Method for adhesion of metal films to ceramics

DOEpatents

Lowndes, Douglas H.; Pedraza, Anthony J.; DeSilva, Melvin J.; Kumar, Rajagopalan A.

1997-01-01

Methods for making strongly bonded metal-ceramic materials. The methods include irradiating a portion of the surface of the ceramic material with a pulsed ultraviolet laser having an energy density sufficient to effect activation of the irradiated surface of the ceramic material so that adhesion of metals subsequently deposited onto the irradiated surface is substantially increased. Advantages of the invention include (i) the need for only a small number of laser pulses at relatively low focused energy density, (ii) a smoother substrate surface, (iii) activation of the laser-treated surface which provides a chemical bond between the surface and a metal deposited thereon, (iv) only low temperature annealing is required to produce the strong metal-ceramic bond; (v) the ability to obtain strong adhesion between ceramic materials and oxidation resistant metals; (vi) ability to store the laser treated ceramic materials for later deposition of metals thereon.

Method for adhesion of metal films to ceramics

DOEpatents

Lowndes, D.H.; Pedraza, A.J.; DeSilva, M.J.; Kumar, R.A.

1997-12-30

Methods for making strongly bonded metal-ceramic materials are disclosed. The methods include irradiating a portion of the surface of the ceramic material with a pulsed ultraviolet laser having an energy density sufficient to effect activation of the irradiated surface of the ceramic material so that adhesion of metals subsequently deposited onto the irradiated surface is substantially increased. Advantages of the invention include (i) the need for only a small number of laser pulses at relatively low focused energy density, (ii) a smoother substrate surface, (iii) activation of the laser-treated surface which provides a chemical bond between the surface and a metal deposited thereon, (iv) only low temperature annealing is required to produce the strong metal-ceramic bond; (v) the ability to obtain strong adhesion between ceramic materials and oxidation resistant metals; (vi) ability to store the laser treated ceramic materials for later deposition of metals thereon. 7 figs.

Surface Modification by Atmospheric Pressure Plasma for Improved Bonding

NASA Astrophysics Data System (ADS)

Williams, Thomas Scott

An atmospheric pressure plasma source operating at temperatures below 150?C and fed with 1.0-3.0 volume% oxygen in helium was used to activate the surfaces of the native oxide on silicon, carbon-fiber reinforced epoxy composite, stainless steel type 410, and aluminum alloy 2024. Helium and oxygen were passed through the plasma source, whereby ionization occurred and ˜10 16 cm-3 oxygen atoms, ˜1015 cm -3 ozone molecules and ˜1016 cm-3 metastable oxygen molecules (O21Deltag) were generated. The plasma afterglow was directed onto the substrate material located 4 mm downstream. Surface properties of the plasma treated materials have been investigated using water contact angle (WCA), atomic force microscopy (AFM), infrared spectroscopy (IR), and x-ray photoelectron spectroscopy (XPS). The work presented herein establishes atmospheric-pressure plasma as a surface preparation technique that is well suited for surface activation and enhanced adhesive bond strength in a variety of materials. Atmospheric plasma activation presents an environmentally friendly alternative to wet chemical and abrasive methods of surface preparation. Attenuated total internal reflection infrared spectroscopy was used to study the aging mechanism of the native oxide on silicon. During storage at ambient conditions, the water contact angle of a clean surface increased from <5° to 40° over a period of 12 hours. When stored under a nitrogen purge, the water contact angle of a clean surface increased from <5° to 30° over a period of 40-60 hours. The change in contact angle resulted from the adsorption of nonanal onto the exposed surface hydroxyl groups. The rate of adsorption of nonanal under a nitrogen purged atmosphere ranged from 0.378+/-0.011 hr-1 to 0.182+/-0.008 hr -1 molecules/(cm2•s), decreasing as the fraction of hydrogen-bonded hydroxyl groups increased from 49% to 96% on the SiO 2 surface. The adsorption of the organic contaminant could be suppressed indefinitely by storing the silicon wafers in the presence of activated carbon or in a freezer at -22°C. The enhancement of adhesive bond strength and durability for carbon-fiber reinforced epoxy composite, stainless steel type 410, and aluminum alloy 2024 was demonstrated with the atmospheric pressure helium-oxygen plasma. All surfaces studied were converted from a hydrophobic state with a water contact angle of 65° to 80° into a hydrophilic state with a water contact angle between 20° and 40° within 5 seconds of plasma exposure. X-ray photoelectron spectroscopy confirmed that the carbon atoms on the carbon-fiber/epoxy composite were oxidized, yielding 17 atom% carboxylic acid groups, 10% ketones or aldehydes and 9% alcohols. Analysis of stainless steel and aluminum by XPS illustrate oxidation of the metal surface and an increase in the concentration of hydroxyl groups in the oxide film. Following plasma activation, the total hydroxyl species concentration on stainless steel increased from 31% to 57%, while aluminum exhibited an increase from 4% to 16% hydroxyl species. Plasma activation of the surface led to an increase in bond strength of the different surfaces by up to 150% when using Cytec FM300 and FM300-2 epoxy adhesives. Wedge crack extension tests following plasma activation revealed cohesive failure percentages of 97% for carbon-fiber/epoxy composite bonded to stainless steel, and 96% for aluminum bonded to itself. The bond strength and durability of the substrates correlated with changes in the specific surface chemistry, not the wetting angle or the morphological properties of the material. This suggests that enhanced chemical bonding at the interface was responsible for the improvement in mechanical properties following plasma activation. The surface preparation of polymers and composites using atmospheric pressure plasmas is a promising technique for replacing traditional methods of surface preparation by sanding, grit blasting or peel ply. After oxygen plasma activation and joining the materials together with epoxy, one observes 100% cohesive failure within the cured film adhesive. Depending on the material, the lap shear strength can be increased several fold over that achieved by either solvent wiping or abrasion. The trends in adhesion with plasma exposure time do not correlate well with surface wetting or roughness; instead they correlate with the fraction of the polymer surface sites that are converted into carboxylic acid groups.

Surface fluorination of zirconia: adhesive bond strength comparison to commercial primers.

PubMed

Piascik, Jeffrey R; Swift, Edward J; Braswell, Krista; Stoner, Brian R

2012-06-01

This study evaluated contact angle and shear bond strength of three commercial zirconia primers and compared them to a recently developed fluorination pre-treatment. Earlier investigations reported that plasma fluorinated zirconia modifies the chemical bonding structure creating a more reactive surface. Yttria-stabilized zirconia (LAVA, 3M ESPE) plates were highly polished using 3μm diamond paste (R(a) ∼200nm) prior to pretreatments. After primer and fluorination treatment, contact angles were measured to quantify surface hydrophobicity before and after ethanol clean. Additionally, simple shear bond tests were performed to measure the adhesion strength to a composite resin. Plasma fluorination produced the lowest contact angle (7.8°) and the highest shear bond strength (37.3MPa) suggesting this pretreatment facilitates a more "chemically" active surface for adhesive bonding. It is hypothesized that plasma fluorination increase hydroxylation at the surface, making it more reactive, thus allowing for covalent bonding between zirconia surface and resin cement. A strong correlation was observed between contact angle and adhesion strength for all specimens; a relationship which may help understand the frequency and modes of failures, clinically. It is also believed that this surface treatment can increase long-term viability of zirconia restorations over other adhesive techniques. Copyright © 2012 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

A facile preparation of TiO2/ACF with Csbnd Ti bond and abundant hydroxyls and its enhanced photocatalytic activity for formaldehyde removal

NASA Astrophysics Data System (ADS)

Liu, R. F.; Li, W. B.; Peng, A. Y.

2018-01-01

The quantum yields and efficiency(ACF) was prepared via a modified deposition-precipitation method to facilitate its photon absorption and of photogenerated charge carriers have been the major issues for photocatalysis on titania catalyst. The TiO2/ACF catalyst with anatase TiO2 uniformly dispersed on activated carbon fibers electron transfer, thus improve the quantum yields and efficiency of the photogenerated electrons and holes. XPS analysis on the catalyst demonstrates the existence of Ti3+ and Ti2+ species, Csbnd Ti bond and abundant hydroxyls, which are also proved by UV-vis DRS and TG-DSC analysis. It is believed that the acid environment in preparation plays an essential role in the formation of Csbnd Ti bond and surface hydroxyls, which can be tuned by changing hydrothermal synthesis time. The Csbnd Ti bond can improve the electron transfer in the catalyst and the substantial surface hydroxyls lead to high absorption for UV lines and enhanced adsorption of water and formaldehyde, resulting in more active OH free radicals and the outstanding photocatalytic activity of TiO2/ACF, which is much higher than the titania powder for photocatalytic removal of low concentration formaldehyde. The essential role of surface hydroxyls for photocatalytic activity was confirmed surpassing that of chemical bond between carbon and titanium in TiO2-carbon composite for the first time.

Dimethyl ether electro-oxidation on platinum surfaces

DOE PAGES

Roling, Luke T.; Herron, Jeffrey A.; Budiman, Winny; ...

2016-02-27

A first-principles density functional theory study was performed in this paper to elucidate the mechanism of dimethyl ether electro-oxidation on three low-index platinum surfaces (Pt(111), Pt(100), and Pt(211)). The goal of this study is to provide a fundamental explanation for the high activity observed experimentally on Pt(100) compared to Pt(111) and stepped surfaces. We determine that the enhanced activity of Pt(100) stems from more facile C–O bond breaking kinetics, as well as from easier removal of CO as a surface poison through activation of water. In general, the C–O bond (in CH xOCH y) becomes easier to break as dimethylmore » ether is dehydrogenated to a greater extent. In contrast, dehydrogenation becomes more difficult as more hydrogen atoms are removed. We perform two analyses of probable reaction pathways, which both identify CHOC and CO as the key reaction intermediates on these Pt surfaces. We show that the reaction mechanism on each surface is dependent on the cell operating potential, as increasing the potential facilitates C–H bond scission, in turn promoting the formation of intermediates for which C–O scission is more facile. We additionally demonstrate that CO oxidation determines the high overpotential required for electro-oxidation on Pt surfaces. Finally, at practical operating potentials (~0.60 V RHE), we determine that C–O bond breaking is most likely the most difficult step on all three Pt surfaces studied.« less

Active sites and states in the heterogeneous catalysis of carbon-hydrogen bonds.

PubMed

Somorjai, Gabor A; Marsh, Anderson L

2005-04-15

C-H bond activation for several alkenes (ethylene, propylene, isobutene, cyclohexene and 1-hexene) and alkanes (methane, ethane, n-hexane, 2-methylpentane and 3-methylpentane) has been studied on the (111) crystal face of platinum as a function of temperature at low (10(-6) Torr) and high (>/=1 Torr) pressures in the absence and presence of hydrogen pressures (>/=10 Torr). Sum frequency generation (SFG) vibrational spectroscopy has been used to characterize the adsorbate structures and high pressure scanning tunnelling microscopy (HP-STM) has been used to monitor their surface mobility under reaction conditions during hydrogenation, dehydrogenation and CO poisoning. C-H bond dissociation occurs at low temperatures, approximately 250 K, for all of these molecules, although only at high pressures for the weakly bound alkanes because of their low desorption temperatures. Bond dissociation is known to be surface structure sensitive and we find that it is also accompanied by the restructuring of the metal surface. The presence of hydrogen slows down dehydrogenation and for some of the molecules it influences the molecular rearrangement, thus altering reaction selectivity. Surface mobility of adsorbates is essential to produce catalytic activity. When surface diffusion is inhibited by CO adsorption, ordered surface structures form and the reaction is poisoned. Ethylene hydrogenation is surface structure insensitive, while cyclohexene hydrogenation and dehydrogenation are structure sensitive. n-Hexane and other C6 alkanes form either upright or flat-lying molecules on the platinum surface which react to produce branched isomers or benzene, respectively.

Shear bond strength to enamel after power bleaching activated by different sources.

PubMed

Can-Karabulut, Deniz C; Karabulut, Baris

2010-01-01

The purpose of the present study was to evaluate enamel bond strength of a composite resin material after hydrogen peroxide bleaching, activated by a diode laser (LaserSmile), an ozone device (HealOzone), a light-emitting diode (BT Cool whitening system), and a quartz-Plus. Fifty extracted caries-free permanent incisors were used in this study. Thirty-eight percent hydrogen peroxidegel was applied to sound, flattened labial enamel surfaces and activated by different sources. Enamel surfaces that had received no treatment were used as control samples. Bonding agent was applied according to the manufacturer's instructions and the adhesion test was performed according to ISO/TS 11405. Statistical analysis showed significant influence of the different activation technique of hydrogen peroxide on shear bond strength to enamel (ANOVA, LSD, P < 0.05). The data in this vitro explorative study suggest the activation of hydrogen peroxide by different sources may further affect the shear bond strength of subsequent composite resin restoration to enamel. Within the limitations of this in vitro study, further studies examining the structural changes of activated hydrogen peroxide-treated enamel are needed. Due to the different activation methods; duration of light irradiation effects, longer time periods may be needed before application of adhesive restorations to enamel, compared with non-activated bleaching.

Algicidal Activity of a Surface-Bonded Organosilicon Quaternary Ammonium Chloride

PubMed Central

Walters, P. A.; Abbott, E. A.; Isquith, A. J.

1973-01-01

The hydrolysis product of a quaternary amine-containing organosilicon salt, 3-(trimethoxysilyl)-propyldimethyloctadecyl ammonium chloride, was found to exhibit algicidal activity while chemically bonded to a variety of substrates. Six representative species of Chlorophyta, Cyanophyta, and Chrysophyta were used to evaluate the algicidal activity. Substrate-bonded 14C-labeled organosilicon quaternary ammonium salt when attached to nonwoven fibers was durable to repeated washings, and algicidal activity could not be attributed to slow release of the chemical. Images PMID:4632852

Method for providing adhesion to a metal surface

DOEpatents

Harrah, L.A.; Allred, R.E.; Wilson, K.V. Jr.

1992-02-18

A process for treating metal surfaces to obtain improved susceptibility to bonding with adhesive compositions is disclosed. A metal surface is oxidized with a halogen to form a monolayer of halide ions on the surface. The halide ions are then exchanged with azide ions to form an azide monolayer on the metal surface. Upon contact of the treated surface with an adhesive composition, the azide layer may be thermally or photochemically decomposed to form active nitrene species, which react to bond the adhesive composition to the metal surface.

Method for providing adhesion to a metal surface

DOEpatents

Harrah, Larry A.; Allred, Ronald E.; Wilson, Jr., Kennard V.

1992-01-01

A process for treating metal surfaces to obtain improved susceptibility to bonding with adhesive compositions is disclosed. A metal surface is oxidized with a halogen to form a monolayer of halide ions on the surface. The halide ions are then exchanged with azide ions to form an azide monolayer on the metal surface. Upon contact of the treated surface with an adhesive composition, the azide layer may be thermally or photochemically decomposed to form active nitrene species, which react to bond the adhesive composition to the metal surface.

The Effect of Interfacial Chemical Bonding in TiO2-SiO2 Composites on Their Photocatalytic NOx Abatement Performance

PubMed Central

Hakki, Amer; Yang, Lu; Wang, Fazhou; Macphee, Donald E.

2017-01-01

The chemical bonding of particulate photocatalysts to supporting material surfaces is of great importance in engineering more efficient and practical photocatalytic structures. However, the influence of such chemical bonding on the optical and surface properties of the photocatalyst and thus its photocatalytic activity/reaction selectivity behavior has not been systematically studied. In this investigation, TiO2 has been supported on the surface of SiO2 by means of two different methods: (i) by the in situ formation of TiO2 in the presence of sand quartz via a sol-gel method employing tetrabutyl orthotitanium (TBOT); and (ii) by binding the commercial TiO2 powder to quartz on a surface silica gel layer formed from the reaction of quartz with tetraethylorthosilicate (TEOS). For comparison, TiO2 nanoparticles were also deposited on the surfaces of a more reactive SiO2 prepared by a hydrolysis-controlled sol-gel technique as well as through a sol-gel route from TiO2 and SiO2 precursors. The combination of TiO2 and SiO2, through interfacial Ti-O-Si bonds, was confirmed by FTIR spectroscopy and the photocatalytic activities of the obtained composites were tested for photocatalytic degradation of NO according to the ISO standard method (ISO 22197−1). The electron microscope images of the obtained materials showed that variable photocatalyst coverage of the support surface can successfully be achieved but the photocatalytic activity towards NO removal was found to be affected by the preparation method and the nitrate selectivity is adversely affected by Ti-O-Si bonding. PMID:28715384

New valve and bonding designs for microfluidic biochips containing proteins.

PubMed

Lu, Chunmeng; Xie, Yubing; Yang, Yong; Cheng, Mark M-C; Koh, Chee-Guan; Bai, Yunling; Lee, L James; Juang, Yi-Je

2007-02-01

Two major concerns in the design and fabrication of microfluidic biochips are protein binding on the channel surface and protein denaturing during device assembly. In this paper, we describe new methods to solve these problems. A "fishbone" microvalve design based on the concept of superhydrophobicity was developed to replace the capillary valve in applications where the chip surface requires protein blocking to prevent nonspecific binding. Our experimental results show that the valve functions well in a CD-like ELISA device. The packaging of biochips containing pre-loaded proteins is also a challenging task since conventional sealing methods often require the use of high temperatures, electric voltages, or organic solvents that are detrimental to the protein activity. Using CO2 gas to enhance the diffusion of polymer molecules near the device surface can result in good bonding at low temperatures and low pressure. This bonding method has little influence on the activity of the pre-loaded proteins after bonding.

Cathode catalyst for primary phosphoric fuel cells

NASA Technical Reports Server (NTRS)

Walsh, F.

1980-01-01

Alkylation of Vulcan XC-72 provided the most stable bond type for linking CoTAA to the surface of the carbon; this result is based on data obtained by cyclic voltammetry, pulse voltammetry and by release of 14C from bonded CoTAA. Half-cell tests at 100 C in 85% phosphoric acid showed that CoTAA bonded to the surface of carbon (Vulcan XC-72) via an alkylation procedure is a more active catalyst than is platinum based on a factor of two improvement in Tafel slope; dimeric CoTAA has catalytic activity equal to platinum. Half-cell tests also showed that bonded CoTAA catalysts do not suffer a loss in potential when air is used as a fuel rather than oxygen. Commercially available PTFE was shown to be stable for four months in 200 C 85% phosphoric acid based on lack of change in surface wetting properties, IR and physical characteristics. When stressed electrochemically in 150 C 85% phosphoric acid, PTFE also showed no changes after one month.

Evaluation of an alternative technique to optimize direct bonding of orthodontic brackets to temporary crowns.

PubMed

Dias, Francilena Maria Campos Santos; Pinzan-Vercelino, Célia Regina Maio; Tavares, Rudys Rodolfo de Jesus; Gurgel, Júlio de Araújo; Bramante, Fausto Silva; Fialho, Melissa Nogueira Proença

2015-01-01

To compare shear bond strength of different direct bonding techniques of orthodontic brackets to acrylic resin surfaces. The sample comprised 64 discs of chemically activated acrylic resin (CAAR) randomly divided into four groups: discs in group 1 were bonded by means of light-cured composite resin (conventional adhesive); discs in group 2 had surfaces roughened with a diamond bur followed by conventional direct bonding by means of light-cured composite resin; discs in group 3 were bonded by means of CAAR (alternative adhesive); and discs in group 4 had surfaces roughened with a diamond bur followed by direct bonding by means of CAAR. Shear bond strength values were determined after 24 hours by means of a universal testing machine at a speed of 0.5 mm/min, and compared by analysis of variance followed by post-hoc Tukey test. Adhesive remnant index (ARI) was measured and compared among groups by means of Kruskal-Wallis and Dunn tests. Groups 3 and 4 had significantly greater shear bond strength values in comparison to groups 1 and 2. Groups 3 and 4 yielded similar results. Group 2 showed better results when compared to group 1. In ARI analyses, groups 1 and 2 predominantly exhibited a score equal to 0, whereas groups 3 and 4 predominantly exhibited a score equal to 3. Direct bonding of brackets to acrylic resin surfaces using CAAR yielded better results than light-cured composite resin. Surface preparation with diamond bur only increased shear bond strength in group 2.

Degree of conversion and bond strength of resin-cements to feldspathic ceramic using different curing modes.

PubMed

Novais, Veridiana Resende; Raposo, Luís Henrique Araújo; Miranda, Rafael Resende de; Lopes, Camila de Carvalho Almança; Simamoto, Paulo Cézar; Soares, Carlos José

2017-01-01

The aim of this study was to assess the performance of resin cements when different curing modes are used, by evaluating the degree of conversion and bond strength to a ceramic substrate. Three resin cements were evaluated, two dual-cured (Variolink II and RelyX ARC) and one light-cured (Variolink Veneer). The dual-cured resin cements were tested by using the dual activation mode (base and catalyst) and light-activation mode (base paste only). For degree of conversion (DC) (n=5), a 1.0 mm thick feldspathic ceramic disc was placed over the resin cement specimens and the set was light activated with a QTH unit. After 24 h storage, the DC was measured with Fourier transform infrared spectroscopy (FTIR). For microshear bond strength testing, five feldspathic ceramic discs were submitted to surface treatment, and three cylindrical resin cement specimens were bonded to each ceramic surface according to the experimental groups. After 24 h, microshear bond testing was performed at 0.5 mm/min crosshead speed until the failure. Data were submitted to one-way ANOVA followed by Tukey test (p<0.05). Scanning electron microscopy (SEM) was used for classifying the failure modes. Higher DC and bond strength values were shown by the resin cements cured by using the dual activation mode. The Variolink II group presented higher DC and bond strength values when using light-activation only when compared with the Variolink Veneer group. The base paste of dual-cured resin cements in light-activation mode can be used for bonding translucent ceramic restorations of up to or less than 1.0 mm thick.

The reactions of thiophene on Mo(110) and Mo(110)-p(2×2)-S

NASA Astrophysics Data System (ADS)

Roberts, Jeffrey T.; Friend, C. M.

1987-07-01

The reactions of thiophene and 2,5-dideuterothiophene on Mo(110) and Mo(110)-p(2×2)-S have been investigated under ultrahigh vacuum conditions using temperature programmed reaction spectroscopy and Auger electron spectroscopy. Thiophene chemisorbed on Mo(110) decomposes during temperature programmed reaction to yield only gaseous dihydrogen, surface carbon, and surface sulfur. At low thiophene exposures, dihydrogen evolves from Mo(110) in a symmetric peak at 440 K. At saturation exposures, three dihydrogen peaks are detected at 360 K, at 420 K and at 565 K. Multilayers of thiophene desorb at 180 K. Temperature programmed reaction of 2,5-dideuterothiophene demonstrates that at high thiophene coverages, one of the α-C-H bonds (those nearest sulfur) breaks first. No bond breaking selectivity is observed at low thiophene exposures. The Mo(110)-p(2×2)-S surface is less active for thiophene decomposition. Thiophene adsorbed on Mo(110)-p(2×2)-S to low coverages decomposes to surface carbon surface sulfur, and hydrogen at 430 K. At reaction saturation, dihydrogen production is observed at 375 and 570 K. In addition, at moderate and high exposures, chemisorbed thiophene desorbs from Mo(110)-p(2×2)-S. At saturation the desorption temperature of the reversibly chemisorbed state is 215 K. Experiments with 2,5-dideuterothiophene demonstrate no surface selectivity for α-C-H bond breaking reactions on Mo(110)-p(2×2)-S. The decomposition mechanism and energetics of thiophene decomposition are proposed to be dependent on the coverage of thiophene. At low thiophene exposures, the ring is proposed to bond parallel to the surface. All C-H bonds in the parallel geometry are sterically available for activation by the surface, accounting for the lack of selectivity in C-H bond breaking. High thiophene coverages are suggested to result in perpendicularly bound thiophene which undergoes selective α-dehydrogenation to an α)-thiophenyl intermediate. The presence of sulfur leads to a high energy pathway for cleavage of C-H bonds in a thiophene derived intermediate. Carbon-hydrogen bonds survive on the surface up to temperatures of 650 K. Comparison of this study with work on Mo(100) demonstrates that the reaction of thiophene on molybdenum is relatively insensitive to the surface geometric structure.

Highly dispersed buckybowls as model carbocatalysts for C–H bond activation

DOE PAGES

Soykal, I. Ilgaz; Wang, Hui; Park, Jewook; ...

2015-03-19

Buckybowl fractions dispersed on mesoporous silica constitute an ideal model for studying the catalysis of graphitic forms of carbon since the dispersed carbon nanostructures contain a high ratio of edge defects and curvature induced by non-six-membered rings. Dispersion of the active centers on an easily accessible high surface area material allowed for high density of surface active sites associated with oxygenated structures. This report illustrates a facile method of creating model polycyclic aromatic nano-structures that are not only active for alkane C-H bond activation and oxidative dehydrogenation but also can be practical catalysts to be eventually used in industry.

Low-temperature direct bonding of glass nanofluidic chips using a two-step plasma surface activation process.

PubMed

Xu, Yan; Wang, Chenxi; Dong, Yiyang; Li, Lixiao; Jang, Kihoon; Mawatari, Kazuma; Suga, Tadatomo; Kitamori, Takehiko

2012-01-01

Owing to the well-established nanochannel fabrication technology in 2D nanoscales with high resolution, reproducibility, and flexibility, glass is the leading, ideal, and unsubstitutable material for the fabrication of nanofluidic chips. However, high temperature (~1,000 °C) and a vacuum condition are usually required in the conventional fusion bonding process, unfortunately impeding the nanofluidic applications and even the development of the whole field of nanofluidics. We present a direct bonding of fused silica glass nanofluidic chips at low temperature, around 200 °C in ambient air, through a two-step plasma surface activation process which consists of an O(2) reactive ion etching plasma treatment followed by a nitrogen microwave radical activation. The low-temperature bonded glass nanofluidic chips not only had high bonding strength but also could work continuously without leakage during liquid introduction driven by air pressure even at 450 kPa, a very high pressure which can meet the requirements of most nanofluidic operations. Owing to the mild conditions required in the bonding process, the method has the potential to allow the integration of a range of functional elements into nanofluidic chips during manufacture, which is nearly impossible in the conventional high-temperature fusion bonding process. Therefore, we believe that the developed low-temperature bonding would be very useful and contribute to the field of nanofluidics.

30 CFR 942.800 - Bond and insurance requirements for surface coal mining and reclamation operations.

Code of Federal Regulations, 2010 CFR

2010-07-01

... chartered by the Office of the Comptroller of the Currency; (iv) An insurance company licensed or authorized...'s or company's activities are examined or regulated by a State or Federal agency. (8) Trust funds... 30 Mineral Resources 3 2010-07-01 2010-07-01 false Bond and insurance requirements for surface...

30 CFR 942.800 - Bond and insurance requirements for surface coal mining and reclamation operations.

Code of Federal Regulations, 2011 CFR

2011-07-01

... chartered by the Office of the Comptroller of the Currency; (iv) An insurance company licensed or authorized...'s or company's activities are examined or regulated by a State or Federal agency. (8) Trust funds... 30 Mineral Resources 3 2011-07-01 2011-07-01 false Bond and insurance requirements for surface...

Heterogeneous integration based on low-temperature bonding for advanced optoelectronic devices

NASA Astrophysics Data System (ADS)

Higurashi, Eiji

2018-04-01

Heterogeneous integration is an attractive approach to manufacturing future optoelectronic devices. Recent progress in low-temperature bonding techniques such as plasma activation bonding (PAB) and surface-activated bonding (SAB) enables a new approach to integrating dissimilar materials for a wide range of photonics applications. In this paper, low-temperature direct bonding and intermediate layer bonding techniques are focused, and their state-of-the-art applications in optoelectronic devices are reviewed. First, we describe the room-temperature direct bonding of Ge/Ge and Ge/Si wafers for photodetectors and of GaAs/SiC wafers for high-power semiconductor lasers. Then, we describe low-temperature intermediate layer bonding using Au and lead-free Sn-3.0Ag-0.5Cu solders for optical sensors and MEMS packaging.

[Bone cement adhesion on ceramic surfaces - surface activation of retention surfaces of knee prostheses by atmospheric plasma versus thermal surface treatment].

PubMed

Marx, B; Marx, R; Reisgen, U; Wirtz, D

2015-04-01

CoCrMo alloys are contraindicated for allergy sufferers. For these patients, uncemented and cemented prostheses made of titanium alloy are indicated. Knee prostheses machined from that alloy, however, may have poor tribological behaviour, especially in relation to UHMWPE inlays. Therefore, for knee replacement cemented high-strength oxide ceramic prostheses are suitable for allergy sufferers and in cases of particle-induced aseptic loosening. For adhesion of bone cement, the ceramic surface, however, only exposes inefficient mechanical retention spots as compared with a textured metal surface. Undercuts generated by corundum blasting which in the short-term are highly efficient on a CoCrMo surface are not possible on a ceramic surface due to the brittleness of ceramics. Textures due to blasting may initiate cracks which will weaken the strength of a ceramic prosthesis. Due to the lack of textures mechanical retention is poor or even not existent. Micromotions are promoted and early aseptic loosening is predictable. Instead silicoating of the ceramic surface will allow specific adhesion and result in better hydrolytic stability of bonding thereby preventing early aseptic loosening. Silicoating, however, presupposes a clean and chemically active surface which can be achieved by atmospheric plasma or thermal surface treatment. In order to evaluate the effectiveness of silicoating the bond strengths of atmospheric plasma versus thermal surface treated and silicate layered ZPTA surfaces were compared with "as-fired" surfaces by utilising TiAlV probes (diameter 6 mm) for traction-adhesive strength tests. After preparing samples for traction-adhesive strength tests (sequence: ceramic substrate, silicate and silane, protective lacquer [PolyMA], bone cement, TiAlV probe) they were aged for up to 150 days at 37 °C in Ringer's solution. The bond strengths observed for all ageing intervals were well above 20 MPa and much higher and more hydrolytically stable for silicate layered compared with "as-fired" ZPTA samples. Silicoating may be effective for achieving high initial bond strength of bone cement on surfaces of oxide ceramics and also suitable to stabilise bond strength under hydrolytic conditions as present in the human body in the long-term. Activation by atmospheric plasma or thermal surface treatment seems to be effective for activation prior to silicoating. Due the proposed silicate layer migration, micromotions and debonding should be widely reduced or even eliminated. Georg Thieme Verlag KG Stuttgart · New York.

Photodegradation of organic contamination in wastewaters by bonding TiO2/single-walled carbon nanotube composites with enhanced photocatalytic activity.

PubMed

Zhou, Wei; Pan, Kai; Qu, Yang; Sun, Fanfei; Tian, Chungui; Ren, Zhiyu; Tian, Guohui; Fu, Honggang

2010-10-01

Bonding TiO(2)/single-walled carbon nanotube (SWCNT) composites have been successfully synthesized through a facile sol-solvothermal technique. The obtained materials were characterized in detail by XRD, FT-IR, Raman and TEM. The results revealed that TiO(2) and SWNCT linked compactly through ester bonds and thus improved their interfaces. Therefore, the recombination of photogenerated electron-hole pairs was inhibited efficiently, which improved the photocatalytic activity. A reasonable mechanism was proposed to explain its formation. The photocatalytic activity was investigated utilizing rhodamine B and nitrobenzene (NB) as models for organic contamination in wastewaters. Experimental results indicated that this bonding composite exhibited higher photocatalytic activity than that of Degussa P25. The excellent photocatalytic activity could be attributed to larger surface area, smaller crystalline size, and especially the ester bonds, which was further confirmed by surface photovoltage spectroscopy. Furthermore, by adding ()OH scavenger tert-butanol, the obvious decrease of NB photodegradation indicated that NB was oxidized primarily by ()OH. The photodegradation products were identified by GC/MS, further indicating that the degradation proceeded via ()OH oxidation. A possible reaction pathway for the degradation of NB was suggested by the evidence presented in this study. Copyright © 2010. Published by Elsevier Ltd.

Oxygen-Promoted Methane Activation on Copper

DOE PAGES

Niu, Tianchao; Jiang, Zhao; Zhu, Yaguang; ...

2017-11-01

The role of oxygen in the activation of C–H bonds in methane on clean and oxygen-precovered Cu(111) and Cu 2O(111) surfaces was studied with combined in situ near-ambient-pressure scanning tunneling microscopy and X-ray photoelectron spectroscopy. Activation of methane at 300 K and “moderate pressures” was only observed on oxygen-precovered Cu(111) surfaces. Density functional theory calculations reveal that the lowest activation energy barrier of C–H on Cu(111) in the presence of chemisorbed oxygen is related to a two-active-site, four-centered mechanism, which stabilizes the required transition-state intermediate by dipole–dipole attraction of O–H and Cu–CH 3 species. Furthermore, the C–H bond activation barriersmore » on Cu 2O(111) surfaces are large due to the weak stabilization of H and CH 3 fragments.« less

Oxygen-Promoted Methane Activation on Copper

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

Niu, Tianchao; Jiang, Zhao; Zhu, Yaguang

The role of oxygen in the activation of C–H bonds in methane on clean and oxygen-precovered Cu(111) and Cu 2O(111) surfaces was studied with combined in situ near-ambient-pressure scanning tunneling microscopy and X-ray photoelectron spectroscopy. Activation of methane at 300 K and “moderate pressures” was only observed on oxygen-precovered Cu(111) surfaces. Density functional theory calculations reveal that the lowest activation energy barrier of C–H on Cu(111) in the presence of chemisorbed oxygen is related to a two-active-site, four-centered mechanism, which stabilizes the required transition-state intermediate by dipole–dipole attraction of O–H and Cu–CH 3 species. Furthermore, the C–H bond activation barriersmore » on Cu 2O(111) surfaces are large due to the weak stabilization of H and CH 3 fragments.« less

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

PubMed

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

2017-07-14

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

Wear and interfacial transport of material

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1975-01-01

Bonding across the interface for two solids in contact and the subsequent transfer of material from one surface to another is a direct result of the interfacial bonds being stronger than the cohesive bonds in either of the two solids. Surface tools such as LEED, Auger emission spectroscopy, field ion microscopy, and the atom probe are used to examine adhesive contacts and to determine the direction, nature, quantity of material transfer and properties of the solids which effect transfer and wear. The electronic nature, cohesive binding energies, surface structure, lattice disregistry and distribution of species in surface layers are all found to effect adhesion and transfer or transport for clean surfaces in solid state contact. The influence of adsorbed and reacted surface films from fractions of a monolayer to multilayer reactive films are considered. It is shown that even fractions of a monolayer of surface active species such as oxygen and sulfur can markedly inhibit adhesion and transport.

The effect of anatase TiO2 surface structure on the behavior of ethanol adsorption and its initial dissociation step: A DFT study

NASA Astrophysics Data System (ADS)

Zhang, Riguang; Liu, Zhixue; Ling, Lixia; Wang, Baojun

2015-10-01

The perfect and defective surfaces of anatase TiO2 including (1 0 1) and (0 0 1) surfaces have been chosen to probe into the effect of anatase TiO2 surface structure on the behavior of ethanol adsorption and initial dissociation step. Here, the results are obtained by density functional theory (DFT) calculation together with the periodic slab model. Our results show that the surface structure of anatase TiO2 can obviously affect the behavior of ethanol adsorption and the catalytic activity of its initial dissociation step; firstly, on the perfect and defective surfaces of anatase (1 0 1), ethanol dominantly exists in the form of molecule adsorption; however, ethanol is the dissociative adsorption on the hydroxylated anatase (0 0 1), and the coexistences of molecular and dissociation adsorption modes on the perfect anatase (0 0 1). On the other hand, the initial dissociation step of ethanol with molecule adsorption prefers to begin with its O-H bond cleavage leading to CH3CH2O and H species rather than the cleavage of its α-C-H, β-C-H, C-C and C-O bonds, namely, the preferable O-H bond cleavage for the initial dissociation step of ethanol is independent of the surface structure of anatase TiO2; however, the corresponding catalytic activity of ethanol initial dissociation step with the O-H bond cleavage on different anatase TiO2 surfaces is in the following order: hydroxylated (0 0 1) > perfect (0 0 1) > defective (1 0 1) > perfect (1 0 1), suggesting that the catalytic activity for the initial dissociation step of ethanol is sensitive to the surface structure of anatase TiO2, and the hydroxylated (0 0 1) is the most favorable surface. Among these surfaces, the most favorable product for the initial dissociation step of ethanol is CH3CH2O species.

Hydroxylation of organic polymer surface: method and application.

PubMed

Yang, Peng; Yang, Wantai

2014-03-26

It may be hardly believable that inert C-H bonds on a polymeric material surface could be quickly and efficiently transformed into C-OH by a simple and mild way. Thanks to the approaches developed recently, it is now possible to transform surface H atoms of a polymeric substrate into monolayer OH groups by a simple/mild photochemical reaction. Herein the method and application of this small-molecular interfacial chemistry is highlighted. The existence of hydroxyl groups on material surfaces not only determines the physical and chemical properties of materials but also provides effective reaction sites for postsynthetic sequential modification to fulfill the requirements of various applications. However, organic synthetic materials based on petroleum, especially polyolefins comprise mainly C and H atoms and thus present serious surface problems due to low surface energy and inertness in reactivity. These limitations make it challenging to perform postsynthetic surface sequential chemical derivatization toward enhanced functionalities and properties and also cause serious interfacial problems when bonding or integrating polymer substrates with natural or inorganic materials. Polymer surface hydroxylation based on direct conversion of C-H bonds on polymer surfaces is thus of significant importance for academic and practical industrial applications. Although highly active research results have reported on small-molecular C-H bond activation in solution (thus homogeneous), most of them, featuring the use of a variety of transition metals as catalysts, present a slow reaction rate, a low atom economy and an obvious environmental pollution. In sharp contrast to these conventional C-H activation strategies, the present Spotlight describes a universal confined photocatalytic oxidation (CPO) system that is able to directly convert polymer surface C-H bonds to C-OSO3(-) and, subsequently, to C-OH through a simple hydrolysis. Generally speaking, these newly implanted hydroxyl groups preserve their own reactivity toward other complementary compounds, thus creating a novel base with distinct surface properties. Thanks to this functionalized platform, a wide range of organic, inorganic and metal materials have been attached to conventional organic polymer substrates through the rational engineering of surface molecular templates from small functional groups to macromolecules. It is expected that the proposed novel CPO method and its versatile usages in advanced material applications will offer new opportunities for a variety of scientific communities, especially for those working on surface/interface modulation.

Decal transfer lithography

DOEpatents

Nuzzo, Ralph G.; Childs, William R.; Motala, Michael J.; Lee, Keon Jae

2010-02-16

A method of making a microstructure includes selectively activating a portion of a surface of a silicon-containing elastomer, contacting the activated portion with a substance, and bonding the activated portion and the substance, such that the activated portion of the surface and the substance in contact with the activated portion are irreversibly attached. The selective activation may be accomplished by positioning a mask on the surface of the silicon-containing elastomer, and irradiating the exposed portion with UV radiation.

Research of Adhesion Bonds Between Gas-Thermal Coating and Pre-Modified Base

NASA Astrophysics Data System (ADS)

Kovalevskaya, Z.; Zaitsev, K.; Klimenov, V.

2016-08-01

Nature of adhesive bonds between gas-thermal nickel alloy coating and carbon steel base was examined using laser profilometry, optical metallography, transmission and scanning electron microscopy. The steel surface was plastically pre-deformed by an ultrasonic tool. Proved that ultrasound pre-treatment modifies the steel surface. Increase of dislocation density and formation of sub micro-structure are base elements of surface modification. While using high-speed gas-flame, plasma and detonation modes of coatings, surface activation occurs and durable adhesion is formed. Ultrasonic pre-treatment of base material is effective when sprayed particles and base material interact through physical-chemical bond formation. Before applying high-speed gas flame and plasma sprayed coatings, authors recommend ultrasonic pretreatment, which creates periodic wavy topography with a stroke of 250 microns on the steel surface. Before applying detonation sprayed coatings, authors recommend ultrasound pretreatment that create modified surface with a uniform micro-topography.

Electrocatalytic Oxidation of Ammonia on Transition-Metal Surfaces: A First-Principles Study

DOE PAGES

Herron, Jeffrey A.; Ferrin, Peter; Mavrikakis, Manos

2015-02-20

Here, we investigate the catalytic electro-oxidation of ammonia on model close-packed surfaces of Au, Ag, Cu, Pd, Pt, Ni, Ir, Co, Rh, Ru, Os, and Re to derive insights for the reaction mechanism and evaluate the catalysts based on their energy efficiency and activity in the context of their application in fuel cells. Two mechanisms, which are differentiated by their N–N bond formation step, are compared: (1) a mechanism proposed by Gerischer and Mauerer, whereby the N–N bond formation occurs between hydrogenated NH x adsorbed species, and (2) a mechanism in which N–N bond formation occurs between N adatoms. Themore » results of our study show that the mechanism proposed by Gerischer and Mauerer is kinetically preferred and that the formation of N adatoms poisons the surface of the catalyst. On the basis of a simple Sabatier analysis, we predict that Pt is the most active monometallic catalyst followed by Ir and Cu, whereas all other metal surfaces studied here have significantly lower activity. We conclude by outlining some design principles for bimetallic alloy catalysts for NH 3 electro-oxidation.« less

Application of atmospheric pressure plasma in polymer and composite adhesion

NASA Astrophysics Data System (ADS)

Yu, Hang

An atmospheric pressure helium and oxygen plasma was used to investigate surface activation and bonding in polymer composites. This device was operated by passing 1.0-3.0 vol% of oxygen in helium through a pair of parallel plate metal electrodes powered by 13.56 or 27.12 MHz radio frequency power. The gases were partially ionized between the capacitors where plasma was generated. The reactive species in the plasma were carried downstream by the gas flow to treat the substrate surface. The temperature of the plasm gas reaching the surface of the substrate did not exceed 150 °C, which makes it suitable for polymer processing. The reactive species in the plasma downstream includes ~ 1016-1017 cm-3 atomic oxygen, ~ 1015 cm-3 ozone molecule, and ~ 10 16 cm-3 metastable oxygen molecule (O2 1Deltag). The substrates were treated at 2-5 mm distance from the exit of the plasma. Surface properties of the substrates were characterized using water contact angle (WCA), atomic force microscopy (AFM), infrared spectroscopy (IR), and X-ray photoelectron spectroscopy (XPS). Subsequently, the plasma treated samples were bonded adhesively or fabricated into composites. The increase in mechanical strength was correlated to changes in the material composition and structure after plasma treatment. The work presented hereafter establishes atmospheric pressure plasma as an effective method to activate and to clean the surfaces of polymers and composites for bonding. This application can be further expanded to the activation of carbon fibers for better fiber-resin interactions during the fabrication of composites. Treating electronic grade FR-4 and polyimide with the He/O2 plasma for a few seconds changed the substrate surface from hydrophobic to hydrophilic, which allowed complete wetting of the surface by epoxy in underfill applications. Characterization of the surface by X-ray photoelectron spectroscopy shows formation of oxygenated functional groups, including hydroxyl, carbonyl, and carboxyl groups, on the polymer surface after plasma treatment. The resulting strength of the bond based on lap-shear and T-peel tests correlates well with the concentration of oxygen on the polymer surface. The failure modes observed for lap-shear and T-peel tests changed from interfacial to cohesive after the plasma activation. Treating carbon-fiber-reinforced epoxy composites with the atmospheric plasma resulted in the removal of fluorinated contaminants in shallow surface layers. For contaminants that diffused deeply into the composite surface, mechanical abrasion was needed in addition to the plasma treatment to remove the impurities. While cleaning the composite, plasma also generated active oxygen groups on the substrate surface. The presence of these groups improved the adhesive bonding strength of the composite even in the presence of residual fluorine contaminants. Thus, it was speculated that plasma treatment can promote better polymer adhesion with or without fluorine contamination. Carbon nanotube sheets were also treated by the helium oxygen plasma, and the CNT surface turn from super hydrophobic to hydrophilic after a few seconds of exposure. The nanotube surface contained 15% of oxygen in the form of hydroxyl groups. Chemical coupling agents were added to the plasma activated CNT surfaces in order to crosslink the CNTs and to create bonding sites for the resin matrix. Stretched, activated and functionalized CNT was cured with dicyclopentadiene (DCPD) to produce a sheet composite with a tensile strength of 636 MPa, a modulus of 28 GPa, and a density of 1.4 g/cm 3. This may be compared to aerospace-grade aluminum with tensile strength of 572 MPa, modulus of 72 GPa, and density of 2.7 g/cm3. This work demonstrates that new high-strength composite can be produced with the use of atmospheric plasma activation and chemical crosslinking of the fiber matrix.

[Effects of different surface conditioning agents on the bond strength of resin-opaque porcelain composite].

PubMed

Liu, Wenjia; Fu, Jing; Liao, Shuang; Su, Naichuan; Wang, Hang; Liao, Yunmao

2014-04-01

The objective of this research is to evaluate the effects of different silane coupling agents on the bond strength between Ceramco3 opaque porcelain and indirect composite resin. Five groups of Co-Cr metal alloy substrates were fabricated according to manufacturer's instruction. The surface of metal alloy with a layer of dental opaque porcelain was heated by fire. After the surface of opaque porcelain was etched, five different surface treatments, i.e. RelyX Ceramic Primer (RCP), Porcelain Bond Activator and SE Bond Primer (mixed with a proportion of 1:1) (PBA), Shofu Porcelain Primer (SPP), SE bond primer (SEP), and no primer treatment (as a control group), were used to combine P60 and opaque porcelain along with resin cement. Shear bond strength of specimens was tested in a universal testing machine. The failure modes of specimens in all groups were observed and classified into four types. Selected specimens were subjected to scanning electron microscope and energy disperse spectroscopy to reveal the relief of the fracture surface and to confirm the failure mode of different types. The experimental results showed that the values of the tested items in all the tested groups were higher than that in the control group. Group PBA exhibited the highest value [(37.52 +/- 2.14) MPa] and this suggested a fact that all of the specimens in group PBA revealed combined failures (failure occurred in metal-porcelain combined surface and within opaque porcelain). Group SPP and RCP showed higher values than SEP (P < 0.05) and most specimens of SPP and RCP performed combined failures (failure occurred in bond surface and within opaque porcelain or composite resin) while all the specimens in group SEP and control group revealed adhesive failures. Conclusions could be drawn that silane coupling agents could reinforce the bond strength of dental composite resin to metal-opaque porcelain substrate. The bond strength between dental composite resin and dental opaque porcelain could meet the clinical requirements.

Realization of MEMS-IC Vertical Integration Utilizing Smart Bumpless Bonding

NASA Astrophysics Data System (ADS)

Shiozaki, Masayoshi; Moriguchi, Makoto; Sasaki, Sho; Oba, Masatoshi

This paper reports fundamental technologies, properties, and new experimental results of SBB (Smart Bumpless Bonding) to realize MEMS-IC vertical integration. Although conventional bonding technologies have had difficulties integrating MEMS and its processing circuit because of their rough bonding surfaces, fragile structures, and thermal restriction, SBB technology realized the vertical integration without thermal treatment, any adhesive materials including bumps, and chemical mechanical polishing. The SBB technology bonds sealing parts for vacuum sealing and electrodes for electrical connection simultaneously as published in previous experimental study. The plasma CVD SiO2 is utilized to realize vacuum sealing as sealing material. And Au projection studs are formed on each electrode and connected electrically between two wafers by compressive plastic deformation and surface activation. In this paper, new experimental results including vacuum sealing properties, electrical improvement, IC bonding results on the described fundamental concept and properties are reported.

Innovations in bonding to zirconia-based materials. Part II: Focusing on chemical interactions.

PubMed

Aboushelib, Moustafa N; Mirmohamadi, Hesam; Matinlinna, Jukka P; Kukk, Edwin; Ounsi, Hani F; Salameh, Ziad

2009-08-01

The zirconia-resin bond strength was enhanced using novel engineered zirconia primers in combination with selective infiltration etching as a surface pre-treatment. The aim of this study was to evaluate the effect of artificial aging on the chemical stability of the established bond and to understand the activation mechanism of the used primers. Selective infiltration etched zirconia discs (Procera; NobelBiocare) were coated with one of four novel engineered zirconia primers containing reactive monomers and were bonded to resin-composite discs (Panavia F2.0). Fourier transform infrared spectroscopy (FT-IR) was carried out to examine the chemical activation of zirconia primers from mixing time and up to 60min. The bilayered specimens were cut into microbars (1mm(2) in cross-section area) and zirconia-resin microtensile bond strength (MTBS) was evaluated immediately and after 90 days of water storage at 37 degrees C. Scanning electron microscopy (SEM) was used to analyze the fracture surface. There was a significant drop in MTBS values after 90 days of water storage for all tested zirconia primers from ca. 28-41MPa to ca. 15-18MPa after completion of artificial aging. SEM revealed increase in percentage of interfacial failure after water storage. FTIR spectra suggested adequate activation of the experimental zirconia primers within 1h of mixing time. The novel engineered zirconia primers produced initially high bond strength values which were significantly reduced after water storage. Long-term bond stability requires developing more stable primers.

Molecular Insight into the Slipperiness of Ice.

PubMed

Weber, Bart; Nagata, Yuki; Ketzetzi, Stefania; Tang, Fujie; Smit, Wilbert J; Bakker, Huib J; Backus, Ellen H G; Bonn, Mischa; Bonn, Daniel

2018-05-16

Measurements of the friction coefficient of steel-on-ice over a large temperature range reveal very high friction at low temperatures (-100 °C) and a steep decrease in the friction coefficient with increasing temperature. Very low friction is only found over the limited temperature range typical for ice skating. The strong decrease in the friction coefficient with increasing temperature exhibits Arrhenius behavior with an activation energy of E a ≈ 11.5 kJ mol -1 . Remarkably, molecular dynamics simulations of the ice-air interface reveal a very similar activation energy for the mobility of surface molecules. Weakly hydrogen-bonded surface molecules diffuse over the surface in a rolling motion, their number and mobility increasing with increasing temperature. This correlation between macroscopic friction and microscopic molecular mobility indicates that slippery ice arises from the high mobility of its surface molecules, making the ice surface smooth and the shearing of the weakly bonded surface molecules easy.

The Effect of Artificial Aging on The Bond Strength of Heat-activated Acrylic Resin to Surface-treated Nickel-chromium-beryllium Alloy.

PubMed

Al Jabbari, Youssef S; Zinelis, Spiros; Al Taweel, Sara M; Nagy, William W

2016-01-01

The debonding load of heat-activated polymethylmethacrylate (PMMA) denture base resin material to a nickel-chromium-beryllium (Ni-Cr-Be) alloy conditioned by three different surface treatments and utilizing two different commercial bonding systems was investigated. Denture resin (Lucitone-199) was bonded to Ni-Cr-Be alloy specimens treated with Metal Primer II, the Rocatec system with opaquer and the Rocatec system without opaquer. Denture base resin specimens bonded to non-treated sandblasted Ni-Cr-Be alloy were used as controls. Twenty samples for each treatment condition (80 specimens) were tested. The 80 specimens were divided into two categories, thermocycled and non-thermocycled, containing four groups of ten specimens each. The non-thermocycled specimens were tested after 48 hours' storage in room temperature water. The thermocycled specimens were tested after 2,000 cycles in 4°C and 55°C water baths. The debonding load was calculated in Newtons (N), and collected data were subjected by non parametric test Kruskal-Wallis One Way Analysis of Variance on Ranks and Dunn's post hoc test at the α = 0.05. The Metal Primer II and Rocatec system without opaquer groups produced significantly higher bond strengths (119.9 and 67.6 N), respectively, than did the sandblasted and Rocatec system with opaquer groups, where the bond strengths were 2.6 N and 0 N, respectively. The Metal Primer II was significantly different from all other groups (P<0.05). The bond strengths of all groups were significantly decreased (P<0.05) after thermocycling. Although thermocycling had a detrimental effect on the debonding load of all surface treatments tested, the Metal Primer II system provided higher values among all bonding systems tested, before and after thermocycling.

Morphological effects of MMPs inhibitors on the dentin bonding

PubMed Central

Li, He; Li, Tianbo; Li, Xiuying; Zhang, Zhimin; Li, Penglian; Li, Zhenling

2015-01-01

Matrix metalloproteinases (MMPs) have been studied extensively, and MMP inhibitors have been used as dental pretreatment agents prior to dentin bonding because they reduce collagen fiber degradation and improve bonding strength. However, morphologic characteristics of the collagen network after etching and of the post-adhesive dentin hybrid layers (DHL) after MMP inhibitors pretreatment have not been evaluated. Thus, we investigated demineralized dentin pretreated with chlorhexidine (CHX) and minocycline (MI) in an etch- and -rinse adhesive system with field emission scanning electron microscopy (FESEM) and immuno-gold labeling markers to observe the collagen network and DHL. FESEM revealed after CHX and MI, a demineralized dentin surface and improved collagen network formation, reduced collagen degradation, and distinct gold-labeling signals. Applying adhesive after either MMP inhibitor created a better dentin interface as evidenced by immuno-gold staining, better adhesive penetration, and higher DHL quality. With microtensile bond strength tests (µTBS) we estimated bonding strength using µTBS data. Immediate µTBS was enhanced with MMP inhibitor application to the bonding surface, and the CHX group was significantly different than non-treated etched surfaces, but no significant change was detected in the MI group. Surface micromorphology of the fractured dentin resin restoration showed that the CHX group had a better resin and dentin tube combination. Both MMP inhibitors created uniform resin coverage. Thus, morphologic results and µTBS data suggest that CHX and MI can inhibit MMP activity, improve immediate bonding strength, and enhance dentin bonding stability with an etch- and -rinse adhesive system. PMID:26379873

Disulfide bonding arrangements in active forms of the somatomedin B domain of human vitronectin.

PubMed

Kamikubo, Yuichi; De Guzman, Roberto; Kroon, Gerard; Curriden, Scott; Neels, Jaap G; Churchill, Michael J; Dawson, Philip; Ołdziej, Stanisław; Jagielska, Anna; Scheraga, Harold A; Loskutoff, David J; Dyson, H Jane

2004-06-01

The N-terminal cysteine-rich somatomedin B (SMB) domain (residues 1-44) of the human glycoprotein vitronectin contains the high-affinity binding sites for plasminogen activator inhibitor-1 (PAI-1) and the urokinase receptor (uPAR). We previously showed that the eight cysteine residues of recombinant SMB (rSMB) are organized into four disulfide bonds in a linear uncrossed pattern (Cys(5)-Cys(9), Cys(19)-Cys(21), Cys(25)-Cys(31), and Cys(32)-Cys(39)). In the present study, we use an alternative method to show that this disulfide bond arrangement remains a major preferred one in solution, and we determine the solution structure of the domain using NMR analysis. The solution structure shows that the four disulfide bonds are tightly packed in the center of the domain, replacing the traditional hydrophobic core expected for a globular protein. The few noncysteine hydrophobic side chains form a cluster on the outside of the domain, providing a distinctive binding surface for the physiological partners PAI-1 and uPAR. The hydrophobic surface consists mainly of side chains from the loop formed by the Cys(25)-Cys(31) disulfide bond, and is surrounded by conserved acidic and basic side chains, which are likely to contribute to the specificity of the intermolecular interactions of this domain. Interestingly, the overall fold of the molecule is compatible with several arrangements of the disulfide bonds. A number of different disulfide bond arrangements were able to satisfy the NMR restraints, and an extensive series of conformational energy calculations performed in explicit solvent confirmed that several disulfide bond arrangements have comparable stabilization energies. An experimental demonstration of the presence of alternative disulfide conformations in active rSMB is provided by the behavior of a mutant in which Asn(14) is replaced by Met. This mutant has the same PAI-1 binding activity as rVN1-51, but its fragmentation pattern following cyanogen bromide treatment is incompatible with the linear uncrossed disulfide arrangement. These results suggest that active forms of the SMB domain may have a number of allowed disulfide bond arrangements as long as the Cys(25)-Cys(31) disulfide bond is preserved.

Influence of preheating the bonding agent of a conventional three-step adhesive system and the light activated resin cement on dentin bond strength

PubMed Central

Holanda, Daniel Brandão Vilela; França, Fabiana Mantovani Gomes; do Amaral, Flávia Lucisano Botelho; Flório, Flávia Martão; Basting, Roberta Tarkany

2013-01-01

Aims: to evaluate the influence of preheating the bonding agent (Scotchbond Multipurpose Adhesive/3M ESPE) and the light-activated resin cement (RelyX Venner/3M ESPE) on dentin microtensile bond strength. Materials and Methods: The exposed flat dentin surface of 40 human third molars were randomly distributed into four groups for cementation (SR Adoro/Ivoclar Vivadent) (n = 10): G1-bond and resin cement, both at room temperature (22°C), G2-bond preheated to 58°C and cement at room temperature (22°C), G3-bond at room temperature (22°C) and the cement preheated to 58°C, G4-bond preheated to 58°C and cement preheated to 58°C. Sticks of dentin/block set measuring approximately 1 mm2 were obtained and used for the microtensile bond strength test. All sticks had their failure mode classified. Statistical analysis used: Factorial analysis of variance was applied, 2 × 2 (bond × cement) (P < 0.05). Results: Preheating the bonding agent (P = 0.8411) or the cement (P = 0.7155), yielded no significant difference. The interaction bond × cement was not significant (P = 0.9389). Conclusions: Preheating the bond and/or the light-activated resin cement did not influence dentin bond strength or fracture failure mode. PMID:24347889

A density functional theory model of mechanically activated silyl ester hydrolysis

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

Pill, Michael F.; Schmidt, Sebastian W.; Institut für Physikalische Chemie, Christian-Albrechts-Universität zu Kiel, Olshausenstraße 40, 24098 Kiel

2014-01-28

To elucidate the mechanism of the mechanically activated dissociation of chemical bonds between carboxymethylated amylose (CMA) and silane functionalized silicon dioxide, we have investigated the dissociation kinetics of the bonds connecting CMA to silicon oxide surfaces with density functional calculations including the effects of force, solvent polarizability, and pH. We have determined the activation energies, the pre-exponential factors, and the reaction rate constants of candidate reactions. The weakest bond was found to be the silyl ester bond between the silicon and the alkoxy oxygen atom. Under acidic conditions, spontaneous proton addition occurs close to the silyl ester such that neutralmore » reactions become insignificant. Upon proton addition at the most favored position, the activation energy for bond hydrolysis becomes 31 kJ mol{sup −1}, which agrees very well with experimental observation. Heterolytic bond scission in the protonated molecule has a much higher activation energy. The experimentally observed bi-exponential rupture kinetics can be explained by different side groups attached to the silicon atom of the silyl ester. The fact that different side groups lead to different dissociation kinetics provides an opportunity to deliberately modify and tune the kinetic parameters of mechanically activated bond dissociation of silyl esters.« less

Computational insights into crystal plane dependence of thermal activity of anion (C and N)-substituted titania.

PubMed

V, Sai Phani Kumar; Arya, Rahul; Deshpande, Parag A

2017-11-29

Geometry optimizations of anion (C and N) doped anatase TiO 2 were carried out by using DFT+U calculations. Various anion vacancy sites were examined to study the synergistic effects of anion doping accompanied with anion vacancy formation on lattice oxygen activation. Two non-identical crystal planes (0 0 1) and (1 0 0) were chosen for C and N substitutions. Energetically favoured N-vacancy pairs were identified on TiO 2 surfaces. Substitution of N along with anion vacancies at various sites was energetically more favoured than that of C-doping in bulk TiO 2 while the energies were comparable for surface substitutions. Bond length distributions due to the formation of differential bonds were determined. Net oxygen activation and accompanying reversible oxygen exchange capacities were compared for TiO 2-2x C x and TiO 2-3x N 2x . Substitution of C in the surface exposed (1 0 0) plane of TiO 2 resulted in 47.6% and 23.8% of bond elongation and compression, respectively, resulting in 23.8% of net oxygen activation which was higher when compared to N substitution in the (1 0 0) plane of TiO 2 resulting in a net oxygen activation of 17%.

Effects of carbon fiber surface characteristics on interfacial bonding of epoxy resin composite subjected to hygrothermal treatments

NASA Astrophysics Data System (ADS)

Li, Min; Liu, Hongxin; Gu, Yizhuo; Li, Yanxia; Zhang, Zuoguang

2014-01-01

The changes of interfacial bonding of three types of carbon fibers/epoxy resin composite as well as their corresponding desized carbon fiber composites subjecting to hygrothermal conditions were investigated by means of single fiber fragmentation test. The interfacial fracture energy was obtained to evaluate the interfacial bonding before and after boiling water aging. The surface characteristics of the studied carbon fiber were characterized using X-ray photoelectron spectroscopy. The effects of activated carbon atoms and silicon element at carbon fiber surface on the interfacial hygrothermal resistance were further discussed. The results show that the three carbon fiber composites with the same resin matrix possess different hygrothermal resistances of interface and the interfacial fracture energy after water aging can not recovery to the level of raw dry sample (irreversible changes) for the carbon fiber composites containing silicon. Furthermore, the activated carbon atoms have little impact on the interfacial hygrothermal resistance. The irreversible variations of interfacial bonding and the differences among different carbon fiber composites are attributed to the silicon element on the carbon fiber bodies, which might result in hydrolyzation in boiling water treatment and degrade interfacial hygrothermal resistance.

Iodine versus Bromine Functionalization for Bottom-Up Graphene Nanoribbon Growth: Role of Diffusion

DOE PAGES

Bronner, Christopher; Marangoni, Tomas; Rizzo, Daniel J.; ...

2017-08-08

Deterministic bottom-up approaches for synthesizing atomically well-defined graphene nanoribbons (GNRs) largely rely on the surface-catalyzed activation of selected labile bonds in a molecular precursor followed by step-growth polymerization and cyclodehydrogenation. While the majority of successful GNR precursors rely on the homolytic cleavage of thermally labile C–Br bonds, the introduction of weaker C–I bonds provides access to monomers that can be polymerized at significantly lower temperatures, thus helping to increase the flexibility of the GNR synthesis process. Scanning tunneling microscopy imaging of molecular precursors, activated intermediates, and polymers resulting from stepwise thermal annealing of both Br and I substituted precursors formore » chevron GNRs reveals that the polymerization of both precursors proceeds at similar temperatures on Au(111). Finally, this surprising observation is consistent with diffusion-controlled polymerization of the surface-stabilized radical intermediates that emerge from homolytic cleavage of either the C–Br or the C–I bonds.« less

Methane combustion reactivity during the metal→metallic oxide transformation of Pd-Pt catalysts: Effect of oxygen pressure

NASA Astrophysics Data System (ADS)

Qi, Wenjie; Ran, Jingyu; Zhang, Zhien; Niu, Juntian; Zhang, Peng; Fu, Lijuan; Hu, Bo; Li, Qilai

2018-03-01

Density functional theory combined with kinetic models were used to probe different kinetics consequences by which methane activation on different oxygen chemical potential surfaces as oxygen pressure increased. The metallic oxide → metal transformation temperature of Pd-Pt catalysts increased with the increase of the Pd content or/and O2 pressure. The methane conversion rate on Pt catalyst increased and then decreased to a constant value when increasing the O2 pressure, and Pd catalyst showed a poor activity performance in the case of low O2 pressure. Moreover, its activity increased as the oxygen chemical potential for O2 pressure increased in the range of 2.5-10 KPa. For metal clusters, the Csbnd H bond and Odbnd O bond activation steps occurred predominantly on *-* site pairs. The methane conversion rate was determined by O2 pressure because the adsorbed O atoms were rapidly consumed by other adsorbed species in this kinetic regime. As the O2 pressure increased, the metallic active sites for methane activation were decreased and there was no longer lack of adsorbed O atoms, resulting in the decrease of the methane conversion rate. Furthermore, when the metallic surfaces were completely covered by adsorbed oxygen atoms at higher oxygen chemical potentials, Pt catalyst showed a poor activity due to a high Csbnd H bond activation barrier on O*sbnd O*. In the case of high O2 pressure, Pd atoms preferred to segregate to the active surface of Pd-Pt catalysts, leading to the formation of PdO surfaces. The increase of Pd segregation promoted a subsequent increase in active sites and methane conversion rate. The PdO was much more active than metallic and O* saturated surfaces for methane activation, inferred from the theory and experimental study. Pd-rich bimetallic catalyst (75% molar Pd) showed a dual high methane combustion activity on O2-poor and O2-rich conditions.

Effect of Atmospheric Pressure Plasma Treatment on Surface Characteristics and Adhesive Bond Quality of Peel Ply Prepared Composites

NASA Astrophysics Data System (ADS)

Tracey, Ashley C.

The purpose of this research was to investigate if atmospheric pressure plasma treatment could modify peel ply prepared composite surfaces to create strong adhesive bonds. Two peel ply surface preparation composite systems previously shown to create weak bonds (low fracture energy and adhesion failure) that were potential candidates for plasma treatment were Toray T800/3900-2 carbon fiber reinforced polymer (CFRP) prepared with Precision Fabrics Group, Inc. (PFG) 52006 nylon peel ply and Hexcel T300/F155 CFRP prepared with PFG 60001 polyester peel ply. It was hypothesized that atmospheric pressure plasma treatment could functionalize and/or remove peel ply remnants left on the CFRP surfaces upon peel ply removal. Surface characterization measurements and double cantilever beam (DCB) testing were used to determine the effects of atmospheric pressure plasma treatment on surface characteristics and bond quality of peel ply prepared CFRP composites. Previous research showed that Toray T800/3900-2 carbon fiber reinforced epoxy composites prepared with PFG 52006 peel ply and bonded with Cytec MetlBond 1515-3M structural film adhesive failed in adhesion at low fracture energies when tested in the DCB configuration. Previous research also showed that DCB samples made of Hexcel T300/F155 carbon fiber reinforced epoxy composites prepared with PFG 60001 peel ply and bonded with Henkel Hysol EA 9696 structural film adhesive failed in adhesion at low fracture energies. Recent research suggested that plasma treatment could be able to activate these "un-bondable" surfaces and result in good adhesive bonds. Nylon peel ply prepared 177 °C cure and polyester peel ply prepared 127 °C cure CFRP laminates were treated with atmospheric pressure plasma after peel ply removal prior to bonding. Atmospheric pressure plasma treatment was capable of significantly increasing fracture energies and changing failure modes. For Toray T800/3900-2 laminates prepared with PFG 52006 and bonded with MetlBond 1515-3M, plasma treatment increased fracture energies from 460 J/m 2. Atmospheric pressure plasma treatment also increased fracture energies of Hexcel T300/F155 laminates prepared with PFG 60001 and bonded with EA 9696 from 1500 J/m2. It was demonstrated that atmospheric pressure plasma treatment was able to transform poor bonding surfaces into acceptable ones by reversing the negative effects of incorrect peel ply usage. To determine if the primary reason for adhesion was functionalization or removal, a number of experiments were performed. Surface characteristics of peel ply only and plasma treated samples were determined using contact angle (CA) measurements, FTIR spectroscopy, X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). CA was used to assess solid surface energy that was useful to determine wetting of the adhesive on the adherend, one requirement of adhesion. FTIR and XPS were used to analyze composite surface chemistry, including the identification of functional groups that were a product of atmospheric pressure plasma treatment, as well as contaminants that can inhibit adhesive bonding. SEM was used to capture surface morphology to identify peel ply remnants and whether these remnants were physically removed or modified due to plasma treatment. This research supported that atmospheric pressure plasma treatment resulted in adhesion primarily due to functionalization of peel ply remnants, though a removal mechanism was not disproven. It was also shown that surface energy exhibited potential for predicting adhesion. Lastly, this research indicated that plasma treatment is a robust surface preparation, as strong bonds were observed up to 30 days after treatment.

Reactive Landing of Gramicidin S and Ubiquitin Ions onto Activated Self-Assembled Monolayer Surfaces

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

Laskin, Julia; Hu, Qichi

2017-03-13

Using mass-selected ion deposition combined with in situ infrared reflection absorption spectroscopy (IRRAS), we examined the reactive landing of gramicidin S and ubiquitin ions onto activated self-assembled monolayer (SAM) surfaces terminated with N-hydroxysuccinimidyl ester (NHS-SAM) and acyl fluoride (COF-SAM) groups. Doubly protonated gramicidin S, [GS+2H]2+, and two charge states of ubiquitin, [U+5H]5+ and [U+13H]13+, were used as model systems, allowing us to explore the effect of the number of free amino groups and the secondary structure on the efficiency of covalent bond formation between the projectile ion and the surface. For all projectile ions, ion deposition resulted in the depletionmore » of IRRAS bands corresponding to the terminal groups on the SAM and the appearance of several new bands not associated with the deposited species. These new bands were assigned to the C=O stretching vibrations of COOH and COO- groups formed on the surface as a result of ion deposition. The presence of these bands was attributed to an alternative reactive landing pathway that competes with covalent bond formation. This pathway with similar yields for both gramicidin S and ubiquitin ions is analogous to the hydrolysis of the NHS ester bond in solution. The covalent bond formation efficiency increased linearly with the number of free amino groups and was found to be lower for the more compact conformation of ubiquitin compared with the fully unfolded conformation. This observation was attributed to the limited availability of amino groups on the surface of the folded conformation. Our results have provided new insights on the efficiency and mechanism of reactive landing of peptides and proteins onto activated SAMs« less

Reactive Landing of Gramicidin S and Ubiquitin Ions onto Activated Self-Assembled Monolayer Surfaces

NASA Astrophysics Data System (ADS)

Laskin, Julia; Hu, Qichi

2017-07-01

Using mass-selected ion deposition combined with in situ infrared reflection absorption spectroscopy (IRRAS), we examined the reactive landing of gramicidin S and ubiquitin ions onto activated self-assembled monolayer (SAM) surfaces terminated with N-hydroxysuccinimidyl ester (NHS-SAM) and acyl fluoride (COF-SAM) groups. Doubly protonated gramicidin S, [GS + 2H]2+, and two charge states of ubiquitin, [U + 5H]5+ and [U + 13H]13+, were used as model systems, allowing us to explore the effect of the number of free amino groups and the secondary structure on the efficiency of covalent bond formation between the projectile ion and the surface. For all projectile ions, ion deposition resulted in the depletion of IRRAS bands corresponding to the terminal groups on the SAM and the appearance of several new bands not associated with the deposited species. These new bands were assigned to the C=O stretching vibrations of COOH and COO- groups formed on the surface as a result of ion deposition. The presence of these bands was attributed to an alternative reactive landing pathway that competes with covalent bond formation. This pathway with similar yields for both gramicidin S and ubiquitin ions is analogous to the hydrolysis of the NHS ester bond in solution. The covalent bond formation efficiency increased linearly with the number of free amino groups and was found to be lower for the more compact conformation of ubiquitin compared with the fully unfolded conformation. This observation was attributed to the limited availability of amino groups on the surface of the folded conformation. Our results have provided new insights on the efficiency and mechanism of reactive landing of peptides and proteins onto activated SAMs.

Tensile bond strength of silicone-based soft denture liner to two chemically different denture base resins after various surface treatments.

PubMed

Akin, Hakan; Tugut, Faik; Guney, Umit; Kirmali, Omer; Akar, Turker

2013-01-01

This study evaluated the effect of various surface treatments on the tensile bond strength of a silicone-based soft denture liner to two chemically different denture base resins, heat-cured polymethyl methacrylate (PMMA), and light-activated urethane dimethacrylate or Eclipse denture base resin. PMMA test specimens were fabricated and relined with a silicone-based soft denture liner (group AC). Eclipse test specimens were prepared according to the manufacturer's recommendation. Before they were relined with a silicone-based soft denture liner, each received one of three surface treatments: untreated (control, group EC), Eclipse bonding agent applied (group EB), and laser-irradiated (group EL). Tensile bond strength tests (crosshead speed = 5 mm/min) were performed for all specimens, and the results were analyzed using the analysis of variance followed by Tukey's test (p = 0.05). Eclipse denture base and PMMA resins presented similar bond strengths to the silicone-based soft denture liner. The highest mean force was observed in group EL specimens, and the tensile bond strengths in group EL were significantly different (p < 0.05) from those in the other groups.

Theoretical aspects of methyl acetate and methanol activation on MgO(100) and (501) catalyst surfaces with application in FAME production

NASA Astrophysics Data System (ADS)

Man, Isabela-Costinela; Soriga, Stefan Gabriel; Parvulescu, Vasile

2017-01-01

Density functional theory (DFT) calculations were carried out to study the activation of methyl acetate and methanol on MgO(100) and MgO(501) surfaces and integrated in the context of transesterification, interesterification and glycerolysis reactions used in biodiesel industry. First results indicate the importance of including of dispersion forces in the calculations. On MgO(100) the reverse reactions steps of Csbnd O and Csbnd H dissociations and on MgO(501) the same reverse reaction step of Csbnd H dissociations of methyl acetate are energetically favorable, while the dissociation of Csbnd O bond into methoxide and acetate fragments on the edge of MgO(501) was found to be exothermic with a low activation energy. For methanol, the dissociation of Osbnd H bond on MgO(100) surface in the presence of the second coadsorbed methanol molecule becomes more energetically favoured compared to the isolated molecule, due to the fact that the methoxide fragment is stabilized by intermolecular hydrogen bonding. This is reflected by the decrease of the activation energy of the forward reaction step and the increase of the activation energy of the backward reaction step, increasing the probability to have dissociated molecules among the undissociated ones. These results represent a step forward for better understanding from atomistic point of view the paths of these reactions on these surfaces for the corresponding catalytic processes.

Ice surfaces in the mesosphere: Absence of dangling bonds in the presence of atomic oxygen

NASA Astrophysics Data System (ADS)

Boulter, James E.; Morgan, Christopher G.; Marschall, Jochen

2005-07-01

Ice deposition experiments in the presence of microwave discharge-dissociated molecular oxygen suggest heterogeneous interactions between dangling OH bonds on the ice surface and atomic oxygen. Ice films deposited on a gold substrate at temperatures of 115, 130, and 140 K from oxygen/water gas mixtures representative of the summertime polar mesosphere exhibit infrared absorption features characteristic of dangling bonds, whereas films grown in the presence of atomic oxygen do not. Dangling bond spectral features are shown to diminish rapidly when the microwave discharge is activated during ice deposition. Similar decreases were not seen when the gas stream was heated or when the ice film was slowly annealed from 130 to 160 K. One interpretation of these results is that atomic oxygen binds to dangling bond sites during ice growth, a phenomenon that may also occur during the formation of ice particles observed just below the cold summertime mesopause.

Vertical and lateral heterogeneous integration

NASA Astrophysics Data System (ADS)

Geske, Jon; Okuno, Yae L.; Bowers, John E.; Jayaraman, Vijay

2001-09-01

A technique for achieving large-scale monolithic integration of lattice-mismatched materials in the vertical direction and the lateral integration of dissimilar lattice-matched structures has been developed. The technique uses a single nonplanar direct-wafer-bond step to transform vertically integrated epitaxial structures into lateral epitaxial variation across the surface of a wafer. Nonplanar wafer bonding is demonstrated by integrating four different unstrained multi-quantum-well active regions lattice matched to InP on a GaAs wafer surface. Microscopy is used to verify the quality of the bonded interface, and photoluminescence is used to verify that the bonding process does not degrade the optical quality of the laterally integrated wells. The authors propose this technique as a means to achieve greater levels of wafer-scale integration in optical, electrical, and micromechanical devices.

Controlling the bond scission sequence of oxygenates for energy applications

NASA Astrophysics Data System (ADS)

Stottlemyer, Alan L.

The so called "Holy Grail" of heterogeneous catalysis is a fundamental understanding of catalyzed chemical transformations which span multidimensional scales of both length and time, enabling rational catalyst design. Such an undertaking is realizable only with an atomic level understanding of bond formation and destruction with respect to intrinsic properties of the metal catalyst. In this study, we investigate the bond scission sequence of small oxygenates (methanol, ethanol, ethylene glycol) on bimetallic transition metal catalysts and transition metal carbide catalysts. Oxygenates are of interest both as hydrogen carriers for reforming to H2 and CO and as fuels in direct alcohol fuel cells (DAFC). To address the so-called "materials gap" and "pressure gap" this work adopted three parallel research approaches: (1) ultra high vacuum (UHV) studies including temperature programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS) on polycrystalline surfaces; (2) DFT studies including thermodynamic and kinetic calculations; (3) electrochemical studies including cyclic voltammetry (CV) and chronoamperometry (CA). Recent studies have suggested that tungsten monocarbide (WC) may behave similarly to Pt for the electrooxidation of oxygenates. TPD was used to quantify the activity and selectivity of oxygenate decomposition for WC and Pt-modifiedWC (Pt/WC) as compared to Pt. While decomposition activity was generally higher on WC than on Pt, scission of the C-O bond resulted in alkane/alkene formation on WC, an undesired product for DAFC. When Pt was added to WC by physical vapor deposition C-O bond scission was limited, suggesting that Pt synergistically modifies WC to improve the selectivity toward C-H bond scission to produce H2 and CO. Additionally, TPD confirmed WC and Pt/WC to be more CO tolerant than Pt. HREELS results verified that surface intermediates were different on Pt/WC as compared to Pt or WC and evidence of aldehyde intermediates was observed on the Pt and Pt/WC surfaces. For CH3OH decomposition, DFT calculations suggested that the bond scission sequence could be controlled using monolayer coverage of Pt on WC. The Ni/Pt bimetallic system was studied as an example for using oxygenates as a hydrogen source. There are two well characterized surface structures for the Ni/Pt system: the surface configuration, in which the Ni atoms reside primarily on the surface of the Pt bulk, and the subsurface configuration, in which the second atomic layer is enriched in Ni atoms and the surface is enriched in Pt atoms. These configurations are denoted NiPtPt and PtNiPt, respectively. DFT results revealed that trends established for the Ni/Pt(111) system extend to the Ni/Pt(100) analogue. TPD studies revealed that the NiPtPt surface was more active for oxygenate reforming than the Pt or PtNiPt surfaces. HREELS confirmed the presence of strongly bound reaction intermediates, including aldehyde-like species, and suggested that the first decomposition step was likely O-H bond scission. Thus, the binding energies of the deprotonated reaction intermediates are important parameters in controlling the decomposition pathways of oxygenates. These studies have demonstrated that the bond scission sequence of oxygenate decomposition can be controlled using bimetallic and transition metal carbide catalysts. While this study has focused on oxygenate decomposition for energy applications, the principles and methodology applied herein are universally applicable to the development of novel and marketable value-added products. The value in such a methodology is in the combination of both calculations to predict catalytic and chemical properties, and experiments to fine-tune theoretical predictions.

Structural requirements and reaction pathways in dimethyl ether combustion catalyzed by supported Pt clusters.

PubMed

Ishikawa, Akio; Neurock, Matthew; Iglesia, Enrique

2007-10-31

The identity and reversibility of the elementary steps required for catalytic combustion of dimethyl ether (DME) on Pt clusters were determined by combining isotopic and kinetic analyses with density functional theory estimates of reaction energies and activation barriers to probe the lowest energy paths. Reaction rates are limited by C-H bond activation in DME molecules adsorbed on surfaces of Pt clusters containing chemisorbed oxygen atoms at near-saturation coverages. Reaction energies and activation barriers for C-H bond activation in DME to form methoxymethyl and hydroxyl surface intermediates show that this step is more favorable than the activation of C-O bonds to form two methoxides, consistent with measured rates and kinetic isotope effects. This kinetic preference is driven by the greater stability of the CH3OCH2* and OH* intermediates relative to chemisorbed methoxides. Experimental activation barriers on Pt clusters agree with density functional theory (DFT)-derived barriers on oxygen-covered Pt(111). Measured DME turnover rates increased with increasing DME pressure, but decreased as the O2 pressure increased, because vacancies (*) on Pt surfaces nearly saturated with chemisorbed oxygen are required for DME chemisorption. DFT calculations show that although these surface vacancies are required, higher oxygen coverages lead to lower C-H activation barriers, because the basicity of oxygen adatoms increases with coverage and they become more effective in hydrogen abstraction from DME. Water inhibits reaction rates via quasi-equilibrated adsorption on vacancy sites, consistent with DFT results indicating that water binds more strongly than DME on vacancies. These conclusions are consistent with the measured kinetic response of combustion rates to DME, O2, and H2O, with H/D kinetic isotope effects, and with the absence of isotopic scrambling in reactants containing isotopic mixtures of 18O2-16O2 or 12CH3O12CH3-13CH3O13CH3. Turnover rates increased with Pt cluster size, because small clusters, with more coordinatively unsaturated surface atoms, bind oxygen atoms more strongly than larger clusters and exhibit lower steady-state vacancy concentrations and a consequently smaller number of adsorbed DME intermediates involved in kinetically relevant steps. These effects of cluster size and metal-oxygen bond energies on reactivity are ubiquitous in oxidation reactions requiring vacancies on surfaces nearly saturated with intermediates derived from O2.

Direct wafer bonding of highly conductive GaSb/GaInAs and GaSb/GaInP heterojunctions prepared by argon-beam surface activation

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

Predan, Felix, E-mail: felix.predan@ise.fraunhofer.de; Reinwand, Dirk; Cariou, Romain

The authors present a low-temperature wafer bonding process for the formation of electrically conductive n-GaSb/n-Ga{sub 0.79}In{sub 0.21}As and n-GaSb/n-Ga{sub 0.32}In{sub 0.68}P heterojunctions. The surfaces are deoxidized by sputter-etching with an argon-beam and bonded in ultrahigh vacuum. The sputtering behavior was investigated for each material, revealing a distinct selective sputtering characteristic for Ga{sub 0.32}In{sub 0.68}P. According to these findings, the settings for the bonding process were chosen. The mechanical and electrical properties of the wafer bonds were studied. Fully bonded 2 in. wafer pairs were found for both material combinations exhibiting high bond energies, which are comparable to the binding energiesmore » in the semiconductors. Furthermore, bond resistances below 5 mΩ cm{sup 2} could be reached, which are in the range of the lowest resistances that have been reported for wafer bonded heterojunctions. This speaks, together with the high bond energies, for a high amount of covalent bonds at the interfaces. These promising bond characteristics make the integration of antimonides with arsenides or phosphides by wafer bonding attractive for various optoelectronic applications such as multijunction solar cells.« less

Revealing the relationship between the photocatalytic property and structure characteristic of reduced TiO2 by hydrogen and carbon monoxide treatment.

PubMed

Liu, Yunpeng; Li, Yuhang; Yang, Siyuan; Lin, Yuan; Zuo, Jianliang; Liang, Hong; Peng, Feng

2018-06-04

The hydrogenation (reduction) has been considered as an effective method to improve the photocatalytic activity of TiO2, however, the underlying relationship between structure and photocatalytic performance has still not been adequately unveiled so far. Herein, to obtain insight into the effect of structure on photocatalytic activity, two types of reduced TiO2 were prepared by CO (CO-TiO2) and H2 (H-TiO2), respectively. For H-TiO2, Ti-H bonds and oxygen vacancies are formed on the surface of H-TiO2, resulting in a more disorder surface lattice. However, for CO-TiO2, the more Ti-OH bonds are formed on the surface and the more bulk oxygen vacancies are introduced, the disorder layer of CO-TiO2 is relatively thin owing to the most of surface vacancies repaired by Ti-OH bonds. Under the simulated solar irradiation, the photocatalytic H2 evolution rate of CO-TiO2 reaches 7.17 mmol g-1 h-1, which is 4.14 and 1.50 times those of TiO2 and H-TiO2, respectively. The photocatalytic degradation rate constant of methyl orange on CO-TiO2 is 2.45 and 6.39 times those on H-TiO2 and TiO2. The superior photocatalytic activity of CO-TiO2 is attributed to the effective separation and transfer of the photo-generated electron-hole pairs, due to the synergistic effects of oxygen vacancies and surface Ti-OH bonds. This study reveals the relation between the photocatalytic property and structure, and provides a new method to prepare highly active TiO2 for H2 production and environmental treatment. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Refolding of autodisplayed anti-NEF scFv through oxidation with glutathione for immunosensors.

PubMed

Bong, Ji-Hong; Song, Hyun-Woo; Kim, Tae-Hun; Kang, Min-Jung; Jose, Joachim; Pyun, Jae-Chul

2018-04-15

In this study, a single-domain antibody against negative regulatory factor (anti-NEF scFv) was autodisplayed on the outer membrane of Escherichia coli and used to detect NEF in an immunoassay based on fluorescence-activated cell sorting, enzyme-linked immunosorbent assay, and surface plasmon resonance biosensors. Next, the autodisplayed single-domain antibody was oxidized to form disulfide bonds by using glutathione, and the change in NEF-binding activity of anti-NEF scFv was analyzed by fluorescence-activated cell sorting-based immunoassay, chromogenic immunoassay, and surface plasmon resonance biosensor. For each type of immunoassays the anti-NEF scFv on the isolated outer membrane showed more NEF binding activity after the disulfide bond formation by glutathione. To determine the role of cysteines in anti-NEF scFv, three mutants were prepared, and the NEF binding activity of mutants was compared with that of wild-type anti-NEF scFv in a competitive immunoassay based on FACS. In these mutant studies, the refolding process of autodisplayed anti-NEF scFv by following oxidation via GSH/GSSG revealed that disulfide bonds formed and increased NEF binding activity. Copyright © 2017 Elsevier B.V. All rights reserved.

Monolayered Bi2WO6 nanosheets mimicking heterojunction interface with open surfaces for photocatalysis

NASA Astrophysics Data System (ADS)

Zhou, Yangen; Zhang, Yongfan; Lin, Mousheng; Long, Jinlin; Zhang, Zizhong; Lin, Huaxiang; Wu, Jeffrey C.-S.; Wang, Xuxu

2015-09-01

Two-dimensional-layered heterojunctions have attracted extensive interest recently due to their exciting behaviours in electronic/optoelectronic devices as well as solar energy conversion systems. However, layered heterojunction materials, especially those made by stacking different monolayers together by strong chemical bonds rather than by weak van der Waal interactions, are still challenging to fabricate. Here the monolayer Bi2WO6 with a sandwich substructure of [BiO]+-[WO4]2--[BiO]+ is reported. This material may be characterized as a layered heterojunction with different monolayer oxides held together by chemical bonds. Coordinatively unsaturated Bi atoms are present as active sites on the surface. On irradiation, holes are generated directly on the active surface layer and electrons in the middle layer, which leads to the outstanding performances of the monolayer material in solar energy conversion. Our work provides a general bottom-up route for designing and preparing novel monolayer materials with ultrafast charge separation and active surface.

Monolayered Bi2WO6 nanosheets mimicking heterojunction interface with open surfaces for photocatalysis

PubMed Central

Zhou, Yangen; Zhang, Yongfan; Lin, Mousheng; Long, Jinlin; Zhang, Zizhong; Lin, Huaxiang; Wu, Jeffrey C.-S.; Wang, Xuxu

2015-01-01

Two-dimensional-layered heterojunctions have attracted extensive interest recently due to their exciting behaviours in electronic/optoelectronic devices as well as solar energy conversion systems. However, layered heterojunction materials, especially those made by stacking different monolayers together by strong chemical bonds rather than by weak van der Waal interactions, are still challenging to fabricate. Here the monolayer Bi2WO6 with a sandwich substructure of [BiO]+–[WO4]2−–[BiO]+ is reported. This material may be characterized as a layered heterojunction with different monolayer oxides held together by chemical bonds. Coordinatively unsaturated Bi atoms are present as active sites on the surface. On irradiation, holes are generated directly on the active surface layer and electrons in the middle layer, which leads to the outstanding performances of the monolayer material in solar energy conversion. Our work provides a general bottom-up route for designing and preparing novel monolayer materials with ultrafast charge separation and active surface. PMID:26359212

Electrical properties of Al foil/n-4H-SiC Schottky junctions fabricated by surface-activated bonding

NASA Astrophysics Data System (ADS)

Morita, Sho; Liang, Jianbo; Matsubara, Moeko; Dhamrin, Marwan; Nishio, Yoshitaka; Shigekawa, Naoteru

2018-02-01

We fabricate 17-µm-thick Al foil/n-4H-SiC Schottky junctions by surface-activated bonding. Their current-voltage and capacitance-voltage characteristics are compared with those of Schottky junctions fabricated by evaporating Al layers on n-4H-SiC epilayers. We find that the ideality factor of Al foil/SiC junctions is larger than that of conventional junctions, which is due to the irradiation of the fast atom beam (FAB) of Ar. The ideality factor of Al foil/SiC junctions is improved by annealing at 400 °C. We also find that the Schottky barrier height is increased by FAB irradiation, which is likely to be due to the negative charges formed at SiC surfaces.

Cathode catalysts for primary phosphoric acid fuel cells

NASA Technical Reports Server (NTRS)

1981-01-01

Alkylation or carbon Vulcan XC-72, the support carbon, was shown to provide the most stable bond type for linking cobalt dehydrodibenzo tetraazannulene (CoTAA) to the surface of the carbon; this result is based on data obtained by cyclic voltammetry, pulse voltammetry and by release of 14C from bonded CoTAA. Half-cell tests at 100 C in 85% phosphoric acid showed that CoTAA bonded to the surface of carbon (Vulcan XC-72) via an alkylation procedure is a more active catalyst than is platinum based on a factor of two improvement in Tafel slope; dimeric CoTAA had catalytic activity equal to platinum. Half-cell tests also showed that bonded CoTAA catalysts do not suffer a loss in potential when air is used as a fuel rather than oxygen. Commercially available polytetrafluroethylene (PTFE) was shown to be unstable in the fuel cell environment with degradation occurring in 2000 hours or less. The PTFE was stressed at 200 C in concentrated phosphoric acid as well as electrochemically stressed in 150 C concentrated phosphoric acid; the surface chemistry of PTFE was observed to change significantly. Radiolabeled PTFE was prepared and used to verify that such chemical changes also occur in the primary fuel cell environment.

Novel fabrication method for 3D microstructures using surface-activated bonding and its application to micro-mechanical parts

NASA Astrophysics Data System (ADS)

Yamada, Takayuki; Takahashi, Mutsuya; Ozawa, Takashi; Tawara, Satoshi; Goto, Takayuki

2002-11-01

The purpose of this work is to demonstrate that a novel fabrication method for 3-D microstructures (FORMULA) is applicable to fabrication of micro mechanical parts with a large flexibility. This method is a kind of layer manufacturing method of thin films for metallic or dielectric microstructures using surface-activated bonding (SAB). The bonding interfaces of thin films are investigated by transmission electron microscope (TEM). Voids were observed at the interfaces of both pure aluminum films and Al-Cu alloy films. The ratio of void on the Al-Cu/Al-Cu interface is much larger than that of Al/Al interface, although the films have the same surface roughness of 3nm in Ra (average roughness). And approximately 10nm-thick amorphous intermediate layers were found at the interfaces. Furthermore, we have fabricated a micro gear of 900μm in diameter and 200μm in height, which is about ten times as large as our previous test pieces. Overhung structures such as a bridge structure and a cantilever were also fabricated without supporting layers beneath them.

Laser Surface Preparation for Adhesive Bonding of Aerospace Structural Composites

NASA Technical Reports Server (NTRS)

Belcher, M. A.; Wohl, C. J.; Hopkins, J. W.; Connell, J. W.

2010-01-01

Adhesive bonds are critical to the integrity of built-up structures. Disbonds can often be detected but the strength of adhesion between surfaces in contact is not obtainable without destructive testing. Typically the number one problem in a bonded structure is surface contamination, and by extension, surface preparation. Standard surface preparation techniques, including grit blasting, manual abrasion, and peel ply, are not ideal because of variations in their application. Etching of carbon fiber reinforced plastic (CFRP) panels using a neodymium-doped yttrium aluminum garnet (Nd:YAG) laser appears to be a highly precise and promising way to both clean a composite surface prior to bonding and provide a bond-promoting patterned surface akin to peel ply without the inherent drawbacks from the same (i.e., debris and curvature). CFRP surfaces prepared using laser patterns conducive to adhesive bonding were compared to typical pre-bonding surface treatments through optical microscopy, contact angle goniometry, and post-bonding mechanical testing.

Active application of primer acid on acid-treated enamel: Influence on the bond effectiveness of self-etch adhesives systems.

PubMed

Araújo, Cíntia Tereza Pimenta; Prieto, Lúcia Trazzi; Costa, Daiane Cristianismo; Bosso, Mariana Avalone; Coppini, Erick Kamiya; Dias, Carlos Tadeu Santos; Paulillo, Luis Alexandre Maffei Sartini

2017-08-01

Evaluate the composite-to-enamel bond after passive or active application of self-etching primer systems on polished or pre-etched enamel with phosphoric acid. Two self-etch adhesives systems (SEAS) were used: Clearfil SE Bond and Easy Bond. Third human molars were divided into 8 groups (N = 10). The crown of each tooth was sectioned into halves and the mesial/distal surfaces were used. The adhesives were actively or passively applied on enamel with or without prior phosphoric-acid etching. Resin composite cylinders were built after adhesive application. After stored in relative humidity for 24 hr/37°C the specimens were subjected to microshear test in universal testing a machine at a crosshead speed of 0.5 mm/minute. The results were analyzed with three-way ANOVA and the Tukey test. The enamel-etching pattern was evaluated under SEM. The 2-step SEAS system presented significantly higher adhesive bond strength means (47.37 MPa) than the 1-step (36.87 MPa). A poor enamel- etching pattern was observed in active mode showing irregular and short resin tags, however there was not compromised the bond strength. Active or passive application produced similar values of bond strength to enamel regardless of enamel pretreatment and type of SEAS. © 2017 Wiley Periodicals, Inc.

Extension of the carotenoid test to superficially porous C18 bonded phases, aromatic ligand types and new classical C18 bonded phases.

PubMed

Lesellier, E

2012-11-30

The recent introduction of new stationary phases for liquid chromatography based on superficially porous particles, called core-shell or fused-core, dramatically improved the separation performances through very high efficiency, due mainly to reduced eddy diffusion. However, few studies have evaluated the retention and selectivity of C18 phases based on such particles, despite some retention order change reported in literature between some of these phases. The carotenoid test has been developed a few years ago in the goal to compare the chromatographic properties of C18 bonded phases. Based on the analysis of carotenoid pigments by using Supercritical Fluid Chromatography (SFC), it allows, with a single analysis, to measure three main properties of reversed phase chromatography stationary phases: hydrophobicity, polar surface activity and shape selectivity. Previous studies showed the effect of the endcapping treatment, the bonding density, the pore size, and the type of bonding (monomeric vs. polymeric) on these studied properties, and described the classification map used for a direct column comparison. It was applied to ten ODS superficially porous stationary phases, showing varied chromatographic behaviors amongst these phases. As expected, due to the lower specific surface area, these superficially porous phases are less hydrophobic than the fully porous one. In regards of the polar surface activity (residual silanols) and to the shape selectivity, some of these superficially porous phases display close chromatographic properties (Poroshell 120, Halo C18, Ascentis Express, Accucore C18, Nucleoshell C18 on one side and Aeris Wide pore, Aeris peptide and Kinetex XDB on the other side), whereas others, Kinetex C18 and Halo peptide ES C18 display more specific ones. Besides, they can be compared to classical fully porous phases, in the goal to improve method transfer from fully to superficially porous particles. By the way, the paper also report the extension of the test to other ligands such as naphtyl, cholester, phenyl-hexyl, or to the new ODS bonded phases, such as charge surface hybrid phases, High Strength Silica, and Hybrid ones, and also presents results for identical brands using different particle size, such as Luna and Synergi phases. Phenyl-hexyl and napthyl ligands show rather close properties, low hydrophobicity, high polar surface activity and specific shape selectivity, whereas, at the opposite, the cholester phase display a polymeric behavior and a high hydrophobicity. Finally, additional classical (fully porous particles) C18 bonded phases are also reported to complete the data set presented in previous papers. Copyright © 2012 Elsevier B.V. All rights reserved.

FTIR and Vis-FUV real time spectroscopic ellipsometry studies of polymer surface modifications during ion beam bombardment

NASA Astrophysics Data System (ADS)

Laskarakis, A.; Gravalidis, C.; Logothetidis, S.

2004-02-01

The continuously increasing application of polymeric materials in many scientific and technological fields has motivated an extensive use of polymer surface treatments, which modify the physical and chemical properties of polymer surfaces leading to surface activation and promotion of the surface adhesion. Fourier transform IR spectroscopic ellipsometry (FTIRSE) and phase modulated ellipsometry (PME) in the IR and Vis-FUV spectral regions respectively have been employed for in situ and real time monitoring of the structural changes on the polymer surface obtained by Ar + ion bombardment. The polymers were industrially supplied polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) membranes. The Ar + ion bombardment has found to change the chemical bonding of the films and especially the amount of the CO, C-C and CC groups. The detailed study of the FTIRSE spectra reveals important information about the effect of the Ar + ion bombardment on each of the above bonding groups. Also, the modification of the characteristic features, attributed to electronic transitions in specific bonds of PET and PEN macromolecules, has been studied using PME.

A novel disulfide bond in the SH2 Domain of the C-terminal Src kinase controls catalytic activity.

PubMed

Mills, Jamie E; Whitford, Paul C; Shaffer, Jennifer; Onuchic, Jose N; Adams, Joseph A; Jennings, Patricia A

2007-02-02

The SH2 domain of the C-terminal Src kinase [Csk] contains a unique disulfide bond that is not present in other known SH2 domains. To investigate whether this unusual disulfide bond serves a novel function, the effects of disulfide bond formation on catalytic activity of the full-length protein and on the structure of the SH2 domain were investigated. The kinase activity of full-length Csk decreases by an order of magnitude upon formation of the disulfide bond in the distal SH2 domain. NMR spectra of the fully oxidized and fully reduced SH2 domains exhibit similar chemical shift patterns and are indicative of similar, well-defined tertiary structures. The solvent-accessible disulfide bond in the isolated SH2 domain is highly stable and far from the small lobe of the kinase domain. However, reduction of this bond results in chemical shift changes of resonances that map to a cluster of residues that extend from the disulfide bond across the molecule to a surface that is in direct contact with the small lobe of the kinase domain in the intact molecule. Normal mode analyses and molecular dynamics calculations suggest that disulfide bond formation has large effects on residues within the kinase domain, most notably within the active-site cleft. Overall, the data indicate that reversible cross-linking of two cysteine residues in the SH2 domain greatly impacts catalytic function and interdomain communication in Csk.

DFT study of ethyl xanthate interaction with sphalerite (1 1 0) surface in the absence and presence of copper

NASA Astrophysics Data System (ADS)

Liu, Jian; Wen, Shuming; Deng, Jiushuai; Chen, Xiumin; Feng, Qicheng

2014-08-01

The interaction among sphalerite (1 1 0) surface, copper and ethyl xanthate (EX) was simulated using the density functional theory (DFT). The results of DFT indicate that four types of stable interaction models exist among sphalerite surface, copper and EX, i.e., EX interacts with the Cu substituted for Zn, Cu adsorbed on the top site of S, Cu adsorbed on the bridge site of S and Cu(OH)2 adsorbed on the sphalerite surface. The four interaction models can result in the activation flotation of sphalerite. Density of states (DOS) analysis shows that the energy level discrepancy of the Zn 3d orbital in ZnS and the bonding S 3p orbital in EX results in the weak adsorption of EX on un-activated sphalerite surface. However, after copper activation, the Cu 3d orbital peak and bonding S 3p orbital peak are just maximally overlapped nearby the Fermi level. This study provides an insight into the nature that sphalerite responds not well to EX and also a comprehensive understanding on the possible interaction cases existing among sphalerite surface, copper and EX.

The effects of dentin and intaglio indirect ceramic optimized polymer restoration surface treatment on the shear bond strength of resin cement

NASA Astrophysics Data System (ADS)

Puspitarini, A.; Suprastiwi, E.; Usman, M.

2017-08-01

Ceramic optimized polymer (ceromer) bonds to the tooth substrate through resin cements. The bond strength between dentin, resin cement, and ceromer depends on the applied surface treatment. To analyze the effects of dentin and intaglio ceromer surface treatment on the shear bond strength self-adhesive resin cement. Forty-five dentin premolar and ceromer specimens were bonded with resin cement and divided into three groups as follows: in group 1, no treatment was applied; in group 2, dentin surface treatment was carried out with acid etching and a bonding agent; and in group 3, dentin surface treatment was carried out with acid etching, a bonding agent, and intaglio ceromer surface treatment with etching and silane. All specimens were incubated at 37 °C for 24 hours, and the shear bond strength was measured using a universal testing machine. Group 3 showed the highest shear bond strength, followed by group 2. The surface treatment of dentin and intaglio ceromer showed significantly improved shear bond strength in the group comparison. Dentin and intaglio ceromer surface treatment can improved the shear bond strength self-adhesive resin cement.

Solvent effects on adsorption of CO over CuCl(1 1 1) surface: A density functional theory study

NASA Astrophysics Data System (ADS)

Zhang, Riguang; Ling, Lixia; Wang, Baojun; Huang, Wei

2010-09-01

DFT calculations have been performed to investigate the effect of dielectric responses of the solvent environment on the CO adsorption over CuCl(1 1 1) surface by using COSMO (conductor-like solvent model) model in Dmol 3. Different dielectric constants, including vacuum, liquid paraffin, methylene chloride, methanol and water solution, are considered. The effects of solvent model on the structural parameters, adsorption energies and vibrational frequency of CO adsorption over CuCl(1 1 1) surface have been investigated. The calculation results suggest that solvent effects can improve the stability of CO adsorption and reduce the intensity of C-O bond, which might mean that solvent is in favor of C-O bond activation and improve the reaction activity of oxidative carbonylation in a slurry reactor.

Hybrid Integrated Platforms for Silicon Photonics

PubMed Central

Liang, Di; Roelkens, Gunther; Baets, Roel; Bowers, John E.

2010-01-01

A review of recent progress in hybrid integrated platforms for silicon photonics is presented. Integration of III-V semiconductors onto silicon-on-insulator substrates based on two different bonding techniques is compared, one comprising only inorganic materials, the other technique using an organic bonding agent. Issues such as bonding process and mechanism, bonding strength, uniformity, wafer surface requirement, and stress distribution are studied in detail. The application in silicon photonics to realize high-performance active and passive photonic devices on low-cost silicon wafers is discussed. Hybrid integration is believed to be a promising technology in a variety of applications of silicon photonics.

Salt-Assisted Ultrasonicated De-Aggregation and Advanced Redox Electrochemistry of Detonation Nanodiamond

PubMed Central

Gupta, Sanju; Evans, Brendan; Henson, Alex; Carrizosa, Sara B.

2017-01-01

Nanodiamond particles form agglomerates in the dry powder state and this poses limitation to the accessibility of their diamond-like core thus dramatically impacting their technological advancement. In this work, we report de-agglomeration of nanodiamond (ND) by using a facile technique namely, salt-assisted ultrasonic de-agglomeration (SAUD). Utilizing ultrasound energy and ionic salts (sodium chloride and sodium acetate), SAUD is expected to break apart thermally treated nanodiamond aggregates (~50–100 nm) and produce an aqueous slurry of de-aggregated stable colloidal nanodiamond dispersions by virtue of ionic interactions and electrostatic stabilization. Moreover, the SAUD technique neither has toxic chemicals nor is it difficult to remove impurities and therefore the isolated nanodiamonds produced are exceptionally suited for engineered nanocarbon for mechanical (composites, lubricants) and biomedical (bio-labeling, biosensing, bioimaging, theranostic) applications. We characterized the microscopic structure using complementary techniques including transmission electron microscopy combined with selected-area electron diffraction, optical and vibrational spectroscopy. We immobilized SAUD produced NDs on boron-doped diamond electrodes to investigate fundamental electrochemical properties. They included surface potential (or Fermi energy level), carrier density and mapping electrochemical (re)activity using advanced scanning electrochemical microscopy in the presence of a redox-active probe, with the aim of understanding the surface redox chemistry and the interfacial process of isolated nanodiamond particles as opposed to aggregated and untreated nanoparticles. The experimental findings are discussed in terms of stable colloids, quantum confinement and predominantly surface effects, defect sites (sp2–bonded C and unsaturated bonds), inner core (sp3–bonded C)/outer shell (sp2–bonded C) structure, and surface functionality. Moreover, the surface electronic states give rise to midgap states which serve as electron donors (or acceptors) depending upon the bonding (or antibonding). These are important as electroanalytical platforms for various electrocatalytic processes. PMID:29125547

Scaling Relations for Adsorption Energies on Doped Molybdenum Phosphide Surfaces

DOE PAGES

Fields, Meredith; Tsai, Charlie; Chen, Leanne D.; ...

2017-03-10

Molybdenum phosphide (MoP), a well-documented catalyst for applications ranging from hydrotreating reactions to electrochemical hydrogen evolution, has yet to be mapped from a more fundamental perspective, particularly in the context of transition-metal scaling relations. In this work, we use periodic density functional theory to extend linear scaling arguments to doped MoP surfaces and understand the behavior of the phosphorus active site. The derived linear relationships for hydrogenated C, N, and O species on a variety of doped surfaces suggest that phosphorus experiences a shift in preferred bond order depending on the degree of hydrogen substitution on the adsorbate molecule. Thismore » shift in phosphorus hybridization, dependent on the bond order of the adsorbate to the surface, can result in selective bond weakening or strengthening of chemically similar species. As a result, we discuss how this behavior deviates from transition-metal, sulfide, carbide, and nitride scaling relations, and we discuss potential applications in the context of electrochemical reduction reactions.« less

Morphology and the Strength of Intermolecular Contact in Protein Crystals

NASA Technical Reports Server (NTRS)

Matsuura, Yoshiki; Chernov, Alexander A.

2002-01-01

The strengths of intermolecular contacts (macrobonds) in four lysozyme crystals were estimated based on the strengths of individual intermolecular interatomic interaction pairs. The periodic bond chain of these macrobonds accounts for the morphology of protein crystals as shown previously. Further in this paper, the surface area of contact, polar coordinate representation of contact site, Coulombic contribution on the macrobond strength, and the surface energy of the crystal have been evaluated. Comparing location of intermolecular contacts in different polymorphic crystal modifications, we show that these contacts can form a wide variety of patches on the molecular surface. The patches are located practically everywhere on this surface except for the concave active site. The contacts frequently include water molecules, with specific intermolecular hydrogen-bonds on the background of non-specific attractive interactions. The strengths of macrobonds are also compared to those of other protein complex systems. Making use of the contact strengths and taking into account bond hydration we also estimated crystal-water interfacial energies for different crystal faces.

Fundamental studies of desulfurization processes: reaction of methanethiol on ZnO and Cs/ZnO

NASA Astrophysics Data System (ADS)

Dvorak, Joseph; Jirsak, Tomas; Rodriguez, José A.

2001-05-01

The reaction of methanethiol on ZnO and Cs promoted ZnO surfaces has been studied with synchrotron based photoemission and thermal desorption spectroscopy. On ZnO, methanethiol undergoes selective reaction to produce carbon monoxide (37-58%), methane (23-38%), formaldehyde (12-15%), ethane (1-11%), and a mixture of ethylene and acetylene (3-13%). At low temperatures (<100 K), methanethiol reacts to yield thiolate intermediate bound to Zn 2+ cations. The thiolate is stable to 500 K. Above this temperature, C-S bond cleavage occurs to yield methyl intermediate and atomic S. Carbon is removed from the surface as gaseous products above 500 K, and atomic sulfur remains bound to the zinc sites of the surface. Submonolayer amounts of cesium do not have a significant promotional effect on C-S bond cleavage, whereas Cs multilayers are found to significantly lower the activation barrier for C-S bond cleavage. This study illustrates the chemistry associated with the desulfurization of thiols on a catalytically relevant oxide surface.

Laser Surface Preparation and Bonding of Aerospace Structural Composites

NASA Technical Reports Server (NTRS)

Belcher, M. A.; Wohl, C. J.; Hopkins, J. W.; Connell, J. W.

2010-01-01

Adhesive bonds are critical to the integrity of built-up structures. Disbonds can often be detected but the strength of adhesion between surfaces in contact is not obtainable without destructive testing. Typically the number one problem in a bonded structure is surface contamination, and by extension, surface preparation. Standard surface preparation techniques, including grit blasting, manual abrasion, and peel ply, are not ideal because of variations in their application. Etching of carbon fiber reinforced plastic (CFRP) panels using a neodymium-doped yttrium aluminum garnet (Nd:YAG) laser appears to be a highly precise and promising way to both clean a composite surface prior to bonding and provide a bond-promoting patterned surface akin to peel ply without the inherent drawbacks from the same (i.e., debris and curvature). CFRP surfaces prepared using laser patterns conducive to adhesive bonding were compared to typical prebonding surface treatments through optical microscopy, contact angle goniometry, and post-bonding mechanical testing.

Effect of salivary pellicle on antibacterial activity of novel antibacterial dental adhesives using a dental plaque microcosm biofilm model

PubMed Central

Li, Fang; Weir, Michael D.; Fouad, Ashraf F.; Xu, Hockin H.K.

2014-01-01

Objectives Antibacterial primer and adhesive are promising to inhibit biofilms and caries. Since restorations in vivo are exposed to saliva, one concern is the attenuation of antibacterial activity due to salivary pellicles. The objective of this study was to investigate the effects of salivary pellicles on bonding agents containing a new monomer dimethylaminododecyl methacrylate (DMADDM) or nanoparticles of silver (NAg) against biofilms for the first time. Methods DMADDM and NAg were synthesized and incorporated into Scotchbond Multi-Purpose adhesive and primer. Specimens were either coated or not coated with salivary pellicles. A microcosm biofilm model was used with mixed saliva from ten donors. Two types of culture medium were used: an artificial saliva medium (McBain), and Brain Heart Infusion (BHI) medium without salivary proteins. Metabolic activity, colony-forming units (CFU), and lactic acid production of plaque microcosm biofilms were measured (n = 6). Results Bonding agents containing DMADDM and NAg greatly inhibited biofilm activities, even with salivary pellicles. When using BHI, the pre-coating of salivary pellicles on resin surfaces significantly decreased the antibacterial effect (p < 0.05). When using artificial saliva medium, pre-coating of salivary pellicles on resin did not decrease the antibacterial effect. These results suggest that artificial saliva yielded medium-derived pellicles on resin surfaces, which provided attenuating effects on biofilms similar to salivary pellicles. Compared with the commercial control, the DMADDM-containing bonding agent reduced biofilm CFU by about two orders of magnitude. Significance Novel DMADDM- and NAg-containing bonding agents substantially reduced biofilm growth even with salivary pellicle coating on surfaces, indicating a promising usage in saliva-rich environment. DMADDM and NAg may be useful in a wide range of primers, adhesives and other restoratives to achieve antibacterial and anti-caries capabilities. PMID:24332270

Effect of salivary pellicle on antibacterial activity of novel antibacterial dental adhesives using a dental plaque microcosm biofilm model.

PubMed

Li, Fang; Weir, Michael D; Fouad, Ashraf F; Xu, Hockin H K

2014-02-01

Antibacterial primer and adhesive are promising to inhibit biofilms and caries. Since restorations in vivo are exposed to saliva, one concern is the attenuation of antibacterial activity due to salivary pellicles. The objective of this study was to investigate the effects of salivary pellicles on bonding agents containing a new monomer dimethylaminododecyl methacrylate (DMADDM) or nanoparticles of silver (NAg) against biofilms for the first time. DMADDM and NAg were synthesized and incorporated into Scotchbond Multi-Purpose adhesive and primer. Specimens were either coated or not coated with salivary pellicles. A microcosm biofilm model was used with mixed saliva from ten donors. Two types of culture medium were used: an artificial saliva medium (McBain), and Brain Heart Infusion (BHI) medium without salivary proteins. Metabolic activity, colony-forming units (CFU), and lactic acid production of plaque microcosm biofilms were measured (n=6). Bonding agents containing DMADDM and NAg greatly inhibited biofilm activities, even with salivary pellicles. When using BHI, the pre-coating of salivary pellicles on resin surfaces significantly decreased the antibacterial effect (p<0.05). When using artificial saliva medium, pre-coating of salivary pellicles on resin did not decrease the antibacterial effect. These results suggest that artificial saliva yielded medium-derived pellicles on resin surfaces, which provided attenuating effects on biofilms similar to salivary pellicles. Compared with the commercial control, the DMADDM-containing bonding agent reduced biofilm CFU by about two orders of magnitude. Novel DMADDM- and NAg-containing bonding agents substantially reduced biofilm growth even with salivary pellicle coating on surfaces, indicating a promising usage in saliva-rich environment. DMADDM and NAg may be useful in a wide range of primers, adhesives and other restoratives to achieve antibacterial and anti-caries capabilities. Published by Elsevier Ltd.

The Influence of Pre-Heated Treatment to Improve Adhesion Bond Coating Strength of Fly Ash Based Geopolymer Ceramic

NASA Astrophysics Data System (ADS)

Jamaludin, L.; Abdullah, M. M. A. B.; Hussin, K.; Kadir, A. Abdul

2018-06-01

The study focus on effect of pre-heated ceramic surface on the adhesion bond strength between geopolymer coating coating and ceramic substrates. Ceramic substrates was pre-heated at different temperature (400 °C, 600 °C, 800 °C and 1000 °C). Fly ash geopolymer coating material potential used to protect surface used in exposure conditions after sintering at high temperature. Fly ash and alkali activator (Al2O3/Na2SiO3) were mixed with 2.0 solids-to-liquid ratios to prepare geopolymer coating material at constant NaOH concentration of 12M. Adhesion test was conducted to determine the adhesion bond between ceramic substrates and fly ash coating material. The results showed the pre-heated ceramic substrates effect the adhesion bond of coating compared with untreated substrates with increasing of strength up to 20 % for temperature 600 °C.

Ultra precision and reliable bonding method

NASA Technical Reports Server (NTRS)

Gwo, Dz-Hung (Inventor)

2001-01-01

The bonding of two materials through hydroxide-catalyzed hydration/dehydration is achieved at room temperature by applying hydroxide ions to at least one of the two bonding surfaces and by placing the surfaces sufficiently close to each other to form a chemical bond between them. The surfaces may be placed sufficiently close to each other by simply placing one surface on top of the other. A silicate material may also be used as a filling material to help fill gaps between the surfaces caused by surface figure mismatches. A powder of a silica-based or silica-containing material may also be used as an additional filling material. The hydroxide-catalyzed bonding method forms bonds which are not only as precise and transparent as optical contact bonds, but also as strong and reliable as high-temperature frit bonds. The hydroxide-catalyzed bonding method is also simple and inexpensive.

Computational Study of the Adsorption of Dimethyl Methylphosphonate (DMMP) on the (010) Surface of Anatase TiO2 With and Without Faceting

DTIC Science & Technology

2009-12-05

surface area of anatase nanocrystals [6] and to be es- pecially active in photocatalysis [7]. Recent work by Dzwigaj et al. [8] has clearly shown that the...two-fold-coordinated (O2c) sites can also be involved in hydrogen bond (H-bond) formation. The effects, on the structure of the (100) and other...To reduce the computational cost , geometry optimization was done at the restricted Hartree Fock (RHF) level. This has previously been shown [36,37

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

Mo, Alan K; Brown, Victoria L.; Rugg, Brandon K.

The adhesion of 100 nm thick electron-beam deposited Au and Pt and magnetron sputtered Au thin films onto poly(methyl methacrylate) (PMMA) substrates can be significantly enhanced to over 90% adhesion by either spin-casting or vapor-exposure to hydrohalocarbon solvents prior to metal deposition compared to samples that are either cleaned in isopropyl alcohol or pre-treated with a remote O2 plasma. X-ray photoelectron spectroscopy (XPS) and evolved gas Fourier transform infrared spectroscopy (EGA-FTIR) reveal the presence of residual halogenated solvent molecules at the PMMA surface which chemically activates the surface to produce a stable chemical interaction between the noble metal film andmore » the PMMA. Density functional theory (DFT) calculations show that the halogenated solvent molecules preferentially form a Lewis acid-base adduct with the oxygen atoms in the ester group in PMMA which is consistent with the measured enthalpy of desorption of chloroform (CHCl3) on PMMA determined by EGA-FTIR to be 36 kJ mol-1. The DFT model also supports the experimentally observed change in the high resolution XPS O 1s peak at 533.77 eV after metallization attributed to a change in the local bonding environment of the bridging O in the PMMA ester group. DFT also predicts that the deposited metal atom (M) inserts into the C-X bond where X is the halogen atom on either CHCl3 or bromoform (CHBr3) to form a O M X interaction that is observed by a M-X bond in the high resolution XPS Cl 2p3/2 peak at 198.03 eV and Br 3p3/2 peak at 182.06 eV. A range of solvents with differing polarities for PMMA pre-treatment have been used and it is proposed that non-complexing solvents result in significant metal adhesion improvement. The Gutmann acceptor number can be used to predict the effectiveness of solvent treatment for noble metal adhesion. A model is proposed in which the bond energy of the C-X bond of the solvent must be sufficiently low so that the C-X bond can be cleaved to form the M-X bond. Supporting this model, a negative control of vapor phase exposure to fluoroform (CHF3) is shown to have no effect on noble metal adhesion due to the higher bond dissociation energy of the C-F bond compared to the C-Cl and C-Br bond energy. The surface activation of vapor-phase exposed PMMA surfaces is technologically significant for the fabrication of polymer microdevices requiring Au or Pt metallization.« less

Metal-dielectric interactions

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1979-01-01

Metal direlectric surface interactions and dielectric films on metal substrates were investigated. Since interfacial interaction depends so heavily on the nature of the surfaces, analytical surface tools such as Auger emission spectroscopy, X-ray photoelectron spectroscopy and field ion microscopy were used to assist in surface and interfacial characterization. The results indicate that with metals contacting certain glasses in the clean state interfacial, bonding produces fractures in the glasses while when a film such as water is present, fractures occur in the metal near the interface. Friction forces were used to measure the interfacial bond strengths. Studies with metals contacting polymers using field ion microscopy revealed that strong bonding forces could develop being between a metal and polymer surface with polymer transferring to the metal surface in various ways depending upon the forces applied to the surface in contact. With the deposition of refractory carbides, silicides and borides onto metal and alloy substrates the presence of oxides at the interface or active gases in the deposition plasma were shown to alter interfacial properties and chemistry. Auger ion depth profile analysis indicated the chemical composition at the interface and this could be related to the mechanical, friction, and wear behavior of the coating.

Reactivity of chemisorbed oxygen atoms and their catalytic consequences during CH4-O2 catalysis on supported Pt clusters.

PubMed

Chin, Ya-Huei Cathy; Buda, Corneliu; Neurock, Matthew; Iglesia, Enrique

2011-10-12

Kinetic and isotopic data and density functional theory treatments provide evidence for the elementary steps and the active site requirements involved in the four distinct kinetic regimes observed during CH(4) oxidation reactions using O(2), H(2)O, or CO(2) as oxidants on Pt clusters. These four regimes exhibit distinct rate equations because of the involvement of different kinetically relevant steps, predominant adsorbed species, and rate and equilibrium constants for different elementary steps. Transitions among regimes occur as chemisorbed oxygen (O*) coverages change on Pt clusters. O* coverages are given, in turn, by a virtual O(2) pressure, which represents the pressure that would give the prevalent steady-state O* coverages if their adsorption-desorption equilibrium was maintained. The virtual O(2) pressure acts as a surrogate for oxygen chemical potentials at catalytic surfaces and reflects the kinetic coupling between C-H and O═O activation steps. O* coverages and virtual pressures depend on O(2) pressure when O(2) activation is equilibrated and on O(2)/CH(4) ratios when this step becomes irreversible as a result of fast scavenging of O* by CH(4)-derived intermediates. In three of these kinetic regimes, C-H bond activation is the sole kinetically relevant step, but occurs on different active sites, which evolve from oxygen-oxygen (O*-O*), to oxygen-oxygen vacancy (O*-*), and to vacancy-vacancy (*-*) site pairs as O* coverages decrease. On O*-saturated cluster surfaces, O*-O* site pairs activate C-H bonds in CH(4) via homolytic hydrogen abstraction steps that form CH(3) groups with significant radical character and weak interactions with the surface at the transition state. In this regime, rates depend linearly on CH(4) pressure but are independent of O(2) pressure. The observed normal CH(4)/CD(4) kinetic isotope effects are consistent with the kinetic-relevance of C-H bond activation; identical (16)O(2)-(18)O(2) isotopic exchange rates in the presence or absence of CH(4) show that O(2) activation steps are quasi-equilibrated during catalysis. Measured and DFT-derived C-H bond activation barriers are large, because of the weak stabilization of the CH(3) fragments at transition states, but are compensated by the high entropy of these radical-like species. Turnover rates in this regime decrease with increasing Pt dispersion, because low-coordination exposed Pt atoms on small clusters bind O* more strongly than those that reside at low-index facets on large clusters, thus making O* less effective in H-abstraction. As vacancies (*, also exposed Pt atoms) become available on O*-covered surfaces, O*-* site pairs activate C-H bonds via concerted oxidative addition and H-abstraction in transition states effectively stabilized by CH(3) interactions with the vacancies, which lead to much higher turnover rates than on O*-O* pairs. In this regime, O(2) activation becomes irreversible, because fast C-H bond activation steps scavenge O* as it forms. Thus, O* coverages are set by the prevalent O(2)/CH(4) ratios instead of the O(2) pressures. CH(4)/CD(4) kinetic isotope effects are much larger for turnovers mediated by O*-* than by O*-O* site pairs, because C-H (and C-D) activation steps are required to form the * sites involved in C-H bond activation. Turnover rates for CH(4)-O(2) reactions mediated by O*-* pairs decrease with increasing Pt dispersion, as in the case of O*-O* active structures, because stronger O* binding on small clusters leads not only to less reactive O* atoms, but also to lower vacancy concentrations at cluster surfaces. As O(2)/CH(4) ratios and O* coverages become smaller, O(2) activation on bare Pt clusters becomes the sole kinetically relevant step; turnover rates are proportional to O(2) pressures and independent of CH(4) pressure and no CH(4)/CD(4) kinetic isotope effects are observed. In this regime, turnover rates become nearly independent of Pt dispersion, because the O(2) activation step is essentially barrierless. In the absence of O(2), alternate weaker oxidants, such as H(2)O or CO(2), lead to a final kinetic regime in which C-H bond dissociation on *-* pairs at bare cluster surfaces limit CH(4) conversion rates. Rates become first-order in CH(4) and independent of coreactant and normal CH(4)/CD(4) kinetic isotope effects are observed. In this case, turnover rates increase with increasing dispersion, because low-coordination Pt atoms stabilize the C-H bond activation transition states more effectively via stronger binding to CH(3) and H fragments. These findings and their mechanistic interpretations are consistent with all rate and isotopic data and with theoretical estimates of activation barriers and of cluster size effects on transition states. They serve to demonstrate the essential role of the coverage and reactivity of chemisorbed oxygen in determining the type and effectiveness of surface structures in CH(4) oxidation reactions using O(2), H(2)O, or CO(2) as oxidants, as well as the diversity of rate dependencies, activation energies and entropies, and cluster size effects that prevail in these reactions. These results also show how theory and experiments can unravel complex surface chemistries on realistic catalysts under practical conditions and provide through the resulting mechanistic insights specific predictions for the effects of cluster size and surface coordination on turnover rates, the trends and magnitude of which depend sensitively on the nature of the predominant adsorbed intermediates and the kinetically relevant steps.

The anti-adherence effect of Piper betle and Psidium guajava extracts on the adhesion of early settlers in dental plaque to saliva-coated glass surfaces.

PubMed

Razak, Fathilah Abdul; Rahim, Zubaidah Haji Abd

2003-12-01

The aqueous extracts of Piper betle and Psidium guajava were prepared and tested for their anti-adherence effect on the adhesion of early plaque settlers (Strep. mitis, Strep. sanguinis and Actinomyces sp.). The saliva-coated glass surfaces were used to simulate the pellicle-coated enamel surface in the oral cavity. Our results showed that the anti-adherence activities of Piper betle and Psidium guajava extracts towards the bacteria were different between the bacterial species. Psidium guajava was shown to have a slightly greater anti-adherence effect on Strep. sanguinis by 5.5% and Actinomyces sp. by 10% and a significantly higher effect on Strep. mitis (70%) compared to Piper betle. The three bacterial species are known to be highly hydrophobic, and that hydrophobic bonding seemed to be an important factor in their adherence activities. It is therefore suggested that the plant extracts, in expressing their anti-adherence activities, could have altered the hydrophobic nature of the bonding between the bacteria and the saliva-coated glass surfaces.

Experimental and Theoretical Approaches for the Surface Interaction between Copper and Activated Sludge Microorganisms at Molecular Scale

NASA Astrophysics Data System (ADS)

Luo, Hong-Wei; Chen, Jie-Jie; Sheng, Guo-Ping; Su, Ji-Hu; Wei, Shi-Qiang; Yu, Han-Qing

2014-11-01

Interactions between metals and activated sludge microorganisms substantially affect the speciation, immobilization, transport, and bioavailability of trace heavy metals in biological wastewater treatment plants. In this study, the interaction of Cu(II), a typical heavy metal, onto activated sludge microorganisms was studied in-depth using a multi-technique approach. The complexing structure of Cu(II) on microbial surface was revealed by X-ray absorption fine structure (XAFS) and electron paramagnetic resonance (EPR) analysis. EPR spectra indicated that Cu(II) was held in inner-sphere surface complexes of octahedral coordination with tetragonal distortion of axial elongation. XAFS analysis further suggested that the surface complexation between Cu(II) and microbial cells was the distorted inner-sphere coordinated octahedra containing four short equatorial bonds and two elongated axial bonds. To further validate the results obtained from the XAFS and EPR analysis, density functional theory calculations were carried out to explore the structural geometry of the Cu complexes. These results are useful to better understand the speciation, immobilization, transport, and bioavailability of metals in biological wastewater treatment plants.

Catalysis by Atomic-Sized Centers: Methane Activation for Partial Oxidation and Combustion

DTIC Science & Technology

2015-07-21

example, H adsorbed alone on an oxide surface will bind to oxygen to form a hydroxide . However, if a Lewis base (e.g. any electron donor) is...that on a gold surface, which is not surprising considering the bonding character between the cluster and metal surfaces. The high mobility verifies

Chlorhexidine stabilizes the adhesive interface: a 2 year in vitro study

PubMed Central

Breschi, Lorenzo; Mazzoni, Annalisa; Nato, Fernando; Carrilho, Marcela; Visintini, Erika; Tjäderhane, Leo; Ruggeri, Alessandra; Tay, Franklin R; De Stefano Dorigo, Elettra; Pashley, David H

2013-01-01

Objectives This study evaluated the role of endogenous dentin MMPs in auto-degradation of collagen fibrils within adhesive-bonded interfaces. The null hypotheses tested were that adhesive blends or chlorhexidine digluconate (CHX) application does not modify dentin MMPs activity and that CHX used as therapeutic primer does not improve the stability of adhesive interfaces over time. Methods Zymograms of protein extracts from human dentin powder incubated with Adper Scotchbond 1XT (SB1XT) on untreated or 0.2–2% CHX treated dentin were obtained to assay dentin MMPs activity. Microtensile bond strength and interfacial nanoleakage expression of SB1XT bonded interfaces (with or without CHX pre-treatment for 30s on the etched surface) were analyzed immediately and after 2 yr of storage in artificial saliva at 37°C. Results Zymograms showed that application of SB1XT to human dentin powder increases MMP-2 activity, while CHX pre-treatment inhibited all dentin gelatinolytic activity, irrespective from the tested concentration. CHX significantly lowered the loss of bond strength and nanoleakage seen in acid-etched resin-bonded dentin artificially aged for 2 yr. Significance The study demonstrates the active role of SB1XT in dentin MMP-2 activation and the efficacy of CHX inhibition of MMPs even if used at low concentration (0.2%). PMID:20045177

Surface texturing of fluoropolymers

NASA Technical Reports Server (NTRS)

Banks, B. A.; Mirtich, M. J.; Sovey, J. S. (Inventor)

1982-01-01

A method is disclosed for improving surface texture for adhesive bonding, metal bonding, substrate plating, decal substrate preparation, and biomedical implant applications. The surface to be bonded is dusted in a controlled fashion to produce a disbursed layer of fine mesh particles which serve as masks. The surface texture is produced by impinging gas ions on the masked surface. The textured surface takes the form of pillars or cones. The bonding material, such as a liquid epoxy, flows between the pillars which results in a bond having increased strength. For bonding metals a thin film of metal is vapor or sputter deposited onto the textured surface. Electroplating or electroless plating is then used to increase the metal thickness in the desired amount.

Adhesion enhancement of Al coatings on carbon/epoxy composite surfaces by atmospheric plasma

NASA Astrophysics Data System (ADS)

Coulon, J. F.; Tournerie, N.; Maillard, H.

2013-10-01

Adhesion strengths between aluminium thin film coatings and manufactured carbon/epoxy composite surfaces were measured by assessing fracture tensile strengths using pull-off tests. The effect of the substrate roughness (nm to μm) of these composite surfaces on adhesion was studied by examining the surface free energies and adhesion strengths. The adhesion strengths of the coatings varied significantly. To improve the coating adhesion, each composite surface was treated with atmospheric plasma prior to deposition, which resulted in an increase in the surface free energy from approximately 40 mJ/m2 to 70 mJ/m2 because the plasma pretreatment led to the formation of hydrophilic Csbnd O and Cdbnd O bonds on the composite surfaces, as demonstrated by X-ray photoelectron spectroscopy analyses. The adhesion strengths of the coatings were enhanced for all surface roughnesses studied. In our study, the effect of mechanical adhesion due to roughness was separated from the effect of modifying the chemical bonds with plasma activation. The adhesion ability of the pure resin was relatively weak. Increasing the surface roughness largely improved the adhesion of the resin surface. Plasma treatment of the pure resin also increased the surface adhesion. Our study shows that plasma activation effectively enhances the adhesion of manufactured composites, even when the surface roughness is on the order of microns. The ageing of the surface activation was also investigated, and the results demonstrate that atmospheric plasma has potential for use in the pretreatment of composite materials.

Enhancement of peptide bond formation by polyribonucleotides on clay surfaces in fluctuating environments

NASA Technical Reports Server (NTRS)

White, D. H.; Erickson, J. C.

1981-01-01

The selective effects of polyribonucleotides on the formation of glycine peptide bonds in glycine on clay surfaces are investigated as a model for a template mechanism for the effects of polynucleotides on peptide bond formation. Free oligoglycine yields were determined for the cycling reaction of glycine in the presence and absence of clay and polyribonucleotides or polydeoxyribonucleotides. The polyribonucleotides are observed to lead to increases of up to fourfold increases in oligoglycine formed, with greater enhancements for poly-G nucleotides than for poly-A, poly-U and poly-C, indicating a codonic bias. Polydeoxyribonucleotides are found to provide no enhancement in peptide formation rates, and yields were also greatly reduced in the absence of clay. A mechanism for peptide synthesis is proposed which involves the activation of glycine on the clay surface, followed by the formation of esters between glycine and the 2-prime OH groups of the polyribonucleotide and peptide bonds between adjacent amino acyl esters. It is pointed out that if this mechanism is correct, it may provide a basis for a direct template translation process, which would produce a singlet genetic code.

Shear bond strength between an indirect composite layering material and feldspathic porcelain-coated zirconia ceramics.

PubMed

Fushiki, Ryosuke; Komine, Futoshi; Blatz, Markus B; Koizuka, Mai; Taguchi, Kohei; Matsumura, Hideo

2012-10-01

This study aims to evaluate the effect of both feldspathic porcelain coating of zirconia frameworks and priming agents on shear bond strength between an indirect composite material and zirconia frameworks. A total of 462 airborne-particle-abraded zirconia disks were divided into three groups: untreated disks (ZR-AB), airborne-particle-abraded zirconia disks coated with feldspathic porcelain, (ZR-PO-AB), and hydrofluoric acid-etched zirconia disks coated with feldspathic porcelain (ZR-PO-HF). Indirect composite (Estenia C&B) was bonded to zirconia specimens with no (CON) or one of four priming agents--Clearfil Photo Bond (CPB), Clearfil Photo Bond with Clearfil Porcelain Bond Activator (CPB + activator), Estenia Opaque primer, or Porcelain Liner M Liquid B (PLB)--with or without an opaque material (Estenia C&B Opaque). All specimens were tested for shear bond strength before and after 20,000 thermocycles. The Steel-Dwass test and Mann-Whitney U test were used to compare shear bond strength. In ZR-AB specimens, the initial bond strength of the CPB and CPB + Activator groups was significantly higher as compared with the other three groups (P < 0.05), whereas the PLB and CPB + Activator groups had the highest pre- and post-thermocycling bond strengths in ZR-PO-AB and ZR-PO-HF specimens. Among CON disks without opaque material, bond strength was significantly lower in ZR-AB specimens than in ZR-PO-AB and ZR-PO-HF specimens (P < 0.05). Feldspathic porcelain coating of a Katana zirconia framework enhanced the bond strength of Estenia C&B indirect composite to zirconia independent of surface treatment. The use of a silane coupling agent and opaque material yields durable bond strength between the indirect composite and feldspathic-porcelain-coated zirconia. The results of the present study suggest that feldspathic porcelain coating of zirconia frameworks is an effective method to obtain clinically acceptable bond strengths of a layering indirect composite material to a zirconia framework.

A noncontacting scanning photoelectron emission technique for bonding surface cleanliness inspection

NASA Technical Reports Server (NTRS)

Gause, Raymond L.

1989-01-01

Molecular contamination of bonding surfaces can drastically affect the bond strength that can be achieved and therefore the structural integrity and reliability of the bonded part. The presence of thin contaminant films on bonding surfaces can result from inadequate or incomplete cleaning methods, from oxide growth during the time between cleaning (such as grit blasting) and bonding, or from failure to properly protect cleaned surfaces from oils, greases, fingerprints, release agents, or deposition of facility airborne molecules generated by adjacent manufacturing or processing operations. Required cleanliness levels for desired bond performance can be determined by testing to correlate bond strength with contaminant type and quantity, thereby establishing the degree of contamination that can be tolerated based on the strength that is needed. Once the maximum acceptable contaminant level is defined, a method is needed to quantitatively measure the contaminant level on the bonding surface prior to bonding to verify that the surface meets the established cleanliness requirement. A photoelectron emission technique for the nondestructive inspection of various bonding surfaces, both metallic and nonmetallic, to provide quantitative data on residual contaminant levels is described. The technique can be used to scan surfaces at speeds of at least 30 ft/min using a servo system to maintain required sensor to surface spacing. The fundamental operation of the photoelectron emission sensor system is explained and the automated scanning system and computer data acquisition hardware and software are described.

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

Relationship between surface area for adhesion and tensile bond strength--evaluation of a micro-tensile bond test.

PubMed

Sano, H; Shono, T; Sonoda, H; Takatsu, T; Ciucchi, B; Carvalho, R; Pashley, D H

1994-07-01

The purpose of this study was to test the null hypothesis that there is no relationship between the bonded surface area of dentin and the tensile strength of adhesive materials. The enamel was removed from the occlusal surface of extracted human third molars, and the entire flat surface was covered with resin composite bonded to the dentin to form a flat resin composite crown. Twenty-four hours later, the bonded specimens were sectioned parallel to the long axis of the tooth into 10-20 thin sections whose upper part was composed of resin composite with the lower half being dentin. These small sections were trimmed using a high speed diamond bur into an hourglass shape with the narrowest portion at the bonded interface. Surface area was varied by altering the specimen thickness and width. Tensile bond strength was measured using custom-made grips in a universal testing machine. Tensile bond strength was inversely related to bonded surface area. At surface areas below 0.4 mm2, the tensile bond strengths were about 55 MPa for Clearfil Liner Bond 2 (Kuraray Co., Ltd.), 38 MPa for Scotchbond MP (3M Dental Products), and 20 MPa for Vitremer (3M Dental Products). At these small surface areas all of the bond failures were adhesive in nature. This new method permits measurement of high bond strengths without cohesive failure of dentin. It also permits multiple measurements to be made within a single tooth.

Precursor-Surface Reactions in Plasma Deposition of Silicon Thin Films

NASA Astrophysics Data System (ADS)

Bakos, Tamas

2005-03-01

Device-quality hydrogenated amorphous silicon (a-Si:H) thin films are usually grown by plasma deposition under conditions where the SiH3 radical is the dominant deposition precursor. In this presentation, we report results of first-principles density functional theory calculations on the interactions of the SiH3 radical with the crystalline Si(100)-(2x1):H surface in conjunction with molecular-dynamics simulations of a-Si:H thin film growth by SiH3 radicals, which elucidate the pathways and energetics of surface reactions that govern important film properties. In particular, we show that an SiH3 radical can insert into strained surface Si-Si dimer bonds, abstract surface H through an Eley-Rideal mechanism, and passivate surface dangling bonds; these reactions follow exothermic and barrierless pathways that lead to a temperature-independent growth rate in agreement with experimental measurements. We also identify a thermally activated surface H abstraction process, in which the SiH3 radical diffuses through overcoordinated surface Si atoms until it encounters a favorable site for H abstraction; the diffusion and H-abstraction steps have commensurate activation barriers. This mechanism explains partly the reduction of the film H content at elevated substrate temperatures.

Release properties of tannic acid from hydrogen bond driven antioxidative cellulose nanofibrous films.

PubMed

Zhou, Bin; Hu, Xiaoqian; Zhu, Jinjin; Wang, Zhenzhen; Wang, Xichang; Wang, Mingfu

2016-10-01

Layer-by-layer (LBL) assembled films have been exploited for surface-mediated bioactive compound delivery. Here, an antioxidative hydrogen-bonded multilayer electrospun nanofibrous film was fabricated from tannic acid (TA), acting as a polyphenolic antioxidant, and poly(ethylene glycol) (PEG) via layer-by-layer assembly. It overcame the burst release behavior of nanofibrous carrier, due to the reversible/dynamic nature of hydrogen bond, which was responded to external stimuli. The PEG/TA nanofibrous films disassembled gradually and released TA to the media, when soaked in aqueous solutions. The release rate of TA increased with increasing bilayer number, pH and temperature, but decreased with enhancing ionic strength. The surface morphology of the nanofibrous mats was observed by scanning electron microscopy (SEM). The following antioxidant activity assay revealed that it could scavenge DPPH free radicals and ABTS(+) cation radicals, a major biological activity of polyphenols. This technology can be used to fabricate other phenolic-containing slowly releasing antioxidative nanofibrous films. Copyright © 2016 Elsevier B.V. All rights reserved.

Efficient Nitrogen Fixation via a Redox-Flexible Single-Iron Site with Reverse-Dative Iron → Boron σ Bonding.

PubMed

Lu, Jun-Bo; Ma, Xue-Lu; Wang, Jia-Qi; Liu, Jin-Cheng; Xiao, Hai; Li, Jun

2018-05-10

Model systems of the FeMo cofactor of nitrogenase have been explored extensively in catalysis to gain insights into their ability for nitrogen fixation that is of vital importance to the human society. Here we investigate the trigonal pyramidal borane-ligand Fe complex by first-principles calculations, and find that the variation of oxidation state of Fe along the reaction path correlates with that of the reverse-dative Fe → B bonding. The redox-flexibility of the reverse-dative Fe → B bonding helps to provide an electron reservoir that buffers and stabilizes the evolution of Fe oxidation state, which is essential for forming the key intermediates of N 2 activation. Our work provides insights for understanding and optimizing homogeneous and surface single-atom catalysts with reverse-dative donating ligands for efficient dinitrogen fixation. The extension of this kind of molecular catalytic active center to heterogeneous catalysts with surface single-clusters is also discussed.

Post-thermocycling shear bond strength of a gingiva-colored indirect composite layering material to three implant framework materials.

PubMed

Komine, Futoshi; Koizuka, Mai; Fushiki, Ryosuke; Taguchi, Kohei; Kamio, Shingo; Matsumura, Hideo

2013-09-01

To evaluate shear bond strength of a gingiva-colored indirect composite to three implant framework materials, before and after thermocycling, and verify the effect of surface pre-treatment for each framework. Commercially pure titanium (CP-Ti), American Dental Association (ADA) type 4 casting gold alloy (Type IV) and zirconia ceramics (Zirconia) were assessed. For each substrate, 96 disks were divided into six groups and primed with one of the following primers: Alloy Primer (ALP), Clearfil Photo Bond (CPB), Clearfil Photo Bond with Clearfil Porcelain Bond Activator (CPB+Activator), Estenia Opaque Primer (EOP), Metal Link (MLP) and V-Primer (VPR). The specimens were then bonded to a gingiva-colored indirect composite (Ceramage Concentrate GUM-D). Shear bond strengths were measured at 0 and 20 000 thermocycles and data were analyzed with the Steel-Dwass test and Mann-Whitney U-test. Shear bond strengths were significantly lower after thermocycling, with the exception of Type IV specimens primed with CPB (p = 0.092) or MLP (p = 0.112). For CP-Ti and Zirconia specimens, priming with CPB or CPB+Activator produced significantly higher bond strengths at 0 and 20 000 thermocycles, as compared with the other groups. For Type IV specimens, priming with ALP or MLP produced higher bond strengths at 0 and 20 000 thermocycles. Shear bond strength of a gingiva-colored indirect composite to CP-Ti, gold alloy and zirconia ceramics was generally lower after thermocycling. Application of a hydrophobic phosphate monomer and polymerization initiator was effective in maintaining bond strength of CP-Ti and zirconia ceramics. Combined use of a thione monomer and phosphoric monomer enhanced the durable bond strength of gold alloy.

The Effect of Nylon and Polyester Peel Ply Surface Preparation on the Bond Quality of Composite Laminates

NASA Astrophysics Data System (ADS)

Moench, Molly K.

The preparation of the surfaces to be bonded is critical to the success of composite bonds. Peel ply surface preparation is attractive from a manufacturing and quality assurance standpoint, but is a well known example of the extremely system-specific nature of composite bonds. This study examined the role of the surface energy, morphology, and chemistry left by peel ply removal in resulting bond quality. It also evaluated the use of contact angle surface energy measurement techniques for predicting the resulting bond quality of a prepared surface. The surfaces created by preparing three aerospace fiber-reinforced composite prepregs were compared when prepared with a nylon vs a polyester peel ply. The prepared surfaces were characterized with contact angle measurements with multiple fluids, scanning electron microscopy (SEM), and x-ray electron spectroscopy. The laminates were bonded with aerospace grade film adhesives. Bond quality was assessed via double cantilever beam testing followed by optical and scanning electron microscopy of the fracture surfaces.The division was clear between strong bonds (GIC of 600- 1000J/m2 and failure in cohesion) and weak bonds (GIC of 80-400J/m2 and failure in adhesion). All prepared laminates showed the imprint of the peel ply texture and evidence of peel ply remnants after fabric removal, either through SEM or XPS. Within an adhesive system, large amounts of SEM-visible peel ply material transfer correlated with poor bond quality and cleaner surfaces with higher bond quality. The both sides of failed weak bonds showed evidence of peel ply remnants under XPS, showing that at least some failure is occurring through the remnants. The choice of adhesive was found to be significant. AF 555 adhesive was more tolerant of peel ply contamination than MB 1515-3. Although the bond quality results varied substantially between tested combinations, the total surface energies of all prepared surfaces were very similar. Single fluid contact angle measurements/water break tests were therefore not predictive of bond quality, and are recommended against. The multiple fluids used allowed the construction of wettability envelopes, a more detailed look at the surface energy profile. The envelopes of nylon and polyester prepared systems were noticeably different, but while potentially useful for detecting changes or errors in surface preparation of known systems, they were not valid for predicting bond quality in new systems. Ultimately, it was determined that wetting is a necessary but not sufficient condition for bonding.

The mystery of gold's chemical activity: local bonding, morphology and reactivity of atomic oxygen.

PubMed

Baker, Thomas A; Liu, Xiaoying; Friend, Cynthia M

2011-01-07

Recently, gold has been intensely studied as a catalyst for key synthetic reactions. Gold is an attractive catalyst because, surprisingly, it is highly active and very selective for partial oxidation processes suggesting promise for energy-efficient "green" chemistry. The underlying origin of the high activity of Au is a controversial subject since metallic gold is commonly thought to be inert. Herein, we establish that one origin of the high activity for gold catalysis is the extremely reactive nature of atomic oxygen bound in 3-fold coordination sites on metallic gold. This is the predominant form of O at low concentrations on the surface, which is a strong indication that it is most relevant to catalytic conditions. Atomic oxygen bound to metallic Au in 3-fold sites has high activity for CO oxidation, oxidation of olefins, and oxidative transformations of alcohols and amines. Among the factors identified as important in Au-O interaction are the morphology of the surface, the local binding site of oxygen, and the degree of order of the oxygen overlayer. In this Perspective, we present an overview of both theory and experiments that identify the reactive forms of O and their associated charge density distributions and bond strengths. We also analyze and model the release of Au atoms induced by O binding to the surface. This rough surface also has the potential for O(2) dissociation, which is a critical step if Au is to be activated catalytically. We further show the strong parallels between product distributions and reactivity for O-covered Au at low pressure (ultrahigh vacuum) and for nanoporous Au catalysts operating at atmospheric pressure as evidence that atomic O is the active species under working catalytic conditions when metallic Au is present. We briefly discuss the possible contributions of oxidants that may contain intact O-O bonds and of the Au-metal oxide support interface in Au catalysis. Finally, the challenges and future directions for fully understanding the activity of gold are considered.

Surface Organometallic Chemistry of Supported Iridium(III) as a Probe for Organotransition Metal–Support Interactions in C–H Activation

DOE PAGES

Kaphan, David M.; Klet, Rachel C.; Perras, Frederic A.; ...

2018-05-11

Systematic study of the interactions between organometallic catalysts and metal oxide support materials is essential for the realization of rational design in heterogeneous catalysis. Herein we describe the stoichiometric and catalytic chemistry of a [Cp*(PMe 3)Ir(III)] complex chemisorbed on a variety of acidic metal oxides as a multifaceted probe for stereoelectronic communication between the support and organometallic center. Electrophilic bond activation was explored in the context of stoichiometric hydrogenolysis as well as catalytic H/D exchange. Further information was obtained from the observation of processes related to dynamic exchange between grafted organometallic species and those in solution. The supported organometallic speciesmore » were characterized by a variety of spectroscopic techniques including dynamic nuclear polarization-enhanced solid-state NMR spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy, and X-ray absorption spectroscopy. Finally, strongly acidic modified metal oxides such as sulfated zirconia engender high levels of activity toward electrophilic bond activation of both sp 2 and sp 3 C–H bonds, including the rapid deuteration of methane at room temperature; however, the global trend for the supports studied here does not suggest a direct correlation between activity and surface Brønsted acidity.« less

Surface Organometallic Chemistry of Supported Iridium(III) as a Probe for Organotransition Metal–Support Interactions in C–H Activation

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

Kaphan, David M.; Klet, Rachel C.; Perras, Frederic A.

Systematic study of the interactions between organometallic catalysts and metal oxide support materials is essential for the realization of rational design in heterogeneous catalysis. Herein we describe the stoichiometric and catalytic chemistry of a [Cp*(PMe 3)Ir(III)] complex chemisorbed on a variety of acidic metal oxides as a multifaceted probe for stereoelectronic communication between the support and organometallic center. Electrophilic bond activation was explored in the context of stoichiometric hydrogenolysis as well as catalytic H/D exchange. Further information was obtained from the observation of processes related to dynamic exchange between grafted organometallic species and those in solution. The supported organometallic speciesmore » were characterized by a variety of spectroscopic techniques including dynamic nuclear polarization-enhanced solid-state NMR spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy, and X-ray absorption spectroscopy. Finally, strongly acidic modified metal oxides such as sulfated zirconia engender high levels of activity toward electrophilic bond activation of both sp 2 and sp 3 C–H bonds, including the rapid deuteration of methane at room temperature; however, the global trend for the supports studied here does not suggest a direct correlation between activity and surface Brønsted acidity.« less

Experimental and computational investigation of acetic acid deoxygenation over oxophilic molybdenum carbide: Surface chemistry and active site identity

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

Schaidle, Joshua A.; Blackburn, Jeffrey; Farberow, Carrie A.

Ex situ catalytic fast pyrolysis (CFP) is a promising route for producing fungible biofuels; however, this process requires bifunctional catalysts that favor C–O bond cleavage, activate hydrogen at near atmospheric pressure and high temperature (350–500 °C), and are stable under high-steam, low hydrogen-to-carbon environments. Recently, early transition-metal carbides have been reported to selectively cleave C–O bonds of alcohols, aldehydes, and oxygenated aromatics, yet there is limited understanding of the metal carbide surface chemistry under reaction conditions and the identity of the active sites for deoxygenation. In this study, we evaluated molybdenum carbide (Mo 2C) for the deoxygenation of acetic acid,more » an abundant component of biomass pyrolysis vapors, under ex situ CFP conditions, and we probed the Mo 2C surface chemistry, identity of the active sites, and deoxygenation pathways using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations.« less

Experimental and computational investigation of acetic acid deoxygenation over oxophilic molybdenum carbide: Surface chemistry and active site identity

DOE PAGES

Schaidle, Joshua A.; Blackburn, Jeffrey; Farberow, Carrie A.; ...

2016-01-21

Ex situ catalytic fast pyrolysis (CFP) is a promising route for producing fungible biofuels; however, this process requires bifunctional catalysts that favor C–O bond cleavage, activate hydrogen at near atmospheric pressure and high temperature (350–500 °C), and are stable under high-steam, low hydrogen-to-carbon environments. Recently, early transition-metal carbides have been reported to selectively cleave C–O bonds of alcohols, aldehydes, and oxygenated aromatics, yet there is limited understanding of the metal carbide surface chemistry under reaction conditions and the identity of the active sites for deoxygenation. In this study, we evaluated molybdenum carbide (Mo 2C) for the deoxygenation of acetic acid,more » an abundant component of biomass pyrolysis vapors, under ex situ CFP conditions, and we probed the Mo 2C surface chemistry, identity of the active sites, and deoxygenation pathways using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations.« less

Probing equilibrium of molecular and deprotonated water on TiO 2 (110)

DOE PAGES

Wang, Zhi-Tao; Wang, Yang-Gang; Mu, Rentao; ...

2017-02-06

Understanding water structure and its deprotonation dynamics on oxide surfaces is key to understanding many physical and chemical processes. In this study, we directly measure the energy barriers associated with the protonation equilibrium of water on the prototypical oxide surface, rutile-TiO2(110) by a combination of a supersonic molecular beam, scanning tunneling microscopy, and ab initio molecular dynamics simulations. We show that long-range electrostatic fields emanating from the oxide lead to steering and reorientation of the molecules approaching the surface, activating the O-H bonds and inducing deprotonation. The incident energy dependent studies allow for a direct determination of the dissociation barrier.more » Temperature dependent imaging yields the reverse barrier and the equilibrium constant. Molecularly bound water is preferred by 0.035 eV over the surface-bound hydroxyls. The techniques developed in this work are readily extended to other systems where the understanding of bond-activation processes is critical.« less

Probing equilibrium of molecular and deprotonated water on TiO 2(110)

DOE PAGES

Wang, Zhi -Tao; Wang, Yang -Gang; Mu, Rentao; ...

2017-02-06

Understanding water structure and its deprotonation dynamics on oxide surfaces is key to understanding many physical and chemical processes. In this study, we directly measure the energy barriers associated with the protonation equilibrium of water on the prototypical oxide surface, rutile-TiO 2(110) by a combination of a supersonic molecular beam, scanning tunneling microscopy, and ab initio molecular dynamics simulations. We show that long-range electrostatic fields emanating from the oxide lead to steering and reorientation of the molecules approaching the surface, activating the O-H bonds and inducing deprotonation. The incident energy dependent studies allow for a direct determination of the dissociationmore » barrier. Temperature dependent imaging yields the reverse barrier and the equilibrium constant. Molecularly bound water is preferred by 0.035 eV over the surface-bound hydroxyls. In conclusion, the techniques developed in this work are readily extended to other systems where the understanding of bond-activation processes is critical.« less

Contamination and Surface Preparation Effects on Composite Bonding

NASA Technical Reports Server (NTRS)

Kutscha, Eileen O.; Vahey, Paul G.; Belcher, Marcus A.; VanVoast, Peter J.; Grace, William B.; Blohowiak, Kay Y.; Palmieri, Frank L.; Connell, John W.

2017-01-01

Results presented here demonstrate the effect of several prebond surface contaminants (hydrocarbon, machining fluid, latex, silicone, peel ply residue, release film) on bond quality, as measured by fracture toughness and failure modes of carbon fiber reinforced epoxy substrates bonded in secondary and co-bond configurations with paste and film adhesives. Additionally, the capability of various prebond surface property measurement tools to detect contaminants and potentially predict subsequent bond performance of three different adhesives is also shown. Surface measurement methods included water contact angle, Dyne solution wettability, optically stimulated electron emission spectroscopy, surface free energy, inverse gas chromatography, and Fourier transform infrared spectroscopy with chemometrics analysis. Information will also be provided on the effectiveness of mechanical and energetic surface treatments to recover a bondable surface after contamination. The benefits and drawbacks of the various surface analysis tools to detect contaminants and evaluate prebond surfaces after surface treatment were assessed as well as their ability to correlate to bond performance. Surface analysis tools were also evaluated for their potential use as in-line quality control of adhesive bonding parameters in the manufacturing environment.

In vitro comparison of an Er:YAG laser-activated bleaching system with different light-activated bleaching systems for color change, surface roughness, and enamel bond strength.

PubMed

Ergin, Esra; Ruya Yazici, A; Kalender, Bercem; Usumez, Aslihan; Ertan, Atilla; Gorucu, Jale; Sari, Tugrul

2018-06-02

To compare an Er:YAG laser-activated bleaching system with different light-activated in-office bleaching systems for color change, surface roughness, and post-bleaching enamel bond strength. 51 enamel slabs were prepared from the sound buccal enamel of extracted bovine teeth. The teeth were randomly divided into three groups according to different light-activated office bleaching systems (n = 17): diode laser (Epic, Biolase) (940 nm, 7 W, continuous mode), Er:YAG laser (LightWalker, Fotona) (2940 nm, 50 mJ, 10 Hz, 1000 μs), and LED (Radii Plus) (440-480 nm, 1500 mW/cm 2 ). All systems were used with their compatible bleaching agents according to manufacturers' recommendations. The tooth color and surface roughness (Ra) were assessed at baseline and after bleaching using a spectrophotometer and a surface profilometer, respectively. The color change was determined by the CIE L*a*b* system (ΔE, ΔL*, Δa*, Δb*). Kruskal-Wallis test was used for color change whereas Kruskal-Wallis and Wilcoxon tests were used to analyze the roughness data. For shear bond strength test (SBS), composite cylinders were bonded on bleached enamel samples 14 days after bleaching procedures and stored in water (37 °C). Specimens were then debonded with a universal testing machine at 1 mm/min and data were analyzed by using Kruskal-Wallis test. All the tested bleaching systems were effective on color change (ΔE > 3.3) and produced similar color change (p > 0.05). There were no significant differences among the Ra values of the groups neither at baseline nor after bleaching (p > 0.05). However, comparing the baseline and after bleaching Ra values, a significant increase was observed for all tested groups (p < 0.05). Significant differences were also found among all systems for SBS (p < 0.05). The highest values were obtained in Er:YAG group, whereas the LED group revealed the lowest values (p < 0.05). All tested bleaching systems were effective on tooth whitening, whereas they all led to an increase on surface roughness. Although the current Er:YAG laser-activated bleaching system did not differ from other tested bleaching systems according to color change and surface roughness, it appears to provide better results in terms of SBS.

Mechanisms of deep benzene oxidation on the Pt(1 1 1) surface using temperature-programmed reaction methods

NASA Astrophysics Data System (ADS)

Marsh, Anderson L.; Gland, John L.

2003-06-01

The catalytic oxidation of benzene on the Pt(1 1 1) surface has been characterized using temperature-programmed reaction spectroscopy (TPRS) over a wide range of benzene and oxygen coverages. Coadsorbed atomic oxygen and benzene are the primary reactants on the surface during the initial oxidation step. Benzene is oxidized over the 300-500 K range to produce carbon dioxide and water. Carbon-hydrogen and carbon-carbon bond activation are clearly rate-limiting steps for these reactions. Preferential oxidation causes depletion of bridge-bonded benzene, suggesting enhanced reactivity in this bonding configuration. When oxygen is in excess on the surface, all of the surface carbon and hydrogen is oxidized. When benzene is in excess on the surface, hydrogen produced by dehydrogenation is desorbed after all of the surface oxygen has been consumed. Repulsive interactions between benzene and molecular oxygen dominate at low temperatures. Preadsorption of oxygen inhibits adsorption of less reactive benzene in threefold hollow sites. The desorption temperature of this non-reactive chemisorbed benzene decreases and overlaps with the multilayer desorption peak with increasing oxygen exposure. The results presented here provide a clear picture of rate-limiting steps during deep oxidation of benzene on the Pt(1 1 1) surface.

Influence of crosshead speed on micro-tensile bond strength of two-step adhesive systems.

PubMed

Yamaguchi, Kanako; Miyazaki, Masashi; Takamizawa, Toshiki; Tsubota, Keishi; Rikuta, Akitomo

2006-05-01

The purpose of this study was to determine the influence of crosshead speed on the micro-tensile bond strength of two separate adhesive systems to dentin. The systems used were the Clearfil SE Bond (Kuraray Medical) and the Single Bond (3M ESPE) combined with a resin composite Clearfil AP-X (Kuraray Medical). Dentin surfaces of bovine madibular incisors were primed with self-etching primer followed by air blowing for Clearfil SE Bond, or etched with phosphoric acid followed by rinsing with distilled water for Single Bond, and adhesive was applied. The resin composite was then built up in three layers and light activated. After 24 h storage in water, specimens were sectioned and trimmed to a cross-sectional area of 1 mm(2) and subjected to a micro-tensile bond-strength test. Ten samples per test group were tested at crosshead speeds of 0.5, 1.0, 5.0 and 10.0 mm/min. Micro-tensile bond-strength values (in MPa) were calculated from the peak load at failure divided by the specimen surface area. Two-way ANOVA was performed at the 0.05 probability level. The mean dentin bond strength at different crosshead speeds ranged from 34.6 to 37.1MPa for Clearfil SE Bond and from 44.3 to 50.4 MPa for Single Bond. There was no significant difference among the same adhesive systems with the different crosshead speeds tested. The influence of the crosshead speed might be negligible when measuring micro-tensile bond strengths.

Surface characterization of carbon fiber reinforced polymers by picosecond laser induced breakdown spectroscopy

NASA Astrophysics Data System (ADS)

Ledesma, Rodolfo; Palmieri, Frank; Connell, John; Yost, William; Fitz-Gerald, James

2018-02-01

Adhesive bonding of composite materials requires reliable monitoring and detection of surface contaminants as part of a vigorous quality control process to assure robust and durable bonded structures. Surface treatment and effective monitoring prior to bonding are essential in order to obtain a surface which is free from contaminants that may lead to inferior bond quality. In this study, the focus is to advance the laser induced breakdown spectroscopy (LIBS) technique by using pulse energies below 100 μJ (μLIBS) for the detection of low levels of silicone contaminants in carbon fiber reinforced polymer (CFRP) composites. Various CFRP surface conditions were investigated by LIBS using ∼10 ps, 355 nm laser pulses with pulse energies below 30 μJ. Time-resolved analysis was conducted to optimize the gate delay and gate width for the detection of the C I emission line at 247.9 nm to monitor the epoxy resin matrix of CFRP composites and the Si I emission line at 288.2 nm for detection of silicone contaminants in CFRP. To study the surface sensitivity to silicone contamination, CFRP surfaces were coated with polydimethylsiloxane (PDMS), the active ingredient in many mold release agents. The presence of PDMS was studied by inspecting the Si I emission lines at 251.6 nm and 288.2 nm. The measured PDMS areal densities ranged from 0.15 to 2 μg/cm2. LIBS measurements were performed before and after laser surface ablation. The results demonstrate the successful detection of PDMS thin layers on CFRP using picosecond μLIBS.

Process for producing an activated carbon adsorbent with integral heat transfer apparatus

NASA Technical Reports Server (NTRS)

Jones, Jack A. (Inventor); Yavrouian, Andre H. (Inventor)

1996-01-01

A process for producing an integral adsorbent-heat exchanger apparatus useful in ammonia refrigerant heat pump systems. In one embodiment, the process wets an activated carbon particles-solvent mixture with a binder-solvent mixture, presses the binder wetted activated carbon mixture on a metal tube surface and thereafter pyrolyzes the mixture to form a bonded activated carbon matrix adjoined to the tube surface. The integral apparatus can be easily and inexpensively produced by the process in large quantities.

Comparative study on the effect of H2 pre-adsorption on CO oxidation in O2-poor atmosphere over Au/TiO2 and TiO2: Temperature programmed surface reaction by a multiplexed mass spectrometer testing

NASA Astrophysics Data System (ADS)

Si, Ruiru; Liu, Junfeng; Zhang, Yujuan; Chen, Xun; Dai, Wenxin; Fu, Xianzhi

2016-11-01

The behaviors of H2 pre-adsorption on CO oxidation in an O2-poor stream containing a trace H2O over Au/TiO2 and TiO2 have been investigated by a temperature programmed surface reaction testing, respectively. It was found that the H2 pre-adsorption could keep CO oxidation without H2O consumption over Au/TiO2, but suppress CO oxidation over TiO2. The chemisorption testing showed that the H2 adsorption at Au/TiO2 could benefit to the formation of Ti-bonded hydroxyl species (Ti4+-OH), while the H2 adsorption at TiO2 would consume the Ti-bonded hydroxyl species and form the bridge hydroxyl species (Ti4+-OH-Ti4+). These results show that only the Ti-bonded hydroxyl species (not all kinds of hydroxyl species) could act as the active species of oxidizing CO. Furthermore, it is suggested that the dissociative hydrogen adsorbed at Au sites could activate the lattice oxygen of TiO2 to form the active Ti-bonded hydroxyl species (hydrogen spillover from Au to TiO2), which exhibit a strong reducibility than the H directly adsorbed at TiO2.

Medical implants and methods of making medical implants

DOEpatents

Shaw, Wendy J; Yonker, Clement R; Fulton, John L; Tarasevich, Barbara J; McClain, James B; Taylor, Doug

2014-09-16

A medical implant device having a substrate with an oxidized surface and a silane derivative coating covalently bonded to the oxidized surface. A bioactive agent is covalently bonded to the silane derivative coating. An implantable stent device including a stent core having an oxidized surface with a layer of silane derivative covalently bonded thereto. A spacer layer comprising polyethylene glycol (PEG) is covalently bonded to the layer of silane derivative and a protein is covalently bonded to the PEG. A method of making a medical implant device including providing a substrate having a surface, oxidizing the surface and reacting with derivitized silane to form a silane coating covalently bonded to the surface. A bioactive agent is then covalently bonded to the silane coating. In particular instances, an additional coating of bio-absorbable polymer and/or pharmaceutical agent is deposited over the bioactive agent.

New Approaches to Waterproofing of Space Shuttle Insulating Materials

NASA Technical Reports Server (NTRS)

Blum, Yigal D.; Johnson, Sylvia M.; Chen, Paul

1997-01-01

Future reusable space vehicles will be in service much more frequently than current space shuttles. Therefore, rapid reconditioning of spacecraft will be required. Currently, the waterproofing of space shuttles after each re-entry takes 72 hours and requires substantial labor. In addition, the currently used waterproofing reagent, DiMethylEthoxySilane (DMES), is considered toxic, and ethanol fumes are released during its hydrolytic activation. Consequently, a long time period, which is not acceptable for future operations, is needed to ensure that 0 the excess volatile compounds are removed before further maintenance of the space vehicle can be performed. The objective of this project was to assist NASA Ames in finding improved waterproofing systems by identifying suitable waterproofing agents that can be applied by vapor phase deposition and will be less toxic, bond more rapidly to the insulation material surface, and potentially have higher thermal stability than the DMES system. Several approaches to achieve faster waterproofing with less toxicity were assessed using the following alternatives: Reactive volatile compounds that are rapidly deposited by chemical bonding at the surface and leave no toxic volatiles. Reactive reagents that are the least toxic. Nonvolatile reagents that are very reactive and bond strongly to the insulating material surface. Three specific types of potential reagents were chosen for evaluation in this project: 1. Volatile reagents with Si-Cl functional groups for vapor deposition 2. Volatile reagents with Si-H functional groups for vapor deposition 3. Nonvolatile oligomeric or polymeric reactive siloxanes that are assumed to have higher thermal stability and/or strong bonding to the insulating material. The chemistry involved in the project was targeted at the generation of intermediates having reactive Si-OH bonds for the formation of either volatile species or polymeric species that bond rapidly to the surface and also cure rapidly. We focused on two chemical reactions@-hydrolysis of Si-Cl bonds and catalytic dehydrocoupling of Si-H bonds.

Improvement and mechanism of interfacial adhesion in PBO fiber/bismaleimide composite by oxygen plasma treatment

NASA Astrophysics Data System (ADS)

Liu, Dong; Chen, Ping; Mu, Jujie; Yu, Qi; Lu, Chun

2011-05-01

The improved interfacial adhesion of PBO fiber-reinforced bismaleimide composite by oxygen plasma processing was investigated in this paper. After treatment, the maximum value of interlaminar shear strength was 57.5 MPa, with an increase of 28.9%. The oxygen concentration of the fiber surface increased, as did the surface roughness, resulting in improvement of the surface wettability. The cleavage and rearrangement of surface bonds created new functional groups O dbnd C sbnd O, N sbnd C dbnd O and N sbnd O, thereby activating the fiber surface. And long-time treatment increased the reaction degree of surface groups while destroyed the newly-created physical structures. The enhancement of adhesion relied primarily on the strengthening of chemical bonding and mechanical interlocking between the fiber and the matrix. The composite rupture planes indicated that the fracture failure shifted from the interface to the matrix or the fiber.

Low-temperature wafer direct bonding of silicon and quartz glass by a two-step wet chemical surface cleaning

NASA Astrophysics Data System (ADS)

Wang, Chenxi; Xu, Jikai; Zeng, Xiaorun; Tian, Yanhong; Wang, Chunqing; Suga, Tadatomo

2018-02-01

We demonstrate a facile bonding process for combining silicon and quartz glass wafers by a two-step wet chemical surface cleaning. After a post-annealing at 200 °C, strong bonding interfaces with no defects or microcracks were obtained. On the basis of the detailed surface and bonding interface characterizations, the bonding mechanism was explored and discussed. The amino groups terminated on the cleaned surfaces might contribute to the bonding strength enhancement during the annealing. This cost-effective bonding process has great potentials for silicon- and glass-based heterogeneous integrations without requiring a vacuum system.

Light Makes a Surface Banana-Bond Split: Photodesorption of Molecular Hydrogen from RuO 2 (110)

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

Henderson, Michael A.; Mu, Rentao; Dahal, Arjun

The coordination of H2 to a metal center via polarization of its bond electron density, known as a Kubas complex, is the means by which H2 chemisorbs at Ru4+ sites on the rutile RuO2(110) surface. This distortion of electron density off an interatomic axis is often described as a ‘banana-bond.’ We show that the Ru-H2 banana-bond can be destabilized, and split, using visible light. Photodesorption of H2 (or D2) is evident by mass spectrometry and scanning tunneling microscopy. From time-dependent density functional theory, the key optical excitation splitting the Ru-H2 banana-bond involves an interband transition in RuO2 which effectively diminishesmore » its Lewis acidity, and thereby weakening the Kubas complex. Such excitations are not expected to affect adsorbates on RuO2 given its metallic properties. Therefore, this common thermal co-catalyst employed in promoting water splitting is, itself, photo-active in the visible.« less

Bond strength of the porcelain repair system to all-ceramic copings and porcelain.

PubMed

Lee, Sang J; Cheong, Chan Wook; Wright, Robert F; Chang, Brian M

2014-02-01

The purpose of this study was to investigate the shear bond strength of the porcelain repair system on alumina and zirconia core ceramics, comparing this strength with that of veneering porcelain. Veneering ceramic (n = 12), alumina core (n = 24), and zirconia core (n = 24) blocks measuring 10 × 5 × 5 mm(3) were fabricated. Veneering ceramic blocks were used as the control. Alumina and zirconia core blocks were divided into 2 groups (n = 12 each), and a slot (2 × 2 × 4 mm(3)) filled with veneering ceramics was prepared into one of the alumina and zirconia core groups (n = 12). Followed by surface treatments of micro-abrasion with 30 μm alumina particles, etching with 35% phosphoric acid and silane primer and bond, composite resin blocks (2 × 2 × 2 mm(3)) were built up and light polymerized onto the treated surfaces by 3 configurations: (a) composite blocks bonded onto veneering ceramic surface alone, (b) composite blocks bonded onto alumina core or zirconia core surfaces, (c) a 50% surface area of the composite blocks bonded to veneering ceramics and the other 50% surface area of the composite blocks to alumina core or zirconia core surfaces. The shear bond strength of the composite to each specimen was tested by a universal testing machine at a 0.5 mm/min crosshead speed. The shear bond strength was analyzed by unpaired t-tests for within the configuration groups and ANOVA for among the different configuration groups. When the mean shear bond strength was compared within groups of the same configuration, there were no statistically significant differences. Comparison of the shear bond strength among groups of different configurations revealed statistically significant differences. The mean shear bond strength of composite onto 100% veneering ceramic surface and composite onto 50% veneering 50% all-ceramic cores was statistically higher than that of composite onto 100% all-ceramic cores; however, the differences of the shear bond strength of composite bonded only onto the veneering ceramic surface were not statistically significant from those of 50% surface area of composite bonded onto all-ceramic cores. No statistically significant differences in the bond strength of a porcelain repair system to alumina and zirconia copings were observed. Increasing the surface of veneering ceramics to a porcelain repair system improved the repair material's bond strength. © 2013 by the American College of Prosthodontists.

Simplified nonplanar wafer bonding for heterogeneous device integration

NASA Astrophysics Data System (ADS)

Geske, Jon; Bowers, John E.; Riley, Anton

2004-07-01

We demonstrate a simplified nonplanar wafer bonding technique for heterogeneous device integration. The improved technique can be used to laterally integrate dissimilar semiconductor device structures on a lattice-mismatched substrate. Using the technique, two different InP-based vertical-cavity surface-emitting laser active regions have been integrated onto GaAs without compromising the quality of the photoluminescence. Experimental and numerical simulation results are presented.

Tensile Bond Strength of Self Adhesive Resin Cement After Various Surface Treatment of Enamel.

PubMed

Sekhri, Sahil; Mittal, Sanjeev; Garg, Sandeep

2016-01-01

In self adhesive resin cements adhesion is achieved to dental surface without surface pre-treatment, and requires only single step application. This makes the luting procedure less technique-sensitive and decreases postoperative sensitivity. The purpose of this study was to evaluate bond strength of self adhesive resin after surface treatment of enamel for bonding base metal alloy. On the labial surface of 64 central incisor rectangular base metal block of dimension 6 mm length, 5mm width and 1 mm height was cemented with RelyX U200 and Maxcem Elite self adhesive cements with and without surface treatment of enamel. Surface treatment of enamel was application of etchant, one step bonding agent and both. Tensile bond strength of specimen was measured with universal testing machine at a cross head speed of 1mm/min. Least tensile bond strength (MPa) was in control group i.e. 1.33 (0.32) & 1.59 (0.299), Highest bond strength observed when enamel treated with both etchant and bonding agent i.e. 2.72 (0.43) & 2.97 (0.19) for Relyx U200 and Elite cement. When alone etchant and bonding agent were applied alone bond strength is 2.19 (0.18) & 2.24 (0.47) for Relyx U200, and 2.38 (0.27) 2.49 (0.16) for Max-cem elite. Mean bond strength was higher in case of Max-cem Elite as compared to RelyX U200 resin cement, although differences were non-significant (p > 0.05). Surface treatment of enamel increases the bond strength of self adhesive resin cement.

Systematic theoretical study of ethylene adsorption on δ-MoC(001), TiC(001), and ZrC(001) surfaces

DOE PAGES

Jimenez-Orozco, Carlos; Florez, Elizabeth; Moreno, Andres; ...

2016-05-31

A systematic study of ethylene adsorption over δ-MoC(001), TiC(001), and ZrC(001) surfaces was conducted by means of calculations based on periodic density functional theory. The structure and electronic properties of each carbide pristine surface had a strong influence in the bonding of ethylene. It was found that the metal and carbon sites of the carbide could participate in the adsorption process. As a consequence of this, very different bonding mechanisms were seen on δ-MoC(001) and TiC(001). The bonding of the molecule on the TMC(001) systems showed only minor similarities to the type of bonding found on a typical metal likemore » Pt(111). In general, the ethylene binding energy follow the trend in stability: ZrC(001) < TiC(001) < δ-MoC(001) < Pt(111). The van der Waals correction to the energy produces large binding energy values, modifies the stability orders and drives the ethylene closer to the surface but the adsorbate geometry parameters remain unchanged. Ethylene was activated on clearly defined binding geometries, changing its hybridization from sp 2 to sp 3 with an elongation (0.16–0.31 Å) of the C=C bond. As a result, on the basis of this theoretical study, δ-MoC(001) is proposed as a potential catalyst for the hydrogenation of olefins, whereas TiC(001) could be useful for their hydrogenolysis.« less

Mitigating external and internal cathode fouling using a polymer bonded separator in microbial fuel cells.

PubMed

Yang, Wulin; Rossi, Ruggero; Tian, Yushi; Kim, Kyoung-Yeol; Logan, Bruce E

2018-02-01

Microbial fuel cell (MFC) cathodes rapidly foul when treating domestic wastewater, substantially reducing power production over time. Here a wipe separator was chemically bonded to an activated carbon air cathode using polyvinylidene fluoride (PVDF) to mitigate cathode fouling and extend cathode performance over time. MFCs with separator-bonded cathodes produced a maximum power density of 190 ± 30 mW m -2 after 2 months of operation using domestic wastewater, which was ∼220% higher than controls (60 ± 50 mW m -2 ) with separators that were not chemically bonded to the cathode. Less biomass (protein) was measured on the bonded separator surface than the non-bonded separator, indicating chemical bonding reduced external bio-fouling. Salt precipitation that contributed to internal fouling was also reduced using separator-bonded cathodes. Overall, the separator-bonded cathodes showed better performance over time by mitigating both external bio-fouling and internal salt fouling. Copyright © 2017 Elsevier Ltd. All rights reserved.

Density function theoretical study on the complex involved in Th atom-activated C-C bond in C2H6

NASA Astrophysics Data System (ADS)

Qing-Qing, Wang; Peng, Li; Tao, Gao; Hong-Yan, Wang; Bing-Yun, Ao

2016-06-01

Density functional theory (DFT) calculations are performed to investigate the reactivity of Th atom toward ethane C-C bond activation. A comprehensive description of the reaction mechanisms leading to two different reaction products is presented. We report a complete exploration of the potential energy surfaces by taking into consideration different spin states. In addition, the intermediate and transition states along the reaction paths are characterized. Total, partial, and overlap population density of state diagrams and analyses are also presented. Furthermore, the natures of the chemical bonding of intermediate and transition states are studied by using topological method combined with electron localization function (ELF) and Mayer bond order. Infrared spectrum (IR) is obtained and further discussed based on the optimized geometries. Project supported by the National Natural Science Foundation of China (Grant Nos. 21371160, 21401173, and 11364023).

Room-temperature activation of methane and dry re-forming with CO 2 on Ni-CeO 2 (111) surfaces: Effect of Ce 3+ sites and metal–support interactions on C–H bond cleavage

DOE PAGES

Lustemberg, Pablo G.; Ramírez, Pedro J.; Liu, Zongyuan; ...

2016-10-27

The results of core-level photoemission indicate that Ni-CeO 2(111) surfaces with small or medium coverages of nickel are able to activate methane at 300 K, producing adsorbed CH x and CO x (x = 2, 3) groups. Calculations based on density functional theory predict a relatively low activation energy of 0.6–0.7 eV for the cleavage of the first C–H bond in the adsorbed methane molecule. Ni and O centers of ceria work in a cooperative way in the dissociation of the C–H bond at room temperature, where a low Ni loading is crucial for the catalyst activity and stability. Themore » strong electronic perturbations in the Ni nanoparticles produced by the ceria supports of varying natures, such as stoichiometric and reduced, result in a drastic change in their chemical properties toward methane adsorption and dissociation as well as the dry reforming of methane reaction. Lastly, the coverage of Ni has a drastic effect on the ability of the system to dissociate methane and catalyze the dry re-forming process.« less

Room-temperature activation of methane and dry re-forming with CO 2 on Ni-CeO 2 (111) surfaces: Effect of Ce 3+ sites and metal–support interactions on C–H bond cleavage

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

Lustemberg, Pablo G.; Ramírez, Pedro J.; Liu, Zongyuan

The results of core-level photoemission indicate that Ni-CeO 2(111) surfaces with small or medium coverages of nickel are able to activate methane at 300 K, producing adsorbed CH x and CO x (x = 2, 3) groups. Calculations based on density functional theory predict a relatively low activation energy of 0.6–0.7 eV for the cleavage of the first C–H bond in the adsorbed methane molecule. Ni and O centers of ceria work in a cooperative way in the dissociation of the C–H bond at room temperature, where a low Ni loading is crucial for the catalyst activity and stability. Themore » strong electronic perturbations in the Ni nanoparticles produced by the ceria supports of varying natures, such as stoichiometric and reduced, result in a drastic change in their chemical properties toward methane adsorption and dissociation as well as the dry reforming of methane reaction. Lastly, the coverage of Ni has a drastic effect on the ability of the system to dissociate methane and catalyze the dry re-forming process.« less

Efficient dehydrogenation of formic acid using Al12N12 nanocage: A DFT study

NASA Astrophysics Data System (ADS)

Esrafili, Mehdi D.; Nurazar, Roghaye

2014-11-01

We have studied the adsorption and decomposition of formic acid (HCOOH) on the surface of Al12N12 fullerene-like nanocage using density functional theory. Different adsorption modes were found for HCOOH on the Al12N12, i.e. molecular and dissociative monodentate or bidentate adsorption. Three reaction pathways were proposed to understand gas-phase HCOOH decomposition on the Al12N12 nanocage. Our results reveal that for the decomposition of HCOOH into CO2 and H2, the most favorable pathway should be the Csbnd H bond activation reaction. The reaction energies and the activation barriers obtained here suggest that for the dissociative adsorption configuration on the Al12N12 surface, the rate-determining step is the Csbnd H bond breaking.

Investigation on the Activity Activation and Cementitious Property of Coal Gangue with High Iron and Silica Contents

NASA Astrophysics Data System (ADS)

Wu, Hong; Li, Yu; Teng, Min; Yang, Yu

2017-11-01

The activity of coal gangue by thermal activation and composite activation technologies was investigated. The crystal composition, framework structure and morphology change were analyzed by XRD, FT-IR and SEM, respectively. The cementitious property of coal gangue was measured by strength test. The results showed that thermal activation decomposed kaolinite in coal gangue, and formed the metastable structure with a porous state, multiple internal broken bonds and large specific surface areas. Based on thermal activation, the added lime provided the alkaline environment, then this reduced the bond energy of reactant particles and the degree of crystallinity of quartz in coal gangue. The two activation methods could effectively improve the cementitious property of coal gangue based unburned bricks, and that the composite activation technology was superior performance.

Bonding of human meniscal and articular cartilage with photoactive 1,8-naphthalimide dyes

NASA Astrophysics Data System (ADS)

Judy, Millard M.; Nosir, Hany R.; Jackson, Robert W.; Matthews, James Lester; Lewis, David E.; Utecht, Ronald E.; Yuan, Dongwu

1996-05-01

This study focused on meniscal cartilage repair by using the laser-activated photoactive 1,8- naphthalimide dye N,N'-bis-{6-[2-(2-(2- aminoethoxy)ethoxy)ethoxyethyl]amino-1H-benz (de)isoquinolin-1,3(2H)-dion-2- yl}-1,11-diamino-3,6,9-trioxaundecane. Harvested cadaveric human menisci were debrided and carved into strips 1 mm thick, 10 mm long, and 3 mm wide. Each strip was divided into two flaps, the surface painted with photoactive dye, the painted surfaces overlapped, the sample wrapped in Saran film, and the composite sandwiched between two glass slides at a pressure of approximately 3 kg/cm2. The sample then was transilluminated by argon ion laser light of 457.9-nm wavelength at a power density of 200 mW/cm2 with exposure times up to 5 h (3902 J/cm2 energy density). Essentially, the same procedures were performed for human femoral articular cartilage samples. Control experiments were conducted with laser irradiation alone and with dye alone. All the specimens were stored in isotonic saline solution for 2 h after irradiation to ensure hydration. The bond shear-strength was then tested and samples prepared for optical and electron transmission microscopy. Shear strength values of up to 1.8 kg/cm2 for meniscal tissues and 1.2 kg/cm2 for articular cartilaginous tissues were obtained for exposures of 3902 J/cm2. Shear strength values of approximately 0.9 kg/cm2 and 0.4 kg/cm2, respectively, for meniscus and cartilage were obtained with 459 J/cm2 exposure. Dye- and light-only controls exhibited 0 kg/cm2 shear strength values. Microscopy revealed close contact at the bonded surface in the laser-activated, dye-treated-specimens. This study shows that the laser-activated photoactive dyes have the capability of athermally bonding the meniscal and articular cartilage surfaces.

Studies of the kinetics and mechanisms of perfluoroether reactions on iron and oxidized iron surfaces

NASA Technical Reports Server (NTRS)

Napier, Mary E.; Stair, Peter C.

1992-01-01

Polymeric perfluoroalkylethers are being considered for use as lubricants in high temperature applications, but have been observed to catalytically decompose in the presence of metals. X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD) were used to explore the decomposition of three model fluorinated ethers on clean polycrystalline iron surfaces and iron surfaces chemically modified with oxygen. Low temperature adsorption of the model fluorinated ethers on the clean, oxygen modified and oxidized iron surfaces was molecular. Thermally activated defluorination of the three model compounds was observed on the clean iron surface at remarkably low temperatures, 155 K and below, with formation of iron fluoride. Preferential C-F bond scission occurred at the terminal fluoromethoxy, CF3O, of perfluoro-1-methoxy-2-ethoxy ethane and perfluoro-1-methoxy-2-ethoxy propane and at CF3/CF2O of perfluoro-1,3-diethoxy propane. The reactivity of the clean iron toward perfluoroalkylether decomposition when compared to other metals is due to the strength of the iron fluoride bond and the strong electron donating ability of the metallic iron. Chemisorption of an oxygen overlayer lowered the reactivity of the iron surface to the adsorption and decomposition of the three model fluorinated ethers by blocking active sites on the metal surface. Incomplete coverage of the iron surface with chemisorbed oxygen results in a reaction which resembles the defluorination reaction observed on the clean iron surface. Perfluoro-1-methoxy-2-ethoxy ethane reacts on the oxidized iron surface at 138 K, through a Lewis acid assisted cleavage of the carbon oxygen bond, with preferential attack at the terminal fluoromethoxy, CF3O. The oxidized iron surface did not passivate, but became more reactive with time. Perfluoro-1-methoxy-2-ethoxy propane and perfluoro-1,3-diethoxy propane desorbed prior to the observation of decomposition on the oxidized iron surface.

Optimization of amino group density on surfaces of titanium dioxide nanoparticles covalently bonded to a silicone substrate for antibacterial and cell adhesion activities.

PubMed

Okada, Masahiro; Yasuda, Shoji; Kimura, Tsuyoshi; Iwasaki, Mitsunobu; Ito, Seishiro; Kishida, Akio; Furuzono, Tsutomu

2006-01-01

A composite consisting of titanium dioxide (TiO2) particle, the surface of which was modified with amino groups, and a silicone substrate through covalent bonding at their interface was developed, and antibacterial and cell adhesion activities of the composite were evaluated. The density of the amino groups on the TiO2 particle surface was controlled by the reaction time of the modification reaction. The degradation rate of CH3CHO in the presence of the TiO2 particles under UV irradiation decreased with an increase in the amino group density on the TiO2 surface. On the other hand, the number of L929 cells adhering on the TiO2/silicone composite increased with an increase in the amino group density. From the above two results, the optimum density of amino groups for both photoreactivity and cell adhesiveness was estimated to be 2.0-4.0 molecules/nm2. The optimum amino group-modified TiO2/silicone composite sheet (amino group density, 3.0 molecules/nm2) showed an effective antibacterial activity for Escherichia coli bacteria under UV irradiation. (c) 2005 Wiley Periodicals, Inc

Photocatalytic mechanism of high-activity anatase TiO2 with exposed (001) facets from molecular-atomic scale: HRTEM and Raman studies

NASA Astrophysics Data System (ADS)

Wu, Jun; Shi, Chentian; Zhang, Yupeng; Fu, Qiang; Pan, Chunxu

2017-12-01

Anatase TiO2 with a variant percentage of exposed (001) facets was prepared under hydrothermal processes by adjusting the volume of HF, and the photocatalytic mechanism was studied from atomic-molecular scale by HRTEM and Raman spectroscopy. It was revealed that: 1) From HRTEM observations, the surface of original TiO2 with exposed (001) facets was clean without impurity, and the crystal lattice was clear and completed; however, when mixed with methylene blue (MB) solution, there were many 1 nm molecular absorbed at the surface of TiO2; after the photocatalytic experiment, MB molecules disappeared and the TiO2 lattice image became fuzzy. 2) The broken path of the MB chemical bond was obtained by Raman spectroscopy, i.e., after the irradiation of the light, the vibrational mode of C-N-C disappeared due to the chemical bond breakage, and the groups containing C-N bond and carbon rings were gradually decomposed. Accordingly, we propose that the driving force for breaking the chemical bond and the disappearance of groups is from the surface lattice distortion of TiO2 during photocatalyzation.

Theoretical investigation on the potential energy surface for the reactions of B, Al and Ga with NO

NASA Astrophysics Data System (ADS)

Zhang, Luning; Zhou, Mingfei

2000-06-01

The structures, binding energies and vibrational frequencies of various MNO structural isomers (M=B, Al and Ga) in their ground triplet states have been determined using the density functional (B3LYP, BP86 and B3PW91) and MP2 methods. The potential energy surfaces of the M+NO reactions have been developed at the B3LYP/6-311+G(d) level of theory, and transition states on the isomerization potential energy surfaces have been characterized. Our calculation results show that four BNO isomers, namely, nitrosyl BNO, isonitrosyl BON, side-bonded B- η2-NO and the inserted NBO molecules are stationary points, while for Al and Ga, only the MNO (nitrosyl), MON (isonitrosyl) and the OMN (insertion) molecules are local minimum. The B+NO reaction products are more strongly bonded compared to the Al and Ga+NO systems due to strong covalent bonding. The interactions of B, Al and Ga atoms with NO to generate nitrosyl and isonitrosyl addition molecules are barrierless, but subsequent isomerization reactions to form the side-bonded molecules and the inserted products require activation energy.

Water Hydrogen-Bonding Network Structure and Dynamics at Phospholipid Multibilayer Surface: Femtosecond Mid-IR Pump-Probe Spectroscopy.

PubMed

Kundu, Achintya; Błasiak, Bartosz; Lim, Joon-Hyung; Kwak, Kyungwon; Cho, Minhaeng

2016-03-03

The water hydrogen-bonding network at a lipid bilayer surface is crucial to understanding membrane structures and its functional activities. With a phospholipid multibilayer mimicking a biological membrane, we study the temperature dependence of water hydrogen-bonding structure, distribution, and dynamics at a lipid multibilayer surface using femtosecond mid-IR pump-probe spectroscopy. We observe two distinguished vibrational lifetime components. The fast component (0.6 ps) is associated with water interacting with a phosphate part, whereas the slow component (1.9 ps) is with bulk-like choline-associated water. With increasing temperature, the vibrational lifetime of phosphate-associated water remains constant though its relative fraction dramatically increases. The OD stretch vibrational lifetime of choline-bound water slows down in a sigmoidal fashion with respect to temperature, indicating a noticeable change of the water environment upon the phase transition. The water structure and dynamics are thus shown to be in quantitative correlation with the structural change of liquid multibilayer upon the gel-to-liquid crystal phase transition.

Visible-light-enhanced interactions of hydrogen sulfide with composites of zinc (oxy)hydroxide with graphite oxide and graphene.

PubMed

Seredych, Mykola; Mabayoje, Oluwaniyi; Bandosz, Teresa J

2012-01-17

Composites of zinc(oxy)hydroxide-graphite oxide and of zinc(oxy)hydroxide-graphene were used as adsorbents of hydrogen sulfide under ambient conditions. The initial and exhausted samples were characterized by XRD, FTIR, potentiometric titration, EDX, thermal analysis, and nitrogen adsorption. An increase in the amount of H(2)S adsorbed/oxidized on their surfaces in comparison with that of pure Zn(OH)(2) is linked to the structure of the composite, the relative number of terminal hydroxyls, and the kind of graphene-based phase used. Although terminal groups are activated by a photochemical process, the graphite oxide component owing to the chemical bonds with the zinc(oxy)hydroxide phase and conductive properties helps in electron transfer, leading to more efficient oxygen activation via the formation of superoxide ions. Elemental sulfur, zinc sulfide, sulfite, and sulfate are formed on the surface. The formation of sulfur compounds on the surface of zinc(oxy)hydroxide during the course of the breakthrough experiments and thus Zn(OH)(2)-ZnS heterojunctions can also contribute to the increased surface activity of our materials. The results show the superiority of graphite oxide in the formation of composites owing to its active surface chemistry and the possibility of interface bond formation, leading to an increase in the number of electron-transfer reactions. © 2011 American Chemical Society

Laser Surface Preparation and Bonding of Aerospace Structural Composites

NASA Technical Reports Server (NTRS)

Belcher, Marcus A.; Wohl, Christopher J.; Connell, John W.

2009-01-01

A Nd:YAG laser was used to etch patterns conducive to adhesive bonding onto CFRP surfaces. These were compared to typical pre-bonding surface treatments including grit blasting, manual abrasion, and peel ply. Laser treated composites were then subjected to optical microscopy, contact angle measurements, and post-bonding mechanical testing.

Influence of air-powder polishing on bond strength and surface-free energy of universal adhesive systems.

PubMed

Tamura, Yukie; Takamizawa, Toshiki; Shimamura, Yutaka; Akiba, Shunsuke; Yabuki, Chiaki; Imai, Arisa; Tsujimoto, Akimasa; Kurokawa, Hiroyasu; Miyazaki, Masashi

2017-11-29

The influences of air-powder polishing with glycine or sodium bicarbonate powders on shear bond strengths (SBS) and surface-free energies of universal adhesives were examined. Scotchbond Universal Adhesive (SU, 3M ESPE), G-Premio Bond (GP, GC), Adhese Universal (AU, Ivoclar Vivadent), and All-Bond Universal (AB, Bisco) were used in this study. Bovine dentin surfaces were air polished with glycine or sodium bicarbonate powders prior to the bonding procedure, and resin pastes were bonded to the dentin surface using universal adhesives. SBSs were determined after 24-h storage in distilled water at 37°C. Surface-free energy was then determined by measuring contact angles using three test liquids on dentin surfaces. Significantly lower SBSs were observed for dentin that was air-powder polished and surface-free energies were concomitantly lowered. This study indicated that air-powder polishing influences SBSs and surface-free energies. However, glycine powder produced smaller changes in these surface parameters than sodium bicarbonate.

Effect of nanoscale surface roughness on the bonding energy of direct-bonded silicon wafers

NASA Astrophysics Data System (ADS)

Miki, N.; Spearing, S. M.

2003-11-01

Direct wafer bonding of silicon wafers is a promising technology for manufacturing three-dimensional complex microelectromechanical systems as well as silicon-on-insulator substrates. Previous work has reported that the bond quality declines with increasing surface roughness, however, this relationship has not been quantified. This article explicitly correlates the bond quality, which is quantified by the apparent bonding energy, and the surface morphology via the bearing ratio, which describes the area of surface lying above a given depth. The apparent bonding energy is considered to be proportional to the real area of contact. The effective area of contact is defined as the area sufficiently close to contribute to the attractive force between the two bonding wafers. Experiments were conducted with silicon wafers whose surfaces were roughened by a buffered oxide etch solution (BOE, HF:NH4F=1:7) and/or a potassium hydroxide solution. The surface roughness was measured by atomic force microscopy. The wafers were direct bonded to polished "monitor" wafers following a standard RCA cleaning and the resulting bonding energy was measured by the crack-opening method. The experimental results revealed a clear correlation between the bonding energy and the bearing ratio. A bearing depth of ˜1.4 nm was found to be appropriate for the characterization of direct-bonded silicon at room temperature, which is consistent with the thickness of the water layer at the interface responsible for the hydrogen bonds that link the mating wafers.

Comparison of the effect of different surface treatments on the bond strength of different cements with nickel chromium metal alloy: An in vitro study

PubMed Central

Kapoor, Saumya; Balakrishnan, Dhanasekar

2017-01-01

Background For success of any indirect metal restoration, a strong bond between cement and the intaglio surface of metal is imperative. The aim of this study is to evaluate and compare the effect of different surface treatment on the tensile and shear bond strength of different cements with nickel–chromium alloy. Material and Methods 120 premolars were sectioned horizontally parallel to the occlusal surface to expose the dentin. Wax patterns were fabricated for individual tooth followed by casting them in nickel chromium alloy. 60 samples were tested for tensile bond strength, and the remaining 60 for shear bond strength. The samples were divided into three groups (of 20 samples each) as per the following surface treatment: oxidation only, oxidation and sandblasting, or oxidation, sandblasting followed by application of alloy primer. Each group was subdivided into 2 subgroups of 10 samples each, according to the bonding cement i.e RM-GIC and resin cement. Samples were subjected to thermocycling procedure followed by evaluation of bond strength. Results Two-way analyses of variance (ANOVA) was performed to compare the means of tensile and shear bond strength across type of surface treatment and cement, followed by post hoc parametric analysis. For all tests ‘p’ value of less than 0.05 was considered statistically significant. Conclusions The surface treatment of oxidation and sandblasting followed by application of alloy primer offered the maximum tensile and shear bond strength for both RM GIC and resin cement. Resin cement exhibited greater tensile and shear bond strength than RM-GIC for all the three surface treatment methods. Key words:Resin cement, resin modified glass ionomer cement, oxidation, sandblasting, alloy primer, tensile bond strength, shear bond strength, universal testing machine. PMID:28828160

Tensile Bond Strength of Self Adhesive Resin Cement After Various Surface Treatment of Enamel

PubMed Central

Sekhri, Sahil; Garg, Sandeep

2016-01-01

Introduction In self adhesive resin cements adhesion is achieved to dental surface without surface pre-treatment, and requires only single step application. This makes the luting procedure less technique-sensitive and decreases postoperative sensitivity. Aim The purpose of this study was to evaluate bond strength of self adhesive resin after surface treatment of enamel for bonding base metal alloy. Materials and Methods On the labial surface of 64 central incisor rectangular base metal block of dimension 6 mm length, 5mm width and 1 mm height was cemented with RelyX U200 and Maxcem Elite self adhesive cements with and without surface treatment of enamel. Surface treatment of enamel was application of etchant, one step bonding agent and both. Tensile bond strength of specimen was measured with universal testing machine at a cross head speed of 1mm/min. Results Least tensile bond strength (MPa) was in control group i.e. 1.33 (0.32) & 1.59 (0.299), Highest bond strength observed when enamel treated with both etchant and bonding agent i.e. 2.72 (0.43) & 2.97 (0.19) for Relyx U200 and Elite cement. When alone etchant and bonding agent were applied alone bond strength is 2.19 (0.18) & 2.24 (0.47) for Relyx U200, and 2.38 (0.27) 2.49 (0.16) for Max-cem elite. Mean bond strength was higher in case of Max-cem Elite as compared to RelyX U200 resin cement, although differences were non–significant (p > 0.05). Conclusion Surface treatment of enamel increases the bond strength of self adhesive resin cement. PMID:26894165

[Influence of different porcelain surface treatment method on the bonding of metal brackets to porcelain].

PubMed

Fan, Cun-Hui; Chen, Jie; Liu, Xin-Qiang; Ma, Xin

2005-08-01

To investigate the influence of different porcelain surface treatment methods on the shear bond strength of metal brackets bonded to porcelain. 80 porcelain facets were divided randomly into two groups according to different adhesive material that was used to bond metal brackets. Adhesive material were Jing-Jin enamel adhesive and light-cured composite resin. Each group was further divided into 4 subgroups according to different surface treatment methods, which were acid etching with 37% phosphoric acid (H3PO4), acid etching with 9.6% hydrofluoric acid (HF), deglazing by grinding and silanating the porcelain surface. All specimens were stored in 37 degrees C water for 24 hours and then the shear bond strength and the porcelain fracture after debonding was determined. The porcelain surfaces after HF etching, H3PO4 etching and deglazing by grinding were examined by scanning electron microscopy respectively. The shear bond strengths in the HF etching groups, the deglazing groups and the silanating groups were much greater than that in the phosphoric etching groups (P < 0.01). Adequate orthodontic bonding strength was achieved both when bonded with light-cured composite resin after deglazing by grinding and when bonded with either of these adhesives after HF etching or surface silanating. There were no differences in the rates of porcelain fractures among groups (P > 0.05). HF etching, deglazing by grinding and silanating can all increase the shear bond strength between metal bracket and porcelain. Surface silanating of porcelain is a better surface treatment when metal brackets bonded to porcelain.

Enhanced van der Waals epitaxy via electron transfer enabled interfacial dative bond formation

DOE PAGES

Xie, Weiyu; Lu, Toh -Ming; Wang, Gwo -Ching; ...

2017-11-14

Enhanced van der Waals (vdW) epitaxy of semiconductors on a layered vdW substrate is identified as the formation of dative bonds. For example, despite that NbSe 2 is a vdW layeredmaterial, first-principles calculations reveal that the bond strength at a CdTe-NbSe 2 interface is five times as large as that of vdW interactions at a CdTe-graphene interface. Finally, the unconventional chemistry here is enabled by an effective net electron transfer from Cd dangling-bond states at a CdTe surface to metallic nonbonding NbSe 2 states, which is a necessary condition to activate the Cd for enhanced binding with Se.

Enhanced van der Waals epitaxy via electron transfer enabled interfacial dative bond formation

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

Xie, Weiyu; Lu, Toh -Ming; Wang, Gwo -Ching

Enhanced van der Waals (vdW) epitaxy of semiconductors on a layered vdW substrate is identified as the formation of dative bonds. For example, despite that NbSe 2 is a vdW layeredmaterial, first-principles calculations reveal that the bond strength at a CdTe-NbSe 2 interface is five times as large as that of vdW interactions at a CdTe-graphene interface. Finally, the unconventional chemistry here is enabled by an effective net electron transfer from Cd dangling-bond states at a CdTe surface to metallic nonbonding NbSe 2 states, which is a necessary condition to activate the Cd for enhanced binding with Se.

CO adsorption on (111) and (100) surfaces of the Pt sub 3 Ti alloy. Evidence for parallel binding and strong activation of CO

NASA Technical Reports Server (NTRS)

Mehandru, S. P.; Anderson, A. B.; Ross, P. N.

1985-01-01

The CO adsorption on a 40 atom cluster model of the (111) surface and a 36 atom cluster model of the (100) surface of the Pt3Ti alloy was studied. Parallel binding to high coordinate sites associated with Ti and low CO bond scission barriers are predicted for both surfaces. The binding of CO to Pt sites occurs in an upright orientation. These orientations are a consequence of the nature of the CO pi donation interactions with the surface. On the Ti sites the orbitals donate to the nearly empty Ti 3d band and the antibonding counterpart orbitals are empty. On the Pt sites, however, they are in the filled Pt 5d region of the alloy band, which causes CO to bond in a vertical orientation by 5 delta donation from the carbon end.

Repair Bond Strength of Aged Resin Composite after Different Surface and Bonding Treatments

PubMed Central

Wendler, Michael; Belli, Renan; Panzer, Reinhard; Skibbe, Daniel; Petschelt, Anselm; Lohbauer, Ulrich

2016-01-01

The aim of this study was to compare the effect of different mechanical surface treatments and chemical bonding protocols on the tensile bond strength (TBS) of aged composite. Bar specimens were produced using a nanohybrid resin composite and aged in distilled water for 30 days. Different surface treatments (diamond bur, phosphoric acid, silane, and sandblasting with Al2O3 or CoJet Sand), as well as bonding protocols (Primer/Adhesive) were used prior to application of the repair composite. TBS of the specimens was measured and the results were analyzed using analysis of variance (ANOVA) and the Student–Newman–Keuls test (α = 0.05). Mechanically treated surfaces were characterized under SEM and by profilometry. The effect of water aging on the degree of conversion was measured by means of FTIR-ATR spectroscopy. An important increase in the degree of conversion was observed after aging. No significant differences in TBS were observed among the mechanical surface treatments, despite variations in surface roughness profiles. Phosphoric acid etching significantly improved repair bond strength values. The cohesive TBS of the material was only reached using resin bonding agents. Application of an intermediate bonding system plays a key role in achieving reliable repair bond strengths, whereas the kind of mechanical surface treatment appears to play a secondary role. PMID:28773669

Genetic selection reveals the role of a buried, conserved polar residue

PubMed Central

Johnson, R. Jeremy; Lin, Shawn R.; Raines, Ronald T.

2007-01-01

The burial of nonpolar surface area is known to enhance markedly the conformational stability of proteins. The contribution from the burial of polar surface area is less clear. Here, we report on the tolerance to substitution of Ser75 of bovine pancreatic ribonuclease (RNase A), a residue that has the unusual attributes of being buried, conserved, and polar. To identify variants that retain biological function, we used a genetic selection based on the intrinsic cytotoxicity of ribonucleolytic activity. Cell growth at 30°C, 37°C, and 44°C correlated with residue size, indicating that the primary attribute of Ser75 is its small size. The side-chain hydroxyl group of Ser75 forms a hydrogen bond with a main-chain nitrogen. The conformational stability of the S75A variant, which lacks this hydrogen bond, was diminished by ΔΔG = 2.5 kcal/mol. Threonine, which can reinstate this hydrogen bond, provided a catalytically active RNase A variant at higher temperatures than did some smaller residues (including aspartate), indicating that a secondary attribute of Ser75 is the ability of its uncharged side chain to accept a hydrogen bond. These results provide insight on the imperatives for the conservation of a buried polar residue. PMID:17656580

Shear bond strength of a new one-bottle dentin adhesive.

PubMed

Swift, E J; Bayne, S C

1997-08-01

To test the shear bond strength of a new adhesive, 3M Single Bond, to dentin surfaces containing different degrees of moisture. Two commercially available one-bottle adhesives (Prime & Bond, One-Step) and a conventional three-step system (Scotchbond Multi-Purpose Plus) were included for comparison. 120 bovine teeth were embedded in acrylic and the labial surfaces were polished to 600 grit to create standardized dentin surfaces for testing. Resin composite was bonded to dentin using a gelatin capsule technique. Four adhesive systems were evaluated with three different degrees of surface moisture (moist, wet, and overwet). Shear bond strengths of adhesives to dentin were determined using a universal testing machine and analyzed by ANOVA and Tukey's post hoc tests. Single Bond had mean shear bond strengths of 19.2, 23.2 and 20.3 MPa to moist, wet, and overwet dentin, respectively. Bond strengths of the three-component system Scotchbond Multi-Purpose Plus ranged from 23.1 to 25.3 MPa, but were not significantly higher than the values for Single Bond. Prime & Bond had bond strengths similar to those of Single Bond, but One-Step had significantly lower bond strengths (P < 0.05) in the wet and overwet conditions.

Immobilization of Hg(II) in water with polysulfide-rubber (PSR) polymer-coated activated carbon.

PubMed

Kim, Eun-Ah; Seyfferth, Angelia L; Fendorf, Scott; Luthy, Richard G

2011-01-01

An effective mercury removal method using polymer-coated activated carbon was studied for possible use in water treatment. In order to increase the affinity of activated carbon for mercury, a sulfur-rich compound, polysulfide-rubber (PSR) polymer, was effectively coated onto the activated carbon. The polymer was synthesized by condensation polymerization between sodium tetrasulfide and 1,2-dichloroethane in water. PSR-mercury interactions and Hg-S bonding were elucidated from x-ray photoelectron spectroscopy, and Fourier transform infra-red spectroscopy analyses. The sulfur loading levels were controlled by the polymer dose during the coating process and the total surface area of the activated carbon was maintained for the sulfur loading less than 2 wt%. Sorption kinetic studies showed that PSR-coated activated carbon facilitates fast reaction by providing a greater reactive surface area than PSR alone. High sulfur loading on activated carbon enhanced mercury adsorption contributing to a three orders of magnitude reduction in mercury concentration. μ-X-ray absorption near edge spectroscopic analyses of the mercury bound to activated carbon and to PSR on activated carbon suggests the chemical bond with mercury on the surface is a combination of Hg-Cl and Hg-S interaction. The pH effect on mercury removal and adsorption isotherm results indicate competition between protons and mercury for binding to sulfur at low pH. Copyright © 2010. Published by Elsevier Ltd.

Ab initio characterization of coupling strength for all types of dangling-bond pairs on the hydrogen-terminated Si(100)-2 × 1 surface

NASA Astrophysics Data System (ADS)

Shaterzadeh-Yazdi, Zahra; Sanders, Barry C.; DiLabio, Gino A.

2018-04-01

Recent work has suggested that coupled silicon dangling bonds sharing an excess electron may serve as building blocks for quantum-cellular-automata cells and quantum computing schemes when constructed on hydrogen-terminated silicon surfaces. In this work, we employ ab initio density-functional theory to examine the details associated with the coupling between two dangling bonds sharing one excess electron and arranged in various configurations on models of phosphorous-doped hydrogen-terminated silicon (100) surfaces. Our results show that the coupling strength depends strongly on the relative orientation of the dangling bonds on the surface and on the separation between them. The orientation of dangling bonds is determined by the anisotropy of the silicon (100) surface, so this feature of the surface is a significant contributing factor to variations in the strength of coupling between dangling bonds. The results demonstrate that simple models for approximating tunneling, such as the Wentzel-Kramer-Brillouin method, which do not incorporate the details of surface structure, are incapable of providing reasonable estimates of tunneling rates between dangling bonds. The results provide guidance to efforts related to the development of dangling-bond based computing elements.

p53 R175H hydrophobic patch and H-bond reorganization observed by MD simulation.

PubMed

Thayer, Kelly M; Quinn, Taylor R

2016-03-01

Molecular dynamics simulations probe the origins of aberrant functionality of R175H p53, which normally prevent tumorigenesis. This hotspot mutation exhibits loss of its essential zinc cofactor, aggregation, and activation of gain of function promoters, characteristics contributing to the loss of normal p53 activity. This study provided molecular level insight into the reorganization of the hydrogen bonding network and the formation of a hydrophobic patch on the surface of the protein. The hydrogen bonding network globally redistributes at the expense of the stability of the β-sandwich structure, and surface residues reorganize to expose a 250 Å(2) hydrophobic patch of residues covering approximately 2% of the solvent accessible surface. These changes could both stabilize the protein in the conformation exposing the patch to solvent to mediate the reported aggregation, and cause a destabilization in the area associated with DNA binding residues to affect the specificity. The development of the patch prior to loss of zinc indicates that stabilizing the patch quickly may prevent zinc loss. Considerations for rational design of small molecule therapeutics in light of the structural insight has been discussed and it suggest the positive ring around the hydrophobic patch and conserved residues may constitute a druggable site. © 2015 Wiley Periodicals, Inc.

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

Jimenez-Orozco, Carlos; Florez, Elizabeth; Moreno, Andres

A systematic study of ethylene adsorption over δ-MoC(001), TiC(001), and ZrC(001) surfaces was conducted by means of calculations based on periodic density functional theory. The structure and electronic properties of each carbide pristine surface had a strong influence in the bonding of ethylene. It was found that the metal and carbon sites of the carbide could participate in the adsorption process. As a consequence of this, very different bonding mechanisms were seen on δ-MoC(001) and TiC(001). The bonding of the molecule on the TMC(001) systems showed only minor similarities to the type of bonding found on a typical metal likemore » Pt(111). In general, the ethylene binding energy follow the trend in stability: ZrC(001) < TiC(001) < δ-MoC(001) < Pt(111). The van der Waals correction to the energy produces large binding energy values, modifies the stability orders and drives the ethylene closer to the surface but the adsorbate geometry parameters remain unchanged. Ethylene was activated on clearly defined binding geometries, changing its hybridization from sp 2 to sp 3 with an elongation (0.16–0.31 Å) of the C=C bond. As a result, on the basis of this theoretical study, δ-MoC(001) is proposed as a potential catalyst for the hydrogenation of olefins, whereas TiC(001) could be useful for their hydrogenolysis.« less

Role of bonding mechanisms during transfer hydrogenation reaction on heterogeneous catalysts of platinum nanoparticles supported on zinc oxide nanorods

NASA Astrophysics Data System (ADS)

Al-Alawi, Reem A.; Laxman, Karthik; Dastgir, Sarim; Dutta, Joydeep

2016-07-01

For supported heterogeneous catalysis, the interface between a metal nanoparticle and the support plays an important role. In this work the dependency of the catalytic efficiency on the bonding chemistry of platinum nanoparticles supported on zinc oxide (ZnO) nanorods is studied. Platinum nanoparticles were deposited on ZnO nanorods (ZnO NR) using thermal and photochemical processes and the effects on the size, distribution, density and chemical state of the metal nanoparticles upon the catalytic activities are presented. The obtained results indicate that the bonding at Pt-ZnO interface depends on the deposition scheme which can be utilized to modulate the surface chemistry and thus the activity of the supported catalysts. Additionally, uniform distribution of metal on the catalyst support was observed to be more important than the loading density. It is also found that oxidized platinum Pt(IV) (platinum hydroxide) provided a more suitable surface for enhancing the transfer hydrogenation reaction of cyclohexanone with isopropanol compared to zero valent platinum. Photochemically synthesized ZnO supported nanocatalysts were efficient and potentially viable for upscaling to industrial applications.

Correlation of bond strength with surface roughness using a new roughness measurement technique.

PubMed

Winkler, M M; Moore, B K

1994-07-01

The correlation between shear bond strength and surface roughness was investigated using new surface measurement methods. Bonding agents and associated resin composites were applied to set amalgam after mechanically roughening its surface. Surface treatments were noe (as set against glass), 80 grit, and 600 grit abrasive paper. Surface roughness (R(a) as measured parallel and perpendicular (+) to the direction of the polishing scratches and true profile length were measured. A knife-edge was applied (rate = 2.54 mm/min) at the bonding agent/amalgam interface of each sample until failure. Coefficients of determination for mean bond strength vs either roughness (R(a), of profile length were significantly higher for measurements in parallel directions than for those measurements in (+) directions. The shear bond strength to set amalgam for a PENTA-containing adhesives system (L.D. Caulk Division) was not significantly different from that of a PENTA-free adhesive (3M Dental Products Division), even though PENTA has been reported to increase bond strength to nonprecious metals. The shear bond strength of resin composite to amalgam is correlated to surface roughness when it is measured parallel to the polishing scratches. This correlation is significantly lower when surface roughness is measured in the typical manner, perpendicular to the polishing scratches.

Bone bonding at natural and biomaterial surfaces.

PubMed

Davies, John E

2007-12-01

Bone bonding is occurring in each of us and all other terrestrial vertebrates throughout life at bony remodeling sites. The surface created by the bone-resorbing osteoclast provides a three-dimensionally complex surface with which the cement line, the first matrix elaborated during de novo bone formation, interdigitates and is interlocked. The structure and composition of this interfacial bony matrix has been conserved during evolution across species; and we have known for over a decade that this interfacial matrix can be recapitulated at a biomaterial surface implanted in bone, given appropriate healing conditions. No evidence has emerged to suggest that bone bonding to artificial materials is any different from this natural biological process. Given this understanding it is now possible to explain why bone-bonding biomaterials are not restricted to the calcium-phosphate-based bioactive materials as was once thought. Indeed, in the absence of surface porosity, calcium phosphate biomaterials are not bone bonding. On the contrary, non-bonding materials can be rendered bone bonding by modifying their surface topography. This paper argues that the driving force for bone bonding is bone formation by contact osteogenesis, but that this has to occur on a sufficiently stable recipient surface which has micron-scale surface topography with undercuts in the sub-micron scale-range.

Effect of surface contamination on adhesive bonding of cast pure titanium and Ti-6Al-4V alloy.

PubMed

Watanabe, I; Watanabe, E; Yoshida, K; Okabe, T

1999-03-01

There is little information regarding bond strengths of resin cements to cast titanium surfaces contaminated by investment material. This study examined the effect of surface contamination on the shear bond strength of resin cements to cast titanium and Ti-6Al-4V alloy. Two types of disks were cast from commercially pure titanium (CP-Ti) and Ti-6Al-4V alloy ingots using an argon-arc pressure casting unit and a phosphate-bonded Al2 O3 /LiAlSiO6 investment. After casting, disks were subjected to 3 surface treatments: (1) cast surface sandblasted (50 microm-sized Al2 O3 ) for 30 seconds; (2) metal surface sanded with silicon-carbide paper (600 grit) after grinding the contaminated cast surface (approximately 200 microm in thickness); and (3) metal surface sandblasted for 30 seconds after treatment 2. Surface structures were examined after each treatment with SEM and optical microscopy. Each type of disk was then bonded with 2 types of luting materials. Bonded specimens were subjected to thermocycling for up to 50,000 cycles, and shear bond strengths were determined after 0 (baseline) and 50,000 thermocycles. Results were statistically analyzed with 3-way ANOVA (P <.05). Microscopic observation of cast CP-Ti and Ti-6Al-4V exhibited noticeable structures on the cast surfaces apparently contaminated with investment material. However, there were no statistical differences (P >.05) in the bond strengths of both cements between contaminated (treatment 1) and uncontaminated surfaces (treatment 3) for both metals at baseline and after 50,000 thermocycles. The bond strength of specimens sanded with silicon-carbide paper (treatment 2) deteriorated dramatically after 50,000 thermocycles. Contamination of the cast metal surfaces by elements of the investment during casting did not affect bond strengths of the luting materials to CP-Ti and Ti-6Al-4V.

The chemical properties of bimetallic surfaces: Importance of ensemble and electronic effects in the adsorption of sulfur and SO 2

NASA Astrophysics Data System (ADS)

Rodriguez, José A.

The understanding of the interaction of sulfur with bimetallic surfaces is a critical issue for preventing the deactivation of hydrocarbon reforming catalysts and for the design of better hydrodesulfurization catalysts. The alloying or combination of two metals can lead to materials with special chemical properties due to an interplay of “ensemble” and “electronic” effects. In recent years, several new interesting phenomena have been discovered when studying the interaction of sulfur with bimetallic surfaces using the modern techniques of surface science. Very small amounts of sulfur are able to induce dramatic changes in the morphology of bimetallic surfaces that combine noble metals (Cu, Ag, Au) and transition metals. This phenomenon can lead to big modifications in the activity and selectivity of bimetallic catalysts used for hydrocarbon reforming. In many cases, bimetallic bonding produces a significant redistribution of charge around the bonded metals. The electronic perturbations associated with the formation of a heteronuclear metal-metal bond can affect the reactivity of the bonded metals toward sulfur. This can be a very important issue to consider when trying to minimize the negative effects of sulfur poisoning (Sn/Pt versus Ag/Pt and Cu/Pt catalysts) or when trying to improve the performance of desulfurization catalysts (Co/Mo and Ni/Mo systems). Clearly much more work is necessary in this area, but new concepts are emerging that can be useful for designing more efficient bimetallic catalysts.

Effect of Er:YAG laser irradiation on bonding property of zirconia ceramics to resin cement.

PubMed

Lin, Yihua; Song, Xiaomeng; Chen, Yaming; Zhu, Qingping; Zhang, Wei

2013-12-01

This study aimed to investigate whether or not an erbium: yttrium-aluminum-garnet (Er:YAG) laser could improve the bonding property of zirconia ceramics to resin cement. Surface treatments can improve the bonding properties of dental ceramics. However, little is known about the effect of Er:YAG laser irradiated on zirconia ceramics. Specimens of zirconia ceramic pieces were made, and randomly divided into 11 groups according to surface treatments, including one control group (no treatment), one air abrasion group, and nine Er:YAG laser groups. The laser groups were subdivided by applying different energy intensities (100, 200, or 300 mJ) and irradiation times (5, 10, or 15 sec). After surface treatments, ceramic pieces had their surface morphology observed, and their surface roughness was measured. All specimens were bonded to resin cement. Shear bond strength was measured after the bonded specimens were stored in water for 24 h, and additionally aged by thermocycling. Statistical analyses were performed using one way analysis of variance (ANOVA) and Tukey's test for shear bond strength, and Dunnett's t test for surface roughness, with α=0.05. Er:YAG laser irradiation changed the morphological characteristics of zirconia ceramics. Higher energy intensities (200, 300 mJ) could roughen the ceramics, but also caused surface cracks. There were no significant differences in the bond strength between the control group and the laser groups treated with different energy intensities or irradiation times. Air abrasion with alumina particles induced highest surface roughness and shear bond strength. Er:YAG laser irradiation cannot improve the bonding property of zirconia ceramics to resin cement. Enhancing irradiation intensities and extending irradiation time have no benefit on the bond of the ceramics, and might cause material defect.

Platinum-catalyzed hydrolysis etching of SiC in water: A density functional theory study

NASA Astrophysics Data System (ADS)

Van Bui, Pho; Toh, Daisetsu; Isohashi, Ai; Matsuyama, Satoshi; Inagaki, Kouji; Sano, Yasuhisa; Yamauchi, Kazuto; Morikawa, Yoshitada

2018-05-01

A comprehensive study of the physicochemical interactions and the reaction mechanism of SiC etching with water by Pt catalysts can reveal key details about the surface treatment and catalytic phenomena at interfaces. Therefore, density functional theory simulations were performed to study the kinetics of Pt-assisted water dissociation and breaking of a Si–C bond compared to the HF-assisted mechanism. These calculations carefully considered the elastic and chemical interaction energies at the Pt–SiC interface, activation barriers of Si–C bond dissociation, and the catalytic role of Pt. It was found that the Pt-catalyzed etching of SiC in water is initiated via hydrolysis reactions that break the topmost Si–C bonds. The activation barrier strongly depends on the elastic and chemical interactions. However, chemical interactions are a dominant factor and mainly contribute to the lowering of the activation barrier, resulting in an increased rate of reaction.

Atomic basis for therapeutic activation of neuronal potassium channels

NASA Astrophysics Data System (ADS)

Kim, Robin Y.; Yau, Michael C.; Galpin, Jason D.; Seebohm, Guiscard; Ahern, Christopher A.; Pless, Stephan A.; Kurata, Harley T.

2015-09-01

Retigabine is a recently approved anticonvulsant that acts by potentiating neuronal M-current generated by KCNQ2-5 channels, interacting with a conserved Trp residue in the channel pore domain. Using unnatural amino-acid mutagenesis, we subtly altered the properties of this Trp to reveal specific chemical interactions required for retigabine action. Introduction of a non-natural isosteric H-bond-deficient Trp analogue abolishes channel potentiation, indicating that retigabine effects rely strongly on formation of a H-bond with the conserved pore Trp. Supporting this model, substitution with fluorinated Trp analogues, with increased H-bonding propensity, strengthens retigabine potency. In addition, potency of numerous retigabine analogues correlates with the negative electrostatic surface potential of a carbonyl/carbamate oxygen atom present in most KCNQ activators. These findings functionally pinpoint an atomic-scale interaction essential for effects of retigabine and provide stringent constraints that may guide rational improvement of the emerging drug class of KCNQ channel activators.

ADHESIVES WITH DIFFERENT PHS: EFFECT ON THE MTBS OF CHEMICALLY ACTIVATED AND LIGHT-ACTIVATED COMPOSITES TO HUMAN DENTIN

PubMed Central

Mallmann, André; de Melo, Renata Marques; Estrela, Verbênia; Pelogia, Fernanda; Campos, Laura; Bottino, Marco Antonio; Valandro, Luiz Felipe

2007-01-01

Purpose: To evaluate the bond strength between human dentin and composites, using two light-activated single-bottle total-etch adhesive systems with different pHs combined with chemically activated and light-activated-composites. The tested hypothesis was that the dentin bond strength is not influenced by an adhesive system of low pH, combined with chemically activated or light-activated composites. Material and Method: Flat dentin surfaces of twenty-eight human third molars were allocated in 4 groups (n=7), depending on the adhesive system: (One Step Plus-OS and Prime & Bond NT-PB) and composite (light-activated Filtek Z-100 [Z100] and chemically activated Bisfil 2B [B2B]). Each adhesive system was applied on acid-etched dentin and then one of the composites was added to form a 5 mm-high resin block. The specimens were stored in tap water (37°C/24 h) and sectioned into two axes, x and y. This was done with a diamond disk under coolant irrigation to obtain beams with a cross-section area of approximately 0.8 mm2. Each specimen was then attached to a custom-made device and submitted to the microtensile test (1 mm.min−1). Data were analyzed using two-way ANOVA and Tukey’s tests (p<0.05). Results: The anticipated hypothesis was not confirmed (p<0.0001). The bond strengths (MPa) were not statistically different between the two adhesive systems when light-activated composite was used (OS+Z100 = 24.7±7.1ª; PB+Z100 = 23.8±5.7ª). However, with use of the chemically activated composite (B2B), PB (7.8±3.6b MPa) showed significantly lower dentin bond strengths than OS (32.2±7.6ª). Conclusion: The low pH of the adhesive system can affect the bond of chemically activated composite to dentin. On the other hand, under the present conditions, the low pH did not seem to affect the bond of light-activated composites to dentin significantly. PMID:19089142

Adhesives with different pHs: effect on the MTBS of chemically activated and light-activated composites to human dentin.

PubMed

Mallmann, André; de Melo, Renata Marques; Estrela, Verbênia; Pelogia, Fernanda; Campos, Laura; Bottino, Marco Antonio; Valandro, Luiz Felipe

2007-08-01

To evaluate the bond strength between human dentin and composites, using two light-activated single-bottle total-etch adhesive systems with different pHs combined with chemically activated and light-activated-composites. The tested hypothesis was that the dentin bond strength is not influenced by an adhesive system of low pH, combined with chemically activated or light-activated composites. Flat dentin surfaces of twenty-eight human third molars were allocated in 4 groups (n=7), depending on the adhesive system: (One Step Plus-OS and Prime & Bond NT-PB) and composite (light-activated Filtek Z-100 [Z100] and chemically activated Bisfil 2B [B2B]). Each adhesive system was applied on acid-etched dentin and then one of the composites was added to form a 5 mm-high resin block. The specimens were stored in tap water (37 degrees C/24 h) and sectioned into two axes, x and y. This was done with a diamond disk under coolant irrigation to obtain beams with a cross-section area of approximately 0.8 mm(2). Each specimen was then attached to a custom-made device and submitted to the microtensile test (1 mm*min-1). Data were analyzed using two-way ANOVA and Tukey's tests (p<0.05). The anticipated hypothesis was not confirmed (p<0.0001). The bond strengths (MPa) were not statistically different between the two adhesive systems when light-activated composite was used (OS+Z100 = 24.7+/-7.1 feminine; PB+Z100 = 23.8+/-5.7 feminine). However, with use of the chemically activated composite (B2B), PB (7.8+/-3.6b MPa) showed significantly lower dentin bond strengths than OS (32.2+/-7.6 feminine). The low pH of the adhesive system can affect the bond of chemically activated composite to dentin. On the other hand, under the present conditions, the low pH did not seem to affect the bond of light-activated composites to dentin significantly.

Internal coating of zirconia restoration with silica-based ceramic improves bonding of resin cement to dental zirconia ceramic.

PubMed

Kitayama, Shuzo; Nikaido, Toru; Ikeda, Masaomi; Alireza, Sadr; Miura, Hiroyuki; Tagami, Junji

2010-01-01

Resin bonding to zirconia ceramic cannot be established by standard methods that are utilized for conventional silica-based dental ceramics. This study was aimed to examine the tensile bond strength of resin cement to zirconia ceramic using a new laboratory technique. Sixty-four zirconia ceramic specimens were air-abraded using Al2O3 particles and divided into two groups; the control group with no pretreatment (Control), and the group pretreated using the internal coating technique (INT), in which the surface of the zirconia specimens were thinly coated by fusing silica-based ceramic and air-abraded in the same manner. The specimens in each group were further divided into two subgroups according to the silane coupling agents applied; a mixture of dentin primer/silane coupling agent (Clearfil SE Bond Primer/Porcelain Bond Activator) or a newly developed single-component silane coupling agent (Clearfil Ceramic Primer). After bonding with dual-cured resin cement (Panavia F 2.0), they were stored in water for 24 h and half of them were additionally subjected to thermal cycling. The tensile bond strengths were tested using a universal testing machine. ANOVAs revealed significant influence of ceramic surface pretreatment (p<0.001), silane coupling agent (p<0.001) and thermal cycling (p<0.001); the INT coating technique significantly increased the bond strengths of resin cement to zirconia ceramic, whereas thermal cycling significantly decreased the bond strengths. The use of a single-component silane coupling agent demonstrated significantly higher bond strengths than that of a mixture of dentin primer/silane coupling agent. The internal coating of zirconia dental restorations with silica-based ceramic followed by silanization may be indicated in order to achieve better bonding for the clinical success.

Nanomagnets La0.8Pb0.2(Fe0.8Co0.2)O3 assembled with a bonded surface graphene oxide: sensitive for sensing small gas molecules.

PubMed

Bhargav, K K; Ram, S; Majumder, S B

2012-04-01

Nanocrystallites La0.8Pb0.2(Fe0.8Co0.2)O3 (LPFC) when bonded through a surface layer (carbon) in small ensembles display surface sensitive magnetism useful for biological probes, electrodes, and toxic gas sensors. A simple dispersion and hydrolysis of the salts in ethylene glycol (EG) in water is explored to form ensembles of the nanocrystallites (NCs) by combustion of a liquid precursor gel slowly in microwave at 70-80 dgrees C (apparent) in a closed container in air. In a dilute sample, the EG molecules mediate hydrolyzed species to configure in small groups in process to form a gel. Proposed models describe how a residual carbon bridges a stable bonded layer of a graphene-oxide-like hybrid structure on the LPFC-NCs in attenuating the magnetic structure. SEM images, measured from a pelletized sample which was used to study the gas sensing features in terms of the electrical resistance, describe plate shaped NCs, typically 30-60 nm widths, 60-180 nm lengths and -50 m2/g surface area (after heating at -750 degrees C). These NCs are arranged in ensembles (200-900 nm size). As per the X-ray diffraction, the plates (a Pnma orthorhombic structure) bear only small strain -0.0023 N/m2 and oxygen vacancies. The phonon and electronic bands from a bonded surface layer disappear when it is etched out slowly by heating above 550 degrees C in air. The surface layer actively promotes selective H2 gas sensor properties.

Influence of handpiece maintenance sprays on resin bonding to dentin.

PubMed

Sugawara, Toyotarou; Kameyama, Atsushi; Haruyama, Akiko; Oishi, Takumi; Kukidome, Nobuyuki; Takase, Yasuaki; Tsunoda, Masatake

2010-01-01

To investigate the influence of maintenance spray on resin bonding to dentin. The crown of extracted, caries-free human molars was transversally sectioned with a model trimmer to prepare the dentin surfaces from mid-coronal sound dentin, and then uniformly abraded with #600 silicon carbide paper. The dentin surfaces were randomly divided into three groups: oil-free spray group where maintenance cleaner for air bearing handpieces was sprayed onto the dentin surface for 1 s and rinsed with water spray for 30 s; oil-containing spray group where maintenance cleaner for micro motor handpieces was sprayed onto the dentin surface for 1 s and rinsed with water spray for 30 s; and control group where the surface was rinsed with water spray for 30 s and then air-dried. These surfaces were then bonded with Clearfil SE Bond (Kuraray Medical), and resin composite (Clearfil AP-X, Kuraray Medical) build-up crowns were incrementally constructed on the bonded surfaces. After storage for 24 h in 37°C water, the bonded teeth were sectioned into hour-glass shaped slices (0.7-mm thick) perpendicular to the bonded surfaces. The specimens were then subjected to microtensile bond strength (μTBS) testing at a crosshead speed of 1.0 mm/min. Data were analyzed with one-way ANOVA and the Tukey-Kramer test. Maintenance spray-contaminated specimens (oil-free and oil-containing spray groups) showed significantly lower μTBS than control specimens (P < 0.05). However, there was no significant difference between the spray-contaminated groups (P > 0.05). Maintenance spray significantly reduces the bond strength of Clearfil SE Bond to dentin.

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

Mei, Donghai; Lebarbier, Vanessa M.; Rousseau, Roger

In a combined experimental and first-principles density functional theory (DFT) study, benzene steam reforming (BSR) over MgAl 2O 4 supported Rh and Ir catalysts was investigated. Experimentally, it has been found that both highly dispersed Rh and Ir clusters (1-2 nm) on the MgAl 2O 4 spinel support are stable during the BSR in the temperature range of 700-850°C. Compared to the Ir/MgAl 2O 4 catalyst, the Rh/MgAl 2O 4 catalyst is more active with higher benzene turnover frequency and conversion. At typical steam conditions with the steam-to-carbon ratio > 12, the benzene conversion is only a weak function ofmore » the H 2O concentration in the feed. This suggests that the initial benzene decomposition step rather than the benzene adsorption is most likely the rate-determined step in BSR over supported Rh and Ir catalysts. In order to understand the differences between the two catalysts, we followed with a comparative DFT study of initial benzene decomposition pathways over two representative model systems for each supported metal (Rh and Ir) catalysts. A periodic terrace (111) surface and an amorphous 50-atom metal cluster with a diameter of 1.0 nm were used to represent the two supported model catalysts under low and high dispersion conditions. Our DFT results show that the decreasing catalyst particle size enhances the benzene decomposition on supported Rh catalysts by lowering both C-C and C-H bond scission. The activation barriers of the C-C and the C-H bond scission decrease from 1.60 and 1.61 eV on the Rh(111) surface to 1.34 and 1.26 eV on the Rh50 cluster. For supported Ir catalysts, the decreasing particle size only affects the C-C scission. The activation barrier of the C-C scission of benzene decreases from 1.60 eV on the Ir(111) surface to 1.35 eV on the Ir50 cluster while the barriers of the C-H scission are practically the same. The experimentally measured higher BSR activity on the supported highly dispersed Rh catalyst can be rationalized by the thermodynamic limitation for the very first C-C bond scission of benzene on the small Ir50 catalyst. The C-C bond scission of benzene on the small Ir50 catalyst is highly endothermic although the barrier is competitive with the barriers of both the C-C and the C-H bond-breakings on the small Rh50 catalyst. The calculations also imply that, for the supported Rh catalysts the C-C and C-H bond scissions are competitive, independently of the Rh cluster sizes. After the initial dissociation step via either the C-C or the C-H bond scission, the C-H bond breaking seems to be more favorable rather than the C-C bond breaking on the larger Rh terrace surface. This work was financially supported by the United States Department of Energy’s Office of Biomass Program’s. Computing time was granted by a user project at the Molecular Science Computing Facility in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory.« less

Locally measuring the adhesion of InP directly bonded on sub-100 nm patterned Si.

PubMed

Pantzas, K; Le Bourhis, E; Patriarche, G; Troadec, D; Beaudoin, G; Itawi, A; Sagnes, I; Talneau, A

2016-03-18

A nano-scale analogue to the double cantilever experiment that combines instrumented nano-indentation and atomic force microscopy is used to precisely and locally measure the adhesion of InP bonded on sub-100 nm patterned Si using oxide-free or oxide-mediated bonding. Surface-bonding energies of 0.548 and 0.628 J m(-2), respectively, are reported. These energies correspond in turn to 51% and 57% of the surface bonding energy measured in unpatterned regions on the same samples, i.e. the proportion of unetched Si surface in the patterned areas. The results show that bonding on patterned surfaces can be as robust as on unpatterned surfaces, provided care is taken with the post-patterning surface preparation process and, therefore, open the path towards innovative designs that include patterns embedded in the Si guiding layer of hybrid III-V/Si photonic integrated circuits.

DFT study on the interaction of TiO2 (001) surface with HCHO molecules

NASA Astrophysics Data System (ADS)

Wu, Guofei; Zhao, Cuihua; Guo, Changqing; Chen, Jianhua; Zhang, Yibing; Li, Yuqiong

2018-01-01

The interactions of formaldehyde (HCHO) molecule with TiO2 (001) surface were studied using density functional theory calculations. HCHO molecules are dissociated by the cleavage of Csbnd H bonds after adsorption on TiO2 surface. The strong interactions between HCHO melecules and TiO2 surface are largely attributed to the bonding of hydrogen of HCHO and oxygen of TiO2 surface, which is mainly from the hybridization of the H 1s, O 2p and O 2s. The newly formed Hsbnd O bonds cause the structure changes of TiO2 surface, and lead to the cleavage of Osbnd Ti bond of TiO2 surface. The Csbnd O bond that the dissociated remains of HCHO and newly formed Hsbnd O bond can be oxidized to form carbon dioxide and water in subsequent action by oxygen from the atomosphere. The charges transfer from HCHO to TiO2 surface, and the sum amount of the charges transferred from four HCHO molecules to TiO2 surface is bigger than that from one HCHO molecule to TiO2 surface due to the combined interaction of four HCHO molecules with TiO2 surface.

Characterizing ceramics and the interfacial adhesion to resin: II- the relationship of surface treatment, bond strength, interfacial toughness and fractography.

PubMed

Della-Bona, Alvaro

2005-06-01

The clinical success of resin bonding procedures for indirect ceramic restorations and ceramic repairs depends on the quality and durability of the bond between the ceramic and the resin. The quality of this bond will depend upon the bonding mechanisms that are controlled in part by the surface treatment that promote micromechanical and/or chemical bonding to the substrate. The objective of this review is to correlate interfacial toughness (K A) with fracture surface morphological parameters of the dental ceramic-resin systems as a function of ceramic surface treatment. This analysis is designed to identify mechanisms that promote adhesion of these ceramic-resin systems and an appropriate bond test method to yield relevant adhesion performance data.

Composite pipe to metal joint

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

Leslie, James C.; Leslie, II, James C.; Heard, James

A method for making a metal to composite tube joint including selecting an elongated interior fitting constructed with an exterior barrel, reduced in exterior diameter to form a distally facing annular shoulder and then projecting still further distally to form an interior sleeve having a radially outwardly facing bonding surface. Selecting an elongated metal outer sleeve formed proximally with a collar constructed for receipt over the barrel and increased in interior diameter and projecting distally to form an exterior sleeve having a radially inwardly facing bonding surface cooperating with the first bonding surface to form an annulus receiving an extremitymore » of a composite tube and a bond bonding the extremity of the tube to the bonding surfaces.« less

Metal modified tungsten carbide (WC) for catalytic and electrocatalytic applications

NASA Astrophysics Data System (ADS)

Mellinger, Zachary J.

One of the major challenges in the commercialization of proton exchange membrane fuel cells (PEMFC) is the cost, and low CO tolerance of the anode electrocatalyst material. The anode typically requires a high loading of precious metal electrocatalyst (Pt or Pt--Ru) to obtain a useful amount of electrical energy from the electrooxidation of methanol (CH3OH) or ethanol (C2H5OH). The complete electro--oxidation of methanol or ethanol on these catalysts produces strongly adsorbed CO on the surface, which reduces the activity of the Pt or Pt--Ru catalysts. Another major disadvantage of these electrocatalyst components is the scarcity and consequently high price of both Pt and Ru. Tungsten monocarbide (WC) has shown similar catalytic properties to Pt, leading to the utilization of WC and metal modified WC as replacements to Pt and Pt--Ru. In this thesis we investigated WC and Pt--modified WC as a potentially more CO--tolerant electrocatalysts as compared to pure Pt. These catalysts would reduce or remove the high loading of Pt used industrially. The binding energy of CO, estimated using temperature programmed desorption, is weaker on WC and Pt/WC than on Pt, suggesting that it should be easier to oxidize CO on WC and Pt/WC. This hypothesis was verified using cyclic voltammetry to compare the electro--oxidation of CO on WC, Pt/WC, and Pt supported on carbon substrates, which showed a lower voltage for the onset of oxidation of CO on WC and Pt/WC than on Pt. After observing these improved properties on the Pt/WC catalysts, we decided to expand our studies to investigate Pd--modified WC as Pd is less expensive than Pt and has shown more ideal properties for alcohol electrocatalysis in alkaline media. Pd/WC showed a lower binding energy of CO than both its parent metal Pd as well as Pt. Then, density functional theory (DFT) calculations were performed to determine how the presence of Pd affected the bonding of methanol and ethanol on the WC surface. The DFT studies showed that the binding energies for methanol and methoxy as well as ethanol and ethoxy on one monolayer (ML) Pd/WC are more similar to Pd than to WC. This predicts that the ML Pd/WC surface should have catalytic properties more similar to Pd than to WC. Ultra--high vacuum (UHV) experiments were then performed to determine the reaction products and pathways for methanol and ethanol on Pd(111), WC, and Pd/WC surfaces. These studies showed that the WC surface was very active toward the O--H bond cleavage to produce a methoxy intermediate, although WC was also undesirable because it was active for C--O bond scission and less active for the C--H bond scission. Adding Pd on WC enhanced the scission of the C--H bonds of methoxy while removing the C--O bond scission reaction pathway, suggesting a synergistic effect of using Pd/WC as electrocatalysts for methanol and ethanol decomposition. Dissociation of water, which is important for CO tolerance, was also investigated using UHV techniques with the conclusion that both the WC and Pd/WC surfaces dissociated water. The predictions from UHV studies was verified in electrochemical experiments using cyclic voltammetry (CV) and chronoamperometry (CA) measurements of electro--oxidation of methanol and ethanol in an alkaline environment. These experiments showed that Pd/WC was electrochemically active towards methanol and ethanol decomposition and has greater electrochemical stability over time than pure Pd, potentially due to higher CO tolerance for Pd/WC.

In situ studies of surface of NiFe 2O 4 catalyst during complete oxidation of methane

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

Zhang, Shiran; Shan, Junjun; Nie, Longhui

2015-12-21

Here, NiFe 2O 4 with an inverse spinel structure exhibits high activity for a complete oxidation of methane at 400 °C–425 °C and a higher temperature. The surface of the catalyst and its adsorbates were well characterized with ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and in situ infrared spectroscopy (IR). In situ studies of the surface of NiFe 2O 4 using AP-XPS suggest the formation of methoxy-like and formate-like intermediates at a temperature lower than 200 °C, supported by the observed vibrational signatures in in situ IR studies. Evolutions of C1s photoemission features and the nominal atomic ratios of C/(Nimore » + Fe) of the catalyst surface suggest that the formate-like intermediate is transformed to product molecules CO 2 and H 2O in the temperature range of 250–300 °C. In situ studies suggest the formation of a spectator, – O lattice – CH 2 – O lattice –. It strongly bonds to surface through C–O bonds and cannot be activated even at 400 °C.« less

Caries-preventive effect of fissure sealant containing surface reaction-type pre-reacted glass ionomer filler and bonded by self-etching primer.

PubMed

Shimazu, Kisaki; Ogata, Kiyokazu; Karibe, Hiroyuki

2012-01-01

We aimed to evaluate the caries-preventive effect of a fissure sealant containing surface reaction-type pre-reacted glass ionomer (S-PRG) filler and bonded by self-etching primer versus those of 2 conventional resin-based sealants bonded by acid etching in terms of its impact on enamel demineralization and remineralization, enamel bond strength, and integrity of debonded enamel surfaces. Demineralization, remineralization, and bond strength on untreated enamel and enamel subsurface lesions of bovine incisors were assessed among the sealants by polarizing microscopy and microradiography; debonded enamel surfaces were examined by scanning electron microscopy. The conventional resin-based sealants bonded by acid etching caused surface defects on the enamel subsurface lesions and significantly increased the lesion depth (p = 0.014), indicative of enamel demineralization. However the S-PRG filler-containing sealant bonded by self-etching primer maintained the enamel surface integrity and inhibited enamel demineralization. No difference in bond strength on both untreated enamel and enamel subsurface lesions was noted among the sealants. An S-PRG filler-containing fissure sealant bonded by self-etching primer can prevent enamel demineralization, microleakage, and gaps without the tags created by acid etching regardless of the enamel condition. Such sealants are suitable for protecting the pits and fissures of immature permanent teeth.

A comparison between the shear bond strength of brackets bonded to glazed and deglazed porcelain surfaces with resin-reinforced glass-ionomer cement and a bis-GMA resin adhesive.

PubMed

Lifshitz, Abraham B; Cárdenas, Marianela

2006-01-01

This study compared the shear bond strength of a light-cure resin-reinforced glass-ionomer cement with a bis-GMA light-cure resin system in the bonding of stainless steel brackets to glazed and deglazed porcelain surfaces. Porcelain surfaces were divided into 4 groups: group 1, deglazed porcelain surfaces with Transbond XT, group 2, glazed porcelain surfaces with Transbond XT; group 3, deglazed porcelain surfaces with Fuji Ortho LC; and group 4, porcelain surfaces with Fuji Ortho LC. Microetching with 50-microm aluminum oxide for 2 seconds at a distance of 5 mm deglazed the porcelain surfaces in groups 1 and 3. All brackets were bonded to the porcelain surfaces using the same procedure and light-cured for 40 seconds with a visible light. All samples were thermocycled between 5 degrees C and 55 degrees C for 300 cycles before testing for shear bond strength with a universal testing machine. The analysis of variance showed no significant difference (P < .05) among the 4 groups; ie, group 1, 10.12 MPa; group 2, 7.00 MPa; group 3, 6.78 MPa; and group 4, 11.15 MPa. The F test also failed to demonstrate any statistical difference among the groups. Conditioning the porcelain surfaces with 37% phosphoric acid immediately followed by a nonhydrolyzed silane coupling agent resulted in clinically adequate bond strength when using either a composite resin or a resin-reinforced glass-ionomer cement. Microetching of these porcelain surfaces apparently offers no bonding advantage.

Hydroxide-catalyzed bonding

NASA Technical Reports Server (NTRS)

Gwo, Dz-Hung (Inventor)

2003-01-01

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

Ethylene decomposition over Pt(100): A mechanism study from first principle calculation

NASA Astrophysics Data System (ADS)

Wang, Yuchun; Dong, Xiuqin; Yu, Yingzhe; Zhang, Minhua

2016-12-01

First principle based density functional theory was used to calculate the complete step-by-step decomposition network of ethylene (C2H4) over Pt(100) as a model for understanding the carbon deposition of olefin hydrocarbon over transition metal surface. We discussed the structural and energetic properties of all the Csbnd H and Csbnd C bond cleavage reactions in order to fully understand the formation pathway of carbon monomer. It is easier for Csbnd H bond cleavage reactions to take place, as the activation barrier of these reactions is relatively lower than that of Csbnd C bond cleavage as a whole. However, vinyl (CH2CH) is likely to be the precursor of Csbnd C bond scission, as the activation barrier of Csbnd C bond cleavage reaction of CH2CH is much lower than that of CH2CH dehydrogenation and the reaction is exothermic by 0.15 eV. CC was another form of depositional carbon on Pt(100), as it is easy to form but difficult to decompose. Finally we proposed six possible routes of carbon monomer formation.

Effects of tributylborane-activated adhesive and two silane agents on bonding computer-aided design and manufacturing (CAD/CAM) resin composite.

PubMed

Shinohara, Ayano; Taira, Yohsuke; Sawase, Takashi

2017-10-01

The present study was conducted to evaluate the effects of an experimental adhesive agent [methyl methacrylate-tributylborane liquid (MT)] and two adhesive agents containing silane on the bonding between a resin composite block of a computer-aided design and manufacturing (CAD/CAM) system and a light-curing resin composite veneering material. The surfaces of CAD/CAM resin composite specimens were ground with silicon-carbide paper, treated with phosphoric acid, and then primed with either one of the two silane agents [Scotchbond Universal Adhesive (SC) and GC Ceramic Primer II (GC)], no adhesive control (Cont), or one of three combinations (MT/SC, MT/GC, and MT/Cont). A light-curing resin composite was veneered on the primed CAD/CAM resin composite surface. The veneered specimens were subjected to thermocycling between 4 and 60 °C for 10,000 cycles, and the shear bond strengths were determined. All data were analyzed using analysis of variance and a post hoc Tukey-Kramer HSD test (α = 0.05, n = 8). MT/SC (38.7 MPa) exhibited the highest mean bond strengths, followed by MT/GC (30.4 MPa), SC (27.9 MPa), and MT/Cont (25.7 MPa), while Cont (12.9 MPa) and GC (12.3 MPa) resulted in the lowest bond strengths. The use of MT in conjunction with a silane agent significantly improved the bond strength. Surface treatment with appropriate adhesive agents was confirmed as a prerequisite for veneering CAD/CAM resin composite restorations.

Cleanliness inspection tool for RSRM bond surfaces

NASA Technical Reports Server (NTRS)

Mattes, Robert A.

1995-01-01

Using optically stimulated electron emission (OSEE), Thiokol has monitored bond surfaces in process for contamination on the Redesigned Solid Rocket Motor (RSRM). This technique provides process control information to help assure bond surface quality and repeatability prior to bonding. This paper will describe OSEE theory of operation and the instrumentation implemented at Thiokol Corporation since 1987. Data from process hardware will be presented.

Shear strengths of a gallium alloy bonded to human enamel following nine different surface treatments.

PubMed

Claire, J; Williams, P T

2001-03-01

Gallium and indium-containing alloys have demonstrated an ability to wet and bond to many types of materials including enamel. The purpose of this study was to evaluate and compare the bond strengths of a gallium-and-indium-containing alloy and a dental amalgam to human enamel surfaces. A flat enamel bonding surface was created by slicing recently extracted human molars with a 180-grit diamond wheel. Cylinders of amalgam or a gallium-indium alloy were bonded to the as-cut surfaces or to as-cut surfaces that had been pumiced, air-abraded or acid-etched for various times. Before testing, samples were stored under different conditions (100% humidity, immersed in water, thermocycled). The shear-bond strength was determined using a crosshead speed of 0.1 mm x min(-1). Sample size was 10. Data was subjected to ANOVA and a post-hoc Tukey's test. The bond strength of amalgam to enamel was zero. The bond strength of the gallium-indium alloy ranged between 6.5 MPa (10s etch with 10% phosphoric acid) and 4.2 MPa (pumiced enamel). Acid-etching significantly increased the bond strength (P>0.0001) The bond strength was not significantly affected by the type of mechanical surface preparation, storage conditions, thermocycling, etching times or acid concentrations. Bonding, particularly chemical bonding, suggests a greater potential for better wetting and therefore better sealing of a cavity. Since microleakage of restorations is one of the principal causes of restoration failure, materials that can bond may in turn posses enhanced resistance to microleakage and ultimately, resistance to restoration failure. The gallium-indium alloy evaluated in this study may be such an alloy.

Two-year water degradation of self-etching adhesives bonded to bur ground enamel.

PubMed

Abdalla, Ali I; Feilzer, Albert J

2009-01-01

To evaluate the effect of water storage on the microshear bond strength to ground enamel of three "all-in-one" self-etch adhesives: Futurabond DC, Clearfil S Tri Bond and Hybrid bond; a self-etching primer; Clearfil SE Bond and an etch-and-rinse adhesive system, Admira Bond. Sixty human molars were used. The root of each tooth was removed and the crown was sectioned into two halves. The convex enamel surfaces were reduced by polishing on silicon paper to prepare a flat surface that was roughened with a parallel-sided diamond bur with abundant water for five seconds. The bonding systems were applied on this surface. Prior to adhesive curing, a hollow cylinder (2.0 mm in height/0.75 mm in internal diameter) was placed on the treated surfaces and cured. A resin composite was then inserted into the tube and cured. For each adhesive, two procedures were carried out: A--the specimens were kept in water for 24 hours, then the tube was removed and the microshear bond strength was determined in a universal testing machine at a crosshead speed of 0.5 mm/minute; B--the specimens were stored in water for two-years before microshear testing. The fractured surface of the bonded specimens after each test procedure was examined by SEM. For the 24-hour control, there was no significant difference in bond strength between the tested adhesives. After two years of water storage, the bond strength of Admira Bond, Clearfil SE Bond and Futurabond DC decreased, but the reduction was not significantly different from that of 24 hours. For Clearfil S Tri Bond and Hybrid Bond, the bond strengths were significantly reduced compared to their 24-hour results.

Enamel Wetness Effects on Microshear Bond Strength of Different Bonding Agents (Adhesive Systems): An in vitro Comparative Evaluation Study.

PubMed

Kulkarni, Girish; Mishra, Vinay K

2016-05-01

The purpose of this study was to compare the effect of enamel wetness on microshear bond strength using different adhesive systems. To evaluate microshear bond strength of three bonding agents on dry enamel; to evaluate microshear bond strength of three bonding agents on wet enamel; and to compare microshear bond strength of three different bonding agents on dry and wet enamel. Sixty extracted noncarious human premolars were selected for this study. Flat enamel surfaces of approximately 3 mm were obtained by grinding the buccal surfaces of premolars with water-cooled diamond disks. This study evaluated one etch-and-rinse adhesive system (Single Bond 2) and two self-etching adhesive systems (Clearfil SE Bond and Xeno-V). The specimens were divided into two groups (n = 30). Group I (dry) was air-dried for 30 seconds and in group II (wet) surfaces were blotted with absorbent paper to remove excess water. These groups were further divided into six subgroups (n = 10) according to the adhesives used. The resin composite, Filtek Z 250, was bonded to flat enamel surfaces that had been treated with one of the adhesives, following the manufacturer's instructions. After being stored in water at 37°C for 24 hours, bonded specimens were stressed in universal testing machine (Fig. 3) at a crosshead speed of 1 mm/min. The data were evaluated with one-way and two-way analysis of variance (ANOVA), t-test, and Tukey's Multiple Post hoc tests (a = 0.05). The two-way ANOVA and Tukey's Multiple Post hoc tests showed significant differences among adhesive systems, but wetness did not influence microshear bond strength (p = 0.1762). The one-way ANOVA and t-test showed that the all-in-one adhesive (Xeno-V) was the only material influenced by the presence of water on the enamel surface. Xeno-V showed significantly higher microshear bond strength when the enamel was kept wet. Single Bond 2 adhesive showed significantly higher microshear bond strength as compared with Xeno-V adhesive but no significant difference when compared with Clearfil SE Bond adhesive in dry enamel. Single Bond 2 adhesive showed no significant difference in microshear bond strength as compared with self-etching adhesive systems (Clearfil SE Bond and Xeno-V), when the enamel was kept wet. From the findings of the results, it was concluded that self-etching adhesives were not negatively affected by the presence of water on the enamel surface. The all-in-one adhesive showed different behavior depending on whether the enamel surface was dry or wet. So the enamel surface should not be desiccated, when self-etching adhesives are used.

Supersonic Retropulsion Surface Preparation of Carbon Fiber Reinforced Epoxy Composites for Adhesive Bonding

NASA Technical Reports Server (NTRS)

Palmieri, Frank L.; Belcher, Marcus A.; Wohl, Christopher J.; Blohowiak, Kay Y.; Connell, John W.

2013-01-01

Surface preparation is widely recognized as a key step to producing robust and predictable bonds in a precise and reproducible manner. Standard surface preparation techniques, including grit blasting, manual abrasion, and peel ply, can lack precision and reproducibility, which can lead to variation in surface properties and subsequent bonding performance. The use of a laser to ablate composite surface resin can provide an efficient, precise, and reproducible means of preparing composite surfaces for adhesive bonding. Advantages include elimination of physical waste (i.e., grit media and sacrificial peel ply layers that ultimately require disposal), reduction in process variability due to increased precision (e.g. increased reproducibility), and automation of surface preparation, all of which improve reliability and process control. This paper describes a Nd:YAG laser surface preparation technique for composite substrates and the mechanical performance and failure modes of bonded laminates thus prepared. Additionally, bonded specimens were aged in a hot, wet environment for approximately one year and subsequently mechanically tested. The results of a one year hygrothermal aging study will be presented.

Characterization of the unique function of a reduced amide bond in a cytolytic peptide that acts on phospholipid membranes.

PubMed Central

Oh, J E; Lee, K H

2000-01-01

The incorporation of a reduced amide bond, psi(CH(2)NH), into peptide results in an increase in the net positive charge and the perturbation of alpha-helical structure. By using this characteristic of the reduced amide bond, we designed and synthesized novel pseudopeptides containing reduced amide bonds, which had a great selectivity between bacterial and mammalian cells. A structure-activity relationship study on pseudopeptides indicated that the decrease in alpha-helicity and the increase in net positive charge in the backbone, caused by the incorporation of a reduced amide bond into the peptide, both contributed to an improvement in the selectivity between lipid membranes with various surface charges. However, activity results in vitro indicated that a perturbation of alpha-helical structure rather than an increase in net positive charge in the backbone is more important in the selectivity between bacterial and mammalian cells. The present result revealed that the backbone of membrane-active peptides were important not only in maintaining the secondary structure for the interactions with lipid membranes but also in direct interactions with lipid membranes. The present study showed the unique function of a reduced amide bond in cytolytic peptides and a direction for developing novel anti-bacterial agents from cytolytic peptides that act on the lipid membrane of micro-organisms. PMID:11104671

Hydrogen-bond dynamics at the bio-water interface in hydrated proteins: a molecular-dynamics study.

PubMed

Nandi, Prithwish K; English, Niall J; Futera, Zdenek; Benedetto, Antonio

2016-12-21

Water is fundamental to the biochemistry of enzymes. It is well known that without a minimum amount of water, enzymes are not biologically active. Bare minimal solvation for biological function corresponds to about a single layer of water covering enzymes' surfaces. Many contradictory studies on protein-hydration-water-coupled dynamics have been published in recent decades. Following prevailing wisdom, a dynamical crossover in hydration water (at around 220 K for hydrated lysozymes) can trigger larger-amplitude motions of the protein, activating, in turn, biological functions. Here, we present a molecular-dynamics-simulation study on a solvated model protein (hen egg-white lysozyme), in which we determine, inter alia, the relaxation dynamics of the hydrogen-bond network between the protein and its hydration water molecules on a residue-per-residue basis. Hydrogen-bond breakage/formation kinetics is rather heterogeneous in temperature dependence (due to the heterogeneity of the free-energy surface), and is driven by the magnitude of thermal motions of various different protein residues which provide enough thermal energy to overcome energy barriers to rupture their respective hydrogen bonds with water. In particular, arginine residues exhibit the highest number of such hydrogen bonds at low temperatures, losing almost completely such bonding above 230 K. This suggests that hydration water's dynamical crossover, observed experimentally for hydrated lysozymes at ∼220 K, lies not at the origin of the protein residues' larger-amplitude motions, but rather arises as a consequence thereof. This highlights the need for new experimental investigations, and new interpretations to link protein dynamics to functions, in the context of key interrelationships with the solvation layer.

Optimized ultra-thin manganin alloy passivated fine-pitch damascene compatible bump-less Cu-Cu bonding at sub 200 °C for three-dimensional Integration applications

NASA Astrophysics Data System (ADS)

Panigrahi, Asisa Kumar; Hemanth Kumar, C.; Bonam, Satish; Ghosh, Tamal; Rama Krishna Vanjari, Siva; Govind Singh, Shiv

2018-02-01

Enhanced Cu diffusion, Cu surface passivation, and smooth surface at the bonding interface are the key essentials for high quality Cu-Cu bonding. Previously, we have demonstrated optimized 3 nm thin Manganin metal-alloy passivation from oxidation and also helps to reduce the surface roughness to about 0.8 nm which substantially led to high quality Cu-Cu bonding. In this paper, we demonstrated an ultra fine-pitch (<25 µm) Cu-Cu bonding using an optimized Manganin metal-alloy passivation. This engineered surface passivation approach led to high quality bonding at sub 200 °C temperature and 0.4 MPa. Very low specific contact resistance of 1.4 × 10-7 Ω cm2 and the defect free bonded interface is clear indication of high quality bonding for future multilayer integrations. Furthermore, electrical characterization of the bonded structure was performed under various robust conditions as per International Technology Roadmap for Semiconductors (ITRS Roadmap) in order to satisfy the stability of the bonded structure.

Influence of enamel surface preparation on composite bond strength.

PubMed

Matos, Adriana Bona; Tate, William H; Powers, John M

2003-09-01

To evaluate the influence of air-particle abrasion and treatments on in vitro tensile bond strength of resin composite bonded to human enamel was evaluated using a single-bottle adhesive. Human teeth were divided into 12 groups of three treatments (none, 27-microm Al2O3 air-particle abrasion, 50-microm Al2O3 air-particle abrasion) and four conditioners [none, phosphoric acid (PA), NRC (no-rinse conditioner), and PA/NRC]. Bonding agent (Prime & Bond NT) and a resin composite (TPH Spectrum) were applied as inverted cones. Specimens were stored for 24 hours at 37 degrees C and debonded in tension using a testing machine at 0.5 mm/minute. Phosphoric acid treatment used with Prime & Bond NT produced the best bond strengths (24 MPa) to enamel for surfaces treated with 27-microm air-particle abrasion and for surfaces not treated with air-particle abrasion (control). With one exception, air-particle abraded surfaces resulted in bond strengths between 9 to 16 MPa. NRC with or without the use of phosphoric acid in general did not improve tensile bond strength to enamel when compared to surfaces not treated with NRC.

Method of making a composite tube to metal joint

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

Leslie, James C.; Leslie, II, James C.; Heard, James

A method for making a metal to composite tube joint including selecting an elongated interior fitting constructed with an exterior barrel, reduced in exterior diameter to form a distally facing annular shoulder and then projecting still further distally to form an interior sleeve having a radially outwardly facing bonding surface. Selecting an elongated metal outer sleeve formed proximally with a collar constructed for receipt over the barrel and increased in interior diameter and projecting distally to form an exterior sleeve having a radially inwardly facing bonding surface cooperating with the first bonding surface to form an annulus receiving an extremitymore » of a composite tube and a bond bonding the extremity of the tube to the bonding surfaces.« less

Effect of Reduced Phosphoric Acid Pre-etching Times 
on Enamel Surface Characteristics and Shear Fatigue Strength Using Universal Adhesives.

PubMed

Tsujimoto, Akimasa; Fischer, Nicholas; Barkmeier, Wayne; Baruth, Andrew; Takamizawa, Toshiki; Latta, Mark; Miyazaki, Masashi

2017-01-01

To examine the effect of reduced phosphoric acid pre-etching times on enamel fatigue bond strength of universal adhesives and surface characteristics by using atomic force microscopy (AFM). Three universal adhesives were used in this study (Clearfil Universal Bond [C], G-Premio Bond [GP], Scotchbond Universal Adhesive [SU]). Four pre-etching groups were employed: enamel pre-etched with phosphoric acid and immediately rinsed with an air-water spray, and enamel pre-etched with phosphoric acid for 5, 10, or 15 s. Ground enamel was used as the control group. For the initial bond strength test, 15 specimens per etching group for each adhesive were used. For the shear fatigue test, 20 specimens per etching group for each adhesive were loaded using a sine wave at a frequency of 20 Hz for 50,000 cycles or until failure occurred. Initial shear bond strengths and fatigue shear strengths of composite adhesively bonded to ground and pre-etched enamel were determined. AFM observations of ground and pre-etched enamel were also conducted, and surface roughness as well as surface area were evaluated. The initial shear bond strengths and fatigue shear strengths of the universal adhesives in the pre-etched groups were significantly higher than those of the control group, and were not influenced by the pre-etching time. Significantly higher surface roughness and surface area of enamel surfaces in pre-etched groups were observed compared with those in the control group. While the surface area was not significantly influenced by etching time, surface roughness of the enamel surfaces in the pre-etched groups significantly increased with pre-etching time. The results of this in vitro study suggest that reduced phosphoric acid pre-etching times do not impair the fatigue bond strength of universal adhesives. Although fatigue bond strength and surface area were not influenced by phosphoric-acid etching times, surface roughness increased with increasing etching time.

Silver Nanoparticles with Surface-Bonded Oxygen for Highly Selective CO 2 Reduction

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

Jiang, Kun; Kharel, Priti; Peng, Yande

Here, the surface electronic structures of catalysts need to be carefully engineered in CO 2 reduction reaction (CO 2RR), where the hydrogen evolution side reaction usually takes over under a significant overpotential, and thus dramatically lows the reaction selectivity. Surface oxides can play a critical role in tuning the surface oxidation state of metal catalysts for a proper binding with CO 2RR reaction intermediates, which may significantly improve the catalyst activity and selectivity. Here, we demonstrate the importance of surface-bonded oxygen on silver nanoparticles in altering the reaction pathways and improving the CO 2RR performances. A comparative investigation on air-annealedmore » Ag (Air-Ag) catalyst with or without the post-treatment of H 2 thermal annealing (H 2-Ag) was performed. In Air-Ag, the subsurface chemically bonded O species (O-Ag δ+) was identified by angle resolved X-ray photoelectron spectroscopy and X-ray absorption spectroscopy techniques, and contributed to the improved CO selectivity rather than H 2 in CO 2RR electrolysis. As a result, while the maximal CO Faradaic efficiency of H 2-Ag is at ~ 30 %, the Air-Ag catalyst presented a high CO selectivity of more than 90 % under a current density of ~ 21 mA/cm 2.« less

Evaluation of mechanical properties in metal wire mesh supported selective catalytic reduction (SCR) catalyst structures

NASA Astrophysics Data System (ADS)

Rajath, S.; Siddaraju, C.; Nandakishora, Y.; Roy, Sukumar

2018-04-01

The objective of this research is to evaluate certain specific mechanical properties of certain stainless steel wire mesh supported Selective catalytic reduction catalysts structures wherein the physical properties of the metal wire mesh and also its surface treatments played vital role thereby influencing the mechanical properties. As the adhesion between the stainless steel wire mesh and the catalyst material determines the bond strength and the erosion resistance of catalyst structures, surface modifications of the metal- wire mesh structure in order to facilitate the interface bonding is therefore very important to realize enhanced level of mechanical properties. One way to enhance such adhesion properties, the stainless steel wire mesh is treated with the various acids, i.e., chromic acid, phosphoric acid including certain mineral acids and combination of all those in various molar ratios that could generate surface active groups on metal surface that promotes good interface structure between the metal- wire mesh and metal oxide-based catalyst material and then the stainless steel wire mesh is dipped in the glass powder slurry containing some amount of organic binder. As a result of which the said catalyst material adheres to the metal-wire mesh surface more effectively that improves the erosion profile of supported catalysts structure including bond strength.

Silver Nanoparticles with Surface-Bonded Oxygen for Highly Selective CO 2 Reduction

DOE PAGES

Jiang, Kun; Kharel, Priti; Peng, Yande; ...

2017-09-12

Here, the surface electronic structures of catalysts need to be carefully engineered in CO 2 reduction reaction (CO 2RR), where the hydrogen evolution side reaction usually takes over under a significant overpotential, and thus dramatically lows the reaction selectivity. Surface oxides can play a critical role in tuning the surface oxidation state of metal catalysts for a proper binding with CO 2RR reaction intermediates, which may significantly improve the catalyst activity and selectivity. Here, we demonstrate the importance of surface-bonded oxygen on silver nanoparticles in altering the reaction pathways and improving the CO 2RR performances. A comparative investigation on air-annealedmore » Ag (Air-Ag) catalyst with or without the post-treatment of H 2 thermal annealing (H 2-Ag) was performed. In Air-Ag, the subsurface chemically bonded O species (O-Ag δ+) was identified by angle resolved X-ray photoelectron spectroscopy and X-ray absorption spectroscopy techniques, and contributed to the improved CO selectivity rather than H 2 in CO 2RR electrolysis. As a result, while the maximal CO Faradaic efficiency of H 2-Ag is at ~ 30 %, the Air-Ag catalyst presented a high CO selectivity of more than 90 % under a current density of ~ 21 mA/cm 2.« less

30 CFR 800.14 - Determination of bond amount.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 800.14 Mineral Resources OFFICE OF SURFACE MINING RECLAMATION AND ENFORCEMENT, DEPARTMENT OF THE INTERIOR BONDING AND INSURANCE REQUIREMENTS FOR SURFACE COAL MINING AND RECLAMATION OPERATIONS BOND AND INSURANCE REQUIREMENTS FOR SURFACE COAL MINING AND RECLAMATION OPERATIONS UNDER REGULATORY PROGRAMS § 800.14...

Dentin surface treatment using a non-thermal argon plasma brush for interfacial bonding improvement in composite restoration

PubMed Central

Ritts, Andy Charles; Li, Hao; Yu, Qingsong; Xu, Changqi; Yao, Xiaomei; Hong, Liang; Wang, Yong

2010-01-01

The objective of this study is to investigate the treatment effects of non-thermal atmospheric gas plasmas on dentin surfaces for composite restoration. Extracted unerupted human third molars were used by removing the crowns and etching the exposed dentin surfaces with 35% phosphoric acid gel. The dentin surfaces were treated by using a non-thermal atmospheric argon plasma brush for various durations. The molecular changes of the dentin surfaces were analyzed using FTIR/ATR and an increase in carbonyl groups on dentin surfaces was detected with plasma treated dentin. Adper Single Bond Plus adhesive and Filtek Z250 dental composite were applied as directed. To evaluate the dentin/composite interfacial bonding, the teeth thus prepared were sectioned into micro-bars as the specimens for tensile test. Student Newman Keuls tests showed that the bonding strength of the composite restoration to peripheral dentin was significantly increased (by 64%) after 30 s plasma treatment. However, the bonding strength to plasma treated inner dentin did not show any improvement. It was found that plasma treatment of peripheral dentin surface up to 100 s gave an increase in interfacial bonding strength, while a prolong plasma treatment of dentin surfaces, e.g., 5 min treatments, showed a decrease in interfacial bonding strength. PMID:20831586

On the ultrafast charge migration and subsequent charge directed reactivity in Cl⋯N halogen-bonded clusters following vertical ionization

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

Chandra, Sankhabrata; Bhattacharya, Atanu, E-mail: atanub@ipc.iisc.ernet.in; Periyasamy, Ganga

2015-06-28

In this article, we have presented ultrafast charge transfer dynamics through halogen bonds following vertical ionization of representative halogen bonded clusters. Subsequent hole directed reactivity of the radical cations of halogen bonded clusters is also discussed. Furthermore, we have examined effect of the halogen bond strength on the electron-electron correlation- and relaxation-driven charge migration in halogen bonded complexes. For this study, we have selected A-Cl (A represents F, OH, CN, NH{sub 2}, CF{sub 3}, and COOH substituents) molecules paired with NH{sub 3} (referred as ACl:NH{sub 3} complex): these complexes exhibit halogen bonds. To the best of our knowledge, this ismore » the first report on purely electron correlation- and relaxation-driven ultrafast (attosecond) charge migration dynamics through halogen bonds. Both density functional theory and complete active space self-consistent field theory with 6-31 + G(d, p) basis set are employed for this work. Upon vertical ionization of NCCl⋯NH{sub 3} complex, the hole is predicted to migrate from the NH{sub 3}-end to the ClCN-end of the NCCl⋯NH{sub 3} complex in approximately 0.5 fs on the D{sub 0} cationic surface. This hole migration leads to structural rearrangement of the halogen bonded complex, yielding hydrogen bonding interaction stronger than the halogen bonding interaction on the same cationic surface. Other halogen bonded complexes, such as H{sub 2}NCl:NH{sub 3}, F{sub 3}CCl:NH{sub 3}, and HOOCCl:NH{sub 3}, exhibit similar charge migration following vertical ionization. On the contrary, FCl:NH{sub 3} and HOCl:NH{sub 3} complexes do not exhibit any charge migration following vertical ionization to the D{sub 0} cation state, pointing to interesting halogen bond strength-dependent charge migration.« less

Effect of Nd: YAG laser irradiation on surface properties and bond strength of zirconia ceramics.

PubMed

Liu, Li; Liu, Suogang; Song, Xiaomeng; Zhu, Qingping; Zhang, Wei

2015-02-01

This study investigated the effect of neodymium-doped yttrium aluminum garnet (Nd: YAG) laser irradiation on surface properties and bond strength of zirconia ceramics. Specimens of zirconia ceramic pieces were divided into 11 groups according to surface treatments as follows: one control group (no treatment), one air abrasion group, and nine laser groups (Nd: YAG irradiation). The laser groups were divided by applying with different output power (1, 2, or 3 W) and irradiation time (30, 60, or 90 s). Following surface treatments, the morphological characteristics of ceramic pieces was observed, and the surface roughness was measured. All specimens were bonded to resin cement. After, stored in water for 24 h and additionally aged by thermocycling, the shear bond strength was measured. Dunnett's t test and one-way ANOVA were performed as the statistical analyses for the surface roughness and the shear bond strength, respectively, with α = .05. Rougher surface of the ceramics could be obtained by laser irradiation with higher output power (2 and 3 W). However, cracks and defects were also found on material surface. The shear bond strength of laser groups was not obviously increased, and it was significantly lower than that of air abrasion group. No significant differences of the shear bond strength were found among laser groups treated with different output power or irradiation time. Nd: YAG laser irradiation cannot improve the surface properties of zirconia ceramics and cannot increase the bond strength of the ceramics. Enhancing irradiation power and extending irradiation time cannot induce higher bond strength of the ceramics and may cause material defect.

Effect of electronic structure of the diamond surface on the strength of the diamond-metal interface

NASA Technical Reports Server (NTRS)

Pepper, S. V.

1981-01-01

A diamond surface undergoes a transformation in its electronic structure by a vacuum anneal at approximately 900 C. The polished surface has no electronic states in the band gap, whereas the annealed surface has both occupied and unoccupied states in the and gap and exhibits some electrical conductivity. The effect of this transformation on the strength of the diamond metal interface was investigated by measuring the static friction force of an atomically clean meta sphere on a diamond flat in ultrahigh vacuum. It was found that low friction (weak bonding) is associated with the diamond surface devoid of gap states whereas high friction (strong bonding) is associated with the diamond surface with gap states. Exposure of the annealed surface to excited hydrogen also leads to weak bonding. The interfacial bond is discussed in terms of interaction of the metal conduction band electrons with the band gap states on the diamond surface. Effects of surface electrical conductivity on the interfacial bond are also be considered.

Laser Surface Preparation of Epoxy Composites for Secondary Bonding: Optimization of Ablation Depth

NASA Technical Reports Server (NTRS)

Palmieri, Frank L.; Hopkins, John; Wohl, Christopher J.; Lin, Yi; Connell, John W.; Belcher, Marcus A.; Blohowiak, Kay Y.

2015-01-01

Surface preparation has been identified as one of the most critical aspects of attaining predictable and reliable adhesive bonds. Energetic processes such as laser ablation or plasma treatment are amenable to automation and are easily monitored and adjusted for controlled surface preparation. A laser ablation process was developed to accurately remove a targeted depth of resin, approximately 0.1 to 20 micrometers, from a carbon fiber reinforced epoxy composite surface while simultaneously changing surface chemistry and creating micro-roughness. This work demonstrates the application of this process to prepare composite surfaces for bonding without exposing or damaging fibers on the surface. Composite panels were prepared in an autoclave and had a resin layer approximately 10 micrometers thick above the fiber reinforcement. These composite panels were laser surface treated using several conditions, fabricated into bonded panels and hygrothermally aged. Bond performance of aged, experimental specimens was compared with grit blast surface treated specimens using a modified double cantilever beam test that enabled accelerated saturation of the specimen with water. Comparison of bonded specimens will be used to determine how ablation depth may affect average fracture energies and failure modes.

Influence of aluminum oxide film on thermocompression bonding of gold wire to evaporated aluminum film

NASA Technical Reports Server (NTRS)

Iwata, S.; Ishizaka, A.; Yamamoto, H.

1984-01-01

The influence of Al surface condition on the thermocompression bonding of Au wires to Al electrodes for integrated electric circuits was studied. Au wires were connected to Al electrodes by nail-head bonding after various Al surface treatments. Bonding was evaluated by measuring the wire pull strength and fraction of the number of failures at Au-Al bonds to the total number of failures. Dependence of the fraction on applied load was derived theoretically with a parameter named critical load to take into consideration the differences in Al surface condition. The relation also held explicately for various surface treatments. Characterization of the Al surface was carried out by electron microscopy for chemical analysis.

Initial and long-term bond strengths of one-step self-etch adhesives with silane coupling agent to enamel-dentin-composite in combined situation.

PubMed

Mamanee, Teerapong; Takahashi, Masahiro; Nakajima, Masatoshi; Foxton, Richard M; Tagami, Junji

2015-01-01

This study evaluated the effect of adding silane coupling agent on initial and long-term bond strengths of one-step self-etch adhesives to enamel-dentin-composite in combined situation. Cervical cavities were prepared on extracted molars and filled with Clearfil AP-X. After water-storage for one-week, the filled teeth were sectioned in halves to expose enamel, dentin and composite surfaces and then enamel-dentin-composite surface was totally applied with one of adhesive treatments (Clearfil SE One, Clearfil SE One with Clearfil Porcelain Bond Activator, Beautibond Multi, Beautibond Multi with Beautibond Multi PR Plus and Scotchbond Universal). After designed period, micro-shear bond strengths (µSBSs) to each substrate were determined. For each period of water-storage, additive silane treatments significantly increased µSBS to composite (p<0.001). On the other hand, they significantly decreased µSBS to dentin (p<0.001), although did not have adverse effect on µSBS to enamel (p>0.05). Moreover, the stability of µSBS was depended on materials and substrates used.

Active sites and mechanisms for H2O2 decomposition over Pd catalysts

PubMed Central

Plauck, Anthony; Stangland, Eric E.; Dumesic, James A.; Mavrikakis, Manos

2016-01-01

A combination of periodic, self-consistent density functional theory (DFT-GGA-PW91) calculations, reaction kinetics experiments on a SiO2-supported Pd catalyst, and mean-field microkinetic modeling are used to probe key aspects of H2O2 decomposition on Pd in the absence of cofeeding H2. We conclude that both Pd(111) and OH-partially covered Pd(100) surfaces represent the nature of the active site for H2O2 decomposition on the supported Pd catalyst reasonably well. Furthermore, all reaction flux in the closed catalytic cycle is predicted to flow through an O–O bond scission step in either H2O2 or OOH, followed by rapid H-transfer steps to produce the H2O and O2 products. The barrier for O–O bond scission is sensitive to Pd surface structure and is concluded to be the central parameter governing H2O2 decomposition activity. PMID:27006504

30 CFR 800.17 - Bonding requirements for underground coal mines and long-term coal-related surface facilities and...

Code of Federal Regulations, 2010 CFR

2010-07-01

... 30 Mineral Resources 3 2010-07-01 2010-07-01 false Bonding requirements for underground coal mines and long-term coal-related surface facilities and structures. 800.17 Section 800.17 Mineral Resources... REQUIREMENTS FOR SURFACE COAL MINING AND RECLAMATION OPERATIONS BOND AND INSURANCE REQUIREMENTS FOR SURFACE...

30 CFR 800.17 - Bonding requirements for underground coal mines and long-term coal-related surface facilities and...

Code of Federal Regulations, 2012 CFR

2012-07-01

... 30 Mineral Resources 3 2012-07-01 2012-07-01 false Bonding requirements for underground coal mines and long-term coal-related surface facilities and structures. 800.17 Section 800.17 Mineral Resources... REQUIREMENTS FOR SURFACE COAL MINING AND RECLAMATION OPERATIONS BOND AND INSURANCE REQUIREMENTS FOR SURFACE...

30 CFR 800.17 - Bonding requirements for underground coal mines and long-term coal-related surface facilities and...

Code of Federal Regulations, 2013 CFR

2013-07-01

... 30 Mineral Resources 3 2013-07-01 2013-07-01 false Bonding requirements for underground coal mines and long-term coal-related surface facilities and structures. 800.17 Section 800.17 Mineral Resources... REQUIREMENTS FOR SURFACE COAL MINING AND RECLAMATION OPERATIONS BOND AND INSURANCE REQUIREMENTS FOR SURFACE...

30 CFR 800.17 - Bonding requirements for underground coal mines and long-term coal-related surface facilities and...

Code of Federal Regulations, 2014 CFR

2014-07-01

... 30 Mineral Resources 3 2014-07-01 2014-07-01 false Bonding requirements for underground coal mines and long-term coal-related surface facilities and structures. 800.17 Section 800.17 Mineral Resources... REQUIREMENTS FOR SURFACE COAL MINING AND RECLAMATION OPERATIONS BOND AND INSURANCE REQUIREMENTS FOR SURFACE...

30 CFR 800.17 - Bonding requirements for underground coal mines and long-term coal-related surface facilities and...

Code of Federal Regulations, 2011 CFR

2011-07-01

... 30 Mineral Resources 3 2011-07-01 2011-07-01 false Bonding requirements for underground coal mines and long-term coal-related surface facilities and structures. 800.17 Section 800.17 Mineral Resources... REQUIREMENTS FOR SURFACE COAL MINING AND RECLAMATION OPERATIONS BOND AND INSURANCE REQUIREMENTS FOR SURFACE...

Sulfur passivation techniques for III-V wafer bonding

NASA Astrophysics Data System (ADS)

Jackson, Michael James

The use of direct wafer bonding in a multijunction III-V solar cell structure requires the formation of a low resistance bonded interface with minimal thermal treatment. A wafer bonded interface behaves as two independent surfaces in close proximity, hence a major source of resistance is Fermi level pinning common in III-V surfaces. This study demonstrates the use of sulfur passivation in III-V wafer bonding to reduce the energy barrier at the interface. Two different sulfur passivation processes are addressed. A dry sulfur passivation method that utilizes elemental sulfur vapor activated by ultraviolet light in vacuum is compared with aqueous sulfide and native oxide etch treatments. Through the addition of a sulfur desorption step in vacuum, the UV-S treatment achieves bondable surfaces free of particles contamination or surface roughening. X-ray photoelectron spectroscopy measurements of the sulfur treated GaAs surfaces find lower levels of oxide and the appearance of sulfide species. After 4 hrs of air exposure, the UV-S treated GaAs actually showed an increase in the amount of sulfide bonded to the semiconductor, resulting in less oxidation compared to the aqueous sulfide treatment. Large area bonding is achieved for sulfur treated GaAs / GaAs and InP / InP with bulk fracture strength achieved after annealing at 400 °C and 300 °C respectively, without large compressive forces. The electrical conductivity across a sulfur treated 400 °C bonded n-GaAs/n-GaAs interface significantly increased with a short anneal (1-2 minutes) at elevated temperatures (50--600 °C). Interfaces treated with the NH4OH oxide etch, on the other hand, exhibited only mild improvement in accordance with previously published studies in this area. TEM and STEM images revealed similar interfacial microstructure changes with annealing for both sulfur treated and NH4OH interfaces, whereby some areas have direct semiconductor-semiconductor contact without any interfacial layer. Fitting the observed temperature dependence of zero bias conductance using a model for tunneling through a grain boundary reveals that the addition of sulfur at the interface lowered the interfacial energy barrier by 0.2 eV. The interface resistance for these sulfur-treated structures is less than 0.03 O·cm 2 at room temperature. These results emphasize that sulfur passivation techniques reduce interface states that otherwise limit the implementation of wafer bonding for high efficiency solar cells and other devices.

Relationship between enamel bond fatigue durability and surface free-energy characteristics with universal adhesives.

PubMed

Nagura, Yuko; Tsujimoto, Akimasa; Barkmeier, Wayne W; Watanabe, Hidehiko; Johnson, William W; Takamizawa, Toshiki; Latta, Mark A; Miyazaki, Masashi

2018-04-01

The relationship between enamel bond fatigue durability and surface free-energy characteristics with universal adhesives was investigated. The initial shear bond strengths and shear fatigue strengths of five universal adhesives to enamel were determined with and without phosphoric acid pre-etching. The surface free-energy characteristics of adhesive-treated enamel with and without pre-etching were also determined. The initial shear bond strength and shear fatigue strength of universal adhesive to pre-etched enamel were higher than those to ground enamel. The initial shear bond strength and shear fatigue strength of universal adhesive to pre-etched enamel were material dependent, unlike those to ground enamel. The surface free-energy of the solid (γ S ) and the hydrogen-bonding force (γSh) of universal adhesive-treated enamel were different depending on the adhesive, regardless of the presence or absence of pre-etching. The bond fatigue durability of universal adhesives was higher to pre-etched enamel than to ground enamel. In addition, the bond fatigue durability to pre-etched enamel was material dependent, unlike that to ground enamel. The surface free-energy characteristics of universal adhesive-treated enamel were influenced by the adhesive type, regardless of the presence or absence of pre-etching. The surface free-energy characteristics of universal adhesive-treated enamel were related to the results of the bond fatigue durability. © 2018 Eur J Oral Sci.

Cohesion and coordination effects on transition metal surface energies

NASA Astrophysics Data System (ADS)

Ruvireta, Judit; Vega, Lorena; Viñes, Francesc

2017-10-01

Here we explore the accuracy of Stefan equation and broken-bond model semiempirical approaches to obtain surface energies on transition metals. Cohesive factors are accounted for either via the vaporization enthalpies, as proposed in Stefan equation, or via cohesive energies, as employed in the broken-bond model. Coordination effects are considered including the saturation degree, as suggested in Stefan equation, employing Coordination Numbers (CN), or as the ratio of broken bonds, according to the bond-cutting model, considering as well the square root dependency of the bond strength on CN. Further, generalized coordination numbers CN bar are contemplated as well, exploring a total number of 12 semiempirical formulations on the three most densely packed surfaces of 3d, 4d, and 5d Transition Metals (TMs) displaying face-centered cubic (fcc), body-centered cubic (bcc), or hexagonal close-packed (hcp) crystallographic structures. Estimates are compared to available experimental surface energies obtained extrapolated to zero temperature. Results reveal that Stefan formula cohesive and coordination dependencies are only qualitative suited, but unadvised for quantitative discussion, as surface energies are highly overestimated, favoring in addition the stability of under-coordinated surfaces. Broken-bond cohesion and coordination dependencies are a suited basis for quantitative comparison, where square-root dependencies on CN to account for bond weakening are sensibly worse. An analysis using Wulff shaped averaged surface energies suggests the employment of broken-bond model using CN to gain surface energies for TMs, likely applicable to other metals.

Catalysis beyond frontier molecular orbitals: Selectivity in partial hydrogenation of multi-unsaturated hydrocarbons on metal catalysts

PubMed Central

Liu, Wei; Jiang, Yingda; Dostert, Karl-Heinz; O’Brien, Casey P.; Riedel, Wiebke; Savara, Aditya; Schauermann, Swetlana; Tkatchenko, Alexandre

2017-01-01

The mechanistic understanding and control over transformations of multi-unsaturated hydrocarbons on transition metal surfaces remains one of the major challenges of hydrogenation catalysis. To reveal the microscopic origins of hydrogenation chemoselectivity, we performed a comprehensive theoretical investigation on the reactivity of two α,β-unsaturated carbonyls—isophorone and acrolein—on seven (111) metal surfaces: Pd, Pt, Rh, Ir, Cu, Ag, and Au. In doing so, we uncover a general mechanism that goes beyond the celebrated frontier molecular orbital theory, rationalizing the C═C bond activation in isophorone and acrolein as a result of significant surface-induced broadening of high-energy inner molecular orbitals. By extending our calculations to hydrogen-precovered surface and higher adsorbate surface coverage, we further confirm the validity of the “inner orbital broadening mechanism” under realistic catalytic conditions. The proposed mechanism is fully supported by our experimental reaction studies for isophorone and acrolein over Pd nanoparticles terminated with (111) facets. Although the position of the frontier molecular orbitals in these molecules, which are commonly considered to be responsible for chemical interactions, suggests preferential hydrogenation of the C═O double bond, experiments show that hydrogenation occurs at the C═C bond on Pd catalysts. The extent of broadening of inner molecular orbitals might be used as a guiding principle to predict the chemoselectivity for a wide class of catalytic reactions at metal surfaces. PMID:28782033

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.

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.

Shear bond strength of resin composite bonded with two adhesives: Influence of Er: YAG laser irradiation distance

PubMed Central

Shirani, Farzaneh; Birang, Reza; Malekipour, Mohammad Reza; Hourmehr, Zahra; Kazemi, Shantia

2014-01-01

Background: Dental surfaces prepared with different Er:YAG laser distance may have different characteristics compared with those prepared with conventional instruments. The aim of this study was to investigate the effect of Er:YAG laser irradiation distance from enamel and dentin surfaces on the shear bond strength of composite with self-etch and etch and rinse bonding systems compared with conventional preparation method. Materials and Methods: Two hundred caries-free human third molars were randomly divided into twenty groups (n = 10). Ten groups were designated for enamel surface (E1-E10) and ten for dentin surface (D1-D10). Er: YAG laser (2940 nm) was used on the E1-E8 (240 mJ, 25 Hz) and D1-D8 (140 mJ, 30 Hz) groups at four different distances of 0.5 (standard), 2, 4 and 11 mm. Control groups (E9, E10, D9 and D10) were ground with medium grit diamond bur. The enamel and dentin specimens were divided into two subgroups that were bonded with either Single Bond or Clearfil SE Bond. Resin composite (Z100) was dispensed on prepared dentin and enamel. The shear bond strengths were tested using a universal testing machine. Data were analyzed by SPSS12 statistical software using three way analysis of variance, Tukey and independent t-test. P < 0.05 was considered as significant. Results: There was a significant difference between enamel and dentin substrates (P < 0.001) and between lased and un-lased groups; the un-lased group had significantly higher bond strength (P < 0.001). Shear bond strength increased significantly with an increase in the laser irradiation distance (P < 0.05) on enamel surfaces (in both bonding agent subgroups) and on dentin surfaces (in the Single Bond subgroup). Conclusion: Laser irradiation decreases shear bond strength. Irradiation distance affects shear bond strength and increasing the distance would decrease the negative effects of laser irradiation. PMID:25540665

Surface Structure and Surface Electronic States Related to Plasma Cleaning of Silicon and Germanium

NASA Astrophysics Data System (ADS)

Cho, Jaewon

This thesis discusses the surface structure and the surface electronic states of Si and Ge(100) surfaces as well as the effects of oxidation process on the silicon oxide/Si(100) interface structure. The H-plasma exposure was performed in situ at low temperatures. The active species, produced in the H-plasma by the rf-excitation of H_2 gas, not only remove microcontaminants such as oxygen and carbon from the surface, but also passivate the surface with atomic hydrogen by satisfying the dangling bonds of the surface atoms. The surfaces were characterized by Angle Resolved UV-Photoemission Spectroscopy (ARUPS) and Low Energy Electron Diffraction (LEED). In the case of Si(100), H-plasma exposure produced ordered H-terminated crystallographic structures with either a 2 x 1 or 1 x 1 LEED pattern. The hydride phases, found on the surfaces of the cleaned Si(100), were shown to depend on the temperature of the surface during H-plasma cleaning. The electronic states for the monohydride and dihydride phases were identified by ARUPS. When the plasma cleaned surface was annealed, the phase transition from the dihydride to monohydride was observed. The monohydride Si-H surface bond was stable up to 460^circC, and the dangling bond surface states were identified after annealing at 500^circC which was accompanied by the spectral shift. The H-terminated surface were characterized to have a flat band structure. For the Ge(100) surface, an ordered 2 x 1 monohydride phase was obtained from the surface cleaned at 180 ^circC. After plasma exposure at <=170^circC a 1 x 1 surface was observed, but the ARUPS indicated that the surface was predominantly composed of disordered monohydride structures. After annealing above the H-dissociation temperatures, the shift in the spectrum was shown to occur with the dangling bond surface states. The H-terminated surfaces were identified to be unpinned. The interface structure of silicon oxide/Si(100) was studied using ARUPS. Spectral shifts were observed, which were dependent on the processes of surface preparation and oxidation. The shift was characterized in association with the band bending. The origins of the spectral shifts were discussed, including defects at interface and H-passivation in Si. The interface structure is considered to be dependent on the surface preparation and oxidation process.

Effect of indirect composite treatment microtensile bond strength of self-adhesive resin cements

PubMed Central

Escribano, Nuria; Baracco, Bruno; Romero, Martin; Ceballos, Laura

2016-01-01

Background No specific indications about the pre-treatment of indirect composite restorations is provided by the manufacturers of most self-adhesive resin cements. The potential effect of silane treatment to the bond strength of the complete tooth/indirect restoration complex is not available.The aim of this study was to determine the contribution of different surface treatments on microtensile bond strength of composite overlays to dentin using several self-adhesive resin cements and a total-etch one. Material and Methods Composite overlays were fabricated and bonding surfaces were airborne-particle abraded and randomly assigned to two different surface treatments: no treatment or silane application (RelyX Ceramic Primer) followed by an adhesive (Adper Scotchbond 1 XT). Composite overlays were luted to flat dentin surfaces using the following self-adhesive resin cements: RelyX Unicem, G-Cem, Speedcem, Maxcem Elite or Smartcem2, and the total-etch resin cement RelyX ARC. After 24 h, bonded specimens were cut into sticks 1 mm thick and stressed in tension until failure. Two-way ANOVA and SNK tests were applied at α=0.05. Results Bond strength values were significantly influenced by the resin cement used (p<0.001). However, composite surface treatment and the interaction between the resin cement applied and surface treatment did not significantly affect dentin bond strength (p>0.05). All self-adhesive resin cements showed lower bond strength values than the total-etch RelyX ARC. Among self-adhesive resin cements, RelyX Unicem and G-Cem attained statistically higher bond strength values. Smartcem2 and Maxcem Elite exhibited 80-90% of pre-test failures. Conclusions The silane and adhesive application after indirect resin composite sandblasting did not improve the bond strength of dentin-composite overlay complex. Selection of the resin cement seems to be a more relevant factor when bonding indirect composites to dentin than its surface treatment. Key words:Bond strength, self-adhesive cement, silane, dentin, indirect composite. PMID:26855700

Bonding Effectiveness of Luting Composites to Different CAD/CAM Materials.

PubMed

Peumans, Marleen; Valjakova, Emilija Bajraktarova; De Munck, Jan; Mishevska, Cece Bajraktarova; Van Meerbeek, Bart

To evaluate the influence of different surface treatments of six novel CAD/CAM materials on the bonding effectiveness of two luting composites. Six different CAD/CAM materials were tested: four ceramics - Vita Mark II; IPS Empress CAD and IPS e.max CAD; Celtra Duo - one hybrid ceramic, Vita Enamic, and one composite CAD/CAM block, Lava Ultimate. A total of 60 blocks (10 per material) received various mechanical surface treatments: 1. 600-grit SiC paper; 2. sandblasting with 30-μm Al2O3; 3. tribochemical silica coating (CoJet). Subsequent chemical surface treatments involved either no further treatment (control), HF acid etching (HF), silanization (S, or HF acid etching followed by silanization (HF+S). Two specimens with the same surface treatment were bonded together using two dual-curing luting composites: Clearfil Esthetic Cement (self-etching) or Panavia SA Cement (self-adhesive). After 1 week of water storage, the microtensile bond strength of the sectioned microspecimens was measured and the failure mode was evaluated. The bonding performance of the six CAD/CAM materials was significantly influenced by surface treatment (linear mixed models, p < 0.05). The luting cement had a significant influence on bond strength for Celtra Duo and Lava Ultimate (linear mixed models, p < 0.05). Mechanical surface treatment significantly influenced the bond strength for Celtra Duo (p = 0.0117), IPS e.max CAD (p = 0.0115), and Lava Ultimate (p < 0.0001). Different chemical surface treatments resulted in the highest bond strengths for the six CAD/CAM materials: Vita Mark II and IPS Empress CAD: S, HF+S; Celtra Duo: HF, HF+S; IPS e.max CAD: HF+S; Vita Enamic: HF+S, S. For Lava Ultimate, the highest bond strengths were obtained with HF, S, HF+S. Failure analysis showed a relation between bond strength and failure type: more mixed failures were observed with higher bond strengths. Mainly adhesive failures were noticed if no further surface treatment was done. The percentage of adhesive failures was higher for CAD/CAM materials with higher flexural strength (Celtra Duo, IPS e.max CAD, and Lava Ultimate). The bond strength of luting composites to novel CAD/CAM materials is influenced by surface treatment. For each luting composite, an adhesive cementation protocol can be specified in order to obtain the highest bond to the individual CAD/CAM materials.

1.3 μm wavelength vertical cavity surface emitting laser fabricated by orientation-mismatched wafer bonding: A prospect for polarization control

NASA Astrophysics Data System (ADS)

Okuno, Yae L.; Geske, Jon; Gan, Kian-Giap; Chiu, Yi-Jen; DenBaars, Steven P.; Bowers, John E.

2003-04-01

We propose and demonstrate a long-wavelength vertical cavity surface emitting laser (VCSEL) which consists of a (311)B InP-based active region and (100) GaAs-based distributed Bragg reflectors (DBRs), with an aim to control the in-plane polarization of output power. Crystal growth on (311)B InP substrates was performed under low-migration conditions to achieve good crystalline quality. The VCSEL was fabricated by wafer bonding, which enables us to combine different materials regardless of their lattice and orientation mismatch without degrading their quality. The VCSEL was polarized with a power extinction ratio of 31 dB.

A Possible Sink for Methane on Mars

NASA Astrophysics Data System (ADS)

Nørnberg, P.; Jensen, S. J. K.; Skibsted, J.; Jakobsen, H. J.; ten Kate, I. L.; Gunnlaugsson, H. P.; Merrison, J. P.; Finster, K.; Bak, E.; Iversen, J. J.; Kondrup, J. C.

2014-07-01

Mechanical simulated wind activation of mineral surfaces act as a trap for Methane through formation of covalent Si-C bonds stable up to temperatures above 250 C. This mechanism is proposed as a Methane sink on Mars.

X-ray photoelectron spectroscopy and friction studies of nickel-zinc and manganese-zinc ferrites in contact with metals

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Buckley, D. H.

1983-01-01

X-ray photoelectron spectroscopy analysis and sliding friction experiments were conducted with hot-pressed, polycrystalline Ni-Zn and Mn-Zn ferrites in sliding contact with various transition metals at room temperature in a vacuum of 30 nPa. The results indicate that the coefficients of friction for Ni-Zn and Mn-Zn ferrites in contact with metals are related to the relative chemical activity in these metals: the more active the metal, the higher is the coefficient of friction. The coefficients of friction for the ferrites correlate with the free energy of formation of the lowest metal oxide. The interfacial bond can be regarded as a chemical bond between the metal atoms and the oxygen anions in the ferrite surfaces. The adsorption of oxygen on clean metal and ferrite surfaces increases the coefficients of friction for the Ni-Zn and Mn-Zn ferrite-metal interfaces.

Influence of atmospheric pressure low-temperature plasma treatment on the shear bond strength between zirconia and resin cement.

PubMed

Ito, Yuki; Okawa, Takahisa; Fukumoto, Takahiro; Tsurumi, Akiko; Tatsuta, Mitsuhiro; Fujii, Takamasa; Tanaka, Junko; Tanaka, Masahiro

2016-10-01

Zirconia exhibits excellent strength and high biocompatibility in technological applications and it is has therefore been investigated for clinical applications and research. Before setting prostheses, a crown prosthesis inner surface is sandblasted with alumina to remove contaminants and form small cavities. This alumina sandblasting causes stress-induced phase transition of zirconia. Atmospheric-pressure low-temperature plasma has been applied in the dental industry, particularly for adhesives, as a surface treatment to activate the surface energy and remove contaminants. The purpose of this study was to examine the influence of atmospheric-pressure low-temperature plasma treatment on the shear bond strength between zirconia and adhesive resin cement. The surface treatment method was classified into three groups: untreated (Cont group), alumina sandblast treatment (Sb group), and atmospheric-pressure low-temperature plasma treatment (Ps group). Adhesive resin cement was applied to stainless steel and bonded to zirconia. Shear adhesion tests were performed after complete hardening of the cement. Multiple comparisons were performed using a one-way analysis of variance and the Bonferroni method. X-ray diffractometry was used to examine the change in zirconia crystal structure. Statistically significant differences were noted between the control and Sb groups and between the control and Ps groups. In contrast, no statistically significant differences were noted for the Ps and Sb bond strength. Atmospheric-pressure low-temperature plasma treatment did not affect the zirconia crystal structure. Atmospheric-pressure low-temperature plasma treatment improves the bonding strength of adhesive resin cement as effectively as alumina sandblasting, and does not alter the zirconia crystal structure. Copyright © 2016 Japan Prosthodontic Society. Published by Elsevier Ltd. All rights reserved.

Gas phase chemistry in gallium nitride CVD: Theoretical determination of the Arrhenius parameters for the first Ga-C bond homolysis of trimethylgallium.

PubMed

Schmid, Rochus; Basting, Daniel

2005-03-24

Experimental evidence suggests that the energy of activation for the first homolytic Ga-C bond fission of GaMe3 of Ea = 249 kJ/mol, measured by Jacko and Price in a hot-wall tube reactor, is affected by surface catalytic effects. In this contribution, the rate constant for this crucial step in the gas-phase pyrolysis of GaMe3 has been calculated by variational transition state theory. By a basis set extrapolation on the MP2/cc-pVXZ level and a correlation correction from CCSD(T)/cc-pVDZ level, a theoretical "best estimate" for the bond energy of Delta H(289K) = 327.2 kJ/mol was derived. For the VTST calculation on the B3LYP/cc-pVDZ level, the energies were corrected to reproduce this bond energy. Partition functions of the transitional modes were approximated by a hindered rotor approximation to be valid along the whole reaction coordinate defined by the Ga-C bond length. On the basis of the canonical transition state theory, reaction rates were determined using the maxima of the free energy Delta G++. An Arrhenius-type rate law was fitted to these rate constants, yielding an apparent energy of activation of Ea = 316.7 kJ/mol. The preexponential factor A = 3.13 x 10(16) 1/s is an order of magnitude larger than the experimental results because of a larger release of entropy at the transition state as compared to that of the unknown surface catalyzed mechanism.

Chemical activation of molecules by metals: Experimental studies of electron distributions and bonding

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

Lichtenberger, D.L.

1991-10-01

The formal relationship between measured molecular ionization energies and thermodynamic bond dissociation energies has been developed into a single equation which unifies the treatment of covalent bonds, ionic bonds, and partially ionic bonds. This relationship has been used to clarify the fundamental thermodynamic information relating to metal-hydrogen, metal-alkyl, and metal-metal bond energies. We have been able to obtain a direct observation and measurement of the stabilization energy provided by the agostic interaction of the C-H bond with the metal. The ionization energies have also been used to correlate the rates of carbonyl substitution reactions of ({eta}{sup 5}-C{sub 5}H{sub 4}X)Rh(CO){sub 2}more » complexes, and to reveal the electronic factors that control the stability of the transition state. The extent that the electronic features of these bonding interactions transfer to other chemical systems is being investigated in terms of the principle of additivity of ligand electronic effects. Specific examples under study include metal- phosphines, metal-halides, and metallocenes. Especially interesting has been the recent application of these techniques to the characterization of the soccer-ball shaped C{sub 60} molecule, buckminsterfullerene, and its interaction with a metal surface. The high-resolution valence ionizations in the gas phase reveal the high symmetry of the molecule, and studies of thin films of C{sub 60} reveal weak intermolecular interactions. Scanning tunneling and atomic force microscopy reveal the arrangement of spherical molecules on gold substrates, with significant delocalization of charge from the metal surface. 21 refs.« less

Solid frustrated-Lewis-pair catalysts constructed by regulations on surface defects of porous nanorods of CeO2

PubMed Central

Zhang, Sai; Huang, Zheng-Qing; Ma, Yuanyuan; Gao, Wei; Li, Jing; Cao, Fangxian; Li, Lin; Chang, Chun-Ran; Qu, Yongquan

2017-01-01

Identification on catalytic sites of heterogeneous catalysts at atomic level is important to understand catalytic mechanism. Surface engineering on defects of metal oxides can construct new active sites and regulate catalytic activity and selectivity. Here we outline the strategy by controlling surface defects of nanoceria to create the solid frustrated Lewis pair (FLP) metal oxide for efficient hydrogenation of alkenes and alkynes. Porous nanorods of ceria (PN-CeO2) with a high concentration of surface defects construct new Lewis acidic sites by two adjacent surface Ce3+. The neighbouring surface lattice oxygen as Lewis base and constructed Lewis acid create solid FLP site due to the rigid lattice of ceria, which can easily dissociate H–H bond with low activation energy of 0.17 eV. PMID:28516952

Mesoporous MnCeO x solid solutions for low temperature and selective oxidation of hydrocarbons

DOE PAGES

Zhang, Pengfei; Lu, Hanfeng; Zhou, Ying; ...

2015-10-15

The development of noble-metal-free heterogeneous catalysts that can realize the aerobic oxidation of C–H bonds at low temperature is a profound challenge in the catalysis community. Here we report the synthesis of a mesoporous Mn 0.5Ce 0.5O x solid solution that is highly active for the selective oxidation of hydrocarbons under mild conditions (100–120 °C). Notably, the catalytic performance achieved in the oxidation of cyclohexane to cyclohexanone/cyclohexanol (100 °C, conversion: 17.7%) is superior to those by the state-of-art commercial catalysts (140–160 °C, conversion: 3-5%). Finally, the high activity can be attributed to the formation of a Mn 0.5Ce 0.5O xmore » solid solution with an ultrahigh manganese doping concentration in the CeO 2 cubic fluorite lattice, leading to maximum active surface oxygens for the activation of C–H bonds and highly reducible Mn 4+ ions for the rapid migration of oxygen vacancies from the bulk to the surface.« less

Mesoporous MnCeOx solid solutions for low temperature and selective oxidation of hydrocarbons

PubMed Central

Zhang, Pengfei; Lu, Hanfeng; Zhou, Ying; Zhang, Li; Wu, Zili; Yang, Shize; Shi, Hongliang; Zhu, Qiulian; Chen, Yinfei; Dai, Sheng

2015-01-01

The development of noble-metal-free heterogeneous catalysts that can realize the aerobic oxidation of C–H bonds at low temperature is a profound challenge in the catalysis community. Here we report the synthesis of a mesoporous Mn0.5Ce0.5Ox solid solution that is highly active for the selective oxidation of hydrocarbons under mild conditions (100–120 °C). Notably, the catalytic performance achieved in the oxidation of cyclohexane to cyclohexanone/cyclohexanol (100 °C, conversion: 17.7%) is superior to those by the state-of-art commercial catalysts (140–160 °C, conversion: 3-5%). The high activity can be attributed to the formation of a Mn0.5Ce0.5Ox solid solution with an ultrahigh manganese doping concentration in the CeO2 cubic fluorite lattice, leading to maximum active surface oxygens for the activation of C–H bonds and highly reducible Mn4+ ions for the rapid migration of oxygen vacancies from the bulk to the surface. PMID:26469151

Antibacterial and remineralizing orthodontic adhesive containing quaternary ammonium resin monomer and amorphous calcium phosphate nanoparticles.

PubMed

Liu, Yan; Zhang, Ling; Niu, Li-Na; Yu, Tao; Xu, Hockin H K; Weir, Michael D; Oates, Thomas W; Tay, Franklin R; Chen, Ji-Hua

2018-05-01

To evaluate the bonding performance, antibacterial activity, and remineralization effect on enamel of the orthodontic adhesive containing MAE-DB and NACP. Eighty non-carious human premolars were divided into 3 groups: Transbond XT (TB), PEHB + 5% MAE-DB (PD), and PEHB + 40% NACP + 5% MAE-DB (PND). Premolars were bonded with orthodontic brackets, the first subgroup (n = 10) and the second subgroup (n = 10) were subjected to shear bond strength testing after immersed in water for 1 day and in demineralization solution for 28 days respectively and then tested surface roughness, while the third subgroup (n = 6) was used for microhardness evaluation after aged in demineralization solution for 28 days. For each adhesive, fifty disk samples were prepared for antibacterial study. Specimens measuring 12 mm × 2 mm × 2 mm were fabricated for ion release test. Bond strengths were in the order TB = PND > PND = PD for "1-day in water", and in the order TB = PND > PD for "28-days in pH 4 solution". No significant difference in the ARI scores for the three adhesive. Numerous bacteria adhered to TB surface, while PD and PND had minimal bacterial growth and activity. PND showed high levels of Ca and P ions release and enamel hardness. The surface roughness of enamel in PND was much lower than TB and PD and showed no significant difference with the sound, control enamel. PND adhesive with 5% MAE-DB and 40% NACP exhibits antibacterial and remineralizing capabilities, and did not adversely affect bond strength compared to commercial adhesive. Novel adhesive containing quaternary ammonium monomer and nano-amorphous calcium phosphate represents a promising candidate in combating enamel white spot lesions and even dental caries. Copyright © 2018 Elsevier Ltd. All rights reserved.

Shear Bond Strength of Three Orthodontic Bonding Systems on Enamel and Restorative Materials.

PubMed

Hellak, Andreas; Ebeling, Jennifer; Schauseil, Michael; Stein, Steffen; Roggendorf, Matthias; Korbmacher-Steiner, Heike

2016-01-01

Objective. The aim of this in vitro study was to determine the shear bond strength (SBS) and adhesive remnant index (ARI) score of two self-etching no-mix adhesives (iBond ™ and Scotchbond ™ ) on different prosthetic surfaces and enamel, in comparison with the commonly used total etch system Transbond XT ™ . Materials and Methods . A total of 270 surfaces (1 enamel and 8 restorative surfaces, n = 30) were randomly divided into three adhesive groups. In group 1 (control) brackets were bonded with Transbond XT primer. In the experimental groups iBond adhesive (group 2) and Scotchbond Universal adhesive (group 3) were used. The SBS was measured using a Zwicki 1120 ™ testing machine. The ARI and SBS were compared statistically using the Kruskal-Wallis test ( P ≤ 0.05). Results . Significant differences in SBS and ARI were found between the control group and experimental groups. Conclusions . Transbond XT showed the highest SBS on human enamel. Scotchbond Universal on average provides the best bonding on all other types of surface (metal, composite, and porcelain), with no need for additional primers. It might therefore be helpful for simplifying bonding in orthodontic procedures on restorative materials in patients. If metal brackets have to be bonded to a metal surface, the use of a dual-curing resin is recommended.

Evaluation of surface roughness of enamel after various bonding and clean-up procedures on enamel bonded with three different bonding agents: An in-vitro study

PubMed Central

Goel, Amit; Singh, Atul; Gupta, Tarun

2017-01-01

Background The purpose of this study was to analyze and compare the enamel surface roughness before bonding and after debonding, to find correlation between the adhesive remnant index and its effect on enamel surface roughness and to evaluate which clean-up method is most efficient to provide a smoother enamel surface. Material and Methods 135 premolars were divided into 3 groups containing 45 premolars in each group. Group I was bonded by using moisture insensitive primer, Group II by using conventional orthodontic adhesive and Group III by using self-etching primer. Each group was divided into 3 sub-groups on the basis of type of clean-up method applied i,e scaling followed by polishing, tungsten carbide bur and Sof-Lex disc. Enamel surface roughness was measured and compared before bonding and after clean-up. Results Evaluation of pre bonding and post clean-up enamel surface roughness (Ra value) with the t test showed that Post clean-up Ra values were greater than Pre bonding Ra values in all the groups except in teeth bonded with self-etching primer cleaned with Sof-Lex disc. Reliability of ARI score taken at different time interval tested with Kruskal Wallis test suggested that all the readings were reliable. Conclusions No clean-up procedure was able to restore the enamel to its original smoothness. Self-etching primer and Sof-Lex disc clean-up method combination restored the enamel surface roughness (Ra value) closest to its pre-treatment value. Key words:Enamel surface roughness, clean-up method, adhesive remnant index. PMID:28512535

Method of bonding functional surface materials to substrates and applications in microtechnology and anti-fouling

DOEpatents

Feng, Xiangdong; Liu, Jun; Liang, Liang

2001-01-01

A simple and effective method to bond a thin coating of poly(N-isopropylacylamide) (NIPAAm) on a glass surface by UV photopolymerization, and the use of such a coated surface in nano and micro technology applications. A silane coupling agent with a dithiocarbamate group is provided as a photosensitizer preferably, (N,N'-diethylamine) dithiocarbamoylpropyl-(trimethoxy) silane (DATMS). The thiocarbamate group of the sensitizer is then bonded to the glass surface by coupling the silane agent with the hydroxyl groups on the glass surface. The modified surface is then exposed to a solution of NIPAAm and a crosslinking agent which may be any organic molecule having an acrylamide group and at least two double bonds in its structure, such as N, N'-methylenebisacrylamide, and a polar solvent which may be any polar liquid which will dissolve the monomer and the crosslinking agent such as acetone, water, ethanol, or combinations thereof. By exposing the glass surface to a UV light, free radicals are generated in the thiocarbamate group which then bonds to the crosslinking agent and the NIPAAm. Upon bonding, the crosslinking agent and the NIPAAm polymerize to form a thin coating of PNIPAAm bonded to the glass. Depending upon the particular configuration of the glass, the properties of the PNIPAAm allow applications in micro and nano technology.

Method of bonding functional surface materials to substrates and applications in microtechnology and antifouling

DOEpatents

Feng, Xiangdong; Liu, Jun; Liang, Liang

1999-01-01

A simple and effective method to bond a thin coating of poly(N-isopropylacylamide) (NIPAAm) on a glass surface by UV photopolymerization, and the use of such a coated surface in nano and micro technology applications. A silane coupling agent with a dithiocarbamate group is provided as a photosensitizer, preferably, (N,N'-diethylamine)dithiocarbamoylpropyl-(trimethoxy)silane (DATMS). The thiocarbamate group of the sensitizer is then bonded to the glass surface by coupling the silane agent with the hydroxyl groups on the glass surface. The modified surface is then exposed to a solution of NIPAAm and a crosslinking agent which may be any organic molecule having an acrylamide group and at least two double bonds in its structure, such as N,N'-methylenebisacrylamide, and a polar solvent which may be any polar liquid which will dissolve the monomer and the crosslinking agent such as acetone, water, ethanol, or combinations thereof. By exposing the glass surface to a UV light, free radicals are generated in the thiocarbamate group which then bonds to the crosslinking agent and the NIPAAm. Upon bonding, the crosslinking agent and the NIPAAm polymerize to form a thin coating of PNIPAAm bonded to the glass. Depending upon the particular configuration of the glass, the properties of the PNIPAAm allow applications in micro and nano technology.

Incorporation of low energy activated nitrogen onto HOPG surface: Chemical states and thermal stability studies by in-situ XPS and Raman spectroscopy

NASA Astrophysics Data System (ADS)

Chandran, Maneesh; Shasha, Michal; Michaelson, Shaul; Hoffman, Alon

2016-09-01

In this paper we report the chemical states analysis of activated nitrogen incorporated highly oriented pyrolytic graphite (HOPG) surface under well-controlled conditions. Nitrogen incorporation is carried out by two different processes: an indirect RF nitrogen plasma and low energy (1 keV) N2+ implantation. Bonding configuration, concentration and thermal stability of the incorporated nitrogen species by aforesaid processes are systematically compared by in-situ X-ray photoelectron spectroscopy (XPS). Relatively large concentration of nitrogen is incorporated onto RF nitride HOPG surface (16.2 at.%), compared to N2+ implanted HOPG surface (7.7 at.%). The evolution of N 1s components (N1, N2, N3) with annealing temperature is comprehensively discussed, which indicates that the formation and reorganization of local chemical bonding states are determined by the process of nitridation and not by the prior chemical conditioning (i.e., amorphization or hydrogenation) of the HOPG surface. A combined XPS and Raman spectroscopy studies revealed that N2+ implantation process resulted in a high level of defects to the HOPG surface, which cannot be annealed-out by heat treatment up to 1000 °C. On the other hand, the RF nitrogen plasma process did not produce a high level of surface defects, while incorporating nearly the same amount of stable nitrogen species.

Does 8-methacryloxyoctyl trimethoxy silane (8-MOTS) improve initial bond strength on lithium disilicate glass ceramic?

PubMed

Maruo, Yukinori; Nishigawa, Goro; Yoshihara, Kumiko; Minagi, Shogo; Matsumoto, Takuya; Irie, Masao

2017-03-01

Dental ceramic surfaces are modified with silane coupling agents, such as γ-methacryloxypropyl trimethoxy silane (γ-MPTS), to improve bond strength. For bonding between lithium disilicate glass ceramic and resin cement, the objective was to investigate if 8-methacryloxyoctyl trimethoxy silane (8-MOTS) could yield a similar performance as the widely used γ-MPTS. One hundred and ten lithium disilicate glass ceramic specimens were randomly divided into 11 groups (n=10) according to pretreatment regime. All specimens were pretreated with a different solution composed of one or a combination of these agents: 10 or 20wt% silane coupling agent of γ-MPTS or 8-MOTS, followed by a hydrolysis solution of acetic acid or 10-methacryloyloxydecyl dihydrogen phosphate (10-MDP). Each pretreated surface was luted to a stainless steel rod of 3.6mm diameter and 2.0mm height with resin cement. Shear bond strength between ceramic and cement was measured after 24-h storage in 37°C distilled water. 8-MOTS produced the same bonding performance as γ-MPTS. Both silane coupling agents significantly increased the bond strength of resin cement, depending on their concentration. When activated by 10-MDP hydrolysis solution, 20wt% concentration produced the highest values (γ-MPTS: 24.9±5.1MPa; 8-MOTS: 24.6±7.4MPa). Hydrolysis with acetic acid produced lower bond strengths than with 10-MDP. Silane coupling pretreatment with 8-MOTS increased the initial bond strength between lithium disilicate glass ceramic and resin cement, rendering the same bonding effect as the conventional γ-MPTS. Copyright © 2016 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Reaction pathways of biomass-derived oxygenates on noble metal surfaces

NASA Astrophysics Data System (ADS)

McManus, Jesse R.

As the global demand for energy continues to rise, the environmental concerns associated with increased fossil fuel consumption have motivated the use of biomass as an alternative, carbon-renewable energy feedstock. Controlling reactive chemistry of the sugars that comprise biomass through the use of catalysis becomes essential in effectively producing green fuels and value-added chemicals. Recent work on biomass conversion catalysts have demonstrated the efficacy of noble metal catalyst systems for the reforming of biomass to hydrogen fuel, and the hydrodeoxygenation of biomass-derived compounds to value-added chemicals. In particular, Pt and Pd surfaces have shown considerable promise as reforming catalysts in preliminary aqueous phase reforming studies. It becomes important to understand the mechanisms by which these molecules react on the catalyst surfaces in order to determine structure-activity relationships and bond scission energetics as to provide a framework for engineering more active and selective catalysts. Fundamental surface science techniques provide the tools to do this; however, work in this field has been so far limited to simple model molecules like ethanol and ethylene glycol. Herein, temperature programmed desorption and high resolution electron energy loss spectroscopy are utilized in an ultra-high vacuum surface science study of the biomass-derived sugar glucose on Pt and Pd single crystal catalysts. Overall, it was determined that the aldehyde function of a ring-open glucose molecule plays an integral part in the initial bonding and reforming reaction pathway, pointing to the use of aldoses glycolaldehyde and glyceraldehyde as the most appropriate model compounds for future studies. Furthermore, the addition of adatom Zn to a Pt(111) surface was found to significantly decrease the C-H and C-C bond scission activity in aldehyde containing compounds, resulting in a preferred deoxygenation pathway in opposition to the decarbonylation pathway common on clean Pt(111). This has implications in the hydrodeoxygenation of biomass-derived compounds for the production of value-added chemicals like 2-methylfuran from furfural, or the catalytic upgrading of sugars. Ultimately, identification of the reactive mechanisms of biomass-derived molecules on different unique surfaces has lead to a greater understanding for what makes a more selective catalyst for specific chemical pathways.

Influence of de/remineralization of enamel on the tensile bond strength of etch-and-rinse and self-etching adhesives.

PubMed

Farias de Lacerda, Ana Julia; Ferreira Zanatta, Rayssa; Crispim, Bruna; Borges, Alessandra Bühler; Gomes Torres, Carlos Rocha; Tay, Franklin R; Pucci, Cesar Rogério

2016-10-01

To evaluate the bonding behavior of resin composite and different adhesives applied to demineralized or remineralized enamel. Bovine tooth crowns were polished to prepare a 5 mm2 enamel bonding area, and divided into five groups (n= 48) according to the surface treatment: CONT (sound enamel control), DEM (demineralized with acid to create white spot lesions), REMS (DEM remineralized with artificial saliva), REMF (DEM remineralized with sodium fluoride) and INF (DEM infiltrated with Icon resin infiltrant). The surface-treated teeth were divided into two subgroups (n= 24) according to adhesive type: ER (etch-and-rinse; Single Bond Universal) and SE (self-etching; Clearfill S3 Bond), and further subdivided into two categories (n= 12) according to aging process: Thermo (thermocycling) and NA (no aging). Composite blocks were made over bonded enamel and sectioned for microtensile bond strength (MTBS) testing. Data were analyzed with three-way ANOVA and post-hoc Tukey's test (α= 0.05). Significant differences were observed for enamel surface treatment (P< 0.0001), adhesive type (P< 0.0001) and aging (P< 0.0001). CONT and INF groups had higher MTBS than the other groups; Single Bond Universal had higher MTBS than Clearfil S3 Bond; thermo-aging resulted in lower MTBS irrespective of adhesive type and surface treatment condition. The predominant failure mode was mixed for all groups. Enamel surface infiltrated with Icon does not interfere with adhesive resin bonding procedures. Treatment of enamel surface containing white spot lesions or cavities with cavosurface margins in partially-demineralized enamel can benefit from infiltration with a low viscosity resin infiltrant prior to adhesive bonding of resin composites.

The effect of Er:YAG laser irradiation on the bond stability of self-etch adhesives at different dentin depths.

PubMed

Karadas, Muhammet; Çağlar, İpek

2017-07-01

The aim of this study was to evaluate the effect of Er:YAG laser irradiation on the micro-shear bond strength of self-etch adhesives to the superficial dentin and the deep dentin before and after thermocycling. Superficial dentin and deep dentin surfaces were prepared by flattening of the occlusal surfaces of extracted human third molars. The deep or superficial dentin specimens were randomized into three groups according to the following surface treatments: group I (control group), group II (Er:YAG laser; 1.2 W), and group III (Er:YAG laser; 0.5 W). Clearfil SE Bond or Clearfil S 3 Bond was applied to each group's dentin surfaces. After construction of the composite blocks on the dentin surface, the micro-shear bond testing of each adhesive was performed at 24 h or after 15,000 thermal cycles. The data were analyzed using a univariate analysis of variance and Tukey's test (p < 0.05). Laser irradiation in superficial dentin did not significantly affect bond strength after thermocycling (p > 0.05). However, deep-dentin specimens irradiated with laser showed significantly higher bond strengths than did control specimens after thermocycling (p < 0.05). Thermocycling led to significant deterioration in the bond strengths of all deep-dentin groups. The stable bond strength after thermocycling was measured for all of the superficial-dentin groups. No significant difference was found between the 0.5 and 1.2 W output power settings. In conclusion, the effect of laser irradiation on the bond strength of self-etch adhesives may be altered by the dentin depth. Regardless of the applied surface treatment, deep dentin showed significant bond degradation.

Sintered silver joints via controlled topography of electronic packaging subcomponents

DOEpatents

Wereszczak, Andrew A.

2014-09-02

Disclosed are sintered silver bonded electronic package subcomponents and methods for making the same. Embodiments of the sintered silver bonded EPSs include topography modification of one or more metal surfaces of semiconductor devices bonded together by the sintered silver joint. The sintered silver bonded EPSs include a first semiconductor device having a first metal surface, the first metal surface having a modified topography that has been chemically etched, grit blasted, uniaxial ground and/or grid sliced connected to a second semiconductor device which may also include a first metal surface with a modified topography, a silver plating layer on the first metal surface of the first semiconductor device and a silver plating layer on the first metal surface of the second semiconductor device and a sintered silver joint between the silver plating layers of the first and second semiconductor devices which bonds the first semiconductor device to the second semiconductor device.

Method for making electro-fluidic connections in microfluidic devices

DOEpatents

Frye-Mason, Gregory C.; Martinez, David; Manginell, Ronald P.; Heller, Edwin J.; Chanchani, Rajen

2004-08-10

A method for forming electro-fluidic interconnections in microfluidic devices comprises forming an electrical connection between matching bond pads on a die containing an active electrical element and a microfluidic substrate and forming a fluidic seal ring that circumscribes the active electrical element and a fluidic feedthrough. Preferably, the electrical connection and the seal ring are formed in a single bonding step. The simple method is particularly useful for chemical microanalytical systems wherein a plurality of microanalytical components, such as a chemical preconcentrator, a gas chromatography column, and a surface acoustic wave detector, are fluidically interconnected on a hybrid microfluidic substrate having electrical connection to external support electronics.

Probing the energetics of organic–nanoparticle interactions of ethanol on calcite

PubMed Central

Wu, Di; Navrotsky, Alexandra

2015-01-01

Knowing the nature of interactions between small organic molecules and surfaces of nanoparticles (NP) is crucial for fundamental understanding of natural phenomena and engineering processes. Herein, we report direct adsorption enthalpy measurement of ethanol on a series of calcite nanocrystals, with the aim of mimicking organic–NP interactions in various environments. The energetics suggests a spectrum of adsorption events as a function of coverage: strongest initial chemisorption on active sites on fresh calcite surfaces, followed by major chemical binding to form an ethanol monolayer and, subsequently, very weak, near-zero energy, physisorption. These thermochemical observations directly support a structure where the ethanol monolayer is bonded to the calcite surface through its polar hydroxyl group, leaving the hydrophobic ends of the ethanol molecules to interact only weakly with the next layer of adsorbing ethanol and resulting in a spatial gap with low ethanol density between the monolayer and subsequent added ethanol molecules, as predicted by molecular dynamics and density functional calculations. Such an ordered assembly of ethanol on calcite NP is analogous to, although less strongly bonded than, a capping layer of organics intentionally introduced during NP synthesis, and suggests a continuous variation of surface structure depending on molecular chemistry, ranging from largely disordered surface layers to ordered layers that nevertheless are mobile and can rearrange or be displaced by other molecules to strongly bonded immobile organic capping layers. These differences in surface structure will affect chemical reactions, including the further nucleation and growth of nanocrystals on organic ligand-capped surfaces. PMID:25870281

Bonded ultrasonic transducer and method for making

DOEpatents

Dixon, Raymond D.; Roe, Lawrence H.; Migliori, Albert

1995-01-01

An ultrasonic transducer is formed as a diffusion bonded assembly of piezoelectric crystal, backing material, and, optionally, a ceramic wear surface. The mating surfaces of each component are silver films that are diffusion bonded together under the application of pressure and heat. Each mating surface may also be coated with a reactive metal, such as hafnium, to increase the adhesion of the silver films to the component surfaces. Only thin silver films are deposited, e.g., a thickness of about 0.00635 mm, to form a substantially non-compliant bond between surfaces. The resulting transducer assembly is substantially free of self-resonances over normal operating ranges for taking resonant ultrasound measurements.

Piezocomposite Actuator Arrays for Correcting and Controlling Wavefront Error in Reflectors

NASA Technical Reports Server (NTRS)

Bradford, Samuel Case; Peterson, Lee D.; Ohara, Catherine M.; Shi, Fang; Agnes, Greg S.; Hoffman, Samuel M.; Wilkie, William Keats

2012-01-01

Three reflectors have been developed and tested to assess the performance of a distributed network of piezocomposite actuators for correcting thermal deformations and total wave-front error. The primary testbed article is an active composite reflector, composed of a spherically curved panel with a graphite face sheet and aluminum honeycomb core composite, and then augmented with a network of 90 distributed piezoelectric composite actuators. The piezoelectric actuator system may be used for correcting as-built residual shape errors, and for controlling low-order, thermally-induced quasi-static distortions of the panel. In this study, thermally-induced surface deformations of 1 to 5 microns were deliberately introduced onto the reflector, then measured using a speckle holography interferometer system. The reflector surface figure was subsequently corrected to a tolerance of 50 nm using the actuators embedded in the reflector's back face sheet. Two additional test articles were constructed: a borosilicate at window at 150 mm diameter with 18 actuators bonded to the back surface; and a direct metal laser sintered reflector with spherical curvature, 230 mm diameter, and 12 actuators bonded to the back surface. In the case of the glass reflector, absolute measurements were performed with an interferometer and the absolute surface was corrected. These test articles were evaluated to determine their absolute surface control capabilities, as well as to assess a multiphysics modeling effort developed under this program for the prediction of active reflector response. This paper will describe the design, construction, and testing of active reflector systems under thermal loads, and subsequent correction of surface shape via distributed peizeoelctric actuation.

Effect of blood and saliva contamination on bond strength of brackets bonded with a protective liquid polish and a light-cured adhesive.

PubMed

Sayinsu, Korkmaz; Isik, Fulya; Sezen, Serdar; Aydemir, Bulent

2007-03-01

The application of a polymer coating to the labial enamel tooth surface before bonding can help keep white spot lesions from forming. Previous studies evaluating the effects of blood and saliva contamination on the bond strengths of light-cured composites showed significant reductions in bond strength values. The purpose of this study was to investigate whether the bond strength of a light-cured system (Transbond XT, 3M Unitek, Puchheim, Germany) used with a liquid polish (BisCover, Bisco, Schaumburg, Ill) is affected by contamination with blood or saliva. One hundred twenty permanent human premolars were randomly divided into 6 groups of 20. Various enamel surface conditions were studied: dry, blood contaminated, and saliva contaminated. A light-cured bonding system (Transbond XT) was used in all groups. The teeth in group 1 were bonded with Transbond XT. In the second group, BisCover polymeric resin polish was applied on the etched tooth surfaces before the brackets were bonded with Transbond XT resin. Comparison of the first and second groups showed no statistically significant difference. Groups 3 through 6 were bonded without Transbond XT. For groups 3 and 5, a layer of blood or saliva, respectively, was applied to the etched enamel followed by BisCover. In groups 4 and 6, blood or saliva, respectively, was applied on the light-cured BisCover. Shear forces were applied to the samples with a universal testing machine, and bond strengths were measured in megapascals. The protective liquid polish (BisCover) layer did not affect bond strength. Blood contamination on acid-etched surfaces affects bond strength more than saliva contamination. When a protective liquid polish (BisCover) is applied to the tooth surface, the effect of contamination by blood or saliva is prevented.

Characterisation of CFRP surface contamination by laser induced fluorescence

NASA Astrophysics Data System (ADS)

Malinowski, Pawel H.; Sawczak, Miroslaw; Wandowski, Tomasz; Ostachowicz, Wieslaw M.; Cenian, Adam

2014-03-01

The application of Carbon Fibre Reinforced Polymers (CFRP) in aeronautics has been increasing. The CFRP elements are joint using rivets and adhesive bonding. The reliability of the bonding limits the use of adhesive bonding for primary aircraft structures, therefore it is important to assess the bond quality. The performance of adhesive bonds depends on the physico-chemical properties of the adhered surfaces. This research is focused on characterization of surfaces before bonding. In-situ examination of large surface materials, determine the group of methods that are preferred. The analytical methods should be non-destructive, enabling large surface analysis in relatively short time. In this work a spectroscopic method was tested that can be potentially applied for surface analysis. Four cases of surface condition were investigated that can be encountered either in the manufacturing process or during aircraft service. The first case is related to contamination of CFRP surface with hydraulic fluid. This fluid reacts with water forming a phosphoric acid that can etch the CFRP. Second considered case was related to silicone-based release agent contamination. These agents are used during the moulding process of composite panels. Third case involved moisture content in CFRP. Moisture content lowers the adhesion quality and leads to reduced performance of CFRP resulting in reduced performance of the adhesive bond. The last case concentrated on heat damage of CFRP. It was shown that laser induced fluorescence method can be useful for non-destructive evaluation of CFRP surface and some of the investigated contaminants can be easily detected.

Importance of interatomic spacing in catalytic reduction of oxygen in phosphoric acid

NASA Technical Reports Server (NTRS)

Jalan, V.; Taylor, E. J.

1983-01-01

A correlation between the nearest-neighbor distance and the oxygen reduction activity of various platinum alloys is reported. It is proposed that the distance between nearest-neighbor Pt atoms on the surface of a supported catalyst is not ideal for dual site absorption of O2 or 'HO2' and that the introduction of foreign atoms which reduce the Pt nearest-neighbor spacing would result in higher oxygen reduction activity. This may allow the critical 0-0 bond interatomic distance and hence the optimum Pt-Pt separation for bond rupture to be determined from quantum chemical calculations. A composite analysis shows that the data on supported Pt alloys are consistent with Appleby's (1970) data on bulk metals with respect to specific activity, activation energy, preexponential factor, and percent d-band character.

Crystalline Structure and Surface Reactivity: Atomistic models are unique tools for dealing with the chemical and physical properties of surfaces.

PubMed

Gatos, H C

1962-08-03

The role of crystalline structure in the surface reactivity of predominantly covalent materials has been examined in terms of chemical bonding concepts. In this context a solid surface can be viewed as a giant lattice defect characterized by dangling bonds. Although it is difficult, at the present stage of development of the quantum mechanical approach to surfaces, to define precisely the perturbations resulting from the abrupt termination of the lattice at the surface, a host of experimental observations can be understood by assuming displacements of surface atoms and distortions of bonding configurations in accordance with simple chemical bonding principles. A purely atomistic approach has been shown to account not only for the chemical behavior but also for certain structural and electrical characteristics of the surfaces considered. A number of phenomena, such as crystal growth and the behavior of certain lattice defects (for example, dislocations), are intimately related to the presence of dangling bonds and the associated distortions of the lattice at the surface (32).

Preparation and Electrocatalytic Activity of Gold Nanoparticles Immobilized on the Surface of 4-Mercaptobenzoyl-Functionalized Multiwalled Carbon Nanotubes

DTIC Science & Technology

2010-12-20

thiolate -Au bonds,30 and so GNP/MB-MWCNT hybrids were synthesized using a modified literature procedure.31 The SEM images show sequential...4 The electrocatalytic stability of GNP/MB-MWCNT supposes to be originated from the formation of stable thiolate -Au bonds that prevent aggregation of...Moon, K.-S.; Wong, C. P. Carbon 2007, 45, 655–661. (19) Sandler, J.; Shaffer, M. S. P.; Prasse, T.; Bauhofer, W.; Schulte, K.; Windle, A. H. Polymer

[The influence of surface conditioning on the shear bond strength of La-Porcelain and titanium].

PubMed

Mo, Anchun; Cen, Yuankun; Liao, Yunmao

2003-04-20

To determine the influence of different surface conditioning methods on bonding strength of low fusing porcelain (La-Porcelain) and titanium. The surface of the samples were sandblasted for 2 min with 80-250 microns Al2O3 or coated for two times with Si-couple agent or conditioned by pre-oxidation. The shear bond strength was examined by push-type shear test with a speed of 0.5 mm/min in a universal testing machine. Scanning electron microscopy (SEM) and electron probe micro-analyzer (EPMA) were employed to explore the relationship between bonding strength and microstructures, as well as the element diffusion at the interface between porcelain coating and titanium when heated at 800 degrees C. Bonding strength was not statistically different (P > 0.05) after sandblasting with Al2O3 in particle size ranged from 80 microns to 250 microns. When a Si-couple agent was used, bond of porcelain to titanium was significantly lower (P < 0.05). The shear bond strength of the porcelain to the pre-oxidized titanium surface remained unchanged after heating (P > 0.05). The SEM results revealed integrity of porcelain and titanium. La-Porcelain showed a small effect of surface coarseness. Sandblasting the titanium surface with 150-180 microns Al2O3 can be recommended as a method for better bonding between La-Porcelain and titanium. The Si-couple agent coating and pre-oxidation of titanium surface is unnecessary.

Laser Ablation Surface Preparation of Ti-6A1-4V for Adhesive Bonding

NASA Technical Reports Server (NTRS)

Palmieri, Frank L.; Watson, Kent A.; Morales, Guillermo; Williams, Thomas; Hicks, Robert; Wohl, Christopher J.; Hopkins, John W.; Connell, John W.

2012-01-01

Adhesive bonding offers many advantages over mechanical fastening, but requires certification before it can be incorporated in primary structures for commercial aviation without disbond-arrestment features or redundant load paths. Surface preparation is widely recognized as the key step to producing robust and predictable bonds. Laser ablation imparts both topographical and chemical changes to a surface which can lead to increased bond durability. A laser based process provides an alternative to chemical-dip, manual abrasion and grit blast treatments which are expensive, hazardous, polluting, and less precise. This report documents preliminary testing of a surface preparation technique using laser ablation as a replacement for the chemical etch and abrasive processes currently applied to Ti-6Al-4V alloy adherends. Failure mode, surface roughness, and chemical makeup were analyzed using fluorescence enhanced visualization, microscopy, and X-ray photoelectron spectroscopy, respectively. Single lap shear tests were conducted on bonded and aged specimens to observe bond strength retention and failure mode. Some promising results showed increasing strength and durability of lap shear specimens as laser ablation coverage area and beam intensity increased. Chemical analyses showed trends for surface chemical species which correlated with improved bond strength and durability. Combined, these results suggest that laser ablation is a viable process for inclusion with or/and replacement of one or more currently used titanium surface treatments. On-going work will focus on additional mechanical tests to further demonstrate improved bond durability.

The effect of water storage, elapsed time and contaminants on the bond strength and interfacial polymerization of a nanohybrid composite.

PubMed

Perriard, Jean; Lorente, Maria Cattani; Scherrer, Susanne; Belser, Urs C; Wiskott, H W Anselm

2009-12-01

To systematically characterize the effect of time lapse, water storage, and selected contaminants on the bond strength of a nanofilled dental composite. Half-dumbbell-shaped samples were fabricated out of light-polymerizing composite resin. To function as substrates they were aged for 30 days in water. Prior to bonding, the substrates' surfaces were subjected to the following treatments: 1) Removing a 0.2- to 0.4-mm layer using a fluted carbide bur; 2) grit blasting with 50 microm alumina particles; 3) etching with phosphoric acid gel; 4) grit blasting followed by etching; 5) blasting with tribochemical particles followed by silane application; 6) sanding with 400-grit paper, air aging of the adherent half-sample before bonding; 7) surface contamination with saliva; 8) surface contamination with blood. In each group (n = 30), freshly polymerized (except in group 6) adherent half-samples were bonded to the substrate half-samples by a layer of unfilled adhesive resin. Fifteen full dumbbell-shaped specimens were subjected to tensile testing after 1 h and 15 after 7 days water storage. In a positive control group, freshly cured half-samples were bonded shortly after fabrication. The tensile strength was analyzed using Weibull statistics and presented in terms of the material's characteristic strength and shape parameter. Fractographs of the two weakest and strongest samples of each group were produced. The surfaces were searched to locate hackle, wake hackle and the origin of the fracture. Surface roughness and time lapse increased the bond strength of the repaired specimens. All groups in which surface roughness was produced before bonding increased in repair strength. Post-bonding aging improved strength. Fractographs yielded interpretable data whenever larger surfaces of single phase bonding resin were present. 1) Roughening and etching an aged composite's surface prior to applying a coat of unfilled resin and the filled material increases repair bond strength by up to 100%. 2) The repair bond strength of a roughened aged composite is 25% to 30% inferior to the tensile strength of solid specimens. 3) After 7 days' storage in water, no detrimental effect could be seen from saliva or blood contamination if the surfaces were properly rinsed.

Importance of electronegativity differences and surface structure in molecular dissociation reactions at transition metal surfaces.

PubMed

Crawford, Paul; Hu, P

2006-12-14

The dissociative adsorption of N2 has been studied at both monatomic steps and flat regions on the surfaces of the 4d transition metals from Zr to Pd. Using density functional theory (DFT) calculations, we have determined and analyzed the trends in both straight reactivity and structure sensitivity across the periodic table. With regards to reactivity, we find that the trend in activation energy (Ea) is determined mainly by a charge transfer from the surface metal atoms to the N atoms during transition state formation, namely, the degree of ionicity of the N-surface bond at the transition state. Indeed, we find that the strength of the metal-N bond at the transition state (and therefore the trend in Ea) can be predicted by the difference in Mulliken electronegativity between the metal and N. Structure sensitivity is analyzed in terms of geometric and electronic effects. We find that the lowering of Ea due to steps is more pronounced on the right-hand side of the periodic table. It is found that for the early transition metals the geometric and electronic effects work in opposition when going from terrace to step active site. In the case of the late 4d metals, however, these effects work in combination, producing a more marked reduction in Ea.

Method for maintaining precise suction strip porosities

NASA Technical Reports Server (NTRS)

Gallimore, Frank H. (Inventor)

1989-01-01

This invention relates to a masking method generally and, more particularly to a method of masking perforated titanium sheets having laminar control suction strips. As illustrated in the drawings, a nonaerodynamic surface of a perforated sheet has alternating suction strip areas and bonding land areas. Suction strip tapes overlie the bonding land areas during application of a masking material to an upper surface of the suction strip tapes. Prior to bonding the perforated sheet to a composite structure, the bonding land tapes are removed. The entire opposite aerodynamic surface is masked with tape before bonding. This invention provides a precise control of suction strip porosities by ensuring that no chemicals penetrate the suction strip areas during bonding.

Picosecond Pulsed Laser Ablation for the Surface Preparation of Epoxy Composites

NASA Technical Reports Server (NTRS)

Palmieri, Frank; Ledesma, Rodolfo; Fulton, Tayler; Arthur, Alexandria; Eldridge, Keishara; Thibeault, Sheila; Lin, Yi; Wohl, Chris; Connell, John

2017-01-01

As part of a technical challenge under the Advanced Composites Program, methods for improving pre-bond process control for aerospace composite surface treatments and inspections, in conjunction with Federal Aviation Administration guidelines, are under investigation. The overall goal is to demonstrate high fidelity, rapid and reproducible surface treatment and surface characterization methods to reduce uncertainty associated with the bonding process. The desired outcomes are reliable bonded airframe structure, and reduced timeline to certification. In this work, laser ablation was conducted using a q-switched Nd:YVO4 laser capable of nominal pulse durations of 8 picoseconds (ps). Aerospace structural carbon fiber reinforced composites with an epoxy resin matrix were laser treated, characterized, processed into bonded assemblies and mechanically tested. The characterization of ablated surfaces were conducted using scanning electron microscopy (SEM), water contact angle (WCA) goniometry, micro laser induced breakdown spectroscopy (uLIBS), and electron spin resonance (ESR). The bond performance was assessed using a double cantilever beam (DCB) test with an epoxy adhesive. The surface characteristics and bond performance obtained from picosecond ablated carbon fiber reinforced plastics (CFRPs) are presented herein.

Ab initio molecular dynamics of H2O adsorbed on solid MgO

NASA Astrophysics Data System (ADS)

Langel, Walter; Parrinello, Michele

1995-08-01

The Car-Parrinello method has been applied to study the adsorption of water on solid magnesium oxide with surface defects. A step consisting of an (100) and an (010) surface on an (011) base plane allows us to model the experimentally observed microfaceting. In and on this step dissociation of water into a hydroxyl group and a H-atom took place following a complicated pathway only accessible by the simulation of thermal motion. Under comparable conditions physisorption only was observed on a regular (001) plane. This solves an experimental controversy and it is in agreement with the observation, that disordered surfaces are more active in initiating the dissociation of the water molecules. Our work allows us to identify an important active center. We can also account for the experimentally observed broadening and shifting to the red of the stretching mode of hydrogen bonded hydroxyl groups, and we provide a detailed explanation of the origin of this effect. This allows us to verify earlier theories of hydrogen bonding such as that of the adiabatic separation of the proton dynamics.

A comparative DFT study on the dehydrogenation of methanol on Rh(100) and Rh(110)

NASA Astrophysics Data System (ADS)

Zhang, Minhua; Wu, Xingyu; Yu, Yingzhe

2018-04-01

Numerous density functional theory calculations have been performed to investigate the complete mechanisms of methanol dehydrogenation on Rh(100) and Rh(110) surfaces. The adsorption properties of relevant species were discussed in details. In addition, a comprehensive reaction network including four reaction pathways was built and analyzed. It is found that the initial Osbnd H bond scission of CH3OH seems to be more favorable than Csbnd H bond cleavage on both Rh(100) and Rh(110) surfaces from the perspective of activation barriers. It is also concluded that path1 (CH3OH → CH3O → CH2O → CHO → CO) is the predominant pathway on both Rh(100) and Rh (110) surfaces. On the whole, in most of the dehydrogenation reactions investigated, the energy barriers on Rh(100) are lower than those on Rh (110). Remarkable differences in the activity and predominant reaction pathway on Rh(100), Rh(110) and Rh(111) indicate that the dehydrogenation of methanol might be structure-sensitive.

Active Free Surface Density Maps

NASA Astrophysics Data System (ADS)

Çelen, S.

2016-10-01

Percolation problems were occupied to many physical problems after their establishment in 1957 by Broadbent and Hammersley. They can be used to solve complex systems such as bone remodeling. Volume fraction method was adopted to set some algorithms in the literature. However, different rate of osteoporosis could be observed for different microstructures which have the same mass density, mechanical stimuli, hormonal stimuli and nutrition. Thus it was emphasized that the bone might have identical porosity with different specific surfaces. Active free surface density of bone refers the used total area for its effective free surface. The purpose of this manuscript is to consolidate a mathematical approach which can be called as “active free surface density maps” for different surface patterns and derive their formulations. Active free surface density ratios were calculated for different Archimedean lattice models according to Helmholtz free energy and they were compared with their site and bond percolation thresholds from the background studies to derive their potential probability for bone remodeling.

Silica-Supported, Single-Site Sc and Y Alkyls for Catalytic Hydrogenation of Propylene

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

Getsoian, Andrew G. Bean; Hu, Bo; Miller, Jeffrey T.

Single site Sc and Y on silica catalysts have been prepared by aqueous and organometallic grafting methods. The former yields Y(III) ions with 5 bonds at an average bond distance of 2.31 Å by X-ray absorption spectroscopy. Although the aqueous synthesis gave single site Y with low coordination number, these were not catalytic for alkane dehydrogenation or olefin hydrogenation. Single site Sc(III) and Y(III) species were also prepared by grafting Sc(CH 2Si(CH 3) 3) 3(THF) 2 and Y(CH 2Si(CH 3) 3) 3(THF) 2, respectively and these are catalysts for olefin hydrogenation at temperatures from about 60 to 100°C; however, theymore » were thermally unstable at higher temperatures necessary for alkane dehydrogenation. The structure of the grafted Y complex was determined by X-ray absorption spectroscopy, IR, and NMR. Grafting lead to protonolysis of 2 of the 3 CH 2Si(CH 3) 3 ligands. Additionally, there was loss of one THF ligand. The EXAFS indicated that there were 4 Y-ligand bonds in the surface species, 2 at 2.16 Å and 2 at 2.39 Å. The metal-alkyl ligand was thought to be necessary for catalytic activity and likely proceeds through a sigma bond metathesis mechanism. In the single site centers without alkyl bonds, Sc and Y ions cannot generate metal-alkyl, or metal-hydride, moieties in situ. We conclude that this is likely due to the very high M-O-Si bond strengths, which must be broken through heterolytic dissociation of C-H bonds during alkane activation for either alkane dehydrogenation or olefin hydrogenation reactions. Lastly, this study demonstrates the importance of pre-catalyst choice versus in situ formation of reactive intermediates to produce active catalysts for alkane bond activation.« less

Silica-Supported, Single-Site Sc and Y Alkyls for Catalytic Hydrogenation of Propylene

DOE PAGES

Getsoian, Andrew G. Bean; Hu, Bo; Miller, Jeffrey T.; ...

2017-09-27

Single site Sc and Y on silica catalysts have been prepared by aqueous and organometallic grafting methods. The former yields Y(III) ions with 5 bonds at an average bond distance of 2.31 Å by X-ray absorption spectroscopy. Although the aqueous synthesis gave single site Y with low coordination number, these were not catalytic for alkane dehydrogenation or olefin hydrogenation. Single site Sc(III) and Y(III) species were also prepared by grafting Sc(CH 2Si(CH 3) 3) 3(THF) 2 and Y(CH 2Si(CH 3) 3) 3(THF) 2, respectively and these are catalysts for olefin hydrogenation at temperatures from about 60 to 100°C; however, theymore » were thermally unstable at higher temperatures necessary for alkane dehydrogenation. The structure of the grafted Y complex was determined by X-ray absorption spectroscopy, IR, and NMR. Grafting lead to protonolysis of 2 of the 3 CH 2Si(CH 3) 3 ligands. Additionally, there was loss of one THF ligand. The EXAFS indicated that there were 4 Y-ligand bonds in the surface species, 2 at 2.16 Å and 2 at 2.39 Å. The metal-alkyl ligand was thought to be necessary for catalytic activity and likely proceeds through a sigma bond metathesis mechanism. In the single site centers without alkyl bonds, Sc and Y ions cannot generate metal-alkyl, or metal-hydride, moieties in situ. We conclude that this is likely due to the very high M-O-Si bond strengths, which must be broken through heterolytic dissociation of C-H bonds during alkane activation for either alkane dehydrogenation or olefin hydrogenation reactions. Lastly, this study demonstrates the importance of pre-catalyst choice versus in situ formation of reactive intermediates to produce active catalysts for alkane bond activation.« less

Electronic structure studies of Ni( 1 0 0 ) surface reconstructions resulting from carbon, nitrogen, or oxygen atom adsorption

NASA Astrophysics Data System (ADS)

Kirsch, Janet E.; Harris, Suzanne

2003-01-01

Solid-state Fenske-Hall band structure calculations have been used to study the different surface structures which result from adsorption of a half monolayer of C, N, or O atoms on the Ni(1 0 0) surface. C or N atoms sit nearly coplanar with the surface Ni atoms and induce the "clock" reconstruction of the surface. In contrast, adsorbed O atoms sit slightly above the Ni(1 0 0) surface plane and have little effect on the overall surface structure. The local environments of the C, N, and O atoms on these surfaces are similar to their environments in a series of late transition metal carbonyl clusters, suggesting that some of the same electronic factors may play a role in favoring the different structures. Results of the calculations indicate that when adsorbates occupy coplanar sites on Ni(1 0 0), much of the Ni-Ni bonding within the surface layer and between the surface- and second-layers is disrupted. On the C- and N-covered surfaces the disruption is more than compensated for by the formation of strong adsorbate-Ni bonds and by new Ni-Ni surface bonds resulting from the clock reconstruction. When O is forced into a coplanar site, however, both the higher electron count and increased electronegativity of the O atoms lead to severe disruption of the surface bonding and weak Ni-O bonds. When O atoms sit above the surface, they form more polar Ni-O bonds, contribute less electron density to the Ni surface bands, and cause less disruption to Ni-Ni surface bonds. These results suggest that, similar to the organometallic clusters, the site preferences of C, N, and O atoms are directly related to their electron count, and in turn to the relative occupation of both Ni-Ni and X-Ni (X=C, N, O) antibonding bands.

Comparing the shear bond strength of direct and indirect composite inlays in relation to different surface conditioning and curing techniques

PubMed Central

Zorba, Yahya Orcun; Ilday, Nurcan Ozakar; Bayındır, Yusuf Ziya; Demirbuga, Sezer

2013-01-01

Objective: The aim of this study was to test the null hypothesis that different surface conditioning (etch and rinse and self-etch) and curing techniques (light cure/dual cure) had no effect on the shear bond strength of direct and indirect composite inlays. Materials and Methods: A total of 112 extracted human molar teeth were horizontally sectioned and randomly divided into two groups according to restoration technique (direct and indirect restorations). Each group was further subdivided into seven subgroups (n = 8) according to bonding agent (etch and rinse adhesives Scotchbond multi-purpose plus, All-Bond 3, Adper Single Bond and Prime Bond NT; and self-etch adhesives Clearfil Liner Bond, Futurabond DC and G bond). Indirect composites were cemented to dentin surfaces using dual-curing luting cement. Shear bond strength of specimens was tested using a Universal Testing Machine. Two samples from each subgroup were evaluated under Scanning electron microscopy to see the failing modes. Data was analyzed using independent sample t-tests and Tukey's tests. Results: Surface conditioning and curing of bonding agents were all found to have significant effects on shear bond strength (P < 0.05) of both direct and indirect composite inlays. With direct restoration, etch and rinse systems and dual-cured bonding agents yielded higher bond strengths than indirect restoration, self-etch systems and light-cured bonding agents. Conclusions: The results of the present study indicated that direct restoration to be a more reliable method than indirect restoration. Although etch and rinse bonding systems showed higher shear bond strength to dentin than self-etch systems, both systems can be safely used for the adhesion of direct as well as indirect restorations. PMID:24932118

Comparison of the tensile bond strength of high-noble, noble, and base metal alloys bonded to enamel.

PubMed

Sen, D; Nayir, E; Pamuk, S

2000-11-01

Although the bond strengths of various resin composite luting materials have been reported in the literature, the evaluation of these systems with various cast alloys of different compositions has not been completely clarified. To evaluate the tensile bond strength of sandblasted high-noble, noble, and base metal alloys bonded to etched enamel by 2 different bonding agents of different chemical composition: Panavia-Ex (BIS-GMA) and Super-Bond (4-META acrylic). Flat enamel surfaces were prepared on buccal surfaces of 60 extracted noncarious human incisors. Teeth were divided into 3 groups of 20 each. Twenty circular disks of 5 mm diameter were prepared for casting for each group. Group I was cast with a high-noble, group II with a noble, and group III with a base metal alloy. The surfaces of the disks were sandblasted with 250 microm Al(2)O(3). Ten disks of each group were bonded to exposed enamel surfaces with Super-Bond and 10 disks with Panavia-Ex as recommended by the manufacturer. The tensile bond strength was measured with an Instron universal testing machine with a crosshead speed of 0.5 mm/min until failure occurred. Two-way ANOVA was used to evaluate the results. The differences in bond strengths of Super-Bond and Panavia-Ex with different alloys were not significant. The highest bond strengths were obtained in base metal alloys, followed by noble and high-noble alloys. These results were significant. Panavia-Ex and Super-Bond exhibited comparable tensile bond strengths. For both luting agents, the highest bond strengths were achieved with base metal alloys and the lowest with high-noble alloys.

Comparing the shear bond strength of direct and indirect composite inlays in relation to different surface conditioning and curing techniques.

PubMed

Zorba, Yahya Orcun; Ilday, Nurcan Ozakar; Bayındır, Yusuf Ziya; Demirbuga, Sezer

2013-10-01

The aim of this study was to test the null hypothesis that different surface conditioning (etch and rinse and self-etch) and curing techniques (light cure/dual cure) had no effect on the shear bond strength of direct and indirect composite inlays. A total of 112 extracted human molar teeth were horizontally sectioned and randomly divided into two groups according to restoration technique (direct and indirect restorations). Each group was further subdivided into seven subgroups (n = 8) according to bonding agent (etch and rinse adhesives Scotchbond multi-purpose plus, All-Bond 3, Adper Single Bond and Prime Bond NT; and self-etch adhesives Clearfil Liner Bond, Futurabond DC and G bond). Indirect composites were cemented to dentin surfaces using dual-curing luting cement. Shear bond strength of specimens was tested using a Universal Testing Machine. Two samples from each subgroup were evaluated under Scanning electron microscopy to see the failing modes. Data was analyzed using independent sample t-tests and Tukey's tests. Surface conditioning and curing of bonding agents were all found to have significant effects on shear bond strength (P < 0.05) of both direct and indirect composite inlays. With direct restoration, etch and rinse systems and dual-cured bonding agents yielded higher bond strengths than indirect restoration, self-etch systems and light-cured bonding agents. The results of the present study indicated that direct restoration to be a more reliable method than indirect restoration. Although etch and rinse bonding systems showed higher shear bond strength to dentin than self-etch systems, both systems can be safely used for the adhesion of direct as well as indirect restorations.

Identification of hydrophilic group formation on polymer surface during Ar{sup +} ion irradiation in O{sub 2} environment

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

Cho, J.S.; Choi, W.K.; Jung, H.J.

1997-12-01

Ar{sup +} ion irradiation on low density polyethylene (LDPE), and polystyrene (PS) was performed in an O{sub 2} environment in order to improve wettability of polymers to water and to identify the formation of hydrophilic groups originated from chemical reactions on the surface of polymers. Doses of a broad Ar{sup +} ion beam of 1 keV energy were changed from 5 {times} 10{sup 15} to 1 {times} 10{sup 17}/cm{sup 2} and the rate of oxygen gas flowing near the sample surface was varied from 0 to 7 ml/min. The contact angle of polymers was not reduced much by Ar{sup +}more » ion irradiation without oxygen gas. However, it dropped largely to a minimum of 35{degree} and 26{degree} for Ar{sup +} ion irradiation in the presence of flowing oxygen gas on LDPE and PS, respectively. From x-ray photoelectron spectroscopy analysis, it was observed that hydrophilic groups were formed on the surface of polymers through an ion-assisted chemical reaction between the ion-induced unstable chains and oxygen. The newly formed hydrophilic group was identified as {single_bond}(C{double_bond}){single_bond} bond and {single_bond}(C{double_bond}O){single_bond}O{single_bond} bond. The contact angle of polymer was greatly dependent on the hydrophilic group formed on the surface.« less

Influence of surface treatments on the shear bond strength of orthodontic brackets to porcelain

NASA Astrophysics Data System (ADS)

Wang, Cong; Zeng, Jishan; Wang, Shaoan; Yang, Zheng; Huang, Qian; Chen, Pixiu; Zhou, Shujuan; Liu, Xiaoqing

2008-11-01

The purpose of this study was to investigate the effect of various surface treatments after different storage time and thermocycling on the shear bond strength of orthodontic brackets to the feldspathic porcelain surfaces. 128 disc-shaped porcelain specimens were randomly assigned to the following surface treatments: 9.6% HFA, 9.6% HFA combined with silane, 50 μ aluminum trioxide sandblasting followed by silane and application of silane after 37% phosphoric acid. Metal or ceramic brackets were bonded onto each treated porcelain facet with light cured resin. The samples were stored in 37 °C water 1 day or 7 days, thermocycled 500 times from 5 to 55 °C. The shear bond strengths were measured (1 mm/min), and statistically analyzed. The bond failure sites were classified according to ARI system. The surface of the glazed, sandblasted, hydrofluoric and phosphoric acid etched porcelain were examined with SEM. All groups achieved reasonable bond strengths to withstand the application of orthodontic forces. Water storage for 7 days caused lower shear bond strength than that of 1 day. But there is no statistically significant difference between the two groups. The mean shear bond strength provided by ceramic bracket with mechanical retention had no statistical difference with that of metal bracket. Therefore, the optimal treatment for orthodontic brackets bonding to feldspathic porcelain was to apply phosphoric acid combined with silane.

Bonding between oxide ceramics and adhesive cement systems: a systematic review.

PubMed

Papia, Evaggelia; Larsson, Christel; du Toit, Madeleine; Vult von Steyern, Per

2014-02-01

The following aims were set for this systematic literature review: (a) to make an inventory of existing methods to achieve bondable surfaces on oxide ceramics and (b) to evaluate which methods might provide sufficient bond strength. Current literature of in vitro studies regarding bond strength achieved using different surface treatments on oxide ceramics in combination with adhesive cement systems was selected from PubMed and systematically analyzed and completed with reference tracking. The total number of publications included for aim a was 127 studies, 23 of which were used for aim b. The surface treatments are divided into seven main groups: as-produced, grinding/polishing, airborne particle abrasion, surface coating, laser treatment, acid treatment, and primer treatment. There are large variations, making comparison of the studies difficult. An as-produced surface of oxide ceramic needs to be surface treated to achieve durable bond strength. Abrasive surface treatment and/or silica-coating treatment with the use of primer treatment can provide sufficient bond strength for bonding oxide ceramics. This conclusion, however, needs to be confirmed by clinical studies. There is no universal surface treatment. Consideration should be given to the specific materials to be cemented and to the adhesive cement system to be used. Copyright © 2013 Wiley Periodicals, Inc.

Initial Reduction of CO2 on Pd-, Ru-, and Cu-Doped CeO2(111) Surfaces: Effects of Surface Modification on Catalytic Activity and Selectivity.

PubMed

Guo, Chen; Wei, Shuxian; Zhou, Sainan; Zhang, Tian; Wang, Zhaojie; Ng, Siu-Pang; Lu, Xiaoqing; Wu, Chi-Man Lawrence; Guo, Wenyue

2017-08-09

Surface modification by metal doping is an effective treatment technique for improving surface properties for CO 2 reduction. Herein, the effects of doped Pd, Ru, and Cu on the adsorption, activation, and reduction selectivity of CO 2 on CeO 2 (111) were investigated by periodic density functional theory. The doped metals distorted the configuration of a perfect CeO 2 (111) by weakening the adjacent Ce-O bond strength, and Pd doping was beneficial for generating a highly active O vacancy. The analyses of adsorption energy, charge density difference, and density of states confirmed that the doped metals were conducive for enhancing CO 2 adsorption, especially for Cu/CeO 2 (111). The initial reductive dissociation CO 2 → CO* + O* on metal-doped CeO 2 (111) followed the sequence of Cu- > perfect > Pd- > Ru-doped CeO 2 (111); the reductive hydrogenation CO 2 + H → COOH* followed the sequence of Cu- > perfect > Ru- > Pd-doped CeO 2 (111), in which the most competitive route on Cu/CeO 2 (111) was exothermic by 0.52 eV with an energy barrier of 0.16 eV; the reductive hydrogenation CO 2 + H → HCOO* followed the sequence of Ru- > perfect > Pd-doped CeO 2 (111). Energy barrier decomposition analyses were performed to identify the governing factors of bond activation and scission along the initial CO 2 reduction routes. Results of this study provided deep insights into the effect of surface modification on the initial reduction mechanisms of CO 2 on metal-doped CeO 2 (111) surfaces.

Influence of dentinal regions on bond strengths of different adhesive systems.

PubMed

Ozer, F; Unlü, N; Sengun, A

2003-06-01

This in vitro study assessed comparatively the shear bond strengths of three composite resins, 3M Valux Plus (3MVP), Herculite (H), Clearfil AP-X (CAP-X), a polyacid modified composite resin Dyract (D), and a resin modified glass-ionomer materials Vitremer (V), to cervical and buccal dentine regions of extracted human molar teeth. Four different bonding systems, 3M ScotchBond Multipurpose (SB), Clearfil Liner Bond 2 (LB2), Opti Bond (OB), and Prime & Bond 2.1 (PB 2.1) were used with the manufacturer's respective composite and compomer materials. One hundred freshly extracted mandibular molar teeth were selected for this study. Flat buccal dentine surfaces were created on 50 teeth and cylindrical rods of the five materials were bonded to the dentine surfaces. For assessment of cervical bond strengths, the materials were bonded to mesial and distal enamel bordered occlusal dentinal surfaces of the remaining 50 teeth. The five groups of restorative procedures were applied as follows; Group 1: SB + 3MVP, Group 2: LB2 + CAP-X, Group 3: OB + H, Group 4: PB2.1 + D, Group 5: Vitremer primer (VP) VP + V. Each restorative procedure thus had 20 specimens (10 buccal + 10 cervical). After 24 h of water storage (37 degrees C), the specimens were tested on a Universal Testing machine in shear with a cross head speed of 0.5 mm min-1. The bond strength values were calculated in MPa and the results were evaluated statistically using Kruskal-Wallis one-way/anova and Mann-Whitney U-tests. It was found that the bond strengths of SB + 3MVP, LB2 + CAP-X and VP + V to buccal dentine surfaces were significantly stronger (P < 0.05) than those to the occluso-cervical dentine floors. When the bond strengths to the occluso-cervical dentine and buccal dentine surface were compared, there was no significant difference between the materials (P > 0.05). Vitremer was found the least successful adhesive material in terms of shear bond strength on both buccal and occluso-cervical dentine surfaces.

Antimicrobial and physical characteristics of orthodontic primers containing antimicrobial agents.

PubMed

Chung, Shin-Hye; Cho, Soha; Kim, Kyungsun; Lim, Bum-Soon; Ahn, Sug-Joon

2017-03-01

To compare the antimicrobial and physical properties of experimental primers containing chlorhexidine (CHX) or ursolic acid (UA) with a commercial primer. Two antibacterial agents, 3 mg each of CHX and UA were incorporated respectively into 1 ml of Transbond XT primer (TX) to form antibacterial primers, TX-CHX and TX-UA. The antimicrobial activity of the three primers (TX, TX-CHX, and TX-UA) against Streptococcus mutans in both planktonic and biofilm phases was analyzed by determining minimum inhibitory and bactericidal concentrations and by performing growth and biofilm assays. Growth and biofilm assays were performed in both the absence and presence of thermocycling in a water tank to analyze the effects of water aging on the antimicrobial activities of primers. After bonding brackets onto bovine incisors using the primers, shear bond strength and mode of fracture were analyzed to compare physical properties. TX-CHX had stronger antimicrobial activity against S. mutans in the planktonic and biofilm phases than did TX or TX-UA. When applied, TX-CHX completely inhibited the growth and biofilm formation of S. mutans . In addition, the antimicrobial activity of TX-CHX was maintained after thermocycling. However, TX-UA did not show significant antimicrobial activity compared with TX. There was no significant difference in either shear bond strength or bond failure interface among the primers. Incorporation of CHX into an orthodontic primer may help prevent enamel demineralization around surfaces without compromising its physical properties.

The effect of surface and interface on Neel transition temperature of low-dimensional antiferromagnetic materials

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

Zhang, Wen; Zhou, Zhaofeng, E-mail: zfzhou@xtu.edu.cn; Zhong, Yuan

2015-11-15

Incorporating the bond order-length-strength (BOLS) notion with the Ising premise, we have modeled the size dependence of the Neel transition temperature (T{sub N}) of antiferromagnetic nanomaterials. Reproduction of the size trends reveals that surface atomic undercoordination induces bond contraction, and interfacial hetero-coordination induces bond nature alteration. Both surface and interface of nanomaterials modulate the T{sub N} by adjusting the atomic cohesive energy. The T{sub N} is related to the atomic cohesive/exchange energy that is lowered by the coordination number (CN) imperfection of the undercoordinated atoms near the surface and altered by the changed bond nature of epitaxial interface. A numericalmore » match between predictions and measurements reveals that the T{sub N} of antiferromagnetic nanomaterials declines with reduced size and increases with both the strengthening of heterogeneous bond and the increase of the bond number.« less

Influence of Hot-Etching Surface Treatment on Zirconia/Resin Shear Bond Strength

PubMed Central

Lv, Pin; Yang, Xin; Jiang, Ting

2015-01-01

This study was designed to evaluate the effect of hot-etching surface treatment on the shear bond strength between zirconia ceramics and two commercial resin cements. Ceramic cylinders (120 units; length: 2.5 mm; diameter: 4.7 mm) were randomly divided into 12 groups (n = 10) according to different surface treatments (blank control; airborne-particle-abrasion; hot-etching) and different resin cements (Panavia F2.0; Superbond C and B) and whether or not a thermal cycling fatigue test (5°–55° for 5000 cycles) was performed. Flat enamel surfaces, mounted in acrylic resin, were bonded to the zirconia discs (diameter: 4.7 mm). All specimens were subjected to shear bond strength testing using a universal testing machine with a crosshead speed of 1 mm/min. All data were statistically analyzed using one-way analysis of variance and multiple-comparison least significant difference tests (α = 0.05). Hot-etching treatment produced higher bond strengths than the other treatment with both resin cements. The shear bond strength of all groups significantly decreased after the thermal cycling test; except for the hot-etching group that was cemented with Panavia F2.0 (p < 0.05). Surface treatment of zirconia with hot-etching solution enhanced the surface roughness and bond strength between the zirconia and the resin cement. PMID:28793699

Porcelain surface conditioning protocols and shear bond strength of orthodontic brackets.

PubMed

Lestrade, Ashley M; Ballard, Richard W; Xu, Xiaoming; Yu, Qingzhao; Kee, Edwin L; Armbruster, Paul C

2016-05-01

The objective of the present study was to determine which of six bonding protocols yielded a clinically acceptable shear bond strength (SBS) of metal orthodontic brackets to CAD/CAM lithium disilicate porcelain restorations. A secondary aim was to determine which bonding protocol produced the least surface damage at debond. Sixty lithium disilicate samples were fabricated to replicate the facial surface of a mandibular first molar using a CEREC CAD/CAM machine. The samples were split into six test groups, each of which received different mechanical/chemical pretreatment protocols to roughen the porcelain surface prior to bonding a molar orthodontic attachment. Shear bond strength testing was conducted using an Instron machine. The mean, maximum, minimal, and standard deviation SBS values for each sample group including an enamel control were calculated. A t-test was used to evaluate the statistical significance between the groups. No significant differences were found in SBS values, with the exception of surface roughening with a green stone prior to HFA and silane treatment. This protocol yielded slightly higher bond strength which was statistically significant. Chemical treatment alone with HFA/silane yielded SBS values within an acceptable clinical range to withstand forces applied by orthodontic treatment and potentially eliminates the need to mechanically roughen the ceramic surface.

Effect of Dentin Wetness on the Bond Strength of Universal Adhesives.

PubMed

Choi, An-Na; Lee, Ji-Hye; Son, Sung-Ae; Jung, Kyoung-Hwa; Kwon, Yong Hoon; Park, Jeong-Kil

2017-10-25

The effects of dentin wetness on the bond strength and adhesive interface morphology of universal adhesives have been investigated using micro-tensile bond strength (μTBS) testing and confocal laser scanning microscopy (CLSM). Seventy-two human third molars were wet ground to expose flat dentin surfaces. They were divided into three groups according to the air-drying time of the dentin surfaces: 0 (without air drying), 5, and 10 s. The dentin surfaces were then treated with three universal adhesives: G-Premio Bond, Single Bond Universal, and All-Bond Universal in self-etch or etch-and-rinse mode. After composite build up, a μTBS test was performed. One additional tooth was prepared for each group by staining the adhesives with 0.01 wt % of Rhodamine B fluorescent dye for CLSM analysis. The data were analyzed statistically using ANOVA and Tukey's post hoc tests (α = 0.05). Two-way ANOVA showed significant differences among the adhesive systems and dentin moisture conditions. An interaction effect was also observed ( p < 0.05). One-way ANOVA showed that All-Bond Universal was the only material influenced by the wetness of the dentin surfaces. Wetness of the dentin surface is a factor influencing the micro-tensile bond strength of universal adhesives.

Effect of Dentin Wetness on the Bond Strength of Universal Adhesives

PubMed Central

Lee, Ji-Hye; Son, Sung-Ae; Jung, Kyoung-Hwa; Kwon, Yong Hoon

2017-01-01

The effects of dentin wetness on the bond strength and adhesive interface morphology of universal adhesives have been investigated using micro-tensile bond strength (μTBS) testing and confocal laser scanning microscopy (CLSM). Seventy-two human third molars were wet ground to expose flat dentin surfaces. They were divided into three groups according to the air-drying time of the dentin surfaces: 0 (without air drying), 5, and 10 s. The dentin surfaces were then treated with three universal adhesives: G-Premio Bond, Single Bond Universal, and All-Bond Universal in self-etch or etch-and-rinse mode. After composite build up, a μTBS test was performed. One additional tooth was prepared for each group by staining the adhesives with 0.01 wt % of Rhodamine B fluorescent dye for CLSM analysis. The data were analyzed statistically using ANOVA and Tukey’s post hoc tests (α = 0.05). Two-way ANOVA showed significant differences among the adhesive systems and dentin moisture conditions. An interaction effect was also observed (p < 0.05). One-way ANOVA showed that All-Bond Universal was the only material influenced by the wetness of the dentin surfaces. Wetness of the dentin surface is a factor influencing the micro-tensile bond strength of universal adhesives. PMID:29068404

The effect of grinding and/or airborne-particle abrasion on the bond strength between zirconia and veneering porcelain: a systematic review

PubMed Central

Lundberg, Karin; Wu, Lindsey; Papia, Evaggelia

2017-01-01

Abstract Objective: The aim of the study was to make an inventory of current literature on the bond strength between zirconia and veneering porcelain after surface treatment of zirconia by grinding with diamond bur and/or with airborne-particle abrasion. Material and methods: The literature search for the present review was made following recommended guidelines using acknowledged methodology on how to do a systematic review. The electronic databases PubMed, Cochrane Library, and Science Direct were used in the present study. Results: Twelve studies were selected. Test methods used in the original studies included shear bond strength (SBS) test, tensile bond strength test, and micro-tensile bond strength test. The majority of studies used SBS. Results showed a large variation within each surface treatment of zirconia, using different grain size, blasting time, and pressure. Conclusions: Airborne-particle abrasion might improve the bond strength and can therefore be considered a feasible surface treatment for zirconia that is to be bonded. Grinding has been recommended as a surface treatment for zirconia to improve the bond strength; however, this recommendation cannot be verified. A standardized test method and surface treatment are required to be able to compare the results from different studies and draw further conclusions. PMID:28642927

Shear Bond Strength of Three Orthodontic Bonding Systems on Enamel and Restorative Materials

PubMed Central

Ebeling, Jennifer; Schauseil, Michael; Stein, Steffen; Roggendorf, Matthias; Korbmacher-Steiner, Heike

2016-01-01

Objective. The aim of this in vitro study was to determine the shear bond strength (SBS) and adhesive remnant index (ARI) score of two self-etching no-mix adhesives (iBond™ and Scotchbond™) on different prosthetic surfaces and enamel, in comparison with the commonly used total etch system Transbond XT™. Materials and Methods. A total of 270 surfaces (1 enamel and 8 restorative surfaces, n = 30) were randomly divided into three adhesive groups. In group 1 (control) brackets were bonded with Transbond XT primer. In the experimental groups iBond adhesive (group 2) and Scotchbond Universal adhesive (group 3) were used. The SBS was measured using a Zwicki 1120™ testing machine. The ARI and SBS were compared statistically using the Kruskal–Wallis test (P ≤ 0.05). Results. Significant differences in SBS and ARI were found between the control group and experimental groups. Conclusions. Transbond XT showed the highest SBS on human enamel. Scotchbond Universal on average provides the best bonding on all other types of surface (metal, composite, and porcelain), with no need for additional primers. It might therefore be helpful for simplifying bonding in orthodontic procedures on restorative materials in patients. If metal brackets have to be bonded to a metal surface, the use of a dual-curing resin is recommended. PMID:27738633

Stabilized sulfur binding using activated fillers

DOEpatents

Kalb, Paul D.; Vagin, Vyacheslav P.; Vagin, Sergey P.

2015-07-21

A method of making a stable, sulfur binding composite comprising impregnating a solid aggregate with an organic modifier comprising unsaturated hydrocarbons with at least one double or triple covalent bond between adjacent carbon atoms to create a modifier-impregnated aggregate; heating and drying the modifier-impregnated aggregate to activate the surface of the modifier-impregnated aggregate for reaction with sulfur.

Bonded ultrasonic transducer and method for making

DOEpatents

Dixon, R.D.; Roe, L.H.; Migliori, A.

1995-11-14

An ultrasonic transducer is formed as a diffusion bonded assembly of piezoelectric crystal, backing material, and, optionally, a ceramic wear surface. The mating surfaces of each component are silver films that are diffusion bonded together under the application of pressure and heat. Each mating surface may also be coated with a reactive metal, such as hafnium, to increase the adhesion of the silver films to the component surfaces. Only thin silver films are deposited, e.g., a thickness of about 0.00635 mm, to form a substantially non-compliant bond between surfaces. The resulting transducer assembly is substantially free of self-resonances over normal operating ranges for taking resonant ultrasound measurements. 12 figs.

Interfacial adhesion of dental ceramic-resin systems

NASA Astrophysics Data System (ADS)

Della Bona, Alvaro

The clinical success of resin bonding procedures for indirect ceramic restorations and ceramic repairs depends on the quality and durability of the bond between the ceramic and the resin. The quality of this bond will depend upon the bonding mechanisms that are controlled in part by the surface treatment that promotes micromechanical and/or chemical bonding to the substrate. The objective of this study is to correlate interfacial toughness (K A) with fracture surface morphological parameters of the dental ceramic-resin systems as a function of ceramic surface treatment. The analytical procedures focused on characterizing the microstructure and fracture properties of EmpressRTM ceramics (a leucite-based core ceramic, two lithia disilicate-based core ceramics, and a glass veneer) and determining the ceramic-resin adhesion zone bond strength characteristics. Microstructure and composition are controlling factors in the development of micromechanical retention produced by etching. Silane treated ceramics negated the effect of surface roughening produced by etching, inducing lower surface energy of the ceramic and, reduced bonding effectiveness. There was a positive correlation between WA, tensile bond strength (a), and KA, i.e., higher mean WA value, and higher mean sigma and KA values. This study suggests that (1) the sigma and KA values for ceramic bonded to resin are affected by the ceramic microstructure and the ceramic surface treatments; (2) the definition of the adhesion zone is essential to classify the modes of failure, which should be an integral component of all failure analyses; (3) the microtensile test may be preferable to conventional shear or flexural tests as an indicator of composite-ceramic bond quality; and (4) careful microscopic analysis of fracture surfaces and an x-ray dot map can produce a more consistent and complete description of the fracture process and interpretation of the modes of failure. The mode of failure and fractographic analyses provide important a more comprehensive assessment of mechanisms that control the survival times of dental adhesive systems. Thus, the quality of the bond should not be assessed based on bond strength data alone.

Fracture surface analysis in composite and titanium bonding: Part 1: Titanium bonding

NASA Technical Reports Server (NTRS)

Sanderson, K. A.; Wightman, J. P.

1985-01-01

Fractured lap shear Ti 6-4 adherends bonded with polyphenyquinoxaline (PPQ) and polysulfone were analyzed. The effects of adherend pretreatment, stress level, thermal aging, anodizing voltage, and modified adhesive of Ti 6-4 adherend bonded with PPQ on lap shear strength were studied. The effect of adherend pretreatment on lap shear strength was investigated for PS samples. Results of scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) used to study the surface topography and surface composition are also discussed.

Effect of prior silane application on the bond strength of a universal adhesive to a lithium disilicate ceramic.

PubMed

Moro, André Fábio Vasconcelos; Ramos, Amanda Barreto; Rocha, Gustavo Miranda; Perez, Cesar Dos Reis

2017-11-01

Universal adhesives combine silane and various monomers in a single bottle to make them more versatile. Their adhesive performance is unclear. The purpose of this in vitro study was to assess the effects of an additional silane application before using a universal adhesive on the adhesion between a disilicate glass ceramic and a composite resin by using a microshear bond strength test (μSBS) and fracture analysis immediately and after thermocycling. One hundred lithium disilicate glass ceramic disks were divided into 10 groups for bond strength testing according to the following 3 surface treatments: silane application (built-in universal adhesive or with additional application), adhesive (Adper Single Bond Plus [SB, 3M ESPE], Scotchbond Universal Adhesive [U, 3M ESPE], and mixed U with Dual Cure Activator [DCA, 3M ESPE]); or thermocycling (half of the specimens were thermocycled 10000 times). After surface treatment, 5 resin cylinders were bonded to each disk and submitted to a μSBS test. The failure mode was analyzed under a stereomicroscope and evaluated by scanning electron microscope and energy-dispersive x-ray spectroscopy. Data from the μSBS test were analyzed by 3-way ANOVA followed by the Tukey HSD post hoc test (α=.05). An additional silane application resulted in a higher μSBS result for all adhesive groups (P<.05). Ceramic surface treatment influenced the performance of adhesives, which may be improved with an additional silane application. Copyright © 2017 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Type-II Superlattice Avalanche Photodiodes

NASA Astrophysics Data System (ADS)

Huang, Jun

Type-II superlattice avalanche photodiodes have shown advantages compared to conventional mercury cadmium telluride photodiodes for infrared wavelength detection. However, surface or interface leakage current has been a major issue for superlattice avalanche photodiodes, especially in infrared wavelength region. First, passivation of the superlattice device with ammonium sulfide and thioacetamide was carried out, and its surface quality was studied by X-ray Photoelectron Spectroscopy. The study showed that both ammonium sulfide and thiacetamide passivation can actively remove the native oxide at the surface. Thiacetamide passivation combine more sulfur bonds with III-V elements than that of ammonium sulfide. Another X-ray photoelectron spectra of thiacetamide-treated atomic layer deposited zinc sulfide capped InAs/GaSb superlattice was performed to investigate the interface sulfur bond conditions. Sb--S and As--S bonds disappear while In-S bond gets enhanced, indicating that Indium Sulfide should be the major components at the interface after ZnS deposition. Second, the simulation of electrical characteristics for zinc sulfide, silicon nitride and silicon dioxide passivated superlattice devices was performed by SILVACO software to fit the experimental results and to discover the surface current mechanism. Different surface current mechanism strengths were found. Third, several novel dual-carrier avalanche photodiode structures were designed and simulated. The structures had alternate carrier multiplication regions, placed next to a wider electron multiplication region, creating dual-carrier multiplication feedback systems. Gain and excess noise factor of these structures were simulated and compared based on the dead space multiplication theory under uniform electric field. From the simulation, the applied bias can be greatly lowered or the thickness can be shrunk to achieve the same gain from the conventional device. The width of the thin region was the most critical parameter determining the device performance.

Low temperature wafer-level bonding for hermetic packaging of 3D microsystems

NASA Astrophysics Data System (ADS)

Tan, C. S.; Fan, J.; Lim, D. F.; Chong, G. Y.; Li, K. H.

2011-07-01

Metallic copper-copper (Cu-Cu) thermo-compression bonding, oxide-oxide (SiO2-SiO2) fusion bonding and silicon-silicon (Si-Si) direct bonding are investigated for potential application as hermetic seal in 3D microsystem packaging. Cavities are etched to a volume of 1.4 × 10-3 cm3 in accordance with the MIL-STD-883E standard prescribed for microelectronics packaging. In the case of metal bonding, a clean Cu layer with a thickness of 300 nm and a Ti barrier layer with an underlying thickness of 50 nm are used. The wafer pair is bonded at 300 °C under the application of a bonding force of 5500 N for 1 h. On the other hand, Si-Si bonding and SiO2-SiO2 bonding are initiated at room ambient after surface activation, followed by annealing in inert ambient at 300 °C for 1 h. The bonded cavities are stored in a helium bomb chamber and the leak rate is measured with a mass spectrometer. An excellent helium leak rate below 5 × 10-9 atm cm3 s-1 is detected for all cases and this is at least ten times better than the reject limit.

Nanoleakage of dentin adhesive systems bonded to Carisolv-treated dentin.

PubMed

Kubo, Shisei; Li, Heping; Burrow, Michael F; Tyas, Martin J

2002-01-01

The hybrid layer created in caries-affected dentin has not been fully elucidated and may influence bond durability. This study investigated the nanoleakage patterns of caries-affected dentin after excavation with Carisolv or conventional instruments treated with one of three adhesive systems. Flat occlusal dentin surfaces, including carious lesions, were prepared from extracted human molars and finished with wet 600-grit silicon carbide paper. Carious dentin was removed with Carisolv or round steel burs in conjunction with Caries Detector. PermaQuik, Single Bond or One-Up Bond F was bonded to the excavated dentin surfaces and adjacent flat occlusal surfaces and it was covered with Silux Plus resin-based composite. After 24-hour storage in 37 degrees C water, the bonded interfaces were polished to remove flash, and the surrounding tooth surfaces were coated with nail varnish. Specimens were immersed in 50% (w/v) silver nitrate solution for 24 hours, exposed to photo developing solution for eight hours, then sectioned longitudinally through the bonded, excavated dentin or "normal" dentin surfaces. The sectioned surfaces were polished, carbon coated and observed in a Field Emission-SEM using back scattered electrons. Silver deposition occurred along the base of the hybrid layer for all specimens. However, Single Bond showed a greater density of silver deposition in the caries-affected dentin compared with normal dentin. PermaQuik had a thicker hybrid layer in caries-affected dentin than normal dentin. One-Up Bond F exhibited a thin hybrid layer in normal dentin, but the hybrid layer was often difficult to detect in caries-affected dentin.

Method of making reflecting film reflector

DOEpatents

Cottingham, James G.

1980-01-01

A reflector of the reflecting film type is disclosed and which may be used in a heliostatic system for concentrating solar energy and comprising a reflecting film bonded to an appropriate rigid substrate in such a way that specularity of a very high order is achieved. A method of bonding the reflecting film to the substrate is also disclosed and comprises the steps of initially adhering the film to a smooth, clean flat rigid surface with a non-bonding liquid between the rigid surface and film, and then bonding the substrate and film. The non-bonding liquid has a molecular adhesion greater than any stresses due to handling or curing of the bonding agent which is applied between the film and the opposing surface of the rigid substrate.

Anti-Arrhenius cleavage of covalent bonds in bottlebrush macromolecules on substrate.

PubMed

Lebedeva, Natalia V; Nese, Alper; Sun, Frank C; Matyjaszewski, Krzysztof; Sheiko, Sergei S

2012-06-12

Spontaneous degradation of bottlebrush macromolecules on aqueous substrates was monitored by atomic force microscopy. Scission of C ─ C covalent bonds in the brush backbone occurred due to steric repulsion between the adsorbed side chains, which generated bond tension on the order of several nano-Newtons. Unlike conventional chemical reactions, the rate of bond scission was shown to decrease with temperature. This apparent anti-Arrhenius behavior was caused by a decrease in the surface energy of the underlying substrate upon heating, which results in a corresponding decrease of bond tension in the adsorbed macromolecules. Even though the tension dropped minimally from 2.16 to 1.89 nN, this was sufficient to overpower the increase in the thermal energy (k(B)T) in the Arrhenius equation. The rate constant of the bond-scission reaction was measured as a function of temperature and surface energy. Fitting the experimental data by a perturbed Morse potential V = V(0)(1 - e(-βx))(2) - fx, we determined the depth and width of the potential to be V(0) = 141 ± 19 kJ/mol and β(-1) = 0.18 ± 0.03 Å, respectively. Whereas the V(0) value is in reasonable agreement with the activation energy E(a) = 80-220 kJ/mol of mechanical and thermal degradation of organic polymers, it is significantly lower than the dissociation energy of a C ─ C bond D(e) = 350 kJ/mol. Moreover, the force constant K(x) = 2β(2)V(0) = 1.45 ± 0.36 kN/m of a strained bottlebrush along its backbone is markedly larger than the force constant of a C ─ C bond K(l) = 0.44 kN/m, which is attributed to additional stiffness due to deformation of the side chains.

Weakly bound water structure, bond valence saturation and water dynamics at the goethite (100) surface/aqueous interface: ab initio dynamical simulations.

PubMed

Chen, Ying; Bylaska, Eric J; Weare, John H

2017-03-31

Many important geochemical and biogeochemical reactions occur in the mineral/formation water interface of the highly abundant mineral, goethite [α-Fe(OOH)]. Ab initio molecular dynamics (AIMD) simulations of the goethite α-FeOOH (100) surface and the structure, water bond formation and dynamics of water molecules in the mineral/aqueous interface are presented. Several exchange correlation functionals were employed (PBE96, PBE96 + Grimme, and PBE0) in the simulations of a (3 × 2) goethite surface with 65 absorbed water molecules in a 3D-periodic supercell (a = 30 Å, FeOOH slab ~12 Å thick, solvation layer ~18 Å thick). The lowest energy goethite (100) surface termination model was determined to have an exposed surface Fe 3+ that was loosely capped by a water molecule and a shared hydroxide with a neighboring surface Fe 3+ . The water molecules capping surface Fe 3+ ions were found to be loosely bound at all DFT levels with and without Grimme corrections, indicative that each surface Fe 3+ was coordinated with only five neighbors. These long bonds were supported by bond valence theory calculations, which showed that the bond valence of the surface Fe 3+ was saturated and surface has a neutral charge. The polarization of the water layer adjacent to the surface was found to be small and affected only the nearest water. Analysis by density difference plots and localized Boys orbitals identified three types of water molecules: those loosely bound to the surface Fe 3+ , those hydrogen bonded to the surface hydroxyl, and bulk water with tetrahedral coordination. Boys orbital analysis showed that the spin down lone pair orbital of the weakly absorbed water interact more strongly with the spin up Fe 3+ ion. These weakly bound surface water molecules were found to rapidly exchange with the second water layer (~0.025 exchanges/ps) using a dissociative mechanism. Water molecules adjacent to the surface were found to only weakly interact with the surface and as a result were readily able to exchange with the bulk water. To account for the large surface Fe-OH 2 distances in the DFT calculations it was proposed that the surface Fe 3+ atoms, which already have their bond valence fully satisfied with only five neighbors, are under-coordinated with respect to the bulk coordination. Graphical abstract All first principle calculations, at all practically achievable levels, for the goethite 100 aqueous interface support a long bond and weak interaction between the exposed surface Fe 3+ and water molecules capping the surface. This result is supported by bond valence theory calculations and is indicative that each surface Fe 3+ is coordinated with only 5 neighbors.

First-principles study of water desorption from montmorillonite surface.

PubMed

Zhang, Yao; Meng, Yingfeng; Liu, Houbin; Yang, Mingli

2016-05-01

Knowledge about water desorption is important to give a full picture of water diffusion in montmorillonites (MMT), which is a driving factor in MMT swelling. The desorption paths and energetics of water molecules from the surface of MMT with trapped Li(+), Na(+) or K(+) counterions were studied using periodic density functional theory calculations. Two paths--surface and vacuum desorption--were designed for water desorption starting from a stationary structure in which water bonds with both the counterion and the MMT surface. Surface desorption is energetically more favorable than vacuum desorption due to water-surface hydrogen bonds that help stabilize the intermediate structure of water released from the counterion. The energy barriers of water desorption are in the order of Li(+) > Na(+) > K(+), which can be attributed to the short ionic radius of Li(+), which favors strong binding with the water molecule. The temperature dependence of water adsorption and desorption rates were compared based on the computed activation energies. Our calculations reveal that the water desorption on the MMT surface has a different mechanism from water adsorption, which results from surface effects favoring stabilization of water conformers during the desorption process.

Effect of sandblasting on surface roughness of zirconia-based ceramics and shear bond strength of veneering porcelain.

PubMed

He, Min; Zhang, Zutai; Zheng, Dongxiang; Ding, Ning; Liu, Yan

2014-01-01

This study aims to investigate the effect of sandblasting on the surface roughness of zirconia and the shear bond strength of the veneering porcelain. Pre-sintered zirconia plates were prepared and divided into four groups. Group A were not treated at all; group B were first sandblasted under 0.2 MPa pressure and then densely sintered; group C and D were sintered first, and then sandblasted under 0.2 MPa and 0.4 MPa pressures respectively. Surface roughness was measured and 3D roughness was reconstructed for the specimens, which were also analyzed with X-ray diffractometry. Finally after veneering porcelain sintering, shear bond tests were conducted. Sandblasting zirconia before sintering significantly increased surface roughness and the shear bond strength between zirconia and veneering porcelain (p<0.05). Sandblasting zirconia before sintering is a useful method to increase surface roughness and could successfully improve the bonding strength of veneering porcelain.

Low-temperature direct copper-to-copper bonding enabled by creep on (111) surfaces of nanotwinned Cu

PubMed Central

Liu, Chien-Min; Lin, Han-Wen; Huang, Yi-Sa; Chu, Yi-Cheng; Chen, Chih; Lyu, Dian-Rong; Chen, Kuan-Neng; Tu, King-Ning

2015-01-01

Direct Cu-to-Cu bonding was achieved at temperatures of 150–250 °C using a compressive stress of 100 psi (0.69 MPa) held for 10–60 min at 10−3 torr. The key controlling parameter for direct bonding is rapid surface diffusion on (111) surface of Cu. Instead of using (111) oriented single crystal of Cu, oriented (111) texture of extremely high degree, exceeding 90%, was fabricated using the oriented nano-twin Cu. The bonded interface between two (111) surfaces forms a twist-type grain boundary. If the grain boundary has a low angle, it has a hexagonal network of screw dislocations. Such network image was obtained by plan-view transmission electron microscopy. A simple kinetic model of surface creep is presented; and the calculated and measured time of bonding is in reasonable agreement. PMID:25962757

Reprogrammable Assembly of Molecular Motor on Solid Surfaces via Dynamic Bonds.

PubMed

Yu, Li; Sun, Jian; Wang, Qian; Guan, Yan; Zhou, Le; Zhang, Jingxuan; Zhang, Lanying; Yang, Huai

2017-06-01

Controllable assembly of molecular motors on solid surfaces is a fundamental issue for providing them to perform physical tasks. However, it can hardly be achieved by most previous methods due to their inherent limitations. Here, a general strategy is designed for the reprogrammable assembly of molecular motors on solid surfaces based on dynamic bonds. In this method, molecular motors with disulfide bonds can be remotely, reversibly, and precisely attached to solid surfaces with disulfide bonds, regardless of their chemical composition and microstructure. More importantly, it not only allows encoding geometric information referring to a pattern of molecular motors, but also enables erasing and re-encoding of geometric information via hemolytic photocleavage and recombination of disulfide bonds. Thus, solid surfaces can be regarded as "computer hardware", where molecular motors can be reformatted and reprogramed as geometric information. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Controlling hydrogenation activity and selectivity of bimetallic surfaces and catalysts

NASA Astrophysics Data System (ADS)

Murillo, Luis E.

Studies of bimetallic systems are of great interest in catalysis due to the novel properties that they often show in comparison with the parent metals. The goals of this dissertation are: (1) to expand the studies of self-hydrogenation and hydrogenation reactions on bimetallic surfaces under ultra high vacuum conditions (UHV) using different hydrocarbon as probe molecules; (2) to attempt to correlate the surface science findings with supported catalyst studies under more realistic conditions; and (3) to investigate the competitive hydrogenation of C=C versus C=O bonds on Pt(111) modified by different 3d transition metals. Hydrogenation studies using temperature programmed desorption (TPD) on Ni/Pt(111) bimetallic surfaces have demonstrated an enhancement in the low temperature hydrogenation activity relative to that of clean Pt(111). This novel hydrogenation pathway can be achieved under UHV conditions by controlling the structures of the bimetallic surfaces. A low temperature hydrogenation activity of 1-hexene and 1-butene has been observed on a Pt-Ni-Pt(111) subsurface structure, where Ni atoms are mainly present on the second layer of the Pt(111) single crystal. These results are in agreement with previous studies of self-hydrogenation and hydrogenation of cyclohexene. However, a much higher dehydrogenation activity is observed in the reaction of cyclohexene to produce benzene, demonstrating that the hydrocarbon structure has an effect on the reaction pathways. On the other hand, self-hydrogenation of 1-butene is not observed on the Pt-Ni-Pt(111) surface, indicating that the chain length (or molecular weight) has a significant effect on the selfhydrogenation activity. The gas phase reaction of cyclohexene on Ni/Pt supported on alumina catalysts has also shown a higher self-hydrogenation activity in comparison with the same reaction performed on supported monometallic catalysts. The effects of metal loading and impregnation sequence of the metal precursors are also discussed. Chemisorption, TPD, FTIR using a batch reactor for the self-hydrogenation of cyclohexene and CO adsorbed on the bimetallic surfaces were carried out to correlate surface science findings with experiments on supported bimetallic catalysts. To expand the studies on the effect of bimetallic structures on hydrogenation reactions, molecules with multiple functional groups such as alpha,beta-unsaturated aldehydes were also investigated. Studies of selective hydrogenation of a,ss-unsaturated aldehydes toward the desired unsaturated alcohols are of interest for the production of fine chemicals and pharmaceuticals. In these compounds, competitive hydrogenation of the C=C and C=O bonds occurs. TPD and HREELS experiments of acrolein (CH2=CH-CH=O) on Pt-based bimetallic surfaces are performed to investigate their effects on the hydrogenation activity of the C-O bond. The production of the desired unsaturated alcohol, allyl alcohol, has been observed for the first time on Pt-Ni-Pt(111) under UHV conditions. However, the propionaldehyde yield is five times higher than the allyl alcohol yield. Thus, a preferential isomerization reaction of allyl alcohol to propionaldehyde is very likely to occur on the Pt-Ni-Pt(111) surface as observed on the desorption studies of allyl alcohol on this surface. The hydrogenation of acrolein is also carried out under UHV conditions on other 3d-transition metal/Pt(111) surfaces such as Co/Pt(111), Fe/Pt(111), and Cu/Pt(111). So far, the highest activity and allyl alcohol yield are found on the Pt-Ni-Pt(111) surface with pre-adsorbed hydrogen.

The Effect of Phosphoric Acid Pre-etching Times on Bonding Performance and Surface Free Energy with Single-step Self-etch Adhesives.

PubMed

Tsujimoto, A; Barkmeier, W W; Takamizawa, T; Latta, M A; Miyazaki, M

2016-01-01

The purpose of this study was to evaluate the effect of phosphoric acid pre-etching times on shear bond strength (SBS) and surface free energy (SFE) with single-step self-etch adhesives. The three single-step self-etch adhesives used were: 1) Scotchbond Universal Adhesive (3M ESPE), 2) Clearfil tri-S Bond (Kuraray Noritake Dental), and 3) G-Bond Plus (GC). Two no pre-etching groups, 1) untreated enamel and 2) enamel surfaces after ultrasonic cleaning with distilled water for 30 seconds to remove the smear layer, were prepared. There were four pre-etching groups: 1) enamel surfaces were pre-etched with phosphoric acid (Etchant, 3M ESPE) for 3 seconds, 2) enamel surfaces were pre-etched for 5 seconds, 3) enamel surfaces were pre-etched for 10 seconds, and 4) enamel surfaces were pre-etched for 15 seconds. Resin composite was bonded to the treated enamel surface to determine SBS. The SFEs of treated enamel surfaces were determined by measuring the contact angles of three test liquids. Scanning electron microscopy was used to examine the enamel surfaces and enamel-adhesive interface. The specimens with phosphoric acid pre-etching showed significantly higher SBS and SFEs than the specimens without phosphoric acid pre-etching regardless of the adhesive system used. SBS and SFEs did not increase for phosphoric acid pre-etching times over 3 seconds. There were no significant differences in SBS and SFEs between the specimens with and without a smear layer. The data suggest that phosphoric acid pre-etching of ground enamel improves the bonding performance of single-step self-etch adhesives, but these bonding properties do not increase for phosphoric acid pre-etching times over 3 seconds.

High-κ Al2O3 material in low temperature wafer-level bonding for 3D integration application

NASA Astrophysics Data System (ADS)

Fan, J.; Tu, L. C.; Tan, C. S.

2014-03-01

This work systematically investigated a high-κ Al2O3 material for low temperature wafer-level bonding for potential applications in 3D microsystems. A clean Si wafer with an Al2O3 layer thickness of 50 nm was applied as our experimental approach. Bonding was initiated in a clean room ambient after surface activation, followed by annealing under inert ambient conditions at 300 °C for 3 h. The investigation consisted of three parts: a mechanical support study using the four-point bending method, hermeticity measurements using the helium bomb test, and thermal conductivity analysis for potential heterogeneous bonding. Compared with samples bonded using a conventional oxide bonding material (SiO2), a higher interfacial adhesion energy (˜11.93 J/m2) and a lower helium leak rate (˜6.84 × 10-10 atm.cm3/sec) were detected for samples bonded using Al2O3. More importantly, due to the excellent thermal conductivity performance of Al2O3, this technology can be used in heterogeneous direct bonding, which has potential applications for enhancing the performance of Si photonic integrated devices.

Vacuum pull down method for an enhanced bonding process

DOEpatents

Davidson, James C.; Balch, Joseph W.

1999-01-01

A process for effectively bonding arbitrary size or shape substrates. The process incorporates vacuum pull down techniques to ensure uniform surface contact during the bonding process. The essence of the process for bonding substrates, such as glass, plastic, or alloys, etc., which have a moderate melting point with a gradual softening point curve, involves the application of an active vacuum source to evacuate interstices between the substrates while at the same time providing a positive force to hold the parts to be bonded in contact. This enables increasing the temperature of the bonding process to ensure that the softening point has been reached and small void areas are filled and come in contact with the opposing substrate. The process is most effective where at least one of the two plates or substrates contain channels or grooves that can be used to apply vacuum between the plates or substrates during the thermal bonding cycle. Also, it is beneficial to provide a vacuum groove or channel near the perimeter of the plates or substrates to ensure bonding of the perimeter of the plates or substrates and reduce the unbonded regions inside the interior region of the plates or substrates.

Free energy of adhesion of lipid bilayers on silica surfaces

NASA Astrophysics Data System (ADS)

Schneemilch, M.; Quirke, N.

2018-05-01

The free energy of adhesion per unit area (hereafter referred to as the adhesion strength) of lipid arrays on surfaces is a key parameter that determines the nature of the interaction between materials and biological systems. Here we report classical molecular simulations of water and 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) lipid bilayers at model silica surfaces with a range of silanol densities and structures. We employ a novel technique that enables us to estimate the adhesion strength of supported lipid bilayers in the presence of water. We find that silanols on the silica surface form hydrogen bonds with water molecules and that the water immersion enthalpy for all surfaces varies linearly with the surface density of these hydrogen bonds. The adhesion strength of lipid bilayers is a linear function of the surface density of hydrogen bonds formed between silanols and the lipid molecules on crystalline surfaces. Approximately 20% of isolated silanols form such bonds but more than 99% of mutually interacting geminal silanols do not engage in hydrogen bonding with water. On amorphous silica, the bilayer displays much stronger adhesion than expected from the crystalline surface data. We discuss the implications of these results for nanoparticle toxicity.

Structure, bonding nature, and binding energy of alkanethiolate on As-rich GaAs (001) surface: a density functional theory study.

PubMed

Voznyy, Oleksandr; Dubowski, Jan J

2006-11-30

Chemisorption of alkanethiols on As-rich GaAs (001) surface under a low coverage condition was studied using first principles density functional calculations in a periodic supercell approach. The thiolate adsorption site, tilt angle and its direction are dictated by the high directionality of As dangling bond and sulfur 3p orbital participating in bonding and steric repulsion of the first three CH2 units from the surface. Small charge transfer between thiolate and surface, strong dependence of total energy on tilt angle, and a relatively short length of 2.28 A of the S-As bond indicate the highly covalent nature of the bonding. Calculated binding energy of 2.1 eV is consistent with the available experimental data.

Effect of surface treatments on the bond strengths of facing composite resins to zirconia copings.

PubMed

Tsumita, M; Kokubo, Y; Kano, T

2012-09-01

The present study evaluated and compared the bond strength between zirconia and facing composite resin using different surface conditioning methods before and after thermocycling. Four primers, three opaque resins, and two facing composite resins were used, and 10 surface treatment procedures were conducted. The bond strength was measured before and after 4,000 cycles of thermocycling. The mean values of each group were statistically analyzed using one-way analysis of variance (ANOVA). The bond strengths of facing composite resins to zirconia after various treatments varied depending on the primers, opaque resins, body resins, and thermocycling. The application of primers and opaque resins to the zirconia surface after sandblasting is expected to yield strong bond strength of the facing composite resin (Estenia CG&B) even after thermocycling.

Palladium nanoparticles deposited on silanized halloysite nanotubes: synthesis, characterization and enhanced catalytic property

NASA Astrophysics Data System (ADS)

Zhang, Yi; He, Xi; Ouyang, Jing; Yang, Huaming

2013-10-01

Palladium (Pd) nanoparticles were deposited on the surface of halloysite nanotubes (HNTs) modified with γ-aminopropyltriethoxysilane (APTES) to produce Pd/NH2-HNTs nanocomposites. The results indicated that Pd nanoparticles were densely immobilized onto NH2-HNTs with an average diameter of ~ 3 nm. The Pd distribution on the surface of silanized HNTs showed much more uniform, and the Pd nanoparticle size became smaller compared with those directly deposited onto HNTs without silanization. Systematic characterization demonstrated that APTES were chemically bonded onto HNTs, and further confirmed the bond formation between Pd and -NH2 groups, which could ensure the firm deposit of Pd nanoparticles on the surface of silanized HNTs. The as-synthesized Pd/NH2-HNTs exhibited an excellent catalytic activity in the liquid-phase hydrogenation of styrene to ethylbenzene with full conversion within 30 min. The mechanism of the deposit of Pd nanoparticles on silanized HNTs was also investigated.

Surface immobilization of heparin on functional polyisobutylene-based thermoplastic elastomer as a potential artificial vascular graft

NASA Astrophysics Data System (ADS)

Wu, Yi-Bo; Li, Kang; Xiang, Dong; Zhang, Min; Yang, Dan; Zhang, Jin-Han; Mao, Jing; Wang, Hao; Guo, Wen-Li

2018-07-01

Polyisobutylene-based thermoplastic elastomer (TPE) is a new soft biomaterial. Hydroxyl functional dendritic polyisobutylene-based TPEs (arb-SIBS-OH), which satisfy the design requirements for small-diameter vascular substitutes, were synthesized by controlled carbocationic polymerization. Creep property, which is the destructive weakness of polyisobutylene-based TPEs, was significantly improved with the formation of a "double network" promoted by branched structure and microphase separation. Compatibility of arb-SIBS-OH with rabbit blood was markedly enhanced by modifying heparin grafted from these hydroxyl functional groups. Application of "click chemistry" to immobilize heparin on arb-SIBS-OH surface was apparently effective in enhancing the bioactivity of heparin. Immobilized heparin, which directly bonded by ester bonds, was more likely to form multi-point binding on arb-SIBS-OH surface. This process hindered the accessibility of the heparin active sequence to antithrombin.

[Influence of carbodiimide-ethanol solution surface treatment on dentin microtensile bond strength].

PubMed

Zhang, Yi; Liu, Yu-hua; Zhou, Yong-sheng; Chung, Kwok-hung

2015-10-18

To evaluate the microtensile bond strength changes and patterns of fractures of the bonding interface after dentine surface treatment with carbodiimide-ethanol solution. 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) dissolved in ethanol was diluted into different concentrations of 2, 1, 0.3, 0.1 and 0.01 mol/L EDC-ethanol solutions. Twenty-eight caries-free extracted human third molars were ground metallurgically to prepare flat occlusal mid-coronal dentin surfaces and etched with 35% (mass fraction) phosphoric acid gel. Then they were treated with EDC-ethanol solution for 60 s before the bonding procedure and randomly divided into five experimental groups corresponding to the tested EDC-ethanol concentrations. The ethanol treated and no pre-treated surfaces were used as controls. Single Bond 2 adhesive was applied and resin composite disk was stacked on the treated dentine surface. The teeth with resin composite disks were stored in water at room temperature for 24 h and then sectioned longitudinally to produce stick specimens for microtensile bond strength test. Fracture patterns were observed with a stereomicroscope. The dentin surfaces pre-treated with 2 mol/L [(22.17±13.31) MPa] and 1 mol/L [(45.31±17.80) MPa] EDC-ethanol solutions resulted in statistically significant lower bond strength value (P<0.05). Increasing numbers of fracture pattern at the resin-dentin interface were also found in this two groups with percentages of 81.2% and 41.3% respectively. No significant difference was observed in the groups with 0.3, 0.1, 0.01 mol/L EDC surface treatment (P>0.05). No significant difference of immediate bond strengths was found in the 0.3, 0.1, 0.01 mol/L groups compared with the control group. EDC-ethanol solution surface treatment with concentrations of 2 mol/L and 1 mol/L resulted in decreasing of the bonding strength.

Adsorption characteristics of Bisphenol-A on tailored activated carbon in aqueous solutions.

PubMed

Yan, Liang; Lv, Di; Huang, Xinwen; Shi, Huixiang; Zhang, Geshan

2016-10-01

The adsorption behavior of pharmaceuticals and personal care product, Bisphenol-A (BPA), according to four coal-based and four wood-based granular activated carbons modified using outgassing treatment, acidic treatment or alkaline treatment was studied. The adsorption isotherm results indicated that carbon surface acidity played a very important role in the adsorption of BPA. It was found that increasing surface acidity would increase the hydrogen bonding effects and increase adsorption of BPA on activated carbon. The acidic modified sample (F600-A and OLC-A) represented the best adsorption capacity, and the equilibrium adsorption amounts reached 346.42 and 338.55 mg/g, respectively. Further, effects of surface charge and surface basicity were examined. It was found that the adsorbed amount of BPA decreased with the increase of surface charge. Finally, there appeared to be a significant oligomerization phenomenon with BPA molecules onto the surface of activated carbon. OLC and OLC-OG, which have higher micropore percentages, are very effective in hampering the oligomerization of BPA under oxic conditions.

Bond efficacy and interface morphology of self-etching adhesives to ground enamel.

PubMed

Abdalla, Ali I; El Zohairy, Ahmed A; Abdel Mohsen, Mohamed M; Feilzer, Albert J

2010-02-01

This study compared the microshear bond strengths to ground enamel of three one-step self-etching adhesive systems, a self-etching primer system and an etch-and-rinse adhesive system. Three self-etching adhesives, Futurabond DC (Voco), Clearfil S Tri Bond (Kuraray) and Hybrid bond (Sun-Medical), a self-etching primer, Clearfil SE Bond (Kuraray), and an etch-and-rinse system, Admira Bond (Voco), were selected. Thirty human molars were used. The root of each tooth was removed and the crown was sectioned into halves. The convex enamel surfaces were reduced by polishing on silicone paper to prepare a flat surface. The bonding systems were applied on this surface. Prior to adhesive curing, a hollow cylinder (2.0 mm height/0.75 mm internal diameter) was placed on the treated surfaces. A resin composite was then inserted into the tube and cured. After water storage for 24 h, the tube was removed and shear bond strength was determined in a universal testing machine at a crosshead speed of 0.5 mm/min. The results were analyzed with ANOVA and the Tukey.-Kramer test at a 59 degrees confidence level. The enamel of five additional teeth was ground, and the etching component of each adhesive was applied and removed with absolute ethanol instead of being light cured. These teeth and selected fractured surfaces were examined by SEM. Adhesion to ground enamel of the Futurabond DC (25 +/- 3.5 MPa) and Clearfil SE Bond (23 +/- 2.9 MPa) self-etching systems was not significantly different from the etch-and-rinse system Admira Bond (27 +/- 2.3 MPa). The two self-etching adhesives Clearfil S Tri bond and Hybrid Bond demonstrated significantly lower bond strengths (14 +/- 1.4 MPa; 11 +/- 1.9 MPa) with no significant differences between them (p < 0.05). Bond strengths to ground enamel of self-etching adhesive systems are dependent on the type of adhesive system. Some of the new adhesive systems showed bond strength values comparable to that of etch-and-rinse systems. There was no correlation between bond strength and morphological changes in enamel.

Adsorbate-induced lifting of substrate relaxation is a general mechanism governing titania surface chemistry.

PubMed

Silber, David; Kowalski, Piotr M; Traeger, Franziska; Buchholz, Maria; Bebensee, Fabian; Meyer, Bernd; Wöll, Christof

2016-09-30

Under ambient conditions, almost all metals are coated by an oxide. These coatings, the result of a chemical reaction, are not passive. Many of them bind, activate and modify adsorbed molecules, processes that are exploited, for example, in heterogeneous catalysis and photochemistry. Here we report an effect of general importance that governs the bonding, structure formation and dissociation of molecules on oxidic substrates. For a specific example, methanol adsorbed on the rutile TiO 2 (110) single crystal surface, we demonstrate by using a combination of experimental and theoretical techniques that strongly bonding adsorbates can lift surface relaxations beyond their adsorption site, which leads to a significant substrate-mediated interaction between adsorbates. The result is a complex superstructure consisting of pairs of methanol molecules and unoccupied adsorption sites. Infrared spectroscopy reveals that the paired methanol molecules remain intact and do not deprotonate on the defect-free terraces of the rutile TiO 2 (110) surface.

A facile and efficient method of enzyme immobilization on silica particles via Michael acceptor film coatings: immobilized catalase in a plug flow reactor.

PubMed

Bayramoglu, Gulay; Arica, M Yakup; Genc, Aysenur; Ozalp, V Cengiz; Ince, Ahmet; Bicak, Niyazi

2016-06-01

A novel method was developed for facile immobilization of enzymes on silica surfaces. Herein, we describe a single-step strategy for generating of reactive double bonds capable of Michael addition on the surfaces of silica particles. This method was based on reactive thin film generation on the surfaces by heating of impregnated self-curable polymer, alpha-morpholine substituted poly(vinyl methyl ketone) p(VMK). The generated double bonds were demonstrated to be an efficient way for rapid incorporation of enzymes via Michael addition. Catalase was used as model enzyme in order to test the effect of immobilization methodology by the reactive film surface through Michael addition reaction. Finally, a plug flow type immobilized enzyme reactor was employed to estimate decomposition rate of hydrogen peroxide. The highly stable enzyme reactor could operate continuously for 120 h at 30 °C with only a loss of about 36 % of its initial activity.

Adsorbate-induced lifting of substrate relaxation is a general mechanism governing titania surface chemistry

NASA Astrophysics Data System (ADS)

Silber, David; Kowalski, Piotr M.; Traeger, Franziska; Buchholz, Maria; Bebensee, Fabian; Meyer, Bernd; Wöll, Christof

2016-09-01

Under ambient conditions, almost all metals are coated by an oxide. These coatings, the result of a chemical reaction, are not passive. Many of them bind, activate and modify adsorbed molecules, processes that are exploited, for example, in heterogeneous catalysis and photochemistry. Here we report an effect of general importance that governs the bonding, structure formation and dissociation of molecules on oxidic substrates. For a specific example, methanol adsorbed on the rutile TiO2(110) single crystal surface, we demonstrate by using a combination of experimental and theoretical techniques that strongly bonding adsorbates can lift surface relaxations beyond their adsorption site, which leads to a significant substrate-mediated interaction between adsorbates. The result is a complex superstructure consisting of pairs of methanol molecules and unoccupied adsorption sites. Infrared spectroscopy reveals that the paired methanol molecules remain intact and do not deprotonate on the defect-free terraces of the rutile TiO2(110) surface.

30 CFR 800.21 - Collateral bonds.

Code of Federal Regulations, 2010 CFR

2010-07-01

... INSURANCE REQUIREMENTS FOR SURFACE COAL MINING AND RECLAMATION OPERATIONS BOND AND INSURANCE REQUIREMENTS FOR SURFACE COAL MINING AND RECLAMATION OPERATIONS UNDER REGULATORY PROGRAMS § 800.21 Collateral bonds... subject to the following conditions: (1) The regulatory authority shall keep custody of collateral...

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.

Mechanistic Insights on C-O and C-C Bond Activation and Hydrogen Insertion during Acetic Acid Hydrogenation Catalyzed by Ruthenium Clusters in Aqueous Medium

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

Shangguan, Junnan; Olarte, Mariefel V.; Chin, Ya-Huei

Catalytic pathways for acetic acid (CH3COOH) and hydrogen (H2) reactions on dispersed Ru clusters in the aqueous medium and the associated kinetic requirements for C-O and C-C bond cleavages and hydrogen insertion are established from rate and isotopic assessments. CH3COOH reacts with H2 in steps that either retain its carbon backbone and lead to ethanol, ethyl acetate, and ethane (47-95 %, 1-23 %, and 2-17 % carbon selectivities, respectively) or break its C-C bond and form methane (1-43 % carbon selectivities) at moderate temperatures (413-523 K) and H2 pressures (10-60 bar, 298 K). Initial CH3COOH activation is the kinetically relevantmore » step, during which CH3C(O)-OH bond cleaves on a metal site pair at Ru cluster surfaces nearly saturated with adsorbed hydroxyl (OH*) and acetate (CH3COO*) intermediates, forming an adsorbed acetyl (CH3CO*) and hydroxyl (OH*) species. Acetic acid turnover rates increase proportionally with both H2 (10-60 bar) and CH3COOH concentrations at low CH3COOH concentrations (<0.83 M), but decrease from first to zero order as the CH3COOH concentration and the CH3COO* coverages increase and the vacant Ru sites concomitantly decrease. Beyond the initial CH3C(O)-OH bond activation, sequential H-insertions on the surface acetyl species (CH3CO*) lead to C2 products and their derivative (ethanol, ethane, and ethyl acetate) and the competitive C-C bond cleavage of CH3CO* causes the eventual methane formation. The instantaneous carbon selectivities towards C2 species (ethanol, ethane, and ethyl acetate) increase linearly with the concentration of proton-type Hδ+ (derived from carboxylic acid dissociation) and chemisorbed H*. The selectivities towards C2 products decrease with increasing temperature, because of higher observed barriers for C-C bond cleavage than H-insertion. This study offers an interpretation of mechanism and energetics and provides kinetic evidence of carboxylic acid assisted proton-type hydrogen (Hδ+) shuffling during H-insertion steps in the aqueous phase, unlike those in the vapor phase, during the hydrogenation of acetic acid on Ru clusters.« less

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.

Activation of Noble Metals on Metal-Carbide Surfaces: Novel Catalysts for CO Oxidation, Desulfurization and Hydrogenation Reactions

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

Rodriguez J. A.; Illas, F.

2012-01-01

This perspective article focuses on the physical and chemical properties of highly active catalysts for CO oxidation, desulfurization and hydrogenation reactions generated by depositing noble metals on metal-carbide surfaces. To rationalize structure-reactivity relationships for these novel catalysts, well-defined systems are required. High-resolution photoemission, scanning tunneling microscopy (STM) and first-principles periodic density-functional (DF) calculations have been used to study the interaction of metals of Groups 9, 10 and 11 with MC(001) (M = Ti, Zr, V, Mo) surfaces. DF calculations give adsorption energies that range from 2 eV (Cu, Ag, Au) to 6 eV (Co, Rh, Ir). STM images show thatmore » Au, Cu, Ni and Pt grow on the carbide substrates forming two-dimensional islands at very low coverage, and three-dimensional islands at medium and large coverages. In many systems, the results of DF calculations point to the preferential formation of admetal-C bonds with significant electronic perturbations in the admetal. TiC(001) and ZrC(001) transfer some electron density to the admetals facilitating bonding of the adatom with electron-acceptor molecules (CO, O{sub 2}, C{sub 2}H{sub 4}, SO{sub 2}, thiophene, etc.). For example, the Cu/TiC(001) and Au/TiC(001) systems are able to cleave both S-O bonds of SO{sub 2} at a temperature as low as 150 K, displaying a reactivity much larger than that of TiC(001) or extended surfaces of bulk copper and gold. At temperatures below 200 K, Au/TiC is able to dissociate O{sub 2} and perform the 2CO + O{sub 2} {yields} 2CO{sub 2} reaction. Furthermore, in spite of the very poor hydrodesulfurization performance of TiC(001) or Au(111), a Au/TiC(001) surface displays an activity for the hydrodesulfurization of thiophene higher than that of conventional Ni/MoS{sub x} catalysts. In general, the Au/TiC system is more chemically active than systems generated by depositing Au nanoparticles on oxide surfaces. Thus, metal carbides are excellent supports for enhancing the chemical reactivity of noble metals.« less

Temperature-dependent dynamical transitions of different classes of amino acid residue in a globular protein.

PubMed

Miao, Yinglong; Yi, Zheng; Glass, Dennis C; Hong, Liang; Tyagi, Madhusudan; Baudry, Jerome; Jain, Nitin; Smith, Jeremy C

2012-12-05

The temperature dependences of the nanosecond dynamics of different chemical classes of amino acid residue have been analyzed by combining elastic incoherent neutron scattering experiments with molecular dynamics simulations on cytochrome P450cam. At T = 100-160 K, anharmonic motion in hydrophobic and aromatic residues is activated, whereas hydrophilic residue motions are suppressed because of hydrogen-bonding interactions. In contrast, at T = 180-220 K, water-activated jumps of hydrophilic side chains, which are strongly coupled to the relaxation rates of the hydrogen bonds they form with hydration water, become apparent. Thus, with increasing temperature, first the hydrophobic core awakens, followed by the hydrophilic surface.

Theoretical investigation of the reactivity in the C-F bond activation of CH 3F by Lu + in the gas phase

NASA Astrophysics Data System (ADS)

Liu, Ze-Yu; Wang, Yong-Cheng; Geng, Zhi-Yuan; Yang, Xiao-Yan; Wang, Han-Qing

2006-11-01

The reaction of Lu + with CH 3F, which was selected as a representative system of the activation of C-F bond in fluorohydrocarbons by late lanthanide cations, has been examined using density functional theory (DFT). The potential energy surfaces (PESs) of [Lu, C, H 3, F] + were explored in detail in both singlet and triplet electronic states. The electron-transfer reactivity of the reaction was analyzed using the two-state model, and a strongly avoided crossing behaviour on the transition state (TS) area was shown. The theoretical results can act as a guide to further theoretical and experimental researches.

40 CFR 63.3092 - How must I control emissions from my electrodeposition primer system if I want to comply with the...

Code of Federal Regulations, 2011 CFR

2011-07-01

... electrodeposition primer system if I want to comply with the combined primer-surfacer, topcoat, final repair, glass bonding primer, and glass bonding adhesive emission limit? 63.3092 Section 63.3092 Protection of...-surfacer, topcoat, final repair, glass bonding primer, and glass bonding adhesive emission limit? If your...

40 CFR 63.3092 - How must I control emissions from my electrodeposition primer system if I want to comply with the...

Code of Federal Regulations, 2010 CFR

2010-07-01

... electrodeposition primer system if I want to comply with the combined primer-surfacer, topcoat, final repair, glass bonding primer, and glass bonding adhesive emission limit? 63.3092 Section 63.3092 Protection of...-surfacer, topcoat, final repair, glass bonding primer, and glass bonding adhesive emission limit? If your...

Thermally robust and biomolecule-friendly room-temperature bonding for the fabrication of elastomer-plastic hybrid microdevices.

PubMed

Nguyen, T P O; Tran, B M; Lee, N Y

2016-08-16

Here, we introduce a simple and fast method for bonding a poly(dimethylsiloxane) (PDMS) silicone elastomer to different plastics. In this technique, surface modification and subsequent bonding processes are performed at room temperature. Furthermore, only one chemical is needed, and no surface oxidation step is necessary prior to bonding. This bonding method is particularly suitable for encapsulating biomolecules that are sensitive to external stimuli, such as heat or plasma treatment, and for embedding fracturable materials prior to the bonding step. Microchannel-fabricated PDMS was first oxidized by plasma treatment and reacted with aminosilane by forming strong siloxane bonds (Si-O-Si) at room temperature. Without the surface oxidation of the amine-terminated PDMS and plastic, the two heterogeneous substrates were brought into intimate physical contact and left at room temperature. Subsequently, aminolysis occurred, leading to the generation of a permanent seal via the formation of robust urethane bonds after only 5 min of assembling. Using this method, large-area (10 × 10 cm) bonding was successfully realized. The surface was characterized by contact angle measurements and X-ray photoelectron spectroscopy (XPS) analyses, and the bonding strength was analyzed by performing peel, delamination, leak, and burst tests. The bond strength of the PDMS-polycarbonate (PC) assembly was approximately 409 ± 6.6 kPa, and the assembly withstood the injection of a tremendous amount of liquid with the per-minute injection volume exceeding 2000 times its total internal volume. The thermal stability of the bonded microdevice was confirmed by performing a chamber-type multiplex polymerase chain reaction (PCR) of two major foodborne pathogens - Escherichia coli O157:H7 and Salmonella typhimurium - and assessing the possibility for on-site direct detection of PCR amplicons. This bonding method demonstrated high potential for the stable construction of closed microfluidic systems socketed with biomolecule-immobilized surfaces such as DNA, antibody, enzyme, peptide, and protein microarrays.

Probing the energetics of organic–nanoparticle interactions of ethanol on calcite

DOE PAGES

Wu, Di; Navrotsky, Alexandra

2015-04-13

Knowing the nature of interactions between small organic molecules and surfaces of nanoparticles (NP) is crucial for fundamental understanding of natural phenomena and engineering processes. In this paper, we report direct adsorption enthalpy measurement of ethanol on a series of calcite nanocrystals, with the aim of mimicking organic–NP interactions in various environments. The energetics suggests a spectrum of adsorption events as a function of coverage: strongest initial chemisorption on active sites on fresh calcite surfaces, followed by major chemical binding to form an ethanol monolayer and, subsequently, very weak, near-zero energy, physisorption. Furthermore, these thermochemical observations directly support a structuremore » where the ethanol monolayer is bonded to the calcite surface through its polar hydroxyl group, leaving the hydrophobic ends of the ethanol molecules to interact only weakly with the next layer of adsorbing ethanol and resulting in a spatial gap with low ethanol density between the monolayer and subsequent added ethanol molecules, as predicted by molecular dynamics and density functional calculations. Such an ordered assembly of ethanol on calcite NP is analogous to, although less strongly bonded than, a capping layer of organics intentionally introduced during NP synthesis, and suggests a continuous variation of surface structure depending on molecular chemistry, ranging from largely disordered surface layers to ordered layers that nevertheless are mobile and can rearrange or be displaced by other molecules to strongly bonded immobile organic capping layers. Finally, these differences in surface structure will affect chemical reactions, including the further nucleation and growth of nanocrystals on organic ligand-capped surfaces.« less

Acetylene and Ethylene Adsorption on a β-Mo 2C(100) Surface: A Periodic DFT Study on the Role of C- and Mo-Terminations for Bonding and Hydrogenation Reactions

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

Jimenez-Orozco, Carlos; Florez, Elizabeth; Moreno, Andres

Mo 2C catalysts are widely used in hydrogenation reactions; however, the role of the C and Mo terminations in these catalysts is not clear. Understanding the binding of adsorbates is key for explaining the activity of Mo 2C. The adsorption of acetylene and ethylene, probe molecules representing alkynes and olefins, respectively, was studied in this paper on a β-Mo 2C(100) surface with C and Mo terminations using calculations based on periodic density functional theory. Moreover, the role of the C/Mo molar ratio was investigated to compare the catalytic potential of cubic (δ-MoC) and orthorhombic (β-Mo 2C) surfaces. The geometry andmore » electronic properties of the clean δ-MoC(001) and β-Mo 2C(100) surfaces have a strong influence on the binding of unsaturated hydrocarbons. The adsorption of ethylene is weaker than that of acetylene on the surfaces of the cubic and orthorhombic systems; adsorption of the hydrocarbons was stronger on β-Mo 2C(100) than on δ-MoC(001). The C termination in β-Mo 2C(100) actively participates in both acetylene and ethylene adsorption and is not merely a spectator. Finally, the results of this work suggest that the β-Mo 2C(100)-C surface could be the one responsible for the catalytic activity during the hydrogenation of unsaturated C≡C and C=C bonds, while the Mo-terminated surface could be poisoned or transformed by the strong adsorption of C and CH x fragments.« less

Acetylene and Ethylene Adsorption on a β-Mo 2C(100) Surface: A Periodic DFT Study on the Role of C- and Mo-Terminations for Bonding and Hydrogenation Reactions

DOE PAGES

Jimenez-Orozco, Carlos; Florez, Elizabeth; Moreno, Andres; ...

2017-08-18

Mo 2C catalysts are widely used in hydrogenation reactions; however, the role of the C and Mo terminations in these catalysts is not clear. Understanding the binding of adsorbates is key for explaining the activity of Mo 2C. The adsorption of acetylene and ethylene, probe molecules representing alkynes and olefins, respectively, was studied in this paper on a β-Mo 2C(100) surface with C and Mo terminations using calculations based on periodic density functional theory. Moreover, the role of the C/Mo molar ratio was investigated to compare the catalytic potential of cubic (δ-MoC) and orthorhombic (β-Mo 2C) surfaces. The geometry andmore » electronic properties of the clean δ-MoC(001) and β-Mo 2C(100) surfaces have a strong influence on the binding of unsaturated hydrocarbons. The adsorption of ethylene is weaker than that of acetylene on the surfaces of the cubic and orthorhombic systems; adsorption of the hydrocarbons was stronger on β-Mo 2C(100) than on δ-MoC(001). The C termination in β-Mo 2C(100) actively participates in both acetylene and ethylene adsorption and is not merely a spectator. Finally, the results of this work suggest that the β-Mo 2C(100)-C surface could be the one responsible for the catalytic activity during the hydrogenation of unsaturated C≡C and C=C bonds, while the Mo-terminated surface could be poisoned or transformed by the strong adsorption of C and CH x fragments.« less

Anatase (101)-like Structural Model Revealed for Metastable Rutile TiO2(011) Surface.

PubMed

Xu, Meiling; Shao, Sen; Gao, Bo; Lv, Jian; Li, Quan; Wang, Yanchao; Wang, Hui; Zhang, Lijun; Ma, Yanming

2017-03-08

Titanium dioxide has been widely used as an efficient transition metal oxide photocatalyst. However, its photocatalytic activity is limited to the ultraviolet spectrum range due to the large bandgap beyond 3 eV. Efforts to reduce the bandgap to achieve a broader spectrum range of light absorption have been successfully attempted via the experimental synthesis of dopant-free metastable surface structures of rutile-type TiO 2 (011) 2 × 1. This new surface phase possesses a reduced bandgap of ∼2.1 eV, showing great potential for an excellent photocatalyst covering a wide range of visible light. There is a need to establish the atomistic structure of this metastable surface to understand the physical cause for the bandgap reduction and to improve the future design of photocatalysts. Here, we report computational investigations in an effort to unravel this surface structure via swarm structure-searching simulations. The established structure adopts the anatase (101)-like structure model, where the topmost 2-fold O atoms form a quasi-hexagonal surface pattern and bond with the unsaturated 5-fold and 4-fold Ti atoms in the next layer. The predicted anatase (101)-like surface model can naturally explain the experimental observation of the STM images, the electronic bandgap, and the oxidation state of Ti 4+ . Dangling bonds on the anatase (101)-like surface are abundant making it a superior photocatalyst. First-principles molecular dynamics simulations have supported the high photocatalytic activity by showing that water and formic acid molecules dissociate spontaneously on the anatase (101)-like surface.

Influence of hydrophilic pre-treatment on resin bonding to zirconia ceramics.

PubMed

Noro, Akio; Kameyama, Atsushi; Haruyama, Akiko; Takahashi, Toshiyuki

2015-01-01

Atmospheric plasma or ultraviolet (UV) treatment alters the surface characteristics of tetragonal zirconia polycrystal (TZP), increasing its hydrophilicity by reducing the contact angle against water to zero. This suggests that such treatment would increase the wettability of bonding resin. The purpose of this study was to determine how increasing the hydrophilicity of TZP through plasma irradiation, UV treatment, or application of ceramic primer affected initial bonding with resin composites. Here, the effect of each pre-treatment on the hydrophilicity of TZP surfaces was determined by evaluating change in shear bond strength. Plasma irradiation, UV, or ceramic primer pre-treatment showed no significant effect on bonding strength between TZP surfaces and resin composites. In addition, alumina blasting yielded no significant increase in bond strength. Plasma irradiation, UV treatment, or ceramic primer pre-treatment did not lead to significant increase in bond strength between TZP and resin composites.

Tensile bond strength of metal bracket bonding to glazed ceramic surfaces with different surface conditionings.

PubMed

Akhoundi, Ms Ahmad; Kamel, M Rahmati; Hashemi, Sh Mahmood; Imani, M

2011-01-01

The objective of this study was to compare the tensile bond strength of metal brackets bonding to glazed ceramic surfaces using three various surface treatments. Forty two glazed ceramic disks were assigned to three groups. In the first and second groups the specimens were etched with 9.5% hydrofluoric acid (HFA). Subsequently in first group, ceramic primer and adhesive were applied, but in second group a bonding agent alone was used. In third group, specimens were treated with 35% phosphoric acid followed by ceramic primer and adhesive application. Brackets were bonded with light cure composites. The specimens were stored in distilled water in the room temperature for 24 hours and thermocycled 500 times between 5°C and 55°C. The universal testing machine was used to test the tensile bond strength and the adhesive remenant index scores between three groups was evaluated. The data were subjected to one-way ANOVA, Tukey and Kruskal-Wallis tests respectively. The tensile bond strength was 3.69±0.52 MPa forfirst group, 2.69±0.91 MPa for second group and 3.60±0.41 MPa for third group. Group II specimens showed tensile strength values significantly different from other groups (P<0.01). In spite of limitations in laboratory studies it may be concluded that in application of Scotch bond multipurpose plus adhesive, phosphoric acid can be used instead of HFA for bonding brackets to the glazed ceramic restorations with enough tensile bond strength.

Hydroxyl migration disorders the surface structure of hydroxyapatite nanoparticles

NASA Astrophysics Data System (ADS)

Cheng, Xiajie; Wu, Hong; Zhang, Li; Ma, Xingtao; Zhang, Xingdong; Yang, Mingli

2017-09-01

The surface structure of nano-hydroxyapatite (HAP) was investigated using a combined simulated annealing and molecular dynamics method. The stationary structures of nano-HAP with 4-7 nm in diameter and annealed under different temperatures were analyzed in terms of pair distribution function, structural factor, mean square displacement and atomic coordination number. The particles possess different structures from bulk crystal. A clear radial change in their atomic arrangements was noted. From core to surface the structures change from ordered to disordered. A three-shell model was proposed to describe the structure evolution of nano-HAP. Atoms in the core zone keep their arrangements as in crystal, while atoms in the surface shell are in short-range order and long-range disorder, adopting a typically amorphous structure. Atoms in the middle shell have small displacements and/or deflections but basically retain their original locations as in crystal. The disordered shell is about 1 nm in thickness, in agreement with experimental observations. The disordering mainly stems from hydroxyl migration during which hydroxyls move to the surface and bond with the exposed Ca ions, and their left vacancies bring about a rearrangement of nearby atoms. The disordering is to some extent different for particles unannealed under different temperatures, resulting from fewer number of migrated hydroxyls at lower temperatures. Particles with different sizes have similar surface structures, and their surface energy decreases with increasing size. Moreover, the surface energy is reduced by hydroxyl migration because the exposed Ca ions on the surface are ionically bonded with the migrated hydroxyls. Our calculations proposed a new structure model for nano-HAP, which indicates a surface structure with activities different from those without surface reorganization. This is particularly interesting because most bioactivities of biomaterials are dominated by their surface activity.

Novel poly(dimethylsiloxane) bonding strategy via room temperature "chemical gluing".

PubMed

Lee, Nae Yoon; Chung, Bong Hyun

2009-04-09

Here we propose a new scheme for bonding poly(dimethylsiloxane) (PDMS), namely, a "chemical gluing", at room temperature by anchoring chemical functionalities on the surfaces of PDMS. Aminosilane and epoxysilane are anchored separately on the surfaces of two PDMS substrates, the reaction of which are well-known to form a strong amine-epoxy bond, therefore acting as a chemical glue. The bonding is performed for 1 h at room temperature without employing heat. We characterize the surface properties and composition by contact angle measurement, X-ray photoelectron spectroscopy analysis, and fluorescence measurement to confirm the formation of surface functionalities and investigate the adhesion strength by means of pulling, tearing, and leakage tests. As confirmed by the above-mentioned analyses and tests, PDMS surfaces were successfully modified with amine and epoxy functionalities, and a bonding based on the amine-epoxy chemical gluing was successfully realized within 1 h at room temperature. The bonding was sufficiently robust to tolerate intense introduction of liquid whose per minute injection volume was almost 2000 times larger than the total internal volume of the microchannel used. In addition to the bonding of PDMS-PDMS homogeneous assembly, the bonding of the PDMS-poly(ethylene terephthalate) heterogeneous assembly was also examined. We also investigate the potential use of the multifunctionalized walls inside the microchannel, generated as a consequence of the chemical gluing, as a platform for the targeted immobilization.

Sandblasting may damage the surface of composite CAD-CAM blocks.

PubMed

Yoshihara, Kumiko; Nagaoka, Noriyuki; Maruo, Yukinori; Nishigawa, Goro; Irie, Masao; Yoshida, Yasuhiro; Van Meerbeek, Bart

2017-03-01

CAD-CAM blocks to fabricate semi-direct and indirect restorations are available in different sorts of ceramics as well as composite. In order to bond restorations prepared out of composite blocks into tooth cavities, it is recommended to gently sandblast the surface prior to the application of a primer/adhesive. Today, the effect of sandblasting composite block surfaces has not thoroughly been investigated. In this study, the ultra-structure of composite CAD-CAM blocks was investigated with special attention to the effect of sandblasting on the surface topography and of silanization on the bonding performance. Five different composite CAD-CAM blocks were involved. We correlatively investigated their structural and chemical composition using X-ray diffraction (XRD), energy dispersion spectroscopy (EDS), scanning electron microscopy (SEM) and (scanning) transmission electron microscopy ((S)TEM). The effect of sandblasting was also imaged in cross-section and at the interface with composite cement. Finally, we measured the shear bond strength to the sandblasted block surface with and without silanization. All composite blocks revealed a different ultra-structure. Sandblasting increased surface roughness and resulted in an irregular surface with some filler exposure. Sandblasting also damaged the surface. When the sandblasted composite blocks were silanized, superior bonding receptiveness in terms of higher bond strength was achieved except for Shofu Block HC. Sandblasting followed by silanization improved the bond strength to composite CAD-CAM blocks. However, sandblasting may also damage the composite CAD-CAM block surface. For the composite CAD-CAM block Shofu Block HC, the damage was so severe that silanization did not improve bond strength. Copyright © 2016 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Scratching technique for the study and analysis of soil surface abrasion mechanism

NASA Astrophysics Data System (ADS)

Ta, Wanquan

2007-11-01

Aeolian abrasion is the most fundamental and active surface process that takes place in arid and semi-arid environments. Its nature is a wear process for wind blown grains impinging on a soil or sediment surface, which causes particles and aggregates to fracture from the soil surface through a series of plastic and brittle cracking deformation such as cutting, ploughing and brittle fracturing. Using a Universal Micro-Tribometer (UMT), a scratching test was carried out on six soil surfaces (sandy soil, sand loam, silt loam, loam, silt clay loam, and silt clay). The results indicate that traces of normal and tangential force vs. time show a jagged curve, which can reflect the plastic deformation and brittle fracturing of aggregates and particles of various sizes fractured from the soil surfaces. The jagged curve peaks, and the area enclosed underneath, may represent the bonding forces and bonding energies of some aggregates and grains on the soil surface, respectively. Connecting the scratching test with an impact abrasion experiment furthermore demonstrates that soil surface abrasion rates are proportional to the square of speeds of impacting particles and to the 2.6 power of mean soil grain size, and inversely proportional to the 1.5 power of specific surface abrasive energy or to the 1.7 power of specific surface hardness.

Hydrogen-Bonding Surfaces for Ice Mitigation

NASA Technical Reports Server (NTRS)

Smith, Joseph G., Jr.; Wohl, Christopher J.; Kreeger, Richard E.; Hadley, Kevin R.; McDougall, Nicholas

2014-01-01

Ice formation on aircraft, either on the ground or in-flight, is a major safety issue. While ground icing events occur predominantly during the winter months, in-flight icing can happen anytime during the year. The latter is more problematic since it could result in increased drag and loss of lift. Under a Phase I ARMD NARI Seedling Activity, coated aluminum surfaces possessing hydrogen-bonding groups were under investigation for mitigating ice formation. Hydroxyl and methyl terminated dimethylethoxysilanes were prepared via known chemistries and characterized by spectroscopic methods. These materials were subsequently used to coat aluminum surfaces. Surface compositions were based on pure hydroxyl and methyl terminated species as well as mixtures of the two. Coated surfaces were characterized by contact angle goniometry. Receding water contact angle data suggested several potential surfaces that may exhibit reduced ice adhesion. Qualitative icing experiments performed under representative environmental temperatures using supercooled distilled water delivered via spray coating were inconclusive. Molecular modeling studies suggested that chain mobility affected the interface between ice and the surface more than terminal group chemical composition. Chain mobility resulted from the creation of "pockets" of increased free volume for longer chains to occupy.

Effects of Mechanical and Chemical Pretreatments of Zirconia or Fiber Posts on Resin Cement Bonding

PubMed Central

Li, Rui; Zhou, Hui; Wei, Wei; Wang, Chen; Sun, Ying Chun; Gao, Ping

2015-01-01

The bonding strength between resin cement and posts is important for post and core restorations. An important method of improving the bonding strength is the use of various surface pretreatments of the post. In this study, the surfaces of zirconia (fiber) posts were treated by mechanical and/or chemical methods such as sandblasting and silanization. The bonding strength between the zirconia (fiber) post and the resin cement was measured by a push-out method after thermocycling based on the adhesion to Panavia F 2.0 resin cement. The zirconia and fiber posts exhibited different bonding strengths after sandblasting and/or silanization because of the different strengths and chemical structures. The zirconia post showed a high bonding strength of up to 17.1 MPa after a combined treatment of sandblasting and silanization because of the rough surface and covalent bonds at the interface. This effect was also enhanced by using 1,2-bis(trimethoxysilyl)ethane for the formation of a flexible layer at the interface. In contrast, a high bonding strength of 13.9 MPa was obtained for the fiber post treated by silane agents because the sandblasting treatment resulted in damage to the fiber post, as observed by scanning electron microscopy. The results indicated that the improvement in the bonding strength between the post and the resin cement could be controlled by different chemical and/or mechanical treatments. Enhanced bonding strength depended on covalent bonding and the surface roughness. A zirconia post with high bonding strength could potentially be used for the restoration of teeth in the future. PMID:26066349

The influence of salivary contamination on shear bond strength of dentin adhesive systems.

PubMed

Park, Jeong-won; Lee, Kyung Chae

2004-01-01

This study evaluated the influence of salivary contamination during dentin bonding procedures on shear bond strength and investigated the effect of contaminant-removing treatments on the recovery of bond strength for two dentin bonding agents. One hundred and ten human molars were embedded in cylindrical molds with self-curing acrylic resin. The occlusal dentin surface was exposed by wet grinding with #800 silicon carbide abrasive paper. The teeth were divided into five groups for One-step (OS) (BISCO, Inc) and six groups for Clearfil SE Bond (SE) (Kuraray Co, Ltd, Osaka, Japan). For One-step, the grinding surface was treated with 32% phosphoric acid; BAC (BISCO Inc) and divided into five groups: OS control group (uncontaminated), OS I (salivary contamination, blot dried), OS II (salivary contamination, completely dried), OS III (salivary contamination, wash and blot dried) and OS IV (salivary contamination, re-etching for 10 seconds, wash and blot dried). For SE bond, the following surface treatments were done: SE control group (primer applied to the fresh dentin surface), SE I (after salivary contamination, primer applied), SE II (primer, salivary contamination, dried), SE III (primer, salivary contamination, wash and dried), SE IV (after procedure of SE II, re-application of primer) and SE V (after procedure of SE III, re-application of primer). Each bonding agent was applied and light cured for 10 seconds. Clearfil AP-X (Kuraray Co, Ltd) composite was packed into the Ultradent mount jig mold and light cured for 40 seconds. The bonded specimens were stored for 24 hours in a 37 degrees C waterbath. The shear bond strengths were measured using an Instron testing machine (Model 4202, Instron Corp). The data for each group were subjected to one-way ANOVA followed by the Newman-Keuls test to make comparisons among the groups. The results were as follows: In the One-step groups, the OS II group showed statistically significant lower shear bond strength than the OS control, I, III and IV (p<0.05). In the Clearfil SE Bond groups, the SE II and SE III groups had decreased shear bond strength compared with the control and SE I, SE IV and SE V groups (p<0.05). In conclusion, when using One-step total etch adhesive and when the etched surface is contaminated by saliva, blotting the surface and applying the primer can recover the bond strength. Complete drying of the salivary contaminated surface should be avoided. In the Clearfil SE Bond groups, the re-priming treatment (SE IV and SE V) resulted in the recovery of shear bond strength in the specimens contaminated after priming.

Effect of Various Laser Surface Treatments on Repair Shear Bond Strength of Aged Silorane-Based Composite

PubMed Central

Alizadeh Oskoee, Parnian; Savadi Oskoee, Siavash; Rikhtegaran, Sahand; Pournaghi-Azar, Fatemeh; Gholizadeh, Sarah; Aleyasin, Yasaman; Kasrae, Shahin

2017-01-01

Introduction: Successful repair of composite restorations depends on a strong bond between the old composite and the repair composite. This study sought to assess the repair shear bond strength of aged silorane-based composite following surface treatment with Nd:YAG, Er,Cr:YSGG and CO2 lasers. Methods: Seventy-six Filtek silorane composite cylinders were fabricated and aged by 2 months of water storage at 37°C. The samples were randomly divided into 4 groups (n=19) of no surface treatment (group 1) and surface treatment with Er,Cr:YSGG (group 2), Nd:YAG (group 3) and CO2 (group 4) lasers. The repair composite was applied and the shear bond strength was measured. The data were analyzed using one-way analysis of variance (ANOVA) and Tukey posthoc test. Prior to the application of the repair composite, 2 samples were randomly selected from each group and topographic changes on their surfaces following laser irradiation were studied using a scanning electron microscope (SEM). Seventeen other samples were also fabricated for assessment of cohesive strength of composite. Results: The highest and the lowest mean bond strength values were 8.99 MPa and 6.69 MPa for Er,Cr:YSGG and control groups, respectively. The difference in the repair bond strength was statistically significant between the Er,Cr:YSGG and other groups. Bond strength of the control, Nd:YAG and CO2 groups was not significantly different. The SEM micrographs revealed variable degrees of ablation and surface roughness in laser-treated groups. Conclusion: Surface treatment with Er,Cr:YSGG laser significantly increase the repair bond strength of aged silorane-based composite resin. PMID:29071025

First-principles study of adsorption-desorption kinetics of aqueous V2+/V3+ redox species on graphite in a vanadium redox flow battery.

PubMed

Jiang, Zhen; Klyukin, Konstantin; Alexandrov, Vitaly

2017-06-14

Vanadium redox flow batteries (VRFBs) represent a promising solution to grid-scale energy storage, and understanding the reactivity of electrode materials is crucial for improving the power density of VRFBs. However, atomistic details about the interactions between vanadium ions and electrode surfaces in aqueous electrolytes are still lacking. Here, we examine the reactivity of the basal (0001) and edge (112[combining macron]0) graphite facets with water and aqueous V 2+ /V 3+ redox species at 300 K employing Car-Parrinello molecular dynamics (CPMD) coupled with metadynamics simulations. The results suggest that the edge surface is characterized by the formation of ketonic C[double bond, length as m-dash]O functional groups due to complete water dissociation into the H/O/H configuration with surface O atoms serving as active sites for adsorption of V 2+ /V 3+ species. The formation of V-O bonds at the surface should significantly improve the kinetics of electron transfer at the edge sites, which is not the case for the basal surface, in agreement with the experimentally hypothesized mechanism.

Surface Redox Chemistry of Immobilized Nanodiamond: Effects of Particle Size and Electrochemical Environment

NASA Astrophysics Data System (ADS)

Gupta, S.; McDonald, B.; Carrizosa, S. B.

2017-07-01

The size of the diamond particle is tailored to nanoscale (nanodiamond, ND), and the ND surface is engineered targeting specific (electrochemical and biological) applications. In this work, we investigated the complex surface redox chemistry of immobilized ND layer on conductive boron-doped diamond electrode with a broad experimental parameter space such as particle size (nano versus micron), scan rate, pH (cationic/acidic versus anionic/basic), electrolyte KCl concentration (four orders of magnitude), and redox agents (neutral and ionic). We reported on the significant enhancement of ionic currents while recording reversible oxidation of neutral ferrocene methanol (FcMeOH) by almost one order of magnitude than traditional potassium ferricyanide (K3Fe(CN)6) redox agent. The current enhancement is inversely related to ND particle diameter in the following order: 1 μm << 1000 nm < 100 nm < 10 nm ≤ 5 nm < 2 nm. We attribute the current enhancement to concurrent electrocatalytic processes, i.e. the electron transfer between redox probes and electroactive surface functional (e.g. hydroxyl, carboxyl, epoxy) moieties and the electron transfer mediated by adsorbed FcMeOH+ (or Fe(CN) 6 3+ ) ions onto ND surface. The first process is pH dependent since it depends upon ND surface functionalities for which the electron transfer is coupled to proton transfer. The adsorption mediated process is observed most apparently at slower scan rates owing to self-exchange between adsorbed FcMeOH+ ions and FcMeOH redox agent molecules in diffusion-limited bulk electrolyte solution. Alternatively, it is hypothesized that the surface functionality and defect sites ( sp 2-bonded C shell and unsaturated bonds) give rise to surface electronic states with energies within the band gap (midgap states) in undoped ND. These surface states serve as electron donors (and acceptors) depending upon their bonding (and antibonding) character and, therefore, they can support electrocatalytic redox processes in the presence of specific redox-active molecules via feedback mechanism. Apparently, FcMeOH+ tended to have electrostatic affinity for negatively charged ND surface functionalities, corroborated by present experiments. We also attempted to study biocatalytic process using model metalloprotein (cytochrome c; Cyt c) immobilized on ND particles for investigating interfacial electron transfer kinetics and compared with those of functionalized graphene (graphene oxide; GO and reduced GO). The findings are discussed in terms of interplay of sp 3-bonded C (ND core) and sp 2-bonded C (ND shell and graphene-based systems).

Laboratory Investigations of Mesospheric Ice Surfaces: Absence of Dangling Bonds in the Presence of Atomic Oxygen

NASA Astrophysics Data System (ADS)

Boulter, J. E.; Morgan, C. G.; Marschall, J.

2006-05-01

Remote observations of PMCs have become more sophisticated and have increased in geographic and temporal coverage, while numerical models have advanced in detail and predictive power. Together, these advances enable new questions of PMC morphology, optical properties, and microphysical processes in their formation and dissipation. Laboratory investigations also advance this understanding, simulating physical and chemical processes unique to this atmospheric region under comparable conditions. In this work, ice deposition experiments in the presence of microwave discharge-dissociated molecular oxygen suggest heterogeneous interactions between dangling OH bonds on the ice surface and atomic oxygen. Ice films deposited on a gold substrate at temperatures of 115, 130, and 140 K from oxygen/water gas mixtures representative of the summertime polar mesosphere exhibit infrared absorption features characteristic of dangling bonds, whereas films grown in the presence of atomic oxygen do not. Dangling bond spectral features are shown to diminish rapidly when the microwave discharge is activated during ice deposition. Similar decreases were not seen when the gas stream was heated or when the ice film was slowly annealed from 130 to 160 K. One interpretation of these results is that atomic oxygen binds to dangling bond sites during ice growth, a phenomenon that may also occur during the formation of ice particles observed just below the cold summertime mesopause.

Improved primer for bonding polyurethane adhesives to metals

NASA Technical Reports Server (NTRS)

Constanza, L. J.

1969-01-01

Primer ensures effective bonding integrity of polyurethane adhesives on metal surfaces at temperatures ranging from minus 423 degrees to plus 120 degrees F. It provides greater metal surface protection and bond strengths over this temperature range than could be attained with other adhesive systems.

Hybrid Quantum/Classical Molecular Dynamics Simulations of the Proton Transfer Reactions Catalyzed by Ketosteroid Isomerase: Analysis of Hydrogen Bonding, Conformational Motions, and Electrostatics

PubMed Central

Chakravorty, Dhruva K.; Soudackov, Alexander V.; Hammes-Schiffer, Sharon

2009-01-01

Hybrid quantum/classical molecular dynamics simulations of the two proton transfer reactions catalyzed by ketosteroid isomerase are presented. The potential energy surfaces for the proton transfer reactions are described with the empirical valence bond method. Nuclear quantum effects of the transferring hydrogen increase the rates by a factor of ~8, and dynamical barrier recrossings decrease the rates by a factor of 3–4. For both proton transfer reactions, the donor-acceptor distance decreases substantially at the transition state. The carboxylate group of the Asp38 side chain, which serves as the proton acceptor and donor in the first and second steps, respectively, rotates significantly between the two proton transfer reactions. The hydrogen bonding interactions within the active site are consistent with the hydrogen bonding of both Asp99 and Tyr14 to the substrate. The simulations suggest that a hydrogen bond between Asp99 and the substrate is present from the beginning of the first proton transfer step, whereas the hydrogen bond between Tyr14 and the substrate is virtually absent in the first part of this step but forms nearly concurrently with the formation of the transition state. Both hydrogen bonds are present throughout the second proton transfer step until partial dissociation of the product. The hydrogen bond between Tyr14 and Tyr55 is present throughout both proton transfer steps. The active site residues are more mobile during the first step than during the second step. The van der Waals interaction energy between the substrate and the enzyme remains virtually constant along the reaction pathway, but the electrostatic interaction energy is significantly stronger for the dienolate intermediate than for the reactant and product. Mobile loop regions distal to the active site exhibit significant structural rearrangements and, in some cases, qualitative changes in the electrostatic potential during the catalytic reaction. These results suggest that relatively small conformational changes of the enzyme active site and substrate strengthen the hydrogen bonds that stabilize the intermediate, thereby facilitating the proton transfer reactions. Moreover, the conformational and electrostatic changes associated with these reactions are not limited to the active site but rather extend throughout the entire enzyme. PMID:19799395

Laser Surface Preparation for Adhesive Bonding of Ti-6Al-4V

NASA Technical Reports Server (NTRS)

Belcher, Marcus A.; List, Martina S.; Wohl, Christopher J.; Ghose, Sayata; Watson, Kent A.; Hopkins, John W.; Connell, John W.

2010-01-01

Adhesively bonded structures are potentially lighter in weight than mechanically fastened ones, but existing surface treatments are often considered unreliable. Two main problems in achieving reproducible and durable adhesive bonds are surface contamination and variability in standard surface preparation techniques. In this work three surface pretreatments were compared: laser etching with and without grit blasting and conventional Pasa-Jell treatment. Ti-6Al-4V surfaces were characterized by contact angle goniometry, optical microscopy, and X-ray photoelectron spectroscopy (XPS). Laser -etching was found to produce clean surfaces with precisely controlled surface topographies and PETI-5 lap shear strengths and durabilities were equivalent to those produced with Pasa-Jell.

Significance of Graphitic Surfaces in Aurodicyanide Adsorption by Activated Carbon: Experimental and Computational Approach

NASA Astrophysics Data System (ADS)

Bhattacharyya, Dhiman; Depci, Tolga; Prisbrey, Keith; Miller, Jan D.

Despite tremendous developments in industrial use of activated carbon (AC) for gold adsorption, specific aurodicyanide [Au(CN)2-] adsorption sites on the carbon have intrigued researchers. The graphitic structure of AC has been well established. Previously radiochemical and now, XPS and Raman characterizations have demonstrated higher site-specific gold adsorption on graphitic edges. Morphological characterizations have revealed the presence of slit-pores (5-10 Å). Molecular-dynamics-simulation (MDS) performed on graphitic slit-pores illustrated gold-cyanide ion-pair preferentially adsorbs on edges. Ab-initio simulations predicted lower barrier for electron sharing in pores with aurodic yanide, indicating tighter bonding than graphitic surface and was well supported by Gibbs energy calculations too. Interaction energy as function of the separation distance indicated tighter bonding of gold cyanide to the graphite edges than water molecules. Selective adsorption of aurodicyanide ion-pair seems to be related to low polarity of gold complex and its accommodation at graphitic edges.

Shear bond strength of composite bonded with three adhesives to Er,Cr:YSGG laser-prepared enamel.

PubMed

Türkmen, Cafer; Sazak-Oveçoğlu, Hesna; Günday, Mahir; Güngör, Gülşad; Durkan, Meral; Oksüz, Mustafa

2010-06-01

To assess in vitro the shear bond strength of a nanohybrid composite resin bonded with three adhesive systems to enamel surfaces prepared with acid and Er,Cr:YSGG laser etching. Sixty extracted caries- and restoration-free human maxillary central incisors were used. The teeth were sectioned 2 mm below the cementoenamel junction. The crowns were embedded in autopolymerizing acrylic resin with the labial surfaces facing up. The labial surfaces were prepared with 0.5-mm reduction to receive composite veneers. Thirty specimens were etched with Er,Cr:YSGG laser. This group was also divided into three subgroups, and the following three bonding systems were then applied on the laser groups and the other three unlased groups: (1) 37% phosphoric acid etch + Bond 1 primer/adhesive (Pentron); (2) Nano-bond self-etch primer (Pentron) + Nano-bond adhesive (Pentron); and (3) all-in-one adhesive-single dose (Futurabond NR, Voco). All of the groups were restored with a nanohybrid composite resin (Smile, Pentron). Shear bond strength was measured with a Zwick universal test device with a knife-edge loading head. The data were analyzed with two-factor ANOVA. There were no significant differences in shear bond strength between self-etch primer + adhesive and all-in-one adhesive systems for nonetched and laser-etched enamel groups (P > .05). However, bond strength values for the laser-etched + Bond 1 primer/adhesive group (48.00 +/- 13.86 MPa) were significantly higher than the 37% phosphoric acid + Bond 1 primer/adhesive group (38.95 +/- 20.07 MPa) (P < .05). The Er,Cr:YSGG laser-powered hydrokinetic system etched the enamel surface more effectively than 37% phosphoric acid for subsequent attachment of composite material.

A critical study of the role of the surface oxide layer in titanium bonding

NASA Technical Reports Server (NTRS)

Dias, S.; Wightman, J. P.

1982-01-01

The molecular understanding of the role which the surface oxide layer of the adherend plays in titanium bonding is studied. The effects of Ti6-4 adherends pretreatment, bonding conditions, and thermal aging of the lap shear specimens were studied. The use of the SEM/EDAX and ESCA techniques to study surface morphology and surface composition was emphasized. In addition, contact angles and both infrared and visible reflection spectroscopy were used in ancillary studies.

Interaction of sulfur dioxide with titanium-carbide nanoparticles and surfaces: A density functional study

NASA Astrophysics Data System (ADS)

Liu, Ping; Rodriguez, José A.

2003-11-01

In the control of environmental pollution, metal carbides are potentially useful for trapping and destroying sulfur dioxide (SO2). In the present study, the density functional theory was employed to study the surface structures and electronic properties of the adsorbed SO2 on titanium carbides: metcar Ti8C12, nanocrystal Ti14C13, and a bulk TiC(001) surface. The geometries and orientations of SO2 were fully optimized on all these substrates. Our calculations show that, in spite of the high C/Ti ratio and C2 groups, metcar Ti8C12 exhibits extremely high activity towards SO2. The S-O bonds of SO2 spontaneously break on Ti8C12. The products of the decomposition reaction (S, O) interact simultaneously with Ti and C sites. The C atoms are not simple spectators, and their participation in the dissociation of SO2 is a key element for the energetics of this process. Nanocrystal Ti14C13 also displays a strong interaction with SO2. Although the dissociation of SO2 on Ti14C13 cannot proceed as easily as that on Ti8C12, it could occur by thermal activation even at very low temperature. SO2 is weakly bonded with the bulk TiC(001) surface. By thermal activation the dissociation of SO2 on a TiC(001) surface may also take place but it should be much more difficult than that on Ti14C13. Therefore, we suggest that the carbide nanoparticles (Ti8C12 and Ti14C13) should have special chemical activity towards SO2 removal associated with their "magic" structures.

Mechanisms of degradation in adhesive joint strength: Glassy polymer thermoset bond in a humid environment

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

Kropka, Jamie Michael; Adolf, Douglas Brian; Spangler, Scott Wilmer

The degradation in the strength of napkin-ring (NR) joints bonded with an epoxy thermoset is evaluated in a humid environment. While adherend composition (stainless steel and aluminum) and surface preparation (polished, grit blasted, primed, coupling agent coated) do not affect virgin (time=0) joint strength, they can significantly affect the role of moisture on the strength of the joint. Adherend surface abrasion and corrosion processes are found to be key factors in determining the reliability of joint strength in humid environments. In cases where surface specific joint strength degradation processes are not active, decreases in joint strength can be accounted formore » by the glass transition temperature, T g, depression of the adhesive associated with water sorption. Under these conditions, joint strength can be rejuvenated to virgin strength by drying. In addition, the decrease in joint strength associated with water sorption can be predicted by the Simplified Potential Energy Clock (SPEC) model by shifting the adhesive reference temperature, T ref, by the same amount as the T g depression. When surface specific degradation mechanisms are active, they can reduce joint strength below that associated with adhesive T g depression, and joint strength is not recoverable by drying. Furthermore, a critical relative humidity (or, potentially, critical water sorption concentration), below which the surface specific degradation does not occur, appears to exist for the polished stainless steel joints.« less

Mechanisms of degradation in adhesive joint strength: Glassy polymer thermoset bond in a humid environment

DOE PAGES

Kropka, Jamie Michael; Adolf, Douglas Brian; Spangler, Scott Wilmer; ...

2015-08-06

The degradation in the strength of napkin-ring (NR) joints bonded with an epoxy thermoset is evaluated in a humid environment. While adherend composition (stainless steel and aluminum) and surface preparation (polished, grit blasted, primed, coupling agent coated) do not affect virgin (time=0) joint strength, they can significantly affect the role of moisture on the strength of the joint. Adherend surface abrasion and corrosion processes are found to be key factors in determining the reliability of joint strength in humid environments. In cases where surface specific joint strength degradation processes are not active, decreases in joint strength can be accounted formore » by the glass transition temperature, T g, depression of the adhesive associated with water sorption. Under these conditions, joint strength can be rejuvenated to virgin strength by drying. In addition, the decrease in joint strength associated with water sorption can be predicted by the Simplified Potential Energy Clock (SPEC) model by shifting the adhesive reference temperature, T ref, by the same amount as the T g depression. When surface specific degradation mechanisms are active, they can reduce joint strength below that associated with adhesive T g depression, and joint strength is not recoverable by drying. Furthermore, a critical relative humidity (or, potentially, critical water sorption concentration), below which the surface specific degradation does not occur, appears to exist for the polished stainless steel joints.« less

Surface chemistry, friction, and wear of Ni-Zn and Mn-Zn ferrites in contact with metals

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Buckley, D. H.

1983-01-01

X-ray photoelectron and Auger electron spectroscopy analysis were used in sliding friction experiments. These experiments were conducted with hot-pressed polycrystalline Ni-Zn and Mn-Zn ferrites, and single-crystal Mn-Zn ferrite in contact with various transition metals at room temperature in both vacuum and argon. The results indicate that Ni2O3 and Fe3O4 were present on the Ni-Zn ferrite surface in addition to the nominal bulk constituents, while MnO2 and Fe3O4 were present on the Mn-Zn ferrite surface in addition to the nominal bulk constituents. The coefficients of friction for the ferrites in contact with metals were related to the relative chemical activity of these metals. The more active the metal, the higher is the coefficient of friction. The coefficients of friction for the ferrites were correlated with the free energy of formation of the lowest metal oxide. The interfacial bond can be regarded as a chemical bond between the metal atoms and the oxygen anions in the ferrite surfaces. The adsorption of oxygen on clean metal and ferrite does strengthen the metal-ferrite contact and increase the friction. The ferrites exhibit local cracking and fracture with sliding under adhesive conditions. All the metals transferred to the surfaces of the ferrites in sliding. Previously announced in STAR as N83-19901

Surface chemistry, friction and wear of Ni-Zn and Mn-Zn ferrites in contact with metals

NASA Technical Reports Server (NTRS)

Miyoshi, K.; Buckley, D. H.

1982-01-01

X-ray photoelectron and Auger electron spectroscopy analysis were used in sliding friction experiments. These experiments were conducted with hot-pressed polycrystalline Ni-Zn and Mn-Zn ferrites, and single-crystal Mn-Zn ferrite in contact with various transition metals at room temperature in both vacuum and argon. The results indicate that Ni2O3 and Fe3O4 were present on the Ni-Zn ferrite surface in addition to the nominal bulk constituents, while MnO2 and Fe3O4 were present on the Mn-Zn ferrite surface in addition to the nominal bulk constituents. The coefficients of friction for the ferrites in contact with metals were related to the relative chemical activity of these metals. The more active the metal, the higher is the coefficient of friction. The coefficients of friction for the ferrites were correlated with the free energy of formation of the lowest metal oxide. The interfacial bond can be regarded as a chemical bond between the metal atoms and the oxygen anions in the ferrite surfaces. The adsorption of oxygen on clean metal and ferrite does strengthen the metal-ferrite contact and increase the friction. The ferrites exhibit local cracking and fracture with sliding under adhesive conditions. All the metals transferred to he surfaces of the ferrites in sliding.

Microshear Bond Strength of OptiBond All-in-One Self-adhesive Agent to Er:YAG Laser Treated Enamel After Thermocycling and Water Storage.

PubMed

Kasraei, Shahin; Yarmohammadi, Ebrahim; Ghazizadeh, Mohammad Vahid

2016-01-01

Introduction: This study aimed to compare the microshear bond strength of composite to enamel treated with Erbium-Doped Yttrium Aluminum Garnet (Er:YAG) laser using a self-etch one step bonding agent. Methods: Seventy-six enamel surfaces were prepared from 38 sound human third molar teeth. Specimens were randomly divided into four groups of 18. The enamel surface in half the specimens was irradiated with Er:YAG laser. One extra specimen from each group was evaluated under a scanning electron microscope (SEM). Composite micro-cylinders were bonded to the specimen surfaces using OptiBond All-In-One (OB) adhesive agent and stored in distilled water for 24 hours. Half the specimens were thermocycled (2000 cycles) and stored in distilled water at 37°C for three months (TW). The microshear bond strength of composite to enamel was measured using a universal testing machine at a crosshead speed of 1 mm/min. The fractured surfaces were evaluated under a stereomicroscope at ×40 magnification to determine the mode of failure. Data were analyzed using repeated measures analysis of variance (ANOVA) and t test. Results: The mean values (±standard deviation) were 17.96 ± 2.92 MPa in OB group, 22.29 ± 4.25 MPa in laser + OB group, 18.11 ± 3.52 MPa in laser + OB + TW group and 9.42 ± 2.47 MPa in OB + TW group. Repeated measures ANOVA showed that laser irradiation increased the microshear bond strength ( P < 0.001). Bond strength decreased when the samples were thermocycled and stored for three months ( P < 0.001). The interaction effect of water storage and laser treatment on bond strength was significant ( P < 0.05). Conclusion: Enamel surface preparation with Er:YAG laser is recommended to enhance the durability of the bond of self-etch bonding systems to enamel.

Microshear Bond Strength of OptiBond All-in-One Self-adhesive Agent to Er:YAG Laser Treated Enamel After Thermocycling and Water Storage

PubMed Central

Kasraei, Shahin; Yarmohammadi, Ebrahim; Ghazizadeh, Mohammad Vahid

2016-01-01

Introduction: This study aimed to compare the microshear bond strength of composite to enamel treated with Erbium-Doped Yttrium Aluminum Garnet (Er:YAG) laser using a self-etch one step bonding agent. Methods: Seventy-six enamel surfaces were prepared from 38 sound human third molar teeth. Specimens were randomly divided into four groups of 18. The enamel surface in half the specimens was irradiated with Er:YAG laser. One extra specimen from each group was evaluated under a scanning electron microscope (SEM). Composite micro-cylinders were bonded to the specimen surfaces using OptiBond All-In-One (OB) adhesive agent and stored in distilled water for 24 hours. Half the specimens were thermocycled (2000 cycles) and stored in distilled water at 37°C for three months (TW). The microshear bond strength of composite to enamel was measured using a universal testing machine at a crosshead speed of 1 mm/min. The fractured surfaces were evaluated under a stereomicroscope at ×40 magnification to determine the mode of failure. Data were analyzed using repeated measures analysis of variance (ANOVA) and t test. Results: The mean values (±standard deviation) were 17.96 ± 2.92 MPa in OB group, 22.29 ± 4.25 MPa in laser + OB group, 18.11 ± 3.52 MPa in laser + OB + TW group and 9.42 ± 2.47 MPa in OB + TW group. Repeated measures ANOVA showed that laser irradiation increased the microshear bond strength (P < 0.001). Bond strength decreased when the samples were thermocycled and stored for three months (P < 0.001). The interaction effect of water storage and laser treatment on bond strength was significant (P < 0.05). Conclusion: Enamel surface preparation with Er:YAG laser is recommended to enhance the durability of the bond of self-etch bonding systems to enamel. PMID:28144434

A parametric study of surface roughness and bonding mechanisms of aluminum alloys with epoxies: a molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Timilsina, Rajendra; Termaath, Stephanie

The marine environment is highly aggressive towards most materials. However, aluminium-magnesium alloys (Al-Mg, specifically, 5xxx series) have exceptionally long service life in such aggressive marine environments. For instance, an Al-Mg alloy, AA5083, is extensively used in naval structures because of its good mechanical strength, formability, seawater corrosion resistance and weldability. However, bonding mechanisms of these alloys with epoxies in a rough surface environment are not fully understood yet. It requires a rigorous investigation at molecular or atomic levels. We performed a molecular dynamics simulation to study an adherend surface preparation and surface bonding mechanisms of Al-Mg alloy (AA5083) with different epoxies by developing several computer models. Various distributions of surface roughness are introduced in the models and performed molecular dynamics simulations. Formation of a beta phase (Al3Mg2) , microstructures, bonding energies at the interface, bonding strengths and durability are investigated. Office of Naval Research.

Bond strengths of Scotchbond Multi-Purpose to moist dentin and enamel.

PubMed

Swift, E J; Triolo, P T

1992-12-01

This in vitro study tested the shear bond strengths of the Scotchbond Multi-Purpose adhesive system to moist and dry enamel and dentin. After the tooth was etched, the surface was either dried with compressed air or blotted with tissue paper, leaving the surface visibly moist. Primer and adhesive were applied according to the manufacturer's directions. Resin composite posts were applied, and the specimens were thermocycled. Shear bond strengths were determined using an Instron universal testing machine. For both enamel and dentin, mean shear bond strengths were higher when the surface was left visibly moist after etching. Bond strengths to moist and dry dentin were 21.8 and 17.8 MPa, respectively. Enamel bond strengths were slightly lower, with values of 17.0 and 14.2 MPa to moist and dry enamel, respectively.

Effect of surface condition of dental zirconia ceramic (Denzir) on bonding.

PubMed

Uo, Motohiro; Sjögren, Göran; Sundh, Anders; Goto, Mitsunari; Watari, Fumio; Bergman, Maud

2006-09-01

Yttria partially stabilized zirconia (YPSZ) ceramics are suitable for dental and medical use because of their high fracture toughness and chemical durability. The purpose of this study was to examine the bonding behavior of a dental YPSZ ceramic, Denzir. After being subjected to various surface treatments, Denzir specimens were bonded to each other using an adhesive resin composite, glass ionomer, or zinc phosphate cement. Bonding strength was then determined by the shearing test. No significant differences (p>0.05) were observed between SiC- and Al2O3-blasted specimens. In all surface treatments, the shear bond strength significantly (p<0.05) increased in the order of adhesive resin composite cement > glass ionomer cement > zinc phosphate cement. Moreover, silanization with methacryloxy propyl trimethoxysilane slightly increased the bonding strength of the adhesive resin composite cement.

Gold-based electrical interconnections for microelectronic devices

DOEpatents

Peterson, Kenneth A.; Garrett, Stephen E.; Reber, Cathleen A.; Watson, Robert D.

2002-01-01

A method of making an electrical interconnection from a microelectronic device to a package, comprising ball or wedge compression bonding a gold-based conductor directly to a silicon surface, such as a polysilicon bonding pad in a MEMS or IMEMS device, without using layers of aluminum or titanium disposed in-between the conductor and the silicon surface. After compression bonding, optional heating of the bond above 363 C. allows formation of a liquid gold-silicon eutectic phase containing approximately 3% (by weight) silicon, which significantly improves the bond strength by reforming and enhancing the initial compression bond. The same process can be used for improving the bond strength of Au--Ge bonds by forming a liquid Au-12Ge eutectic phase.

Effect of surface treatment methods on the shear bond strength of auto-polymerized resin to thermoplastic denture base polymer.

PubMed

Koodaryan, Roodabeh; Hafezeqoran, Ali

2016-12-01

Polyamide polymers do not provide sufficient bond strength to auto-polymerized resins for repairing fractured denture or replacing dislodged denture teeth. Limited treatment methods have been developed to improve the bond strength between auto-polymerized reline resins and polyamide denture base materials. The objective of the present study was to evaluate the effect of surface modification by acetic acid on surface characteristics and bond strength of reline resin to polyamide denture base. 84 polyamide specimens were divided into three surface treatment groups (n=28): control (N), silica-coated (S), and acid-treated (A). Two different auto-polymerized reline resins GC and Triplex resins were bonded to the samples (subgroups T and G, respectively, n=14). The specimens were subjected to shear bond strength test after they were stored in distilled water for 1 week and thermo-cycled for 5000 cycles. Data were analyzed with independent t-test, two-way analysis of variance (ANOVA), and Tukey's post hoc multiple comparison test (α=.05). The bond strength values of A and S were significantly higher than those of N ( P <.001 for both). However, statistically significant difference was not observed between group A and group S. According to the independent Student's t-test, the shear bond strength values of AT were significantly higher than those of AG ( P <.001). The surface treatment of polyamide denture base materials with acetic acid may be an efficient and cost-effective method for increasing the shear bond strength to auto-polymerized reline resin.

Effect of sandblasting, silica coating, and laser treatment on the microtensile bond strength of a dental zirconia ceramic to resin cements.

PubMed

Mahmoodi, Nasrin; Hooshmand, Tabassom; Heidari, Solmaz; Khoshro, Kimia

2016-02-01

The purpose of this in vitro study was to evaluate the effect of laser irradiation as well as other surface treatment methods on the microtensile bond strength of a dental zirconia ceramic to the two types of resin cements. Zirconia ceramic blocks (ICE Zirkon) were sintered according to the manufacturer's instructions and duplicated in resin composites. The ceramic specimens were divided into four groups according to the following surface treatments: no surface treatment (control), sandblasting with alumina, silica coating plus silanization, and Nd:YAG laser irradiation. The specimens were divided equally and then bonded with Panavia F2.0 (self-etching resin cement) and Clearfil SA Luting (self-adhesive resin cement) to the composite blocks. The bonded ceramic-composite blocks were stored in distilled water at 37 °C for 72 h, cut to prepare bar-shaped specimens with a bonding area of approximately 1 mm(2), and thermocycled for 3000 cycles between 5 and 55 °C, and the microtensile bond strengths were measured using a universal testing machine. The data were analyzed by ANOVA and Tukey post hoc test. The results showed that the self-adhesive resin cement used in this study did not improve the microtensile bond strength when the zirconia surface was sandblasted by alumina. The use of the Nd:YAG laser did not enhance the bond strength between the zirconia and both types of resin cements. In addition, silica coating of the zirconia surfaces plus silane application significantly improved the bond strength regardless of the type of resin cement utilized.

Plates for vacuum thermal fusion

DOEpatents

Davidson, James C.; Balch, Joseph W.

2002-01-01

A process for effectively bonding arbitrary size or shape substrates. The process incorporates vacuum pull down techniques to ensure uniform surface contact during the bonding process. The essence of the process for bonding substrates, such as glass, plastic, or alloys, etc., which have a moderate melting point with a gradual softening point curve, involves the application of an active vacuum source to evacuate interstices between the substrates while at the same time providing a positive force to hold the parts to be bonded in contact. This enables increasing the temperature of the bonding process to ensure that the softening point has been reached and small void areas are filled and come in contact with the opposing substrate. The process is most effective where at least one of the two plates or substrates contain channels or grooves that can be used to apply vacuum between the plates or substrates during the thermal bonding cycle. Also, it is beneficial to provide a vacuum groove or channel near the perimeter of the plates or substrates to ensure bonding of the perimeter of the plates or substrates and reduce the unbonded regions inside the interior region of the plates or substrates.

Irreversible bonding of polyimide and polydimethylsiloxane (PDMS) based on a thiol-epoxy click reaction

NASA Astrophysics Data System (ADS)

Hoang, Michelle V.; Chung, Hyun-Joong; Elias, Anastasia L.

2016-10-01

Polyimide is one of the most popular substrate materials for the microfabrication of flexible electronics, while polydimethylsiloxane (PDMS) is the most widely used stretchable substrate/encapsulant material. These two polymers are essential in fabricating devices for microfluidics, bioelectronics, and the internet of things; bonding these materials together is a crucial challenge. In this work, we employ click chemistry at room temperature to irreversibly bond polyimide and PDMS through thiol-epoxy bonds using two different methods. In the first method, we functionalize the surfaces of the PDMS and polyimide substrates with mercaptosilanes and epoxysilanes, respectively, for the formation of a thiol-epoxy bond in the click reaction. In the second method, we functionalize one or both surfaces with mercaptosilane and introduce an epoxy adhesive layer between the two surfaces. When the surfaces are bonded using the epoxy adhesive without any surface functionalization, an extremely small peel strength (<0.01 N mm-1) is measured with a peel test, and adhesive failure occurs at the PDMS surface. With surface functionalization, however, remarkably higher peel strengths of ~0.2 N mm-1 (method 1) and  >0.3 N mm-1 (method 2) are observed, and failure occurs by tearing of the PDMS layer. We envision that the novel processing route employing click chemistry can be utilized in various cases of stretchable and flexible device fabrication.

Nanobonding: A key technology for emerging applications in health and environmental sciences

NASA Astrophysics Data System (ADS)

Howlader, Matiar M. R.; Deen, M. Jamal; Suga, Tadatomo

2015-03-01

In this paper, surface-activation-based nanobonding technology and its applications are described. This bonding technology allows for the integration of electronic, photonic, fluidic and mechanical components into small form-factor systems for emerging sensing and imaging applications in health and environmental sciences. Here, we describe four different nanobonding techniques that have been used for the integration of various substrates — silicon, gallium arsenide, glass, and gold. We use these substrates to create electronic (silicon), photonic (silicon and gallium arsenide), microelectromechanical (glass and silicon), and fluidic (silicon and glass) components for biosensing and bioimaging systems being developed. Our nanobonding technologies provide void-free, strong, and nanometer scale bonding at room temperature or at low temperatures (<200 °C), and do not require chemicals, adhesives, or high external pressure. The interfaces of the nanobonded materials in ultra-high vacuum and in air correspond to covalent bonds, and hydrogen or hydroxyl bonds, respectively.

Veneer Ceramic to Y-TZP Bonding: Comparison of Different Surface Treatments.

PubMed

Kirmali, Omer; Kapdan, Alper; Kustarci, Alper; Er, Kursat

2016-06-01

The purpose of this study was to evaluate the effects of various surface-treatment techniques for enhancing the bond strength between veneering ceramic and yttria-stabilized tetragonal zirconia polycrystals (Y-TZP). Pre-sintered Y-TZP specimens were divided into eight groups (n = 10) according to the surface-treatment technique used: (a) untreated (control); (b) air abrasion with aluminum oxide particles; (c) erbium, chromium:yttrium-scandium-gallium-garnet (Er,Cr:YSGG) laser irradiation at different energy intensities (1 to 6 W). All specimens were then sintered and veneered with veneering ceramic according to the manufacturer's instructions. The obtained zirconia-ceramic specimens were immersed in 37°C distilled water for 24 hours before a shear bond strength test using a universal testing device at a 1 mm/min crosshead speed. The average values were calculated. After debonding, the Y-TZP surfaces were examined under a stereomicroscope to determine their fracture pattern, and the surface topography was evaluated with scanning electron microscopy after surface treatments. The bond strength ranged from 13.24 to 20.54 MPa. All surface treatments increased the bond strength between the veneering ceramic and Y-TZP; however, the value for the 6 W irradiation group was significantly different from the values for other groups (p ˂ 0.05). The present study's findings showed that higher energy densities were needed for the laser irradiation to improve the bond strength between the veneering ceramic and zirconia. Y-TZP is commonly used as a core material in fixed restorations. The bond strength between zirconia and the veneering ceramic can be affected by various surface treatments. © 2015 by the American College of Prosthodontists.

Comparative evaluation of bonding strength of computer aided machined ceramic, pressable ceramic, and milled metal implant abutment copings and effect of surface conditioning on bonding strength: An in vitro study

PubMed Central

Rani, Sapna; Verma, Mahesh; Gill, Shubhra; Gupta, Rekha

2016-01-01

Background/Purpose: The aim of this study was to compare the shear bond strength of computer aided design/computer aided machined ceramic (CAD/CAM), pressable ceramic, and milled metal implant copings on abutment and the effect of surface conditioning on bonding strength. Materials and Methods: A total of 90 test samples were fabricated on three titanium abutments. Among 90 test samples, 30 copings were fabricated by CAD/CAM, 30 by pressable, and 30 by milling of titanium metal. These 30 test samples in each group were further subdivided equally for surface treatment. Fifteen out of 30 test samples in each group were surface conditioned with airborne particle abrasion. All the 90 test samples were luted on abutment with glass ionomer cement. Bonding strength was evaluated for all the samples using universal testing machine at a crosshead speed of 5 mm/min. The results obtained were compared and evaluated using one-way ANOVA with post-hoc and unpaired t-test at a significance level of 0.05. Results: The mean difference for CAD/CAM surface conditioned subgroup was 1.28 ± 0.12, for nonconditioned subgroup was 1.20 ± 0.11. The mean difference for pressable surface conditioned subgroup was 1.18 ± 0.04, and for nonconditioned subgroup was 0.75 ± 0.28. The mean difference for milled metal surface conditioned subgroup was 2.57 ± 0.58, and for nonconditioned subgroup was 1.49 ± 0.15. Conclusions: On comparison of bonding strength, milled metal copings had an edge over the other two materials, and surface conditioning increased the bond strength. PMID:27141163

Solvent-Free Manufacturing of Electrodes for Lithium-ion Batteries

NASA Astrophysics Data System (ADS)

Ludwig, Brandon; Zheng, Zhangfeng; Shou, Wan; Wang, Yan; Pan, Heng

2016-03-01

Lithium ion battery electrodes were manufactured using a new, completely dry powder painting process. The solvents used for conventional slurry-cast electrodes have been completely removed. Thermal activation time has been greatly reduced due to the time and resource demanding solvent evaporation process needed with slurry-cast electrode manufacturing being replaced by a hot rolling process. It has been found that thermal activation time to induce mechanical bonding of the thermoplastic polymer to the remaining active electrode particles is only a few seconds. Removing the solvent and drying process allows large-scale Li-ion battery production to be more economically viable in markets such as automotive energy storage systems. By understanding the surface energies of various powders which govern the powder mixing and binder distribution, bonding tests of the dry-deposited particles onto the current collector show that the bonding strength is greater than slurry-cast electrodes, 148.8 kPa as compared to 84.3 kPa. Electrochemical tests show that the new electrodes outperform conventional slurry processed electrodes, which is due to different binder distribution.

Catalysts for hydrogen evolution from the [NiFe] hydrogenase to the Ni2P(001) surface: the importance of ensemble effect.

PubMed

Liu, Ping; Rodriguez, José A

2005-10-26

Density functional theory (DFT) was employed to investigate the behavior of a series of catalysts used in the hydrogen evolution reaction (HER, 2H(+) + 2e(-) --> H(2)). The kinetics of the HER was studied on the [NiFe] hydrogenase, the [Ni(PS3*)(CO)](1)(-) and [Ni(PNP)(2)](2+) complexes, and surfaces such as Ni(111), Pt(111), or Ni(2)P(001). Our results show that the [NiFe] hydrogenase exhibits the highest activity toward the HER, followed by [Ni(PNP)(2)](2+) > Ni(2)P > [Ni(PS3*)(CO)](1)(-) > Pt > Ni in a decreasing sequence. The slow kinetics of the HER on the surfaces is due to the fact that the metal hollow sites bond hydrogen too strongly to allow the facile removal of H(2). In fact, the strong H-Ni interaction on Ni(2)P(001) can lead to poisoning of the highly active sites of the surface, which enhances the rate of the HER and makes it comparable to that of the [NiFe] hydrogenase. In contrast, the promotional effect of H-poisoning on the HER on Pt and Ni surfaces is relatively small. Our calculations suggest that among all of the systems investigated, Ni(2)P should be the best practical catalyst for the HER, combining the high thermostability of the surfaces and high catalytic activity of the [NiFe] hydrogenase. The good behavior of Ni(2)P(001) toward the HER is found to be associated with an ensemble effect, where the number of active Ni sites is decreased due to presence of P, which leads to moderate bonding of the intermediates and products with the surface. In addition, the P sites are not simple spectators and directly participate in the HER.

Controlled Contamination of Epoxy Composites with PDMS and Removal by Laser Ablation

NASA Technical Reports Server (NTRS)

Palmieri, Frank; Ledesma, Rodolfo; Cataldo, Daniel; Lin, Yi; Wohl, Christopher; Gupta, Mool; Connell, John

2016-01-01

Surface preparation is critical to the performance of adhesively bonded composites. During manufacturing, minute quantities of mold release compounds are inevitably deposited on faying surfaces and may compromise bond performance. To ensure safety, mechanical fasteners and other crack arrest features must be installed in the bondlines of primary structures, which negates some advantages of adhesively bonded construction. Laser ablation is an automated, repeatable, and scalable process with high potential for the surface preparation of metals and composites in critical applications such as primary airframe structures. In this study, laser ablation is evaluated on composite surfaces for the removal of polydimethylsiloxane (PDMS), a common mold release material. Composite panels were contaminated uniformly with PDMS film thicknesses as low as 6.0 nm as measured by variable angle spectroscopic ellipsometry. Bond performance was assessed by mechanical testing using a 250 F cure, epoxy adhesive and compared with pre-bond surface inspection results. Water contact angle, optically stimulated electron emission, and laser induced breakdown spectroscopy were used to characterize contaminated and laser ablated surfaces. The failure mode obtained from double cantilever beam tests correlated well with surface characterization data. The test results indicated that even low levels of PDMS were not completely removed by laser ablation.

Bond strength of novel CAD/CAM restorative materials to self-adhesive resin cement: the effect of surface treatments.

PubMed

Elsaka, Shaymaa E

2014-12-01

To evaluate the effect of different surface treatments on the microtensile bond strength (μTBS) of novel CAD/CAM restorative materials to self-adhesive resin cement. Two types of CAD/CAM restorative materials (Vita Enamic [VE] and Lava Ultimate [LU]) were used. The specimens were divided into five groups in each test according to the surface treatment performed; Gr 1 (control; no treatment), Gr 2 (sandblasted [SB]), Gr 3 (SB+silane [S]), Gr 4 (hydrofluoric acid [HF]), and Gr 5 (HF+S). A dual-curing self-adhesive resin cement (Bifix SE [BF]) was applied to each group for testing the adhesion after 24 h of storage in distilled water or after 30 days using the μTBS test. Following fracture testing, specimens were examined with a stereomicroscope and SEM. Surface roughness and morphology of the CAD/CAM restorative materials were characterized after treatment. Data were analyzed using ANOVA and Tukey's test. The surface treatment, type of CAD/CAM restorative material, and water storage periods showed a significant effect on the μTBS (p<0.001). For the LU/BF system, there was no significant difference in the bond strength values between different surface treatments (p>0.05). On the other hand, for the VE/BF system, surface treatment with HF+S showed higher bond strength values compared with SB and HF surface treatments (p<0.05). Surface roughness and SEM analyses showed that the surface topography of CAD/CAM restorative materials was modified after treatments. The effect of surface treatments on the bond strength of novel CAD/CAM restorative materials to resin cement is material dependent. The VE/BF CAD/CAM material provided higher bond strength values compared with the LU/BF CAD/CAM material.

Influence of temporary cement contamination on the surface free energy and dentine bond strength of self-adhesive cements.

PubMed

Takimoto, Masayuki; Ishii, Ryo; Iino, Masayoshi; Shimizu, Yusuke; Tsujimoto, Akimasa; Takamizawa, Toshiki; Ando, Susumu; Miyazaki, Masashi

2012-02-01

The surface free energy and dentine bond strength of self-adhesive cements were examined after the removal of temporary cements. The labial dentine surfaces of bovine mandibular incisors were wet ground with #600-grit SiC paper. Acrylic resin blocks were luted to the prepared dentine surfaces using HY Bond Temporary Cement Hard (HY), IP Temp Cement (IP), Fuji TEMP (FT) or Freegenol Temporary Cement (TC), and stored for 1 week. After removal of the temporary cements with an ultrasonic tip, the contact angle values of five specimens per test group were determined for the three test liquids, and the surface-energy parameters of the dentine surfaces were calculated. The dentine bond strengths of the self-adhesive cements were measured after removal of the temporary cements in a shear mode at a crosshead speed of 1.0mm/min. The data were subjected to one-way analysis of variance (ANOVA) followed by Tukey's HSD test. For all surfaces, the value of the estimated surface tension component γ(S)(d) (dispersion) was relatively constant at 41.7-43.3 mJm(-2). After removal of the temporary cements, the value of the γ(S)(h) (hydrogen-bonding) component decreased, particularly with FT and TC. The dentine bond strength of the self-adhesive cements was significantly higher for those without temporary cement contamination (8.2-10.6 MPa) than for those with temporary cement contamination (4.3-7.1 MPa). The γ(S) values decreased due to the decrease of γ(S)(h) values for the temporary cement-contaminated dentine. Contamination with temporary cements led to lower dentine bond strength. The presence of temporary cement interferes with the bonding performance of self-adhesive cements to dentine. Care should be taken in the methods of removal of temporary cement when using self-adhesive cements. Copyright © 2011 Elsevier Ltd. All rights reserved.

Modeling the acid-base properties of bacterial surfaces: A combined spectroscopic and potentiometric study of the gram-positive bacterium Bacillus subtilis.

PubMed

Leone, Laura; Ferri, Diego; Manfredi, Carla; Persson, Per; Shchukarev, Andrei; Sjöberg, Staffan; Loring, John

2007-09-15

In this study, macroscopic and spectroscopic data were combined to develop a surface complexation model that describes the acid-base properties of Bacillus subtilis. The bacteria were freeze-dried and then resuspended in 0.1 M NaCl ionic medium. Macroscopic measurements included potentiometric acid-base titrations and electrophoretic mobility measurements. In addition, ATR-FTIR spectra of wet pastes from suspensions of Bacillus subtilis at different pH values were collected. The least-squares program MAGPIE was used to generate a surface complexation model that takes into account the presence of three acid-base sites on the surface: tripple bond COOH, tripple bond NH+, and tripple bond PO-, which were identified previously by XPS measurements. Both potentiometric titration data and ATR-FTIR spectra were used quantitatively, and electrostatic effects at the charged bacterial surface were accounted for using the constant capacitance model. The model was calculated using two different approaches: in the first one XPS data were used to constrain the ratio of the total concentrations of all three surface sites. The capacitance of the double layer, the total buffer capacity, and the deprotonation constants of the tripple bond NH+, tripple bond POH, and tripple bond COOH species were determined in the fit. A second approach is presented in which the ratio determined by XPS of the total concentrations of tripple bond NH+ to tripple bond PO- sites is relaxed. The total concentration of tripple bond PO- sites was determined in the fit, while the deprotonation constant for tripple bond POH was manually varied until the minimization led to a model which predicted an isoelectric point that resulted in consistency with electrophoretic mobility data. The model explains well the buffering capacity of Bacillus subtilis suspensions in a wide pH range (between pH=3 and pH=9) which is of considerable environmental interest. In particular, a similar quantitative use of the IR data opens up possibilities to model other bacterial surfaces at the laboratory scale and help estimate the buffering capacity of carboxylate-containing compounds in natural samples.

Inspecting the microstructure of electrically active defects at the Ge/GeOx interface

NASA Astrophysics Data System (ADS)

Fanciulli, Marco; Baldovino, Silvia; Molle, Alessandro

2012-02-01

High mobility substrates are important key elements in the development of advanced devices targeting a vast range of functionalities. Among them, Ge showed promising properties promoting it as valid candidate to replace Si in CMOS technology. However, the electrical quality of the Ge/oxide interface is still a problematic issue, in particular for the observed inversion of the n-type Ge surface, attributed to the presence of dangling bonds inducing a severe band bending [1]. In this scenario, the identification of electrically active defects present at the Ge/oxide interface and the capability to passivate or anneal them becomes a mandatory issue aiming at an electrically optimized interface. We report on the application of highly sensitive electrically detected magnetic resonance (EDMR) techniques in the investigation of defects at the interface between Ge and GeO2 (or GeOx), including Ge dangling bonds and defects in the oxide [2]. In particular we will investigate how different surface orientations, e.g. the (001) against the (111) Ge surface, impacts the microstructure of the interface defects. [1] P. Tsipas and A. Dimoulas, Appl. Phys. Lett. 94, 012114 (2009) [2] S. Baldovino, A. Molle, and M. Fanciulli, Appl. Phys. Lett. 96, 222110 (2010)

Shear bond strength in zirconia veneered ceramics using two different surface treatments prior veneering.

PubMed

Gasparić, Lana Bergman; Schauperl, Zdravko; Mehulić, Ketij

2013-03-01

Aim of the study was to assess the effect of different surface treatments on the shear bond strength (SBS) of the veneering ceramics to zirconia core. In a shear test the influence of grinding and sandblasting of the zirconia surface on bonding were assessed. Statistical analysis was performed using SPSS statistical package (version 17.0, SPSS Inc., Chicago, IL, USA) and Microsoft Office Excel 2003 (Microsoft, Seattle, WA, USA). There was a significant difference between the groups considering shear bond strength (SBS) values, i.e. ground and sandblasted samples had significantly higher SBS values than only ground samples (mean difference = -190.67; df = 10, t = -6.386, p < 0.001). The results of the present study indicate that ground and sandblasted cores are superior to ground cores, allowing significantly higher surface roughness and significantly higher shear bond strength between the core and the veneering material.

Influence of light intensity on surface free energy and dentin bond strength of core build-up resins.

PubMed

Shimizu, Y; Tsujimoto, A; Furuichi, T; Suzuki, T; Tsubota, K; Miyazaki, M; Platt, J A

2015-01-01

We examined the influence of light intensity on surface free energy characteristics and dentin bond strength of dual-cure direct core build-up resin systems. Two commercially available dual-cure direct core build-up resin systems, Clearfil DC Core Automix with Clearfil Bond SE One and UniFil Core EM with Self-Etching Bond, were studied. Bovine mandibular incisors were mounted in acrylic resin and the facial dentin surfaces were wet ground on 600-grit silicon carbide paper. Adhesives were applied to dentin surfaces and cured with light intensities of 0 (no irradiation), 200, 400, and 600 mW/cm(2). The surface free energy of the adhesives (five samples per group) was determined by measuring the contact angles of three test liquids placed on the cured adhesives. To determine the strength of the dentin bond, the core build-up resin pastes were condensed into the mold on the adhesive-treated dentin surfaces according to the methods described for the surface free energy measurement. The resin pastes were cured with the same light intensities as those used for the adhesives. Ten specimens per group were stored in water maintained at 37°C for 24 hours, after which they were shear tested at a crosshead speed of 1.0 mm/minute in a universal testing machine. Two-way analysis of variance (ANOVA) and a Tukey-Kramer test were performed, with the significance level set at 0.05. The surface free energies of the adhesive-treated dentin surfaces decreased with an increase in the light intensity of the curing unit. Two-way ANOVA revealed that the type of core build-up system and the light intensity significantly influence the bond strength, although there was no significant interaction between the two factors. The highest bond strengths were achieved when the resin pastes were cured with the strongest light intensity for all the core build-up systems. When polymerized with a light intensity of 200 mW/cm(2) or less, significantly lower bond strengths were observed. CONClUSIONS: The data suggest that the dentin bond strength of core build-up systems are still affected by the light intensity of the curing unit, which is based on the surface free energy of the adhesives. On the basis of the results and limitations of the test conditions used in this study, it appears that a light intensity of >400 mW/cm(2) may be required for achieving the optimal dentin bond strength.

Diffusion bonding of IN 718 to VM 350 grade maraging steel

NASA Technical Reports Server (NTRS)

Crosby, S. R.; Biederman, R. R.; Reynolds, C. C.

1972-01-01

Diffusion bonding studies have been conducted on IN 718, VM 350 and the dissimilar alloy couple, IN 718 to maraging steel. The experimental processing parameters critical to obtaining consistently good diffusion bonds between IN 718 and VM 350 were determined. Interrelationships between temperature, pressure and surface preparation were explored for short bending intervals under vacuum conditions. Successful joining was achieved for a range of bonding cycle temperatures, pressures and surface preparations. The strength of the weaker parent material was used as a criterion for a successful tensile test of the heat treated bond. Studies of VM-350/VM-350 couples in the as-bonded condition showed a greater yielding and failure outside the bond region.

Adsorption mechanisms of metal ions on the potassium dihydrogen phosphate (1 0 0) surface: A density functional theory-based investigation.

PubMed

Wu, Yulin; Zhang, Lei; Liu, Yao; Qu, Yunpeng

2018-07-15

The adsorption of metal ions (K + , Na + , Ca 2+ , Cu 2+ , Al 3+ , Cr 3+ ) on the (1 0 0) surface of potassium dihydrogen phosphate (KDP) has been studied using density functional theory (DFT). Calculation results show that all the investigated metal ions can be spontaneously adsorbed on the surface with negative adsorption energies. The adsorption stability increases in the order of Na +  < K +  < Cu 2+  < Ca 2+  < Al 3+  < Cr 3+ , and shows a consistent trend as the adsorbed metal ion valence (monovalent < divalent < trivalent). Three types of stable adsorption configurations are observed, corresponding to three different bonding mechanisms. Na + , K + and Ca 2+ ions with a large radius can form two ionic bonds and one weak covalent bond with the O and H atoms respectively. In addition, the medium-sized ion of Cu 2+ forms two covalent bonds with the O and H atoms. Furthermore, Al 3+ and Cr 3+ ions with the smallest radius form two metal-oxygen and one metal-hydrogen covalent bonds with the surface, making one H-O bond broken. Compared with other metal ions, Al 3+ and Cr 3+ have the strongest interactions with the surface, which can be explained by the significant electron transfer and more stable covalent bond formations between these two ions and the surface. Copyright © 2018 Elsevier Inc. All rights reserved.

[Bonding strength of resin and tooth enamel after teeth bleaching with cold plasma].

PubMed

Zhu, Meng-meng; Wang, Guo-min; Sun, Ke; Li, Ying-long; Pan, Jie

2016-02-18

To investigate the immediate bond strength and surface structure of resin and the tooth enamel which treated by cold plasma. In the study, 40 bovine incisors were divided into two equal parts. In this sense, all enamel adhesive samples were prepared and then randomly divided into 4 groups (n =20). group 1: acid + single bond 2+resin composite (control group); group 2:beyond bleaching+ acid+single bond 2+resin composite; group 3: treated by cold plasma for 5 minutes+ acid+single bond 2+resin composite; group 4: treated by cold plasma for 5 minutes+single bond 2+resin composite. Single bond 2 bonding system and Filtek Z250 resin were used in this experiment. The shear bond strength was tested by universal testing machine. The surface of the enamel in different processes was observed by scanning electron microscope (SEM). Statistical analyses by the single factor analysis of variance and multiple pairwise comparisons were performed with SPSS 17.0 . The shear bond strength of group 4 (8.60 MPa) was significantly lower than that of the other three groups (P<0.05). The shear bond strength of group 2 (17.89 MPa) was higher than that of group 4, but lower than group 1 and group 3 (P<0.05).There was no significant difference between group 1 (34.82 MPa) and group 3 (34.69 MPa). Scanning electron microscope indicated that the enamel treated by cold plasma had slight molten form, which was different from etched enamel surface.The fractured surface of group 3 was mix fracture, which was similar to the control group (group 1). Compared with the conventional clinic bleaching, immediate bond strength of resin-enamel that treated by cold plasma has not been affected.

An evaluation of shear bond strength of self-etch adhesive on pre-etched enamel: an in vitro study.

PubMed

Rao, Bhadra; Reddy, Satti Narayana; Mujeeb, Abdul; Mehta, Kanchan; Saritha, G

2013-11-01

To determine the shear bond strength of self-etch adhesive G-bond on pre-etched enamel. Thirty caries free human mandibular premolars extracted for orthodontic purpose were used for the study. Occlusal surfaces of all the teeth were flattened with diamond bur and a silicon carbide paper was used for surface smoothening. The thirty samples were randomly grouped into three groups. Three different etch systems were used for the composite build up: group 1 (G-bond self-etch adhesive system), group 2 (G-bond) and group 3 (Adper single bond). Light cured was applied for 10 seconds with a LED unit for composite buildup on the occlusal surface of each tooth with 8 millimeters (mm) in diameter and 3 mm in thickness. The specimens in each group were tested in shear mode using a knife-edge testing apparatus in a universal testing machine across head speed of 1 mm/ minute. Shear bond strength values in Mpa were calculated from the peak load at failure divided by the specimen surface area. The mean shear bond strength of all the groups were calculated and statistical analysis was carried out using one-way Analysis of Variance (ANOVA). The mean bond strength of group 1 is 15.5 Mpa, group 2 is 19.5 Mpa and group 3 is 20.1 Mpa. Statistical analysis was carried out between the groups using one-way ANOVA. Group 1 showed statistically significant lower bond strength when compared to groups 2 and 3. No statistical significant difference between groups 2 and 3 (p < 0.05). Self-etch adhesive G-bond showed increase in shear bond strength on pre-etched enamel.

Influence of Hydrogen Bonding on the Surface Diffusion of Molecular Glasses: Comparison of Three Triazines

DOE PAGES

Chen, Yinshan; Zhu, Men; Laventure, Audrey; ...

2017-06-26

Surface grating decay measurements have been performed on three closely related molecular glasses to study the effect of intermolecular hydrogen bonds on surface diffusion. The three molecules are derivatives of bis(3,5-dimethyl-phenylamino)-1,3,5-triazine and differ only in the functional group R at the 2-position, with R being C 2H 5, OCH 3, and NHCH 3, and referred to as “Et”, “OMe”, and “NHMe”, respectively. Of the three molecules, NHMe forms more extensive intermolecular hydrogen bonds than Et and OMe and was found to have slower surface diffusion. For Et and OMe, surface diffusion is so fast that it replaces viscous flow asmore » the mechanism of surface grating decay as temperature is lowered. In contrast, no such transition was observed for NHMe under the same conditions, indicating significantly slower surface diffusion. This result is consistent with the previous finding that extensive intermolecular hydrogen bonds slow down surface diffusion in molecular glasses and is attributed to the persistence of hydrogen bonds even in the surface environment. Here, this result is also consistent with the lower stability of the vapor-deposited glass of NHMe relative to those of Et and OMe and supports the view that surface mobility controls the stability of vapor-deposited glasses.« less

Cohesive zone modelling of wafer bonding and fracture: effect of patterning and toughness variations

NASA Astrophysics Data System (ADS)

Kubair, D. V.; Spearing, S. M.

2006-03-01

Direct wafer bonding has increasingly become popular in the manufacture of microelectromechanical systems and semiconductor microelectronics components. The success of the bonding process is controlled by variables such as wafer flatness and surface preparation. In order to understand the effects of these variables, spontaneous planar crack propagation simulations were performed using the spectral scheme in conjunction with a cohesive zone model. The fracture-toughness on the bond interface is varied to simulate the effect of surface roughness (nanotopography) and patterning. Our analysis indicated that the energetics of crack propagation is sensitive to the local surface property variations. The patterned wafers are tougher (well bonded) than the unpatterned ones of the same average fracture-toughness.

Polydopamine and Polydopamine-Silane Hybrid Surface Treatments in Structural Adhesive Applications.

PubMed

Tran, Ngon T; Flanagan, David P; Orlicki, Joshua A; Lenhart, Joseph L; Proctor, Kenneth L; Knorr, Daniel B

2018-01-30

Numerous studies have focused on the remarkable adhesive properties of polydopamine, which can bind to substrates with a wide range of surface energies, even under aqueous conditions. This behavior suggests that polydopamine may be an attractive option as a surface treatment in structural bonding applications, where good bond durability is required. Here, we assessed polydopamine as a surface treatment for bonding aluminum plates with an epoxy resin. A model epoxy adhesive consisting of diglycidyl ether of bisphenol A (DGEBA) and Jeffamine D230 polyetheramine was employed, and lap shear measurements (ASTM D1002 10) were made (i) under dry conditions to examine initial bond strength and (ii) after exposure to hot/wet (63 °C in water for 14 days) conditions to assess bond durability. Surprisingly, our results showed that polydopamine alone as a surface treatment provided no benefit beyond that obtained by exposing the substrates to an alkaline solution of tris buffer used for the deposition of polydopamine. This implies that polydopamine has a potential Achilles' heel, namely, the formation of a weak boundary layer that was identified using X-ray photoelectron spectroscopy (XPS) of the fractured surfaces. In fact, for longer deposition times (2.5 and 18 h), the tris buffer-treated surface outperformed the polydopamine surface treatments, suggesting that tris buffer plays a unique role in improving adhesive performance even in the absence of polydopamine. We further showed that the use of polydopamine-3-aminopropyltriethoxysilane (APTES) hybrid surface treatments provided significant improvements in bond durability at extended deposition times relative to both polydopamine and an untreated control.

Enhanced photocatalytic degradation of Amaranth dye on mesoporous anatase TiO2: evidence of C-N, N[double bond, length as m-dash]N bond cleavage and identification of new intermediates.

PubMed

Naik, Amarja P; Salkar, Akshay V; Majik, Mahesh S; Morajkar, Pranay P

2017-07-01

The photocatalytic degradation mechanism of Amaranth, a recalcitrant carcinogenic azo dye, was investigated using mesoporous anatase TiO 2 under sunlight. Mesoporous anatase TiO 2 of a high photocatalytic activity has been synthesized using a sol-gel method and its photocatalytic activity for the degradation of Amaranth dye has been evaluated with respect to Degussa P25. The effect of bi-dentate complexing agents like oxalic acid, ethylene glycol and urea on the surface properties of TiO 2 catalyst has been investigated using TG-DTA, FTIR, HR-TEM, SAED, PXRD, EDS, UV-DRS, PL, BET N 2 adsorption-desorption isotherm studies and BJH analysis. The influence of catalyst properties such as the mesoporous network, pore volume and surface area on the kinetics of degradation of Amaranth as a function of irradiation time under natural sunlight has been monitored using UV-Vis spectroscopy. The highest rate constant value of 0.069 min -1 was obtained for the photocatalytic degradation of Amaranth using TiO 2 synthesized via a urea assisted sol-gel synthesis method. The effect of the reaction conditions such as pH, TiO 2 concentration and Amaranth concentration on the photodegradation rate has been investigated. The enhanced photocatalytic activity of synthesized TiO 2 in comparison with P25 is attributed to the mesoporous nature of the catalyst leading to increased pore diameter, pore volume, surface area and enhanced charge carrier separation efficiency. New intermediates of photocatalytic degradation of Amaranth, namely, sodium-3-hydroxynaphthalene-2,7-disulphonate, 3-hydroxynaphthalene, sodium-4-aminonaphthalenesulphonate and sodium-4-aminobenzenesulphonate have been identified using LC-ESI-MS for the very first time, providing direct evidence for simultaneous bond cleavage pathways (-C-N-) and (-N[double bond, length as m-dash]N-). A new plausible mechanism of TiO 2 catalysed photodegradation of Amaranth along with the comparison of its toxicity to that of its degradation intermediates and products is proposed.

Adhesive permeability affects coupling of resin cements that utilise self-etching primers to dentine.

PubMed

Carvalho, R M; Pegoraro, T A; Tay, F R; Pegoraro, L F; Silva, N R F A; Pashley, D H

2004-01-01

To examine the effects of an experimental bonding technique that reduces the permeability of the adhesive layer on the coupling of resin cements to dentine. Extracted human third molars had their mid to deep dentin surface exposed flat by transversally sectioning the crowns. Resin composite overlays were constructed and cemented to the surfaces using either Panavia F (Kuraray) or Bistite II DC (Tokuyama) resin cements mediated by their respective one-step or two-step self-etch adhesives. Experimental groups were prepared in the same way, except that the additional layer of a low-viscosity bonding resin (LVBR, Scotchbond Multi-Purpose Plus, 3M ESPE) was placed on the bonded dentine surface before luting the overlays with the respective resin cements. The bonded assemblies were stored for 24 h in water at 37 degrees C and subsequently prepared for microtensile bond strength testing. Beams of approximately 0.8 mm(2) were tested in tension at 0.5 mm/min in a universal tester. Fractured surfaces were examined under scanning electron microscopy (SEM). Additional specimens were prepared and examined with TEM using a silver nitrate-staining technique. Two-way ANOVA showed significant interactions between materials and bonding protocols (p<0.05). When bonded according to manufacturer's directions, Panavia F produced bond strengths that were significantly lower than Bistite II DC (p<0.05). The placement of an additional layer of a LVBR improved significantly the bond strengths of Panavia F (p<0.05), but not of Bistite II DC (p>0.05). SEM observation of the fractured surfaces in Panavia F showed rosette-like features that were exclusive for specimens bonded according to manufacturer's directions. Such features corresponded well with the ultrastructure of the interfaces that showed more nanoleakage associated with the more permeable adhesive interface. The application of the additional layer of the LVBR reduced the amount of silver impregnation for both adhesives suggesting that reduced permeability of the adhesives resulted in improved coupling of the resin cements to dentin. Placement of an intermediate layer of a LVBR between the bonded dentine surface and the resin cements resulted in improved coupling of Panavia F to dentine.

Bonding durability between acrylic resin adhesives and titanium with surface preparations.

PubMed

Yanagida, Hiroaki; Minesaki, Yoshito; Matsumura, Kousuke; Tanoue, Naomi; Muraguchi, Koichi; Minami, Hiroyuki

2017-01-31

The purpose of the present study was to evaluate the efficacy of pretreatment on the bonding durability between titanium casting and two acrylic adhesives. Cast titanium disk specimens treated with four polymer-metal bonding systems as follow: 1) air-abraded with 50-70 μm alumina, 2) 1)+Alloy Primer, 3) 1)+M.L. Primer and 4) tribochemical silica/silane coating system (Rocatec System). The specimens were bonded with M bond or Super-bond C&B adhesive. The shear bond strengths were determined before and after thermocycling (20,000 cycles). The surface characteristics after polishing, and for the 1) and 4) preparations were determined. The bond strengths for all combinations significantly decreased after thermocycling. The combination of Super-bond C&B adhesive and 2) led to significantly higher bond strength than the other preparations after thermocycling. The maximum height of the profile parameters for the polishing group was lower than other preparations.

Surface pretreatments for medical application of adhesion

PubMed Central

Erli, Hans J; Marx, Rudolf; Paar, Othmar; Niethard, Fritz U; Weber, Michael; Wirtz, Dieter C

2003-01-01

Medical implants and prostheses (artificial hips, tendono- and ligament plasties) usually are multi-component systems that may be machined from one of three material classes: metals, plastics and ceramics. Typically, the body-sided bonding element is bone. The purpose of this contribution is to describe developments carried out to optimize the techniques , connecting prosthesis to bone, to be joined by an adhesive bone cement at their interface. Although bonding of organic polymers to inorganic or organic surfaces and to bone has a long history, there remains a serious obstacle in realizing long-term high-bonding strengths in the in vivo body environment of ever present high humidity. Therefore, different pretreatments, individually adapted to the actual combination of materials, are needed to assure long term adhesive strength and stability against hydrolysis. This pretreatment for metal alloys may be silica layering; for PE-plastics, a specific plasma activation; and for bone, amphiphilic layering systems such that the hydrophilic properties of bone become better adapted to the hydrophobic properties of the bone cement. Amphiphilic layering systems are related to those developed in dentistry for dentine bonding. Specific pretreatment can significantly increase bond strengths, particularly after long term immersion in water under conditions similar to those in the human body. The bond strength between bone and plastic for example can be increased by a factor approaching 50 (pealing work increasing from 30 N/m to 1500 N/m). This review article summarizes the multi-disciplined subject of adhesion and adhesives, considering the technology involved in the formation and mechanical performance of adhesives joints inside the human body. PMID:14561228

Insights into Interfacial Changes and Photoelectrochemical Stability of In(x)Ga(1-x)N (0001) Photoanode Surfaces in Liquid Environments.

PubMed

Caccamo, Lorenzo; Cocco, Giulio; Martín, Gemma; Zhou, Hao; Fundling, Sönke; Gad, Alaaeldin; Mohajerani, Matin Sadat; Abdelfatah, Mahmoud; Estradé, Sonia; Peiró, Francesca; Dziony, Wanja; Bremers, Heiko; Hangleiter, Andreas; Mayrhofer, Leonhard; Lilienkamp, Gerhard; Moseler, Michael; Daum, Winfried; Waag, Andreas

2016-03-01

The long-term stability of InGaN photoanodes in liquid environments is an essential requirement for their use in photoelectrochemistry. In this paper, we investigate the relationships between the compositional changes at the surface of n-type In(x)Ga(1-x)N (x ∼ 0.10) and its photoelectrochemical stability in phosphate buffer solutions with pH 7.4 and 11.3. Surface analyses reveal that InGaN undergoes oxidation under photoelectrochemical operation conditions (i.e., under solar light illumination and constant bias of 0.5 VRHE), forming a thin amorphous oxide layer having a pH-dependent chemical composition. We found that the formed oxide is mainly composed of Ga-O bonds at pH 7.4, whereas at pH 11.3 the In-O bonds are dominant. The photoelectrical properties of InGaN photoanodes are intimately related to the chemical composition of their surface oxides. For instance, after the formation of the oxide layer (mainly Ga-O bonds) at pH 7.4, no photocurrent flow was observed, whereas the oxide layer (mainly In-O bonds) at pH 11.3 contributes to enhance the photocurrent, possibly because of its reported high photocatalytic activity. Once a critical oxide thickness was reached, especially at pH 7.4, no significant changes in the photoelectrical properties were observed for the rest of the test duration. This study provides new insights into the oxidation processes occurring at the InGaN/liquid interface, which can be exploited to improve InGaN stability and enhance photoanode performance for biosensing and water-splitting applications.

Self-assembled monolayer and method of making

DOEpatents

Fryxell, Glen E [Kennewick, WA; Zemanian, Thomas S [Richland, WA; Liu, Jun [West Richland, WA; Shin, Yongsoon [Richland, WA

2003-03-11

According to the present invention, the previously known functional material having a self-assembled monolayer on a substrate has a plurality of assembly molecules each with an assembly atom with a plurality of bonding sites (four sites when silicon is the assembly molecule) wherein a bonding fraction (or fraction) of fully bonded assembly atoms (the plurality of bonding sites bonded to an oxygen atom) has a maximum when made by liquid solution deposition, for example a maximum of 40% when silicon is the assembly molecule, and maximum surface density of assembly molecules was 5 silanes per square nanometer. Note that bonding fraction and surface population are independent parameters. The method of the present invention is an improvement to the known method for making a siloxane layer on a substrate, wherein instead of a liquid phase solution chemistry, the improvement is a supercritical phase chemistry. The present invention has the advantages of greater fraction of oxygen bonds, greater surface density of assembly molecules and reduced time for reaction of about 5 minutes to about 24 hours.

Self-assembled monolayer and method of making

DOEpatents

Fryxell, Glen E.; Zemanian, Thomas S.; Liu, Jun; Shin, Yongsoon

2004-05-11

According to the present invention, the previously known functional material having a self-assembled monolayer on a substrate has a plurality of assembly molecules each with an assembly atom with a plurality of bonding sites (four sites when silicon is the assembly molecule) wherein a bonding fraction (or fraction) of fully bonded assembly atoms (the plurality of bonding sites bonded to an oxygen atom) has a maximum when made by liquid solution deposition, for example a maximum of 40% when silicon is the assembly molecule, and maximum surface density of assembly molecules was 5 silanes per square nanometer. Note that bonding fraction and surface population are independent parameters. The method of the present invention is an improvement to the known method for making a siloxane layer on a substrate, wherein instead of a liquid phase solution chemistry, the improvement is a supercritical phase chemistry. The present invention has the advantages of greater fraction of oxygen bonds, greater surface density of assembly molecules and reduced time for reaction of about 5 minutes to about 24 hours.

Self-Assembled Monolayer And Method Of Making

DOEpatents

Fryxell, Glen E.; Zemanian, Thomas S.; Liu, Jun; Shin, Yongsoon

2004-06-22

According to the present invention, the previously known functional material having a self-assembled monolayer on a substrate has a plurality of assembly molecules each with an assembly atom with a plurality of bonding sites (four sites when silicon is the assembly molecule) wherein a bonding fraction (or fraction) of fully bonded assembly atoms (the plurality of bonding sites bonded to an oxygen atom) has a maximum when made by liquid solution deposition, for example a maximum of 40% when silicon is the assembly molecule, and maximum surface density of assembly molecules was 5 silanes per square nanometer. Note that bonding fraction and surface population are independent parameters. The method of the present invention is an improvement to the known method for making a siloxane layer on a substrate, wherein instead of a liquid phase solution chemistry, the improvement is a supercritical phase chemistry. The present invention has the advantages of greater fraction of oxygen bonds, greater surface density of assembly molecules and reduced time for reaction of about 5 minutes to about 24 hours.

Self-Assembled Monolayer And Method Of Making

DOEpatents

Fryxell, Glen E.; Zemanian, Thomas S.; Liu, Jun; Shin, Yongsoon

2005-01-25

According to the present invention, the previously known functional material having a self-assembled monolayer on a substrate has a plurality of assembly molecules each with an assembly atom with a plurality of bonding sites (four sites when silicon is the assembly molecule) wherein a bonding fraction (or fraction) of fully bonded assembly atoms (the plurality of bonding sites bonded to an oxygen atom) has a maximum when made by liquid solution deposition, for example a maximum of 40% when silicon is the assembly molecule, and maximum surface density of assembly molecules was 5 silanes per square nanometer. Note that bonding fraction and surface population are independent parameters. The method of the present invention is an improvement to the known method for making a siloxane layer on a substrate, wherein instead of a liquid phase solution chemistry, the improvement is a supercritical phase chemistry. The present invention has the advantages of greater fraction of oxygen bonds, greater surface density of assembly molecules and reduced time for reaction of about 5 minutes to about 24 hours.

Bond strength of one-step self-etch adhesives and their predecessors to ground versus unground enamel

PubMed Central

Yazici, A. Ruya; Yildirim, Zeren; Ertan, Atila; Ozgunaltay, Gül; Dayangac, Berrin; Antonson, Sibel A; Antonson, Donald E

2012-01-01

Objective The aim of this study was to compare the shear bond strength of several self-etch adhesives to their two-step predecessors to ground and unground enamel. Methods: Seventy-five extracted, non-carious human third molar teeth were selected for this study. The buccal surfaces of each tooth were mechanically ground to obtain flat enamel surfaces (ground enamel), while the lingual surfaces were left intact (unground enamel). The teeth were randomly divided into five groups according to the adhesive systems (n=15): one-step self-etch adhesive - Clearfil S3 Bond, its two-step predecessor - Clearfil SE Bond, one-step self-etch adhesive - AdheSE One, and its two-step predecessor - AdheSE, and a two-step etch-and-rinse adhesive - Adper Single Bond 2(control). After application of the adhesives to the buccal and lingual enamel surfaces of each tooth, a cylindrical capsule filled with a hybrid composite resin (TPH) was seated against the surfaces. The specimens were stored in distilled water at 37°C for 24 hours, followed by thermocy-cling (5°C–55°C/500 cycles). They were subjected to shear bond strength test in a universal testing machine at a crosshead speed of 1.0 mm/minute. The data were compared using a two-way ANOVA, followed by Bonferroni test at P<.05. Results: All adhesives exhibited statistically similar bond strengths to ground and unground enamel except for the etch-and-rinse adhesive that showed significantly higher bond strengths than the self-etch adhesives (P<.05). No significant differences in bond strength values were observed between ground and unground enamel for any of the adhesives tested (P=.17). Conclusion: Similar bond strengths to ground and unground enamel were achieved with one-step self-etch adhesives and their predecessors. Enamel preparation did not influence the bonding performance of the adhesives tested. PMID:22904656

Bond strength of one-step self-etch adhesives and their predecessors to ground versus unground enamel.

PubMed

Yazici, A Ruya; Yildirim, Zeren; Ertan, Atila; Ozgunaltay, Gül; Dayangac, Berrin; Antonson, Sibel A; Antonson, Donald E

2012-07-01

The aim of this study was to compare the shear bond strength of several self-etch adhesives to their two-step predecessors to ground and unground enamel. Seventy-five extracted, non-carious human third molar teeth were selected for this study. The buccal surfaces of each tooth were mechanically ground to obtain flat enamel surfaces (ground enamel), while the lingual surfaces were left intact (unground enamel). The teeth were randomly divided into five groups according to the adhesive systems (n=15): one-step self-etch adhesive - Clearfil S3 Bond, its two-step predecessor - Clearfil SE Bond, one-step self-etch adhesive - AdheSE One, and its two-step predecessor - AdheSE, and a two-step etch-and-rinse adhesive - Adper Single Bond 2(control). After application of the adhesives to the buccal and lingual enamel surfaces of each tooth, a cylindrical capsule filled with a hybrid composite resin (TPH) was seated against the surfaces. The specimens were stored in distilled water at 37°C for 24 hours, followed by thermocy-cling (5°C-55°C/500 cycles). They were subjected to shear bond strength test in a universal testing machine at a crosshead speed of 1.0 mm/minute. The data were compared using a two-way ANOVA, followed by Bonferroni test at P<.05. All adhesives exhibited statistically similar bond strengths to ground and unground enamel except for the etch-and-rinse adhesive that showed significantly higher bond strengths than the self-etch adhesives (P<.05). No significant differences in bond strength values were observed between ground and unground enamel for any of the adhesives tested (P=.17). Similar bond strengths to ground and unground enamel were achieved with one-step self-etch adhesives and their predecessors. Enamel preparation did not influence the bonding performance of the adhesives tested.

Shear-bond-strength of orthodontic brackets to aged nano-hybrid composite-resin surfaces using different surface preparation.

PubMed

Demirtas, Hatice Kubra; Akin, Mehmet; Ileri, Zehra; Basciftci, Faruk Ayhan

2015-01-01

The aim of this study was to evaluate the effects of different surface preparation methods on the shear bond strength (SBS) of orthodontic metal brackets to aged nano-hybrid resin composite surfaces in vitro. A total of 100 restorative composite resin discs, 6 mm in diameter and 3 mm thick, were obtained and treated with an ageing procedure. After ageing, the samples were randomly divided as follows according to surface preparation methods: (1)Control, (2)37% phosphoric acid gel, (3)Sandblasting, (4)Diamond bur, (5)Air-flow and 20 central incisor teeth were used for the control etched group. SBS test were applied on bonded metal brackets to all samples. SBS values and residual adhesives were evaluated. Analysis of variance showed a significant difference (p<0.001) between the groups. Sandblasted group had the highest SBS value (12.85 MPa) in experimental groups. The sandblasting surface treatment is recommended as an effective method of bonding orthodontic metal brackets to nano-hybrid composite resin surfaces.

Effects of femtosecond laser and other surface treatments on the bond strength of metallic and ceramic orthodontic brackets to zirconia

PubMed Central

García-Sanz, Verónica; Bellot-Arcís, Carlos; Mendoza-Yero, Omel; Doñate-Buendía, Carlos; Montero, Javier; Albaladejo, Alberto

2017-01-01

Femtosecond laser has been proposed as a method for conditioning zirconia surfaces to boost bond strength. However, metallic or ceramic bracket bonding to femtosecond laser-treated zirconia surfaces has not been tested. This study compared the effects of four conditioning techniques, including femtosecond laser irradiation, on shear bond strength (SBS) of metallic and ceramic brackets to zirconia.Three hundred zirconia plates were divided into five groups: 1) control (C); 2) sandblasting (APA); 3) silica coating and silane (SC); 4) femtosecond laser (FS); 5) sandblasting followed by femtosecond laser (APA+SC). A thermal imaging camera measured temperature changes in the zirconia during irradiation. Each group was divided into 2 subgroups (metallic vs ceramic brackets). SBS was evaluated using a universal testing machine. The adhesive remnant index (ARI) was registered and surfaces were observed under SEM. Surface treatment and bracket type significantly affected the bracket-zirconia bond strength. SBS was significantly higher (p<0.001) for ceramic brackets in all groups (APA+FS > APA > FS > SC > control) than metallic brackets (APA+FS > FS > SC > APA > control). For metallic brackets, groups SC (5.99 ± 1.86 MPa), FS (6.72 ± 2.30 MPa) and APA+FS (7.22 ± 2.73 MPa) reported significantly higher bond strengths than other groups (p < 0.05). For ceramic brackets, the highest bond strength values were obtained in groups APA (25.01 ± 4.45 MPa), FS (23.18 ± 6.51 MPa) and APA+FS (29.22 ± 8.20 MPa).Femtosecond laser enhances bond strength of ceramic and metallic brackets to zirconia. Ceramic brackets provide significantly stronger adhesion than metallic brackets regardless of the surface treatment method. PMID:29049418

Investigating failure behavior and origins under supposed "shear bond" loading.

PubMed

Sultan, Hassam; Kelly, J Robert; Kazemi, Reza B

2015-07-01

This study evaluated failure behavior when resin-composite cylinders bonded to dentin fractured under traditional "shear" testing. Failure was assessed by scaling of failure loads to changes in cylinder radii and fracture surface analysis. Three stress models were examined including failure by: bonded area; flat-on-cylinder contact; and, uniformly-loaded, cantilevered-beam. Nine 2-mm dentin occlusal dentin discs for each radii tested were embedded in resin and bonded to resin-composite cylinders; radii (mm)=0.79375; 1.5875; 2.38125; 3.175. Samples were "shear" tested at 1.0mm/min. Following testing, disks were finished with silicone carbide paper (240-600grit) to remove residual composite debris and tested again using different radii. Failure stresses were calculated for: "shear"; flat-on-cylinder contact; and, bending of a uniformly-loaded cantilevered beam. Stress equations and constants were evaluated for each model. Fracture-surface analysis was performed. Failure stresses calculated as flat-on-cylinder contact scaled best with its radii relationship. Stress equation constants were constant for failure from the outside surface of the loaded cylinders and not with the bonded surface area or cantilevered beam. Contact failure stresses were constant over all specimen sizes. Fractography reinforced that failures originated from loaded cylinder surface and were unrelated to the bonded surface area. "Shear bond" testing does not appear to test the bonded interface. Load/area "stress" calculations have no physical meaning. While failure is related to contact stresses, the mechanism(s) likely involve non-linear damage accumulation, which may only indirectly be influenced by the interface. Copyright © 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Effects of femtosecond laser and other surface treatments on the bond strength of metallic and ceramic orthodontic brackets to zirconia.

PubMed

García-Sanz, Verónica; Paredes-Gallardo, Vanessa; Bellot-Arcís, Carlos; Mendoza-Yero, Omel; Doñate-Buendía, Carlos; Montero, Javier; Albaladejo, Alberto

2017-01-01

Femtosecond laser has been proposed as a method for conditioning zirconia surfaces to boost bond strength. However, metallic or ceramic bracket bonding to femtosecond laser-treated zirconia surfaces has not been tested. This study compared the effects of four conditioning techniques, including femtosecond laser irradiation, on shear bond strength (SBS) of metallic and ceramic brackets to zirconia.Three hundred zirconia plates were divided into five groups: 1) control (C); 2) sandblasting (APA); 3) silica coating and silane (SC); 4) femtosecond laser (FS); 5) sandblasting followed by femtosecond laser (APA+SC). A thermal imaging camera measured temperature changes in the zirconia during irradiation. Each group was divided into 2 subgroups (metallic vs ceramic brackets). SBS was evaluated using a universal testing machine. The adhesive remnant index (ARI) was registered and surfaces were observed under SEM. Surface treatment and bracket type significantly affected the bracket-zirconia bond strength. SBS was significantly higher (p<0.001) for ceramic brackets in all groups (APA+FS > APA > FS > SC > control) than metallic brackets (APA+FS > FS > SC > APA > control). For metallic brackets, groups SC (5.99 ± 1.86 MPa), FS (6.72 ± 2.30 MPa) and APA+FS (7.22 ± 2.73 MPa) reported significantly higher bond strengths than other groups (p < 0.05). For ceramic brackets, the highest bond strength values were obtained in groups APA (25.01 ± 4.45 MPa), FS (23.18 ± 6.51 MPa) and APA+FS (29.22 ± 8.20 MPa).Femtosecond laser enhances bond strength of ceramic and metallic brackets to zirconia. Ceramic brackets provide significantly stronger adhesion than metallic brackets regardless of the surface treatment method.

Modification of titanium surfaces by adding antibiotic-loaded PHB spheres and PEG for biomedical applications.

PubMed

Rodríguez-Contreras, Alejandra; Marqués-Calvo, María Soledad; Gil, Francisco Javier; Manero, José María

2016-08-01

Novel researches are focused on the prevention and management of post-operative infections. To avoid this common complication of implant surgery, it is preferable to use new biomaterials with antibacterial properties. Therefore, the aim of this work is to develop a method of combining the antibacterial properties of antibiotic-loaded poly(3-hydroxybutyrate) (PHB) nano- and micro-spheres and poly(ethylene glycol) (PEG) as an antifouling agent, with titanium (Ti), as the base material for implants, in order to obtain surfaces with antibacterial activity. The Ti surfaces were linked to both PHB particles and PEG by a covalent bond. This attachment was carried out by firstly activating the surfaces with either Oxygen plasma or Sodium hydroxide. Further functionalization of the activated surfaces with different alkoxysilanes allows the reaction with PHB particles and PEG. The study confirms that the Ti surfaces achieved the antibacterial properties by combining the antibiotic-loaded PHB spheres, and PEG as an antifouling agent.

Disulfide bond exchanges in integrins αIIbβ3 and αvβ3 are required for activation and post-ligation signaling during clot retraction.

PubMed

Mor-Cohen, Ronit; Rosenberg, Nurit; Averbukh, Yulia; Seligsohn, Uri; Lahav, Judith

2014-05-01

Integrin αIIbβ3 mediates platelet adhesion, aggregation and fibrin clot retraction. These processes require activation of αIIbβ3 and post-ligation signaling. Disulfide bond exchanges are involved in αIIbβ3 and αvβ3 activation. In order to investigate the role of integrin activation and disulfide bond exchange during αIIbβ3- and αvβ3-mediated clot retraction, we co-expressed in baby hamster kidney cells wild-type (WT) human αIIb and WT or mutated human β3 that contain single or double cysteine substitutions disrupting C523-C544 or C560-C583 bonds. Flow cytometry was used to measure surface expression and activation state of the integrins. Time-course of fibrin clot retraction was examined. Cells expressed WT or mutated human αIIbβ3 as well as chimeric hamster/human αvβ3. The αIIbβ3 mutants were constitutively active and the thiol blocker dithiobisnitrobenzoic acid (DTNB) did not affect their activation state. WT cells retracted the clot and addition of αvβ3 inhibitors decreased the retraction rate. The active mutants and WT cells activated by anti-LIBS6 antibody retracted the clot faster than untreated WT cells, particularly in the presence of αvβ3 inhibitor. DTNB substantially inhibited clot retraction by WT or double C523S/C544S mutant expressing cells, but minimally affected single C523S, C544S or C560S mutants. Anti-LIBS6-enhanced clot retraction was significantly inhibited by DTNB when added prior to anti-LIBS6. Both αIIbβ3 and αvβ3 contribute to clot retraction without prior activation of the integrins. Activation of αIIbβ3, but not of αvβ3 enhances clot retraction. Both αIIbβ3 activation and post-ligation signaling during clot retraction require disulfide bond exchange. Copyright © 2014 Elsevier Ltd. All rights reserved.

Innovations in bonding to zirconia-based materials: Part I.

PubMed

Aboushelib, Moustafa N; Matinlinna, Jukka P; Salameh, Ziad; Ounsi, Hani

2008-09-01

Establishing a reliable bond to zirconia-based materials has proven to be difficult which is the major limitation against fabricating adhesive zirconia restorations. This bond could be improved using novel selective infiltration etching conditioning in combination with engineered zirconia primers. Aim of the work was to evaluate resin-to-zirconia bond strength using selective infiltration etching and novel silane-based zirconia primers. Zirconia discs (Procera Zirconia) received selective infiltration etching surface treatment followed by coating with either of five especially engineered experimental zirconia primers. Pre-aged resin-composite discs (Tetric Ivo Ceram) were bonded to the treated surface using an MDP-containing resin-composite (Panavia F 2.0). The bilayered specimens were cut into microbars and the microtensile bond strength (MTBS) was evaluated. 'As-sintered' zirconia discs served as a control (alpha=0.05). The broken microbars were examined using a scanning electron microscope (SEM). The combination of selective infiltration etching with experimental zirconia primers significantly improved (F=3805, P<0.0001) the MTBS values (41+/-5.8 MPa) compared to the 'as-sintered' surface using the same primers which demonstrated spontaneous failure and very low bond strength values (2.6+/-3.1 MPa). SEM analysis revealed that selective infiltration etching surface treatment resulted in a nano-retentive surface where the zirconia primers were able to penetrate and interlock which explained the higher MTBS values observed for the treated specimens.

Effect of maleic anhydride pretreatment on tensile bond strength of a silicone soft liner to a denture base polymer.

PubMed

Demir, Hakan; Soygun, Koray; Dogan, Arife; Keskin, Selda; Dogan, Orhan Murat; Bolayir, Giray

2011-10-01

To determine the effect of resin surface treatment with dissolved maleic anhydride in butanone added into primer on the tensile bond strength between an acrylic denture base resin and a silicone soft liner. To test tensile bond strength, standard dumbbell-shaped acrylic specimens were prepared. Five experimental groups, including the control, were tested (n = 5). Maleic anhydride solutions prepared in butanone at concentrations of 1%, 5%, 10% or 20% were then mixed with 1 ml of Primo adhesive and the mixtures were applied onto the resin bonding surfaces. Silicone liner material was applied to resin surfaces in the conventional manner. Tensile bond strength of the specimens was measured in a universal testing machine. Fractured surfaces were observed under the scanning electron microscope, and resulting chemical changes with the solutions used were analyzed spectroscopically. The highest bond strength value was obtained for the group treated with 5% maleic anhydride (2.53 ± 0.48 MPa); the lowest value was for the group treated with 20% maleic anhydride (1.59 ± 0.29 MPa). Mixed failure was the dominant type seen in the experimental groups. Spectroscopic analysis showed the interaction of the anhydride carbonyl groups with the Primo primer. The treatment of resin surfaces with maleic anhydride added to Primo adhesive effectively increased bond strength between silicone soft liner and denture base resin.

Assembling strategy to synthesize palladium modified kaolin nanocomposites with different morphologies

PubMed Central

Li, Xiaoyu; Ouyang, Jing; Zhou, Yonghua; Yang, Huaming

2015-01-01

Nanocomposites of aluminosilicate minerals, kaolins (kaolinite and halloysite) with natural different morphologies assembling with palladium (Pd) nanoparticles have been successfully synthesized through strong electrostatic adsorption and chemical bonding after surface modification with 3-aminopropyl triethoxysilane (APTES). Meanwhile, the influence of different morphologies supports on catalytic hydrogenation properties was explored. The surface concentration of amino groups on the kaolins was related to the morphology and surface nature. Electronmicroscopy revealed that the monodisperse Pd nanoparticles were uniformly deposited onto the surface of kaolins, ranging in diameter from 0.5 nm to 5.5 nm. The functional groups could not only improve the dispersion of kaolins with different morphologies in solution, but also enhance the interaction between Pd precursors and kaolins, thus preventing small Pd nanoparticles from agglomerating and leading to high activity for the catalytic hydrogenation of styrene. Pd-FK@APTES was more active compared to other samples. Selecting the kaolin morphology with a different surface nature allows the selective surface modification of a larger fraction of the reactive facets on which the active sites can be enriched and tuned. This desirable surface coordination of catalytically active atoms could substantially improve catalytic activity. PMID:26333629

Assembling strategy to synthesize palladium modified kaolin nanocomposites with different morphologies

NASA Astrophysics Data System (ADS)

Li, Xiaoyu; Ouyang, Jing; Zhou, Yonghua; Yang, Huaming

2015-09-01

Nanocomposites of aluminosilicate minerals, kaolins (kaolinite and halloysite) with natural different morphologies assembling with palladium (Pd) nanoparticles have been successfully synthesized through strong electrostatic adsorption and chemical bonding after surface modification with 3-aminopropyl triethoxysilane (APTES). Meanwhile, the influence of different morphologies supports on catalytic hydrogenation properties was explored. The surface concentration of amino groups on the kaolins was related to the morphology and surface nature. Electronmicroscopy revealed that the monodisperse Pd nanoparticles were uniformly deposited onto the surface of kaolins, ranging in diameter from 0.5 nm to 5.5 nm. The functional groups could not only improve the dispersion of kaolins with different morphologies in solution, but also enhance the interaction between Pd precursors and kaolins, thus preventing small Pd nanoparticles from agglomerating and leading to high activity for the catalytic hydrogenation of styrene. Pd-FK@APTES was more active compared to other samples. Selecting the kaolin morphology with a different surface nature allows the selective surface modification of a larger fraction of the reactive facets on which the active sites can be enriched and tuned. This desirable surface coordination of catalytically active atoms could substantially improve catalytic activity.

Assembling strategy to synthesize palladium modified kaolin nanocomposites with different morphologies.

PubMed

Li, Xiaoyu; Ouyang, Jing; Zhou, Yonghua; Yang, Huaming

2015-09-03

Nanocomposites of aluminosilicate minerals, kaolins (kaolinite and halloysite) with natural different morphologies assembling with palladium (Pd) nanoparticles have been successfully synthesized through strong electrostatic adsorption and chemical bonding after surface modification with 3-aminopropyl triethoxysilane (APTES). Meanwhile, the influence of different morphologies supports on catalytic hydrogenation properties was explored. The surface concentration of amino groups on the kaolins was related to the morphology and surface nature. Electronmicroscopy revealed that the monodisperse Pd nanoparticles were uniformly deposited onto the surface of kaolins, ranging in diameter from 0.5 nm to 5.5 nm. The functional groups could not only improve the dispersion of kaolins with different morphologies in solution, but also enhance the interaction between Pd precursors and kaolins, thus preventing small Pd nanoparticles from agglomerating and leading to high activity for the catalytic hydrogenation of styrene. Pd-FK@APTES was more active compared to other samples. Selecting the kaolin morphology with a different surface nature allows the selective surface modification of a larger fraction of the reactive facets on which the active sites can be enriched and tuned. This desirable surface coordination of catalytically active atoms could substantially improve catalytic activity.

Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C-H activation

NASA Astrophysics Data System (ADS)

Marcinkowski, Matthew D.; Darby, Matthew T.; Liu, Jilei; Wimble, Joshua M.; Lucci, Felicia R.; Lee, Sungsik; Michaelides, Angelos; Flytzani-Stephanopoulos, Maria; Stamatakis, Michail; Sykes, E. Charles H.

2018-03-01

The recent availability of shale gas has led to a renewed interest in C-H bond activation as the first step towards the synthesis of fuels and fine chemicals. Heterogeneous catalysts based on Ni and Pt can perform this chemistry, but deactivate easily due to coke formation. Cu-based catalysts are not practical due to high C-H activation barriers, but their weaker binding to adsorbates offers resilience to coking. Using Pt/Cu single-atom alloys (SAAs), we examine C-H activation in a number of systems including methyl groups, methane and butane using a combination of simulations, surface science and catalysis studies. We find that Pt/Cu SAAs activate C-H bonds more efficiently than Cu, are stable for days under realistic operating conditions, and avoid the problem of coking typically encountered with Pt. Pt/Cu SAAs therefore offer a new approach to coke-resistant C-H activation chemistry, with the added economic benefit that the precious metal is diluted at the atomic limit.

Adhesives for Achieving Durable Bonds with Acetylated Wood

Treesearch

Charles Frihart; Rishawn Brandon; James Beecher; Rebecca Ibach

2017-01-01

Acetylation of wood imparts moisture durability, decay resistance, and dimensional stability to wood; however, making durable adhesive bonds with acetylated wood can be more difficult than with unmodified wood. The usual explanation is that the acetylated surface has fewer hydroxyl groups, resulting in a harder-to-wet surface and in fewer hydrogen bonds between wood...

Elaboration of antibiofilm surfaces functionalized with antifungal-cyclodextrin inclusion complexes.

PubMed

Gharbi, Aïcha; Humblot, Vincent; Turpin, Frédéric; Pradier, Claire-Marie; Imbert, Christine; Berjeaud, Jean-Marc

2012-07-01

To tackle the loss of activity of surfaces functionalized by coating and covalently bound molecules to materials, an intermediate system implying the noncovalent immobilization of active molecules in the inner cavity of grafted cyclodextrins (CDs) was investigated. The antifungal and antibiofilm activities of the most stable complexes of Anidulafungin (ANF; echinocandin) and thymol (THY; terpen) in various CDs were demonstrated to be almost the same as the free molecules. The selected CD was covalently bond to self-assembled monolayers on gold surfaces. The immobilized antifungal agents reduced the number of culturable Candida albicans ATCC 3153 attached to the surface by 64 ± 8% for ANF and 75 ± 15% for THY. The inhibitory activity was persistent for THY-loaded samples, whereas it was completely lost for ANF-loaded surfaces after one use. However, reloading of the echinocandin restored the activity. Using fluorescent dying and confocal microscopy, it was proposed that the ANF-loaded surfaces inhibited the adherence of the yeasts, whereas the activity of immobilized THY was found fungicidal. This kind of tailored approach for functionalizing surfaces that could allow a progressive release of ANF or THY gave promising results but still needs to be improved to display a full activity. © 2012 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. All rights reserved.

Synthesis and processing of ELISA polymer substitute: The influence of surface chemistry and morphology on detection sensitivity

NASA Astrophysics Data System (ADS)

Hosseini, Samira; Ibrahim, Fatimah; Djordjevic, Ivan; Rothan, Hussin A.; Yusof, Rohana; van der Marel, Cees; Koole, Leo H.

2014-10-01

Despite the known drawbacks of enzyme-linked immunosorbent assay (ELISA), one of the deficiencies that have relatively been ignored is the performance of ELISA substrate itself. Polystyrene (PS), as the cost effective material of choice for mass production of ELISA well-plates, has shown obvious lacks of suitable physical and chemical properties for protein attachment. The general concept of this work was to develop a potential substrate that can be suggested as a material of choice for production of a new generation of ELISA analytical kits. Spin-coated thin films of polymethyl methacrylate-co-methacrylic acid (PMMA-co-MAA) on silicon surfaces were designed and processed for detection of dengue virus. Coated surfaces of different molar ratios have been investigated as carboxyl-functionalized layers for obtaining platform for biomolecule immobilization with high level of protein activity. To improve the sensitivity of detection, we have used amine functional "spacers", hexamethylenediamine (HMDA) and polyethyleneimine (PEI), which were covalently bonded to the surfaces of PMMA-co-MAA coatings. Results demonstrate that the variation of surface concentration of carboxyl groups of PMMA-co-MAA can be used to control the amine surface concentration after carbodiimide coupling with HMDA and PEI spacers. The presence of amine spacers increases hydrophilicity of the coatings and significantly impacts the polymer surface morphology. In particular, protein immobilization via amine-bearing spacers has been achieved in two effective steps: (1) carbodiimide bonding between amine spacer molecules and PMMA-co-MAA polymer coatings; and (2) covalent immobilization of antibody via glutaraldehyde reaction with amine groups from amine-treated surfaces. The application of PEI spacer in comparison to HMDA has shown much higher intensity of detection signal in ELISA experiment, indicating better immobilization efficiency and preservation of antibody activity upon attachment to the polymer surface.

Effect of surface treatments on the bond strength of soft denture lining materials to an acrylic resin denture base.

PubMed

Gundogdu, Mustafa; Yesil Duymus, Zeynep; Alkurt, Murat

2014-10-01

Adhesive failure between acrylic resin and resilient liner material is commonly encountered in clinical practice. The purpose of this study was to evaluate the effect of different surface treatments on the bond strength of 2 different resilient lining materials to an acrylic resin denture base. Ninety-six dumbbell-shaped specimens were fabricated from heat-polymerized acrylic resin, and 3 mm of the material was cut from the thin midsection. The specimens were divided into 6 groups according to their surface treatments: no surface treatment (control group), 36% phosphoric acid etching (acid group), erbium:yttrium-aluminum-garnet (Er:YAG) laser (laser group), airborne-particle abrasion with 50-μm Al2O3 particles (abrasion group), an acid+laser group, and an abrasion+laser group. The specimens in each group were divided into 2 subgroups according to the resilient lining material used: heat-polymerized silicone based resilient liner (Molloplast B) and autopolymerized silicone-based resilient liner (Ufi Gel P). After all of the specimens had been polymerized, they were stored in distilled water at 37°C for 1 week. A tensile bond strength test was then performed. Data were analyzed with a 2-way ANOVA, and the Sidak multiple comparison test was used to identify significant differences (α=.05). The effects of the surface treatments and resilient lining materials on the surface of the denture base resin were examined with scanning electron microscopy. The tensile bond strength was significantly different between Molloplast B and Ufi Gel P (P<.001). The specimens of the acid group had the highest tensile bond strength, whereas those of the abrasion group had the lowest tensile bond strength. The scanning electron microscopy observations showed that the application of surface treatments modified the surface of the denture base resin. Molloplast B exhibited significantly higher bond strength than Ufi Gel P. Altering the surface of the acrylic resin denture base with 36% phosphoric acid etching increased bond strength. Copyright © 2014 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

A DFT investigation of a bulky biomimetic model catalyzing the 5'-outer ring deiodination of thyroxine.

PubMed

Fortino, Mariagrazia; Marino, Tiziana; Russo, Nino; Sicilia, Emilia

2016-12-01

This paper illustrates the outcomes of a density functional theory investigation aimed at unraveling mechanistic aspects of the 5'-outer ring deiodination process of thyroxine (T4) assisted by the sterically protected organoselenol compound BpqSeH. BpqSeH, which was previously synthesized and tested for its deiodinase activity, is able to afford the active hormone 3,5,3'-tetraiodothyronine (T3) by selective outer-ring deiodination of T4, and to protect the SeH moiety inside the nano-sized molecular cavity from further reactivity, allowing its isolation and characterization. Calculations were also performed including an imidazole ring that, mimicking a His residue in the active site of the original enzyme, plays an crucial role in deprotonating the selenol moiety. Both the suggested enol/keto tautomerization and the previously proven formation of an intermediate whose main characteristic is the presence of a Se⋯I⋯C halogen bond, were examined along the pathway leading to 5'-outer ring deiodination. The calculated potential energy surface showed that neither the pathway encompassing enol/keto tautomerism nor the formation of a halogen bond paving the way to C-I bond breaking and chalcogen-I bond forming is viable. The exergonic formation of the final selenenyl iodide product confirms the stabilization effect of the molecular cavity. Graphical Abstract Computed free energy profile describing the 5'-outer deiodination of thyroxine assisted by the steric hindered organoselenol BpqSH compound. The molecular electrostatic potential map reoported for the INT1 intermediate shows the non-covalent Se-I interaction, due to the attraction between charges of opposite sign, that weakens the C-I bond and prepares the formation of the new Se-I bond.

Density functional study of the adsorption of aspirin on the hydroxylated (0 0 1) α-quartz surface

NASA Astrophysics Data System (ADS)

Abbasi, A.; Nadimi, E.; Plänitz, P.; Radehaus, C.

2009-08-01

In this study the adsorption geometry of aspirin molecule on a hydroxylated (0 0 1) α-quartz surface has been investigated using DFT calculations. The optimized adsorption geometry indicates that both, adsorbed molecule and substrate are strongly deformed. Strong hydrogen bonding between aspirin and surface hydroxyls, leads to the breaking of the original hydroxyl-hydroxyl hydrogen bonds (Hydrogenbridges) on the surface. In this case new hydrogen bonds on the hydroxylated (0 0 1) α-quartz surface appear which significantly differ from those at the clean surface. The 1.11 eV adsorption energy reveals that the interaction of aspirin with α-quartz is an exothermic chemical interaction.

Facile construction of a highly sensitive DNA biosensor by in-situ assembly of electro-active tags on hairpin-structured probe fragment

PubMed Central

Wang, Qingxiang; Gao, Feng; Ni, Jiancong; Liao, Xiaolei; Zhang, Xuan; Lin, Zhenyu

2016-01-01

An ultrasensitive DNA biosensor has been developed through in-situ labeling of electroactive melamine-Cu2+ complex (Mel-Cu2+) on the end of hairpin-like probe using gold nanoparticles (AuNPs) as the signal amplification platform. The 3′-thiolated hairpin-like probe was first immobilized to the gold electrode surface by the Au-S bond. The AuNPs were then tethered on the free 5′-end of the immobilized probe via the special affinity between Au and the modified -NH2. Followed by, the Mel and Cu2+ were assembled on the AuNPs surface through Au-N bond and Cu2+-N bond, respectively. Due to the surface area and electrocatalytic effects of the AuNPs, the loading amount and electron transfer kinetic of the Mel-Cu2+ were enhanced greatly, resulting in significantly enhanced electrochemical response of the developed biosensor. Compared with the synthesis process of conventional electroactive probe DNA accomplished by homogeneous method, the method presented in this work is more reagent- and time-saving. The proposed biosensor showed high selectivity, wide linear range and low detection limit. This novel strategy could also be extended to the other bioanalysis platforms such as immunosensors and aptasensors. PMID:26931160

Influence of heat-pretreatments on the microstructural and mechanical properties of galfan-coated metal bonds

NASA Astrophysics Data System (ADS)

Hordych, Illia; Rodman, Dmytro; Nürnberger, Florian; Schmidt, Hans Christian; Orive, Alejandro Gonzalez; Homberg, Werner; Grundmeier, Guido; Maier, Hans Jürgen

2018-05-01

In the present study, heat-treatment assisted bonding of galfan-coated low-carbon steel sheets was investigated. Steel sheets were bonded by cold rolling subsequently to a heat treatment in the temperature range from 400 °C to 550°C. The reduction ratio during cold rolling was varied in the range from 50% to 80%. Such high reduction ratios were achieved by splitting the bonding process into three stages. By employing heat-treatments, the mechanical properties of the bonds were improved. The heat-pretreatment allowed the formation of brittle intermetallic phases that were easily fractured in the rolling gap during the bonding process. Thus, juvenile non-oxidized surfaces were formed, which facilitated the bonding between the steel layers, and thus increased the bond strength. The intermetallic phases were actively formed at temperatures of 450 °C and above; however increasing temperatures resulted in decreasing mechanical properties due to oxidation processes. The local microstructure was analyzed by scanning electron microscopy in order to characterize the contact zone on the micro level with a focus on the formation of intermetallic phases. The mechanical properties were determined in tensile shear tests. Interestingly, it was found that the galfan coating allowed for bonding at room temperature, and the aluminum fraction was primarily responsible for the enhanced oxide formation during the heat-pretreatment.

Repairability of CAD/CAM high-density PMMA- and composite-based polymers.

PubMed

Wiegand, Annette; Stucki, Lukas; Hoffmann, Robin; Attin, Thomas; Stawarczyk, Bogna

2015-11-01

The study aimed to analyse the shear bond strength of computer-aided design and computer-aided manufacturing (CAD/CAM) polymethyl methacrylate (PMMA)- and composite-based polymer materials repaired with a conventional methacrylate-based composite after different surface pretreatments. Each 48 specimens was prepared from six different CAD/CAM polymer materials (Ambarino high-class, artBloc Temp, CAD-Temp, Lava Ultimate, Telio CAD, Everest C-Temp) and a conventional dimethacrylate-based composite (Filtek Supreme XTE, control) and aged by thermal cycling (5000 cycles, 5-55 °C). The surfaces were left untreated or were pretreated by mechanical roughening, aluminium oxide air abrasion or silica coating/silanization (each subgroup n = 12). The surfaces were further conditioned with an etch&rinse adhesive (OptiBond FL) before the repair composite (Filtek Supreme XTE) was adhered to the surface. After further thermal cycling, shear bond strength was tested, and failure modes were assessed. Shear bond strength was statistically analysed by two- and one-way ANOVAs and Weibull statistics, failure mode by chi(2) test (p ≤ 0.05). Shear bond strength was highest for silica coating/silanization > aluminium oxide air abrasion = mechanical roughening > no surface pretreatment. Independently of the repair pretreatment, highest bond strength values were observed in the control group and for the composite-based Everest C-Temp and Ambarino high-class, while PMMA-based materials (artBloc Temp, CAD-Temp and Telio CAD) presented significantly lowest values. For all materials, repair without any surface pretreatment resulted in adhesive failures only, which mostly were reduced when surface pretreatment was performed. Repair of CAD/CAM high-density polymers requires surface pretreatment prior to adhesive and composite application. However, four out of six of the tested CAD/CAM materials did not achieve the repair bond strength of a conventional dimethacrylate-based composite. Repair of PMMA- and composite-based polymers can be achieved by surface pretreatment followed by application of an adhesive and a conventional methacrylate-based composite.

Four chemical methods of porcelain conditioning and their influence over bond strength and surface integrity

PubMed Central

Stella, João Paulo Fragomeni; Oliveira, Andrea Becker; Nojima, Lincoln Issamu; Marquezan, Mariana

2015-01-01

OBJECTIVE: To assess four different chemical surface conditioning methods for ceramic material before bracket bonding, and their impact on shear bond strength and surface integrity at debonding. METHODS: Four experimental groups (n = 13) were set up according to the ceramic conditioning method: G1 = 37% phosphoric acid etching followed by silane application; G2 = 37% liquid phosphoric acid etching, no rinsing, followed by silane application; G3 = 10% hydrofluoric acid etching alone; and G4 = 10% hydrofluoric acid etching followed by silane application. After surface conditioning, metal brackets were bonded to porcelain by means of the Transbond XP system (3M Unitek). Samples were submitted to shear bond strength tests in a universal testing machine and the surfaces were later assessed with a microscope under 8 X magnification. ANOVA/Tukey tests were performed to establish the difference between groups (α= 5%). RESULTS: The highest shear bond strength values were found in groups G3 and G4 (22.01 ± 2.15 MPa and 22.83 ± 3.32 Mpa, respectively), followed by G1 (16.42 ± 3.61 MPa) and G2 (9.29 ± 1.95 MPa). As regards surface evaluation after bracket debonding, the use of liquid phosphoric acid followed by silane application (G2) produced the least damage to porcelain. When hydrofluoric acid and silane were applied, the risk of ceramic fracture increased. CONCLUSIONS: Acceptable levels of bond strength for clinical use were reached by all methods tested; however, liquid phosphoric acid etching followed by silane application (G2) resulted in the least damage to the ceramic surface. PMID:26352845

Shear Bond Strength of Al2O3 Sandblasted Y-TZP Ceramic to the Orthodontic Metal Bracket

PubMed Central

Byeon, Seon Mi; Lee, Min Ho; Bae, Tae Sung

2017-01-01

As the proportion of adult orthodontic treatment increases, mainly for aesthetic reasons, orthodontic brackets are directly attached to yttria-stabilized tetragonal zirconia polycrystal (Y-TZP) restorations. This, study analyzed the shear bond strength (SBS) between various surface treated Y-TZP and orthodontic metal brackets. The Y-TZP specimens were conditioned by 110 μm Al2O3 sandblasting, or sandblasting followed by coating with one of the primers (silane, MDP, or an MDP-containing silane primer). After surface treatment, the orthodontic metal bracket was bonded to the specimen using a resin cement, and then 24 h storage in water and thermal cycling (5000 cycles, 5–55 °C), SBS was measured. Surface roughness was analyzed for surface morphology, and X-ray photoelectron spectroscopy (XPS) was employed for characterization of the chemical bond between the Y-TZP and the MDP-based primers (MDP, MDP containing silane primer). It was found that after surface treatment, the surface roughness of all groups increased. The groups treated with 110 μm Al2O3 sandblasting and MDP, or MDP-containing silane primer showed the highest SBS values, at 11.92 ± 1.51 MPa and 13.36 ± 2.31 MPa, respectively. The SBS values significantly decreased in all the groups after thermal cycling. Results from XPS analysis demonstrated the presence of chemical bonds between Y-TZP and MDP. Thus, the application of MDP-based primers after Al2O3 sandblasting enhances the resin bond strength between Y-TZP and the orthodontic metal bracket. However, bonding durability of all the surface-treated groups decreased after thermal cycling. PMID:28772508

To evaluate and compare the effect of different Post Surface treatments on the Tensile Bond Strength between Fiber Posts and Composite Resin.

PubMed

Shori, Deepa; Pandey, Swapnil; Kubde, Rajesh; Rathod, Yogesh; Atara, Rahul; Rathi, Shravan

2013-10-01

Fiber posts are widely used for restoration of mutilated teeth that lack adequate coronal tooth structure to retain a core for definitive restoration, bond between the fiber post and composite material depends upon the chemical reaction between the post surface and the resin material used for building up the core. In attempt to maximize the resin bonding with fiber post, different post surface conditioning is advocated. Therefore the purpose of the study is to examine the interfacial strength between fiber post and composite, as core build-up material after different surface treatments of fiber posts. Twenty fiber posts were split into four groups off five each according to different surface treatments viz. Group I-(Negative Control), Group II-Silanization (Positive control), Group III-(37% Phosphoric Acid & Silanization) ,Group IV- (10% Hydrogen Peroxide and Silanization). With the preformed plastic mould, a core of dual cure composite resin around the fiber post having the uniform thickness was created. Tensile bond strength of each specimen was measured under Universal Testing Machine (UTM) at the cross head speed of 3mm/min. The results achieved with 10% Hydrogen peroxide had a marked effect on micro tensile bond strength values between the tested materials. Immense enhancement in the silanization efficiency of quartz fiber phase was observed with different surface chemical treatment of the resin phase of fiber posts with the marked increase in the micro-tensile bond strength between fiber post and composite core. Shori D, Pandey S, Kubde R, Rathod Y, Atara R, Rathi S. To evaluate and compare the effect of different Post Surface treatments on the Tensile Bond Strength between Fiber Posts and Composite Resin. J Int Oral Health 2013; 5(5):27-32.

The effect of denture base surface pretreatments on bond strengths of two long term resilient liners

PubMed Central

Parkhedkar, Rambhau

2011-01-01

PURPOSE Purpose of this study was to evaluate effect of two surface treatments, sandblasting and monomer treatment, on tensile bond strength between two long term resilient liners and poly (methyl methacrylate) denture base resin. MATERIALS AND METHODS Two resilient liners Super-Soft and Molloplast-B were selected.Sixty acrylic resin (Trevalon) specimens with cross sectional area of 10×10 mm were prepared and divided into two groups of 30 specimens each. Each group was surface treated (n = 10) by sandblasting (250 µ alumina particles), monomer treatment (for 180 sec) and control (no surface treatment). Resilient liners were processed between 2 poly(methyl methacrylate) surfaces, in the dimensions of 10×10×3 mm. Tensile strength was determined with Instron Universal testing machine, at a crosshead speed of 5 mm/min; and the modes of failure (adhesive, cohesive or mixed) were recorded. The data were analyzed using one-way ANOVA, followed by Tukey HSD test (α = 0.05). RESULTS Monomer pretreatment of acrylic resin produced significantly higher bond strengths when compared to sandblasting and control for both resilient liners (P < .001). Sandblasting significantly decreased the bond strength for both the liners when compared to monomer pretreatment and control (P < .001). Mean bond strength of Super-Soft lined specimens was significantly higher than Molloplast-B in various surface treatment groups (P < .05). CONCLUSION Surface pretreatment of the acrylic resin with monomer prior to resilient liner application is an effective method to increase bond strength between the base and soft liner. Sandblasting, on the contrary, is not recommended as it weakens the bond between the two. PMID:21503188

Surface Protonation at the Rutile (110) Interface: Explicit Incorporation of Solvation Structure within the Refined MUSIC Model Framework

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

Machesky, Michael L.; Predota, M.; Wesolowski, David J

The detailed solvation structure at the (110) surface of rutile ({alpha}-TiO{sub 2}) in contact with bulk liquid water has been obtained primarily from experimentally verified classical molecular dynamics (CMD) simulations of the ab initio-optimized surface in contact with SPC/E water. The results are used to explicitly quantify H-bonding interactions, which are then used within the refined MUSIC model framework to predict surface oxygen protonation constants. Quantum mechanical molecular dynamics (QMD) simulations in the presence of freely dissociable water molecules produced H-bond distributions around deprotonated surface oxygens very similar to those obtained by CMD with nondissociable SPC/E water, thereby confirming thatmore » the less computationally intensive CMD simulations provide accurate H-bond information. Utilizing this H-bond information within the refined MUSIC model, along with manually adjusted Ti-O surface bond lengths that are nonetheless within 0.05 {angstrom} of those obtained from static density functional theory (DFT) calculations and measured in X-ray reflectivity experiments (as well as bulk crystal values), give surface protonation constants that result in a calculated zero net proton charge pH value (pHznpc) at 25 C that agrees quantitatively with the experimentally determined value (5.4 {+-} 0.2) for a specific rutile powder dominated by the (110) crystal face. Moreover, the predicted pH{sub znpc} values agree to within 0.1 pH unit with those measured at all temperatures between 10 and 250 C. A slightly smaller manual adjustment of the DFT-derived Ti-O surface bond lengths was sufficient to bring the predicted pH{sub znpc} value of the rutile (110) surface at 25 C into quantitative agreement with the experimental value (4.8 {+-} 0.3) obtained from a polished and annealed rutile (110) single crystal surface in contact with dilute sodium nitrate solutions using second harmonic generation (SHG) intensity measurements as a function of ionic strength. Additionally, the H-bond interactions between protolyzable surface oxygen groups and water were found to be stronger than those between bulk water molecules at all temperatures investigated in our CMD simulations (25, 150 and 250 C). Comparison with the protonation scheme previously determined for the (110) surface of isostructural cassiterite ({alpha}-SnO{sub 2}) reveals that the greater extent of H-bonding on the latter surface, and in particular between water and the terminal hydroxyl group (Sn-OH) results in the predicted protonation constant for that group being lower than for the bridged oxygen (Sn-O-Sn), while the reverse is true for the rutile (110) surface. These results demonstrate the importance of H-bond structure in dictating surface protonation behavior, and that explicit use of this solvation structure within the refined MUSIC model framework results in predicted surface protonation constants that are also consistent with a variety of other experimental and computational data.« less

Surface protonation at the rutile (110) interface: explicit incorporation of solvation structure within the refined MUSIC model framework.

PubMed

Machesky, Michael L; Predota, Milan; Wesolowski, David J; Vlcek, Lukas; Cummings, Peter T; Rosenqvist, Jörgen; Ridley, Moira K; Kubicki, James D; Bandura, Andrei V; Kumar, Nitin; Sofo, Jorge O

2008-11-04

The detailed solvation structure at the (110) surface of rutile (alpha-TiO2) in contact with bulk liquid water has been obtained primarily from experimentally verified classical molecular dynamics (CMD) simulations of the ab initio-optimized surface in contact with SPC/E water. The results are used to explicitly quantify H-bonding interactions, which are then used within the refined MUSIC model framework to predict surface oxygen protonation constants. Quantum mechanical molecular dynamics (QMD) simulations in the presence of freely dissociable water molecules produced H-bond distributions around deprotonated surface oxygens very similar to those obtained by CMD with nondissociable SPC/E water, thereby confirming that the less computationally intensive CMD simulations provide accurate H-bond information. Utilizing this H-bond information within the refined MUSIC model, along with manually adjusted Ti-O surface bond lengths that are nonetheless within 0.05 A of those obtained from static density functional theory (DFT) calculations and measured in X-ray reflectivity experiments (as well as bulk crystal values), give surface protonation constants that result in a calculated zero net proton charge pH value (pHznpc) at 25 degrees C that agrees quantitatively with the experimentally determined value (5.4+/-0.2) for a specific rutile powder dominated by the (110) crystal face. Moreover, the predicted pHznpc values agree to within 0.1 pH unit with those measured at all temperatures between 10 and 250 degrees C. A slightly smaller manual adjustment of the DFT-derived Ti-O surface bond lengths was sufficient to bring the predicted pHznpcvalue of the rutile (110) surface at 25 degrees C into quantitative agreement with the experimental value (4.8+/-0.3) obtained from a polished and annealed rutile (110) single crystal surface in contact with dilute sodium nitrate solutions using second harmonic generation (SHG) intensity measurements as a function of ionic strength. Additionally, the H-bond interactions between protolyzable surface oxygen groups and water were found to be stronger than those between bulk water molecules at all temperatures investigated in our CMD simulations (25, 150 and 250 degrees C). Comparison with the protonation scheme previously determined for the (110) surface of isostructural cassiterite (alpha-SnO2) reveals that the greater extent of H-bonding on the latter surface, and in particular between water and the terminal hydroxyl group (Sn-OH) results in the predicted protonation constant for that group being lower than for the bridged oxygen (Sn-O-Sn), while the reverse is true for the rutile (110) surface. These results demonstrate the importance of H-bond structure in dictating surface protonation behavior, and that explicit use of this solvation structure within the refined MUSIC model framework results in predicted surface protonation constants that are also consistent with a variety of other experimental and computational data.

Shear bond strength of a denture base acrylic resin and gingiva-colored indirect composite material to zirconia ceramics.

PubMed

Kubochi, Kei; Komine, Futoshi; Fushiki, Ryosuke; Yagawa, Shogo; Mori, Serina; Matsumura, Hideo

2017-04-01

To evaluate the shear bond strengths of two gingiva-colored materials (an indirect composite material and a denture base acrylic resin) to zirconia ceramics and determine the effects of surface treatment with various priming agents. A gingiva-colored indirect composite material (CER) or denture base acrylic resin (PAL) was bonded to zirconia disks with unpriming (UP) or one of seven priming agents (n=11 each), namely, Alloy Primer (ALP), Clearfil Photo Bond (CPB), Clearfil Photo Bond with Clearfil Porcelain Bond Activator (CPB+Act), Metal Link (MEL), Meta Fast Bonding Liner (MFB), MR. bond (MRB), and V-Primer (VPR). Shear bond strength was determined before and after 5000 thermocycles. The data were analyzed with the Kruskal-Wallis test and Steel-Dwass test. The mean pre-/post-thermalcycling bond strengths were 1.0-14.1MPa/0.1-12.1MPa for the CER specimen and 0.9-30.2MPa/0.1-11.1MPa for the PAL specimen. For the CER specimen, the ALP, CPB, and CPB+Act groups had significantly higher bond strengths among the eight groups, at both 0 and 5000 thermocycles. For the PAL specimen, shear bond strength was significantly lower after thermalcycling in all groups tested. After 5000 thermocycles, bond strengths were significantly higher in the CPB and CPB+Act groups than in the other groups. For the PAL specimens, bond strengths were significantly lower after thermalcycling in all groups tested. The MDP functional monomer improved bonding of a gingiva-colored indirect composite material and denture base acrylic resin to zirconia ceramics. Copyright © 2016 Japan Prosthodontic Society. Published by Elsevier Ltd. All rights reserved.

Universal cements: dual activated and chemically activated

PubMed Central

de Lima, Eliane; Santos, Ricardo; Durão, Márcia; Nascimento, Armiliana; Braz, Rodivan

2016-01-01

Abstract Objective: The aim of the present study was to assess the bond strength of universal cements cured either dually or chemically only. Methods: Three cements were assessed using different types of application: dual activated (DA) or chemically activated (CA). In total 80 dentin blocks were used, obtained through the enamel wear of the lingual and buccal surfaces of bovine incisors. Standard cone-shaped cavity preparations were created using diamond burs. Subsequently, indirect restoration blocks were designed with Filtek Z350 (3M ESPE) composite resin. The teeth were divided into two groups (DA and CA) and then subdivided into four subgroups (n = 10) prior to cementation with the respective products: Duo-Link (Bisco); RelyX Ultimate (3M ESPE); Nexus 3 (Kerr) and conventional RelyX ARC (3M ESPE) as the control. The cementation in the PA group was applied following the manufacturer’s instructions. The CA group was cemented in a darkroom to avoid exposure to light. They were stored in distilled water at 37 °C for 24 h and submitted to the push-out test. Data were analyzed by two-way ANOVA and Tukey’s post-hoc test (p < .05). Results: The greatest bond strength results were obtained for photoactivated universal cements. Conclusion: Chemical activation is not sufficient to ensure acceptable bond strength. PMID:28642922

Low-temperature poly(oxymethylene) direct bonding via self-assembled monolayer

NASA Astrophysics Data System (ADS)

Fu, Weixin; Ma, Bo; Kuwae, Hiroyuki; Shoji, Shuichi; Mizuno, Jun

2018-02-01

A direct bonding of poly(oxymethylene) (POM) was feasible at 100 °C by using self-assembled monolayer (SAM) as a surface modification method. (3-aminopropyl)triethoxysilane (APTES) and (3-glycidyloxypropyl)trimethoxysilane (GOPTS) were used in our work. X-ray photoelectron spectroscopy showed that both APTES and GOPTS modified the POM surface successfully. Bonding strength evaluation revealed that surface modification was affected by pretreatment (VUV/O3) process time. In addition, the bonding condition with highest strength had an average strength of 372 kPa. This technology is expected to be used in packaging for micro-/nano-electromechanical systems, such as biomedical devices.

Comparison of embedded, surface bonded and reusable piezoelectric transducers for monitoring of concrete structures

NASA Astrophysics Data System (ADS)

Sabet Divsholi, Bahador; Yang, Yaowen

2011-04-01

Piezoelectric lead zirconate titanate (PZT) transducers have been used for health monitoring of various structures over the last two decades. There are three methods to install the PZT transducers to structures, namely, surface bonded, reusable setup and embedded PZTs. The embedded PZTs and reusable PZT setups can be used for concrete structures during construction. On the other hand, the surface bonded PZTs can be installed on the existing structures. In this study, the applicability and limitations of each installation method are experimentally studied. A real size concrete structure is cast, where the surface bonded, reusable setup and embedded PZTs are installed. Monitoring of concrete hydration and structural damage is conducted by the electromechanical impedance (EMI), wave propagation and wave transmission techniques. It is observed that embedded PZTs are suitable for monitoring the hydration of concrete by using both the EMI and the wave transmission techniques. For damage detection in concrete structures, the embedded PZTs can be employed using the wave transmission technique, but they are not suitable for the EMI technique. It is also found that the surface bonded PZTs are sensitive to damage when using both the EMI and wave propagation techniques. The reusable PZT setups are able to monitor the hydration of concrete. However they are less sensitive in damage detection in comparison to the surface bonded PZTs.

Reaction of Si(100) with NH3: Rate-limiting steps and reactivity enhancement via electronic excitation

NASA Astrophysics Data System (ADS)

Bozso, F.; Avouris, Ph.

1986-09-01

We report on the low-temperature reaction of ammonia with Si(100)-(2×1). The dangling bonds in the clean Si surface promote NH3 dissociation even at temperatures as low as 90 K. The N atoms thus produced occupy subsurface sites, while the H atoms bind to surface Si atoms, tie up the dangling bonds, and inactivate the surface. Thermal or electronic-excitation-induced hydrogen desorption restores the dangling bonds and the reactivity of the surface. Silicon nitride film growth is achieved at 90 K by simultaneous exposure of the Si surface to NH3 and an electron beam.

Bond strength between a polymer-infiltrated ceramic network and a composite for repair: effect of several ceramic surface treatments.

PubMed

Silva, Pollyanna Nogueira Ferreira da; Martinelli-Lobo, Carolina Machado; Bottino, Marco Antonio; Melo, Renata Marques de; Valandro, Luiz Felipe

2018-01-01

The effects of several ceramic surface treatments on bond strength of a polymer-infiltrated ceramic network and resin composite as repair material were evaluated. CAD-CAM blocks of a polymer-infiltrated ceramic network (Vita Enamic) were sliced and subjected to aging process, followed by embedding in acrylic resin. The bonding/repair area was treated as follows (n = 30): C- without treatment; UA- universal adhesive application; FM- 10% hydrofluoric acid and silane application; OM-airborne-particle abrasion with aluminum oxide and silane application; RP- tribochemical silica coating; and CA- surface grinding and application of universal adhesive. Composite resin cylinders were made on the treated surface. Specimens from each group were assigned randomly to two subgroups (n = 15) considering storage condition: Baseline (shear tests after 48 hours) or Storage (tests after 6 months under distilled water). The treated surfaces were analyzed by goniometry, roughness, and SEM. Two-way ANOVA and 1-way ANOVA were applied to analyze the bond data and roughness / contact angle data, respectively, followed by Tukey's test (α = 5%). Surface treatments and storage conditions affected bond strengths (p < 0.01). Surface grinding (CA) followed by universal adhesive promoted the highest value of bond strength (14.5 ± 4.8 MPa for baseline, 8.5 ± 3.4 MPa for storage) and the roughest ceramic surface. Grinding with silicon carbide paper (simulating diamond bur) followed by the application of a universal adhesive system is the best option for repairing fractures of the polymer-infiltrated ceramic network.

Evaluation of metal bond strength to dentin and enamel using different adhesives and surface treatments.

PubMed

Dundar, Mine; Gungor, Mehmet Ali; Cal, Ebru; Darcan, Alev; Erdem, Adalet

2007-01-01

Because adherence of base metal alloys is important for the long-term clinical success of adhesive fixed partial dentures, it has been necessary to improve adhesion to metal substrate by using different surface treatments. This study used different surface conditioning methods and two different luting resins to evaluate the shear bond strength of base metal alloys to dentin and enamel. Sixty noncarious freshly extracted human teeth were mounted in a plastic holder filled with autopolymerized acrylic resin. After the roots were removed and 30 flat enamel and 30 flat dentin surfaces were exposed, the specimens were divided randomly into two main luting cement groups. Sixty nickel chromium (NiCr) metal specimens were fabricated and subjected to three different surface conditioning procedures: sandblasting with 50 microm aluminum oxide, tribochemical silica coating, and a combination of the two. Scanning electron mircoscopy (SEM) evaluations revealed mainly cohesive failures. Self-cure adhesive resulted in higher bond strengths to dental substrates. Higher bond strengths were achieved through a combination of sandblasting and tribochemical silica coating; however, further clinical research is required. A surface treatment that combines sandblasting with tribochemical silica coating can achieve a more effective bond for adhesive restorations with metal substrates.

Progress in cold roll bonding of metals

PubMed Central

Li, Long; Nagai, Kotobu; Yin, Fuxing

2008-01-01

Layered composite materials have become an increasingly interesting topic in industrial development. Cold roll bonding (CRB), as a solid phase method of bonding same or different metals by rolling at room temperature, has been widely used in manufacturing large layered composite sheets and foils. In this paper, we provide a brief overview of a technology using layered composite materials produced by CRB and discuss the suitability of this technology in the fabrication of layered composite materials. The effects of process parameters on bonding, mainly including process and surface preparation conditions, have been analyzed. Bonding between two sheets can be realized when deformation reduction reaches a threshold value. However, it is essential to remove surface contamination layers to produce a satisfactory bond in CRB. It has been suggested that the degreasing and then scratch brushing of surfaces create a strong bonding between the layers. Bonding mechanisms, in which the film theory is expressed as the major mechanism in CRB, as well as bonding theoretical models, have also been reviewed. It has also been showed that it is easy for bcc structure metals to bond compared with fcc and hcp structure metals. In addition, hardness on bonding same metals plays an important part in CRB. Applications of composites produced by CRB in industrial fields are briefly reviewed and possible developments of CRB in the future are also described. PMID:27877949

Effects of surface treatments and bonding types on the interfacial behavior of fiber metal laminate based on magnesium alloy

NASA Astrophysics Data System (ADS)

Zhang, Xi; Ma, Quanyang; Dai, Yu; Hu, Faping; Liu, Gang; Xu, Zouyuan; Wei, Guobing; Xu, Tiancai; Zeng, Qingwen; Xie, Weidong

2018-01-01

Fiber metal laminates based on magnesium alloys (MgFML) with different surface treatments and different bonding types were tested and analyzed. By using dynamic contact angle measurement and scanning electron microscopy (SEM), it was found that phosphating treatment can significantly improve the surface energy and wettability of magnesium alloy, and the surface energy of phosphated magnesium alloy was approximately 50% higher than that of abraded-only magnesium alloy. The single cantilever beam (SCB) test showed that the interfacial fracture energies of directly bonded MgFMLs based on abraded-only magnesium and abraded + phosphated magnesium were 650 J/m2 and 1030 J/m2, respectively, whereas the interfacial fracture energies of indirectly bonded MgFMLs were 1650 J/m2 and 2260 J/m2, respectively. Phosphating treatment and modified polypropylene interleaf were observed to improve the tensile strength and interfacial fracture toughness of MgFML. In addition, the rougher surface was more conducive to enhance the bonding strength and interfacial fracture toughness of MgFML.

[Effects of magnetron sputtered ZrN on the bonding strength of titanium porcelain].

PubMed

Zhou, Shu; Zhang, Wen-yan; Guang, Han-bing; Xia, Yang; Zhang, Fei-min

2009-04-01

To investigate the effect of magnetron sputtered ZrN on the bonding strength between a low-fusing porcelain (Ti/Vita titankeramik system) and commercially pure cast titanium. Sixteen specimens were randomly assigned to test group and control group (n=8). The control group received no surface treated. Magnetron sputtered ZrN film was deposited on the surface of specimens in the test group. Then the sixteen titanium-porcelain specimens were prepared in a rectangular shape and went through three-point bending test on a universal test machine. The bond strength of Ti/porcelain was recorded. The phase composition of the specimens was analyzed using X-ray diffraction (XRD). The interface at titanium and porcelain and the titanium surface after debonding were observed with a scanning electron microscopy (SEM) and analyzed using energy depressive spectrum (EDS). New phase of ZrN was found with XRD in the test group. Statistical analysis showed higher bond strength following ZrN surface treatment in the test group [(45.991+/-0.648) MPa] than that in the control group [(29.483+/-1.007) MPa] (P=0.000). Bonded ceramic could be observed in test group, the amount of bonded ceramic was more than that in the control group. No obvious bonded ceramic in control group was found. Magnetron sputtered ZrN can improve bond strength of Ti/Vita titankeramik system significantly.

Repeated bonding of fixed retainer increases the risk of enamel fracture.

PubMed

Chinvipas, Netrporn; Hasegawa, Yuh; Terada, Kazuto

2014-01-01

The aim of this study was to investigate the influences of repeated bonding, using 2 different orthodontic adhesive systems, on the shear bond strength (SBS) and the enamel surface morphology. Sixty premolars were divided into 2 groups (n = 30), and either Transbond XT (T group) or Fuji Ortho LC (F group) adhesives were used. SBS was measured 24 h after bonding, using a universal testing machine. Then, the enamel surfaces were investigated and the mode of failure was described using adhesive remnant index (ARI) scores. After each debonding, 10 teeth from each group were examined by scanning electron microscopy to determine the penetration of adhesives, the length of resin tags, and the state of the enamel surface. The other teeth were subjected to two more bonding/debonding procedures. In T group, the second debonding sequences had significantly higher bond strengths than the other sequences. The length of resin tags was greatest in the second debonding sequence, although there was no significant difference. In F group, the SBS increased with further rebonding and the failure mode tended towards cohesive failure. In both groups, the ARI scores increased with rebonding. Enamel loss could have occurred with both adhesives, although the surfaces appeared unchanged to the naked eye. From this study, we suggest that enamel damage caused by repeated bonding is of concern. To prevent bond failure, we should pay attention to the adhesion method used for bondable retainers.

Influence of nano-structured alumina coating on shear bond strength between Y-TZP ceramic and various dual-cured resin cements.

PubMed

Lee, Jung-Jin; Choi, Jung-Yun; Seo, Jae-Min

2017-04-01

The purpose of this study was to evaluate the effect of nano-structured alumina surface coating on shear bond strength between Y-TZP ceramic and various dual-cured resin cements. A total of 90 disk-shaped zirconia specimens (HASS CO., Gangneung, Korea) were divided into three groups by surface treatment method: (1) airborne particle abrasion, (2) tribochemicalsilica coating, and (3) nano-structured alumina coating. Each group was categorized into three subgroups of ten specimens and bonded with three different types of dual-cured resin cements. After thermocycling, shear bond strength was measured and failure modes were observed through FE-SEM. Two-way ANOVA and the Tukey's HSD test were performed to determine the effects of surface treatment method and type of cement on bond strength ( P <.05). To confirm the correlation of surface treatment and failure mode, the Chi-square test was used. Groups treated with the nanostructured alumina coating showed significantly higher shear bond strength compared to other groups treated with airborne particle abrasion or tribochemical silica coating. Clearfil SA Luting showed a significantly higher shear bond strength compared to RelyX ARC and RelyX Unicem. The cohesive failure mode was observed to be dominant in the groups treated with nano-structured alumina coating, while the adhesive failure mode was prevalent in the groups treated with either airborne particle abrasion or tribochemical silica coating. Nano-structured alumina coating is an effective zirconia surface treatment method for enhancing the bond strength between Y-TZP ceramic and various dual-cured resin cements.

Method for vacuum pressing electrochemical cell components

NASA Technical Reports Server (NTRS)

Andrews, Craig C. (Inventor); Murphy, Oliver J. (Inventor)

2004-01-01

Assembling electrochemical cell components using a bonding agent comprising aligning components of the electrochemical cell, applying a bonding agent between the components to bond the components together, placing the components within a container that is essentially a pliable bag, and drawing a vacuum within the bag, wherein the bag conforms to the shape of the components from the pressure outside the bag, thereby holding the components securely in place. The vacuum is passively maintained until the adhesive has cured and the components are securely bonded. The bonding agent used to bond the components of the electrochemical cell may be distributed to the bonding surface from distribution channels in the components. To prevent contamination with bonding agent, some areas may be treated to produce regions of preferred adhesive distribution and protected regions. Treatments may include polishing, etching, coating and providing protective grooves between the bonding surfaces and the protected regions.

Shear bond strength of a new self-adhering flowable composite resin for lithium disilicate-reinforced CAD/CAM ceramic material

PubMed Central

Sancakli, Hande Sar; Sancakli, Erkan; Eren, Meltem Mert; Ozel, Sevda; Yucel, Taner; Yildiz, Esra

2014-01-01

PURPOSE The purpose of this study was to evaluate and compare the effects of different surface pretreatment techniques on the surface roughness and shear bond strength of a new self-adhering flowable composite resin for use with lithium disilicate-reinforced CAD/CAM ceramic material. MATERIALS AND METHODS A total of one hundred thirty lithium disilicate CAD/CAM ceramic plates with dimensions of 6 mm × 4 mm and 3 mm thick were prepared. Specimens were then assigned into five groups (n=26) as follows: untreated control, coating with 30 µm silica oxide particles (Cojet™ Sand), 9.6% hydrofluoric acid etching, Er:YAG laser irradiation, and grinding with a high-speed fine diamond bur. A self-adhering flowable composite resin (Vertise Flow) was applied onto the pre-treated ceramic plates using the Ultradent shear bond Teflon mold system. Surface roughness was measured by atomic force microscopy. Shear bond strength test were performed using a universal testing machine at a crosshead speed of 1 mm/min. Surface roughness data were analyzed by one-way ANOVA and the Tukey HSD tests. Shear bond strength test values were analyzed by Kruskal-Wallis and Mann-Whitney U tests at α=.05. RESULTS Hydrofluoric acid etching and grinding with high-speed fine diamond bur produced significantly higher surface roughness than the other pretreatment groups (P<.05). Hydrofluoric acid etching and silica coating yielded the highest shear bond strength values (P<.001). CONCLUSION Self-adhering flowable composite resin used as repair composite resin exhibited very low bond strength irrespective of the surface pretreatments used. PMID:25551002

Bond strength of metal brackets bonded to a silica-based ceramic with light-cured adhesive : Influence of various surface treatment methods.

PubMed

Zhang, Zhe-Chen; Qian, Yu-Fen; Yang, Yi-Ming; Feng, Qi-Ping; Shen, Gang

2016-09-01

The purpose of this work was to evaluate the effects of several surface treatment methods on the shear bond strengths of metal brackets bonded to a silica-based ceramic with a light-cured adhesive. Silica-based ceramic (IPS Classic(®)) with glazed surfaces was cut into discs that were used as substrates. A total of 80 specimens were randomly divided into four groups according to the method used: 9.6 % hydrofluoric acid (group 1), 9.6 % hydrofluoric acid (HF) + silane coupling agent (group 2), sandblasting (aluminum trioxide, 50 μm) + silane (group 3), and tribochemical silica coating (CoJet™ sand, 30 μm) + silane (group 4). Brackets were bonded to the treated specimens with a light-cure adhesive (Transbond XT, 3 M Unitek). Shear bond strength was tested after bracket bonding, and the Adhesive Remnant Index (ARI) scores were quantified after debonding. Group 4 showed the highest bond strength (12.3 ± 1.0 MPa), which was not significantly different from that of group 3 (11.6 ± 1.2 MPa, P > 0.05); however, the bond strength of group 4 was substantially higher than that of group 2 (9.4 ± 1.1 MPa, P < 0.05). The shear bond strength of group 1 (3.1 ± 0.6 MPa, P< 0.05) was significantly lower than that of the other groups. Shear bond strengths exceeded the optimal range of ideal bond strength for clinical practice, except for the isolated HF group. HF acid etching followed by silane was the best suited method for bonding on IPS Classic(®). Failure modes in the sandblasting and silica-coating groups revealed signs of damaged ceramic surfaces.

Microwave Induced Direct Bonding of Single Crystal Silicon Wafers

NASA Technical Reports Server (NTRS)

Budraa, N. K.; Jackson, H. W.; Barmatz, M.

1999-01-01

We have heated polished doped single-crystal silicon wafers in a single mode microwave cavity to temperatures where surface to surface bonding occurred. The absorption of microwaves and heating of the wafers is attributed to the inclusion of n-type or p-type impurities into these substrates. A cylindrical cavity TM (sub 010) standing wave mode was used to irradiate samples of various geometry's at positions of high magnetic field. This process was conducted in vacuum to exclude plasma effects. This initial study suggests that the inclusion of impurities in single crystal silicon significantly improved its microwave absorption (loss factor) to a point where heating silicon wafers directly can be accomplished in minimal time. Bonding of these substrates, however, occurs only at points of intimate surface to surface contact. The inclusion of a thin metallic layer on the surfaces enhances the bonding process.

Surface chemical composition of human maxillary first premolar as assessed by X-ray photoelectron spectroscopy (XPS)

NASA Astrophysics Data System (ADS)

Lou, Leo; Nelson, Alan E.; Heo, Giseon; Major, Paul W.

2008-08-01

The surface chemical composition of dental enamel has been postulated as a contributing factor in the variation of bond strength of brackets bonded to teeth, and hence, the probability of bracket failure during orthodontic treatment. This study systematically investigated the chemical composition of 98 bonding surfaces of human maxillary premolars using X-ray photoelectron spectroscopy (XPS) to ascertain compositional differences between right and left first premolars. The major elements detected in all samples were calcium, phosphorus, oxygen, nitrogen and carbon. Surface compositions were highly variable between samples and several elements were found to be highly correlated. No statistical significant difference in the chemical composition of the maxillary right and left first premolars was found ( p > 0.05). Knowledge of the chemical composition of enamel surfaces will facilitate future studies that relate this information to the variations in dental enamel bond strength.

Structure and energetics of hydrogen-bonded networks of methanol on close packed transition metal surfaces

NASA Astrophysics Data System (ADS)

Murphy, Colin J.; Carrasco, Javier; Lawton, Timothy J.; Liriano, Melissa L.; Baber, Ashleigh E.; Lewis, Emily A.; Michaelides, Angelos; Sykes, E. Charles H.

2014-07-01

Methanol is a versatile chemical feedstock, fuel source, and energy storage material. Many reactions involving methanol are catalyzed by transition metal surfaces, on which hydrogen-bonded methanol overlayers form. As with water, the structure of these overlayers is expected to depend on a delicate balance of hydrogen bonding and adsorbate-substrate bonding. In contrast to water, however, relatively little is known about the structures methanol overlayers form and how these vary from one substrate to another. To address this issue, herein we analyze the hydrogen bonded networks that methanol forms as a function of coverage on three catalytically important surfaces, Au(111), Cu(111), and Pt(111), using a combination of scanning tunneling microscopy and density functional theory. We investigate the effect of intermolecular interactions, surface coverage, and adsorption energies on molecular assembly and compare the results to more widely studied water networks on the same surfaces. Two main factors are shown to direct the structure of methanol on the surfaces studied: the surface coverage and the competition between the methanol-methanol and methanol-surface interactions. Additionally, we report a new chiral form of buckled hexamer formed by surface bound methanol that maximizes the interactions between methanol monomers by sacrificing interactions with the surface. These results serve as a direct comparison of interaction strength, assembly, and chirality of methanol networks on Au(111), Cu(111), and Pt(111) which are catalytically relevant for methanol oxidation, steam reforming, and direct methanol fuel cells.

Direct quantitative identification of the “surface trans-effect”

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

Deimel, Peter S.; Bababrik, Reda M.; Wang, Bin

The strong parallels between coordination chemistry and adsorption on metal surfaces, with molecules and ligands forming local bonds to individual atoms within a metal surface, have been established over many years of study. The recently proposed “surface trans-effect” (STE) appears to be a further manifestation of this analogous behaviour, but so far the true nature of the modified molecule–metal surface bonding has been unclear. The STE could play an important role in determining the reactivities of surface-supported metal–organic complexes, influencing the design of systems for future applications. However, the current understanding of this effect is incomplete and lacks reliable structuralmore » parameters with which to benchmark theoretical calculations. Using X-ray standing waves, we demonstrate that ligation of ammonia and water to iron phthalocyanine (FePc) on Ag(111) increases the adsorption height of the central Fe atom; dispersion corrected density functional theory calculations accurately model this structural effect. The calculated charge redistribution in the FePc/H 2O electronic structure induced by adsorption shows an accumulation of charge along the σ-bonding direction between the surface, the Fe atom and the water molecule, similar to the redistribution caused by ammonia. Finally, this apparent σ-donor nature of the observed STE on Ag(111) is shown to involve bonding to the delocalised metal surface electrons rather than local bonding to one or more surface atoms, thus indicating that this is a true surface trans-effect.« less

Direct quantitative identification of the “surface trans-effect”

DOE PAGES

Deimel, Peter S.; Bababrik, Reda M.; Wang, Bin; ...

2016-06-09

The strong parallels between coordination chemistry and adsorption on metal surfaces, with molecules and ligands forming local bonds to individual atoms within a metal surface, have been established over many years of study. The recently proposed “surface trans-effect” (STE) appears to be a further manifestation of this analogous behaviour, but so far the true nature of the modified molecule–metal surface bonding has been unclear. The STE could play an important role in determining the reactivities of surface-supported metal–organic complexes, influencing the design of systems for future applications. However, the current understanding of this effect is incomplete and lacks reliable structuralmore » parameters with which to benchmark theoretical calculations. Using X-ray standing waves, we demonstrate that ligation of ammonia and water to iron phthalocyanine (FePc) on Ag(111) increases the adsorption height of the central Fe atom; dispersion corrected density functional theory calculations accurately model this structural effect. The calculated charge redistribution in the FePc/H 2O electronic structure induced by adsorption shows an accumulation of charge along the σ-bonding direction between the surface, the Fe atom and the water molecule, similar to the redistribution caused by ammonia. Finally, this apparent σ-donor nature of the observed STE on Ag(111) is shown to involve bonding to the delocalised metal surface electrons rather than local bonding to one or more surface atoms, thus indicating that this is a true surface trans-effect.« less

Effect of different surface treatments on the push-out bond strength of fiber post to root canal dentin.

PubMed

Demiryürek, Ebru Ozsezer; Külünk, Safak; Saraç, Duygu; Yüksel, Gözde; Bulucu, Bilinç

2009-08-01

The purpose of this study was to evaluate the effects of different surface treatments on the bond strength of a fiber post to dentin. Sixty extracted human maxillary incisor teeth were manually shaped with K-files using the step-back technique. ISO size 45 files were used as master apical files. Post spaces were prepared and then the root canals were subjected to one of the following 5 surface treatments: irrigation with 5% sodium hypochlorite (NaOCl); treatment with ethanol, ethyl acetate, and acetone-based cleansing agent (Sikko Tim); irrigation with 17% EDTA; etching with 37% orthophosphoric acid for 15 seconds; and etching with 10% citric acid for 15 seconds. Fiber posts were luted using self-etching/self-priming dual polymerized resin cement. From the coronal part of each root, 3 slides of 0.6-mm thickness were obtained. A push-out bond strength test was performed by a universal testing machine at a crosshead speed of 0.5 mm/min. Dentin surfaces were examined under scanning electron microscopy (SEM) after different surface treatments. Data were analyzed with a one-way analysis of variance (ANOVA) and Tukey HSD test. ANOVA revealed that canal surface treatment affected the bond strength (P < .001). The highest bond strength was obtained in the Sikko Tim group. The results also showed that surface treatment methods increased the bond strength to dentin when compared with the control group. Sikko Tim group was the more effective surface treatment agent compared with EDTA, orthophosphoric acid, citric acid, and control groups; however, it could not remove the smear layer and sealer remnants effectively on radicular dentin surfaces. Removal of the smear layer and opening of dentinal tubules are not recommended when a self-etching/self-priming adhesive system is used.

Study on contaminants on flight and other critical surfaces

NASA Technical Reports Server (NTRS)

Workman, Gary L.; Hughes, Charles; Arendale, William F.

1994-01-01

The control of surface contamination in the manufacture of space hardware can become a critical step in the production process. Bonded surfaces have been shown to be affected markedly by contamination. It is important to insure surface cleanliness by preventing contamination prior to bonding. In this vein techniques are needed in which the contamination which may affect bonding are easily found and removed. Likewise, if materials which are detrimental to bonding are not easily removed, then they should not be used in the manufacturing process. This study will address the development of techniques to locate and quantify contamination levels of particular contaminants. With other data becoming available from MSFC and its contractors, this study will also quantify how certain contaminants affect bondlines and how easily they are removed in manufacturing.

Anti-Arrhenius cleavage of covalent bonds in bottlebrush macromolecules on substrate

PubMed Central

Lebedeva, Natalia V.; Nese, Alper; Sun, Frank C.; Matyjaszewski, Krzysztof; Sheiko, Sergei S.

2012-01-01

Spontaneous degradation of bottlebrush macromolecules on aqueous substrates was monitored by atomic force microscopy. Scission of C─C covalent bonds in the brush backbone occurred due to steric repulsion between the adsorbed side chains, which generated bond tension on the order of several nano-Newtons. Unlike conventional chemical reactions, the rate of bond scission was shown to decrease with temperature. This apparent anti-Arrhenius behavior was caused by a decrease in the surface energy of the underlying substrate upon heating, which results in a corresponding decrease of bond tension in the adsorbed macromolecules. Even though the tension dropped minimally from 2.16 to 1.89 nN, this was sufficient to overpower the increase in the thermal energy (kBT) in the Arrhenius equation. The rate constant of the bond-scission reaction was measured as a function of temperature and surface energy. Fitting the experimental data by a perturbed Morse potential V = V0(1 - e-βx)2 - fx, we determined the depth and width of the potential to be V0 = 141 ± 19 kJ/mol and β-1 = 0.18 ± 0.03 Å, respectively. Whereas the V0 value is in reasonable agreement with the activation energy Ea = 80–220 kJ/mol of mechanical and thermal degradation of organic polymers, it is significantly lower than the dissociation energy of a C─C bond De = 350 kJ/mol. Moreover, the force constant Kx = 2β2V0 = 1.45 ± 0.36 kN/m of a strained bottlebrush along its backbone is markedly larger than the force constant of a C─C bond Kl = 0.44 kN/m, which is attributed to additional stiffness due to deformation of the side chains. PMID:22645366

Use of Several Thermal Analysis Techniques to Study the Cracking of a Nitrile Butadiene Rubber (NBR) Insulator on the Booster Separation Motor (BSM) of the Space Shuttle

NASA Technical Reports Server (NTRS)

Wingard, Charles D.

1999-01-01

Two different vendor rubber formulations have been used to produce the silica-filled NBR insulators for the BSM of each of the two Solid Rocket Boosters (SRBs) on the Space Shuttle. Each cured insulator is bonded to the BSM aluminum aft closure with an epoxy adhesive, and some of the curved areas in the rubber may have significant residual stresses. A number of recently bonded NBR insulators have shown fine surface cracks, and stressed insulator areas may be aging at a faster rate than unstressed areas, thus hastening the surface cracking. Thermal analysis data on both vendor insulators by Dynamic Mechanical Analysis (DMA) through a temperature/frequency sweep from 24 to 74 C have shown a higher flexural storage modulus and Arrhenius activation energy for the stressed area than for the unstressed area. Other thermal analysis techniques are being used to study the insulator surface vs. bulk interior for better understanding this anomaly.

Synthesis and characterization of bifunctional surfaces with tunable functional group pairs

NASA Astrophysics Data System (ADS)

Galloway, John M.; Kung, Mayfair; Kung, Harold H.

2016-06-01

Grafting of pairs of functional groups onto a silica surface was demonstrated by tethering both terminals of an organochlorosilane precursor molecule, Cl2(CH3)Si(CH2)4(CO)(OSi(i-Pr)2)(CH2)2Si(CH3)Cl2, that possess a cleavable silyl ester bond, onto a silica surface. Hydrolytic cleavage of the silyl ester bond of the grafted molecule resulted in the generation of organized pairs of carboxylic acid and organosilanol groups. This organosilanol moiety was easily transformed into other functional groups through condensation reactions to form, together with the neighboring acid group, pairs such as carboxylic acid/secondary amine, carboxylic acid/pyridine, and carboxylic acid/phosphine. In the case of carboxylic acid/amine pairing, there was evidence of the formation of amide. A sample grafted with amine-carboxylic acid pairs was three times more active (per free amine) than a sample without such pairs for the nitroaldol condensation of 4-nitrobenzaldehyde and nitromethane.

Palladium nanoparticles deposited on silanized halloysite nanotubes: synthesis, characterization and enhanced catalytic property

PubMed Central

Zhang, Yi; He, Xi; Ouyang, Jing; Yang, Huaming

2013-01-01

Palladium (Pd) nanoparticles were deposited on the surface of halloysite nanotubes (HNTs) modified with γ-aminopropyltriethoxysilane (APTES) to produce Pd/NH2-HNTs nanocomposites. The results indicated that Pd nanoparticles were densely immobilized onto NH2-HNTs with an average diameter of ~ 3 nm. The Pd distribution on the surface of silanized HNTs showed much more uniform, and the Pd nanoparticle size became smaller compared with those directly deposited onto HNTs without silanization. Systematic characterization demonstrated that APTES were chemically bonded onto HNTs, and further confirmed the bond formation between Pd and -NH2 groups, which could ensure the firm deposit of Pd nanoparticles on the surface of silanized HNTs. The as-synthesized Pd/NH2-HNTs exhibited an excellent catalytic activity in the liquid-phase hydrogenation of styrene to ethylbenzene with full conversion within 30 min. The mechanism of the deposit of Pd nanoparticles on silanized HNTs was also investigated. PMID:24126604

Surface topography and bond strengths of feldspathic porcelain prepared using various sandblasting pressures.

PubMed

Moravej-Salehi, Elham; Moravej-Salehi, Elahe; Valian, Azam

2016-11-01

The purpose of this study was to determine the bond strength of composite resin to feldspathic porcelain and its surface topography after sandblasting at different pressures. In this in vitro study, 68 porcelain disks were fabricated and randomly divided into four groups of 17. The porcelain surface in group 1 was etched with hydrofluoric acid. Groups 2, 3, and 4 were sandblasted at 2, 3 and 4 bars pressure, respectively. Surface topography of seven samples in each of the four groups was examined by a scanning electron microscope (SEM). The remaining 40 samples received the same silane agent, bonding agent, and composite resin and they were then subjected to 5000 thermal cycles and evaluated for shear bond strength. Data were analyzed using one-way anova. The mode of failure was determined using stereomicroscope and SEM. The highest shear bond strength was seen in group 4. however, statistically significant differences were not seen between the groups (P = 0.780). The most common mode of failure was cohesive in porcelain. The SEM showed different patterns of hydrofluoric acid etching and sandblasting. Increasing the sandblasting pressure increased the surface roughness of feldspathic porcelain but no difference in bond strength occurred. © 2015 Wiley Publishing Asia Pty Ltd.

Effects of ultraviolet irradiation on the bond strength of a composite resin adhered to stainless steel crowns.

PubMed

Baeza-Robleto, Selene J; Villa-Negrete, Dulce M; García-Contreras, René; Scougall-Vílchis, Rogelio J; Guadarrama-Quiroz, Luis J; Robles-Bermeo, Norma L

2013-01-01

A technique whereby the practitioner could improve the esthetic appearance of anterior stainless steel crowns (SSC) could provide a cost-effective alternative to more expensive commercially available preveneered SSCs, which may not be uniformly available. The purpose of this study was to evaluate the effects of ultraviolet (UV) irradiation of the metal crown surface on the shear bond strength of composite resin adhered to stainless steel crowns. Seventy extracted anterior bovine teeth randomly divided into 2 groups (n=35/group), were restored with primary maxillary left central incisor SSCs. Surface roughening with a green stone was performed on the labial surfaces, and the crowns of the experimental group were exposed to UV irradiation for 80 minutes. All samples were treated with metal-composite adhesive, followed by composite opaquer. Standardized composite blocks were bonded on the treated surfaces, and the shear bond strength was tested at 1 mm/minute. The values were recorded in MPa and statistically analyzed. The mean value of shear bond strength was significantly higher for the experimental group (19.7 ± 4.3 MPa) than the control group (16.3 ± 4.5 MPa). Ultraviolet irradiation of primary tooth stainless steel crowns significantly increased the shear bond strength of composite resin adhered to the facial surface.

Micellar electrokinetic chromatography with acid labile surfactant.

PubMed

Stanley, Bob; Lucy, Charles A

2012-02-24

We present a study of a degradable surfactant, sodium 4-[(2-methyl-2-undecyl-1,3-dioxolan-4-yl)methoxy]-1-propane sulfonate that is also known as an acid-labile surfactant (ALS). The performance of ALS as a pseudostationary phase is assessed and compared with established pseudostationary phases such as sodium dodecyl sulphate (SDS), volatile surfactants and polymeric micelles. ALS achieves separation efficiency of 100,000-145,000 theoretical plates and relative standard deviation (RSD) of electrophoretic mobility (n=5) of less than 3%. Retention factors with ALS are strongly correlated with those with SDS. This is shown by the R2=0.79 for all eleven analytes and an R2=0.992 for specifically the non-hydrogen bonding (NHB) analytes. However, ALS displays different selectivity than SDS for hydrogen bond donor (HBD) and hydrogen bond acceptor (HBA) solutes (R2 of 0.74 and 0.88, respectively). ALS is degraded to less surface active compounds in acidic solution. These less surface-active compounds are more compatible with the electrospray ionization mass spectrometry (ESI-MS). ALS has a half-life of 48 min at pH 4. ALS has the potential to couple micellar electrokinetic chromatography (MEKC) with the ESI-MS. ALS can be used as a pseudostationary phase for a high efficiency separation and later acid hydrolyzed to enable an ESI-MS analysis. Copyright © 2011 Elsevier B.V. All rights reserved.

Theoretical investigation of the reaction of Mn+ with ethylene oxide.

PubMed

Li, Yuanyuan; Guo, Wenyue; Zhao, Lianming; Liu, Zhaochun; Lu, Xiaoqing; Shan, Honghong

2012-01-12

The potential energy surfaces of Mn(+) reaction with ethylene oxide in both the septet and quintet states are investigated at the B3LYP/DZVP level of theory. The reaction paths leading to the products of MnO(+), MnO, MnCH(2)(+), MnCH(3), and MnH(+) are described in detail. Two types of encounter complexes of Mn(+) with ethylene oxide are formed because of attachments of the metal at different sites of ethylene oxide, i.e., the O atom and the CC bond. Mn(+) would insert into a C-O bond or the C-C bond of ethylene oxide to form two different intermediates prior to forming various products. MnO(+)/MnO and MnH(+) are formed in the C-O activation mechanism, while both C-O and C-C activations account for the MnCH(2)(+)/MnCH(3) formation. Products MnO(+), MnCH(2)(+), and MnH(+) could be formed adiabatically on the quintet surface, while formation of MnO and MnCH(3) is endothermic on the PESs with both spins. In agreement with the experimental observations, the excited state a(5)D is calculated to be more reactive than the ground state a(7)S. This theoretical work sheds new light on the experimental observations and provides fundamental understanding of the reaction mechanism of ethylene oxide with transition metal cations.

Synthesis and Characterization of Supramolecular Colloids.

PubMed

Vilanova, Neus; De Feijter, Isja; Voets, Ilja K

2016-04-22

Control over colloidal assembly is of utmost importance for the development of functional colloidal materials with tailored structural and mechanical properties for applications in photonics, drug delivery and coating technology. Here we present a new family of colloidal building blocks, coined supramolecular colloids, whose self-assembly is controlled through surface-functionalization with a benzene-1,3,5-tricarboxamide (BTA) derived supramolecular moiety. Such BTAs interact via directional, strong, yet reversible hydrogen-bonds with other identical BTAs. Herein, a protocol is presented that describes how to couple these BTAs to colloids and how to quantify the number of coupling sites, which determines the multivalency of the supramolecular colloids. Light scattering measurements show that the refractive index of the colloids is almost matched with that of the solvent, which strongly reduces the van der Waals forces between the colloids. Before photo-activation, the colloids remain well dispersed, as the BTAs are equipped with a photo-labile group that blocks the formation of hydrogen-bonds. Controlled deprotection with UV-light activates the short-range hydrogen-bonds between the BTAs, which triggers the colloidal self-assembly. The evolution from the dispersed state to the clustered state is monitored by confocal microscopy. These results are further quantified by image analysis with simple routines using ImageJ and Matlab. This merger of supramolecular chemistry and colloidal science offers a direct route towards light- and thermo-responsive colloidal assembly encoded in the surface-grafted monolayer.

Grafting of activated carbon cloths for selective adsorption

NASA Astrophysics Data System (ADS)

Gineys, M.; Benoit, R.; Cohaut, N.; Béguin, F.; Delpeux-Ouldriane, S.

2016-05-01

Chemical functionalization of an activated carbon cloth with 3-aminophthalic acid and 4-aminobenzoic acid groups by the in situ formation of the corresponding diazonium salt in aqueous acidic solution is reported. The nature and amount of selected functions on an activated carbon surface, in particular the grafted density, were determined by potentiometric titration, elemental analysis and X-ray photoelectron spectroscopy (XPS). The nanotextural properties of the modified carbon were explored by gas adsorption. Functionalized activated carbon cloth was obtained at a discrete grafting level while preserving interesting textural properties and a large porous volume. Finally, the grafting homogeneity of the carbon surface and the nature of the chemical bonding were investigated using Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) technique.

Use of spectroscopic techniques for uranium(VI)/montmorillonite interaction modeling.

PubMed

Kowal-Fouchard, A; Drot, R; Simoni, E; Ehrhardt, J J

2004-03-01

To experimentally identify both clay sorption sites and sorption equilibria and to understand the retention mechanisms at a molecular level, we have characterized the structure of hexavalent uranium surface complexes resulting from the interaction between the uranyl ions and the surface retention groups of a montmorillonite clay. We have performed laser-induced fluorescence spectroscopy (LIFS) and X-ray photoelectron spectroscopy (XPS) on uranyl ion loaded montmorillonite. These structural results were then compared to those obtained from the study of uranyl ions sorbed onto an alumina and also from U(VI) sorbed on an amorphous silica. This experimental approach allowed for a clear determination of the reactive surface sites of montmorillonite for U(VI) sorption. The lifetime values and the U4f XPS spectra of uranium(VI) sorbed on montmorillonite have shown that this ion is sorbed on both exchange and edge sites. The comparison of U(VI)/clay and U(VI)/oxide systems has determined that the interaction between uranyl ions and montmorillonite edge sites occurs via both [triple bond]AlOH and [triple bond]SiOH surface groups and involves three distinct surface complexes. The surface complexation modeling of the U(VI)/montmorillonite sorption edges was determined using the constant capacitance model and the above experimental constraints. The following equilibria were found to account for the uranyl sorption mechanisms onto montmorillonite for metal concentrations ranged from 10(-6) to 10(-3) M and two ionic strengths (0.1 and 0.5 M): 2[triple bond]XNa + UO2(2+) <==> ([triple bond]X)2UO2 + 2Na+, log K0(exch) = 3.0; [triple bond]Al(OH)2 + UO2(2+) <==> [triple bond]Al(OH)2UO2(2+), log K0(Al) = 14.9; [triple bond]Si(OH)2 + UO2(2+) <==> [triple bond]SiO2UO2 + 2H+, log K0(Si1) = -3.8; and [triple bond]Si(OH)2 + 3UO2(2+) + 5H2O <==> [triple bond]SiO2(UO2)3(OH)5- + 7H+, log K0(Si2) = -20.0.

A comparison of shear bond strength of orthodontic brackets bonded with four different orthodontic adhesives

PubMed Central

Sharma, Sudhir; Tandon, Pradeep; Nagar, Amit; Singh, Gyan P; Singh, Alka; Chugh, Vinay K

2014-01-01

Objectives: The objective of this study is to compare the shear bond strength (SBS) of stainless steel (SS) orthodontic brackets bonded with four different orthodontic adhesives. Materials and Methods: Eighty newly extracted premolars were bonded to 0.022 SS brackets (Ormco, Scafati, Italy) and equally divided into four groups based on adhesive used: (1) Rely-a-Bond (self-cure adhesive, Reliance Orthodontic Product, Inc., Illinois, USA), (2) Transbond XT (light-cure adhesive, 3M Unitek, CA, USA), (3) Transbond Plus (sixth generation self-etch primer, 3M Unitek, CA, USA) with Transbond XT (4) Xeno V (seventh generation self-etch primer, Dentsply, Konstanz, Germany) with Xeno Ortho (light-cure adhesive, Dentsply, Konstanz, Germany) adhesive. Brackets were debonded with a universal testing machine (Model No. 3382 Instron Corp., Canton, Mass, USA). The adhesive remnant index (ARI) was recordedIn addition, the conditioned enamel surfaces were observed under a scanning electron microscope (SEM). Results: Transbond XT (15.49 MPa) attained the highest bond strength. Self-etching adhesives (Xeno V, 13.51 MPa; Transbond Plus, 11.57 MPa) showed clinically acceptable SBS values and almost clean enamel surface after debonding. The analysis of variance (F = 11.85, P < 0.0001) and Chi-square (χ2 = 18.16, P < 0.05) tests revealed significant differences among groups. The ARI score of 3 (i.e., All adhesives left on the tooth) to be the most prevalent in Transbond XT (40%), followed by Rely-a-Bond (30%), Transbond Plus with Transbond XT (15%), and Xeno V with Xeno Ortho (10%). Under SEM, enamel surfaces after debonding of the brackets appeared porous when an acid-etching process was performed on the surfaces of Rely-a-Bond and Transbond XT, whereas with self-etching primers enamel presented smooth and almost clean surfaces (Transbond Plus and Xeno V group). Conclusion: All adhesives yielded SBS values higher than the recommended bond strength (5.9-7–8 MPa), Seventh generation self-etching primer Xeno V with Xeno Ortho showed clinically acceptable SBS and the least amount of residual adhesive left on the enamel surface after debonding. PMID:24987660

Significant Quantum Effects in Hydrogen Activation

DOE PAGES

Kyriakou, Georgios; Davidson, Erlend R. M.; Peng, Guowen; ...

2014-03-31

Dissociation of molecular hydrogen is an important step in a wide variety of chemical, biological, and physical processes. Due to the light mass of hydrogen, it is recognized that quantum effects are often important to its reactivity. However, understanding how quantum effects impact the reactivity of hydrogen is still in its infancy. Here, we examine this issue using a well-defined Pd/Cu(111) alloy that allows the activation of hydrogen and deuterium molecules to be examined at individual Pd atom surface sites over a wide range of temperatures. Experiments comparing the uptake of hydrogen and deuterium as a function of temperature revealmore » completely different behavior of the two species. The rate of hydrogen activation increases at lower sample temperature, whereas deuterium activation slows as the temperature is lowered. Density functional theory simulations in which quantum nuclear effects are accounted for reveal that tunneling through the dissociation barrier is prevalent for H 2 up to ~190 K and for D 2 up to ~140 K. Kinetic Monte Carlo simulations indicate that the effective barrier to H 2 dissociation is so low that hydrogen uptake on the surface is limited merely by thermodynamics, whereas the D 2 dissociation process is controlled by kinetics. These data illustrate the complexity and inherent quantum nature of this ubiquitous and seemingly simple chemical process. Here, examining these effects in other systems with a similar range of approaches may uncover temperature regimes where quantum effects can be harnessed, yielding greater control of bond-breaking processes at surfaces and uncovering useful chemistries such as selective bond activation or isotope separation.« less

Nanolubrication: patterned lubricating films using ultraviolet (UV) irradiation on hard disks.

PubMed

Zhang, J; Hsu, S M; Liew, Y F

2007-01-01

Nanolubrication is emerging to be the key technical barrier in many devices. One of the key attributes for successful device lubrication is self-sustainability using only several molecular layers. For single molecular species lubrication, one desires bonding strength and molecular mobility to repair the contact by diffusing back to the contact. One way to achieve this is the use of mask to shield the surface with a patterned surface texture, put a monolayer on the surface and induce bonding. Then re-deposit mobile molecules on the surface to bring the thickness back to the desired thickness. This paper describes the use of long wavelength UV irradiation (320-390 nm) to induce bonding of a perfluoropolyether (PFPE) on CN(x) disks for magnetic hard disk application. This allows the use of irradiation to control the degree of bonding on CN(x) coatings. The effect of induced bonding based on this wavelength was studied by comparing 100% mobile PFPE, 100% bonded PFPE, and a mixture of mobile and bonded PFPE in a series of laboratory tests. Using a lateral force microscope, a diamond-tipped atomic force microscope, and a ball-on-inclined plane apparatus, the friction and wear characteristics of these three cases were obtained. Results suggested that the mixed PFPE has the highest shear rupture strength.

Effect of different surface treatments on tensile bond strength of silicone-based soft denture liner.

PubMed

Akin, Hakan; Tugut, Faik; Mutaf, Burcu; Akin, Gulsah; Ozdemir, A Kemal

2011-11-01

Failure of the bond between the acrylic resin and resilient liner material is commonly encountered in clinical practice. The purpose of this study was to investigate the effect of different surface treatments (sandblasting, Er:YAG, Nd:YAG, and KTP lasers) on tensile bond strength of silicone-based soft denture liner. Polymethyl methacrylate test specimens were fabricated and each received one of eight surface treatments: untreated (control), sandblasted, Er:YAG laser irradiated, sandblasted + Er:YAG laser irradiated, Nd:YAG laser irradiated, sandblasted + Nd:YAG laser irradiated, KTP laser irradiated, and sandblasted + KTP laser irradiated. The resilient liner specimens (n = 15) were processed between two polymethyl methacrylate (PMMA) blocks. Bonding strength of the liners to PMMA were compared by tensile test with the use of a universal testing machine at a crosshead speed of 5 mm/min. Kruskal-Wallis and Wilcoxon tests were used to analyze the data (α = 0.05). Altering the polymethyl methacrylate surface by Er:YAG laser significantly increased the bond strengths in polymethyl methacrylate/silicone specimens, however, sandblasting before applying a lining material had a weakening effect on the bond. In addition, Nd:YAG and KTP lasers were found to be ineffective for increasing the strength of the bond.

Evaluation of Scotchbond Multipurpose and maleic acid as alternative methods of bonding orthodontic brackets.

PubMed

Olsen, M E; Bishara, S E; Damon, P; Jakobsen, J R

1997-05-01

Damage to the enamel surface during bonding and debonding of orthodontic brackets is a clinical concern. Alternative bonding methods that minimize enamel surface damage while maintaining a clinically useful bond strength is an aim of current research. The purpose of this study was to compare the effects on bond strength and bracket failure location of two adhesives (System 1+ and Scotchbond Multipurpose, 3M Dental Products Division) and two enamel conditioners (37% phosphoric acid and 10% maleic acid). Forty-eight freshly extracted human premolars were pumiced and divided into four groups of 12 teeth, and metal orthodontic brackets were attached to the enamel surface by one of four protocols: (1) System 1+ and phosphoric acid, (2) Scotchbond and phosphoric acid, (3) System 1+ and maleic acid, and (4) Scotchbond and maleic acid. After bracket attachment, the teeth were mounted in phenolic rings and stored in deionized water at 37 degrees C for 72 hours. A Zwick universal testing machine (Zwick GmbH & Co.) was used to determine shear bond strengths. The residual adhesive on the enamel surface was evaluated with the Adhesive Remnant Index. The analysis of variance was used to compare the four groups. Significance was predetermined at p < or = 0.05. The results indicated that there were no significant differences in bond strength among the four groups (p = 0.386). The results of the Chi square test, evaluating the residual adhesives on the enamel surfaces, revealed significant differences among the four groups (mean 2 = 0.005). A Duncan multiple range test revealed the difference occurred between the phosphoric acid and maleic acid groups, with maleic acid having bond failures at the enamel-adhesive interface. In conclusion, the use of Scotchbond Multipurpose and/or maleic acid does not significantly effect bond strength, however, the use of maleic acid resulted in an unfavorable bond failure location.

Durability of resin cement bond to aluminium oxide and zirconia ceramics after air abrasion and laser treatment.

PubMed

Foxton, Richard M; Cavalcanti, Andrea N; Nakajima, Masatoshi; Pilecki, Peter; Sherriff, Martyn; Melo, Luciana; Watson, Timothy F

2011-02-01

The erbium laser has been introduced for cutting enamel and dentin and may have an application in the surface modification of high-strength aluminum oxide and zirconia ceramics. The aim of this study was to evaluate the durability of the bond of conventional dual-cured resin cements to Procera Al(2)O(3) and zirconium oxide ceramics after surface treatment with air abrasion and erbium laser. One hundred twenty Al(2)O(3) and 120 zirconia specimens measuring 3 × 3 × 0.7 mm(3) were divided equally into three groups, and their surfaces treated as follows: either untreated (controls), air abraded with Al(2)O(3) particles, or erbium-laser-treated at a power setting of 200 mJ. The surface of each specimen was then primed and bonded with one of two dual-cured resin cements (either SCP-100 Ceramic Primer and NAC-100 or Monobond S and Variolink II) using a 1-mm thick Tygon tube mold with a 0.75-mm internal bore diameter. After 24 hours and 6 months of water storage at 37°C, a microshear bond strength test was performed at a crosshead speed of 1 mm/min. Surface morphology was examined using a confocal microscope, and failure modes were observed using an optical microscope. The data were analyzed using the Kaplan-Meier nonparametric survival analysis. In the case of zirconia, air abrasion and Erbium:yttrium-aluminum-garnet (Er:YAG) laser treatment of the ceramic surface resulted in a significant reduction in the bond strengths of both resin cements after 6 months water storage; however, when the zirconia surface was left untreated, the SCP-100/NAC-100 group did not significantly reduce in bond strength. In the case of alumina, no treatment, air abrasion and Er:YAG laser treatment of the surface led to no significant reduction in the bond strengths of the three SCP-100/NAC-100 groups after 6 months water storage, whereas all three Monobond S/Variolink II groups showed a significant reduction. Er:YAG laser treatment of the zirconia surface did not result in a durable resin cement/ceramic bond; however, a durable bond between a conventional dual-cured resin cement and Procera All Ceram and Procera All Zirkon was formed using a ceramic primer containing the phosphate monomer, MDP, without any additional surface treatment. © 2011 by The American College of Prosthodontists.

Bonding by Hydroxide-Catalyzed Hydration and Dehydration

NASA Technical Reports Server (NTRS)

Gwo, Dz-Hung

2008-01-01

A simple, inexpensive method for bonding solid objects exploits hydroxide-catalyzed hydration and dehydration to form silicate-like networks in thin surface and interfacial layers between the objects. The method can be practiced at room temperature or over a wide range of temperatures. The method was developed especially to enable the formation of precise, reliable bonds between precise optical components. The bonds thus formed exhibit the precision and transparency of bonds formed by the conventional optical-contact method and the strength and reliability of high-temperature frit bonds. The method also lends itself to numerous non-optical applications in which there are requirements for precise bonds and/or requirements for bonds, whether precise or imprecise, that can reliably withstand severe environmental conditions. Categories of such non-optical applications include forming composite materials, coating substrates, forming laminate structures, and preparing objects of defined geometry and composition. The method is applicable to materials that either (1) can form silicate-like networks in the sense that they have silicate-like molecular structures that are extensible into silicate-like networks or (2) can be chemically linked to silicate-like networks by means of hydroxide-catalyzed hydration and dehydration. When hydrated, a material of either type features surface hydroxyl (-OH) groups. In this method, a silicate-like network that bonds two substrates can be formed either by a bonding material alone or by the bonding material together with material from either or both of the substrates. Typically, an aqueous hydroxide bonding solution is dispensed and allowed to flow between the mating surfaces by capillary action. If the surface figures of the substrates do not match precisely, bonding could be improved by including a filling material in the bonding solution. Preferably, the filling material should include at least one ingredient that can be hydrated to have exposed hydroxyl groups and that can be chemically linked, by hydroxide catalysis, to a silicate-like network. The silicate-like network could be generated in situ from the filling material and/or substrate material, or could be originally present in the bonding material.

Enhanced bonding property of cold-sprayed Zn-Al coating on interstitial-free steel substrate with a nanostructured surface layer

NASA Astrophysics Data System (ADS)

Liang, Y. L.; Wang, Z. B.; Zhang, J.; Zhang, J. B.; Lu, K.

2016-11-01

By means of surface mechanical attrition treatment (SMAT), a gradient nanostructured surface layer was fabricated on a hot-rolled interstitial-free steel plate. A Zn-Al coating was subsequently deposited on the SMAT sample by using cold spray process. The bonding property of the coating on the SMAT substrate was compared with that on the coarse-grained (CG) sample. Stud-pull tests showed that the bonding strength in the as-sprayed SMAT sample is ∼30% higher than that in the as-sprayed CG sample. No further improvement in bonding strength was achieved in the coated SMAT sample after annealing at 400 °C, mostly due to the formation of cracks and intermetallic compounds at the coating/substrate interface in an earlier stage (<30 min) and in a final stage (>90 min), respectively. The enhanced bonding property of the Zn-Al coating on the SMAT sample might be related with the promoted atomic diffusion and hardness in the nanostructured surface layer.

First evidence of bioflocculant from Shinella albus with flocculation activity on harvesting of Chlorella vulgaris biomass.

PubMed

Li, Yi; Xu, Yanting; Liu, Lei; Jiang, Xiaobing; Zhang, Kun; Zheng, Tianling; Wang, Hailei

2016-10-01

Bioflocculant from Shinella albus xn-1 could be used to harvest energy-producing microalga Chlorella vulgaris biomass for the first time. In this study, we investigated the flocculation activity and mode of strain xn-1, the characteristics of bioflocculant, the effect of flocculation conditions and optimized the flocculation efficiency. The results indicated that strain xn-1 exhibited flocculation activity through secreting bioflocculant; the bioflocculant with high thermal stability, pH stability and low molecular weight was proved to be not protein and polysaccharide, and flocculation active component was confirmed to contain triple bond and cumulated double bonds; algal pH, temperature and metal ions showed great impacts on the flocculation efficiency of bioflocculant; the maximum flocculation activity of bioflocculant reached 85.65% after the response surface optimization. According to the results, the bioflocculant from S. albus xn-1 could be a good potential in applications for high-efficiency harvesting of microalgae. Copyright © 2016 Elsevier Ltd. All rights reserved.

Deposition of gold nano-particles and nano-layers on polyethylene modified by plasma discharge and chemical treatment

NASA Astrophysics Data System (ADS)

Švorčík, V.; Chaloupka, A.; Záruba, K.; Král, V.; Bláhová, O.; Macková, A.; Hnatowicz, V.

2009-08-01

Polyethylene (PE) was treated in Ar plasma discharge and then grafted from methanol solution of 1,2-ethanedithiol to enhance adhesion of gold nano-particles or sputtered gold layers. The modified PE samples were either immersed into freshly prepared colloid solution of Au nano-particles or covered by sputtered, 50 nm thick gold nano-layer. Properties of the plasma modified, dithiol grafted and gold coated PE were studied using XPS, UV-VIS, AFM, EPR, RBS methods and nanoindentation. It was shown that the plasma treatment results in degradation of polymer chain, creation of excessive free radicals and conjugated double bonds. After grafting with 1,2-ethanedithiol the concentration of free radicals declined but the concentration of double bonds remained unchanged. Plasma treatment changes PE surface morphology and increases surface roughness too. Another significant change in the surface morphology and roughness was observed after deposition of Au nano-particles. The presence of Au on the sample surface after the coating with Au nano-particles was proved by XPS and RBS methods. Nanoindentation measurements shown that the grafting of plasma activated PE surface with dithiol increases significantly adhesion of sputtered Au nano-layer.

The adsorption of human serum albumin (HSA) on CO2 laser modified magnesia partially stabilised zirconia (MgO-PSZ).

PubMed

Hao, L; Lawrence, J

2004-03-15

Magnesia partially stabilised zirconia (MgO-PSZ), a bioinert ceramic, exhibits high mechanical strength, excellent corrosion resistance and good biocompatibility, but it does not naturally form a direct bond with bone resulting in a lack of osteointegration. The surface properties and structure of a biomaterial play an essential role in protein adsorption. As such, changes in the surface properties and structure of biomaterials may in turn alter their bioactivity. So, the fundamental reactions at the interface of biomaterials and tissue should influence their integration and bone-bonding properties. To this end, CO2 laser radiation was used to modify the surface roughness, crystal size, phase and surface energy of the MgO-PSZ. The basic mechanisms active in improving the surface energy were analysed and found to be the phase change and augmented surface area. The adsorption of human serum albumin (HSA), which is a non-cell adhesive protein, was compared on the untreated and CO2 laser modified MgO-PSZ. It was observed that the thickness of the adsorbed HSA decreased as the polar surface energy of the MgO-PSZ increased, indicating that HSA adsorbed more effectively on the hydrophobic MgO-PSZ surface than the hydrophilic surface. The current study provided important information regarding protein-biomaterial interactions and possible mechanisms behind the cell interaction and in vivo behaviour.

On the nature of the {SO2-4}/{Ag(111) } and {SO2-4}/{Au(111) } surface bonding

NASA Astrophysics Data System (ADS)

Patrito, E. M.; Olivera, P. Paredes; Sellers, Harrell

1997-05-01

The nature of sulfate-Ag(111) and sulfate-Au(111) surface bonding has been investigated at the SCF + MP2 level of theory. Convergence of binding energy with cluster size is investigated and, unlike neutral adsorbates, large clusters are required in order to obtain reliable binding energies. In the most stable adsorption mode, sulfate binds to the surface via three oxygen atoms (C 3v symmetry) with a binding energy of 159.3 kcal/mol on Ag(111) and 143.9 kcal/mol on Au(111). The geometry of adsorbed sulfate was optimized at the SCF level. While the bond length between sulfur and the oxygens coordinated to the surface increases, the sulfur-uncoordinated oxygen bond length decreases. This weakening and strengthening of the bonds, respectively, is consistent with bond order conservation in adsorbates on metal surfaces. Although a charge transfer of 0.4 electrons towards the metal is observed, the adsorbate remains very much sulfate-like. The molecular orbital analysis indicates that there is also some charge back-donation towards unoccupied orbitals of sulfate. This results in an increased electron density around sulfur as revealed in the electron density difference maps. Analysis of the Laplacian of the charge density of free sulfate provides a suitable framework to understand the nature of the different charge transfer processes and allows us to establish some similarities with the CO- and SO 2-metal bondings.

Article coated with flash bonded superhydrophobic particles

DOEpatents

Simpson, John T [Clinton, TN; Blue, Craig A [Knoxville, TN; Kiggans, Jr., James O [Oak Ridge, TN

2010-07-13

A method of making article having a superhydrophobic surface includes: providing a solid body defining at least one surface; applying to the surface a plurality of diatomaceous earth particles and/or particles characterized by particle sizes ranging from at least 100 nm to about 10 .mu.m, the particles being further characterized by a plurality of nanopores, wherein at least some of the nanopores provide flow through porosity, the particles being further characterized by a plurality of spaced apart nanostructured features that include a contiguous, protrusive material; flash bonding the particles to the surface so that the particles are adherently bonded to the surface; and applying a hydrophobic coating layer to the surface and the particles so that the hydrophobic coating layer conforms to the nanostructured features.

Direct Wafer Bonding and Its Application to Waveguide Optical Isolators

PubMed Central

Mizumoto, Tetsuya; Shoji, Yuya; Takei, Ryohei

2012-01-01

This paper reviews the direct bonding technique focusing on the waveguide optical isolator application. A surface activated direct bonding technique is a powerful tool to realize a tight contact between dissimilar materials. This technique has the potential advantage that dissimilar materials are bonded at low temperature, which enables one to avoid the issue associated with the difference in thermal expansion. Using this technique, a magneto-optic garnet is successfully bonded on silicon, III-V compound semiconductors and LiNbO3. As an application of this technique, waveguide optical isolators are investigated including an interferometric waveguide optical isolator and a semileaky waveguide optical isolator. The interferometric waveguide optical isolator that uses nonreciprocal phase shift is applicable to a variety of waveguide platforms. The low refractive index of buried oxide layer in a silicon-on-insulator (SOI) waveguide enhances the magneto-optic phase shift, which contributes to the size reduction of the isolator. A semileaky waveguide optical isolator has the advantage of large fabrication-tolerance as well as a wide operation wavelength range. PMID:28817020

Shear bond strength of orthodontic brackets and disinclusion buttons: effect of water and saliva contamination.

PubMed

Sfondrini, Maria Francesca; Fraticelli, Danilo; Gandini, Paola; Scribante, Andrea

2013-01-01

The aim of this study was to assess the effect of water and saliva contamination on the shear bond strength and failure site of orthodontic brackets and lingual buttons. 120 bovine permanent mandibular incisors were randomly divided into 6 groups of 20 specimens each. Both orthodontic brackets and disinclusion buttons were tested under three different enamel surface conditions: (a) dry, (b) water contamination, and (c) saliva contamination. Brackets and buttons were bonded to the teeth and subsequently tested using a Instron universal testing machine. Shear bond strength values and adhesive failure rate were recorded. Statistical analysis was performed using ANOVA and Tukey tests (strength values) and Chi squared test (ARI Scores). Noncontaminated enamel surfaces showed the highest bond strengths for both brackets and buttons. Under water and saliva contamination orthodontic brackets groups showed significantly lower shear strengths than disinclusion buttons groups. Significant differences in debond locations were found among the groups under the various enamel surface conditions. Water and saliva contamination of enamel during the bonding procedure lowers bond strength values, more with orthodontic brackets than with disinclusion buttons.

Bone bonding strength of diamond-structured porous titanium-alloy implants manufactured using the electron beam-melting technique.

PubMed

Hara, Daisuke; Nakashima, Yasuharu; Sato, Taishi; Hirata, Masanobu; Kanazawa, Masayuki; Kohno, Yusuke; Yoshimoto, Kensei; Yoshihara, Yusuke; Nakamura, Akihiro; Nakao, Yumiko; Iwamoto, Yukihide

2016-02-01

The present study examined the bone bonding strength of diamond-structured porous titanium-alloy (Porous-Ti-alloy) manufactured using the electron beam-melting technique in comparison with fiber mesh-coated or rough-surfaced implants. Cylindrical implants with four different pore sizes (500, 640, 800, and 1000μm) of Porous-Ti-alloy, titanium fiber mesh (FM), and surfaces roughened by titanium arc spray (Ti-spray) were implanted into the distal femur of rabbits. Bone bonding strength and histological bone ingrowth were evaluated at 4 and 12weeks after implantation. The bone bonding strength of Porous-Ti-alloy implants (640μm pore size) increased over time from 541.4N at 4weeks to 704.6N at 12weeks and was comparable to that of FM and Ti-spray implants at both weeks. No breakage of the porous structure after mechanical testing was found with Porous-Ti-alloy implants. Histological bone ingrowth that increased with implantation time occurred along the inner structure of Porous-Ti-alloy implants. There was no difference in bone ingrowth in Porous-Ti-alloy implants with pore sizes among 500, 640, and 800μm; however, less bone ingrowth was observed with the 1000μm pore size. These results indicated Porous-Ti-alloy implants with pore size under 800μm provided biologically active and mechanically stable surface for implant fixation to bone, and had potential advantages for weight bearing orthopedic implants such as acetabular cups. Copyright © 2015 Elsevier B.V. All rights reserved.

Effect of surface treatments on shear bond strength of resin composite bonded to CAD/CAM resin-ceramic hybrid materials

PubMed Central

Güngör, Merve Bankoğlu; Bal, Bilge Turhan; Ünver, Senem; Doğan, Aylin

2016-01-01

PURPOSE The purpose of this study was to assess the effect of surface treatments on shear bond strength of resin composite bonded to thermocycled and non-thermocycled CAD/CAM resin-ceramic hybrid materials. MATERIALS AND METHODS 120 specimens (10×10×2 mm) from each material were divided into 12 groups according to different surface treatments in combination with thermal aging procedures. Surface treatment methods were airborne-particle abrasion (abraded with 50 micron alumina particles), dry grinding (grinded with 125 µm grain size bur), and hydrofluoric acid (9%) and silane application. According to the thermocycling procedure, the groups were assigned as non-thermocycled, thermocycled after packing composites, and thermocycled before packing composites. The average surface roughness of the non-thermocycled specimens were measured after surface treatments. After packing composites and thermocycling procedures, shear bond strength (SBS) of the specimens were tested. The results of surface roughness were statistically analyzed by 2-way Analysis of Variance (ANOVA), and SBS results were statistically analyzed by 3-way ANOVA. RESULTS Surface roughness of GC were significantly lower than that of LU and VE (P<.05). The highest surface roughness was observed for dry grinding group, followed by airborne particle abraded group (P<.05). Comparing the materials within the same surface treatment method revealed that untreated surfaces generally showed lower SBS values. The values of untreated LU specimens showed significantly different SBS values compared to those of other surface treatment groups (P<.05). CONCLUSION SBS was affected by surface treatments. Thermocycling did not have any effect on the SBS of the materials except acid and silane applied GC specimens, which were subjected to thermocycling before packing of the composite resin. PMID:27555894

PREFACE Surface Modifications of Diamond and Related Materials (Session D, E-MRS Spring Meeting)

NASA Astrophysics Data System (ADS)

Nebel, Christoph E.

2010-11-01

This special issue contains selected papers which were presented at the E-MRS Symposium BIOMATERIALS, SENSORS & SURFACES, D: 'Surface modifications of diamond and related materials' which was held on 7-9 June 2010 in Strasbourg (France). With about 54 oral and poster presentations given from teams all over the world it was a very interesting, dense and lively meeting. The symposium focused on chemical modifications applied to graft surfaces of diamond, nano-diamond particles, diamond-like carbon, graphene, graphite and carbon nano-tubes with linker molecular layers for realization of bio-sensors, bio-markers, separation techniques, and switchable chemical links. Presented techniques span spontaneous bonding to photo-chemical attachment, electrochemical modifications, to Suzuki-coupling of aryl molecules. Special attention was drawn to mechanisms driving bonding kinetics such as electron transfer reactions, hydrogen cleavage reactions by nucleophilic molecules and growths schemas which vary from correlated two-dimensional chain reactions to three-dimensional cross polymerization. Hydrogen terminations, surface defects, surface roughness and atomic arrangements of surface carbon atoms were of interest to elucidate bonding mechanisms. In addition, bonding stability, either of linker molecules or of complex functionalized surfaces with DNA, proteins and enzymes was discussed by several speakers as well as details of the electronic interfaces between solid transducers and bio-layers. Here the characterization of surface and interface defect densities, of Fermi level pinning and of electron transfer rates was a major topic. Miniaturization of sensor area and application of new detection schemas was discussed. Diamond nano-particles which are increasingly used as biomarkers in drug delivery experiments also attracted attention. The organizers express our gratitude to the international members of the scientific committee who actively contributed to ensure an attractive program in proposing invited speakers. Finally, our symposium would not have been successful without the strong involvement and implication of the EMRS headquarter especially P Siffert, T Lippert, S Schoeffter and C Kocher. They will all find here our sincere thanks. Christoph E Nebel (Chair) Fraunhofer-Institute for Applied Solid State Physics (IAF), Germany Takako Nakamura National Institute of Advanced Industrial Science and Technology (AIST), Japan Philippe Bergonzo CEA-LIST, France John Foord University of Oxford, United Kingdom Kian-Ping Loh National University of Singapore, Singapore

A study of laser surface treatment in bonded repair of composite aircraft structures.

PubMed

Li, Shaolong; Sun, Ting; Liu, Chang; Yang, Wenfeng; Tang, Qingru

2018-03-01

Surface pre-treatment is one of the key processes in bonded repair of aircraft carbon fibre reinforced polymer composites. This paper investigates the surface modification of physical and chemical properties by laser ablation and conventional polish treatment techniques. Surface morphology analysed by laser scanning confocal microscopy and scanning electron microscopy showed that a laser-treated surface displayed higher roughness than that of a polish-treated specimen. The laser-treated laminate exhibited more functional groups in the form of O 1 s/C 1 s atomic ratio of 30.89% for laser-treated and 20.14% for polish-treated as evidenced by X-ray photoelectron spectroscopy observation. Contact angle goniometry demonstrated that laser treatment can provide increased surface free energy and wettability. In the light of mechanical interlocking, molecular bonding and thermodynamics theories on adhesion, laser etching process displayed enhanced bonding performance relative to the polishing surface treatment. These properties resulted in an increased single lap shear strength and a cohesive failure mode for laser etching while an adhesive failure mode occurred in polish-treated specimen.

A study of laser surface treatment in bonded repair of composite aircraft structures

NASA Astrophysics Data System (ADS)

Li, Shaolong; Sun, Ting; Liu, Chang; Yang, Wenfeng; Tang, Qingru

2018-03-01

Surface pre-treatment is one of the key processes in bonded repair of aircraft carbon fibre reinforced polymer composites. This paper investigates the surface modification of physical and chemical properties by laser ablation and conventional polish treatment techniques. Surface morphology analysed by laser scanning confocal microscopy and scanning electron microscopy showed that a laser-treated surface displayed higher roughness than that of a polish-treated specimen. The laser-treated laminate exhibited more functional groups in the form of O 1 s/C 1 s atomic ratio of 30.89% for laser-treated and 20.14% for polish-treated as evidenced by X-ray photoelectron spectroscopy observation. Contact angle goniometry demonstrated that laser treatment can provide increased surface free energy and wettability. In the light of mechanical interlocking, molecular bonding and thermodynamics theories on adhesion, laser etching process displayed enhanced bonding performance relative to the polishing surface treatment. These properties resulted in an increased single lap shear strength and a cohesive failure mode for laser etching while an adhesive failure mode occurred in polish-treated specimen.

A study of laser surface treatment in bonded repair of composite aircraft structures

PubMed Central

Sun, Ting; Liu, Chang; Yang, Wenfeng; Tang, Qingru

2018-01-01

Surface pre-treatment is one of the key processes in bonded repair of aircraft carbon fibre reinforced polymer composites. This paper investigates the surface modification of physical and chemical properties by laser ablation and conventional polish treatment techniques. Surface morphology analysed by laser scanning confocal microscopy and scanning electron microscopy showed that a laser-treated surface displayed higher roughness than that of a polish-treated specimen. The laser-treated laminate exhibited more functional groups in the form of O 1 s/C 1 s atomic ratio of 30.89% for laser-treated and 20.14% for polish-treated as evidenced by X-ray photoelectron spectroscopy observation. Contact angle goniometry demonstrated that laser treatment can provide increased surface free energy and wettability. In the light of mechanical interlocking, molecular bonding and thermodynamics theories on adhesion, laser etching process displayed enhanced bonding performance relative to the polishing surface treatment. These properties resulted in an increased single lap shear strength and a cohesive failure mode for laser etching while an adhesive failure mode occurred in polish-treated specimen. PMID:29657748

Ceramic microstructure and adhesion

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1984-01-01

When a ceramic is brought into contact with a ceramic, a polymer, or a metal, strong bond forces can develop between the materials. The bonding forces will depend upon the state of the surfaces, cleanliness and the fundamental properties of the two solids, both surface and bulk. Adhesion between a ceramic and another solid are discussed from a theoretical consideration of the nature of the surfaces and experimentally by relating bond forces to interface resulting from solid state contact. Surface properties of ceramics correlated with adhesion include, orientation, reconstruction and diffusion as well as the chemistry of the surface specie. Where a ceramic is in contact with a metal their interactive chemistry and bond strength is considered. Bulk properties examined include elastic and plastic behavior in the surficial regions, cohesive binding energies, crystal structures and crystallographic orientation. Materials examined with respect to interfacial adhesive interactions include silicon carbide, nickel zinc ferrite, manganese zinc ferrite, and aluminum oxide. The surfaces of the contacting solids are studied both in the atomic or molecularly clean state and in the presence of selected surface contaminants.

Ceramic microstructure and adhesion

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1985-01-01

When a ceramic is brought into contact with a ceramic, a polymer, or a metal, strong bond forces can develop between the materials. The bonding forces will depend upon the state of the surfaces, cleanliness and the fundamental properties of the two solids, both surface and bulk. Adhesion between a ceramic and another solid are discussed from a theoretical consideration of the nature of the surfaces and experimentally by relating bond forces to interface resulting from solid state contact. Surface properties of ceramics correlated with adhesion include, orientation, reconstruction and diffusion as well as the chemistry of the surface specie. Where a ceramic is in contact with a metal their interactive chemistry and bond strength is considered. Bulk properties examined include elastic and plastic behavior in the surficial regions, cohesive binding energies, crystal structures and crystallographic orientation. Materials examined with respect to interfacial adhesive interactions include silicon carbide, nickel zinc ferrite, manganese zinc ferrite, and aluminum oxide. The surfaces of the contacting solids are studied both in the atomic or molecularly clean state and in the presence of selected surface contaminants.

Fracture surface analysis in composite and titanium bonding

NASA Technical Reports Server (NTRS)

Devilbiss, T. A.; Wightman, J. P.

1985-01-01

To understand the mechanical properties of fiber-reinforced composite materials, it is necessary to understand the mechanical properties of the matrix materials and of the reinforcing fibers. Another factor that can affect the mechanical properties of a composite material is the interaction between the fiber and the matrix. In general, composites with strong fiber matrix bonding will give higher modulus, lower toughness composites. Composites with weak bonding will have a lower modulus and more ductility. The situation becomes a bit more complex when all possibilities are examined. To be considered are the following: the properties of the surface layer on the fiber, the interactive forces between polymer and matrix, the surface roughness and porosity of the fiber, and the morphology of the matrix polymer at the fiber surface. In practice, the surface of the fibers is treated to enhance the mechanical properties of a composite. These treatments include anodization, acid etching, high temperature oxidation, and plasma oxidation, to name a few. The goal is to be able to predict the surface properties of carbon fibers treated in various ways, and then to relate surface properties to fiber matrix bonding.

The effect of dentine surface preparation and reduced application time of adhesive on bonding strength.

PubMed

Saikaew, Pipop; Chowdhury, A F M Almas; Fukuyama, Mai; Kakuda, Shinichi; Carvalho, Ricardo M; Sano, Hidehiko

2016-04-01

This study evaluated the effects of surface preparation and the application time of adhesives on the resin-dentine bond strengths with universal adhesives. Sixty molars were cut to exposed mid-coronal dentine and divided into 12 groups (n=5) based on three factors; (1) adhesive: G-Premio Bond (GP, GC Corp., Tokyo, Japan), Clearfil Universal Bond (CU, Kuraray Noritake Dental Inc., Okayama, Japan) and Scotchbond Universal Adhesive (SB, 3M ESPE, St. Paul, MN, USA); (2) smear layer preparation: SiC paper ground dentine or bur-cut dentine; (3) application time: shortened time or as manufacturer's instruction. Fifteen resin-dentine sticks per group were processed for microtensile bond strength test (μTBS) according to non-trimming technique (1mm(2)) after storage in distilled water (37 °C) for 24h. Data were analyzed by three-way ANOVA and Dunnett T3 tests (α=0.05). Fractured surfaces were observed under scanning electron microscope (SEM). Another 12 teeth were prepared and cut into slices for SEM examination of bonded interfaces. μTBS were higher when bonded to SiC-ground dentine according to manufacturer's instruction. Bonding to bur-cut dentine resulted in significantly lower μTBS (p<0.000). Shortening the application time resulted in significantly lower bond strength for CU on SiC and GP on bur-cut dentine. SEM of fractured surfaces revealed areas with a large amount of porosities at the adhesive resin interface. This was more pronounced when adhesives were bonded with a reduced application time and on bur cut dentine. The performance of universal adhesives can be compromised on bur cut dentine and when applied with a reduced application time. Copyright © 2016 Elsevier Ltd. All rights reserved.

Influence of laser structuring of PEEK, PEEK-GF30 and PEEK-CF30 surfaces on the shear bond strength to a resin cement.

PubMed

Henriques, Bruno; Fabris, Douglas; Mesquita-Guimarães, Joana; Sousa, Anne C; Hammes, Nathalia; Souza, Júlio C M; Silva, Filipe S; Fredel, Márcio C

2018-08-01

The aim of this study was to evaluate the influence of a surface conditioning technique using laser ablation and acid etching on PEEK substrate on its bonding strength to a resin cement. Cylindrical specimens of unfilled PEEK, 30% glass fiber reinforced PEEK and 30% carbon fiber reinforced PEEK were separated in four groups according to the following surface treatments: acid etching with H 2 SO 4 , laser ablation with 200 µm holes spaced 400 µm apart (D2E4), laser ablation with 200 µm holes spaced 600 µm apart (D2E6), and laser ablation (D2E4) followed by acid etching. A dual-curing resin cement (Allcem CORE) was then applied to the PEEK surface. Specimens were aged in distilled water at 37 °C for 24 h. Shear bond strength tests were performed to the fracture of the samples. Two-way ANOVA statistical analysis was performed with a significance level of 0.05. Scanning electron microscopy analysis was performed to analyse the conditioned and fracture surfaces. SEM images of the test interfaces showed that the resin cement could not flow in the holes designed by the laser ablation on the PEEK surface. The shear bond strength of PEEK to resin cement was not improved by the surface modification of the PEEK. Also, there was a statistically significant decrease in shear bond strength for unfilled PEEK specimens. On carbon or glass reinforced PEEK, the change was not significant. SEM images of the fracture surfaces revealed that the failure mode was mainly adhesive. Although laser ablation promoted the PEEK surface modification by the formation of retentive holes, the test resin cement could not thoroughly flow on the rough modified surfaces to establish an effective mechanical interlocking. That negatively affected the shear bonding strength of PEEK to the resin cement. Further studies should be carried out to increase the bonding between PEEK and resin cements. Copyright © 2018 Elsevier Ltd. All rights reserved.

GROUT-CONCRETE INTERFACE BOND PERFORMANCE: EFFECT OF INTERFACE MOISTURE ON THE TENSILE BOND STRENGTH AND GROUT MICROSTRUCTURE.

PubMed

De la Varga, I; Muñoz, J F; Bentz, D P; Spragg, R P; Stutzman, P E; Graybeal, B A

2018-05-01

Bond between two cementitious materials is crucial in applications such as repairs, overlays, and connections of prefabricated bridge elements (PBEs), to name just a few. It is the latter that has special interest to the authors of this paper. After performing a dimensional stability study on grout-like materials commonly used as connections between PBEs, it was observed that the so-called 'non-shrink' cementitious grouts showed a considerable amount of early-age shrinkage. This might have negative effects on the integrity of the structure, due not only to the grout material's early degradation, but also to a possible loss of bond between the grout and the prefabricated concrete element. Many factors affect the bond strength between two cementitious materials (e.g., grout-concrete), the presence of moisture at the existing concrete substrate surface being one of them. In this regard, pre-moistening the concrete substrate surface prior to the application of the grout material is sometimes recommended for bond enhancement. This topic has been the focus of numerous research studies in the past; however, there is still controversy among practitioners on the real benefits that this practice might provide. This paper evaluates the tensile bond performance of two non-shrink cementitious grouts applied to the exposed aggregate surface of a concrete substrate, and how the supply of moisture at the grout-concrete interface affects the bond strength. "Pull-off" bond results show increased tensile bond strength when the concrete surface is pre-moistened. Reasons to explain the observed increased bond strength are given after a careful microstructural analysis of the grout-concrete interface. Interfaces where sufficient moisture is provided to the concrete substrate such that moisture movement from the grout is prevented show reduced porosity and increased hydration on the grout side of the interface, which is thought to directly contribute to the increased tensile bond strength.

Incorporation of TiO2 nanotubes in a polycrystalline zirconia: Synthesis of nanotubes, surface characterization, and bond strength.

PubMed

Dos Santos, Angélica Feltrin; Sandes de Lucena, Fernanda; Sanches Borges, Ana Flávia; Lisboa-Filho, Paulo Noronha; Furuse, Adilson Yoshio

2018-04-05

Despite numerous advantages such as high strength, the bond of yttria-stabilized zirconia polycrystal (Y-TZP) to tooth structure requires improvement. The purpose of this in vitro study was to evaluate the incorporation of TiO 2 nanotubes into zirconia surfaces and the bond strength of resin cement to the modified ceramic. TiO 2 nanotubes were produced by alkaline synthesis, mixed with isopropyl alcohol (50 wt%) and applied on presintered zirconia disks. The ceramics were sintered, and the surfaces were characterized by confocal laser microscopy, scanning electron microscopy (SEM), and energy-dispersive x-ray spectroscopy (EDS) analysis. For bond strength, the following 6 groups (n=16) were evaluated: without TiO 2 and Single Bond Universal; with TiO 2 nanotubes and Single Bond Universal; without TiO 2 nanotubes and Z-prime; with TiO 2 nanotubes and Z-prime; without TiO 2 and Signum Zirconia Bond; with TiO 2 and Signum Zirconia Bond. After sintering, resin cement cylinders, diameter of 1.40 mm and 1 mm in height, were prepared and polymerized for 20 seconds. Specimens were stored in water at 37°C for 30 days and submitted to a shear test. Data were analyzed by 2-way ANOVA and Tukey honest significant difference (α=.05) tests. EDS analysis confirmed that nanoagglomerates were composed of TiO 2 . The shear bond strength showed statistically significant differences among bonding agents (P<.001). No significant differences were found with the application of nanotubes, regardless of the group analyzed (P=.682). The interaction among the bonding agent factors and addition of nanotubes was significant (P=.025). Nanotubes can be incorporated into zirconia surfaces. However, this incorporation did not improve bond strength. Copyright © 2017 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Examining the free radical bonding mechanism of benzoquinone- and hydroquinone-methanol passivation of silicon surfaces

NASA Astrophysics Data System (ADS)

Kotulak, Nicole A.; Chen, Meixi; Schreiber, Nikolas; Jones, Kevin; Opila, Robert L.

2015-11-01

The surface passivation of p-benzoquinone (BQ) and hydroquinone (HQ) when dissolved in methanol (ME) has been examined through effective lifetime testing of crystalline silicon (c-Si) wafers treated with the aforementioned solutions. Changes in the availability of both photons and protons in the solutions were demonstrated to affect the level of passivation achieved. The requirement of both excess protons and ambient light exposure to maintain high effective lifetimes supports the presence of a free radical species that drives the surface passivation. Surface analysis suggests a 1:1 ratio of HQ-like bonds to methoxy bonds on the c-Si surface after treatment with a BQ/ME solution.

Enhancing the reactivity of gold: Nanostructured Au(111) adsorbs CO

DOE PAGES

Hoffmann, F. M.; Hrbek, J.; Ma, S.; ...

2015-12-02

Low-coordinated sites are surface defects whose presence can transform a surface of inert or noble metal such as Au into an active catalyst. We prepared gold surfaces modified by pits, starting with a well-ordered Au(111) surface; we then used microscopy (STM) for their structural characterization and CO spectroscopy (IRAS and NEXAFS) for probing reactivity of surface defects. In contrast to the Au(111) surface CO adsorbs readily on the pitted surfaces bonding to low-coordinated sites identified as step atoms forming {111} and {100} microfacets. Finally, pitted nanostructured surfaces can serve as interesting and easily prepared models of catalytic surfaces with definedmore » defects that offer an attractive alternative to vicinal surfaces or nanoparticles commonly employed in catalysis science.« less

Comparison of the Microtensile Bond Strength of a Polyetherketoneketone (PEKK) Tooth Post Cemented with Various Surface Treatments and Various Resin Cements.

PubMed

Song, Chan-Hong; Choi, Jae-Won; Jeon, Young-Chan; Jeong, Chang-Mo; Lee, So-Hyoun; Kang, Eun-Sook; Yun, Mi-Jung; Huh, Jung-Bo

2018-05-29

The aim of this in-vitro research was to evaluate the microtensile bond strength in the newly introduced PEKK tooth post with various surface treatments and resin cements. A fiberglass tooth post was included in order to compare it with PEKK as a possible post material. The microtensile bond strengths of the fiberglass post (FRC Postec Plus) and the PEKK post (Pekkton ® ) were tested using three kinds of self-adhesive resin cements (G-CEM LinkAce, Multilink Speed, and RelyX U200) and one self-etching resin cement (PANAVIA F2.0). The surface treatments of the fiberglass posts were processed according to the manufacturer's recommendations (F1, application of 37% phosphoric acid etching gel and silanization). For the PEKK post groups, various surface treatments were performed like no surface treatment (P1), sandblasting (P2), silica-coating and silanization (P3), and sandblasting with a composite primer (P4). In the surface treatment, PEKK posts with silica coating and silane treatment (P3) showed a significantly higher microtensile bond strength (mean MPa: 18.09, p < 0.05). The highest microtensile bond strength was shown when the PEKK posts were treated with a silica coating and silane treatment and cemented with RelyX U200 (mean MPa: 22.22). The PEKK posts with surface treatments of silica-coating and silanization or sandblasting displayed superior microtensile bond strengths (mean MPa: 18.09 and 16.25, respectively) compared to the conventional fiberglass posts (mean MPa: 14.93, p < 0.05).

Lanthanides as Catalysts: Guided Ion Beam and Theoretical Studies of Sm+ + COS.

PubMed

Armentrout, P B; Cox, Richard M; Sweeny, Brendan C; Ard, Shaun G; Shuman, Nicholas S; Viggiano, Albert A

2018-01-25

Reactions of samarium cations with carbonyl sulfide are examined using a guided ion beam tandem mass spectrometer and a variable temperature selected ion flow tube apparatus. Formation of SmS + + CO is observed in both instruments with a kinetic energy and temperature dependence demonstrating a barrierless reaction occurring with an efficiency of 26 ± 9%. Formation of SmO + + CS is also observed at high kinetic energies and exhibits a threshold determined as 2.81 ± 0.32 eV, substantially higher than expected from known thermochemistry. The potential energy surfaces for these reactions along sextet and octet spin surfaces are also examined theoretically at the MP2 and CCSD(T) levels. The observed barrier for oxidation is shown to likely correspond to the energy of the crossing between surfaces corresponding to the ground state electronic configuration of Sm + ( 8 F,4f 6 6s 1 ) and an excited surface having two electrons in the valence space (excluding 4f), which are needed to form the strong SmO + bond. In contrast, the S-CO bond is activated much more readily because this crossing occurs at much lower energies. This result is attributed to the much weaker S-CO bond energy as well as the ability of sulfur to bind effectively at different angles. Although both reactions are spin-forbidden, evidence for a more efficient spin-allowed process is also observed in the SmS + + CO cross section.

Mechanochemical Association Reaction of Interfacial Molecules Driven by Shear.

PubMed

Khajeh, Arash; He, Xin; Yeon, Jejoon; Kim, Seong H; Martini, Ashlie

2018-05-29

Shear-driven chemical reaction mechanisms are poorly understood because the relevant reactions are often hidden between two solid surfaces moving in relative motion. Here, this phenomenon is explored by characterizing shear-induced polymerization reactions that occur during vapor phase lubrication of α-pinene between sliding hydroxylated and dehydroxylated silica surfaces, complemented by reactive molecular dynamics simulations. The results suggest that oxidative chemisorption of the α-pinene molecules at reactive surface sites, which transfers oxygen atoms from the surface to the adsorbate molecule, is the critical activation step. Such activation takes place more readily on the dehydroxylated surface. During this activation, the most strained part of the α-pinene molecules undergoes a partial distortion from its equilibrium geometry, which appears to be related to the critical activation volume for mechanical activation. Once α-pinene molecules are activated, association reactions occur between the newly attached oxygen and one of the carbon atoms in another molecule, forming ether bonds. These findings have general implications for mechanochemistry because they reveal that shear-driven reactions may occur through reaction pathways very different from their thermally induced counterparts and specifically the critical role of molecular distortion in such reactions.

Shearography for Non-destructive Inspection with applications to BAT Mask Tile Adhesive Bonding and Specular Surface Honeycomb Panels

NASA Technical Reports Server (NTRS)

Lysak, Daniel B.

2003-01-01

The applicability of shearography techniques for non-destructive evaluation in two unique application areas is examined. In the first application, shearography is used to evaluate the quality of adhesive bonds holding lead tiles to the B.4T gamma ray mask for the NASA Swift program. Using a vibration excitation, the more poorly bonded tiles are readily identifiable in the shearography image. A quantitative analysis is presented that compares the shearography results with a destructive pull test measuring the force at bond failure. The second application is to evaluate the bonding between the skin and core of a honeycomb structure with a specular (mirror-like) surface. In standard shearography techniques, the object under test must have a diffuse surface to generate the speckle patterns in laser light, which are then sheared. A novel configuration using the specular surface as a mirror to image speckles from a diffuser is presented, opening up the use of shearography to a new class of objects that could not have been examined with the traditional approach. This new technique readily identifies large scale bond failures in the panel, demonstrating the validity of this approach.

Shear bond strength of indirect composite material to monolithic zirconia.

PubMed

Sari, Fatih; Secilmis, Asli; Simsek, Irfan; Ozsevik, Semih

2016-08-01

This study aimed to evaluate the effect of surface treatments on bond strength of indirect composite material (Tescera Indirect Composite System) to monolithic zirconia (inCoris TZI). Partially stabilized monolithic zirconia blocks were cut into with 2.0 mm thickness. Sintered zirconia specimens were divided into different surface treatment groups: no treatment (control), sandblasting, glaze layer & hydrofluoric acid application, and sandblasting + glaze layer & hydrofluoric acid application. The indirect composite material was applied to the surface of the monolithic zirconia specimens. Shear bond strength value of each specimen was evaluated after thermocycling. The fractured surface of each specimen was examined with a stereomicroscope and a scanning electron microscope to assess the failure types. The data were analyzed using one-way analysis of variance (ANOVA) and Tukey LSD tests (α=.05). Bond strength was significantly lower in untreated specimens than in sandblasted specimens (P<.05). No difference between the glaze layer and hydrofluoric acid application treated groups were observed. However, bond strength for these groups were significantly higher as compared with the other two groups (P<.05). Combined use of glaze layer & hydrofluoric acid application and silanization are reliable for strong and durable bonding between indirect composite material and monolithic zirconia.

Partially linearized external models to active-space coupled-cluster through connected hextuple excitations.

PubMed

Xu, Enhua; Ten-No, Seiichiro L

2018-06-05

Partially linearized external models to active-space coupled-cluster through hextuple excitations, for example, CC{SDtqph} L , CCSD{tqph} L , and CCSD{tqph} hyb, are implemented and compared with the full active-space CCSDtqph. The computational scaling of CCSDtqph coincides with that for the standard coupled-cluster singles and doubles (CCSD), yet with a much large prefactor. The approximate schemes to linearize the external excitations higher than doubles are significantly cheaper than the full CCSDtqph model. These models are applied to investigate the bond dissociation energies of diatomic molecules (HF, F 2 , CuH, and CuF), and the potential energy surfaces of the bond dissociation processes of HF, CuH, H 2 O, and C 2 H 4 . Among the approximate models, CCSD{tqph} hyb provides very accurate descriptions compared with CCSDtqph for all of the tested systems. © 2018 Wiley Periodicals, Inc. © 2018 Wiley Periodicals, Inc.

Effect of an internal coating technique on tensile bond strengths of resin cements to zirconia ceramics.

PubMed

Kitayama, Shuzo; Nikaido, Toru; Maruoka, Rena; Zhu, Lei; Ikeda, Masaomi; Watanabe, Akihiko; Foxton, Richard M; Miura, Hiroyuki; Tagami, Junji

2009-07-01

This study was conducted to enhance the tensile bond strengths of resin cements to zirconia ceramics. Fifty-six zirconia ceramic specimens (Cercon Base) and twenty-eight silica-based ceramic specimens (GN-1, GN-1 Ceramic Block) were air-abraded using alumina. Thereafter, the zirconia ceramic specimens were divided into two subgroups of 28 each according to the surface pretreatment; no pretreatment (Zr); and the internal coating technique (INT). For INT, the surface of zirconia was coated by fusing silica-based ceramics (Cercon Ceram Kiss). Ceramic surfaces were conditioned with/without a silane coupling agent followed by bonding with one of two resin cements; Panavia F 2.0 (PF) and Superbond C&B (SB). After 24 hours storage in water, the tensile bond strengths were tested (n=7). For both PF and SB, silanization significantly improved the bond strength to GN-1 and INT (p<0.05). The INT coating followed by silanizaton demonstrated enhancement of bonding to zirconia ceramics.