Insights into effects and mechanism of pre-dispersant on surface morphologies of silica or alumina coated rutile TiO2 particles

NASA Astrophysics Data System (ADS)

Dong, Xiongbo; Sun, Zhiming; Liu, Yangyu; Jiang, Lei; Zheng, Shuilin

2018-05-01

Silica and alumina coated rutile TiO2 samples with various surface morphologies were fabricated using four different pre-dispersants. Using sodium silicate nonahydrate (SSNH) as pre-dispersant, the received sample displayed the best acidic stability. The addition of SSNH could induce layer-by-layer growth of hydrous silica via enhancing the dispersion of hydrous silica nucleus and accelerating the dehydration condensation rate of silica film. Alumina coated rutile TiO2 sample obtained by polyethyleneglycol 1000 (PEG) presented the highest dispersion stability. The existence of PEG can induce the formation of fibrous hydrous alumina film, which would increase the steric hindrance and the promotion of dispersion stability.

Fabrication of superhydrophilic and antireflective silica coatings on poly(methyl methacrylate) substrates

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

Geng, Zhi; Graduate University of Chinese Academy of Sciences; He, Junhui, E-mail: jhhe@mail.ipc.ac.cn

2012-06-15

Graphical abstract: Self-cleaning and antireflection properties were successfully achieved by assembling (PDDA/S-20){sub n} coatings on PMMA substrates followed by oxygen plasma treatment. Highlights: ► Porous silica coatings were created by layer-by-layer assembly on PMMA substrates. ► Silica coatings were treated by oxygen plasma. ► Porous silica coatings were highly antireflective and superhydrophilic on PMMA substrates. -- Abstract: Silica nanoparticles of ca. 20 nm in size were synthesized, from which hierarchically porous silica coatings were fabricated on poly(methyl methacrylate) (PMMA) substrates via layer-by-layer (LbL) assembly followed by oxygen plasma treatment. These porous silica coatings were highly transparent and superhydrophilic. The maximummore » transmittance reached as high as 99%, whereas that of the PMMA substrate is only 92%. After oxygen plasma treatment, the time for a water droplet to spread to a contact angle of lower than 5° decreased to as short as 0.5 s. Scanning and transmission electron microscopy were used to observe the morphology and structure of nanoparticles and coating surfaces. Transmission and reflection spectra were recorded on UV–vis spectrophotometer. Surface wettability was studied by a contact angle/interface system. The influence of mesopores on the transmittance and wetting properties of coatings was discussed on the basis of experimental observations.« less

Surface studies on superhydrophobic and oleophobic polydimethylsiloxane-silica nanocomposite coating system

NASA Astrophysics Data System (ADS)

Basu, Bharathibai J.; Dinesh Kumar, V.; Anandan, C.

2012-11-01

Superhydrophobic and oleophobic polydimethylsiloxane (PDMS)-silica nanocomposite double layer coating was fabricated by applying a thin layer of low surface energy fluoroalkyl silane (FAS) as topcoat. The coatings exhibited WCA of 158-160° and stable oleophobic property with oil CA of 79°. The surface morphology was characterized by field emission scanning electron microscopy (FESEM) and surface chemical composition was determined by energy dispersive X-ray spectrometery (EDX) and X-ray photoelectron spectroscopy (XPS). FESEM images of the coatings showed micro-nano binary structure. The improved oleophobicity was attributed to the combined effect of low surface energy of FAS and roughness created by the random distribution of silica aggregates. This is a facile, cost-effective method to obtain superhydrophobic and oleophobic surfaces on larger area of various substrates.

Asymmetric orientation of toluene molecules at oil-silica interfaces

NASA Astrophysics Data System (ADS)

Ledyastuti, Mia; Liang, Yunfeng; Kunieda, Makoto; Matsuoka, Toshifumi

2012-08-01

The interfacial structure of heptane and toluene at oil-silica interfaces has previously been studied by sum frequency generation [Z. Yang et al., J. Phys. Chem. C. 113, 20355 (2009)], 10.1021/jp9043122. It was found that the toluene molecule is almost perpendicular to the silica surface with a tilt angle of about 25°. Here, we have investigated the structural properties of toluene and heptane at oil-silica interfaces using molecular dynamics simulations for two different surfaces: the oxygen-bridging (hydrophobic) and hydroxyl-terminated (hydrophilic) surfaces of quartz (silica). Based on the density profile, it was found that both heptane and toluene oscillate on silica surfaces, with heptane showing more oscillation peaks. Furthermore, the toluene molecules of the first layer were found to have an asymmetric distribution of orientations, with more CH3 groups pointed away from the silica surface than towards the silica surface. These findings are generally consistent with previous experiments, and reveal enhanced molecular structures of liquids at oil-silica interfaces.

Asymmetric orientation of toluene molecules at oil-silica interfaces.

PubMed

Ledyastuti, Mia; Liang, Yunfeng; Kunieda, Makoto; Matsuoka, Toshifumi

2012-08-14

The interfacial structure of heptane and toluene at oil-silica interfaces has previously been studied by sum frequency generation [Z. Yang et al., J. Phys. Chem. C. 113, 20355 (2009)]. It was found that the toluene molecule is almost perpendicular to the silica surface with a tilt angle of about 25°. Here, we have investigated the structural properties of toluene and heptane at oil-silica interfaces using molecular dynamics simulations for two different surfaces: the oxygen-bridging (hydrophobic) and hydroxyl-terminated (hydrophilic) surfaces of quartz (silica). Based on the density profile, it was found that both heptane and toluene oscillate on silica surfaces, with heptane showing more oscillation peaks. Furthermore, the toluene molecules of the first layer were found to have an asymmetric distribution of orientations, with more CH(3) groups pointed away from the silica surface than towards the silica surface. These findings are generally consistent with previous experiments, and reveal enhanced molecular structures of liquids at oil-silica interfaces.

NASA Astrophysics Data System (ADS)

Wang, Mao-Hua; Zhang, Bo; Zhou, Fu

2014-07-01

Silica was homogeneously coated on the surface of CaCu3Ti4O12 (CCTO) particles via the sol-gel method. The obtained powders were characterized by x-ray diffraction analysis, Fourier-transform infrared spectroscopy, transmission electron microscopy (TEM), energy-dispersive spectroscopy, scanning electron microscopy, and zeta potential analysis. The results demonstrate that there were silica layers on the surface of the CCTO particles. Physical and dielectric properties of silica-coated CCTO were also studied. TEM imaging showed that the thickness of the silica layer on the CCTO particles was about 20 nm to 35 nm. The specimen coated with 1.0 wt.% silica showed the maximum relative density of 96.7% with high dielectric constant (12.78 × 104) and low dielectric loss (0.005) at 20°C after sintering at 1000°C for 6 h.

Molecular Dynamics Simulations of the Oil-Detachment from the Hydroxylated Silica Surface: Effects of Surfactants, Electrostatic Interactions, and Water Flows on the Water Molecular Channel Formation.

PubMed

Tang, Jian; Qu, Zhou; Luo, Jianhui; He, Lanyan; Wang, Pingmei; Zhang, Ping; Tang, Xianqiong; Pei, Yong; Ding, Bin; Peng, Baoliang; Huang, Yunqing

2018-02-15

The detachment process of an oil molecular layer situated above a horizontal substrate was often described by a three-stage process. In this mechanism, the penetration and diffusion of water molecules between the oil phase and the substrate was proposed to be a crucial step to aid in removal of oil layer/drops from substrate. In this work, the detachment process of a two-dimensional alkane molecule layer from a silica surface in aqueous surfactant solutions is studied by means of molecular dynamics (MD) simulations. By tuning the polarity of model silica surfaces, as well as considering the different types of surfactant molecules and the water flow effects, more details about the formation of water molecular channel and the expansion processes are elucidated. It is found that for both ionic and nonionic type surfactant solutions, the perturbation of surfactant molecules on the two-dimensional oil molecule layer facilitates the injection and diffusion of water molecules between the oil layer and silica substrate. However, the water channel formation and expansion speed is strongly affected by the substrate polarity and properties of surfactant molecules. First, only for the silica surface with relative stronger polarity, the formation of water molecular channel is observed. Second, the expansion speed of the water molecular channel upon the ionic surfactant (dodecyl trimethylammonium bromide, DTAB and sodium dodecyl benzenesulfonate, SDBS) flooding is more rapidly than the nonionic surfactant system (octylphenol polyoxyethylene(10) ether, OP-10). Third, the water flow speed may also affect the injection and diffusion of water molecules. These simulation results indicate that the water molecular channel formation process is affected by multiple factors. The synergistic effects of perturbation of surfactant molecules and the electrostatic interactions between silica substrate and water molecules are two key factors aiding in the injection and diffusion of water molecules and helpful for the oil detachment from silica substrate.

Adhesive Stretchable Printed Conductive Thin Film Patterns on PDMS Surface with an Atmospheric Plasma Treatment.

PubMed

Li, Chun-Yi; Liao, Ying-Chih

2016-05-11

In this study, a plasma surface modification with printing process was developed to fabricate printed flexible conductor patterns or devices directly on polydimethylsiloxane (PDMS) surface. An atmospheric plasma treatment was first used to oxidize the PDMS surface and create a hydrophilic silica surface layer, which was confirmed with photoelectron spectra. The plasma operating parameters, such as gas types and plasma powers, were optimized to obtain surface silica layers with the longest lifetime. Conductive paste with epoxy resin was screen-printed on the plasma-treated PDMS surface to fabricate flexible conductive tracks. As a result of the strong binding forces between epoxy resin and the silica surface layer, the printed patterns showed great adhesion on PDMS and were undamaged after several stringent adhesion tests. The printed conductive tracks showed strong mechanical stability and exhibited great electric conductivity under bending, twisting, and stretching conditions. Finally, a printed pressure sensor with good sensitivity and a fast response time was fabricated to demonstrate the capability of this method for the realization of printed electronic devices.

Adsorption of water from aqueous acetonitrile on silica-based stationary phases in aqueous normal-phase liquid chromatography.

PubMed

Soukup, Jan; Jandera, Pavel

2014-12-29

Excess adsorption of water from aqueous acetonitrile mobile phases was investigated on 16 stationary phases using the frontal analysis method and coulometric Karl-Fischer titration. The stationary phases include silica gel and silica-bonded phases with different polarities, octadecyl and cholesterol, phenyl, nitrile, pentafluorophenylpropyl, diol and zwitterionic sulfobetaine and phosphorylcholine ligands bonded on silica, hybrid organic-silica and hydrosilated matrices. Both fully porous and core-shell column types were included. Preferential uptake of water by the columns can be described by Langmuir isotherms. Even though a diffuse rather than a compact adsorbed discrete layer of water on the adsorbent surface can be formed because of the unlimited miscibility of water with acetonitrile, for convenience, the preferentially adsorbed water was expressed in terms of a hypothetical monomolecular water layer equivalent in the inner pores. The uptake of water strongly depends on the polarity and type of the column. Less than one monomolecular water layer equivalent was adsorbed on moderate polar silica hydride-based stationary phases, Ascentis Express F5 and Ascentis Express CN column at the saturation capacity, while on more polar stationary phases, several water layer equivalents were up-taken from the mobile phase. The strongest affinity to water was observed on the ZIC cHILIC stationary phases, where more than nine water layer equivalents were adsorbed onto its surface at its saturation capacity. Columns with bonded hydroxyl and diol ligands show stronger water adsorption in comparison to bare silica. Columns based on hydrosilated silica generally show significantly decreased water uptake in comparison to stationary phases bonded on ordinary silica. Significant correlations were found between the water uptake and the separation selectivity for compounds with strong polarity differences. Copyright © 2014 Elsevier B.V. All rights reserved.

Influence of hydrophobic surface treatment toward performance of air filter

NASA Astrophysics Data System (ADS)

Shahfiq Zulkifli, Nazrul; Zaini Yunos, Muhamad; Ahmad, Azlinnorazia; Harun, Zawati; Akhair, Siti Hajar Mohd; Adibah Raja Ahmad, Raja; Hafeez Azhar, Faiz; Rashid, Abdul Qaiyyum Abd; Ismail, Al Emran

2017-08-01

This study investigated the performance of hydrophobic surface treatment by using silica aerogel powder via spray coating techniques. Hydrophobic properties were determined by measuring the level of the contact angle. Meanwhile, performance was evaluated in term of the hydrogen gas flow and humidity rejection. The results are shown by contact angle that the microstructure filter, especially in the upper layer and sub-layer has been changed. The results also show an increase of hydrophobicity due to the increased quantity of silica aerogel powder. Results also showed that the absorption and rejection filter performance filter has increased after the addition of silica aerogel powder. The results showed that with the addition of 5 grams of powder of silica aerogel have the highest result of wetting angle 134.11°. The highest humidity rejection found with 5 grams of powder of silica aerogel.

Synergic combination of the sol–gel method with dip coating for plasmonic devices

PubMed Central

Patrini, Maddalena; Floris, Francesco; Fornasari, Lucia; Pellacani, Paola; Marchesini, Gerardo; Valsesia, Andrea; Artizzu, Flavia; Marongiu, Daniela; Saba, Michele; Marabelli, Franco; Mura, Andrea; Bongiovanni, Giovanni

2015-01-01

Summary Biosensing technologies based on plasmonic nanostructures have recently attracted significant attention due to their small dimensions, low-cost and high sensitivity but are often limited in terms of affinity, selectivity and stability. Consequently, several methods have been employed to functionalize plasmonic surfaces used for detection in order to increase their stability. Herein, a plasmonic surface was modified through a controlled, silica platform, which enables the improvement of the plasmonic-based sensor functionality. The key processing parameters that allow for the fine-tuning of the silica layer thickness on the plasmonic structure were studied. Control of the silica coating thickness was achieved through a combined approach involving sol–gel and dip-coating techniques. The silica films were characterized using spectroscopic ellipsometry, contact angle measurements, atomic force microscopy and dispersive spectroscopy. The effect of the use of silica layers on the optical properties of the plasmonic structures was evaluated. The obtained results show that the silica coating enables surface protection of the plasmonic structures, preserving their stability for an extended time and inducing a suitable reduction of the regeneration time of the chip. PMID:25821692

Hydrophobic and optical characteristics of graphene and graphene oxide films transferred onto functionalized silica particles deposited glass surface

NASA Astrophysics Data System (ADS)

Yilbas, B. S.; Ibrahim, A.; Ali, H.; Khaled, M.; Laoui, T.

2018-06-01

Hydrophobic and optical transmittance characteristics of the functionalized silica particles on the glass surface prior and after transfer of graphene and graphene oxide films on the surface are examined. Nano-size silica particles are synthesized and functionalized via chemical grafting and deposited onto a glass surface. Graphene film, grown on copper substrate, was transferred onto the functionalized silica particles surface through direct fishing method. Graphene oxide layer was deposited onto the functionalized silica particles surface via spin coating technique. Morphological, hydrophobic, and optical characteristics of the functionalized silica particles deposited surface prior and after graphene and graphene oxide films transfer are examined using the analytical tools. It is found that the functionalized silica particles are agglomerated at the surface forming packed structures with few micro/nano size pores. This arrangement gives rise to water droplet contact angle and contact angle hysteresis in the order of 163° and 2°, respectively, and remains almost uniform over the entire surface. Transferring graphene and depositing graphene oxide films over the functionalized silica particles surface lowers the water droplet contact angle slightly (157-160°) and increases the contact angle hysteresis (4°). The addition of the graphene and graphene oxide films onto the surface of the deposited functionalized silica particles improves the optical transmittance.

Morphology studies of hydrophobic silica on filter surface prepared via spray technique

NASA Astrophysics Data System (ADS)

Shahfiq Zulkifli, Nazrul; Zaini Yunos, Muhamad; Ahmad, Azlinnorazia; Harun, Zawati; Akhair, Siti Hajar Mohd; Adibah Raja Ahmad, Raja; Hafeez Azhar, Faiz; Rashid, Abdul Qaiyyum Abd; Ismail, Al Emran

2017-08-01

This study investigated the effect of the hydrophobic surface treatment effect of air filter performance by using silica aerogel powder as an additive by using spray coating techniques. The membrane characterization tests were carried out on a filter prepared from different additive concentration. Studies on the cross-section and the distribution of particles on the membrane were carried out using a scanning electron microscope (SEM), and the surface morphology was investigated by x-ray spectroscopy (EDS). The results are shown by SEM and EDS that the microstructure filter, especially in the upper layer and sub-layer has been changed. The results also show an increase of hydrophobicity due to the increased quantity of silica aerogel powder.

Facile preparation of robust microcapsules by manipulating metal-coordination interaction between biomineral layer and bioadhesive layer.

PubMed

Zhang, Lei; Shi, Jiafu; Jiang, Zhongyi; Jiang, Yanjun; Meng, Ruijie; Zhu, Yuanyuan; Liang, Yanpeng; Zheng, Yang

2011-02-01

A novel approach combining biomimetic mineralization and bioadhesion is proposed to prepare robust and versatile organic-inorganic hybrid microcapsules. More specifically, these microcapsules are fabricated by sequential deposition of inorganic layer and organic layer on the surface of CaCO(3) microparticles, followed by the dissolution of CaCO(3) microparticles using EDTA. During the preparation process, protamine induces the hydrolysis and condensation of titania or silica precursor to form the inorganic layer or the biomineral layer. The organic layer or bioadhesive layer was formed through the rapid, spontaneous oxidative polymerization of dopamine into polydopamine (PDA) on the surface of the biomineral layer. There exist multiple interactions between the inorganic layer and the organic layer. Thus, the as-prepared organic-inorganic hybrid microcapsules acquire much higher mechanical stability and surface reactivity than pure titania or pure silica microcapsules. Furthermore, protamine/titania/polydopamine hybrid microcapsules display superior mechanical stability to protamine/silica/polydopamine hybrid microcapsules because of the formation of Ti(IV)-catechol coordination complex between the biomineral layer and the bioadhesive layer. As an example of application, three enzymes are respectively immobilized through physical encapsulation in the lumen, in situ entrapment within the wall and chemical attachment on the out surface of the hybrid microcapsules. The as-constructed multienzyme system displays higher catalytic activity and operational stability. Hopefully, the approach developed in this study will evolve as a generic platform for facile and controllable preparation of organic-inorganic hybrid materials with different compositions and shapes for a variety of applications in catalysis, sensor, drug/gene delivery.

High reactive sulphide chemically supported on silica surface to prepare functional nanoparticle

NASA Astrophysics Data System (ADS)

Chen, Lijuan; Guo, Xiaohui; Jia, Zhixin; Tang, Yuhan; Wu, Lianghui; Luo, Yuanfang; Jia, Demin

2018-06-01

A solid-phase preparation method was applied to obtain a novel, green and effective functional nanoparticle, silica-supported sulfur monochloride (silica-s-S2Cl2), by the chemical reaction between chlorine atom and silicon hydroxyl on the silica surface. Through this chemical reaction, silica surface supported with high content of sulfur, and the functional nanoparticles can not only vulcanize the rubber instead of sulfur or other vulcanizing agent with high performance, but also improve the filler-rubber interaction as a modifier due to the improved modification effect. 29Si NMR, Raman spectroscopy, Element analysis and TGA confirm that the sulfur monochloride is chemically bonded on the silica surface. Cure properties measurement, morphology of filler dispersion, mechanical properties measurement, immobilized polymer layer and oxidation induction time increment together show that the novel vulcanizing agent silica-s-S2Cl2 instead of sulfur in rubber vulcanization gives rise to significant improvement in the crosslinking density and the interfacial adhesion between silica particles and the rubber matrix, which is on account of the promoted vulcanizing on the functional silica nanoparticles surface with the supported sulfur.

Numerical modeling of mineral dissolution - precipitation kinetics integrating interfacial processes

NASA Astrophysics Data System (ADS)

Azaroual, M. M.

2016-12-01

The mechanisms of mineral dissolution/precipitation are complex and interdependent. Within a same rock, the geochemical modelling may have to manage kinetic reactions with high ratios between the most reactive minerals (i.e., carbonates, sulfate salts, etc.) and less reactive minerals (i.e., silica, alumino-silicates, etc.). These ratios (higher than 10+6) induce numerical instabilities for calculating mass and energy transfers between minerals and aqueous phases at the appropriate scales of time and space. The current scientific debate includes: i) changes (or not) of the mineral reactive surface with the progress of the dissolution/precipitation reactions; ii) energy jumps (discontinuity) in the thermodynamic affinity function of some dissolution/precipitation reactions and iii) integration of processes at the "mineral - aqueous solution" interfaces for alumino-silicates, silica and carbonates. In recent works dealing with the specific case of amorphous silica, measurements were performed on nano-metric cross-sections indicating the presence of surface layer between the bulk solution and the mineral. This thin layer is composed by amorphous silica and hydrated silica "permeable" to the transfer of water and ionic chemical constituents. The boundary/interface between the initial mineral and the silica layer is characterized by a high concentration jump of chemical products at the nanoscale and some specific interfacial dissolution/precipitation processes.In this study, the results of numerical simulations dealing with different mechanisms of silicate and carbonate dissolution/precipitation reactions and integrating interfacial processes will be discussed. The application of this approach to silica precipitation is based on laboratory experiments and it highlights the significant role of the "titration" surface induced by surface complexation reactions in the determination of the kinetics of precipitation.

Silica coating of nanoparticles by the sonogel process.

PubMed

Chen, Quan; Boothroyd, Chris; Tan, Gim Hong; Sutanto, Nelvi; Soutar, Andrew McIntosh; Zeng, Xian Ting

2008-02-05

A modified aqueous sol-gel route was developed using ultrasonic power for the silica coating of indium tin oxide (ITO) nanoparticles. In this approach, organosilane with an amino functional group was first used to cover the surface of as-received nanoparticles. Subsequent silica coating was initiated and sustained under power ultrasound irradiation in an aqueous mixture of surface-treated particles and epoxy silane. This process resulted in a thin but homogeneous coverage of silica on the particle surface. Particles coated with a layer of silica show better dispersability in aqueous and organic media compared with the untreated powder. Samples were characterized by high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and the zeta potential.

Sol–gel method as a way of carbonyl iron powder surface modification for interaction improvement

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

Małecki, P., E-mail: pawel.malecki@pwr.edu.pl; Kolman, K.; Pigłowski, J.

2015-03-15

This article presents a method for modification of carbonyl iron particles’ surface (CIP), (d{sub 50}=4–9 µm) by silica coatings obtained using the sol–gel method. Reaction parameters were determined to obtain dry magnetic powder with homogeneous silica coatings without further processing and without any by-product in the solid or liquid phase. This approach is new among the commonly used methods of silica coating of iron particles. No attempt has been made to cover a carbonyl iron surface by silica in a waste-free method, up to date. In the current work two different silica core/shell structures were made by the sol–gel process,more » based on different silica precursors: tetraethoxy-silane (TEOS) and tetramethoxy-silane (TMOS). The dependence between the synthesis procedure and thickness of silica shell covering carbonyl iron particles has been described. Surface morphology of the modified magnetic particles and the coating thickness were characterized with the use of scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Determination of the physicochemical structure of the obtained materials was performed by the energy-dispersive X-ray spectroscope (EDS), and the infrared technique (IR). The surface composition was analyzed using X-ray photoelectron spectroscopy (XPS). Additionally, distribution of particle size was measured using light microscopy. The new, efficient process of covering micro-size CIP with a nanometric silica layer was shown. Results of a performed analysis confirm the effectiveness of the presented method. - Highlights: • Proper covering CIP by sol–gel silica layer avoids agglomeration. • A new solid waste-free method of CIP coating is proposed. • Examination of the properties of modified CIP in depends on washing process. • Coatings on CIP particles doesn’t change the magnetic properties of particles.« less

Polar silica-based stationary phases. Part II- Neutral silica stationary phases with surface bound maltose and sorbitol for hydrophilic interaction liquid chromatography.

PubMed

Rathnasekara, Renuka; El Rassi, Ziad

2017-07-28

Two neutral polyhydroxylated silica bonded stationary phases, namely maltose-silica (MALT-silica) and sorbitol-silica (SOR-silica), have been introduced and chromatographically characterized in hydrophilic interaction liquid chromatography (HILIC) for a wide range of polar compounds. The bonding of the maltose and sorbitol to the silica surface was brought about by first converting bare silica to an epoxy-activated silica surface via reaction with γ-glycidoxypropyltrimethoxysilane (GPTMS) followed by attaching maltose and sorbitol to the epoxy surface in the presence of the Lewis acid catalyst BF 3 .ethereate. Both silica based columns offered the expected retention characteristics usually encountered for neutral polar surface. The retention mechanism is majorly based on solute' differential partitioning between an organic rich hydro-organic mobile phase (e.g., ACN rich mobile phase) and an adsorbed water layer on the surface of the stationary phase although additional hydrogen bonding was also responsible in some cases for solute retention. The MALT-silica column proved to be more hydrophilic and offered higher retention, separation efficiency and resolution than the SOR-silica column among the tested polar solutes such as derivatized mono- and oligosaccharides, weak phenolic acids, cyclic nucleotide monophosphate and nucleotide-5'-monophosphates, and weak bases, e.g., nucleobases and nucleosides. Copyright © 2017 Elsevier B.V. All rights reserved.

Durable superhydrophobic surfaces made by intensely connecting a bipolar top layer to the substrate with a middle connecting layer.

PubMed

Zhi, Jinghui; Zhang, Li-Zhi

2017-08-30

This study reported a simple fabrication method for a durable superhydrophobic surface. The superhydrophobic top layer of the durable superhydrophobic surface was connected intensely to the substrate through a middle connecting layer. Glycidoxypropyltrimethoxysilane (KH-560) after hydrolysis was used to obtain a hydrophilic middle connecting layer. It could be adhered to the hydrophilic substrate by covalent bonds. Ring-open reaction with octadecylamine let the KH-560 middle layer form a net-like structure. The net-like sturcture would then encompass and station the silica particles that were used to form the coarse micro structures, intensely to increase the durability. The top hydrophobic layer with nano-structures was formed on the KH-560 middle layer. It was obtained by a bipolar nano-silica solution modified by hexamethyldisilazane (HMDS). This layer was connected to the middle layer intensely by the polar Si hydroxy groups, while the non-polar methyl groups on the surface, accompanied by the micro and nano structures, made the surface rather hydrophobic. The covalently interfacial interactions between the substrate and the middle layer, and between the middle layer and the top layer, strengthened the durability of the superhydrophobic surface. The abrasion test results showed that the superhydrophobic surface could bear 180 abrasion cycles on 1200 CW sandpaper under 2 kPa applied pressure.

Silica nanoparticles with a substrate switchable luminescence

NASA Astrophysics Data System (ADS)

Bochkova, O. D.; Mustafina, A. R.; Fedorenko, S. V.; Konovalov, A. I.

2011-04-01

Silica nanoparticles with visible (Tb and Ru doped), near IR (Yb doped) and dual visible-near IR luminescence (Ru-Yb doped) were obtained by reverse w/o microemulsion procedure. Plenty of luminescent complexes (from 4900 to 10000) encapsulated into each nanoparticle ensures the intensive luminescence of nanoparticles and their applicability as biomarkers. The silica surface decoration by definite anchor groups is the required step for the gaining to these nanoparticles marking and sensing functions. Thus covalent and non-covalent surface modification of these nanoparticles was developed to provide the binding with biotargets and sensing of anions. The dicationic surfactant coating of negatively charged Tb(III)-TCAS doped silica nanoparticles was chosen as the basis for the anion responsible system. The reversible insertion of the quenching anions (namely phenol red) into the surfactant based layer at the surface of luminescent nanoparticles switches off the Tb-centered luminescence. In turn the reversible reestablishment of the luminescence results from the competitive insertion of the non-quenching anions into the surfactant layer at the silica/water interface. The hydrophobic anions exemplified by dodecylsulfates versus hydrophilic ones (hydrophosphates) are preferable in the competition with phenol red anions.

Nano- and micro-structuring of fused silica using time-delay adjustable double flash ns-laser radiation

NASA Astrophysics Data System (ADS)

Lorenz, Pierre; Zhao, Xiongtao; Ehrhardt, Martin; Zagoranskiy, Igor; Zimmer, Klaus; Han, Bing

2018-02-01

Large area, high speed, nanopatterning of surfaces by laser ablation is challenging due to the required high accuracy of the optical and mechanical systems fulfilling the precision of nanopatterning process. Utilization of self-organization approaches can provide an alternative decoupling spot precision and field of machining. The laser-induced front side etching (LIFE) and laser-induced back side dry etching (LIBDE) of fused silica were studied using single and double flash nanosecond laser pulses with a wavelength of 532 nm where the time delay Δτ of the double flash laser pulses was adjusted from 50 ns to 10 μs. The fused silica can be etched at both processes assisted by a 10 nm chromium layer where the etching depth Δz at single flash laser pulses is linear to the laser fluence and independent on the number of laser pulses, from 2 to 12 J/cm2, it is Δz = δLIFE/LIBDE . Φ with δLIFE 16 nm/(J/cm2) and δLIBDE 5.2 nm/(J/cm2) 3 . δLIFE. At double flash laser pulses, the Δz is dependent on the time delay Δτ of the laser pulses and the Δz slightly increased at decreasing Δτ. Furthermore, the surface nanostructuring of fused silica using IPSM-LIFE (LIFE using in-situ pre-structured metal layer) method with a single double flash laser pulse was tested. The first pulse of the double flash results in a melting of the metal layer. The surface tension of the liquid metal layer tends in a droplet formation process and dewetting process, respectively. If the liquid phase life time ΔtLF is smaller than the droplet formation time the metal can be "frozen" in an intermediated state like metal bare structures. The second laser treatment results in a evaporation of the metal and in a partial evaporation and melting of the fused silica surface, where the resultant structures in the fused silica surface are dependent on the lateral geometry of the pre-structured metal layer. A successful IPSM-LIFE structuring could be achieved assisted by a 20 nm molybdenum layer at Δτ >= 174 ns. That path the way for the high speed ultra-fast nanostructuring of dielectric surfaces by self-organizing processes. The different surface structures were analyzed by scanning electron microscopy (SEM) and white light interferometry (WLI).

Forsterite surface composition in aqueous solutions: a combined potentiometric, electrokinetic, and spectroscopic approach

NASA Astrophysics Data System (ADS)

Pokrovsky, Oleg S.; Schott, Jacques

2000-10-01

Surfaces of natural and synthetic forsterite (Fo 91 and Fo 100) in aqueous solutions at 25°C were investigated using surface titrations in batch and limited residence time reactors, column filtration experiments, electrokinetic measurements (streaming potential and electrophoresis techniques), Diffuse Reflectance Infrared Spectroscopy (DRIFT), and X-ray Photoelectron Spectroscopy (XPS). At pH < 9, a Mg-depleted, Si-rich layer (<20 Å thick) is formed on the forsterite surface due to a Mg 2+ ↔ H + exchange reaction. Electrokinetic measurements yield a pH IEP value of 4.5 corresponding to the dominance of SiO 2 in the surface layer at pH < 9. In contrast, surface titrations of fresh powders give an apparent pH PZC of about 10 with the development of a large positive charge (up to 10 -4 mol/m 2 or 10 C/m 2) in the acid pH region. This may be explained by penetration of H + into the first unit cells of forsterite surface. The surface charge of acid-reacted forsterite is one or two orders of magnitude lower than that of unreacted forsterite with an apparent pH PZC at around 6.5 and a pH IEP value of 2.1 which is close to that for amorphous silica and reflects the formation of a silica-rich layer on the surface. XPS analyses indicate the penetration of hydrogen into the surface and the polymerization of silica tetrahedra in this leached layer. At pH > 10, a Si-deficient, Mg-rich surface layer is formed as shown by XPS analyses and the preferential Si release from the surface during column filtration experiments.

Optical fiber humidity sensor based on evanescent-wave scattering.

PubMed

Xu, Lina; Fanguy, Joseph C; Soni, Krunal; Tao, Shiquan

2004-06-01

The phenomenon of evanescent-wave scattering (EWS) is used to design an optical-fiber humidity sensor. Porous solgel silica (PSGS) coated on the surface of a silica optical-fiber core scatters evanescent waves that penetrate the coating layer. Water molecules in the gas phase surrounding the optical fiber can be absorbed into the inner surface of the pores of the porous silica. The absorbed water molecules form a thin layer of liquid water on the inner surface of the porous silica and enhance the EWS. The amount of water absorbed into the PSGS coating is in dynamic equilibrium with the water-vapor pressure in the gas phase. Therefore the humidity in the air can be quantitatively determined with fiber-optic EWS caused by the PSGS coating. The humidity sensor reported here is fast in response, reversible, and has a wide dynamic range. The possible interference caused by EWS to an optical-fiber gas sensor with a reagent-doped PSGS coating as a transducer is also discussed.

The effect of clay on the dissolution of nuclear waste glass

NASA Astrophysics Data System (ADS)

Lemmens, K.

2001-09-01

In a nuclear waste repository, the waste glass can interact with metals, backfill materials (if present) and natural host rock. Of the various host rocks considered, clays are often reported to delay the onset of the apparent glass saturation, where the glass dissolution rate becomes very small. This effect is ascribed to the sorption of silica or other glass components on the clay. This can have two consequences: (1) the decrease of the silica concentration in solution increases the driving force for further dissolution of glass silica, and (2) the transfer of relatively insoluble glass components (mainly silica) from the glass surface to the clay makes the alteration layer less protective. In recent literature, the latter explanation has gained credibility. The impact of the environmental materials on the glass surface layers is however not well understood. Although the glass dissolution can initially be enhanced by clay, there are arguments to assume that it will decrease to very low values after a long time. Whether this will indeed be the case, depends on the fate of the released glass components in the clay. If they are sorbed on specific sites, it is likely that saturation of the clay will occur. If however the released glass components are removed by precipitation (growth of pre-existing or new secondary phases), saturation of the clay is less likely, and the process can continue until exhaustion of one of the system components. There are indications that the latter mechanism can occur for varying glass compositions in Boom Clay and FoCa clay. If sorption or precipitation prevents the formation of protective surface layers, the glass dissolution can in principle proceed at a high rate. High silica concentrations are assumed to decrease the dissolution rate (by a solution saturation effect or by the impact on the properties of the glass alteration layer). In glass corrosion tests at high clay concentrations, silica concentrations are, however, often higher than the silica concentrations in equilibrium with the glass surface ( C ∗Si, saturation) that are found in absence of clay. Nevertheless, the glass dissolution proceeds at relatively high rate. C ∗Si, saturation seems to be increased by the presence of clay. To understand this, more knowledge is necessary concerning the fate of the released silica and the silica speciation in solution.

Locating a silane coupling agent in silica-filled rubber composites by EFTEM.

PubMed

Dohi, Hidehiko; Horiuchi, Shin

2007-11-20

A silane coupling agent (SA) was added to silica/rubber composites at different mixing temperatures and the formation of a coupling layer at the silica/rubber interface was investigated by energy-filtering transmission electron microscopy. Bis(triethoxysilypropyl)tetrasulfane (TESPT), which was used as the SA, reacted with the silanol groups on the silica surface and with styrene-butadiene rubber to form an interfacial coupling layer. The silicon and sulfur elemental distributions were analyzed by electron energy loss spectroscopy (EELS) and elemental mapping. The amount of TESPT trapped in the rubber matrix could be qualitatively estimated by EELS, and the in situ formed coupling layer could be characterized by elemental mapping. The result indicated that the formation of the coupling layer was affected by the mixing temperature. The technique described here will contribute to the study of interface-property relationships and the evaluation of the role of SAs in polymeric composites.

Anticorrosion efficiency of ultrasonically deposited silica coatings on titanium

NASA Astrophysics Data System (ADS)

Ertaş, Fatma Sinem; Kaş, Recep; Mikó, Annamária; Birer, Özgür

2013-07-01

We utilized high intensity ultrasound to prepare coatings of silica and organically modified silica composed of multiple layers of densely packed nanoparticles. Ultrasound was used to collide nanoparticles onto an activated titanium surface with high speed. Large areas could be homogeneously coated by this method. These coatings were characterized by spectroscopy and microscopy methods and the anticorrosion efficiency in NaCl solution was evaluated by electrochemical measurements. The results indicated that the composite coatings provided good quality barrier layer on bare titanium and decreased the anodic corrosion rate. It was found that increase in the organic content of the coating shifted the passivation potential towards more positive direction. The comparison of the impedance results recorded at the corrosion potential pointed out that in each case a good quality barrier layer was formed on the titanium surface. The outstanding corrosion resistance of the composite coatings with only ~200 nm thickness shows that ultrasound assisted deposition can be a competitive method to obtain corrosion protective layers.

Comparison of the surface ion density of silica gel evaluated via spectral induced polarization versus acid-base titration

NASA Astrophysics Data System (ADS)

Hao, Na; Moysey, Stephen M. J.; Powell, Brian A.; Ntarlagiannis, Dimitrios

2016-12-01

Surface complexation models are widely used with batch adsorption experiments to characterize and predict surface geochemical processes in porous media. In contrast, the spectral induced polarization (SIP) method has recently been used to non-invasively monitor in situ subsurface chemical reactions in porous media, such as ion adsorption processes on mineral surfaces. Here we compare these tools for investigating surface site density changes during pH-dependent sodium adsorption on a silica gel. Continuous SIP measurements were conducted using a lab scale column packed with silica gel. A constant inflow of 0.05 M NaCl solution was introduced to the column while the influent pH was changed from 7.0 to 10.0 over the course of the experiment. The SIP measurements indicate that the pH change caused a 38.49 ± 0.30 μS cm- 1 increase in the imaginary conductivity of the silica gel. This increase is thought to result from deprotonation of silanol groups on the silica gel surface caused by the rise in pH, followed by sorption of Na+ cations. Fitting the SIP data using the mechanistic model of Leroy et al. (Leroyet al., 2008), which is based on the triple layer model of a mineral surface, we estimated an increase in the silica gel surface site density of 26.9 × 1016 sites m- 2. We independently used a potentiometric acid-base titration data for the silica gel to calibrate the triple layer model using the software FITEQL and observed a total increase in the surface site density for sodium sorption of 11.2 × 1016 sites m- 2, which is approximately 2.4 times smaller than the value estimated using the SIP model. By simulating the SIP response based on the calibrated surface complexation model, we found a moderate association between the measured and estimated imaginary conductivity (R2 = 0.65). These results suggest that the surface complexation model used here does not capture all mechanisms contributing to polarization of the silica gel captured by the SIP data.

In vivo penetration of bare and lipid-coated silica nanoparticles across the human stratum corneum.

PubMed

Iannuccelli, Valentina; Bertelli, Davide; Romagnoli, Marcello; Scalia, Santo; Maretti, Eleonora; Sacchetti, Francesca; Leo, Eliana

2014-10-01

Skin penetration of silica nanoparticles (NP) currently used in pharmaceutical and cosmetic products is a topic of interest not only to evaluate their possible toxicity, but also to understand their behaviour upon contact with the skin and to exploit their potential positive effects in drug or cosmetic delivery field. Therefore, the present work aimed to elucidate the in vivo mechanism by which amorphous hydrophilic silica NP enter human stratum corneum (SC) through the evaluation of the role played by the nanoparticle surface polarity and the human hair follicle density. Two silica samples, bare hydrophilic silica (B-silica, 162±51nm in size) and hydrophobic lipid-coated silica (LC-silica, 363±74nm in size) were applied on both the volar and dorsal side of volunteer forearms. Twelve repetitive stripped tapes were removed from the human skin and evaluated for elemental composition by Energy Dispersive X-ray (EDX) analysis and for silicon content by Inductively Coupled Plasma quadrupole Mass Spectrometry (ICP-MS). All the stripped tapes revealed nanosized structures generally located in the broad spaces between corneocytes and characterized by the same elemental composition (relative weight percentage of silicon and silicon to oxygen weight ratio) than that of the applied samples. However, only about 10% B-silica permeated until the deepest SC layers considered in the study indicating a silica retention in the upper layers of SC, regardless of the hair follicle density. Otherwise, the exposure to LC-silica led to a greater silica skin penetration extent into the deeper SC layers (about 42% and 18% silica following volar and dorsal forearm application, respectively) indicating that the NP surface polarity played a predominant role on that of their size in determining the route and the extent of penetration. Copyright © 2014 Elsevier B.V. All rights reserved.

Face-specific Replacement of Calcite by Amorphous Silica Nanoparticles

NASA Astrophysics Data System (ADS)

Liesegang, M.; Milke, R.; Neusser, G.; Mizaikoff, B.

2016-12-01

Amorphous silica, composed of nanoscale spheres, is an important biomineral, alteration product of silicate rocks on the Earth's surface, and precursor material for stable silicate minerals. Despite constant progress in silica sphere synthesis, fundamental knowledge of natural silica particle interaction and ordering processes leading to colloidal crystals is absent so far. To understand the formation pathways of silica spheres in a geologic environment, we investigated silicified Cretaceous mollusk shell pseudomorphs from Coober Pedy (South Australia) using focused ion beam (FIB)-SEM tomography, petrographic microscopy, µ-XRD, and EMPA. The shells consist of replaced calcite crystals (<2 mm) composed of ordered arrays of uniform, close-packed silica spheres 300 ± 10 nm in size. Concentric layered spheres composed of 40 nm-sized subparticles provide evidence that, at least in the final stage, particle aggregation was the major sphere growth mechanism. Silica sphere arrays in periodically changing orientations perfectly replicate polysynthetic twinning planes of calcite. FIB-SEM tomography shows that cubic closed-packed sphere arrangements preserve the twin lamellae, while the twin plane consists of a submicrometer layer of randomly ordered spheres and vacancies. To transfer crystallographic information from parent to product, the advancement of synchronized dissolution and precipitation fronts along lattice planes is essential. We assume that the volume-preserving replacement process proceeds via a face-specific dissolution-precipitation mechanism with intermediate subparticle aggregation and subsequent layer-by-layer deposition of spheres along a planar surface. Porosity created during the replacement reaction allows permanent fluid access to the propagating reaction interface. Fluid pH and ionic strength remain constant throughout the replacement process, permitting continuous silica nanoparticle formation and diffusion-limited colloid aggregation. Our study provides a natural example of the transformation of an atomic crystal to an amorphous, mesoscale ordered material; thus, links the research fields of natural colloidal crystal formation, carbonate-silica replacement, and crystallization by oriented particle aggregation (CPA).

Chemistry and Formation of the Beilby Layer During Polishing of Fused Silica Glass

DOE PAGES

Suratwala, Tayyab; Steele, William; Wong, Lana; ...

2015-05-19

The chemical characteristics and the proposed formation mechanisms of the modified surface layer (called the Beilby layer) on polished fused silica glasses are described. Fused silica glass samples were polished using different slurries, polyurethane pads, and at different rotation rates. The concentration profiles of several key contaminants, such as Ce, K, and H, were measured in the near surface layer of the polished samples using Secondary Ion Mass Spectroscopy (SIMS). The penetration of K, originating from KOH used for pH control during polishing, decreased with increase in polishing material removal rate. In contrast, penetration of the Ce and H increasedmore » with increase in polishing removal rate. In addition, Ce penetration was largely independent of the other polishing parameters (e.g., particle size distribution and the properties of the polishing pad). The resulting K concentration depth profiles are described using a two-step diffusion process: (1) steady-state moving boundary diffusion (due to material removal during polishing) followed by (2) simple diffusion during ambient postpolishing storage. Using known alkali metal diffusion coefficients in fused silica glass, this diffusion model predicts concentration profiles that are consistent with the measured data at various polishing material removal rates. On the other hand, the observed Ce profiles are inconsistent with diffusion based transport. Rather we propose that Ce penetration is governed by the ratio of Ce–O–Si and Si–O–Si hydrolysis rates; where this ratio increases with interface temperature (which increases with polishing material removal rate) resulting in greater Ce penetration into the Beilby layer. Calculated Ce surface concentrations using this mechanism are in good agreement to the observed change in measured Ce surface concentrations with polishing material removal rate. In conclusion, these new insights into the chemistry of the Beilby layer, combined together with details of the single particle removal function during polishing, are used to develop a more detailed and quantitative picture of the polishing process and the formation of the Beilby layer.« less

Determination of Surface Potential and Electrical Double-Layer Structure at the Aqueous Electrolyte-Nanoparticle Interface

NASA Astrophysics Data System (ADS)

Brown, Matthew A.; Abbas, Zareen; Kleibert, Armin; Green, Richard G.; Goel, Alok; May, Sylvio; Squires, Todd M.

2016-01-01

The structure of the electrical double layer has been debated for well over a century, since it mediates colloidal interactions, regulates surface structure, controls reactivity, sets capacitance, and represents the central element of electrochemical supercapacitors. The surface potential of such surfaces generally exceeds the electrokinetic potential, often substantially. Traditionally, a Stern layer of nonspecifically adsorbed ions has been invoked to rationalize the difference between these two potentials; however, the inability to directly measure the surface potential of dispersed systems has rendered quantitative measurements of the Stern layer potential, and other quantities associated with the outer Helmholtz plane, impossible. Here, we use x-ray photoelectron spectroscopy from a liquid microjet to measure the absolute surface potentials of silica nanoparticles dispersed in aqueous electrolytes. We quantitatively determine the impact of specific cations (Li+ , Na+ , K+ , and Cs+ ) in chloride electrolytes on the surface potential, the location of the shear plane, and the capacitance of the Stern layer. We find that the magnitude of the surface potential increases linearly with the hydrated-cation radius. Interpreting our data using the simplest assumptions and most straightforward understanding of Gouy-Chapman-Stern theory reveals a Stern layer whose thickness corresponds to a single layer of water molecules hydrating the silica surface, plus the radius of the hydrated cation. These results subject electrical double-layer theories to direct and falsifiable tests to reveal a physically intuitive and quantitatively verified picture of the Stern layer that is consistent across multiple electrolytes and solution conditions.

Effect of Surface Functionalization on Structural and Optical Properties of Luminescent LaF₃:Sm Nanoparticles.

PubMed

Ansari, Anees A

2018-02-01

Samarium (Sm3+)-doped LaF3 nanoparticles (NPs) subsequently encapsulated with inert crystalline LaF3 and amorphous silica layers were prepared by polyol and sol-gel chemical process, respectively. These surface modified core/shell/SiO2-nanostructured were characterized by X-ray diffraction (XRD), FE-transmission electron microscopy (TEM), thermal analysis, FTIR, UV/Vis absorption, bang gap energy and photoluminescence spectroscopy. The FETEM, EDX and FTIR spectral studies clearly revealed that the silica layer has been formed surrounding the core-NPs. Comparative spectral analysis indicated that core/shell/SiO2-NPs revealed high solubility in aqueous and non-aqueous solvents. The decrease in band gap energy after surface growth of an inert LaF3 and silica shells is directly correlated to the increase in grain size. On comparing the emission intensity, a significant enhancement was observed after inert layer coating, whereas, it suppress after silica encapsulation due to the non-radiative transitions. The increase luminescent intensity after inert shell growth indicates that a significant amount of non-radiative centers existing on the surface of core/shell nanoparticles can be eliminated by the shielding effect of LaF3 shells. These observed results indicate that the as-prepared core/shell/SiO2-NPs could be highly useful in broad photonic based applications such as optical sensor/optical bio-probe and light emitting diode.

Modification of surfaces of silver nanoparticles for controlled deposition of silicon, manganese, and titanium dioxides

NASA Astrophysics Data System (ADS)

Apostolova, Tzveta; Obreshkov, B. D.; Ionin, A. A.; Kudryashov, S. I.; Makarov, S. V.; Mel'nik, N. N.; Rudenko, A. A.

2018-01-01

In this work we show that nanometric-thick layers of SiO2, MnO2, and TiO2 may be effectively deposited on various silver nanoparticles (including cubic Ag nanoparticles) covered by a very thin (below 0.4 nm) layer of silver sulphide. The background in Raman measurements generated by sulphide-protected Ag nanoparticles is significantly smaller than that for analogous Ag nanoparticles protected by a monolayer formed from alkanethiols - depositing alkanethiols on a surface of anisotropic silver nanoparticles is the current standard method used for protecting a surface of Ag nanoparticles before depositing a layer of silica. Because of significantly smaller generated Raman background, Ag@SiO2 nanostructures with an Ag2S linkage layer between the silver core and the silica shell are very promising low-background electromagnetic nanoresonators for carrying out Raman analysis of various surfaces - especially using what is known as shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). Sample SHINERS analyses of various surfaces (including pesticide-contaminated surfaces of tomatoes) using cubic-Ag@SiO2 nanoparticles as electromagnetic nanoresonators are also presented.

Wettability of modified silica layers deposited on glass support activated by plasma

NASA Astrophysics Data System (ADS)

Terpiłowski, Konrad; Rymuszka, Diana; Goncharuk, Olena V.; Sulym, Iryna Ya.; Gun'ko, Vladimir M.

2015-10-01

Fumed silica modified by hexamethyldisilazane [HDMS] and polydimethylsiloxane [PDMS] was dispersed in a polystyrene/chloroform solution. To increase adhesion between deposited silica layers and a glass surface, the latter was pretreated with air plasma for 30 s. The silica/polystyrene dispersion was deposited on the glass support using a spin coater. After deposition, the plates were dried in a desiccator for 24 h. Water advancing and receding contact angles were measured using the tilted plate method. The apparent surface free energy (γS) was evaluated using the contact angle hysteresis approach. The surface topography was determined using the optical profilometry method. Contact angles changed from 59.7° ± 4.4 (at surface coverage with trimethylsilyl groups Θ = 0.14) to 155° ± 3.1 at Θ = 1. The value of γS decreased from 51.3 ± 2.8 mJ/m2 (for the sample at the lowest value of Θ) to 1.0 ± 0.4 mJ/m2 for the most hydrophobic sample. Thus, some systems with a high degree of modification by HDMS showed superhydrophobicity, and the sliding angle amounted to about 16° ± 2.1.

Bioinspired assembly of surface-roughened nanoplatelets.

PubMed

Lin, Tzung-Hua; Huang, Wei-Han; Jun, In-Kook; Jiang, Peng

2010-04-15

Here we report a novel electrophoretic deposition technology for assembling surface-roughened inorganic nanoplatelets into ordered multilayers that mimic the brick-and-mortar nanostructure found in the nacreous layer of mollusk shells. A thin layer of sol-gel silica is coated on smooth gibbsite nanoplatelets in order to increase the surface roughness to mimic the asperity of aragonite platelets found in nacres. To avoid the severe cracking caused by the shrinkage of sol-gel silica during drying, polyelectrolyte polyethyleneimine is used to reverse the surface charge of silica-coated-gibbsite nanoplatelets and increase the adherence and strength of the electrodeposited films. Polymer nanocomposites can then be made by infiltrating the interstitials of the aligned nanoplatelet multilayers with photocurable monomer followed by photopolymerization. The resulting self-standing films are highly transparent and exhibit nearly three times higher tensile strength and one-order-of-magnitude higher toughness than those of pure polymer. The measured tensile strength agrees with that predicted by a simple shear lag model. Published by Elsevier Inc.

Nano-structured surface plasmon resonance sensor for sensitivity enhancement

NASA Astrophysics Data System (ADS)

Kim, Jae-Ho; Kim, Hyo-Sop; Kim, Jin-Ho; Choi, Sung-Wook; Cho, Yong-Jin

2008-08-01

A new nano-structured SPR sensor was devised to improve its sensitivity. Nano-scaled silica particles were used as the template to fabricate nano-structure. The surface of the silica particles was modified with thiol group and a single layer of the modified silica particles was attached on the gold or silver thin film using Langmuir-Blodgett (LB) method. Thereafter, gold or silver was coated on the template by an e-beam evaporator. Finally, the nano-structured surface with basin-like shape was obtained after removing the silica particles by sonication. Applying the new developed SPR sensor to a model food of alcoholic beverage, the sensitivities for the gold and silver nano-structured sensors, respectively, had 95% and 126% higher than the conventional one.

Synthesis and characterization of (3-Aminopropyl)trimethoxy-silane (APTMS) functionalized Gd2O3:Eu(3+) red phosphor with enhanced quantum yield.

PubMed

Jain, Akhil; Hirata, G A; Farías, M H; Castillón, F F

2016-02-12

We report the surface modification of nanocrystalline Gd2O3:Eu(3+) phosphor by (3-Aminopropyl)trimethoxysilane (APTMS). The nanoparticles were first coated with silica using the Stöber process, and then annealed at 650 °C for 2 h. Afterwards, APTMS was functionalized onto the silica layer to obtain Gd2O3:Eu(3+) nanoparticles bearing amine groups on the surface. The effect of silica coating, and the subsequent annealing process on the crystallization of the nanophosphor were analyzed by x-ray diffraction (XRD). High-resolution transmission electron microscopy (HR-TEM) confirmed the presence of a silica layer of ∼45 nm thickness. X-ray photoelectron (XPS) and Fourier transform infrared (FTIR) spectroscopy confirmed the presence of silica and the amine groups. Photoluminescence (PL) analysis demonstrated an increased emission after functionalization of nanoparticles. Absolute quantum yield (QY) measurements revealed an 18% enhancement in QY in functionalized nanoparticles compared with unmodified nanoparticles, which is of great importance for their biomedical applications.

Synthesis and characterization of (3-Aminopropyl)trimethoxy-silane (APTMS) functionalized Gd2O3:Eu3+ red phosphor with enhanced quantum yield

NASA Astrophysics Data System (ADS)

Jain, Akhil; Hirata, G. A.; Farías, M. H.; Castillón, F. F.

2016-02-01

We report the surface modification of nanocrystalline Gd2O3:Eu3+ phosphor by (3-Aminopropyl)trimethoxysilane (APTMS). The nanoparticles were first coated with silica using the Stöber process, and then annealed at 650 °C for 2 h. Afterwards, APTMS was functionalized onto the silica layer to obtain Gd2O3:Eu3+ nanoparticles bearing amine groups on the surface. The effect of silica coating, and the subsequent annealing process on the crystallization of the nanophosphor were analyzed by x-ray diffraction (XRD). High-resolution transmission electron microscopy (HR-TEM) confirmed the presence of a silica layer of ∼45 nm thickness. X-ray photoelectron (XPS) and Fourier transform infrared (FTIR) spectroscopy confirmed the presence of silica and the amine groups. Photoluminescence (PL) analysis demonstrated an increased emission after functionalization of nanoparticles. Absolute quantum yield (QY) measurements revealed an 18% enhancement in QY in functionalized nanoparticles compared with unmodified nanoparticles, which is of great importance for their biomedical applications.

Fundamental study of FC-72 pool boiling surface temperature fluctuations and bubble behavior

NASA Astrophysics Data System (ADS)

Griffin, Alison R.

A heater designed to monitor surface temperature fluctuations during pool boiling experiments while the bubbles were simultaneously being observed has been fabricated and tested. The heat source was a transparent indium tin oxide (ITO) layer commercially deposited on a fused quartz substrate. Four copper-nickel thin film thermocouples (TFTCs) on the heater surface measured the surface temperature, while a thin layer of sapphire or fused silica provided electrical insulation between the TFTCs and the ITO. The TFTCs were micro-fabricated using the liftoff process to deposit the nickel and copper metal films. The TFTC elements were 50 mum wide and overlapped to form a 25 mum by 25 mum junction. TFTC voltages were recorded by a DAQ at a sampling rate of 50 kHz. A high-speed CCD camera recorded bubble images from below the heater at 2000 frames/second. A trigger sent to the camera by the DAQ synchronized the bubble images and the surface temperature data. As the bubbles and their contact rings grew over the TFTC junction, correlations between bubble behavior and surface temperature changes were demonstrated. On the heaters with fused silica insulation layers, 1--2°C temperature drops on the order of 1 ms occurred as the contact ring moved over the TFTC junction during bubble growth and as the contact ring moved back over the TFTC junction during bubble departure. These temperature drops during bubble growth and departure were due to microlayer evaporation and liquid rewetting the heated surface, respectively. Microlayer evaporation was not distinguished as the primary method of heat removal from the surface. Heaters with sapphire insulation layers did not display the measurable temperature drops observed with the fused silica heaters. The large thermal diffusivity of the sapphire compared to the fused silica was determined as the reason for the absence of these temperature drops. These findings were confirmed by a comparison of temperature drops in a 2-D simulation of a bubble growing over the TFTC junction on both the sapphire and fused silica heater surfaces. When the fused silica heater produced a temperature drop of 1.4°C, the sapphire heater produced a drop of only 0.04°C under the same conditions. These results verified that the lack of temperature drops present in the sapphire data was due to the thermal properties of the sapphire layer. By observing the bubble departure frequency and site density on the heater, as well as the bubble departure diameter, the contribution of nucleate boiling to the overall heat removal from the surface could be calculated. These results showed that bubble vapor generation contributed to approximately 10% at 1 W/cm2, 23% at 1.75 W/cm2, and 35% at 2.9 W/cm 2 of the heat removed from a fused silica heater. Bubble growth and contact ring growth were observed and measured from images obtained with the high-speed camera. Bubble data recorded on a fused silica heater at 3 W/cm2, 4 W/cm2, and 5 W/cm 2 showed that bubble departure diameter and lifetime were negligibly affected by the increase in heat flux. Bubble and contact ring growth rates demonstrated significant differences when compared on the fused silica and sapphire heaters at 3 W/cm2. The bubble departure diameters were smaller, the bubble lifetimes were longer, and the bubble departure frequency was larger on the sapphire heater, while microlayer evaporation was faster on the fused silica heater. Additional considerations revealed that these differences may be due to surface conditions as well as differing thermal properties. Nucleate boiling curves were recorded on the fused silica and sapphire heaters by adjusting the heat flux input and monitoring the local surface temperature with the TFTCs. The resulting curves showed a temperature drop at the onset of nucleate boiling due to the increase in heat transfer coefficient associated with bubble nucleation. One of the TFTC locations on the sapphire heater frequently experienced a second temperature drop at a higher heat flux. When the heat flux was started from 1 W/cm2 instead of zero or returned to zero only momentarily, the temperature overshoot did not occur. In these cases sufficient vapor remained in the cavities to initiate boiling at a lower superheat.

Synthesis of a fluorine-free polymeric water-repellent agent for creation of superhydrophobic fabrics

NASA Astrophysics Data System (ADS)

Shen, Keke; Yu, Miao; Li, Qianqian; Sun, Wei; Zhang, Xiting; Quan, Miao; Liu, Zhengtang; Shi, Suqing; Gong, Yongkuan

2017-12-01

A non-fluorinated polymeric alkylsilane, poly(isobutyl methacrylate-co-3-methacryloxypropyltrimethoxysilane) (PIT), is designed and synthesized to replace the commercial long-chain perfluoroalkylsilane (FAS) water-repellent agent. The superhydrophobic polyester fabrics are prepared by anchoring sol-gel derived silica nanoparticles onto alkali-treated polyester fabric surfaces and subsequently hydrophobilizing with PIT, using FAS as control. The surface chemical composition, surface morphology, wetting behavior and durability of the modified polyester fabrics are characterized by scanning electron microscopy (SEM), X-ray photoelectron spectrophotometer (XPS) and video-based contact angle goniometer, respectively. The results show that a porous silica layer could be successfully fabricated onto the surface of polyester fabric through base-catalyzed sol-gel process with tetraethoxysilane (TEOS) as precursor, incorporating additional nanostructured roughness essential for superhydrophobicity. At the same time, such a silica primer layer could provide both secondary reactive moieties (-Si - OH) for the subsequent surface hydrophobization and acceptable adhesion at the silica-polyester fabric interface. When silica modified polyester fabric (SiO2@ fabric) is hydrophobized by PIT solution (10 mg/mL), excellent water-repellency could be obtained. The water contact angle is up to 154° and the sliding angle is about 5°. Compared with small molecule water-repellent agent FAS, PIT modified SiO2@ fabric exhibits greatly improved solvent resistance under ultra-sonication, abrasion and simulated laundering durability. The anti-stain property of PIT-modified SiO2@ fabric is also evaluated by using different aqueous colored solutions.

Repetitive heterocoagulation of oppositely charged particles for enhancement of magnetic nanoparticle loading into monodisperse silica particles.

PubMed

Matsumoto, Hideki; Nagao, Daisuke; Konno, Mikio

2010-03-16

Oppositely charged particles were repetitively heterocoagulated to fabricate highly monodisperse magnetic silica particles with high loading of magnetic nanoparticles. Positively charged magnetic nanoparticles prepared by surface modification with N-trimethoxysilylpropyl-N,N,N-trimethylammonium chloride (TSA) were used to heterocoagulate with silica particles under basic conditions to give rise to negative silica surface charge and prevent the oxidation of the magnetic nanoparticles. The resultant particles of silica core homogeneously coated with the magnetic nanoparticles were further coated with thin silica layer with sodium silicate in order to enhance colloidal stability and avoid desorption of the magnetic nanoparticles from the silica cores. Five repetitions of the heterocoagulation and the silica coating could increase saturation magnetization of the magnetic silica particles to 27.7 emu/g, keeping the coefficient of variation of particle sizes (C(V)) less than 6.5%. Highly homogeneous loading of the magnetic component was confirmed by measuring Fe-to-Si atomic ratios of individual particles with energy dispersive X-ray spectroscopy.

Silica-sol-based spin-coating barrier layer against phosphorous diffusion for crystalline silicon solar cells

PubMed Central

2014-01-01

The phosphorus barrier layers at the doping procedure of silicon wafers were fabricated using a spin-coating method with a mixture of silica-sol and tetramethylammonium hydroxide, which can be formed at the rear surface prior to the front phosphorus spin-on-demand (SOD) diffusion and directly annealed simultaneously with the front phosphorus layer. The optimization of coating thickness was obtained by changing the applied spin-coating speed; from 2,000 to 8,000 rpm. The CZ-Si p-type silicon solar cells were fabricated with/without using the rear silica-sol layer after taking the sheet resistance measurements, SIMS analysis, and SEM measurements of the silica-sol material evaluations into consideration. For the fabrication of solar cells, a spin-coating phosphorus source was used to form the n+ emitter and was then diffused at 930°C for 35 min. The out-gas diffusion of phosphorus could be completely prevented by spin-coated silica-sol film placed on the rear side of the wafers coated prior to the diffusion process. A roughly 2% improvement in the conversion efficiency was observed when silica-sol was utilized during the phosphorus diffusion step. These results can suggest that the silica-sol material can be an attractive candidate for low-cost and easily applicable spin-coating barrier for any masking purpose involving phosphorus diffusion. PMID:25520602

Silica-sol-based spin-coating barrier layer against phosphorous diffusion for crystalline silicon solar cells.

PubMed

Uzum, Abdullah; Fukatsu, Ken; Kanda, Hiroyuki; Kimura, Yutaka; Tanimoto, Kenji; Yoshinaga, Seiya; Jiang, Yunjian; Ishikawa, Yasuaki; Uraoka, Yukiharu; Ito, Seigo

2014-01-01

The phosphorus barrier layers at the doping procedure of silicon wafers were fabricated using a spin-coating method with a mixture of silica-sol and tetramethylammonium hydroxide, which can be formed at the rear surface prior to the front phosphorus spin-on-demand (SOD) diffusion and directly annealed simultaneously with the front phosphorus layer. The optimization of coating thickness was obtained by changing the applied spin-coating speed; from 2,000 to 8,000 rpm. The CZ-Si p-type silicon solar cells were fabricated with/without using the rear silica-sol layer after taking the sheet resistance measurements, SIMS analysis, and SEM measurements of the silica-sol material evaluations into consideration. For the fabrication of solar cells, a spin-coating phosphorus source was used to form the n(+) emitter and was then diffused at 930°C for 35 min. The out-gas diffusion of phosphorus could be completely prevented by spin-coated silica-sol film placed on the rear side of the wafers coated prior to the diffusion process. A roughly 2% improvement in the conversion efficiency was observed when silica-sol was utilized during the phosphorus diffusion step. These results can suggest that the silica-sol material can be an attractive candidate for low-cost and easily applicable spin-coating barrier for any masking purpose involving phosphorus diffusion.

A bioactive coating of a silica xerogel/chitosan hybrid on titanium by a room temperature sol-gel process.

PubMed

Jun, Shin-Hee; Lee, Eun-Jung; Yook, Se-Won; Kim, Hyoun-Ee; Kim, Hae-Won; Koh, Young-Hag

2010-01-01

A bioactive coating consisting of a silica xerogel/chitosan hybrid was applied to Ti at room temperature as a novel surface treatment for metallic implants. A crack-free thin layer (<2 microm) was coated on Ti with a chitosan content of >30 vol.% through a sol-gel process. The coating layer became more hydrophilic with increasing silica xerogel content, as assessed by contact angle measurement. The hybrid coatings afforded excellent bone bioactivity by inducing the rapid precipitation of apatite on their surface when immersed in a simulated body fluid (SBF). Osteoblastic cells cultured on the hybrid coatings were more viable than those on a pure chitosan coating. Furthermore, the alkaline phosphate activity of the cells was significantly higher on the hybrid coatings than on a pure chitosan coating, with the highest level being achieved on the hybrid coating containing 30% chitosan. These results indicate that silica xerogel/chitosan hybrids are potentially useful as room temperature bioactive coating materials on titanium-based medical implants.

Zinc-decorated silica-coated magnetic nanoparticles for protein binding and controlled release.

PubMed

Bele, Marjan; Hribar, Gorazd; Campelj, Stanislav; Makovec, Darko; Gaberc-Porekar, Vladka; Zorko, Milena; Gaberscek, Miran; Jamnik, Janko; Venturini, Peter

2008-05-01

The aim of this study was to be able to reversibly bind histidine-rich proteins to the surface of maghemite magnetic nanoparticles via coordinative bonding using Zn ions as the anchoring points. We showed that in order to adsorb Zn ions on the maghemite, the surface of the latter needs to be modified. As silica is known to strongly adsorb zinc ions, we chose to modify the maghemite nanoparticles with a nanometre-thick silica layer. This layer appeared to be thin enough for the maghemite nanoparticles to preserve their superparamagnetic nature. As a model the histidine-rich protein bovine serum albumin (BSA) was used. The release of the BSA bound to Zn-decorated silica-coated maghemite nanoparticles was analysed using sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE). We demonstrated that the bonding of the BSA to such modified magnetic nanoparticles is highly reversible and can be controlled by an appropriate change of the external conditions, such as a pH decrease or the presence/supply of other chelating compounds.

Self-assembly of supramolecular triarylamine nanowires in mesoporous silica and biocompatible electrodes thereof

NASA Astrophysics Data System (ADS)

Licsandru, Erol-Dan; Schneider, Susanne; Tingry, Sophie; Ellis, Thomas; Moulin, Emilie; Maaloum, Mounir; Lehn, Jean-Marie; Barboiu, Mihail; Giuseppone, Nicolas

2016-03-01

Biocompatible silica-based mesoporous materials, which present high surface areas combined with uniform distribution of nanopores, can be organized in functional nanopatterns for a number of applications. However, silica is by essence an electrically insulating material which precludes applications for electro-chemical devices. The formation of hybrid electroactive silica nanostructures is thus expected to be of great interest for the design of biocompatible conducting materials such as bioelectrodes. Here we show that we can grow supramolecular stacks of triarylamine molecules in the confined space of oriented mesopores of a silica nanolayer covering a gold electrode. This addressable bottom-up construction is triggered from solution simply by light irradiation. The resulting self-assembled nanowires act as highly conducting electronic pathways crossing the silica layer. They allow very efficient charge transfer from the redox species in solution to the gold surface. We demonstrate the potential of these hybrid constitutional materials by implementing them as biocathodes and by measuring laccase activity that reduces dioxygen to produce water.Biocompatible silica-based mesoporous materials, which present high surface areas combined with uniform distribution of nanopores, can be organized in functional nanopatterns for a number of applications. However, silica is by essence an electrically insulating material which precludes applications for electro-chemical devices. The formation of hybrid electroactive silica nanostructures is thus expected to be of great interest for the design of biocompatible conducting materials such as bioelectrodes. Here we show that we can grow supramolecular stacks of triarylamine molecules in the confined space of oriented mesopores of a silica nanolayer covering a gold electrode. This addressable bottom-up construction is triggered from solution simply by light irradiation. The resulting self-assembled nanowires act as highly conducting electronic pathways crossing the silica layer. They allow very efficient charge transfer from the redox species in solution to the gold surface. We demonstrate the potential of these hybrid constitutional materials by implementing them as biocathodes and by measuring laccase activity that reduces dioxygen to produce water. Electronic supplementary information (ESI) available: Synthetic protocols, XPS measurements, contact angle measurements, additional cyclic voltammograms and electrochemical impedance spectroscopy. See DOI: 10.1039/c5nr06977g

Ions, metabolites, and cells: Water as a reporter of surface conditions during bacterial growth.

PubMed

Jarisz, Tasha A; Lane, Sarah; Gozdzialski, Lea; Hore, Dennis K

2018-06-14

Surface-specific nonlinear vibrational spectroscopy, combined with bulk solution measurements and imaging, is used to study the surface conditions during the growth of E. coli. As a result of the silica high surface charge density, the water structure at the silica-aqueous interface is known to be especially sensitive to pH and ionic strength, and surface concentration profiles develop that can be appreciably different from the bulk solution conditions. We illustrate that, in the presence of growing cells, a unique surface micro-environment is established as a result of metabolites accumulating on the silica surface. Even in the subsequent absence of the cells, this surface layer works to reduce the interfacial ionic strength as revealed by the enhanced signal from surface water molecules. In the presence of growing cells, an additional boost in surface water signal is attributed to a local pH that is higher than that of the bulk solution.

Ions, metabolites, and cells: Water as a reporter of surface conditions during bacterial growth

NASA Astrophysics Data System (ADS)

Jarisz, Tasha A.; Lane, Sarah; Gozdzialski, Lea; Hore, Dennis K.

2018-06-01

Surface-specific nonlinear vibrational spectroscopy, combined with bulk solution measurements and imaging, is used to study the surface conditions during the growth of E. coli. As a result of the silica high surface charge density, the water structure at the silica-aqueous interface is known to be especially sensitive to pH and ionic strength, and surface concentration profiles develop that can be appreciably different from the bulk solution conditions. We illustrate that, in the presence of growing cells, a unique surface micro-environment is established as a result of metabolites accumulating on the silica surface. Even in the subsequent absence of the cells, this surface layer works to reduce the interfacial ionic strength as revealed by the enhanced signal from surface water molecules. In the presence of growing cells, an additional boost in surface water signal is attributed to a local pH that is higher than that of the bulk solution.

X-ray Study of the Electric Double Layer at the n-Hexane/Nanocolloidal Silica Interface

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

Tikhonov,A.

The spatial structure of the transition region between an insulator and an electrolyte solution was studied with x-ray scattering. The electron-density profile across the n-hexane/silica sol interface (solutions with 5, 7, and 12 nm colloidal particles) agrees with the theory of the electrical double layer and shows separation of positive and negative charges. The interface consists of three layers, i.e., a compact layer of Na{sup +}, a loose monolayer of nanocolloidal particles as part of a thick diffuse layer, and a low-density layer sandwiched between them. Its structure is described by a model in which the potential gradient at themore » interface reflects the difference in the potentials of 'image forces' between the cationic Na{sup +} and anionic nanoparticles and the specific adsorption of surface charge. The density of water in the large electric field ({approx}10{sup 9}-10{sup 10} V/m) of the transition region and the layering of silica in the diffuse layer is discussed.« less

Method for reducing formation of electrically resistive layer on ferritic stainless steels

DOEpatents

Rakowski, James M.

2013-09-10

A method of reducing the formation of electrically resistive scale on a an article comprising a silicon-containing ferritic stainless subjected to oxidizing conditions in service includes, prior to placing the article in service, subjecting the article to conditions under which silica, which includes silicon derived from the steel, forms on a surface of the steel. Optionally, at least a portion of the silica is removed from the surface to placing the article in service. A ferritic stainless steel alloy having a reduced tendency to form silica on at least a surface thereof also is provided. The steel includes a near-surface region that has been depleted of silicon relative to a remainder of the steel.

Simulated molecular-scale interaction of supercritical fluid mobile and stationary phases.

PubMed

Siders, Paul D

2017-12-08

In supercritical fluid chromatography, molecules from the mobile phase adsorb on the stationary phase. Stationary-phase alkylsilane-terminated silica surfaces might adsorb molecules at the silica, among the silanes, on a silane layer, or in pore space between surfaces. Mobile phases of carbon dioxide, pure and modified with methanol, and stationary phases were simulated at the molecular scale. Classical atomistic force fields were used in Gibbs-ensemble hybrid Monte Carlo calculations. Excess adsorption of pure carbon dioxide mobile phase peaked at fluid densities of 0.002-0.003Å -3 . Mobile phase adsorption from 7% methanol in carbon dioxide peaked at lower fluid density. Methanol was preferentially adsorbed from the mixed fluid. Surface silanes prevented direct interaction of fluid-phase molecules with silica. Some adsorbed molecules mixed with tails of bonded silanes; some formed layers above the silanes. Much adsorption occurred by filling the space between surfaces in the stationary-phase model. The distribution in the stationary phase of methanol molecules from a modified fluid phase varied with pressure. Copyright © 2017 Elsevier B.V. All rights reserved.

Influence of SiO2 shell thickness on power conversion efficiency in plasmonic polymer solar cells with Au nanorod@SiO2 core-shell structures

PubMed Central

Zhang, Ran; Zhou, Yongfang; Peng, Ling; Li, Xue; Chen, Shufen; Feng, Xiaomiao; Guan, Yuqiao; Huang, Wei

2016-01-01

Locating core-shell metal nanoparticles into a photoactive layer or at the interface of photoactive layer/hole extraction layer is beneficial for fully employing surface plasmon energy, thus enhancing power conversion efficiency (PCE) in plasmonic organic photovoltaic devices (OPVs). Herein, we first investigated the influence of silica shell thickness in Au nanorods (NRs)@SiO2 core-shell structures on OPV performances by inserting them into poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) and thieno[3,4-b]thiophene/benzodithiophene (PTB7) interface, and amazedly found that a 2–3 nm silica shell onto Au NRs induces a highest short-circuit current density of 21.2 mA cm−2 and PCE of 9.55%. This is primarily due to an extremely strong local field and a much slower attenuation of localized surface plasmon resonance around ultrathin silica-coated Au NRs, with which the field intensity remains a high value in the active layer, thus sufficiently improves the absorption of PTB7. Our work provides a clear design concept on precise control of the shell of metal nanoparticles to realize high performances in plasmonic OPVs. PMID:27125309

Influence of SiO2 shell thickness on power conversion efficiency in plasmonic polymer solar cells with Au nanorod@SiO2 core-shell structures.

PubMed

Zhang, Ran; Zhou, Yongfang; Peng, Ling; Li, Xue; Chen, Shufen; Feng, Xiaomiao; Guan, Yuqiao; Huang, Wei

2016-04-29

Locating core-shell metal nanoparticles into a photoactive layer or at the interface of photoactive layer/hole extraction layer is beneficial for fully employing surface plasmon energy, thus enhancing power conversion efficiency (PCE) in plasmonic organic photovoltaic devices (OPVs). Herein, we first investigated the influence of silica shell thickness in Au nanorods (NRs)@SiO2 core-shell structures on OPV performances by inserting them into poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) and thieno[3,4-b]thiophene/benzodithiophene (PTB7) interface, and amazedly found that a 2-3 nm silica shell onto Au NRs induces a highest short-circuit current density of 21.2 mA cm(-2) and PCE of 9.55%. This is primarily due to an extremely strong local field and a much slower attenuation of localized surface plasmon resonance around ultrathin silica-coated Au NRs, with which the field intensity remains a high value in the active layer, thus sufficiently improves the absorption of PTB7. Our work provides a clear design concept on precise control of the shell of metal nanoparticles to realize high performances in plasmonic OPVs.

Microviscosity of supercooled water confined within aminopropyl-modified mesoporous silica as studied by time-resolved fluorescence spectroscopy.

PubMed

Yamaguchi, Akira; Namekawa, Manato; Itoh, Tetsuji; Teramae, Norio

2012-01-01

The fluorescence dynamics of rhodamine B (RhB) immobilized on the pore surface of aminopropyl (AP)-modified mesoporous silica (diameter of the silica framework, 3.1 nm) was examined at temperatures between 293 and 193 K to study the microviscosity of supercooled water confined inside the pores. The mesoporous silica specimen with a dense AP layer (2.1 molecules nm(-2)) was prepared, and RhB isothiocyanate was covalently bound to part of the surface AP groups. The fluorescence lifetime of the surface RhB increased with decreasing temperature from 293 to 223 K, indicating that freezing of the confined water did not occur in this temperature range. The microviscosity of the supercooled confined water was evaluated from an analysis of the lifetime data based on a frequency-dependent friction model.

Silicanizing Process On Mild Steel Substrate by Using Tronoh Silica Sand: Microstructure, composition and coating growth

NASA Astrophysics Data System (ADS)

Y, Yusnenti F. M.; M, Othman; Mustapha, Mazli; I, MohdYusri

2016-02-01

A new Silicanizing process on formation of coating on mild steel using Tronoh Silica Sand (TSS) is presented. The process was performed in the temperature range 1000- 1100°C and with varying deposition time of 1-4 hours. Influence of the layer and the substrate constituents on the coating compatibility of the whole silicanized layer is described in detail. Morphology and structure of the silicanized layer were investigated by XRF, XRD and SEM. It is observed that diffusion coatings containing high concentrations of silica which profile distribution of SiO2 in the silicanized layer was encountered and the depth from the surface to the substrate was taken as the layer thickness. The results also depicted that a longer deposition time have tendency to produce a looser and larger grain a hence rougher layer. The silicanized layer composed of FeSi and Fe2SiO4 phases with preferred orientation within the experimental range. It is also found that longer deposition time and higher temperature resulted in an increase in SiO2 concentration on the substrate (mild steel).

In vitro characterisation of a sol-gel derived in situ silica-coated silicate and carbonate co-doped hydroxyapatite nanopowder for bone grafting.

PubMed

Latifi, Seyed Mohsen; Fathi, Mohammadhossein; Sharifnabi, Ali; Varshosaz, Jaleh

2017-06-01

Design and synthesis of materials with better properties and performance are essential requirements in the field of biomaterials science that would directly improve patient quality of life. For this purpose, in situ silica-coated silicate and carbonate co-doped hydroxyapatite (Sc/S.C.HA) nanopowder was synthesized via the sol-gel method. Characterisation of the prepared nanopowder was carried out by XRD, FTIR, TEM, SEM, EDX, ICP, zeta potential, acid dissolution test, and cell culture test. The substitution of the silicate and carbonate ions into hydroxyapatite structure was confirmed by FTIR analysis. XRD analysis showed that silica is an amorphous phase, which played a role in covering the surface of the S.C.HA nanoparticles as confirmed by acid dissolution test. Low thickness and low integrity of the amorphous silica surface layer facilitated ions release from S.C.HA nanoparticles into physiological saline solution. Zeta potential of the prepared nanopowder suspended in physiological saline solution was -27.3±0.2mV at pH7.4. This negatively charged surface, due to the presence of amorphous silica layer upon the S.C.HA nanoparticles, not only had an accelerating effect on in vitro biomineralization of apatite, but also had a positive effect on cell attachment. Copyright © 2017 Elsevier B.V. All rights reserved.

Hydrophilic nano-silica coating agents with platinum and diamond nanoparticles for denture base materials.

PubMed

Yoshizaki, Taro; Akiba, Norihisa; Inokoshi, Masanao; Shimada, Masayuki; Minakuchi, Shunsuke

2017-05-31

Preventing microorganisms from adhering to the denture surface is important for ensuring the systemic health of elderly denture wearers. Silica coating agents provide high hydrophilicity but lack durability. This study investigated solutions to improve the durability of the coating layer, determine an appropriate solid content concentration of SiO 2 in the silica coating agent, and evaluate the effect of adding platinum (Pt) and diamond nanoparticles (ND) to the agent. Five coating agents were prepared with different SiO 2 concentrations with/without Pt and ND additives. The contact angle was measured, and the brush-wear test was performed. Scanning electron microscopy was used to investigate the silica coating layer. The appropriate concentration of SiO 2 was found to be 0.5-0.75 wt%. The coating agents with additives showed significantly high hydrophilicity immediately after coating and after the brush-wear test. The coating agents with/without additives formed a durable coating layer even after the brush-wear test.

Lubricant-infused nanoparticulate coatings assembled by layer-by-layer deposition

DOE PAGES

Sunny, Steffi; Vogel, Nicolas; Howell, Caitlin; ...

2014-09-01

Omniphobic coatings are designed to repel a wide range of liquids without leaving stains on the surface. A practical coating should exhibit stable repellency, show no interference with color or transparency of the underlying substrate and, ideally, be deposited in a simple process on arbitrarily shaped surfaces. We use layer-by-layer (LbL) deposition of negatively charged silica nanoparticles and positively charged polyelectrolytes to create nanoscale surface structures that are further surface-functionalized with fluorinated silanes and infiltrated with fluorinated oil, forming a smooth, highly repellent coating on surfaces of different materials and shapes. We show that four or more LbL cycles introducemore » sufficient surface roughness to effectively immobilize the lubricant into the nanoporous coating and provide a stable liquid interface that repels water, low-surface-tension liquids and complex fluids. The absence of hierarchical structures and the small size of the silica nanoparticles enables complete transparency of the coating, with light transmittance exceeding that of normal glass. The coating is mechanically robust, maintains its repellency after exposure to continuous flow for several days and prevents adsorption of streptavidin as a model protein. As a result, the LbL process is conceptually simple, of low cost, environmentally benign, scalable, automatable and therefore may present an efficient synthetic route to non-fouling materials.« less

Lubricant-Infused Nanoparticulate Coatings Assembled by Layer-by-Layer Deposition

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

Sunny, S; Vogel, N; Howell, C

2014-09-01

Omniphobic coatings are designed to repel a wide range of liquids without leaving stains on the surface. A practical coating should exhibit stable repellency, show no interference with color or transparency of the underlying substrate and, ideally, be deposited in a simple process on arbitrarily shaped surfaces. We use layer-by-layer (LbL) deposition of negatively charged silica nanoparticles and positively charged polyelectrolytes to create nanoscale surface structures that are further surface-functionalized with fluorinated silanes and infiltrated with fluorinated oil, forming a smooth, highly repellent coating on surfaces of different materials and shapes. We show that four or more LbL cycles introducemore » sufficient surface roughness to effectively immobilize the lubricant into the nanoporous coating and provide a stable liquid interface that repels water, low-surface-tension liquids and complex fluids. The absence of hierarchical structures and the small size of the silica nanoparticles enables complete transparency of the coating, with light transmittance exceeding that of normal glass. The coating is mechanically robust, maintains its repellency after exposure to continuous flow for several days and prevents adsorption of streptavidin as a model protein. The LbL process is conceptually simple, of low cost, environmentally benign, scalable, automatable and therefore may present an efficient synthetic route to non-fouling materials.« less

Monoatomic layer removal mechanism in chemical mechanical polishing process: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Si, Lina; Guo, Dan; Luo, Jianbin; Lu, Xinchun

2010-03-01

Molecular dynamics simulations of nanoscratching processes were used to study the atomic-scale removal mechanism of single crystalline silicon in chemical mechanical polishing (CMP) process and particular attention was paid to the effect of scratching depth. The simulation results under a scratching depth of 1 nm showed that a thick layer of silicon material was removed by chip formation and an amorphous layer was formed on the silicon surface after nanoscratching. By contrast, the simulation results with a depth of 0.1 nm indicated that just one monoatomic layer of workpiece was removed and a well ordered crystalline surface was obtained, which is quite consistent with previous CMP experimental results. Therefore, monoatomic layer removal mechanism was presented, by which it is considered that during CMP process the material was removed by one monoatomic layer after another, and the mechanism could provide a reasonable understanding on how the high precision surface was obtained. Also, the effects of the silica particle size and scratching velocity on the removal mechanism were investigated; the wear regimes and interatomic forces between silica particle and workpiece were studied to account for the different removal mechanisms with indentation depths of 0.1 and 1 nm.

Interferences of Silica Nanoparticles in Green Fluorescent Protein Folding Processes.

PubMed

Klein, Géraldine; Devineau, Stéphanie; Aude, Jean Christophe; Boulard, Yves; Pasquier, Hélène; Labarre, Jean; Pin, Serge; Renault, Jean Philippe

2016-01-12

We investigated the relationship between unfolded proteins, silica nanoparticles and chaperonin to determine whether unfolded proteins could stick to silica surfaces and how this process could impair heat shock protein activity. The HSP60 catalyzed green fluorescent protein (GFP) folding was used as a model system. The adsorption isotherms and adsorption kinetics of denatured GFP were measured, showing that denaturation increases GFP affinity for silica surfaces. This affinity is maintained even if the surfaces are covered by a protein corona and allows silica NPs to interfere directly with GFP folding by trapping it in its unstructured state. We determined also the adsorption isotherms of HSP60 and its chaperonin activity once adsorbed, showing that SiO2 NP can interfere also indirectly with protein folding through chaperonin trapping and inhibition. This inhibition is specifically efficient when NPs are covered first with a layer of unfolded proteins. These results highlight for the first time the antichaperonin activity of silica NPs and ask new questions about the toxicity of such misfolded proteins/nanoparticles assembly toward cells.

Layer-by-layer-based silica encapsulation of individual yeast with thickness control.

PubMed

Lee, Hojae; Hong, Daewha; Choi, Ji Yu; Kim, Ji Yup; Lee, Sang Hee; Kim, Ho Min; Yang, Sung Ho; Choi, Insung S

2015-01-01

In the area of cell-surface engineering with nanomaterials, the metabolic and functional activities of the encapsulated cells are manipulated and controlled by various parameters of the artificial shells that encase the cells, such as stiffness and elasticity, thickness, and porosity. The mechanical durability and physicochemical stability of inorganic shells prove superior to layer-by-layer-based organic shells with regard to cytoprotection, but it has been difficult to vary the parameters of inorganic shells including their thickness. In this work, we combine the layer-by-layer technique with a process of bioinspired silicification to control the thickness of the silica shells that encapsulate yeast Saccharomyces cerevisiae cells individually, and investigate the thickness-dependent microbial growth. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Density profile of nitrogen in cylindrical pores of MCM-41

NASA Astrophysics Data System (ADS)

Soper, Alan K.; Bowron, Daniel T.

2017-09-01

A straightforward approach using radiation scattering (X-ray or neutron) combined with atomistic modelling is used to accurately assess the pore dimensions in the porous silica, MCM-41. The method is used to calculate the density profile of nitrogen absorbed in this material at a variety of fractional pressures, p/p0, where p0 is the saturated vapour pressure, up to p/p0 = 0.36 at T = 87 K in the present instance. At this pressure two distinct layers of liquid nitrogen occur on the silica surface, with a relatively sharp gas-liquid interface. It is suggested surface tension effects at this interface strongly influence the growth of further layers.

Effect of carrier properties on surface characteristics of sorbents modified with acetylacetonates Ni (II), Cu (II)

NASA Astrophysics Data System (ADS)

Faustova, Zhanna; Matveeva, Tatiana; Slizhov, Yuriy

2017-11-01

Sorbents based on Chromaton N-AW with layers of mesoporous silica gel modified with acetylacetonate nickel (II) and copper (II) were obtained. The porous structure of sorbents based on synthesized silica gel and industrial samples of Chromaton N, Silipore 075, Silochrom C-120 was studied. All studied samples are mesoporous. For sorbents based on commercially available Chromaton N, Silipore 075, and Silochrome 120, the mesopore dimensions vary in a wide range from 10 to 50 nm. For synthesized silica gel and chelate-containing sorbents, a narrower pore distribution is observed in the range of 5-15 nm, which indicates the uniformity of its surface. A comparative analysis of the effect of carrier properties on the acid-base properties of the surface of chelate-containing sorbents is carried out. The acid-base nature of the modifier is more pronounced in the case of synthesized silica gel by the sol-gel method.

Method for reducing formation of electrically resistive layer on ferritic stainless steels

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

Rakowski, James M.

A method of reducing the formation of electrically resistive scale on a an article comprising a silicon-containing ferritic stainless subjected to oxidizing conditions in service includes, prior to placing the article in service, subjecting the article to conditions under which silica, which includes silicon derived from the steel, forms on a surface of the steel. Optionally, at least a portion of the silica is removed from the surface to placing the article in service. A ferritic stainless steel alloy having a reduced tendency to form silica on at least a surface thereof also is provided. The steel includes a near-surfacemore » region that has been depleted of silicon relative to a remainder of the steel.« less

Water at silica/liquid water interfaces investigated by DFT-MD simulations

NASA Astrophysics Data System (ADS)

Gaigeot, Marie-Pierre

This talk is dedicated to probing the microscopic structural organization of water at silica/liquid water interfaces including electrolytes by first principles DFT-based molecular dynamics simulations (DFT-MD). We will present our very recent DFT-MD simulations of electrolytic (KCl, NaCl, NaI) silica/liquid water interfaces in order to unravel the intertwined structural properties of water and electrolytes at the crystalline quartz/liquid water and amorphous silica/liquid water interfaces. DFT-MD simulations provide direct knowledge of the structural organization of water and the H-Bond network formed between the water molecules within the different water layers above the silica surface. One can furthermore extract vibrational signatures of the water molecules within the interfacial layers from the DFT-MD simulations, especially non-linear SFG (Sum Frequency generation) signatures that are active at solid/liquid interfaces. The strength of the simulated spectra is that a detailed analysis of the signatures in terms of the water/water H-Bond networks formed within the interfacial water layers and in terms of the water/silica or water/electrolytes H-Bond networks can be given. Comparisons of SFG spectra between quartz/water/electrolytes and amorphous silica/water/electrolytes interfaces allow us to definitely conclude on how the structural arrangements of liquid water at these electrolytic interfaces modulate the final spectroscopic signatures. Invited speaker.

W-containing oxide layers obtained on aluminum and titanium by PEO as catalysts in thiophene oxidation

NASA Astrophysics Data System (ADS)

Rudnev, V. S.; Lukiyanchuk, I. V.; Vasilyeva, M. S.; Morozova, V. P.; Zelikman, V. M.; Tarkhanova, I. G.

2017-11-01

W-containing oxide layers fabricated on titanium and aluminum alloys by Plasma electrolytic oxidation (PEO) have been tested in the reaction of the peroxide oxidation of thiophene. Samples with two types of coatings have been investigated. Coatings I contained tungsten oxide in the matrix and on the surface of amorphous silica-titania or silica-alumina layers, while coatings II comprised crystalline WO3 and/or Al2(WO4)3. Aluminum-supported catalyst containing a smallest amount of transition metals in the form of tungsten oxides and manganese oxides in low oxidation levels showed high activity and stability.

Effect of cation size and charge on the interaction between silica surfaces in 1:1, 2:1, and 3:1 aqueous electrolytes.

PubMed

Dishon, Matan; Zohar, Ohad; Sivan, Uri

2011-11-01

Application of two complementary AFM measurements, force vs separation and adhesion force, reveals the combined effects of cation size and charge (valency) on the interaction between silica surfaces in three 1:1, three 2:1, and three 3:1 metal chloride aqueous solutions of different concentrations. The interaction between the silica surfaces in 1:1 and 2:1 salt solutions is fully accounted for by ion-independent van der Waals (vdW) attraction and electric double-layer repulsion modified by cation specific adsorption to the silica surfaces. The deduced ranking of mono- and divalent cation adsorption capacity (adsorbability) to silica, Mg(2+) < Ca(2+) < Na(+) < Sr(2+) < K(+) < Cs(+), follows cation bare size as well as cation solvation energy but does not correlate with hydrated ionic radius or with volume or surface ionic charge density. In the presence of 3:1 salts, the coarse phenomenology of the force between the silica surfaces as a function of salt concentration resembles that in 1:1 and 2:1 electrolytes. Nevertheless, two fundamental differences should be noticed. First, the attraction between the silica surfaces is too large to be attributed solely to vdW force, hence implying an additional attraction mechanism or gross modification of the conventional vdW attraction. Second, neutralization of the silica surfaces occurs at trivalent cation concentrations that are 3 orders of magnitude smaller than those characterizing surface neutralization by mono- and divalent cations. Consequently, when trivalent cations are added to our cation adsorbability series the correlation with bare ion size breaks down abruptly. The strong adsorbability of trivalent cations to silica contrasts straightforward expectations based on ranking of the cationic solvation energies, thus suggesting a different adsorption mechanism which is inoperative or weak for mono- and divalent cations.

Silica decorated on porous activated carbon nanofiber composites for high-performance supercapacitors

NASA Astrophysics Data System (ADS)

Kim, So Yeun; Kim, Bo-Hye

2016-10-01

A hybrid of silica decorated on porous activated carbon nanofibers (ACNFs) is fabricated in the form of a web via electrospinning and an activation process as an electrode material for electrochemical capacitors in an organic electrolyte. The introduction of PhSiH3 (PS) into the polyacrylonitrile (PAN) solution induces a porous ACNF structure containing silica nanoparticles (NPs) via the spontaneous sol-gel process of PS by steam in the subsequent physical activation process. These inorganic-organic hybrid composites of porous ACNF containing silica NPs show superior specific capacitance and energy density in electrochemical tests, along with good rate capability and excellent cycle life in an organic electrolyte, which is attributed to the combination of ACNF's high surface area and silica's hydrophilicity. The electrochemical performance decreases with increasing PS concentration, and this trend is consistent with the specific surface area results, which reveal the rapid formation of a double layer.

Self-assembly of supramolecular triarylamine nanowires in mesoporous silica and biocompatible electrodes thereof.

PubMed

Licsandru, Erol-Dan; Schneider, Susanne; Tingry, Sophie; Ellis, Thomas; Moulin, Emilie; Maaloum, Mounir; Lehn, Jean-Marie; Barboiu, Mihail; Giuseppone, Nicolas

2016-03-14

Biocompatible silica-based mesoporous materials, which present high surface areas combined with uniform distribution of nanopores, can be organized in functional nanopatterns for a number of applications. However, silica is by essence an electrically insulating material which precludes applications for electro-chemical devices. The formation of hybrid electroactive silica nanostructures is thus expected to be of great interest for the design of biocompatible conducting materials such as bioelectrodes. Here we show that we can grow supramolecular stacks of triarylamine molecules in the confined space of oriented mesopores of a silica nanolayer covering a gold electrode. This addressable bottom-up construction is triggered from solution simply by light irradiation. The resulting self-assembled nanowires act as highly conducting electronic pathways crossing the silica layer. They allow very efficient charge transfer from the redox species in solution to the gold surface. We demonstrate the potential of these hybrid constitutional materials by implementing them as biocathodes and by measuring laccase activity that reduces dioxygen to produce water.

Mesoporous silica nanoparticles engineered for ultrasound-induced uptake by cancer cells.

PubMed

Paris, Juan L; Manzano, Miguel; Cabañas, M Victoria; Vallet-Regí, María

2018-04-05

A novel smart hierarchical ultrasound-responsive mesoporous silica nanocarrier for cancer therapy is presented here. This dynamic nanosystem has been designed to display different surface characteristics during its journey towards tumor cells. Initially, the anticancer-loaded nanocarriers are shielded with a polyethylene glycol layer. Upon exposure to high frequency ultrasound, the polymer shell detaches from the nanoparticles, exposing a positively charged surface. This favors the internalization in human osteosarcoma cells, where the release of topotecan takes place, drastically enhancing the cytotoxic effect.

Variables related to materials and preparing for bond strength testing irrespective of the test protocol.

PubMed

Mair, Lawrence; Padipatvuthikul, P

2010-02-01

Resin bonding can be compared to making a sandwich with the tooth on one side and the restoration on the other, a layer of bonding resin is applied to either side and a filled resin (composite) placed in between. This presentation considers factors that influence the restoration side of the sandwich and various ways that the assembled testpieces may be "aged" prior to testing. The materials to be bonded may be either ceramic, metal or composite formed by methods such as casting, pressing, sintering or machining. The fabrication method determines the susceptibility of the bonding surface to physical or chemical modification. The treatment of the surface prior to bonding can be physical (e.g. sandblasting) or chemical (e.g. metal primer); but is more likely to be a combination (e.g. silica deposition+silane). Successful bonding depends on establishing a surface with a high population of unreacted vinyl groups (-CC) that can then be cross-polymerized to the resin in the bonding composite. The physical approach has involved etching or sandblasting the surfaces; but the ability to form a microretentive surface in this way depends on a heterogeneous surface. Noble metals and modern high strength ceramics have a more homogeneous surface and are not easily etched. To overcome this problem a number of ways to deposit a silica layer on the bonding surface have been developed: the Silicoater that involves baking on a silica layer, the Rocatec technique (CoJet) that involves air blasting silica onto the surface in conjunction with an abrasive; and two more modern approaches: sol-gel evaporation and molecular vapor deposition (MVD). All these techniques require the subsequent application of a silane layer to provide the -CC moieties. The use of primers without an intervening silica layer has been tested and found to be successful with some specialized bonding systems that contain agents such as methacryloyloxydecyldihydrogen-phosphate (MDP) (PanaviaEX). AGING OF TESTPIECES PRIOR TO BONDING: The most common type of aging is storage in water at temperatures from ambient to 100 degrees Celsius. This generally decreases bond strengths; but not to catastrophic values. A more exacting pre-test regime is thermal cycling. In some studies this caused a slightly greater reduction in bond strength than storage in water; but in other tests it resulted in total failure. As some testpieces have spontaneously debonded during thermal cycling, it seems sensible to include TC in any screening test of new materials. Mechanical cycling (fatigue) prior to testing has a very significant effect and the bond strength that can withstand 1,000,000 cycles can be one sixth of the bond strength in a simple monotonic test (tensile, shear or compression). Whereas simple monotonic tests provide a blunt instrument for eliminating poorly performing techniques their use for discriminating between established techniques is open to discussion. Copyright 2009 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Polyethylenimine-impregnated mesoporous silica: effect of amine loading and surface alkyl chains on CO2 adsorption.

PubMed

Heydari-Gorji, Aliakbar; Belmabkhout, Youssef; Sayari, Abdelhamid

2011-10-18

Poly(ethyleneimine) (PEI) supported on pore-expanded MCM-41 whose surface is covered with a layer of long-alkyl chains was found to be a more efficient CO(2) adsorbent than PEI supported on the corresponding calcined silica and all PEI-impregnated materials reported in the literature. The layer of surface alkyl chains plays an important role in enhancing the dispersion of PEI, thus decreasing the diffusion resistance. It was also found that at low temperature, adsorbents with relatively low PEI contents are more efficient than their highly loaded counterparts because of the increased adsorption rate. Extensive CO(2) adsorption-desorption cycling showed that the use of humidified feed and purge gases affords materials with enhanced stability, despite limited loss due to amine evaporation. © 2011 American Chemical Society

Dynamic behaviour of the silica-water-bio electrical double layer in the presence of a divalent electrolyte.

PubMed

Lowe, B M; Maekawa, Y; Shibuta, Y; Sakata, T; Skylaris, C-K; Green, N G

2017-01-25

Electronic devices are becoming increasingly used in chemical- and bio-sensing applications and therefore understanding the silica-electrolyte interface at the atomic scale is becoming increasingly important. For example, field-effect biosensors (BioFETs) operate by measuring perturbations in the electric field produced by the electrical double layer due to biomolecules binding on the surface. In this paper, explicit-solvent atomistic calculations of this electric field are presented and the structure and dynamics of the interface are investigated in different ionic strengths using molecular dynamics simulations. Novel results from simulation of the addition of DNA molecules and divalent ions are also presented, the latter of particular importance in both physiological solutions and biosensing experiments. The simulations demonstrated evidence of charge inversion, which is known to occur experimentally for divalent electrolyte systems. A strong interaction between ions and DNA phosphate groups was demonstrated in mixed electrolyte solutions, which are relevant to experimental observations of device sensitivity in the literature. The bound DNA resulted in local changes to the electric field at the surface; however, the spatial- and temporal-mean electric field showed no significant change. This result is explained by strong screening resulting from a combination of strongly polarised water and a compact layer of counterions around the DNA and silica surface. This work suggests that the saturation of the Stern layer is an important factor in determining BioFET response to increased salt concentration and provides novel insight into the interplay between ions and the EDL.

Improving Powder Magnetic Core Properties via Application of Thin, Insulating Silica-Nanosheet Layers on Iron Powder Particles

PubMed Central

Ishizaki, Toshitaka; Nakano, Hideyuki; Tajima, Shin; Takahashi, Naoko

2016-01-01

A thin, insulating layer with high electrical resistivity is vital to achieving high performance of powder magnetic cores. Using layer-by-layer deposition of silica nanosheets or colloidal silica over insulating layers composed of strontium phosphate and boron oxide, we succeeded in fabricating insulating layers with high electrical resistivity on iron powder particles, which were subsequently used to prepare toroidal cores. The compact density of these cores decreased after coating with colloidal silica due to the substantial increase in the volume, causing the magnetic flux density to deteriorate. Coating with silica nanosheets, on the other hand, resulted in a higher electrical resistivity and a good balance between high magnetic flux density and low iron loss due to the thinner silica layers. Transmission electron microscopy images showed that the thickness of the colloidal silica coating was about 700 nm, while that of the silica nanosheet coating was 30 nm. There was one drawback to using silica nanosheets, namely a deterioration in the core mechanical strength. Nevertheless, the silica nanosheet coating resulted in nanoscale-thick silica layers that are favorable for enhancing the electrical resistivity. PMID:28336835

Surface-dependent chemical equilibrium constants and capacitances for bare and 3-cyanopropyldimethylchlorosilane coated silica nanochannels.

PubMed

Andersen, Mathias Bækbo; Frey, Jared; Pennathur, Sumita; Bruus, Henrik

2011-01-01

We present a combined theoretical and experimental analysis of the solid-liquid interface of fused-silica nanofabricated channels with and without a hydrophilic 3-cyanopropyldimethylchlorosilane (cyanosilane) coating. We develop a model that relaxes the assumption that the surface parameters C(1), C(2), and pK(+) are constant and independent of surface composition. Our theoretical model consists of three parts: (i) a chemical equilibrium model of the bare or coated wall, (ii) a chemical equilibrium model of the buffered bulk electrolyte, and (iii) a self-consistent Gouy-Chapman-Stern triple-layer model of the electrochemical double layer coupling these two equilibrium models. To validate our model, we used both pH-sensitive dye-based capillary filling experiments as well as electro-osmotic current-monitoring measurements. Using our model we predict the dependence of ζ potential, surface charge density, and capillary filling length ratio on ionic strength for different surface compositions, which can be difficult to achieve otherwise. Copyright © 2010 Elsevier Inc. All rights reserved.

Silica nanogelling of environment-responsive PEGylated polyplexes for enhanced stability and intracellular delivery of siRNA.

PubMed

Gouda, Noha; Miyata, Kanjiro; Christie, R James; Suma, Tomoya; Kishimura, Akihiro; Fukushima, Shigeto; Nomoto, Takahiro; Liu, Xueying; Nishiyama, Nobuhiro; Kataoka, Kazunori

2013-01-01

In this study, poly(ethylene glycol) (PEG)-block-polycation/siRNA complexes (PEGylated polyplexes) were wrapped with a hydrated silica, termed "silica nanogelling", in order to enhance their stability and functionality. Silica nanogelling was achieved by polycondensation of soluble silicates onto the surface of PEGylated polyplexes comprising a disulfide cross-linked core. Formation of silica nanogel layer on the PEGylated cross-linked polyplexes was confirmed by particle size increase, surface charge reduction, and elemental analysis of transmission electron micrographs. Silica nanogelling substantially improved polyplex stability against counter polyanion-induced dissociation under non-reductive condition, without compromising the reductive environment-responsive siRNA release triggered by disulfide cleavage. Silica nanogelling significantly enhanced the sequence-specific gene silencing activity of the polyplexes in HeLa cells without associated cytotoxicity, probably due lower endosomal entrapment (or lysosomal degradation) of delivered siRNA. The lower endosomal entrapment of the silica nanogel system could be explained by an accelerated endosomal escape triggered by deprotonated silanol groups in the silica (the proton sponge hypothesis) and/or a modulated intracellular trafficking, possibly via macropinocytosis, as evidenced by the cellular uptake inhibition assay. Henceforth, silica nanogelling of PEGylated siRNA polyplexes is a promising strategy for preparation of stable and functional siRNA delivery vehicles. Copyright © 2012 Elsevier Ltd. All rights reserved.

Timescales and mechanisms of formation of amorphous silica coatings on fresh basalts at Kīlauea Volcano, Hawai'i

NASA Astrophysics Data System (ADS)

Chemtob, Steven M.; Rossman, George R.

2014-10-01

Young basalts from Kīlauea Volcano, Hawai'i, frequently feature opaque surface coatings, 1-80 μm thick, composed of amorphous silica and Fe-Ti oxides. These coatings are the product of interaction of the basaltic surface with volcanically-derived acidic fluids. Previous workers have identified these coatings in a variety of contexts on Hawai'i, but the timescales of coating development, coating growth rates, and factors controlling lateral coating heterogeneity were largely unconstrained. We sampled and analyzed young lava flows (of varying ages, from hours to ~ 40 years) along Kīlauea's southwest and east rift zones to characterize variation in silica coating properties across the landscape. Coating thickness varies as a function of flow age, flow surface type, and proximity to acid sources like local fissure vents and regional plumes emitted from Kīlauea Caldera and Pu'u Ō'ō. Silica coatings that form in immediate proximity to acid sources are more chemically pure than those forming in higher pH environments, which contain significant Al and Fe. Incipient siliceous alteration was observed on basalt surfaces as young as 8 days old, but periods of a year or more are required to develop contiguous coatings with obvious opaque coloration. Inferred coating growth rates vary with environmental conditions but were typically 1-5 μm/year. Coatings form preferentially on flow surfaces with glassy outer layers, such as spatter ramparts, volcanic bombs, and dense pahoehoe breakouts, due to glass strain weakening during cooling. Microtextural evidence suggests that the silica coatings form both by in situ dissolution-reprecipitation and by deposition of silica mobilized in solution. Thin films of water, acidified by contact with volcanic vapors, dissolved near-surface basalt, then precipitated amorphous silica in place, mobilizing more soluble cations. Additional silica was transported to and deposited on the surface by silica-bearing altering fluids derived from the basalt interior.

Fabrication of semi-aromatic polyamide/spherical mesoporous silica nanocomposite reverse osmosis membrane with superior permeability

NASA Astrophysics Data System (ADS)

Li, Qiang; Yu, Hui; Wu, Feiyang; Song, Jie; Pan, Xianhui; Zhang, Meng

2016-02-01

Semi-aromatic polyamide (SAP)/spherical mesoporous silica nanocomposite reverse osmosis (RO) membrane was successfully fabricated using m-phenylene diamine aqueous solution and cyclohexane-1,3,5-tricarbonyl chloride/mesoporous-silica-sphere (MSS) organic solution as main raw materials. The experimental suggests that the microstructures and surface features are significantly different from those of the contrast samples (the full- and semi-aromatic polyamide membranes), including the surface morphology, polymer framework structure, surface charge density, hydrophilicity, and the thickness of barrier layer. It was observed that many MSSs with ca. 1.5 nm of pore size are evenly embedded on the surface of the fabricated SAP/MSS RO membrane. Furthermore, the separation performance testing results indicate that the permeabilities range from 62.53 to 72.73 L/m2 h with the increase of the introduced MSSs from 0.02 to 0.08 w/v % under 1.5 MPa operating pressure and 2000 mg/L NaCl solution, which is obviously better than the contrast samples. Simultaneously, their salt rejections can be still maintained at a comparable level (94.78-91.46%). The excellent separation performance of the nanocomposite RO membrane is closely related to the higher-freedom-degree semi-aromatic framework, the incorporation of MSSs, the improved surface hydrophilicity, the thinner barrier layer, and the enhanced surface negative charge density.

Bifunctional silica nanospheres with 3-aminopropyl and phenyl groups. Synthesis approach and prospects of their applications

NASA Astrophysics Data System (ADS)

Kotsyuda, Sofiya S.; Tomina, Veronika V.; Zub, Yuriy L.; Furtat, Iryna M.; Lebed, Anastasia P.; Vaclavikova, Miroslava; Melnyk, Inna V.

2017-10-01

Spherical silica particles with bifunctional (tbnd Si(CH2)3NH2/tbnd SiC6H5) surface layers were synthesized by the Stöber method using ternary alkoxysilanes systems. The influence of the synthesis conditions, such as temperature and stirring time on the process of nanoparticles formation was studied. The presence of introduced functional groups was confirmed by FTIR. The composition of the surface layers examined by elemental analysis and acid-base titration was shown to be independent from the synthesis temperature. However, the size of the obtained particles depends on the synthesis temperature and, according to photon cross-correlation spectroscopy, can be varied from 50 to 846 nm. The variation of electric charges of N-functional groups was disclosed in obtained nanospheres and attributed to different surface location of these groups and their surrounding with other groups. The sorption of Cu(II) ions by functionalized silicas depends on the concentration of amino groups, which correlates with the isoelectric point values (determined to vary from 8.26 to 9.21). Bifunctional nanoparticles adsorb 99.0 mg/g of methylene blue, compared with 48.0 mg/g by silica sample with only amino groups. The nanospheres, both with and without adsorbed Cu2+, demonstrate reasonable antibacterial activity against S. aureus ATCC 25923, depending on particle concentration in water suspension.

Pore radius fine tuning of a silica matrix (MCM-41) based on the synthesis of alumina nanolayers with different thicknesses by atomic layer deposition

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

Zemtsova, Elena G., E-mail: ezimtsova@yandex.ru; Arbenin, Andrei Yu.; Plotnikov, Alexander F.

2015-03-15

The authors investigated a new approach to modify the surface of the mesoporous silica matrix MCM-41. This approach is based on manipulating the chemical composition of the porous surface layer and also on fine tuning the pore radius by applying the atomic layer deposition (ALD) technique. The synthesis of alumina nanolayers was performed on the planar and the porous matrix (MCM-41) by the ALD technique using aluminum tri-sec-butoxide and water as precursors. The authors show that one cycle on silicon, using aluminum tri-sec-butoxide and water as precursors, results in a 1–1.2 Å increase in alumina nanolayer thickness. This is comparable tomore » the increase in thickness per cycle for other precursors such as trimethylaluminum and aluminum chloride. The authors show that the synthesis of an Al{sub 2}O{sub 3} nanolayer on the pore surface of the mesoporous silica matrix MCM-41 by the ALD technique results in a regular change in the porous structure of the samples. The specific porosity (ml/g) of the MCM-41 was 0.95 and that of MCM-41 after 5 ALD cycles was 0.39. The pore diameter (nm) of MCM-41 was 3.3 and that of MCM-41 after 5 ALD cycles was 2.3.« less

Molecular Imprinting of Silica Nanoparticle Surfaces via Reversible Addition-Fragmentation Polymerization for Optical Biosensing Applications

NASA Astrophysics Data System (ADS)

Oluz, Zehra; Nayab, Sana; Kursun, Talya Tugana; Caykara, Tuncer; Yameen, Basit; Duran, Hatice

Azo initiator modified surface of silica nanoparticles were coated via reversible addition-fragmentation polymerization (RAFT) of methacrylic acid and ethylene glycol dimethacrylate using 2-phenylprop 2-yl dithobenzoate as chain transfer agent. Using L-phenylalanine anilide as template during polymerization led molecularly imprinted nanoparticles. RAFT polymerization offers an efficient control of grafting process, while molecularly imprinted polymers shows enhanced capacity as sensor. L-phenylalanine anilide imprinted silica particles were characterized by X-Ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM). Performances of the particles were followed by surface plasmon resonance spectroscopy (SPR) after coating the final product on gold deposited glass substrate against four different analogous of analyte molecules: D-henylalanine anilide, L-tyrosine, L-tryptophan and L-phenylalanine. Characterizations indicated that silica particles coated with polymer layer do contain binding sites for L-phenylalanine anilide, and are highly selective for the molecule of interest. This project was supported by TUBITAK (Project No:112M804).

Silica-covered star-shaped Au-Ag nanoparticles as new electromagnetic nanoresonators for Raman characterisation of surfaces.

PubMed

Krajczewski, Jan; Kołątaj, Karol; Pietrasik, Sylwia; Kudelski, Andrzej

2018-03-15

One of the tools used for determining the composition of surfaces of various materials is shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). SHINERS is a modification of "standard" surface-enhanced Raman spectroscopy (SERS), in which, before Raman spectra are recorded, the surfaces analysed are covered with a layer of plasmonic nanoparticles protected by a very thin layer of a transparent dielectric. The plasmonic cores of the core-shell nanoparticles used in SHINERS measurements generate a local enhancement of the electric field of the incident electromagnetic radiation, whereas the transparent coatings prevent the metal cores from coming into direct contact with the material being analysed. In this contribution, we propose a new type of SHINERS nanoresonators that contain spiky, star-shaped metal cores (produced from a gold/silver alloy). These spiky, star-shaped Au-Ag nanoparticles have been covered by a layer of silica. The small radii of the ends of the tips of the spikes of these plasmonic nanostructures make it possible to generate a very large enhancement of the electromagnetic field there, with the result that such SHINERS nanoresonators are significantly more efficient than the standard semi-spherical nanostructures. The Au-Ag alloy nanoparticles were synthesised by the reduction of a solution containing silver nitrate and chloroauric acid by ascorbic acid. The final geometry of the nanostructures thus formed was controlled by changing the ratio between the concentrations of AuCl 4 - and Ag + ions. The shape of the synthesised star-shaped Au-Ag nanoparticles does not change significantly during the two standard procedures for depositing a layer of silica (by the decomposition of sodium silicate or the decomposition of tetraethyl orthosilicate). Copyright © 2017 Elsevier B.V. All rights reserved.

Silica-covered star-shaped Au-Ag nanoparticles as new electromagnetic nanoresonators for Raman characterisation of surfaces

NASA Astrophysics Data System (ADS)

Krajczewski, Jan; Kołątaj, Karol; Pietrasik, Sylwia; Kudelski, Andrzej

2018-03-01

One of the tools used for determining the composition of surfaces of various materials is shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). SHINERS is a modification of "standard" surface-enhanced Raman spectroscopy (SERS), in which, before Raman spectra are recorded, the surfaces analysed are covered with a layer of plasmonic nanoparticles protected by a very thin layer of a transparent dielectric. The plasmonic cores of the core-shell nanoparticles used in SHINERS measurements generate a local enhancement of the electric field of the incident electromagnetic radiation, whereas the transparent coatings prevent the metal cores from coming into direct contact with the material being analysed. In this contribution, we propose a new type of SHINERS nanoresonators that contain spiky, star-shaped metal cores (produced from a gold/silver alloy). These spiky, star-shaped Au-Ag nanoparticles have been covered by a layer of silica. The small radii of the ends of the tips of the spikes of these plasmonic nanostructures make it possible to generate a very large enhancement of the electromagnetic field there, with the result that such SHINERS nanoresonators are significantly more efficient than the standard semi-spherical nanostructures. The Au-Ag alloy nanoparticles were synthesised by the reduction of a solution containing silver nitrate and chloroauric acid by ascorbic acid. The final geometry of the nanostructures thus formed was controlled by changing the ratio between the concentrations of AuCl4- and Ag+ ions. The shape of the synthesised star-shaped Au-Ag nanoparticles does not change significantly during the two standard procedures for depositing a layer of silica (by the decomposition of sodium silicate or the decomposition of tetraethyl orthosilicate).

Performance and durability of carbon black-supported Pd catalyst covered with silica layers in membrane-electrode assemblies of proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Fujii, Keitaro; Ito, Mizuki; Sato, Yasushi; Takenaka, Sakae; Kishida, Masahiro

2015-04-01

Pd metal particles supported on a high surface area carbon black (Pd/CB) were covered with silica layers to improve the durability under severe cathode condition of proton exchange membrane fuel cells (PEMFCs). The performance and the durability of the silica-coated Pd/CB (SiO2/Pd/CB) were investigated by rotating disk electrode (RDE) in aqueous HClO4 and single cell test of the membrane-electrode assemblies (MEAs). SiO2/Pd/CB showed excellent durability exceeding Pt/CB during potential cycle in single cell test as well as in RDE measurement while Pd/CB significantly degraded. Furthermore, the MEA using SiO2/Pd/CB as the cathode catalyst showed higher performance than that using Pd/CB even in the initial state. The catalytic activity of SiO2/Pd/CB was higher than that of Pd/CB, and the drop of the cell performances due to the inhibition of electron conduction, proton conduction, and oxygen diffusion by the silica layer was not significant. It has been shown that the silica-coating is a very practical technique that can stabilize metal species originally unstable in the cathode condition of PEMFCs without a decrease in the cell performance.

Sorption of perfluoroalkyl substances to two types of minerals.

PubMed

Hellsing, Maja S; Josefsson, Sarah; Hughes, Arwel V; Ahrens, Lutz

2016-09-01

The sorption of perfluoroalkyl substances (PFASs) was investigated for two model soil mineral surfaces, alumina (Al2O3) and silica (SiO2), on molecular level using neutron scattering. The PFASs were selected (i.e. perfluorohexanoic acid (PFHxA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluorooctane sulfonic acid (PFOS)) to examine the role of hydrophobic chain length and hydrophilic functional group on their sorption behaviour. All four PFASs were found to sorb to alumina surface (positively charged) forming a hydrated layer consisting of 50% PFASs. The PFAS solubility limit, which decrease with chain length, was found to strongly influence the sorption behaviour. The sorbed PFAS layer could easily be removed by gentle rinsing with water, indicating release upon rainfall in the environment. No sorption was observed for PFOA and PFOS at silica surface (negatively charged), showing electrostatic interaction being the driving force in the sorption process. Copyright © 2016 Elsevier Ltd. All rights reserved.

Constitutive law for the densification of fused silica with applications in polishing and microgrinding

NASA Astrophysics Data System (ADS)

Lambropoulos, John C.; Fang, Tong; Xu, Su; Gracewski, Sheryl M.

1995-09-01

We discuss a constitutive model describing the permanent densification of fused silica under large applied pressures and shear stresses. The constitutive law is assumed to be rate- independent, and uses a yield function coupling hydrostatic pressure and shear stress, a flow rule describing the evolution of permanent strains after initial densification, and a hardening rule describing the dependence of the incremental densification on the levels of applied stresses. The constitutive law accounts for multiaxial states of stress, since during polishing and grinding operations complex stress states occur in a thin surface layer due to the action of abrasive particles. Due to frictional and other abrasive forces, large shear stresses are present near the surface during manufacturing. We apply the constitutive law in estimating the extent of the densified layer during the mechanical interaction of an abrasive grain and a flat surface.

Facile preparation in two steps of highly hydrophobic coatings on polypropylene surface

NASA Astrophysics Data System (ADS)

Petcu, Cristian; Nistor, Cristina Lavinia; Purcar, Violeta; Cinteză, Ludmila Otilia; Spătaru, Cătălin-Ilie; Ghiurea, Marius; Ianchiş, Raluca; Anastasescu, Mihai; Stoica, Mihai

2015-08-01

Monolayer and bilayer coatings deposited on polypropylene (PP) surface were prepared by sol-gel process at room temperature. Monolayer coatings were produced from sol-gel acidic solutions, containing tetraethylorthosilicate (TEOS) and different co-precursors such as phenyltriethoxysilane (PhTES), octylmethyldimethoxysilane (OMDMS) and dodecyltriethoxysilane (DOTES). Bilayer coatings consist of one layer prepared in a similar way described for monolayer coatings, followed by a second layer, obtained from fluorinated silica nanoparticles dispersion. The fluorinated group has been confirmed by the presence of Csbnd F bonds along with network Sisbnd Osbnd Si vibrational mode. Water contact angle values registered for bilayer-coated polypropylene are higher, comparing with the reference (pristine PP) and with the monolayer-coated substrate, and varies as a function of the hydrophobic functional groups of the silica co-precursors: phenyl < octyl < dodecyl. The fluorooctyl functions lead to a significant decrease in the surface energy values for bilayer coating, with very small values of polar component.

The influence of Lifshitz forces and gas on premelting of ice within porous materials

NASA Astrophysics Data System (ADS)

Boström, M.; Malyi, O. I.; Thiyam, P.; Berland, K.; Brevik, I.; Persson, C.; Parsons, D. F.

2016-07-01

Premelting of ice within pores in earth materials is shown to depend on the presence of vapor layers. For thick vapor layers between ice and pore surfaces, a nanosized water sheet can be formed due to repulsive Lifshitz forces. In the absence of vapor layers, ice is inhibited from melting near pore surfaces. In between these limits, we find an enhancement of the water film thickness in silica and alumina pores. In the presence of metallic surface patches in the pore, the Lifshitz forces can dramatically widen the water film thickness, with potential complete melting of the ice surface.

Superlubricity of Graphite Induced by Multiple Transferred Graphene Nanoflakes.

PubMed

Li, Jinjin; Gao, Tianyang; Luo, Jianbin

2018-03-01

2D or 3D layered materials, such as graphene, graphite, and molybdenum disulfide, usually exhibit superlubricity properties when sliding occurs between the incommensurate interface lattices. This study reports the superlubricity between graphite and silica under ambient conditions, induced by the formation of multiple transferred graphene nanoflakes on the asperities of silica surfaces after the initial frictional sliding. The friction coefficient can be reduced to as low as 0.0003 with excellent robustness and is independent of the surface roughness, sliding velocities, and rotation angles. The superlubricity mechanism can be attributed to the extremely weak interaction and easy sliding between the transferred graphene nanoflakes and graphite in their incommensurate contact. This finding has important implications for developing approaches to achieve superlubricity of layered materials at the nanoscale by tribointeractions.

Superlubricity of Graphite Induced by Multiple Transferred Graphene Nanoflakes

PubMed Central

Gao, Tianyang; Luo, Jianbin

2018-01-01

Abstract 2D or 3D layered materials, such as graphene, graphite, and molybdenum disulfide, usually exhibit superlubricity properties when sliding occurs between the incommensurate interface lattices. This study reports the superlubricity between graphite and silica under ambient conditions, induced by the formation of multiple transferred graphene nanoflakes on the asperities of silica surfaces after the initial frictional sliding. The friction coefficient can be reduced to as low as 0.0003 with excellent robustness and is independent of the surface roughness, sliding velocities, and rotation angles. The superlubricity mechanism can be attributed to the extremely weak interaction and easy sliding between the transferred graphene nanoflakes and graphite in their incommensurate contact. This finding has important implications for developing approaches to achieve superlubricity of layered materials at the nanoscale by tribointeractions. PMID:29593965

Control of Nanoscale Friction on Gold in an Ionic Liquid by a Potential-Dependent Ionic Lubricant Layer

NASA Astrophysics Data System (ADS)

Sweeney, James; Hausen, Florian; Hayes, Robert; Webber, Grant B.; Endres, Frank; Rutland, Mark W.; Bennewitz, Roland; Atkin, Rob

2012-10-01

The lubricating properties of an ionic liquid on gold surfaces can be controlled through application of an electric potential to the sliding contact. A nanotribology approach has been used to study the frictional behavior of 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl) trifluorophosphate ([Py1,4]FAP) confined between silica colloid probes or sharp silica tips and a Au(111) substrate using atomic force microscopy. Friction forces vary with potential because the composition of a confined ion layer between the two surfaces changes from cation-enriched (at negative potentials) to anion-enriched (at positive potentials). This offers a new approach to tuning frictional forces reversibly at the molecular level without changing the substrates, employing a self-replenishing boundary lubricant of low vapor pressure.

The polarization modulation and fabrication method of two dimensional silica photonic crystals based on UV nanoimprint lithography and hot imprint

PubMed Central

Guo, Shuai; Niu, Chunhui; Liang, Liang; Chai, Ke; Jia, Yaqing; Zhao, Fangyin; Li, Ya; Zou, Bingsuo; Liu, Ruibin

2016-01-01

Based on a silica sol-gel technique, highly-structurally ordered silica photonic structures were fabricated by UV lithography and hot manual nanoimprint efforts, which makes large-scale fabrication of silica photonic crystals easy and results in low-cost. These photonic structures show perfect periodicity, smooth and flat surfaces and consistent aspect ratios, which are checked by scanning electron microscopy (SEM) and atomic force microscopy (AFM). In addition, glass substrates with imprinted photonic nanostructures show good diffraction performance in both transmission and reflection mode. Furthermore, the reflection efficiency can be enhanced by 5 nm Au nanoparticle coating, which does not affect the original imprint structure. Also the refractive index and dielectric constant of the imprinted silica is close to that of the dielectric layer in nanodevices. In addition, the polarization characteristics of the reflected light can be modulated by stripe nanostructures through changing the incident light angle. The experimental findings match with theoretical results, making silica photonic nanostructures functional integration layers in many optical or optoelectronic devices, such as LED and microlasers to enhance the optical performance and modulate polarization properties in an economical and large-scale way. PMID:27698465

The polarization modulation and fabrication method of two dimensional silica photonic crystals based on UV nanoimprint lithography and hot imprint.

PubMed

Guo, Shuai; Niu, Chunhui; Liang, Liang; Chai, Ke; Jia, Yaqing; Zhao, Fangyin; Li, Ya; Zou, Bingsuo; Liu, Ruibin

2016-10-04

Based on a silica sol-gel technique, highly-structurally ordered silica photonic structures were fabricated by UV lithography and hot manual nanoimprint efforts, which makes large-scale fabrication of silica photonic crystals easy and results in low-cost. These photonic structures show perfect periodicity, smooth and flat surfaces and consistent aspect ratios, which are checked by scanning electron microscopy (SEM) and atomic force microscopy (AFM). In addition, glass substrates with imprinted photonic nanostructures show good diffraction performance in both transmission and reflection mode. Furthermore, the reflection efficiency can be enhanced by 5 nm Au nanoparticle coating, which does not affect the original imprint structure. Also the refractive index and dielectric constant of the imprinted silica is close to that of the dielectric layer in nanodevices. In addition, the polarization characteristics of the reflected light can be modulated by stripe nanostructures through changing the incident light angle. The experimental findings match with theoretical results, making silica photonic nanostructures functional integration layers in many optical or optoelectronic devices, such as LED and microlasers to enhance the optical performance and modulate polarization properties in an economical and large-scale way.

Interactions of PAMAM dendrimers with SDS at the solid-liquid interface.

PubMed

Arteta, Marianna Yanez; Eltes, Felix; Campbell, Richard A; Nylander, Tommy

2013-05-14

This work addresses structural and nonequilibrium effects of the interactions between well-defined cationic poly(amidoamine) PAMAM dendrimers of generations 4 and 8 and the anionic surfactant sodium dodecyl sulfate (SDS) at the hydrophilic silica-water interface. Neutron reflectometry and quartz crystal microbalance with dissipation monitoring were used to reveal the adsorption from premixed dendrimer/surfactant solutions as well as sequential addition of the surfactant to preadsorbed layers of dendrimers. PAMAM dendrimers of both generations adsorb to hydrophilic silica as a compact monolayer, and the adsorption is irreversible upon rinsing with salt solution. SDS adsorbs on the dendrimer layer and at low bulk concentrations causes the expansion of the dendrimer layers on the surface. When the bulk concentration of SDS is increased, the surfactant layer consists of aggregates or bilayer-like structures. The adsorption of surfactant is reversible upon rinsing, but slight changes of the structure of the preadsorbed PAMAM monolayer were observed. The adsorption from premixed solutions close to charge neutrality results in thick multilayers, but the surface excess is lower when the bulk complexes have a net negative charge. A critical examination of the pathway of adsorption for the interactions of SDS with preadsorbed PAMAM monolayers and premixed PAMAM/SDS solutions with hydrophilic silica revealed that nonequilibrium effects are important only in the latter case, and the application of a thermodynamic model to such experimental data would be inappropriate.

Sol-Gel Synthesis of Ordered β-Cyclodextrin-Containing Silicas

NASA Astrophysics Data System (ADS)

Trofymchuk, Iryna Mykolaivna; Roik, Nadiia; Belyakova, Lyudmila

2016-03-01

New approaches for β-cyclodextrin-containing silicas synthesis were demonstrated. Materials with hexagonally ordered mesoporous structure were prepared by postsynthesis grafting and by co-condensation methods. β-Cyclodextrin activated by a N, N'-carbonyldiimidazole was employed for postsynthesis treatment of 3-aminopropyl-modified MCM-41 support as well as for sol-gel synthesis with β-cyclodextrin-containing organosilane and tetraethyl orthosilicate participation in the presence of cetyltrimethylammonium bromide. The successful incorporation of cyclic oligosaccharide moieties in silica surface layer was verified by means of FT-IR spectroscopy and chemical analysis. Obtained β-cyclodextrin-containing materials were characterized by X-ray diffraction, transmission electron microscopy, and low-temperature adsorption-desorption of nitrogen. In spite of commensurable loading of β-cyclodextrin groups attained by both proposed approaches (up to 0.028 μmol · m-2), it was found that co-condensation procedure provides uniform distribution of β-cyclodextrin functionalities in silica framework, whereas postsynthesis grafting results in modification of external surface of silica surface. Adsorption of benzene from aqueous solutions onto the surface of β-cyclodextrin-containing materials prepared by co-condensation method was studied as the function of time and equilibrium concentration. Langmuir and Freundlich models were used to evaluate adsorption processes and parameters. Adsorption experiments showed that β-cyclodextrin-containing silicas could be promising for the trace amount removal of aromatics from water.

A shift in the biogenic silica of sediment in the Larsen B continental shelf, off the Eastern Antarctic Peninsula, resulting from climate change.

PubMed

Sañé, Elisabet; Isla, Enrique; Bárcena, María Ángeles; DeMaster, David J

2013-01-01

In 2002, section B of the Larsen ice shelf, off of the Eastern Antarctic Peninsula, collapsed and created the opportunity to study whether the changes at the sea surface left evidence in the sedimentary record. Biogenic silica is major constituent of Antarctic marine sediment, and its presence in the sediment column is associated with diatom production in the euphotic zone. The abundance of diatom valves and the number of sponge spicules in the biogenic silica was analyzed to determine how the origin of the biogenic silica in the upper layers of the sediment column responded to recent environmental changes. Diatom valves were present only in the upper 2 cm of sediment, which roughly corresponds to the period after the collapse of the ice shelf. In contrast, sponge spicules, a more robust form of biogenic silica, were also found below the upper 2 cm layer of the sediment column. Our results indicate that in this region most of the biogenic silica in the sedimentary record originated from sponge spicules rather than diatoms during the time when the sea surface was covered by the Larsen ice shelf. Since the collapse of the ice shelf, the development of phytoplankton blooms and the consequent influx of diatom debris to the seabed have shifted the biogenic silica record to one dominated by diatom debris, as occurs in most of the Antarctic marine sediment. This shift provides further evidence of the anthropogenic changes to the benthic habitats of the Antarctic and will improve the interpretation of the sedimentary record in Polar Regions where these events occur.

A 2H nuclear magnetic resonance study of the state of water in neat silica and zwitterionic stationary phases and its influence on the chromatographic retention characteristics in hydrophilic interaction high-performance liquid chromatography.

PubMed

Wikberg, Erika; Sparrman, Tobias; Viklund, Camilla; Jonsson, Tobias; Irgum, Knut

2011-09-23

2H NMR has been used as a tool for probing the state of water in hydrophilic stationary phases for liquid chromatography at temperatures between -80 and +4 °C. The fraction of water that remained unfrozen in four different neat silicas with nominal pore sizes between 60 and 300 Å, and in silicas with polymeric sulfobetaine zwitterionic functionalities prepared in different ways, could be determined by measurements of the line widths and temperature-corrected integrals of the 2H signals. The phase transitions detected during thawing made it possible to estimate the amount of non-freezable water in each phase. A distinct difference was seen between the neat and modified silicas tested. For the neat silicas, the relationship between the freezing point depression and their pore size followed the expected Gibbs-Thomson relationship. The polymeric stationary phases were found to contain considerably higher amounts of non-freezable water compared to the neat silica, which is attributed to the structural effect that the sulfobetaine polymers have on the water layer close to the stationary phase surface. The sulfobetaine stationary phases were used alongside the 100 Å silica to separate a number of polar compounds in hydrophilic interaction (HILIC) mode, and the retention characteristics could be explained in terms of the surface water structure, as well as by the porous properties of the stationary phases. This provides solid evidence supporting a partitioning mechanism, or at least of the existence of an immobilized layer of water into which partitioning could be occurring. Copyright © 2011 Elsevier B.V. All rights reserved.

Understanding the surface properties and rheology of a silica suspension mediated by a comb-type poly(acrylic acid)/poly(ethylene oxide) (PAA/PEO) copolymer: effect of salinity.

PubMed

Yang, Dingzheng; Yan, Bin; Xiang, Li; Xu, Haolan; Wang, Xiaogang; Zeng, Hongbo

2018-06-13

Understanding the surface properties and rheology of colloidal suspensions in the presence of polymer additives with high salinity are of great importance in formulating construction materials and optimizing process conditions in the mining and petroleum industry. In this work, the surface properties and rheology of a model spherical silica aqueous suspension mediated by a comb-type poly(acrylic acid)/poly(ethylene oxide) (PAA/PEO) copolymer at various salt concentrations have been investigated. Adsorption measurements using a Quartz Crystal Microbalance with Dissipation monitoring (QCM-D) align well with zeta potential tests and show that polymer adsorption on silica surfaces is enhanced at high salinity (i.e., 3 M NaCl) than at low salinity (i.e., 1 mM NaCl) due to the suppression of the electrical double layer. Surface Forces Apparatus (SFA) measurements reveal that for interactions between two mica surfaces (the basal plane of which has a similar structure as silica) at a high polymer concentration (e.g., 2 wt%), steric repulsion dominates in 1 mM NaCl while bridging attraction is observed in 3 M NaCl. Surface force measurements agree with rheological results on silica suspensions with 0.5 to 2 wt% of PAA/PEO addition, which shows a significant decrease in yield stress in 1 mM NaCl due to steric repulsion but an insignificant variation in yield stress in 3 M NaCl due to attractive bridging interactions. This work provides useful information regarding the surface properties and rheological properties of comb-type polymer-mediated silica suspensions under different salinity conditions, with implications on designing and processing complex colloidal suspensions with polymer additives for various applications.

The synthesis of silica nanotubes through chlorosilanization of single wall carbon nanotubes

NASA Astrophysics Data System (ADS)

Lin, Tsung-Wu; Shen, Hsin-Hui

2010-09-01

We demonstrate that single wall carbon nanotubes (SWCNTs) can be coated by a layer of silica through the reaction between chlorosilane and acid-treated SWCNTs. The presence of carboxylic acid groups in the SWCNTs provides the active sites where chlorosilane can be anchored to form the silica coating. Silica nanotubes with diameters ranging from 5 to 23 nm were synthesized after the calcination of silica coated SWCNTs at 900 °C in air. It was found that the presence of SWCNT templates and carboxylic acid groups on the SWCNTs' surface is essential to the formation of silica nanotubes. Furthermore, the dependence of the inner diameters of the silica nanotubes on the diameters of bundled or isolated SWCNTs was observed. This novel technique can be applied to the synthesis of other oxide nanotubes if a precursor such as TiCl4 or ZrCl4 is used.

Polarization-induced local pore-wall functionalization for biosensing: from micropore to nanopore.

PubMed

Liu, Jie; Pham, Pascale; Haguet, Vincent; Sauter-Starace, Fabien; Leroy, Loïc; Roget, André; Descamps, Emeline; Bouchet, Aurélie; Buhot, Arnaud; Mailley, Pascal; Livache, Thierry

2012-04-03

The use of biological-probe-modified solid-state pores in biosensing is currently hindered by difficulties in pore-wall functionalization. The surface to be functionalized is small and difficult to target and is usually chemically similar to the bulk membrane. Herein, we demonstrate the contactless electrofunctionalization (CLEF) approach and its mechanism. This technique enables the one-step local functionalization of the single pore wall fabricated in a silica-covered silicon membrane. CLEF is induced by polarization of the pore membrane in an electric field and requires a sandwich-like composition and a conducting or semiconducting core for the pore membrane. The defects in the silica layer of the micropore wall enable the creation of an electric pathway through the silica layer, which allows electrochemical reactions to take place locally on the pore wall. The pore diameter is not a limiting factor for local wall modification using CLEF. Nanopores with a diameter of 200 nm fabricated in a silicon membrane and covered with native silica layer have been successfully functionalized with this method, and localized pore-wall modification was obtained. Furthermore, through proof-of-concept experiments using ODN-modified nanopores, we show that functionalized nanopores are suitable for translocation-based biosensing.

Enhanced adhesion by high energy bombardment

NASA Technical Reports Server (NTRS)

Griffith, Joseph E. (Inventor); Qiu, Yuanxun (Inventor); Tombrello, Thomas A. (Inventor)

1984-01-01

Films (12) of gold, copper, silicon nitride, or other materials are firmly bonded to insulator substrates (12) such as silica, a ferrite, or Teflon (polytetrafluorethylene) by irradiating the interface with high energy ions. Apparently, track forming processes in the electronic stopping region cause intermixing in a thin surface layer resulting in improved adhesion without excessive doping. Thick layers can be bonded by depositing or doping the interfacial surfaces with fissionable elements or alpha emitters.

Silica-forming articles having engineered surfaces to enhance resistance to creep sliding under high-temperature loading

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

Lipkin, Don Mark; Johnson, Curtis Alan; Meschter, Peter Joel

An article includes a silicon-containing region; at least one outer layer overlying a surface of the silicon-containing region; and a constituent layer on the surface of the silicon-containing region and between and contacting the silicon-containing region and the at least one outer layer, the constituent layer being formed by constituents of the silicon-containing region and being susceptible to creep within an operating environment of the article, wherein the silicon-containing region defines a plurality of channels and a plurality of ridges that interlock within the plurality of channels are formed in the silicon-containing region to physically interlock the at least onemore » outer layer with the silicon-containing region through the constituent layer.« less

Fabrication of Uniform Hydrogel Microparticles with Alternate Polyelectrolyte/Silica Shell Layers for Applications of Controlled Loading and Releasing

NASA Astrophysics Data System (ADS)

Jeong, Eun Sook; Kim, Jin Woong

2015-03-01

Hydrogel particles, also known as microgels, consist of cross-linked three-dimensional water-soluble polymer networks. They play an essential role in loading and delivering active ingredients in medicine, cosmetics, and foods. Despite their excellent biocompatibility as well as structural diversity, much wider applications are limited due mainly to their intrinsically loose network nature. This study introduces a practical and straightforward method that enables fabrication of hydrogel microparticles layered with a mechanically robust hybrid thin shell. Basically highly monodisperse hydrogel microparticles were produced in microcapillary devices. Then, their surface was coated with alternate polyelectrolyte layers through the layer-by-layer deposition. Finally a thin silica layer was again formed by reduction of silicate on the amino-functionalized polyelectrolyte layer. We have figured out that these hybrid hydrogel microparticles showed controlled loading and releasing behaviors for water-soluble probe molecules. Moreover, we have demonstrated that they can be applied for immobilization of biomacromolecules, such as bacteria and living cells, and even for targeted releasing.

Development of Si3N4 and SiC of improved toughness. [for gas turbine engines

NASA Technical Reports Server (NTRS)

Brennan, J. J.; Hulse, C. O.

1977-01-01

The application of energy absorbing surface layers to Si3N4 and SiC was investigated. Among the layers studied were microcracked materials such as iron titanate and a silica-zircon mixture and porous materials such as reaction sintered Si3N4. Energy absorption due to microcrack extension upon impact was found not to be an important mechanism. Instead, the fivefold improvement in Charpy and ballistic impact at elevated temperature (1250 C and 1370 C) found for Fe2TiO5 was due to plastic deformation while similar improvement found for silica-zircon mixtures at RT was due to crushing of the porous material. Due to thermal expansion mismatch, these two materials could not withstand thermal cycling when used as energy absorbing surface layers on Si3N4. Reaction sintered Si3N4 layers on dense Si3N4 were found to give up to a sevenfold increase in ballistic impact resistance due to crushing of the layer upon impact. High porosity (45%), large particle size R.S. Si3N4 layers fabricated from -100, +200 mesh Si powder gave better impact improvement than less porous (30%), small particle size layers fabricated from -325 mesh Si powder.

Processing of catalysts by atomic layer epitaxy: modification of supports

NASA Astrophysics Data System (ADS)

Lindblad, Marina; Haukka, Suvi; Kytökivi, Arla; Lakomaa, Eeva-Liisa; Rautiainen, Aimo; Suntola, Tuomo

1997-11-01

Different supports were modified with titania, zirconia and chromia by the atomic layer epitaxy technique (ALE). In ALE, a metal precursor is bound to the support in saturating gas-solid reactions. Surface oxides are grown by alternating reactions of the metal precursor and an oxidizing agent. Growth mechanisms differ depending on the precursor-support pair and the processing conditions. In this work, the influences of the support, precursor and reaction temperature were investigated by comparing the growth of titania from Ti(OCH(CH 3) 2) 4 on silica and alumina, titania from TiCl 4 and Ti(OCH(CH 3) 2) 4 on silica, and zirconia from ZrCl 4 on silica and alumina. The modification of porous oxides supported on metal substrates (monoliths) was demonstrated for the growth of chromia from Cr(acac) 3.

Super-hydrophobic multilayer coatings with layer number tuned swapping in surface wettability and redox catalytic anti-corrosion application.

PubMed

Syed, Junaid Ali; Tang, Shaochun; Meng, Xiangkang

2017-06-30

The wetting characteristic of a metal surface can be controlled by employing different coating materials and external stimuli, however, layer number (n) modulated surface swapping between hydrophobicity and hydrophilicity in a multilayer structure to achieve prolonged anti-corrosion ability was not taken into consideration. In this study, we proposed a layer-by-layer (LbL) spin assembled polyaniline-silica composite/tetramethylsilane functionalized silica nanoparticles (PSC/TMS-SiO 2 ) coating with the combined effect of super-hydrophobicity and enhanced anti-corrosion ability. Interestingly, the hierarchical integration of two coating materials with inherently different surface roughness and energy in a multilayer structure allows the wetting feature to swap from hydrophobic to hydrophilic state by modulating n with decreasing hydrophilicity. The samples with odd n (TMS-SiO 2 surface) are hydrophobic while the samples with even n (PSC surface) exhibits the hydrophilic character. The TMS-SiO 2 content was optimized to achieve super-hydrophobic coating with significantly high water contact angle (CA) 153° ± 2° and small sliding angle (SA) 6° ± 2°. Beside its self-cleaning behavior, the electro-active PSC/TMS-SiO 2 coating also exhibits remarkably enhanced corrosion resistance against aggressive media. The corrosion resistance of the coating was remained stable even after 240 h of exposure, this enhancement is attributed to super-hydrophobicity and anodic shift in corrosion potential.

Superhydrophobic Surfaces with Very Low Hysteresis Prepared by Aggregation of Silica Nanoparticles During In Situ Urea-Formaldehyde Polymerization.

PubMed

Diwan, Anubhav; Jensen, David S; Gupta, Vipul; Johnson, Brian I; Evans, Delwyn; Telford, Clive; Linford, Matthew R

2015-12-01

We present a new method for the preparation of superhydrophobic materials by in situ aggregation of silica nanoparticles on a surface during a urea-formaldehyde (UF) polymerization. This is a one-step process in which a two-tier topography is obtained. The polymerization is carried out for 30, 60, 120, 180, and 240 min on silicon shards. Silicon surfaces are sintered to remove the polymer. SEM and AFM show both an increase in the area covered by the nanoparticles and their aggregation with increasing polymerization time. Chemical vapor deposition of a fluorinated silane in the presence of a basic catalyst gives these surfaces hydrophobicity. Deposition of this low surface energy silane is confirmed by the F 1s signal in XPS. The surfaces show advancing water contact angles in excess of 160 degrees with very low hysteresis (< 7) after 120 min and 60 min polymerization times for 7 nm and 14 nm silica, respectively. Depositions are successfully demonstrated on glass substrates after they are primed with a UF polymer layer. Superhydrophobic surfaces can also be prepared on unsintered substrates.

Effects of surface hydroxylation on adhesion at zinc/silica interfaces.

PubMed

Le, Ha-Linh Thi; Goniakowski, Jacek; Noguera, Claudine; Koltsov, Alexey; Mataigne, Jean-Michel

2018-06-06

The weak interaction between zinc and silica is responsible for the poor performance of anti-corrosive galvanic zinc coatings on modern advanced high-strength steels, which are fundamental in the automotive industry, and important for rail transport, shipbuilding, and aerospace. With the goal of identifying possible methods for its improvement, we report an ab initio study of the effect of surface hydroxylation on the adhesion characteristics of model zinc/β-cristobalite interfaces, representative of various surface hydroxylation/hydrogenation conditions. We show that surface silanols resulting from dissociative water adsorption at the most stable stoichiometric (001) and (111) surfaces prevent strong zinc-silica interactions. However, dehydrogenation of such interfaces produces oxygen-rich zinc/silica contacts with excellent adhesion characteristics. These are due to partial zinc oxidation and the formation of strong iono-covalent Zn-O bonds between zinc atoms and the under-coordinated excess anions, remnant of the hydroxylation layer. Interestingly, these interfaces appear as the most thermodynamically stable in a wide range of realistic oxygen-rich and hydrogen-lean environments. We also point out that the partial oxidation of zinc atoms in direct contact with the oxide substrate may somewhat weaken the cohesion in the zinc deposit itself. This fundamental analysis of the microscopic mechanisms responsible for the improved zinc wetting on pre-hydroxylated silica substrates provides useful guidelines towards practical attempts to improve adhesion.

Biomimetic silica encapsultation of living cells

NASA Astrophysics Data System (ADS)

Jaroch, David Benjamin

Living cells perform complex chemical processes on size and time scales that artificial systems cannot match. Cells respond dynamically to their environment, acting as biological sensors, factories, and drug delivery devices. To facilitate the use of living systems in engineered constructs, we have developed several new approaches to create stable protective microenvironments by forming bioinspired cell-membrane-specific silica-based encapsulants. These include vapor phase deposition of silica gels, use of endogenous membrane proteins and polysaccharides as a site for silica nucleation and polycondensation in a saturated environment, and protein templated ordered silica shell formation. We demonstrate silica layer formation at the surface of pluripotent stem-like cells, bacterial biofilms, and primary murine and human pancreatic islets. Materials are characterized by AFM, SEM and EDS. Viability assays confirm cell survival, and metabolite flux measurements demonstrate normal function and no major diffusion limitations. Real time PCR mRNA analysis indicates encapsulated islets express normal levels of genetic markers for β-cells and insulin production. The silica glass encapsulant produces a secondary bone like calcium phosphate mineral layer upon exposure to media. Such bioactive materials can improve device integration with surrounding tissue upon implantation. Given the favorable insulin response, bioactivity, and long-term viability observed in silica-coated islets, we are currently testing the encapsulant's ability to prevent immune system recognition of foreign transplants for the treatment of diabetes. Such hybrid silica-cellular constructs have a wide range of industrial, environmental, and medical applications.

Layer-by-layer self-assembled graphene oxide/silica microsphere composites as stationary phase for high performance liquid chromatography.

PubMed

Liang, Xiaojing; Liu, Shujuan; Song, Xinwang; Zhu, Yangwen; Jiang, Shengxiang

2012-11-21

Graphene oxide (GO) has been layer-by-layer assembled onto silica microspheres to form a GO/SiO(2) composite stationary phase. All the characterizations of GO/SiO(2) by elemental analysis, Raman spectroscopy and Fourier transformed infrared spectrometry confirmed that with the increase of the assembled layer, GO gradually increases on the silica surface. The chromatographic properties of bare SiO(2) and GO/SiO(2) with different GO assembled layers show that the amount of GO plays an important role in the separation of analytes. Only the appropriate amount of GO on SiO(2) can perform a good chromatographic separation. The comparison between chromatographic performances of bare SiO(2) column, GO/SiO(2)-2 column and C18 commercial column clearly show that GO/SiO(2)-2 and C18 columns obtained a better separation; GO/SiO(2)-2 exhibits a large π-electron system and C18 exhibits hydrophobicity. The eluting order, peak width and resolution of analyte on GO/SiO(2)-2 column was highly dependent on the size of its π-electron system, while on the C18 column the decisive factor is its hydrophobic property.

Application of functionalized nanofluid in thermosyphon

PubMed Central

2011-01-01

A water-based functionalized nanofluid was made by surface functionalizing the ordinary silica nanoparticles. The functionalized nanofluid can keep long-term stability. and no sedimentation was observed. The functionalized nanofluid as the working fluid is applied in a thermosyphon to understand the effect of this special nanofluid on the thermal performance of the thermosyphon. The experiment was carried out under steady operating pressures. The same work was also explored for traditional nanofluid (consisting of water and the same silica nanoparticles without functionalization) for comparison. Results indicate that a porous deposition layer exists on the heated surface of the evaporator during the operating process using traditional nanofluid; however, no coating layer exists for functionalized nanofluid. Functionalized nanofluid can enhance the evaporating heat transfer coefficient, while it has generally no effect on the maximum heat flux. Traditional nanofluid deteriorates the evaporating heat transfer coefficient but enhances the maximum heat flux. The existence of the deposition layer affects mainly the thermal performance, and no meaningful nanofluid effect is found in the present study. PMID:21846362

Wollastonite Carbonation in Water-Bearing Supercritical CO2: Effects of Particle Size.

PubMed

Min, Yujia; Li, Qingyun; Voltolini, Marco; Kneafsey, Timothy; Jun, Young-Shin

2017-11-07

The performance of geologic CO 2 sequestration (GCS) can be affected by CO 2 mineralization and changes in the permeability of geologic formations resulting from interactions between water-bearing supercritical CO 2 (scCO 2 ) and silicates in reservoir rocks. However, without an understanding of the size effects, the findings in previous studies using nanometer- or micrometer-size particles cannot be applied to the bulk rock in field sites. In this study, we report the effects of particle sizes on the carbonation of wollastonite (CaSiO 3 ) at 60 °C and 100 bar in water-bearing scCO 2 . After normalization by the surface area, the thickness of the reacted wollastonite layer on the surfaces was independent of particle sizes. After 20 h, the reaction was not controlled by the kinetics of surface reactions but by the diffusion of water-bearing scCO 2 across the product layer on wollastonite surfaces. Among the products of reaction, amorphous silica, rather than calcite, covered the wollastonite surface and acted as a diffusion barrier to water-bearing scCO 2 . The product layer was not highly porous, with a specific surface area 10 times smaller than that of the altered amorphous silica formed at the wollastonite surface in aqueous solution. These findings can help us evaluate the impacts of mineral carbonation in water-bearing scCO 2 .

Enhancement of surface damage resistance by selective chemical removal of CeO2

NASA Astrophysics Data System (ADS)

Kamimura, Tomosumi; Motokoshi, Shinji; Sakamoto, Takayasu; Jitsuno, Takahisa; Shiba, Haruya; Akamatsu, Shigenori; Horibe, Hideo; Okamoto, Takayuki; Yoshida, Kunio

2005-02-01

The laser-induced damage threshold of polished fused silica surfaces is much lower than the damage threshod of its bulk. It is well known that contaminations of polished surface are one of the causes of low threshold of laser-induced surface damage. Particularly, polishing contamination such as cerium dioxide (CeO2) compound used in optical polishing process is embedded inside the surface layer, and cannot be removed by conventional cleaning. For the enhancement of surface damage resistance, various surface treatments have been applied to the removal of embedded polishing compound. In this paper, we propose a new method using slective chemical removal with high-temperature sulfuric acid (H2SO4). Sulfuric acid could dissolve only CeO2 from the fused silica surface. The surface roughness of fused silica treated H2SO4 was kept through the treatment process. At the wavelength of 355 nm, the surface damage threshold was drastically improved to the nearly same as bulk quality. However, the effect of our treatment was not observed at the wavelength of 1064 nm. The comparison with our previous results obtained from other surface treatments will be discussed.

Interaction of fullerene (C60) nanoparticles with humic acid and alginate coated silica surfaces: measurements, mechanisms, and environmental implications.

PubMed

Chen, Kai Loon; Elimelech, Menachem

2008-10-15

The deposition kinetics of fullerene (C60) nanoparticles onto bare silica surfaces and surfaces precoated with humic acid and alginate are investigated over a range of monovalent (NaCI) and divalent (CaCl2) salt concentrations using a quartz crystal microbalance. Because simultaneous aggregation of the fullerene nanoparticles occurs, especially at higher electrolyte concentrations, we normalize the observed deposition rates by the corresponding favorable (transport-limited) deposition rates to obtain the attachment efficiencies, alpha. The deposition kinetics of fullerene nanoparticles onto bare silica surfaces are shown to be controlled by electrostatic interactions and van der Waals attraction, consistent with the classical particle deposition behavior where both favorable and unfavorable deposition regimes are observed. The presence of dissolved humic acid and alginate in solution leads to significantly slower deposition kinetics due to steric repulsion. Precoating the silica surfaces with humic acid and alginate exerts similar steric stabilization in the presence of NaCl. In the presence of CaCl2, the deposition kinetics of fullerene nanoparticles onto both humic acid- and alginate-coated surfaces are relatively high, even at relatively low (0.3 mM) calcium concentration. This behavior is attributed to the macromolecules undergoing complex formation with calcium ions, which reduces the charge and steric influences of the adsorbed macromolecular layers.

Metal-enhanced fluorescence of dye-doped silica nano particles.

PubMed

Gunawardana, Kalani B; Green, Nathaniel S; Bumm, Lloyd A; Halterman, Ronald L

2015-03-01

Recent advancements in metal-enhanced fluorescence (MEF) suggest that it can be a promising tool for detecting molecules at very low concentrations when a fluorophore is fixed near the surface of metal nanoparticles. We report a simple method for aggregating multiple gold nanoparticles (GNPs) on Rhodamine B (RhB)-doped silica nanoparticles (SiNPs) utilizing dithiocarbamate (DTC) chemistry to produce MEF in solution. Dye was covalently incorporated into the growing silica framework via co-condensation of a 3-aminopropyltriethoxysilane (APTES) coupled RhB precursor using the Stöber method. Electron microscopy imaging revealed that these mainly non-spherical particles were relatively large (80 nm on average) and not well defined. Spherical core-shell particles were prepared by physisorbing a layer of RhB around a small spherical silica particle (13 nm) before condensing an outer layer of silica onto the surface. The core-shell method produced nanospheres (~30 nm) that were well defined and monodispersed. Both dye-doped SiNPs were functionalized with pendant amines that readily reacted with carbon disulfide (CS2) under basic conditions to produce DTC ligands that have exhibited a high affinity for gold surfaces. GNPs were produced via citrate reduction method and the resulting 13 nm gold nanospheres were then recoated with an ether-terminated alkanethiol to provide stability in ethanol. Fluorescent enhancement was observed when excess GNPs were added to DTC coated dye-doped SiNPs to form nanoparticle aggregates. Optimization of this system gave a fluorescence brightness enhancement of over 200 fold. Samples that gave fluorescence enhancement were characterized through Transmission Emission Micrograph (TEM) to reveal a pattern of multiple aggregation of GNPs on the dye-doped SiNPs.

Facile silicification of plastic surface for bioassays

PubMed Central

Hong, Seonki; Park, Ki Soo; Weissleder, Ralph; Castro, Cesar M.; Lee, Hakho

2017-01-01

We herein report a biomimetic technique to modify plastic substrates for bioassays. The method first places a polydopamine adhesion layer to plastic surface, and then grows conformal silica coating. As proof of principle, we coated plastic microbeads to construct a disposable filter for point-of-care nucleic acid extraction. PMID:28134385

Adsorption properties of BSA and DsRed proteins deposited on thin SiO2 layers: optically non-absorbing versus absorbing proteins

NASA Astrophysics Data System (ADS)

Scarangella, A.; Soumbo, M.; Villeneuve-Faure, C.; Mlayah, A.; Bonafos, C.; Monje, M.-C.; Roques, C.; Makasheva, K.

2018-03-01

Protein adsorption on solid surfaces is of interest for many industrial and biomedical applications, where it represents the conditioning step for micro-organism adhesion and biofilm formation. To understand the driving forces of such an interaction we focus in this paper on the investigation of the adsorption of bovine serum albumin (BSA) (optically non-absorbing, model protein) and DsRed (optically absorbing, naturally fluorescent protein) on silica surfaces. Specifically, we propose synthesis of thin protein layers by means of dip coating of the dielectric surface in protein solutions with different concentrations (0.01-5.0 g l-1). We employed spectroscopic ellipsometry as the most suitable and non-destructive technique for evaluation of the protein layers’ thickness and optical properties (refractive index and extinction coefficient) after dehydration, using two different optical models, Cauchy for BSA and Lorentz for DsRed. We demonstrate that the thickness, the optical properties and the wettability of the thin protein layers can be finely controlled by proper tuning of the protein concentration in the solution. These results are correlated with the thin layer morphology, investigated by AFM, FTIR and PL analyses. It is shown that the proteins do not undergo denaturation after dehydration on the silica surface. The proteins arrange themselves in a lace-like network for BSA and in a rod-like structure for DsRed to form mono- and multi-layers, due to different mechanisms driving the organization stage.

Magneto-Fluorescent Core-Shell Supernanoparticles

PubMed Central

Chen, Ou; Riedemann, Lars; Etoc, Fred; Herrmann, Hendrik; Coppey, Mathieu; Barch, Mariya; Farrar, Christian T.; Zhao, Jing; Bruns, Oliver T.; Wei, He; Guo, Peng; Cui, Jian; Jensen, Russ; Chen, Yue; Harris, Daniel K.; Cordero, Jose M.; Wang, Zhongwu; Jasanoff, Alan; Fukumura, Dai; Reimer, Rudolph; Dahan, Maxime; Jain, Rakesh K.; Bawendi, Moungi G.

2014-01-01

Magneto-fluorescent particles have been recognized as an emerging class of materials that exhibit great potential in advanced applications. However, synthesizing such magneto-fluorescent nanomaterials that simultaneously exhibit uniform and tunable sizes, high magnetic content loading, maximized fluorophore coverage at the surface, and a versatile surface functionality has proven challenging. Here we report a simple approach for co-assembling magnetic nanoparticles with fluorescent quantum dots to form colloidal magneto-fluorescent supernanoparticles. Importantly, these supernanoparticles exhibit a superstructure consisting of a close packed magnetic nanoparticle “core” which is fully surrounded by a “shell” of fluorescent quantum dots. A thin layer of silica-coating provides high colloidal stability and biocompatiblity and a versatile surface functionality. We demonstrate that after surface pegylation, these silica-coated magneto-fluorescent supernanoparticles can be magnetically manipulated inside living cells while being optically tracked. Moreover, our silica-coated magneto-fluorescent supernanoparticles can also serve as an in vivo multi-photon and magnetic resonance dual-modal imaging probe. PMID:25298155

Aqueous route to facile, efficient and functional silica coating of metal nanoparticles at room temperature

NASA Astrophysics Data System (ADS)

Shah, Kwok Wei; Sreethawong, Thammanoon; Liu, Shu-Hua; Zhang, Shuang-Yuan; Tan, Li Sirh; Han, Ming-Yong

2014-09-01

Various metal (Ag, Au, and Pt)@thiol-functionalized silica (SiO2-SH) nanoparticles (NPs) are successfully prepared at room temperature by a facile, efficient, functional, universal and scalable coating process in alcohol-free aqueous solution using pre-hydrolyzed 3-(mercaptopropyl)trimethoxysilane (MPTMS). The controlled pre-hydrolysis of the silane precursor in water and the consecutive condensation processes are the key to achieve the effective and uniform silica coating on metal NPs in aqueous solution. The thickness of the silica shell is tuned by simply varying the coating time. The silica shell can act as an effective protecting layer for Ag NPs in Ag@SiO2-SH NPs under conditions for silica coating in aqueous solution; however, it leads to a directional dissolution of Ag NPs in a more strongly basic ammonia solution. The environmentally friendly silica coating process in water is also applied to prepare highly surface-enhanced Raman scattering (SERS)-active Ag@SiO2-SH NPs with different types of Raman molecules for highly sensitive SERS-based applications in various fields.Various metal (Ag, Au, and Pt)@thiol-functionalized silica (SiO2-SH) nanoparticles (NPs) are successfully prepared at room temperature by a facile, efficient, functional, universal and scalable coating process in alcohol-free aqueous solution using pre-hydrolyzed 3-(mercaptopropyl)trimethoxysilane (MPTMS). The controlled pre-hydrolysis of the silane precursor in water and the consecutive condensation processes are the key to achieve the effective and uniform silica coating on metal NPs in aqueous solution. The thickness of the silica shell is tuned by simply varying the coating time. The silica shell can act as an effective protecting layer for Ag NPs in Ag@SiO2-SH NPs under conditions for silica coating in aqueous solution; however, it leads to a directional dissolution of Ag NPs in a more strongly basic ammonia solution. The environmentally friendly silica coating process in water is also applied to prepare highly surface-enhanced Raman scattering (SERS)-active Ag@SiO2-SH NPs with different types of Raman molecules for highly sensitive SERS-based applications in various fields. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr03306j

The role of interfacial water layer in atmospherically relevant charge separation

NASA Astrophysics Data System (ADS)

Bhattacharyya, Indrani

Charge separation at interfaces is important in various atmospheric processes, such as thunderstorms, lightning, and sand storms. It also plays a key role in several industrial processes, including ink-jet printing and electrostatic separation. Surprisingly, little is known about the underlying physics of these charging phenomena. Since thin films of water are ubiquitous, they may play a role in these charge separation processes. This talk will focus on the experimental investigation of the role of a water adlayer in interfacial charging, with relevance to meteorologically important phenomena, such as atmospheric charging due to wave actions on oceans and sand storms. An ocean wave generates thousands of bubbles, which upon bursting produce numerous large jet droplets and small film droplets that are charged. In the 1960s, Blanchard showed that the jet droplets are positively charged. However, the charge on the film droplets was not known. We designed an experiment to exclusively measure the charge on film droplets generated by bubble bursting on pure water and aqueous salt solution surfaces. We measured their charge to be negative and proposed a model where a slight excess of hydroxide ions in the interfacial water layer is responsible for generating these negatively charged droplets. The findings from this research led to a better understanding of the ionic disposition at the air-water interface. Sand particles in a wind-blown sand layer, or 'saltation' layer, become charged due to collisions, so much so, that it can cause lightning. Silica, being hydrophilic, is coated with a water layer even under low-humidity conditions. To investigate the importance of this water adlayer in charging the silica surfaces, we performed experiments to measure the charge on silica surfaces due to contact and collision processes. In case of contact charging, the maximum charge separation occurred at an optimum relative humidity. On the contrary, in collisional charging process, no humidity effect was observed. We proposed an ion transfer mechanism in case of contact charging. However, an electron transfer mechanism explained the collisional charging process. The effects of temperature, surface roughness, and chemical nature of surface were also studied for both contact and collisional charging processes.

Fused silica reflecting heat shields for outer planet entry probes

NASA Technical Reports Server (NTRS)

Congdon, W. M.; Peterson, D. L.

1975-01-01

The development of slip-cast fused silica is discussed as a heat shield designed to meet the needs of outer-planet entry probes. The distinguishing feature of silica is its ability to reflect the radiation imposed by planetary-entry environments. This reflectivity is particularly sensitive to degradation by the presence of trace amounts of contaminants introduced by the starting materials or by processing. The microstructure of a silica configuration also significantly influences the reflectivity and other thermomechanical properties. The processing techniques attendant on controlling microstructure while maintaining purity are discussed. The selection of a starting material of essential purity precludes the use of purified natural quartz and requires the use of synthetic fused silica. The silica is characterized in a limited combined heating test environment. The surface mass loss is controlled by liquid runoff from a relatively low-temperature melt layer; the reflectance is basically maintained and the material achieves a surprisingly high heat of ablation.

Remedy and Recontamination Assessment Array

DTIC Science & Technology

2017-03-01

of silica sand visual tracer at interface, (C) addition of thin sand layer, and (D) final result with treatment and overlying water added...Final result for thin clean sediment layer treatment after final installation of treatment and overlying water ... treatment sediments were held in the sediment cells or tubs with overlying surface water under cool conditions overnight prior to application of the

Mixed mode HILIC/anion exchange separations on latex coated silica monoliths.

PubMed

Ibrahim, Mohammed E A; Lucy, Charles A

2012-10-15

Bare silica monoliths do not possess anion exchange sites hence they show low retention for anions. Moreover, bare silica monoliths show low retention in hydrophilic interaction liquid chromatography (HILIC). Coating the silica surface with cationic nanoparticles e.g. AS9-SC (latex A), AS12A (latex B) and DNApac (latex C) increases the thickness of the water layer on the Onyx silica monolith 8-10 times enabling HILIC retention when a high % acetonitrile (ACN) mobile phase is used. The formed water layer by itself is not sufficient to perform good separation of the studied anions (acetate, formate, nitrate, bromate, thiocyanate and iodide). On the other hand, the latex nanoparticles introduce positively charged sites, making anion exchange chromatography possible, with the anion exchange capacity varying with the latex adsorbed (44.1 ± 0.2, 4.4 ± 0.1 and 14.0 ± 0.7 μeq/column for latex A, B and C, respectively). Latex A nanoparticles which provided the highest ion exchange capacity separated all tested anions with reasonable resolution. Fast separation (2.5 min) of acetate, formate, nitrate, bromate, thiocyanate and iodide was performed using the latex A coated silica monolith. The obtained efficiencies are 13,000-50,000 plates/m at 3 mL/min with a minimum resolution of 0.85. Retention is mixed mode under HILIC conditions with HILIC dominating for the kosmotropic anions and ion exchange dominating for the chaotropic anions. The two different brands of silica monoliths (Merck Chromolith and Phenomenex Onyx) coated with the same latex A nanoparticles displayed similar water layer volumes, ion exchange capacity and selectivity. Copyright © 2012 Elsevier B.V. All rights reserved.

Control of the wrinkle structure on surface-reformed poly(dimethylsiloxane) via ion-beam bombardment

NASA Astrophysics Data System (ADS)

Park, Hong-Gyu; Jeong, Hae-Chang; Jung, Yoon Ho; Seo, Dae-Shik

2015-07-01

We investigated the surface reformation of poly(dimethylsiloxane) (PDMS) elastomers by means of ion beam bombardment for fabricating wrinkle structures. Oxidation on the PDMS surface formed a silica-like outer layer that interacted with the inner PDMS layer, leading to the formation of wrinkle structures that minimized the combined bending energy of the outer layer and stretching energy of the inner layer. In addition, we controlled the amplitude and period of the wrinkle structures by adjusting the PDMS annealing temperature. As the PDMS annealing temperature was increased, the amplitude and period of the wrinkles formed by IB irradiation changed from 604.35 to 69.01 nm and from 3.07 to 0.80 μm, respectively.

Preparation of porous hollow silica spheres via a layer-by-layer process and the chromatographic performance

NASA Astrophysics Data System (ADS)

Wei, Xiaobing; Gong, Cairong; Chen, Xujuan; Fan, Guoliang; Xu, Xinhua

2017-03-01

Hollow silica spheres possessing excellent mechanical properties were successfully prepared through a layer-by-layer process using uniform polystyrene (PS) latex fabricated by dispersion polymerization as template. The formation of hollow SiO2 micro-spheres, structures and properties were observed in detail by zeta potential, SEM, TEM, FTIR, TGA and nitrogen sorption porosimetry. The results indicated that the hollow spheres were uniform with particle diameter of 1.6 μm and shell thickness of 150 nm. The surface area was 511 m2/g and the pore diameter was 8.36 nm. A new stationary phase for HPLC was obtained by using C18-derivatized hollow SiO2 micro-spheres as packing materials and the chromatographic properties were evaluated for the separation of some regular small molecules. The packed column showed low column pressure, high values of efficiency (up to about 43 000 plates/m) and appropriate asymmetry factors.

Double-Layer Surface Modification of Polyamide Denture Base Material by Functionalized Sol-Gel Based Silica for Adhesion Improvement.

PubMed

Hafezeqoran, Ali; Koodaryan, Roodabeh

2017-09-21

Limited surface treatments have been proposed to improve the bond strength between autopolymerizing resin and polyamide denture base materials. Still, the bond strength of autopolymerizing resins to nylon polymer is not strong enough to repair the fractured denture effectively. This study aimed to introduce a novel method to improve the adhesion of autopolymerizing resin to polyamide polymer by a double layer deposition of sol-gel silica and N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (AE-APTMS). The silica sol was synthesized by acid-catalyzed hydrolysis of tetraethylorthosilicate (TEOS) as silica precursors. Polyamide specimens were dipped in TEOS-derived sol (TS group, n = 28), and exposed to ultraviolet (UV) light under O 2 flow for 30 minutes. UV-treated specimens were immersed in AE-APTMS solution and left for 24 hours at room temperature. The other specimens were either immersed in AE-APTMS solution (AP group, n = 28) or left untreated (NT group, n = 28). Surface characterization was investigated by fourier transform infrared spectroscopy (FTIR) and atomic force microscopy (AFM). Two autopolymerizing resins (subgroups G and T, n = 14) were bonded to the specimens, thermocycled, and then tested for shear bond strength with a universal testing machine. Data were analyzed with one-way ANOVA followed by Tukey's HSD (α = 0.05). FTIR spectra of treated surfaces confirmed the chemical modification and appearance of functional groups on the polymer. One-way ANOVA revealed significant differences in shear bond strength among the study groups. Tukey's HSD showed that TS T and TS G groups had significantly higher shear bond strength than control groups (p = 0.001 and p < 0.001, respectively). Moreover, bond strength values of AP T were statistically significant compared to controls (p = 0.017). Amino functionalized TEOS-derived silica coating is a simple and cost-effective method for improving the bond strength between the autopolymerizing resin and polyamide denture base. Amino-functionalized silica coating could represent a more applicable and convenient option for improving the repair strength of autopolymerizing resin to polyamide polymer. © 2017 by the American College of Prosthodontists.

Synthesis and spectroscopic properties of silica-dye-semiconductor nanocrystal hybrid particles.

PubMed

Ren, Ting; Erker, Wolfgang; Basché, Thomas; Schärtl, Wolfgang

2010-12-07

We prepared silica-dye-nanocrystal hybrid particles and studied the energy transfer from semiconductor nanocrystals (= donor) to organic dye molecules (= acceptor). Multishell CdSe/CdS/ZnS semiconductor nanocrystals were adsorbed onto monodisperse Stöber silica particles with an outer silica shell of thickness 2-23 nm containing organic dye molecules (Texas Red). The thickness of this dye layer has a strong effect on the energy transfer efficiency, which is explained by the increase in the number of dye molecules homogeneously distributed within the silica shell, in combination with an enhanced surface adsorption of nanocrystals with increasing dye amount. Our conclusions were underlined by comparison of the experimental results with numerically calculated FRET efficiencies and by control experiments confirming attractive interaction between the nanocrystals and Texas Red freely dissolved in solution.

SERS-fluorescence joint spectral encoded magnetic nanoprobes for multiplex cancer cell separation.

PubMed

Wang, Zhuyuan; Zong, Shenfei; Chen, Hui; Wang, Chunlei; Xu, Shuhong; Cui, Yiping

2014-11-01

A new kind of cancer cell separation method is demonstrated, using surface-enhanced Raman scattering (SERS) and fluorescence dual-encoded magnetic nanoprobes. The designed nanoprobes can realize SERS-fluorescence joint spectral encoding (SFJSE) and greatly improve the multiplexing ability. The nanoprobes have four main components, that is, the magnetic core, SERS generator, fluorescent agent, and targeting antibody. These components are assembled with a multi-layered structure to form the nanoprobes. Specifically, silica-coated magnetic nanobeads (MBs) are used as the inner core. Au core-Ag shell nanorods (Au@Ag NRs) are employed as the SERS generators and attached on the silica-coated MBs. After burying these Au@Ag NRs with another silica layer, CdTe quantum dots (QDs), that is, the fluorescent agent, are anchored onto the silica layer. Finally, antibodies are covalently linked to CdTe QDs. SFJSE is fulfilled by using different Raman molecules and QDs with different emission wavelengths. By utilizing four human cancer cell lines and one normal cell line as the model cells, the nanoprobes can specifically and simultaneously separate target cancer cells from the normal ones. This SFJSE-based method greatly facilitates the multiplex, rapid, and accurate cancer cell separation, and has a prosperous potential in high-throughput analysis and cancer diagnosis. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Manipulating interfacial polymer structures through mixed surfactant adsorption and complexation.

PubMed

Cattoz, Beatrice; de Vos, Wiebe M; Cosgrove, Terence; Crossman, Martin; Prescott, Stuart W

2012-04-17

The effects of a nonionic alcohol ethoxylate surfactant, C(13)E(7), on the interactions between PVP and SDS both in the bulk and at the silica nanoparticle interface are studied by photon correlation spectroscopy, solvent relaxation NMR, SANS, and optical reflectometry. Our results confirmed that, in the absence of SDS, C(13)E(7) and PVP are noninteracting, while SDS interacts strongly both with PVP and C(13)E(7) . Studying interfacial interactions showed that the interfacial interactions of PVP with silica can be manipulated by varying the amounts of SDS and C(13)E(7) present. Upon SDS addition, the adsorbed layer thickness of PVP on silica increases due to Coulombic repulsion between micelles in the polymer layer. When C(13)E(7) is progressively added to the system, it forms mixed micelles with the complexed SDS, reducing the total charge per micelle and thus reducing the repulsion between micelle and the silica surface that would otherwise cause the PVP to desorb. This causes the amount of adsorbed polymer to increase with C(13)E(7) addition for the systems containing SDS, demonstrating that addition of C(13)E(7) hinders the SDS-mediated desorption of an adsorbed PVP layer. © 2012 American Chemical Society

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

Chen, Kuangcai; Lin, Chia -Cheng; Vela, Javier

In this study, three-layer core–shell plasmonic nanorods (Au/Ag/SiO 2–NRs), consisting of a gold nanorod core, a thin silver shell, and a thin silica layer, were synthesized and used as optical imaging probes under a differential interference contrast microscope for single particle orientation and rotational tracking. The localized surface plasmon resonance modes were enhanced upon the addition of the silver shell, and the anisotropic optical properties of gold nanorods were maintained. The silica coating enables surface functionalization with silane coupling agents and provides enhanced stability and biocompatibility. Taking advantage of the longitudinal LSPR enhancement, the orientation and rotational information of themore » hybrid nanorods on synthetic lipid bilayers and on live cell membranes were obtained with millisecond temporal resolution using a scientific complementary metal-oxide-semiconductor camera. The results demonstrate that the as-synthesized hybrid nanorods are promising imaging probes with improved sensitivity and good biocompatibility for single plasmonic particle tracking experiments in biological systems.« less

Effects of excess oxygen on the 4.5-6.3 eV absorption spectra of oxygen-rich high purity silica

NASA Astrophysics Data System (ADS)

Magruder, R. H.; Robinson, S. J.

2016-05-01

Type III silica samples were implanted with O using a multi-energy process that produced a layer of constant concentration to within ±5% beginning ∼80 nm from the surface and extending to ∼640 nm below the surfaces of the samples. The concentrations of excess oxygen in the layer ranged from 0.035 to ∼2.1at.%. In these samples we show that E‧ centers and NBOHCs, as well as the normal cadre of ODC (II) centers, were suppressed, and the optical absorption from 4.7 to 6.4 eV was primarily due to oxygen excess defects. Using Gaussian fitting techniques to examine the optical difference spectra, we have been able to identify four defect centers that are related to excess oxygen defect bands at 4.76 eV, 5.42 eV, 5.75 eV and 6.25 eV.

Nylon surface modification: 2. Nylon-supported composite films.

PubMed

Herrera-Alonso, Margarita; McCarthy, Thomas J; Jia, Xinqiao

2006-02-14

We have developed techniques for the introduction of reactive functional groups to nylon surfaces via site-specific reactions targeting at the naturally abundant amide repeating units on the surface. In this report, we describe the fabrication of nylon-supported composite surfaces using the most efficient modification methods we have developed. N-Alkylation with (3-glycidoxypropyl)triethoxysilane (GPTES) in the presence of potassium tert-butoxide (t-BuOK) leads to surfaces with silica-like reactivity. Subsequent chemical vapor deposition using tetrachlorosilane (SiCl4) and water results in composite films with a thin layer of silica, which was made hydrophobic by reaction with a fluorinated silane reagent. Reduction of the amide groups with borane-THF (BH3-THF) complex leads to a 69% conversion of surface amides to the corresponding secondary amine groups. Alginate was chosen as the model polyelectrolyte for the introduction of a hydrated surface layer. Because of the strong electrostatic interaction between alginate and the amine-enriched nylon surfaces, the adsorption is fast and concentration-independent (within the concentration range studied). The polysaccharide coats the surface homogeneously, without the formation of large aggregates. The amine surfaces obtained by reduction with BH3-THF ((BH3-THF)nylon-NH) and by alkylation with 2-bromoethylamine hydrobromide (BEA-HBr, (EBA-HBr)nylon-NH2) were also used to study gold deposition through electroless plating. Immobilization of a negatively charged metal complex (AuCl4(-)) was achieved through electrostatic interaction. Gold particles disperse preferentially in the bulk of (EBA-HBr)nylon-NH2 films, while they remain confined to the outer surface layer of (BH3-THF)nylon-NH films.

Silica-modified luminescent LaPO4 :Eu@LaPO4 @SiO2 core/shell nanorods: Synthesis, structural and luminescent properties.

PubMed

Ansari, Anees A

2018-02-01

Monoclinic-type tetragonal LaPO 4 :Eu (core) and LaPO 4 :Eu@LaPO 4 (core/shell) nanorods (NRs) were successfully prepared using a urea-based co-precipitation process under ambient conditions. An amorphous silica layer was coated around the luminescent core/shell NRs via the sol-gel process to improve their solubility and colloidal stability in aqueous and non-aqueous media. The prepared nano-products were systematically characterized by X-ray diffraction pattern, transmission electron microscopy, energy dispersive X-ray analysis, and FTIR, UV/Vis, and photoluminescence spectroscopy to examine their phase purity, crystal phase, surface chemistry, solubility and luminescence characteristics. The length and diameter of the nano-products were in the range 80-120 nm and 10-15 nm, respectively. High solubility of the silica-modified core/shell/Si NRs was found for the aqueous medium. The luminescent core NRs exhibited characteristic excitation and emission transitions in the visible region that were greatly affected by surface growth of insulating LaPO 4 and silica layers due to the multiphonon relaxation rate. Our luminescence spectral results clearly show a distinct difference in intensities for core, core/shell, and core/shell/Si NRs. Highly luminescent NRs with good solubility could be useful candidates for a variety of photonic-based biomedical applications. Copyright © 2017 John Wiley & Sons, Ltd.

Preparation and Characterization of WS2@SiO2 and WS2@PANI Core-Shell Nanocomposites

PubMed Central

Sade, Hagit

2018-01-01

Two tungsten disulfide (WS2)-based core-shell nanocomposites were fabricated using readily available reagents and simple procedures. The surface was pre-treated with a surfactant couple in a layer-by-layer approach, enabling good dispersion of the WS2 nanostructures in aqueous media and providing a template for the polymerization of a silica (SiO2) shell. After a Stöber-like reaction, a conformal silica coating was achieved. Inspired by the resulting nanocomposite, a second one was prepared by reacting the surfactant-modified WS2 nanostructures with aniline and an oxidizing agent in an aqueous medium. Here too, a conformal coating of polyaniline (PANI) was obtained, giving a WS2@PANI nanocomposite. Both nanocomposites were analyzed by electron microscopy, energy dispersive X-ray spectroscopy (EDS) and FTIR, verifying the core-shell structure and the character of shells. The silica shell was amorphous and mesoporous and the surface area of the composite increases with shell thickness. Polyaniline shells slightly differ in their morphologies dependent on the acid used in the polymerization process and are amorphous like the silica shell. Electron paramagnetic resonance (EPR) spectroscopy of the WS2@PANI nanocomposite showed variation between bulk PANI and the PANI shell. These two nanocomposites have great potential to expand the use of transition metals dichalcogenides (TMDCs) for new applications in different fields. PMID:29534426

Synthesis of robust water-soluble ZnS:Mn/SiO2 core/shell nanoparticles

NASA Astrophysics Data System (ADS)

Sun, Jing; Zhuang, Jiaqi; Guan, Shaowei; Yang, Wensheng

2008-04-01

Water-soluble Mn doped ZnS (ZnS:Mn) nanocrystals synthesized by using 3-mercaptopropionic acid (MPA) as stabilizer were homogeneously coated with a dense silica shell through a multi-step procedure. First, 3-mercaptopropyl triethoxy silane (MPS) was used to replace MPA on the particle surface to form a vitreophilic layer for further silica deposition under optimal experimental conditions. Then a two-step silica deposition was performed to form the final water-soluble ZnS:Mn/SiO2 core/shell nanoparticles. The as-prepared core/shell nanoparticles show little change in fluorescence intensity in a wide range of pH value.

A novel strategy for durable superhydrophobic coating on glass substrate via using silica chains to fix silica particles

NASA Astrophysics Data System (ADS)

Huang, Qi-Zhang; Fang, Yue-Yun; Liu, Peng-Yi; Zhu, Yan-Qing; Shi, Ji-Fu; Xu, Gang

2018-01-01

The practical application of superhydrophobic coatings on glass is usually restricted by their poor wear resistance due to the insufficient adhesion. A double-silica-layered structure was proposed to reinforce the coating adhesion on glass substrate. The wettability, surface morphologies, and chemical composition were investigated by water contact angle measurement, scanning electron microscopy (SEM), and fourier transformed infrared (FTIR) spectroscopy. The prepared superhydrophobic coating displays a good wear-resistance by emery paper and sand abrasion, which also has excellent thermal stability and UV resistance. This strategy shows a bright future for durable superhydrophobic coating on glass.

Target-triggered signal turn-on detection of prostate specific antigen based on metal-enhanced fluorescence of Ag@SiO2@SiO2-RuBpy composite nanoparticles

NASA Astrophysics Data System (ADS)

Deng, Yun-Liang; Xu, Dang-Dang; Pang, Dai-Wen; Tang, Hong-Wu

2017-02-01

A three-layer core-shell nanostructure consisting of a silver core, a silica spacer, and a fluorescent dye RuBpy-doped outer silica layer was fabricated, and the optimal metal-enhanced fluorescence (MEF) distance was explored through adjusting the thickness of the silica spacer. The results show that the optimal distance is ˜10.4 nm with the maximum fluorescence enhancement factor 2.12. Then a new target-triggered MEF ‘turn-on’ strategy based on the optimized composite nanoparticles was successfully constructed for quantitative detection of prostate specific antigen (PSA), by using RuBpy as the energy donor and BHQ-2 as the acceptor. The hybridization of the complementary DNA of PSA-aptamer immobilized on the surface of the MEF nanoparticles with PSA-aptamer modified with BHQ-2, brought BHQ-2 in close proximity to RuBpy-doped silica shell and resulted in the decrease of fluorescence. In the presence of target PSA molecules, the BHQ-PSA aptamer is dissociated from the surface of the nanoparticles with the fluorescence switched on. Therefore, the assay of PSA was achieved by measuring the varying fluorescence intensity. The results show that PSA can be detected in the range of 1-100 ng ml-1 with a detection limit of 0.20 ng ml-1 (6.1 pM), which is 6.7-fold increase of that using hollow RuBpy-doped silica nanoparticles. Moreover, satisfactory results were obtained when PSA was detected in 1% serum.

Microstructure and rheology of particle stabilized emulsions: Effects of particle shape and inter-particle interactions.

PubMed

Katepalli, Hari; John, Vijay T; Tripathi, Anubhav; Bose, Arijit

2017-01-01

Using fumed and spherical silica particles of similar hydrodynamic size, we investigated the effects of particle shape and inter-particle interactions on the formation, stability and rheology of bromohexadecane-in-water Pickering emulsions. The interparticle interactions were varied from repulsive to attractive by modifying the salt concentration in the aqueous phase. Optical microscope images revealed smaller droplet sizes for the fumed silica stabilized emulsions. All the emulsions remained stable for several weeks. Cryo-SEM images of the emulsion droplets showed a hexagonally packed single layer of particles at oil-water interfaces in emulsions stabilized with silica spheres, irrespective of the nature of the inter-particle interactions. Thus, entropic, excluded volume interactions dominate the fate of spherical particles at oil-water interfaces. On the other hand, closely packed layers of particles were observed at oil-water interfaces for the fumed silica stabilized emulsions for both attractive and repulsive interparticle interactions. At the high salt concentrations, attractive inter-particles interactions led to aggregation of fumed silica particles, and multiple layers of these particles were then observed on the droplet surfaces. A network of fumed silica particles was also observed between the emulsion droplets, suggesting that enthalpic interactions are responsible for the determining particle configurations at oil-water interfaces as well as in the aqueous phase. Steady shear viscosity measurements over a range of shear stresses, as well as oscillatory shear measurements at 1Hz confirm the presence of a network in fumed silica suspensions and emulsions, and the lack of such a network when spherical particles are used. The fractal structure of fumed silica leads to several contact points and particle interlocking in the water as well as on the bromohexadecane-water interfaces, with corresponding effects on the structure and rheology of the emulsions. The attenuation of droplet motion due to the formation of a particle network can be exploited for stabilizing emulsions and for modulating their rheology. Copyright © 2016 Elsevier Inc. All rights reserved.

[Comparison of the shear bond strength by using nano silica sol to zirconia basement and veneer porcelain].

PubMed

Wang, Si-qian; Zhang, Da-feng; Zhen, Tie-li; Yang, Jing-yuan; Lin, Ting-ting; Ma, Jian-feng

2016-04-01

To investigate the feasibility of using sol gel technique to produce thin layer nano silicon dioxide on zirconia ceramic surface and the effect of improving shear bond strength between zirconia and veneer porcelain. The presintered zirconia specimen was cut into a rectangle block piece (15 mm×10 mm×2.5 mm), a total of 40 pieces were obtained and divided into 4 groups, each group had 10 pieces. Four different treatments were used in each group respectively. Pieces in group A (control group) were only sintered at 1450°C to crystallization; pieces in group B underwent 30% nano silica sol infiltration first and then were sintered at 1450°C to crystallization; piece in group C underwent crystallization first at 1450°C, then 30% nano silica sol infiltration and were sintered at 1450°C again; pieces in group D was coated by nano silica sol and then sintered at 1450°C to crystallization; ten rectangle block pieces (12 mm×8 mm×2 mm) in group E were made. Cylinder veneers 5 mm in diameter and 4 mm in height were produced in each group and the shear bond strength was tested. Data were statistically analyzed by SPSS 19.0 software package. The shear bond strength of the 5 group specimens were: (28.12±2.95) MPa in group A, (31.09±3.94) MPa in group B, (25.60±2.45) MPa in group C, (31.75±4.90) MPa in group D, (28.67±3.95) MPa in group E, respectively. Significant differences existed between the 5 groups, and group C had significant difference compared with group B and D. CONCLUSIONS：① Use of nano silicon sol gel on presintered zirconia surface to make thin layer of nano silicon dioxide can improve the shear bond strength between zirconia and veneer; ②Using nano silicon sol gel on crystallization zirconia surface to make thin layer of nano silicon dioxide will decrease the shear bond strength between zirconia and veneer; ③ Zirconia veneer bilayer ceramic has the same shear bond strength with porcelain fused to Ni Cr alloy; ④Use of sol gel technique to produce thin layer nano silicon dioxide on zirconia ceramic surface is feasible and can improve shear bond strength between zirconia and veneer porcelain.

Mass transport at rotating disk electrodes: effects of synthetic particles and nerve endings.

PubMed

Chiu, Veronica M; Lukus, Peter A; Doyle, Jamie L; Schenk, James O

2011-11-01

An unstirred layer (USL) exists at the interface of solids with solutions. Thus, the particles in brain tissue preparations possess a USL as well as at the surface of a rotating disk electrode (RDE) used to measure chemical fluxes. Time constraints for observing biological kinetics based on estimated thicknesses of USLs at the membrane surface in real samples of nerve endings were estimated. Liposomes, silica, and Sephadex were used separately to model the tissue preparation particles. Within a solution stirred by the RDE, both diffusion and hydrodynamic boundary layers are formed. It was observed that the number and size of particles decreased the following: the apparent diffusion coefficient excluding Sephadex, boundary layer thicknesses excluding silica, sensitivity excluding diluted liposomes (in agreement with results from other laboratories), limiting current potentially due to an increase in the path distance, and mixing time. They have no effect on the detection limit (6 ± 2 nM). The RDE kinetically resolves transmembrane transport with a timing of approximately 30 ms. Copyright © 2011 Elsevier Inc. All rights reserved.

Hydraulic transport across hydrophilic and hydrophobic nanopores: Flow experiments with water and n-hexane.

PubMed

Gruener, Simon; Wallacher, Dirk; Greulich, Stefanie; Busch, Mark; Huber, Patrick

2016-01-01

We experimentally explore pressure-driven flow of water and n-hexane across nanoporous silica (Vycor glass monoliths with 7- or 10-nm pore diameters, respectively) as a function of temperature and surface functionalization (native and silanized glass surfaces). Hydraulic flow rates are measured by applying hydrostatic pressures via inert gases (argon and helium, pressurized up to 70 bar) on the upstream side in a capacitor-based membrane permeability setup. For the native, hydrophilic silica walls, the measured hydraulic permeabilities can be quantitatively accounted for by bulk fluidity provided we assume a sticking boundary layer, i.e., a negative velocity slip length of molecular dimensions. The thickness of this boundary layer is discussed with regard to previous capillarity-driven flow experiments (spontaneous imbibition) and with regard to velocity slippage at the pore walls resulting from dissolved gas. Water flow across the silanized, hydrophobic nanopores is blocked up to a hydrostatic pressure of at least 70 bar. The absence of a sticking boundary layer quantitatively accounts for an enhanced n-hexane permeability in the hydrophobic compared to the hydrophilic nanopores.

Theoretical and experimental studies on silica-coated carbon spheres composites

NASA Astrophysics Data System (ADS)

Guo, Xingmei; Liu, Haixing; Shen, Yinghua; Niu, Mei; Yang, Yongzhen; Liu, Xuguang

2013-10-01

In order to prepare carbon-based photonic crystals, first of all, theoretical modeling calculation was used to predict the bandgap characteristics of silica-coated carbon spheres. Then, silica-coated carbon spheres composites were synthesized using tetraethyl orthosilicate as precursor of silica by a sol-gel method combined with Stöber method. Effect of reaction conditions on surface coating of carbon spheres with silica, including the pH, the amount of precursor and reaction time, was emphasized. The morphology and structure of the composites and the effect coating of carbon spheres with silica were characterized by field-emission scanning electron microscopy, high resolution transmission electron microscopy and Fourier-transform infrared spectrometry. The coating ratio of silica was investigated by thermogravimetry. The results show that pH value played an important role in coating reaction, the dosage of the precursor and reaction time had significant effect on coating layer thickness, that is, coating ratio. Carbon spheres coated with silica had good dispersibility and dispersion stability in water and ethanol, which is preconditions of reactivity of carbon spheres in liquid phase and lays the basis for the application of carbon spheres.

Fracture-induced amorphization of polycrystalline SiO2 stishovite: a potential platform for toughening in ceramics

PubMed Central

Nishiyama, Norimasa; Wakai, Fumihiro; Ohfuji, Hiroaki; Tamenori, Yusuke; Murata, Hidenobu; Taniguchi, Takashi; Matsushita, Masafumi; Takahashi, Manabu; Kulik, Eleonora; Yoshida, Kimiko; Wada, Kouhei; Bednarcik, Jozef; Irifune, Tetsuo

2014-01-01

Silicon dioxide has eight stable crystalline phases at conditions of the Earth's rocky parts. Many metastable phases including amorphous phases have been known, which indicates the presence of large kinetic barriers. As a consequence, some crystalline silica phases transform to amorphous phases by bypassing the liquid via two different pathways. Here we show a new pathway, a fracture-induced amorphization of stishovite that is a high-pressure polymorph. The amorphization accompanies a huge volume expansion of ~100% and occurs in a thin layer whose thickness from the fracture surface is several tens of nanometers. Amorphous silica materials that look like strings or worms were observed on the fracture surfaces. The amount of amorphous silica near the fracture surfaces is positively correlated with indentation fracture toughness. This result indicates that the fracture-induced amorphization causes toughening of stishovite polycrystals. The fracture-induced solid-state amorphization may provide a potential platform for toughening in ceramics. PMID:25297473

Fracture-induced amorphization of polycrystalline SiO2 stishovite: a potential platform for toughening in ceramics.

PubMed

Nishiyama, Norimasa; Wakai, Fumihiro; Ohfuji, Hiroaki; Tamenori, Yusuke; Murata, Hidenobu; Taniguchi, Takashi; Matsushita, Masafumi; Takahashi, Manabu; Kulik, Eleonora; Yoshida, Kimiko; Wada, Kouhei; Bednarcik, Jozef; Irifune, Tetsuo

2014-10-09

Silicon dioxide has eight stable crystalline phases at conditions of the Earth's rocky parts. Many metastable phases including amorphous phases have been known, which indicates the presence of large kinetic barriers. As a consequence, some crystalline silica phases transform to amorphous phases by bypassing the liquid via two different pathways. Here we show a new pathway, a fracture-induced amorphization of stishovite that is a high-pressure polymorph. The amorphization accompanies a huge volume expansion of ~100% and occurs in a thin layer whose thickness from the fracture surface is several tens of nanometers. Amorphous silica materials that look like strings or worms were observed on the fracture surfaces. The amount of amorphous silica near the fracture surfaces is positively correlated with indentation fracture toughness. This result indicates that the fracture-induced amorphization causes toughening of stishovite polycrystals. The fracture-induced solid-state amorphization may provide a potential platform for toughening in ceramics.

Preparation and Structural Studies on Hybrid Core-Shell Nanoparticles Consisting of Silica Core and Conjugated Block Copolymer Shell Prepared by Surface-Initiated Polymerization

NASA Astrophysics Data System (ADS)

Chatterjee, Sourav; Karam, Tony; Rosu, Cornelia; Li, Xin; Do, Changwoo; Youm, Sang Gil; Haber, Louis; Russo, Paul; Nesterov, Evgueni

Controlled Kumada catalyst-transfer polymerization occurring by chain-growth mechanism was developed for the synthesis of conjugated polymers and block copolymers from the surface of inorganic substrates such as silica nanoparticles. Although synthesis of conjugated polymers via Kumada polymerization became an established method for solution polymerization, carrying out the same reaction in heterogeneous conditions to form monodisperse polymer chains still remains a challenge. We developed and described a simple and efficient approach to the preparation of surface-immobilized layer of catalytic Ni(II) initiator, and demonstrated using it to prepare polymers and block copolymers on silica nanoparticle. The structure of the resulting hybrid nanostructures was thoroughly studied using small-angle neutron and X-ray scattering, thermal analysis, and optical spectroscopy. The photoexcitation energy transfer processes in the conjugated polymer shell were studied via steady-state and time resolved transient absorption spectroscopy. This study uncovered important details of the energy transfer, which will be discussed in this presentation.

Composite multilayer insulations for thermal protection of aerospace vehicles

NASA Technical Reports Server (NTRS)

Kourtides, Demetrius A.; Pitts, William C.

1989-01-01

Composite flexible multilayer insulation systems (MLI), consisting of alternating layers of metal foil and scrim cloth or insulation quilted together using ceramic thread, were evaluated for thermal performance and compared with a silica fibrous (baseline) insulation system. The systems studied included: (1) alternating layers of aluminoborosilicate (ABS) scrim cloth and stainless steel foil, with silica, ABS, or alumina insulation; (2) alternating layers of scrim cloth and aluminum foil, with silica or ABS insulation; (3) alternating layers of aluminum foil and silica or ABS insulation; and (4) alternating layers of aluminum-coated polyimide placed on the bottom of the silica insulation. The MLIs containing aluminum were the most efficient, measuring as little as half the backface temperature increase of the baseline system.

Enhanced pearl-chain formation by electrokinetic interaction with the bottom surface of vessel.

PubMed

Nishimura, Satoshi; Matsumura, Hideo; Kosuge, Katsunori; Yamaguchi, Tomohiko

2007-08-14

Counterions in an electric double layer (EDL) around a colloidal particle accumulate on one side of the EDL and are deficient on the other side under an electric field, resulting in an imbalance of ionic concentration in the EDL, that is to say, the ionic polarization of EDL. It is well known that the ionic polarization of EDL induces electric dipole moments whereby the alignments of colloidal particles (e.g., pearl chains) are formed under alternating electric fields. In this study, we focus on the effect of the frequency of applied electric fields (100 Hz-1 kHz) on the alignment of silica particles settling at the bottom of a silica glass vessel. In digital imaging analyses for pearl chains of silica particles, it is confirmed that surface distances between two neighboring particles decrease but the number of particles in a pearl chain increases as the frequency of the applied electric field is lowered from 1 kHz to 100 Hz. More interestingly, electrical conductance measurements suggest that the induced ionic polarization of EDL around silica particles at the bottom of the silica vessel is enhanced as the frequency is lowered from 1 kHz to 100 Hz, whereas the ionic polarization around isolated silica particles in uniform dispersions is alleviated by the relaxation of ionic concentration in the EDL as a result of the diffusion of counterions. This curious phenomenon can be explained by considering that the ionic polarization of EDL of silica particles at the bottom of a vessel is affected by the electro-osmosis of the silica surface at the bottom of the vessel.

Control of spectral transmission enhancement properties of random anti-reflecting surface structures fabricated using gold masking

NASA Astrophysics Data System (ADS)

Peltier, Abigail; Sapkota, Gopal; Potter, Matthew; Busse, Lynda E.; Frantz, Jesse A.; Shaw, L. Brandon; Sanghera, Jasbinder S.; Aggarwal, Ishwar D.; Poutous, Menelaos K.

2017-02-01

Random anti-reflecting subwavelength surface structures (rARSS) have been shown to suppress Fresnel reflection and scatter from optical surfaces. The structures effectively function as a gradient-refractive-index at the substrate boundary, and the spectral transmission properties of the boundary have been shown to depend on the structure's statistical properties (diameter, height, and density.) We fabricated rARSS on fused silica substrates using gold masking. A thin layer of gold was deposited on the surface of the substrate and then subjected to a rapid thermal annealing (RTA) process at various temperatures. This RTA process resulted in the formation of gold "islands" on the surface of the substrate, which then acted as a mask while the substrate was dry etched in a reactive ion etching (RIE) process. The plasma etch yielded a fused silica surface covered with randomly arranged "rods" that act as the anti-reflective layer. We present data relating the physical characteristics of the gold "island" statistical populations, and the resulting rARSS "rod" population, as well as, optical scattering losses and spectral transmission properties of the final surfaces. We focus on comparing results between samples processed at different RTA temperatures, as well as samples fabricated without undergoing RTA, to relate fabrication process statistics to transmission enhancement values.

Ion-specific effects under confinement: the role of interfacial water.

PubMed

Argyris, Dimitrios; Cole, David R; Striolo, Alberto

2010-04-27

All-atom molecular dynamics simulations were employed for the study of the structure and dynamics of aqueous electrolyte solutions within slit-shaped silica nanopores with a width of 10.67 A at ambient temperature. All simulations were conducted for 250 ns to capture the dynamics of ion adsorption and to obtain the equilibrium distribution of multiple ionic species (Na+, Cs+, and Cl(-)) within the pores. The results clearly support the existence of ion-specific effects under confinement, which can be explained by the properties of interfacial water. Cl(-) strongly adsorbs onto the silica surface. Although neither Na+ nor Cs+ is in contact with the solid surface, they show ion-specific behavior. The differences between the density distributions of cations within the pore are primarily due to size effects through their interaction with confined water molecules. The majority of Na+ ions appear within one water layer in close proximity to the silica surface, whereas Cs+ is excluded from well-defined water layers. As a consequence of this preferential distribution, we observe enhanced in-plane mobility for Cs+ ions, found near the center of the pore, compared to that for Na+ ions, closer to the solid substrate. These observations illustrate the key role of interfacial water in determining ion-specific effects under confinement and have practical importance in several fields, from geology to biology.

Influence of Size and Shape of Silica Supports on the Sol⁻Gel Surface Molecularly Imprinted Polymers for Selective Adsorption of Gossypol.

PubMed

Zhi, Keke; Wang, Lulu; Zhang, Yagang; Jiang, Yingfang; Zhang, Letao; Yasin, Akram

2018-05-11

The influence of various silica gel supports with different shapes and sizes on the recognition properties of surface molecular imprinted polymers (MIPs) was investigated. MIPs for selective recognition and adsorption of gossypol were synthesized via the sol⁻gel process with a surface imprinting technique on silica gel substrates. 3-aminopropyltriethoxysilane (APTES) and tetraethoxysilane (TEOS) were chosen as the functional monomer and the cross-linker. The morphology and structure of the gossypol-MIPs were characterized using Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and a standard Brunauer⁻Emett⁻Teller (BET) analysis. Results indicated that the surface imprinted polymer layer facilitated the removal and rebinding of the template, and thus, achieved fast binding kinetics. Compared with the MIPs prepared on irregularly shaped silica with a broad particle size distribution, the MIPs using regularly-shaped silica of uniform size showed higher imprinting factor (IF), and the MIP made with a relatively larger sized (60 μm) spherical silica, demonstrated higher adsorption capacity compared to the MIPs made with smaller sized, spherical silica. The MIP prepared with 60 μm spherically shaped silica, featured a fast adsorption kinetic of 10 min, and a saturated adsorption capacity of 204 mg·g −1 . The gossypol-MIP had higher selectivity (IF = 2.20) for gossypol over its structurally-similar analogs ellagic acid (IF = 1.13) and quercetin (IF = 1.20). The adsorption data of the MIP correlated well with the pseudo-second-order kinetic model and the Freundlich isotherm model, which implied that chemical adsorption dominated, and that multilayer adsorption occurred. Furthermore, the MIP exhibited an excellent regeneration performance, and the adsorption capacity of the MIP for gossypol only decreased by 6% after six reused cycles, indicating good application potential for selective adsorption of gossypol.

Reactive Diazonium-Modified Silica Fillers for High-Performance Polymers.

PubMed

Sandomierski, Mariusz; Strzemiecka, Beata; Chehimi, Mohamed M; Voelkel, Adam

2016-11-08

We describe a simple way of modification of three silica-based fillers with in situ generated 4-hydroxymethylbenzenediazonium salt ( + N 2 -C 6 H 4 -CH 2 OH). The rationale for using a hydroxyl-functionalized diazonium salt is that it provides surface-functionalized fillers that can react with phenolic resins. The modification of silica by diazonium salts was assessed using Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). FTIR spectroscopy permitted the tracking of benzene ring breathing and C-C. The absence of the characteristic N≡N stretching vibration in the 2200-2300 cm -1 range indicates the loss of the diazonium group. XPS results indicate a higher C/Si atomic ratio after the diazonium modification of fillers and the presence of π-π* C1s satellite peaks characteristic of the surface-tethered aromatic species. Adhesion of aryl layers to the silicas is excellent because they withstand harsh thermal and organic solvent treatments. Phenolic resins (used, for example, as binders in abrasive products) were filled with diazonium-modified silicas at 10-25 wt %. The reactivity of the fillers toward phenolic resins was evaluated by the determination of the flow distance. After annealing at 180 °C, the diazonium-modified silica/phenolic resin composites were mechanically tested using the three-point flexural method. The flexural strength was found to be up to 35% higher than that of the composites prepared without any diazonium salts. Diazonium-modified silica with surface-bound -CH 2 -OH groups is thus ideal reactive filler for phenolic resins. Such filler ensures interfacial chemical reactions with the matrix and imparts robust mechanical properties to the final composites. This specialty diazonium-modified silica will find potential application as fillers in the composites for the abrasive industry. More generally, aryl diazonium salts are a unique new series of compounds for tailoring the surface properties of fillers and tuning the physicochemical and mechanical properties of polymer composites.

Atomic Layer Deposition for the Conformal Coating of Nanoporous Materials

DOE PAGES

Elam, Jeffrey W.; Xiong, Guang; Han, Catherine Y.; ...

2006-01-01

Amore » tomic layer deposition ( LD ) is ideal for applying precise and conformal coatings over nanoporous materials. We have recently used LD to coat two nanoporous solids: anodic aluminum oxide ( O ) and silica aerogels. O possesses hexagonally ordered pores with diameters d ∼ 40 nm and pore length L ∼ 70 microns. The O membranes were coated by LD to fabricate catalytic membranes that demonstrate remarkable selectivity in the oxidative dehydrogenation of cyclohexane. dditional O membranes coated with LD Pd films show promise as hydrogen sensors. Silica aerogels have the lowest density and highest surface area of any solid material. Consequently, these materials serve as an excellent substrate to fabricate novel catalytic materials and gas sensors by LD .« less

Volatility of Common Protective Oxides in High-Temperature Water Vapor: Current Understanding and Unanswered Questions

NASA Technical Reports Server (NTRS)

Opila, Elizabeth J.

2004-01-01

Many structural materials rely on the formation of chromia, silica or alumina as a protective layer when exposed in high temperature oxidizing environments. The presence of these oxide layers provides a protective diffusion barrier which slows down further oxidation. In atmospheres containing water vapor, however, reactions to form volatile hydroxide species occur which remove the surface oxide, thus, lowering the protective capability of the oxide scale. This paper summarizes the current understanding of volatility of chromia, silica and alumina in water vapor containing combustion environments. In addition unanswered questions in each system are discussed. Th current paper represents an update on the considerable information learned in the past five years for these systems.

Template-Stripped Smooth Ag Nanohole Arrays with Silica Shells for Surface Plasmon Resonance Biosensing

PubMed Central

Im, Hyungsoon; Lee, Si Hoon; Wittenberg, Nathan J.; Johnson, Timothy W.; Lindquist, Nathan C.; Nagpal, Prashant; Norris, David J.; Oh, Sang-Hyun

2011-01-01

Inexpensive, reproducible and high-throughput fabrication of nanometric apertures in metallic films can benefit many applications in plasmonics, sensing, spectroscopy, lithography and imaging. Here we use template stripping to pattern periodic nanohole arrays in optically thick, smooth Ag films with a silicon template made via nanoimprint lithography. Ag is a low-cost material with good optical properties, but it suffers from poor chemical stability and biocompatibility. However, a thin silica shell encapsulating our template-stripped Ag nanoholes facilitates biosensing applications by protecting the Ag from oxidation as well as providing a robust surface that can be readily modified with a variety of biomolecules using well-established silane chemistry. The thickness of the conformal silica shell can be precisely tuned by atomic layer deposition, and a 15-nm-thick silica shell can effectively prevent fluorophore quenching. The Ag nanohole arrays with silica shells can also be bonded to polydimethylsiloxane (PDMS) microfluidic channels for fluorescence imaging, formation of supported lipid bilayers, and real-time, label-free SPR sensing. Additionally, the smooth surfaces of the template-stripped Ag films enhance refractive index sensitivity compared with as-deposited, rough Ag films. Because nearly centimeter-sized nanohole arrays can be produced inexpensively without using any additional lithography, etching or lift-off, this method can facilitate widespread applications of metallic nanohole arrays for plasmonics and biosensing. PMID:21770414

Structural and mechanical properties of glassy water in nanoscale confinement.

PubMed

Lombardo, Thomas G; Giovambattista, Nicolás; Debenedetti, Pablo G

2009-01-01

We investigate the structure and mechanical properties of glassy water confined between silica-based surfaces with continuously tunable hydrophobicity and hydrophilicity by computing and analyzing minimum energy, mechanically stable configurations (inherent structures). The structured silica substrate imposes long-range order on the first layer of water molecules under hydrophobic confinement at high density (p > or = 1.0 g cm(-3)). This proximal layer is also structured in hydrophilic confinement at very low density (p approximately 0.4 g cm(-3)). The ordering of water next to the hydrophobic surface greatly enhances the mechanical strength of thin films (0.8 nm). This leads to a substantial stress anisotropy; the transverse strength of the film exceeds the normal strength by 500 MPa. The large transverse strength results in a minimum in the equation of state of the energy landscape that does not correspond to a mechanical instability, but represents disruption of the ordered layer of water next to the wall. In addition, we find that the mode of mechanical failure is dependent on the type of confinement. Under large lateral strain, water confined by hydrophilic surfaces preferentially forms voids in the middle of the film and fails cohesively. In contrast, water under hydrophobic confinement tends to form voids near the walls and fails by loss of adhesion.

Hierarchical roughness of sticky and non-sticky superhydrophobic surfaces

NASA Astrophysics Data System (ADS)

Raza, Muhammad; Kooij, Stefan; van Silfhout, Arend; Zandvliet, Harold; Poelsema, Bene

2011-11-01

The importance of superhydrophobic substrates (contact angle >150° with sliding angle <10°) in modern technology is undeniable. We present a simple colloidal route to manufacture superstructured arrays with single- and multi-length-scaled roughness to obtain sticky and non-sticky superhydrophobic surfaces. The largest length scale is provided by (multi-)layers of silica spheres (1 μm, 500nm and 150nm diameter). Decoration with gold nanoparticles (14nm, 26nm and 47nm) gives rise to a second length scale. To lower the surface energy, gold nanoparticles are functionalized with dodecanethiol and the silica spheres by perfluorooctyltriethoxysilane. The morphology was examined by helium ion microscopy (HIM), while wettability measurements were performed by using the sessile drop method. We conclude that wettability can be controlled by changing the surface chemistry and/or length scales of the structures. To achieve truly non-sticky superhydrophobic surfaces, hierarchical roughness plays a vital role.

Water Density in the Electric Double Layer at the Insulator/Electrolyte Solution Interface

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

Tikhonov,A.

I studied the spatial structure of the thick transition region between n-hexane and a colloidal solution of 7-nm silica particles by X-ray reflectivity and grazing incidence small-angle scattering. The interfacial structure is discussed in terms of a semiquantitative interface model wherein the potential gradient at the n-hexane/sol interface reflects the difference in the potentials of 'image forces' between the cationic Na{sup +} and anions (nanoparticles) and the specific adsorption of surface charge at the interface between the adsorbed layer and the solution, as well as at the interface between the adsorbed layer and n-hexane. The X-ray scattering data revealed thatmore » the average density of water in the field {approx}10{sup 9}-10{sup 10} V/m of the electrical double layer at the hexane/silica sol interface is the same as, or only few percent higher (1-7%) than, its density under normal conditions.« less

Self-immobilization and/or thermal treatment for preparing silica-poly(methyloctylsiloxane) stationary phases.

PubMed

Bottoli, Carla B G; Vigna, Camila R M; Fischer, Gerd; Albert, Klaus; Collins, Kenneth E; Collins, Carol H

2004-03-19

Batches of poly(methyloctylsiloxane) (PMOS)-loaded silica were prepared by the deposition of PMOS, into the pores of HPLC silica. Portions of PMOS-loaded silica were allowed to remain at ambient temperature, without further treatment for 2, 9, 20, 31, 51, 105 and 184 days after preparation to undergo self-immobilization (irreversible adsorption of a layer of polymer on silica at ambient temperature in the absence of initiators). Other portions were subjected to a thermal treatment (100 degrees C for 4h) after 1, 2, 5, 7, 9, 15, 20, 25, 70, 111 and 184 days. Self-immobilized and thermally treated samples were characterized by % C, 29Si cross-polarization magic angle spinning (CP/MAS) NMR spectroscopy and reversed-phase column performance. The results show that thermal immobilization accelerates the distribution and rearrangement of the polymer on the silica surface. However, from the time that a monolayer has been formed by self-immobilization (approximately 100 days for PMOS on Kromasil silica), the thermal treatment does not alter this configuration and, thus, does not change the resulting chromatographic parameters.

Isomerization Reaction of mer- to fac-Tris(2-phenylpyridinato-N,C2')Iridium(III) Monitored by Using Surface-Enhanced Raman Spectroscopy.

PubMed

Wu, Bo-Han; Huang, Min-Jie; Lai, Cheng-Chang; Cheng, Chien-Hong; Chen, I-Chia

2018-04-16

We developed a new method by enclosing the complex tris(2-phenylpyridinato-N,C2')Iridium(III), Ir(ppy) 3 with surfactant cetyltrimethylammonium bromide (CATB), coated with a thin layer of silica then bonded to the surface of silver nanoparticle. These samples were used to acquire surface-enhanced Raman scattering (SERS) spectra. The thickness of silica layer was controlled to have efficient phosphorescence quenching and Raman enhancement by metal nanoparticle. The SERS spectra of fac- and mer-Ir(ppy) 3 , recorded at 633 nm excitation, display distinct ring breathing mode features because the total symmetric vibrational bands were enhanced. This provides a convenient means to differentiate these isomers with great sensitivity and to study their isomerization process. A direct conversion reaction of mer- to fac- isomerization is identified with time constant 3.1 min when mer was irradiated with Xe light. Via thermal activation, under moderate conditions (pH 5.5 and 343 K), we observed an intermediate particularly with new bands 320/662 cm -1 after heating for 17.5 h, and then those bands disappeared to form fac-Ir(ppy) 3 . On the basis of DFT calculations, the intermediate is proposed to contain octahedral N-N Ir(ppy) 3 -HO-silica structure; band at 320 cm -1 is assigned to iridium oxygen stretching mode ν Ir-O of this intermediate. Under acidic conditions, pH 1-2 catalyzed by silanol in silica, byproduct with band at 353 cm -1 was observed. According to the SERS bands and the calculation, this byproduct is assigned to be iridium(III) siloxide, and the new band is assigned to ν Ir-O .

An ultrasensitive hollow-silica-based biosensor for pathogenic Escherichia coli DNA detection.

PubMed

Ariffin, Eda Yuhana; Lee, Yook Heng; Futra, Dedi; Tan, Ling Ling; Karim, Nurul Huda Abd; Ibrahim, Nik Nuraznida Nik; Ahmad, Asmat

2018-03-01

A novel electrochemical DNA biosensor for ultrasensitive and selective quantitation of Escherichia coli DNA based on aminated hollow silica spheres (HSiSs) has been successfully developed. The HSiSs were synthesized with facile sonication and heating techniques. The HSiSs have an inner and an outer surface for DNA immobilization sites after they have been functionalized with 3-aminopropyltriethoxysilane. From field emission scanning electron microscopy images, the presence of pores was confirmed in the functionalized HSiSs. Furthermore, Brunauer-Emmett-Teller (BET) analysis indicated that the HSiSs have four times more surface area than silica spheres that have no pores. These aminated HSiSs were deposited onto a screen-printed carbon paste electrode containing a layer of gold nanoparticles (AuNPs) to form a AuNP/HSiS hybrid sensor membrane matrix. Aminated DNA probes were grafted onto the AuNP/HSiS-modified screen-printed electrode via imine covalent bonds with use of glutaraldehyde cross-linker. The DNA hybridization reaction was studied by differential pulse voltammetry using an anthraquinone redox intercalator as the electroactive DNA hybridization label. The DNA biosensor demonstrated a linear response over a wide target sequence concentration range of 1.0×10 -12 -1.0×10 -2 μM, with a low detection limit of 8.17×10 -14 μM (R 2 = 0.99). The improved performance of the DNA biosensor appeared to be due to the hollow structure and rough surface morphology of the hollow silica particles, which greatly increased the total binding surface area for high DNA loading capacity. The HSiSs also facilitated molecule diffusion through the silica hollow structure, and substantially improved the overall DNA hybridization assay. Graphical abstract Step-by-step DNA biosensor fabrication based on aminated hollow silica spheres.

Quantification of the Influence of Protein-Protein Interactions on Adsorbed Protein Structure and Bioactivity

PubMed Central

Wei, Yang; Thyparambil, Aby A.; Latour, Robert A.

2013-01-01

While protein-surface interactions have been widely studied, relatively little is understood at this time regarding how protein-surface interaction effects are influenced by protein-protein interactions and how these effects combine with the internal stability of a protein to influence its adsorbed-state structure and bioactivity. The objectives of this study were to develop a method to study these combined effects under widely varying protein-protein interaction conditions using hen egg-white lysozyme (HEWL) adsorbed on silica glass, poly(methyl methacrylate), and polyethylene as our model systems. In order to vary protein-protein interaction effects over a wide range, HEWL was first adsorbed to each surface type under widely varying protein solution concentrations for 2 h to saturate the surface, followed by immersion in pure buffer solution for 15 h to equilibrate the adsorbed protein layers in the absence of additionally adsorbing protein. Periodic measurements were made at selected time points of the areal density of the adsorbed protein layer as an indicator of the level of protein-protein interaction effects within the layer, and these values were then correlated with measurements of the adsorbed protein’s secondary structure and bioactivity. The results from these studies indicate that protein-protein interaction effects help stabilize the structure of HEWL adsorbed on silica glass, have little influence on the structural behavior of HEWL on HDPE, and actually serve to destabilize HEWL’s structure on PMMA. The bioactivity of HEWL on silica glass and HDPE was found to decrease in direct proportion to the degree of adsorption-induce protein unfolding. A direct correlation between bioactivity and the conformational state of adsorbed HEWL was less apparent on PMMA, thus suggesting that other factors influenced HEWL’s bioactivity on this surface, such as the accessibility of HEWL’s bioactive site being blocked by neighboring proteins or the surface itself. The developed methods provide an effective means to characterize the influence of protein-protein interaction effects and provide new molecular-level insights into how protein-protein interaction effects combine with protein-surface interaction and internal protein stability effects to influence the structure and bioactivity of adsorbed protein. PMID:23751416

Effect of surface charge density on the affinity of oxide nanoparticles for the vapor-water interface.

PubMed

Brown, Matthew A; Duyckaerts, Nicolas; Redondo, Amaia Beloqui; Jordan, Inga; Nolting, Frithjof; Kleibert, Armin; Ammann, Markus; Wörner, Hans Jakob; van Bokhoven, Jeroen A; Abbas, Zareen

2013-04-23

Using in-situ X-ray photoelectron spectroscopy at the vapor-water interface, the affinity of nanometer-sized silica colloids to adsorb at the interface is shown to depend on colloid surface charge density. In aqueous suspensions at pH 10 corrected Debye-Hückel theory for surface complexation calculations predict that smaller silica colloids have increased negative surface charge density that originates from enhanced screening of deprotonated silanol groups (≡Si-O(-)) by counterions in the condensed ion layer. The increased negative surface charge density results in an electrostatic repulsion from the vapor-water interface that is seen to a lesser extent for larger particles that have a reduced charge density in the XPS measurements. We compare the results and interpretation of the in-situ XPS and corrected Debye-Hückel theory for surface complexation calculations with traditional surface tension measurements. Our results show that controlling the surface charge density of colloid particles can regulate their adsorption to the interface between two dielectrics.

Highly luminescent and photostable quantum dot-silica monolith and its application to light-emitting diodes.

PubMed

Jun, Shinae; Lee, Junho; Jang, Eunjoo

2013-02-26

A highly luminescent and photostable quantum dot-silica monolith (QD-SM) substance was prepared by preliminary surface exchange of the QDs and base-catalyzed sol-gel condensation of silica. The SM was heavily doped with 6-mercaptohexanol exchanged QDs up to 12 vol % (26 wt %) without particle aggregation. Propylamine catalyst was important in maintaining the original luminescence of the QDs in the SM during sol-gel condensation. The silica layer was a good barrier against oxygen and moisture, so that the QD-SM maintained its initial luminescence after high-power UV radiation (∼1 W) for 200 h and through the 150 °C LED encapsulant curing process. Green and red light-emitting QD-SMs were applied as color-converting layers on blue LEDs, and the external quantum efficiency reached up to 89% for the green QD-SM and 63% for the red one. A white LED made with a mixture of green and red QDs in the SM, in which the color coordinate was adjusted at (0.23, 0.21) in CIE1931 color space for a backlight application, showed an efficacy of 47 lm/W, the highest value yet reported.

Preparation and application of hollow molecularly imprinted polymers with a super-high selectivity to the template protein.

PubMed

Chen, Yang; He, Xi-Wen; Mao, Jie; Li, Wen-You; Zhang, Yu-Kui

2013-10-01

Protein-imprinted polymers with hollow cores that have a super-high imprinting factor were prepared by etching the core of the surface-imprinted polymers that used silica particles as the support. Lysozyme as template was modified onto the surface of silica particles by a covalent method, and after polymerization and the removal of template molecules, channels through the polymer layer were formed, which allowed a single-protein molecule to come into the hollow core and attach to the binding sites inside the polymer layer. The adsorption experiments demonstrated that the hollow imprinted polymers had an extremely high binding capacity and selectivity, and thus a super-high imprinting factor was obtained. The as-prepared imprinted polymers were used to separate the template lysozyme from egg white successfully, indicating its high selectivity and potential application in the field of separation of protein from real samples. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High temperature solar selective coatings

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

Kennedy, Cheryl E

Improved solar collectors (40) comprising glass tubing (42) attached to bellows (44) by airtight seals (56) enclose solar absorber tubes (50) inside an annular evacuated space (54. The exterior surfaces of the solar absorber tubes (50) are coated with improved solar selective coatings {48} which provide higher absorbance, lower emittance and resistance to atmospheric oxidation at elevated temperatures. The coatings are multilayered structures comprising solar absorbent layers (26) applied to the meta surface of the absorber tubes (50), typically stainless steel, topped with antireflective Savers (28) comprising at least two layers 30, 32) of refractory metal or metalloid oxides (suchmore » as titania and silica) with substantially differing indices of refraction in adjacent layers. Optionally, at least one layer of a noble metal such as platinum can be included between some of the layers. The absorbent layers cars include cermet materials comprising particles of metal compounds is a matrix, which can contain oxides of refractory metals or metalloids such as silicon. Reflective layers within the coating layers can comprise refractory metal silicides and related compounds characterized by the formulas TiSi. Ti.sub.3SiC.sub.2, TiAlSi, TiAN and similar compounds for Zr and Hf. The titania can be characterized by the formulas TiO.sub.2, Ti.sub.3O.sub.5. TiOx or TiO.sub.xN.sub.1-x with x 0 to 1. The silica can be at least one of SiO.sub.2, SiO.sub.2x or SiO.sub.2xN.sub.1-x with x=0 to 1.« less

Ceramic Composite Thin Films

NASA Technical Reports Server (NTRS)

Dikin, Dmitriy A. (Inventor); Nguyen, SonBinh T. (Inventor); Ruoff, Rodney S. (Inventor); Stankovich, Sasha (Inventor)

2013-01-01

A ceramic composite thin film or layer includes individual graphene oxide and/or electrically conductive graphene sheets dispersed in a ceramic (e.g. silica) matrix. The thin film or layer can be electrically conductive film or layer depending the amount of graphene sheets present. The composite films or layers are transparent, chemically inert and compatible with both glass and hydrophilic SiOx/silicon substrates. The composite film or layer can be produced by making a suspension of graphene oxide sheet fragments, introducing a silica-precursor or silica to the suspension to form a sol, depositing the sol on a substrate as thin film or layer, at least partially reducing the graphene oxide sheets to conductive graphene sheets, and thermally consolidating the thin film or layer to form a silica matrix in which the graphene oxide and/or graphene sheets are dispersed.

Tunable Pickering Emulsions with Environmentally Responsive Hairy Silica Nanoparticles.

PubMed

Liu, Min; Chen, Xiaoli; Yang, Zongpeng; Xu, Zhou; Hong, Liangzhi; Ngai, To

2016-11-30

Surface modification of the nanoparticles using surface anchoring of amphiphilic polymers offers considerable scope for the design of a wide range of brush-coated hybrid nanoparticles with tunable surface wettability that may serve as new class of efficient Pickering emulsifiers. In the present study, we prepared mixed polymer brush-coated nanoparticles by grafting ABC miktoarm star terpolymers consisting of poly(ethylene glycol), polystyrene, and poly[(3-triisopropyloxysilyl)propyl methacrylate] (μ-PEG-b-PS-b-PIPSMA) on the surface of silica nanoparticles. The wettability of the as-prepared nanoparticles can be precisely tuned by a change of solvent or host-guest complexation. 1 H NMR result confirmed that such wettability change is due to the reorganization of the polymer chain at the grafted layer. We show that this behavior can be used for stabilization and switching between water-in-oil (W/O) and oil-in-water (O/W) emulsions. For hairy particles initially dispersed in oil, W/O emulsions were always obtained with collapsed PEG chains and mobile PS chains at the grafted layer. However, initially dispersing the hairy particles in water resulted in O/W emulsions with collapsed PS chains and mobile PEG chains. When a good solvent for both PS and PEG blocks such as toluene was used, W/O emulsions were always obtained no matter where the hairy particles were dispersed. The wettability of the mixed polymer brush-coated silica particles can also be tuned by host-guest complexation between PEG block and α-CD. More importantly, our result showed that surprisingly the resultant mixed brush-coated hairy nanoparticles can be employed for the one-step production of O/W/O multiple emulsions that are not attainable from conventional Pickering emulsifiers. The functionalized hairy silica nanoparticles at the oil-water interface can be further linked together utilizing poly(acrylic acid) as the reversible linker to form supramolecular colloidosomes, which show pH-dependent release of cargo.

First-order dissolution rate law and the role of surface layers in glass performance assessment

NASA Astrophysics Data System (ADS)

Grambow, B.; Müller, R.

2001-09-01

The first-order dissolution rate law is used for nuclear waste glass performance predictions since 1984. A first discussion of the role of saturation effects was initiated at the MRS conference that year. In paper (1) it was stated that "For glass dissolution A* (the reaction affinity) cannot become zero since saturation only involves the reacting surface while soluble elements still might be extracted from the glass" [B. Grambow, J. Mater. Res. Soc. Symp. Proc. 44 (1985) 15]. Saturation of silica at the surface and condensation of surface silanol groups was considered as being responsible for the slow down of reaction rates by as much as a factor of 1000. Precipitation of Si containing secondary phases such as quartz was invoked as a mechanism for keeping final dissolution affinities higher than zero. Another (2) paper [A.B. Barkatt, P.B. Macedo, B.C. Gibson, C.J. Montrose, J. Mater. Res. Soc. Symp. Proc. 44 (1985) 3] stated that "… under repository conditions the extent of glass dissolution will be moderate due to saturation with respect to certain major elements (in particular, Si, Al and Ca). Consequently, the concentration levels of the more soluble glass constituents in the aqueous medium are expected to fall appreciable below their solubility limit." The formation of dense surface layers was considered responsible for explaining the saturation effect. The mathematical model assumed stop of reaction in closed systems, once solubility limits were achieved. For more than 15 years the question of the correctness of one or the other concept has seldom been posed and has not yet been resolved. The need of repository performance assessment for validated rate laws demands a solution, particularly since the consequences of the two concepts and research requirements for the long-term glass behavior are quite different. In concept (1) the stability of the `equilibrium surface region' is not relevant because, by definition, this region is stable chemically and after a potential mechanical destruction it will be reformed instantaneously. The same is true for radiation damage. The dissolution of silica from the surface in this concept is considered as rate limiting for the release of soluble elements from the glass. After surface stabilization by local solid/solution equilibrium the release of soluble radionuclides continues with lower rates, but this is considered as resulting from parallel leaching mechanism. In fact, the deconvolutions of the overall leach mechanism into individual parallel and sequential rate limiting steps (not necessarily elementary reactions) is fundamental to this concept. In concept (2) surface stability as well as surface morphology are fundamental. A fracture in the protective surface would increase glass corrosion. The protective effect is based on the low diffusivities of radionuclides and other glass constituents in this layer. However, a true relation between layer thickness and rates is seldom observed. Diffusion coefficients are considered to vary with time as well as with the surface area to solution volume S/ V ratio. Sometimes, extremely low diffusivities in extremely thin layers are invoked to explain experimental data. The two concepts are not so different from each other and one is tempted to think of a problem of semantics. In fact, there are two alternative ways by which the protective layer concept can be coupled to the saturation concept: (a) the layer may be formed by solubility effects as proposed in [loc.cit] and/or (b) the layer plays the role of a silica diffusion barrier limiting glass dissolution rates according to the first-order rate law at the interface between the pristine glass and the surface layer. However, the mathematical models based on these conceptual models yield quite different long-term predictions, even though the models may equally well fit a given set of experimental data. The models are also different with respect to the number of interrelated parameters. In the case of a model based on a surface layer slowing down glass network dissolution, the numerical value of the diffusion coefficient of silica, the layer thickness and the saturation concentration of dissolved silica are interrelated. Often, none of the parameters are measured directly. As a consequence this leads to not-sufficiently constrained models with poor predictive capacity. Recent research has indicated that there might be problems with the applicability of the first-order rate law [C. Jegou, thesis, University of Montpellier II, 1998]. Fresh glass or pre-altered glass samples were put in solutions over-saturated with silica. A decrease in reaction rates by as much as a factor of 10 was observed, but the rates remained much higher than predicted from a first-order rate law. It was argued that none of the kinetic models based on the notions of `chemical affinity' and `deviation from an equilibrium' is adapted to describe the kinetics of glass corrosion. In contrast, the formation of a surface gel and condensation of silanol groups are considered responsible for the decrease in reaction rates. The present communication argues against this view. Based on recent results of Monte Carlo calculations [M. Aertsens, Mater. Res. Soc. Symp. Proc. 556 (1999) 409] it is shown that some time of surface restructuration is necessary before saturation effects become fully effective in controlling long-term release of soluble glass constituents. The formation of a gel layer is not opposed to an affinity based kinetic concept, but it is in contrast a manifestation of this concept. It is the belief of the authors that much of the confusion related to the first-order rate law results from the fact that glass network dissolution is not considered as only one of a series of reaction mechanism and that glass network hydration and alkali ion exchange were ignored as parallel leaching mechanism. Our experimental results show that glass network hydration and ion exchange are important in short-term laboratory tests and in certain cases (closed system) also in the long term.

Experimental and Theoretical Investigations of Glass Surface Charging Phenomena

NASA Astrophysics Data System (ADS)

Agnello, Gabriel

Charging behavior of multi-component display-type (i.e. low alkali) glass surfaces has been studied using a combination of experimental and theoretical methods. Data obtained by way of a Rolling Sphere Test (RST), streaming/zeta potential and surface energy measurements from commercially available display glass surfaces (Corning EAGLE XGRTM and Lotus(TM) XT) suggest that charge accumulation is highly dependent on surface treatment (chemical and/or physical modification) and measurement environment, presumably through reactionary mechanisms at the surface with atmospheric moisture. It has been hypothesized that water dissociation, along with the corresponding hydroxylation of the glass surface, are important processes related to charging in glass-metal contact systems. Classical Molecular Dynamics (MD) simulations, in conjunction with various laboratory based measurements (RST, a newly developed ElectroStatic Gauge (ESG) and Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS)) on simpler Calcium AluminoSilicate (CAS) glass surfaces were used to further explore these phenomena. Analysis of simulated high-silica content (≥50%) (CAS) glass structures suggest that controlled variation of bulk chemistry can directly affect surface defect concentrations, such as non-bridging oxygen (NBO), which can be suitable high-energy sites for hydrolysis-type reactions to occur. Calculated NBO surface concentrations correlate well with charge based measurements on laboratory fabricated CAS surfaces. The data suggest that a directional/polar shift in contact-charge transfer occurs at low silica content (≤50%) where the highest concentrations of NBOs are observed. Surface charging sensitivity with respect to NBO concentration decreases as the relative humidity of the measurement environment increases; which should be expected as the highly reactive sites are progressively covered by liquid water layers. DRIFTS analysis of CAS powders expand on this analysis showing a gradual increase in molecular water absorption at the surface in samples containing ≥60% silica, and an abrupt decrease in those with ≤60% silica. This behavior is very likely related to the aforementioned charge polarity shift (negative (-) to positive (+)) in low silica containing glasses, leading to the conclusion that structural defect mediated charge accumulation and/or transfer are likely to be important mechanisms related to the contact charging of glass surfaces.

Carbonate formation on bioactive glasses.

PubMed

Cerruti, Marta; Morterra, Claudio

2004-07-20

The system termed 58S is a sol-gel-synthesized bioactive glass composed of SiO2, CaO, and P2O5, used in medicine as bone prosthetic because, when immersed in a physiological fluid, a layer of hydroxycarbonate apatite is formed on its surface. The mechanism of bioactive glass 58S carbonation was studied in the vacuum by means of in-situ FTIR spectroscopy with the use of CO2, H2O, and CD3CN as probe molecules. The study in the vacuum was necessary to identify both the molecules specifically involved in the carbonation process and the type of carbonates formed. Bioactive glass 58S was compared to a Ca-doped silica and to CaO. On CaO, ionic carbonates could form by contact with CO2 alone, whereas on 58S and on Ca-doped silica carbonation occurred only if both CO2 and an excess of H2O were present on the sample. The function of H2O was not only to block surface cationic sites, so that CO2 could not manifest its Lewis base behavior, but also to form a liquid-like (mono)layer that allowed the formation of carbonate ions. The presence of H2O is also supposed to promote Ca2+ migration from the bulk to the surface. Carbonates formed at the surface of CaO and of Ca-bearing silicas (thus including bioactive glasses) are of the same type, but are produced through two different mechanisms. The finding that a water excess is necessary to start heavy carbonation on bioactive glasses seemed to imply that the mechanism leading to in-situ carbonation simulates, in a simplified and easy-to-reproduce system, what happens both in solution, when carbonates are incorporated in the apatite layer, and during sample shelf-aging. Copyright 2004 American Chemical Society

Integrated High Payoff Rocket Propulsion Technology (IHPRPT) SiC Recession Model

NASA Technical Reports Server (NTRS)

Opila, E. J.

2009-01-01

SiC stability and recession rates were modeled in hydrogen/oxygen combustion environments for the Integrated High Payoff Rocket Propulsion Technology (IHPRPT) program. The IHPRPT program is a government and industry program to improve U.S. rocket propulsion systems. Within this program SiC-based ceramic matrix composites are being considered for transpiration cooled injector faceplates or rocket engine thrust chamber liners. Material testing under conditions representative of these environments was conducted at the NASA Glenn Research Center, Cell 22. For the study described herein, SiC degradation was modeled under these Cell 22 test conditions for comparison to actual test results: molar mixture ratio, MR (O2:H2) = 6, material temperatures to 1700 C, combustion gas pressures between 0.34 and 2.10 atm, and gas velocities between 8,000 and 12,000 fps. Recession was calculated assuming rates were controlled by volatility of thermally grown silica limited by gas boundary layer transport. Assumptions for use of this model were explored, including the presence of silica on the SiC surface, laminar gas boundary layer limited volatility, and accuracy of thermochemical data for volatile Si-O-H species. Recession rates were calculated as a function of temperature. It was found that at 1700 C, the highest temperature considered, the calculated recession rates were negligible, about 200 m/h, relative to the expected lifetime of the material. Results compared favorably to testing observations. Other mechanisms contributing to SiC recession are briefly described including consumption of underlying carbon and pitting. A simple expression for liquid flow on the material surface was developed from a one-dimensional treatment of the Navier-Stokes Equation. This relationship is useful to determine under which conditions glassy coatings or thermally grown silica would flow on the material surface, removing protective layers by shear forces. The velocity of liquid flow was found to depend on the gas velocity, the viscosity of gas and liquid, as well as the thickness of the gas boundary layer and the liquid layer. Calculated flow rates of a borosilicate glass coating compared well to flow rates observed for this coating tested on a SiC panel in Cell 22.

Studies of mobile dust in scrape-off layer plasmas using silica aerogel collectors

NASA Astrophysics Data System (ADS)

Bergsåker, H.; Ratynskaia, S.; Litnovsky, A.; Ogata, D.; Sahle, W.

2011-08-01

Dust capture with ultralow density silica aerogel collectors is a new method, which allows time resolved in situ capture of dust particles in the scrape-off layers of fusion devices, without substantially damaging the particles. Particle composition and morphology, particle flux densities and particle velocity distributions can be determined through appropriate analysis of the aerogel surfaces after exposure. The method has been applied in comparative studies of intrinsic dust in the TEXTOR tokamak and in the Extrap T2R reversed field pinch. The analysis methods have been mainly optical microscopy and SEM. The method is shown to be applicable in both devices and the results are tentatively compared between the two plasma devices, which are very different in terms of edge plasma conditions, time scale, geometry and wall materials.

Surface-enhanced Raman scattering of amorphous silica gel adsorbed on gold substrates for optical fiber sensors

NASA Astrophysics Data System (ADS)

Degioanni, S.; Jurdyc, A. M.; Cheap, A.; Champagnon, B.; Bessueille, F.; Coulm, J.; Bois, L.; Vouagner, D.

2015-10-01

Two kinds of gold substrates are used to produce surface-enhanced Raman scattering (SERS) of amorphous silica obtained via the sol-gel route using tetraethoxysilane Si(OC2H5)4 (TEOS) solution. The first substrate consists of a gold nanometric film elaborated on a glass slide by sputter deposition, controlling the desired gold thickness and sputtering current intensity. The second substrate consists of an array of micrometer-sized gold inverted pyramidal pits able to confine surface plasmon (SP) enhancing electric field, which results in a distribution of electromagnetic energy inside the cavities. These substrates are optically characterized to observe SPR with, respectively, extinction and reflectance spectrometries. Once coated with thin layers of amorphous silica (SiO2) gel, these samples show Raman amplification of amorphous SiO2 bands. This enhancement can occur in SERS sensors using amorphous SiO2 gel as shells, spacers, protective coatings, or waveguides, and represents particularly a potential interest in the field of Raman distributed sensors, which use the amorphous SiO2 core of optical fibers as a transducer to make temperature measurements.

A molecular investigation of adsorption onto mineral pigments

NASA Astrophysics Data System (ADS)

Ninness, Brian J.

Pigment suspensions are important in several processes such as ceramics, paints, inks, and coatings. In the wet state, pigments are combined with a variety of chemical species such as polymers, surfactants, and polyelectrolytes which produce a complex colloidal system. The adsorption, desorption, and redistribution of these species at the pigment-aqueous solution interface can have an impact on the behavior in both the wet state or its final dried state. The goal of this work is to establish a molecular picture of the adsorption properties of these pigmented systems. A novel in situ infrared technique has been developed which allows the detection of adsorbed surface species on pigment particles in an aqueous environment. The technique involves the use of a polymeric binder to anchor the colloidal pigment particles to the surface of an internal reflection element (IRE). The binder only weakly perturbs about 25% of the reactive surface sites (hydroxyl groups) on silica. The reaction of succinic anhydride with an aminosilanized silica surface has been quantified using this technique. The adsorption dynamics of the cationic surfactant cetyltrimethylammonium bromide (C16TAB) at the TiO2-aqueous solution interface has been investigated using Fourier transform infrared-attenuated total reflection spectroscopy (FTIR-ATR) and electrokinetic analysis. At low bulk concentrations, C16TAB is shown to adsorb as isolated islands with a "defective" bilayer structure. Anionic probe molecules are shown to effectively "tune" the adsorbed surfactant microstructure. The results indicate that the structure of the adsorbed surfactant layer, and not the amount of adsorbed surfactant, dictates the subsequent adsorption behavior of the system. Atomic Layer Deposition is used to deposit a TiO2 layer onto the surfaces of silica and kaolin pigments. The process involves the cyclic reaction sequence of the vapors of TiCl4 and H2O. Three complete deposition cycles are needed before the surfaces of the modified pigments are dominated by the presence of TiO2. The modified kaolin pigments display increased dispersion stability as compared to the parent kaolin. The electrokinetic behavior of the modified kaolin is shown to be identical to that of pure TiO2 pigments.

Chiral permselectivity in surface-modified nanoporous opal films.

PubMed

Cichelli, Julie; Zharov, Ilya

2006-06-28

Nanoporous 7 mum thin opal films comprising 35 layers of 200 nm diameter SiO2 spheres were assembled on Pt electrodes and modified with chiral selector moieties on the silica surface. Diffusion of chiral redox species through the opals was studied by cyclic voltammetry. The chiral opal films demonstrate high selectivity for transport of one enantiomer over the other. This chiral permselectivity is attributed to the surface-facilitated transport utilizing noncovalent interactions between the chiral permeant molecules and surface-bound chiral selectors.

Electroless growth of silver nanoparticles into mesostructured silica block copolymer films.

PubMed

Bois, Laurence; Chassagneux, Fernand; Desroches, Cédric; Battie, Yann; Destouches, Nathalie; Gilon, Nicole; Parola, Stéphane; Stéphan, Olivier

2010-06-01

Silver nanoparticles and silver nanowires have been grown inside mesostructured silica films obtained from block copolymers using two successive reduction steps: the first one involves a sodium borohydride reduction or a photoreduction of silver nitrate contained in the film, and the second one consists of a silver deposit on the primary nanoparticles, carried out by silver ion solution reduction with hydroxylamine chloride. We have demonstrated that the F127 block copolymer ((PEO)(106)(PPO)(70)(PEO)(106)), "F type", mesostructured silica film is a suitable "soft" template for the fabrication of spherical silver nanoparticles arrays. Silver spheres grow from 7 to 11 nm upon the second reduction step. As a consequence, a red shift of the surface plasmon resonance associated with metallic silver has been observed and attributed to plasmonic coupling between particles. Using a P123 block copolymer ((PEO)(20)(PPO)(70)(PEO)(20)), "P type", mesostructured silica film, we have obtained silver nanowires with typical dimension of 10 nm x 100 nm. The corresponding surface plasmon resonance is blue-shifted. The hydroxylamine chloride treatment appears to be efficient only when a previous chemical reduction is performed, assuming that the first sodium borohydride reduction induces a high concentration of silver nuclei in the first layer of the porous silica (film/air interface), which explains their reactivity for further growth.

Surface Acidity and Properties of TiO2/SiO2 Catalysts Prepared by Atomic Layer Deposition: UV-visible Diffuse Reflectance, DRIFTS, and Visible Raman Spectroscopy Studies

DTIC Science & Technology

2009-06-15

titanium isopropoxide (TTIP) as metal precursors. The deposition rate of titania films from TiCl4 was found to be stable in the 150-300 °C...tetrachloride (TiCl4) and titanium isopropoxide (TTIP) are widely used as metal precursors and water or hydrogen peroxide are used as oxygen precursors.29-36... titanium dioxide supported on high surface area silica gel have been synthesized by atomic layer deposition (ALD) using titanium tetrachloride (TiCl4) and

Formation of broadband antireflective and superhydrophilic subwavelength structures on fused silica using one-step self-masking reactive ion etching

PubMed Central

Ye, Xin; Jiang, Xiaodong; Huang, Jin; Geng, Feng; Sun, Laixi; Zu, Xiaotao; Wu, Weidong; Zheng, Wanguo

2015-01-01

Fused silica subwavelength structures (SWSs) with an average period of ~100 nm were fabricated using an efficient approach based on one-step self-masking reactive ion etching. The subwavelength structures exhibited excellent broadband antireflection properties from the ultraviolet to near-infrared wavelength range. These properties are attributable to the graded refractive index for the transition from air to the fused silica substrate that is produced by the ideal nanocone subwavelength structures. The transmittance in the 400–700 nm range increased from approximately 93% for the polished fused silica to greater than 99% for the subwavelength structure layer on fused silica. Achieving broadband antireflection in the visible and near-infrared wavelength range by appropriate matching of the SWS heights on the front and back sides of the fused silica is a novel strategy. The measured antireflection properties are consistent with the results of theoretical analysis using a finite-difference time-domain (FDTD) method. This method is also applicable to diffraction grating fabrication. Moreover, the surface of the subwavelength structures exhibits significant superhydrophilic properties. PMID:26268896

Plasmonic activity on gold nanoparticles embedded in nanopores formed in a surface layer of silica glass by swift-heavy-ion irradiation.

PubMed

Nomura, Ken-ichi; Ohki, Yoshimichi; Fujimaki, Makoto; Wang, Xiaomin; Awazu, Koichi; Komatsubara, Tetsuro

2009-11-25

Silica glass was irradiated by swift heavy ions by selecting the ion species and its energy in order to induce the largest damaged regions. These regions were then selectively etched by hydrofluoric acid vapour to form nanopores on the glass surface. Subsequently, gold nanoparticles were embedded into the nanopores by vacuum evaporation, followed by thermal treatment. In the new plasmonic structure obtained with these procedures, the localized surface plasmon excitation wavelength induced around the gold nanoparticles was found to show a redshift, which agreed well with the theoretical calculation, when water was introduced into the nanopores. This indicates that the fabricated structure can be used as a sensing element to detect the adhesion of substances such as biomolecules to the nanoparticles by measuring the redshift.

Tailoring bifunctional hybrid organic–inorganic nanoadsorbents by the choice of functional layer composition probed by adsorption of Cu2+ ions

PubMed Central

Tomina, Veronika V; Melnyk, Inna V; Zub, Yuriy L; Kareiva, Aivaras; Vaclavikova, Miroslava; Kessler, Vadim G

2017-01-01

Spherical silica particles with bifunctional (≡Si(CH2)3NH2/≡SiCH3, ≡Si(CH2)3NH2/≡Si(CH2)2(CF2)5CF3) surface layers were produced by a one-step approach using a modified Stöber method in three-component alkoxysilane systems, resulting in greatly increased contents of functional components. The content of functional groups and thermal stability of the surface layers were analyzed by diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, and 13C and 29Si solid-state NMR spectroscopy revealing their composition and organization. The fine chemical structure of the surface in the produced hybrid adsorbent particles and the ligand distribution were further investigated by electron paramagnetic resonance (EPR) and electron spectroscopy of diffuse reflectance (ESDR) spectroscopy using Cu2+ ion coordination as a probe. The composition and structure of the emerging surface complexes were determined and used to provide an insight into the molecular structure of the surfaces. It was demonstrated that the introduction of short hydrophobic (methyl) groups improves the kinetic characteristics of the samples during the sorption of copper(II) ions and promotes fixation of aminopropyl groups on the surface of silica microspheres. The introduction of long hydrophobic (perfluoroctyl) groups changes the nature of the surface, where they are arranged in alternately hydrophobic/hydrophilic patches. This makes the aminopropyl groups huddled and less active in the sorption of metal cations. The size and aggregation/morphology of obtained particles was optimized controlling the synthesis conditions, such as concentrations of reactants, basicity of the medium, and the process temperature. PMID:28243572

Possible silica gel in the Olive Fault, Naukluft Nappe Complex, Namibia: A geologic record of dynamic weakening in faults during continental orogenesis

NASA Astrophysics Data System (ADS)

Faber, C.; Rowe, C. D.; Miller, J. A.; Backeberg, N.; Sylvester, F.

2009-12-01

The apparently low frictional strength of faults during earthquake slip is not sufficiently well explained. Dynamic weakening has been observed in recent laboratory experiments at seismic slip rates, even if materials are strong at slow slip rates. Di Toro et al. (2004) performed experiments on crystalline rocks at slip rates of 1m/s and observed frictional strength drops to near zero. Examination of the slip surface revealed an amorophous silica had formed during fast slip and interpreted this as a solidified silica gel. If similar silica gel forms during earthquakes, and solidifies to amorphous silica, it would be expected to slowly crystallize over time. Ujiie et al (2007) reported a microcrystalline silica fault vein from the Shimanto Complex (Japan) which contains colloidal microspheres of silica, consistent with its origin as a silica gel. This vein may have been created during seismic slip, although other explanations are possible. No other natural examples of this potentially important coseismic weakening mechanism have been reported. To investigate whether silica gel actually forms during seismic slip, it will be necessary to discover and fully characterize additional natural examples. The Naukluft Nappe Complex in central Namibia is a foreland thrust stack at the distal southern margin of the Pan-African Damara Orogen (active at ~ 550Ma). A fault vein of microcrystalline silica has been found in an intra-nappe thrust fault . The vein occurs as a mostly continuous, planar, 0.1-1.0cm-thick fault vein within dolomite breccias of the Olive Fault. There are no other veins of silica associated with the fault. The hanging wall and footwall are dolomite and calcareous shales, respectively. The layer is petrographically similar to the microcrystalline silica described by Ujiie et al. (2007). The silica layer is purple-blue to white in color cathodoluminescence, in contrast to the bright turquoise typical of quartz. Although X-ray diffraction spectra show only silica and minor dolomite in the fault vein, SEM revealed the presence of small grains of Ti-oxides which have not been observed in the host rock. The cathodoluminescence has also revealed primary textures in the dolomite breccias which are overprinted by recrystallization and invisible in transmitted light . Transmission Electron Microscopy will be used to determine whether colloidal silica particles are present. The possible finding of the solidified silica gel in the Olive Fault is significant because it may represent a new way to identify fault surfaces which have slipped seismically in the past. In particular, the presence of this unusual silica vein in a carbonate-dominated environment is consistent with the experiments of Di Toro et al (2004) who suggested that quartz need not be present in the source rocks in order to form silica gel. Di Toro, G. et al. (2004) Friction falls towards zero in quartz rock as slip velocity approaches seismic rates. Nature, 427, 436-439 Ujie, K. et al. (2007) Fluidization of granular material in a subduction thrust at seismogenic depths. EPSL, 259, 307-318

Surface mapping and drilling of extinct seafloor massive sulphide deposits (eSMS) from the TAG Hydrothermal Field, 26oN: A tale of two `Jaspers'

NASA Astrophysics Data System (ADS)

Stobbs, I. J.; Lusty, P.; Petersen, S.; Murton, B. J.

2017-12-01

Two extinct seafloor massive sulphide (eSMS) deposits within the TAG hydrothermal field, 26oN, mid-Atlantic ridge, were mapped and drilled: Southern Mound and the newly discovered `Rona Mound'. Surface mapping was undertaken by combining high definition video footage and high resolution bathymetry to interpret surface geological and geomorphological features. Drill core was recovered using the BGS RD2 robotic drilling rig. Surface mapping of the mounds revealed a superficial cover of carbonate and iron-oxyhydroxides sediments, observed to directly overly oxide coated sulphide material within fault scarps, which dissect the flanks of both mounds. Drilling at the summits of the mounds revealed similar stratigraphy to the mapping, with the addition of a coherent and dense layer of red-coloured silica-rich `jasper', up to 3m thick, underlying the sediments and overlying unoxidised massive sulphides. The jasper mineralogy is dominated by silica, with minor iron oxides and rare disseminated sulphides. It displays a range of complex textures including filamentous and dendritic iron oxides often coated in silica. Drill core samples show the material to be porous, but relatively impermeable. Strong and positive Eu (REE) anomalies indicates a hydrothermal origin with little evidence of a seawater signature (lack of negative Ce anomaly). Silica precipitation is associated with low temperature hydrothermal activity, chert and jasper materials are locally present within the nearby hydrothermally active TAG mound and are more widespread at low-temperature diffuse hydrothermal sites such as within the MESO field. We interpret the `jasper' layers to be a common product, formed during the waning, low temperature, stage of the hydrothermal cycle which may form an impermeable and resistant `cap' that protects the underlying massive sulphide ore body from oxidation and dissolution. The formation of a `jasper cap' could act automatically to preserve eSMS deposits when hydrothermal circulation ceases and is essential to preserving the resource potential of eSMS deposits. This `jasper' capping layer is important from an economic perspective, and reinforces the need for shallow sub-seafloor mapping as part of any deep-sea mineral exploration. This research received funding from the EC FP7 project Blue Mining (604500).

Colloidal and electrochemical aspects of copper-CMP

NASA Astrophysics Data System (ADS)

Sun, Yuxia

Copper based interconnects with low dielectric constant layers are currently used to increase interconnect densities and reduce interconnect time delays in integrated circuits. The technology used to develop copper interconnects involves Chemical Mechanical Planarization (CMP) of copper films deposited on low-k layers (silica or silica based films), which is carried out using slurries containing abrasive particles. One issue using such a structure is copper contamination over dielectric layers (SiO2 film), if not reduced, this contamination will cause current leakage. In this study, the conditions conducive to copper contamination onto SiO2 films during Cu-CMP process were studied, and a post-CMP cleaning technique was discussed based on experimental results. It was found that the adsorption of copper onto a silica surface is kinetically fast (<0.5 minute). The amount of copper absorbed is pH and concentration dependent and affected by presence of H2O2, complexing agents, and copper corrosion inhibitor Benzotrazole. Based on de-sorption results, DI water alone was unable to reduce adsorbed copper to an acceptable level, especially for adsorption that takes place at a higher pH condition. The addition of complex agent, citric acid, proved effective in suppressing copper adsorption onto oxide silica during polishing or post-CMP cleaning by forming stable copper-CA complexes. Surface Complexation Modeling was used to simulate copper adsorption isotherms and predict the copper contamination levels on SiO2 surfaces. Another issue with the application of copper CMP is its environmental impact. CMP is a costly process due to its huge consumption of pure water and slurry. Additionally, Cu-CMP processing generates a waste stream containing certain amounts of copper and abrasive slurry particles. In this study, the separation technique electrocoagulation was investigated to remove both copper and abrasive slurry particles simultaneously. For effluent containing ˜40 ppm dissolved copper, it was found that ˜90% dissolved copper was removed from the waste streams through electroplating and in-situ chemical precipitation. The amount of copper removed through plating is impacted by membrane surface charge, type/amount of complexing agents, and solid content in the slurry suspension. The slurry particles can be removed ˜90% within 2 hours of EC through multiple mechanisms.

Environmentally Resistant Mo-Si-B-Based Coatings

NASA Astrophysics Data System (ADS)

Perepezko, J. H.; Sossaman, T. A.; Taylor, M.

2017-06-01

High-temperature applications have demonstrated aluminide-coated nickel-base superalloys to be remarkably effective, but are reaching their service limit. Alternate materials such as refractory (e.g., W, Mo) silicide alloys and SiC composites are being considered to extend high temperature capability, but the silica surfaces on these materials require coatings for enhanced environmental resistance. This can be accomplished with a Mo-Si-B-based coating that is deposited by a spray deposition of Mo followed by a chemical vapor deposition of Si and B by pack cementation to develop an aluminoborosilica surface. Oxidation of the as-deposited (Si + B)-pack coatings proceeds with partial consumption of the initial MoSi2 forming amorphous silica. This Si depletion leads to formation of a B-saturated Mo5Si3 (T1) phase. Reactions between the Mo and the B rich phases develop an underlying Mo5SiB2 (T2) layer. The T1 phase saturated with B has robust oxidation resistance, and the Si depletion is prevented by the underlying diffusion barrier (T2). Further, due to the natural phase transformation characteristics of the Mo-Si-B system, cracks or scratches to the outer silica and T1 layers can be repaired from the Si and B reservoirs of T2 + MoB layer to yield a self-healing characteristic. Mo-Si-B-based coatings demonstrate robust performance up to at least 1700 °C not only to the rigors of elevated temperature oxidation, but also to CMAS attack, hot corrosion attack, water vapor and thermal cycling.

Efficiency of magnetorheological fluid finishing on the elimination of defects in fused silica optics

NASA Astrophysics Data System (ADS)

Catrin, R.; Taroux, D.; Cormont, P.; Maunier, C.; Corbineau, T.; Razé, G.; Néauport, J.

2013-09-01

The MegaJoule laser being constructed at the CEA near Bordeaux (France) is designed to focus more than 1 MJ of energy of UV light, on a millimeter scale target in the centre of an experiment chamber. After amplification and transport at the wavelength of 1053 nm, frequency conversion at 351 nm is done with KH2PO4 crystals. The final optic assembly of this system is made up of large fused silica optics, working in transmission, that are used to convey, focus or shape the laser beam. When exposed to fluences of some joules per square centimeter at 351 nm within nanosecond pulse duration, fused silica optics can exhibit localized damage. Damage sites grow exponentially after further laser exposition and therefore dramatically limit the optic lifetime. The nature of the surface finishing process has been established to determine the lifetime of these components under high UV fluences (i.e. more than 5 J/cm2 for 3 ns pulses). Being able to reduce or eliminate the damage initiators such as subsurface cracks present in subsurface damage (SSD) layer of conventionally polished optical components aims this study. Magneto-rheological fluid finishing (MRF) is chosen as a final polishing tool to remove layers of material without inducing further damages. MRF enables to process optics with very small normal stresses applied to the surface during material removal and thus permits the elimination of the residual subsurface cracks. This study offers a better understanding of the efficiency of MRF polishing on the elimination of subsurface cracks in SSD layers.

Nitriles at Silica Interfaces Resemble Supported Lipid Bilayers.

PubMed

Berne, Bruce J; Fourkas, John T; Walker, Robert A; Weeks, John D

2016-09-20

Nitriles are important solvents not just for bulk reactions but also for interfacial processes such as separations, heterogeneous catalysis, and electrochemistry. Although nitriles have a polar end and a lipophilic end, the cyano group is not hydrophilic enough for these substances to be thought of as prototypical amphiphiles. This picture is now changing, as research is revealing that at a silica surface nitriles can organize into structures that, in many ways, resemble lipid bilayers. This unexpected organization may be a key component of unique interfacial behavior of nitriles that make them the solvents of choice for so many applications. The first hints of this lipid-bilayer-like (LBL) organization of nitriles at silica interfaces came from optical Kerr effect (OKE) experiments on liquid acetonitrile confined in the pores of sol-gel glasses. The orientational dynamics revealed by OKE spectroscopy suggested that the confined liquid is composed of a relatively immobile sublayer of molecules that accept hydrogen bonds from the surface silanol groups and an interdigitated, antiparallel layer that is capable of exchanging into the centers of the pores. This picture of acetonitrile has been borne out by molecular dynamics simulations and vibrational sum-frequency generation (VSFG) experiments. Remarkably, these simulations further indicate that the LBL organization is repeated with increasing disorder at least 20 Å into the liquid from a flat silica surface. Simulations and VSFG and OKE experiments indicate that extending the alkyl chain to an ethyl group leads to the formation of even more tightly packed LBL organization featuring entangled alkyl tails. When the alkyl portion of the molecule is a bulky t-butyl group, packing constraints prevent well-ordered LBL organization of the liquid. In each case, the surface-induced organization of the liquid is reflected in its interfacial dynamics. Acetonitrile/water mixtures are favored solvent systems for separations technologies such as hydrophilic interaction chromatography. Simulations had suggested that although a monolayer of water partitions to the silica surface in such mixtures, acetonitrile tends to associate with this monolayer. VSFG experiments reveal that, even at high water mole fractions, patches of well-ordered acetonitrile bilayers remain at the silica surface. Due to its ability to donate and accept hydrogen bonds, methanol also partitions to a silica surface in acetonitrile/methanol mixtures and can serve to take the place of acetonitrile in the sublayer closest to the surface. These studies reveal that liquid nitriles can exhibit an unexpected wealth of new organizational and dynamic behaviors at silica surfaces, and presumably at the surfaces of other chemically important materials as well. This behavior cannot be predicted from the bulk organization of these liquids. Our new understanding of the interfacial behavior of these liquids will have important implications for optimizing a wide range of chemical processes in nitrile solvents.

Plasmid DNA Delivery: Nanotopography Matters.

PubMed

Song, Hao; Yu, Meihua; Lu, Yao; Gu, Zhengying; Yang, Yannan; Zhang, Min; Fu, Jianye; Yu, Chengzhong

2017-12-20

Plasmid DNA molecules with unique loop structures have widespread bioapplications, in many cases relying heavily on delivery vehicles to introduce them into cells and achieve their functions. Herein, we demonstrate that control over delicate nanotopography of silica nanoparticles as plasmid DNA vectors has significant impact on the transfection efficacy. For silica nanoparticles with rambutan-, raspberry-, and flower-like morphologies composed of spike-, hemisphere-, and bowl-type subunit nanotopographies, respectively, the rambutan-like nanoparticles with spiky surfaces demonstrate the highest plasmid DNA binding capability and transfection efficacy of 88%, higher than those reported for silica-based nanovectors. Moreover, it is shown that the surface spikes of rambutan nanoparticles provide a continuous open space to bind DNA chains via multivalent interactions and protect the gene molecules sheltered in the spiky layer against nuclease degradation, exhibiting no significant transfection decay. This unique protection feature is in great contrast to a commercial transfection agent with similar transfection performance but poor protection capability against enzymatic cleavage. Our study provides new understandings in the rational design of nonviral vectors for efficient gene delivery.

Controllable formation of high density SERS-active silver nanoprism layers on hybrid silica-APTES coatings

NASA Astrophysics Data System (ADS)

Pilipavicius, J.; Kaleinikaite, R.; Pucetaite, M.; Velicka, M.; Kareiva, A.; Beganskiene, A.

2016-07-01

In this work sol-gel process for preparation of the uniform hybrid silica-3-aminopropyltriethoxysilane (APTES) coatings on glass surface is presented from mechanistic point of view. The suggested synthetic approach is straightforward, scalable and provides the means to tune the amount of amino groups on the surface simply by changing concentration of APTES in the initial sol. Deposition rate of different size silver nanoprisms (AgNPRs) on hybrid silica coatings of various amounts of APTES were studied and their performance as SERS materials were probed. The acquired data shows that the deposition rate of AgNPRs can be tuned by changing the amount of APTES. The optimal amount of APTES was found to be crucial for successful AgNPRs assembly and subsequent uniformity of the final SERS substrate-too high APTES content may result in rapid non-stable aggregation and non-uniform assembly process. SERS study revealed that SERS enhancement is the strongest at moderate AgNPRs aggregation level whereas it significantly drops at high aggregation levels.

Method of forming a multiple layer dielectric and a hot film sensor therewith

NASA Technical Reports Server (NTRS)

Hopson, Purnell, Jr. (Inventor); Tran, Sang Q. (Inventor)

1990-01-01

The invention is a method of forming a multiple layer dielectric for use in a hot-film laminar separation sensor. The multiple layer dielectric substrate is formed by depositing a first layer of a thermoelastic polymer such as on an electrically conductive substrate such as the metal surface of a model to be tested under cryogenic conditions and high Reynolds numbers. Next, a second dielectric layer of fused silica is formed on the first dielectric layer of thermoplastic polymer. A resistive metal film is deposited on selected areas of the multiple layer dielectric substrate to form one or more hot-film sensor elements to which aluminum electrical circuits deposited upon the multiple layered dielectric substrate are connected.

Durable superhydrophobic paper enabled by surface sizing of starch-based composite films

NASA Astrophysics Data System (ADS)

Chen, Gang; Zhu, Penghui; Kuang, Yudi; Liu, Yu; Lin, Donghan; Peng, Congxing; Wen, Zhicheng; Fang, Zhiqiang

2017-07-01

Superhydrophobic paper with remarkable durability is of considerable interest for its practical applications. In this study, a scalable, inexpensive, and universal surface sizing technique was implemented to prepare superhydrophobic paper with enhanced durability. A thin layer of starch-based composite, acting as a bio-binder, was first coated onto the paper surface by a sophisticated manufacturing technique called surface sizing, immediately followed by a spray coating of hexamethyl disilazane treated silica nanoparticles (HMDS-SiNPs) dispersed in ethanol on the surface of the wet starch-coated sheet, and the dual layers dried at the same time. Consequently, durable superhydrophobic paper with bi-layer structure was obtained after air drying. The as-prepared superhydrophobic paper not only exhibited a self-cleaning behavior, but also presented an enhanced durability against scratching, bending/deformation, as well as moisture. The universal surface sizing of starch-based composites may pave the way for the up-scaled and cost-effective production of durable superhydrophobic paper.

Electrochemical characteristics of discrete, uniform, and monodispersed hollow mesoporous carbon spheres in double-layered supercapacitors.

PubMed

Chen, Xuecheng; Kierzek, Krzysztof; Wenelska, Karolina; Cendrowski, Krzystof; Gong, Jiang; Wen, Xin; Tang, Tao; Chu, Paul K; Mijowska, Ewa

2013-11-01

Core-shell-structured mesoporous silica spheres were prepared by using n-octadecyltrimethoxysilane (C18TMS) as the surfactant. Hollow mesoporous carbon spheres with controllable diameters were fabricated from core-shell-structured mesoporous silica sphere templates by chemical vapor deposition (CVD). By controlling the thickness of the silica shell, hollow carbon spheres (HCSs) with different diameters can be obtained. The use of ethylene as the carbon precursor in the CVD process produces the materials in a single step without the need to remove the surfactant. The mechanism of formation and the role played by the surfactant, C18TMS, are investigated. The materials have large potential in double-layer supercapacitors, and their electrochemical properties were determined. HCSs with thicker mesoporous shells possess a larger surface area, which in turn increases their electrochemical capacitance. The samples prepared at a lower temperature also exhibit increased capacitance as a result of the Brunauer-Emmett-Teller (BET) area and larger pore size. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Interpolymer complexation: comparisons of bulk and interfacial structures.

PubMed

Cattoz, Beatrice; de Vos, Wiebe M; Cosgrove, Terence; Crossman, Martin; Espidel, Youssef; Prescott, Stuart W

2015-04-14

The interactions between the strong polyelectrolyte sodium poly(styrenesulfonate), NaPSS, and the neutral polymer poly(vinylpyrrolidone), PVP, were investigated in bulk and at the silica/solution interface using a combination of diffusion nuclear magnetic resonance spectroscopy (NMR), small-angle neutron scattering (SANS), solvent relaxation NMR, and ellipsometry. We show for the first time that complex formation occurs between NaPSS and PVP in solution; the complexes formed were shown not to be influenced by pH variation, whereas increasing the ionic strength increases the complexation of NaPSS but does not influence the PVP directly. The complexes formed contained a large proportion of NaPSS. Study of these interactions at the silica interface demonstrated that complexes also form at the nanoparticle interface where PVP is added in the system prior to NaPSS. For a constant PVP concentration and varying NaPSS concentration, the system remains stable until NaPSS is added in excess, which leads to depletion flocculation. Surface complex formation using the layer-by-layer technique was also reported at a planar silica interface.

Silica surface characterization as a function of formation and surface treatment using traditional methods and proteins as surface probes

NASA Astrophysics Data System (ADS)

Korwin-Edson, Michelle Lynn

Previous works have shown that cells proliferate differently depending on the chemistry of the glass on which they are growing. Since proteins form the bonds between cells and glass, the hypothesis of this study is that proteins can distinguish between surface chemical variations of glass. This theory was examined through the use of various silica forms, a few select proteins, four surface treatment procedures, and a variety of characterization techniques. The silica forms include amorphous slides, cane, fiber, microspheres, fumed silica and quartz crystal terminals. The proteins selected were human serum albumin, mouse Immunoglobulin G, streptavidin, antimouse IgG, and biotin. The surface treatments utilized to bring about chemical variation on the silica surface were HF acid etching, ethanol cleaning, water plasma treatments, and 1000°C heat treatments. The characterization techniques encompassed both traditional material techniques and biological methods. The techniques studied were atomic force microscopy (AFM), chemical force microscopy (CFM), glancing incidence X-ray analysis (GIXA), fluorescence spectrometry, polyacrylamide gel electrophoresis (SDS-PAGE), and bicinchoninic acid (BCA) assay. It was the main goal of this project to determine the feasibility of these techniques in utilizing proteins as glass surface probes. Proteins were adsorbed to all of the various forms and the binding ability was studied by either stripping off the protein and quantifying them, or by deductive reasoning through the use of "depleted" protein solutions. Fluorimetry and BCA assay both utilized the depleted solutions, but the high error associated with this protocol was prohibitive. SDS-PAGE with streptavidin was very difficult due to staining problems, however the IgG proteins were able to be quantified with some success. GIXA showed that the protein layer thickness is monolayer in nature, which agrees well with the AFM fluid tapping data on protein height, but in addition showed features on the order of ten protein agglomerations. CFM is by far the most promising technique for utilizing proteins as surface probes. Functionalized tips of -COOH, streptavidin and -CH3 are able to discern between surface treatments, but not forms. A general conclusion is that adhesion forces are greatest for -COOH, then streptavidin, and least for -CH3.

Investigation of the interface in silica-encapsulated liposomes by combining solid state NMR and first principles calculations.

PubMed

Folliet, Nicolas; Roiland, Claire; Bégu, Sylvie; Aubert, Anne; Mineva, Tzonka; Goursot, Annick; Selvaraj, Kaliaperumal; Duma, Luminita; Tielens, Frederik; Mauri, Francesco; Laurent, Guillaume; Bonhomme, Christian; Gervais, Christel; Babonneau, Florence; Azaïs, Thierry

2011-10-26

In the context of nanomedicine, liposils (liposomes and silica) have a strong potential for drug storage and release schemes: such materials combine the intrinsic properties of liposome (encapsulation) and silica (increased rigidity, protective coating, pH degradability). In this work, an original approach combining solid state NMR, molecular dynamics, first principles geometry optimization, and NMR parameters calculation allows the building of a precise representation of the organic/inorganic interface in liposils. {(1)H-(29)Si}(1)H and {(1)H-(31)P}(1)H Double Cross-Polarization (CP) MAS NMR experiments were implemented in order to explore the proton chemical environments around the silica and the phospholipids, respectively. Using VASP (Vienna Ab Initio Simulation Package), DFT calculations including molecular dynamics, and geometry optimization lead to the determination of energetically favorable configurations of a DPPC (dipalmitoylphosphatidylcholine) headgroup adsorbed onto a hydroxylated silica surface that corresponds to a realistic model of an amorphous silica slab. These data combined with first principles NMR parameters calculations by GIPAW (Gauge Included Projected Augmented Wave) show that the phosphate moieties are not directly interacting with silanols. The stabilization of the interface is achieved through the presence of water molecules located in-between the head groups of the phospholipids and the silica surface forming an interfacial H-bonded water layer. A detailed study of the (31)P chemical shift anisotropy (CSA) parameters allows us to interpret the local dynamics of DPPC in liposils. Finally, the VASP/solid state NMR/GIPAW combined approach can be extended to a large variety of organic-inorganic hybrid interfaces.

Laser damage threshold measurements of microstructure-based high reflectors

NASA Astrophysics Data System (ADS)

Hobbs, Douglas S.

2008-10-01

In 2007, the pulsed laser induced damage threshold (LIDT) of anti-reflecting (AR) microstructures built in fused silica and glass was shown to be up to three times greater than the LIDT of single-layer thin-film AR coatings, and at least five times greater than multiple-layer thin-film AR coatings. This result suggested that microstructure-based wavelength selective mirrors might also exhibit high LIDT. Efficient light reflection over a narrow spectral range can be produced by an array of sub-wavelength sized surface relief microstructures built in a waveguide configuration. Such surface structure resonant (SSR) filters typically achieve a reflectivity exceeding 99% over a 1-10nm range about the filter center wavelength, making SSR filters useful as laser high reflectors (HR). SSR laser mirrors consist of microstructures that are first etched in the surface of fused silica and borosilicate glass windows and subsequently coated with a thin layer of a non-absorbing high refractive index dielectric material such as tantalum pent-oxide or zinc sulfide. Results of an initial investigation into the LIDT of single layer SSR laser mirrors operating at 532nm, 1064nm and 1573nm are described along with data from SEM analysis of the microstructures, and spectral reflection measurements. None of the twelve samples tested exhibited damage thresholds above 3 J/cm2 when illuminated at the resonant wavelength, indicating that the simple single layer, first order design will need further development to be suitable for high power laser applications. Samples of SSR high reflectors entered in the Thin Film Damage Competition also exhibited low damage thresholds of less than 1 J/cm2 for the ZnS coated SSR, and just over 4 J/cm2 for the Ta2O5 coated SSR.

KSC-04pd0618

NASA Image and Video Library

2004-03-24

KENNEDY SPACE CENTER, FLA. -- In the Thermal Protection System Facility, Pilar Ryan, with United Space Alliance, stitches a piece of insulation blanket for Atlantis's nose cap. The blankets consist of layered, pure silica felt sandwiched between a layer of silica fabric (the hot side) and a layer of S-Glass fabric. The blankets are semi-rigid and can be made as large as 30 inches by 30 inches. The blanket is through-stitched with pure silica thread in a 1-inch grid pattern. After fabrication, the blanket is bonded directly to the vehicle structure and finally coated with a high purity silica coating that improves erosion resistance.

Process for manufacturing hollow fused-silica insulator cylinder

DOEpatents

Sampayan, Stephen E.; Krogh, Michael L.; Davis, Steven C.; Decker, Derek E.; Rosenblum, Ben Z.; Sanders, David M.; Elizondo-Decanini, Juan M.

2001-01-01

A method for building hollow insulator cylinders that can have each end closed off with a high voltage electrode to contain a vacuum. A series of fused-silica round flat plates are fabricated with a large central hole and equal inside and outside diameters. The thickness of each is related to the electron orbit diameter of electrons that escape the material surface, loop, and return back. Electrons in such electron orbits can support avalanche mechanisms that result in surface flashover. For example, the thickness of each of the fused-silica round flat plates is about 0.5 millimeter. In general, the thinner the better. Metal, such as gold, is deposited onto each top and bottom surface of the fused-silica round flat plates using chemical vapor deposition (CVD). Eutectic metals can also be used with one alloy constituent on the top and the other on the bottom. The CVD, or a separate diffusion step, can be used to defuse the deposited metal deep into each fused-silica round flat plate. The conductive layer may also be applied by ion implantation or gas diffusion into the surface. The resulting structure may then be fused together into an insulator stack. The coated plates are aligned and then stacked, head-to-toe. Such stack is heated and pressed together enough to cause the metal interfaces to fuse, e.g., by welding, brazing or eutectic bonding. Such fusing is preferably complete enough to maintain a vacuum within the inner core of the assembled structure. A hollow cylinder structure results that can be used as a core liner in a dielectric wall accelerator and as a vacuum envelope for a vacuum tube device where the voltage gradients exceed 150 kV/cm.

Layer-by-Layer Self-Assembling Gold Nanorods and Glucose Oxidase onto Carbon Nanotubes Functionalized Sol-Gel Matrix for an Amperometric Glucose Biosensor.

PubMed

Wu, Baoyan; Hou, Shihua; Miao, Zhiying; Zhang, Cong; Ji, Yanhong

2015-09-18

A novel amperometric glucose biosensor was fabricated by layer-by-layer self-assembly of gold nanorods (AuNRs) and glucose oxidase (GOD) onto single-walled carbon nanotubes (SWCNTs)-functionalized three-dimensional sol-gel matrix. A thiolated aqueous silica sol containing SWCNTs was first assembled on the surface of a cleaned Au electrode, and then the alternate self-assembly of AuNRs and GOD were repeated to assemble multilayer films of AuNRs-GOD onto SWCNTs-functionalized silica gel for optimizing the biosensor. Among the resulting glucose biosensors, the four layers of AuNRs-GOD-modified electrode showed the best performance. The sol-SWCNTs-(AuNRs- GOD)₄/Au biosensor exhibited a good linear range of 0.01-8 mM glucose, high sensitivity of 1.08 μA/mM, and fast amperometric response within 4 s. The good performance of the proposed glucose biosensor could be mainly attributed to the advantages of the three-dimensional sol-gel matrix and stereo self-assembly films, and the natural features of one-dimensional nanostructure SWCNTs and AuNRs. This study may provide a new facile way to fabricate the enzyme-based biosensor with high performance.

Hydrothermal performance of catalyst supports

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

Elam, Jeffrey W.; Marshall, Christopher L.; Libera, Joseph A.

A high surface area catalyst with a mesoporous support structure and a thin conformal coating over the surface of the support structure. The high surface area catalyst support is adapted for carrying out a reaction in a reaction environment where the thin conformal coating protects the support structure within the reaction environment. In various embodiments, the support structure is a mesoporous silica catalytic support and the thin conformal coating comprises a layer of metal oxide resistant to the reaction environment which may be a hydrothermal environment.

Improvement of transmission properties of visible pilot beam for polymer-coated silver hollow fibers with acrylic silicone resin as buffer layer for sturdy structure

NASA Astrophysics Data System (ADS)

Iwai, Katsumasa; Takaku, Hiroyuki; Miyagi, Mitsunobu; Shi, Yi-Wei; Zhu, Xiao-Song; Matsuura, Yuji

2017-02-01

Flexible hollow fibers with 530-μm-bore size were developed for infrared laser delivery. Sturdy hollow fibers were fabricated by liquid-phase coating techniques. A silica glass capillary is used as the substrate. Acrylic silicone resin is used as a buffer layer and the buffer layer is firstly coated on the inner surface of the capillary to protect the glass tube from chemical damages due to the following silver plating process. A silver layer was inner-plated by using the conventional silver mirror-plating technique. To improve adhesion of catalyst to the buffer layer, a surface conditioner has been introduced in the method of silver mirror-plating technique. We discuss improvement of transmission properties of sturdy polymer-coated silver hollow fibers for the Er:YAG laser and red pilot beam delivery.

Investigation of mechanical dissipation in CO2 laser-drawn fused silica fibres and welds

NASA Astrophysics Data System (ADS)

Heptonstall, Alastair; Barton, Mark; Cantley, Caroline; Cumming, Alan; Cagnoli, Geppo; Hough, James; Jones, Russell; Kumar, Rahul; Martin, Iain; Rowan, Sheila; Torrie, Calum; Zech, Steven

2010-02-01

The planned upgrades to the LIGO gravitational wave detectors include monolithic mirror suspensions to reduce thermal noise. The mirrors will be suspended using CO2 laser-drawn fused silica fibres. We present here measurements of mechanical dissipation in synthetic fused silica fibres drawn using a CO2 laser. The level of dissipation in the surface layer is investigated and is found to be at a similar level to fibres produced using a gas flame. Also presented is a method for examining dissipation at welded interfaces, showing clear evidence of the existence of this loss mechanism which forms an additional component of the total detector thermal noise. Modelling of a typical detector suspension configuration shows that the thermal noise contribution from this loss source will be negligible.

Fused Silica Surface Coating for a Flexible Silica Mat Insulation System

NASA Technical Reports Server (NTRS)

Rhodes, W. H.

1973-01-01

Fused silica insulation coatings have been developed for application to a flexible mat insulation system. Based on crystalline phase nucleation and growth kinetics, a 99+% SiO2 glass was selected as the base composition. A coating was developed that incorporated the high emissivity phase NiCr2O4 as a two phase coating with goals of high emittance and minimum change in thermal expansion. A second major coating classification has a plasma sprayed emittance coating over a sealed pure amorphous SiO2 layer. A third area of development centered on extremely thin amorphous SiO2 coatings deposited by chemical vapor deposition. The coating characterization studies presented are mechanical testing of thin specimens extracted from the coatings, cyclic arc exposures, and emittance measurements before and after arc exposures.

Acid leaching of natural chrysotile asbestos to mesoporous silica fibers

NASA Astrophysics Data System (ADS)

Maletaškić, Jelena; Stanković, Nadežda; Daneu, Nina; Babić, Biljana; Stoiljković, Milovan; Yoshida, Katsumi; Matović, Branko

2018-04-01

Nanofibrous silica with a high surface area was produced from chrysotile by the acid-leaching method. Natural mineral chrysotile asbestos from Stragari, Korlace in Serbia was used as the starting material. The fibers were modified by chemical treatment with 1 M HCl and the mineral dissolution was monitored by transmission electron microscopy, X-ray powder diffraction, inductively coupled plasma spectrometry and low-temperature nitrogen adsorption techniques to highlight the effects of the leaching process. The results showed that the applied concentration of acid solution and processing time of 4 h were sufficient to effectively remove the magnesium hydroxide layer and transform the crystal structure of the hazardous starting chrysotile to porous SiO2 nanofibers. With prolonged acid leaching, the specific surface area, S BET, calculated by BET equation, was increased from 147 up to 435 m2 g- 1, with micropores representing a significant part of the specific surface.

Bacterial interactions and transport in geological formation of alumino-silica clays.

PubMed

Vu, Kien; Yang, Guang; Wang, Boya; Tawfiq, Kamal; Chen, Gang

2015-01-01

Bacterial transport in the subsurface is controlled by their interactions with the surrounding environment, which are determined by the surface properties of the geological formation and bacterial surfaces. In this research, surface thermodynamic properties of Escherichia coli and the geological formation of alumino-silica clays were characterized based on contact angle measurements, which were utilized to quantify the distance-dependent interactions between E. coli and the geological formation according to the traditional and extended Derjaguin, Landau, Verwey and Overbeek (DLVO) theory. E. coli attachment to alumino-silica clays was evaluated in laboratory columns under saturated and steady-state flow conditions. E. coli deposition coefficient and desorption coefficient were simulated using convection-dispersion transport models against E. coli breakthrough curves, which were then linked to interactions between E. coli and the geological formation. It was discovered that E. coli deposition was controlled by the long-ranged electrostatic interaction and E. coli desorption was attributed to the short-ranged Lifshitz-van der Waals and Lewis acid-base interactions. E. coli transport in three layers of different alumino-silica clays was further examined and the breakthrough curve was simulated using E. coli deposition coefficient and desorption coefficient obtained from their individual column experiments. The well-fitted simulation confirmed that E. coli transport observations were interaction-dependent phenomena between E. coli and the geological formation. Published by Elsevier B.V.

Multishell Au/Ag/SiO 2 nanorods with tunable optical properties as single particle orientation and rotational tracking probes

DOE PAGES

Chen, Kuangcai; Lin, Chia -Cheng; Vela, Javier; ...

2015-04-07

In this study, three-layer core–shell plasmonic nanorods (Au/Ag/SiO 2–NRs), consisting of a gold nanorod core, a thin silver shell, and a thin silica layer, were synthesized and used as optical imaging probes under a differential interference contrast microscope for single particle orientation and rotational tracking. The localized surface plasmon resonance modes were enhanced upon the addition of the silver shell, and the anisotropic optical properties of gold nanorods were maintained. The silica coating enables surface functionalization with silane coupling agents and provides enhanced stability and biocompatibility. Taking advantage of the longitudinal LSPR enhancement, the orientation and rotational information of themore » hybrid nanorods on synthetic lipid bilayers and on live cell membranes were obtained with millisecond temporal resolution using a scientific complementary metal-oxide-semiconductor camera. The results demonstrate that the as-synthesized hybrid nanorods are promising imaging probes with improved sensitivity and good biocompatibility for single plasmonic particle tracking experiments in biological systems.« less

Direct visualization of nanoparticle dynamics at liquid interfaces

NASA Astrophysics Data System (ADS)

Gao, Yige; Kim, Paul; Hoagland, David; Russell, Tom

Ionic liquids, because of their negligible vapor pressures and moderate viscosities, are suitable media to investigate the dynamics of different types of dispersed nanoparticles by scanning electron microscopy. No liquid cell is necessary. Here, Brownian motions of nanoparticles partially wetted at the vacuum-liquid interface are visualized by low voltage SEM under conditions that allow single particle tracking for tens-of-minutes or longer. Conductive, nonconductive, semiconductive, and core-shell conductive-nonconductive nanoparticles have all been studied, and their interactions with each other in one- and two-component layers, as manifested in particle trajectories, differ significantly. For example, Au-coated silica nanoparticles aggregate above a threshold current, whereas aggregated silica-coated Au nanoparticles disaggregate at the same conditions. The impacts of surface concentration of nanoparticle dynamics were observed for one-component and two-component layers, with both global and localized motions visualized for single particles even in dense environments. As the surface concentration increases, the diffusion coefficient drops, and when the concentration reaches a critical threshold, the nanoparticles are essentially frozen. Financial support from NSF DMR-1619651 is acknowledged.

Superhydrophobicity of electrospray-synthesized fluorinated silica layers.

PubMed

Kim, Eun-Kyeong; Lee, Chul-Sung; Kim, Sang Sub

2012-02-15

The preparation of superhydrophobic SiO(2) layers through a combination of a nanoscale surface roughness and a fluorination treatment is reported. Electrospraying SiO(2) precursor solutions that had been prepared by a sol-gel chemical route produced very rough SiO(2) layers. Subsequent fluorination treatment with a solution containing trichloro(1H,1H,2H,2H-perfluorooctyl)silane resulted in highly rough, fluorinated SiO(2) layers. The fluorinated rough SiO(2) layers exhibited excellent repellency toward various liquid droplets. In particular, water repellency of 168° was observed. On the bases of Cassie-Baxter and Young-Dupre equations, the surface fraction and the work of adhesion of the rough, fluorinated SiO(2) layers were respectively estimated. In light of the durability in water, ultraviolet resistance, and thermal stability, the superhydrophobic SiO(2) layers prepared in this work hold promise in a range of practical applications. Copyright © 2011 Elsevier Inc. All rights reserved.

Enhanced structural color generation in aluminum metamaterials coated with a thin polymer layer

DOE PAGES

Cheng, Fei; Yang, Xiaodong; Rosenmann, Daniel; ...

2015-09-18

A high-resolution and angle-insensitive structural color generation platform is demonstrated based on triple-layer aluminum-silica-aluminum metamaterials supporting surface plasmon resonances tunable across the entire visible spectrum. The color performances of the fabricated aluminum metamaterials can be strongly enhanced by coating a thin transparent polymer layer on top. The results show that the presence of the polymer layer induces a better impedance matching for the plasmonic resonances to the free space so that strong light absorption can be obtained, leading to the generation of pure colors in cyan, magenta, yellow and black (CMYK) with high color saturation.

Toward an Understanding of Surface Layer Formation, Growth, and Transformation at the Glass–Fluid Interface

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

Hopf, Juliane; Eskelsen, Jeremy R.; Chiu, Michelle Y.

Silicate glass is a metastable and durable solid that has application to a number of energy and environmental challenges (e.g., microelectronics, fiber optics, and nuclear waste storage). If allowed to react with water over time silicate glass develops an altered layer at the solid-fluid interface. In this study, we used borosilicate glass (LAWB45) as model material to develop a robust understanding of altered layer formation (i.e., amorphous hydrated surface layer and crystalline reaction products). Experiments were conducted at high surface area-to-volume ratio (~200,000 m-1) and 90 °C in the pressurized unsaturated flow (PUF) apparatus for 1.5-years to facilitate the formationmore » of thick altered layers and allow for the effluent solution chemistry to be monitored continuously. A variety of microscopy techniques were used to characterized reacted grains and suggest the average altered layer thickness is 13.2 ± 8.3 μm with the hydrated and clay layer representing 74.8% and 25.2% of the total altered layer, respectively. This estimate is within the experimental error of the value estimated from the B release rate data (~10 ±1 μm/yr) over the 1.5-year duration. PeakForce® quantitative nanomechanical mapping results suggest the hydrated layer has a modulus that ranges between ~20 to 40 GPa, which is in the range of porous silica that contains from ~20 to ~50% porosity, yet significantly lower than dense silica (~70 to 80 GPa). Scanning transmission electron microscopy (STEM) images confirm the presence of pores and an analysis of a higher resolution image of a region provides a qualitative estimate of ≥ 22% porosity in this layer with variations in the hydrated layer in void volume with increasing distance from the unaltered glass. Chemical composition analyses, based on a combination of time-of-flight secondary-ion mass spectrometry (ToF-SIMS) and scanning electron microscopy with X-ray energy dispersive spectroscopy (EDS) and STEM-EDS, clearly show that the altered layer is mainly composed of Al, H, Si, and O with the clay layer being enriched in Li, Zn, Fe, and Mg. The amorphous hydrated layer is enriched in Ca, H, and Zr with a minor amount of K. Furthermore, ToF-SIMS results also suggest the B profile is anti-correlated with the H profile in the hydrated layer. Our selected-area electron diffraction results suggest the structure of the hydrated layer closely resembles opal-AG (amorphous gel-like) with an average crystallite size of ~0.7 nm which is smaller than the critical nucleus for silica nanoparticles (i.e., 1.4 to 3 nm). These results suggest the hydrated layer is more consistent with a polymeric gel rather than a colloidal gel and is comprised of molecular units (<1 nm in size) that result from the difficult to hydrolyze bonds, such as Si—O—Zr units, during the glass corrosion process. The size of individual particles or molecular units is a function of formation conditions (e.g., pH, ionic strength, nano-confinement, solute composition) in the hydrated layer.« less

Toward an Understanding of Surface Layer Formation, Growth, and Transformation at the Glass–Fluid Interface

DOE PAGES

Hopf, Juliane; Eskelsen, Jeremy R.; Chiu, Michelle Y.; ...

2018-02-01

Silicate glass is a metastable and durable solid that has application to a number of energy and environmental challenges (e.g., microelectronics, fiber optics, and nuclear waste storage). If allowed to react with water over time silicate glass develops an altered layer at the solid-fluid interface. In this study, we used borosilicate glass (LAWB45) as model material to develop a robust understanding of altered layer formation (i.e., amorphous hydrated surface layer and crystalline reaction products). Experiments were conducted at high surface area-to-volume ratio (~200,000 m-1) and 90 °C in the pressurized unsaturated flow (PUF) apparatus for 1.5-years to facilitate the formationmore » of thick altered layers and allow for the effluent solution chemistry to be monitored continuously. A variety of microscopy techniques were used to characterized reacted grains and suggest the average altered layer thickness is 13.2 ± 8.3 μm with the hydrated and clay layer representing 74.8% and 25.2% of the total altered layer, respectively. This estimate is within the experimental error of the value estimated from the B release rate data (~10 ±1 μm/yr) over the 1.5-year duration. PeakForce® quantitative nanomechanical mapping results suggest the hydrated layer has a modulus that ranges between ~20 to 40 GPa, which is in the range of porous silica that contains from ~20 to ~50% porosity, yet significantly lower than dense silica (~70 to 80 GPa). Scanning transmission electron microscopy (STEM) images confirm the presence of pores and an analysis of a higher resolution image of a region provides a qualitative estimate of ≥ 22% porosity in this layer with variations in the hydrated layer in void volume with increasing distance from the unaltered glass. Chemical composition analyses, based on a combination of time-of-flight secondary-ion mass spectrometry (ToF-SIMS) and scanning electron microscopy with X-ray energy dispersive spectroscopy (EDS) and STEM-EDS, clearly show that the altered layer is mainly composed of Al, H, Si, and O with the clay layer being enriched in Li, Zn, Fe, and Mg. The amorphous hydrated layer is enriched in Ca, H, and Zr with a minor amount of K. Furthermore, ToF-SIMS results also suggest the B profile is anti-correlated with the H profile in the hydrated layer. Our selected-area electron diffraction results suggest the structure of the hydrated layer closely resembles opal-AG (amorphous gel-like) with an average crystallite size of ~0.7 nm which is smaller than the critical nucleus for silica nanoparticles (i.e., 1.4 to 3 nm). These results suggest the hydrated layer is more consistent with a polymeric gel rather than a colloidal gel and is comprised of molecular units (<1 nm in size) that result from the difficult to hydrolyze bonds, such as Si—O—Zr units, during the glass corrosion process. The size of individual particles or molecular units is a function of formation conditions (e.g., pH, ionic strength, nano-confinement, solute composition) in the hydrated layer.« less

Toward an understanding of surface layer formation, growth, and transformation at the glass-fluid interface

NASA Astrophysics Data System (ADS)

Hopf, J.; Eskelsen, J. R.; Chiu, M.; Ievlev, A. V.; Ovchinnikova, O. S.; Leonard, D.; Pierce, E. M.

2018-05-01

Silicate glass is a metastable and durable solid that has application to a number of energy and environmental challenges (e.g., microelectronics, fiber optics, and nuclear waste storage). If allowed to react with water over time silicate glass develops an altered layer at the solid-fluid interface. In this study, we used borosilicate glass (LAWB45) as a model material to develop a robust understanding of altered layer formation (i.e., amorphous hydrated surface layer and crystalline reaction products). Experiments were conducted at high surface area-to-volume ratio (∼200,000 m-1) and 90 °C in the pressurized unsaturated flow (PUF) apparatus for 1.5-years to facilitate the formation of thick altered layers and allow for the effluent solution chemistry to be monitored continuously. A variety of microscopy techniques were used to characterize reacted grains and suggest the average altered layer thickness is 13.2 ± 8.3 μm with the hydrated and clay layer representing 74.8% and 25.2% of the total altered layer, respectively. The estimate of hydrated layer thickness is within the experimental error of the value estimated from the B release rate data (∼10 ± 1 μm/yr) over the 1.5-year duration. PeakForce® quantitative nanomechanical mapping results suggest the hydrated layer has a modulus that ranges between ∼20 and 40 GPa, which is in the range of porous silica that contains from ∼20 to ∼50% porosity, yet significantly lower than dense silica (∼70-80 GPa). Scanning transmission electron microscopy (STEM) images confirm the presence of pores and an analysis of a higher resolution image provides a qualitative estimate of ≥22% porosity in the hydrated layer with variations in void volume with increasing distance from the unaltered glass. Chemical composition analyses, based on a combination of time-of-flight secondary-ion mass spectrometry (ToF-SIMS), scanning electron microscopy with X-ray energy dispersive spectroscopy (EDS), and STEM-EDS, clearly show that the altered layer is mainly composed of Al, H, Si, and O with the clay layer being enriched in Li, Zn, Fe, and Mg. The amorphous hydrated layer is enriched in Ca, H, and Zr with a minor amount of K. Furthermore, ToF-SIMS results also suggest the B profile is anti-correlated with the H profile in the hydrated layer. Our selected-area electron diffraction results suggest the structure of the hydrated layer closely resembles opal-AG (amorphous gel-like) with an average crystallite size of ∼0.7 nm which is smaller than the critical nucleus for silica nanoparticles (i.e., 1.4-3 nm). These results suggest the hydrated layer is more consistent with a polymeric gel rather than a colloidal gel and is comprised of molecular units (<1 nm in size) that result from the difficult to hydrolyze bonds, such as Sisbnd Osbnd Zr units, during the glass corrosion process. The size of individual particles or molecular units is a function of formation conditions (e.g., pH, ionic strength, nano-confinement, solute composition) in the hydrated layer.

In situ Silver Spot Preparation and on-Plate Surface-Enhanced Raman Scattering Detection in Thin Layer Chromatography Separation

NASA Astrophysics Data System (ADS)

Herman, K.; Mircescu, N. E.; Szabo, L.; Leopold, L. F.; Chiş, V.; Leopold, N.

2013-05-01

An improved approach for surface-enhanced Raman scattering (SERS) detection of mixture constituents after thin layer chromatography (TLC) separation is presented. A SERS active silver substrate was prepared under open air conditions, directly on the thin silica film by photo-reduction of silver nitrate, allowing the detection of binary mixtures of cresyl violet, bixine, crystal violet, and Cu(II) complex of 4-(2-pyridylazo)resorcinol. The recorded SERS spectrum provides a unique spectral fingerprint for each molecule; therefore the use of analyte standards is avoided, thus rendering the presented procedure advantageous compared to the conventional detection methodology in TLC.

The effect of TiO2 phase on the surface plasmon resonance of silver thin film

NASA Astrophysics Data System (ADS)

Hong, Ruijin; Jing, Ming; Tao, Chunxian; Zhang, Dawei

2016-10-01

A series of silver films with various thicknesses were deposited on TiO2 covered silica substrates by magnetron sputtering at room temperature. The effects of TiO2 phase on the structure, optical properties and surface plasmon resonance of silver thin films were investigated by x-ray diffraction, optical absorption and Raman scattering measurements, respectively. By adjusting the silver layer thickness, the resonance wavelength shows a redshift, which is due to a change in the electromagnetic field coupling strength from the localized surface plasmons excited between the silver thin film and TiO2 layer. Raman scattering measurement results showed that optical absorption plays an important role in surface plasmon enhancement, which is also related to different crystal phase.

Constructing a superhydrophobic surface on polydimethylsiloxane via spin coating and vapor-liquid sol-gel process.

PubMed

Peng, Yu-Ting; Lo, Kuo-Feng; Juang, Yi-Je

2010-04-06

In this study, a superhydrophobic surface on polydimethylsiloxane (PDMS) substrate was constructed via the proposed vapor-liquid sol-gel process in conjunction with spin coating of dodecyltrichlorosilane (DTS). Unlike the conventional sol-gel process where the reaction takes place in the liquid phase, layers of silica (SiO(2)) particles were formed through the reaction between the reactant spin-coated on the PDMS surface and vapor of the acid solution. This led to the SiO(2) particles inlaid on the PDMS surface. Followed by subsequent spin coating of DTS solution, the wrinkle-like structure was formed, and the static contact angle of the water droplet on the surface could reach 162 degrees with 2 degrees sliding angle and less than 5 degrees contact angle hysteresis. The effect of layers of SiO(2) particles, concentrations of DTS solution and surface topography on superhydrophobicity of the surface is discussed.

Enhanced catalyst stability for cyclic co methanation operations

DOEpatents

Risch, Alan P.; Rabo, Jule A.

1983-01-01

Carbon monoxide-containing gas streams are passed over a catalyst to deposit a surface layer of active surface carbon thereon essentially without the formation of inactive coke. The active carbon is thereafter reacted with steam or hydrogen to form methane. Enhanced catalyst stability for long term, cyclic operation is obtained by the incorporation of an alkali or alkaline earth dopant in a silica binding agent added to the catalyst-support additive composition.

Organosilane-functionalized graphene quantum dots and their encapsulation into bi-layer hollow silica spheres for bioimaging applications.

PubMed

Wen, Ting; Yang, Baocheng; Guo, Yanzhen; Sun, Jing; Zhao, Chunmei; Zhang, Shouren; Zhang, Miao; Wang, Yonggang

2014-11-14

Graphene quantum dots (GQDs) represent an important class of luminescent quantum dots owing to their low toxicity and superior biocompatibility. Chemical functionalization of GQDs and subsequent combination with other materials further provide attractive techniques for advanced bioapplications. Herein, we report the facile fabrication of fluorescent organosilane-functionalized graphene quantum dots (Si-GQDs) and their embedding into mesoporous hollow silica spheres as a biolabel for the first time. Well-proportioned Si-GQDs with bright and excitation dependent tunable emissions in the visible region were obtained via a simple and economical solvothermal route adopting graphite oxide as a carbon source and 3-(2-aminoethylamino)-propyltrimethoxysilane as a surface modifier. The as-synthesized Si-GQDs can be well dispersed and stored in organic solvents, easily manufactured into transparent film and bulk form, and particularly provide great potential to be combined with other materials. As a proof-of-principle experiment, we demonstrate the successful incorporation of Si-GQDs into hollow mesoporous silica spheres and conduct preliminary cellular imaging experiments. Interestingly, the Si-GQDs not only serve as fluorescent chromophores in the composite material, but also play a crucial role in the formation of mesoporous hollow silica spheres with a distinctive bi-layer architecture. The layer thickness and optical properties can be precisely controlled by simply adjusting the silane coupling agent addition procedure in the preparation process. Our demonstration of low-cost Si-GQDs and their encapsulation into multifunctional composites may expand the applications of carbon-based nanomaterials for future biomedical imaging and other optoelectronic applications.

KSC-04pd0615

NASA Image and Video Library

2004-03-24

KENNEDY SPACE CENTER, FLA. -- A closeup of the stitching being done on pieces of insulation blankets inside the ring that fits in the nose cap of Discovery. The blankets consist of layered, pure silica felt sandwiched between a layer of silica fabric (the hot side) and a layer of S-Glass fabric. The blankets are semi-rigid and can be made as large as 30 inches by 30 inches. The blanket is through-stitched with pure silica thread in a 1-inch grid pattern. After fabrication, the blanket is bonded directly to the vehicle structure and finally coated with a high purity silica coating that improves erosion resistance.

KSC-04pd0624

NASA Image and Video Library

2004-03-25

KENNEDY SPACE CENTER, FLA. -- Damon Petty, with United Space Alliance, removes a piece of insulation blanket from an “oven” after heat cleaning. The blankets fit inside the nose cap of an orbiter. They consist of layered, pure silica felt sandwiched between a layer of silica fabric (the hot side) and a layer of S-Glass fabric. The blanket is through-stitched with pure silica thread in a 1-inch grid pattern. After fabrication, the blanket is bonded directly to the vehicle structure and finally coated with a high purity silica coating that improves erosion resistance. The blankets are semi-rigid and can be made as large as 30 inches by 30 inches.

KSC-04pd0626

NASA Image and Video Library

2004-03-25

KENNEDY SPACE CENTER, FLA. -- Damon Petty, with United Space Alliance, covers another insulation blanket in the “oven” prior to heat cleaning. The blankets fit inside the nose cap of an orbiter. They consist of layered, pure silica felt sandwiched between a layer of silica fabric (the hot side) and a layer of S-Glass fabric. The blanket is through-stitched with pure silica thread in a 1-inch grid pattern. After fabrication, the blanket is bonded directly to the vehicle structure and finally coated with a high purity silica coating that improves erosion resistance. The blankets are semi-rigid and can be made as large as 30 inches by 30 inches.

KSC-04pd0623

NASA Image and Video Library

2004-03-25

KENNEDY SPACE CENTER, FLA. -- Damon Petty, with United Space Alliance, places pieces of insulation blanket into an “oven” for heat cleaning. The blankets fit inside the nose cap of an orbiter. They consist of layered, pure silica felt sandwiched between a layer of silica fabric (the hot side) and a layer of S-Glass fabric. The blanket is through-stitched with pure silica thread in a 1-inch grid pattern. After fabrication, the blanket is bonded directly to the vehicle structure and finally coated with a high purity silica coating that improves erosion resistance. The blankets are semi-rigid and can be made as large as 30 inches by 30 inches.

KSC-04pd0628

NASA Image and Video Library

2004-03-25

KENNEDY SPACE CENTER, FLA. -- Damon Petty, with United Space Alliance, gets ready to place insulation blankets on the shelf after they have been heated. The blankets fit inside the nose cap of an orbiter. They consist of layered, pure silica felt sandwiched between a layer of silica fabric (the hot side) and a layer of S-Glass fabric. The blanket is through-stitched with pure silica thread in a 1-inch grid pattern. After fabrication, the blanket is bonded directly to the vehicle structure and finally coated with a high purity silica coating that improves erosion resistance. The blankets are semi-rigid and can be made as large as 30 inches by 30 inches.

KSC-04pd0625

NASA Image and Video Library

2004-03-25

KENNEDY SPACE CENTER, FLA. -- Damon Petty, with United Space Alliance, removes another insulation blanket from a shelf prior to heat cleaning and waterproofing. The blankets fit inside the nose cap of an orbiter. They consist of layered, pure silica felt sandwiched between a layer of silica fabric (the hot side) and a layer of S-Glass fabric. The blanket is through-stitched with pure silica thread in a 1-inch grid pattern. After fabrication, the blanket is bonded directly to the vehicle structure and finally coated with a high purity silica coating that improves erosion resistance. The blankets are semi-rigid and can be made as large as 30 inches by 30 inches.

KSC-04pd0627

NASA Image and Video Library

2004-03-25

KENNEDY SPACE CENTER, FLA. -- Damon Petty, with United Space Alliance, prepares the cover of another insulation blanket in the “oven” prior to heat cleaning. The blankets fit inside the nose cap of an orbiter. They consist of layered, pure silica felt sandwiched between a layer of silica fabric (the hot side) and a layer of S-Glass fabric. The blanket is through-stitched with pure silica thread in a 1-inch grid pattern. After fabrication, the blanket is bonded directly to the vehicle structure and finally coated with a high purity silica coating that improves erosion resistance. The blankets are semi-rigid and can be made as large as 30 inches by 30 inches.

KSC-04pd0622

NASA Image and Video Library

2004-03-25

KENNEDY SPACE CENTER, FLA. -- Damon Petty, with United Space Alliance, removes an insulation blanket from a shelf prior to heat cleaning and waterproofing. The blankets fit inside the nose cap of an orbiter. They consist of layered, pure silica felt sandwiched between a layer of silica fabric (the hot side) and a layer of S-Glass fabric. The blanket is through-stitched with pure silica thread in a 1-inch grid pattern. After fabrication, the blanket is bonded directly to the vehicle structure and finally coated with a high purity silica coating that improves erosion resistance. The blankets are semi-rigid and can be made as large as 30 inches by 30 inches.

KSC-04pd0614

NASA Image and Video Library

2004-03-24

KENNEDY SPACE CENTER, FLA. -- United Space Alliance workers Michael Williams and Ginger Morrison stitch together pieces of insulation blankets inside the ring that fits in the nose cap of Discovery. The blankets consist of layered, pure silica felt sandwiched between a layer of silica fabric (the hot side) and a layer of S-Glass fabric. The blankets are semi-rigid and can be made as large as 30 inches by 30 inches. The blanket is through-stitched with pure silica thread in a 1-inch grid pattern. After fabrication, the blanket is bonded directly to the vehicle structure and finally coated with a high purity silica coating that improves erosion resistance.

KSC-04pd0613

NASA Image and Video Library

2004-03-24

KENNEDY SPACE CENTER, FLA. -- United Space Alliance workers Ginger Morrison and Michael Williams stitch together pieces of insulation blankets inside the ring that fits in the nose cap of Discovery. The blankets consist of layered, pure silica felt sandwiched between a layer of silica fabric (the hot side) and a layer of S-Glass fabric. The blanket is through-stitched with pure silica thread in a 1-inch grid pattern. After fabrication, the blanket is bonded directly to the vehicle structure and finally coated with a high purity silica coating that improves erosion resistance. The blankets are semi-rigid and can be made as large as 30 inches by 30 inches.

KSC-04PD-0613

NASA Technical Reports Server (NTRS)

2004-01-01

KENNEDY SPACE CENTER, FLA. -- United Space Alliance workers Ginger Morrison and Michael Williams stitch together pieces of insulation blankets inside the ring that fits in the nose cap of Discovery. The blankets consist of layered, pure silica felt sandwiched between a layer of silica fabric (the hot side) and a layer of S-Glass fabric. The blanket is through-stitched with pure silica thread in a 1-inch grid pattern. After fabrication, the blanket is bonded directly to the vehicle structure and finally coated with a high purity silica coating that improves erosion resistance. The blankets are semi-rigid and can be made as large as 30 inches by 30 inches.

KSC-04PD-0616

NASA Technical Reports Server (NTRS)

2004-01-01

KENNEDY SPACE CENTER, FLA. -- United Space Alliance workers Ginger Morrison and Michael Williams stitch together pieces of insulation blankets inside the ring that fits in the nose cap of Discovery. The blankets consist of layered, pure silica felt sandwiched between a layer of silica fabric (the hot side) and a layer of S-Glass fabric. The blankets are semi-rigid and can be made as large as 30 inches by 30 inches. The blanket is through- stitched with pure silica thread in a 1-inch grid pattern. After fabrication, the blanket is bonded directly to the vehicle structure and finally coated with a high purity silica coating that improves erosion resistance.

KSC-04pd0616

NASA Image and Video Library

2004-03-24

KENNEDY SPACE CENTER, FLA. -- United Space Alliance workers Ginger Morrison and Michael Williams stitch together pieces of insulation blankets inside the ring that fits in the nose cap of Discovery. The blankets consist of layered, pure silica felt sandwiched between a layer of silica fabric (the hot side) and a layer of S-Glass fabric. The blankets are semi-rigid and can be made as large as 30 inches by 30 inches. The blanket is through-stitched with pure silica thread in a 1-inch grid pattern. After fabrication, the blanket is bonded directly to the vehicle structure and finally coated with a high purity silica coating that improves erosion resistance.

KSC-04PD-0614

NASA Technical Reports Server (NTRS)

2004-01-01

KENNEDY SPACE CENTER, FLA. -- United Space Alliance workers Michael Williams and Ginger Morrison stitch together pieces of insulation blankets inside the ring that fits in the nose cap of Discovery. The blankets consist of layered, pure silica felt sandwiched between a layer of silica fabric (the hot side) and a layer of S-Glass fabric. The blankets are semi-rigid and can be made as large as 30 inches by 30 inches. The blanket is through- stitched with pure silica thread in a 1-inch grid pattern. After fabrication, the blanket is bonded directly to the vehicle structure and finally coated with a high purity silica coating that improves erosion resistance.

Relating Silica Scaling in Reverse Osmosis to Membrane Surface Properties.

PubMed

Tong, Tiezheng; Zhao, Song; Boo, Chanhee; Hashmi, Sara M; Elimelech, Menachem

2017-04-18

We investigated the relationship between membrane surface properties and silica scaling in reverse osmosis (RO). The effects of membrane hydrophilicity, free energy for heterogeneous nucleation, and surface charge on silica scaling were examined by comparing thin-film composite polyamide membranes grafted with a variety of polymers. Results show that the rate of silica scaling was independent of both membrane hydrophilicity and free energy for heterogeneous nucleation. In contrast, membrane surface charge demonstrated a strong correlation with the extent of silica scaling (R 2 > 0.95, p < 0.001). Positively charged membranes significantly facilitated silica scaling, whereas a more negative membrane surface charge led to reduced scaling. This observation suggests that deposition of negatively charged silica species on the membrane surface plays a critical role in silica scale formation. Our findings provide fundamental insights into the mechanisms governing silica scaling in reverse osmosis and highlight the potential of membrane surface modification as a strategy to reduce silica scaling.

Assessing bio-available silver released from silver nanoparticles embedded in silica layers using the green algae Chlamydomonas reinhardtii as bio-sensors.

PubMed

Pugliara, Alessandro; Makasheva, Kremena; Despax, Bernard; Bayle, Maxime; Carles, Robert; Benzo, Patrizio; BenAssayag, Gérard; Pécassou, Béatrice; Sancho, Maria Carmen; Navarro, Enrique; Echegoyen, Yolanda; Bonafos, Caroline

2016-09-15

Silver nanoparticles (AgNPs) because of their strong antibacterial activity are widely used in health-care sector and industrial applications. Their huge surface-volume ratio enhances the silver release compared to the bulk material, leading to an increased toxicity for microorganisms sensitive to this element. This work presents an assessment of the toxic effect on algal photosynthesis due to small (size <20nm) AgNPs embedded in silica layers. Two physical approaches were originally used to elaborate the nanocomposite structures: (i) low energy ion beam synthesis and (ii) combined silver sputtering and plasma polymerization. These techniques allow elaboration of a single layer of AgNPs embedded in silica films at defined nanometer distances (from 0 to 7nm) beneath the free surface. The structural and optical properties of the nanostructures were studied by transmission electron microscopy and optical reflectance. The silver release from the nanostructures after 20h of immersion in buffered water was measured by inductively coupled plasma mass spectrometry and ranges between 0.02 and 0.49μM. The short-term toxicity of Ag to photosynthesis of Chlamydomonas reinhardtii was assessed by fluorometry. The obtained results show that embedding AgNPs reduces the interactions with the buffered water free media, protecting the AgNPs from fast oxidation. The release of bio-available silver (impacting on the algal photosynthesis) is controlled by the depth at which AgNPs are located for a given host matrix. This provides a procedure to tailor the toxicity of nanocomposites containing AgNPs. Copyright © 2016 Elsevier B.V. All rights reserved.

Plasmonic properties and enhanced fluorescence of gold and dye-doped silica nanoparticle aggregates

NASA Astrophysics Data System (ADS)

Green, Nathaniel Scott

The development of metal-enhanced fluorescence has prompted a great interest in augmenting the photophysical properties of fluorescent molecules with noble metal nanostructures. Our research efforts, outlined in this dissertation, focus on augmenting properties of fluorophores by conjugation with gold nanostructures. The project goals are split into two separate efforts; the enhancement in brightness of fluorophores and long distance non-radiative energy transfer between fluorophores. We believe that interacting dye-doped silica nanoparticles with gold nanoparticles can facilitate both of these phenomena. Our primary research interest is focused on optimizing brightness, as this goal should open a path to studying the second goal of non-radiative energy transfer. The two major challenges to this are constructing suitable nanomaterials and functionalizing them to promote plasmonically active complexes. The synthesis of dye-doped layered silica nanoparticles allows for control over the discrete location of the dye and a substrate that can be surface functionalized. Controlling the exact location of the dye is important to create a silica spacer, which promotes productive interactions with metal nanostructures. Furthermore, the synthesis of silica nanoparticles allows for various fluorophores to be studied in similar environments (removing solvent and other chemo-sensitive issues). Functionalizing the surface of silica nanoparticles allows control over the degree of silica and gold nanoparticle aggregation in solution. Heteroaggregation in solution is useful for producing well-aggregated clusters of many gold around a single silica nanoparticle. The dye-doped surface functionalized silica nanoparticles can than be mixed efficiently with gold nanomaterials. Aggregating multiple gold nanospheres around a single dye-doped silica nanoparticle can dramatically increase the fluorescent brightness of the sample via metal-enhanced fluorescence due to increase plasmonic scattering. Our aim is to promote heteroaggregation with functionalized silica nanoparticles while minimizing homoaggregation of silica-silica or gold-gold species. Reproducible production of multiple gold nanospheres about a dye-doped silica nanoparticle should lead to dramatic fluorescence brightness enhancements in solution. Gold nanorods can potentially be used to establish radiationless energy transfer between hetero dye-doped silica nanoparticles via gold nanorod plasmon mediated FRET by aggregating two different dye-doped silica nanoparticles preferentially at opposite ends of the nanorod. End-cap binding is accomplished by tuning the strength of gold binding ligands that functionalize the surface of the silica nanoparticles. The gold nanorod can then theoretically serve as a waveguide by employing the longitudinal plasmon as a non-radiative energy transfer agent between the two different fluorophores, giving rise to a new ultrafast signaling paradigm. Heteroaggregation of dye-doped silica nanoparticles and gold nanorods can be potentially employed to as nano waveguides. Construction and aggregation of functionalized silica and gold nano-materials provides an opportunity to advance the field of fluorescence. The synthesis of gold nano-particles allows control over their size and shape, which give rise to useful optical and electronic properties. Silica nanoparticles provide a framework allowing control over a requisite distance for increasing beneficial and deceasing non-radiative dye-metal interactions as well fluorophore protection. Our aim is to take advantage of fine-tuned synthetic control of functionalized nanomaterials to realize the great potential of solution based metal-enhanced fluorescence for future applications.

Determination of migration of ion-implanted Ar and Zn in silica by backscattering spectrometry

NASA Astrophysics Data System (ADS)

Szilágyi, E.; Bányász, I.; Kótai, E.; Németh, A.; Major, C.; Fried, M.; Battistig, G.

2015-03-01

It is well known that the refractive indices of lots of materials can be modified by ion implantation, which is important for waveguide fabrication. In this work the effect of Ar and Zn ion implantation on silica layers was investigated by Rutherford Backscattering Spectrometry (RBS) and Spectroscopic Ellipsometry (SE). Silica layers produced by chemical vapour deposition technique on single crystal silicon wafers were implanted by Ar and Zn ions with a fluence of 1-2 ×1016 Ar/cm2 and 2.5 ×1016 Zn/cm2, respectively. The refractive indices of the implanted silica layers before and after annealing at 300°C and 600°C were determined by SE. The migration of the implanted element was studied by real-time RBS up to 500°C. It was found that the implanted Ar escapes from the sample at 300°C. Although the refractive indices of the Ar-implanted silica layers were increased compared to the as-grown samples, after the annealing this increase in the refractive indices vanished. In case of the Zn-implanted silica layer both the distribution of the Zn and the change in the refractive indices were found to be stable. Zn implantation seems to be an ideal choice for producing waveguides.

Surface modification for enhanced silanation of zirconia ceramics.

PubMed

Piascik, J R; Swift, E J; Thompson, J Y; Grego, S; Stoner, B R

2009-09-01

The overall goal of this research was to develop a practical method to chemically modify the surface of high strength dental ceramics (i.e. zirconia) to facilitate viable, robust adhesive bonding using commercially available silanes and resin cements. Investigation focused on a novel approach to surface functionalize zirconia with a Si(x)O(y) "seed" layer that would promote chemical bonding with traditional silanes. ProCAD and ZirCAD blocks were bonded to a dimensionally similar composite block using standard techniques designed for silica-containing materials (silane and resin cement). ZirCAD blocks were treated with SiCl4 by vapor deposition under two different conditions prior to bonding. Microtensile bars were prepared and subjected to tensile forces at a crosshead speed of 1 mm/min scanning electron microscopy was used to analyze fracture surfaces and determine failure mode; either composite cohesive failure (partial or complete cohesive failure within composite) or adhesive failure (partial or complete adhesive failure). Peak stress values were analyzed using single-factor ANOVA (p<0.05). Microtensile testing results revealed that zirconia with a surface treatment of 2.6 nm Si(x)O(y) thick "seed" layer was similar in strength to the porcelain group (control). Analysis of failure modes indicated the above groups displayed higher percentages of in-composite failures. Other groups tested had lower strength values and displayed adhesive failure characteristics. Mechanical data support that utilizing a gas-phase chloro-silane pretreatment to deposit ultra-thin silica-like seed layers can improve adhesion to zirconia using traditional silanation and bonding techniques. This technology could have clinical impact on how high strength dental materials are used today.

Separation of pharmacologically active nitrogen-containing compounds on silica gels modified with 6,10-ionene, dextran sulfate, and gold nanoparticles

NASA Astrophysics Data System (ADS)

Ioutsi, A. N.; Shapovalova, E. N.; Ioutsi, V. A.; Mazhuga, A. G.; Shpigun, O. A.

2017-12-01

New stationary phases for HPLC are obtained via layer-by-layer deposition of polyelectrolytes and studied: (1) silica gel modified layer-by-layer with 6,10-ionene and dextran sulfate (Sorbent 1); (2) silica gel twice subjected to the above modification (Sorbent 2); and (3) silica gel modified with 6,10-ionene, gold nanoparticles, and dextran sulfate (Sorbent 3). The effect the content of the organic solvent in the mobile phase and the concentration and pH of the buffer solution have on the chromatographic behavior of several pharmacologically active nitrogen-containing compounds is studied. The sorbents are stable during the process and allow the effective separation of beta-blockers, calcium channel blockers, alpha-agonists, and antihistamines. A mixture of caffeine, nadolol, tetrahydrozoline, pindolol, orphenadrine, doxylamine, carbinoxamine, and chlorphenamine is separated in 6.5 min on the silica gel modified with 6,10-ionene, gold nanoparticles, and dextran sulfate.

‘Green’-synthesized near-infrared PbS quantum dots with silica-PEG dual-layer coating: ultrastable and biocompatible optical probes for in vivo animal imaging

NASA Astrophysics Data System (ADS)

Wang, D.; Qian, J.; Cai, F.; He, S.; Han, S.; Mu, Y.

2012-06-01

In this paper, PbS semiconductor quantum dots (QDs) with near-infrared (NIR) photoluminescence were synthesized in oleic acid and paraffin liquid mixture by using an easily handled and ‘green’ approach. Surface functionalization of the QDs was accomplished with a silica and polyethylene glycol (PEG) phospholipid dual-layer coating and the excellent chemical stability of the nanoparticles is demonstrated. We then successfully applied the ultrastable PbS QDs to in vivo sentinel lymph node (SLN) mapping of mice. Histological analyses were also carried out to ensure that the intravenously injected nanoparticles did not produce any toxicity to the organism of mice. These experimental results suggested that our ultrastable NIR PbS QDs can serve as biocompatible and efficient probes for in vivo optical bioimaging and has great potentials for disease diagnosis and clinical therapies in the future.

Corrosion control of cement-matrix and aluminum-matrix composites

NASA Astrophysics Data System (ADS)

Hou, Jiangyuan

Corrosion control of composite materials, particularly aluminum-matrix and cement-matrix composites, was addressed by surface treatment, composite formulation and cathodic protection. Surface treatment methods studied include anodization in the case of aluminum-matrix composites and oxidation treatment (using water) in the case of steel rebar for reinforcing concrete. The effects of reinforcement species (aluminum nitride (AIN) versus silicon carbide (SiC) particles) in the aluminum-matrix composites and of admixtures (carbon fibers, silica fume, latex and methylcellulose) in concrete on the corrosion resistance of composites were addressed. Moreover, the effect of admixtures in concrete and of admixtures in mortar overlay (as anode on concrete) on the efficiency of cathodic protection of steel reinforced concrete was studied. For SiC particle filled aluminum, anodization was performed successfully in an acid electrolyte, as for most aluminum alloys. However, for AlN particle filled aluminum, anodization needs to be performed in an alkaline (0.7 N NaOH) electrolyte instead. The concentration of NaOH in the electrolyte was critical. It was found that both silica fume and latex improved the corrosion resistance of rebar in concrete in both Ca(OH)sb2 and NaCl solutions, mainly because these admixtures decreased the water absorptivity. Silica fume was more effective than latex. Methylcellulose improved the corrosion resistance of rebar in concrete a little in Ca(OH)sb2 solution. Carbon fibers decreased the corrosion resistance of rebar in concrete, but this effect could be made up for by either silica fume or latex, such that silica fume was more effective than latex. Surface treatment in the form of water immersion for two days was found to improve the corrosion resistance of rebar in concrete. This treatment resulted in a thin uniform layer of black iron oxide (containing Fesp{2+}) on the entire rebar surface except on the cross-sectional surface. Prior to the treatment, the surface was non-uniform due to rusting. Sand blasting also made the surface uniform, but is an expensive process, compared to the water immersion method. For cathodic protection of steel rebar reinforced concrete, mortar overlay containing carbon fibers and latex needed 11% less driving voltage to protect the rebar in concrete than plain mortar overlay. However, multiple titanium electrical contacts were necessary, whether the overlay contained carbon fibers or not. For the same overlay (containing carbon fibers and latex), admixtures in the concrete also made a significant difference on the effect of cathodic protection; concrete with carbon fibers and silica fume needed 18% less driving voltage than plain concrete and 28% less than concrete containing silica fume.

Sulfonated mesoporous silica-carbon composites and their use as solid acid catalysts

NASA Astrophysics Data System (ADS)

Valle-Vigón, Patricia; Sevilla, Marta; Fuertes, Antonio B.

2012-11-01

The synthesis of highly functionalized porous silica-carbon composites made up of sulfonic groups attached to a carbon layer coating the pores of three types of mesostructured silica (i.e. SBA-15, KIT-6 and mesocellular silica) is presented. The synthesis procedure involves the following steps: (a) removal of the surfactant, (b) impregnation of the silica pores with a carbon precursor, (c) carbonization and (d) sulfonation. The resulting silica-carbon composites contain ˜30 wt % of carbonaceous matter with a high density of acidic groups attached to the deposited carbon (i.e.sbnd SO3H, sbnd COOH and sbnd OH). The structural characteristics of the parent silica are retained in the composite materials, which exhibit a high surface area, a large pore volume and a well-ordered porosity made up uniform mesopores. The high density of the sulfonic groups in combination with the mesoporous structure of the composites ensures that a large number of active sites are easily accessible to reactants. These sulfonated silica-carbon composites behave as eco-friendly, active, selective, water tolerant and recyclable solid acids. In this study we demonstrate the usefulness of these composites as solid acid catalysts for the esterification of maleic anhydride, succinic acid and oleic acid with ethanol. These composites exhibit a superior intrinsic catalytic activity to other commercial solid acids such as Amberlyst-15.

Luminescence of Yb3+ ions in silica-based glasses synthesized by SPCVD

NASA Astrophysics Data System (ADS)

Savel'ev, E. A.; Krivovichev, A. V.; Yapaskurt, V. O.; Golant, K. M.

2017-02-01

The spectra and decay kinetics of Yb3+ single-ion and cooperative luminescence in silica-based optical slab waveguides are investigated. The slab waveguides with a high content of Yb and various amounts of P and Al additives to the light-guiding core glass were fabricated on the basis of fused and unfused glassy layers synthesized via surface-plasma chemical vapor deposition (SPCVD). Luminescence was pumped by laser diodes at ∼904 nm and ∼967 nm wavelengths and recorded in the 450-1175 nm spectral band. For the pure silica host doped with Yb, only the influence of cluster sizes on the luminescence decay kinetics is determined. It is found that the profusion of deposited glass with increased Al content favors separation by geometry of the Yb3+ and Tm3+ ions; the latter are present in the glass as an uncontrollable contamination. Evidence was found that at least two different types of Yb clusters were formed in P doped silica as a result of profusion.

Durability of Environmental Barrier Coatings in a Water Vapor/Oxygen Environment

NASA Technical Reports Server (NTRS)

Holchin, John E.

2004-01-01

Silicon carbide (Sic) and silicon nitride (Si3N4) show potential for application in the hot sections of advanced jet engines. The oxidation behavior of these materials has been studied in great detail. In a pure oxygen environment, a silica (SiO2) layer forms on the surface and provides protection from further oxidation. Initial oxidation is rapid, but slows as silica layer grows; this is known as parabolic oxidation. When exposed to model fuel-lean combustion applications (standard in jet engines), wherein the partial pressure of water vapor is approximately 0.5 atm., these materials exhibit different characteristics. In such an environment, the primary oxidant to form silica is water vapor. At the same time, water vapor reacts with the surface oxide to form gaseous silicon hydroxide (Si(OH)4). The simultaneous formation of both silica and Si(OH)4 -the latter which is lost to the atmosphere- the material continues to recede. Recession rates for uncoated Sic and Si3N4 are unacceptably high, for use in jet engines, - on the order of 1mm/4000h. External coatings have been developed that protect Si-based materials from water vapor attack. One such coating consists of a Ba(0.75)Sr(0.25)Al2Si2O8 (BSAS) topcoat, a mullite/BSAS intermediate layer and a Si bond coat. The key function of the topcoat is to protect the Si-base material from water vapor; therefore it must be fairly stable in water vapor (recession rate of about 1mm/40,000h) and remain crack free. Although BSAS is much more resistant to water vapor attack than pure silica, it exhibits a linear weight loss in 50% H2O - 50% O2 at 1500 C. The objective of my research is to determine the oxidation behavior of a number of alternate hot-pressed monolithic top coat candidates. Potential coatings were exposed at 1500 C to a 50% H2O - 50% O2 gas mixture flowing at 4.4 cm/s . These included rare- earth silicates, barium-strontium aluminosilicates. When weight changes were measured with a continuously recording microbalance, linear weight loss was observed. BSAS materials have a fairly high volatility at this temperature, but rare-earth mono-silicate compounds were significantly more stable.

Superficially porous particles columns for super fast HPLC separations.

PubMed

Ali, Imran; Al-Othman, Zeid A; Al-Za'abi, Mohammed

2012-08-01

Superficially porous silica particles columns (SPSPCs) are manufactured by different companies. The most common have the brand names Halo, Ascentis Express and Kinetex. These columns provide super fast, sharp peaks and moderate sample loading and back pressure. These are available in different chemistries such as C₈, C₁₈, RP Amide and Hilic. Normally, the silica gel particles have 2.7 and 1.7 µm total and inner solid core diameters with 0.5 µm thick outer porous layer, 90 Å pore size and 150 m²/g surface area. They have been used for the separation and identification of low and high molecular weight compounds. The present article describes the state of the art of superficially porous silica particles based columns with special emphasis on their structures, mechanisms of separation, applications and comparison. Copyright © 2012 John Wiley & Sons, Ltd.

KSC-04pd0621

NASA Image and Video Library

2004-03-24

KENNEDY SPACE CENTER, FLA. -- In the Thermal Protection System Facility, Pilar Ryan, with United Space Alliance, stitches a piece of insulation blanket for Atlantis' nose cap. Behind her is a cover for the nose cap. The blankets consist of layered, pure silica felt sandwiched between a layer of silica fabric (the hot side) and a layer of S-Glass fabric. The blankets are semi-rigid and can be made as large as 30 inches by 30 inches. The blanket is through-stitched with pure silica thread in a 1-inch grid pattern. After fabrication, the blanket is bonded directly to the vehicle structure and finally coated with a high purity silica coating that improves erosion resistance.

Effect of atmospheric-pressure plasma treatment on the adhesion properties of a thin adhesive layer in a selective transfer process

NASA Astrophysics Data System (ADS)

Yoon, Min-Ah; Kim, Chan; Hur, Min; Kang, Woo Seok; Kim, Jaegu; Kim, Jae-Hyun; Lee, Hak-Joo; Kim, Kwang-Seop

2018-01-01

The adhesion between a stamp and thin film devices is crucial for their transfer on a flexible substrate. In this paper, a thin adhesive silicone layer on the stamp was treated by atmospheric pressure plasma to locally control the adhesion strength for the selective transfer. The adhesion strength of the silicone layer was significantly reduced after the plasma treatment, while its surface energy was increased. To understand the inconsistency between the adhesion strength and surface energy changes, the surface properties of the silicone layer were characterized using nanoindentation and X-ray photoelectron spectroscopy. These techniques revealed that a thin, hard, silica-like layer had formed on the surface from plasma-enhanced oxidation. This layer played an important role in decreasing the contact area and increasing the interfacial slippage, resulting in decreased adhesion. As a practical application, the transfer process was demonstrated on GaN LEDs that had been previously delaminated by a laser lift-off (LLO) process. Although the LEDs were not transferred onto the treated adhesive layer due to the reduced adhesion, the untreated adhesive layer could readily pick up the LEDs. It is expected that this simple method of controlling the adhesion of a stamp with a thin adhesive layer would enable a continuous, selective and large-scale roll-to-roll selective transfer process and thereby advance the development of flexible, stretchable and wearable electronics.

Fluorescent magnetic nanoparticles for cell labeling: flux synthesis of manganite particles and novel functionalization of silica shell.

PubMed

Kačenka, Michal; Kaman, Ondřej; Kikerlová, Soňa; Pavlů, Barbora; Jirák, Zdeněk; Jirák, Daniel; Herynek, Vít; Černý, Jan; Chaput, Frédéric; Laurent, Sophie; Lukeš, Ivan

2015-06-01

Novel synthetic approaches for the development of multimodal imaging agents with high chemical stability are demonstrated. The magnetic cores are based on La0.63Sr0.37MnO3 manganite prepared as individual grains using a flux method followed by additional thermal treatment in a protective silica shell allowing to enhance their magnetic properties. The cores are then isolated and covered de novo with a hybrid silica layer formed through the hydrolysis and polycondensation of tetraethoxysilane and a fluorescent silane synthesized from rhodamine, piperazine spacer, and 3-iodopropyltrimethoxysilane. The aminoalkyltrialkoxysilanes are strictly avoided and the resulting particles are hydrolytically stable and do not release dye. The high colloidal stability of the material and the long durability of the fluorescence are reinforced by an additional silica layer on the surface of the particles. Structural and magnetic studies of the products using XRD, TEM, and SQUID magnetometry confirm the importance of the thermal treatment and demonstrate that no mechanical treatment is required for the flux-synthesized manganite. Detailed cell viability tests show negligible or very low toxicity at concentrations at which excellent labeling is achieved. Predominant localization of nanoparticles in lysosomes is confirmed by immunofluorescence staining. Relaxometric and biological studies suggest that the functionalized nanoparticles are suitable for imaging applications. Copyright © 2015 Elsevier Inc. All rights reserved.

Interfacing superhydrophobic silica nanoparticle films with graphene and thermoplastic polyurethane for wear/abrasion resistance.

PubMed

Naderizadeh, Sara; Athanassiou, Athanassia; Bayer, Ilker S

2018-06-01

Nanoparticle films are one of the most suitable platforms for obtaining sub-micrometer and nanometer dual-scale surface texture required for liquid repellency. The assembly of superhydrophobic nanoparticles into conformal and strongly adherent films having abrasion-induced wear resistance still poses a significant challenge. Various techniques have been developed over the years to render nanoparticle films with good liquid repellent properties and transparency. However, forming abrasion resistant superhydrophobic nanoparticle films on hard surfaces is challenging. One possibility is to partially embed or weld nanoparticles in thin thermoplastic primers applied over metals. Hexamethyldisilazane-functionalized fumed silica nanoparticle films spray deposited on aluminum surfaces were rendered abrasion resistant by thermally welding them into thermoplastic polyurethane (TPU) primer applied a priori over aluminum. Different solvents, nanoparticle concentrations and annealing temperatures were studied to optimize nanoparticle film morphology and hydrophobicity. Thermal annealing at 150 °C enhanced stability and wear resistance of nanoparticle films. A thin thermal interface layer of graphene nanoplatelets (GnPs) between the primer and the nanoparticle film significantly improved superhydrophobic wear resistance after annealing. As such, superhydrophobic nanocomposite films with the GnPs thermal interface layer displayed superior abrasion-induced wear resistance under 20 kPa compared to films having no GnPs-based thermal interface. Copyright © 2018 Elsevier Inc. All rights reserved.

A FRET system built on quartz plate as a ratiometric fluorescence sensor for mercury ions in water.

PubMed

Liu, Baoyu; Zeng, Fang; Liu, Yan; Wu, Shuizhu

2012-04-07

Due to the hazardous nature of mercury ions, the development of a cost effective, sensitive and field-portable sensor is of high significance for both industry and civilian use. In this work, a FRET-based ratiometric sensor for detecting mercury ions in water was fabricated by depositing a multilayered silica structure on a quartz plate. For the preparation of the film-based sensor, a silica support layer was first deposited on the quartz plate by using the sol-gel spin-coating procedure, and three ultrathin functional layers (donor, spacer and receptor) were then deposited on the support layer by dip-coating in a stepwise manner in toluene solution. As the film-based sensor was placed into an aqueous solution of Hg(2+), the non-fluorescent receptor (a spirolactam rhodamine derivative) on the film surface could form a complex with the mercury ion and act as the acceptor of the energy transfer. Upon excitation, the donor (a nitrobenzoxadiazolyl derivative, NBD) could transfer its excited energy from the donor layer to the acceptor on the film surface via the 'through space' energy transfer process, thus realizing the FRET-based ratiometric sensing for mercury ions. The sensor can selectively detect Hg(2+) in water with the detection limit of 1 μM. This solid film sensor is capable of being easily-portable and visualized detection. This strategy may offer new approaches for constructing other FRET-based solid-state devices.

Synthesis of 1D Fe₃O₄/P(MBAAm-co-MAA) nanochains as stabilizers for Ag nanoparticles and templates for hollow mesoporous structure, and their applications in catalytic reaction and drug delivery.

PubMed

Zhang, Wei; Si, Xiaowei; Liu, Bin; Bian, Guomin; Qi, Yonglin; Yang, Xinlin; Li, Chenxi

2015-10-15

One-dimensional (1D) magnetic Fe3O4/P(MBAAm-co-MAA) nanochains were prepared by distillation-precipitation polymerization of MBAAm and MAA in the presence of Fe3O4 nanoparticles as building blocks under a magnetic heating stirrer, which played two critical roles: serving as magnetic field to induce the self-assembly of Fe3O4 nanoparticles into 1D nanochains and providing thermal energy to induce the polymerization of MAA and MBAAm on the surface of the Fe3O4 nanoparticles. The thickness of the P(MBAAm-co-MAA) layer can be easily tuned by adjusting the successive polymerization steps. The polymer layer that contained carboxyl groups was used as stabilizers for loading Ag nanoparticles and the reaction locus for deposition of outer silica layer via a sol-gel method in presence of C18TMS as the pore directing agent for tri-layer nanochains. The corresponding hollow mesoporous silica nanochains with movable maghemite cores (γ-Fe2O3@mSiO2) were produced after removal of the polymer mid-layer and the alkyl groups of the pore directing agent via calcination of the tri-layer nanochains at high temperature. The Fe3O4/P(MBAAm-co-MAA)/Ag nanochains exhibited a highly catalytic efficiency and well reusable property toward the reduction of nitrophenol. Furthermore, the γ-Fe2O3@mSiO2 nanochains possessed hollow mesoporous structure and high specific surface area (197.2 m(2) g(-1)) were used as a drug carrier, which displayed a controlled release property. Copyright © 2015 Elsevier Inc. All rights reserved.

Anionic surfactants templating route for synthesizing silica hollow spheres with different shell porosity

NASA Astrophysics Data System (ADS)

Han, Lu; Gao, Chuanbo; Wu, Xiaowei; Chen, Qianru; Shu, Peng; Ding, Zhiguang; Che, Shunai

2011-04-01

Silica hollow spheres with different shell porosity were simply synthesized with micelle and emulsion dual templating route. Various anionic surfactants, such as palmitic acid (C 16AA), N-acyl- L-phenylalanine (C 18Phe), N-palmitoyl- L-alanine (C 16AlaA) and oleic acid (OA) have been used as templates, and 3-aminopropyl-triethoxysilane (APES) and tetraethyl orthosilicate (TEOS) have been used as co-structure directing agent (CSDA) and silica source, respectively. The circle lamellar layer structure and mesopores vertical to the silica hollow spheres surface are believed to originate from the initial formation of amphiphilic carboxylic acid oil drop, which afterwards self-assemble to form the shell of hollow spheres and its mesostructure upon addition of CSDA and silica source. The mesoporous silica hollow spheres with high porosity could be achieved by adding a moderate amount of ethanol in the OA synthesis system, depending on the co-surfactant effect of ethanol that changes the curvature of micelles. The particle diameter and the hollow structure have been controlled by choosing different templates and by manipulating synthesis gel composition. The average particle diameter of the mesoporous silica hollow spheres were controlled in the range of 80-220 nm with constant shell thickness of ˜20 nm and constant mesopore size of ˜4 nm. Besides, the formation of the silica hollow spheres has been investigated in detail with reaction time. These mesoporous silica hollow spheres would have potential applications on catalysis, bimolecular encapsulation, adsorption, drug release, etc.

Gas-Phase Synthesis of Gold- and Silica-Coated Nanoparticles

NASA Astrophysics Data System (ADS)

Boies, Adam Meyer

2011-12-01

Composite nanoparticles consisting of separate core-shell materials are of interest for a variety of biomedical and industrial applications. By combining different materials at the nanoscale, particles can exhibit enhanced or multi-functional behavior such as plasmon resonance combined with superparamagnetism. Gas-phase nanoparticle synthesis processes are promising because they can continuously produce particles with high mass-yield rates. In this dissertation, new methods are investigated for producing gas-phase coatings of nanoparticles in an "assembly-line" fashion. Separate processes are developed to create coatings from silica and gold that can be used with a variety of core-particle chemistries. A photoinduced chemical vapor deposition (photo-CVD) method is used to produce silica coatings from tetraethyl orthosilicate (TEOS) on the surface of nanoparticles (diameter ˜5--70 nm). Tandem differential mobility analysis (TDMA) of the process demonstrates that particle coatings can be produced with controllable thicknesses (˜1--10 nm) by varying system parameters such as precursor flow rate. Electron microscopy and infrared spectroscopy confirm that the photo-CVD films uniformly coat the particles and that the coatings are silica. In order to describe the coating process a chemical mechanism is proposed that includes gas-phase, surface and photochemical reactions. A chemical kinetics model of the mechanism indicates that photo-CVD coating proceeds primarily through the photodecomposition of TEOS which removes ethyl groups, thus creating activated TEOS species. The activated TEOS then adsorbs onto the surface of the particle where a series of subsequent reactions remove the remaining ethyl groups to produce a silica film with an open site for further attachment. The model results show good agreement with the experimentally measured coating trends, where increased TEOS flow increases coating thickness and increased nitrogen flow decreases coating thickness. Gold decoration of nanoparticles is accomplished by evaporation of solid gold in the presence of an aerosol flow. A hot-wire generation method is developed where gold particles are produced from a composite gold-platinum wire. Investigations of the hot-wire generator show that it can produce particles with a range of sizes and that more uniform, non-agglomerated particles are produced when using smaller diameter tubes where gas velocities across the wire are higher and recirculation zones are diminished. When gold is evaporated in the presence of silica nanoparticles, the silica aerosol is decorated by gold through either homogeneous gold nucleation and subsequent scavenging by the silica nanoparticles, or by heterogeneous nucleation on the silica surface in which the gold "balls up" due to the high surface tension of gold on silica. In both cases the resulting particles exhibit a plasmon absorbance resonance typical of gold nanoparticles (lambda˜550 nm). Finally, the silica coating and gold decoration processes are combined with a thermal plasma technique for synthesizing iron-oxide to produce tri-layer nanoparticles.

Formation of grafted surface layers on silicon dioxide particles and their investigation by means of thermoprogrammed oxidation

NASA Astrophysics Data System (ADS)

Aleksandrova, E. O.; Novichkov, R. V.; Olenin, A. Yu.; Zuev, B. K.

2017-03-01

Silica nanoparticles are obtained according to the Stober-Fink-Bohn method, and their surfaces are chemically modified with 1H,1H,2H,2H-perfluorodecyltriethoxysilane. It is estimated that sols of porous silica nanoparticles (average sizes, 50-200 nm) form during primary chemical process; the average size of the particles can be increased to 400-500 nm by consecutive growth. Oxythermography (thermoprogrammed oxidation) measurements reveal a stepped dependence between the content of organic substance of nanoparticles and the duration of chemical modification reaction exists. It is concluded that this could be due to the formation of dense shell (or shells) as a result of sols aging between the cycles of growth; such shells impose diffusive restrictions when molecules penetrate into the pores of the internal volume of the particles.

Facile synthesis of novel magnetic silica nanoparticles functionalized with layer-by-layer detonation nanodiamonds for secretome study.

PubMed

Li, Hong; Wang, Yi; Zhang, Lei; Lu, Haojie; Zhou, Zhongjun; Wei, Liming; Yang, Pengyuan

2015-12-07

Novel magnetic silica nanoparticles functionalized with layer-by-layer detonation nanodiamonds (dNDs) were prepared by coating single submicron-size magnetite particles with silica and subsequently modified with dNDs. The resulting layer-by-layer dND functionalized magnetic silica microspheres (Fe3O4@SiO2@[dND]n) exhibit a well-defined magnetite-core-silica-shell structure and possess a high content of magnetite, which endow them with high dispersibility and excellent magnetic responsibility. Meanwhile, dNDs are known for their high affinity and biocompatibility towards peptides or proteins. Thus, a novel convenient, fast and efficient pretreatment approach of low-abundance peptides or proteins was successfully established with Fe3O4@SiO2@[dND]n microspheres. The signal intensity of low-abundance peptides was improved by at least two to three orders of magnitude in mass spectrometry analysis. The novel microsphere also showed good tolerance to salt. Even with a high concentration of salt, peptides or proteins could be isolated effectively from samples. Therefore, the convenient and efficient enrichment process of this novel layer-by-layer dND-functionalized microsphere makes it a promising candidate for isolation of protein in a large volume of culture supernatant for secretome analysis. In the application of Fe3O4@SiO2@[dND]n in the secretome of hepatoma cells, 1473 proteins were identified and covered a broad range of pI and molecular weight, including 377 low molecular weight proteins.

Layer-by-Layer Self-Assembling Gold Nanorods and Glucose Oxidase onto Carbon Nanotubes Functionalized Sol-Gel Matrix for an Amperometric Glucose Biosensor

PubMed Central

Wu, Baoyan; Hou, Shihua; Miao, Zhiying; Zhang, Cong; Ji, Yanhong

2015-01-01

A novel amperometric glucose biosensor was fabricated by layer-by-layer self-assembly of gold nanorods (AuNRs) and glucose oxidase (GOD) onto single-walled carbon nanotubes (SWCNTs)-functionalized three-dimensional sol-gel matrix. A thiolated aqueous silica sol containing SWCNTs was first assembled on the surface of a cleaned Au electrode, and then the alternate self-assembly of AuNRs and GOD were repeated to assemble multilayer films of AuNRs-GOD onto SWCNTs-functionalized silica gel for optimizing the biosensor. Among the resulting glucose biosensors, the four layers of AuNRs-GOD-modified electrode showed the best performance. The sol-SWCNTs-(AuNRs-GOD)4/Au biosensor exhibited a good linear range of 0.01–8 mM glucose, high sensitivity of 1.08 μA/mM, and fast amperometric response within 4 s. The good performance of the proposed glucose biosensor could be mainly attributed to the advantages of the three-dimensional sol-gel matrix and stereo self-assembly films, and the natural features of one-dimensional nanostructure SWCNTs and AuNRs. This study may provide a new facile way to fabricate the enzyme-based biosensor with high performance. PMID:28347080

Bioactive potential of silica coatings and its effect on the adhesion of proteins to titanium implants.

PubMed

Romero-Gavilan, F; Araújo-Gomes, N; Sánchez-Pérez, A M; García-Arnáez, I; Elortza, F; Azkargorta, M; de Llano, J J Martín; Carda, C; Gurruchaga, M; Suay, J; Goñi, I

2018-02-01

There is an ever-increasing need to develop dental implants with ideal characteristics to achieve specific and desired biological response in the scope of improve the healing process post-implantation. Following that premise, enhancing and optimizing titanium implants through superficial treatments, like silica sol-gel hybrid coatings, are regarded as a route of future research in this area. These coatings change the physicochemical properties of the implant, ultimately affecting its biological characteristics. Sandblasted acid-etched titanium (SAE-Ti) and a silica hybrid sol-gel coating (35M35G30T) applied onto the Ti substrate were examined. The results of in vitro and in vivo tests and the analysis of the protein layer adsorbed to each surface were compared and discussed. In vitro analysis with MC3T3-E1 osteoblastic cells, showed that the sol-gel coating raised the osteogenic activity potential of the implants (the expression of osteogenic markers, the alkaline phosphatase (ALP) and IL-6 mRNAs, increased). In the in vivo experiments using as model rabbit tibiae, both types of surfaces promoted osseointegration. However, the coated implants demonstrated a clear increase in the inflammatory activity in comparison with SAE-Ti. Mass spectrometry (LC-MS/MS) analysis showed differences in the composition of protein layers formed on the two tested surfaces. Large quantities of apolipoproteins were found attached predominantly to SAE-Ti. The 35M35G30T coating adsorbed a significant quantity of complement proteins, which might be related to the material intrinsic bioactivity, following an associated, natural and controlled immune response. The correlation between the proteomic data and the in vitro and in vivo outcomes is discussed on this experimental work. Copyright © 2017 Elsevier B.V. All rights reserved.

Preparation, characterization, and infrared emissivity property of optically active polyurethane/TiO{sub 2}/SiO{sub 2} multilayered microspheres

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

Yang Yong; Zhou Yuming, E-mail: ymzhou@seu.edu.cn; Ge Jianhua

Optically active polyurethane/titania/silica (LPU/TiO{sub 2}/SiO{sub 2}) multilayered core-shell composite microspheres were prepared by the combination of titania deposition on the surface of silica spheres and subsequent polymer grafting. LPU/TiO{sub 2}/SiO{sub 2} was characterized by FT-IR, UV-vis spectroscopy, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), SEM and TEM, and the infrared emissivity value (8-14 {mu}m) was investigated in addition. The results indicated that titania and polyurethane had been successfully coated onto the surfaces of silica microspheres. LPU/TiO{sub 2}/SiO{sub 2} exhibited clearly multilayered core-shell construction. The infrared emissivity values reduced along with the increase of covering layers thus provedmore » that the interfacial interactions had direct influence on the infrared emissivity. Besides, LPU/TiO{sub 2}/SiO{sub 2} multilayered microspheres based on the optically active polyurethane took advantages of the orderly secondary structure and strengthened interfacial synergistic actions. Consequently, it possessed the lowest infrared emissivity value. - Graphical Abstract: Optically active polyurethane/titania/silica (LPU/TiO{sub 2}/SiO{sub 2}) multilayered core-shell composite microspheres were prepared by the combination of titania deposition on the surface of silica spheres and subsequent polymer grafting. Highlights: > Optically active polyurethane based on tyrosine was used for the modification of nanoparticles. > LPU/TiO{sub 2}/SiO{sub 2} multilayered core-shell microspheres were prepared and characterized. > Interfacial interactions and secondary structure affected the infrared emissivity of composite.« less

Heterogeneous Nucleation of Dicalcium Phosphate Dihydrate on Modified Silica Surfaces

PubMed Central

Miller, Carrie; Komunjer, Ljepša; Hlady, Vladimir

2012-01-01

Heterogeneous nucleation of dicalcium phosphate dihydrate, CaHPO4•2H2O (DCPD) was studied on untreated planar fused silica and on three modified silica surfaces: octadecylsilyl (OTS) modified silica, human serum albumin treated OTS silica, and UV-oxidized 3-mercaptopropyltriethoxysilyl (MTS) modified silica. The supersaturation ratio of calcium and phosphate solution with respect to DCPD was kept below ~10. The nucleated crystals were observed 24 hours and one week after initial contact between supersaturated solutions and substrate surfaces using bright field and reflectance interference contrast microscopy. No DCPD crystals nucleated on albumin-treated OTS-silica. Majority of the DCDP crystals formed on the other modified silica surfaces appeared to be morphologically similar irrespective of the nature of nucleating substrate. Reflectance interference contrast microscopy provided a proof that the majority of the crystals on these substrates do not develop an extended contact with the substrate surface. The images showed that the most extended contact planes were between the DCPD crystals and MTS modified silica surface. The crystals nucleated on OTS-treated and untreated silica surfaces showed only few or none well-developed contact planes. PMID:25264399

Adsorption of benzyldimethylhexadecylammonium chloride at the hydrophobic silica-water interface studied by total internal reflection Raman spectroscopy: effects of silica surface properties and metal salt addition.

PubMed

Grenoble, Zlata; Baldelli, Steven

2013-08-29

The adsorption of the cationic surfactant benzyldimethylhexadecylammonium (BDMHA(+)) chloride was studied at an octadecyltrichlorosilane (OTS)-monolayer-modified silica-water interface by Raman spectroscopy in total internal reflection (TIR) geometry. The present study demonstrates the capabilities of this spectroscopic technique to evaluate thermodynamic and kinetic BDMHA(+)Cl(-) adsorption properties at the hydrophobic silica surface. The surface coverage of BDMHA(+) decreased by 50% at the hydrophobic OTS-silica surface relative to the surface coverage on bare silica; the dominating driving mechanisms for surfactant adsorption were identified as hydrophobic effects and head group charge screening by the electrolyte counterions. Addition of magnesium metal salt (MgCl2) to the aqueous solution (∼ neutral pH) lowered the surface coverage and moderately increased the Langmuir adsorption constants relative to those of the pure surfactant. These trends were previously observed at the hydrophilic, negatively charged silica surface but with a smaller change in the Gibbs free energy of adsorption at the hydrophobic silica surface. The hydrophobic OTS-silica surface properties resulted in shorter times for the surfactant to reach steady-state adsorption conditions compared to the slow adsorption kinetics previously seen with the surfactant at the hydrophilic surface. Adsorption isotherms, based on Raman signal intensities from spectral analysis, were developed according to the Langmuir adsorption model for the pure surfactant at the OTS-silica-water interface; the modified Langmuir model was applied to the surfactant adsorption in the presence of 5, 10, 50, and 100 mM magnesium chloride. Spectral analysis of the Raman scattering intensities and geometric considerations suggests a hemimicelle-type surface aggregate as the most likely surfactant structure at the OTS-silica surface. The different kinetics observed at the hydrophilic versus the hydrophobic silica surface further indicate that the surface charge and potential influence the surfactant diffusion and kinetic rates of adsorption at the silica-water interface.

KSC-04pd0620

NASA Image and Video Library

2004-03-24

KENNEDY SPACE CENTER, FLA. -- In the Thermal Protection System Facility, Pilar Ryan, with United Space Alliance, stitches a piece of insulation blanket for Atlantis. In the foreground is a ring inside of which the blankets will be sewn to fit in the orbiter's nose cap. The blankets consist of layered, pure silica felt sandwiched between a layer of silica fabric (the hot side) and a layer of S-Glass fabric. The blankets are semi-rigid and can be made as large as 30 inches by 30 inches. The blanket is through-stitched with pure silica thread in a 1-inch grid pattern. After fabrication, the blanket is bonded directly to the vehicle structure and finally coated with a high purity silica coating that improves erosion resistance.

Multilayered silica-biopolymer nanocapsules with a hydrophobic core and a hydrophilic tunable shell thickness

NASA Astrophysics Data System (ADS)

Vecchione, Raffaele; Luciani, Giuseppina; Calcagno, Vincenzo; Jakhmola, Anshuman; Silvestri, Brigida; Guarnieri, Daniela; Belli, Valentina; Costantini, Aniello; Netti, Paolo A.

2016-04-01

Stable, biocompatible, multifunctional and multicompartment nanocarriers are much needed in the field of nanomedicine. Here, we report a simple, novel strategy to design an engineered nanocarrier system featuring an oil-core/hybrid polymer/silica-shell. Silica shells with a tunable thickness were grown in situ, directly around a highly mono-disperse and stable oil-in-water emulsion system, stabilized by a double bio-functional polyelectrolyte heparin/chitosan layer. Such silica showed a complete degradation in a physiological medium (SBF) in a time frame of three days. Moreover, the outer silica shell was coated with polyethyleneglycol (PEG) in order to confer antifouling properties to the final nanocapsule. The outer silica layer combined its properties (it is an optimal bio-interface for bio-conjugations and for the embedding of hydrophilic drugs in the porous structure) with the capability to stabilize the oil core for the confinement of high payloads of lipophilic tracers (e.g. CdSe quantum dots, Nile Red) and drugs. In addition, polymer layers - besides conferring stability to the emulsion while building the silica shell - can be independently exploited if suitably functionalized, as demonstrated by conjugating chitosan with fluorescein isothiocyanate. Such numerous features in a single nanocarrier system make it very intriguing as a multifunctional platform for smart diagnosis and therapy.Stable, biocompatible, multifunctional and multicompartment nanocarriers are much needed in the field of nanomedicine. Here, we report a simple, novel strategy to design an engineered nanocarrier system featuring an oil-core/hybrid polymer/silica-shell. Silica shells with a tunable thickness were grown in situ, directly around a highly mono-disperse and stable oil-in-water emulsion system, stabilized by a double bio-functional polyelectrolyte heparin/chitosan layer. Such silica showed a complete degradation in a physiological medium (SBF) in a time frame of three days. Moreover, the outer silica shell was coated with polyethyleneglycol (PEG) in order to confer antifouling properties to the final nanocapsule. The outer silica layer combined its properties (it is an optimal bio-interface for bio-conjugations and for the embedding of hydrophilic drugs in the porous structure) with the capability to stabilize the oil core for the confinement of high payloads of lipophilic tracers (e.g. CdSe quantum dots, Nile Red) and drugs. In addition, polymer layers - besides conferring stability to the emulsion while building the silica shell - can be independently exploited if suitably functionalized, as demonstrated by conjugating chitosan with fluorescein isothiocyanate. Such numerous features in a single nanocarrier system make it very intriguing as a multifunctional platform for smart diagnosis and therapy. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01192f

Chemically Layered Porous Solids

NASA Technical Reports Server (NTRS)

Koontz, Steve

1991-01-01

Aerogels and other porous solids in which surfaces of pores have chemical properties varying with depth below macroscopic surfaces prepared by sequences of chemical treatments. Porous glass or silica bead treated to make two depth zones having different chemical properties. Beads dropped along tube filled with flowing gas containing atomic oxygen, generated in microwave discharge. General class of materials treatable include oxides of aluminum, silicon, zirconium, tin, titanium, and nickel, and mixtures of these oxides. Potential uses of treated materials include chromatographic separations, membrane separations, controlled releases of chemicals, and catalysis.

Highly Dispersed and Active ReOx on Alumina-Modified SBA-15 Silica for 2-Butanol Dehydration

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

She, Xiaoyan; Kwak, Ja Hun; Sun, Junming

2012-05-23

SBA-15 silica supported rhenium catalysts were synthesized using solution-based atomic layer deposition method, and their activity and stability were studied in the acid-catalyzed 2-butanol dehydration. We find that ReOx/SBA-15 exhibited an extremely high initial activity but a fast deactivation for 2-butanol dehydration at 90-105 C. Fast deactivation was likely due to the sintering, sublimation, and reduction of rhenia as confirmed by TEM, elemental analysis, and in situ UV vis (DRS) measurements. To overcome these issues, ReOx/AlOx/SBA-15 catalysts with significantly improved stability were prepared by first modifying the surface identity of SBA-15 with alumina followed by dispersion of rhenia using atomicmore » layer deposition. The AlOx phase stabilizes the dispersion of small and uniform rhenia clusters (<2 nm) as as confirmed by TEM, STEM and UV-vis (DRS) characterizations. Additional 27Al MAS NMR characterization revealed that modification of the SBA-15 surface with alumina introduces a strong interaction between rhenia and alumina, which consequently improves the stability of supported rhenia catalysts by suppressing the sintering, sublimation, and reduction of rhenia albeit at a moderately reduced initial catalytic dehydration activity« less

Limiting diffusion current at rotating disk electrode with dense particle layer.

PubMed

Weroński, P; Nosek, M; Batys, P

2013-09-28

Exploiting the concept of diffusion permeability of multilayer gel membrane and porous multilayer we have derived a simple analytical equation for the limiting diffusion current at rotating disk electrode (RDE) covered by a thin layer with variable tortuosity and porosity, under the assumption of negligible convection in the porous film. The variation of limiting diffusion current with the porosity and tortuosity of the film can be described in terms of the equivalent thickness of stagnant solution layer, i.e., the average ratio of squared tortuosity to porosity. In case of monolayer of monodisperse spherical particles, the equivalent layer thickness is an algebraic function of the surface coverage. Thus, by means of cyclic voltammetry of RDE with a deposited particle monolayer we can determine the monolayer surface coverage. The effect of particle layer adsorbed on the surface of RDE increases non-linearly with surface coverage. We have tested our theoretical results experimentally by means of cyclic voltammetry measurements of limiting diffusion current at the glassy carbon RDE covered with a monolayer of 3 μm silica particles. The theoretical and experimental results are in a good agreement at the surface coverage higher than 0.7. This result suggests that convection in a monolayer of 3 μm monodisperse spherical particles is negligibly small, in the context of the coverage determination, in the range of very dense particle layers.

PAMAM-Based Dendrimers with Different Alkyl Chains Self-Assemble on Silica Surfaces: Controllable Layer Structure and Molecular Aggregation.

PubMed

Zhang, Minghui; Yang, Hui; Wang, Shujuan; Zhang, Wei; Hou, Qingfeng; Guo, Donghong; Liu, Fanghui; Chen, Ting; Wu, Xu; Wang, Jinben

2018-06-20

Amphiphilic poly(amidoamine) (PAMAM) dendrimers are a well-known dendritic family due to their remarkable ability to self-assemble on solid surface. However, the relationship between molecular conformation (or adsorption kinetics) of a self-assembled layer and molecular amphiphilicity of such kind of dendrimer is still lacking, which limits the development of modulating self-assembling structures and surface functionality. With this in mind, we synthesized a series of amphiphilic PAMAM-based dendrimers, denoted as G 1 C n , with different alkyl chains ( n = 8, 12, and 16), and investigated the molecular aggregation on silica surfaces by means of quartz crystal microbalance with dissipation, atomic force microscopy, and contact angle. After rinsing, remaining adsorption amounts of G 1 C 12 were higher than those of G 1 C 8 at high concentrations, suggesting that G 1 C 12 adlayers were more stable due to the stronger intermolecular hydrophobic interactions, whereas it preferred to adopt the intramolecular hydrophobic interactions for G 1 C 16 , with low adsorption amounts and unstable adlayers. Bilayer-like structures were inferred in G 1 C 8 and G 1 C 12 adlayers with loose conformation, whereas monolayer structures were likely to exist in the sparse adsorption film of G 1 C 16 . Our results provided more detailed understanding of the effect of molecular structure on the self-assembled structures of amphiphilic dendrimers on solid surfaces, shedding light on the controlled microstructure and wettability of functional surface by modulating the length of hydrophobic chains of dendrimers and a potential application of dendrimer-substrate combinations.

Antifouling Transparent ZnO Thin Films Fabricated by Atmospheric Pressure Cold Plasma Deposition

NASA Astrophysics Data System (ADS)

Suzaki, Yoshifumi; Du, Jinlong; Yuji, Toshifumi; Miyagawa, Hayato; Ogawa, Kazufumi

2015-09-01

One problem with outdoor-mounted solar panels is that power generation efficiency is reduced by face plate dirt; a problem with electronic touch panels is the deterioration of screen visibility caused by finger grease stains. To solve these problems, we should fabricate antifouling surfaces which have superhydrophobic and oil-repellent properties without spoiling the transparency of the transparent substrate. In this study, an antifouling surface with both superhydrophobicity and oil-repellency was fabricated on a glass substrate by forming a fractal microstructure. The fractal microstructure was constituted of transparent silica particles 100 nm in diameter and transparent zinc-oxide columns grown on silica particles through atmospheric pressure cold plasma deposition; the sample surface was coated with a chemically adsorbed monomolecular layer. Samples were obtained which had a superhydrophobic property (with a water droplet contact angle of more than 150°) and a high average transmittance of about 90% (with wavelengths ranging from 400 nm to 780 nm).

What Governs Friction of Silicon Oxide in Humid Environment: Contact Area between Solids, Water Meniscus around the Contact, or Water Layer Structure?

PubMed

Chen, Lei; Xiao, Chen; Yu, Bingjun; Kim, Seong H; Qian, Linmao

2017-09-26

In order to understand the interfacial parameters governing the friction force (F t ) between silicon oxide surfaces in humid environment, the sliding speed (v) and relative humidity (RH) dependences of F t were measured for a silica sphere (1 μm radius) sliding on a silicon oxide (SiO x ) surface, using atomic force microscopy (AFM), and analyzed with a mathematical model describing interfacial contacts under a dynamic condition. Generally, F t decreases logarithmically with increasing v to a cutoff value below which its dependence on interfacial chemistry and sliding condition is relatively weak. Above the cutoff value, the logarithmic v dependence could be divided into two regimes: (i) when RH is lower than 50%, F t is a function of both v and RH; (ii) in contrast, at RH ≥ 50%, F t is a function of v only, but not RH. These complicated v and RH dependences were hypothesized to originate from the structure of the water layer adsorbed on the surface and the water meniscus around the annulus of the contact area. This hypothesis was tested by analyzing F t as a function of the water meniscus area (A m ) and volume (V m ) estimated from a thermally activated water-bridge formation model. Surprisingly, it was found that F t varies linearly with V m and correlates poorly with A m at RH < 50%; and then its V m dependence becomes weaker as RH increases above 50%. Comparing the friction data with the attenuated total reflection infrared (ATR-IR) spectroscopy analysis result of the adsorbed water layer, it appeared that the solidlike water layer structure formed on the silica surface plays a critical role in friction at RH < 50% and its contribution diminishes at RH ≥ 50%. These findings give a deeper insight into the role of water condensation in friction of the silicon oxide single asperity contact under ambient conditions.

Investigate the complex process in particle-fluid based surface generation technology using reactive molecular dynamics method

NASA Astrophysics Data System (ADS)

Han, Xuesong; Li, Haiyan; Zhao, Fu

2017-07-01

Particle-fluid based surface generation process has already become one of the most important materials processing technology for many advanced materials such as optical crystal, ceramics and so on. Most of the particle-fluid based surface generation technology involves two key process: chemical reaction which is responsible for surface softening; physical behavior which is responsible for materials removal/deformation. Presently, researchers cannot give a reasonable explanation about the complex process in the particle-fluid based surface generation technology because of the small temporal-spatial scale and the concurrent influence of physical-chemical process. Molecular dynamics (MD) method has already been proved to be a promising approach for constructing effective model of atomic scale phenomenon and can serve as a predicting simulation tool in analyzing the complex surface generation mechanism and is employed in this research to study the essence of surface generation. The deformation and piles of water molecule is induced with the feeding of abrasive particle which justifies the property mutation of water at nanometer scale. There are little silica molecule aggregation or materials removal because the water-layer greatly reduce the strength of mechanical interaction between particle and materials surface and minimize the stress concentration. Furthermore, chemical effect is also observed at the interface: stable chemical bond is generated between water and silica which lead to the formation of silconl and the reaction rate changes with the amount of water molecules in the local environment. Novel ring structure is observed in the silica surface and it is justified to be favored of chemical reaction with water molecule. The siloxane bond formation process quickly strengthened across the interface with the feeding of abrasive particle because of the compressive stress resulted by the impacting behavior.

Fluorescent proteins as efficient tools for evaluating the surface PEGylation of silica nanoparticles

NASA Astrophysics Data System (ADS)

Zhang, Wei; Ma, Minyan; Zhang, Xiao-ai; Zhang, Ze-yu; Saleh, Sayed M.; Wang, Xu-dong

2017-06-01

Surface PEGylation is essential for preventing non-specific binding of biomolecules when silica nanoparticles are utilized for in vivo applications. Methods for installing poly(ethylene glycol) on a silica surface have been widely explored but varies from study to study. Because there is a lack of a satisfactory method for evaluating the properties of silica surface after PEGylation, the prepared nanoparticles are not fully characterized before use. In some cases, even non-PEGylated silica nanoparticles were produced, which is unfortunately not recognized by the end-user. In this work, a fluorescent protein was employed, which acts as a sensitive material for evaluating the surface protein adsorption properties of silica nanoparticles. Eleven different methods were systematically investigated for their reaction efficiency towards surface PEGylation. Results showed that both reaction conditions (including pH, catalyst) and surface functional groups of parent silica nanoparticles play critical roles in producing fully PEGylated silica nanoparticles. Great care needs to be taken in choosing the proper coupling chemistry for surface PEGylation. The data and method shown here will guarantee high-quality PEGylated silica nanoparticles to be produced and guide their applications in biology, chemistry, industry and medicine.

Experimental performance of an ablative material as an external insulator for a hypersonic research aircraft

NASA Technical Reports Server (NTRS)

Puster, R. L.; Chapman, A. J.

1977-01-01

An ablative material composed of silica-filled elastomeric silicone was tested to evaluate its thermal and structural performance as an external insulator, or heat shield, for a hypersonic research aircraft. The material was also tested to determine whether it would form a durable char layer when initially heated and thereafter function primarily as an insulator with little further pyrolysis or char removal. Aerothermal tests were representative of nominal Mach 6 cruise conditions of the aircraft, and additional tests were representative of Mach 8 cruise and interference heating conditions. Radiant heating tests were used to simulate the complete nominal Mach 6 surface-temperature history. The silica char that formed during aerothermal tests was not durable. The char experienced a general and preferential surface recession, with the primary mechanism for char removal being erosion. Tests revealed that radiant heating is not a valid technique for simulating aerodynamic heating of the material.

Unraveling the Molecular Weight Dependence of Interfacial Interactions in Poly(2-vinylpyridine)/Silica Nanocomposites

DOE PAGES

Voylov, Dmitry N.; Holt, Adam P.; Doughty, Benjamin; ...

2017-01-10

In this paper, the structure and polymer–nanoparticle interactions among physically adsorbed poly(2-vinylpyridine) chains on the surface of silica nanoparticles (NPs) were systematically studied as a function of molecular weight (MW) by sum frequency generation (SFG) and X-ray photoelectron (XPS) spectroscopies. Analysis of XPS data identified hydrogen bonds between the polymer and NPs, while SFG evaluated the change in the number of free OH sites on the NP’s surface. Our data revealed that the hydrogen bonds and amount of the free ¯OH sites have a significant dependence on the polymer’s MW. Finally, these results provide clear experimental evidence that the interactionmore » of physically adsorbed chains with nanoparticles is strongly MW dependent and aids in unraveling the microscopic mechanism responsible for the strong MW dependence of dynamics of the interfacial layer in polymer nanocomposites.« less

Unraveling the Molecular Weight Dependence of Interfacial Interactions in Poly(2-vinylpyridine)/Silica Nanocomposites

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

Voylov, Dmitry N.; Holt, Adam P.; Doughty, Benjamin

In this paper, the structure and polymer–nanoparticle interactions among physically adsorbed poly(2-vinylpyridine) chains on the surface of silica nanoparticles (NPs) were systematically studied as a function of molecular weight (MW) by sum frequency generation (SFG) and X-ray photoelectron (XPS) spectroscopies. Analysis of XPS data identified hydrogen bonds between the polymer and NPs, while SFG evaluated the change in the number of free OH sites on the NP’s surface. Our data revealed that the hydrogen bonds and amount of the free ¯OH sites have a significant dependence on the polymer’s MW. Finally, these results provide clear experimental evidence that the interactionmore » of physically adsorbed chains with nanoparticles is strongly MW dependent and aids in unraveling the microscopic mechanism responsible for the strong MW dependence of dynamics of the interfacial layer in polymer nanocomposites.« less

Iron oxide nanoparticle layer templated by polydopamine spheres: a novel scaffold toward hollow-mesoporous magnetic nanoreactors

NASA Astrophysics Data System (ADS)

Huang, Liang; Ao, Lijiao; Xie, Xiaobin; Gao, Guanhui; Foda, Mohamed F.; Su, Wu

2014-12-01

Superparamagnetic iron oxide nanoparticle layers with high packing density and controlled thickness were in situ deposited on metal-affinity organic templates (polydopamine spheres), via one-pot thermal decomposition. The as synthesized hybrid structure served as a facile nano-scaffold toward hollow-mesoporous magnetic carriers, through surfactant-assisted silica encapsulation and its subsequent calcination. Confined but accessible gold nanoparticles were successfully incorporated into these carriers to form a recyclable catalyst, showing quick magnetic response and a large surface area (642.5 m2 g-1). Current nano-reactors exhibit excellent catalytic performance and high stability in reduction of 4-nitrophenol, together with convenient magnetic separability and good reusability. The integration of compact iron oxide nanoparticle layers with programmable polydopamine templates paves the way to fabricate magnetic-response hollow structures, with high permeability and multi-functionality.Superparamagnetic iron oxide nanoparticle layers with high packing density and controlled thickness were in situ deposited on metal-affinity organic templates (polydopamine spheres), via one-pot thermal decomposition. The as synthesized hybrid structure served as a facile nano-scaffold toward hollow-mesoporous magnetic carriers, through surfactant-assisted silica encapsulation and its subsequent calcination. Confined but accessible gold nanoparticles were successfully incorporated into these carriers to form a recyclable catalyst, showing quick magnetic response and a large surface area (642.5 m2 g-1). Current nano-reactors exhibit excellent catalytic performance and high stability in reduction of 4-nitrophenol, together with convenient magnetic separability and good reusability. The integration of compact iron oxide nanoparticle layers with programmable polydopamine templates paves the way to fabricate magnetic-response hollow structures, with high permeability and multi-functionality. Electronic supplementary information (ESI) available: Fig. S1-S5. See DOI: 10.1039/c4nr05931j

Porous SiO2 nanofiber grafted novel bioactive glass-ceramic coating: A structural scaffold for uniform apatite precipitation and oriented cell proliferation on inert implant.

PubMed

Das, Indranee; De, Goutam; Hupa, Leena; Vallittu, Pekka K

2016-05-01

A composite bioactive glass-ceramic coating grafted with porous silica nanofibers was fabricated on inert glass to provide a structural scaffold favoring uniform apatite precipitation and oriented cell proliferation. The coating surfaces were investigated thoroughly before and after immersion in simulated body fluid. In addition, the proliferation behavior of fibroblast cells on the surface was observed for several culture times. The nanofibrous exterior of this composite bioactive coating facilitated homogeneous growth of flake-like carbonated hydroxyapatite layer within a short period of immersion. Moreover, the embedded porous silica nanofibers enhanced hydrophilicity which is required for proper cell adhesion on the surface. The cells proliferated well following a particular orientation on the entire coating by the assistance of nanofibrous scaffold-like structural matrix. This newly engineered composite coating was effective in creating a biological structural matrix favorable for homogeneous precipitation of calcium phosphate, and organized cell growth on the inert glass surface. Copyright © 2016 Elsevier B.V. All rights reserved.

Evanescent wave cavity ring-down spectroscopy (EW-CRDS) as a probe of macromolecule adsorption kinetics at functionalized interfaces.

PubMed

O'Connell, Michael A; de Cuendias, Anne; Gayet, Florence; Shirley, Ian M; Mackenzie, Stuart R; Haddleton, David M; Unwin, Patrick R

2012-05-01

Evanescent wave cavity ring-down spectroscopy (EW-CRDS) has been employed to study the interfacial adsorption kinetics of coumarin-tagged macromolecules onto a range of functionalized planar surfaces. Such studies are valuable in designing polymers for complex systems where the degree of interaction between the polymer and surface needs to be tailored. Three tagged synthetic polymers with different functionalities are examined: poly(acrylic acid) (PAA), poly(3-sulfopropyl methacrylate, potassium salt) (PSPMA), and a mannose-modified glycopolymer. Adsorption transients at the silica/water interface are found to be characteristic for each polymer, and kinetics are deduced from the initial rates. The chemistry of the adsorption interfaces has been varied by, first, manipulation of silica surface chemistry via the bulk pH, followed by surfaces modified by poly(L-glutamic acid) (PGA) and cellulose, giving five chemically different surfaces. Complementary atomic force microscopy (AFM) imaging has been used for additional surface characterization of adsorbed layers and functionalized interfaces to allow adsorption rates to be interpreted more fully. Adsorption rates for PSPMA and the glycopolymer are seen to be highly surface sensitive, with significantly higher rates on cellulose-modified surfaces, whereas PAA shows a much smaller rate dependence on the nature of the adsorption surface.

Surface-Initiated Polymerization with Poly(n-hexylisocyanate) to Covalently Functionalize Silica Nanoparticles.

PubMed

Vatansever, Fatma; Hamblin, Michael R

2017-02-01

New methods are needed for covalent functionalization of nanoparticles-surface with organic polymer coronas to generate polymeric nanocomposite in a controlled manner. Here we report the use of a surface-initiated polymerization approach, mediated by titanium (IV) catalysis, to grow poly( n -hexylisocyanate) chains from silica surface. Two pathways were used to generate the interfacing in these nano-hybrids. In the first one, the nanoparticles was "seeded" with SiCl4, followed by reaction with 1,6-hexanediol to form hydroxyl groups attached directly to the surface via O-Si-O bonding. In the second pathway, the nanoparticles were initially exposed to a 9:1 mixture of trimethyl silyl chloride and chlorodimethyl octenyl silane which was then followed by hydroboration of the double bonds, to afford hydroxyl groups with a spatially controlled density and surface-attachment via O-Si-C bonding. These functionalized surfaces were then activated with the titanium tetrachloride catalyst. In our approach, thus surface tethered catalyst provided the sites for n -hexyl isocyanate monomer insertion, to "build up" the surface-grown polymer layers from the "bottom-up". A final end-capping, to seal off the chain ends, was done via acetyl chloride. Compounds were characterized by FT-IR, 1H-NMR, GC-MS, GPC, and thermogravimetric analyses.

Surface-Initiated Polymerization with Poly(n-hexylisocyanate) to Covalently Functionalize Silica Nanoparticles

PubMed Central

Vatansever, Fatma; Hamblin, Michael R.

2017-01-01

New methods are needed for covalent functionalization of nanoparticles-surface with organic polymer coronas to generate polymeric nanocomposite in a controlled manner. Here we report the use of a surface-initiated polymerization approach, mediated by titanium (IV) catalysis, to grow poly(n-hexylisocyanate) chains from silica surface. Two pathways were used to generate the interfacing in these nano-hybrids. In the first one, the nanoparticles was “seeded” with SiCl4, followed by reaction with 1,6-hexanediol to form hydroxyl groups attached directly to the surface via O-Si-O bonding. In the second pathway, the nanoparticles were initially exposed to a 9:1 mixture of trimethyl silyl chloride and chlorodimethyl octenyl silane which was then followed by hydroboration of the double bonds, to afford hydroxyl groups with a spatially controlled density and surface-attachment via O-Si-C bonding. These functionalized surfaces were then activated with the titanium tetrachloride catalyst. In our approach, thus surface tethered catalyst provided the sites for n-hexyl isocyanate monomer insertion, to “build up” the surface-grown polymer layers from the “bottom-up”. A final end-capping, to seal off the chain ends, was done via acetyl chloride. Compounds were characterized by FT-IR, 1H-NMR, GC-MS, GPC, and thermogravimetric analyses. PMID:28989336

Effect of Er,Cr:YSGG laser, air abrasion, and silane application on repaired shear bond strength of composites.

PubMed

Cho, S D; Rajitrangson, P; Matis, B A; Platt, J A

2013-01-01

Aged resin composites have a limited number of carbon-carbon double bonds to adhere to a new layer of resin. Study objectives were to 1) evaluate various surface treatments on repaired shear bond strength between aged and new resin composites and 2) to assess the influence of a silane coupling agent after surface treatments. Eighty disk-shape resin composite specimens were fabricated and thermocycled 5000 times prior to surface treatment. Specimens were randomly assigned to one of the three surface treatment groups (n=20): 1) air abrasion with 50-μm aluminum oxide, 2) tribochemical silica coating (CoJet), or 3) Er,Cr:YSGG (erbium, chromium: yttrium-scandium-gallium-garnet) laser or to a no-treatment control group (n=20). Specimens were etched with 35% phosphoric acid, rinsed, and dried. Each group was divided into two subgroups (n=10): A) no silanization and B) with silanization. The adhesive agent was applied and new resin composite was bonded to each conditioned surface. Shear bond strength was evaluated and data analyzed using two-way analysis of variance (ANOVA). Air abrasion with 50-μm aluminum oxide showed significantly higher repair bond strength than the Er,Cr:YSGG laser and control groups. Air abrasion with 50-μm aluminum oxide was not significantly different from tribochemical silica coating. Tribochemical silica coating had significantly higher repair bond strength than Er,Cr:YSGG laser and the control. Er,Cr:YSGG laser and the control did not have significantly different repair bond strengths. Silanization had no influence on repair bond strength for any of the surface treatment methods. Air abrasion with 50-μm aluminum oxide and tribochemical silica followed by the application of bonding agent provided the highest repair shear bond strength values, suggesting that they might be adequate methods to improve the quality of repairs of resin composites.

Supercritical Fluid Atomic Layer Deposition: Base-Catalyzed Deposition of SiO2.

PubMed

Kalan, Roghi E; McCool, Benjamin A; Tripp, Carl P

2016-07-19

An in situ FTIR thin film technique was used to study the sequential atomic layer deposition (ALD) reactions of SiCl4, tetraethyl orthosilicate (TEOS) precursors, and water on nonporous silica powder using supercritical CO2 (sc-CO2) as the solvent. The IR work on nonporous powders was used to identify the reaction sequence for using a sc-CO2-based ALD to tune the pore size of a mesoporous silica. The IR studies showed that only trace adsorption of SiCl4 occurred on the silica, and this was due to the desiccating power of sc-CO2 to remove the adsorbed water from the surface. This was overcome by employing a three-step reaction scheme involving a first step of adsorption of triethylamine (TEA), followed by SiCl4 and then H2O. For TEOS, a three-step reaction sequence using TEA, TEOS, and then water offered no advantage, as the TEOS simply displaced the TEA from the silica surface. A two-step reaction involving the addition of TEOS followed by H2O in a second step did lead to silica film growth. However, higher growth rates were obtained when using a mixture of TEOS/TEA in the first step. The hydrolysis of the adsorbed TEOS was also much slower than that of the adsorbed SiCl4, and this was overcome by using a mixture of water/TEA during the second step. While the three-step process with SiCl4 showed a higher linear growth rate than obtained with two-step process using TEOS/TEA, its use was not practical, as the HCl generated led to corrosion of our sc-CO2 delivery system. However, when applying the two-step ALD reaction using TEOS on an MCM-41 powder, a 0.21 nm decrease in pore diameter was obtained after the first ALD cycle whereas further ALD cycles did not lead to further pore size reduction. This was attributed to the difficulty in removal of the H2O in the pores after the first cycle.

Materials based on carbon-filled porous layers of PVC cyclam derivatives cross-linked with the surfaces of asbestos fabric fibers

NASA Astrophysics Data System (ADS)

Tzivadze, A. Yu.; Fridman, A. Ya.; Morozova, E. M.; Sokolova, N. P.; Voloshchuk, A. M.; Petukhova, G. A.; Bardishev, I. I.; Gorbunov, A. M.; Novikov, A. K.; Polyakova, I. Ya.; Titova, V. N.; Yavich, A. A.; Petrova, N. V.

2016-08-01

The synthesis of bilayer materials with porous upper layers composed of PVC hydroxyethylcyclam derivatives filled with carbon and a layer consisting of hydroxyethylcyclam, cross-linked via Si-O-C groups with the silica chains of a developed surface of asbestos fabric, is described. The aza-crown groups in these materials are bound with aqua complexes of H2SO4 or NaOH. The structure of the materials is examined, their adsorption characteristics are determined, and the rate of motion of H+ or OH- ions in electrochemical bridges is measured, while the formation of H2 and O2 in their cathodic and anodic polarization is determined as a function of voltage. It is shown that the upper layer of these materials is adsorption-active and electronand H+- or OH-- conductive, while the bottom layer is only H+- or OH-- conductive; through it, the upper layer is supplied with the H+ or OH- ions needed for the regeneration of the aqua complexes broken down to H2 and O2 on carbon particles.

Enzyme Armoring by an Organosilica Layer: Synthesis and Characterization of Hybrid Organic/Inorganic Nanobiocatalysts.

PubMed

Correro, M Rita; Sykora, Sabine; Corvini, Philippe F-X; Shahgaldian, Patrick

2017-01-01

The availability of highly stable and reusable enzymes is one of the main challenges in bio-based industrial processes. Enzyme immobilization and encapsulation represent promising strategies to reach this goal. In this chapter, the synthetic strategy to produce hybrid organic/inorganic nanobiocatalysts (NBC) is reported. This strategy is based on the sequential immobilization of an enzyme on the surface of silica nanoparticles followed by the growth, at the surface of the nanoparticles, of a shielding layer which serves as an armor to protect the enzyme against denaturation/degradation. This armor is produced through a thickness-controlled organosilane poly-condensation onto the nanoparticle surface around the enzyme to form a protective organosilica layer. The armored nanobiocatalysts present enhanced catalytic activity and improved stability against heat, pH, chaotropic agents, proteases, and ultrasound. The method is versatile in that it can be successfully adapted to a number of different enzymes. © 2017 Elsevier Inc. All rights reserved.

Influence of subsurface defects on damage performance of fused silica in ultraviolet laser

NASA Astrophysics Data System (ADS)

Huang, Jin; Zhou, Xinda; Liu, Hongjie; Wang, Fengrui; Jiang, Xiaodong; Wu, Weidong; Tang, Yongjian; Zheng, Wanguo

2013-02-01

In ultraviolet pulse laser, damage performance of fused silica optics is directly dependent on the absorptive impurities and scratches in subsurface, which are induced by mechanical polishing. In the research about influence of subsurface defects on damage performance, a series of fused silica surfaces with various impurity concentrations and scratch structures were created by hydrofluoric (HF) acid solution etching. Time of Flight secondary ion mass spectrometry and scanning probe microprobe revealed that with increasing etching depth, impurity concentrations in subsurface layers are decreased, the scratch structures become smoother and the diameter:depth ratio is increased. Damage performance test with 355-nm pulse laser showed that when 600 nm subsurface thickness is removed by HF acid etching, laser-induced damage threshold of fused silica is raised by 40 percent and damage density is decreased by over one order of magnitude. Laser weak absorption was tested to explain the cause of impurity elements impacting damage performance, field enhancement caused by change of scratch structures was calculated by finite difference time domain simulation, and the calculated results are in accord with the damage test results.

Engineered silica nanoparticles as additives in lubricant oils

PubMed Central

López, Teresa Díaz-Faes; González, Alfonso Fernández; Del Reguero, Ángel; Matos, María; Díaz-García, Marta E; Badía-Laíño, Rosana

2015-01-01

Silica nanoparticles (SiO2 NPs) synthesized by the sol–gel approach were engineered for size and surface properties by grafting hydrophobic chains to prevent their aggregation and facilitate their contact with the phase boundary, thus improving their dispersibility in lubricant base oils. The surface modification was performed by covalent binding of long chain alkyl functionalities using lauric acid and decanoyl chloride to the SiO2 NP surface. The hybrid SiO2 NPs were characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, simultaneous differential thermal analysis, nuclear magnetic resonance and dynamic light scattering, while their dispersion in two base oils was studied by static multiple light scattering at low (0.01% w/v) and high (0.50%w/v) concentrations. The nature of the functional layer and the functionalization degree seemed to be directly involved in the stability of the suspensions. The potential use of the functional SiO2 NPs as lubricant additives in base oils, specially designed for being used in hydraulic circuits, has been outlined by analyzing the tribological properties of the dispersions. The dendritic structure of the external layer played a key role in the tribological characteristics of the material by reducing the friction coefficient and wear. These nanoparticles reduce drastically the waste of energy in friction processes and are more environmentally friendly than other additives. PMID:27877840

Numerical modelling on stimulated Brillouin scattering characterization for Graphene-clad tapered silica fiber

NASA Astrophysics Data System (ADS)

Lee, Hui Jing; Abdullah, Fairuz; Ismail, Aiman

2017-11-01

This paper presents finite numerical modelling on the cross-sectional region of tapered single mode fiber and graphene-clad tapered fiber. Surface acoustic wave propagation across the tapered surface region on tapered single mode fiber has a high threshold power at 61.87 W which is challenging to overcome by the incident pump wave. Surface acoustic wave propagation of fiber surface however made tapered wave plausible in the optical sensor application. This research introduces graphene as the cladding layer on tapered fiber, acoustic confinement occurs due to the graphene cladding which lowers the threshold power from 61.87 W to 2.17 W.

Evanescent fields of laser written waveguides

NASA Astrophysics Data System (ADS)

Jukić, Dario; Pohl, Thomas; Götte, Jörg B.

2015-03-01

We investigate the evanescent field at the surface of laser written waveguides. The waveguides are written by a direct femtosecond laser writing process into fused silica, which is then sanded down to expose the guiding layer. These waveguides support eigenmodes which have an evanescent field reaching into the vacuum above the waveguide. We study the governing wave equations and present solution for the fundamental eigenmodes of the modified waveguides.

Fabrication and characterization of epoxy/silica functionally graded composite material

NASA Astrophysics Data System (ADS)

Misra, N.; Kapusetti, G.; Pattanayak, D. K.; Kumar, A.

2011-09-01

Increased use of composites in aerospace and defense application induces the search for heat resistant material. In present study silica reinforced epoxy functionally graded material using quartz fabric is prepared with different thickness. The gradation in silica : epoxy matrix is maintained with one side pure epoxy to opposite side pure silica. Thermal and mechanical behaviour of the composites were studied. It was found that the temperature gradient of 350°C to 950°C could be maintained for 2 to 5 min if the thickness of insulating silica layer is increased from 0.5 mm to 16 mm. Mechanical properties such as flexural modulus and strength of FGM composites were also evaluated. Strength and modulus decreased with increase of insulating layer.

A silver nanoislands on silica spheres platform: enriching trace amounts of analytes for ultrasensitive and reproducible SERS detection.

PubMed

Wang, Zhongshun; Feng, Lei; Xiao, Dongyang; Li, Ning; Li, Yao; Cao, Danfeng; Shi, Zuosen; Cui, Zhanchen; Lu, Nan

2017-11-09

The performance of surface-enhanced Raman scattering (SERS) for detecting trace amounts of analytes depends highly on the enrichment of the diluted analytes into a small region that can be detected. A super-hydrophobic delivery (SHD) process is an excellent process to enrich even femtomolar analytes for SERS detection. However, it is still challenging to easily fabricate a low detection limit, high sensitivity and reproducible SHD-SERS substrate. In this article, we present a cost-effective and fewer-step method to fabricate a SHD-SERS substrate, named the "silver nanoislands on silica spheres" (SNOSS) platform. It is easily prepared via the thermal evaporation of silver onto a layer of super-hydrophobic paint, which contains single-scale surface-fluorinated silica spheres. The SNOSS platform performs reproducible detection, which brings the relative standard deviation down to 8.85% and 5.63% for detecting 10 -8 M R6G in one spot and spot-to-spot set-ups, respectively. The coefficient of determination (R 2 ) is 0.9773 for R6G. The SNOSS platform can be applied to the quantitative detection of analytes whose concentrations range from sub-micromolar to femtomolar levels.

Molecular Dynamics Simulations of Poly(ethylene oxide) Grafted onto Silica Immersed in Melt of Homopolymers.

PubMed

Benková, Zuzana; Cordeiro, M Natália D S

2015-09-22

Tuning of surface properties plays an important role in applications ranging from material engineering to biomedicine/chemistry. The interactions of chains grafted to a solid support and exposed to a matrix of chemically identical chains represent an intriguing issue. In this work, the behavior of poly(ethylene oxide) (PEO) chains grafted irreversibly onto an amorphous silica and immersed in the matrix of free PEO chains of different polymerization degree is studied using molecular dynamics simulations. The density distributions of grafted and free PEO chains, the height of the grafted layer, overlap parameters, and orientation order parameters depend not only on the grafting density but also on the length of free chains which confirm the entropic nature of the interactions between the grafted and free chains. In order to achieve a complete expulsion of the free chains from the grafted layer, a grafting density as high as 3.5 nm(-2) is necessary. Free PEO chains of 9 monomers leave the grafted layer at lower grafting densities than the longer PEO chains of 18 monomers in contrast with the theoretical predictions. The height of the grafted layer evolves with the grafting density in the presence of free chains in qualitative agreement with the theoretical phase diagram.

Defect prevention in silica thin films synthesized using AP-PECVD for flexible electronic encapsulation

NASA Astrophysics Data System (ADS)

Elam, Fiona M.; Starostin, Sergey A.; Meshkova, Anna S.; van der Velden-Schuermans, Bernadette C. A. M.; van de Sanden, Mauritius C. M.; de Vries, Hindrik W.

2017-06-01

Industrially and commercially relevant roll-to-roll atmospheric pressure-plasma enhanced chemical vapour deposition was used to synthesize smooth, 80 nm silica-like bilayer thin films comprising a dense ‘barrier layer’ and comparatively porous ‘buffer layer’ onto a flexible polyethylene 2,6 naphthalate substrate. For both layers, tetraethyl orthosilicate was used as the precursor gas, together with a mixture of nitrogen, oxygen and argon. The bilayer films demonstrated exceptionally low effective water vapour transmission rates in the region of 6.1  ×  10-4 g m-2 d-1 (at 40 °C, 90% relative humidity), thus capable of protecting flexible photovoltaics and thin film transistors from degradation caused by oxygen and water. The presence of the buffer layer within the bilayer architecture was mandatory in order to achieve the excellent encapsulation performance. Atomic force microscopy in addition to solvent permeation measurements, confirmed that the buffer layer prevented the formation of performance-limiting defects in the bilayer thin films, which likely occur as a result of excessive plasma-surface interactions during the deposition process. It emerged that the primary function of the buffer layer was therefore to act as a protective coating for the flexible polymer substrate material.

Amorphous Silica-Promoted Lysine Dimerization: a Thermodynamic Prediction

NASA Astrophysics Data System (ADS)

Kitadai, Norio; Nishiuchi, Kumiko; Nishii, Akari; Fukushi, Keisuke

2018-03-01

It has long been suggested that mineral surfaces played a crucial role in the abiotic polymerization of amino acids that preceded the origin of life. Nevertheless, it remains unclear where the prebiotic process took place on the primitive Earth, because the amino acid-mineral interaction and its dependence on environmental conditions have yet to be understood adequately. Here we examined experimentally the adsorption of L-lysine (Lys) and its dimer (LysLys) on amorphous silica over a wide range of pH, ionic strength, adsorbate concentration, and the solid/water ratio, and determined the reaction stoichiometries and the equilibrium constants based on the extended triple-layer model (ETLM). The retrieved ETLM parameters were then used, in combination with the equilibrium constant for the peptide bond formation in bulk water, to calculate the Lys-LysLys equilibrium in the presence of amorphous silica under various aqueous conditions. Results showed that the silica surface favors Lys dimerization, and the influence varies greatly with changing environmental parameters. At slightly alkaline pH (pH 9) in the presence of a dilute NaCl (1 mM), the thermodynamically attainable LysLys from 0.1 mM Lys reached a concentration around 50 times larger than that calculated without silica. Because of the versatility of the ETLM, which has been applied to describe a wide variety of biomolecule-mineral interactions, future experiments with the reported methodology are expected to provide a significant constraint on the plausible geological settings for the condensation of monomers to polymers, and the subsequent chemical evolution of life.

Nanoscale Roughness and Morphology Affect the IsoElectric Point of Titania Surfaces

PubMed Central

Borghi, Francesca; Vyas, Varun; Podestà, Alessandro; Milani, Paolo

2013-01-01

We report on the systematic investigation of the role of surface nanoscale roughness and morphology on the charging behaviour of nanostructured titania (TiO2) surfaces in aqueous solutions. IsoElectric Points (IEPs) of surfaces have been characterized by direct measurement of the electrostatic double layer interactions between titania surfaces and the micrometer-sized spherical silica probe of an atomic force microscope in NaCl aqueous electrolyte. The use of a colloidal probe provides well-defined interaction geometry and allows effectively probing the overall effect of nanoscale morphology. By using supersonic cluster beam deposition to fabricate nanostructured titania films, we achieved a quantitative control over the surface morphological parameters. We performed a systematical exploration of the electrical double layer properties in different interaction regimes characterized by different ratios of characteristic nanometric lengths of the system: the surface rms roughness Rq, the correlation length ξ and the Debye length λD. We observed a remarkable reduction by several pH units of IEP on rough nanostructured surfaces, with respect to flat crystalline rutile TiO2. In order to explain the observed behavior of IEP, we consider the roughness-induced self-overlap of the electrical double layers as a potential source of deviation from the trend expected for flat surfaces. PMID:23874708

Polymer-Silica Nanocomposites: A Versatile Platform for Multifunctional Materials

NASA Astrophysics Data System (ADS)

Chiu, Chi-Kai

Solution sol-gel synthesis is a versatile approach to create polymer-silica nanocomposite materials. The solution-to-solid transformation results in a solid consisting of interconnected nanoporous structure in 3D space, making it the ideal material for filtration, encapsulation, optics, electronics, drug release, and biomaterials, etc. Although the pore between nano and meso size may be tunable using different reaction conditions, the intrinsic properties such as limited diffusion within pore structure, complicated interfacial interactions at the pore surfaces, shrinkage and stress-induced cracking and brittleness have limited the applications of this material. To overcome these problems, diffusion, pore size, shrinkage and stress-induced defects need further investigation. Thus, the presented thesis will address these important questions such as whether these limitations can be utilized as the novel method to create new materials and lead to new applications. First, the behaviors of polymers such as poly(ethylene glycol) inside the silica pores are examined by studying the nucleation and growth of AgCl at the surface of the porous matrix. The pore structure and the pressure induced by the shrinkage affect have been found to induce the growth of AgCl nanocrystals. When the same process is carried out at 160 °C, silver metallization is possible. Due to the shrinkage-induced stresses, the polymer tends to move into open crack spaces and exterior surfaces, forming interconnected silver structure. This interconnected silver structure is very unique because its density is not related to the size scale of nanopore structures. These findings suggest that it is possible to utilize defect surface of silica material as the template to create interconnected silver structure. When the scale is small, polymer may no longer be needed if the diffusion length of Ag is more than the size of silica particles. To validate our assumption, monoliths of sol-gel sample containing AgNO3 was ground into two different sizes of powder followed by powder pressing, heat-treating and etching. A new robust porous silver foam was then successfully made. By combining the results from room temperature and high temperature processes, we further study the patterned silver nanoparticles arrays in order to examine how mobility of silver can be controlled on a quantifiable scale. Furthermore, we have identified a thiolcontaining sol-gel precursor to control the affinity between silver and silica matrix. Lastly, the effects of interfacial interactions between sol-gel silica and other nanocomposite components and the effect of thickness of the sol-gel layer on mechanical properties were investigated. These studies were applied to the biomimetic hydroxyapatite-gelatin system. We have found that by limiting the thickness while maintaining interfacial interactions of the sol-gel layer, a unique moldable property and short hardening time from these nanocomposites can be achieved without compromising its biocompatibility. Their biocompatibility has been proven based on the in vitro and in vivo testing of these materials. In conclusion, the present study has demonstrated that polymer-silica nanocomposite is a versatile platform to carry out applications in nanocrystal growth, nanoporous metals, metal-ceramic composites, nano-imprint thin film, and bone grafts. These important findings not only provide new insights into nanocomposites but also give new meanings to the previously functional-limited sol-gel materials.

Rapid vapor deposition of highly conformal silica nanolaminates.

PubMed

Hausmann, Dennis; Becker, Jill; Wang, Shenglong; Gordon, Roy G

2002-10-11

Highly uniform and conformal coatings can be made by the alternating exposures of a surface to vapors of two reactants, in a process commonly called atomic layer deposition (ALD). The application of ALD has, however, been limited because of slow deposition rates, with a theoretical maximum of one monolayer per cycle. We show that alternating exposure of a surface to vapors of trimethylaluminum and tris(tert-butoxy)silanol deposits highly conformal layers of amorphous silicon dioxide and aluminum oxide nanolaminates at rates of 12 nanometers (more than 32 monolayers) per cycle. This process allows for the uniform lining or filling of long, narrow holes. We propose that these ALD layers grow by a previously unknown catalytic mechanism that also operates during the rapid ALD of many other metal silicates. This process should allow improved production of many devices, such as trench insulation between transistors in microelectronics, planar waveguides, microelectromechanical structures, multilayer optical filters, and protective layers against diffusion, oxidation, or corrosion.

In vitro effects of cisplatin-functionalized silica nanoparticles on chondrocytes

NASA Astrophysics Data System (ADS)

Bhowmick, Tridib Kumar; Yoon, Diana; Patel, Minal; Fisher, John; Ehrman, Sheryl

2010-10-01

In this study, we evaluated the combined effect of a known toxic molecule, cisplatin, in combination with relatively nontoxic nanoparticles, amorphous fumed silica, on chondrocyte cells. Cisplatin was attached to silica nanoparticles using aminopropyltriethoxy silane as a linker molecule, and characterized in terms of size, shape, specific surface area, as well as the dissolution of cisplatin from the silica surface. The primary particle diameter of the as-received silica nanoparticles ranged from 7.1 to 61 nm, estimated from measurements of specific surface area, and the primary particles were aggregated. The effects of cisplatin-functionalized silica particles with different specific surface areas (41, 85, 202, 237, and 297 m2/g) were compared in vitro on chondrocytes, the parenchymal cell of hyaline cartilage. The results show that adverse effects on cell function, as evidenced by reduced metabolic activity measured by the MTT assay and increased membrane permeability observed using the Live/Dead stain, can be correlated with specific surface area of the silica. Cisplatin-functionalized silica nanoparticles with the highest specific surface area incited the greatest response, which was almost equivalent to that induced by free cisplatin. This result suggests the importance of particle specific surface area in interactions between cells and surface-functionalized nanomaterials.

Water Contact Angle Dependence with Hydroxyl Functional Groups on Silica Surfaces under CO2 Sequestration Conditions.

PubMed

Chen, Cong; Zhang, Ning; Li, Weizhong; Song, Yongchen

2015-12-15

Functional groups on silica surfaces under CO2 sequestration conditions are complex due to reactions among supercritical CO2, brine and silica. Molecular dynamics simulations have been performed to investigate the effects of hydroxyl functional groups on wettability. It has been found that wettability shows a strong dependence on functional groups on silica surfaces: silanol number density, space distribution, and deprotonation/protonation degree. For neutral silica surfaces with crystalline structure (Q(3), Q(3)/Q(4), Q(4)), as silanol number density decreases, contact angle increases from 33.5° to 146.7° at 10.5 MPa and 318 K. When Q(3) surface changes to an amorphous structure, water contact angle increases 20°. Water contact angle decreases about 12° when 9% of silanol groups on Q(3) surface are deprotonated. When the deprotonation degree increases to 50%, water contact angle decreases to 0. The dependence of wettability on silica surface functional groups was used to analyze contact angle measurement ambiguity in literature. The composition of silica surfaces is complicated under CO2 sequestration conditions, the results found in this study may help to better understand wettability of CO2/brine/silica system.

Hematite/silica nanoparticle bilayers on mica: AFM and electrokinetic characterization.

PubMed

Morga, Maria; Adamczyk, Zbigniew; Kosior, Dominik; Oćwieja, Magdalena

2018-06-06

Quantitative studies on self-assembled hematite/silica nanoparticle (NP) bilayers on mica were performed by applying scanning electron microscopy (SEM), atomic force microscopy (AFM), and streaming potential measurements. The coverage of the supporting hematite layers was adjusted by changing the bulk concentration of the suspension and the deposition time. The coverage was determined by direct enumeration of deposited particles from AFM images and SEM micrographs. Afterward, silica nanoparticle monolayers were assembled under diffusion-controlled transport. A unique functional relationship was derived connecting the silica coverage with the hematite precursor layer coverage. The formation of the hematite monolayer and the hematite/silica bilayer was also monitored in situ by streaming potential measurements. It was confirmed that the zeta potential of the bilayers was independent of the supporting layer coverage, exceeding 0.15. These measurements were theoretically interpreted in terms of the general electrokinetic model that allowed for deriving a formula for calculating nanoparticle coverage in the bilayers. Additionally, from desorption experiments, the interactions among hematite/silica particles in the bilayers were determined using DLVO theory. These results facilitate the development of a robust method of preparing nanoparticle bilayers with controlled properties, with potential applications in catalytic processes.

Incorporation of polyoxotungstate complexes in silica spheres and in situ formation of tungsten trioxide nanoparticles.

PubMed

Zhao, Yuanyuan; Fan, Haimei; Li, Wen; Bi, Lihua; Wang, Dejun; Wu, Lixin

2010-09-21

In this paper, we demonstrated a new convenient route for in situ fabrication of well separated small sized WO(3) nanoparticles in silica spheres, through a predeposition of surfactant encapsulated polyoxotungates as tungsten source, and followed by a calcination process. In a typical procedure, selected polyoxotungates with different charges were enwrapped with dioctadecyldimethylammonium cations through electrostatic interaction. Elemental analysis, thermogravimetric analysis, and spectral characterization confirmed the formation of prepared complexes with the anticipated chemical structure. The complexes were then phase-transferred into aqueous solution that predissolved surfactant cetyltrimethylammonium bromide, and finally incorporated into silica spheres through a joint sol-gel reaction with tetraethyl orthosilicate in a well dispersed state under the protection of organic layer for polyoxotungates from the alkaline reaction condition. Transmission electron microscopic images illustrated the well dispersed WO(3) nanoparticles in the size range of ca. 2.2 nm in the silica spheres after the calcination at 465 °C. The sizes of both the silica spheres and WO(3) nanoparticles could be adjusted independently through changing the doping content to a large extent. Meanwhile, the doped polyoxotungate complexes acted as the template for the mesoporous structure in silica spheres after the calcination. Along with the increase of doping content and surfactant, the mesopore size changed little (2.0-2.9 nm), but the specific surface areas increased quite a lot. Importantly, the WO(3)-nanoparticle-doped silica spheres displayed an interesting photovoltaic property, which is favorable for the funtionalization of these nanomaterials.

Adsorption and Exchange Dynamics in Aging Hydroxyethylcellulose Layers on Silica.

PubMed

Mubarekyan; Santore

2000-07-15

The adsorption kinetics of hydroxyethylcellulose (HEC) on silica and relaxations in adsorbed HEC layers were probed using total internal reflectance fluorescence and near-Brewster reflectivity. Like many random-coil polymers, HEC was found to adsorb at the transport-limited rate. Relaxations occurred at nearly constant interfacial mass when HEC layers were exposed to aqueous solvent, causing the subsequent exchange of chains between the layer and the free solution to become increasingly hindered. Eventually, on the time scale of a day, layers became immobilized and unable to accommodate chains from free solution. A continued fluorescence decay, beyond time scales that could be probed with self exchange, suggested further relaxations of the adsorbed HEC. The polydisperse HEC system (with an average molecular weight near 450,000) behaved qualitatively similar to molecular weight standard polyethylene oxide (PEO) layers on silica. For instance, relaxations in PEO layers occurred on a time scale of 10-20 h, like the HEC layers. Young layers of the latter, however, exhibited self-exchange kinetics that were an order of magnitude slower than PEO layers of similar age. This difference in adsorbed layer dynamics was attributed to HEC's stiffer backbone, compared with flexible PEO. Copyright 2000 Academic Press.

TEM and STEM Studies on the Cross-sectional Morphologies of Dual-/Tri-layer Broadband SiO2 Antireflective Films

NASA Astrophysics Data System (ADS)

Wang, Shuangyue; Yan, Hongwei; Li, Dengji; Qiao, Liang; Han, Shaobo; Yuan, Xiaodong; Liu, Wei; Xiang, Xia; Zu, Xiaotao

2018-02-01

Dual-layer and tri-layer broadband antireflective (AR) films with excellent transmittance were successfully fabricated using base-/acid-catalyzed mixed sols and propylene oxide (PO) modified silica sols. The sols and films were characterized by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), transmission electron microscope (TEM), and scanning transmission electron microscope (STEM). FTIR and TEM results suggest that the PO molecules were covalently bonded to the silica particles and the bridge structure existing in PO modified silica sol is responsible for the low density of the top layer. The density ratio between different layers was measured by cross-sectional STEM, and the results are 1.69:1 and 2.1:1.7:1 from bottom-layer to top-layer for dual-layer and tri-layer films, respectively. The dual-layer film demonstrates good stability with 99.8% at the central wavelength of 351 nm and nearly 99.5% at the central wavelength of 1053 nm in laser system, and for the tri-layer AR film, the maximum transmittance reached nearly 100% at both the central wavelengths of 527 and 1053 nm.

Batchwise growth of silica cone patterns via self-assembly of aligned nanowires.

PubMed

Luo, Shudong; Zhou, Weiya; Chu, Weiguo; Shen, Jun; Zhang, Zengxing; Liu, Lifeng; Liu, Dongfang; Xiang, Yanjuan; Ma, Wenjun; Xie, Sishen

2007-03-01

Silica-cone patterns self-assembled from well-aligned nanowires are synthesized using gallium droplets as the catalyst and silicon wafers as the silicon source. The cones form a triangular pattern array radially on almost the whole surface of the molten Ga ball. Detailed field-emission scanning electron microscopy (SEM) analysis shows that the cone-pattern pieces frequently slide off and are detached from the molten Ga ball surface, which leads to the exposure of the catalyst surface and the growth of a new batch of silicon oxide nanowires as well as the cone patterns. The processes of growth and detachment alternate, giving rise to the formation of a volcano-like or a flower-like structure with bulk-quantity pieces of cone patterns piled up around the Ga ball. Consequently, the cone-patterned layer grows batch by batch until the reaction is terminated. Different to the conventional metal-catalyzed growth model, the batch-by-batch growth of the triangular cone patterns proceeds on the molten Ga balls via alternate growth on and detachment from the catalyst surface of the patterns; the Ga droplet can be used continuously and circularly as an effective catalyst for the growth of amorphous SiO(x) nanowires during the whole growth period. The intriguing batchwise growth phenomena may enrich our understanding of the vapour-liquid-solid (VLS) growth mechanism for the catalyst growth of nanowires or other nanostructures and may offer a different way of self-assembling novel silica nanostructures.

Human Growth Hormone Adsorption Kinetics and Conformation on Self-Assembled Monolayers

PubMed Central

Buijs, Jos; Britt, David W.; Hlady, Vladimir

2012-01-01

The adsorption process of the recombinant human growth hormone on organic films, created by self-assembly of octadecyltrichlorosilane, arachidic acid, and dipalmitoylphosphatidylcholine, is investigated and compared to adsorption on silica and methylated silica substrates. Information on the adsorption process of human growth hormone (hGH) is obtained by using total internal reflection fluorescence (TIRF). The intensity, spectra, and quenching of the intrinsic fluorescence emitted by the growth hormone’s single tryptophan are monitored and related to adsorption kinetics and protein conformation. For the various alkylated hydrophobic surfaces with differences in surface density and conformational freedom it is observed that the adsorbed amount of growth hormone is relatively large if the alkyl chains are in an ordered structure while the amounts adsorbed are considerably lower for adsorption onto less ordered alkyl chains of fatty acid and phospholipid layers. Adsorption on methylated surfaces results in a relatively large conformational change in the growth hormone’s structure, as displayed by a 7 nm blue shift in emission wavelength and a large increase in the effectiveness of fluorescence quenching. Conformational changes are less evident for hGH adsorption onto the fatty acid and phospholipid alkyl chains. Adsorption kinetics on the hydrophilic head groups of the self-assembled monolayers are similar to those on solid hydrophilic surfaces. The relatively small conformational changes in the hGH structure observed for adsorption on silica are even further reduced for adsorption on fatty acid head groups. PMID:25125795

Electrokinetics of the silica and aqueous electrolyte solution interface: Viscoelectric effects.

PubMed

Hsu, Wei-Lun; Daiguji, Hirofumi; Dunstan, David E; Davidson, Malcolm R; Harvie, Dalton J E

2016-08-01

The manipulation of biomolecules, fluid and ionic current in a new breed of integrated nanofluidic devices requires a quantitative understanding of electrokinetics at the silica/water interface. The conventional capacitor-based electrokinetic Electric Double Layer (EDL) models for this interface have some known shortcomings, as evidenced by a lack of consistency within the literature for the (i) equilibrium constants of surface silanol groups, (ii) Stern layer capacitance, (iii) zeta (ζ) potential measured by various electrokinetic methods, and (iv) surface conductivity. In this study, we consider how the experimentally observable viscoelectric effect - that is, the increase of the local viscosity due to the polarisation of polar solvents - affects electrokinetcs at the silica/water interface. Specifically we consider how a model that considers viscoelectric effects (the VE model) performs against two conventional electrokinetic models, namely the Gouy-Chapman (GC) and Basic Stern capacitance (BS) models, in predicting four fundamental electrokinetic phenomena: electrophoresis, electroosmosis, streaming current and streaming potential. It is found that at moderate to high salt concentrations (>5×10(-3)M) predictions from the VE model are in quantitative agreement with experimental electrokinetic measurements when the sole additional adjustable parameter, the viscoelectric coefficient, is set equal to a value given by a previous independent measurement. In contrast neither the GS nor BS models is able to reproduce all experimental data over the same concentration range using a single, robust set of parameters. Significantly, we also show that the streaming current and potential in the moderate to high surface charge range are insensitive to surface charge behaviour (including capacitances) when viscoelectric effects are considered, in difference to models that do not consider these effects. This strongly questions the validity of using pressure based electrokinetic experiments to measure surface charge characteristics within this experimentally relevant high pH and moderate to high salt concentration range. At low salt concentrations (<5×10(-3)M) we find that there is a lack of consistency in previously measured channel conductivities conducted under similar solution conditions (pH, salt concentration), preventing a conclusive assessment of any model suitability in this regime. Copyright © 2016 Elsevier B.V. All rights reserved.

Preparation, characterization, and catalytic activity of zirconocene bridged on surface of silica gel

NASA Astrophysics Data System (ADS)

El Majdoub, Lotfia; Shi, Yasai; Yuan, Yuan; Zhou, Annan; Abutartour, Abubaker; Xu, Qinghong

2015-10-01

Zirconocene catalyst supported on silica gel was prepared for olefin polymerization by surface modification of calcined silica with SiCl4, and the reaction between the modified silica and cyclopentadienyl sodium and ZrCl4. The catalyst was characterized by using Fourier-transform infrared (FT-IR) spectrometer, thermogravimetric (TG), and differential scanning calorimetric (DSC) analytic spectrometer. It was found that the metallocene structure could be formed and connected on silica surface by chemical bond. Initial catalytic tests showed that the supported metallocene was catalytically active (methylaluminoxane as a cocatalyst), producing polymer with higher molecular weight than the metallocene just immobilized on the surface of silica gel.

Supramolecular structures on silica surfaces and their adsorptive properties.

PubMed

Belyakov, Vladimir N; Belyakova, Lyudmila A; Varvarin, Anatoly M; Khora, Olexandra V; Vasilyuk, Sergei L; Kazdobin, Konstantin A; Maltseva, Tetyana V; Kotvitskyy, Alexey G; Danil de Namor, Angela F

2005-05-01

The study of adsorptive and chemical immobilization of beta-cyclodextrin on a surface of hydroxylated silicas with various porous structure is described. Using IR spectroscopy, thermal gravimetrical analysis with a programmed heating, and chemical analysis of the silica surface, it is shown that the process of adsorption-desorption of beta-cyclodextrin depends on the porous structure of the silica. The reaction of esterification was used for chemical grafting of beta-cyclodextrin on the surface of hydroxylated silicas. Hydrolytic stability of silicas chemically modified by beta-cyclodextrin apparently is explained by simultaneous formation of chemical and hydrogen bonds between surface silanol groups and hydroxyl groups of beta-cyclodextrin. The uptake of the cations Cu(II), Cd(II), and Pb(II) and the anions Cr(VI) and As(V) by silicas modified with beta-cyclodextrin is investigated as a function of equilibrium ion concentrations. The increase of ion uptake and selectivity of ion extraction in comparison with starting silicas is established. It is due to the formation of surface inclusion complexes of the "host-guest" type in which one molecule of beta-cyclodextrin interacts simultaneously with several ions.

Nano-Welding of Multi-Walled Carbon Nanotubes on Silicon and Silica Surface by Laser Irradiation.

PubMed

Yuan, Yanping; Chen, Jimin

2016-02-24

In this study, a continuous fiber laser (1064 nm wavelength, 30 W/cm²) is used to irradiate multi-walled carbon nanotubes (MWCNTs) on different substrate surfaces. Effects of substrates on nano-welding of MWCNTs are investigated by scanning electron microscope (SEM). For MWCNTs on silica, after 3 s irradiation, nanoscale welding with good quality can be achieved due to breaking C-C bonds and formation of new graphene layers. While welding junctions can be formed until 10 s for the MWCNTs on silicon, the difference of irradiation time to achieve welding is attributed to the difference of thermal conductivity for silica and silicon. As the irradiation time is prolonged up to 12.5 s, most of the MWCNTs are welded to a silicon substrate, which leads to their frameworks of tube walls on the silicon surface. This is because the accumulation of absorbed energy makes the temperature rise. Then chemical reactions among silicon, carbon and nitrogen occur. New chemical bonds of Si-N and Si-C achieve the welding between the MWCNTs and silicon. Vibration modes of Si₃N₄ appear at peaks of 363 cm -1 and 663 cm -1 . There are vibration modes of SiC at peaks of 618 cm -1 , 779 cm -1 and 973 cm -1 . The experimental observation proves chemical reactions and the formation of Si₃N₄ and SiC by laser irradiation.

Noble Metal Immersion Spectroscopy of Silica Alcogels and Aerogels

NASA Technical Reports Server (NTRS)

Smith, David D.; Sibille, Laurent; Cronise, Raymond J.; Noever, David A.

1998-01-01

We have fabricated aerogels containing gold and silver nanoparticles for gas catalysis applications. By applying the concept of an average or effective dielectric constant to the heterogeneous interlayer surrounding each particle, we extend the technique of immersion spectroscopy to porous or heterogeneous media. Specifically, we apply the predominant effective medium theories for the determination of the average fractional composition of each component in this inhomogeneous layer. Hence, the surface area of metal available for catalytic gas reaction is determined. The technique is satisfactory for statistically random metal particle distributions but needs further modification for aggregated or surfactant modified systems. Additionally, the kinetics suggest that collective particle interactions in coagulated clusters are perturbed during silica gelation resulting in a change in the aggregate geometry.

Centrifugal sedimentation for selectively packing channels with silica microbeads in three-dimensional micro/nanofluidic devices.

PubMed

Gong, Maojun; Bohn, Paul W; Sweedler, Jonathan V

2009-03-01

Incorporation of nanofluidic elements into microfluidic channels is one approach for adding filtration and partition functionality to planar microfluidic devices, as well as providing enhanced biomolecular separations. Here we introduce a strategy to pack microfluidic channels with silica nanoparticles and microbeads, thereby indirectly producing functional nanostructures; the method allows selected channels to be packed, here demonstrated so that a separation channel is packed while keeping an injection channel unpacked. A nanocapillary array membrane is integrated between two patterned microfluidic channels that cross each other in vertically separated layers. The membrane serves both as a frit for bead packing and as a fluid communication conduit between microfluidic channels. Centrifugal force-assisted sedimentation is then used to selectively pack the microfluidic channels using an aqueous silica bead suspension loaded into the appropriate inlet reservoirs. This packing approach may be used to simultaneously pack multiple channels with silica microbeads having different sizes and surface properties. The chip design and packing method introduced here are suitable for packing silica particles in sizes ranging from nanometers to micrometers and allow rapid (approximately 10 min) packing with high quality. The liquid/analyte transport characteristics of these packed micro/nanofluidic devices have potential utility in a wide range of applications, including electroosmotic pumping, liquid chromatographic separations, and electrochromatography.

Magnet-induced temporary superhydrophobic coatings from one-pot synthesized hydrophobic magnetic nanoparticles.

PubMed

Fang, Jian; Wang, Hongxia; Xue, Yuhua; Wang, Xungai; Lin, Tong

2010-05-01

In this paper, we report on the production of superhydrophobic coatings on various substrates (e.g., glass slide, silicon wafer, aluminum foil, plastic film, nanofiber mat, textile fabrics) using hydrophobic magnetic nanoparticles and a magnet-assembly technique. Fe(3)O(4) magnetic nanoparticles functionalized with a thin layer of fluoroalkyl silica on the surface were synthesized by one-step coprecipitation of Fe(2+)/Fe(3+) under an alkaline condition in the presence of a fluorinated alkyl silane. Under a magnetic field, the magnetic nanoparticles can be easily deposited on any solid substrate to form a thin superhydrophobic coating with water contact angle as high as 172 degrees , and the surface superhydrophobicity showed very little dependence on the substrate type. The particulate coating showed reasonable durability because of strong aggregation effect of nanoparticles, but the coating layer can be removed (e.g., by ultrasonication) to restore the original surface feature of the substrates. By comparison, the thin particle layer deposited under no magnetic field showed much lower hydrophobicity. The main reason for magnet-induced superhydrophobic surfaces is the formation of nano- and microstructured surface features. Such a magnet-induced temporary superhydrophobic coating may have wide applications in electronic, biomedical, and defense-related areas.

Layer-by-Layer Templated Assembly of Silica at the Nanoscale

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

Hinestrosa, Juan Pablo; Sutton, Jonathan E.; Allison, David P.

2013-01-29

Bioinspired bottom-up assembly and layer-by-layer (LbL) construction of inorganic materials from lithographically defined organic templates enables the fabrication of nanostructured systems under mild temperature and pH conditions. Such processes open the door to low-impact manufacturing and facile recycling of hybrid materials for energy, biology, and information technologies. Here, templated LbL assembly of silica was achieved using a combination of electron beam lithography, chemical lift-off, and aqueous solution chemistry. Nanopatterns of lines, honeycomb-lattices, and dot arrays were defined in polymer resist using electron beam lithography. Following development, exposed areas of silicon were functionalized with a vapor deposited amine-silane monolayer. Silicic acidmore » solutions of varying pH and salt content were reacted with the patterned organic amine-functional templates. Vapor treatment and solution reaction could be repeated, allowing LbL deposition. Conditions for the silicic acid deposition had a strong effect on thickness of each layer, and the morphology of the amorphous silica formed. Defects in the arrays of silica nanostructures were minor and do not affect the overall organization of the layers. In conclusion, the bioinspired method described here facilitates the bottom-up assembly of inorganic nanostructures defined in three dimensions and provides a path, via LbL processing, for the construction of layered hybrid materials under mild conditions.« less

Stimuli-responsive polyaniline coated silica microspheres and their electrorheology

NASA Astrophysics Data System (ADS)

Park, Dae Eun; Choi, Hyoung Jin; Vu, Cuong Manh

2016-05-01

Silica/polyaniline (PANI) core-shell structured microspheres were synthesized by coating the surface of silica micro-beads with PANI and applied as a candidate inorganic/polymer composite electrorheological (ER) material. The silica micro-beads were initially modified using N-[(3-trimethoxysilyl)-propyl] aniline to activate an aniline functional group on the silica surface for a better PANI coating. The morphology of the PANI coating on the silica surface was examined by scanning electron microscopy and the silica/PANI core-shell structure was confirmed by transmission electron microscopy. The chemical structure of the particles was confirmed by Fourier transform infrared spectroscopy. Rotational rheometry was performed to confirm the difference in the ER properties between pure silica and silica/PANI microsphere-based ER fluids when dispersed in silicone oil.

Boundary-layer exchange by bubble: A novel method for generating transient nanofluidic layers

NASA Astrophysics Data System (ADS)

Jennissen, Herbert P.

2005-10-01

Unstirred layers (i.e., Nernst boundary layers) occur on every dynamic solid-liquid interface, constituting a diffusion barrier, since the velocity of a moving liquid approaches zero at the surface (no slip). If a macromolecule-surface reaction rate is higher than the diffusion rate, the Nernst layer is solute depleted and the reaction rate becomes mass-transport limited. The thickness of a Nernst boundary layer (δN) generally lies between 5 and 50μm. In an evanescent wave rheometer, measuring fibrinogen adsorption to fused silica, we made the fundamental observation that an air bubble preceding the sample through the flow cell abolishes the mass-transport limitation of the Nernst diffusion layer. Instead exponential kinetics are found. Experimental and simulation studies strongly indicate that these results are due to the elimination of the Nernst diffusion layer and its replacement by a dynamic nanofluidic layer (δν) maximally 200-300nm thick. It is suggested that the air bubble leads to a transient boundary-layer separation into a novel nanoboundary layer on the surface and the bulk fluid velocity profile separated by a vortex sheet with an estimated lifetime of 30-60s. A bubble-induced boundary-layer exchange from the Nernst to the nanoboundary layer and back is obtained, giving sufficient time for the measurement of unbiased exponential surface kinetics. Noteworthy is that the nanolayer can exist at all and displays properties such as (i) a long persistence and resistance to dissipation by the bulk liquid (boundary-layer-exchange-hysteresis) and (ii) a lack of solute depletion in spite of boundary-layer separation. The boundary-layer-exchange by bubble (BLEB) method therefore appears ideal for enhancing the rates of all types of diffusion-limited macromolecular reactions on surfaces with contact angles between 0° and 90° and only appears limited by slippage due to nanobubbles or an air gap beneath the nanofluidic layer on very hydrophobic surfaces. The possibility of producing nanoboundary layers without any nanostructuring or nanomachining should also be useful for fundamental physical studies in nanofluidics.

Layer by Layer, Nano-particle "Only" Surface Modification of Filtration Membranes

NASA Astrophysics Data System (ADS)

Escobar-Ferrand, Luis

Layer by Layer (LbL) deposition using primarily inorganic silica nanoparticles is employed for the modification of polymeric micro and ultrafiltration (MF/UF) membranes to produce thin film composites (TFC) with potential nanofiltration (NF) and reverse osmosis (RO) capabilities.. A variety of porous substrate membranes with different membrane surface characteristics are employed, but exhibiting in common that wicking of water does not readily occur into the pore structure, including polycarbonate track etched (PCTE), polyethersulfone (PES) and sulfonated PES (SPEES) MF/UF membranes. Both spherical (cationic/anionic) and eccentric elongated (anionic) silica nanoparticles are deposited using conditions similar to those reported by Lee et al. Appropriate selection of the pH's for anionic and cationic particle deposition enables the construction of nanoparticle only layers 100--1200 nm in thickness atop the original membrane substrates. The surface layer thickness varies monotonically with the number of bilayers (anionic/cationic deposition cycles) as expected. The deposition process is optimized to eliminate drying induced cracking and to improve mechanical durability via thickness control and post-deposition hydro-thermal treatment. The hydrodynamic permeability of these TFC membranes is measured to evaluate their performance under typical NF operating conditions using dead-end permeation experiments and their performance compared quantitatively with realistic hydrodynamic models, with favorable results. For track etched polycarbonate MF substrates, surface modification causes a permeability reduction of approximately two orders of magnitude with respect to the bare substrates, to values comparable to those for typical commercial NF membranes. Good quantitative agreement with hydrodynamic models with no adjustable parameters was also established for this case, providing indirect confirmation that the LbL deposited surface layers are largely defect (crack) free. Imaging of our TFC membranes after permeation tests confirmed that no significant mechanical damage resulted, indicating integrity and robustness of the LbL deposited surface layers in typical applications. The selectivity of these novel TFC membranes was also tested using standard "rejection" tests normally used to characterize NF and RO membranes for their capabilities in typical applications, such as water softening or desalination. We report the dextran standards molecular weight "cut-off" (MWCO) using mixed dextrans from 1.5 to 500 KDa in dead-end stir cells, and the percentage of rejection of standard bivalent and monovalent salt solutions using steady cross flow permeation experiments. The results confirm rejection of at least 60% of even the smallest dextrans, an estimated dextran MWCO of 20 KDa, and rejection of 10% and 20% for monovalent (NaCl) and bivalent (MgSO4) salts, respectively, for all the TFC membranes studied, while the unmodified membranes showed no rejection capability at all. The work supports that nanoparticle based LbL surface modification of MF/UF membranes can produce filtration quality media for important water purification applications, such as nanofiltration (NF) softening processes, natural organic matter (NOM) elimination and possibly reverse osmosis (RO) desalination.

In Situ Growth of Mesoporous Silica with Drugs on Titanium Surface and Its Biomedical Applications.

PubMed

Wan, Mimi; Zhang, Jin; Wang, Qi; Zhan, Shuyue; Chen, Xudong; Mao, Chun; Liu, Yuhong; Shen, Jian

2017-06-07

Mesoporous silica has been developed for the modification of titanium surfaces that are used as implant materials. Yet, the traditional modification methods failed to effectively construct mesoporous silica on the titanium surface evenly and firmly, in which the interaction between mesoporous silica and titanium was mainly physical. Here, in situ growth of mesoporous silica on a titanium surface was performed using a simple evaporation-induced self-assembly strategy. Meantime, in situ introduction of drugs (heparin and vancomycin) to mesoporous silica was also adopted to improve the drug-loading amount. Both the above-mentioned processes were completed at the same time. Transmission electron microscopy, N 2 adsorption-desorption isotherms, Fourier transform infrared spectroscopy, scanning electron microscopy, and water contact angle measurements were used to characterize the structure of the mesoporous silica film. Results indicated that the mesoporous silica film that in situ grew on the titanium surface was smooth, thin, transparent, and stable. Cytotoxicity, proliferation performance of osteoblast cells, and in vitro and in vivo studies of the antibacterial activity of the coating were tested. This is the first study to modify the titanium surface by the in situ growth of a mesoporous silica coating with two kinds of drugs. The stability of the mesoporous silica coating can be attributed to the chemical bonding between dopamine and silicon hydroxyl of the mesoporous silica coating, and the smooth surface of mesoporous silica is a result of the method of in situ growth. The large amount of drug-loading also could be ascribed to the in situ introduction of drugs during the synthetic process. The strategy proposed in this work will bring more possibilities for the preparation of advanced functional materials based on the combination of mesoporous structure and metallic materials.

Enhanced hydrothermal stability of Cu-ZSM-5 catalyst via surface modification in the selective catalytic reduction of NO with NH3

NASA Astrophysics Data System (ADS)

Zhang, Tao; Shi, Juan; Liu, Jian; Wang, Daxi; Zhao, Zhen; Cheng, Kai; Li, Jianmei

2016-07-01

The surface of Cu-ZSM-5 catalyst was modified by chemical liquid deposition (CLD) of tetraethoxysilane (TEOS) for enhancing its hydrothermal stability in the selective catalytic reduction of NO with NH3. After hydrothermal aging at 750 °C for 13 h, the catalytic performance of Cu-ZSM-5-Aged catalyst was significantly reduced for NO reduction in the entire temperature range, while that of Cu-ZSM-5-CLD-Aged catalyst was affected very little. The characterization results indicated that an inert silica layer was deposited on the surface of Cu-ZSM-5 and formed a protective layer, which prevents the detachment of Cu2+ from ZSM-5 ion-exchange positions and the dealumination of zeolite during the hydrothermal aging process. Based on the data it is hypothesized to be the primary reason for the high hydrothermal stability of Cu-ZSM-5-CLD catalyst.

Determination of isoelectric points and the role of pH for common quartz crystal microbalance sensors.

PubMed

Cuddy, Michael F; Poda, Aimee R; Brantley, Lauren N

2013-05-01

Isoelectric points (IEPs) were determined by the method of contact angle titration for five common quartz crystal microbalance (QCM) sensors. The isoelectric points range from mildly basic in the case of Al2O3 sensors (IEP = 8.7) to moderately acidic for Au (5.2) and SiO2 (3.9), to acidic for Ag (3.2) and Ti (2.9). In general, the values reported here are indicative of inherent surface oxides. A demonstration of the effect of the surface isoelectric point on the packing efficiency of thin mucin films is provided for gold and silica QCM sensors. It is determined that mucin layers on both substrates achieve a maximum and equal layer density of ∼3500 kg/m(3) at the corresponding IEP of either QCM sensor. This implies that mucin film packing is dependent upon short-range electrostatic interactions at the sensor surface.

Topography and Mechanical Property Mapping of International Simple Glass Surfaces with Atomic Force Microscopy

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

Pierce, Eric M

2014-01-01

Quantitative Nanomechanical Peak Force (PF-QNM) TappingModeTM atomic force microscopy measurements are presented for the first time on polished glass surfaces. The PF-QNM technique allows for topography and mechanical property information to be measured simultaneously at each pixel. Results for the international simple glass which represents a simplified version of SON68 glass suggests an average Young s modulus of 78.8 15.1 GPa is within the experimental error of the modulus measured for SON68 glass (83.6 2 GPa) with conventional approaches. Application of the PF-QNM technique will be extended to in situ glass corrosion experiments with the goal of gaining atomic-scale insightsmore » into altered layer development by exploiting the mechanical property differences that exist between silica gel (e.g., altered layer) and pristine glass surface.« less

The development, characterization, and application of biomimetic nanoscale enzyme immobilization

NASA Astrophysics Data System (ADS)

Haase, Nicholas R.

The utilization of enzymes is of interest for applications such as biosensors and biofuel cells. Immobilizing enzymes provides a means to develop these applications. Previous immobilization efforts have been accomplished by exposing surfaces on which silica-forming molecules are present to solutions containing an enzyme and a silica precursor. This approach leads to the enzyme being entrapped in a matrix three orders of magnitude larger than the enzyme itself, resulting in low retention of enzyme activity. The research herein introduces a method for the immobilization of enzymes during the layer-by-layer buildup of Si-O and Ti-O coatings which are nanoscale in thickness. This approach is an application of a peptide-induced mineral deposition method developed in the Sandhage and Kroger groups, and it involves the alternating exposure of a surface to solutions containing the peptide protamine and then an aqueous precursor solution of silicon- or titanium-oxide at near-neutral pH. A method has been developed that enables in situ immobilization of enzymes in the protamine/mineral oxide coatings. Depending on the layer and mineral (silica or titania) within which the enzyme is incorporated, the resulting multilayer biocatalytic hybrid materials retain 20 -- 100% of the enzyme activity. Analyses of kinetic properties of the immobilized enzyme, coupled with characterization of physical properties of the mineral-bearing layers (thickness, porosity, pore size distribution), indicates that the catalytic activities of the enzymes immobilized in the different layers are largely determined by substrate diffusion. The enzyme was also found to be substantially stabilized against heat-induced denaturation and largely protected from proteolytic attack. These functional coatings are then developed for use as antimicrobial materials. Glucose oxidase, which catalyzes production of the cytotoxic agent hydrogen peroxide, was immobilized with silver nanoparticles, can release antimicrobial silver ions. It is demonstrated that these two antimicrobial agents work in a synergistic manner for enhanced antimicrobial efficacy. Evidence of the proposed mechanism of synergy, namely enhanced release of silver ions by reaction of H2O2 with silver nanoparticles, is provided. Finally, the deployment of these materials in silk fibroins for development as wound dressings is also presented. Protamine cross-linking was then extended to the oxygen-reducing enzyme laccase to explore the use of this modified enzyme in an enzymatic biocathode. In this application laccase accepts electrons from the electrode and uses them to reduce oxygen to water molecules. The protamine-cross-linked enzyme exhibits a higher degree of immobilization, better retention of activity once immobilized, and superior electrochemical activity versus the native enzyme. Finally, preliminary research on the structure-function relationships of 16-mer peptides which adsorb to surfaces and deposit titanium oxide is presented. Specifically, the effect of content and distribution of arginine residues on the ability of peptides to adsorb to surfaces and subsequently deposit mineral oxides was investigated. The data demonstrate that surface adsorption of the peptides relies on both a critical number of arginine residues and their position within the peptide. Furthermore, the exchange of serine against arginine residues in surface-adsorbed peptides is detrimental to Ti-O deposition.

Affinity Interaction between Hexamer Peptide Ligand HWRGWV and Immunoglobulin G Studied by Quartz Crystal Microbalance and Surface Plasmon Resonance

NASA Astrophysics Data System (ADS)

Shen, Fei

Immunoglobulins (Ig), also referred to as antibodies, act as protective agents against pathogens trying to invade an organism. Human immunoglobulin G (hIgG), as the most prominent immunoglobulin presented in serum and other human fluids, has broad applications in fields like immunotherapy and clinical diagnostics. Staphylococcus aureus Protein A and Streptococcus Protein G are the most common affinity ligands for IgG purifaction and detection. However, drawbacks associated with these two protein ligands have motivated searches for alternative affinity ligands. The hexamer peptide ligand HWRGWV identified from a one-bead-one-peptide combinatorial library synthesized on chromatography resins has demonstrated high affinity and specificity to the Fc fragment of hIgG. A chromatography resin with HWRGWV can purify human IgG (hIgG) from complete minimum essential medium (cMEM) with purities and yields as high as 95%, which are comparable to using Protein A as affinity ligand (4). As a short peptide ligand, HWRGWV can be produced at relatively low costs under good manufacturing practices (GMP) conditions, it is highly robust, less immunogenic and allows for milder elution conditions for the bound antibody (3, 5). Although this short peptide ligand has exhibited promising properties for IgG capture and purification, limited information is available on the intrinsic mechanisms of affinity interaction between the peptide ligand and target protein. In this study, the affinity interaction between hIgG and peptide ligand immobilized on solid surfaces was studied by quartz crystal microbalance (QCM) and surface plasmon resonance (SPR). Compared with previous methods employed for the peptide characterization, QCM and SPR can provide direct measurements of equilibrium adsorption isotherms and rates of adsorption, allowing a complete kinetic and thermodynamics analyses of the ligand-target interactions. New methods were developed to modify gold and silica surfaces of QCM and SPR sensors for the immobilization of peptide ligands with low nonspecific binding. The silica surface was first modified by the formation of self-assembling monolayer (SAM) of 3-amino-propyl triethoxy silane as an anchor layer. Short chains of poly(ethylene glycol) (PEG) with Fmoc-protected amino groups at one end and carboxyl groups at the other end were then coupled through the carboxyl terminal to the amino groups on the silane. The short PEG chains served as spacer arms to reduce nonspecific binding to the substrate. The gold surface was modified by a two-component SAM using mixtures of HS(CH 2)11(CH2CH2O)6NH2 and HS(CH2)11(CH2CH2O)3OH. The advantage of using a modified silica surface is its relatively higher stability than the SAM on gold during the peptide functionalization step, however the SPR sensors do not work on silica surfaces. In addition, the modification process of the gold surface is relatively simple compared with that of the silica surface. The peptide immobilization process was optimized with silica surfaces and the best conditions were applied for the immobilization on gold surfaces. The results of surface modifications and peptide immobilizations were characterized by various surface analysis techniques including, ellipsometry, contact angle goniometer, chemical force microscopy (CFM), x-ray photoelectron spectroscopy (XPS) and time of flight secondary ion mass spectroscopy (ToF-SIMS). QCM and SPR results indicated that this peptide ligand HWRGWV immobilized on modified silica or gold surfaces has high affinity and specificity to hIgG binding even in a complex medium such as cMEM. Both thermodynamic and kinetic parameters of affinity interaction were obtained by the analysis of QCM and SPR data. Compared with QCM, SPR is more suitable for quantitative analysis of the protein binding, which is essential for the investigation of thermodynamics and kinetics parameters. The maximum binding capacity (4.15 mg m-2 ) and the dissociation constant (1.83 muM) derived from SPR data are both close to those obtained with chromatography techniques. The association and dissociation rate constants (0.68 m3 mol-1 s-1 and 1.24 s-1 respectively) were acquired for the first time for the affinity binding of IgG on peptide ligand HWRGWV functionalized surface. Although QCM is not as quantitative as SPR, it provides additional information on the status of the adsorbed layers. For instance, the dissipation measurement of QCM indicated that no significant denaturation of adsorbed hIgG occurred during the adsorption process. In addition, it was shown that the peptide ligand immobilized on modified silica surfaces has similar affinity and binding characteristics for IgG adsorption as on modified gold surfaces. In summary, new surface modification strategies were developed to study the affinity interaction between peptide ligands and target biomolecules. The use of Fc-specific binding peptides on QCM and SPR sensors could result in new devices for IgG concentration determination and also have promise as platforms for the development of immunosensors.

Quantifying microbe-mineral interactions leading to remotely detectable induced polarization signals

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

Ntarlagiannis, Dimitrios; Moysey, Stephen; Dean, Delphine

2013-11-14

The objective of this project was to investigate controls on induced polarization responses in porous media. The approach taken in the project was to compare electrical measurements made on mineral surfaces with atomic force microscopy (AFM) techniques to observations made at the column-scale using traditional spectral induced polarization measurements. In the project we evaluated a number of techniques for investigating the surface properties of materials, including the development of a new AFM measurement protocol that utilizes an external electric field to induce grain-scale polarizations that can be probed using a charged AFM tip. The experiments we performed focused on idealizedmore » systems (i.e., glass beads and silica gel) where we could obtain the high degree of control needed to understand how changes in the pore environment, which are determined by biogeochemical controls in the subsurface, affect mechanisms contributing to complex electrical conductivity, i.e., conduction and polarization, responses. The studies we performed can be classified into those affecting the chemical versus physical properties of the grain surface and pore space. Chemical alterations of the surface focused on evaluating how changes in pore fluid pH and ionic composition control surface conduction. These were performed as column flow through experiments where the pore fluid was exchanged in a column of silica gel. Given that silica gel has a high surface area due to internal grain porosity, high-quality data could be obtained where the chemical influences on the surface are clearly apparent and qualitatively consistent with theories of grain (i.e., Stern layer) polarization controlled by electrostatic surface sorption processes (i.e., triple layer theory). Quantitative fitting of the results by existing process-based polarization models (e.g., Leroy et al., 2008) has been less successful, however, due to what we have attributed to differences between existing models developed for spherical grains versus the actual geometry associated with the nano-pores in the silica gel, though other polarization processes, e.g., proton hopping along the surface (Skold et al., 2013), may also be a contributing factor. As an alternative model-independent approach to confirming the link between surface sorption and SIP we initiated a study that will continue (unfunded) beyond the completion of this project to independently measure the accumulation of gamma emitting isotopes on the silica gel during the SIP monitoring experiments. Though our analyses of the project data are ongoing, our preliminary analyses are generally supportive of the grain (Stern layer) polarization theory of SIP. Experiments focused on evaluating the impact of physical modifications of the medium on polarization included etching and biotic and abiotic facilitated precipitation of carbonate and iron oxides to alter the roughness and electrical conductivity of the surfaces. These experiments were performed for both silica gel and glass beads, the latter of which lacked the interior porosity and high surface area of the silica gel. The results appear to be more nuanced that the chemical modifications of the system. In general, however, it was found that deposition of iron oxides and etching had relatively minimal or negative impacts on the polarization response of the medium, whereas carbonate coatings increased the polarization response. These results were generally consistent with changes in surface charge observed via AFM. Abiotic and biotic column flow through experiments demonstrated that precipitation of carbonate within the medium significantly impacted the real and imaginary conductivity over time in a manner generally consistent with the carbonate precipitation as observed from the batch grain coating experiments. Biotic effects were not observed to provide distinctly different signatures, but may have contributed to differences in the rate of changes observed with SIP. AFM was used in a variety of different ways to investigate the grain surfaces throughout the course of the project. Standard imaging methods were used to evaluate surface roughness and charge density, which showed that these data could provide qualitative insights about consistency between surface trends and the electrical behavior at the column scale (for the case of glass beads). Polarization and conductive force microscopy (PCFM) measurements were developed by the original project PI (Treavor Kendall), which illustrated the importance of the initial few monolayers of water on the mineral surface for producing surface conductivity. The technique allowed for initial local estimates of complex electrical conductivity on mineral surfaces, but could not be pursued after Kendall left the project due to phase locking limitations with the AFM instrument at Clemson and an inability to perform measurements in solution, which limited their value for linking the measurements to column-scale SIP responses. As a result, co-PI Dean developed a new methodology for making AFM measurements within an externally applied electric field. In this method, the charged tip of an AFM probe is brought within the proximity of a polarization domain while an external electric field is applied to the sample. The premise of the approach is that the tip will be attracted to or rebound from charge accumulations on the surface, which allow for detection of the local polarization response. Initial experiments showed promise in terms of the general trends of responses observed, though we have not yet been able to develop a quantitative interpretation technique that can be applied to predicting column scale responses.« less

Quantifying Microbe-Mineral Interactions Leading to Remotely Detectable Induced Polarization Signals (Final Project Report)

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

Moysey, Stephen; Dean, Delphine; Dimitrios, Ntarlagiannis

2013-11-13

The objective of this project was to investigate controls on induced polarization responses in porous media. The approach taken in the project was to compare electrical measurements made on mineral surfaces with atomic force microscopy (AFM) techniques to observations made at the column-scale using traditional spectral induced polarization measurements. In the project we evaluated a number of techniques for investigating the surface properties of materials, including the development of a new AFM measurement protocol that utilizes an external electric field to induce grain-scale polarizations that can be probed using a charged AFM tip. The experiments we performed focused on idealizedmore » systems (i.e., glass beads and silica gel) where we could obtain the high degree of control needed to understand how changes in the pore environment, which are determined by biogeochemical controls in the subsurface, affect mechanisms contributing to complex electrical conductivity, i.e., conduction and polarization, responses. The studies we performed can be classified into those affecting the chemical versus physical properties of the grain surface and pore space. Chemical alterations of the surface focused on evaluating how changes in pore fluid pH and ionic composition control surface conduction. These were performed as column flow through experiments where the pore fluid was exchanged in a column of silica gel. Given that silica gel has a high surface area due to internal grain porosity, high-quality data could be obtained where the chemical influences on the surface are clearly apparent and qualitatively consistent with theories of grain (i.e., Stern layer) polarization controlled by electrostatic surface sorption processes (i.e., triple layer theory). Quantitative fitting of the results by existing process-based polarization models (e.g., Leroy et al., 2008) has been less successful, however, due to what we have attributed to differences between existing models developed for spherical grains versus the actual geometry associated with the nano-pores in the silica gel, though other polarization processes, e.g., proton hopping along the surface (Skold et al., 2013), may also be a contributing factor. As an alternative model-independent approach to confirming the link between surface sorption and SIP we initiated a study that will continue (unfunded) beyond the completion of this project to independently measure the accumulation of gamma emitting isotopes on the silica gel during the SIP monitoring experiments. Though our analyses of the project data are ongoing, our preliminary analyses are generally supportive of the grain (Stern layer) polarization theory of SIP. Experiments focused on evaluating the impact of physical modifications of the medium on polarization included etching and biotic and abiotic facilitated precipitation of carbonate and iron oxides to alter the roughness and electrical conductivity of the surfaces. These experiments were performed for both silica gel and glass beads, the latter of which lacked the interior porosity and high surface area of the silica gel. The results appear to be more nuanced that the chemical modifications of the system. In general, however, it was found that deposition of iron oxides and etching had relatively minimal or negative impacts on the polarization response of the medium, whereas carbonate coatings increased the polarization response. These results were generally consistent with changes in surface charge observed via AFM. Abiotic and biotic column flow through experiments demonstrated that precipitation of carbonate within the medium significantly impacted the real and imaginary conductivity over time in a manner generally consistent with the carbonate precipitation as observed from the batch grain coating experiments. Biotic effects were not observed to provide distinctly different signatures, but may have contributed to differences in the rate of changes observed with SIP. AFM was used in a variety of different ways to investigate the grain surfaces throughout the course of the project. Standard imaging methods were used to evaluate surface roughness and charge density, which showed that these data could provide qualitative insights about consistency between surface trends and the electrical behavior at the column scale (for the case of glass beads). Polarization and conductive force microscopy (PCFM) measurements were developed by the original project PI (Treavor Kendall), which illustrated the importance of the initial few monolayers of water on the mineral surface for producing surface conductivity. The technique allowed for initial local estimates of complex electrical conductivity on mineral surfaces, but could not be pursued after Kendall left the project due to phase locking limitations with the AFM instrument at Clemson and an inability to perform measurements in solution, which limited their value for linking the measurements to column-scale SIP responses. As a result, co-PI Dean developed a new methodology for making AFM measurements within an externally applied electric field. In this method, the charged tip of an AFM probe is brought within the proximity of a polarization domain while an external electric field is applied to the sample. The premise of the approach is that the tip will be attracted to or rebound from charge accumulations on the surface, which allow for detection of the local polarization response. Initial experiments showed promise in terms of the general trends of responses observed, though we have not yet been able to develop a quantitative interpretation technique that can be applied to predicting column scale responses.« less

High Temperature Solar Reflector, Its Preparation and Use

NASA Technical Reports Server (NTRS)

Jaworske, Donald A. (Inventor)

1999-01-01

A coating-substrate combination having high specular reflectivity at high temperatures reaching 8000 C in a vacuum is described. The substrate comprises pure nickel metal or a nickel-containing metal alloy such as stainless steel having a highly polished reflective surface. The coating is a layer of silver deposited on the substrate to a thickness of 300 A to 3000 A. A 300 A to 5000 A protective coating of silica, alumina or magnesium fluoride is used to cover the silver and to protect it from oxidation. The combination is useful as a parabolic shaped secondary concentrator for collecting solar radiation for generating power or thermal energy for satellite uses. The reflective layer and protective coating preferably are applied to the reflective surface of the substrate by electron beam evaporation or by ion sputtering.

Colloidal silica films for high-capacity DNA arrays

NASA Astrophysics Data System (ADS)

Glazer, Marc Irving

The human genome project has greatly expanded the amount of genetic information available to researchers, but before this vast new source of data can be fully utilized, techniques for rapid, large-scale analysis of DNA and RNA must continue to develop. DNA arrays have emerged as a powerful new technology for analyzing genomic samples in a highly parallel format. The detection sensitivity of these arrays is dependent on the quantity and density of immobilized probe molecules. We have investigated substrates with a porous, "three-dimensional" surface layer as a means of increasing the surface area available for the synthesis of oligonucleotide probes, thereby increasing the number of available probes and the amount of detectable bound target. Porous colloidal silica films were created by two techniques. In the first approach, films were deposited by spin-coating silica colloid suspensions onto flat glass substrates, with the pores being formed by the natural voids between the solid particles (typically 23nm pores, 35% porosity). In the second approach, latex particles were co-deposited with the silica and then pyrolyzed, creating films with larger pores (36 nm), higher porosity (65%), and higher surface area. For 0.3 mum films, enhancements of eight to ten-fold and 12- to 14-fold were achieved with the pure silica films and the films "templated" with polymer latex, respectively. In gene expression assays for up to 7,000 genes using complex biological samples, the high-capacity films provided enhanced signals and performed equivalently or better than planar glass on all other functional measures, confirming that colloidal silica films are a promising platform for high-capacity DNA arrays. We have also investigated the kinetics of hybridization on planar glass and high-capacity substrates. Adsorption on planar arrays is similar to ideal Langmuir-type adsorption, although with an "overshoot" at high solution concentration. Hybridization on high-capacity films is controlled by traditional adsorption (ka) and desorption (kd) coefficients, as well as morphology factors and transient binding interactions between the target and probes. The strength of the transient probe/target binding interactions are on the order of 5--7 DNA base pairs, which suggests the formation of nucleation or other metastable complexes, rather than fully-zippered duplexes.

Adsorption of Small Cationic Nanoparticles onto Large Anionic Particles from Aqueous Solution: A Model System for Understanding Pigment Dispersion and the Problem of Effective Particle Density.

PubMed

North, S M; Jones, E R; Smith, G N; Mykhaylyk, O O; Annable, T; Armes, S P

2017-02-07

The present study focuses on the use of copolymer nanoparticles as a dispersant for a model pigment (silica). Reversible addition-fragmentation chain transfer (RAFT) alcoholic dispersion polymerization was used to synthesize sterically stabilized diblock copolymer nanoparticles. The steric stabilizer block was poly(2-(dimethylamino)ethyl methacrylate) (PDMA) and the core-forming block was poly(benzyl methacrylate) (PBzMA). The mean degrees of polymerization for the PDMA and PBzMA blocks were 71 and 100, respectively. Transmission electron microscopy (TEM) studies confirmed a near-monodisperse spherical morphology, while dynamic light scattering (DLS) studies indicated an intensity-average diameter of 30 nm. Small-angle X-ray scattering (SAXS) reported a volume-average diameter of 29 ± 0.5 nm and a mean aggregation number of 154. Aqueous electrophoresis measurements confirmed that these PDMA 71 -PBzMA 100 nanoparticles acquired cationic character when transferred from ethanol to water as a result of protonation of the weakly basic PDMA chains. Electrostatic adsorption of these nanoparticles from aqueous solution onto 470 nm silica particles led to either flocculation at submonolayer coverage or steric stabilization at or above monolayer coverage, as judged by DLS. This technique indicated that saturation coverage was achieved on addition of approximately 465 copolymer nanoparticles per silica particle, which corresponds to a fractional surface coverage of around 0.42. These adsorption data were corroborated using thermogravimetry, UV spectroscopy and X-ray photoelectron spectroscopy. TEM studies indicated that the cationic nanoparticles remained intact on the silica surface after electrostatic adsorption, while aqueous electrophoresis confirmed that surface charge reversal occurred below pH 7. The relatively thick layer of adsorbed nanoparticles led to a significant reduction in the effective particle density of the silica particles from 1.99 g cm -3 to approximately 1.74 g cm -3 , as judged by disk centrifuge photosedimentometry (DCP). Combining the DCP and SAXS data suggests that essentially no deformation of the PBzMA cores occurs during nanoparticle adsorption onto the silica particles.

Adsorption of Poly(ethylene oxide)-Poly(lactide) Copolymers. Effects of Composition and Degradation.

PubMed

Muller, Dries; Carlsson, Fredrik; Malmsten, Martin

2001-04-01

The effect of chemical degradation of two diblock copolymers of poly(ethylene oxide) (E) and poly(lactide) (L), E(39)L(5) and E(39)L(20), on their adsorption at silica and methylated silica was investigated with in situ ellipsometry. Steric stablization of polystyrene dispersions was investigated in relation to degradation. Hydrolysis of the poly(lactide) block of the copolymers was followed at different temperatures and pH by using HPLC to measure the occurrence of lactic acid in solution. The block copolymers were quite stable in pH-unadjusted solution at low temperature, whereas degradation was facilitated by increasing temperature or lowering of the pH. Lower degradation rates of E(39)L(20) where observed at low temperature in comparison with those of E(39)L(5), whereas the degradation rates of the copolymers were quantitatively similar at high temperature. The adsorption of the copolymers at methylated silica substrates decreased with increasing degree of degradation due to the reduction in the ability of hydrophobic block to anchor the copolymer layer at the surface. At silica the adsorption initially increased with increasing degradation, particularly for E(39)L(20) due to deposition of aggregates onto the surface. After extensive degradation the adsorption of the copolymers at both silica and methylated silica resembled that of the corresponding poly(ethylene oxide) homopolymer. Overall, it was found that the eventual reduction in adsorption occurred at a lower degree of degradation for E(39)L(5) than for E(39)L(20). Mean-field calculations showed a reduced anchoring for the block copolymers with decreasing poly(lactide) block length at hydrophobic surfaces. In accordance with this finding, it was observed that polystyrene dispersions were stabilized by E(39)L(20) or E(39)L(5) in a way that depended on both the lactide block length and the degree of degradation. Upon degradation of the hydrophobic block, stabilization of the polystyrene dispersions was maintained initially, but eventually degradation resulted in destabilization. The average residual copolymer concentration required for stabilization of the polystyrene dispersions was much higher than the corresponding concentration of intact copolymer required for stabilization. Copyright 2001 Academic Press.

Cathodoluminescence of SiOx under-stoichiometric silica layers

NASA Astrophysics Data System (ADS)

Salh, Roushdey; von Czarnowski, A.; Zamoryanskaya, M. V.; Kolesnikova, E. V.; Fitting, H.-J.

2006-06-01

Under-stoichiometric thin silica layers SiOx with different stoichiometric degree 1 x 2, were prepared by thermal evaporation of silicon monoxide in vacuum and in ambient oxygen atmosphere of various pressure onto crystalline silicon substrates. The chemical composition has been determined by Fourier transform infrared spectroscopy (FTIR). A special formula is derived to correlate the stoichiometric degree x with the wavenumber of the main TO stretching mode (Si-O-Si) in silica, finally to determine the actual composition values x of the layers. Cathodoluminescence (CL) of these layers shows the development of typical amorphous SiO2 luminescence bands at the composition threshold x > 1.5 and then onwards to x = 2. These luminescence bands were observed at 4.3, 2.7, 2.15, and 1.9 eV. The green-yellow luminescence (2.15 eV) is strongly increasing with the annealing temperature up to 1300 °C and is assigned to phase separation of SiOx into Si and SiO2 and formation of hexamer silicon rings in the understoichiometric silica network. Finally we observe Si nanoclusters by means of transmission elec- tron microscopy (TEM) micrographs.

Controlling mechanisms of metals release form cement-based waste form in acetic acid solution

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

Cheng, Kuang Ye.

1991-01-01

The purpose of this dissertation is to identify the individual leaching mechanisms of metals by knowing the pH profile within the leached specimen and the physical and chemical properties of the leached material. Leaching of cement-based waste form in acetic acid solutions with different acidic strengths has been investigated in this work. The pH profile along the acid penetration route in the cement-based waste form was identified by various pH color indicators. The pH in the surface altered layer varies from 5.0 to 6.0, which is very close to the pH in the bulk leachate. A reacting zone, where themore » pH abruptly changes from 6 to 12, sharply divides the altered surface layer from the remaining unleached waste form or kernel. Leaching of metals is controlled by the acidity available in the leachant. Dissolution of alkaline materials leaves a silica-rich layer on the surface of the cement-based waste form. This surface layer exhibits different properties than those of the unleached material. The surface layer has a higher water content, is lighter weight, and is soft and friable. Furthermore, the abundant silicate content on the solid surface detains portion of the leached metals, while they are moving through the leached layer into bulk solution. The leaching of metals is a consequence of acid penetration. The distance from the solid/solution interface to the front of the leaching boundary can be regarded as the depth of leaching zone, where the metals dissolve and diffuse out of the waste form. The metal ions diffuse through the leached layer may be retarded on the solid surface by the pH-dependent adsorption reactions. It is found that the leaching process through the leached layer is diffusion-controlled for calcium and cadmium, whereas diffusion and adsorption occur simultaneously in the leached layer for lead and arsenic.« less

Effect of vertically oriented few-layer graphene on the wettability and interfacial reactions of the AgCuTi-SiO2f/SiO2 system.

PubMed

Sun, Z; Zhang, L X; Qi, J L; Zhang, Z H; Hao, T D; Feng, J C

2017-03-22

With the aim of expanding their applications, particularly when joining metals, a simple but effective method is reported whereby the surface chemical reactivity of SiO 2f /SiO 2 (SiO 2f /SiO 2 stands for silica fibre reinforced silica based composite materials and f is short for fibre) composites with vertically oriented few-layer graphene (VFG, 3-10 atomic layers of graphene vertically oriented to the substrate) can be tailored. VFG was uniformly grown on the surface of a SiO 2f /SiO 2 composite by using plasma enhanced chemical vapour deposition (PECVD). The wetting experiments were conducted by placing small pieces of AgCuTi alloy foil on SiO 2f /SiO 2 composites with and without VFG decoration. It was demonstrated that the contact angle dropped from 120° (without VFG decoration) to 50° (with VFG decoration) when the holding time was 10 min. The interfacial reaction layer in SiO 2f /SiO 2 composites with VFG decoration became continuous without any unfilled gaps compared with the composites without VFG decoration. High-resolution transmission electron microscopy (HRTEM) was employed to investigate the interaction between VFG and Ti from the AgCuTi alloy. The results showed that VFG possessed high chemical reactivity and could easily react with Ti even at room temperature. Finally, a mechanism of how VFG promoted the wetting of the SiO 2f /SiO 2 composite by the AgCuTi alloy is proposed and thoroughly discussed.

Highly aligned porous Ti scaffold coated with bone morphogenetic protein-loaded silica/chitosan hybrid for enhanced bone regeneration.

PubMed

Jung, Hyun-Do; Yook, Se-Won; Han, Cheol-Min; Jang, Tae-Sik; Kim, Hyoun-Ee; Koh, Young-Hag; Estrin, Yuri

2014-07-01

Porous Ti has been widely investigated for orthopedic and dental applications on account of their ability to promote implant fixation via bone ingrowth into pores. In this study, highly aligned porous Ti scaffolds coated with a bone morphogenetic protein (BMP)-loaded silica/chitosan hybrid were produced, and their bone regeneration ability was evaluated by in vivo animal experiments. Reverse freeze casting allowed for the creation of highly aligned pores, resulting in a high compressive strength of 254 ± 21 MPa of the scaffolds at a porosity level of ∼51 vol %. In addition, a BMP-loaded silica/chitosan hybrid coating layer with a thickness of ∼1 μm was uniformly deposited on the porous Ti scaffold, which enabled the sustained release of the BMP over a prolonged period of time up to 26 days. The cumulative amount of the BMP released was ∼4 μg, which was much higher than that released from the specimen without a hybrid coating layer. In addition, the bone regeneration ability of the porous Ti scaffold with a BMP-loaded silica/chitosan coating layer was examined by in vivo animal testing using a rabbit calvarial defect model and compared with those of the as-produced porous Ti scaffold and porous Ti scaffold with a silica/chitosan coating layer. After 4 weeks of healing, the specimen coated with a BMP-loaded silica/chitosan hybrid showed a much higher bone regeneration volume (∼36%) than the as-produced specimen (∼15%) (p < 0.005) and even the specimen coated with a silica/chitosan hybrid (∼25%) (p < 0.05). © 2013 Wiley Periodicals, Inc.

[Application of surface-enhanced Raman spectra to the analysis of Chinese Ephedra soup medicines].

PubMed

Zhang, J; Wang, Y

1998-06-01

A new method was developed to analyse the spectra of ephedrine in Chinese ephedra soup medicines, using surface-enhanced technique to combine thin layer chromatographic (TLC) technique with surface-enhanced Raman spectroscopy (SERS). The study indicates that the main vibrant characteristic spec tral band of the ephedrine molecules can be obtained by TLC in the samples of about 8 microg, and expounds char acteristics of the sample molecules and the silica gel. Therefore, it is clarified that the main chemical composi tion of Chinese medicines can be carried as finger-print type appraisal by combining TLC and SERS.

Recent trends in ultra-fast HPLC: new generation superficially porous silica columns.

PubMed

Ali, Imran; Al-Othman, Zeid A; Nagae, Norikaju; Gaitonde, Vinay D; Dutta, Kamlesh K

2012-12-01

New generation columns, i.e. packed with superficially porous silica particles are available as trade names with following manufacturers: Halo, Ascentis Express, Proshell 120, Kinetex, Accucore, Sunshell, and Nucleoshell. These provide ultra-fast HPLC separations for a variety of compounds with moderate sample loading capacity and low back pressure. Chemistries of these columns are C(8), C(18), RP-Amide, hydrophilic interaction liquid chromatography, penta fluorophenyl (PFP), F5, and RP-aqua. Normally, the silica gel particles are of 2.7 and 1.7 μm as total and inner solid core diameters, respectively, with 0.5-μm-thick of outer porous layer having 90 Å pore sizes and 150 m(2)/g surface area. This article describes these new generation columns with special emphasis on their textures and chemistries, separations, optimization, and comparison (inter and intra stationary phases). Besides, future perspectives have also been discussed. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multifunctional enveloped mesoporous silica nanoparticles for subcellular co-delivery of drug and therapeutic peptide.

PubMed

Luo, Guo-Feng; Chen, Wei-Hai; Liu, Yun; Lei, Qi; Zhuo, Ren-Xi; Zhang, Xian-Zheng

2014-08-14

A multifunctional enveloped nanodevice based on mesoporous silica nanoparticle (MSN) was delicately designed for subcellular co-delivery of drug and therapeutic peptide to tumor cells. Mesoporous silica MCM-41 nanoparticles were used as the core for loading antineoplastic drug topotecan (TPT). The surface of nanoparticles was decorated with mitochondria-targeted therapeutic agent (Tpep) containing triphenylphosphonium (TPP) and antibiotic peptide (KLAKLAK)2 via disulfide linkage, followed by coating with a charge reversal polyanion poly(ethylene glycol)-blocked-2,3-dimethylmaleic anhydride-modified poly(L-lysine) (PEG-PLL(DMA)) via electrostatic interaction. It was found that the outer shielding layer could be removed at acidic tumor microenvironment due to the degradation of DMA blocks and the cellular uptake was significantly enhanced by the formation of cationic nanoparticles. After endocytosis, due to the cleavage of disulfide bonds in the presence of intracellular glutathione (GSH), pharmacological agents (Tpep and TPT) could be released from the nanoparticles and subsequently induce specific damage of tumor cell mitochondria and nucleus respectively with remarkable synergistic antitumor effect.

U-Pb ages of secondary silica at Yucca Mountain, Nevada: Implications for the paleohydrology of the unsaturated zone

USGS Publications Warehouse

Neymark, L.A.; Amelin, Y.; Paces, J.B.; Peterman, Z.E.

2002-01-01

Uranium, Th and Pb isotopes were analyzed in layers of opal and chalcedony from individual mm- to cm-thick calcite and silica coatings at Yucca Mountain, Nevada, USA, a site that is being evaluated for a potential high-level nuclear waste repository. These calcite and silica coatings on fractures and in lithophysal cavities in Miocene-age tuffs in the unsaturated zone (UZ) precipitated from descending water and record a long history of percolation through the UZ. Opal and chalcedony have high concentrations of U (10 to 780 ppm) and low concentrations of common Pb as indicated by large values of 206Pb/204Pb (up to 53,806), thus making them suitable for U-Pb age determinations. Interpretations of U-Pb isotope systems in opal samples at Yucca Mountain are complicated by the incorporation of excess 234U at the time of mineral formation, resulting in reverse discordance of U-Pb ages. However, the 207PB/235U ages are much less affected by deviation from initial secular equilibrium and provide reliable ages of most silica deposits between 0.6 and 9.8 Ma. For chalcedony subsamples showing normal age discordance, these ages may represent minimum times of deposition. Typically, 207Pb/235U ages are consistent with the microstratigraphy in the mineral coating samples, such that the youngest ages are for subsamples from outer layers, intermediate ages are from inner layers, and oldest ages are from innermost layers. 234U and 230Th in most silica layers deeper in the coatings are in secular equilibrium with 238U, which is consistent with their old age and closed system behavior during the past -0.5 Ma. The ages for subsamples of silica layers from different microstratigraphic positions in individual calcite and silica coating samples collected from lithophysal cavities in the welded part of the Topopah Spring Tuff yield slow long-term average growth rates of 1 to 5 mm/Ma. These data imply that the deeper parts of the UZ at Yucca Mountain maintained long-term hydrologic stability over the past 10 Ma. despite significant climate variations. U-Pb ages for subsamples of silica layers from different microstratigraphic positions in individual calcite and silica coating samples collected from fractures in the shallower part of the UZ (welded part of the overlying Tiva Canyon Tuff) indicate larger long-term average growth rates up to 23 mm/Ma and an absence of recently deposited materials (ages of outermost layers are 3-5 Ma.). These differences between the characteristics of the coatings for samples from the shallower and deeper parts of the UZ may indicate that the nonwelded tuffs (PTn), located between the welded parts of the Tiva Canyon and Topopah Spring Tuffs, play an important role in moderating UZ flow.

A new silica-infiltrated Y-TZP obtained by the sol-gel method.

PubMed

Campos, T M B; Ramos, N C; Machado, J P B; Bottino, M A; Souza, R O A; Melo, R M

2016-05-01

The aim of this study was to evaluate silica infiltration into dental zirconia (VITA In-Ceram 2000 YZ, Vita Zahnfabrik) and its effects on zirconia's surface characteristics, structural homogeneity and bonding to a resin cement. Infiltration was performed by immersion of the pre-sintered zirconia specimens in silica sols for five days (ZIn). Negative (pure zirconia specimens, ZCon-) and positive controls (specimens kept in water for 5 days, ZCon+) were also performed. After sintering, the groups were evaluated by X-ray diffraction (XRD), grazing angle X-ray diffraction (DRXR), scanning electron microscopy (SEM), contact angle measurements, optical profilometry, biaxial flexural test and shear bonding test. Weibull analysis was used to determine the Weibull modulus (m) and characteristic strength (σ0) of all groups. There were no major changes in strength for the infiltrated group, and homogeneity (m) was also increased. A layer of ZrSiO4 was formed on the surface. The bond strength to resin cement was improved after zirconia infiltration, acid conditioning and the use of an MDP primer. The sol-gel method is an efficient and simple method to increase the homogeneity of zirconia. Infiltration also improved bonding to resin cement. The performance of a zirconia infiltrated by silica gel improved in at least two ways: structural homogeneity and bonding to resin cement. The infiltration is simple to perform and can be easily managed in a prosthesis laboratory. Copyright © 2016 Elsevier Ltd. All rights reserved.

IR spectroscopy study of SBA-15 silicas functionalized with the ethylthiocarbamidepropyl groups and their interactions with Ag(I) and Hg(II) ions

NASA Astrophysics Data System (ADS)

Melnyk, Inna V.; Nazarchuk, Galyna I.; Václavíková, Miroslava; Zub, Yuriy L.

2018-04-01

Mesoporous structure of silica is determined by the type of template, but the introduction of functional groups during the synthesis has additional influence. The structure of SBA-15 may be violated by the introduction of long functions, such as ≡Si(CH2)3NHC(=S)NHC2H5. These ethylthiocarbamidepropyl groups can form complexes with metal ions in thiol or thione tautomeric forms. We determined that the 2D hexagonal p6 mm structure is preserved for SBA-15 with thiourea groups at maximal TEOS:trifunctional silane ratio (mol) = 10:2, which was confirmed by TEM and by the presence of an intense reflex in the small-angle region of diffractograms of the final product. It was shown that the obtained sorbents possess high kinetic characteristics. The experimental data fit pseudo-second-order kinetic equation, but the rate constants depend on the content of functional groups in the surface layer. Template Pluronic P-123 defines the porosity of functional mesoporous silica materials even at increasing content of trifunctional silane in the initial solution. Infrared spectroscopy analysis showed that thione form of thiourea ligand is prevalent on the surface of pores of mesoporous samples. However, during the sorption of silver(I) ions, there are both thione and thiol forms on the surface. Thione form is transformed into thiol with increasing concentration of mercury(II) ions in the sorption solution. Adsorption experiments showed that the SBA-15 silicas functionalized with ethylthiocarbamidepropyl groups had high selectivity for silver(I) ions and could concentrate Ag(I) ions from metal ions mixture at pH 2.

Microfluidic Examination of the "Hard" Biomolecular Corona Formed on Engineered Particles in Different Biological Milieu.

PubMed

Weiss, Alessia C G; Kempe, Kristian; Förster, Stephan; Caruso, Frank

2018-04-18

The formation of a biomolecular corona around engineered particles determines, in large part, their biological behavior in vitro and in vivo. To gain a fundamental understanding of how particle design and the biological milieu influence the formation of the "hard" biomolecular corona, we conduct a series of in vitro studies using microfluidics. This setup allows the generation of a dynamic incubation environment with precise control over the applied flow rate, stream orientation, and channel dimensions, thus allowing accurate control of the fluid flow and the shear applied to the proteins and particles. We used mesoporous silica particles, poly(2-methacryloyloxyethylphosphorylcholine) (PMPC)-coated silica hybrid particles, and PMPC replica particles (obtained by removal of the silica particle templates), representing high-, intermediate-, and low-fouling particle systems, respectively. The protein source used in the experiments was either human serum or human full blood. The effects of flow, particle surface properties, incubation medium, and incubation time on the formation of the biomolecular corona formation are examined. Our data show that protein adhesion on particles is enhanced after incubation in human blood compared to human serum and that dynamic incubation leads to a more complex corona. By varying the incubation time from 2 s to 15 min, we demonstrate that the "hard" biomolecular corona is kinetically subdivided into two phases comprising a tightly bound layer of proteins interacting directly with the particle surface and a loosely associated protein layer. Understanding the influence of particle design parameters and biological factors on the corona composition, as well as its dynamic assembly, may facilitate more accurate prediction of corona formation and therefore assist in the design of advanced drug delivery vehicles.

A new record of silica-rich coating on carbonate substrates in southeast-central Iran: Constraints on geochemical signatures

NASA Astrophysics Data System (ADS)

Aftabi, Alijan; Atapour, Habibeh

2018-10-01

There exist few data on the geochemical signatures and occurrence of silica-rich coatings developed on siliceous carbonate substrates. The rock coatings in the Maran-e-Galu area in southeast-central Iran are composed of four layers; a lower thick layer (1 mm) of silica, a lower thin film of Fe-Mn oxide, an upper thick (1 mm) silica-rich layer, and an upper thin film of Fe-Mn oxide. Energy dispersive X-ray spectrometer (EDS), X-ray diffraction and bulk coating geochemistry data obtained by XRF and ICP-MS highlight that the 1-3 mm thick silica-rich coatings occur as a silica glaze of opal composition on the siliceous carbonate substrate. The coatings were probably formed by the interaction of rainfall, water vapor or dew with silicate and carbonate-rich detrital atmospheric dust, releasing H4SiO4with a pH of 5-10 in this semiarid-arid desert environment. This led to the formation of silica gels as well as minor Fe-Mn oxide gels by evaporation and supersaturation, and finally changed to the black brown silica glaze probably at ambient temperatures of >40 °C Major and minor element signatures are consistent with the known silica glazes, displaying enrichment in Ba, Sr, P, and LREEs with little to no Eu and Ce anomalies and a weak Tm anomaly. However, the very low content of aluminum oxide is well correlated with the known classified silica glaze of genetic type 1, reflecting the absence of detrital clay minerals. The low Fe and Mn contents in bulk coatings (3.6 and 10 magnitudes lower than crustal abundance, respectively) and lack of biochemical processes in the atmospheric dust highlight the semiarid-arid climate setting. We thereby conclude that a new variant of silica glaze of 1-3 mm thickness could form on siliceous carbonate substrates under an alkaline pH in semiarid-arid regions.

Naturally weathered feldspar surfaces in the Navajo Sandstone aquifer, Black Mesa, Arizona: Electron microscopic characterization

NASA Astrophysics Data System (ADS)

Zhu, Chen; Veblen, David R.; Blum, Alex E.; Chipera, Stephen J.

2006-09-01

Naturally weathered feldspar surfaces in the Jurassic Navajo Sandstone at Black Mesa, Arizona, was characterized with high-resolution transmission and analytical electron microscope (HRTEM-AEM) and field emission gun scanning electron microscope (FEG-SEM). Here, we report the first HRTEM observation of a 10-nm thick amorphous layer on naturally weathered K-feldspar in currently slightly alkaline groundwater. The amorphous layer is probably deficient in K and enriched in Si. In addition to the amorphous layer, the feldspar surfaces are also partially coated with tightly adhered kaolin platelets. Outside of the kaolin coatings, feldspar grains are covered with a continuous 3-5 μm thick layer of authigenic smectite, which also coats quartz and other sediment grains. Authigenic K-feldspar overgrowth and etch pits were also found on feldspar grains. These characteristics of the aged feldspar surfaces accentuate the differences in reactivity between the freshly ground feldspar powders used in laboratory experiments and feldspar grains in natural systems, and may partially contribute to the commonly observed apparent laboratory-field dissolution rate discrepancy. At Black Mesa, feldspars in the Navajo Sandstone are dissolving at ˜10 5 times slower than laboratory rate at comparable temperature and pH under far from equilibrium condition. The tightly adhered kaolin platelets reduce the feldspar reactive surface area, and the authigenic K-feldspar overgrowth reduces the feldspar reactivity. However, the continuous smectite coating layer does not appear to constitute a diffusion barrier. The exact role of the amorphous layer on feldspar dissolution kinetics depends on the origin of the layer (leached layer versus re-precipitated silica), which is uncertain at present. However, the nanometer thin layer can be detected only with HRTEM, and thus our study raises the possibility of its wide occurrence in geological systems. Rate laws and proposed mechanisms should consider the possibility of this amorphous layer on feldspar surface.

Naturally weathered feldspar surfaces in the Navajo Sandstone aquifer, Black Mesa, Arizona: Electron microscopic characterization

USGS Publications Warehouse

Zhu, Chen; Veblen, D.R.; Blum, A.E.; Chipera, S.J.

2006-01-01

Naturally weathered feldspar surfaces in the Jurassic Navajo Sandstone at Black Mesa, Arizona, was characterized with high-resolution transmission and analytical electron microscope (HRTEM-AEM) and field emission gun scanning electron microscope (FEG-SEM). Here, we report the first HRTEM observation of a 10-nm thick amorphous layer on naturally weathered K-feldspar in currently slightly alkaline groundwater. The amorphous layer is probably deficient in K and enriched in Si. In addition to the amorphous layer, the feldspar surfaces are also partially coated with tightly adhered kaolin platelets. Outside of the kaolin coatings, feldspar grains are covered with a continuous 3-5 ??m thick layer of authigenic smectite, which also coats quartz and other sediment grains. Authigenic K-feldspar overgrowth and etch pits were also found on feldspar grains. These characteristics of the aged feldspar surfaces accentuate the differences in reactivity between the freshly ground feldspar powders used in laboratory experiments and feldspar grains in natural systems, and may partially contribute to the commonly observed apparent laboratory-field dissolution rate discrepancy. At Black Mesa, feldspars in the Navajo Sandstone are dissolving at ???105 times slower than laboratory rate at comparable temperature and pH under far from equilibrium condition. The tightly adhered kaolin platelets reduce the feldspar reactive surface area, and the authigenic K-feldspar overgrowth reduces the feldspar reactivity. However, the continuous smectite coating layer does not appear to constitute a diffusion barrier. The exact role of the amorphous layer on feldspar dissolution kinetics depends on the origin of the layer (leached layer versus re-precipitated silica), which is uncertain at present. However, the nanometer thin layer can be detected only with HRTEM, and thus our study raises the possibility of its wide occurrence in geological systems. Rate laws and proposed mechanisms should consider the possibility of this amorphous layer on feldspar surface. ?? 2006 Elsevier Inc. All rights reserved.

Improvement of Interaction in a Composite Structure by Using a Sol-Gel Functional Coating on Carbon Fibers.

PubMed

Szczurek, Anna; Barcikowski, Michał; Leluk, Karol; Babiarczuk, Bartosz; Kaleta, Jerzy; Krzak, Justyna

2017-08-25

The modification of carbon fibers for improving adhesion between fibers and an epoxy resin in composite materials has become the focus of attention. In this work the carbon fiber coating process has been devised in a way preventing the stiffening and clumping of fibers. To improve interactions between coated fibers and a resin in composites, four types of silica coatings with different organic functional groups (3-aminopropyl-coating 1, 3-mercaptopropyl-coating 2, 2-(3,4-epoxycyclohexyl) ethyl-coating 3, methyl-coating 4) were obtained. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to distinguish the changes of a carbon fibers surface after coating deposition. The thickness of the obtained coatings, including the diversity of thickness, was determined by transmission electron microscopy (TEM). The increase in surface free energy (SFE) of modified fibers, including the distinction between the polar and dispersive parts, was examined by wettability measurements using a tensometric test. The developed coating preparation process allowed to cover fibers separately with nanoscale silica layers, which changed their morphology. The introduction of organic functional groups resulted in surface free energy changes, especially an increase in specific polar surface energy components.

Improvement of Interaction in a Composite Structure by Using a Sol-Gel Functional Coating on Carbon Fibers

PubMed Central

Barcikowski, Michał; Leluk, Karol; Babiarczuk, Bartosz; Kaleta, Jerzy

2017-01-01

The modification of carbon fibers for improving adhesion between fibers and an epoxy resin in composite materials has become the focus of attention. In this work the carbon fiber coating process has been devised in a way preventing the stiffening and clumping of fibers. To improve interactions between coated fibers and a resin in composites, four types of silica coatings with different organic functional groups (3-aminopropyl–coating 1, 3-mercaptopropyl–coating 2, 2-(3,4-epoxycyclohexyl) ethyl–coating 3, methyl–coating 4) were obtained. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to distinguish the changes of a carbon fibers surface after coating deposition. The thickness of the obtained coatings, including the diversity of thickness, was determined by transmission electron microscopy (TEM). The increase in surface free energy (SFE) of modified fibers, including the distinction between the polar and dispersive parts, was examined by wettability measurements using a tensometric test. The developed coating preparation process allowed to cover fibers separately with nanoscale silica layers, which changed their morphology. The introduction of organic functional groups resulted in surface free energy changes, especially an increase in specific polar surface energy components. PMID:28841187

Environmental response nanosilica for reducing the pressure of water injection in ultra-low permeability reservoirs

NASA Astrophysics Data System (ADS)

Liu, Peisong; Niu, Liyong; Li, Xiaohong; Zhang, Zhijun

2017-12-01

The super-hydrophobic silica nanoparticles are applied to alter the wettability of rock surface from water-wet to oil-wet. The aim of this is to reduce injection pressure so as to enhance water injection efficiency in low permeability reservoirs. Therefore, a new type of environmentally responsive nanosilica (denote as ERS) is modified with organic compound containing hydrophobic groups and "pinning" groups by covalent bond and then covered with a layer of hydrophilic organic compound by chemical adsorption to achieve excellent water dispersibility. Resultant ERS is homogeneously dispersed in water with a size of about 4-8 nm like a micro-emulsion system and can be easily injected into the macro or nano channels of ultra-low permeability reservoirs. The hydrophobic nanosilica core can be released from the aqueous delivery system owing to its strong dependence on the environmental variation from normal condition to injection wells (such as pH and salinity). Then the exposed silica nanoparticles form a thin layer on the surface of narrow pore throat, leading to the wettability from water-wet to oil-wet. More importantly, the two rock cores with different permeability were surface treated with ERS dispersion with a concentration of 2 g/L, exhibit great reduce of water injection pressure by 57.4 and 39.6%, respectively, which shows great potential for exploitation of crude oil from ultra-low permeability reservoirs during water flooding. [Figure not available: see fulltext.

Hydroxyapatite-TiO2-SiO2-Coated 316L Stainless Steel for Biomedical Application

NASA Astrophysics Data System (ADS)

Sidane, Djahida; Khireddine, Hafit; Bir, Fatima; Yala, Sabeha; Montagne, Alex; Chicot, Didier

2017-07-01

This study investigated the effectiveness of titania (TiO2) as a reinforcing phase in the hydroxyapatite (HAP) coating and silica (SiO2) single layer as a bond coat between the TiO2-reinforced hydroxyapatite (TiO2/HAP) top layer and 316L stainless steel (316L SS) substrate on the corrosion resistance and mechanical properties of the underlying 316L SS metallic implant. Single layer of SiO2 film was first deposited on 316L SS substrate and studied separately. Water contact angle measurements, X-ray photoelectron spectroscopy, and Fourier transform infrared spectrophotometer analysis were used to evaluate the hydroxyl group reactivity at the SiO2 outer surface. The microstructural and morphological results showed that the reinforcement of HAP coating with TiO2 and SiO2 reduced the crystallite size and the roughness surface. Indeed, the deposition of 50 vol pct TiO2-reinforced hydroxyapatite layer enhanced the hardness and the elastic modulus of the HAP coating, and the introduction of SiO2 inner layer on the surface of the 316L SS allowed the improvement of the bonding strength and the corrosion resistance as confirmed by scratch studies, nanoindentation, and cyclic voltammetry tests.

Silane Modification of Glass and Silica Surfaces to Obtain Equally Oil-Wet Surfaces in Glass-Covered Silicon Micromodel Applications

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

Grate, Jay W.; Warner, Marvin G.; Pittman, Jonathan W.

2013-08-05

The wettability of silicon and glass surfaces can be modified by silanization. However, similar treatments of glass and silica surfaces using the same silane do not necessarily yield the same wettability as determined by the oil-water contact angle. In this technical note, surface cleaning pretreatments were investigated to determine conditions that would yield oil-wet surfaces on glass with similar wettability to silica surfaces treated with the same silane, and both air-water and oil-water contact angles were determined. Air-water contact angles were less sensitive to differences between silanized silica and glass surfaces, often yielding similar values while the oil-water contact anglesmore » were quite different. Borosilicate glass surfaces cleaned with standard cleaning solution 1 (SC1) yield intermediate-wet surfaces when silanized with hexamethyldisilazane, while the same cleaning and silanization yields oil-wet surfaces on silica. However, cleaning glass in boiling concentrated nitric acid creates a surface that can be silanized to obtain oil-wet surfaces using HDMS. Moreover, this method is effective on glass with prior thermal treatment at an elevated temperature of 400oC. In this way, silica and glass can be silanized to obtain equally oil-wet surfaces using HMDS. It is demonstrated that pretreatment and silanization is feasible in silicon-silica/glass micromodels previously assembled by anodic bonding, and that the change in wettability has a significant observable effect on immiscisble fluid displacements in the pore network.« less

Optical monitoring of thin film electro-polymerization on surface of ITO-coated lossy-mode resonance sensor

NASA Astrophysics Data System (ADS)

Sobaszek, Michał; Dominik, Magdalena; Burnat, Dariusz; Bogdanowicz, Robert; Stranak, Viteszlav; Sezemsky, Petr; Śmietana, Mateusz

2017-04-01

This work presents an optical fiber sensors based on lossy-mode resonance (LMR) phenomenon supported by indium tin oxide (ITO) thin overlay for investigation of electro-polymerization effect on ITO's surface. The ITO overlays were deposited on core of polymer-clad silica (PCS) fibers using reactive magnetron sputtering (RMS) method. Since ITO is electrically conductive and electrochemically active it can be used as a working electrode in 3-electrode cyclic voltammetry setup. For fixed potential applied to the electrode current flow decrease with time what corresponds to polymer layer formation on the ITO surface. Since LMR phenomenon depends on optical properties in proximity of the ITO surface, polymer layer formation can be monitored optically in real time. The electrodeposition process has been performed with Isatin which is a strong endogenous neurochemical regulator in humans as it is a metabolic derivative of adrenaline. It was found that optical detection of Isatin is possible in the proposed configuration.

Interfacial engineering of microstructured materials

NASA Astrophysics Data System (ADS)

Poda, Aimee

The tribological behavior of octadecyltrichlorosilane self assembled monolayers (OTS-SAMs) has been successfully exploited to reduce energy losses and to produce adequate adhesion barrier properties on many MEMS surfaces. Unfortunately, performance discrepancies are reported in the literature between films produced on smooth surfaces as compared to typical MEMS surfaces maintaining topographical roughness. Rational explanations in terms of reproducibility issues, production considerations, and the scale of measurement technique have been introduced to account for some of the variation. The tribological phenomena at the micro-scale are complicated by the fact that rather than inertial effects, the forces associated with the surface become dominant factors influencing the mechanical behavior of contacting components. In MEMS, real mechanical contacts typically consist of a few nanometer scale asperities. Furthermore, various surface topographies exist for MEMS device fabrication and their corresponding asperity profiles can vary drastically based on the production process. This dissertation presents research focusing on the influence of topographical asperities on OTS film properties of relevance for efficient tribological improvement. A fundamental approach has been taken to carefully examine the factors that contribute to high quality film formation, specifically formation temperature and the role of interfacial water layer associated with the sample surface. As evidenced on smooth surfaces, the characteristics for successful tribological performance of OTS films are strongly dependent on the lateral packing density and molecular orientation of the monolayer. Limited information is available on how monolayers associate on topographical asperities and whether these topographical asperities influence the interfacial reactivity of MEMS surfaces. A silica film produced from a low temperature, vapor-phase hydrolysis of tetrachlorosilane with a tunable topography is introduced and leveraged as a novel investigative platform for advanced analytical investigations often restricted to use on smooth surfaces. This tunable surface allows intellectual insight into the nature of surface properties associated with silica surfaces, the uptake of interfacial water and the subsequent influence of surface morphology on OTS film formation. FTIR analysis was utilized for an examination of interfacial properties on both smooth Si(100) surfaces and on the tunable MVD topography in combination with an investigation of OTS film formation mechanism. A dilute etchant technique is developed to provide topographic contrast for AFM imaging to allow direct examination of film packing characteristics in relation to surface asperities. A relationship between monolayer adsorption characteristics and topographical asperities with observed variations in monolayer order resultant from surface roughness has been elucidated. Results show that the packing structure of OTS monolayers is dependent on the local asperity curvature which is qualitatively different from that observed on flat surfaces. In addition, a difference in surface reactivity is observed as a result of different surface topographies with thicker silica layers maintaining a thicker interfacial water layer resulting in a higher coverage of OTS monolayers at similar reaction times and conditions. This work shows changes in surface reactivity as a consequence of different morphological surface characteristics and preparation procedures. Additional research is presented on a new class of SAM, namely octadecylphoshonic acid and its monolayer formation mechanism and properties are compared to conventional OTS monolayers. This monolayer is translated to investigative probes based on Aluminum oxide specifically tailored for a tribological comparison across multi-scale friction regimes.

Investigating the Catalytic Growth of Carbon Nanotubes with In Situ Raman Monitoring

DTIC Science & Technology

2015-06-01

single-walled carbon nanotube growth using cobalt deposited on Si/SiO2 as a model system. In situ Raman studies revealed that thin catalyst layers... cobalt thickness were studied. Surface analyses showed that during the catalyst preparation, catalyst atoms at the interface with silica form small...nanostructures. However, highly-reducing conditions are required to reduce the small silicate domains into small cobalt particles able to grow single-walled

Hierarchical Composite Membranes with Robust Omniphobic Surface Using Layer-By-Layer Assembly Technique.

PubMed

Woo, Yun Chul; Kim, Youngjin; Yao, Minwei; Tijing, Leonard D; Choi, June-Seok; Lee, Sangho; Kim, Seung-Hyun; Shon, Ho Kyong

2018-02-20

In this study, composite membranes were fabricated via layer-by-layer (LBL) assembly of negatively charged silica aerogel (SiA) and 1H,1H,2H,2H-perfluorodecyltriethoxysilane (FTCS) on a polyvinylidene fluoride phase inversion membrane and interconnecting them with positively charged poly(diallyldimethylammonium chloride) (PDDA) via electrostatic interaction. The results showed that the PDDA-SiA-FTCS coated membrane had significantly enhanced the membrane structure and properties. New trifluoromethyl and tetrafluoroethylene bonds appeared at the surface of the coated membrane, which led to lower surface free energy of the composite membrane. Additionally, the LBL membrane showed increased surface roughness. The improved structure and property gave the LBL membrane an omniphobic property, as indicated by its good wetting resistance. The membrane performed a stable air gap membrane distillation (AGMD) flux of 11.22 L/m 2 h with very high salt rejection using reverse osmosis brine from coal seam gas produced water as feed with the addition of up to 0.5 mM SDS solution. This performance was much better compared to those of the neat membrane. The present study suggests that the enhanced membrane properties with good omniphobicity via LBL assembly make the porous membranes suitable for long-term AGMD operation with stable permeation flux when treating challenging saline wastewater containing low surface tension organic contaminants.

Structural enhancement of ZnO on SiO2 for photonic applications

NASA Astrophysics Data System (ADS)

Ruth, Marcel; Meier, Cedrik

2013-07-01

Multi-layer thin films are often the basis of photonic devices. Zinc oxide (ZnO) with its excellent optoelectronic properties can serve as a high quality emitter in structures like microdisks or photonic crystals. Here, we present a detailed study on the enhancement of the structural properties of low-temperature MBE grown ZnO on silica (SiO2). By thermal annealing a grain coalescence of the initially polycrystalline layer leads to an enhancement of the electronic structure, indicated by a blue shift of the photoluminescence (PL) signal maximum. Oxygen atmosphere during the annealing process prevents the creation of intrinsic defects by out-diffusion. Pre-annealing deposited SiO2 capping layers instead obstruct the recrystallization and lead to less intense emission. While thin capping layers partially detach from the ZnO film at high temperatures and cause higher surface roughness and the weakest emission, thicker layers remain smoother and exhibit a significantly stronger photoluminescence.

Novel hybrid structure silica/CdTe/molecularly imprinted polymer: synthesis, specific recognition, and quantitative fluorescence detection of bovine hemoglobin.

PubMed

Li, Dong-Yan; He, Xi-Wen; Chen, Yang; Li, Wen-You; Zhang, Yu-Kui

2013-12-11

This work presented a novel strategy for the synthesis of the hybrid structure silica/CdTe/molecularly imprinted polymer (Si-NP/CdTe/MIP) to recognize and detect the template bovine hemoglobin (BHb). First, amino-functionalized silica nanoparticles (Si-NP) and carboxyl-terminated CdTe quantum dots (QDs) were assembled into composite nanoparticles (Si-NP/CdTe) using the EDC (1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride) chemistry. Next, Si-NP/CdTe/MIP was synthesized by anchoring molecularly imprinted polymer (MIP) layer on the surface of Si-NP/CdTe through the sol-gel technique and surface imprinting technique. The hybrid structure possessed the selectivity of molecular imprinting technique and the sensitivity of CdTe QDs as well as well-defined morphology. The binding experiment and fluorescence method demonstrated its special recognition performance toward the template BHb. Under the optimized conditions, the fluorescence intensity of the Si-NP/CdTe/MIP decreased linearly with the increase of BHb in the concentration range 0.02-2.1 μM, and the detection limit was 9.4 nM. Moreover, the reusability and reproducibility and the successful applications in practical samples indicated the synthesis of Si-NP/CdTe/MIP provided an alternative solution for special recognition and determination of protein from real samples.

Surface plasmon resonance sensor based on photonic crystal fiber filled with gold-silica-gold multilayer nanoshells

NASA Astrophysics Data System (ADS)

Liu, Baolin; Lu, Ying; Yang, Xianchao; Yao, Jianquan

2017-12-01

We present a surface plasmon resonance sensor based on photonic crystal fiber filled with gold-silica-gold (GSG) multilayer nanoshells for measurement of the refractive index of liquid analyte. The GSG multilayer nanoshells, composed of a silica-coated gold nanosphere surrounded by a gold shell layer, are designed to be the functional material of the sensor because of their attractive optical properties. Two resonant peaks are obtained due to the hybridization of nanosphere plasmon modes and nanoshell plasmon modes. It is demonstrated that the resonant wavelength of the two peaks can be precisely tuned in 560-716 nm and 849-2485 nm, respectively, by varying the structural parameters of the GSG multilayer nanoshells in a compact, sub-200 nm size range. The excellent spectral tunability makes the sensor attractive in a wide range of applications, especially in biosensing in near-infrared region. Furthermore, the influences of the parameters on the performance of the sensor are systematically simulated and discussed. It is observed that the spectral sensitivities of 1894.3 nm/RIU and 3011.4 nm/RIU can be achieved respectively by the two resonant peaks in the sensing range of 1.33-1.38. The existence of two loss peaks also provides the possibility to realize self-reference in the sensing process.

Influence of coating material on the flowability and dissolution of dry-coated fine ibuprofen powders.

PubMed

Qu, Li; Zhou, Qi Tony; Denman, John A; Stewart, Peter J; Hapgood, Karen P; Morton, David A V

2015-10-12

This study investigates the effects of a variety of coating materials on the flowability and dissolution of dry-coated cohesive ibuprofen powders, with the ultimate aim to use these in oral dosage forms. A mechanofusion approach was employed to apply a 1% (w/w) dry coating onto ibuprofen powder with coating materials including magnesium stearate (MgSt), L-leucine, sodium stearyl fumarate (SSF) and silica-R972. No significant difference in particle size or shape was measured following mechanofusion with any material. Powder flow behaviours characterised by the Freeman FT4 system indicated coatings of MgSt, L-leucine and silica-R972 produced a notable surface modification and substantially improved flow compared to the unprocessed and SSF-mechanofused powders. ToF-SIMS provided a qualitative measure of coating extent, and indicated a near-complete layer on the drug particle surface after dry coating with MgSt or silica-R972. Of particular note, the dissolution rates of all mechanofused powders were enhanced even with a coating of a highly hydrophobic material such as magnesium stearate. This surprising increase in dissolution rate of the mechanofused powders was attributed to the lower cohesion and the reduced agglomeration after mechanical coating. Copyright © 2015 Elsevier B.V. All rights reserved.

Influence of the silane modifiers on the surface thermodynamic characteristics and dispersion of the silica into elastomer compounds.

PubMed

Castellano, Maila; Conzatti, Lucia; Turturro, Antonio; Costa, Giovanna; Busca, Guido

2007-05-03

A good dispersion of silica into elastomers, typically used in tire tread production, is obtained by grafting of the silica with multifunctional organosilanes. In this study, the influence of the chemical structure of a triethoxysilane (TES), octadecyltriethoxysilane (ODTES), and ODTES/bistriethoxysilylpropyltetrasulfane (TESPT) mixture was investigated by inverse gas chromatography (IGC) at infinite dilution. Thermodynamic results indicate a higher polarity of the silica surface modified with TES as compared to that of the unmodified silica due to new OH groups deriving from the hydrolysis of ethoxy groups of the silane; the long hydrocarbon substituent of the ODTES lies on the surface of silica and reduces the dispersive component of the silica surface tension. A comparison with silica modified with TESPT is discussed. An accurate morphological investigation by transmission electron microscopy (TEM) and automated image analysis (AIA) was carried out on aggregates of silica dispersed into a SBR compound loaded with 35 phr (per hundred rubber) of untreated and TESPT-treated silica. Morphological descriptors such as the projected area/perimeter ratio (A/P) and roundness (P2/4piA) provided direct and quantitative indications about the distribution of the filler into the rubber matrix.

Synthesis and characterization of nanoporous silica aerogel beads using cheap industrial grade sodium silacte precursor

NASA Astrophysics Data System (ADS)

Khan, Tasneem M. A.; Khan, Asiya; Sarawade, Pradip B.

2018-05-01

We report a method to synthesize low-density transparent mesoporous silica aerogel beads by ambient pressure drying (APD). The beads were prepared by acid-base sol-gel polymerization of sodium silicate in via the ball dropping method (BDM). To minimize shrinkage during drying, wet silica beads were initially prepared; their surfaces were then modified using trimethylchlorosilane (TMCS) via simultaneous solvent exchange and surface modification. The specific surface area and cumulative pore volume of the silica aerogel beads increased with an increase in the %V of TMCS. Silica aerogel beads with low packing bed density, high surface area, and large cumulative pore volume was obtained when TMCS was used. Properties of the final product were examined by BET, and TG-DT analyses. The hydrophobic silica aerogel beads were thermally stable up to 350°C. We discuss our results and compare our findings for modified versus unmodified silica beads.

Silica Encapsulation of Ferrimagnetic Zinc Ferrite Nanocubes Enabled by Layer-by-layer Polyelectrolyte Deposition

PubMed Central

Park, Jooneon; Porter, Marc D.; Granger, Michael C.

2016-01-01

Stable suspensions of magnetic nanoparticles (MNPs) with large magnetic moment, m, per particle have tremendous utility in a wide range of biological applications. However, due to the strong magnetic coupling interactions often present in these systems, it is challenging to stabilize individual, high moment, ferro- and ferrimagnetic nanoparticles. A novel approach to encapsulate large, i.e., >100 nm, ferrimagnetic zinc ferrite nanocubes (ZFNCs) with silica after an intermediary layer-by-layer polyelectrolyte deposition step is described in this paper. The seed ZFNCs are uniform in shape and size and have high saturation mass magnetic moment (σs ~100 emu/g, m~4×10−13 emu/particle at 150 Oe). For the MNP system described within, successful silica encapsulation and creation of discrete ZFNCs were realized only after depositing polyelectrolyte multilayers composed of alternating polyallylamine and polystyrene sulfonate. Without the intermediary polyelectrolyte layers, magnetic dipole-dipole interactions led to the formation of linearly chained ZFNCs embedded in a silica matrix. Characterization of particle samples was performed by electron microscopy, energy-dispersive X-ray spectroscopy, infrared spectroscopy, powder X-ray diffraction, dynamic light scattering (hydrodynamic size and ζ-potential), and vibrating sample magnetometry. The results of these characterizations, which were performed after each of the synthetic steps, and synthetic details are presented. PMID:25756216

Preparation of thick silica coatings on carbon fibers with fine-structured silica nanotubes induced by a self-assembly process

PubMed Central

Baumgärtner, Benjamin; Möller, Hendrik; Neumann, Thomas

2017-01-01

A facile method to coat carbon fibers with a silica shell is presented in this work. By immobilizing linear polyamines on the carbon fiber surface, the high catalytic activity of polyamines in the sol–gel-processing of silica precursors is used to deposit a silica coating directly on the fiber’s surface. The surface localization of the catalyst is achieved either by attaching short-chain polyamines (e.g., tetraethylenepentamine) via covalent bonds to the carbon fiber surface or by depositing long-chain polyamines (e.g., linear poly(ethylenimine)) on the carbon fiber by weak non-covalent bonding. The long-chain polyamine self-assembles onto the carbon fiber substrate in the form of nanoscopic crystallites, which serve as a template for the subsequent silica deposition. The silicification at close to neutral pH is spatially restricted to the localized polyamine and consequently to the fiber surface. In case of the linear poly(ethylenimine), silica shells of several micrometers in thickness can be obtained and their morphology is easily controlled by a considerable number of synthesis parameters. A unique feature is the hierarchical biomimetic structure of the silica coating which surrounds the embedded carbon fiber by fibrillar and interconnected silica fine-structures. The high surface area of the nanostructured composite fiber may be exploited for catalytic applications and adsorption purposes. PMID:28685115

Preparation of thick silica coatings on carbon fibers with fine-structured silica nanotubes induced by a self-assembly process.

PubMed

Baumgärtner, Benjamin; Möller, Hendrik; Neumann, Thomas; Volkmer, Dirk

2017-01-01

A facile method to coat carbon fibers with a silica shell is presented in this work. By immobilizing linear polyamines on the carbon fiber surface, the high catalytic activity of polyamines in the sol-gel-processing of silica precursors is used to deposit a silica coating directly on the fiber's surface. The surface localization of the catalyst is achieved either by attaching short-chain polyamines (e.g., tetraethylenepentamine) via covalent bonds to the carbon fiber surface or by depositing long-chain polyamines (e.g., linear poly(ethylenimine)) on the carbon fiber by weak non-covalent bonding. The long-chain polyamine self-assembles onto the carbon fiber substrate in the form of nanoscopic crystallites, which serve as a template for the subsequent silica deposition. The silicification at close to neutral pH is spatially restricted to the localized polyamine and consequently to the fiber surface. In case of the linear poly(ethylenimine), silica shells of several micrometers in thickness can be obtained and their morphology is easily controlled by a considerable number of synthesis parameters. A unique feature is the hierarchical biomimetic structure of the silica coating which surrounds the embedded carbon fiber by fibrillar and interconnected silica fine-structures. The high surface area of the nanostructured composite fiber may be exploited for catalytic applications and adsorption purposes.

Self-assembly of silica nanoparticles by tuning substrate-adsorbate interaction

NASA Astrophysics Data System (ADS)

Utsav, Khanna, Sakshum; Mukhopadhayay, Indrajit; Banerjee, Rupak

2018-05-01

We report on self-assembled nanodisc formations of silica nanoparticles on a surface modified silicon substrate using modified Langmuir-Schafer deposition technique (stamping). The size, inter-particle separation as well as the packing of the silica nanoparticles within the nanodiscs formed spontaneously can be tuned by the surface pressure applied on the water surface. We obtain self-assembled nanodiscs of silica nanoparticle arranged in a hexagonal symmetry. We also observe that by varying the surface pressure of deposition at the water-molecule-air interface we obtain such 2D disc-shaped structure with varying sizes and a packing ratio of the silica nanoparticle.

Investigation of the spatial distribution of second-order nonlinearity in thermally poled optical fibers.

PubMed

An, Honglin; Fleming, Simon

2005-05-02

The spatial distribution of second-order nonlinearity in thermally poled optical fibers was characterized by second-harmonic microscopy. The second-order nonlinearity was found to be confined to a thin layer close to the anode surface and progressed further into the silica as the poling time increased. Position uncertainty of the anode metal wire was observed to have an effect, as the nonlinear layers were found not always symmetrically located around the nearest points between the anode and cathode. Optical microscopy results were obtained on etched poled fiber cross-sections and compared with those from second-harmonic microscopy.

Adhesive strength of total knee endoprostheses to bone cement - analysis of metallic and ceramic femoral components under worst-case conditions.

PubMed

Bergschmidt, Philipp; Dammer, Rebecca; Zietz, Carmen; Finze, Susanne; Mittelmeier, Wolfram; Bader, Rainer

2016-06-01

Evaluation of the adhesive strength of femoral components to the bone cement is a relevant parameter for predicting implant safety. In the present experimental study, three types of cemented femoral components (metallic, ceramic and silica/silane-layered ceramic) of the bicondylar Multigen Plus knee system, implanted on composite femora were analysed. A pull-off test with the femoral components was performed after different load and several cementing conditions (four groups and n=3 components of each metallic, ceramic and silica/silane-layered ceramic in each group). Pull-off forces were comparable for the metallic and the silica/silane-layered ceramic femoral components (mean 4769 N and 4298 N) under standard test condition, whereas uncoated ceramic femoral components showed reduced pull-off forces (mean 2322 N). Loading under worst-case conditions led to decreased adhesive strength by loosening of the interface implant and bone cement using uncoated metallic and ceramic femoral components, respectively. Silica/silane-coated ceramic components were stably fixed even under worst-case conditions. Loading under high flexion angles can induce interfacial tensile stress, which could promote early implant loosening. In conclusion, a silica/silane-coating layer on the femoral component increased their adhesive strength to bone cement. Thicker cement mantles (>2 mm) reduce adhesive strength of the femoral component and can increase the risk of cement break-off.

The role of an organic matrix during the formation of siliceous scales in the heliozoon Actinophrys sol (actinophryida, protista).

PubMed

Newman, P J; Patterson, D J

1993-07-25

Actinophrys sol is a freshwater heliozoon which has trophic and encysted body forms. During encystment, siliceous scales are laid down in silica deposition vesicles. The scales form one layer of a multi-layered cyst wall. Scale production is described using light microscopy, transmission electron microscopy, scanning electron microscopy, and X-ray microanalysis. Silica is laid down on an organic matrix which is visible prior to silicification and after removal of silica with hydrofluoric acid. Actinophrys sol can be cultured under silica impoverished conditions, with the result that the siliceous plates are absent. The cysts continue to form but are fragile. Silica is not a prerequisite for the processes of encystment and cyst formation. Copyright © 1993 Gustav Fischer Verlag · Stuttgart · Jena · New York. Published by Elsevier GmbH.. All rights reserved.

Synthesis of zirconia monoliths for chromatographic separations.

PubMed

Randon, Jérôme; Huguet, Samuel; Piram, Anne; Puy, Guillaume; Demesmay, Claire; Rocca, Jean-Louis

2006-03-17

The aim of this work is to join the advantages of two different kinds of stationary phases: monolithic columns and zirconia-based supports. On the one hand, silica monolithic columns allow a higher efficiency with a lower back-pressure than traditional packed columns. On the other hand, chromatographic stationary phases based on zirconia have a higher thermal and chemical stability and specific surface properties. Combining these advantages, a zirconia monolith with a macroporous framework could be a real improvement in separation sciences. Two main strategies can be used in order to obtain a zirconia surface on a monolithic skeleton: coating or direct synthesis. The coverage by a zirconia layer of the surface of a silica-based monolith can be performed using the chemical properties of the silanol surface groups. We realized this coverage using zirconium alkoxide and we further grafted n-dodecyl groups using phosphate derivatives. Any loss of efficiency was observed and fast separations have been achieved. The main advance reported in this paper is related to the preparation of zirconia monoliths by a sol-gel process starting from zirconium alkoxide. The synthesis parameters (hydrolysis ratio, porogen type, precursor concentration, drying step, etc.) were defined in order to produce a macroporous zirconia monoliths usable in separation techniques. We produced various homogeneous structures: zirconia rod 2 cm long with a diameter of 2.3 mm, and zirconia monolith inside fused silica capillaries with a 75 microm I.D. These monoliths have a skeleton size of 2 microm and have an average through pore size of 6 microm. Several separations have been reported.

Nitrogen-doped carbon capsules via poly(ionic liquid)-based layer-by-layer assembly.

PubMed

Zhao, Qiang; Fellinger, Tim-Patrick; Antonietti, Markus; Yuan, Jiayin

2012-07-13

Layer-by-layer (LbL) assembly technique is applied for the first time for the preparation of nitrogen-doped carbon capsules. This approach uses colloid silica as template and two polymeric deposition components, that is, poly(ammonium acrylate) and a poly (ionic liquid) poly(3-cyanomethyl-1-vinylimidazolium bromide), which acts as both the carbon precursor and nitrogen source. Nitrogen-doped carbon capsules are prepared successfully by polymer wrapping, subsequent carbonization and template removal. The as-synthesized carbon capsules contain ≈7 wt% of nitrogen and have a structured specific surface area of 423 m(2) g(-1). Their application as supercapacitor has been briefly introduced. This work proves that LbL assembly methodology is available for preparing carbon structures of complex morphology. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Formation and characterization of high surface area thermally stabilized titania/silica composite materials via hydrolysis of titanium(IV) tetra-isopropoxide in sols of spherical silica particles.

PubMed

Khalil, Kamal M S; Elsamahy, Ahmed A; Elanany, Mohamed S

2002-05-15

A direct synthetic route leading to titania particles dispersed on nonporous spherical silica particles has been investigated; 5, 10, and 20% (w/w) titania/silica sols mixtures were achieved via hydrolyzation of titanium tetra-isopropxide solution in the mother liquor of a freshly prepared sol of spherical silica particles (Stöber particles). Titania/silica materials were produced by subsequent drying and calcination of the xerogels so obtained for 3 h at 400 and 600 degrees C. The materials were investigated by means of thermal analyses (TGA and DSC), FT-IR, N(2) gas adsorption-desorption, powder X-ray diffraction (XRD), and transmission electron microscopy (TEM). In spite of the low surface area (13.1 m(2)/g) of the pure spherical silica particles calcined at 400 degrees C, high surface area and mesoporous texture titania/silica materials were obtained (e.g., S(BET) ca. 293 m(2)/g for the 10% titania/silica calcined at 400 degrees C). Moreover, the materials were shown to be amorphous toward XRD up to 600 degrees C, while reasonable surface areas were preserved. It has been concluded that dispersion of titania particles onto the surface of the nonporous spherical silica particles increase their roughness, therefore leading to composite materials of less firm packing and mesoporosity.

Facile synthesis of mesoporous silica sublayer with hierarchical pore structure on ceramic membrane using anionic polyelectrolyte.

PubMed

Kang, Taewook; Oh, Seogil; Kim, Honggon; Yi, Jongheop

2005-06-21

A facile method for introducing mesoporous silica sublayer onto the surface of a ceramic membrane for use in liquid-phase separation is described. To reduce the electrostatic repulsion between the mesoporous silica sol and the ceramic membrane in highly acidic conditions (pH < 2), thus facilitating the approach of hydrolyzed silica sol to the surface of the membrane, poly(sodium 4-styrenesulfonate) (Na+PSS-, denoted as PSS-) was used as an ionic linker. The use of PSS- led to a significant reduction in positive charge on the ceramic membrane, as confirmed by experimental titration data. Consistent with the titration results, the amount of mesoporous silica particles on the surface of the ceramic membrane was low, in the absence of PSS- treatment, whereas mesoporous silica sublayer with hierarchical pore structure was produced, when 1 wt % PSS- was used. The results show that mesoporous silica grows in the confined surface, eventually forming a multistacked surface architecture. The mesoporous silica sublayer contained uniform, ordered (P6 mm) mesopores of ca. 7.5 nm from mesoporous silica as well as macropores ( approximately mum) from interparticle voids, as evidenced by transmission electron microscopy and scanning electron microscopy analyses. The morphologies of the supported mesoporous silica could be manipulated, thus permitting the generation of uniform needlelike forms or uniform spheroid particles by varying the concentration of PSS-.

Shear bond strengths of an indirect composite layering material to a tribochemically silica-coated zirconia framework material.

PubMed

Iwasaki, Taro; Komine, Futoshi; Fushiki, Ryosuke; Kubochi, Kei; Shinohara, Mitsuyo; Matsumura, Hideo

2016-01-01

This study evaluated shear bond strengths of a layering indirect composite material to a zirconia framework material treated with tribochemical silica coating. Zirconia disks were divided into two groups: ZR-PRE (airborne-particle abrasion) and ZR-PLU (tribochemical silica coating). Indirect composite was bonded to zirconia treated with one of the following primers: Clearfil Ceramic Primer (CCP), Clearfil Mega Bond Primer with Clearfil Porcelain Bond Activator (MGP+Act), ESPE-Sil (SIL), Estenia Opaque Primer, MR. Bond, Super-Bond PZ Primer Liquid A with Liquid B (PZA+PZB), and Super-Bond PZ Primer Liquid B (PZB), or no treatment. Shear bond testing was performed at 0 and 20,000 thermocycles. Post-thermocycling shear bond strengths of ZR-PLU were higher than those of ZR-PRE in CCP, MGP+Act, SIL, PZA+PZB, and PZB groups. Application of silane yielded better durable bond strengths of a layering indirect composite material to a tribochemically silica-coated zirconia framework material.

Characterization of the adsorption of water vapor and chlorine on microcrystalline silica

NASA Technical Reports Server (NTRS)

Skiles, J. A.; Wightman, J. P.

1979-01-01

The characterization of water adsorption on silica is necessary to an understanding of how hydrogen chloride interacts with silica. The adsorption as a function of outgas temperatures of silica and as a function of the isotherm temperature was studied. Characterization of the silica structure by infrared analysis, X-ray diffraction and differential scanning calorimetry, surface area determinations, characterization of the sample surface by electron spectroscopy for chemical analysis (ESCA), and determinations of the heat of immersion in water of silica were investigated. The silica with a scanning electron microscope was examined.

Development of silicon nitride of improved toughness

NASA Technical Reports Server (NTRS)

Brennan, J. J.

1979-01-01

The application of reaction sintered Si2N4 energy absorbing surface layers to hot-pressed Si3N4 was investigated. The surface layer was formed by in-place nitridation of silicon powder. It was found that reaction sintered Si3N4 layers of 1 mm thickness, fabricated from either -100, +200, -200, or -325 mesh Si powder and nitrided in 96% N2/4% H2 so that approximately 20-25 vol % unnitrided Si remained in the layer, resulted in a sevenfold increase in ballistic impact resistance of a 0.64 cm thick hot-pressed SI3N4 substrate from RT 1370 C. Both NC-132 SI3N4, with MgO additive, and NCX-34 Si3N4, with Y2O3 additive, were evaluated as substrate material. The finer grain size -200 and -325 mesh nitrided Si layers were for their smoothness and relatively high density. It was found that nitriding in N2/H2 mixtures, rather than pure N2, resulted in a microstructure that did not substantially degrade the strength of the hot-pressed Si3N4 substrate. Thermal cycling tests on the RSSN/HPSN combinations from 200 C to 1370 C for 75 cycles in air did not degrade the impact resistance nor the interfacial bonding, although a large amount of internal silica formation occurred within the RSSN layer. Mach 0.8, 5 hr, hot gas erosion tests showed no surface recession of RSSN layers at 1200 C and slight surface recession at 1370 C.

Development of multifunctional nanoparticles towards applications in non-invasive magnetic resonance imaging and axonal tracing.

PubMed

Du, Yan; Qin, Yubo; Li, Zizhen; Yang, Xiuying; Zhang, Jingchang; Westwick, Harrison; Tsai, Eve; Cao, Xudong

2017-12-01

A multifunctional nanobiomaterial has been developed by deliberately combining functions of superparamagnetism, fluorescence, and axonal tracing into one material. Superparamagnetic iron oxide nanoparticles were first synthesized and coated with a silica layer to prevent emission quenching through core-dye interactions; a fluorescent molecule, fluorescein isothiocyanate, was doped inside second layer of silica shell to improve photo-stability and to enable further thiol functionalization. Subsequently, biotinylated dextran amine, a sensitive axonal tracing reagent, was immobilized on the thiol-functionalized nanoparticle surfaces. The resulting nanoparticles were characterized by transmission electron microscopy, dynamic light scattering, X-ray diffraction, X-ray photoelectron spectroscopy, UV-Vis spectroscopy, magnetic resonance imaging and fluorescence confocal microscopy. In vitro cell experiments using both undifferentiated and differentiated Neuro-2a cells showed that the cells were able to take up the nanoparticles intracellularly and that the nanoparticles showed good biocompatibilities. In summary, this new material demonstrated promising performances for both optical and magnetic resonance imaging modalities, suggesting its promising potentials in applications such as in non-invasive imaging, particularly in neuronal tracing.

Rapid, conformal gas-phase formation of silica (SiO2) nanotubes from water condensates

NASA Astrophysics Data System (ADS)

Bae, Changdeuck; Kim, Hyunchul; Yang, Yunjeong; Yoo, Hyunjun; Montero Moreno, Josep M.; Bachmann, Julien; Nielsch, Kornelius; Shin, Hyunjung

2013-06-01

An innovative atomic layer deposition (ALD) concept, with which nanostructures of water condensates with high aspect ratio at equilibrium in cylindrical nanopores can be transformed uniformly into silica (SiO2) at near room temperature and ambient pressure, has been demonstrated for the first time. As a challenging model system, we first prove the conversion of cylindrical water condensates in porous alumina membranes to silica nanotubes (NTs) by introducing SiCl4 as a metal reactant without involving any catalytic reaction. Surprisingly, the water NTs reproducibly transformed into silica NTs, where the wall thickness of the silica NTs deposited per cycle was found to be limited by the amount of condensed water, and it was on the orders of ten nanometers per cycle (i.e., over 50 times faster than that of conventional ALD). More remarkably, the reactions only took place for 10-20 minutes or less without vacuum-related equipment. The thickness of initially adsorbed water layers in cylindrical nanopores was indirectly estimated from the thickness of formed SiO2 layers. With systematic experimental designs, we tackle the classical Kelvin equation in the nanosized pores, and the role of van der Waals forces in the nanoscale wetting phenomena, which is a long-standing issue lacking experimental insight. Moreover, we show that the present strategy is likely generalized to other oxide systems such as TiO2. Our approach opens up a new avenue for ultra-simple preparation of porous oxides and allows for the room temperature formation of dielectric layers toward organic electronic and photovoltaic applications.An innovative atomic layer deposition (ALD) concept, with which nanostructures of water condensates with high aspect ratio at equilibrium in cylindrical nanopores can be transformed uniformly into silica (SiO2) at near room temperature and ambient pressure, has been demonstrated for the first time. As a challenging model system, we first prove the conversion of cylindrical water condensates in porous alumina membranes to silica nanotubes (NTs) by introducing SiCl4 as a metal reactant without involving any catalytic reaction. Surprisingly, the water NTs reproducibly transformed into silica NTs, where the wall thickness of the silica NTs deposited per cycle was found to be limited by the amount of condensed water, and it was on the orders of ten nanometers per cycle (i.e., over 50 times faster than that of conventional ALD). More remarkably, the reactions only took place for 10-20 minutes or less without vacuum-related equipment. The thickness of initially adsorbed water layers in cylindrical nanopores was indirectly estimated from the thickness of formed SiO2 layers. With systematic experimental designs, we tackle the classical Kelvin equation in the nanosized pores, and the role of van der Waals forces in the nanoscale wetting phenomena, which is a long-standing issue lacking experimental insight. Moreover, we show that the present strategy is likely generalized to other oxide systems such as TiO2. Our approach opens up a new avenue for ultra-simple preparation of porous oxides and allows for the room temperature formation of dielectric layers toward organic electronic and photovoltaic applications. Electronic supplementary information (ESI) available: TEM gallery of silica NTs under different experimental conditions, detailed calculation of estimating the thickness of condensed water and Hamaker constants, and a comparison of processing times. See DOI: 10.1039/c3nr00906h

Study of plasmonics in hybrids made from a quantum emitter and double metallic nanoshell dimer

NASA Astrophysics Data System (ADS)

Guo, Jiaohan; Black, Kevin; Hu, Jiawen; Singh, Mahi

2018-05-01

We developed a theory for the fluorescence (FL) for quantum emitter and double metallic nanoshell dimer hybrids using the density matrix method. The dimer is made from two identical double metallic nanoshells, which are made of a dielectric core, a gold metallic shell and a dielectric spacer layer. The quantum emitters are deposited on the surface of the spacer layers of the dimers due to the electrostatic absorptions. We consider that dimer hybrids are surrounded by biological cells. This can be achieved by injecting them into human or animal cells. The surface plasmon polaritons (SPP) are calculated for the dimer using Maxwell’s equations in the static wave approximation. The calculated SPP energy agrees with experimental data from Zhai et al (2017 Plasmonics 12 263) for the dimer made from a silica core, a gold metallic nanoshell and a silica spacer layer. We have also obtained an analytical expression of the FL using the density matrix method. We compare our theory with FL experimental data from Zhai et al (2017 Plasmonics 12 263) where the FL spectrum was measured by varying the thickness of the spacer layer from 9 nm to 40 nm. A good agreement between theory and experiment is found. We have shown that the enhancement of the FL increases as the thickness of the spacer layer decreases. We have also found that the enhancement of the FL increases as the distance between the double metallic nanoshells in the dimer decreases. These are interesting findings which are consistent with the experiments of Zhai et al (2017 Plasmonics 12 263) and can be used to control the FL enhancement in the FL-based biomedical imaging and cancer treatment. These interesting findings may also be useful in the fabrication of nanosensors and nanoswitches for applications in medicine.

Surface forces between hydrophilic silica surfaces in a moisture-sensitive oleophilic diacrylate monomer liquid

NASA Astrophysics Data System (ADS)

Ito, Shunya; Kasuya, Motohiro; Kurihara, Kazue; Nakagawa, Masaru

2018-02-01

We measured the surface forces generated between fused silica surfaces in a low-viscosity oleophilic diacrylate monomer for reliably repeated ultraviolet (UV) nanoimprinting, and studied the influence of water in monomer liquids on the forces. Fused silica surfaces, with a static contact angle of 52.6 ± 1.7° for water, owing to the low degree of hydroxylation, hardly showed reproducible surface forces with repeated scan cycles, comprising approach and separation, even in an identical liquid monomer medium with both of low and high water content. The monomer liquid with a high water content of approximately 420 ppm showed a greater tendency to increase the surface forces at longer surface-surface distances compared with the monomer liquid with a low water content of approximately 60 ppm. On the other hand, silica surfaces with a water contact angle of < 5° after exposure to vacuum UV (VUV) light under a reduced air pressure showed reproducible profiles of surfaces forces using the monomer with a low water concentration of approximately 60 ppm for repeated surface forces scan cycles even in separately prepared silica surfaces, whilst they showed less reproducible profiles in the liquids with high water content of 430 ppm. These results suggested that water possibly adsorbed on the hydrophilic and hydrophobic silica surfaces in the monomer liquid of the high water concentration influenced the repeatability of the surface forces profiles.

Combining surface enhanced Raman scattering (SERS) and high-performance thin-layer chromatography (HPTLC)

NASA Astrophysics Data System (ADS)

Koglin, E.

A new method for preparing SERS active surfaces using silver colloidal spheres deposited on HPTLC plates, used for thin-layer chromatography, is discussed in detail. The sensitivity of these activated HPTLC plates is so high that in-situ vibrational investigations of chromatogram spots are possible at the nanogram level. The HPTLC/SERS spectra of purine, benzoic acid and 1-nitro-pyrene adsorbed on silver colloidal activated silica gel plates are measured in the nanogram region. In addition we also report in this paper on the results of a feasibility study performed to evaluate the analytical potential of micro-Raman spectroscopy (triple monochromator, multichannel detection system) in SERS/HPTLC spot characterization. It permits the acquisition of Raman spectra from HPTLC spots down to 1 μm in size or other forms of microsamples approaching the picogram level in mass.

Nano-Welding of Multi-Walled Carbon Nanotubes on Silicon and Silica Surface by Laser Irradiation

PubMed Central

Yuan, Yanping; Chen, Jimin

2016-01-01

In this study, a continuous fiber laser (1064 nm wavelength, 30 W/cm2) is used to irradiate multi-walled carbon nanotubes (MWCNTs) on different substrate surfaces. Effects of substrates on nano-welding of MWCNTs are investigated by scanning electron microscope (SEM). For MWCNTs on silica, after 3 s irradiation, nanoscale welding with good quality can be achieved due to breaking C–C bonds and formation of new graphene layers. While welding junctions can be formed until 10 s for the MWCNTs on silicon, the difference of irradiation time to achieve welding is attributed to the difference of thermal conductivity for silica and silicon. As the irradiation time is prolonged up to 12.5 s, most of the MWCNTs are welded to a silicon substrate, which leads to their frameworks of tube walls on the silicon surface. This is because the accumulation of absorbed energy makes the temperature rise. Then chemical reactions among silicon, carbon and nitrogen occur. New chemical bonds of Si–N and Si–C achieve the welding between the MWCNTs and silicon. Vibration modes of Si3N4 appear at peaks of 363 cm−1 and 663 cm−1. There are vibration modes of SiC at peaks of 618 cm−1, 779 cm−1 and 973 cm−1. The experimental observation proves chemical reactions and the formation of Si3N4 and SiC by laser irradiation. PMID:28344293

Evaporation of sessile drops containing colloidal rods: coffee-ring and order-disorder transition.

PubMed

Dugyala, Venkateshwar Rao; Basavaraj, Madivala G

2015-03-05

Liquid drops containing insoluble solutes when dried on solid substrates leave distinct ring-like deposits at the periphery or along the three-phase contact line-a phenomena popularly known as the coffee-ring or the coffee stain effect. The formation of such rings as well as their suppression is shown to have applications in particle separation and disease diagnostics. We present an experimental study of the evaporation of sessile drops containing silica rods to elucidate the structural arrangement of particles in the ring, an effect of the addition of surfactant and salt. To this end, the evaporation of aqueous sessile drops containing model rod-like silica particles of aspect ratio ranging from ∼4 to 15 on a glass slide is studied. We first show that when the conditions such as (1) solvent evaporation, (2) nonzero contact angle, (3) contact line pinning, (4) no surface tension gradient driven flow, and (5) repulsive particle-particle/particle-substrate interactions, that are necessary for the formation of the coffee-ring are met, the suspension drops containing silica rods upon evaporation leave a ring-like deposit. A closer examination of the ring deposits reveals that several layers of silica rods close to the edge of the drop are ordered such that the major axis of the rods are oriented parallel to the contact line. After the first few layers of ordered arrangement of particles, a random arrangement of particles in the drop interior is observed indicating an order-disorder transition in the ring. We monitor the evolution of the ring width and particle velocity during evaporation to elucidate the mechanism of the order-disorder transition. Moreover, when the evaporation rate is lowered, the ordering of silica rods is observed to extend over large areas. We demonstrate that the nature of the deposit can be tuned by the addition of a small quantity of surfactant or salt.

Revealing spatially heterogeneous relaxation in a model nanocomposite.

PubMed

Cheng, Shiwang; Mirigian, Stephen; Carrillo, Jan-Michael Y; Bocharova, Vera; Sumpter, Bobby G; Schweizer, Kenneth S; Sokolov, Alexei P

2015-11-21

The detailed nature of spatially heterogeneous dynamics of glycerol-silica nanocomposites is unraveled by combining dielectric spectroscopy with atomistic simulation and statistical mechanical theory. Analysis of the spatial mobility gradient shows no "glassy" layer, but the α-relaxation time near the nanoparticle grows with cooling faster than the α-relaxation time in the bulk and is ∼20 times longer at low temperatures. The interfacial layer thickness increases from ∼1.8 nm at higher temperatures to ∼3.5 nm upon cooling to near bulk Tg. A real space microscopic description of the mobility gradient is constructed by synergistically combining high temperature atomistic simulation with theory. Our analysis suggests that the interfacial slowing down arises mainly due to an increase of the local cage scale barrier for activated hopping induced by enhanced packing and densification near the nanoparticle surface. The theory is employed to predict how local surface densification can be manipulated to control layer dynamics and shear rigidity over a wide temperature range.

Revealing spatially heterogeneous relaxation in a model nanocomposite

DOE PAGES

Cheng, Shiwang; Mirigian, Stephen; Carrillo, Jan-Michael Y.; ...

2015-11-18

The detailed nature of spatially heterogeneous dynamics of glycerol-silica nanocomposites is unraveled by combining dielectric spectroscopy with atomistic simulation and statistical mechanical theory. Analysis of the spatial mobility gradient shows no glassy layer, but the -relaxation time near the nanoparticle grows with cooling faster than the -relaxation time in the bulk and is ~20 times longer at low temperatures. The interfacial layer thickness increases from ~1.8 nm at higher temperatures to ~3.5 nm upon cooling to near bulk T g. A real space microscopic description of the mobility gradient is constructed by synergistically combining high temperature atomistic simulation with theory.more » Our analysis suggests that the interfacial slowing down arises mainly due to an increase of the local cage scale barrier for activated hopping induced by enhanced packing and densification near the nanoparticle surface. As a result, the theory is employed to predict how local surface densification can be manipulated to control layer dynamics and shear rigidity over a wide temperature range.« less

Nanoasperity: structure origin of nacre-inspired nanocomposites.

PubMed

Xia, Shuang; Wang, Zuoning; Chen, Hong; Fu, Wenxin; Wang, Jianfeng; Li, Zhibo; Jiang, Lei

2015-02-24

Natural nacre with superior mechanical property is generally attributed to the layered "brick-and-mortar" nanostructure. However, the role of nanograins on the hard aragonite platelets, which is so-called nanoasperity, is rarely addressed. Herein, we prepared silica platelets with aragonite-like nanoasperities via biomineralization strategy and investigated the effects of nanoasperity on the mechanical properties of resulting layered nanocomposites composed of roughened silica platelets and poly(vinyl alcohol). The tensile deformation behavior of the nanocomposites demonstrates that nanograins on silica platelets are responsive for strain hardening, improved strength, and toughness. The structure origin is attributed to the nanoasperity-controlled platelet sliding.

Effects of oxidation on surface heterogeneity of carbosils

NASA Astrophysics Data System (ADS)

Charmas, B.; Leboda, R.; Gérard, G.; Villiéras, F.

2002-08-01

Carbon-silica adsorbents (carbosils), prepared by pyrolysis of methylene chloride (CH 2Cl 2) on the surface of a porous silica gel, were subjected to an oxidizing hydrothermal treatment (HTT) at 200 °C, using a hydrogen peroxide water solution as a modification medium. Conventional nitrogen adsorption volumetry and low-pressure argon and nitrogen adsorption techniques were used to analyze and compare textural properties and surface heterogeneity of initial and hydrothermally treated samples. In the presence of carbon, the mesoporous network of silica gel is protected from the massive collapse generally observed after oxidizing HTT. For carbosils, some changes occur during HTT, leading to a slight decrease of specific surface areas accompanied by an increase in mean mesopore size. The argon and nitrogen condensation energy distributions, derived from low-pressure adsorption experiments, indicate that both silica and pyrocarbon materials were modified during HTT. Depolymerization and recondensation processes occur for silica, creating new silica surfaces. These processes are responsible of the decrease in specific surface areas. For pyrocarbon, similar depolymerization and recondensation processes probably occur, creating new and high-energy surface sites.

Controlling adsorption and passivation properties of bovine serum albumin on silica surfaces by ionic strength modulation and cross-linking.

PubMed

Park, Jae Hyeon; Sut, Tun Naw; Jackman, Joshua A; Ferhan, Abdul Rahim; Yoon, Bo Kyeong; Cho, Nam-Joon

2017-03-29

Understanding the physicochemical factors that influence protein adsorption onto solid supports holds wide relevance for fundamental insights into protein structure and function as well as for applications such as surface passivation. Ionic strength is a key parameter that influences protein adsorption, although how its modulation might be utilized to prepare well-coated protein adlayers remains to be explored. Herein, we investigated how ionic strength can be utilized to control the adsorption and passivation properties of bovine serum albumin (BSA) on silica surfaces. As protein stability in solution can influence adsorption kinetics, the size distribution and secondary structure of proteins in solution were first characterized by dynamic light scattering (DLS), nanoparticle tracking analysis (NTA), and circular dichroism (CD) spectroscopy. A non-monotonic correlation between ionic strength and protein aggregation was observed and attributed to colloidal agglomeration, while the primarily α-helical character of the protein in solution was maintained in all cases. Quartz crystal microbalance-dissipation (QCM-D) experiments were then conducted in order to track protein adsorption onto silica surfaces as a function of ionic strength, and the measurement responses indicated that total protein uptake at saturation coverage is lower with increasing ionic strength. In turn, the QCM-D data and the corresponding Voigt-Voinova model analysis support that the surface area per bound protein molecule is greater with increasing ionic strength. While higher protein uptake under lower ionic strengths by itself did not result in greater surface passivation under subsequent physiologically relevant conditions, the treatment of adsorbed protein layers with a gluteraldehyde cross-linking agent stabilized the bound protein in this case and significantly improved surface passivation. Collectively, our findings demonstrate that ionic strength modulation influences BSA adsorption uptake on account of protein spreading and can be utilized in conjunction with covalent cross-linking strategies to prepare well-coated protein adlayers for improved surface passivation.

[Surface modification of dental alumina ceramic with silica coating].

PubMed

Xie, Hai-Feng; Zhang, Fei-Min; Wang, Xiao-Zu; Xia, Yang

2006-12-01

To make silica coating through sol-gel process, and to evaluate the wettability of dental alumina ceramic with or without coating. Silica coating was prepared with colloidal silica sol on In-Ceram alumina ceramic surface which had been treated with air particle abrasion. Coating gel after heat treatment was observed with atomic force microscope (AFM), and was analyzed by infrared spectrum (IR) with gel without sintered as control. Contact angles of oleic acid to be finished, sandblasted and coated ceramic surface of were measured. AFM pictures showed that some parts of nano-particles in coating gel conglomerated after heat treatment. It can be seen from the IR picture that bending vibration absorption kurtosis of Si-OH also vanished after heat treatment. Among contact angles of three treated surface, the ones on polished surface were the biggest (P = 0.000, P = 0.000), and sandblasting+silica coating surface the smallest (P = 0.000, P = 0.003). Silica coating can be made with sol-gel process successfully. Heat treatment may reinforce Si-O-Si net structure of coating gel. Wettability of dental alumina ceramic with silica coating is higher than with sandblasting and polishing.

Arsenic sulfide layers for dielectric reflection mirrors prepared from solution

NASA Astrophysics Data System (ADS)

Matějec, Vlastimil; Pedlikova, Jitka; BartoÅ, Ivo; Podrazký, Ondřej

2017-12-01

Chalcogenide materials due to high refractive indices, transparency in the mid-IR spectral region, nonlinear refractive indices, etc, have been employed as fibers and films in different photonic devices such as light amplifiers, optical regenerators, broadband radiation sources. Chalcogenide films can be prepared by physical methods as well as by solution-based techniques in which solutions of chalcogenides in amines are used. This paper presents results on the solution-based fabrication and optical characterization of single arsenic sulfide layers and multilayer stacks containing As2S3 layers together with porous silica layers coated on planar and fiber-optic substrates. Input As2S3 solutions for the layer fabrications were prepared by dissolving As2S3 powder in n-propylamine in a concentration of 0.50 mol/l. These solutions were applied on glass slides by dip-coating method and obtained layers were thermally treated in vacuum at temperatures up to 180 °C. Similar procedure was used for As2S3 layers in multilayer stacks. Such stacks were fabricated by repeating the application of one porous silica layer prepared by the sol-gel method and one As2S3 layer onto glass slides or silica fibers (a diameter of 0.3 mm) by using the dip-coating method. It has been found that the curing process of the applied layers has to be carefully controlled in order to obtain stacks with three pairs of such layers. Single arsenic and porous silica layers were characterized by optical microscopy, and by measuring their transmission spectra in a range of 200-2500 nm. Thicknesses and refractive indices were estimated from the spectra. Transmission spectra of planar multilayer stacks were measured, too. Interference bands have been determined from optical measurements on the multilayer stacks with a minimum transmittance of about 50% which indicates the possibility of using such stacks as reflecting mirrors.

Nanomaterial Solutions for the Protection of Insulin Producing Beta Cells

NASA Astrophysics Data System (ADS)

Atchison, Nicole Ann

Islet transplantation is a promising treatment for type 1 diabetes. However, even with the many successes, islet transplantation has yet to reach its full potential. Limited islet sources, loss of cell viability during isolation and culture, and post-transplant graft loss are a few of the issues preventing extensive use of islet transplantation. The application of biomaterial systems to alleviate some of the stresses affecting islet viability has led to improvements in isolation and transplantation outcomes, but problems persist. In this work we approach two distinct issues affecting islet viability; ischemic conditions and immunological attack post-transplant. Ischemic conditions have been linked to a loss of islet graft function and occur during organ preservation, islet isolation and culture, and after islets are transplanted. We show that liposomal delivery of adenosine triphosphate (ATP) to beta cells can limit cell death and loss of function in ischemic conditions. We demonstrate that by functionalizing liposomes with the fibronectin-mimetic peptide PR_b, delivery of liposomes to porcine islets and rat beta cells is increased compared to nontargeted controls. Additionally, liposomes are shown to protect by providing both ATP and lipids to the ischemic cells. The delivery of ATP was investigated here but application of PR_b functionalized liposomes could be extended to other interesting cargos as well. The second area of investigation involves encapsulation of islets with silica nanoparticles to create a permselective barrier. Silica nanoparticles are an interesting material for encapsulation given their ability to be fine-tuned and further functionalized. We demonstrate that size-tunable, fluorescent silica nanoparticles can be assembled layer-by-layer on the surface of cells and that silica nanoparticle encapsulated islets are able to secrete insulin in response to a glucose challenge.

A novel liquid template corrosion approach for layered silica with various morphologies and different nanolayer thicknesses

NASA Astrophysics Data System (ADS)

Yang, Wanliang; Li, Baoshan

2014-01-01

A novel liquid template corrosion (LTC) method has been developed for the synthesis of layered silica materials with a variety of morphologies, including hollow nanospheres, trilobite-like nanoparticles, spherical particles and a film resembling the van Gogh painting `Starry Night'. Lamellar micelles and microemulsion droplets are first formed in an oil-water (O/W) mixture of ethyl acetate (EA), cetyltrimethylammonium bromide (CTAB) and water. After adding aqueous ammonia the EA becomes hydrolyzed, which results in corrosion of microemulsion droplets. These droplets subsequently act as templates for the synthesis of silica formed by hydrolysis of tetraethyl orthosilicate. The morphological evolution of silica can be tuned by varying the concentration of aqueous ammonia which controls the degree of corrosion of the microemulsion droplet templates. A possible mechanism is proposed to explain why the LTC approach affords layered silica nanostructured materials with various morphologies and nanolayer thickness (2.6-4.5 nm), rather than the usual ordered mesostructures formed in the absence of EA. Our method provides a simple way to fabricate a variety of building blocks for assembling nanomaterials with novel structures and functionality, which are not available using conventional template methods.A novel liquid template corrosion (LTC) method has been developed for the synthesis of layered silica materials with a variety of morphologies, including hollow nanospheres, trilobite-like nanoparticles, spherical particles and a film resembling the van Gogh painting `Starry Night'. Lamellar micelles and microemulsion droplets are first formed in an oil-water (O/W) mixture of ethyl acetate (EA), cetyltrimethylammonium bromide (CTAB) and water. After adding aqueous ammonia the EA becomes hydrolyzed, which results in corrosion of microemulsion droplets. These droplets subsequently act as templates for the synthesis of silica formed by hydrolysis of tetraethyl orthosilicate. The morphological evolution of silica can be tuned by varying the concentration of aqueous ammonia which controls the degree of corrosion of the microemulsion droplet templates. A possible mechanism is proposed to explain why the LTC approach affords layered silica nanostructured materials with various morphologies and nanolayer thickness (2.6-4.5 nm), rather than the usual ordered mesostructures formed in the absence of EA. Our method provides a simple way to fabricate a variety of building blocks for assembling nanomaterials with novel structures and functionality, which are not available using conventional template methods. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr04733d

Vertical Distributions of Coccolithophores, PIC, POC, Biogenic Silica, and Chlorophyll a Throughout the Global Ocean.

PubMed

Balch, William M; Bowler, Bruce C; Drapeau, David T; Lubelczyk, Laura C; Lyczkowski, Emily

2018-01-01

Coccolithophores are a critical component of global biogeochemistry, export fluxes, and seawater optical properties. We derive globally significant relationships to estimate integrated coccolithophore and coccolith concentrations as well as integrated concentrations of particulate inorganic carbon (PIC) from their respective surface concentration. We also examine surface versus integral relationships for other biogeochemical variables contributed by all phytoplankton (e.g., chlorophyll a and particulate organic carbon) or diatoms (biogenic silica). Integrals are calculated using both 100 m integrals and euphotic zone integrals (depth of 1% surface photosynthetically available radiation). Surface concentrations are parameterized in either volumetric units (e.g., m -3 ) or values integrated over the top optical depth. Various relationships between surface concentrations and integrated values demonstrate that when surface concentrations are above a specific threshold, the vertical distribution of the property is biased to the surface layer, and when surface concentrations are below a specific threshold, the vertical distributions of the properties are biased to subsurface maxima. Results also show a highly predictable decrease in explained-variance as vertical distributions become more vertically heterogeneous. These relationships have fundamental utility for extrapolating surface ocean color remote sensing measurements to 100 m depth or to the base of the euphotic zone, well beyond the depths of detection for passive ocean color remote sensors. Greatest integrated concentrations of PIC, coccoliths, and coccolithophores are found when there is moderate stratification at the base of the euphotic zone.

Vertical Distributions of Coccolithophores, PIC, POC, Biogenic Silica, and Chlorophyll a Throughout the Global Ocean

PubMed Central

Bowler, Bruce C.; Drapeau, David T.; Lubelczyk, Laura C.; Lyczkowski, Emily

2018-01-01

Abstract Coccolithophores are a critical component of global biogeochemistry, export fluxes, and seawater optical properties. We derive globally significant relationships to estimate integrated coccolithophore and coccolith concentrations as well as integrated concentrations of particulate inorganic carbon (PIC) from their respective surface concentration. We also examine surface versus integral relationships for other biogeochemical variables contributed by all phytoplankton (e.g., chlorophyll a and particulate organic carbon) or diatoms (biogenic silica). Integrals are calculated using both 100 m integrals and euphotic zone integrals (depth of 1% surface photosynthetically available radiation). Surface concentrations are parameterized in either volumetric units (e.g., m−3) or values integrated over the top optical depth. Various relationships between surface concentrations and integrated values demonstrate that when surface concentrations are above a specific threshold, the vertical distribution of the property is biased to the surface layer, and when surface concentrations are below a specific threshold, the vertical distributions of the properties are biased to subsurface maxima. Results also show a highly predictable decrease in explained‐variance as vertical distributions become more vertically heterogeneous. These relationships have fundamental utility for extrapolating surface ocean color remote sensing measurements to 100 m depth or to the base of the euphotic zone, well beyond the depths of detection for passive ocean color remote sensors. Greatest integrated concentrations of PIC, coccoliths, and coccolithophores are found when there is moderate stratification at the base of the euphotic zone. PMID:29576683

Gallium(III) adsorption on carbonates and oxides: X-ray absorption fine structure spectroscopy study and surface complexation modeling.

PubMed

Pokrovsky, O S; Pokrovski, G S; Schott, J

2004-11-15

Adsorption of Ga on calcite, magnesite, amorphous silica, and manganese oxide as a function of pH and gallium concentration in solution was studied using a batch adsorption technique. Adsorbed complexes of Ga on calcite, magnesite, and delta-MnO2 were further characterized using XAFS spectroscopy. At high surface loadings from supersaturated solutions, Ga is likely to form a polymeric network at the surface (edge- and corner-sharing octahedra). At low surface loadings, Ga presents as isolated octahedra, probably attached to the Me-O sites on the surface, and coordinated by water molecules and hydroxide groups at 1.90-1.94 A. At pH>6, Ga therefore changes its coordination from 4 to 6 when adsorbing from solution (Ga(OH)(-)4(aq)) onto metal surface sites (MeOGa(OH)n(H2O)2-n(5-n), Me = Ca, Mg, or Mn, and n=1 and 2 for carbonate minerals and MnO2, respectively). Because the EXAFS is not capable of seeing hydrogen atoms, the protonation of surface complexes was determined by fitting the experimental pH-dependent Ga adsorption edge. A surface complexation model which assumes the constant capacitance of the electric double layer (CCM) and postulates the formation of positively charged, neutral and negatively charged surface complexes for carbonates, manganese oxide and silica, respectively, was used to describe the dependence of adsorption equilibria on aqueous solution composition in a wide range of pH and Ga concentration.

Adsorption and wetting characterization of hydrophobic SBA-15 silicas.

PubMed

Bernardoni, Frank; Fadeev, Alexander Y

2011-04-15

This work describes adsorption and wetting characterization of hydrophobic ordered mesoporous silicas (OMSs) with the SBA-15 motif. Three synthetic approaches to prepare hydrophobic SBA-15 silicas were explored: grafting with (1) covalently-attached monolayers (CAMs) of C(n)H(2)(n+1)Si(CH(3))(2)N(CH(3))(2), (2) self-assembled monolayers (SAMs) of C(n)H(2)(n+1)Si(OEt)(3), and (3) direct ("one-pot") co-condensation of TEOS with C(n)H(2)(n+1)Si(OEt)(3) in presence of P123 (n=1-18). The materials prepared were characterized by nitrogen adsorption, TEM, and chemical analysis. The surface properties of the materials were assessed by water contact angles (CAs) and by BET C constants. The results showed that, while loadings of the alkyl groups (%C) were comparable, the surface properties and pore ordering of the materials prepared through different methods were quite different. The best quality hydrophobic surfaces were prepared for SBA-15 grafted with CAMs of alkylsilanes. For these materials, the water CAs were above ∼120°/100° (adv/rec) and BET C constants were in the range of ∼15-25, indicating uniform low-energy surfaces of closely packed alkyl groups on external and internal surfaces of the pores respectively. Moreover, surfaces grafted with the long-chained (C(12)-C(18)) silanes showed super-hydrophobic behavior (CAs∼150-180°) and extremely low adhesion for water. The pore uniformity of parental SBA-15 was largely preserved and the pore volume and pore diameter were consistent with the formation of a single layer of alkylsilyl groups inside the pores. Post-synthesis grafting of SBA-15 with SAMs worked not as well as CAMs: the surfaces prepared demonstrated lower water CAs and higher BET C constants, thereby indicating a small amount of accessible polar groups (Si-OH) related to packing constrains for SAMs supported on highly curved surfaces of mesopores. The co-condensation method produced substantially more disordered materials and less hydrophobic surfaces than any of the grafting methods. The surfaces of these materials showed low water CAs and high BET C constants (∼100-200) thereby demonstrating a non-uniform surface coverage and presence of unmodified silica. It is concluded that CAMs chemistry is the most efficient approach in preparation of the functionalized OMS materials with uniform surfaces and pores. Copyright © 2011 Elsevier Inc. All rights reserved.

Effect of solvents on morphology, magnetic and dielectric properties of (α-Fe2O3@SiO2) core-shell nanoparticles.

PubMed

Joshi, Deepika P; Pant, Geeta; Arora, Neha; Nainwal, Seema

2017-02-01

Present work describes the formation of α-Fe 2 O 3 @SiO 2 core shell structure by systematic layer by layer deposition of silica shell on core iron oxide nanoparticles prepared via various solvents. Sol-gel method has been used to synthesize magnetic core and the dielectric shell. The average crystallite size of iron oxide nanoparticles was calculated ∼20 nm by X-ray diffraction pattern. Morphological study by scanning electron microscopy revealed that the core-shell nanoparticles were spherical in shape and the average size of nanoparticles increased by varying solvent from methanol to ethanol to isopropanol due to different chemical structure and nature of the solvents. It was also observed that the particles prepared by solvent ethanol were more regular and homogeneous as compared to other solvents. Magnetic measurements showed the weak ferromagnetic behaviour of both core α-Fe 2 O 3 and silica-coated iron oxide nanoparticles which remained same irrespective of the solvent chosen. However, magnetization showed dependency on the types of solvent chosen due to the variation in shell thickness. At room temperature, dielectric constant and dielectric loss of silica nanoparticles for all the solvents showed decrement with the increment in frequency. Decrement in the value of dielectric constant and increment in dielectric loss was observed for silica coated iron oxide nanoparticles in comparison of pure silica, due to the presence of metallic core. Homogeneous and regular silica layer prepared by using ethanol as a solvent could serve as protecting layer to shield the magnetic behaviour of iron oxide nanoparticles as well as to provide better thermal insulation over pure α-Fe 2 O 3 nanoparticles.

In situ pH within particle beds of bioactive glasses.

PubMed

Zhang, Di; Hupa, Mikko; Hupa, Leena

2008-09-01

The in vitro behavior of three bioactive glasses with seven particle size distributions was studied by measuring the in situ pH inside the particle beds for 48h in simulated body fluid (SBF). After immersion, the surface of the particles was characterized with a field emission scanning electron microscope equipped with an energy-dispersive X-ray analyzer. In addition, the results were compared with the reactions of the same glasses formed as plates. A similar trend in pH as a function of immersion time was observed for all systems. However, the pH inside the particle beds was markedly higher than that in the bulk SBF of the plates. The pH decreased as power functions with increasing particle size, i.e. with decreasing surface area. The in vitro reactivity expressed as layer formation strongly depended on the particle size and glass composition. The average thickness of the total reaction layer decreased with the increase in sample surface area. Well-developed silica and calcium phosphate layers typically observed on glass plates could be detected only on some particles freely exposed to the solution. No distinct reaction layers were observed on the finest particles, possibly because the layers spread out on the large surface area. Differences in the properties of the bulk SBF and the solution inside the particle bed were negligible for particles larger than 800microm. The results enhance our understanding of the in vitro reactions of bioactive glasses in various product forms and sizes.

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.

Removal of dissolved and colloidal silica

DOEpatents

Midkiff, William S.

2002-01-01

Small amorphous silica particles are used to provide a relatively large surface area upon which silica will preferentially adsorb, thereby preventing or substantially reducing scaling caused by deposition of silica on evaporative cooling tower components, especially heat exchange surfaces. The silica spheres are contacted by the cooling tower water in a sidestream reactor, then separated using gravity separation, microfiltration, vacuum filtration, or other suitable separation technology. Cooling tower modifications for implementing the invention process have been designed.

Electron tube

DOEpatents

Suyama, Motohiro [Hamamatsu, JP; Fukasawa, Atsuhito [Hamamatsu, JP; Arisaka, Katsushi [Los Angeles, CA; Wang, Hanguo [North Hills, CA

2011-12-20

An electron tube of the present invention includes: a vacuum vessel including a face plate portion made of synthetic silica and having a surface on which a photoelectric surface is provided, a stem portion arranged facing the photoelectric surface and made of synthetic silica, and a side tube portion having one end connected to the face plate portion and the other end connected to the stem portion and made of synthetic silica; a projection portion arranged in the vacuum vessel, extending from the stem portion toward the photoelectric surface, and made of synthetic silica; and an electron detector arranged on the projection portion, for detecting electrons from the photoelectric surface, and made of silicon.

Biomimetic synthesis of chiral erbium-doped silver/peptide/silica core-shell nanoparticles (ESPN)

NASA Astrophysics Data System (ADS)

Mantion, Alexandre; Graf, Philipp; Florea, Ileana; Haase, Andrea; Thünemann, Andreas F.; Mašić, Admir; Ersen, Ovidiu; Rabu, Pierre; Meier, Wolfgang; Luch, Andreas; Taubert, Andreas

2011-12-01

Peptide-modified silver nanoparticles have been coated with an erbium-doped silica layer using a method inspired by silica biomineralization. Electron microscopy and small-angle X-ray scattering confirm the presence of an Ag/peptide core and silica shell. The erbium is present as small Er2O3 particles in and on the silica shell. Raman, IR, UV-Vis, and circular dichroism spectroscopies show that the peptide is still present after shell formation and the nanoparticles conserve a chiral plasmon resonance. Magnetic measurements find a paramagnetic behavior. In vitro tests using a macrophage cell line model show that the resulting multicomponent nanoparticles have a low toxicity for macrophages, even on partial dissolution of the silica shell.Peptide-modified silver nanoparticles have been coated with an erbium-doped silica layer using a method inspired by silica biomineralization. Electron microscopy and small-angle X-ray scattering confirm the presence of an Ag/peptide core and silica shell. The erbium is present as small Er2O3 particles in and on the silica shell. Raman, IR, UV-Vis, and circular dichroism spectroscopies show that the peptide is still present after shell formation and the nanoparticles conserve a chiral plasmon resonance. Magnetic measurements find a paramagnetic behavior. In vitro tests using a macrophage cell line model show that the resulting multicomponent nanoparticles have a low toxicity for macrophages, even on partial dissolution of the silica shell. Electronic supplementary information (ESI) available: Figures S1 to S12, Tables S1 and S2. See DOI: 10.1039/c1nr10930h

Mechanical and thermal stability of molecularly engineered copper-silica interfaces using organosilane nanolayers

NASA Astrophysics Data System (ADS)

Gandhi, Darshan Dinesh

Future generation silicon integrated circuits requires new materials with low dielectric permittivity kappa < 2.0 and ultra-thin barrier layers (e.g., <3 nm) to create high-reliability, high-performance wiring. Preserving the structural and functional integrity of interfaces is a crucial aspect of realizing reliable integrated circuits with nanodevice components. Molecular nanolayers (MNLs) provide the unique ability to tailor interface properties by adjusting molecular termini, layering, branching or length, thereby making them attractive alternatives to conventional barrier materials. Developing a fundamental understanding of the stability and properties of MNLs at thin film interfaces, and their correlation with parameters such as terminal group chemistries molecular length and surface coverage are key to utilizing them in nanodevice applications. This work addresses some of the key challenges pertaining to modifying Cu-silica interfaces with MNLs with appropriate terminal groups. The resultant effects on, and the inter-relationships between, the chemical, mechanical and electrical properties are investigated. Modifying Cu-silica interface with MNLs results in increased Cu diffusioninduced time-to-failure when subject to electrothermal stresses. The extent of enhancement depends on the terminal chemistry of the MNLs interacting with the overlying Cu. Upon annealing, it is found that MNLs form strong covalent linkages at both Cu-MNL and MNL-silica interfaces resulting in unprecedented values of interface toughness, values exceeding 20 Jm-2. Although strong bonding at Cu-MNL and MNL-dielectric interfaces may be sufficient for blocking copper transport across polyelectrolyte MNL bilayers, strong interlayer molecular bonding is a necessary condition for interface toughening. Exposing MNLs to UV light, results in photo-oxidation of the terminal mercaptan groups. These photo-oxidized termini form strong complexes with Cu that results in enhancement by a factor-of-10 in device failure times. Using a combination of UV-exposure prior to Cu metallization and annealing after Cu metallization should result in enhanced device failure times and interface toughness, resulting in chemically isolated and mechanically strong interfaces. This work also shows that passivating Cu surfaces with MNLs can decrease surface leakage currents due to curtailed in-plane Cu transport (low voltages). Formation of strong complexes with Cu can immobilize Cu and reduce the leakage currents and result in higher breakdown voltages. Moreover, the strategy of using MNLs can be applied to passivate pore surfaces in mesoporous silica (MPS) films to suppress water uptake and Cu penetration. The molecularly passivated dielectrics (S-MPS) exhibit 50% lower fracture toughness than unfunctionalized films, and fracture closer to the Cu/S-MPS interface. Electron spectroscopy analyses show that the fracture pathway is governed by the Cu penetration depth into the MPS. Our results show that molecular passivation of porous films not only inhibit metal penetration and water uptake, but also can be used to tune the fracture pathway. The results from this thesis are of importance for harnessing MNLs for the use in future device wiring applications.

CH4 Hydrate Formation between Silica and Graphite Surfaces: Insights from Microsecond Molecular Dynamics Simulations.

PubMed

He, Zhongjin; Linga, Praveen; Jiang, Jianwen

2017-10-31

Microsecond simulations have been performed to investigate CH 4 hydrate formation from gas/water two-phase systems between silica and graphite surfaces, respectively. The hydrophilic silica and hydrophobic graphite surfaces exhibit substantially different effects on CH 4 hydrate formation. The graphite surface adsorbs CH 4 molecules to form a nanobubble with a flat or negative curvature, resulting in a low aqueous CH 4 concentration, and hydrate nucleation does not occur during 2.5 μs simulation. Moreover, an ordered interfacial water bilayer forms between the nanobubble and graphite surface thus preventing their direct contact. In contrast, the hydroxylated-silica surface prefers to be hydrated by water, with a cylindrical nanobubble formed in the solution, leading to a high aqueous CH 4 concentration and hydrate nucleation in the bulk region; during hydrate growth, the nanobubble is gradually covered by hydrate solid and separated from the water phase, hence slowing growth. The silanol groups on the silica surface can form strong hydrogen bonds with water, and hydrate cages need to match the arrangements of silanols to form more hydrogen bonds. At the end of the simulation, the hydrate solid is separated from the silica surface by liquid water, with only several cages forming hydrogen bonds with the silica surface, mainly due to the low CH 4 aqueous concentrations near the surface. To further explore hydrate formation between graphite surfaces, CH 4 /water homogeneous solution systems are also simulated. CH 4 molecules in the solution are adsorbed onto graphite and hydrate nucleation occurs in the bulk region. During hydrate growth, the adsorbed CH 4 molecules are gradually converted into hydrate solid. It is found that the hydrate-like ordering of interfacial water induced by graphite promotes the contact between hydrate solid and graphite. We reveal that the ability of silanol groups on silica to form strong hydrogen bonds to stabilize incipient hydrate solid, as well as the ability of graphite to adsorb CH 4 molecules and induce hydrate-like ordering of the interfacial water, are the key factors to affect CH 4 hydrate formation between silica and graphite surfaces.

CW laser damage testing of RAR nano-textured fused silica and YAG

NASA Astrophysics Data System (ADS)

MacLeod, Bruce D.; Hobbs, Douglas S.; Manni, Anthony D.; Sabatino, Ernest; Bernot, David M.; DeFrances, Sage; Randi, Joseph A.; Thomas, Jeffrey

2017-11-01

A study of the continuous wave (CW) laser induced damage threshold (LiDT) of fused silica and yttrium aluminum garnet (YAG) optics was conducted to further illustrate the enhanced survivability within high power laser systems of an anti-reflection (AR) treatment consisting of randomly distributed surface relief nanostructures (RAR). A series of three CW LiDT tests using the 1070nm wavelength, 16 KW fiber laser test bed at Penn State Electro-Optic Center (PSEOC) were designed and completed, with improvements in the testing protocol, areal coverage, and maximum exposure intensities implemented between test cycles. Initial results for accumulated power, stationary site exposures of RAR nano-textured optics showed no damage and low surface temperatures similar to the control optics with no AR treatment. In contrast, optics with thin-film AR coatings showed high surface temperatures consistent with absorption by the film layers. Surface discriminating absorption measurements made using the Photothermal Common-path Interferometry (PCI) method, showed zero added surface absorption for the RAR nanotextured optics, and absorption levels in the 2-5 part per million range for thin-film AR coated optics. In addition, the surface absorption of thin-film AR coatings was also found to have localized absorption spikes that are likely pre-cursors for damage. Subsequent CW LiDT testing protocol included raster scanning an increased intensity focused beam over the test optic surface where it was found that thin-film AR coated optics damaged at intensities in the 2 to 5 MW/cm2 range with surface temperatures over 250C during the long-duration exposures. Significantly, none of the 10 RAR nano-textured fused silica optics tested could be damaged up to the maximum system intensity of 15.5 MW/cm2, and surface temperatures remained low. YAG optics tested during the final cycle exhibited a similar result with RAR nano-textured surfaces surviving intensities over 3 times higher than thin-film AR coated surfaces. This result was correlated with PCI measurements that also show zero-added surface absorption for the RAR nano-textured YAG optics.

Is the boundary layer of an ionic liquid equally lubricating at higher temperature?

PubMed

Hjalmarsson, Nicklas; Atkin, Rob; Rutland, Mark W

2016-04-07

Atomic force microscopy has been used to study the effect of temperature on normal forces and friction for the room temperature ionic liquid (IL) ethylammonium nitrate (EAN), confined between mica and a silica colloid probe at 25 °C, 50 °C, and 80 °C. Force curves revealed a strong fluid dynamic influence at room temperature, which was greatly reduced at elevated temperatures due to the reduced liquid viscosity. A fluid dynamic analysis reveals that bulk viscosity is manifested at large separation but that EAN displays a nonzero slip, indicating a region of different viscosity near the surface. At high temperatures, the reduction in fluid dynamic force reveals step-like force curves, similar to those found at room temperature using much lower scan rates. The ionic liquid boundary layer remains adsorbed to the solid surface even at high temperature, which provides a mechanism for lubrication when fluid dynamic lubrication is strongly reduced. The friction data reveals a decrease in absolute friction force with increasing temperature, which is associated with increased thermal motion and reduced viscosity of the near surface layers but, consistent with the normal force data, boundary layer lubrication was unaffected. The implications for ILs as lubricants are discussed in terms of the behaviour of this well characterised system.

Dynamics of spallation during femtosecond laser ablation studied by time-resolved reflectivity with double pump pulses

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

Kumada, Takayuki, E-mail: kumada.takayuki@jaea.go.jp; Otobe, Tomohito; Nishikino, Masaharu

2016-01-04

The dynamics of photomechanical spallation during femtosecond laser ablation of fused silica was studied by time-resolved reflectivity with double pump pulses. Oscillation of reflectivity was caused by interference between the probe pulses reflected at the sample surface and the spallation layer, and was enhanced when the surface was irradiated with the second pump pulse within a time interval, Δτ, of several picoseconds after the first pump pulse. However, as Δτ was increased, the oscillation amplitude decreased with an exponential decay time of 10 ps. The oscillation disappeared when Δτ exceeded 20 ps. This result suggests that the formation time of the spallationmore » layer is approximately 10 ps. A second pump pulse with Δτ shorter than 10 ps excites the bulk sample. The spallation layer that is photo-excited by the first and second pump pulses is separated afterward. In contrast, a pulse with Δτ longer than the formation time excites and breaks up the spallation layer that has already been separated from the bulk. The formation time of the spallation layer, as determined in this experiment, is attributed to the characteristic time of the mechanical equilibration corresponding to the thickness divided by the sound velocity of the photo-excited layer.« less

Study of the influence of the agarose hydrogel layer thickness on sensitivity of the coated silica microsphere resonator to humidity.

PubMed

Mallik, Arun Kumar; Farrell, Gerald; Wu, Qiang; Semenova, Yuliya

2017-05-10

In this paper, we investigate both theoretically and experimentally the influence of the agarose hydrogel layer thickness on the sensitivity of a proposed relative humidity (RH) sensor based on a silica microsphere resonator coated with agarose hydrogel. The operating principle of the sensor relies on excitation of whispering gallery modes (WGMs) in the coated silica microsphere using the evanescent field of a tapered fiber. A change in the ambient relative humidity is detected by measuring the wavelength shift of the WGMs in the transmission spectrum of the tapered fiber. Using perturbation theory, we analyze the influence of the agarose coating thickness on the sensitivity of the proposed sensor and compare the results of this analysis with experimental findings for different coating layer thicknesses. We demonstrate that an increase in the coating layer thickness initially leads to an increase in the sensitivity to RH and reaches saturation at higher values of the agarose layer thickness. The results of the study are useful for the design and optimization of microsphere sensor parameters to meet a performance specification.

Ad-hoc surface-enhanced Raman spectroscopy methodologies for the detection of artist dyestuffs: thin layer chromatography-surface enhanced Raman spectroscopy and in situ on the fiber analysis.

PubMed

Brosseau, Christa L; Gambardella, Alessa; Casadio, Francesca; Grzywacz, Cecily M; Wouters, Jan; Van Duyne, Richard P

2009-04-15

Tailored ad-hoc methods must be developed for successful identification of minute amounts of natural dyes on works of art using Surface-Enhanced Raman Spectroscopy (SERS). This article details two of these successful approaches using silver film over nanosphere (AgFON) substrates and silica gel coupled with citrate-reduced Ag colloids. The latter substrate functions as the test system for the coupling of thin-layer chromatography and SERS (TLC-SERS), which has been used in the current research to separate and characterize a mixture of several artists' dyes. The poor limit of detection of TLC is overcome by coupling with SERS, and dyes which co-elute to nearly the same spot can be distinguished from each other. In addition, in situ extractionless non-hydrolysis SERS was used to analyze dyed reference fibers, as well as historical textile fibers. Colorants such as alizarin, purpurin, carminic acid, lac dye, crocin, and Cape jasmine were thus successfully identified.

Surface modification of nano-silica on the ligament advanced reinforcement system for accelerated bone formation: primary human osteoblasts testing in vitro and animal testing in vivo

NASA Astrophysics Data System (ADS)

Li, Mengmeng; Wang, Shiwen; Jiang, Jia; Sun, Jiashu; Li, Yuzhuo; Huang, Deyong; Long, Yun-Ze; Zheng, Wenfu; Chen, Shiyi; Jiang, Xingyu

2015-04-01

The Ligament Advanced Reinforcement System (LARS) has been considered as a promising graft for ligament reconstruction. To improve its biocompatibility and effectiveness on new bone formation, we modified the surface of a polyethylene terephthalate (PET) ligament with nanoscale silica using atom transfer radical polymerization (ATRP) and silica polymerization. The modified ligament is tested by both in vitro and in vivo experiments. Human osteoblast testing in vitro exhibits an ~21% higher value in cell viability for silica-modified grafts compared with original grafts. Animal testing in vivo shows that there is new formed bone in the case of a nanoscale silica-coated ligament. These results demonstrate that our approach for nanoscale silica surface modification on LARS could be potentially applied for ligament reconstruction.The Ligament Advanced Reinforcement System (LARS) has been considered as a promising graft for ligament reconstruction. To improve its biocompatibility and effectiveness on new bone formation, we modified the surface of a polyethylene terephthalate (PET) ligament with nanoscale silica using atom transfer radical polymerization (ATRP) and silica polymerization. The modified ligament is tested by both in vitro and in vivo experiments. Human osteoblast testing in vitro exhibits an ~21% higher value in cell viability for silica-modified grafts compared with original grafts. Animal testing in vivo shows that there is new formed bone in the case of a nanoscale silica-coated ligament. These results demonstrate that our approach for nanoscale silica surface modification on LARS could be potentially applied for ligament reconstruction. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr01439e

Preparation and flow cytometry of uniform silica-fluorescent dye microspheres.

PubMed

Bele, Marjan; Siiman, Olavi; Matijević, Egon

2002-10-15

Uniform fluorescent silica-dye microspheres have been prepared by coating preformed monodispersed silica particles with silica layers containing rhodamine 6G or acridine orange. The resulting dispersions exhibit intense fluorescent emission between 500 and 600 nm, over a broad excitation wavelength range of 460 to 550 nm, even with exceedingly small amounts of dyes incorporated into the silica particles (10-30 ppm, expressed as weight of dye relative to weight of dry particles). The fluorescent particles can be prepared in micrometer diameters suitable for analyses using flow cytometry with 488-nm laser excitation.

Effect of surface roughness and subsurface damage on grazing-incidence x-ray scattering and specular reflectance.

PubMed

Lodha, G S; Yamashita, K; Kunieda, H; Tawara, Y; Yu, J; Namba, Y; Bennett, J M

1998-08-01

Grazing-incidence specular reflectance and near-specular scattering were measured at Al-K(alpha) (1.486-keV, 8.34-?) radiation on uncoated dielectric substrates whose surface topography had been measured with a scanning probe microscope and a mechanical profiler. Grazing-incidence specular reflectance was also measured on selected substrates at the Cu-K(alpha) (8.047-keV, 1.54-?) wavelength. Substrates included superpolished and conventionally polished fused silica; SiO(2) wafers; superpolished and precision-ground Zerodur; conventionally polished, float-polished, and precision-ground BK-7 glass; and superpolished and precision-ground silicon carbide. Roughnesses derived from x-ray specular reflectance and scattering measurements were in good agreement with topographic roughness values measured with a scanning probe microscope (atomic force microscope) and a mechanical profiler that included similar ranges of surface spatial wavelengths. The specular reflectance was also found to be sensitive to the density of polished surface layers and subsurface damage down to the penetration depth of the x rays. Density gradients and subsurface damage were found in the superpolished fused-silica and precision-ground Zerodur samples. These results suggest that one can nondestructively evaluate subsurface damage in transparent materials using grazing-incidence x-ray specular reflectance in the 1.5-8-keV range.

Corundum ceramic materials modified with silica nanopowders: structure and mechanical properties

NASA Astrophysics Data System (ADS)

Kostytsyn, M. A.; Muratov, D. S.; Lysov, D. V.; Chuprunov, K. O.; Yudin, A. G.; Leybo, D. V.

2016-01-01

Filtering elements are often used in the metallurgy of rare earth metals. Corundum ceramic is one of the most suitable materials for this purpose. The process of formation and the properties of nanomodified ceramic materials, which are proposed as filtering materials with tunable effective porosity, are described. A silica nanopowder is used as a porosity-increasing agent. Vortex layer apparatus is used for mixing of precursor materials. The obtained results show that nanomodification with the vortex layer apparatus using 0.04 wt. % silica nanopowder as a modifying agent leads to an increase in the compression strength of corundum ceramic by the factor of 1.5.

Zirconium(IV) oxide: New coating material for nanoresonators for shell-isolated nanoparticle-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Krajczewski, Jan; Abdulrahman, Heman Burhanalden; Kołątaj, Karol; Kudelski, Andrzej

2018-03-01

One tool that can be used for determining the structure and composition of surfaces of various materials (even in in situ conditions) is shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). In SHINERS measurements, the surface under investigation is covered with a layer of surface-protected plasmonic nanoparticles, and then the Raman spectrum of the surface analysed is recorded. The plasmonic cores of the used core-shell structures act as electromagnetic nanoresonators, significantly locally enhancing the intensity of the electric field of the incident radiation, leading to a large increase in the efficiency of the generation of the Raman signal from molecules in the close proximity to the deposited SHINERS nanoresonators. A protective layer (from transparent dielectrics such as SiO2, Al2O3 or TiO2) prevents direct interaction between the plasmonic metal and the analysed surface (such interactions may lead to changes in the structure of the surface) and, in the case of plasmonic cores other than gold cores, the dielectric layer increases the chemical stability of the metal core. In this contribution, we show for the first time that core-shell nanoparticles having a silver core (both a solid and hollow one) and a shell of zirconium(IV) oxide are very efficient SHINERS nanoresonators that are significantly more stable in acidic and alkaline media than the silver-silica core-shell structures typically used for SHINERS experiments.

Adsorption of silica colloids onto like-charged silica surfaces of different roughness

DOE PAGES

Dylla-Spears, R.; Wong, L.; Shen, N.; ...

2017-01-17

Particle adsorption was explored in a model optical polishing system, consisting of silica colloids and like-charged silica surfaces. The adsorption was monitored in situ under various suspension conditions, in the absence of surfactants or organic modifiers, using a quartz crystal microbalance with dissipation monitoring (QCM-D). Changes in surface coverage with particle concentration, particle size, pH, ionic strength and ionic composition were quantified by QCM-D and further characterized ex situ by atomic force microscopy (AFM). A Monte Carlo model was used to describe the kinetics of particle deposition and provide insights on scaling with particle concentration. Transitions from near-zero adsorption tomore » measurable adsorption were compared with equilibrium predictions made using the Deraguin-Verwey-Landau-Overbeek (DLVO) theory. In addition, the impact of silica surface roughness on the propensity for particle adsorption was studied on various spatial scale lengths by intentionally roughening the QCM sensor surface using polishing methods. It was found that a change in silica surface roughness at the AFM scale from 1.3 nm root-mean-square (rms) to 2.7 nm rms resulted in an increase in silica particle adsorption of 3-fold for 50-nm diameter particles and 1.3-fold for 100-nm diameter particles—far exceeding adsorption observed by altering suspension conditions alone, potentially because roughness at the proper scale reduces the total separation distance between particle and surface.« less

Synthesis, characterization, and protein labeling of difunctional magnetic nanoparticles modified with thiazole orange dye

NASA Astrophysics Data System (ADS)

Fei, Xuening; Zhu, Huifang; Zhou, Jianguo; Yu, Lu

2014-03-01

A dual functional nanoparticle was designed and synthesized by encapsulating magnetic core inside silica particles and subsequently a thiazole orange (TO) dye derivative was modified on the surface of the nanoparticles. The obtained particles were characterized by Fourier transform infrared spectroscope, Uv-Vis spectrophotometer, fluorescence spectrophotometer, transmission electron microscope, dynamic light scattering, etc. The size of preliminary magnetic particles is ca. 7 nm, but after coating a silica layer and dye, the size of particles is increased to ca. 60 nm. The hydrodynamic diameter, water dispersibility, and zeta potential were also determined. The hydrodynamic diameter of particles with silica and dye is 65.2 and 70.5 nm, respectively, with positive zeta potential (25.1, 38.5 mV). Furthermore magnetic properties of the particles were measured and the experimental results suggested that it could meet the requirement of application as magnetic resonance imaging agent. Finally to verify the availability of the particles as fluorescent labeling, protein labeling experiment was performed using bovine serum albumin (BSA) protein and the results showed that the dual functional particle has higher affinity with BSA than TO molecule itself.

Hydrogen Crystallization in Low-Density Aerogels

DOE PAGES

Kucheyev, S. O.; Van Cleve, E.; Johnston, L. T.; ...

2015-03-17

Crystallization of liquids confined in disordered low-density nanoporous scaffolds is poorly understood. Here in this work, we use relaxation calorimetry to study the liquid–solid phase transition of H 2 in a series of silica and carbon (nanotube- and graphene-based) aerogels with porosities ≳94%. Results show that freezing temperatures of H 2 inside all the aerogels studied are depressed but do not follow predictions of the Gibbs–Thomson theory based on average pore diameters measured by conventional gas sorption techniques. Instead, we find that, for each material family investigated, the depression of average freezing temperatures scales linearly with the ratio of themore » internal surface area (measured by gas sorption) and the total pore volume derived from the density of aerogel monoliths. The slope of such linear dependences is, however, different for silica and carbon aerogels, which we attribute to microporosity of carbons and the presence of macropores in silica aerogels. In conclusion, our results have important implications for the analysis of pore size distributions of low-density nanoporous materials and for controlling crystallization of fuel layers in targets for thermonuclear fusion energy applications.« less

Chemical functionalization of diatom silica microparticles for adsorption of gold (III) ions.

PubMed

Yu, Yang; Addai-Mensah, Jonas; Losic, Dusan

2011-12-01

Diatom silica microparticles from natural diatomaceous earth (DE) silica have been functionalized with 3-mercaptopropyltrimethoxysilane (MPTMS) and their application for adsorption of gold (III) ions from aqueous solutions is demonstrated. Fourier transform infrared spectroscopy (FTIR) and X-ray Photoelectron spectroscopy (XPS) analyses of the MPTMS modified diatom microparticles revealed that the silane layer with functional group (-SH) was successfully introduced to the diatom surface. The adsorption study of Au(III) ions using MPTMS-DE indicated that the process depends on initial gold (III) concentration and pH showing maximum adsorption capacity at pH = 3. The Au(III) adsorption kinetics results showed that the adsorption was very fast and followed a pseudo-second-order reaction model. The Langmuir model was used to provide a sound mechanistic basis for the theoretical of the adsorption equilibrium data. Gold recovery from MPTMS-DE structures was also investigated by using acidified thiourea solution and found to be high (> 95%). These results show that chemically modified DE microparticles can be used as a new, cost effective and environmentally benign adsorbent suitable for adsorption of gold metal ions from aqueous solutions.

Multifunctional Enveloped Mesoporous Silica Nanoparticles for Subcellular Co-delivery of Drug and Therapeutic Peptide

PubMed Central

Luo, Guo-Feng; Chen, Wei-Hai; Liu, Yun; Lei, Qi; Zhuo, Ren-Xi; Zhang, Xian-Zheng

2014-01-01

A multifunctional enveloped nanodevice based on mesoporous silica nanoparticle (MSN) was delicately designed for subcellular co-delivery of drug and therapeutic peptide to tumor cells. Mesoporous silica MCM-41 nanoparticles were used as the core for loading antineoplastic drug topotecan (TPT). The surface of nanoparticles was decorated with mitochondria-targeted therapeutic agent (Tpep) containing triphenylphosphonium (TPP) and antibiotic peptide (KLAKLAK)2 via disulfide linkage, followed by coating with a charge reversal polyanion poly(ethylene glycol)-blocked-2,3-dimethylmaleic anhydride-modified poly(L-lysine) (PEG-PLL(DMA)) via electrostatic interaction. It was found that the outer shielding layer could be removed at acidic tumor microenvironment due to the degradation of DMA blocks and the cellular uptake was significantly enhanced by the formation of cationic nanoparticles. After endocytosis, due to the cleavage of disulfide bonds in the presence of intracellular glutathione (GSH), pharmacological agents (Tpep and TPT) could be released from the nanoparticles and subsequently induce specific damage of tumor cell mitochondria and nucleus respectively with remarkable synergistic antitumor effect. PMID:25317538

Hydrogen crystallization in low-density aerogels.

PubMed

Kucheyev, S O; Van Cleve, E; Johnston, L T; Gammon, S A; Worsley, M A

2015-04-07

Crystallization of liquids confined in disordered low-density nanoporous scaffolds is poorly understood. Here, we use relaxation calorimetry to study the liquid-solid phase transition of H2 in a series of silica and carbon (nanotube- and graphene-based) aerogels with porosities ≳94%. Results show that freezing temperatures of H2 inside all the aerogels studied are depressed but do not follow predictions of the Gibbs-Thomson theory based on average pore diameters measured by conventional gas sorption techniques. Instead, we find that, for each material family investigated, the depression of average freezing temperatures scales linearly with the ratio of the internal surface area (measured by gas sorption) and the total pore volume derived from the density of aerogel monoliths. The slope of such linear dependences is, however, different for silica and carbon aerogels, which we attribute to microporosity of carbons and the presence of macropores in silica aerogels. Our results have important implications for the analysis of pore size distributions of low-density nanoporous materials and for controlling crystallization of fuel layers in targets for thermonuclear fusion energy applications.

Silica micro- and nanoparticles reduce the toxicity of surfactant solutions.

PubMed

Ríos, Francisco; Fernández-Arteaga, Alejandro; Fernández-Serrano, Mercedes; Jurado, Encarnación; Lechuga, Manuela

2018-04-20

In this work, the toxicity of hydrophilic fumed silica micro- and nanoparticles of various sizes (7 nm, 12 nm, and 50 μm) was evaluated using the luminescent bacteria Vibrio fischeri. In addition, the toxicity of an anionic surfactant solution (ether carboxylic acid), a nonionic surfactant solution (alkyl polyglucoside), and a binary (1:1) mixture of these solutions all containing these silica particles was evaluated. Furthermore, this work discusses the adsorption of surfactants onto particle surfaces and evaluates the effects of silica particles on the surface tension and critical micellar concentration (CMC) of these anionic and nonionic surfactants. It was determined that silica particles can be considered as non-toxic and that silica particles reduce the toxicity of surfactant solutions. Nevertheless, the toxicity reduction depends on the ionic character of the surfactants. Differences can be explained by the different adsorption behavior of surfactants onto the particle surface, which is weaker for nonionic surfactants than for anionic surfactants. Regarding the effects on surface tension, it was found that silica particles increased the surface activity of anionic surfactants and considerably reduced their CMC, whereas in the case of nonionic surfactants, the effects were reversed. Copyright © 2018 Elsevier B.V. All rights reserved.

PROGRA2 experiment: New results for dust clouds and regoliths analogs

NASA Astrophysics Data System (ADS)

Hadamcik, E.; Renard, J.-B.; Levasseur-Regourd, A. C.; Worms, J.-C.

2006-01-01

With the PROGRA2 experience, linear polarization of scattered light is measured on various types of dust clouds lifted by microgravity, or by an air-draught. The aim is to compare the phase curves for dust analogs with those obtained in the Solar System (cometary comae, and solid particles in planetary atmospheres) by remote-sensing and in situ techniques. Measurements are also performed on layers of particles (on the ground) and compared with remote measurements on asteroidal regoliths and planetary surfaces. New phase curves have been obtained, e.g., for quartz samples, crystals, fluffy mixtures of silica and carbon blacks and a high porosity regolith analog made of micron-sized silica spheres. This work will contribute to the choice of the samples to be studied with the ICAPS experiment onboard the ISS and on the precursor experiment.

Architecture of optical sensor for recognition of multiple toxic metal ions from water.

PubMed

Shenashen, M A; El-Safty, S A; Elshehy, E A

2013-09-15

Here, we designed novel optical sensor based on the wormhole hexagonal mesoporous core/multi-shell silica nanoparticles that enabled the selective recognition and removal of these extremely toxic metals from drinking water. The surface-coating process of a mesoporous core/double-shell silica platforms by several consequence decorations using a cationic surfactant with double alkyl tails (CS-DAT) and then a synthesized dicarboxylate 1,5-diphenyl-3-thiocarbazone (III) signaling probe enabled us to create a unique hierarchical multi-shell sensor. In this design, the high loading capacity and wrapping of the CS-DAT and III organic moieties could be achieved, leading to the formation of silica core with multi-shells that formed from double-silica, CS-DAT, and III dressing layers. In this sensing system, notable changes in color and reflectance intensity of the multi-shelled sensor for Cu(2+), Co(2+), Cd(2+), and Hg(2+) ions, were observed at pH 2, 8, 9.5 and 11.5, respectively. The multi-shelled sensor is added to enable accessibility for continuous monitoring of several different toxic metal ions and efficient multi-ion sensing and removal capabilities with respect to reversibility, selectivity, and signal stability. Copyright © 2013 Elsevier B.V. All rights reserved.

Viscoelastic properties of cationic starch adsorbed on quartz studied by QCM-D.

PubMed

Tammelin, Tekla; Merta, Juha; Johansson, Leena-Sisko; Stenius, Per

2004-12-07

The adsorption and viscoelastic properties of layers of a cationic polyelectrolyte (cationic starch, CS, with 2-hydroxy-3-trimethylammoniumchloride as the substituent) adsorbed from aqueous solutions (pH 7.5, added NaCl 0, 1, 100, and 500 mM) on silica were studied with a quartz crystal microbalance with dissipation (QCM-D). Three different starches were investigated (weight-average molecular weights M(w) approximately 8.7 x 10(5) and 4.5 x 10(5) with degree of substitution DS = 0.75 and M(w) approximately 8.8 x 10(5) with DS = 0.2). At low ionic strength, the adsorbed layers are thin and rigid and the amount adsorbed can be calculated using the Sauerbrey equation. When the ionic strength is increased, significant changes take place in the amount of adsorbed CS and the viscoelasticity of the adsorbed layer. These changes were analyzed assuming that the layer can be described as a Voigt element on a rigid surface in contact with purely viscous solvent. It was found that CS with low charge density forms a thicker and more mobile layer with higher viscosity and elasticity than CS with high charge density. The polymers adsorbed on the silica even when the ionic strength was so high that electrostatic interactions were effectively screened. At this high ionic strength, it was possible to study the effect of molecular weight and molecular weight distribution of the CS on the properties of the adsorbed film. Increasing the molecular weight of CS resulted in a larger hydrodynamic thickness. CS with a narrow molecular weight distribution formed a more compact and rigid layer than broadly distributed CS, presumably due to the better packing of the molecules.

In-situ fabrication of halloysite nanotubes/silica nano hybrid and its application in unsaturated polyester resin

NASA Astrophysics Data System (ADS)

Lin, Jing; Zhong, Bangchao; Jia, Zhixin; Hu, Dechao; Ding, Yong; Luo, Yuanfang; Jia, Demin

2017-06-01

Silica nanoparticles was in-situ grown on the surface of halloysite nanotubes (HNTs) by a facile one-step approach to prepare a unique nano-structured hybrid (HNTs-g-Silica). The structure, morphology and composition of HNTs-g-Silica were investigated. It was confirmed that silica nanoparticles with the diameter of 10-20 nm were chemically grafted through Sisbnd O bonds and uniformly dispersed onto the surface of HNTs, leading to the formation of nano-protrusions on the nanotube surface. Due to the significantly improved interface strength between HNTs-g-Silica and polymer matrix, HNTs-g-Silica effectively toughened unsaturated polyester resin (UPE) and endowed UPE with superior thermal stability compared to HNTs. Based on the unique hybrid architecture and the improved properties of UPE nanocomposites, it is envisioned that HNTs-g-Silica may be a promising filler for more high performance and functional polymers composites and the fabrication method may have implications in the synthesis of nano hybrid materials.

Anti-reflection coatings applied by acid leaching process

NASA Technical Reports Server (NTRS)

Pastirik, E.

1980-01-01

The Magicote C process developed by S.M. Thompsen was evaluated for use in applying an antireflective coating to the cover plates of solar panels. The process uses a fluosilicic acid solution supersaturated with silica at elevated temperature to selectively attack the surface of soda-lime glass cover plates and alter the physical and chemical composition of a thin layer of glass. The altered glass layer constitutes an antireflective coating. The process produces coatings of excellent optical quality which possess outstanding resistance to soiling and staining. The coatings produced are not resistant to mechanical abrasion and are attacked to some extent by glass cleansers. Control of the filming process was found to be difficult.

Supramolecular Complex Antioxidant Consisting of Vitamins C, E and Hydrophilic-Hydrophobic Silica Nanoparticles

NASA Astrophysics Data System (ADS)

Laguta, I. V.; Kuzema, P. O.; Stavinskaya, O. N.; Kazakova, O. A.

Samples with varied amount of surface trimethylsilyl groups were obtained via gas-phase chemical modification of silica nanoparticles. The biocompatibility tests conducted in erythrocyte suspension have shown that hydrophobization of silica decreases its damaging effect to the cells. Being wettable in aqueous media, partially silylated silicas have higher affinity to hydrophobic bioactive molecules in comparison with the initial silica. Novel antioxidant consisting of vitamins C and E and silica with 40% of surface trimethylsilyl groups was formulated. It was found that supramolecular complexes are formed on the silica surface due to the affinity of water- and fat-soluble antioxidants to hydrophilic silanol and hydrophobic trimethylsilyl groups, respectively. Test reactions (total phenolic index determination, DPPH test) and in vitro studies (spectral analysis of erythrocyte suspensions undergoing UV irradiation) revealed the correlation between antioxidant activity of the complex antioxidant and the vitamins’ content. The antioxidant remained active during long-term storage under standard conditions.

Supramolecular Complex Antioxidant Consisting of Vitamins C, E and Hydrophilic-Hydrophobic Silica Nanoparticles

NASA Astrophysics Data System (ADS)

Laguta, I. V.; Kuzema, P. O.; Stavinskaya, O. N.; Kazakova, O. A.

Samples with varied amount of surface trimethylsilyl groups were obtained via gas-phase chemical modification of silica nanoparticles. The biocompatibility tests conducted in erythrocyte suspension have shown that hydrophobization of silica decreases its damaging effect to the cells. Being wettable in aqueous media, partially silylated silicas have higher affinity to hydrophobic bioactive molecules in comparison with the initial silica. Novel antioxidant consisting of vitamins C and E and silica with 40% of surface trimethylsilyl groups was formulated. It was found that supramolecular complexes are formed on the silica surface due to the affinity of water- and fat-soluble antioxidants to hydrophilic silanol and hydrophobic trimethylsilyl groups, respectively. Test reactions (total phenolic index determination, DPPH test) and in vitro studies (spectral analysis of erythrocyte suspensions undergoing UV irradiation) revealed the correlation between antioxidant activity of the complex antioxidant and the vitamins' content. The antioxidant remained active during long-term storage under standard conditions.

Non-destructive evaluation of UV pulse laser-induced damage performance of fused silica optics.

PubMed

Huang, Jin; Wang, Fengrui; Liu, Hongjie; Geng, Feng; Jiang, Xiaodong; Sun, Laixi; Ye, Xin; Li, Qingzhi; Wu, Weidong; Zheng, Wanguo; Sun, Dunlu

2017-11-24

The surface laser damage performance of fused silica optics is related to the distribution of surface defects. In this study, we used chemical etching assisted by ultrasound and magnetorheological finishing to modify defect distribution in a fused silica surface, resulting in fused silica samples with different laser damage performance. Non-destructive test methods such as UV laser-induced fluorescence imaging and photo-thermal deflection were used to characterize the surface defects that contribute to the absorption of UV laser radiation. Our results indicate that the two methods can quantitatively distinguish differences in the distribution of absorptive defects in fused silica samples subjected to different post-processing steps. The percentage of fluorescence defects and the weak absorption coefficient were strongly related to the damage threshold and damage density of fused silica optics, as confirmed by the correlation curves built from statistical analysis of experimental data. The results show that non-destructive evaluation methods such as laser-induced fluorescence and photo-thermal absorption can be effectively applied to estimate the damage performance of fused silica optics at 351 nm pulse laser radiation. This indirect evaluation method is effective for laser damage performance assessment of fused silica optics prior to utilization.

Investigating the properties and interaction mechanism of nano-silica in polyvinyl alcohol/polyacrylamide blends at an atomic level.

PubMed

Wei, Qinghua; Wang, Yanen; Wang, Shuzhi; Zhang, Yingfeng; Chen, Xiongbiao

2017-11-01

The nano-silica can be incorporated into polymers for improved mechanical properties. Notably, the interaction between nano-silica and polymer is of a microscopic phenomenon and thus, hard to observe and study by using experimental methods. Based on molecular dynamics, this paper presents a study on the properties and the interaction mechanism of nano-silica in the polyvinyl alcohol (PVA)/polyacrylamide (PAM) blends at an atomic level. Specifically, six blends of PVA/PAM with varying concentrations of nano-silica (0-13wt%) and two interfacial interaction models of polymers on the silica surface were designed and analyzed at an atomic level in terms of concentration profile, mechanical properties, fractional free volume (FFV), dynamic properties of polymers and X-ray diffraction patterns. The concentration profile results and micromorphologies of equilibrium models suggest PAM molecular chains are easier to be adsorbed on the silica surface than PVA molecular chains in blends. The incorporation of nano-silica into the PVA/PAM blends can increase the blend mechanical properties, densities, and semicrystalline character. Meanwhile, the FFV and the mobility of polymer chain decrease with the silica concentration, which agrees with the results of mechanical properties, densities, and semicrystalline character. Our results also illustrate that an analysis of binding energies and pair correlation functions (PCF) allows for the discovery of the interaction mechanism of nano-silica in PVA/PAM blends; and that hydrogen bond interactions between polar functional groups of polymer molecular chains and the hydroxyl groups of the silica surface are involved in adsorption of the polymers on the silica surface, thus affecting the interaction mechanism of nano-silica in PVA/PAM blend systems. Copyright © 2017 Elsevier Ltd. All rights reserved.

Reflecting heat shields made of microstructured fused silica

NASA Technical Reports Server (NTRS)

Congdon, W. M.

1975-01-01

Heat sheidls constructed from selected monodisperse distributions of high-purity fused-silica particles are efficient reflectors of visible and near-UV radiation generated in shock-layer of space probe during atmospheric entry.

Energy Landscape of Water and Ethanol on Silica Surfaces

DOE PAGES

Wu, Di; Guo, Xiaofeng; Sun, Hui; ...

2015-06-26

Fundamental understanding of small molecule–silica surface interactions at their interfaces is essential for the scientific, technological, and medical communities. We report direct enthalpy of adsorption (Δh ads) measurements for ethanol and water vapor on porous silica glass (CPG-10), in both hydroxylated and dehydroxylated (hydrophobic) forms. Results suggest a spectrum of energetics as a function of coverage, stepwise for ethanol but continuous for water. The zero-coverage enthalpy of adsorption for hydroxylated silica shows the most exothermic enthalpies for both water (-72.7 ± 3.1 kJ/mol water) and ethanol (-78.0 ± 1.9 kJ/mol ethanol). The water adsorption enthalpy becomes less exothermic gradually untilmore » reaching its only plateau (-20.7 ± 2.2 kJ/mol water) reflecting water clustering on a largely hydrophobic surface, while the enthalpy of ethanol adsorption profile presents two well separated plateaus, corresponding to strong chemisorption of ethanol on adsorbate-free silica surface (-66.4 ± 4.8 kJ/mol ethanol), and weak physisorption of ethanol on ethanol covered silica (-4.0 ± 1.6 kJ/mol ethanol). On the other hand, dehydroxylation leads to missing water–silica interactions, whereas the number of ethanol binding sites is not impacted. The isotherms and partial molar properties of adsorption suggest that water may only bind strongly onto the silanols (which are a minor species on silica glass), whereas ethanol can interact strongly with both silanols and the hydrophobic areas of the silica surface.« less

Development of a tuned interfacial force field parameter set for the simulation of protein adsorption to silica glass.

PubMed

Snyder, James A; Abramyan, Tigran; Yancey, Jeremy A; Thyparambil, Aby A; Wei, Yang; Stuart, Steven J; Latour, Robert A

2012-12-01

Adsorption free energies for eight host-guest peptides (TGTG-X-GTGT, with X = N, D, G, K, F, T, W, and V) on two different silica surfaces [quartz (100) and silica glass] were calculated using umbrella sampling and replica exchange molecular dynamics and compared with experimental values determined by atomic force microscopy. Using the CHARMM force field, adsorption free energies were found to be overestimated (i.e., too strongly adsorbing) by about 5-9 kcal/mol compared to the experimental data for both types of silica surfaces. Peptide adsorption behavior for the silica glass surface was then adjusted using a modified version of the CHARMM program, which we call dual force-field CHARMM, which allows separate sets of nonbonded parameters (i.e., partial charge and Lennard-Jones parameters) to be used to represent intra-phase and inter-phase interactions within a given molecular system. Using this program, interfacial force field (IFF) parameters for the peptide-silica glass systems were corrected to obtain adsorption free energies within about 0.5 kcal/mol of their respective experimental values, while IFF tuning for the quartz (100) surface remains for future work. The tuned IFF parameter set for silica glass will subsequently be used for simulations of protein adsorption behavior on silica glass with greater confidence in the balance between relative adsorption affinities of amino acid residues and the aqueous solution for the silica glass surface.

Development of a Tuned Interfacial Force Field Parameter Set for the Simulation of Protein Adsorption to Silica Glass

PubMed Central

Snyder, James A.; Abramyan, Tigran; Yancey, Jeremy A.; Thyparambil, Aby A.; Wei, Yang; Stuart, Steven J.; Latour, Robert A.

2012-01-01

Adsorption free energies for eight host–guest peptides (TGTG-X-GTGT, with X = N, D, G, K, F, T, W, and V) on two different silica surfaces [quartz (100) and silica glass] were calculated using umbrella sampling and replica exchange molecular dynamics and compared with experimental values determined by atomic force microscopy. Using the CHARMM force field, adsorption free energies were found to be overestimated (i.e., too strongly adsorbing) by about 5–9 kcal/mol compared to the experimental data for both types of silica surfaces. Peptide adsorption behavior for the silica glass surface was then adjusted using a modified version of the CHARMM program, which we call dual force-field CHARMM, which allows separate sets of nonbonded parameters (i.e., partial charge and Lennard-Jones parameters) to be used to represent intra-phase and inter-phase interactions within a given molecular system. Using this program, interfacial force field (IFF) parameters for the peptide-silica glass systems were corrected to obtain adsorption free energies within about 0.5 kcal/mol of their respective experimental values, while IFF tuning for the quartz (100) surface remains for future work. The tuned IFF parameter set for silica glass will subsequently be used for simulations of protein adsorption behavior on silica glass with greater confidence in the balance between relative adsorption affinities of amino acid residues and the aqueous solution for the silica glass surface. PMID:22941539

Luminescent Properties of Eu(III) Chelates on Metal Nanorods

PubMed Central

Zhang, Jian; Fu, Yi; Ray, Krishanu; Wang, Yuan; Lakowicz, Joseph. R.

2013-01-01

In this article, we report the change of optical properties for europium chelates on silver nanorods by near-field interactions. The silver rods were fabricated in a seed-growth method followed by depositing thin layers of silica on the surfaces. The europium chelates were physically absorbed in the silica layers on the silver rods. The silver rods were observed to exhibit two plasmon absorption bands from longitudinal and transverse directions, respectively, centered at 394 and 675 nm, close to absorption and emission bands from the Eu(III) chelates. As a result, the immobilized Eu(III) chelates on the silver rods should have strong interactions with the silver nanorods and lead to greatly improved optical properties. The Eu–Ag rod complexes were observed to have enhanced emission intensity up to 240-fold in comparison with the Eu(III) chelates in the metal-free silica templates. This enhancement is much larger than the value for the Eu(III) chelates on the gold rods or silver spheres indicating the presence of stronger interactions for the Eu(III) chelates with the silver rods. The interactions of Eu(III) chelates with the silver rods were also proven by extremely reduced lifetime. Moreover, the Eu–Ag rod complexes exhibited a polarized emission, which was also due to strong interactions of the Eu(III) chelates with the silver rods. All of these features may promise that the Eu(III)–Ag rod complexes have great potential for use as fluorescence imaging agents in biological assays. PMID:24363816

Selective hydrophobic derivatization on the surface of helical silica nanotubes

NASA Astrophysics Data System (ADS)

Jin, Sun-Mi; Sung, Ji Yeong; Sim, Eun-Kyung; Jo, Nam-Ju; Kim, Jong Wook; Lee, Sumin; Jin, Jong Sung

2018-02-01

The chiral 1,2-diphenylethylenediamine derivative that is capable of spontaneous self-assembly was employed as an organogel template to produce a helical mesoporous silica nanotube containing gelators therein by following sol-gel polycondensation of TEOS. The synthesis enabled the successful introduction of the hydrocarbon of octyl silane (hydrophobic functional group) onto the outer surface of the silica nanotube while preserving the hydrophilic silanol (Sisbnd OH) group on internal surface of silica nanotube free from the gelators. This synthetic condition consists of a pre-stage of the introduction of a hydrophobic hydrocarbon functional group onto the outer surface of the silica nanotube selectively, and the post-stage washing of the gelators was presented together with a method analyzing the actions of organogels in the respective experimental processes.

Silicon carbide sewing thread

NASA Technical Reports Server (NTRS)

Sawko, Paul M. (Inventor)

1995-01-01

Composite flexible multilayer insulation systems (MLI) were evaluated for thermal performance and compared with currently used fibrous silica (baseline) insulation system. The systems described are multilayer insulations consisting of alternating layers of metal foil and scrim ceramic cloth or vacuum metallized polymeric films quilted together using ceramic thread. A silicon carbide thread for use in the quilting and the method of making it are also described. These systems provide lightweight thermal insulation for a variety of uses, particularly on the surface of aerospace vehicles subject to very high temperatures during flight.

Preparation and Application of Hollow Silica/magnetic Nanocomposite Particle

NASA Astrophysics Data System (ADS)

Wang, Cheng-Chien; Lin, Jing-Mo; Lin, Chun-Rong; Wang, Sheng-Chang

The hollow silica/cobalt ferrite (CoFe2O4) magnetic microsphere with amino-groups were successfully prepared via several steps, including preparing the chelating copolymer microparticles as template by soap-free emulsion polymerization, manufacturing the hollow cobalt ferrite magnetic microsphere by in-situ chemical co-precipitation following calcinations, and surface modifying of the hollow magnetic microsphere by 3-aminopropyltrime- thoxysilane via the sol-gel method. The average diameter of polymer microspheres was ca. 200 nm from transmission electron microscope (TEM) measurement. The structure of the hollow magnetic microsphere was characterized by using TEM and scanning electron microscope (SEM). The spinel-type lattice of CoFe2O4 shell layer was identified by using XRD measurement. The diameter of CoFe2O4 crystalline grains ranged from 54.1 nm to 8.5 nm which was estimated by Scherrer's equation. Additionally, the hollow silica/cobalt ferrite microsphere possesses superparamagnetic property after VSM measurement. The result of BET measurement reveals the hollow magnetic microsphere which has large surface areas (123.4m2/g). After glutaraldehyde modified, the maximum value of BSA immobilization capacity of the hollow magnetic microsphere was 33.8 mg/g at pH 5.0 buffer solution. For microwave absorption, when the hollow magnetic microsphere was compounded within epoxy resin, the maximum reflection loss of epoxy resins could reach -35dB at 5.4 GHz with 1.9 mm thickness.

Designing of luminescent GdPO4:Eu@LaPO4@SiO2 core/shell nanorods: Synthesis, structural and luminescence properties

NASA Astrophysics Data System (ADS)

Ansari, Anees A.; Labis, Joselito P.; Aslam Manthrammel, M.

2017-09-01

GdPO4:Eu3+ (core) and GdPO4:Eu@LaPO4 (core/shell) nanorods (NRs) were successfully prepared by urea based co-precipitation process at ambient conditions which was followed by coating with amorphous silica shell via the sol-gel chemical route. The role of surface coating on the crystal structure, crystallinity, morphology, solubility, surface chemistry and luminescence properties were well investigated by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray (EDX) analysis, Fourier Transform Infrared (FTIR), UV-Vis, and photoluminescence spectroscopy. XRD pattern revealed highly purified, well-crystalline, single phase-hexagonal-rhabdophane structure of GdPO4 crystal. The TEM micrographs exhibited highly crystalline and narrow size distributed rod-shaped GdPO4:Eu3+ nanostructures with average width 14-16 nm and typical length 190-220 nm. FTIR spectra revealed characteristic infrared absorption bands of amorphous silica. High absorbance in a visible region of silica modified core/shell/Si NRs in aqueous environment suggests the high solubility along with colloidal stability. The photoluminescence properties were remarkably enhanced after growth of undoped LaPO4 layers due to the reduction of nonradiative transition rate. The advantages of presented high emission intensity and high solubility of core/shell and core/shell/Si NRs indicated the potential applications in monitoring biological events.

Surface properties and water treatment capacity of surface engineered silica coated with 3-(2-aminoethyl) aminopropyltrimethoxysilane

NASA Astrophysics Data System (ADS)

Majewski, Peter; Keegan, Alexandra

2012-01-01

This study's focus was on the water-based, one-pot preparation and characterisation of silica particles coated with 3-(2-aminoethyl)aminopropyltrimethoxysilane (Diamo) and the efficiency of the material in removing the pathogens Escherichia coli, Pseudomonas aeruginosa, Mycobacterium immunogenum, Vibrio cholerae, poliovirus, and Cryptosporidium parvum. The water-based processing resulted in Diamo coated silica particles with significantly increased positive surface charge as determined by zeta potential measurements. In addition, X-ray photoelectron spectrometry of pure and Diamo coated silica confirmed the presence of Diamo on the surface of the particles. Thermogravimetric measurements and chemical analysis of the silica indicated a surface concentration of amine groups of about 1 mmol/gsilica. Water treatment tests with the pathogens showed that a dose of about 10 g appeared to be sufficient to remove pathogens from pure water samples which were spiked with pathogen concentrations between about 102 and 104 cfu/mL.

The development of chiral nematic mesoporous materials.

PubMed

Kelly, Joel A; Giese, Michael; Shopsowitz, Kevin E; Hamad, Wadood Y; MacLachlan, Mark J

2014-04-15

Cellulose nanocrystals (CNCs) are obtained from the sulfuric acid-catalyzed hydrolysis of bulk cellulose. The nanocrystals have diameters of ~5-15 nm and lengths of ~100-300 nm (depending on the cellulose source and hydrolysis conditions). This lightweight material has mostly been investigated to reinforce composites and polymers because it has remarkable strength that rivals carbon nanotubes. But CNCs have an additional, less explored property: they organize into a chiral nematic (historically referred to as cholesteric) liquid crystal in water. When dried into a thin solid film, the CNCs retain the helicoidal chiral nematic order and assemble into a layered structure where the CNCs have aligned orientation within each layer, and their orientation rotates through the stack with a characteristic pitch (repeating distance). The cholesteric ordering can act as a 1-D photonic structure, selectively reflecting circularly polarized light that has a wavelength nearly matching the pitch. During CNC self-assembly, it is possible to add sol-gel precursors, such as Si(OMe)4, that undergo hydrolysis and condensation as the solvent evaporates, leading to a chiral nematic silica/CNC composite material. Calcination of the material in air destroys the cellulose template, leaving a high surface area mesoporous silica film that has pore diameters of ~3-10 nm. Importantly, the silica is brilliantly iridescent because the pores in its interior replicate the chiral nematic structure. These films may be useful as optical filters, reflectors, and membranes. In this Account, we describe our recent research into mesoporous films with chiral nematic order. Taking advantage of the chiral nematic order and nanoscale of the CNC templates, new functional materials can be prepared. For example, heating the silica/CNC composites under an inert atmosphere followed by removal of the silica leaves highly ordered, mesoporous carbon films that can be used as supercapacitor electrodes. The composition of the mesoporous films can be varied by using assorted organosilica precursors. After removal of the cellulose by acid-catalyzed hydrolysis, highly porous, iridescent organosilica films are obtained. These materials are flexible and offer the ability to tune the chemical and mechanical properties through variation of the organic spacer. Chiral nematic mesoporous silica and organosilica materials, obtainable as centimeter-scale freestanding films, are interesting hosts for nanomaterials. When noble metal nanoparticles are incorporated into the pores, they show strong circular dichroism signals associated with their surface plasmon resonances that arise from dipolar coupling of the particles within the chiral nematic host. Fluorescent conjugated polymers show induced circular dichroism spectra when encapsulated in the chiral nematic host. The porosity, film structure, and optical properties of these materials could enable their use in sensors. We describe the development of chiral nematic mesoporous silica and organosilica, demonstrate different avenues of host-guest chemistry, and identify future directions that exploit the unique combination of properties present in these materials. The examples covered in this Account demonstrate that there is a rich diversity of composite materials accessible using CNC templating.

Multilayer encapsulated mesoporous silica nanospheres as an oral sustained drug delivery system for the poorly water-soluble drug felodipine.

PubMed

Hu, Liang; Sun, Hongrui; Zhao, Qinfu; Han, Ning; Bai, Ling; Wang, Ying; Jiang, Tongying; Wang, Siling

2015-02-01

We used a combination of mesoporous silica nanospheres (MSN) and layer-by-layer (LBL) self-assembly technology to establish a new oral sustained drug delivery system for the poorly water-soluble drug felodipine. Firstly, the model drug was loaded into MSN, and then the loaded MSN were repeatedly encapsulated by chitosan (CHI) and acacia (ACA) via LBL self-assembly method. The structural features of the samples were studied using scanning electron microscopy (SEM), transmission electron microscopy (TEM) and nitrogen adsorption. The encapsulating process was monitored by zeta-potential and surface tension measurements. The physical state of the drug in the samples was characterized by differential scanning calorimetry (DSC) and X-ray diffractometry (XRD). The influence of the multilayer with different number of layers on the drug release rate was studied using thermal gravimetric analysis (TGA) and surface tension measurement. The swelling effect and the structure changes of the multilayer were investigated to explore the relationship between the drug release behavior and the state of the multilayer under different pH conditions. The stability and mucosa adhesive ability of the prepared nanoparticles were also explored. After multilayer coating, the drug release rate was effectively controlled. The differences in drug release behavior under different pH conditions could be attributed to the different states of the multilayer. And the nanoparticles possessed good stability and strong mucosa adhesive ability. We believe that this combination offers a simple strategy for regulating the release rate of poorly water-soluble drugs and extends the pharmaceutical applications of inorganic materials and polymers. Copyright © 2014 Elsevier B.V. All rights reserved.

Development of plasma chemical vaporization machining

NASA Astrophysics Data System (ADS)

Mori, Yuzo; Yamauchi, Kazuto; Yamamura, Kazuya; Sano, Yasuhisa

2000-12-01

Conventional machining processes, such as turning, grinding, or lapping are still applied for many materials including functional ones. But those processes are accompanied with the formation of a deformed layer, so that machined surfaces cannot perform their original functions. In order to avoid such points, plasma chemical vaporization machining (CVM) has been developed. Plasma CVM is a chemical machining method using neutral radicals, which are generated by the atmospheric pressure plasma. By using a rotary electrode for generation of plasma, a high density of neutral radicals was formed, and we succeeded in obtaining high removal rate of several microns to several hundred microns per minute for various functional materials such as fused silica, single crystal silicon, molybdenum, tungsten, silicon carbide, and diamond. Especially, a high removal rate equal to lapping in the mechanical machining of fused silica and silicon was realized. 1.4 nm (p-v) was obtained as a surface roughness in the case of machining a silicon wafer. The defect density of a silicon wafer surface polished by various machining method was evaluated by the surface photo voltage spectroscopy. As a result, the defect density of the surface machined by plasma CVM was under 1/100 in comparison with the surface machined by mechanical polishing and argon ion sputtering, and very low defect density which was equivalent to the chemical etched surface was realized. A numerically controlled CVM machine for x-ray mirror fabrication is detailed in the accompanying article in this issue.

Interaction of NaOH solutions with silica surfaces

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

Rimsza, Jessica M.; Jones, Reese E.; Criscenti, Louise J.

Sodium adsorption on silica surfaces depends on the solution counter-ion. Here, we use NaOH solutions to investigate basic environments. Sodium adsorption on hydroxylated silica surfaces from NaOH solutions were investigated through molecular dynamics with a dissociative force field, allowing for the development of secondary molecular species. Furthermore, across the NaOH concentrations (0.01 M – 1.0 M), ~50% of the Na + ions were concentrated in the surface region, developing silica surface charges between –0.01 C/m 2 (0.01 M NaOH) and –0.76 C/m 2 (1.0 M NaOH) due to surface site deprotonation. Five inner-sphere adsorption complexes were identified, including monodentate, bidentate,more » and tridentate configurations and two additional structures, with Na + ions coordinated by bridging oxygen and hydroxyl groups or water molecules. Coordination of Na + ions by bridging oxygen atoms indicates partial or complete incorporation of Na + ions into the silica surface. Residence time analysis identified that Na + ions coordinated by bridging oxygen atoms stayed adsorbed onto the surface four times longer than the mono/bi/tridentate species, indicating formation of relatively stable and persistent Na + ion adsorption structures. Such inner-sphere complexes form only at NaOH concentrations of > 0.5 M. Na + adsorption and lifetimes have implications for the stability of silica surfaces.« less

Interaction of NaOH solutions with silica surfaces

DOE PAGES

Rimsza, Jessica M.; Jones, Reese E.; Criscenti, Louise J.

2018-01-16

Sodium adsorption on silica surfaces depends on the solution counter-ion. Here, we use NaOH solutions to investigate basic environments. Sodium adsorption on hydroxylated silica surfaces from NaOH solutions were investigated through molecular dynamics with a dissociative force field, allowing for the development of secondary molecular species. Furthermore, across the NaOH concentrations (0.01 M – 1.0 M), ~50% of the Na + ions were concentrated in the surface region, developing silica surface charges between –0.01 C/m 2 (0.01 M NaOH) and –0.76 C/m 2 (1.0 M NaOH) due to surface site deprotonation. Five inner-sphere adsorption complexes were identified, including monodentate, bidentate,more » and tridentate configurations and two additional structures, with Na + ions coordinated by bridging oxygen and hydroxyl groups or water molecules. Coordination of Na + ions by bridging oxygen atoms indicates partial or complete incorporation of Na + ions into the silica surface. Residence time analysis identified that Na + ions coordinated by bridging oxygen atoms stayed adsorbed onto the surface four times longer than the mono/bi/tridentate species, indicating formation of relatively stable and persistent Na + ion adsorption structures. Such inner-sphere complexes form only at NaOH concentrations of > 0.5 M. Na + adsorption and lifetimes have implications for the stability of silica surfaces.« less

Polymer adsorption on silica and wettability of graphene oxide surfaces, experiments and simulations

NASA Astrophysics Data System (ADS)

Mortazavian, Hamid

Among the various classifications of polymer composites, studying polymers adsorbed to a surface such as silica is important due to their numerous applications. Adsorbed polymers usually show different properties than their bulk counterparts due to their interactions with the surface. In this study, we observed tightly- and loosely-bound polymer and mobile components in poly(vinyl acetate) (PVAc) on silica both with temperature-modulated differential scanning calorimetry (TMDSC) experiments and computer simulations. The more-mobile component which correlated to the region of low density at the air interface is reported for the first time using TMDSC thermograms. Pore size distribution and pore volume development of adsorbed PMMA samples showed different behavior below and above the tightly-bound amount of the polymer. The amount of tightly-bound polymer was obtained by a linear regression analysis of the ratio of the area under the two glass transitions. The values obtained vary from 0.52 to 0.86 mg PVAc/m2 silica depending upon the molecular mass for the amounts of PVAc and the specific surface area of fumed silica. Direct comparisons of the thermal properties and intermolecular interactions were performed between PVAc and poly(methyl methacrylate) (PMMA) with similar molecular masses and adsorbed amounts on silica. A larger amount of tightly-bound polymer and a greater change in glass transition were observed for adsorbed PMMA compared to adsorbed PVAc. These observations suggested that the interactions between PMMA and silica were stronger than those between PVAc and silica. Molecular modeling of these surface polymers showed that PMMA associates more strongly with silica than does PVAc through additional hydrogen-bonding interactions. Graphene oxide (GO) material surface characteristics make it easy to functionalize, making it a water repellant surface. To test the effect of chemical makeup and size of attached groups on the surface wettability of GO, we performed experimental water contact angle measurements and molecular modeling investigations on functionalized GO surfaces. Experimental and molecular simulation water contact angle measurements showed quantitative agreement for functionalizing groups with the same chain length at a variety of surface coverages.

Effect of surface hydroxyl groups on heat capacity of mesoporous silica

NASA Astrophysics Data System (ADS)

Marszewski, Michal; Butts, Danielle; Lan, Esther; Yan, Yan; King, Sophia C.; McNeil, Patricia E.; Galy, Tiphaine; Dunn, Bruce; Tolbert, Sarah H.; Hu, Yongjie; Pilon, Laurent

2018-05-01

This paper quantifies the effect of surface hydroxyl groups on the effective specific and volumetric heat capacities of mesoporous silica. To achieve a wide range of structural diversity, mesoporous silica samples were synthesized by various methods, including (i) polymer-templated nanoparticle-based powders, (ii) polymer-templated sol-gel powders, and (iii) ambigel silica samples dried by solvent exchange at room temperature. Their effective specific heat capacity, specific surface area, and porosity were measured using differential scanning calorimetry and low-temperature nitrogen adsorption-desorption measurements. The experimentally measured specific heat capacity was larger than the conventional weight-fraction-weighted specific heat capacity of the air and silica constituents. The difference was attributed to the presence of OH groups in the large internal surface area. A thermodynamic model was developed based on surface energy considerations to account for the effect of surface OH groups on the specific and volumetric heat capacity. The model predictions fell within the experimental uncertainty.

Surface Area, and Oxidation Effects on Nitridation Kinetics of Silicon Powder Compacts

NASA Technical Reports Server (NTRS)

Bhatt, R. T.; Palczer, A. R.

1998-01-01

Commercially available silicon powders were wet-attrition-milled from 2 to 48 hr to achieve surface areas (SA's) ranging from 1.3 to 70 sq m/g. The surface area effects on the nitridation kinetics of silicon powder compacts were determined at 1250 or 1350 C for 4 hr. In addition, the influence of nitridation environment, and preoxidation on nitridation kinetics of a silicon powder of high surface area (approximately equals 63 sq m/g) was investigated. As the surface area increased, so did the percentage nitridation after 4 hr in N2 at 1250 or 1350 C. Silicon powders of high surface area (greater than 40 sq m/g) can be nitrided to greater than 70% at 1250 C in 4 hr. The nitridation kinetics of the high-surface-area powder compacts were significantly delayed by preoxidation treatment. Conversely, the nitridation environment had no significant influence on the nitridation kinetics of the same powder. Impurities present in the starting powder, and those accumulated during attrition milling, appeared to react with the silica layer on the surface of silicon particles to form a molten silicate layer, which provided a path for rapid diffusion of nitrogen and enhanced the nitridation kinetics of high surface area silicon powder.

Diverse 2D structures obtained by adsorption of charged ABA triblock copolymer on different surfaces

NASA Astrophysics Data System (ADS)

Kontturi, Katri S.; Vesterinen, Arja-Helena; Seppälä, Jukka; Laine, Janne

2012-11-01

In the larger context of 2D polymeric structures, the morphologies obtained by adsorption and subsequent drying of charged, ABA type amphiphilic triblock copolymer of poly[2-(dimethylamino)ethyl metacrylate] (PDMAEMA) and poly(propylene oxide) (PPO) were investigated with atomic force microscopy and X-ray photoelectron spectroscopy as well as in situ adsorption analysis with quartz crystal microbalance with dissipation monitoring. Hydrophilic silica and hydrophobic polystyrene (PS) were used as substrates for adsorption. The structures emerging from the self-assembly of adsorbing polymer were profoundly influenced by composition of the aqueous solution and the choice of substrate. When adsorbed from dilute polymer solution where the concentration is so low that the polymer does not yet show surface-active behavior, the triblock copolymer unimers associated on hydrophilic silica surface forming large, irregular clustered aggregates, with sizes increasing with electrolyte concentration of the solution. On a hydrophobic PS substrate, on the other hand, unimers spread much more evenly, forming clear surface patterns. The roughness of these patterned structures was tuned with the electrolyte concentration of the solution. Adsorption from a more concentrated polymer solution, where the surface-activity of the polymer is perceptible, resulted in the formation of a smooth film with complete coverage over the hydrophilic silica substrate when the electrolyte concentration was high. On PS, on the other hand, nucleation of evenly scattered globular, disk-like micelles was induced. Besides the dry film morphology, the even distribution of the irreversibly adsorbed polymer over the PS surface was likely to serve as an optimal platform for the build-up of reversible hydrophobically bound multilayers at high electrolyte concentration. The multilayer formation was reversible because a decrease in the electrolyte concentration of the solution re-introduces strong electrostatic repulsion between the multilayered polymer coils which results in breakdown of the layer.

Process development for waveguide chemical sensors with integrated polymeric sensitive layers

NASA Astrophysics Data System (ADS)

Amberkar, Raghu; Gao, Zhan; Park, Jongwon; Henthorn, David B.; Kim, Chang-Soo

2008-02-01

Due to the proper optical property and flexibility in the process development, an epoxy-based, high-aspect ratio photoresist SU-8 is now attracting attention in optical sensing applications. Manipulation of the surface properties of SU-8 waveguides is critical to attach functional films such as chemically-sensitive layers. We describe a new integration process to immobilize fluorescence molecules on SU-8 waveguide surface for application to intensity-based optical chemical sensors. We use two polymers for this application. Spin-on, hydrophobic, photopatternable silicone is a convenient material to contain fluorophore molecules and to pattern a photolithographically defined thin layer on the surface of SU-8. We use fumed silica powders as an additive to uniformly disperse the fluorophores in the silicone precursor. In general, additional processes are not critically required to promote the adhesion between the SU-8 and silicone. The other material is polyethylene glycol diacrylate (PEGDA). Recently we demonstrated a novel photografting method to modify the surface of SU-8 using a surface bound initiator to control its wettability. The activated surface is then coated with a monomer precursor solution. Polymerization follows when the sample is exposed to UV irradiation, resulting in a grafted PEGDA layer incorporating fluorophores within the hydrogel matrix. Since this method is based the UV-based photografting reaction, it is possible to grow off photolithographically defined hydrogel patterns on the waveguide structures. The resulting films will be viable integrated components in optical bioanalytical sensors. This is a promising technique for integrated chemical sensors both for planar type waveguide and vertical type waveguide chemical sensors.

Sol-Generating Chemical Vapor into Liquid (SG-CViL) deposition – A facile method for encapsulation of diverse cell types in silica matrices

DOE PAGES

Johnston, Robert; Rogelj, Snezna; Harper, Jason C.; ...

2014-12-12

In nature, cells perform a variety of complex functions such as sensing, catalysis, and energy conversion which hold great potential for biotechnological device construction. However, cellular sensitivity to ex vivo environments necessitates development of bio–nano interfaces which allow integration of cells into devices and maintain their desired functionality. In order to develop such an interface, the use of a novel Sol-Generating Chemical Vapor into Liquid (SG-CViL) deposition process for whole cell encapsulation in silica was explored. In SG-CViL, the high vapor pressure of tetramethyl orthosilicate (TMOS) is utilized to deliver silica into an aqueous medium, creating a silica sol. Cellsmore » are then mixed with the resulting silica sol, facilitating encapsulation of cells in silica while minimizing cell contact with the cytotoxic products of silica generating reactions (i.e. methanol), and reduce exposure of cells to compressive stresses induced from silica condensation reactions. Using SG-CVIL, Saccharomyces cerevisiae (S. cerevisiae) engineered with an inducible beta galactosidase system were encapsulated in silica solids and remained both viable and responsive 29 days post encapsulation. By tuning SG-CViL parameters, thin layer silica deposition on mammalian HeLa and U87 human cancer cells was also achieved. Thus, the ability to encapsulate various cell types in either a multi cell (S. cerevisiae) or a thin layer (HeLa and U87 cells) fashion shows the promise of SG-CViL as an encapsulation strategy for generating cell–silica constructs with diverse functions for incorporation into devices for sensing, bioelectronics, biocatalysis, and biofuel applications.« less

Rapid, conformal gas-phase formation of silica (SiO2) nanotubes from water condensates.

PubMed

Bae, Changdeuck; Kim, Hyunchul; Yang, Yunjeong; Yoo, Hyunjun; Montero Moreno, Josep M; Bachmann, Julien; Nielsch, Kornelius; Shin, Hyunjung

2013-07-07

An innovative atomic layer deposition (ALD) concept, with which nanostructures of water condensates with high aspect ratio at equilibrium in cylindrical nanopores can be transformed uniformly into silica (SiO2) at near room temperature and ambient pressure, has been demonstrated for the first time. As a challenging model system, we first prove the conversion of cylindrical water condensates in porous alumina membranes to silica nanotubes (NTs) by introducing SiCl4 as a metal reactant without involving any catalytic reaction. Surprisingly, the water NTs reproducibly transformed into silica NTs, where the wall thickness of the silica NTs deposited per cycle was found to be limited by the amount of condensed water, and it was on the orders of ten nanometers per cycle (i.e., over 50 times faster than that of conventional ALD). More remarkably, the reactions only took place for 10-20 minutes or less without vacuum-related equipment. The thickness of initially adsorbed water layers in cylindrical nanopores was indirectly estimated from the thickness of formed SiO2 layers. With systematic experimental designs, we tackle the classical Kelvin equation in the nanosized pores, and the role of van der Waals forces in the nanoscale wetting phenomena, which is a long-standing issue lacking experimental insight. Moreover, we show that the present strategy is likely generalized to other oxide systems such as TiO2. Our approach opens up a new avenue for ultra-simple preparation of porous oxides and allows for the room temperature formation of dielectric layers toward organic electronic and photovoltaic applications.

DNA adsorption to and elution from silica surfaces: influence of amino acid buffers.

PubMed

Vandeventer, Peter E; Mejia, Jorge; Nadim, Ali; Johal, Malkiat S; Niemz, Angelika

2013-09-19

Solid phase extraction and purification of DNA from complex samples typically requires chaotropic salts that can inhibit downstream polymerase amplification if carried into the elution buffer. Amino acid buffers may serve as a more compatible alternative for modulating the interaction between DNA and silica surfaces. We characterized DNA binding to silica surfaces, facilitated by representative amino acid buffers, and the subsequent elution of DNA from the silica surfaces. Through bulk depletion experiments, we found that more DNA adsorbs to silica particles out of positively compared to negatively charged amino acid buffers. Additionally, the type of the silica surface greatly influences the amount of DNA adsorbed and the final elution yield. Quartz crystal microbalance experiments with dissipation monitoring (QCM-D) revealed multiphasic DNA adsorption out of stronger adsorbing conditions such as arginine, glycine, and glutamine, with DNA more rigidly bound during the early stages of the adsorption process. The DNA film adsorbed out of glutamate was more flexible and uniform throughout the adsorption process. QCM-D characterization of DNA elution from the silica surface indicates an uptake in water mass during the initial stage of DNA elution for the stronger adsorbing conditions, which suggests that for these conditions the DNA film is partly dehydrated during the prior adsorption process. Overall, several positively charged and polar neutral amino acid buffers show promise as an alternative to methods based on chaotropic salts for solid phase DNA extraction.

LOW-LOSS CABLE AND METHOD OF FABRICATION

DOEpatents

McCarthy, R.L. et al.

1960-09-27

A radiation-resistant coaxial electrical cable capable of carrying very small currents at high voltages with little leakage is described. The cable comprises an inner axial conductor separated from an outer coaxial tubular conductor by annular layer of fibrous silica insulation. The silica insulation is formed by leaching boron from spun horosilicate glass and then heat treating the silica at a high temperature.

Nanostructured antistatic and antireflective thin films made of indium tin oxide and silica over-coat layer

NASA Astrophysics Data System (ADS)

Cho, Young-Sang; Hong, Jeong-Jin; Yang, Seung-Man; Choi, Chul-Jin

2010-08-01

Stable dispersion of colloidal indium tin oxide nanoparticles was prepared by using indium tin oxide nanopowder, organic solvent, and suitable dispersants through attrition process. Various comminution parameters during the attrition step were studied to optimize the process for the stable dispersion of indium tin oxide sol. The transparent and conductive films were fabricated on glass substrate using the indium tin oxide sol by spin coating process. To obtain antireflective function, partially hydrolyzed alkyl silicate was deposited as over-coat layer on the pre-fabricated indium tin oxide film by spin coating technique. This double-layered structure of the nanostructured film was characterized by measuring the surface resistance and reflectance spectrum in the visible wavelength region. The final film structure was enough to satisfy the TCO regulations for EMI shielding purposes.

Back-surface gold mirrors for vibrationally resonant sum-frequency (VR-SFG) spectroscopy using 3-mercaptopropyltrimethoxysilane as an adhesion promoter.

PubMed

Quast, Arthur D; Zhang, Feng; Linford, Matthew R; Patterson, James E

2011-06-01

Back-surface mirrors are needed as reference materials for vibrationally resonant sum-frequency generation (VR-SFG) probing of liquid-solid interfaces. Conventional noble metal mirrors are not suitable for back-surface applications due to the presence of a metal adhesion layer (chromium or titanium) between the window substrate and the reflective metal surface. Using vapor deposited 3-mercaptopropyltrimethoxysilane (MPTMS) as a bi-functional adhesion promoter, gold mirrors were fabricated on fused silica substrates. These mirrors exhibit excellent gold adhesion as determined by the Scotch(®) tape test. They also produce minimal spectroscopic interference in the C-H stretching region (2800-3000 cm(-1)), as characterized by VR-SFG. These mirrors are thus robust and can be used as back-surface mirrors for a variety of applications, including reference mirrors for VR-SFG.

Surface modification of nano-silica on the ligament advanced reinforcement system for accelerated bone formation: primary human osteoblasts testing in vitro and animal testing in vivo.

PubMed

Li, Mengmeng; Wang, Shiwen; Jiang, Jia; Sun, Jiashu; Li, Yuzhuo; Huang, Deyong; Long, Yun-Ze; Zheng, Wenfu; Chen, Shiyi; Jiang, Xingyu

2015-05-07

The Ligament Advanced Reinforcement System (LARS) has been considered as a promising graft for ligament reconstruction. To improve its biocompatibility and effectiveness on new bone formation, we modified the surface of a polyethylene terephthalate (PET) ligament with nanoscale silica using atom transfer radical polymerization (ATRP) and silica polymerization. The modified ligament is tested by both in vitro and in vivo experiments. Human osteoblast testing in vitro exhibits an ∼21% higher value in cell viability for silica-modified grafts compared with original grafts. Animal testing in vivo shows that there is new formed bone in the case of a nanoscale silica-coated ligament. These results demonstrate that our approach for nanoscale silica surface modification on LARS could be potentially applied for ligament reconstruction.

Fabrication of highly hydrophobic two-component thermosetting polyurethane surfaces with silica nanoparticles

NASA Astrophysics Data System (ADS)

Yang, Guang; Song, Jialu; Hou, Xianghui

2018-05-01

Highly hydrophobic thermosetting polyurethane (TSU) surfaces with micro-nano hierarchical structures were developed by a simple process combined with sandpaper templates and nano-silica embellishment. Sandpapers with grit sizes varying from 240 to 7000 grit were used to obtain micro-scale roughness on an intrinsic hydrophilic TSU surface. The surface wettability was investigated by contact angle measurement. It was found that the largest contact angle of the TSU surface without nanoparticles at 102 ± 3° was obtained when the template was 240-grit sandpaper and the molding progress started after 45 min curing of TSU. Silica nanoparticles modified with polydimethylsiloxane were scattered onto the surfaces of both the polymer and the template to construct the desirable nanostructures. The influences of the morphology, surface composition and the silica content on the TSU surface wettability were studied by scanning electron microscopy (SEM), attenuated total reflection (ATR) infrared (IR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and contact angle measurements. The surface of the TSU/SiO2 nanocomposites containing 4 wt% silica nanoparticles exhibited a distinctive dual-scale structure and excellent hydrophobicity with the contact angle above 150°. The mechanism of wettability was also discussed by Wenzel model and Cassie-Baxter model.

Highly porous layers of silica nanospheres sintered by drying: scaling up of the elastic properties of the beads to the macroscopic mechanical properties.

PubMed

Lesaine, Arnaud; Bonamy, Daniel; Gauthier, Georges; Rountree, Cindy L; Lazarus, Véronique

2018-05-16

Layers obtained by drying a colloidal dispersion of silica spheres are found to be a good benchmark to test the elastic behaviour of porous media, in the challenging case of high porosities and nano-sized microstructures. Classically used for these systems, Kendall's approach explicitly considers the effect of surface adhesive forces onto the contact area between the particles. This approach provides the Young's modulus using a single adjustable parameter (the adhesion energy) but provides no further information on the tensorial nature and possible anisotropy of elasticity. On the other hand, homogenization approaches (e.g. rule of mixtures, and Eshelby, Mori-Tanaka and self-consistent schemes), based on continuum mechanics and asymptotic analysis, provide the stiffness tensor from the knowledge of the porosity and the elastic constants of the beads. Herein, the self-consistent scheme accurately predicts both bulk and shear moduli, with no adjustable parameter, provided the porosity is less than 35%, for layers composed of particles as small as 15 nm in diameter. Conversely, Kendall's approach is found to predict the Young's modulus over the full porosity range. Moreover, the adhesion energy in Kendall's model has to be adjusted to a value of the order of the fracture energy of the particle material. This suggests that sintering during drying leads to the formation of covalent siloxane bonds between the particles.

Investigations on photolon-and porphyrin-doped sol-gel fiberoptic coatings for laser-assisted applications in medicine

NASA Astrophysics Data System (ADS)

Bindig, U.; Ulatowska-Jarza, A.; Kopaczynska, M.; Müller, G.; Podbielska, H.

2008-01-01

In view of laser-assisted medical applications, the construction of silica-based sol-gel fiberoptic sensors based on photolon (Ph) and protoporphyrin IX (PP IX) is discussed. Electron microscopy and AFM were used to characterize the silica sol-gel coatings. AFM measurements indicate a change in the surface porosity. The PP IX-based sensors were constructed as a one-layer optode as well as a multilayered structure. An additional hybrid sensor made up of alternate layers of PP IX-and Ph-doped sol-gel was also constructed and examined. Sol-gel matrices were prepared from silicate precursor tetraethylorthosilicate (TEOS) mixed with ethanol in acid-catalyzed hydrolysis. The carrier matrices of photosensitive dyes were produced with factor R = 20, where R denotes the ratio of solvent moles (ethanol) to the number of TEOS moles. A multilayered coating was built up using the reverse-dipping technique. The overall coating thickness was determined by electron microscopy. Doped sol-gels with different PP IX concentrations were used to produce fiberoptic coatings. The film optodes with a different number of layers were examined by fluorescence spectroscopy. It was found that photolon and protoporphyrin IX entrapped in sol-gel preserve their chemical reactivity and have contact with the external environment. The hybrid sensor demonstrated clear fluorescence and a reversible behavior in gaseous environments.

Inner Surface Chirality of Single-Handed Twisted Carbonaceous Tubular Nanoribbons.

PubMed

Liu, Dan; Li, Baozong; Guo, Yongmin; Li, Yi; Yang, Yonggang

2015-11-01

Single-handed twisted 4,4'-biphenylene-bridged polybissilsesquioxane tubular nanoribbons and single-layered nanoribbons were prepared by tuning the water/ethanol volume ratio in the reaction mixture at pH = 11.6 through a supramolecular templating approach. The single-layered nanoribbons were formed by shrinking tubular nanoribbons after the removal of the templates. In addition, solvent-induced handedness inversion was achieved. The handedness of the polybissilsesquioxanes could be controlled by changing the ethanol/water volume ratio in the reaction mixture. After carbonization at 900 °C for 4.0 h and removal of silica, single-handed twisted carbonaceous tubular nanoribbons and single-layered nanoribbons with micropores in the walls were obtained. X-ray diffraction and Raman spectroscopy analyses indicated that the carbon is predominantly amorphous. The circular dichroism spectra show that the twisted tubular nanoribbons exhibit optical activity, while the twisted single-layered nanoribbons do not. The results shown here indicate that chirality is transferred from the organic self-assemblies to the inner surfaces of the 4,4'-biphenylene-bridged polybissilsesquioxane tubular nanoribbons and subsequently to those of the carbonaceous tubular nanoribbons. © 2015 Wiley Periodicals, Inc.

Deposition and characterization of titania-silica optical multilayers by asymmetric bipolar pulsed dc sputtering of oxide targets

NASA Astrophysics Data System (ADS)

Sagdeo, P. R.; Shinde, D. D.; Misal, J. S.; Kamble, N. M.; Tokas, R. B.; Biswas, A.; Poswal, A. K.; Thakur, S.; Bhattacharyya, D.; Sahoo, N. K.; Sabharwal, S. C.

2010-02-01

Titania-silica (TiO2/SiO2) optical multilayer structures have been conventionally deposited by reactive sputtering of metallic targets. In order to overcome the problems of arcing, target poisoning and low deposition rates encountered there, the application of oxide targets was investigated in this work with asymmetric bipolar pulsed dc magnetron sputtering. In order to evaluate the usefulness of this deposition methodology, an electric field optimized Fabry Perot mirror for He-Cd laser (λ = 441.6 nm) spectroscopy was deposited and characterized. For comparison, this mirror was also deposited by the reactive electron beam (EB) evaporation technique. The mirrors developed by the two complementary techniques were investigated for their microstructural and optical reflection properties invoking atomic force microscopy, ellipsometry, grazing incidence reflectometry and spectrophotometry. From these measurements the layer geometry, optical constants, mass density, topography, surface and interface roughness and disorder parameters were evaluated. The microstructural properties and spectral functional characteristics of the pulsed dc sputtered multilayer mirror were found to be distinctively superior to the EB deposited mirror. The knowledge gathered during this study has been utilized to develop a 21-layer high-pass edge filter for radio photoluminescence dosimetry.

Silica sacrificial layer-assisted in-plane incorporation of Au nanoparticles into mesoporous titania thin films through different reduction methods.

PubMed

Liang, Chih-Peng; Yamauchi, Yusuke; Liu, Chia-Hung; Wu, Kevin C-W

2013-06-28

This study focuses on the incorporation of gold nanoparticles (Au NPs) into our previously synthesized mesoporous titania thin films consisting of titania nanopillars and inverse mesospace (C. W. Wu, T. Ohsuna, M. Kuwabara and K. Kuroda, J. Am. Chem. Soc., 2006, 128, 4544-4545, denoted as MTTFs). Recently, mesoporous titania materials doped with noble metals such as gold have attracted considerable attention because noble metals can enhance the efficiency of mesoporous titania-based devices. In this research, we attempted to use four different reduction methods (i.e., thermal treatment, photo irradiation, liquid immersion, and vapor contacting) to introduce gold nanoparticles (Au NPs) into MTTFs. The synthesized Au@MTTFs were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). We further systematically investigated the formation mechanism of gold nanoparticles on the external and internal surfaces of the MTTFs. With the assistance of a silica sacrificial layer, well-dispersed Au NPs with sizes of 4.1 nm were obtained inside the MTTF by photo irradiation. The synthesized Au@MTTF materials show great potential in various photo-electronic and photo-catalytic applications.

Erbium-implanted silica colloids with 80% luminescence quantum efficiency

NASA Astrophysics Data System (ADS)

Slooff, L. H.; de Dood, M. J. A.; van Blaaderen, A.; Polman, A.

2000-06-01

Silica colloids with a diameter of 240-360 nm, grown by wet chemical synthesis using ethanol, ammonia, water, and tetraethoxysilane, were implanted with 350 keV Er ions, to peak concentrations of 0.2-1.1 at. % and put onto a silicon or glass substrate. After annealing at 700-900 °C the colloids show clear room-temperature photoluminescence at 1.53 μm, with lifetimes as high as 17 ms. By comparing data of different Er concentrations, the purely radiative lifetime is estimated to be 20-22 ms, indicating a high quantum efficiency of about 80%. This high quantum efficiency indicates that, after annealing, the silica colloids are almost free of OH impurities. Spinning a layer of polymethylmethacrylate over the silica spheres results in an optically transparent nanocomposite layer, that can be used as a planar optical waveguide amplifier at 1.5 μm that is fully compatible with polymer technology.

Embedding Luminescent Nanocrystals in Silica Sol-Gel Matrices

DTIC Science & Technology

2006-01-01

procedure necessary to form low-density silica aerogels using supercritical drying procedures. The resulting aerogel networks show a high surface area...reactions. Recent research that just begins to delve into the subject of taking quantum dot semiconductors in silica aerogels was published in...surface of the QD is desirable. As such, ultra low-density silica aerogel materials are an excellent medium for sensor applications as they can be

Molecular Dynamics Simulations of Surface Processes: Oxygen Recombination on Silica Surfaces at High Temperature

DTIC Science & Technology

2007-07-01

SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT UU 18 . NUMBER OF PAGES 22 19a. NAME OF RESPONSIBLE PERSON a. REPORT unclassified b. ABSTRACT...unclassified c. THIS PAGE unclassified Standard Form 298 (Rev. 8-98) Prescribed by ANSI Std Z39- 18 Molecular Dynamics Simulations of Surface...phase. O + Oad + silica -------> O2(v,j) + silica ( 18 ) The first step is

Quantitative Comparison of Protein Adsorption and Conformational Changes on Dielectric-Coated Nanoplasmonic Sensing Arrays.

PubMed

Ferhan, Abdul Rahim; Jackman, Joshua A; Sut, Tun Naw; Cho, Nam-Joon

2018-04-22

Nanoplasmonic sensors are a popular, surface-sensitive measurement tool to investigate biomacromolecular interactions at solid-liquid interfaces, opening the door to a wide range of applications. In addition to high surface sensitivity, nanoplasmonic sensors have versatile surface chemistry options as plasmonic metal nanoparticles can be coated with thin dielectric layers. Within this scope, nanoplasmonic sensors have demonstrated promise for tracking protein adsorption and substrate-induced conformational changes on oxide film-coated arrays, although existing studies have been limited to single substrates. Herein, we investigated human serum albumin (HSA) adsorption onto silica- and titania-coated arrays of plasmonic gold nanodisks by localized surface plasmon resonance (LSPR) measurements and established an analytical framework to compare responses across multiple substrates with different sensitivities. While similar responses were recorded on the two substrates for HSA adsorption under physiologically-relevant ionic strength conditions, distinct substrate-specific behavior was observed at lower ionic strength conditions. With decreasing ionic strength, larger measurement responses occurred for HSA adsorption onto silica surfaces, whereas HSA adsorption onto titania surfaces occurred independently of ionic strength condition. Complementary quartz crystal microbalance-dissipation (QCM-D) measurements were also performed, and the trend in adsorption behavior was similar. Of note, the magnitudes of the ionic strength-dependent LSPR and QCM-D measurement responses varied, and are discussed with respect to the measurement principle and surface sensitivity of each technique. Taken together, our findings demonstrate how the high surface sensitivity of nanoplasmonic sensors can be applied to quantitatively characterize protein adsorption across multiple surfaces, and outline broadly-applicable measurement strategies for biointerfacial science applications.

Poly(2-aminothiazole)-silica nanocomposite particles: Synthesis and morphology control

NASA Astrophysics Data System (ADS)

Zou, Hua; Wu, Di; Sun, Hao; Chen, Suwu; Wang, Xia

2018-04-01

Synthesis of conducting polymer-silica colloidal nanocomposites has been recognized as an effective method to overcome the poor processability of heterocyclic conducting polymers prepared by chemical oxidative method. However, the morphology control of such conducting polymer-silica nanocomposites was seldomly reported in the literature. Novel poly(2-aminothiazole)(PAT)-silica nanocomposite particles can be conveniently prepared by chemical oxidative polymerization of 2-aminothiazole using CuCl2 oxidant in the presence of ∼20 nm silica nanoparticles. The effects of varying the oxidant/monomer ratio and silica sol concentration on the morphology and size of the resulting PAT-silica nanocmposites have been studied. Optimization of the oxidant/monomer molar ratio and initial silica sol concentration allows relatively round spherical particles of 150-350 nm in diameter to be achieved. The nanocomposite particles have a well-defined raspberry-like morphology with a silica-rich surface, but a significant fraction of PAT component still exists on the surface and, which is beneficial for its applications. Furthermore, the surface compositions of the colloidal nanocomposites could be regulated to some extent. Based on the above results, a possible formation mechanism of the spherical nanocomposite particles is proposed.

Synthesis of silica aerogel monoliths with controlled specific surface areas and pore sizes

NASA Astrophysics Data System (ADS)

Gao, Bingying; Lu, Shaoxiang; Kalulu, Mulenga; Oderinde, Olayinka; Ren, Lili

2017-07-01

To replace traditional preparation methods of silica aerogels, a small-molecule 1,2-epoxypropane (PO) has been introduced into the preparation process instead of using ammonia as the cross-linking agent, thus generating a lightweight, high porosity, and large surface area silica aerogel monolithic. We put forward a simple solution route for the chemical synthesis of silica aerogels, which was characterized by scanning electron microscopy (SEM), TEM, XRD, FTIR, thermogravimetric analysis (TGA) and the Brunauer-Emmett-Teller (BET) method In this paper, the effect of the amount of PO on the microstructure of silica aerogels is discussed. The BET surface areas and pore sizes of the resulting silica aerogels can be freely adjusted by changing the amount of PO, which will be helpful in promoting the development of silica aerogels to fabricate other porous materials with similar requirements. We also adopted a new organic solvent sublimation drying (OSSD) method to replace traditional expensive and dangerous drying methods such as critical point drying and freeze drying. This simple approach is easy to operate and has good repeatability, which will further facilitate actual applications of silica aerogels.

Science of Water Leaks: Validated Theory for Moisture Flow in Microchannels and Nanochannels.

PubMed

Lei, Wenwen; Fong, Nicole; Yin, Yongbai; Svehla, Martin; McKenzie, David R

2015-10-27

Water is ubiquitous; the science of its transport in micro- and nanochannels has applications in electronics, medicine, filtration, packaging, and earth and planetary science. Validated theory for water vapor and two-phase water flows is a "missing link"; completing it enables us to define and quantify flow in a set of four standard leak configurations with dimensions from the nanoscale to the microscale. Here we report the first measurements of water vapor flow rates through four silica microchannels as a function of humidity, including under conditions when air is present as a background gas. An important finding is that the tangential momentum accommodation coefficient (TMAC) is strongly modified by surface layers of adsorbed water molecules, in agreement with previous work on the TMAC for nitrogen molecules impacting a silica surface in the presence of moisture. We measure enhanced flow rates for two-phase flows in silica microchannels driven by capillary filling. For the measurement of flows in nanochannels we use heavy water mass spectrometry. We construct the theory for the flow rates of the dominant modes of water transport through each of the four standard configurations and benchmark it against our new measurements in silica and against previously reported measurements for nanochannels in carbon nanotubes, carbon nanopipes, and porous alumina. The findings show that all behavior can be described by the four standard leak configurations and that measurements of leak behavior made using other molecules, such as helium, are not reliable. Single-phase water vapor flow is overestimated by a helium measurement, while two-phase flows are greatly underestimated for channels larger than 100 nm or for all channels when boundary slip applies, to an extent that depends on the slip length for the liquid-phase flows.

Characterization of silica particles modified with γ-methacryloxypropyltrimethoxysilane

NASA Astrophysics Data System (ADS)

Jiang, Jun; Wang, Wang; Shen, Haiying; Wang, Jiamin; Cao, Jinzhen

2017-03-01

The surface of hydrophilic silica particles was modified with different concentrations (2, 4, 6, 8 and 10%) of γ-methacryloxypropyltrimethoxysilane (MPTS). The hydrophobicity and hygroscopicity of unmodified and modified silica were investigated through water contact angle (WCA) tests and dynamic vapor sorption (DVS) method, respectively. The results showed that the surface properties of silica were closely related with the MPTS concentration. Within the range of MPTS concentration applied, 8% MPTS modified silica showed the least aggregation. With the increasing MPTS concentration, the WCAs on modified silica film increased correspondingly, and finally exceeded 90° at 6% and 8% concentrations. The equilibrium moisture contents (EMCs) of modified silica also decreased with the increasing MPTS concentration. The improvement on hydrophobicity can be correlated with the reduction of residual hydroxyl groups (-OH) on modified silica. The self-condensation of MPTS began to occur at concentrations higher than 4%, especially at 8%. Owing to this effect, the modified silica with 8% MPTS showed a slightly higher EMC than 6% MPTS within low relative humidity (RH) range up to 40%. At a higher RH ranging from 40 to 90%, 8% group showed the lowest EMCs because of its highest hydrophobicity and low specific surface area. A mechanism concerning the MPTS modification of silica was also proposed in this study based on the research results.

Innovative nanostructures for highly sensitive vibrational biosensing (Conference Presentation)

NASA Astrophysics Data System (ADS)

Popp, Juergen; Mayerhöfer, Thomas; Cialla-May, Dana; Weber, Karina; Huebner, Uwe

2016-03-01

Employing vibrational spectroscopy (IR-absorption and Raman spectroscopy) allows for the labelfree detection of molecular specific fingerprints of inorganic, organic and biological substances. The sensitivity of vibrational spectroscopy can be improved by several orders of magnitude via the application of plasmonic active surfaces. Within this contribution we will discuss two such approaches, namely surface enhanced Raman spectroscopy (SERS) as well as surface enhanced IR absorption (SEIRA). It will be shown that SERS using metal colloids as SERS active substrate in combination with a microfluidic lab-on-a-chip (LOC) device enables high throughput and reproducible measurements with highest sensitivity and specificity. The application of such a LOC-SERS approach for therapeutic drug monitoring (e.g. quantitative detection of antibiotics in a urine matrix) will be presented. Furthermore, we will introduce innovative bottom-up strategies to prepare SERS-active nanostructures coated with a lipophilic sensor layer as one-time use SERS substrates for specific food analysis (e.g. quantitative detection of toxic food colorants). The second part of this contribution presents a slit array metamaterial perfect absorber for IR sensing applications consisting of a dielectric layer sandwiched between two metallic layers of which the upper layer is perforated with a periodic array of slits. Light-matter interaction is greatly amplified in the slits, where also the analyte is concentrated, as the surface of the substrate is covered by a thin silica layer. Thus, already small concentrations of analytes down to a monolayer can be detected by refractive index sensing and identified by their spectral fingerprints with a standard mid-infrared lab spectrometer.

Sequential and competitive adsorption of peptides at pendant PEO layers.

PubMed

Wu, Xiangming; Ryder, Matthew P; McGuire, Joseph; Snider, Joshua L; Schilke, Karl F

2015-06-01

Earlier work provided direction for development of responsive drug delivery systems based on modulation of the structure, amphiphilicity, and surface density of bioactive peptides entrapped within pendant polyethylene oxide (PEO) brush layers. In this work, we describe the sequential and competitive adsorption behavior of such peptides at pendant PEO layers. Three cationic peptides were used for this purpose: the arginine-rich, amphiphilic peptide WLBU2, a peptide chemically identical to WLBU2 but of scrambled sequence (S-WLBU2), and the non-amphiphilic peptide poly-L-arginine (PLR). Optical waveguide lightmode spectroscopy (OWLS) was used to quantify the rate and extent of peptide adsorption and elution at surfaces coated with PEO. UV spectroscopy and time-of-flight secondary ion mass spectrometry (TOF-SIMS) were used to quantify the extent of peptide exchange during the course of sequential and competitive adsorption. Circular dichroism (CD) was used to evaluate conformational changes after adsorption of peptide mixtures at PEO-coated silica nanoparticles. Results indicated that amphiphilic peptides are able to displace adsorbed, non-amphiphilic peptides in PEO layers, while non-amphiphilic peptides were not able to displace more amphiphilic peptides. In addition, peptides of greater amphiphilicity dominated the adsorption at the PEO layer from mixtures with less amphiphilic or non-amphiphilic peptides. Copyright © 2015 Elsevier B.V. All rights reserved.

Alternating current impedance spectroscopic analysis of biofunctionalized vertically-aligned silica nanospring surface for biosensor applications

NASA Astrophysics Data System (ADS)

Timalsina, Yukta P.

In this dissertation, a process of vertically-aligned (silica) nanosprings (VANS) based biosensor development is presented. Alternating current (AC) impedance spectroscopy has been used to analyze sensor response as a function of saline phosphate (SP) buffer and biological solutions. The sensor is a parallel plate capacitor consisting of two glass substrates coated with indium tin oxide (ITO), where the VANS [or randomly-aligned nanosprings (RANS)] grown on one substrate serve as the dielectric spacer layer. The response of a VANS device as a function of ionic concentration in SP buffer was examined and an equivalent circuit model was developed. The results demonstrated that VANS sensors exhibited greater sensitivity to the changes in SP concentration relative to the ITO sensors, which serve as controls. The biofunctionalized VANS surface via physisorption and the cross-linker method demonstrates the repeatability, specificity, and selectivity of the binding. The physisorption of biotinylated immunoglobulin G (B-IgG) onto the VANS surface simplifies the whole sensing procedure for the detection of glucose oxidase, since the avidin-conjugated glucose oxidase (Av-GOx) can directly be immobilized on the B-IgG. The cross linker method involves the covalent attachment of antibodies onto the functionalized VANS surface via imine bond. The experiments revealed that the VANS sensor response is solely the result of the interaction of target molecule i.e. mouse IgG with the probe layer, i.e. goat antimouse IgG (GalphaM IgG). It was determined that VANS-based sensors exhibit a greater magnitude of change between successive bio-layers relative to the controls above 100 Hz, which indicates that the addition of biomolecules inhibits the diffusion of ions and changes the effective dielectric response of the VANS via biomolecular polarization. The study of ionic transport in nanosprings suggested that conductance follows a scaling law. It was demonstrated that a VANS-based device exhibits a greater magnitude of change relative to the RANS device below 10 kHz, which has equivalent property of the ITO controls. This dissertation demonstrates the potential for VANS as a novel nanomaterial platform for the development of highly sensitive, selective, low cost, and label free biosensors.

Additive manufacturing of tools for lapping glass

NASA Astrophysics Data System (ADS)

Williams, Wesley B.

2013-09-01

Additive manufacturing technologies have the ability to directly produce parts with complex geometries without the need for secondary processes, tooling or fixtures. This ability was used to produce concave lapping tools with a VFlash 3D printer from 3D Systems. The lapping tools were first designed in Creo Parametric with a defined constant radius and radial groove pattern. The models were converted to stereolithography files which the VFlash used in building the parts, layer by layer, from a UV curable resin. The tools were rotated at 60 rpm and used with 120 grit and 220 grit silicon carbide lapping paste to lap 0.750" diameter fused silica workpieces. The samples developed a matte appearance on the lapped surface that started as a ring at the edge of the workpiece and expanded to the center. This indicated that as material was removed, the workpiece radius was beginning to match the tool radius. The workpieces were then cleaned and lapped on a second tool (with equivalent geometry) using a 3000 grit corundum aluminum oxide lapping paste, until a near specular surface was achieved. By using lapping tools that have been additively manufactured, fused silica workpieces can be lapped to approach a specified convex geometry. This approach may enable more rapid lapping of near net shape workpieces that minimize the material removal required by subsequent polishing. This research may also enable development of new lapping tool geometry and groove patterns for improved loose abrasive finishing.

Optical and Atomic Force Microscopy Characterization of PbI2 Quantum Dots

NASA Technical Reports Server (NTRS)

Mu, R.; Tung, Y. S.; Ueda, A.; Henderson, D. O.

1997-01-01

Lead iodide (PbI2) clusters were synthesized from the chemical reaction of NaI (or KI) with Pb(NO3)2 in H2O, D2O, CH3OH, and C3H7OH media. The observation of the absorption features above 350 nm with the help of integrating sphere accessory strongly suggests the quantum dot formation of PbI2 in solution. Spectral comparison between the synthesized PbI2 clusters in solution and PbI2 nanophase by impregnation of PbI2 in four different pore-sized porous silica indicates that the PbI2 cluster size in solution is less than 2.5 nm in lateral dimension. Atomic force microscopy (AFM) measurements show that the PbL clusters deposited onto three different molecularly flat surfaces are single-layered. The measured height is 1.0 - 0.1 nm. The swollen layer thickness can be attributed to the intralayer contraction from the strong lateral interaction among PbI2 molecules, which is supported by ab initio calculation. Raman scattering measurement of LO and TO modes of PbI2 in bulk and in the confined state were also conducted in 50-150 cu cm region. The observed three bands at 74, %, 106 1/cm are assigned to TO2, LO2, and LO, mode, respectively. The relatively small red-shift in LO modes may be caused by the surface phonon polaritons of PbI2 nanophase in the porous silica.

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

Krotov, V.V.; Staroverov, S.M.; Nesterenko, P.N.

A series of heterogeneous catalysts for asymmetric Michael additions was synthesized based on ephedrine chemically bound to the surface of silica. The length of the hydrocarbon chain binding the active center to the support surface affects the sign of rotation of the reaction product from the asymmetric addition of thiophenol to benzylideneacetophenone. Grafting ephedrine to the silica surface via a short hydrocarbon chain results in a change in the configuration of the reaction product. Silanol groups on the silica surface are involved in the transition state, as evidenced by data obtained using silica which has been exhaustively treated with trimethylchlorosilane.more » The absolute specific rotation of 1,3-diphenyl-3-thiophenylpropan-1-one has been established.« less

Nanosecond laser-induced back side wet etching of fused silica with a copper-based absorber liquid

NASA Astrophysics Data System (ADS)

Lorenz, Pierre; Zehnder, Sarah; Ehrhardt, Martin; Frost, Frank; Zimmer, Klaus; Schwaller, Patrick

2014-03-01

Cost-efficient machining of dielectric surfaces with high-precision and low-roughness for industrial applications is still challenging if using laser-patterning processes. Laser induced back side wet etching (LIBWE) using UV laser pulses with liquid heavy metals or aromatic hydrocarbons as absorber allows the fabrication of well-defined, nm precise, free-form surfaces with low surface roughness, e.g., needed for optical applications. The copper-sulphatebased absorber CuSO4/K-Na-Tartrate/NaOH/formaldehyde in water is used for laser-induced deposition of copper. If this absorber can also be used as precursor for laser-induced ablation, promising industrial applications combining surface structuring and deposition within the same setup could be possible. The etching results applying a KrF excimer (248 nm, 25 ns) and a Nd:YAG (1064 nm, 20 ns) laser are compared. The topography of the etched surfaces were analyzed by scanning electron microscopy (SEM), white light interferometry (WLI) as well as laser scanning microscopy (LSM). The chemical composition of the irradiated surface was studied by energy-dispersive X-ray spectroscopy (EDX) and Fourier transform infrared spectroscopy (FT-IR). For the discussion of the etching mechanism the laser-induced heating was simulated with finite element method (FEM). The results indicate that the UV and IR radiation allows micro structuring of fused silica with the copper-based absorber where the etching process can be explained by the laser-induced formation of a copper-based absorber layer.

Simulation of the evolution of fused silica's surface defect during wet chemical etching

NASA Astrophysics Data System (ADS)

Liu, Taixiang; Yang, Ke; Li, Heyang; Yan, Lianghong; Yuan, Xiaodong; Yan, Hongwei

2017-08-01

Large high-power-laser facility is the basis for achieving inertial confinement fusion, one of whose missions is to make fusion energy usable in the near future. In the facility, fused silica optics plays an irreplaceable role to conduct extremely high-intensity laser to fusion capsule. But the surface defect of fused silica is a major obstacle limiting the output power of the large laser facility and likely resulting in the failure of ignition. To mitigate, or event to remove the surface defect, wet chemical etching has been developed as a practical way. However, how the surface defect evolves during wet chemical etching is still not clearly known so far. To address this problem, in this work, the three-dimensional model of surface defect is built and finite difference time domain (FDTD) method is developed to simulate the evolution of surface defect during etching. From the simulation, it is found that the surface defect will get smooth and result in the improvement of surface quality of fused silica after etching. Comparatively, surface defects (e.g. micro-crack, scratch, series of pinholes, etc.) of a typical fused silica at different etching time are experimentally measured. It can be seen that the simulation result agrees well with the result of experiment, indicating the FDTD method is valid for investigating the evolution of surface defect during etching. With the finding of FDTD simulation, one can optimize the treatment process of fused silica in practical etching or even to make the initial characterization of surface defect traceable.

Compact 3D photonic crystals sensing platform with 45 degree angle polished fibers

NASA Astrophysics Data System (ADS)

Guo, Yuqing; Chen, Lu; Zhu, Jiali; Ni, Haibin; Xia, Wei; Wang, Ming

2017-07-01

Three dimensional photonic crystals are a kind of promising sensing materials in biology and chemistry. A compact structure, consists of planner colloidal crystals and 45 degree angle polished fiber, is proposed as a platform for accurate, fast, reliable three dimensional photonic crystals sensing in practice. This structure show advantages in compact size for integration and it is ease for large scale manufacture. Reflectivity of the 45 degree angle polished surface with and without a layer of Ag film are simulated by FDTD simulation. Refractive index sensing properties as well as mode distribution of this structure consists of both polystyrene opal and silica inverse opal film is investigated, and an experimental demonstration of silica inverse opal film is performed, which shows a sensitivity of 733 nm/RIU. Different kinds of three dimensional photonic crystals can also be applied in this structure for particular purpose.

Hierarchically structured activated carbon for ultracapacitors

NASA Astrophysics Data System (ADS)

Kim, Mok-Hwa; Kim, Kwang-Bum; Park, Sun-Min; Roh, Kwang Chul

2016-02-01

To resolve the pore-associated bottleneck problem observed in the electrode materials used for ultracapacitors, which inhibits the transport of the electrolyte ions, we designed hierarchically structured activated carbon (HAC) by synthesizing a mesoporous silica template/carbon composite and chemically activating it to simultaneously remove the silica template and increase the pore volume. The resulting HAC had a well-designed, unique porous structure, which allowed for large interfaces for efficient electric double-layer formation. Given the unique characteristics of the HAC, we believe that the developed synthesis strategy provides important insights into the design and fabrication of hierarchical carbon nanostructures. The HAC, which had a specific surface area of 1,957 m2 g-1, exhibited an extremely high specific capacitance of 157 F g-1 (95 F cc-1), as well as a high rate capability. This indicated that it had superior energy storage capability and was thus suitable for use in advanced ultracapacitors.

Mesoporous carbon synthesized from different pore sizes of SBA-15 for high density electrode supercapacitor application

NASA Astrophysics Data System (ADS)

Jamil, Farinaa Md; Sulaiman, Mohd Ali; Ibrahim, Suhaina Mohd; Masrom, Abdul Kadir; Yahya, Muhd Zu Azhan

2017-12-01

A series of mesoporous carbon sample was synthesized using silica template, SBA-15 with two different pore sizes. Impregnation method was applied using glucose as a precursor for converting it into carbon. An appropriate carbonization and silica removal process were carried out to produce a series of mesoporous carbon with different pore sizes and surface areas. Mesoporous carbon sample was then assembled as electrode and its performance was tested using cyclic voltammetry and impedance spectroscopy to study the effect of ion transportation into several pore sizes on electric double layer capacitor (EDLC) system. 6M KOH was used as electrolyte at various scan rates of 10, 20, 30 and 50 mVs-1. The results showed that the pore size of carbon increased as the pore size of template increased and the specific capacitance improved as the increasing of the pore size of carbon.

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

NASA Astrophysics Data System (ADS)

Catauro, Michelina; Bollino, Flavia; Gloria, Antonio

2016-05-01

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

Molecular dynamics study of oil adsorption on the rock surface in presence of silica nanoparticles

NASA Astrophysics Data System (ADS)

Salehzadeh, Jamal; Tohidi, Zahra; Jafari, Arezou

2018-01-01

Despite the increasing applications of nanoparticles in enhanced oil recovery (EOR), there is not enough information about the mechanisms and microscopic aspects of nanoparticles' effects. Therefore, in this research, molecular dynamics simulation is used to provide the molecular-scale insight for investigation of the silica nanoparticles effects on the oil adsorption on calcite surface for the first time. The surface interacts with the mixture of heptane and decane as the oil phase with mole ratio of 1/2 and silica nanoparticles are dispersed in distilled water with concentration of 7000 ppm. Based on the simulation results, by using nanoparticles surface adsorption behavior have been changed to hydrophilic and the oil molecules departed from the calcite. This result is based on the oil-calcite binding energy calculation which is decreased from 5224 kcal/mol to 3278 kcal/mol by using silica nanoparticles. In addition, calculation of radial distribution functions showed that after adding silica nanoparticles, the picks fall which means increasing in average distance between oil and calcite surface.

Preparation and Characterization of Single Ion Conductors from High Surface Area Fumed Silica

NASA Technical Reports Server (NTRS)

Zhang, H.; Maitra, P.; Liu, B.; Wunder, S. L.; Lin, H.-P.; Salomon, M.; Hagedorn, Norman H. (Technical Monitor)

2002-01-01

Anions that can form dissociative salts with Li(+) have been prepared and covalently attached to high surface area fumed silica. When blended with polyethylene oxide (PEO), the functionalized fumed silica suppresses the crystallization of the PEO, provides dimensional stability, and serves as a single ion conductor. Since functionalized fumed silica is easily dispersed in common polar solvents, it can be incorporated in both the polymer electrolyte and the electrodes.

[Collagenolytic activity in several species of deuteromycetes under various storage conditions].

PubMed

Iakovleva, M B; Khoang, T L; Nikitina, Z K

2006-01-01

The ability of deuteromycetes of the genera Penicillium, Aspergillus, and Botrytis to retain collagenolytic activity was studied after both 2 and 10 years of storage on a Czapek medium under a layer of mineral oil at 4 degrees C, as well as in silica gel granules at 20 and -60 degrees C. The enzymatic activity of several species, including Botrytis terrestris, Penicillium janthinellum, Penicillium chrysogenum, and Penicillium citrinum, was retained under both conditions of storage. Aspergillus repens retained enzymatic activity only if stored under a layer of mineral oil. The viability of conidia and the collagenolytic activity of Botrytis terrestris, P. janthinellum, P. chrysogenum, and Penicillium citrinum, maintained on silica gel for 10 years, depended on the storage temperature. The viability of the test strains improved after storage on a silica gel at -60 degrees C. A strain of Aspergillus repens lost its ability to dissolve collagen at various storage temperatures on the silica gel. The index of lysis for three strains of Penicillium deuteromycetes (Penicillium janthinellum, Penicillium chrysogenum, and Penicillium citrinum) increased after a 10-year storage on silica gel at -60 degrees C.

One-by-one imprinting in two eccentric layers of hollow core-shells: Sequential electroanalysis of anti-HIV drugs.

PubMed

Singh, Kislay; Jaiswal, Swadha; Singh, Richa; Fatma, Sana; Prasad, Bhim Bali

2018-07-15

Double layered one-by-one imprinted hollow core-shells@ pencil graphite electrode was fabricated for sequential sensing of anti-HIV drugs. For this, two eccentric layers were developed on the surface of vinylated silica nanospheres to obtain double layered one-by-one imprinted solid core-shells. This yielded hollow core-shells on treatment with hydrofluoric acid. The modified hollow core-shells (single layered dual imprinted) evolved competitive diffusion of probe/analyte molecules. However, the corresponding double layered one-by-one imprinted hollow core-shells (outer layer imprinted with Zidovudine, and inner layer with Lamivudine) were found relatively better owing to their bilateral diffusions into molecular cavities, without any competition. The entire work is based on differential pulse anodic stripping voltammetry at double layered one-by-one imprinted hollow core-shells. This resulted in indirect detection of electro inactive targets with limits of detection as low as 0.91 and 0.12 (aqueous sample), 0.94 and 0.13 (blood serum), and 0.99 and 0.20 ng mL -1 (pharmaceutics) for lamivudine and zidovudine, respectively in anti-HIV drug combination. Copyright © 2018 Elsevier B.V. All rights reserved.

Synthesis and Characterization of Superhydrophobic, Self-cleaning NIR-reflective Silica Nanoparticles

NASA Astrophysics Data System (ADS)

Sriramulu, Deepa; Reed, Ella Louise; Annamalai, Meenakshi; Venkatesan, Thirumalai Venky; Valiyaveettil, Suresh

2016-11-01

Multifunctional coatings offer many advantages towards protecting various surfaces. Here we apply aggregation induced segregation of perylene diimide (PDI) to control the surface morphology and properties of silica nanoparticles. Differentially functionalized PDI was incorporated on the surface of silica nanoparticles through Si-O-Si bonds. The absorption and emission spectra of the resultant functionalised nanoparticles showed monomeric or excimeric peaks based on the amounts of perylene molecules present on the surface of silica nanoparticles. Contact angle measurements on thin films prepared from nanoparticles showed that unfunctionalised nanoparticles were superhydrophilic with a contact angle (CA) of 0°, whereas perylene functionalised silica particles were hydrophobic (CA > 130°) and nanoparticles functionalised with PDI and trimethoxy(octadecyl)silane (TMODS) in an equimolar ratio were superhydrophobic with static CA > 150° and sliding angle (SA) < 10°. In addition, the near infrared (NIR) reflectance properties of PDI incorporated silica nanoparticles can be used to protect various heat sensitive substrates. The concept developed in this paper offers a unique combination of super hydrophobicity, interesting optical properties and NIR reflectance in nanosilica, which could be used for interesting applications such as surface coatings with self-cleaning and NIR reflection properties.

The radiolysis and radioracemization of amino acids on silica surfaces

NASA Technical Reports Server (NTRS)

Bonner, W. A.; Lemmon, R. M.

1981-01-01

Results are presented of experiments on the radioracemization of amino acids in the presence of silica surfaces such as may have been found on the prebiotic earth. L-leucine and a DL-leucine mixture deposited on samples of 1-quartz and an amorphous silica preparation (Syloid 63) was subjected to Co-60 gamma-ray irradiation, then analyzed by gas chromatography to determine the radiolysis and racemization rates. The quartz surface is found to have a marginal efficacy in enhancing radiolysis when compared with a crystalline L-leucine control, although enhancing radioracemization symmetrically by a factor of two. Both the radiolysis and radioracemization of L-leucine and DL-leucine on a Syloid-63 silica surface are observed to increase with increasing radiation dose, and to be substantially greater than in the crystalline controls. Additional experiments with the nonprotein amino acid isovaline deposited on Syloid 63 confirm the greater radiolysis susceptibility of amino acids deposited on silica with respect to the crystalline state, although racemization is not observed. The observations suggest that the presence of a silica surface would have a deleterious effect on any mechanism for the origin of molecular chirality relying on stereoselective beta-radiolysis.