispersion and dissipation properties of high-order finite-difference schemes is proposed. The new framework enables tailoring of dispersion and dissipation as function of wavenumber. The optimal linear scheme has minimum dispersion error and a dissipation error that satisfies a dispersion-dissipation relation. Employing the optimal linear scheme, a sixth-order TENO8-opt scheme is constructed. A set of benchmark cases involving strong discontinuities and broadband fluctuations is computed to demonstrate the high-resolution properties of the new schemes.

Elucidation of Peptide-Directed Palladium Surface Structure for Biologically Tunable Nanocatalysts

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

Bedford, Nicholas M.; Ramezani-Dakhel, Hadi; Slocik, Joseph M.

Peptide-enabled synthesis of inorganic nanostructures represents an avenue to access catalytic materials with tunable and optimized properties. This is achieved via peptide complexity and programmability that is missing in traditional ligands for catalytic nanomaterials. Unfortunately, there is limited information available to correlate peptide sequence to particle structure and catalytic activity to date. As such, the application of peptide-enabled nanocatalysts remains limited to trial and error approaches. In this paper, a hybrid experimental and computational approach is introduced to systematically elucidate biomolecule-dependent structure/function relationships for peptide-capped Pd nanocatalysts. Synchrotron X-ray techniques were used to uncover substantial particle surface structural disorder, whichmore » was dependent upon the amino acid sequence of the peptide capping ligand. Nanocatalyst configurations were then determined directly from experimental data using reverse Monte Carlo methods and further refined using molecular dynamics simulation, obtaining thermodynamically stable peptide-Pd nanoparticle configurations. Sequence-dependent catalytic property differences for C-C coupling and olefin hydrogenation were then eluddated by identification of the catalytic active sites at the atomic level and quantitative prediction of relative reaction rates. This hybrid methodology provides a clear route to determine peptide-dependent structure/function relationships, enabling the generation of guidelines for catalyst design through rational tailoring of peptide sequences« less

High-energy radiation and polymers: A review of commercial processes and emerging applications

NASA Astrophysics Data System (ADS)

Clough, R. L.

2001-12-01

Ionizing radiation has been found to be widely applicable in modifying the structure and properties of polymers, and can be used to tailor the performance of either bulk materials or surfaces. Fifty years of research in polymer radiation chemistry has led to numerous applications of commercial and economic importance, and work remains active in the application of radiation to practical uses involving polymeric materials. This paper provides a survey of radiation-processing methods of industrial interest, ranging from technologies already commercially well established, through innovations in the active R&D stage which show exceptional promise for future commercial use. Radiation-processing technologies are discussed under the following categories: cross-linking of plastics and rubbers, curing of coatings and inks, heat-shrink products, fiber-matrix composites, chain-scission for processing control, surface modification, grafting, hydrogels, sterilization, natural product enhancement, plastics recycling, ceramic precursors, electronic property materials, ion-track membranes and lithography for microdevice production. In addition to new technological innovations utilizing conventional gamma and e-beam sources, a number of promising new applications make use of novel radiation types which include ion beams (heavy ions, light ions, highly focused microscopic beams and high-intensity pulses), soft X-rays which are focused, coherent X-rays (from a synchrotron) and e-beams which undergo scattering to generate patterns.

Design Rules for Tailoring Antireflection Properties of Hierarchical Optical Structures

DOE PAGES

Leon, Juan J. Diaz; Hiszpanski, Anna M.; Bond, Tiziana C.; ...

2017-05-18

Hierarchical structures consisting of small sub-wavelength features stacked atop larger structures have been demonstrated as an effective means of reducing the reflectance of surfaces. However, optical devices require different antireflective properties depending on the application, and general unifying guidelines on hierarchical structures' design to attain a desired antireflection spectral response are still lacking. The type of reflectivity (diffuse, specular, or total/hemispherical) and its angular- and spectral-dependence are all dictated by the structural parameters. Through computational and experimental studies, guidelines have been devised to modify these various aspects of reflectivity across the solar spectrum by proper selection of the features ofmore » hierarchical structures. In this wavelength regime, micrometer-scale substructures dictate the long-wavelength spectral response and effectively reduce specular reflectance, whereas nanometer-scale substructures dictate primarily the visible wavelength spectral response and reduce diffuse reflectance. Coupling structures having these two length scales into hierarchical arrays impressively reduces surfaces' hemispherical reflectance across a broad spectrum of wavelengths and angles. Furthermore, such hierarchical structures in silicon are demonstrated having an average total reflectance across the solar spectrum of 1.1% (average weighted reflectance of 1% in the 280–2500 nm range of the AM 1.5 G spectrum) and specular reflectance <1% even at angles of incidence as high as 67°.« less

Internal-Modified Dithiol DNA-Directed Au Nanoassemblies: Geometrically Controlled Self-Assembly and Quantitative Surface-Enhanced Raman Scattering Properties

NASA Astrophysics Data System (ADS)

Yan, Yuan; Shan, Hangyong; Li, Min; Chen, Shu; Liu, Jianyu; Cheng, Yanfang; Ye, Cui; Yang, Zhilin; Lai, Xuandi; Hu, Jianqiang

2015-11-01

In this work, a hierarchical DNA-directed self-assembly strategy to construct structure-controlled Au nanoassemblies (NAs) has been demonstrated by conjugating Au nanoparticles (NPs) with internal-modified dithiol single-strand DNA (ssDNA) (Au-B-A or A-B-Au-B-A). It is found that the dithiol-ssDNA-modified Au NPs and molecule quantity of thiol-modified ssDNA grafted to Au NPs play critical roles in the assembly of geometrically controlled Au NAs. Through matching Au-DNA self-assembly units, geometrical structures of the Au NAs can be tailored from one-dimensional (1D) to quasi-2D and 2D. Au-B-A conjugates readily give 1D and quasi-2D Au NAs while 2D Au NAs can be formed by A-B-Au-B-A building blocks. Surface-enhanced Raman scattering (SERS) measurements and 3D finite-difference time domain (3D-FDTD) calculation results indicate that the geometrically controllable Au NAs have regular and linearly “hot spots”-number-depended SERS properties. For a certain number of NPs, the number of “hot spots” and accordingly enhancement factor of Au NAs can be quantitatively evaluated, which open a new avenue for quantitative analysis based on SERS technique.

3D-printed conductive static mixers enable all-vanadium redox flow battery using slurry electrodes

NASA Astrophysics Data System (ADS)

Percin, Korcan; Rommerskirchen, Alexandra; Sengpiel, Robert; Gendel, Youri; Wessling, Matthias

2018-03-01

State-of-the-art all-vanadium redox flow batteries employ porous carbonaceous materials as electrodes. The battery cells possess non-scalable fixed electrodes inserted into a cell stack. In contrast, a conductive particle network dispersed in the electrolyte, known as slurry electrode, may be beneficial for a scalable redox flow battery. In this work, slurry electrodes are successfully introduced to an all-vanadium redox flow battery. Activated carbon and graphite powder particles are dispersed up to 20 wt% in the vanadium electrolyte and charge-discharge behavior is inspected via polarization studies. Graphite powder slurry is superior over activated carbon with a polarization behavior closer to the standard graphite felt electrodes. 3D-printed conductive static mixers introduced to the slurry channel improve the charge transfer via intensified slurry mixing and increased surface area. Consequently, a significant increase in the coulombic efficiency up to 95% and energy efficiency up to 65% is obtained. Our results show that slurry electrodes supported by conductive static mixers can be competitive to state-of-the-art electrodes yielding an additional degree of freedom in battery design. Research into carbon properties (particle size, internal surface area, pore size distribution) tailored to the electrolyte system and optimization of the mixer geometry may yield even better battery properties.

Elucidation of peptide-directed palladium surface structure for biologically tunable nanocatalysts.

PubMed

Bedford, Nicholas M; Ramezani-Dakhel, Hadi; Slocik, Joseph M; Briggs, Beverly D; Ren, Yang; Frenkel, Anatoly I; Petkov, Valeri; Heinz, Hendrik; Naik, Rajesh R; Knecht, Marc R

2015-05-26

Peptide-enabled synthesis of inorganic nanostructures represents an avenue to access catalytic materials with tunable and optimized properties. This is achieved via peptide complexity and programmability that is missing in traditional ligands for catalytic nanomaterials. Unfortunately, there is limited information available to correlate peptide sequence to particle structure and catalytic activity to date. As such, the application of peptide-enabled nanocatalysts remains limited to trial and error approaches. In this paper, a hybrid experimental and computational approach is introduced to systematically elucidate biomolecule-dependent structure/function relationships for peptide-capped Pd nanocatalysts. Synchrotron X-ray techniques were used to uncover substantial particle surface structural disorder, which was dependent upon the amino acid sequence of the peptide capping ligand. Nanocatalyst configurations were then determined directly from experimental data using reverse Monte Carlo methods and further refined using molecular dynamics simulation, obtaining thermodynamically stable peptide-Pd nanoparticle configurations. Sequence-dependent catalytic property differences for C-C coupling and olefin hydrogenation were then elucidated by identification of the catalytic active sites at the atomic level and quantitative prediction of relative reaction rates. This hybrid methodology provides a clear route to determine peptide-dependent structure/function relationships, enabling the generation of guidelines for catalyst design through rational tailoring of peptide sequences.

Imaging of conformational changes

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

Michl, Josef

2016-03-13

Control of intramolecular conformational change in a small number of molecules or even a single one by an application of an outside electric field defined by potentials on nearby metal or dielectric surfaces has potential applications in both 3-D and 2-D nanotechnology. Specifically, the synthesis, characterization, and understanding of designed solids with controlled built-in internal rotational motion of a dipole promises a new class of materials with intrinsic dielectric, ferroelectric, optical and optoelectronic properties not found in nature. Controlled rotational motion is of great interest due to its expected utility in phenomena as diverse as transport, current flow in molecularmore » junctions, diffusion in microfluidic channels, and rotary motion in molecular machines. A direct time-resolved observation of the dynamics of motion on ps or ns time scale in a single molecule would be highly interesting but is also very difficult and has yet to be accomplished. Much can be learned from an easier but still challenging comparison of directly observed initial and final orientational states of a single molecule, which is the basis of this project. The project also impacts the understanding of surface-enhanced Raman spectroscopy (SERS) and single-molecule spectroscopic detection, as well as the synthesis of solid-state materials with tailored properties from designed precursors.« less

Restored in vivo-like membrane lipidomics positively influence in vitro features of cultured mesenchymal stromal/stem cells derived from human placenta.

PubMed

Chatgilialoglu, Alexandros; Rossi, Martina; Alviano, Francesco; Poggi, Paola; Zannini, Chiara; Marchionni, Cosetta; Ricci, Francesca; Tazzari, Pier Luigi; Taglioli, Valentina; Calder, Philip C; Bonsi, Laura

2017-02-07

The study of lipid metabolism in stem cell physiology has recently raised great interest. The role of lipids goes beyond the mere structural involvement in assembling extra- and intra-cellular compartments. Nevertheless, we are still far from understanding the impact of membrane lipidomics in stemness maintenance and differentiation patterns. In the last years, it has been reported how in vitro cell culturing can modify membrane lipidomics. The aim of the present work was to study the membrane fatty acid profile of mesenchymal stromal cells (MSCs) derived from human fetal membranes (hFM-MSCs) and to correlate this to specific biological properties by using chemically defined tailored lipid supplements (Refeed®). Freshly isolated hFM-MSCs were characterized for their membrane fatty acid composition. hFM-MSCs were cultivated in vitro following a classical protocol and their membrane fatty acid profile at different passages was compared to the profile in vivo. A tailored Refeed® lipid supplement was developed with the aim of reducing the differences created by the in vitro cultivation and was tested on cultured hFM-MSCs. Cell morphology, viability, proliferation, angiogenic differentiation, and immunomodulatory properties after in vitro exposure to the tailored Refeed® lipid supplement were investigated. A significant modification of hFM-MSC membrane fatty acid composition occurred during in vitro culture. Using a tailored lipid supplement, the fatty acid composition of cultured cells remained more similar to their in vivo counterparts, being characterized by a higher polyunsaturated and omega-6 fatty acid content. These changes in membrane composition had no effect on cell morphology and viability, but were linked with increased cell proliferation rate, angiogenic differentiation, and immunomodulatory properties. In particular, Refeed®-supplemented hFM-MSCs showed greater ability to express fully functional cell membrane molecules. Culturing hFM-MSCs alters their fatty acid composition. A tailored lipid supplement is able to improve in vitro hFM-MSC functional properties by recreating a membrane environment more similar to the physiological counterpart. This approach should be considered in cell therapy applications in order to maintain a higher cell quality during in vitro passaging and to influence the outcome of cell-based therapeutic approaches when cells are administered to patients.

Coatings with controlled porosity and chemical properties

DOEpatents

Frye, Gregory C.; Brinker, C. Jeffrey; Doughty, Daniel H.; Bein, Thomas; Moller, Karin

1996-01-01

Coatings and sensors having both steric and chemical selectivity. Controlled porosity provides the steric selectivity, whereas chemically tailored film properties, using controlled composition or modification by coupling agents, chemical species replacement, or chemical species within pores, provide the chemical selectivity. Single or multiple layers may be provided.

Coatings with controlled porosity and chemical properties

DOEpatents

Frye, Gregory C.; Brinker, C. Jeffrey; Doughty, Daniel H.; Bein, Thomas; Moller, Karin

1993-01-01

Coatings and sensors having both steric and chemical selectivity. Controlled porosity provides the steric selectivity, whereas chemically tailored film properties, using controlled composition or modification by coupling agents, chemical species replacement, or chemical species within pores, provide the chemical selectivity. Single or multiple layers may be provided.

Phased laser array with tailored spectral and coherence properties

DOEpatents

Messerly, Michael J [Danville, CA; Dawson, Jay W [Livermore, CA; Beach, Raymond J [Livermore, CA

2011-03-29

Architectures for coherently combining an array of fiber-based lasers are provided. By matching their lengths to within a few integer multiples of a wavelength, the spatial and temporal properties of a single large laser are replicated, while extending the average or peak pulsed power limit.

Phased laser array with tailored spectral and coherence properties

DOEpatents

Messerly, Michael J; Dawson, Jay W; Beach, Raymond J

2014-05-20

Architectures for coherently combining an array of fiber-based lasers are provided. By matching their lengths to within a few integer multiples of a wavelength, the spatial and temporal properties of a single large laser are replicated, while extending the average or peak pulsed power limit.

Cation coordination reactions on nanocrystals: surface/interface, doping control and advanced photocatalysis applications (Conference Presentation)

NASA Astrophysics Data System (ADS)

Zhang, Jiatao

2016-10-01

Abstract: Including the shape and size effect, the controllable doping, hetero-composite and surface/interface are the prerequisite of colloidal nanocrystals for exploring their optoelectronic properties, such as fluorescence, plasmon-exciton coupling, efficient electron/hole separation, and enhanced photocatalysis applications. By controlling soft acid-base coordination reactions between cation molecular complexes and colloidal nanocrystals, we showed that chemical thermodynamics could drive nanoscale monocrystalline growth of the semiconductor shell on metal nano-substrates and the substitutional heterovalent doping in semiconductor nanocrystals. We have demonstrated evolution of relative position of Au and II-VI semiconductor in Au-Semi from symmetric to asymmetric configuration, different phosphines initiated morphology engineering, oriented attachment of quantum dots into micrometer nanosheets with synergistic control of surface/interface and doing, which can further lead to fine tuning of plasmon-exciton coupling. Therefore, different hydrogen photocatalytic performance, Plasmon enhanced photocatalysis properties have been achieved further which lead to the fine tuning of plasmon-exciton coupling. Substitutional heterovalent doping here enables the tailoring of optical, electronic properties and photocatalysis applications of semiconductor nanocrystals because of electronic impurities (p-, n-type doping) control. References: (1) J. Gui, J. Zhang*, et al. Angew. Chem. Int. Ed. 2015, 54, 3683. (2) Q. Zhao, J. Zhang*, etc., Adv. Mater. 2014, 26, 1387. (3) J. Liu, Q. Zhao, S. G. Wang*, J. Zhang*, etc., Adv. Mater. 2015, 27-2753-2761. (4) H. Qian, J. Zhang*, etc., NPG Asia Mater. (2015) 7, e152. (5) M. Ji, M. Xu, etc., J. Zhang*, Adv. Mater. 2016, in proof. (6) S. Yu, J. T. Zhang, Y. Tang, M. Ouyang*, Nano Lett. 2015, 15, 6282-6288. (7) J. Zhang, Y. Tang, K. Lee and M. Ouyang*, Science 2010, 327, 1634. (8) J. Zhang, Y. Tang, K. Lee, M. Ouyang*, Nature 2010, 466, 91.

Effect of solid surface charge on the binding behaviour of a metal-binding peptide

PubMed Central

Donatan, Senem; Sarikaya, Mehmet; Tamerler, Candan; Urgen, Mustafa

2012-01-01

Over the last decade, solid-binding peptides have been increasingly used as molecular building blocks coupling bio- and nanotechnology. Despite considerable research being invested in this field, the effects of many surface-related parameters that define the binding of peptide to solids are still unknown. In the quest to control biological molecules at solid interfaces and, thereby, tailoring the binding characteristics of the peptides, the use of surface charge of the solid surface may probably play an important role, which then can be used as a potential tuning parameter of peptide adsorption. Here, we report quantitative investigation on the viscoelastic properties and binding kinetics of an engineered gold-binding peptide, 3RGBP1, adsorbed onto the gold surface at different surface charge densities. The experiments were performed in aqueous solutions using an electrochemical dissipative quartz crystal microbalance system. Hydrodynamic mass, hydration state and surface coverage of the adsorbed peptide films were determined as a function of surface charge density of the gold metal substrate. Under each charged condition, binding of 3rGBP1 displayed quantitative differences in terms of adsorbed peptide amount, surface coverage ratio and hydration state. Based on the intrinsically disordered structure of the peptide, we propose a possible mechanism for binding of the peptide that can be used for tuning surface adsorption in further studies. Controlled alteration of peptide binding on solid surfaces, as shown here, may provide novel methods for surface functionalization used for bioenabled processing and fabrication of future micro- and nanodevices. PMID:22491974

Toward tunable doping in graphene FETs by molecular self-assembled monolayers

NASA Astrophysics Data System (ADS)

Li, Bing; Klekachev, Alexander V.; Cantoro, Mirco; Huyghebaert, Cedric; Stesmans, André; Asselberghs, Inge; de Gendt, Stefan; de Feyter, Steven

2013-09-01

In this paper, we report the formation of self-assembled monolayers (SAMs) of oleylamine (OA) on highly oriented pyrolytic graphite (HOPG) and graphene surfaces and demonstrate the potential of using such organic SAMs to tailor the electronic properties of graphene. Molecular resolution Atomic Force Microscopy (AFM) and Scanning Tunneling Microscopy (STM) images reveal the detailed molecular ordering. The electrical measurements show that OA strongly interacts with graphene leading to n-doping effects in graphene devices. The doping levels are tunable by varying the OA deposition conditions. Importantly, neither hole nor electron mobilities are decreased by the OA modification. As a benefit from this noncovalent modification strategy, the pristine characteristics of the device are recoverable upon OA removal. From this study, one can envision the possibility to correlate the graphene-based device performance with the molecular structure and supramolecular ordering of the organic dopant.In this paper, we report the formation of self-assembled monolayers (SAMs) of oleylamine (OA) on highly oriented pyrolytic graphite (HOPG) and graphene surfaces and demonstrate the potential of using such organic SAMs to tailor the electronic properties of graphene. Molecular resolution Atomic Force Microscopy (AFM) and Scanning Tunneling Microscopy (STM) images reveal the detailed molecular ordering. The electrical measurements show that OA strongly interacts with graphene leading to n-doping effects in graphene devices. The doping levels are tunable by varying the OA deposition conditions. Importantly, neither hole nor electron mobilities are decreased by the OA modification. As a benefit from this noncovalent modification strategy, the pristine characteristics of the device are recoverable upon OA removal. From this study, one can envision the possibility to correlate the graphene-based device performance with the molecular structure and supramolecular ordering of the organic dopant. Electronic supplementary information (ESI) available: AFM images of self-assembled monolayers of OA on HOPG; AFM height image of the graphene surface on a SiC substrate; high resolution STM image of a self-assembled monolayer of OA on HOPG; transfer curves of a graphene FET with and without baking steps; transfer curves of a graphene FET under high vacuum conditions; transfer curves of a graphene FET and its Raman response before and after OA treatment; transfer curves of a graphene FET before and after rinsing with n-hexane. See DOI: 10.1039/c3nr01255g

Core-shell quantum dots tailor the fluorescence of dental resin composites.

PubMed

Alves, Leandro P; Pilla, Viviane; Murgo, Dírian O A; Munin, Egberto

2010-02-01

We characterized the optical properties, such as absorbance and fluorescence, of dental resins containing quantum dots (QD). We also determined the doping level needed to obtain a broad and nearly flat emission spectrum that provides the perception of white color. The samples studied were resin composites from Charisma (Heraeus Kulzer) prepared with CdSe/ZnS core-shell QD (0.05-0.77 mass%). The results showed that the fluorescence of dental resin composites can be tailored by using CdSe/ZnS core-shell quantum dots. QD core incorporation into dental resins allows the fabrication of restorative materials with fluorescence properties that closely match those of natural human teeth. Copyright 2009 Elsevier Ltd. All rights reserved.

Dual-peak long-period fiber gratings with enhanced refractive index sensitivity by finely tailored mode dispersion that uses the light cladding etching technique.

PubMed

Chen, Xianfeng; Zhou, Kaiming; Zhang, Lin; Bennion, Ian

2007-02-01

We have experimentally investigated the mode dispersion property and refractive index sensitivity of dual-peak long-period fiber gratings (LPGs) that were sensitized by hydrofluoric acid (HF) etching. The nature of the coupled cladding modes close to the dispersion turning point makes the dual-peak LPGs ultrasensitive to cladding property, permitting a fine tailoring of the mode dispersion and index sensitivity by the light cladding etching method using HF acid of only 1% concentration. As an implementation of an optical biosensor, the etched device was used to detect the concentration of hemoglobin protein in a sugar solution, showing a sensitivity as high as 20 nm/1%.

Au-Ag-Cu nano-alloys: tailoring of permittivity

NASA Astrophysics Data System (ADS)

Hashimoto, Yoshikazu; Seniutinas, Gediminas; Balčytis, Armandas; Juodkazis, Saulius; Nishijima, Yoshiaki

2016-04-01

Precious metal alloys enables new possibilities to tailor materials for specific optical functions. Here we present a systematic study of the effects of a nanoscale alloying on the permittivity of Au-Ag-Cu metals at 38 different atomic mixing ratios. The permittivity was measured and analyzed numerically by applying the Drude model. X-ray diffraction (XRD) revealed the face centered cubic lattice of the alloys. Both, optical spectra and XRD results point towards an equivalent composition-dependent electron scattering behavior. Correlation between the fundamental structural parameters of alloys and the resulting optical properties is elucidated. Plasmonic properties of the Au-Ag-Cu alloy nanoparticles were investigated by numerical simulations. Guidelines for designing plasmonic response of nano- structures and their patterns are presented from the material science perspective.

Engineering the performance of mixed matrix membranes for gas separations

NASA Astrophysics Data System (ADS)

Shu, Shu

Mixed matrix membranes that comprise domains of organic and inorganic components are investigated in this research. Such materials effectively circumvent the polymeric 'upper bound trade-off curve' and show properties highly attractive for industrial gas separations. Nevertheless, lack of intrinsic compatibility between the organic polymers and inorganic fillers poses the biggest challenge to successful fabrication of mixed matrix membranes. Consequently, control of the nanoscale interface between the sieve and polymer has been the key technical challenge to the implementation of composite membrane materials. The overarching goal of this research was to devise and explore approaches to enhance the performance of mixed matrix membranes by properly tailoring the sieve/polymer interface. In an effort to pursue the aforementioned objective, three approaches were developed and inspected: (i) use of silane coupling agents, (ii) hydrophobizing of sieve surface through alcohol etherification reactions, and (iii) a two-step modification sequence involving the use of a Grignard reagent. A comparison was drawn to evaluate these methodologies and the most effective strategy (Grignard treatment) was selected and further investigated. Successful formulation and characterization of mixed matrix membranes constituting zeolite 4A modified via the Grignard treatment are described in detail. Membranes with impressive improvements in gas separation efficiency and mechanical properties were demonstrated. The basis for the improvements in polymer/sieve compatibility enabled by this specific process were proposed and investigated. A key aspect of the present study was illuminating the detailed chemical mechanisms involved in the Grignard modification. Systematic characterization and carefully designed experiments revealed that the formation of distinctive surface structures is essentially a heterogeneous nucleation process, where Mg(OH)2 crystals grow from the nuclei previously extracted from zeolites. In addition to the main work, discovery of sonication-induced dealumination of zeolites was made during the systematic exploration of Grignard chemistry. The new procedure employing sonication can potentially be applied to prepare zeolites with a variety of Si/Al ratios under relatively mild conditions. The last part of this thesis focused on development of a technique to generalize the highly specific Grignard treatment to inorganic materials other than zeolite 4A. This work delivered composite membranes with improved interfacial adhesion. Moreover, research revealed the effect of surface nuclei density on the ultimate morphology of deposited nanostructures and how different surface morphologies influence polymer/filler interaction in composite membranes. Methods were devised to tailor the morphologies of such structures in order to optimize adhesion enhancement. The acquired results demonstrated the potential of extending this modification process to a broad domain of materials and render it a general methodology for interfacial adhesion promotion.

A review on g-C3N4-based photocatalysts

NASA Astrophysics Data System (ADS)

Wen, Jiuqing; Xie, Jun; Chen, Xiaobo; Li, Xin

2017-01-01

As one of the most appealing and attractive technologies, heterogeneous photocatalysis has been utilized to directly harvest, convert and store renewable solar energy for producing sustainable and green solar fuels and a broad range of environmental applications. Due to their unique physicochemical, optical and electrical properties, a wide variety of g-C3N4-based photocatalysts have been designed to drive various reduction and oxidation reactions under light irradiation with suitable wavelengths. In this review, we have systematically summarized the photocatalytic fundamentals of g-C3N4-based photocatalysts, including fundamental mechanism of heterogeneous photocatalysis, advantages, challenges and the design considerations of g-C3N4-based photocatalysts. The versatile properties of g-C3N4-based photocatalysts are highlighted, including their crystal structural, surface phisicochemical, stability, optical, adsorption, electrochemical, photoelectrochemical and electronic properties. Various design strategies are also thoroughly reviewed, including band-gap engineering, defect control, dimensionality tuning, pore texture tailoring, surface sensitization, heterojunction construction, co-catalyst and nanocarbon loading. Many important applications are also addressed, such as photocatalytic water splitting (H2 evolution and overall water splitting), degradation of pollutants, carbon dioxide reduction, selective organic transformations and disinfection. Through reviewing the important state-of-the-art advances on this topic, it may provide new opportunities for designing and constructing highly effective g-C3N4-based photocatalysts for various applications in photocatalysis and other related fields, such as solar cell, photoelectrocatalysis, electrocatalysis, lithium battery, supercapacitor, fuel cell and separation and purification.

Photosystem I assembly on chemically tailored SAM/ Au substrates for bio-hybrid device fabrication

NASA Astrophysics Data System (ADS)

Mukherjee, Dibyendu; Khomami, Bamin

2011-03-01

Photosystem I (PS I), a supra-molecular protein complex and a biological photodiode responsible for driving natural photosynthesis mechanism, charge separates upon exposure to light. Effective use of the photo-electrochemical activities of PS I for future bio-hybrid electronic devices requires controlled attachment of these proteins onto organic/ inorganic substrates. Our results indicate that various experimental parameters alter the surface topography of PS I deposited from colloidal aqueous buffer suspensions onto OH-terminated alkanethiolate SAM /Au substrates, thereby resulting in complex columnar structures that affect the electron capture pathway of PS I. Specifically, solution phase characterizations indicate that specific detergents used for PS I stabilization in buffer solutions drive the unique colloidal chemistry to tune protein-protein interactions and prevent aggregation, thereby allowing us to tailor the morphology of surface immobilized PS I. We present surface topographical, adsorption, and electrochemical characterizations of PSI /SAM/Au substrates to elucidate protein-surface attachment dynamics and its effect on the photo-activated electronic activities of surface immobilized PS I. Sustainable Energy Education and Research Center (SEERC).

A self-sacrifice template route to iodine modified BiOIO3: band gap engineering and highly boosted visible-light active photoreactivity.

PubMed

Feng, Jingwen; Huang, Hongwei; Yu, Shixin; Dong, Fan; Zhang, Yihe

2016-03-21

The development of high-performance visible-light photocatalysts with a tunable band gap has great significance for enabling wide-band-gap (WBG) semiconductors visible-light sensitive activity and precisely tailoring their optical properties and photocatalytic performance. In this work we demonstrate the continuously adjustable band gap and visible-light photocatalysis activation of WBG BiOIO3via iodine surface modification. The iodine modified BiOIO3 was developed through a facile in situ reduction route by applying BiOIO3 as the self-sacrifice template and glucose as the reducing agent. By manipulating the glucose concentration, the band gap of the as-prepared modified BiOIO3 could be orderly narrowed by generation of the impurity or defect energy level close to the conduction band, thus endowing it with a visible light activity. The photocatalytic assessments uncovered that, in contrast to pristine BiOIO3, the modified BiOIO3 presents significantly boosted photocatalytic properties for the degradation of both liquid and gaseous contaminants, including Rhodamine B (RhB), methyl orange (MO), and ppb-level NO under visible light. Additionally, the band structure evolution as well as photocatalysis mechanism triggered by the iodine surface modification is investigated in detail. This study not only provides a novel iodine surface-modified BiOIO3 for environmental application, but also provides a facile and general way to develop highly efficient visible-light photocatalysts.

Electronic Structure and Band Gap of Fullerenes on Tungsten Surfaces: Transition from a Semiconductor to a Metal Triggered by Annealing.

PubMed

Monazami, Ehsan; McClimon, John B; Rondinelli, James; Reinke, Petra

2016-12-21

The understanding and control of molecule-metal interfaces is critical to the performance of molecular electronics and photovoltaics devices. We present a study of the interface between C 60 and W, which is a carbide-forming transition metal. The complex solid-state reaction at the interface can be exploited to adjust the electronic properties of the molecule layer. Scanning tunneling microscopy/spectroscopy measurements demonstrate the progression of this reaction from wide band gap (>2.5 eV) to metallic molecular surface during annealing from 300 to 800 K. Differential conduction maps with 10 4 scanning tunneling spectra are used to quantify the transition in the density of states and the reduction of the band gap during annealing with nanometer spatial resolution. The electronic transition is spatially homogeneous, and the surface band gap can therefore be adjusted by a targeted annealing step. The modified molecules, which we call nanospheres, are quite resistant to ripening and coalescence, unlike any other metallic nanoparticle of the same size. Densely packed C 60 and isolated C 60 molecules show the same transition in electronic structure, which confirms that the transformation is controlled by the reaction at the C 60 -W interface. Density functional theory calculations are used to develop possible reaction pathways in agreement with experimentally observed electronic structure modulation. Control of the band gap by the choice of annealing temperature is a unique route to tailoring molecular-layer electronic properties.

Recent advances in functionalized micro and mesoporous carbon materials: synthesis and applications.

PubMed

Benzigar, Mercy R; Talapaneni, Siddulu Naidu; Joseph, Stalin; Ramadass, Kavitha; Singh, Gurwinder; Scaranto, Jessica; Ravon, Ugo; Al-Bahily, Khalid; Vinu, Ajayan

2018-04-23

Functionalized nanoporous carbon materials have attracted the colossal interest of the materials science fraternity owing to their intriguing physical and chemical properties including a well-ordered porous structure, exemplary high specific surface areas, electronic and ionic conductivity, excellent accessibility to active sites, and enhanced mass transport and diffusion. These properties make them a special and unique choice for various applications in divergent fields such as energy storage batteries, supercapacitors, energy conversion fuel cells, adsorption/separation of bulky molecules, heterogeneous catalysts, catalyst supports, photocatalysis, carbon capture, gas storage, biomolecule detection, vapour sensing and drug delivery. Because of the anisotropic and synergistic effects arising from the heteroatom doping at the nanoscale, these novel materials show high potential especially in electrochemical applications such as batteries, supercapacitors and electrocatalysts for fuel cell applications and water electrolysis. In order to gain the optimal benefit, it is necessary to implement tailor made functionalities in the porous carbon surfaces as well as in the carbon skeleton through the comprehensive experimentation. These most appealing nanoporous carbon materials can be synthesized through the carbonization of high carbon containing molecular precursors by using soft or hard templating or non-templating pathways. This review encompasses the approaches and the wide range of methodologies that have been employed over the last five years in the preparation and functionalisation of nanoporous carbon materials via incorporation of metals, non-metal heteroatoms, multiple heteroatoms, and various surface functional groups that mostly dictate their place in a wide range of practical applications.

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

Aden, Bethany; Kite, Camille M.; Hopkins, Benjamin W.

Designing thin films or surface scaffolds with an appropriate display of chemical functionality is useful for biomedical applications, sensing platforms, adhesives, and barrier coatings. Relationships between the structural characteristics of model thin films based on reactive poly(2-vinyl-4,4-dimethyl azlactone) (PVDMA) brushes and the amount and distribution of primary amines used to chemically functionalize these layers in situ are quantitatively detailed via neutron reflectometry and compared with results from ellipsometry. After functionalization, the PVDMA brush thickness increases as a result of the primary amines reacting with the azlactone rings. Both techniques show that the extent of functionalization by small-molecule amines depends onmore » the size of the amine, the grafting density of brush chains, and their molecular weight. However, constrained analysis of neutron reflectivity data predicated on that technique’s sensitivity to isotopic substitution and its ability to resolve structure at the nanoscale shows that the extent of functionalization is not accurately represented by the average extent of functionalization determined from ellipsometric thickness: reactive modification is not uniform, even in modestly dense brushes, except when the penetrant is small. In addition, there appears to be a loss of PVDMA chains during functionalization, attributed to chain scission resulting from additional stretching brought about by functionalization. In conclusion, these findings provide unprecedented insight into the alteration of surface properties by reactive modification and broadly support efforts to produce tailored surfaces in which properties such as friction, colloidal stability, adhesion, wettability, and biocompatibility can be modulated in situ by chemical modification.« less

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

Aden, Bethany; Kite, Camille M.; Hopkins, Benjamin W.

Designing thin films or surface scaffolds with an appropriate display of chemical functionality is useful for biomedical applications, sensing platforms, adhesives, and barrier coatings. Relationships between the structural characteristics of model thin films based on reactive poly(2-vinyl-4,4-dimethylazlactone) (PVDMA) brushes and the amount and distribution of primary amines used to chemically functionalize the layer in situ are quantitatively detailed via neutron reflectometry and compared with results from ellipsometry. After functionalization, the PVDMA brush thickness increases as a result of the primary amines reacting with the azlactone rings. Both techniques show that the extent of functionalization by small-molecule amines depends on themore » size of the amine, the grafting density of brush chains and their molecular weight. However, constrained analysis of neutron reflectivity data predicated on that technique’s sensitivity to isotopic substitution and its ability to resolve structure at the nanoscale, shows that the extent of functionalization is not accurately represented by the average extent of functionalization determined from ellipsometric thickness: reactive modification is not uniform, even in modestly dense brushes, except when the penetrant is small. Additionally, there appears to be a loss of PVDMA chains during functionalization, attributed to chain scission resulting from additional stretching brought about by functionalization. These findings provide unprecedented insight into the alteration of surface properties by reactive modification and broadly support efforts to produce tailored surfaces in which properties such as friction, colloidal stability, adhesion, wettability, and biocompatibility can be modulated in situ by chemical modification.« less

Observation of end-vortex nucleation in individual ferromagnetic nanotubes

NASA Astrophysics Data System (ADS)

Mehlin, A.; Gross, B.; Wyss, M.; Schefer, T.; Tütüncüoglu, G.; Heimbach, F.; Fontcuberta i Morral, A.; Grundler, D.; Poggio, M.

2018-04-01

The reversal of uniform axial magnetization in a ferromagnetic nanotube (FNT) has been predicted to occur through the nucleation and propagation of vortex domains forming at the ends. We provide experimental evidence for this behavior through dynamic cantilever magnetometry measurements of individual FNTs. In particular, we identify the nucleation of the vortex end domains as a function of applied magnetic field and show that they mark the onset of magnetization reversal. We find that the nucleation field depends sensitively on the angle between the end surface of the FNT and the applied field. Micromagnetic simulations substantiate the experimental results and highlight the importance of the ends in determining the reversal process. The control over end-vortex nucleation enabled by our findings is promising for the production of FNTs with tailored reversal properties.

Line tension effects on the wetting of nanostructures: an energy method

NASA Astrophysics Data System (ADS)

Guo, Hao-Yuan; Li, Bo; Feng, Xi-Qiao

2017-09-01

The superhydrophobicity and self-cleaning property of micro/nano-structured solid surfaces require a stable Cassie-Baxter (CB) wetting state at the liquid-solid interface. We present an energy method to investigate how the three-phase line tension affects the CB wetting state on nanostructured materials. For some nanostructures, the line tension may engender a distinct energy barrier, which restricts the position of the three-phase contact line and affects the stability of the CB wetting state. We ascertain the upper and lower limits of the critical pressure at the CB-Wenzel transition. Our results suggest that superhydrophobicity on nanostructures can be modulated by tailoring the line tension and harnessing the curvature effect. This study also provides new insights into the sinking phenomena observed in the nanoparticle-floating experiment.

Solar Absorptance of Cermet Coatings Evaluated

NASA Technical Reports Server (NTRS)

Jaworske, Donald A.

2004-01-01

Cermet coatings, molecular mixtures of metal and ceramic, are being considered for the heat inlet surface of solar Stirling convertors. In this application, the key role of the cermet coating is to absorb as much of the incident solar energy as possible. To achieve this objective, the cermet coating has a high solar absorptance value. Cermet coatings are manufactured utilizing sputter deposition, and many different metal and ceramic combinations can be created. The ability to mix metal and ceramic at the atomic level offers the opportunity to tailor the composition, and hence, the optical properties of these coatings. The NASA Glenn Research Center has prepared and characterized a wide variety of cermet coatings utilizing different metals deposited in an aluminum oxide ceramic matrix. In addition, the atomic oxygen durability of these coatings has been evaluated.

Biofabrication and biomaterials for urinary tract reconstruction

PubMed Central

Elsawy, Moustafa M; de Mel, Achala

2017-01-01

Reconstructive urologists are constantly facing diverse and complex pathologies that require structural and functional restoration of urinary organs. There is always a demand for a biocompatible material to repair or substitute the urinary tract instead of using patient’s autologous tissues with its associated morbidity. Biomimetic approaches are tissue-engineering tactics aiming to tailor the material physical and biological properties to behave physiologically similar to the urinary system. This review highlights the different strategies to mimic urinary tissues including modifications in structure, surface chemistry, and cellular response of a range of biological and synthetic materials. The article also outlines the measures to minimize infectious complications, which might lead to graft failure. Relevant experimental and preclinical studies are discussed, as well as promising biomimetic approaches such as three-dimensional bioprinting. PMID:28546955

Angular distribution of hybridization in sputtered carbon thin film

NASA Astrophysics Data System (ADS)

Liu, Y.; Wang, H.; Wei, Z. C.

2017-08-01

The sp3/sp2 ratio of sputtered carbon thin film depends on the ion bombardment process and tailors the physical properties of carbon thin film. In present work, we report the angular distribution of hybridization in magnetron sputtered carbon thin film for the first time. By x-ray photoelectron spectra analyses, it is found that the sp3/sp2 ratio increases linearly with increasing the deposition angle from 0 to 90 degree, which could be attributed to the enhancement of direct knocking-out of near-surface target atoms. In addition, we also derive the sp3/sp2 ratio by simulation on complex permittivity in terahertz frequency using a modified percolation approximation tunneling model. Those derived data consist with the results from x-ray photoelectron spectroscopy.

Parallel Grand Canonical Monte Carlo (ParaGrandMC) Simulation Code

NASA Technical Reports Server (NTRS)

Yamakov, Vesselin I.

2016-01-01

This report provides an overview of the Parallel Grand Canonical Monte Carlo (ParaGrandMC) simulation code. This is a highly scalable parallel FORTRAN code for simulating the thermodynamic evolution of metal alloy systems at the atomic level, and predicting the thermodynamic state, phase diagram, chemical composition and mechanical properties. The code is designed to simulate multi-component alloy systems, predict solid-state phase transformations such as austenite-martensite transformations, precipitate formation, recrystallization, capillary effects at interfaces, surface absorption, etc., which can aid the design of novel metallic alloys. While the software is mainly tailored for modeling metal alloys, it can also be used for other types of solid-state systems, and to some degree for liquid or gaseous systems, including multiphase systems forming solid-liquid-gas interfaces.